THE 
VOLATILE OILS 
BY 
E, GILDEMEISTER and FR. HOFFMANN. 
/LEIPZIG BERLIN 
Written under the auspices of the firm of 
SCHIMMEL & CO., 
LEIPZIG. 
Authorized translation by 
a 
EDWARD KREMERS 
MADISON, WIS. 
With four maps and numerous illustrations. 
MILWAUKEE. 
PHARMACEUTICAL REVIEW PUBL. CO. 
1900. A Copyrighted by Edward Kremers, Madison, Wis. 
Germania Publishing Co,, Milwaukee. Wis. THE 
VOLaA^TILaEI oius. PREFACE. 
It is only within the last few decades that the former empiric 
manufacture of volatile oils has been placed on a scientific basis,' which 
has enabled it to develop into an independent branch of chemical 
industry. During- the period of transition in which this branch still 
finds itself, those factories which have done pioneer work, both scien- 
tifically and technically, as well as those which use the oils in various 
manufactures, are often compelled to suffer from the competition of 
inferior and adulterated products. As a matter of fact, the proper 
understanding- of the estimation and appreciation of quality and purity 
of the much used volatile oils is not as common as is desirable for 
industry, commerce and the trades. The principal cause for this 
condition is the fact that the recent chemical investigations and 
their application to the arts have not yet been generally offered in 
suitable form. 
The want of a work which from a modern standpoint treats in an 
exhaustive and critical manner the entire subject of volatile oils, has 
caused the firm of Schimmel & Co. of Leipzig to commission the 
authors with the preparation of a treatise that would meet the present 
demands. The successful completion of this task was greatly facilitated 
by having placed at their disposal the observation records of many 
years of manufacturing on a large scale. 
Special stress has been laid on the description of properties and 
on tried methods of testing the commercially more important oils. 
Thus the consumer is placed in a position to distinguish pure from 
adulterated oils, good oils from those of inferior quality. Inasmuch as 
rational methods of examination are dependent on a knowledge of the 
physical properties and chemical composition of the oils, it became 
necessary to thoroughly discuss the results of the scientific investigations VI 
Preface. 
of, the subject. Those investigations, however, that cannot claim 
permanent value as well as antiquated methods, such as color 
reactions, etc., have not been included. 
Fully realizing the importance of an historical basis for such a 
work, this has received special attention. Detailed references to the 
original sources enable the reader to make farther investigations in this 
direction. 
Although the object and aim of this book are primarily of a 
practical nature, the authors venture to hope that it also offers to the 
scientific investigator a complete summary, with numerous references to 
original literature, of everything that has been accomplished in this line. 
The authors acknowledge with thanks the cooperation of Dr. C. 
von Rechenberg who wrote the chapter ''Theoretical foundation for the 
preparation of volatile oils by steam distillation;" also of Dr. J. Helle 
who contributed "The more common constituents of volatile oils;" 
finally that of Dr. J. Bertram who kindly assisted in reading proof and 
who repeatedly made valuable suggestions. 
With regard to the share in the work by the two authors whose 
names appear on the title page: the "Historical introduction," also 
everything that pertains to the history of the volatile oils and the 
crude materials, as well as the description of the methods of production 
of the American products, and in part the statements regarding origin 
and production of the drugs, are from the pen of Dr. Friedrich 
Hoffmann; the entire chemical text and those parts not specially 
enumerated have been written by Dr. Eduard Grildemeister. 
Leipzig and Berlin, June 1899. PREFACE TO THE AMERICAN EDITION. 
In the work of Doctors Gildemeister and Hoffmann we find a happy 
blending of history with chemical science and technology that is quite 
unique in modern chemical literature. Moreover it covers a chapter of 
organic chemistry of which Professor Emil Fischer of Berlin recently 
remarked that it had undergone more rapid development within the 
past fifteen years than any other. 
The translation of such a work should indeed prove of value. To 
make such a translation and to take cognizance of the numerous con- 
tributions on volatile oils and related subjects that have appeared since 
the original German edition was issued a year ago, has proved a severe 
task for one whose time was already divided between instructional duties 
and editorial labors. In judging the English edition, it is hoped that 
the limitations as to time and the difficulties encountered will be taken 
into consideration. 
Owing to the impossibility of satisfactorily translating many of the 
numerous quotations in the historical introduction, chapters two and 
three have been condensed. Inasmuch as but very few if any readers 
are in position to consult the numerous historical works quoted by 
Dr. Hoffmann, all bibliographic information has been placed in an 
appendix. 
To the special part a few oils were added, and changes rendered 
necessary by recent investigations were made as far as time permitted. 
The writer desires to acknowledge with thanks his indebtedness to 
Mr. Carl Fritzsche and to Dr. Hoffmann for suggestions, as to the 
scope of the translation and as to minor details. Mr. 0. Schreiner has 
assisted in the translation and proof reading and Dr. C. Kleber of 
Garfield, N. J., has kindly read one proof. His long experience as 
chemical expert on the subject of volatile oils rendered his cooperation 
especially valuable. 
EDWARD KREMERS. 
Madison, Wis., July 1900. TABLE OF CONTENTS. 
Page 
Historical Introduction . ;... 1 
1. The spice-trade in antiquity and during the middle ages 3 
2. History of volatile oils 13 
3. History of the methods of distillation and of distilling apparatus 51 
General Part 83 
1. Theoretical basis for obtaining volatile oils by steam distillation 85 
2. The more commonly occurring constituents of volatile oils 97 
3. The examination of volatile oils.. 183 
4. List of plants, arranged according to families, from which volatile oils 
are obtained 212 
Special Part .• 223 
History, origin, preparation, properties, composition, examination, and 
commercial statistics of the volatile oils ... 225 
Bibliographic Notes 693 
Index 709 HISTORICAL INTRODUCTION. 1. THE SPICE-TRADE IN ANTIQUITY AND DURING THE 
MIDDLE AGES. 
(With two maps.) 
Parts of plants as well as natural plant products which have been 
used since antiquity on account of their agreeable odor, their pleasant 
taste, or their medicinal virtue, enter the world's commerce up to the 
present time in their original form, being either previously dried or 
prepared in some other expedient manner. The essential constituents 
of these crude materials (drugs), the aromatic volatile oils, the resins, 
gum resins, bitter principles, alkaloids and glucosides, have been recog- 
nized in the course of development of the natural sciences. With the 
improvements in technology they have gradually been prepared in a 
purer and better condition. 
Of these various products of the plant world, the spices and aro- 
matics have from the very beginning ministered to the needs and well- 
fare of man, and have, therefore, been appreciate^ by him in a special 
degree. As a result, they have always been a prominent and influential 
factor in the intercourse of nations as well as in the world's commerce. 
After several thousand years of knowledge and actual use of the spices 
in their original form, their essential constituents, the volatile oils, have 
since the middle ages and more particularly in modern times been 
successfully isolated in their natural freshness and entire efficiency. 
In a treatise on volatile oils, a brief historical retrospect of the 
origin of and commerce in the bearers of these products, viz. the spices 
and aromatics, may be regarded as eminently proper. This all the 
more, since in this branch of knowledge as well as in others the 
historical element constitutes a valuable basis for a proper under- 
standing and investigation. 4 
Historical Introduction. 
All investigation in the realm of the history of civilization, that 
considers not merely a single people but mankind in general, and that 
goes back to the earliest historic documents, invariably leads to the 
wonderful orient so rich in legends-to central Asia, the traditional 
cradle of mankind. This is also true of the history of the trade of the 
oldest peoples, and especially of the source and distribution of the use- 
ful spices and aromatics. 
Its geographical position and topographical configuration make 
Asia a very highly favored continent. Broad as it is, it extends from 
pole to equator. Favored by mighty mountain chains and rivers, its 
most beautiful and richest countries lie in latitudes where soil and 
climate afford all conditions for a profusion of luxuriant subtropical 
vegetation. The eastern and southern coastlands are cleft by large 
bays which penetrate far inland. Many navigable rivers which flow into 
these bays have their origin in distant highlands. The mainland is 
bordered by a wreath of islands extending from the Japanese island 
realm through the Malay archipelago to Ceylon. These islands abound 
in tropical vegetation. The entire continent, therefore, reveals a 
diversity and richness of plant life such as no other possesses. 
These advantages have made southern Asia and the islands 
bordering on its shore the oldest and principal scene of international 
traffic and commerce, spices and aromatics constituting the main 
articles of exchange. They not only found general use on account of 
their agreeable odor and aromatic taste, but were employed by most 
peoples in religious rites and sacrificial customs, and thus acquired 
symbolic meaning. With the increase of prosperity and luxury, also 
with the development of the sense of cleanliness and of physical well- 
being, spices and aromatics not only became more valuable, but their 
consumption increased. 
According to documents discovered in recent years, the territory 
between the Indus and the Oxus was the starting point of the early 
commerce between the oldest peoples of central and southern Asia. 
Attock, Cabura, Bactra and Maracanda seem to have been the first 
larger centres for storage and exchange of oriental products. These 
were spices and aromatics, the noble metals, silk, and jewelry. To 
Attock were brought the products of the eastern Chinese empire, which, 
at an early date, closed its markets to the rest of the world. 
From Attock, at the junction of the Kabul river with the Indus, 
the caravan road led via Cabura (the present capital Kabul of 
Afghanistan) to the north via Bactra, Bokhara and Maracanda The Spice-Trade in Antiquity and During the Middle Ages. 
5 
(Samarkand) to the countries of the Oxus and to the Scythian tribes. 
Also from Cabura southward to Kandahar, thence in a western direction 
through the realm of the Parthians to the Pylae Caspiae (Caspian 
gate), and to Ecbatana in Media. Thence the land route crossed the 
Tigris to Babylon on the Euphrates. In a later period, after the traffic 
along the water routes had developed, a round-about way via Susa to 
the mouth of the Tigris was taken and the caravan freight shipped up 
the Euphrates to Babylon. Between Attock and the ports on the Black 
and Mediterranean seas, Babylon - existing 3000 years B. C. - was in 
early antiquity the most important place of traffic and commerce for 
westward bound Chinese and Indian merchandise. To the northward 
the caravan roads led out of Babylon through Assyria and Armenia 
to the Black sea (Pontus Euxinus) and westward through Syria to 
the Mediterranean sea (Mare Internum), thence through Palestine to 
Egypt. In spite of their highly developed industry the Egyptians, as 
is well known, closed their doors to foreign peoples as did the Chinese. 
As a result commercial centres were wanting in Egypt that were open 
to foreign merchants and to transitory commerce. 
During the prime of the Babylonian empire, about 2000 to 
1000 B. C., a lively caravan trade was developed which extended from 
China, India and Arabia to Egypt, Palestine, Syria and the Black sea. 
During this period, Arabia acquired a special importance by means 
of the sea traffic of her southern coast, which was favored by the 
Persian gulf and the Red sea. At an early date, the Arabian population 
conducted a lively intermediate trade with Indian and Egyptian goods 
which were brought to the Arabian ports. By means of caravans these 
were carried northward to Babylonia, Syria and other countries. The 
principal route from southwestern Arabia to Babylon, Damascus and 
Egypt led from Cane on the Arabian gulf (Erythraean sea) via Saba, 
Macoraba, Hippos and Onne to Elath (the present Akabah) at the 
north-eastern end of the Red sea. From this point the eastern route 
crossed the Jordan via Petra, Kir Moab, Ammonitis and Dan to 
Damascus; the western route to Egypt via Azab, Axomis and Meroe. 
About 15 centuries before the Christian era, the world's commerce 
was gradually and, in the course of time, very greatly expanded by the 
Phoenicians, who lived on the narrow Syrian coast district. Iu the 
industrial and commercial field they acquired a prominent position; as 
mariners, however, a dominating position among the nations of their 
time. Besides having practical control of sea navigation, the Phoeni- 
cians were the first extensive and successful colonizing nation of 6 
Historical Introduction. 
antiquity. They established or extended commerce with the peoples 
living along the coast of the Mediterranean, they ventured through the 
"Pillars of Hercules" (Gibraltar) into the ocean and made accessible 
the products of the Madeira and Canary islands, the western coasts of 
Spain and France, the British islands, and the northland as far as the 
amber coasts of the Baltic sea. 
For almost a thousand years, during which time they held their 
prominent position in marine traffic, the Phoenicians were the principal 
commercial agents between the nations of the orient and the Occident. 
Sidon and, since the ninth century B. C., Tyre became prominent centres 
of the world's commerce of that time. x) 
The Phoenicians also extended their navigation to the Red sea and 
the Arabian gulf and from these to the Persian gulf. In the latter they 
established the colonies on Arados and Tylos, islands belonging to the 
present Bahrein group. From the twelfth century up to their decline in 
the fifth century B. C., these cities carried on a large transit-trade with 
goods from India and Ceylon to Babylon, Damascus, Tyre and Sidon, 
and to Egypt. A caravan route led from Gerra via Salma, Thaema 
and Madiana to Elath. From Elath the older routes to the north, to 
Damascus, Tyre and Sidon were followed, also westward to Egypt. 
To Babylon, on the other hand, the water route up the Euphrates or 
Tigris was taken from Arados and Tylos. 
Carthage, a Phoenician colony established in 8-16 B. C., soon 
flourished and developed such power that it became the greatest rival 
of the mother country in the following century. 
Owing to the rise of the Persian empire, the inland commerce of 
western Asia was somewhat shifted during the period from the sixth to 
the fourth century B. C. The old routes of traffic passing through 
countries controlled by the Persians were not only kept in good 
condition but extensions were also made. These old highways of trans- 
continental commerce underwent further changes at the time of the 
Greek conquests under Alexander the Great at the close of the fourth 
century B. C. Still greater, however, were the changes brought about 
by the migration of nations during the fourth and fifth centuries of the 
Christian era. Wars and other disturbances of the commercial inter- 
course along the old caravan routes frequently restricted traffic to the 
; Asis well known, the Phoenicians supplied King Solomon with the material 
for the building of the temple at Jerusalem about 1000 B. C. (1. Kings, 5: 9-10; 
also 2. Chron., 2: 3, 9; Ezekiel, 27.) THE HIGHWAYS OF COMMERCE IN ANCIENT TIMES. 
(Spicery and. Grocery Trades in Ancient Times and in the Middle Ages.) 
Dr. Er. Hoffmawi. 
Printed by FA.Brockhans, Leipzig. rivers and seas. Upon the reestablishment of peace, however, commerce 
always seems to have found its way back to the traditional caravan 
routes. 
In the course of time, however, and especially during the sixth and 
seventh centuries still other changes were made. Thus, e. g. the products 
of the Chinese and Indian coast districts and of the Indian islands were 
brought in part by ship over the Bay of Bengal and by way of Ceylon 
to the commercial centres of the Persian gulf and the Red sea. From 
these they were distributed by coast-wise trade, by river navigation up 
the Tigris and Euphrates, or by caravan to the north and west. 
From the more northern Chinese and,Indian districts the caravans 
passed through the present East-Turkestan following the older routes 
mentioned on p. 8 through the countries of the Oxus to the Araxes. 
The goods, instead of being carried by river to Phasis and the Black 
sea, were taken as far as Artaxata and then by caravan through 
Persia to the ports of Asia Minor. The old route from Kandahar 
along the northern border of the Iranian plateau, which likewise led 
through Persian territory, was also followed by caravans. 
During the reign of the East Roman emperor Justinian, in the sixth 
century, when the world empire of the Romans was broken up by the 
migration of nations, Persia experienced a new rise to power under the 
Sassanidse. The Persians ruled the entire territory from the Caspian to 
the Arabian seas and from Afghanistan of to-day to Syria and Armenia. 
They improved the old high-ways and caravansaries, kept them in 
repair and promoted commerce and traffic, directing both over routes 
leading through their own territory. Owing to the wealth and luxury of 
the Roman empire, the commerce in oriental spices, aromatics etc. had 
risen to an unusual height. The East Roman empire which at that 
time was the principal western state with its capital at Constantinople, 
was forced by the Persians to procure such oriental goods as were not 
shipped by water, from and through Persia and to pay a heavy duty 
on them. The principal places of storage and for the collection of 
revenue at that time were Artaxata on the Araxes, Nisibis, south of the 
Tigris, and Callinicum (Rakka) on the Euphrates. To Artaxata were 
brought the goods from the countries of the Oxus over the Caspian sea. 
Those that were conveyed along the caravan routes south of the Caspian 
sea, and those that came from the coastlands of the Persian bay up 
the Tigris or Euphrates centered at Nisibis. For nearly five centuries, 
the aromatics of China and India, of the Malayan archipelago which 
came via Ceylon, and in part those of Arabia were transported over 
The Spice-Trade in Antiquity and During the Middle Ages. 
7 8 
Historical Introduction. 
the two last mentioned routes to the western countries. About this 
time also, the levant commerce, which became so important in a future 
period, had its beginning'. 
During the life of the Persian empire (up to the middle of the seventh 
century A. D.) all attempts, made by Justinian and his successors, to 
divert the transmarine commerce from its course through Persian 
territory remained unsuccessful. They did not even succeed in opening- 
up marine traffic between India and Ethiopia, because Persian merchants 
visited the Indian markets and persuaded the Indians and Chinese not 
to sell their goods to new customers. In the course of time, however, 
the Greeks succeeded in obtaining larger consignments by water from 
the ports of India and Ceylon and more particularly from the coast- 
lands of the Arabian sea, which were rich in spices. These were delivered 
directly to their own ports, Kolsum, and Akabah and Berenice near 
the entrance to the Red sea. 
About this time there existed three great caravan routes from 
China westward. They began in the territory of the Hoang Ho and the 
Yangtsekiang and passed through the Gobi desert. The northern route 
then took its course through the oasis of Chami, then northward along 
the Thian-Shan mountains through the present Dsungarai, past the 
Balkash sea, and via Talas. It then followed the Syr-Darya river to 
the Aral sea and the Caspian sea. 
The middle route passed to the south of the Thian-Shan mountains 
through the northern part of East Turkestan via Chami, Turfan, 
Karaschar, Kutscha, and Aksu to Kashgar; thence over the Terek pass 
to Ferghana via Samarkand, Buchara and Merw to Persia. 
From the Gobi desert, the southern route passed through the 
southern part of East Turkestan via Chotan and Yarkand, then over 
the Pamir plateau and through Afghanistan to the Pandschab (India) 
crossing the Bamian and Gazna passes to Multan. Goods intended for 
the west, coming via this route, were taken down the Indus river to 
Daybal. From this port they were shipped by sea with other goods 
from India and Ceylon. 
During the seventh and eighth centuries A. D. the Arabs carried on 
an extensive marine commerce with India and China, especially in spices 
and aromatics. These were supplied in large quantities to the luxurious 
courts of the caliphs and the Byzantine emperors. The principal centres 
between China and Arabia were at that time on the Malay peninsula, 
to which were also brought the products of Java and other Sunda 
islands. Later commerce concentrated itself in Kalah, a city on the The Spice-Trade in Antiquity and During the Middle Ages. 
9 
east shore of the Malay peninsula. In the tenth century there existed 
between Kalah and Siraf, a city on the east coast of the Persian gulf, 
regular commercial intercourse between the Arabians and Chinese. 
From the northern point of Sumatra the Chinese crossed the bay of 
Bengal to Ceylon. 
Arabian merchants also settled along the Malabar coast, in Ceylon 
and in the Indian sea ports. From the eighth to the tenth century, 
Daybal at the mouth of the Indus was the most important commercial 
centre and seaport of India. It was the principal emporium for the 
products of the Indus valley and the Pandschab on the one side and of 
Mesopotamia. Persia and Arabia on the other. For the products of 
northern India, Multan on the Dschelam river in the Pandschab, was 
the first larger rallying point. It was also a place of pilgrimage that 
was much revered and visited by the Hindoos. 
From the eighth century on, Suhar and Muscat, near the entrance of 
the Persian bay, developed as rival ports for Indian and Chinese 
commerce with occidental countries. At the same time Aden, at the 
entrance to the Red sea, became the principal port and commercial 
centre for the products from Yemen, Hedsjaz, Ethiopia and Egypt. 
In addition there were caravan routes: one from India to Persia 
through Seistan; the other via Gazna and Kabul to Afghanistan. 
Seti I. and Rameses II., Egyptian pharaohs, had during the first 
quarter of the fourteenth century B. C. connected the Red sea with the 
Mediterranean sea. In order to reestablish this sea-route, Pharaoh Necho 
toward the end of the seventh century B. C. tried to have a new canal 
constructed from Bubastis on the Nile to Patumos on the Red sea. 
This was not completed, however, until 500 B. C. by Darius Hystaspes 
and was widened and improved by the Ptolemies. Before the beginning 
of the Christian era it was again choked up with sand. Under the caliph 
Omar in the seventh century A. D. the canal from Cairo to the Red sea 
was again restored, but did not exist longer than a century. 
From the seventh to the twelfth century there also existed several land 
routes across the Suez isthmus. One of these followed the course of the 
old canal (choked up with sand) from the Red sea to Cairo, whence the 
goods were shipped down the. Nile and then by sea. If the passage of 
the goods through Alexandria was not necessary, the shorter route over 
the isthmus from Kolsum to Pelusium (Faramiah) was preferred. At this 
time Damascus and Jerusalem were also important commercial centres. 
Here also oriental goods were exchanged by the merchants of Mecca on 
the one hand and those of Tripoli, Beirut, Tyre and Acre on the other. 10 
Historical Introduction. 
From the seventh to the twelfth century there existed an active coast- 
wise trade along the north African coast, having its centres in Syria and 
Egypt and extending as far as Morrocco and Spain. This commerce 
acquired a special importance for spices and ^aromatics although for a 
time it was limited by Mohammedan laws against intercourse with 
Christians. Commerce also soon flourished among the Greeks, who 
obtained spices and aromatics, possibly also rose water and aromatized 
fatty oils from Antioch, Alexandria and Trapezunt and brought them 
to Constantinople, Thessalionica and Cherson. Already in the tenth 
century Trapezunt was an important emporium for the spices and 
aromatics of India and Arabia and for Persian perfumes. The Greeks, 
however, purchased these luxuries only for home consumption, which 
was large, without distributing them farther to other nations. 
From the tenth to the fifteenth centuries, the commerce of the 
Mediterranean was conducted principally by Italian cities. In the tenth 
and eleventh centuries Bari, Salerno, Naples, Gaeta, and above all Amalfi, 
Pisa and Venice were the principal commercial centres. The levant 
commerce, which was in its prime from the twelfth to the fifteenth 
century centered in Venice and Genoa. In the levant itself, at the time 
of the crusades during the twelfth and thirteenth centuries, Acre on the 
Palestine coast was the most important commercial port. When this 
city, the last held by the Christians, likewise fell into the hands of the 
Mohammedans in 1291, Famagusta on Cyprus, and, for a longer period, 
Lajazza on the bay of Alexandretta, became the commercial centres of 
the Levant up to the fifteenth century. The latter port was the junction 
for the western merchants with those coming from Asia. 
Toward the end of the thirteenth century, the cities of Bagdad and 
Basra on the Euphrates, lost their commercial supremacy which they 
held for several centuries to Tebriz, the new rising capital of Persia, near 
the Caspian sea. When Egypt in the thirteenth and fourteenth centuries 
began to levy a high toll on the finer Indian spices and aromatics, the 
land transportation was deviated more and more through Persia via 
Bagdad and Tebriz to Lajazzo and Trapezunt. 
During the fourteenth century, the island port Ormuz in the Persian 
gulf became an emporium for the westward bound goods from India and 
Ceylon. It maintained this position until its capture by the Portugese 
at the beginning of the sixteenth century. The more important ports 
along the western coast of India at that time were Mangalore, Calicut 
and Quilon. Ginger, cinnamon, cardamoms, pepper, cloves, nutmegs, 
sandalwood, lignaloes, indigo, etc., were brought to these ports THE HIGHWAYS OF COMMERCE IN THE MIDDLE AGES. 
(Spicery and Grocery Trades in Ancient Times and in the Middle Ages.) 
in oo on .tn en 7A on uh icn 
Dr. Ft. Hoffmann. 
Printed by P.A-Broclthaus,Leipzig. The Spice-Trade in Antiquity and During the Middle Ages. 
11 
from the interior. From the Chinese ports and the East Indian 
islands large importations of these and other spices and aromatics 
were received. 
Toward the close of the thirteenth and at the beginning of the 
fourteenth century the direct traffic between Europe and China became 
very active, more particularly over the land route. Under the protection 
of the Mongols the caravan routes through central Asia were generally 
safe. The greater part of the Chinese empire was also accessible to 
Europeans. About this time also Marco Polo, the first European 
world-traveler, visited China, India and the islands of the Indian 
ocean. 
Owing to disturbances and invasions of central Asia, the overland 
traffic diminished after the middle of the fourteenth century. Up to the 
discovery of the sea route around Africa at the close of the fifteenth 
century, Tebriz, however, remained an important centre for transitory 
trade. The capture of Constantinople by the Turks in 1453 enabled 
them to interrupt the trade of the Italians via Trapezunt and the 
Crimea and soon to cut it off altogether. Cyprus also lost its former 
importance for the levant trade about this time. 
Egyptian commerce, however, once more increased considerably 
toward the close of the fourteenth and in the course of the fifteenth 
century. In place of Aden, Dschidda, the sea-port of Mecca, became the 
principal junction of commerce between the Indian seas and the Occident. 
The heavier goods were transported by water, the lighter by pilgrim 
caravans to Tor on the Sinai peninsula. The high toll levied by the 
Egyptians caused some of this trade to be deviated for the time being 
to Syria. Owing to the occupation of Lajazzo by the Turks in 1347, 
and the conquest of the Crimea in the fifteenth century, this traffic 
became very prosperous for a short time. 
Thus in the course of several thousand years, the commercial 
intercourse between the nations of Asia, later also those of Africa, and 
of Europe underwent a variety of changes as did also the various 
routes of traffic. The circumnavigation of Africa by the Portugese in 
1498, their conquest of Ormuz, the key to the Persian gulf, and their 
extended marine traffic brought about important changes in the 
traditional channels of traffic. The transport by means of caravans 
was gradually diminished; the highways, formerly well kept, got out 
of repair, the ocean ship displaced the "ship of the desert," the camel 
of the caravans. 12 
Historical Introduction. 
From the sixteenth century on, the ocean became the preferred high- 
way of international commerce. Hence the levant commerce, which had 
flourished for several centuries and had enriched the commercial centres 
of Italy and of other Mediterranean countries, lost its importance and 
finally ceased. 
Numerous ruins of architecturally magnificent structures in cities 
once large and powerful and in fortified markets, well built high-ways 
covered with the sand and alluvium of centuries, also caravansaries on 
the plateau and desert lands of western Asia and the Arabian peninsula 
reveal to these after-days the former greatness, the artistic skill and 
the commercial prosperity of peoples who still live in history but 
principally in name only. 
The spices and aromatics of southern Asia and the Asiatic islands, 
which constituted the first foundation of international commerce and 
which have played an important role in the commerce of all ages, have 
retained their original value in spite of all changes in the world's history 
and in spite of all mismanagement and waste on the part of foreign 
nations. The same spicy cinnamon, cloves, nutmegs and cardamoms, 
pepper and ginger and other spices used and highly appreciated 
since antiquity; frankincense and myrrh, benzoin and other incenses, 
camphor, sandalwood and lignaloes and other plant products acquiring 
use in ever increasing numbers thrive after thousands of years in the 
sunny countries and islands of the orient in the primitive freshness and 
profusion. 
However, they are no longer brought to the Occident on the backs 
of camels stretched out into almost endless chains over the plateaus 
and deserts of Asia, but in trim sailing vessels and speedy steamships 
crossing the ocean; or they are transported in freight cars that hasten 
over steel tracks encircling the continents. They are used either in their 
original state, or in a concentrated form, purified as it were by the 
giant stills of modern chemical industry. They still serve man in the 
humble hut as well as in the palace. 2. HISTORY OF VOLATILE OILS. 
In the course of centuries various more or less independent branches 
have separated from the common trunk of natural science and have 
made a history of their own. This is true also of the subject presented 
in this treatise. To be sure a true knowledge and application of those 
plant products, which are termed volatile oils, has been gained only in 
recent periods. Nevertheless the nature and value of these substances, 
that so materially enhance the attractiveness of plant life, does not 
appear to have escaped the observation of the oldest peoples. It seems 
almost certain that not only the grace and vivid coloring of the flowers 
but. also the fragrance of the vegetation in southern Asia and the 
islands encircling the mainland, must have aroused the curiosity of man, 
as well as the use of the plants for the purpose of food, clothing and 
other necessaries. Indeed, those plants and plant products that were 
conspicuous on account of their aromatic odor and taste, seem to have 
attracted the attention of man in a special degree. These very properties 
seem to have induced him to use them and to seek proper methods for 
their cultivation and preservation. 
It is true that the oldest documents pertaining to the history of 
the beginning of human industry have recorded only the most primitive 
methods for the preparation of implements that were used in the chase, 
the cultivation of the soil, and for the collection and preparation of food- 
stuffs and other useful products. Nevertheless it may not be amiss to 
suppose that the exigencies of self-preservation, of protection, and of 
wellbeing at an early period caused man to utilize the heat of the sun 
and of fire for the preparation of foodstuffs as well as for various other 
purposes in the production and preparation of a variety of natural 
products. It may have required long periods of time before fire was 
rfsed for the preserving of perishable foodstuffs, for the separation of 14 
Historical Introduction. 
more valuable substances from those of lesser value, or of the pleasant 
from disagreeable ones: so e. g., the distillation of the "spirit of wine" 
from the wine itself; the separation of the "subtle principle," the aroma, 
from spices and balsams. The earliest documents, however, show that 
the spices were among the earliest and most highly prized articles of 
barter and commerce during antiquity; that, as products of nature 
agreeable to the gods, they were offered as sacrifices in religious cere- 
monies, and were also used in the embalming of the dead preparatory 
to their transit into the realm of the gods. 
It is especially this use of spices and of aromatic plant products by 
the priests, those promotors and supporters of natural science during 
antiquity, that renders it probable that their knowledge was early 
applied to the production, preparation and improvement of the spices 
which were used in the sacrifices and in embalming. Whether a beginning 
in the preparation of the aromatic principles of plants, our modern 
volatile oils, was made previous to early Hindoo and Egyptian civilization, 
does not become apparent from the oldest documents. Even the Bible, 
which gives so much information concerning the customs of the Jews, 
makes no other statements than those pertaining to the spices and 
aromatics used in various countries. The early preparation of the 
metals and the manufacture of metallic utensils would indicate that 
furnaces and other apparatus for heating were early used in a variety 
of ways. One may suppose, therefore, that they w'ere gradually used in 
primitive attempts to separate the spirit from wine, from other fermented 
fruit juices and honey; also the subtle aromatic principles from spices, 
balsams and oleoresins. These crude experiments may be considered as 
constituting the first stages in the art of distillation which later became 
of such great importance. 
The Egyptians, owing to the continuity of their early and highly 
developed civilization and to the preservation of their monuments and 
literary productions, are generally considered as standing at the portals 
of history. With reference to time, however, the Chinese and Aryans 
are probably the oldest peoples. These races, with whom civilization 
seems to have had its beginning, lived in central and southern Asia, a 
mountainous district favored with a mild climate and a luxuriant 
vegetation rich in useful and spicy products. Our knowledge of the 
peoples who first occupied this wide territory is but legendary. Con- 
cerning their industrial and technical accomplishments as well as their 
literary productions, but little definite information has come down to 
us. These Chinese and Indians may have developed considerable de*- History of Volatile Oils. 
15 
terity in industrial pursuits and may even have accomplished much in 
the scientific realm. Their attitude of exclusiveness, however, toward 
the outside world and their secrecy have prevented them from exerting 
a lasting influence on other nations. The oldest documents that throw 
light on their early scientific accomplishments are the Ayur-Veda (book 
of the science of life) by Charaka and Susruta. x) As is the case with 
so many writings of early antiquity, nothing definite is known with 
regard to the age of these documents. It is possible that they are 
traditions reduced to writing at a rather late time. From this work 
it becomes apparent that the Indians were acquainted with primitive 
apparatus for distillation, with fermentation and the products obtained 
by distillation. Of "distilled oils," those of rose, schoenus (andropogon), 
and calamus are mentioned.2). Whether these oils%are "distilled" in 
the modern sense of this term can not be ascertained. 
From the likewise legendary documents of the old Persians it 
would seem that they also were acquainted with the process of 
distillation and distilling apparatus. 3) 
With regard to the Egyptians, however, whose history goes back as 
far as 4000 B. C., we have definite information concerning the early 
development.of industry and art, the acquirement of scientific knowledge 
and its practical application. Their commerce, which extended as far 
as India, Babylonia, Syria, Ethiopia and other countries, as well as 
their industry and art undoubtedly developed slowly before it reached 
that height which we now admire. The application of their scientific 
knowledge finds manifold expression. Thus, they were acquainted with 
the preparation of the more common and useful metals, with furnaces 
and distilling apparatus, with the distillation of wine, of cedar resin,4) 
the preparation of soda, alum, vinegar,5) soap, leather, with the 
preparation and use of colors' and the manufacture of glass. The 
Egyptians were acquainted with and used cedar (turpentine) oil6) and 
colophonium, 7) and probably knew how to obtain plant aromatics in 
purified form, possibly as distilled oils. 
1) See under Bibliography. 
2) Susruta's Ayur-veda, pp. Ill & 130. 
s) Gebri de alchimia; Schmieder, Gesch. 
d. Alch., p. 34. 
*) Aetii medici graeci, fol. 10. 
s) Numbers 6: 3. 
6) Herodoti historiae II, 85. 
Dioscoridis, De mat. med., lib. 1, 
cap. 34, 39, 80, 95, 97. 
Plinii sec. ; Nat. hist., lib. 15, 
cap. 6 & 7, and lib. 16, cap. 
22. 
Scrib. Largi, Comp, med., p. 323. 
Theophrasti opera: Hist, plant., 
lib. 9, cap. 3. 
7) Dioscoridis, De mat. med., vol. 1, 
p. 660; and vol. 2, p. 639. 16 
Historical Introduction. 
The height which Egyptian civilization reached is revealed better by 
the architectural monuments and their contents, in the case of the 
pyramids, than by the few written documents that have come down to 
us. Like their writings, many of their trades were lost at least in part 
to the civilized nations succeeding them and had to be rediscovered. 
In judging the relationship between their scientific knowledge and their 
accomplishments in the arts and trades, it should be remembered that 
the manufacture of metals, of glass, and even dyeing were based on a 
rather crude empiricism and seem to have been almost wholly inde- 
pendent of the theoretical consideration of the age. Thus, with but 
little scientific knowledge of permanent value, these most ancient 
peoples, the Hindoos, Egyptians, Assyrians, Babylonians and Phoeni- 
cians,- like the Chinese, who stand at the dawn of civilization, have in 
the course of centuries of development accomplished much. They, and 
among them the Egyptians more particularly, served as the teachers 
of the classical nations of Greece and Rome. 
The scientific knowledge as well as the industrial and artistic 
accomplishments of the Hebrews and the Greeks, and indirectly also of 
the Romans, had their root in Egyptian civilization. However, the 
Greeks like the Hebrews tended toward the ideal rather than the 
practical in their conception of nature. They did not experiment and 
were not bent on .applying their scientific knowledge. Their philosophers 
and writers collected and systematized the information that had come 
down to them and thus aided in preserving it, without, however, putting 
it to practical use or adding anything new to it. 
The Greeks, however, wrere well informed as to the Egyptian arts: 
they understood the preparation and working of the metals and the 
manufacture of glass and other industrial arts. Their commerce, how- 
ever, was mostly barter in natural products. The oriental spices were 
highly prized by them for incenses, cosmetic and sanitary purposes. 
Whether the primitive method of distillation practiced by the Egyptians 
and Persians was known to the Greeks does not appear from their 
literature. It is not improbable, however, for medicine and the 
cosmetics were hardly less thought of by the Greeks than by the 
Egyptians. Owing to the luxury of the later Greeks, perfumes and 
spices were extensively used. The much praised oriental perfumes, 
especially the sandal wood (£vXa ivSiKa) were considered a necessity at 
all festivities. 
When Greek culture spread westward and became the basis of Roman 
civilization, Greek views concerning nature and Greek knowledge of it History of Volatile Oils. 
17 
were likewise transmitted. In their numerous conquests, the Romans 
increased their knowledge of oriental natural products. These were 
brought by the old caravan routes and then by sea to Rome. Among 
them were the finest spices and aromatics for the kitchen, perfumes and 
ointments for the toilet, balsams and incenses. Whether aromatized 
fats, or distilled oils as well, were used cannot be ascertained definitely 
from Roman literature. That the Romans themselves were adept in the 
preparation of toilet articles seems highly probable. That'the natural 
sciences, including the science of drugs, were well cultivated is shown by 
the writings of Dioscorides, *) Pliny*) and Galen.*) Yet, although the 
Romans were good observers of natural objects and phenomena, and 
equally good compilers of the knowledge of their own period and of 
previous periods, they did not, in general, penetrate into the secrets of 
nature. Neither did they add much to the stock of knowledge handed 
down to them. The natural sciences and medicine were, therefore, but 
little advanced by them. 
With the decay of Greek and Roman culture and the long night in 
the history of civilization that followed, many of the earlier discoveries in 
the arts and sciences were lost. At the close of that period which we 
now designate as antiquity, birth was given to a new civilization, of 
which the Arabians were the forerunners. They themselves, however, 
contributed but little to this Mohammedan or Arabian period of civili- 
zation. This had its roots in the Alexandrian school, the spirit of which 
was imparted to the later Mohammedan conglomerate of peoples through 
the Syrians and Persians and their languages, also through the Greeks 
of Asia Minor. 
Permeated by the conceptions of the Alexandrian school, the Arabs 
revived the study of the natural sciences in the ninth century. Mathe- 
matics, astronomy and medicine were rapidly developed. With their 
tendency to faith in the miraculous, alchemy and magic developed with 
the natural sciences and played an important role in the theory' of 
transmutation of the metals and in medicine. The philosopher's stone 
and a universal medicine were to banish all misery and disease from 
this world. 
Above all it was Geber1) (Dschabir), one of the most influential and 
prominent scholars of his time, who developed this theory and established 
a firm faith in it which lasted for centuries. During the period when 
*) See Bibliography. 
i) Summa perfectionis etc., lib. 4, pp. 156-178 Alchimiae Gebri etc., lib. 2, cap. 
12; Bergmann, De prim, chem., § 3 D & § 4 C. 18 
Historical Introduction. 
Bagdad, Bassora and Damascus were the principal centres of commerce, 
no people was more skilled and more productive in the arts and trades 
and also in natural science. Their commercial relations extended to 
almost all known countries, and the use and knowledge of Eastern 
spices and aromatics was greatly fostered by them. 
With the development of the traditional knowledge, the Arabians 
also fostered the process of distillation in connection with the hermetic 
art.1) As early as the fourth century, the Greek scholars Synesios of 
Ptolomais2) and Zosimos of Panopolis3) had described the distilling 
apparatus and methods of the Egyptians. Aetius of Amida, a physician 
and writer who lived in Constantinople during the beginning of the 
sixth century, also described the preparation of empyreumatic oils by 
downward distillation {Destillatio per descen sum).4} This as well as 
the upward distillation {Destillatio pjer ascensum) are reported by Geber. 
According to Porta5) and other writers of the sixteenth century the 
Arabian physicians and alchemists introduced the condensing tube 
{Serpentina} for the better cooling of the distillate, and a kind of 
fractionation for the distillation of wine. Geber is indeed the first, 
since the Egyptians, who possessed a thorough knowledge of the subject 
of distillation: of dry distillation and distillation with water vapor, of 
utensils of glass and glazed earthenware used in the process. 
Next to the writings of Geber, those of Mesue, who lived some time 
between the eighth and tenth centuries, reveal what knowledge the 
Arabians had on the subject of distillation and volatile oils. In the 
•chapter on oils6) their method of preparation is described. Most of 
them are aromatised fatty oils, only juniper oil and oil from asphaltum 
were prepared by destructive distillation. According to Bergmann,7) 
Mesue is supposed to have been acquainted with distilled rose oil and 
oil of amber. 
Other Arabian physicians also give information about distilled 
waters and oils of that period. Thus Ibn Khaldun8) of the ninth 
century mentions that distilled rose water was an important article of 
commerce of the Persians during his and the previous century. Nonus 
Theophanes9) who in the tenth century was physician of Emperor 
Michael VIII in Constantinople, recommended rose water as a medica- 
1) Conringius, De berm. Aegypt., lib. 
II, cap. 4; Bergmann, Hist, chem., vol. 4; 
Schmieder's Gesch. d. Alch., p. 85. 
2) Synesii Tract, chimicus. 
3) See Bibliography; also Hoefer, Hist, 
de la chim., I, pp. 261-270. 
4) Aetius, Libri medicinales, fol. 10. 
5) De destillatione. 
6) Antidotarium, fol. 80. 
7) Historiae che.miae etc., p. 7. 
») Notices et extraits, 19, p. 364. 
9) Synesius de febribus, cap. 28, p. 142. History of Volatile Oils. 
19 
ment. The Syrian physician Serapion (Janus Damascenus) who lived 
in the ninth century; also Avenzoar1) who lived about a century later 
and who was physician to the Caliph Ebn Attafin of Morocco, used rose 
water as an eye-remedy and rose oil sugar as an internal remedy. In 
the medical writings of Abn Dschafar Achmed, an Arabian physician of 
the eleventh century, which were translated into Greek by Synesius of 
Constantinople, rose water, rose oil and camphor are mentioned among 
the current remedies. 2) 
While Geber was the first, and also the most important Arabian 
writer who was acquainted with distillation, the writings of Albucasis 
who lived three centuries later, reveal Such an exact knowledge of the 
subject, that the thought seems justified that distillation was largely 
practiced by the Arabians. The "Liber servitoris"3) of Albucasis con- 
tains a very clear description of the process of distillation, also specific 
directions for the distillation e. g. of water, acetic acid and alcohol. 
Torbert Bergmann,4) the Swedish chemical historian, regards this 
description as one of the first and best. 
During the period from the eighth to the twelfth centuries, many 
Arabian scientists were especially active in furthering the sciences of 
medicine and materia medica. Distillation was frequently resorted to 
as a means of securing the active constituents of drugs. In spite of 
the crude methods often employed, it seems probable, therefore, that 
the volatile oils which, no doubt, separated at times must have 
attracted the attention of the curious experimenter. Owing to the 
complete lack of knowledge regarding the nature of the oils as well as 
on account of the idea that the distilled waters contained the subtle 
active ingredients of the drugs, the oils which separated may have 
received but little consideration, being regarded as crude separations. 
They were, therefore, not valued highly and, as the literature of that 
period shows, only a few of them found application. 
The desire to transmute the baser metals into gold, which began to 
predominate in the eleventh century, brought, about the decay of 
Arabian science. From the conquest of Bagdad by the Mongols in 
1258 dates the political downfall of the Arabs. In Spain and also in 
Italy, through their school at Salerno, Arabian science still held sway 
1) Liber Theizier etc., Liber 7, fol. 1; Lib. 5, cap. 9, fol. 44. 
2) Synesius de febribus, pp. 58 & 240. 
3) See Arabian writer under Bibliography. 
4) Bergmann, Historiae chimiae. Comp, also Liber Servitoris, fol. 339 b, 341b & 342. 20 
Historical Introduction. 
for some time. In these countries also, through the crusades, Europeans 
became acquainted with Arabian scientific ideas, as well as with their 
methods, among others with the process of distillation and the utensils 
used in this process. In the European countries alchemistic speculations 
were welcomed in the monasteries where mysticism and faith in miracles 
were at home. Though distillation did not become a lost art by any 
means, it was employed principally in the search for the philosopher's 
stone and the panacea for all human woes. 
The distillation of alcohol also was given much attention during 
this period. Thus the Cardinal Vitalis de Furno at the beginning of 
the fourteenth century declared it a true panacea. Albertus Magnus 
(1193-1280), Bishop of Regensburg, carefully described the distillation 
of alcohol in his works. Arnoldus Villanovus (1235-1312) seems first 
to have introduced the Arabian term alcohol into German literature, and 
on account of its properties, designated it aqua vitae. x) The latter was 
also acquainted with the distillation of the oils of turpentine,2) rose- 
mary,3) and sage. His oleum mirabile consisted principally of an alcoholic 
solution of two of these oils. This mixture was used as an external 
remedy and later, with the omission of the turpentine oil, as an 
aromatic perfume. For centuries it remained a much praised specialty 
under the name of Hungarian water. 
Alcohol was also used for the extraction of spices and . other plant 
products. In this manner alcoholic solutions of volatile oils, of aromatic 
resins and balsams were obtained.4) 
From the thirteenth century on distilled aromatic waters were more 
extensively used as medicaments. The separation of oils both at the 
surface and beneath the aqueous distillate was observed, but apparently 
received but little attention. Owing to the practice of using alcohol in 
the preparation of many of these aromatic waters, the oil must 
frequently have remained in solution wholly or in part. Thus, e. g. the 
plants or plant products to be distilled were moistened with wine or 
aqua vitae before distillation; or steeped in water they were first 
allowed to undergo fermentation. Both alcohol and volatile oil were 
lost, in part at least, by submitting the plant products to a process 
known as circulation, a preliminary operation consisting of more or less 
prolonged digestion. In this manner inferior distilled aromatic waters 
were obtained. 
i) Opera omnia, Lib. de vinis, p. 558. 
2) Berviarum praeticae, p. 1055. 
3) Opera omnia, Lib. de vinis, p. 589. 
4) Ph. Ulstadii, Coelum philosophorum. History of Volatile Oils. 
21 
Nevertheless, several of the more important experimenters and 
writers of that period knew and described volatile oils. In addition to 
the oils of turpentine and rosemary already mentioned, Arnoldus 
Villanovus1) and Raymundus Lullus2) describe the distillation of oil 
of sage; Sancto Amando3) that of bitter almond oil, oil of rue and oil 
of cinnamon; Saladinus of Aesculo 4) that of oil of rose and oil of sandal- 
wood. The writings of their contemporaries also reveal a knowledge of 
these and other distilled oils without, however, making mention of their 
use in medicine or the arts. 
The epoch-making inventions and discoveries of the fourteenth and 
fifteenth centuries wrought great changes in the natural sciences and 
their application. The discovery of the new world and the circum- 
navigation of Africa to the East Indies widened the horizon of the 
people. The period of the Renaissance and the Reformation assisted in 
doing away with the blind faith in authority, not only in theology but 
in the natural sciences, as well. The founding of universities and the 
invention of printing assisted largely in the spreading of knowledge. 
Thus information and skill, previously the secret of the few, now soon 
became common property of many. 
With the rise of Paracelsus, who taught that the object of chemistry 
was to make remedies and not gold, and the establishment of the 
iatrochemical school, the art of distillation was once more directed into 
its more proper course. More particularly, with the separation of 
pharmacy from medicine and the establishment of apothecary shops, 
the distillation of aromatic waters was carried on in the laboratories 
of these pharmacies and was here developed until the distillation of 
volatile oils became an independent industry. 
As was largely the case with the Arabians, the progress of the art 
of distillation again finds expression in medical literature. Though 
medical books became much more numerous with the invention of 
printing, they cease largely to be a source of information with regard 
to methods of preparation of volatile oils and their introduction. 
Nevertheless, they give information about the introduction of aromatic 
drugs and aromatic waters. The numerous works that come under 
consideration may be classed in three groups of equal importance: the 
antidotaries and later dispensatories; the treatises on distillation, 
which were prominent from the close of the fifteenth to the close of the 
i) Opera omnia, Lib. de vinis, fol. 589. 
2) Experimenta nova, vol. 5, fol. 829. 
3) Expositio supra Antidot., fol 328. 
*) Compendium aromatariorum, fol. 349b. 22 
Historical Introduction. 
sixteenth centuries; and the price ordinances for spices and drugs of 
various cities, which came into use about the same time. 
Before discussing these works, attention should once more be 
called to the fact that the term "distilled" as used in ancient and 
mediaeval writings is not always employed in the same sense as to-day. 
In fact, up to and including the middle ages it was a collective term 
implying the preparation of vegetable and animal extracts according 
to the rules of the art, or rectification and separation: it involved 
such processes as maceration, digestion, expression, straining, filtering 
and even processes of fermentation and decay. 
Aside from turpentine or cedar oil, the term distilled oil, as it is 
used in older literature, applies as a rule to fatty oils which had been 
aromatised with the respective plants or parts of plants. That many 
seeds and fruits often yielded aromatic oils upon hot or cold expression, 
or when boiled with water was also known in early antiquity. These 
aromatic and aromatised fats and fatty oils were used medicinally as 
ointments and for cosmetic purposes. 
Whether the oils of rose, andropogon, and calamus, mentioned in 
the Ayur-Veda as distilled oils, were such in the modern sense of the 
term, cannot be decided. The same is true of the oils of spike, 
rosemary and sage, as well as of other oils of later writers. Although 
the Indians, the Babylonians, and especially the Egyptians were 
acquainted with the art of distillation, and also with volatile oils, a 
sharp distinction between true distilled oils and aromatised fatty oils 
does not seem to have existed at the beginning of the Christian era. 
Inasmuch as the aromatised oils were used principally in religious rites 
and for purposes of toilet, it seems natural that they were given 
preference over the distilled volatile oils. Indeed, the process of 
preparation of "distilled" oils described by Dioscorides1) and copied by 
Pliny2) is one of aromatization. It may well be doubted that volatile 
oils escaped observation by Arabian naturalists and others who distilled 
aromatic waters, although, as has already been pointed out, the 
presence of alcohol in the distillate may frequently have kept the oil in 
solution. Though a number of distilled oils are mentioned in various 
treatises and were evidently known, yet one of the oldest known lists of 
current drugs and spices, that of the city of Frankfort-on-the-Main of the 
i) Matthioli Opera quaeet., lib. 1, cap. 53: Germ, translation of Dioscorides' works 
in Trommsdorff's Jour. d. Pharni., 11, pp. 112. 
2) Naturalis historiae, lib. 13, cap. 2. Xiber be arte biltillandi. besimplidbus. 
Bas bud? ver reel?ten hunft 
jiiviftilierenvie eintjigeving 
?tunrc§wy^/?urt:i^ vnwunt>ar^or^er^etferU^e ffye 
un getruckt burcb ben woblgeacbte Jobannem grueninger 3U Strassburg 
in ben acbte tag bes me^en als man selt von ber geburt Cbristi 
tuntsebnbunbert. 2Lob s$ got. Hnno 1500. 
Fig. 1. 24 
Historical Introduction. 
year 1450, does not mention any distilled oils. However, a similar 
list of the same city for 1582 mentions forty-two, and another of the 
year 1587 enumerates fifty-nine such oils.1) 
To return, however, to the literary documents of the sixteenth 
century. Among the most interesting, if not the most valuable, are the 
treatises on distillation, the "Destillirbiicher". The first larger work 
of this class was written by the Strassburg physician, Hieronymus 
Brunschwig (1450-1534), the two volumes being published in 1500 
and 1507 respectively.2) The work describes principally the preparation 
and use of the much lauded distilled waters (gebrannte Wasser), dis- 
tilled wines (gebrannte Weine), life elixirs, simple and mixed oils and 
balsams. How little attention was given to distilled oils is shown by 
the fact that but four distilled oils are mentioned and described, viz., 
the oils of spike,3) turpentine,4) juniper wood5) and rosemary.6) 
Directions for the rectification of turpentine oil are also given, viz., by 
shaking first with water, then with rose water or wine, and by final 
distillation. An oleum benedictum compositum7) consists of a distillate 
of rosemary, turpentine, olibanum, mastic, ammoniac, galbanum, 
opopanax, cloves and cinnamon. Directions are further given for the 
preparation of a number of aromatic balsams, mixtures of volatile 
oils, by the distillation of mixtures of oleo resins and spices with the 
addition of turpentine oil. 8) 
How little the nature of the distillates was understood becomes 
apparent from Brunschwig's definition of the process of distillation. 
He states that it consists merely of the separation of the subtle from 
the crude, to make that which is fragile and destructible indestructible, 
to render immaterial that which is material, spiritual that which is 
corporeal, handsome that which is not handsome. Nevertheless he dis- 
plays a considerable knowledge of the technique of distillation. For 
this very reason, however, it seems strange that no mention is made 
of the observation of oils when such aromatic plant products as the 
umbelliferous fruits, the labiate leaves, juniper berries, cloves, cinnamon 
and other spices were subjected to distillation with water. This is all the 
more remarkable since the volatile and even empyreumatic oils and other 
products of distillation such as acetic acid were regarded, like alcohol, as 
the quintessences of the crude materials from which they were obtained. 
1) See the price ordinances for the 
corresponding years under Bibliography. 
2) See fig. 1 and 2, pp. 23 and 25. 
3) Hieron. Brunschwig, Liber de arte 
distillandi, Vol. 1, fol. 72. 
*) ibidem, Vol. 1, fol. 33. 
5) do Vol. 2, fol. 289 
6) do Vol. 1, fol. 52. 
7) do Vol. 1. fol. 53. 
8) do Vol. 2. fol. 271. liber be arte Biftil 
landibeCompofitfa. 
®aa bud? bet mren huult jtibiRilliereti bie 
Compoftta vn ftmpltcM/vnb tn t$e(nurn& PWetu^m $ Mint ge* 
nac^Oicntiu/bie brofanlin cjefallm vo be bifc^etn Zlr^nyzvnb bnrc^ *£j>pernnet 
v5 mir J^etoiiinw b:ufc^wtcf vff geclnbt vn geoffenbatt >u tro|r bene bie es begere* 
History of Volatile Oils. 
25 
getruckt un genbigt in die heisserlicbe frve statt Strassburg 
utt sanct Zlbatbis abent in bem jar 1507. 
Fig. 2. 26 
Historical Introduction. 
Brunschwig's "Destillirbuch" was followed by a number of similar 
treatises, all of which reveal the important position which the distilled 
waters held in the materia medica of the sixteenth century. To some 
extent they contribute to the history of the volatile oils themselves. 
About twenty-five years after the publication of Brunschwig's treatise, 
the smaller work of Philipp Ulstad, physician and professor of medicine 
in Nurnberg, appeared1) and became widely known. Ulstad held 
notions similar to those of Brunschwig with regard to the nature of 
distillates, and since his quintessences contained more or less alcohol, 
no mention is made of the oils themselves. The principal value which 
these works have at the present time as far as the history of volatile 
oils is concerned, lies in the thorough and careful description and 
figurative reproduction of the methods of distillation and utensils 
employed at that time. 
About 56 years after the appearance of Brunschwig's "Destillir- 
buch" and 28 years after that of the first edition of Ulstad's 
"Coelum Philosophorum," Walther Hermann Reiff (Gualtherus H. 
Ryff), who was surgeon in Strassburg during the first half of the 
sixteenth century, published a third treatise2) of this kind which for a 
long time was held in high repute. His definition of distillation does not 
differ materially from that of Brunschwig. In the last part of the book 
he also describes "the correct method of preparing by means of artificial 
distillation several precious oils." They are distilled, some of them with 
wine, from myrrh, liquid storax, sagapenum, opopanax, ammoniac,, 
storax calami "a, sacocolla, benzoin, labdanum, galbanum, turpentine, 
mastic, sandarac, guaiac wood, rosemary, spike, anise, cloves, cinnamon, 
mace, safron, and from various mixtures of spices (balsams). 
Under spike and lavender oil (fol. 186) he mentions that these oils 
are commonly imported from France in small bottles and sold at a 
high price. In his "Reformirte Apothek" which was published in 1563 
he states (fol. 191) that "when lavender flowers are distilled a fragrant 
oil usually floats on the surface of the distillate. In France, in the 
province about Narbonne, where' the plant grows abundantly it .is 
especially distilled; likewise oils from other useful and fragrant herbs, 
flowers, fruits and roots." This statement is of special interest inas- 
much as it seems to be the earliest reference in German literature to 
the French volatile oil industry which evidently dates; back as far as 
the early part of the sixteenth century. 
i) See Bibliography. 
2) Gualth. Ryff, Neu gross Destillirbuch. See Bibliography. Histoi'y of Volatile Oils. 
27 
How little Ryff knew about the nature of volatile oils becomes 
apparent from fol. 187 and 188 where he describes "how from several 
strong and good spices precious oils can be distilled." To prepare 
specially good oils from cloves, nutmeg, mace and safron these spices 
are to be comminuted and distilled with rectified spirit. When the 
"spirits" have been distilled off and oil begins to come over, the mass 
is to be taken out and pressed between warm plates. The oil thus 
obtained is to be rectified by "circulation" until it is clear. 
Brunschwig's "Destillirbuch" seems to have stimulated the distilla- 
tion of aromatic waters and of spirituous aromatic distillates, and their 
introduction into medicine, as well as the art of distillation itself. It 
would appear that his and other treatises of a like nature, in a measure 
at least, displaced the older antidotaries. However, in the course of the 
sixteenth century the latter were also reprinted and revised in various 
European cities. Among the principal treatises in this group are those 
of Valerius Cordus and Conrad Gesner, whose writings acquired great 
reputation and served as the standard for others. Valerius Cordus 
was born in 1515 in Simshausen. His father was professor of medicine 
in Marburg. Here he studied medicine, receiving the bachelor's degree in 
1531. In the same year he went to Wittenberg to attend the lectures 
of Melanchthon, and soon received permission to deliver a course of 
lectures on the materia medica of Dioscorides. He died 1544 in Rome. 
His commentaries1) on Dioscorides and other scientific writings were 
published after his death by Conrad Gesner (1516-1565) of Zurich, a 
talented medical writer, who probably made additions of his own to 
the text of Cordus. 
These "Annotationes" of Cordus are of special importance in the 
history of volatile oils, partly on account of the reputation of the 
author, partly because of his knowledge of the subject and also because 
they appeared in a century that was so productive of literature. Whereas 
Brunschwig's book reveals a retrogression in the technique of dis- 
tillation as compared with the Arabian period, Ulstad, Ryff, Matthiolus, 
Lonicer and others made many improvements themselves and also made 
known many of the older pieces of apparatus that had been forgotten. 
Cordus and Gesner utilized their discoveries and went even farther. 
In the chapter on the distillation of oils,*) Cordus discussed the 
nature of the "extracts" of plants obtained by expression and dis- 
tillation. Concerning the oily plant extracts, Cordus distinguished 
i) See Bibliography. 
*) Liber de artificiosis extractionibus, fol. 226 of the Annotationes. 28 
between the viscid, fatty oils (oleum crassum, viscosum, terrestre) 
obtained by expression, e. g. of seeds, and those of a spirituous nature 
(aerea) which can be separated from the " ter res trial" substances by 
distillation. As illustrations of the first class, he mentions a number 
of the common fatty oils, as illustrations of the second class the oils 
of carpobalsam, i) cardamom, cubeb, pepper, cloves, cinnamon, mace, 
nutmeg, lignaloes and those of some of the common umbelliferous 
fruits, such as anise, fennel, caraway, cumin, angelica, Ligustrum, 
Libanotus, Pastinaca, Apium, Petroselinum, Pimpinella and Anethum. 
In his description of the properties of volatile oils, Cordus makes 
mention of the remarkable property of the oils of anise and fennel to 
congeal to a butyraceous or'spermaceti-like mass; also of the property 
of the oils of cinnamon and cloves to sink under water. The method 
of distillation of volatile oils has been carefully described by Cordus, 
the description being accompanied by a cut of a primitive glass still 
constructed by himself.2) 
Of still greater value than the "Annotationes" of Cordus is the 
"Thesaurus Euonymi Philiatri" of Conrad Gesner. The Latin edition 
was possibly published as early as 1550; a German edition in 1555 
under the title of' "Ein kbstlicher theurer Schatz des Euonymus 
Philiatrus." Compared with Brunschwig's treatise it not only reveals a 
decided advance in the technique of distillation, but the first German 
edition of 1555 also contains several chapters on distilled oils 
(pp. 212-249) and on "balsams" and other mixed oils (pp. 249-273). 
The distillation of a number of oils, viz.: of the oils of lavender, rose- 
mary, rue, cinnamon, cloves, nutmeg and others, is described, and the 
description accompanied with cuts of the apparatus to be used; also 
the distillation of juniper berries and juniper wood by destillatio per 
ascensum and destillatio per descensum. The oils of galbanum, lab- 
danum, myrrh, opopanax, liquid storax and styrax calamita, mastic 
and turpentine are described. The oils from guaiac wood and sandal 
wood and from several other woods and barks are mentioned (pp. 244- 
247) and their distillation described. 
Gesner's notion about the nature of the volatile oils does not differ 
much from the traditional one mentioned in connection with Brunschwig. 
His practical conception of a volatile oil is also rather confused, for in 
describing the several methods according to which one and the same 
Historical Introduction. 
1) The fruits of Balsamea meccanensis Gleditsch (Balsamodendron opobalsamum 
Kunth) were formerly known as carpobaJsamum and used medicinally. 
2) De artificiosis extractionibus, vol. 2, fol. 226. History of Volatile Oils. 
29 
"distilled" oil can be obtained, lie not only enumerates distillation 
proper, but also the digestion with fatty oils, e. g. for rose oil (pp. 224 
and 236), lavender oil (p. 337), marjoram, myrrh and other oils (p. 332). 
Another method applied to nutmegs, mace, etc., is to moisten with 
alcohol and distill until oil begins to come over. The process is then 
interrupted and the oil expressed with the aid of warm plates. The 
aromatized fatty oil thus obtained is then distilled.T) He also 
frequently directs the plant material to be moistened with alcohol. 
Such flowers as have a delicate fragrance are directed to be placed in 
layers in the still which are separated by similar layers of odorless 
flowers or leaves. These are to absorb part of the aroma and thus 
assist in imparting it to the distillate. The oil of lavender flowers he 
directs to be made by first distilling the aromatic water from a glass 
retort. This water is set aside in a warm place during the entire 
summer when the oil and some wrater will distill over spontaneously. 
The oil thus obtained is to be carefully separated from the water and 
preserved in a glass vial. 2) 
Of this period, one important author remains to be mentioned, viz.: 
Giovanni Battista della Porta (1537-1615), a broadly educated 
Neapolitan nobleman. Of his works, published in twenty books,3) two 
are of special importance for the history of volatile oils, his "Liber de 
destillatione," and his "Liber de vinis." Porta has a clearer conception 
of the process and of the products of distillation than any of his 
contemporaries. Both books, published about 1560, reveal a more 
comprehensive knowledge of facts and of literature than any of their 
predecessors. They are further characterized by originality of in- 
vestigation and presentation. 
Porta distinguishes clearly between expressed fatty and distilled 
oils and describes the methods according to which they are prepared. 
He also describes the preparation of aromatic waters and the apparatus 
by means of which the volatile oils can be separated from the aqueous 
distillate. However, in spite of his practical insight, Porta still adheres 
to the traditional conception of the nature of volatile oils.4) He also 
retains the term oil for hygroscopic substances, such as oleum ex 
salibus, ol. ex tartaro, ol. ex soda, etc. 
These sixteenth century treatises on herbs and their distillation, as 
well as a number of less important ones, were the principal hand- 
books for the preparation of medicaments, especially of distilled waters, 
1) Ein kostlichertheurerSchatz, fol. 215-217. 
2) Ibidem, fol. 222. 
3) Portae, Magiae naturalis. See Bibi. 
4) De destillatione, p. 367. 30 
Historical Introduction. 
oils, and vinous distillates. At first they supplemented the older anti- 
dotaries, later they replaced them. The gradual change from these 
treatises on distillation to the so-called dispensatories is marked by the 
appearance of several works classed with the latter. Those of Ortolff 
Meydenberger,1) and the later ones of Otto Brunfels2) (1488-1534), 
Leonhard Fuchs3) (1501-1566) and of W. H. Ryff4) (first half of 
sixteenth century) may here be mentioned. 
With the appearance of Paracelsus (1493-1541) and the spread of 
his iatrochemical ideas in medicine, vegetable remedies lost their former 
importance, their place being taken more or less by chemical products. 
Thus the distilled waters had to surrender their supremacy. This 
resulted in a lessening of appreciation of the "Krauter-" and "Destillir- 
biicher." The volatile oils, however, gradually taking the place of the 
distilled waters, gained in importance. This change was contempo- 
raneous with the transition from the "Destillirbiicher" to the dis- 
pensatories. Although this change was brought about gradually, it is 
usually identified historically with the appearance of the "Dispensa- 
torium Noricum" of Valerius Cordus in the year 1546. 
While in Wittenberg, Cordus was in the habit of visiting with his 
uncle who from 1532 to 1560 was proprietor of the "Salomo-Apotheke" 
in Leipzig. Here he seems to have taken an active interest in the art 
of distillation and in making chemico-pharmaceutical preparations. 
At Raila's instigation and with his assistance, Cordus collected tried 
formulas for the preparation of distilled waters and other current 
pharmaceutical preparations. These were published by Raila. 
This compilation, and still more his lectures on the materia medica 
of Dioscorides as well as his ''Historia Plantarum" published in 1540, 
had established the fame of the young scholar. On one of his botanical 
excursions, Cordus appears to have stopped at Nurnberg where he 
received due attention in medical circles. In 1542 the council of that 
city charged him with the preparation of a dispensatory for the 
guidance of physicians and apothecaries of that municipality. This 
task Cordus accomplished with the aid of his uncle Raila and of Caspar 
Pfreund, a friend and able apothecary at Torgau. The book was 
favorably received by the council of Nurnberg and was published 
in 1546, two years after the death of its author. Several editions 
appeared in rapid succession, the third Niirnberg edition bearing the 
1) Arzneibuch. 
2) Spiegel der Arznei; and Reformation der Apotheken. 
3) Annotationes de simplieibus. 
4) Reformirte deutsche Apothek. History of Volatile Oils. 
31 
date 1548. As an authoritative treatise, the book seems to have found 
general recognition. It was frequently reprinted, both in its original 
form and with the additions made by Conrad Gesner. 
The long title of this work was abbreviated to "Dispensatorium 
Noricum" l) and it is commonly regarded as the first German pharma- 
copoeia, though this is not quite true.2) It was recognized as standard 
up to the close of the seventeenth century, although it had to share 
honors with the Augsburg Pharmacopoeia of Adolph Occo, and several 
other local pharmacopoeias. 3) 
Notwithstanding the want of a clear understanding of the nature of 
the distilled oils during the whole of the sixteenth and part of the 
seventeenth centuries, their preparation was fostered and their use in 
medicine, the arts and in the household increased. Among the medical 
experimenters and writers of this period, Johann Winther,3) professor 
of medicine in Strassburg, seems to have distilled a large number of 
the more common volatile oils with great care. Moreover, the dis- 
tillation of aromatic waters and volatile oils was being conducted 
principally in the pharmaceutical laboratories where both the process 
and the utensils were variously improved in the course of time. 
In addition to the Nurnberg and Augsburg pharmacopoeias and 
similar authoritative works, the municipal price ordinances, which since 
the sixteenth century were issued in various cities to regulate the sale 
of drugs and spices, are reliable sources of information concerning the 
introduction of distilled oils into medicine and the arts. As documents 
they are of similar importance to the price lists of modern wholesale 
merchants and manufacturers. 
The following list has been prepared with the aid of the previously dis- 
cussed historical documents.4) It should, however, be definitely under- 
stood that the dates given are not necessarily those of the first intro- 
duction or use, but those of their legal recognition as articles of commerce. 
1) Comp. Bibliography. 
2) See Ortloff v. Bayrland, Arzneibuch. 
s) See Bibliography: Pharmacopoeias of Augsburg, Antwerp, Cologne and Metz. 
*) In addition to the "Destillirbiicher" previously mentioned, the following pharma- 
copoeia! works have been used in the compilation of this list: Of the "Dispensatorium 
Noricum" the editions of 1546, 1552, 1559, 1563, 1580. 1589, 1592 and 1612; of the 
"Pharmacopoea Augustana" the editions of 1580, 1597 and 1640; and the "Dispensa- 
torium Brandenburgicum" of 1698. 
Of the large number of municipal price ordinances the following were consulted: 
Frankfort-on-the-Main, for 1582, 1587, 1668, 1710; Nurnberg, for 1552, 1613, 1624, 
1644, 1652; Worms, 1582; Strassburg, 1586; Wittenberg, 1599, 1632; Halberstadt, 
1607, 1697; Halle, 1643, 1700; Ulm, 1649; Bremen, 1644, 1664; Dresden, 1652; 
Leipzig, 1669, 1689, 1694; Berlin, 1574; Cologne, 1628. 
Oils of animal origin are not included in this list. 32 
Historical Introduction. 
Up to the beginning of the sixteenth century: 
The oils of benzoin, calamus, cedarwood, costus root, mastix, rose, 
rosemary, sage, spike, turpentine, juniperwood, frankincense, cinnamon. 
To these were added: 
From 1500 to 1540: 
The oils of lignaloes, angelica, anise, cardamom, carpobalsam,x) 
cubeb, wild caraway, fennel, caraway, libauotis, lovage, mace, nutmeg, 
Pastinaca sativa L., pimpinella, pepper (from Piper nigrum'), celery, 
sandal wood, juniper berries, juniper tar (Oleum cadinum), mastix. 
From 1540 to 1589: 
The oils of elecampane, ammoniac, horehound, anime, asafetida, 
basilicum, bdellium, mountain melissa (Calaminta montana), mountain 
thyme (Thymus acinos), amber, citrus, coriander, "costiver", dill, 
origanum, sweet marjoram, elemi, galbanum, galangal, guaiac, chamo- 
mile, Roman cjiamomile, spearmint, labdanum, lavender, lemon, spoon- 
wort, laurel, "marum verum", marjorum, balm, mints, carrot seeds, 
feverfew, cumin, myrrh, cloves, opopanax, parsley, pepper (from Piper 
longum), summer savoy (Satureja hortensis), European penny-royal, 
orange peel, tansy, wild thyme, rue, rhodium, sagpen um. sandarac, 
sassafras, false cumin, storax, tacamahac, tar, thyme, iris, worm- 
wood, hyssop, zedoary (root), saffron, grains of paradise. 
From 1589 to 1607: 
The oils of Chaerophyllum bulbosum, peppermint, savin, white 
mustard, seseli, zedoary (flowers). 
From 1607 to 1652: 
The oils of ginger, arbor vitae, costmary (Tanacetum balsamita). 
Prom 1652 to 1672: 
The oil of cow-parsnip (Heracleum sphondylium), cascarilla, cypress, 
Anthriscus cerefolium, Eupatorium cannabinum, black mustard. 
From 1672 to 1708: 
The oils of valerian, bergamot, mugwort, box-tree, masterwort, 
neroli, Oleum templinum (from Pinus pumilo). 
From 1708 to 1730: 
Bitter almond oil2) and oil of cajeput. 
Distilled oils known and in use: 
i) See footnote, p. 28. 
2) Bitter almond oil and several other poisonous oils, such as cherry laurel oil were 
excluded from general commerce on account of their poisonous properties. Hence they 
do not appear in the price ordinances. Inasmuch as they were not used medicinally 
when they first became known, they do not appear in the pharmacopoeial treatises. 
Both of the above mentioned oils were known before the middle of the sixteenth 
century, bitter almond oil even during the middle ages. History of Volatile Oils. 
33 
As lias already been shown, the art of distillation, particularly as 
applied to volatile oils, made considerable progress during the sixteenth 
century. The knowledge of the nature of the oils themselves, however, 
made but little genuine advance. During the seventeenth century the 
conditions for advancement were even less favorable than during the 
sixteenth. The thirty years' war, which affected so many European 
countries, well nigh crushed Germany and for almost a century stag- 
nated the scientific and industrial life of the nation. In many instances, 
traditional knowledge of the arts and trades became lost. Superstition 
flourished and with it alchemy. During the seventeenth century there 
were more alchemists in Germany than during the two previous ones. 
The war had produced a lack of funds at the courts so that these 
became a productive field for cultivation by the adepts. But few of 
these attained practical results of any kind. Among the few was 
Boettger (1685-1719) who instead of transmuting baser metals into 
gold succeeded in making porcelain. That under such conditions science 
could make but little progress is self-evident. Indeed, scientists and 
physicians as well as all classes of intelligent society were either open 
or secret adherents of the theory of transmutation. 
While the desire to convert the baser metals into gold once more 
became well nigh universal, there were a few who, away from the seat 
of war, cultivated science and with it the art of distillation. Among 
these are Joli. Baptista van Hehnont in Brussels (1577-1644), Johann 
Rudolph Glauber in Amsterdam (1604-1668), Nicolas Lemery in Paris 
(1645-1715) and Wilhelm Homberg in Paris (1652-1715). 
About this time salts were added to the water in the still, e. g. 
common salt, potash, alum, tartar. The idea was to make the water 
heavier and thus prevent the plants from settling to the bottom and 
being burnt. 'Possibly it was found that in some instances a larger 
yield of oil was obtained. Glauber also made similar use of muriatic 
acid. 
These presumptive improvements, however, did not raise the art of 
distillation in general above the basis of empirical experimentation, and 
the seventeenth century closes without having made any material con- 
tribution to the history of volatile oils. Neither did the eighteenth 
century have much to add. The phlogistic theory conceived by J. J. 
Becher (1635-1681) and logicaly worked out by G. E. Stahl (1660- 
1734) failed altogether in throwing new light on the organic world and 
thus could not assist in a better understanding of the composition of 
volatile oils. 34 
Historical In troduction. 
Renewed progress, however, in the manufacture and use of volatile oils 
is to be recorded during the eighteenth century. The technique of distilla- 
tion was improved in the laboratories of the apothecary shops where the 
oils were largely distilled and a better product was prepared. The oils 
found application not only in medicine, but also in the arts and in the 
household. The number of oils mentioned in municipal price ordinances 
and other literature up to 1500 had been only thirteen; in 1540 the 
number had increased to thirty-four and in 1589 to one hundred and eight 
oils. The "Dispensatorium Noricum" of Cordus mentions only three oils 
in 1543; the edition of 1552 mentions five; that of 1563 six; and 
that of 1589 fifty-six oils. In 1708 one hundred and twenty oils are 
mentioned in the price ordinances of that time. 
The distillation of pure volatile oils and the skill to mix them so 
as to produce agreeably fragrant mixtures, not only stimulated the 
improvement of methods of preparation, but also their use for purposes 
of comfort and luxury. As has already been indicated1) a volatile oil 
industry seems to have developed from small beginnings in southern 
France during the fifteenth and sixteenth centuries with the distillation 
of lavender and rosemary oils. In like manner, the perfume industry 
seems to have had its origin. The preparation of "Hungarian water" 
in the sixteenth century by making an alcoholic distillate from fresh 
rosemary has already been referred to.2) During the seventeenth 
century, a "Karmeliter Geist," an alcoholic distillate from balm and 
lavender,3) was introduced. In 1725 Johann Maria Farina of Cologne 
introduced his famous Eau de Cologne. The successful mixture of 
several odors and the prime quality of the oils used proved an 
important stimulus to the manufacture of these oils.4) From these 
small beginnings the perfume industry gradually developed into the 
important position it has held since the middle of this century. 
With the increased importance of the volatile oils, more attention 
was bestowed upon their nature and composition. Boerhaave, who at 
the beginning of the eighteenth century' was professor of medicine, 
botany and chemistry at the University of Leyden, in his treatise on 
chemistry states that volatile oils consist of two elements: the one 
cruder and resinous, insoluble in water (mater); the other more subtle, 
ethereal, which can scarcely be weighed and which by itself is possibly 
gaseous (spiritus rector). The first part he considered to be common 
to all oils and a unit by itself. The characteristic odor and taste, 
1) See p. 26. 
2) See p. 20. 
s) See Oil of Balm 
*) See Oil of Spike, History of Volatile Oils. 
35 
however, of the various oils were due to the spiritus rector which was 
peculiar to each oil. It was water soluble and therefore gave to the 
distilled waters their odor, taste and medicinal virtue. The changes 
produced in volatile oils upon exposure to air and light were attributed, 
in harmony with this theory, to the escape of the spiritus rector.1) 
This conception was perfectly in harmony with the belief in the 
subtle properties and medicinal virtues of aromatic plant substances 
and their aqueous distillates. With the assumption of the water 
solubility of the spiritus rector the distilled waters were naturally 
regarded as being charged in the highest degree with the medicinal 
properties of the crude drugs Boerhaave's dualistic theory was 
therefore received as the most rational explanation of the firmly estab- 
lished belief in the efficacy of distilled waters, and was also accepted as 
a further argument for their retention in medicine. Even after the anti- 
phlogistic nomenclature came into vogue after 1787, the spiritus rector 
was not discarded, being rebaptized as arome. 
The first chemists who discarded the dualistic theory of the volatile 
oils in their writings, and claimed that odor and taste are due to the 
oil as such, are T. A. C. Gren,2) Professor of Medicine in Halle, and the 
French chemist Ant. Francois de Fourcroy3) of Paris. The former 
exposed the untenability of Boerhaave's theory in 1796, the latter in 
1798. Indeed Fr. Hoffmann (1660-1742), a contemporary of Boerhaave 
and professor at Halle, had not accepted the latter's theory without 
reserve. A many-sided investigator and writer, he had prepared and 
studied the volatile oils with great care.4) Yet he had no clearer 
conception concerning the preparation, yield and properties of the oils 
than his contemporaries. He distinguished between oils obtained by 
■expression, by destillatio per ascensum and per descensum.^) He 
regarded sulphur as a fundamental principle of all oils, the bituminous 
and empyreumatic oils containing a relatively large amount of sulphur.6) 
He also believed that the color and odor of oils was influenced by their 
larger or lesser sulphur content. 
1) Boerhaave; Elementa chemiae, vol 2, p. 124. 
2) Grundriss d. Chemie, vol. 2, p. 217. 
3) Ann. de chimie, 25, p. 232; also Systeme des connaissances chimique. 
4) Opera omnia. See Bibliography. 
s) The destillatio per ascensum corresponds to the method now generally used, 
allowing the vapors to pass upwards in the still and removing them from above. In 
the destillatio per descensum the vapors were forced downward through the material 
and collected in a receptacle underneath the still. An incomplete extraction was thus 
affected. (Comp, chapter 3.) 
6) Opera omnia, tom 4, liber 1, p. 449-451. 36 
Historical Introduction. 
It should be of interest to note that camphor which had been 
regarded as a volatile organic salt, was pronounced by Hoffmann to 
be a congealed volatile oil.1) He also made the observation that most 
of the commercial oils of his time were adulterated with turpentine 
oil, oleum vini, alcohol and fatty oils.2) Further he determined the 
yield3) and specific gravity4) of many oils. Glauber's suggestion that 
oils which had become colored by age be rectified with dilute hydro- 
chloric acid5) was opposed by Hoffmann. He declared the employment 
of spiritus salis,6) dilute sulphuric acid,7) potash, tartar and alum8) in 
the distillation of volatile oils as useless, but consented to the use of 
common salt. He argued that the addition of salt facilitated the 
separation of the oil particles and prevented decay; that it made the 
water "heavier" and thus prevented the settling and burning of the 
plant material; that it also purified the distillate.9) 
In some instances recourse was again taken to the process of 
fermentation before distillation which was in vogue during the fifteenth 
and sixteenth centuries. This was done e. g. with juniper berries, 
wormwood, sage and other herbs, honey and yeast10) occasionally being 
added. The old practice of previously moistening the plant material 
with alcohol11) was also resorted to. In this manner a larger yield of 
oil was obtained but it would seem that the dilution of the oil with 
alcohol was not recognized. Downward distillation (destillatio per 
descensum) was applied by Hoffmann12) in the preparation of oils with 
high specific gravity such as the oils of cinnamon and cloves. This 
method was evidently regarded as being better because the dark colored 
oils thus obtained were supposed to contain more sulphur. 
With the increased use of volatile oils during the first half of the 
eighteenth century it became more and more desirable not only to 
prepare oils of good quality but to obtain the largest possible yield as 
well. As guides there appeared new treatises on distillation which had 
1) Opera omnia. Liber 72. Observatio 13, p. 44-50. 
2) Ibidem. Liber 67. Observatio 2, p. 9-11. 
3) " " 65. " 1, p. 1-9. 
*) " " 72. " 8, p. 27-30. 
5) Glauberii, Furni novi philosophic!, pars 1, pp 35, 36 et 41; et pars 3, p. 30. 
6) Ibidem. Pars 1, p. 36. Crude hydrochloric acid prepared by distillation of salt 
with alum or sulphuric acid. 
7) Crell's Chem. Journ., 3, p. 30.-Pfaff, System der Materia medica (1815), vol. 4,p. 50. 
s) Glauberii, Furni novi philosophic!, pars 1, p. 38; et pars 3, p. 31. 
9) Hoffmann, Opera omnia. Suppiementum secundum. Pars 1, p. 730. 
io) Berl. Jahrb. f. Pharm., 1804, p. 380. 
ii) Demachy, Laborant im Grossen, p. 238. 
12) Hoffmann, Opera omnia, tom. 4, lib. 1, p. 449-451. - Suppiementum secundum, 
pars 1, p. 730. History of Volatile Oils. 
37 
little more than the title in common with the older Destillirbucher. Of 
these the works of Burghart,1) Dejean and Demachy1) may here be 
mentioned. 
Following the lead of Winther,2) Boerhaave and Hoffmann, a number 
of investigators of the eighteenth century ascertained the yield of oil 
obtainable from the more common aromatic plant products. Of these 
the following deserve special mention: Joh. Fr. Cartheuser3) (1704- 
1769), Professor of Medicine, Botany and Chemistry at the University 
of Frankfurt-on-the-Oder; Caspar Neumann4) (1683-1737), a Berlin 
apothecary; Claude Joseph Geoffroy,5) a Parisian apothecary; and 
Francois Rouelle5) (1703-1770). Their experiments were conducted 
on a small scale and with simple apparatus. Their results, however, 
published in their works and in journals,6) were regarded as standard 
and were quite generally introduced into the literature on the subject. 
Through the dispensatory of the English physician and chemist, 
William Lewis,7) the results of the above mentioned investigators and 
of others found their way into English literature. 
Aside from the publications already* mentioned, the interest shown in 
the study of volatile oils toward the close of the seventeenth and during 
the course of the eighteenth century is possibly best shown by the number 
of dissertations on the subject which were written at German universities 
under the stimulus of a number of university teachers. The more 
important ones are herewith enumerated: 
1670. ''De oleorum destillatiorum natura et usu in genere." Dissertatio ab 
David Kellner. Helmstadii. 
1696. "De oleis destillatis." Dissertatio ab Henrico Rosenberg. Jenae. 
1744. "De oleis destillatis empyreumaticis." Dissertatio ab Christian Lindner. 
Francofurti ad Viadrum. 
i) See Bibliography. 
2) See p. 31. 
s) See works enumerated under Bibliography. 
<) In the second volume of his Chymia medica, etc. 
5) Memoires de l'Academie Royale des Sciences de Paris, 1730-1760. 
6) In 1789, Render of Erfurt collected and tabulated the observations relative to 
the yield and properties of volatile oils published up to that year. A similar 
tabular compilation taking into consideration also the origin of the oils was published 
in the "Journal de pharmacie" for August 1834 by Raybaud of Paris in connection 
with the industrial exposition of the previous year. A German translation appeared 
in Buchner's "Repert. d. Pharm." for 1835, vol. 51, p. 54. Two further treatises on 
this subject appeared by G. H. Zeller in 1850 and 1855 respectively in the "Jahrbuch 
fiir praktische Pharmacie und verwandte Facher." The former appeared also as a 
separate under the title of "Studien iiber atherische Oele," Landau, 1850; the latter 
under the title "Ausbeute und Darstellung der atherischen Oele." 'Stuttgart, 1855. 
7) See Bibliography. 38 
Historical Introduction. 
1744. ''De sale volatili oleoso solido in oleis aethereis nonnunquam reperto.'7 
Dissertatio ab Fr. Giinther. Francofurti ad Viadrum. 
1745. ''De oleis vegetabiliuni essentialibus." Dissertatio ab A. Fr. Walther. 
Lipsiae. 
1746. "De spiritu rectore in regno animali, vegetabili et fossili, atmosphaerico.'7 
Dissertatio ab Gottfried de Xhora. Leydae. 
1747. "De oleorum destillatorum usu multiplice prineipue in castris." Dis- 
sertatio ab Job. Paul Ziegler. Altorfii. 
1748. "Dissertatio chemica inauguralis sistens Dosimasiam concretiOnum in 
nonnullis oleis aethereis observatum" ab F. Hagen. Regiomontanae. 
1 752. "De oleis essentialibus aethereis eorumque modo operandi et usu." Dis- 
sertatio ab Johann Friedr. Vangerow. Hallae. 
1759. "De oleis destillatis aethereis." Dissertatio ab Fr. W. Eiken. Helmstadii. 
1765. "De partibus oleorum aethereorum constitutivis." Dissertatio ab 
Johannes Christ. Schmidtius. Jenae. 
1765. "De partibus oleorum aethereorum constitutivis." Dissertatio ab J. Fr. 
Faselius. Jenae. 
1765. "De oleis vegetabiliuni essentialibus, eorumque partibus constitutivis.'7 
Dissertatio ab W. B. Trommsdorff. Erfurti. 
1778. "De adulterationibus oleum aethereorum. Dissertatio ab K. W. Chr. 
Muller. Goettingen. 
The investigations reported in these dissertations, however, rest on 
false premises and, therefore, produced no valuable results. Research 
based on the phlogistic theory and the doctrines of Boerhaave and 
Hoffmann concerning the constitution of volatile oils, could hardly be 
expected to yield results of any importance. How crude the notions 
concerning the chemical nature of volatile oils were even at the time of 
Scheele, is shown in a dissertation1) of the year 1765 accepted by the 
University of Jena. From it the following propositions or conclusions 
are quoted: 
"The essential constituents of volatile oils are of two kinds, solid and 
liquid. To the first class belong sulphur, phlogiston, earth and salts; to the 
second class air, fire and water. The presence of the first is revealed by the 
inflammability of the oils, for every object that burns with a flame contains 
much sulphur or phlogiston. The color as well as the coloration of the oil 
likewise argue in favor of their presence. Some oils are yellow, others green or 
blue; with age, the colors become darker. As is known, all coloration is due 
to particles of sulphur or phlogiston. Such oils have a penetrating odor, which 
is caused by their content of volatile saline sulphur particles. They, therefore, 
contain sulphur or phlogiston in sufficiently large quantities. 
"In the course of time these oils are converted into a resinous mass, a 
change that is not conceivable without phlogiston. 
i) ,-De partibus oleorum aethereorum constitutivis." Dissertatio inauguralis per 
Johannes Christianas Schmidtius. Jenae d. 30. Maerz 1765. History of Volatile Oils. 
39 
"Volatile oils always burn with a smoking flame. All soot, however, 
consists of earth, salt, water and phlogiston. When the oils are treated with 
nitric acid, a residue of earth and carbon remains. 
"Some volatile oils have a higher specific gravity than water. This is due 
to their larger content of earthy constituents and salts." 
The crystalline deposits formed in some oils upon standing1, also the 
congealing of certain oils at lower temperatures, which had been observed 
by Valerius Cordus in 1539, by Kunkel in 1685, by J. H. Link in 1717, 
by Friedr. Hoffmann in 1701, by Caspar Neumann in 1719 and by 
others, were studied. The crystalline parts were regarded as a volatile 
salt, later as a camphor peculiar to each oil, at times also as benzoic 
acid.1) Hoffmann explained the congealing of oils of rose, anise and 
fennel by assuming the formation of a curdled modification of the oil. 
Neumann in 1719 and Geoffroy in 1726 regarded the crystals formed 
upon standing as camphor.2) The formation of such crystals was 
observed in the oils of thyme, cardamom and marjoram by Neumann;3) 
in peppermint oil by Gaubius4) of Leyden in 1770; in oil of mace by 
Wiegleb5) in 1774-; in the oils of lavender, rosemary, sage and marjoram 
by Arezula6) in 1785. They regarded these separations as varieties of 
camphor, only Wiegleb thought them to be peculiar combustible salts.7) 
In 1793 and 1794 Margueran studied the action of frost on volatile 
oils and observed the formation of crystals and congealing in connection 
with a number of the more common oils. 8) 
The study of the action of various reagents on volatile oils, which 
was begun about the middle of the seventeenth century, yielded but a 
superficial insight into their nature. The repeated distillation of oils 
over chalk or burnt lime,9) conducted by the excellent chemist Homberg 
about the year 1700, produced no results whatever. The action of 
strong acids had been observed by Glauber10) as early as 1663. The 
i) Hagen, "Dissertatio chemica inauguralis sistens dosimasiam, eoneretionum in 
nonnullis oleis aethereis observatorum." Regiomontanae 1748. 
P. J. Macquer's "Dictionnaire de Chymie." Germ, transl. by J. G. Leonhardi. Vol. 
4, p. 465, foot note 9. 
2) Mem. de l'Acad., 1726, p. 95. 
3) De salibus alcalino Axis et camphora. Berolini 1727, p. 105. 
4) Adversariorum varii argument! liber unus. Leidae 1771. Sectio 7, p. 99-112 
5) Vogel's Lehrsatze der Chemie, § 342. 
6) Resultato de las experleneas hachas sobre alcanfor de Murcia con licencia. En 
Segovia 1789. 
7) Comp. Vogel's Lehrsatze der Chemie, edited by Wiegleb. 
8) Jour, de chim. et de phys., 2, p. 178; Crell's Chern. Ann., 2, pp. 195, 310 and 430. 
9) M^m. de l'Acad., 1700, p. 298; and 1701, p. 129; also Chern, u. botan. Abhandh, 
vol. 3, p. 155-157. 
io) Prosperitas Germaniae. 40 
Historical Introduction. 
effect of strong nitric acid on a number of distilled oils was studied by 
Borrichius1) in 1671, by Tournefort2) in 1698, by Hasse3) in 1783; 
that of sulphuric acid by Kunkel4) in 1700 and by Homberg5) in 1701. 
A more detailed study of the action of strong acids on volatile oils was 
made by Hoffmann6) and by Geoffroy7) in 1726 and by Rouelle8) 
in 1747. Upon distillation of oils with strong hydrochloric acid, 
especially if the acid was generated in an almost anhydrous condition 
in the experiment, it was supposed that compounds of the oil with the 
acid were obtained. Such a supposed compound was known to 
Homberg9) as early as 1709. The preparation, however, of such a 
compound of definite chemical composition was first accomplished by 
Kind,10) an apothecary in Eutin, in 1803 by the action of hydrogen 
chloride gas on turpentine oil. 
The solubility and color of distilled oils also received attention 
during the eighteenth century. Thus Macquer11) in 1745 published his 
investigations on the solubility of distilled oils in alcohol, which were 
the most extensive on this subject. The color of oils and the changes in 
color were studied by Homberg12) in 1707 and by Bindheim13) of Moscow 
in 1788. The latter arrived at the conclusion that the color depends 
on a larger or lesser amount of resin carried over in the process of 
distillation, hence the darker colored oils are apt to contain considerable 
resin. 
As has already been pointed out, the phlogistic theory afforded no 
satisfactory basis for the study of organic substances and consequently 
of volatile oils. With the discovery of oxygen by Scheele and Priestley 
during the years 177114) to 1774 and the ingenious interpretation of 
this and other discoveries by Lavoisier with the aid of the balance, a 
reaction against the phlogistic theory set in which resulted in the 
inauguration of the present chemical period. The study of the chemical 
constitution of substances was placed on a rational scientific basis. 
Inorganic chemistry, having to deal with the simpler substances, 
i) Acta med. et phil. Haffn., 1671, 
p. 133. 
2) Hist. reg. scient. acad., p. 495. 
3) Crell's Neueste Entd. in d. Chem., 9, 
p. 38; Crell's Chem. Ann., 1, p. 417. 
4) Laboratorium chymicum, p. 347. 
5) Chem. bot. Abh., 1. p. 720. 
6) Observat. phys.-chim.. lib. 3, p. 123. 
7) M^m. de l'Acad., 1726, p. 95. 
8) Ibidem, 1747, p. 45. 
9) Chem. bot. Abh., 3, p. 155. 
io) Trommsdorff's Journ. d. Pharm. 
11, p. 132. 
11) M£m. de l'Acad., 1745, p. 4. 
12) Chem. botan. Abh., 3. p, 155. 
13) Crell's Chem. Ann., 1788 «•. pp. 219 
and 248. 
i*) A. E. von Nordensklold, Scheele's 
Nachgelassene Briefe mid Aufzelchnungen, 
pp. xxi, 86, 408, 458 and 466; Pharm. 
Rundschau, 11, pp. 28 and 48. History of Volatile Oils. 
41 
profited first by the new theories of the opponents of the phlogistic 
school. Organic chemistry, and with it the study of the volatile oils, 
were benefited somewhat later. 
Though of little consequence, the experiments of the Dutch chemists 
Deimann, Troostwyck, Bond and Lauwerenburg1) should here be 
mentioned. They passed the vapors of volatile oils through red hot 
iron tubes and examined the resulting gases. At the same time they 
made the bold attempt to synthesize oils by the action of gaseous 
hydrogen chloride on olefiant gas. 
The first investigation suggested by the new theories that was of 
positive value, was the elementary analysis of turpentine oil made by 
Houtton-Labilliadiere.2) He found the ratio of carbon to hydrogen to 
be five to eight, the same that was later established for all hemiterpenes, 
terpenes, sesquiterpenes and polyterpenes. 
Attention has already been called to the crystalline deposits that 
had been observed in the course of several centuries. These were mostly 
considered as identical with ordinary camphor because like it they were 
volatile, soluble in alcohol and fatty oils, and burned with a smoky 
flame. Only in a few instances, however, had these deposits been 
proven to be identical with camphor. Berzelius,3) therefore, argued 
against the indiscriminate generic use of the term camphor. In its place 
he suggested the use of the term stearoptene (from areap, tallow, and 
Tmjvov, volatile). He pointed out the analogy existing between volatile 
and fatty oils in so far as they can be a mixture of several oils having 
different congealing points. Thus oils may, under favorable circum- 
stances, be separated into an oil which is solid at ordinary temperature, 
the stearoptene, and one which is liquid at low temperatures, the 
elaoptene (from eXaiov, oil, and tttt/vov, volatile). The result of this was 
that the solid deposits from volatile oils were thereafter designated 
alternately stearoptene as well as camphor. Up to this day the older 
abuse of the term camphor has not ceased as becomes apparent from 
such words as cedar camphor, cubeb camphor, juniper camphor, etc. 
Soubeiran and Capitaine4) even made things worse by applying the 
term "liquid camphor" to the liquid hydrogen-chloride addition products 
of the terpenes. After it had been shown that true camphor contained 
oxygen, the term camphor in its generic sense was also applied to 
other oxygenated constituents of volatile oils though they were liquid. 
1) Journ. de ehim. et de phys , 2, p. 
178; Crell's Chem. Ann., 2, pp. 195, 310 
and 430. 
2) Journ. de pharm., 4, p. 5. 
3) Lehrb. d. Chemie [31, vol. 6, p. 580. 
2) Liebig's Annalen, 34, p. 311. 42 
In 1833 Dumas published an article entitled "Ueber die vegetabili- 
schen Substanzen, welche sich dem Campher nahern und iiber einige 
atherische Oele."1) Although a number of important observations of 
rather striking properties of individual oils had been made, the 
systematic study of the volatile oils may be said to have begun with 
the analysis of a number of stearoptenes by Dumas. He suggested the 
following classification of volatile oils: 
1.) Those that consist of carbon and hydrogen only, like turpentine oil and 
oil of lemon; 
2.) Those that contain oxygen, like camphor and anise oil; 
3.) Those that contain sulphur,2) like mustard oil, or nitrogen, like oil of 
bitter almonds. 
The elementary analysis of solid peppermint oil, camphor and solid 
anise oil revealed the composition CsHio^O, CsHs^O and CsHe^O. By 
doubling these formulas of Dumas the modern formulas for the 
respective substances are obtained. Of the oxygen free oils, he analyzed 
turpentine oil and the hydrocarbons of lemon oil, verifying the earlier 
results of Houtton Labilliardiere. During the years 1833-1835, Dumas 
published further contributions on the subject of volatile oils, several 
jointly with Pelouze and Peligot. They pertain to artificial camphor 
(pinene hydrochloride), mustard oil, cinnamon oil, terpin hydrate, orris 
oil, pepper oil, oil of juniper berries and others. 
Almost simultaneously with the first publications by Dumas, 
Blanchet and Sell3) published the results of their investigation which 
had been carried out in Liebig's laboratory and which involve in large 
part the same substances studied by Dumas. The most noteworthy 
result of these investigations is the recognition of the identity of the 
stearoptene from fennel oil and that from anise oil. 
Several years later, in 1837, the highly important and very inter- 
esting results of Liebig and Woehler's work on bitter almond oil were 
published.4) As early as 1802 Schrader and Vauquelin had discovered 
hydrocyanic acid in the distillate of bitter almonds. In 1822 Robiquet 
showed that no volatile oil preexisted in the almonds, and with Boutron- 
Charlard he 'had prepared amygdalin in 1830. They had not succeeded. 
Historical Introduction. 
i) Liebig's Annalen, 6, p. 245. 
2) The fact that mustard oil contains sulphur was recognized by Thibierge in 1819' 
(.Journ. de pharm., 5, pp. 20, 43!) and 446; Trommsdorff's Neues Journ. d. Pharm., 
4n, p. 250.) That sulphuretted hydrogen is given off during the distillation of several 
umbelliferous fruits, such as caraway, dill, fennel, etc., was pointed out by L. A. Planche 
of Paris in 1820. (Trommsdorff's Neues Journ. d. Pharm., 7', p. 356.) 
3) Liebig's Annalen, 7, p. 154. 
*) Ibidem. 22, p. 1. History of Volatile Oils. 
43 
however, in preparing- bitter almond oil from amygdalin. That this is 
decomposed by emulsin into benzaldehyde, hydrocyanic acid and sugar 
was demonstrated by Liebig and Woehler. They also point out that 
the manner of formation of mustard oil must be closely related to that 
of bitter almond oil. for the mustard seeds deprived of their fatty oil 
possess no odor, this being produced only when water is present. The 
investigation of mustard oil by Will1) in 184-1- substantiated this 
supposition. 
Chemists now became especially interested in the action of hydrogen 
chloride on various terpenes and in the resulting hydrochlorides, some 
of which were solid, others liquid; also in the study of terpin hydrate 
and its decomposition products. The study of the literature pertaining 
to these subjects is rendered difficult by the error of regarding mixtures of 
several substances as chemical individuals and describing them as 
such; further by the fact that almost every author, irrespective of the 
work of others, coined a nomenclature of his own. This confusion 
continued until very recently when Wallach and his disciples created 
order.2) ✓ 
Crystalline pinene monohydrochloride had been discovered by Kindt,3) 
an apothecary, in 1802. He regarded it as artificial camphor, a view 
shared by Trommsdorff.4) The true composition of this compound was 
ascertained by Dumas in 1833. Crystalline dipentene dihydrochloride 
was discovered by Thenard in 1807. It is the "salzsaures Citronenol," 
muriate of lemon oil. of Blanchet and Sell, the artificial lemon camphor 
of Dumas. These and similar substances were investigated by Soubeiran 
and Capitaine (turpentine oil), Deville (turpentine oil and elemi oil), 
Schweizer (carvene) and Berthelot (turpentine oil).5) The formation of 
terpin hydrate and the action of acids on this substance was studied 
principally by Wiggers, List, Deville and Berthelot.0) 
1) Liebig's Annalen, 52, p. 1. A more complete insight into the mechanism of the 
reaction by which mustard oil is produced was supplied by the later investigations 
of Will and Koerner in 1863. (Liebig's Annalen, 125, p. 257.) See Oil of Mustard. 
2) The historical development of this chapter of the chemistry of the terpenes is 
described in "Terpene und Terpenderivate, ein Beitrag zur Geschichte der atherischen 
Oele" by E. Kremers (Pharm. Rundschau, 9, pp. 55, 110, 159, 217. 237; and 10, pp. 
10, 31. 60; also Proc. Wise. Acad. Sc. Arts and Letters, 8, pp. 312-362. 
3) Trommsdorff's Journ. d. Pharm., 11 n, p. 132. 
*) Ibidem, p. 135. 
5) Of later investigators of this subject Oppenheim (1864), Hell and Ritter (1884), 
Bouchardat and Lafont (1886), and finally Wallach (1884-1887) may be mentioned. 
6) The same subject was later investigated by Oppenheim (1884), Flawitzky (1879), 
Tilden (1878-79), Bouchardat and Voiry (1887). Here also Wallach's exact investi- 
gations revealed the fact that different acids, as well as the same acid in different 
degrees of concentration, produce different results. 44 
Historical Introduction. 
A paper published about this time (1841) by Gerhardt and Cahours1) 
is of special interest in so far as it contains a definition of a volatile 
oil which in a general way holds good to-day. It also makes known new 
methods of investigation. About oils in general the authors state: 
"There are, indeed, but very few oils which can be crystallized; most oils 
are liquid and consist of a mixture of two and even three peculiar substances, 
which rarely are obtained by themselves when distilled at different temperatures." 
The separation of the individual substances is effected by first 
allowing any solid constituent to crystallize out, then the lower boiling 
hydrocarbon is isolated by distillation at a temperature 20-30° below 
the boiling point of the crude oil.2) Inasmuch, however, as the hydro- 
carbon cannot be completely freed from oxygenated constituents in this 
manner it is treated with fused alkali. The oxygenated constituents also 
are subjected to like treatment with fused alkali, and cumin oil is thus 
made to yield cuminic acid, oil of valerian valerianic acid. 
Strong reagents are also employed by Rochleder, Persoz, Laurent 
and Gerhardt in order to obtain an insight into the nature of volatile 
oils. They oxidized either the entire oil or fractions thereof with chromic 
acid or nitric acid. Their investigations included the oils of valerian, 
sage, anise, staranise, fennel, cumin, cinnamon, tansy and estragon. 
The conclusions drawn from these oxidation experiments were in part 
correct, in part wrong. Thus e. g. Gerhardt pointed out the identity 
of dragonic acid, obtained from estragon oil. with anisic acid, and 
claimed that estragon oil and anise oil were absolutely identical. This 
conclusion was wrong, for the anethol of anise oil is paramethoxypropenyl- 
benzene, whereas the formation of anisic acid from estragon oil is due 
to the presence of paramethoxy allylbenzene.3) 
This method, however, rendered it impossible to decide whether a 
substance obtained after the oxidation preexisted in the oil or not. 
Thus camphor was found in several oxidized oils and was regarded as 
an original constituent although, as was the case in the oils of valerian 
and sage, it had resulted from borneol. Persoz, however, seems to have 
i) Liebig's Annalen. 38, p. 67. 
2) Fractional distillation, however, was previously employed in the examination 
of volatile oils. As early as 1838 Walter had subjected peppermint oil to interrupted 
distillation, "gebrochene Destination" (Gmelin, Handbuch d. Chern. [4], vol. 7a, p. 404). 
In 1840 Volckel (Liebig's Annalen, 35, p. 306) speaks of ''fractional distillation." 
Already Blanchet and Sell in 1833 had applied fractionation with water vapor as a 
means of separation and had found that the first fraction of lemon oil boiled at 167°, 
the last fraction at 173°. 
s) This difference was first ascertained in the laboratory of Schimmel & Co. (Bericht 
S. & Co., April 1892, p. 17) and verified by Grimaux in 1893 (Compt. rend., 117. 
p. 1189). History of Volatile Oils. 
45 
had doubts as to the reliability of these conclusions, for he leaves it 
undecided whether the camphor obtained from oil of tansy was contained 
in the oil or not. As a matter of fact, tansy oil contains camphor as 
an original constituent,1) this being less readily attacked by the oxidizing 
agents than the other constituents of the oil. 
Of considerable importance in the farther development of the 
chemistry of volatile oils are the investigations of Berthelot from 1852 
to 1863, which involve principally the hydrocarbons contained in these 
oils. He studied first of all the hydrocarbon of turpentine oil2) and its 
isomers and polymers obtained from its hydrochloride. By heating 
pinene hydrochloride with barium stearate or sodium benzoate he 
obtained a new hydrocarbon which he regarded as "camphene proper" 3) 
and which is identical with the camphene of to-day. This new camphene 
was either dextrogyrate, laevogyrate or optically inactive according to 
the turpentine oil employed. Berthelot, therefore, distinguished between 
the following hydrocarbons: 
1.) Terebentene (1-pinene) from French turpentine oil, laevogyrate 4) 
b. p. 161°. It yields a laevogyrate monhydrochloride, also under proper 
conditions an inactive dihydrochloride (dipentene dihydrochloride). 
2.) Terecamphene (1-camphene) from terebentene hydrochloride, laevogyrate, 
m. p. 45°, b. p. 160°. With hydrogen chloride it forms a dextrogyrate 
hydrochloride. 
3.) Australene (d-pinene) from American turpentine oil, b. p. 161°, dextro- 
gyrate like its hydrochloride. Its behavior to hydrogen chloride is analogous 
to that of terebentene. 
4.) Austracamphene (d-camphene) from australene hydrochloride. It 
corresponds to terecamphene. 
5.) Inactive camphene (i-camphene) can be obtained by proper treatment 
from the hydrochloride of terebentpne as well as that of australene. 
6. Terebene,5) b. p. 160°. 
i) Bericht von S. &.Co., Oct. 1895, p. 34. 
2) Compt. rend. 55, pp. 496 and 544; also Liebig's Annalen, Suppl. II, p. 226. 
3) Soubeiran and Capitaine in 1840 had applied the term camphene to all hydro- 
carbons CsHg (Liebig's Annalen. 34, p. 311). 
A) The rotatory power of volatile oils was first observed by Biot in 1817 in 
connection with French oil of turpentine (M£m. d. 1'Acad. des Sc., 13), later also with 
oil of lemon. The turpentine oil was shown to be laevogyrate, the oil of lemon 
dextrogyrate. In 1843, Leeson of London found that American turpentine oil possessed 
a rotatory power opposite to that of the French oil. This observation was soon after 
verified by Pereira and Guibourt. Pareira introduced the terms laevo-gyrate and 
dextro-gyrate. (Pharm. Journ., 5, p. 70.) 
5) This substance which was considered a chemical unit by Berthelot was shown 
by Riban to be a mixture of a terp'ene, cymene and camphor. Power and Kleber in 
1894 found camphene, dipentene, terpinene and cymene in terebene. (Pharm. Rundsch., 
12, p. 16.) 46 
Historical Introduction. 
These six hydrocarbons are isomeric and have the formula CioHig. 
With these the following are polymeric: 
1.) A liquid hydrocarbon boiling at 250° which is probably a sesqui- 
terebene, C15H24. 
2.) Diterebene (Deville's colophene) C20H32, an inactive liquid boiling at 
about 300°. 
3.) Several polyterebenes CionHion, optically inactive liquids becoming 
more and more viscid, which boil between 360° and a dark red heat. 
After a discussion of the methods of formation of the individual 
hydrocarbons, Berthelot continues: 
In accordance with the known facts, the hydrocarbon CioHig-e. g. tere- 
bentene-may be regarded as the starting point of two series: 
1.) Of a monatomic or eamphol1) series (monohydrochlorides or chlorine 
esters of eamphol, C10H17CI; camphene, CioHig: eamphol alcohols, CioHisO); 
2.) Of a diatomic or terpil series (dihydrochlorides, CioHisCh; terpilene, 
CioHig; hydrate C10H2002). 
Each of these two series constitutes a larger group, which can be divided 
into secondary series (australene, terebentene, etc.) the parallel and isomeric 
members of which occur in twos; each has as type an inactive hydrocarbon, 
namely camphene in the first group, terpilene in the second. 
A similar, but much less detailed classification was attempted by 
Gladstone2) in 1864, after having determined the specific gravity, the 
index of refraction and the optical rotation of a number of oils. By 
means of fractional distillation he isolated the hydrocarbons of various 
oils, rectified them by distillation over sodium and arranged them into 
three large groups: 
1.) Hydrocarbons of the formula CioHig which boil between 160-170°; 
2.) Hydrocarbons of the formula C15H24 which boil between 249-260°; 
3.) Colophene, C20H32, b. p. 315°, representing the third group. 
About this time the word terpene was introduced, evidently by 
Kekule.3) His investigations, preceded by those of Barbier and Oppen- 
heim were of considerable importance, ifiasmuch as by revealing the 
relations between the terpenes and cymene, they threw new light on the 
molecular structure of these hydrocarbons. Almost simultaneously 
Barbier4) (1872) and Oppenheim5) (1872) obtained cymene by heating 
the dibromide of terpin either by itself or with aniline. By the action 
1) Berthelot in 1858 changed the name borneol to eamphol. Liebig's Annalen, 
110, p. 368; from Compt. rend., 47, p. 266. 
2) Jour. Chem. Soe., 17, p. 1. A second contribution appeared eight years later. 
Ibidem, 25, p. 1. 
3) Lehrbuch der organischen Chemie (1866), vol. 2, p. 437: ".... on the other hand 
the oil of turpentine and numerous isomeric hydrocarbons, which may be designated 
by the generic term terpenes." 
4) Compt. rend., 74, p. 194. 
s) Berichte, 5, p. 94. History of Volatile Oils. 
47 
of iodine on turpentine oil, Kekule1) (1873) obtained the same hydro- 
carbon. He, therefore, thought himself justified in supposing six atoms 
of the turpentine oil to be arranged in similar manner as in benzene. 
Further that the methyl and propyl groups in the turpentine oil occupy 
the same relative positions as in cymene.2) This view of the constitution 
of the terpenes was the predominant one for a long time. With this 
the question of the constitution of the terpenes had its origin. Important 
in this direction was also the synthesis of a terpene - the polymerization 
of isoprene to dipentene-by Bouchardat3) in 1875. 
In the same year, Tilden4) found that the hydrocarbon of turpentine 
oil combines with nitrosylchloride to form a well crystallizing compound. 
Together with Stenhouse, he applied this reaction to the terpenes from 
the oils of sage, orange, lemon and bergamot. On the behavior of these 
hydrocarbons to nitrosylchloride he based a new classification, concerning 
which he makes the following statement: 
The natural terpenes are colorless limpid liquids which vary in specific 
gravity from about 0.84 to about 0.86. They are divisible into two groups 
as follows:- 
1. Turpentine group: b. p. 156° to 160°; m. p. of nitroso-derivative 
129°; form solid crystalline hydrated terpin C1OH2OO2H2O. 
2. Orange group: b. p. 174° to 176°: m. p. of nitroso-derivative 
71°; form (by Wigger's process) no solid crystalline terpin hydrate.5) 
The liquids included in each group are allotropic modifications of the same 
hydrocarbon distinguished one from another by their various rotatory action 
on the polarized ray. It will, how'ever, be found I believe that the terpenes 
from several different plants will on further examination be conclusively proved 
to be really identical and not simply isomeric. This, I believe, to be the case 
with the terpenes from French turpentine and sage, also with the terpenes 
from orange peel, bergamot and lemon.'" 
Tilden's prediction, that the number of terpenes would be shown to 
be much smaller than assumed in his days, has proven itself true. His 
classification, however, was insufficient, for it included only a small 
number of terpenes. Indeed the material at hand was not sufficiently 
sifted for an attempt of that kind. It consisted of a large number of 
disconnected observations, the study of which was rendered difficult by 
an arbitrary nomenclature. Only by a systematic exploration of this 
disorderly realm could a clear insight into the subject be gained. 
i) Berichte. 6, p. 437. 
2) Kekul^'s formula for camphor was based on the same consideration. 
3) Compt. rend., 80, p. 1446. 
*) Jour. C'hem. Soc., 28, p. 514; Ibidem, 31, p. 554: Pharm. Journ., 1877, p. 101. 
5; This statement is incorrect for dipentene and limonene likewise produce terpin 
hydrate. Comp. Fliickiger, Arch. d. Pharm., 222, p. 362; also Kremers, Am. Chem. 
Journ., 17, p. 695. 48 
Historical Introduction. 
That we are able to-day to distinguish sharply between so many 
terpenes and their derivatives is due primarily to the excellent experi- 
mental researches of Otto Wallach, the founder of modern terpene 
chemistry. 
Inasmuch as it was impossible to isolate the numerous terpenes 
boiling between 155 and 185° by fractional distillation, methods had 
to be sought which enabled the characterization of these hydrocarbons, 
even in mixtures, by means of crystalline derivatives. Only after the 
characterization of the numerous isomers was accomplished was it 
possible' to study successfully the relation of one terpene to another, 
the relation of the terpenes to their oxygenated derivatives, and the 
problem of their constitution. 
These problems have been solved in so far that it is now possible to 
identify many if not most terpenes without great difficulty. The 
inversions, or changes from one to the other, are also better under- 
stood. The problem of their constitution, however, is still far from a 
satisfactory solution, though structural formulas have been proposed 
for a number the terpenes. 
In 1884 Wallach1) began his researches on this subject with the 
investigation of the oil of wormseed {Oleum cinae). Three years later 
he was in a position to characterize eight terpenes by means of crystalline 
derivatives (tetrabromides, hydrochlorides, hydrobromides, nitrosites 
etc.), viz. pinene, camphene, limonene, dipentene, sylvestrene, terpinolene, 
terpinene' and phellandrene. To these fenchene was added later. The 
sesquiterpenes were also included in his investigations as well as the 
oxygen derivatives of the terpenes with their greater capacity for 
reaction, viz.: cineol, terpin hydrate, terpineol, pinol, fenchone, thujone, 
pulegone, menthone, carvone, methyl heptenone, patchouly alcohol, 
caryophyllene hydrate and guajol. 
After Wallach had removed the principal difficulties in the investi- 
gation of volatile oils, other chemists also developed a successful activity. 
A. v. Baeyer's valuable investigations into the constitution of the 
terpenes and related compounds appeared in the Proceedings of the 
German Chemical Society since 1893. Whereas Wallach and v. Baeyer 
i) Wallach's contributions are to be found in the following volumes of Liebig's 
Annalen: 225, 227, 230, 238, 239' 241, 245, 246, 252, 253, 258, 259, 263, 264, 268, 
269, 270, 271, 272, 275, 276, 277, 278, 279, 281, 284, 286, 287. 289, 291, 296, 300, 
302, 305, 306, 309. Several papers froin his pen also appeared in the Proceedings of 
the German Chemical Society since 1890. Of the latter, his lecture before this society 
in 1891 in which he presented a general survey of his work up to that date should 
receive special mention (Berichte, 24, p. 1525). History of Volatile Oils. 
49 
investigated primarily the cyclic compounds, Semmler paid special 
attention to chain compounds. He showed that the alcohols geraniol 
and linalool and the aldehydes citral and citronellal, which occur fre- 
quently in volatile oils, are chain compounds; also that they, like the 
more or less closely related cyclic compounds, can be converted into 
cymene.1) Other chapters of the chemistry of volatile oils were included 
in his researches,2) some of which were conducted jointly with Tiemann.3) 
The investigations by the latter and Kruger of orris oil and irone, led 
to the discovery of ionone, the artificial perfume of violets. 
In addition to these, numerous other chemists have investigated the 
composition of volatile oils and the constitution of their constituents. 
In so far as their results pertain to the composition of volatile oils, 
their results are included in the special part of this treatise. 
The constitutional problems involved in the study of the terpenes 
and their derivatives are among the most difficult of organic chemistry 
because of the readiness with which rearrangements within the molecule 
take place under the influence of ordinary physical and chemical reagents. 
A typical example of some of the difficulties involved may be had in 
ordinary camphor. Although investigators had an almost unlimited 
supply at their disposal and in spite of the fact that many chemists 
have been incessantly investigating this compound for several decades 
in order to obtain an insight into its constitution, the views held with 
regard to its structure4) are still divided. 
This brief history of volatile oils would not be complete without 
some reference to the literature on the subject since the beginning of 
this century. So long as the volatile oils were principally prepared in 
the laboratories of apothecary shops, the description of the oils and of 
the methods of their preparation was found in pharmaceutical reference 
works and pharmacopoeial commentaries. The results of scientific and 
technical studies were also published in pharmaceutical rather than in 
purely chemical journals. With the early forties the preparation of 
volatile oils was taken out of the pharmaceutical laboratories and a 
separate literature was created. 
i) The reverse process, the conversion of the cyclic menthone into chain compounds 
of the citronellal series was accomplished by Wallach in 1897. (Liebig's Annalen, 296). 
2) The oils of Allium ursinum, asafetida, garlic, onion; also tanacetone (thujone), 
menthone, pulegone, terpineol, etc. 
3) Bergamot oil, lavender oil, citral, pinene, methyl-heptenone, tanacetone, etc. 
4) Not less than two dozen structural formulas have been proposed for camphor in 
the course of these investigations. 50 
Historical Introduction. 
Zeller's*) publications (1850-1855), already mentioned on p. 37, 
contain a compilation of the yield, also a very meagre description of 
the physical properties of the oils and their behavior toward reagents. 
Maier's*) treatise (1867) also takes into consideration the scientific inves- 
tigations. The methods of preparation and the subject of distillation are 
described in detail by Mierzinski*) (1872). A similar work was written 
by Askinson*) in 1876. "Die Toiletten-chemie" of Hirzel*) which passed 
through four editions, also ''The art of perfumery" by Piesse,*) which 
was translated into several languages, may here be mentioned. 
The results of the earlier papers by Wallach are contained in the 
excellent work of Bornemann*) (1891), whereas the "Odorographia" of 
Sawer*) emphasizes the botanical side of the subject. Finally the 
monograph by Heusler*) on the terpenes should be mentioned for it 
has proven itself well nigh indispensable for the scientific investigation 
of terpenes and their derivatives. 
Although remarkable progress has been made in the chemistry of 
the volatile oils during the past fifteen years, the investigations of this 
branch of science are far from being completed. On the contrary, the 
newly acquired knowledge has caused an ever increasing number of 
problems to present themselves for solution. It is quite remarkable, 
however, that the interest bestowed upon purely theoretical questions 
has caused a falling off in the systematic analytical study of volatile 
oils. There are still a considerable number of oils that are much used 
and readily accessible, the composition of which is but imperfectly 
known. Even many oils that have been repeatedly examined will be 
made to yield still other constituents when carefully reexamined. 
Plant physiological problems also have scarcely been touched upon, and 
the assay of volatile oils is just beginning to assume a modern 
scientific aspect in harmony with recent theoretical results. Hence there 
still remains a large field for profitable work. 
It may well be said, therefore, that in spite of the unprecedented 
progress in recent years, the chemistry of volatile oils is but in its 
initial stages. Following the paths of Wallach and of other reformers, 
chemical investigators of all civilized countries are busily at work 
opening up new fields for investigation. Science and industry are 
working hand in hand and it may reasonably be expected that both 
will profit greatly by the results of the incessant labor thus fostered 
and stimulated. 
*) See Bibliography. 3. HISTORY OF THE METHODS OF DISTILLATION AND OF 
DISTILLING APPARATUS. 
The literary documents considered in the previous chapter, reveal 
the slow process of evolution leading up to a better understanding of 
the subject of volatile oils. In like manner, a short historical retrospect 
of the methods of distillation and distilling apparatus may result in an 
insight into the gradual development of the art of distillation and the 
methods of preparation of distilled oils. 
The history of the evolution from the 
primitive Cucui'bita,, the Alembic, and the 
Berchile to the steam and vacuum appa- 
ratus of our own time reveals a long and 
varied course which had to be followed by 
this apparently modern branch of industry 
in order to bring it to its present technical 
and scientific perfection. 
The first definite statement found in 
ancient writings which indicates a kind of 
primitive distillation, although probably 
not pictured until the middle ages, is the 
mention of the method for obtaining oil of 
cedar (Trio-creXaiov) in the writings of Hero- 
dotus,1) Dioscorides2) and Pliny.3) This 
oil is said to have been obtained from the 
oleoresin by boiling with water in an open earthen kettle. The oil either 
collected at the surface of the liquid and ivas removed, or its vapors 
were condensed in layers of wool spread over sticks of wood laid crosswise 
Fig. 3. 
i) Historiae, lib. 2, p. 85. 
2) De mat. med., lib. I, 34. 39, 80. 
s) Hist, nat., lib. 15, cap. 6-7; lib. 16, cap. 22. 52 
Historical Introduction. 
on the kettle as m figure 3. The wool was replaced from time to time by 
fresh portions and the saturated wool expressed with the hands. 
Authentic representations of the distilling vessels used by the 
Egyptians do not exist. Some of their forms of apparatus were 
undoubtedly adopted by the Arabians and improved by them. 
To the oldest known writings which 
give information on methods of dis- 
tillation and distilling apparatus belong 
those of the Greek physician Dios- 
corides1) and of the Greek philosopher 
Zosimos.1) 
Fig. 4. 
Fig. 5. 
In a manuscript Arabian translation of Dioscorides' Materia Medica 
in the library at Leyden distilling ranges and apparatus are mentioned 
and described. These descriptions probably occur in the original Greek 
text. Among them are found the cucurbita and the alembic.2) 
Fig. 6. 
Fig 7. 
Just as pictures of animals have served as symbols in the oldest 
mythology and as characters in writing' of the earliest peoples, the 
forms of animals were used by the ancients as prototypes in the making 
of jewelry, and of all kinds of useful articles and apparatus. The same 
i) Compare Bibliography. 
2) Extracts from this as well as the much later Arabic writings of Rhases and an 
unimportant illustration of an Arabic distilling apparatus were published in 1878 by 
Prof. Wiedemann in the Ztsch. d. deutsch. morgenland. Gesell., 32, p. 575. History of the Methods of Distillation and of Distilling Apparatus. 
53 
seems to have occured in the preparation of primitive digestion and 
distilling vessels. Such pictorial representations have been carried over 
from the writings of Zosimos and probably also of others into the 
writings of the Arabians and from these into other alchemical works of 
the middle ages.1) 
As prototype of a common flask 
the figure of an ostrich is given 
(fig. 4); as that of a retort a goose 
(fig. 5) or a pelican (fig. 6). The 
shape of a bear served for a still 
(cucurbita) and head (alembicus) 
(fig. 7). An improved form of this 
simple distilling apparatus is found 
in the writings of Geber2) and 
Albucasis.3) The latter not only 
described glass distilling vessels, but 
Fig. 8. Fig. 9. 
also those prepared of glazed earthenware (fig. 8) and a kind of 
fractional distillation for the purpose of a better condensation and 
separation of subtle spirits by placing several alembices^ on top 
of one another (fig. 9). 
From the writings of Geber and Albucasis, also from those of the 
excellent physician and writer Rhases (El Razi), it becomes apparent 
that the Arabians distinguished as early as the eighth century between 
distillation over open fire and from a water bath and ash bath.5) 
Geber described both methods in detail.6) 
For the purpose of better condensation, Costaeus of Lodi,7) a 
physician and alchemist of Bologna, recommended that the beak of the 
1) Joannis Rhenani. See Bibliography. 
2) Summa perfectionis magisterii. 
3) See Bibliography. 
4) Albucasis, Liber servitoris, lib. 27, p. 247. 
5) Rhases, Das Buch der Geheimnisse. 
6) Summa perfectionis mag., cap. 50. 
7) See Mesue, Simplicia et composita. 54 
Historical Introduction. 
alembic be cooled by water (figs. 10 and 11), also that the distillate 
be improved by the use of the water bath (balneum Mariae) 
(fig. 12) and the sand bath (balneum arenae) (fig. 13). Among 
the writings left by the Arabians, 
the work of Albucasis 'previously 
mentioned probably contains one of 
the first and most striking descrip- 
tions of the manner of distillation 
and distilling apparatus. From the 
fourteenth century on the practice 
of making distilled liquors increased 
very considerably. As a result the 
methods of distillation a,nd the 
Fig. 10. 
Fig. 11. 
distilling apparatus, especially those parts employed for the con 
densation of the vapors, were greatly improved. The method of con- 
Fig. 12. Fig. 13. 
densation of the vapors, already well known to the Arabians, of passing 
the straight or bent tube of the alembic, or an elongation of the same 
wound into a spiral (wormtube, serpentina^) through cold water was History of the Methods of Distillation and of Distilling Apparatus. 
55 
already in general use at that time for the distillation of wine and 
fermented plant juices. As examples of such distilling apparatus and 
methods, "die mancherley Kuhlungen der Teutschen und Welsche Wein- 
brenner" are described and illustrated in treatises on distillation of the 
first half of the sixteenth century, namely in those of Brunschwig, 
Ulstad, Ryff and Lonicer. In these a distilling apparatus constructed 
with considerable skill is described. The helm of the still and the outer 
condenser jacket were made of sheet copper. The form of the headlike 
expansion of the helm with the outer jacket, the lower open rim of 
which was tightly luted to the still, gave rise to the name of "Mohren- 
kopf." The condensation was effected by a continuous flow of cold 
water through the outer jacket (fig. 14). 
Fig. 14. 
The method of condensation derived from the Arabians was con- 
sidered as the most perfect for the distillation of spirit of wine {aqua 
vitae). The illustration of this apparatus was selected for the title 
page of the second volume of Brunschwig's Destillirbuch published in 
the year 1507 and is reproduced on page 25. 
Where the two upright serpentine connecting tubes {serpentinae) 
between the retorts {cucurbitae) and the receivers {receptacula) cross 56 
Historical Introduction. 
each other they pass through a condensing tube filled with cold water. 
The cooling effect thus produced is not sufficient for the condensation 
of all the vapor. The worm acts therefore, as a dephlegmator and 
increases the alcoholic strength of the distillate. This is emphasized 
correctly by Brunschwig.1) 
The perfection of the apparatus for the preparation of distilled 
liquors, also distilled oils, which up to that time had received but little 
attention, seems to have progressed much more slowly and with greater 
difficulty. 
In comparison with the ready volatility of the alcohol, water was 
considered as that product of distillation most closely related to it, 
whereas the oil was regarded as the "obese and fatty substance that 
had to be driven over with a stronger and more violent heat." This 
had led to the firmly established belief that in the process of purification, 
Fig. 15. 
Fig. 16. 
the volatile and subtle part must penetrate and exhaust the material 
as much as possible. As a result all sorts of queer apparatus and 
sources of heat were invented. They all resulted in a prolonged digestion 
and an unintentional loss of the alcohol ofttimes formed by fermentation, 
and of the aroma. 
Circulation was therefore considered not only as the. essence of 
distillation but also as an important preparatory part of it. It was 
believed that the plant and animal material finally to be distilled was 
thereby prepared for the refinement and purification of the "geistige 
Wesen" contained in them and for their better and easier separation and 
purification. A large variety of vessels, usually constructed after some 
symbolic prototype was used for this purpose. The simple Circulatoria 
were ordinary glass flasks, retorts with the tubes bent in a variety of 
ways, also so-called urine glasses used by physicians for diagnosis. 
it De arte distillandi, vol. 2, lib. 1. History of the Methods of Distillation and of Distilling Apparatus. 
57 
The operation performed in the pelican (fig. 15) and double or twin 
circulatoria (fig. 16) provided with reflux tubes were considered as the 
most perfect kinds of circulation, especially for refining the "spirits." 
Fig. 17. 
Fig. 18. 
Still more peculiar than the form of the circulatoria was the source 
of heat used for the purpose of circulation, usually accompanied by 
fermentation, and even decomposition processes. Not only was the 
water bath (balneum Mariae) (fig. 17) and the ash bath (balneum 
per cinerem) (fig. 18) employed, but 
also the sun bath (destillatio solu) 
(fig. 19). The circulation vessels 
were also immersed in fermenting 
dough, and heated with this in an 
oven (destillatio panis); or they 
were imbedded in decomposing well 
Fig. 19. 
Fig. 20. 
wetted horse manure which was placed in a layer above unslaked lime 
in pits (destillatio per ventrem equinum) (fig-. 20). 
With the introduction of aromatic waters as one of the principal 
forms of medication, the condensation of the vapors gave rise to 
difficulties, because a greater degree of heat was necessary for their 58 
Historical Introduction. 
distillation. Plant material lying on the bottom of the still was also 
easily burnt, and the distillate received therefrom an empyreumatic 
odor and taste. With a strong heat a serious overheating of the helm 
and tube, which were usually constructed of lead or tin, took place, 
while with the employment of a moderate heat the yield of the distillate 
remained unsatisfactory. In order to overcome these disadvantages 
and to prevent the flowing back of the distillate condensed in the helm, 
as well as to increase the cooling effect of the air, the helm known as 
the "Rosenhut" (fig. 1, p. 23) and (fig. 21) was constructed as early 
Fig. 21. 
as the fifteenth century. Near the base, at about the height of the 
outlet tube, this had a groove extending around the inside of the 
helm, and through which the water condensing on the upper wall of 
the helm and running down was conducted into the outlet tube and 
from there into the receiver. The "Rosenhut" was therefore in itself an 
inefficient air condenser, which served its purpose with much less 
efficiency than did the "Mohrenkopf" in the alcohol distillation 
(fig. 14). 
The first step toward a better condensation with cold water, in the 
preparation of the distilled waters, consisted in surrounding the head History of the Methods of Distillation and of Distilling Apparatus. 
59 
of the helm (alembic) with an oxbladder. It was securely fastened and 
provided with a wooden stop-cock. The hood-like basin thus formed 
(fig. 22) was kept cold by means of flowing water. In a similar 
manner the helm was also surrounded by a basin-like metallic addition 
which was either fastened by luting or soldering. Thus the helm could 
be well cooled by running water (flg. 23). By means of an inner 
horizontal groove like that in the "Rosenhut" (fig. 21) the distillate which 
condensed on the walls of the helm was conducted into the receiver. 
Walter Ryff in his treatise on 
distillation describes and illustrates 
distilling apparatus with condens- 
ing tubes which are passed through 
vessels of cold water. The first 
apparatus has two tubes connected 
with the helm (fig. 24) which are 
passed through a barrel of water. 
Fig. 22. 
Fig'. 23. 
However, Ryff declares this method of condensation as insufficient and 
recommends a worm tube for the shape of which he gives two forms 
(figs. 25 and 26) and concerning the use of which he gives a detailed 
account. 
A peculiarly constructed apparatus for .the distillation of aromatic 
waters and oils was recommended by Adam Lonicer in his "Krauter- 
und Destillirbuch" published in 1573. The construction of the apparatus 
becomes readily apparent from the accompanying cut (fig. 27). 
Finally, the Arabians and probably others before them practiced 
"downward distillation" which corresponds on the whole to our modern 60 
Historical Introduction. 
dry distillation for obtaining empyreumatic and tar oils. At the time 
of the revival of the distilling art this method was also used in the 
preparation of the oils of certain woods, barks and spices. Juniper 
Fig. 25. 
wood especially had been submitted to this destillatio per descensum 
since antiquity, later also guaiac wood, cinnamon, cloves, mace and 
other spices were distilled in this manner. The furnace contained a History of the Methods of Distillation and of Distilling Apparatus. 
61 
division in the middle, with a central opening into which a pot provided 
with a beak-like opening at the bottom was either hung, or plastered 
in. On top of the opening extending into the upper part of the furnace 
Fig. 27. 
was placed a wire gauze and a second pot filled with the dry substance 
to be distilled was luted with its opening on the top of the lower pot. 
The heating was then effected by building a fire around the upper pot 62 
Historical Introduction. 
(fig. 28). Sometimes the lower pot was buried in the earth and a fire 
built about the upper pot fastened on top of this one in the same 
manner. 
For the destillatio per descensum on a small scale glass vessels 
heated from the side (fig. 29) were also employed and even for some 
easily distilled substances the heat of the 
sun {destillatio soils') (fig. 30) was used. 
At present the preparation of empyreumatic 
oils as well as of the finer tars is effected 
in cast iron or earthenware cylinders. 
The treatises on distillation published 
during the sixteenth century reveal by. both 
text and illustration that about that time 
more attention was again given to the 
construction of furnaces and implements 
used for the purpose of distillation. 
Besides the distilling apparatus most 
generally used at that time and repro- 
duced in figs. 10, 11, 14, 17, 21, 23, 24 and 25, the socalled 
"faule Heinz" or Athanor (from d^dvaros, imperishable) called by 
Ulstad furnus Acediae (fig. 31) was much in favor and was used to 
a great extent for the distillation of waters and oils. Above a common 
Fig. 28 
Fig. 29. 
Fig. 30. 
fireplace were placed three or more distilling retorts with '"Rosenhut- 
hehn" (p. 104, fig. 21). The fireplace ended in a central iron, copper 
or earthenware pipe the opening of which could be closed by a cover. 
By means of slides at the sides of the fireplace the heat could be 
conducted under any one of the stills or retorts as desired and the 
distillation was thus regulated. History of the Methods of Distillation and of Distilling Apparatus. 
63 
For the distillation of large quantities in a large number of single 
retorts or stills, larger cupil furnaces after the manner of the so-called 
"galley furnaces" appear also to have been in use. The illustrations 
and descriptions of these in the treatises on 
distillation of the sixteenth century represent 
no doubt more the possibility than the 
realization of perfection. The illustrations 
of these furnaces were transferred from one 
distilling book to another, but probably 
have not been generally used in practice. 
Among others they are thoroughly described 
in the text and reproduced in illustration in 
the works of Matthiolus and of Lonicer 
previously mentioned. They are built either 
in the shape of a terrace (fig. 32) or of a 
bee hive (fig. 33). 
Although the compilers of the distilling- 
books of the sixteenth century have in 
succession followed the pioneer work of 
Brunschwig, especially in regard to illus- 
trations, their writings nevertheless quite often show considerable 
differences in views, practical skill, and experience, and also in the 
originality of their knowledge and ability. 
Fig. 3>. 
Fig. 32. 
With but little public intercourse these secluded workers and writers 
toiled mostly far from one another, each in his own sphere and manner, 
often with but a slight knowledge of the older writings and of the 64 
Historical Introduction. 
work of his contemporaries. With regard to the manner of distillation 
of the aromatic waters and oils this is shown in an unmistakable 
manner in works compiled in the course of the first half of the sixteenth 
century by Philipp Ulstad, Walter Ryff, Adam Lonicer, Valerius Cordus 
Fig. 33. 
and Conrad Gesner. All of these were mainly based on the writings of 
Hieronymus Brunschwig. Their views, however, as to the nature of 
distillation itself and of the distilling methods and apparatus are 
neither in accord with those of Brunschwig, nor with those of their 
contemporaries. History ol the Methods of Distillation and of Distilling Apparatus. 
65 
How little personal skill, practical experience and familiarity with 
the literature on the subject may be found in the writings and methods 
of working of the most prominent experimenters of that time becomes 
apparent e. g. from the construction of and preference for the distilling 
vessels employed. Thus for instance, Valerius Cordus, profound in 
theoretical science, but ignoring the rationally constructed distilling 
apparatus then well known, used and recommended "ein Kolb mit einem 
angeschmelztem Helm" (fig. 3d) as an efficient apparatus meeting all the 
requirements of the art. At the same time Conrad Gesner, his con- 
temporary, used for the same purpose a distilling furnace (fig. 35), 
which had been used for some time. 
As has already been mentioned, the seventeenth century, crippled as 
it was by the destructive storms of the Thirty Years war, added but 
little to the further development of the art of distillation a,nd other 
technical scientific industries. The few active experimenters, however, 
favored with a better understanding, endeavored to perfect not only 
the apparatus used but the processes as well. 
Fig. 34. 
Fig. 35. 
As the "Destillirbuch" of Brunschwig and similar treatises of his 
successors reflect the practical and theoretical knowledge of the sixteenth 
century with its mistakes and imperfections, so Glauber's treatise on 
distillation reflects the condition of the art and science of distillation 
during the second half of the seventeenth century. Although Glauber's 
laboratory work and the character of his writings was of a wider scope 
than that covered by the older "Destillirbucher," yet he also paid 
special attention to the distillation of aromatic plants and spices. In 
this, he and his contemporaries seem to have paid special attention to the 
improvement of the methods of distillation for the purpose of relatively 
increasing the products of distillation. For this purpose as has already 
been mentioned on page 33, a very rational expedient of increasing 
the specific gravity and thus raising the boiling point of the water used 66 
Historical Introduction. 
for the distillation, was resorted to. This was effected by the addition 
of salts. The use of muriatic acid (spiritus salis) recommended by 
Glauber for the distillation of oil of cinnamon and other expensive oils 
has also been alluded to (p. 33). His idea was that the acid penetrated 
the material and thus drove out the oil. A small amount of muriatic 
acid was supposed to take the place of a large quantity of water 
thereby avoiding loss of oil. He also recommends that dark colored 
and resinified oils be rectified with spiritus salis. 
Glauber's authority was recognized until the middle of the eighteenth 
century, and the methods of distillation recommended by him in his 
several writings were employed by his contemporaries and their 
successors. Boerhaave, therefore, and Hoffmann, their contemporaries, 
and later investigators prepared the volatile oils by using common and 
other salts or hydrochloric acid. 
It is perhaps due to the observation that metal was present in an 
oil or a distilled water, especially if an acid had been used in its 
preparation, that in the course of the eighteenth century more attention 
was again bestowed upon the material from which the still was 
constructed. In consequence glass and glazed earthenware were 
substituted for metal. As a matter of fact it seems that as early as 
the sixteenth century the presence of metals in the distillates obtained 
from metallic stills did not escape the notice of some of the experimenters. 
Among others Job. Krafft1) (1519-1585) cautions against the use 
of copper distilling vessels. The famous Parisian physician Ambroise 
Pare2) (1510-1590) warns against the use of lead helms and con- 
denser tubes "which ofttimes cause the distilled water to be milky.'' 
The Bologna physician and professor Benedetto Vettori of Faenza 
(14-81-1561) declared about the year 1555, that water on being 
conducted through lead pipes, dissolves lead and thus becomes 
poisonous.3) 
However, these observations like so many others made in the art 
of distillation appear either to have been known to but a few or else 
were unheeded and again forgotten, for even during the seventeenth 
and eighteenth centuries when oils were distilled with acids, lead and tin 
heads and condensers were in general use in connection with copper stills 
or glass and earthenware retorts. 
i) Conciliorum et epist., 1, fol. 190. 
2) Les oeuvres, p. 746. 
3) Practicae maguae, 1, cap. 21, fol. 144. History of the Methods of Distillation and of Distilling Apparatus. 
67 
As already mentioned in the preceding chapter, the distillation 
of the volatile oils and the construction of the distilling apparatus 
received more attention and underwent a more rapid development 
with their general introduction into the laboratories of apothecaries. 
In these the volatile oils used in medicine and the arts were prepared 
up to the first decades of the nineteenth century. Only a few oils, such 
as the oils of lavender, rosemary and rose which could be readily 
produced in some countries and which were largely used in the perfume 
and soap industries, have been obtained since the sixteenth century in 
larger quantities by means of primitive portable distilling apparatus.1) 
Fig. 3(5. 
The distilling vessels used in the apothecary laboratories and the 
itinerant stills {Wanderdestillirgerathe), or alambics voyageants used in 
France, Spain, Italy and Bulgaria, consisted of copper stills with a 
copper or tin head and tin condensing tubes of various shapes. 
One of the better distilling apparatus used for the distillation of 
volatile oils in the eighteenth century consisted of a tin or copper body 
1) Comp. p. 26; also under Oil of Lavender, Oil of Rose and Oil of Rosemary. 68 
Historical Introduction. 
suspended in a water bath, and provided with a "Mohrenkopf" (fig. 14, 
p. 55), a "Rosenhut" (fig. 21, p. 58) and a spiral tube for condensation. 
An illustration (fig. 36) and description of this distilling apparatus was 
published in 1784 by Francois Demachy,1) director of the apothecary 
laboratories of the civil hospitals of Paris. 
The copper kettle v serves as a waterbath which can be turned by the 
handles ss and refilled with a fresh supply of water through the side tube m. 
The tin still d rests with the upper ring n on the rim 7? of the kettle. The 
lower neck q of the head of the still b rests at n on the upper rim of the still. 
Around the lower edge of the head runs the trough c in which the distillate 
that has been condensed in the cone collects and passes with uncondensed 
vapors through the tube c-u into the spiral condenser. 
The "Mohrenkopf" a serving as a cooler for the "Rosenhut" b is soldered 
to the neck k of the condensing cone. The water in the cooler warmed during 
the process of distillation, runs off through the upper tube e as fast as cold 
water is added. 
Fig. 87. 
Since the beginning1 of the nineteenth century attempts have been 
macle to simplify and to improve the construction of the distilling 
apparatus, more especially of the cooler, also to prevent the burning 
of the plants on the bottom of the still with the use of direct heat. 
Such improvements were made especially by Joli. Gottfr. Dingier, the 
apothecary, in Augsburg2) during the years 1815-1820, by Smithson 
Tennant3) in 1815 and by Henry Tritton4) in 1818, both of England. 
i) L'art du destillateur. Germ, transl. by Hahnemann, vol. 1, p. 192, and plate2, fig. 1. 
2) Trommsdorff's Journ. d. Pharm., lit, p. 241; also Buchner's Repert., 3, p. 137, 
and 6, p. 142. 
3) Phil. Trans. 1815; Repertory of Arts, Sept. 1815. 
4) Annals of Phil., June 1818; Buchner's Repert., 6, p. 98. History of the Methods of Distillation and ol Distilling Apparatus. 
69 
The latter attempted to carry on the distillation at a lower temperature 
by putting the apparatus in connection with an air pump. The distilling 
apparatus more commonly in use at that time for the distillation of 
volatile oils was the one shown in the accompanying cut (fig. 37). 
Steam distillation was recommended in 1826 by H. Zeise1) and 
especially for volatile oils by van Dyk in Utrecht,2) who thereby 
materially aided in its introduction. He demonstrated that the volatile 
oils which were obtained by steam alone from the vegetable material, 
distinguished themselves from those obtained by distillation over open 
tire, by a lighter color and purer odor. Clove oil distilled with steam 
is nearly colorless, cinnamon oil light straw yellow and orange peel oil 
completely colorless.3) The first steam distillation on a larger scale in 
a pharmaceutical laboratory appears to have been that in the old 
Apothecary's Hall in London.4) 
Fig. 38. 
i) Beitrase zur Nutzanwendung der WasserdSmpfe; Arch. d. Pharm., 16, p. 69. 
2) Buchner's Repert., 29, p. 94. 
3) Ibidem, 29, p. 110. 
<) do., 29, pp. 112 & 133. 70 
Historical Introduction. 
Iii Germany steam distillation for the preparation of volatile oils in 
apothecary laboratories was also made possible by the introduction of 
a steam distilling apparatus,1) constructed about the year 1826 by 
Johann Beindorff, mechanic and tin founder in Frankfurt a. M. (fig. 38). 
With this apparatus, soon perfected in many ways, the distillation of 
volatile oils with steam under pressure was possible. The condensing 
arrangement also had the advantage over the spiral tube of being made 
up of separable parts, and thus allowing it to be readily cleaned even 
on the inside. 
For the preparation of volatile oils on a small scale, the arrange- 
ments based on the original steam distilling apparatus of Beindorff 
remained, until the industry conducted on a large scale became dominant 
also in this field and prepared products of a quality and at prices 
with which the preparation on a small scale could not compete. 
Of the arrangements used for a long time for the separation and 
removal of the oils from the water the Florentine flask in various forms 
and sizes has shown its utility and has been in continual use. It 
probably came into use in the middle ages. A method of separation of 
oil and water which in its principles corresponds to those of the 
Florentine flask has, it appears been described for the first time by 
Porta2) in the latter half of the sixteenth century. 
The Florentine flask like many other facts and improvements per- 
taining to the art of distillation which were not generally known, was 
soon forgotten. As a result it was rediscovered several times from the 
beginning of the seventeenth century to the year 1823. 
Thus the flask was again described and introduced by Homberg8) 
at the end of the seventeenth century about one hundred years after 
Porta's description - only, however, to be again forgotten for a con- 
siderable period of time. A century later, in the year 1803, the Florentine 
flask was again recommended for the distillation of volatile oils by the 
Augsburg apothecary Johann Gottfried Dingier4) and later in 1823 
once more introduced as something new by the apothecary Samuel Peetz 
in Pesth.5) 
The Florentine flask of older construction as described by Porta, 
has been in use for a long time. The oil was siphoned off by means 
of a porous siphon consisting of a lampwick into small bottles (fig. 39). 
i) Geiger's Magazin f. Pharm., 11, pp. 174 & 291; Buchner's Repert., 33, p. 43G. 
2) Magiae naturaiis, lib. decimns, p. 367. 
3) Philippe und Ludwig, Geschiehte der Apotheker, p. 513. 
4) Trommsdorff's Journ. d. Pharm., lln, p. 242. 
5) Buchner's Repert., 14m, p. 481. History of the Methods of Distillation and of Distilling Apparatus. 
71 
Later the Florentine flask shown in figure 4-0 was also used. The flask 
used at the present time in the large factories is not only larger, but 
contains in the upper part in the level of the oily layer a glass stopcock 
through which the oil can be drawn off from time to time, or an over- 
flow tube through which the oil when it reaches a certain level runs 
into a receiver (fig. 41). 
In the course of time a number of differently constructed receivers 
for the separation of the volatile oils have been proposed, without 
however, causing the Florentine flask to be discarded. The first of these 
was proposed by Amblard of Paris1) in 1825. It consisted of a glass 
tube, open at both ends and drawn out to a taper. This tube was 
suspended by means of a cork ring at its upper end in a high glass 
mixing' cylinder. This cylinder was provided at the top with an over- 
flow tube. The oil collects in the glass tube and can be removed from 
this after (dosing the small lower opening, by pouring out as often as 
desired. 
The more salable volatile oils, which were used in larger quantities 
in the perfume industry that had developed in France in the course of 
the eighteenth century were still prepared during the first quarter of 
the present century in the traditional primitive distilling vessels and 
improved by rectification. In Germany the apparatus shown in figs. 37 
and 38 were principally used. While the oils of lavender, rosemary, 
orange flower, etc., were manufactured in France and rose-oil in 
Turkey, Germany and Hungary supplied the market with the oils of 
caraway, fennel, anise, coriander, calamus, peppermint, spearmint, 
Fig. 39. 
Fig. 40. 
Fig 41. 
i) Bull, des trav. de la Soc. de Pharm., 1825. p. 247 72 
Historical Introduction. 
valerian, chamomile, and others used in medicine and in the fine arts. 
In southern France, especially on the sunny slopes of the Alps near the 
Mediterranean coast, the industry of the aromatic oils developed con- 
siderable proportions in the early part of this century. The oils 
principally used for medicinal purposes, however, were still prepared in 
apothecary laboratories. In the course of time individual apothecaries 
and druggists, having made a beginning on a small scale, erected much 
larger establishments for the preparation of volatile oils. This was 
done especially in regions suited to the culture of medicinal plants, for 
instance, in Thuringia on the Saale and the Elbe, in Saxony, Bohemia, 
Franconia and also in Hungary. Only a few of these, however, remained 
in existence for any appreciable length of time. As in chemical and 
other branches of industry, these originally small distilling operations 
were replaced everywhere, by a larger, more rational and efficient 
industry. This new industry has worked hand in hand with science and 
technology. Whereas on the one hand it utilized the results of science, 
on the other it not only stimulated science but gave direct assistance. 
Beginning about the middle of the present century the earlier, simple 
apparatus took on a different shape in the factories of this larger 
industry of the volatile oils. The original small distilling apparatus 
were replaced by larger and more rationally constructed ones which not 
only effected a better exhaustion of the vegetable matter and thus 
increased the yield, but also produced oils of a better and purer quality. 
The apparatus commohly used in the factories about the middle of 
the present century, were the stills arranged for the so-called water- 
distillation, and others for the so-called dry steam-distillation. 
The first type of stills (fig. 42) is a simply constructed apparatus 
for the distillation of plant material in water, as well as for the 
rectification of crude oils by steam. The still is heated by means of steam 
admitted under pressure through the holes of a ring at the bottom or 
by allowing the steam to escape directly into the lower double walled 
jacket B. The advantage possessed by the receiving flask E over the 
ordinary Florentine flask consists in the flowing back of the distillation 
water saturated with oil, through the tube F, into the still. 
In the distillation with dry steam (fig. 43) the still is filled with the 
plant material without the addition of water and distilled with steam 
passing through the material from the bottom upwards. These or 
similarly constructed steam distilling apparatus are employed even at 
the present time for the distillation of some of the oils, only in place 
of the spiral a tube condenser is used. History of the Methods of Distillation and of Distilling Apparatus. 
73 
With the introduction of these apparatus during the middle of this 
century the volatile oil industry had taken its position as a branch 
of the rapidly developing chemical industry at large with southern 
France and central Germany as the principal centers of production. 
Since then this branch of chemical industry has witnessed great technical 
improvements which have reacted favorably on its growth and 
peri n a nen t devel(>pnlent. 
Fig. 42. 
Owing to the remarkable development of the entire perfume 
industry during the second half of this century, the consumption and 
commerce of the volatile oils assumed entirely unanticipated proportions 
and importance. Scientific and technical attainment, commercial 
interests and business competition brought about numerous changes in 
rapid succession. More rational methods of distillation were devised, 
large apparatus for the distillation of enormous quantities were 74 
Historical Introduction. 
constructed, the quality of the product was improved while the price 
of its production was diminished. Some of the largest stills used in 
the manufacture of volatile oils have a capacity of 30,000 to 60,000 
liters (= 7,926 to 15,852 gallons). Commensurate with their size is 
their construction and operation, the arrangement for charging and 
discharging, for the condensation of the vapors in as quick and 
efficient a manner as possible, and above all their productiveness. 
Considerable historical interest is attached not only to the theory 
and practice of the present art of distillation in its application to the 
preparation of the volatile oils but to the gradual development of the 
distilling vessels as well, which are employed for this purpose. 
Fig. 43. 
On tlie following pages will be found a number of illustrations of some 
of the modern stills used in German and French factories. Looking back- 
ward it might seem as though no relation existed between the modern 
giant stills and their prototypes. Yet every one of them is but a link in 
the long chain of development of the art of distillation. That the process 
of evolution has been exceedingly rapid during the past ten years does not 
affect the truth of this statement. Almost every one of these pieces of 
apparatus has been newly created out of the ruins of its immediate 
predecessor. 
In modern chemical industry Germany unquestionably ranks first. 
Of the various branches of this industry that of the manufacture of 
volatile oils and synthetic aromatics has acquired an importance 
previously unsuspected and with it a correspondingly influential position. History of the Methods of Distillation and of Distilling Apparatus. 
75 
Fig. 44. 
Modern Distilling and Rectifying Apparatus. 76 
Historical Introduction. 
t'ig. 45. 
Distilling- and Rectifying Apparatus. History of the Methods of Distillation and of Distilling Apparatus. 
77 
Fig. 46. 
Apparatus for Distillation with Water. 78 
Historical Introduction. 
Fig-. 47. 
Distilling Apparatus of 30,000 Liter Capacity. History of the Methods of Distillation and of Distilling Apparatus. 
79 
Fig'. 48. 
Distilling Apparatus for Spices. 80 
Historical Introduction. 
Fig. 49. 
Great Still of 60,000 Liter Capacity. History of the Methods of Distillation and of Distilling Apparatus. 
81 
Fig. 50. 
Distillation of Rose Oil. 82 
Historical Introduction. 
. Fig. 51. 
Distilling Apparatus GENERAL PART 1. THEORETICAL BASIS FOR OBTAINING VOLATILE OILS 
BY STEAM DISTILLATION. 
From the foregoing chapters it becomes apparent that the manu- 
facture of volatile oils was formerly conducted on a small scale, largely 
after the style of the small mechanic. But a single process for obtaining 
the oils was used, even though here and there it was conducted in a 
scientific manner, i. e., corresponding to the status of science at the 
time. All crude materials and all oils were distilled in the same manner 
from a distilling apparatus consisting of still, head, and condenser. 
When the still was heated directly by fire, only one kind of distillation 
took place, namely water distillation, in which case the material to be 
distilled was either in the water, or it was suspended dry above the 
water. If the distillation was conducted with steam, there was a choice 
between water distillation and dry steam distillation. The introduction 
of steam as the immediate source of heat was unquestionably in itself 
an advance. A new impetus, however, was first given to the industry 
of volatile oils by the use of steam under pressure. That this change 
should at first have given rise to many difficulties was inevitable. 
Out of the large number of small factories and laboratories where 
oils were distilled on a small scale, a few have risen during the last 
few decades, and have developed to such an extent as to impart to the 
entire industry a different aspect. It is. however, not merely the matter of 
size which separates the past from the present. The rapid development of 
chemical science is even more responsible for this difference. Through it 
the preparation of essential oils has developed into a real industry, 
a branch of chemical technology. The successful investigations of 
Wallach have not only led the way in chemical science, but they have 
also done pioneer service in practice. 86 
General Part. 
This development of the volatile oil industry has taken place in a 
remarkably short period of time. Indeed the unusually rapid growth 
of chemical knowledge made it difficult for progressive factories to keep 
abreast with the theoretical advancement, as did also the fact that the 
simple apparatus and methods no longer sufficed for the new require- 
ments. Some apparatus could be borrowed from other technical branches 
but much had to be specially designed and made. In addition to the 
simple stills formerly used, new rather complicated apparatus were con- 
structed. Although these required greater ability and more attention on 
the part of the operator, they gave in every respect more satisfactory 
results. 
The evolution from the simple to the more highly perfected technique 
can best be compared to that of the alcohol manufacture from the 
whisky distillation on a small scale. The simple stills of a past time, 
which are now only used here and there for the preparation of whisky 
on a small scale, will scarcely be recognized as the prototypes of the 
column apparatus with continuous supply of wort and continuous or 
periodic removal of the wash, as they may now be seen in their most 
perfect construction and operation in modern alcohol distilleries. Whereas 
the former whisky distiller first distilled off an intermediate product, and 
from this by rectification obtained a whisky of only 30 to 4-0% alcohol, 
the present column apparatus yields with less attention, time and fuel, 
a spirit of over 90% alcohol in a single operation. 
In the alcohol distillation the conditions are, however, much simpler 
than in the preparation of the volatile oils. There a few raw materials: 
potatoes, corn or maize, and only one end product: alcohol. The 
knowledge of the apparatus is common property. It can be constructed 
by any reliable coppersmith; and its manipulation is shown by the 
builder. Here on the other hand, there are numerous crude materials 
as well as numerous different products, which according to the use to 
which they are to be put require different methods for production and 
purification. The apparatus necessary for these various operations 
must be constructed and perfected by the manufacturer himself, if he 
does not wish to remain behind in the competition brought about by 
changes in the methods of production. 
The advantages of the present over the former industry are a 
saving in time, labor and steam, an increase in the yield and especially 
an improvement in the quality of the oils. Coupled with these are, 
however, a considerable increase in the cost of the whole plant, and 
resulting from this, the necessity for production on a large scale. Theoretical Basis for Obtaining Volatile Oils, etc. 
87 
Briefly described, the manufacture takes place in the following 
manner. The prepared raw material is filled into the distilling apparatus, 
which is heated by steam. The vapors saturated with oil particles are 
condensed in the cooler. The distillate, consisting of water and oil, 
collects and separates in the receiver, and the crude oil thus obtained 
is purified when necessary, in order to yield the finished product. The 
manufacture consists therefore of the following operations: 
1. Preparation of the oil-containing material for distillation; 
2. Distillation; 
3. Cooling and condensing the vapors; 
4. Purification of the crude oil. 
Preparation of the oil-containing material. The proper prepa- 
ration of the raw material is one of the most important requirements 
for the distillation. The essential oils belong to the secretion products 
in the life process of the plant cell and are found in the cytoplasm of 
the cells, in the inter-cellular spaces, in resin duets, (in the conifers) etc. 
If the cell walls are very tender, the steam may gradually rupture them 
and bring the volatile oil to boiling. But when they are more or less 
woody and thick, the raw material must be comminuted before distil- 
lation, so that the volatile oil may be removed gradually from the 
fragments. 
The comminution apparatus necessary for this operation are of 
various designs. Herbs, leaves, and fresh roots are cut; barks, dry 
roots and dry fruits are ground; woods rasped; seeds crushed. Each 
raw material requires a method of comminution depending on its 
properties, which must be further modified according to the method 
of distillation to be employed. The process of distillation depends 
wholly upon the proper preparation of the crude material. An insuf- 
ficient or unsuitable comminution not only raises the cost of the 
necessary steam, but also decreases the yield of oil. With oils not 
readily volatile, the material still retains some oil, in spite of an increase 
in the time of distillation. On the other hand many oils require rapid 
distillation, as they decompose when in contact with the moist steam, 
yielding useless decomposition products which are wholly or partly 
soluble in water, or because they become resinified. 
Distillation. The distillation of the essential oils with steam 
depends upon the physical fact, that the boiling point of a mixture of 
two liquids which are not miscible must always be lower than that 
of the most volatile liquid. 88 
General Part. 
The boiling- of a liquid consists in the change from the liquid to 
the gaseous state. A liquid begins to boil when, in the course of heating, 
its vapor pressure has increased to such an extent that it is able to 
overcome the outside pressure on the liquid, i. e. when it overcomes the 
pressure of the atmosphere by heating in an open vessel. The vapor 
pressure of the heated liquid has then risen to the height of the outer 
pressure. If the liquid consists of two immiscible liquids, for instance 
water and a volatile oil. then on heating the mixture, not only does 
the water give rise to a vapor pressure, but also the volatile oil, and 
the mixture will therefore be brought to boiling, when the sum of the 
two vapor pressures is equal to the outer pressure. 
The distillation of water and oil of turpentine may serve as illus- 
tration. Let the outer pressure be the normal atmospheric pressure of 
760 mm. Under this pressure the water, if heated alone would boil at 
100° C. and the oil of turpentine, for the greater part, would not boil 
until about 158°. If, however, a mixture of water ami oil of turpentine 
is heated, the vapor pressure of the water and also that of the oil of 
turpentine, take part in overcoming the outer pressure of 760 mm. 
The mixture of water and oil of turpentine will, therefore, boil when the 
sum of the two vapor pressures is equal to 760 mm. and this takes 
place at 95.6°, for at this temperature the water has a vapor pressure 
of 647 mm. and the oil of turpentine 113 mm. (both according to 
Reguault). or both together 760 mm. 
This explains why a mixture of water with a volatile oil. although 
the boiling point of the volatile oil when distilled alone is usually 
higher than that of the water, will boil lower than the boiling point of 
the water and form a mixture of oil and water vapors. 
Every liquid or solid body that shows a vapor pressure at the 
temperature of the water vapor employed can be distilled.1) 
By lowering the boiling point of the volatile oils by distilling them 
with water or water vapor, it is possible to obtain certain chemical 
bodies, which when heated by themselves would volatilize only with 
decomposition at their high boiling points. On the other hand 
many bodies are but slightly volatile at the low temperature at which 
the distillation with water or water vapor is conducted and require 
comparatively large quantities of water vapor for volatilization, so 
that the production of these difficultly volatile bodies with water vapor 
is excluded. 
i) Slightly under 100°, when saturated water vapor of any pressure is conducted 
into the distilling apparatus which is under atmospheric pressure. Theoretical Basis for Obtaining Volatile Oils, etc. 
89 
The water vapor is the source of the heat for the distillation of the 
volatile oils. A thorough study of the amount of service obtainable 
from this heating material is therefore of great importance from an 
economic standpoint. 
Distinction should be made between two ways of heating, the direct 
and the indirect heating by steam. According to requirements they 
are employed either separate or together. In the first the steam 
is conducted into the oil-containing material which is either dry or 
suspended in water. In the latter the steam does not come into 
immediate contact with the oil-containing material. The material lies 
in the water, and the water is heated to boiling by means of steam in 
the outer jacket of the still, or passing through a coiled tube. 
If the indirect heating is accomplished with saturated water vapor 
of 150°, consequently under a pressure of nearly five atmospheres, the 
steam is condensed to water of 100°. provided the water separator is 
working well and removes only water and no steam. To change 1 k. 
of watei- from 0° into saturated vapor of 150° there are required 652.3 
calories1) of heat. If we deduct from this the heat necessary to raise 
the water from 0° to 100°. namely 100.5 caL. we have for the heat of 
vaporization of 1 k. of water of 100° into saturated vapor of 150° 
under pressure. 652.3 - 100.5 = 551.8 cal. This same amount of heat 
is again liberated when the vapor of 150° is condensed to watei- of 
100°. According to a similar calculation. 1 k. of saturated compressed 
steam of 180°. used for indirect heating, when changed to water of 100° 
liberates 661.4 - 100.5 = 560.9 cal., i. e., only about 9 cal. more than 
saturated steam of 150°. 
In the direct heating process, the steam passing through the still 
will, at the expense of a part of the steam which is condensed, carry 
with it some of the oil as vapor. In the most fa vorable case, the ratio 
of oil vapor and water vapor will be that of their vapor tensions at 
the temperature at which the distillation is conducted. 
For the sake of simplicity, the calculation of the cost of steam for 
a distillation, may be made as though all the steam was condensed to 
water of 100° and that the mixture of vapors of water and oil going- 
over into the condenser was formed from liquids of 100°. According to 
this the amount of service obtainable from the steam is the same with the 
direct as with the indirect heating process. In practice, however, the two 
ways of heating are not equally efficient. With the indirect heating 
i) One calory, abbreviated 1 cal., is the unit quantity of heat. It is the amount 
of heat required to raise 1 k. of water of about 15° one degree C.) 90 
General Part. 
process all of the heat contained in the steam cannot be utilized, as loss 
of heat cannot be prevented. On the other hand in the direct heating- 
process, if the steam is conducted into the oil-containing' material 
suspended in water, or into the volatile oil itself, in case of rectification 
or fractionation a loss of heat is only possible through careless 
conduction of the steam. If the oil-containing- material is dry in the still, 
the loss of heat in direct heating will be usually large, and with careless 
manipulation may become so large, that only a small part of the 
direct steam is utilized, while the larger paid goes unused into the 
condenser. The theoretical heating effect of the steam may also be 
obtained when the oil-containing material is dry. but this can be done 
only under certain suppositions. 
In order to calculate from the above heat values of the steam the 
cost of the steam for a distillation, the product of the distillation, i. e., 
the distillate, must first be more closely examined. The distillate consists 
of water and volatile oil. The question therefore arises, how much 
water and how much volatile oil is a certain amount of steam capable 
of distilling? Evidently the answer to this question depends first of all on 
the relative weights of the water and the oil in the distillate. This relation, 
of course, differs with the character of the volatile oils, and is further- 
more dependent for each and every oil upon the distilling temperature 
employed, and the changeable composition of the oil; on the other hand 
the ratio is fixed, so that 1) with a surplus of steam the water content 
in the mixture of vapors going into the condenser may indeed be 
increased; 2) in spite of an economic supply of steam ami a generous 
supply of oil the amount of the former cannot be decreased. The amount 
of oil which is volatilized with the steam, is determined by the vapor 
pressures of both at the distilling temperature. 
The quantity of oil in the distillate can be determined experimentally 
if the distillation be so conducted that the vapor contains the greatest 
possible quantity of oil. It can also be calculated if the vapor pressure 
of the essential oil at the distilling temperature be known, for the parts 
by volume in the mixture of the vapors of two immiscible liquids, are 
to each other as the vapor pressures of these liquids at the boiling- 
temperature of the mixture; or the parts by weight are to each other 
as the vapor pressures multiplied by the vapor densities or the mole- 
cular weights. If . 
ini - the molecular weight of one of the liquids, 
= the vapor pressure at the distilling temperature. 
gi = the part.by weight in the yqpor, Theoretical Basis for Obtaining Volatile Oils, etc. 
91 
and further 11)2. P2, g2, be the corresponding' values of the other 
liquid then 
g\ : g2 = pr : m2P2. 
As an example of such a calculation, the distillation of caraway oil 
with water vapor under atmospheric pressure may be taken. Caraway 
oil consists of a mixture of limonene and carvone in nearly equal parts 
by weight. Its boiling temperature by distillation with steam under 
atmospheric pressure, namely 760 mm., is a few degrees below 100°; at 
the beginning of the distillation somewhat lower, toward the last nearly 
100°. The vapor pressure of the limonene (molecular weight 136) at 
57.5° amounts to 12 mm., that of the water (molecular weight 18) at 
the same temperature is 132 mm. At the distilling temperature of 57.5°. 
there will, therefore, be in the distillate for every 100 k. of water, 70 k. 
of limonene. At 176°, the boiling point of the limonene under 760 mm. 
pressure. the water exerts a vapor pressure of 6962 mm. of mercury; 
therefore at 1 76°, with 100 k. of water there distill over 83 k. of limonene. 
According to this, at a distilling temperature of 96°, for 100 k. of water 
in the distillate there would be about 75 k. of limonene. An experiment 
with limonene of sp. gr. 0.850 and still containing some carvone, gave 
for 100 k. of water in the distillate 60 k. of limonene. Calculation and 
experiment agree, therefore, fairly well. For carvone (molecular weight 
150) the calculation is simpler, because its vapor pressure has been 
determined at about 100°, namely 104.1°. At this temperature it 
amounts to 12 mm., that of water at 104.1° being 880 mm. For every 
100 k. of water in the distillate there will be therefore 11 k. of carvone. 
By experiment 9 k. were obtained. Thus are obtained the quantities of 
oil. which theoretically are distilled from caraway seed with every 100 k. 
of water under atmospheric pressure; namely. 75k. of oil at the beginning 
of the distillation, which amount drops down gradually to 11 k. of oil 
when pure carvone distills over. But as even the very first parts of the 
distillate contain some carvone, they will not contain 75 k. of oil for 
('very 100 k. of water, but much less. According to a carefully performed 
experiment of a caraway oil distillation from a simple still, there were 
obtained in the beginning of the distillation 37 parts by weight of oil. 
and past the middle of the distillation Oparts by weight of oil to every 
100 parts by weight of water. 
After the heat effect of the steam for the distillation and the 
relation of water and oil in the distillate have been determined, the 
heat necessary for obtaining a certain amount of distillate remains to 
be ascertained. 92 
General Part. 
Aside from the heat consumed in warming' the distilling apparatus 
and its contents to the distilling temperature, the distillation requires 
a heat supply for the vaporization of liquid bodies at about 100° tem- 
perature at atmospheric pressure. This heat of vaporization for 1 k. of 
water amounts to 536.5 cal. The heat of vaporization of caraway oil or 
rather of its constituents has as yet not been determined, but it can be 
fairly accurately calculated by F. Trouton's law.1) according to which the 
molecular heat of vaporization is proportional to the absolute temper- 
ature of the boiling point. For limonene the calculation gives 65.5 cal., 
for carvone 66 cal. for the unit of mass. To be sure, these are the heats 
of vaporization at the boiling temperatures of limonene ami carvone, 
namely at 175° and 230° respectively. The difference from the heats of 
vaporization at 100° is. however, probably small, as the specific heats 
of organic bodies in the liquid ami in the gaseous state are nearly the 
same. 
As has already been shown, when the steam is utilized to the 
greatest possible extent, the distillate from caraway oil will contain at 
the beginning of the distillation 37 k. of oil. beyond the middle of the 
distillation 9 k. of oil for every 100 k. of water. Consequently there 
will be in 100 k. of distillate from 73 k. of water and 27 k. of oil. to 
92 k. of water and 8 k. of oil, the heat required for 1 k. of distillate 
therefore is from 4-09 to 4-99 cal. In other words 1 k. of saturated 
steam of 150° may, with its available heat of 551.7 cal., yield in the most 
favorable case of a caraway oil distillation 1.3 k. to 1.1 k. of distillate. 
Or when the heat required is based only on the volatile oil. 1 k. of 
caraway oil costs in the course of the distillation from 1552 cal. to 
6275 cal.; or from 2.81 k. to 11.38 k. of saturated steam of 150°; or 
from 2.77 k. to 11.19 k. of saturated steam of 180°. 
The heats of vaporization of the volatile oils are, as already 
mentioned, small; still smaller are their differences. They cannot, 
therefore, give rise to a high cost of steam for the distillation. With 
the different volatility of the essential oils, it is. however, otherwise. 
The caraway oil distillation of which the distillate contains at the 
beginning 27% of oil, and later at least 8%, is an example of an easily 
volatile oil. Other oils, for instance sandelwood oil. require more than 
the twentyfold amount of steam for distillation, others still more. It 
is therefore an important requirement of an economic management, to 
decrease the loss of heat as much as possible, i. e. to conduct the 
i) W. Ostwald, Allgemeine Chemie, II. Ed., vol. 1. p. 354. Theoretical Basis for Obtaining Volatile Oils, etc. 
93 
distillation in such a manner, that as far as possible, not more than 
the necessary minimum amount of steam be used. 
Incidental Io an investigation of the influence of the addition of salt 
to the water in obtaining the heavy essential oils, the French chemist 
E. Soubeiran1) in 1837 closed his observations with the words: "My 
experiments definitely show that the preparation of the essential oils, 
which is considered as a well known operation, is on the contrary 
worthy of an entirely new investigation.'' The study of the history of 
a science is not only useful for a better understanding of the science 
itself, but is also psychologically interesting and instructive. The 
mistake of considering studies in any part of a branch of science as 
concluded, as completely investigated, only because through a series of 
years no new promising investigations have been recorded, is made 
quite frequently. The preparation of the volatile oils from the plants 
was considered to be a well known operation not only 60 years ago. 
but also a little more than a decade ago. Now, that this industry has 
so enormously developed through successful investigation of the 
volatile oils and with the aid of better mechanical appliances, when 
out of the formei- "Destillirkunst" there has grown a scientifically con- 
ducted industry, which, combined with commercial experience 1ms 
reached unthought of results, we know, that this development is by no 
means completed. 
The following may serve as the most important characterizations 
of the different processes of distillation for oil-containing material, or 
for the rectification or fractionation of the oils themselves: 
a) Dry steam distillation with saturated steam under pressure. 
I)) The same, but with superheated steam. 
c) Water distillation. 
d) Distillation under diminished pressure. 
e) Continuous distillation. 
Through modifications in the conducting of a certain process of 
distillation in an apparatus with the requisite construction, further 
through suitable combination of these main processes, according to the 
distilling material, or according to the desired composition of the oil. 
important advantages may be gained. 
In the larger factories the distillation of oil-containing materials by 
direct heating of the apparatus over a free fire is no longer used. 
1) Liebig's Annalen, 25, p. 245. 94 
Genera / Part. 
There is no limit to the size of the apparatus. If the enormous 
masses of distilling material are at hand, which such an apparatus 
requires for its economic operation, there is nothing in the way of 
erecting as large an apparatus as may be desired. 
Cooling and condensing of the vapors. Cold water is used 
in general for cooling and condensing the vapors from the distilling 
apparatus. The vapors are conducted into the condenser through a 
tube which connects the still with the condenser. In the smaller 
factories. Liebig condensers, spiral condensers, and jacket condensers 
according to Mitscherlich are used, but in the larger ones they are used 
only exceptionally for certain purposes. Even moderately large dis- 
tilling operations require that the cooling effect of the water be used to 
the best advantage. To condense several cubic meters of distillate in 
an hour, is an impossibility with these condensers. Tube condensers 
serve for this purpose in which the vapors are conducted through a 
bundle of tubes, which are surrounded by flowing water. Vapor and 
water flow in opposite directions. The capacity for work of these 
condensers is such that the distillate leaves the condenser at a temper- 
ature of 20°, and the condensing water up to 80°. 
It is very simple to calculate, if desired, from the steam used from 
the boiler or for a distilling apparatus, the quantity of water required 
to condense the vapors. 1 k. of saturated steam of 150° underpressure 
has taken for its generation from water of 10° 642 cal. of the heat of 
combustion of the coal. If the distillate is at 20°, then the steam 
gives back 632 cal. in forming the distillate. If the water flows through 
the condenser with a beginning temperature of 10° and with an average 
end temperature of 60°, then 1 k. of water is capable of taking up 50 cal. 
of heat, according to which 12 to 13 k. of water are required to condense 
1 k. of saturated steam under pressure. With water of a beginning 
temperature of 20° about 16 k. are required for the condensation. 
The collection of the distillate in receivers and the separation of 
the oil from the whter according to the different specific gravities of 
the two, offers nothing of particular interest. 
Purification of the crude oil. The odor, taste, and color of 
the oil. are of the utmost importance in the manufacture. In steam 
distillation decomposition of the plant material occurs to a greater or 
less extent. When the distillation is a prolonged one or is carelessly 
conducted, decomposition of the albumins and albuminous constituents, 
of ammonia derivatives, of fats and other fatty acid compounds, even Theoretical Basis for Obtaining Volatile Oils, etc. 
95 
of the carbohydrates takes place. Volatile decomposition products are 
formed, such for instance as sulphuretted hydrogen, ammonia, carbonic 
acid, trimethylamine, lower and higher fatty acids, acrolein, furfurol, 
acetaldehyde, phenols of creosote like odor and numerous other bodies, 
which with few exceptions possess a disagreeable odor, that imparts 
itself to the volatile oil. In order to understand the character of these 
decomposition products, it must be remembered, that the process of 
distillation takes place in the absence of air. for the steam expells the 
air from the still, so that the reactions of decompositions are largely 
hydration processes. In addition to this decomposition of the crude 
material, the volatile oil itself may suffer changes. These may be 
brought about by the heat, the water and also by the decomposition 
products of the plant material. They consist of reduction, oxidation, 
polymerization, condensation, saponification of esters, etc. These 
changes in the composition of the oil may be slight, but sometimes 
they are very important. Finally there is still a third source of con- 
tamination in the volatile oil. namely that of volatile substances 
which occur along with the useful volatile oil in the plant. It is true 
that for the purposes of obtaining the volatile oil. plant material is 
classified as that containing oil and that which is free from oil. This 
is correctly expressed if we understand by the term volatile oil, not 
all volatile substances, but only those which have a commercial value, 
'"or there are volatile substances, other than water, in all plants. 
Volatility is a very common property of organic bodies of low chemical 
composition, and bodies of this nature, intermediate products of the 
constructive and destructive metabolism in plant life, are constituents 
of all plants. The common herbaceous odor of the green parts of 
plants, the herbaceous and hay-like odor of dried leaves, the woody 
odor, or the pungent fetid odor of the stems of many blossoms are 
very apt to cover the odor of a mild smelling volatile oil which is 
present in only small quantities. This may take place to such an 
extent, as to make the product wholly worthless. 
From this it will be seen, how numerous the causes are for the 
deterioration of the volatile oils. The foreign odor which is thereby 
given to the oil. was formerly and probably is even now called 
"Blasengeruch." This is an old. very inappropriate term, which 
arose at a time when the various causes of this odor were still unknown. 
The socalled "Blasengeruch'' was formerly the distinguishing property 
of every crude oil. If it was slight, attempts were made to remove it 
by long exposure of the oil in open vessels. The more easily volatile 96 
General Part. 
impurities gradually evaporate during this treatment, such as sulphur- 
etted hydrogen, acetaldehyde, and ammonia, while the rest are held 
back by the oil. The more difficultly volatile substances, such as the 
phenols with a sharp and penetrating odor remain nearly all in the 
oil. A part of these impurities form new compounds with the con- 
stituents of the oils. Finally, the exposure in open vessels is also 
favorable to the resinification of the oils. On the whole this method 
for the purification of the oils can only be considered as an inadequate 
apology. 
When the accompanying odor was stronger, or when the oil was 
colored, it was again distilled, i. e. rectified, and when this was not 
sufficient, the operation was repeated, hence the terms "twice, thrice 
rectified oil." At present there are known many methods of purification, 
entirely different, and each suited for a particular case. In some cases 
a single rectification by distillation is a useful means for purification, 
but only when the presence of volatile impurities is small. If properly 
conducted a single rectification should be sufficient. 2. THE MORE COMMONLY OCCURRING CONSTITUENTS 
OF VOLATILE OILS. 
The volatile oils are widely distributed in the vegetable kingdom, 
more particularly, however, in the phanerogams. From the cryptogams, 
a volatile oil has so far been obtained only from the male fern. In 
most cases the oils exists preformed in the various organs of the plant, 
the leaves, flowers, fruits, stems and roots. They occur secreted either 
in glands or in canal-like, intercellular receptacles. Only a few are 
formed by hydrolysis during the process of preparation from other 
substances in the plant, e. g. bitter almond oil from amygdalin, mustard 
oil from sinigrin. Nothing definite is known with regard to their 
function or their relation to the other constituents of the plant 
organism. It appears, however, to be well established that they are 
excretions formed during the life process of the plant, which are of no 
further importance in the processes of metabolism. It does not follow 
from this that they are therefore useless, for they act as a means of 
attracting insects that bring about fertilization, they also protect 
plants against enemies. These oils are not definite chemical units, but 
mixtures of substances belonging to many series and classes of com- 
pounds. The oil from one and the same plant does not even always 
possess the same composition. Thus e. g. the distillates from various 
organs of a plant show differences in odor and physical properties. 
These differences may become marked even more strongly if plants in 
different stages of development are distilled. If volatile oils are never- 
theless grouped under one generic name, it is because they have several 
physical properties in common and because almost all of them are 
prepared in like manner. They have generally been regarded as being 
closely related to those organic compounds commonly designated as 
aromatic, but not being of uniform composition they can naturally 
not be classed with them. 98 
General Part. 
Among- the various constituents of an oil, one frequently attracts 
attention as the principal bearer of the odor. In many instances this 
constituent is, therefore, the most valuable. The desire to obtain it in 
a concentrated and pure form, may have given the first impetus to the 
scientific investigation of essential oils. So long as organic chemistry 
was in its infancy, these investigations could not be crowned with great 
success. Only after the methods of investigation had been improved 
hand in hand with the progress of science, an insight into the nature 
of volatile oils was obtainable. This insight revealed the fact that the 
oils are as a rule mixtures of a number of complex substances. 
How slow this progress was formerly, and how rapid during the past 
two decades, lias been shown in the historical introduction. This chapter 
will present the results of investigations in so far as they pertain to 
substances commonly found in volatile oils. For reasons readily under- 
stood. only these could be included within the scope of this work. For 
the same reason a detailed chemical account had to be excluded. 
Details of chemical and physical properties will be found in the larger 
chemical handbooks of Beilstein and Ladenburg, and more particularly 
in the excellent monograph on terpene derivatives by Heusler. 
The analysis of a volatile oil is difficult because most of the constit- 
uents are liquid, and can, therefore, be separated only by fractional 
distillation. This operation, imperfect at best, is often rendered more 
unsatisfactory by the fact that certain constituents are not volatile 
without decomposition. For this and other reasons it is best to subject 
an oil to a preliminary examination, the results of which often suggest 
modifications which simplify the examination considerably. The pre- 
liminary examination consists primarily in the determination of the 
physical properties of the oil and of its elementary composition ; also 
in a study of the behavior of the oil toward certain group reagents, 
whereby the presence or absence of certain classes of chemical compounds 
can be ascertained. 
Of the physical constants, the specific gravity, the optical properties 
and the behavior of an oil toward heat and cold allow conclusions to 
be drawn as to its composition. A specific gravity, e. g. of less than 
0.00 indicates the presence of a large amount of terpenes or of com- 
pounds of the fatty series. Heracleum oil (dis0 -0.80- 0.88) and oil 
of rue (di5° = 0.833 - 8.40) belong to those with a very low specific 
gravity. Both consist of derivatives of the fatty series. Oil of orange. 
sp.gr. 0.848-0.852, consists largely of the terpene limonene; turpentine 
oil. with a specific gravity of 0.850 - 0.875, almost completely of The More Commonly Occurring Constituents of Volatile Oils. 
99 
hydrocarbons CioHie of the terpene series. A specific gravity higher 
than 0.90, as is the case with most oils, indicates a mixture of terpenes 
and possibly their oxygen derivatives; whereas a specific gravity of 
more than 1.0 indicates the presence of compounds of the aromatic 
series, or if the compound contains sulphur or nitrogen, of sulphides, 
nitriles, or isosulphocyanides. , 
The optical properties, rotation and refraction, a're of less 
importance unless pure chemical compounds are to be examined or 
adulterations to be looked for. The optical activity of an oil indicates 
the presence of a compound or compounds with one or more asym- 
metric carbon atoms; a high index of refraction the presence of a 
substance or substances with double bonds. 
When exposed to low temperatures, a number of oils deposit one or 
more of their constituents in crystalline form. Some oils, like rose oil, 
contain crystals even at ordinary temperature, others, like orris oil are 
butyraceous in consistency. These substances have been designated 
stearoptenes or camphors and are paraffins, higher members of the 
series of fatty acids, such as lauric, myristic and palmitic acids, and 
derivatives of aromatic and hydroaromatic hydrocarbons. 
Most oils that can be distilled under ordinary pressure without 
decomposition begin to boil above 150°. Exceptions to this rule are 
e. g. those containing sulphur, and the oil of the Digger's pine, which 
contains normal heptane. In the absence of oxygenated constituents, 
a boiling point below 200° indicates the presence of terpenes, between 
250 and 280° sesquiterpenes, above 300° polyterpenes. 
In their elementary composition the volatile oils do not manifest 
great variety. All contain carbon and hydrogen; most of them also 
contain oxygen in larger or smaller quantity; few contain nitrogen or 
sulphur or both. The presence or absence of oxygen can be determined 
by elementary analysis only. The presence of only a small amount of 
this element, up to 5 p. c., indicates a high hydrocarbon content. The 
presence of sulphur, which can be oxidized to sulphuric acid by means 
of concentrated nitric acid in sealed tubes, indicates sulphides or poly- 
sulphides. Nitrogenous compounds are converted into cyanides by 
heating with metallic sodium or potassium and recognize'd by means of 
the Prussian blue reaction. The nitrogen content of an oil is mostly 
due to nitriles. If sulphur is also found, mustard oils are present 
which, as a rule, betray their presence by their characteristic odor. 
After the elementary composition of an oil has been ascertained, a 
few group reagents can be applied to learn whether special attention 100 
General Part. 
should be given to one class or another of chemical compounds. If an 
oil shows an acid reaction, it contains acids or phenols. Small 
amounts of fatty acids occur occasionally as decomposition products 
of esters present. Larger amounts reveal their presence by the 
diminution of volume when the oil is shaken with an aqueous solution 
of caustic or carbonated alkali. The presence of an ester or lactone can 
be ascertained when an oil is heated with alcoholic potassa of known 
strength and titrated back with standard acid. This test presupposes 
the absence of free acids and aldehydes. Alcohols can be converted 
into acetic esters by heating the oil with acetic acid anhydride. Sub- 
sequent saponification will then reveal the presence or absence of an 
alcohol in the oil. Aldehydes and ketones can be recognized by their 
addition products with alkali bisulphites, or by their condensation 
products with hydroxylamine. The latter contain nitrogen and as a 
rule are difficultly volatile with water vapor. Ethers, which are some- 
times present as phenol ethers, can be recognized by means of Zeisel's 
method. 
After these preliminary tests have revealed the presence of a substance 
belonging to one of the above mentioned classes, it is sometimes possible 
to separate it without fractional distillation; provided, however, that 
this method of separation does not change the other constituents of 
the oil. It should also be noted that these methods of separation never 
effect a perfect isolation because the other constituents of the oil prevent 
a part of the substance to be isolated from reacting. When, therefore, 
the non-reacting portion of the oil is fractionated small amounts of 
this substance should not be overlooked. Thus it is possible with these 
group reagents to separate aldehydes and many ketones with acid 
sulphite solution - a reaction that can at times be facilitated by the 
addition of alcohol. The crystalline addition product is washed with 
alcohol and ether and the aldehyde or ketone regenerated by the 
addition of alkali or dilute acid. Free acids and phenols can be shaken 
out with aqueous alkali; indifferent substances are then removed from 
the aqueous solution by shaking it with ether, and then the acid or 
phenol is set free with dilute mineral acid. If acids and phenols are 
both present, • the former are separated with carbonate solution. 
Lactones yield salts of the corresponding oxyacids when heated with 
alcoholic potassa. They are precipitated as lactones or oxyacids by 
the addition of a mineral acid. Esters that may be present are saponi- 
fied by this treatment with alkali, aldehydes and ketones, however, are 
modified thereby and at times destroyed. The More Commonly Occurring Constituents of Volatile Oils. 
101 
If none of these short cuts is possible the oil is fractionated either 
under ordinary or diminished pressure. If esters are present, the oil is 
first saponified. It may be taken for granted that the apparatus to be 
used and the methods to be employed are known. A good guide for 
distillation under diminished pressure will be found in a small mono- 
graph on this subject by Anschutz.1 The various fractions obtained 
upon a careful fractionation are examined for compounds, in part 
according to the methods already mentioned. A trained sense of smell 
will prove an important additional factor. Suspected compounds are. 
if possible, converted into crystalline derivatives and thus purified and 
identified. 
Ketones that will not combine with acid sulphites, such as menthone, 
camphor, fenchone, carvone, are converted into oximes or semi- 
carbazones. Inasmuch as the oximes suffer rearrangement with acids, 
the semicarbazones are at times to be preferred because the ketones 
can in most cases be regenerated. 
Alcohols are characterized by their capacity to form esters, also 
phenylurethanes with phenylisocyanate (carbanil). They can be purified 
by means of difficultly volatile esters of monobasic acids, such as benzoic 
acid; or by means of acid esters of dibasic acids, such as succinic acid, 
phthalic acid, etc. Some of the primary alcohols can also be purified 
by converting them into calcium chloride addition products from which 
they are easily regenerated by means of water. 
From the hydrocarbons traces of oxygenated compounds can be 
removed by repeated treatment with metallic sodium. If low boiling 
hydrocarbons are to be distilled under diminished pressure a liquid 
alloy of potassium and sodium is preferable. 
As to the compounds themselves that are found in volatile oils, they 
belong in part to the aliphatic, in part to Ihe aromatic and hydro- 
aromatic series and are distributed over a large number of classes. 
The hydrocarbons, especially those of the formula CioHio, are widely 
distributed. Of greater importance, however, are the oxygenated sub- 
stances. because they are mostly the bearers of the characteristic odor 
of the oil in which they are contained. In addition to the hydrocarbons 
there have been found alcohols, aldehydes, acids, esters, ketones, 
phenols, phenolethers, lactones and oxides, further sulphides, nitriles 
and isothiocyanates. 
1) Die Destination unter vermindertem Drucke. 102 
General Part. 
Hydrocarbons. 
The lowest hydrocarbon of the paraffin series which has been found 
in a volatile oil is the normal heptane, C7H16 (b. p. 98°). It constitutes 
the bulk of the oil obtained from the oleoresin of the Digger's pine. 
Pinus sabiniana. 
The higher members of the paraffin, and probably of the olefine series 
also, appear to be quite widely distributed in the vegetable kingdom. 
They constitute the waxlike coating and secretions on leaves, flowers, 
fruits etc. In volatile oils, however, they are not met with commonly 
because of their sparing volatility. Sometimes they separate in crystalline 
form when the oil is exposed to a low temperature, or they remain 
behind upon fractional distillation. In the oils of rose and chamomile, 
however, the amount of paraffin is so large, that the oil congeals even 
at middle temperature. Apparently these hydrocarbons seldom occur 
alone, but as mixtures of homologues as has been shown in the case of 
rose oil. Their melting points seldom if ever agree with those of known 
members of the series. With the exception of the heptane referred to. 
they are obtained principally as white, colorless, laminar-crystalline 
masses which are with difficulty soluble in cold alcohol, but readily soluble 
in hot alcohol and other organic solvents. They are remarkable on 
account of their stability toward concentrated acids and oxidizing 
agents at ordinary temperatures. 
The rose oil stearoptene melts at 35° and when distilled in vacuum 
can be resolved into two fractions melting at 22° and 40-4-1° respectively. 
In addition to this solid mixture, paraffin (or olefine) hydrocarbons 
have been found in the following volatile oils: 
a. Aliphatic. 
Arnica flower oil P. 63° 
Chamomile oil " 53-54° 
Dill oil " 64° 
Caraway oil (from herb) " 64° 
Neroli oil (Aurade) " 55° 
Sassafras leaf oil M. P. 58° 
Oil of gaultheria " 65.5° 
Oil of sweet birch " 65.5° 
Oil of wild bergamot " 62° 
Diolefinic hydrocarbons have so far not been found in volatile oils. 
The hydrocarbon isoprene, CsHs, which belongs here and which is closely 
related to the terpenes, has been found only as a decomposition product 
of caoutchouc and of turpentine oil. For its preparation consult 
Mokiewsky's recent work.1 
1) Chem. Centrbl., 70>. p. 589. The More Commonly Occurring Constituents of Volatile Oils. 
103 
However, chain hydrocarbons of the formula of saturation CnH2n-4 
with three double bonds have been found. In composition they agree 
with the terpenes but differ in having a lower specific gravity and 
in their index of refraction. These hydrocarbons which have been 
termed "olefinic terpenes" by Semmler have not yet been well character- 
ized. They show a great tendency to resinify, especially when distilled 
under ordinary pressure. 
The first representative of this class was found in oil of bay by 
Power and Kleber1 in 1895 and termed myrcene by them. It boils at 
167° with partial resinification, under 20 mm. pressure at 67-68°; 
di5° = 0.8023; iin = 1.4673. 
The only known reaction by which, in the absence of crystalline ad- 
dition products, it can be identified is by means of its hydration with 
glacial acetic and sulphuric acids at 40° according to Bertram's 
method.2 Myrcene is thereby converted into an acetate of lavender-like 
odor, which upon saponification yields linalool. Permanganate oxidizes 
myrcene to succinic acid. 
Similar hydrocarbons have been found by Chapman3 in oil of hops 
in 1894; by Gildemeister4 in Smyrna origanum oil in 1895; and finally 
by Kleber5 in sassafras leaf oil in 1896. 
b. Aromatic and hydroaromatic. 
A hydrocarbon of the aromatic series of the composition C10H13 
was isolated by Lunge a,nd Steinkauler6 in 1880 from the oil of the 
needles of the mammoth fir, Sequoia gigantea and was termed sequoi- 
ene by them. It consists of laminar crystals which melt at 105° and 
boil at 290-300° (uncorr.). It is not identical with fluorene and other 
hydrocarbons of like composition. 
Styrene. 
The simplest aromatic hydrocarbon with an unsaturated side chain 
that is found in volatile oils is styrene, CttHs.CH = CH2. It occurs in 
storax oil and recently has been found in xanthorroea resin oil. It is 
probably formed by the decomposition of cinnamic acid. 
Styrene is a colorless, highly refractory liquid of a pleasant odor, 
which polymerizes to a transparent, glasslike and odorless mass, meta- 
styrene (CsHs)n, by being kept for some time, and more rapidly by 
i) Pharm. Rundsch., 13, p. 61. 
2) G. I. P. 80711. 
3) Journ. Chern. Soe., 67, p. 54. 
*) Arch. d. Pharm., 233, p. 184. 
3) Bericht S. & Co., April 1896, p. 71. 
6) Beriehte. 13, p. 1656; 14. p. 2202. 104 
General Part. 
heating' or when in contact witli acids. The boiling point of pure 
styrene is 14-4-144.5°. 
As to its physical properties, the following statements have been 
made: 
B. p. 140° at 760 mm.; d2o° = <h9O74; na=l.54030 (Brtihl,11886). 
B. p. 146.20; d0° = 0.9251 (Weger,2 1883); 4^ = 0.90595; n„ = 
1.54344 (Nasini & Bernheimer,3 1885). 
Pure styrene is optically inactive. Dilute nitric acid or chromic acid 
mixture oxidize it to benzoic acid. 
For identifying styrene the well crystallized styrene dibromide 
CoHs. ('H Br. CH^Br is used, and is obtained by allowing bromine 
(17 parts) to drop into a solution of the hydrocarbon (lOparts) in 
twice its volume of ether (Zincke.4 1883). On evaporation, the bromide 
separates in crystals, which after being recrystallized from 80 percent 
alcohol have the melting point 74-74.5°. 
Cymene. 
Of the hydrocarbons designated as cymenes only the meta and pAra 
compounds are of importance to the chemistry of the volatile oils. 
While m-cymene has been observed only as a decomposition or "Abbau" 
product (Kelbe, dry distillation of colophony; Wallach, dehydration of 
fenchone; Baeyer, splitting off hydrogen from sylvestrene), p-cymene is 
a frequent constituent of volatile oils. Up to the present it has been 
found in the volatile oils from Thymus vulgaris, Th. serpyllum. 
Th. capitatus, Satureja hortensis, S. thymbra, Monarda punctata. 
Ptychotis ajowan, in origanum oil from Trieste and Smyrna, in 
Roman caraway oil from Cuminum cyminum, in the oil from the seeds 
of water-hemlock, Cicuta virosa, and in the oil from Eucalyptus 
haemastoma. Like m-cymene it has also been frequently obtained as a 
transformation product. Formerly it was thought that all terpenes 
were related to this hydrocarbon; that they were its hydroderivatives. 
According to recent investigations, however, this conception is not 
wholly correct. It is worthy of mention, that several compounds of the 
formula CioHieO can be changed to p-cymene by the abstraction of 
water, for instance, camphor and citral. 
1) Liebig's Annalen, 235, p. 13. 
2) Liebig's Annalen, 221, p. 69. 
3) Gazz. chim., 15, p. 59; Jahresber. f. Chern., 1885, p. 314. 
*) Liebig's Annalen, 216, p. 288. The More Commonly Occurring Constituents of Volatile Oils. 
105 
Cymene is a colorless, pleasant smelling liquid, which possesses the 
peculiarity of becoming turbid, with separation of water on standing 
for some time; the reason for this behavior is not known with certainty, 
perhaps it is due to a gradual oxidation. For common cymene was 
found: 
B. p. 175-176°; di5° = 0.8602 (Widman,1 1891). 
B. p. 175.2-175.9° (at 752mm.); d-^o° =0.8551; n„ = 1.48465 (Briihl,2 
1892). 
B. p. 173.5-174.5° (at 763 mm.); di5° -0.8595; d2<>° - 0.8588; nI( = 
1.479 (Wolpian,3 1896). 
The pure hydrocarbon is optically inactive. Dilute nitric acid and 
chromic acid mixture oxidize it to p-toluic acid and finally to terephthalic 
acid. Potassium permanganate acts on it only with difficulty and 
changes it, particularly with heat, into p-oxyisopropylbenzoic acid 
(m. p. 155-156°) which with dilute hydrochloric acid yields p-isopro- 
penyl benzoic acid (m. p. 255-2(50°) by splitting off water (R. Meyer & 
Rosicki.4 1883). Oxyisopropylbenzoic acid is characteristic for p-cymene 
and is used for its identification. For its preparation Wallach in 1891 
gave the following directions:5 
2 g. at a time of the hydrocarbon, prepared as pure as possible, are heated 
with a solution of 12 g. of potassium permanganate in 330 g. of water on a 
waterbath with reflux condenser, the mixture being frequently agitated. When 
the oxidation is complete, the filtrate from the oxides of manganese is evaporated 
to dryness and the saline residue boiled with alcohol. The potassium salt 
which is soluble in the alcohol, is decomposed in aqueous solution with dilute 
sulphuric acid and the precipitated acid recrystallized from alcohol. 
The barium salt of the sulphonic acid produced by treating the 
hydrocarbon with concentrated sulphuric acid is also characteristic for 
cymene. It (CioHis. SOs^Ba crystallizes in shining, difficultly soluble 
laminae and contains three molecules of water of crystallization which 
can be completely driven off at 190°. The sulphone amide which can 
be prepared from the chloride of this sulphonic acid melts at 115-116°. 
That cymene sulphonic acid may also result from the action of sulphuric 
acid on different terpenes must, however, be remembered. 
Terpenes. 
The principal hydrocarbons occurring in volatile oils have the com- 
position CioHie, are of a cyclic nature and belong to the class of 
i) Beriehte, 24, p. 452. 
2) Beriehte, 25, p. 172. 
s) Pharm. Zeitsehr. f. Russl., 35, p. 115 
4) Liebig's Annalen, 219, p. 282. 
s) Liebig's Annalen, 264, p. 10. 106 
General Part. 
"terpenes proper." As to their formation in the plant organism nothing- 
definite is known. They possibly are genetically related to oxygenated 
chain compounds from which hydrocarbons CioHie can be prepared 
artificially by splitting off water. It is remarkable, however, that the 
terpene content of an oil is greater the less developed the plant was at 
the time of distillation. 
The majority of the known hydrocarbons of the terpene group are 
found ready formed in nature: viz., pinene, camphene, limonene, dipen- 
tene, phellandrene, sylvestrene, terpinene. With exception of the racemic 
dipentene and the inactive terpinene, these hydrocarbons occur in both 
optical modifications, though in different volatile oils and with a 
varying degree of rotation. It might appear doubtful, therefore, whether 
dipentene and terpinene are natural hydrocarbons or decomposition 
products of readily changeable terpenes. 
To isolate a- terpene in pure form from a volatile oil by means of 
fractional distillation is mostly impossible. Neither is it necessary, for 
it suffices to remove oxygenated compounds from the fraction 150-180° 
by repeated distillation over sodium. The physical constants can then 
be determined and a characteristic crystalline derivative prepared. 
These will be described under the individual hydrocarbons. 
Pinene. 
Pinene is the principal constituent of the distillates from the resinous 
excretions of different species of Pinus, which occur in commerce under 
the name of turpentine oils. In smaller amounts, usually together with 
other terpenes, it has been found in a large number of volatile oils. 
Both optically active modifications occur; American turpentine oil, 
German and Swedish pine needle oil from Pinus silvestris, the tar oil 
(Kienbl) from the same species and the distillate from the needles of 
Pinus cembra consist mainly of d-pinene, while French turpentine oil 
contains mostly 1-pinene. 
d-Pinene (australene) has been shown to be present in cypress oil, 
star anise oil, camphor oil, oil of laurel leaves and berries, mace oil, 
fennel oil, galbanum oil, coriander oil, niaouli oil, myrtle oil, oil of 
cheken leaves, eucalyptus oil (E. globulus). French basilicum oil, spike 
oil. and tansy oil. 1-Pinene (terebentene) occurs in the following coni- 
ferous oils: in the oil from the leaves and cones of Abies alba, in the 
pine needle oils, in the oil of P. montana Miller, in English pine needle 
oil from P. silvestris, hemlock oil, in the oils of Abies sibirica. and .1. 
canadensis, further in canella oil. olibanum oil, cajeput oil, valerian and The More Commonly Occurring Constituents of Volatile Oils. 
107 
kesso-root oils, in thyme oil, spearmint oil. in the oil from the fruit of 
Petroselinum sativum (parsley seed oil), and the oil of Asarum 
europaeum. In small amounts pinene has also been found in elderberry 
oil, thuja oil, nutmeg oil, massoy bark oil, sassafras leaf oil, rosemary 
oil, in peppermint oil, sage oil, lavender oil. and the oils of Thymus 
capitatus, Satureja thymbra and Asafoetida. 
Pinene is one of the few terpenes which can be obtained in a com- 
paratively pure state. It is obtained, although optically inactive, by 
treating the solid pinene nitrosochloride with aniline in alcoholic 
solution (Wallach.1 1889 and 1890). The pinene thus obtained shows 
the following properties: 
B. p. 155-156°; d2o° -0.858; ud21° -1-46553 (Wallach.2 1890). 
For the preparation of the active modification of pinene, American 
or French turpentine oil is used, the fraction boiling below 160° being- 
purified by fractional distillation until the hydrocarbons obtained coin- 
cide in boiling point and in the other properties with i-pinene. The 
highest rotations so far observed are: 
for d-pinene from the oil of the needles of the Siberian cedar, 
Pinus cembra (Flawitzky,3 1892) 
[^]di8°-+45.04° (B. p. 156° corr. at 753 mm B.; d-^ = 0.8585);8 
for 1-pinene from French turpentine oil (Flawitzky.4 1879) 
[«]d2o°--1-3.4° (B. p. 155°; d2o° -0.8587).4 
If it is necessary to employ solvents in determining the direction and 
magnitude of the rotation, the influence which these exert must be 
considered (Landolt,5 1877; Bimbach,6 1892). 
Pinene is a colorless, mobile liquid which, like all terpenes, takes up 
oxygen from the air on standing and becomes partly resinified. It is 
readily converted into other terpenes, thus it is changed by a higher 
temperature (250-270°) or by moist hydrochloric acid into dipentene 
and its dihydrochloride respectively; by alcoholic sulphuric acid into 
terpinolene and terpinene, probably with dipentene as an intermediate 
step. By treating pinene monohydrochloride with sodium acetate or 
aniline, camphene is formed, pinene nitrosochloride, however, yields 
under the same conditions pure pinene. In contact with dilute mineral 
acids, pinene is converted in time into terpin hydrate CioHis(OH)2 . H2O 
i) Liebig's Annalen, 252, p. 132; and 
258, p. 343. 
2) Liebig's Annalen, 258, p. 344. 
3) Journ. f. pr. Chem.. II, 45, p. 115. 
4) Berichte, 12, p. 2357. 
5) Liebig's Annalen. 189, p. 311-317. 
6) Zeitschr. phys. Chem., 9, p. 701. 108 
General Part. 
(in. p. 116-117°), and by hydration with sulphuric acid and glacial 
acetic acid it is converted into terpineol. Oxidizing agents act differently 
on pinene. While concentrated nitric acid produces so violent a reaction 
that ignition often takes place, dilute nitric acid, like chromic acid 
mixture yields besides lower fatty acids and other products, terephthalic 
acid CsHeO4 and terebic acid C7H1OO4. Entirely different results are 
obtained with potassium permanganate; very dilute permanganate 
solution induces, as the investigations of Wagner1 (1894- and 1896) 
have shown, chiefly the formation of neutral oxidation products, such as 
pinene glycol, etc. By employing a concentrated solution a monobasic 
keto acid CioHiqOs, pinonic acid (m. p. 103-105°) is formed (Tiemann 
and Semmler2 1895-1896; Baeyer3 1896). This on the one hand, 
yields finally terebic acid, on the other hand the same "Abbau" products 
as those formed by the oxidation of the derivatives of camphor. 
Pinene is an unsaturated hydrocarbon witli one double bond which 
may be removed by addition. By conducting dry hydrochloric acid gas 
or hydrobromic acid gas into perfectly dry -and cooled pinene, the 
monohydrohalogen derivatives of pinene are formed, of which the hydro- 
chloride, CioHisHCl, called "artificial camphor" on account of its 
camphorlike odor, melts at 125°, the hydrobromide at 90°. Both are 
converted into camphene on splitting off the hydrohalogen. If bromine 
in a dry solvent is allowed to act on pinene, one molecule is readily taken 
up with decoloration. On further addition the absorption takes place 
only very slowly and is accompanied by evolution of hydrobromic acid. 
From the product formed by the addition of one molecule of bromine 
to pinene a dibromide melting at 169-170° may be obtained by 
distillation with water vapor4 (Wallach, 1891). A larger yield of this 
dibromide is obtained by treating pinene with hypobromous acid5 
(Wagner and Ginsberg, 1896). By splitting off hydrobromic acid by 
means of aniline the dibromide is changed to cymene, while when treated 
with zinc dust in alcoholic solution it yields a new terpene of the melting 
point 65-66°, tricyclene6 (Godlewski and Wagner, 1897). 
The compounds which are best suited for the characterization of 
pinene are pinene nitrosochloride, formed by the addition of nitrosyl- 
chloride to pinene, and. the nitrolamines which may be prepared from it 
i) Beriehte, 27, p. 2270; 29, p. 881. 
2) Beriehte, 28, p, 1345; 29, pp. 529, 3027. 
3) Beriehte, 29, pp. 22, 326. 1907. 1923, 
2775. 
4) Liebig's Annalen, 264, p. 8. 
5) Beriehte, 29, p. 890. 
6) ('hem. Zeitung, 21, p. 98. The More Commonly Occurring Constituents of Volatile Oils. 
109 
by treatment with organic bases. For the preparation of the nitroso- 
chloride Wallach (1888 and 1889) has given the following directions:1 
A mixture of 50 g. each of turpentine oil (immaterial whether laevo- or 
dextrogyrate) glacial acetic acid and ethyl nitrite2 are well cooled in a freezing- 
mixture and 15 cc. of crude (33 percent) hydrochloric acid are gradually added. 
The nitrosochloride soon separates in a crystalline form, and is obtained in a 
fairly pure state when it is filtered off with a suction pump and well washed 
with alcohol. From the filtrate some more nitrosochloride separates on standing- 
in the cold. It is profitable in regard to yield to work with small quantities, 
as only then can the low temperature be maintained which is necessary for the 
satisfactory conduct of the reaction; large quantities of pinol CioHibO are 
formed as a by-product. 
The nitrosochloride is a white crystalline powder, which is readily 
soluble in chloroform and may be again separated from this solution by 
methyl alcohol. The melting point of the recrystallized compound is 103°. 
Like its derivatives it is optically inactive. According to observations by 
Baeyer3 pinene nitrosochloride is a bisnitroso compound (CioHieCl^NaOa, 
which in ethereal solution is changed by hydrochloric acid into 
hydrochlorcarvoxime.4 By splitting off hydrochloric acid with alcoholic 
potassa it is converted into nitrosopinene (m. p. 132°)5 which has been 
recognized as the oxime of an unknown ketone C10H14C).6 Aromatic 
bases, such as aniline and toluidine split off nitrosylehloride, regenerating 
pinene with the formation of amidoazo-compounds. Quite different is 
the behavior of the nitrosochloride to bases of the fatty series and those 
which possess their characteristics, as for instance, benzylamine and 
piperidine. With primary bases as well as with piperidine nitrolamines 
result; the secondary bases, like diethylamine, however, produce a 
splitting off of hydrochloric acid and formation of nitrosopinene. 
As the nitrosochlorides of different terpenes show very similar melting- 
points and besides decompose very readily, they are less suitable for 
characterization than the nitrolamines, which are very stable and 
crystallize readily; these have been prepared in large numbers, although 
the compounds produced by the reaction with benzylamine and piperidine 
t) Liebig's Annalen, 245, p. 251 ; 253, p. 251. 
2) This is easily obtained by allowing a mixture of 200 g. of concentrated 
sulphuric acid, 1.5 liters of water and 100 g. of alcohol to flow into a solution 
of 250 g. of sodium nitrite in 1 liter of water and 100 g. of alcohol. The ethyl 
nitrite which forms at once must be condensed in well cooled receivers. (Wallach.) 
3) Berichte, 28, p. 648. 
*) Berichte, 29, p. 12. 
5) Wallach & Lorentz, Liebig's Annalen, 268 (1891), p. 198. 
6) Urban & Kremers, Amer. Chern. Journ., 16 (1894', p. 404, Baeyer, Berichte, 28 
(1895), p. 646: Mead & Kremers, Amer. Chem. Journ.. 17 (1895), p. 607. 110 
General Part. 
are preferably used. For their preparation1 the nitrosochloride is 
treated in excess with the base dissolved in alcohol and heated on a 
water bath; the nitrolamine formed is separated by the addition of 
water. The melting- point of pinene nitrolpiperidine is 118-119°, that 
of the nitrolbenzylamine 122-123°. 
Camphene. 
Camphene is the only hydrocarbon CioHie known in the solid form. 
Ln spite of this apparent advantage it has, with the exception of a 
single case, not been possible to separate it as a crystalline body from 
a volatile oil. Camphene is found in the vegetable kingdom in both 
active modifications: as d-camphene (austracamphene of Berthelot) it 
is contained in ginger oil and spike oil; as 1-camphene (terecamphene2 
of Berthelot) in citronella, valerian and kesso oils. It has also been 
obtained from rosemary oil, camphor oil, French and American turpen- 
tine oils, as well as from the oil of Pinus sibirica, but only from the 
last in the solid form. Artificially camphene is obtained in various 
ways, generally by splitting off hydrochloric acid from pinene monohydro- 
chloride or bromide, or bornylchloride (borneo camphene). It is most 
readily prepared from isoborneol by the abstraction of water with zinc 
chloride. 
It is a white, crumbling, crystalline mass with a faint camphorlike 
odor, and shows a great tendency to sublime, but otherwise is much 
more stable than the other terpenes toward air and light. As it is 
obtained in a solid form and may be freed from adhering liquid bodies 
by dissolving in alcohol and carefully adding water, it is one of the few 
terpenes which can be prepared in a pure state. The following constants 
are given: 
for borneocamphene: 
M. p. 48-49°; b. p. 160-161° (Wallach,8 1885); d48° = 0.850; nc4s° = 
1.4555 (Wallach,4 1888); 
M. p. 53.5-54°; d ^^=0.83808; udss-g0 -1.45314 (Briihl,5 1892); 
for camphene from pinene chlorhydrate: 
M. p. 51-52°; b. p. 158.5-159.5°; d^ = 0.84224; nD54° = 1.45514 
(Briihl,« 1892); 
Camphene. 
1) Wallach, Liebig's Annalen, 245 (1888), 
p. 253; 252 (1889), p. 130. 
2) Camphene prepared from pinene hydro- 
chloride is also sometimes designated as 
terecamphene. 
3) Liebig's Annalen, 20, p. 234. 
4) Liebig's Annalen, 245, p. 210. 
s) Berichte, 25, p. 164. 
6) Berichte. 25, p. 162. The More Commonly Occurring Constituents of Volatile Oils. 
111 
for camphene from isobomeol: 
M. p. 50°; b. p. 159-160° (Bertram & W albauni,1 1894); 56° at 15mm. 
The rotation of the hydrocarbon artificially prepared from pinene 
hydrochloride or bornylchloride varies according to the extent of the 
rotation of the material used and the height and length of time of the 
temperature employed during the reaction; thus Bouchardat and 
Lafont2 (1887) obtained hydrocarbons whose rotation [a]D was 
between - 80° 37' and - 30° 30' by treating 1-pinene monohydrochloride 
( [«]T> =- 28°30') with potassium acetate in alcoholic solution at 150 
to 170°. 
For a d-camphene obtained from bornyl chloride Kaehler3 observed 
[a] D85o - + 20° (100.3 mm). 
Camphene is not as readily inverted into isomers as the other 
terpenes. Although it is changed by heating for a long time to a high 
temperature or by treatment with dehydrating agents such as zinc 
chloride, phosphoric acid anhydride or concentrated sulphuric acid, the 
resulting products do not have the formula CioHkj. 
As a terpene with one double bond camphene yields addition 
products with halogens (dibromide m. p. 90°) as well as with hydro- 
halogens, but not with nitrosylchloride. Whether the hydrohalogen 
derivatives are identical with the corresponding compounds of borneol 
or isoborneol has not been definitely settled.4 The hydrochloride is 
obtained by conducting gaseous hydrochloric acid into an alcoholic 
solution of camphene. According to Reychler4 (189(5) it melts at 
150-152°; Kaehler and Spitzer5 (1880) report 15(5-157°. 
Oxidizing agents, such as chromic acid mixture, permanganate and 
nitric acid, do not act in like manner on the hydrocarbon. Thus dilute 
permanganate solution in the cold yields first camphene glycol 
CioHi6(OH)2, melting at 192°. On further oxidation it produces 
camphene-camphoric acid C1OH16O4, small quantities of a ketone, cam- 
phenilone C9H14O (in. p. 3(5-38°), homologous with camphor, and 
principally an acid CioHieOa of the melting point 171-172° (Wagner's 
camphenylic acid, Bredt's oxycamphenilanic acid).. Nitric acid oxidizes 
camphene principally to the tribasic camphoylic acid (Marsh and 
Gardner) C1OH14O6 (Bredt's carboxyl-apocamphoric acid). Accompany- 
i) Journ. f. prakt. Chern. II., 49, p. 8. 
2) Compt. rend., 104, p. 694; Bull. Soc. ehim. II., 47, p. 488. 
s) Liebig's Annalen, 197, p. 97. 
4) Junger & Klages, 1896, Berlchte, 29, p. 544; Reychler, ibid. p. 696. 
5) Liebig's Annalen, 200, p. 343. 112 
General Part. 
ing this are small quantities of the ketone C9H14O already mentioned. 
Chromic acid mixture yields for the main part camphor with a little 
camphoric acid and other products. 
All of these derivatives of camphene, however, do not admit of 
being used for its characterization. If fairly pure camphene fractions 
are under consideration, the hydrocarbon may be separated in the form 
of its chlorhydrate. Camphene may, however, be better identified by 
converting it into isoborneol. Only when larger quantities of pinene 
are present at the same time with the camphene the detection is 
unsatisfactory even with this method, because the inactive terpineol 
which is formed at the same time with the isoborneol retains the latter 
in solution and a separation of the mixture can be only partially 
accomplished. 
According to Bertram and Walbaum (1894) camphene can be con- 
verted into isoborneol according to the following method:1 
100 parts of the camphene fraction are heated with 250 parts of glacial 
acetic acid and 10 parts of 50 percent sulphuric acid for 2-3 hours to 50-60° 
with frequent shaking; the mixture which at first separates into^two layers 
becomes finally homogeneous and has a. slightly reddish color. When tin? 
reaction is ended the acetate formed is separated by water, washed repeatedly 
and then saponified by heating with a solution of 50 g. of potassium hydrate 
in 250 g. of alcohol. After removing the alcohol the isoborneol is precipitated 
as a crumbly mass by the addition of water and is purified by recrystallization 
from petroleum ether. The melting point of isoborneol is about 212°; the 
determination must, however, be made in a sealed capillary tubexon account 
of its great tendency to sublime. For the further characterization of the 
isoborneol its bromal compound, m. p. 71-72°2 may be used. 
Fenchene. 
A strict proof that fenchene exists in volatile oils has not been 
furnished up to the present. By the action of different acids Bouchardat 
and Lafont3 (1891) have obtained from French turpentine oil and 
Bouchardat and Tardy4 (1895) from fractions of the oil of Eucalyptus 
globulus an alcohol of the melting point 42-45°, the identity of which 
with fenchylalcohol has been shown5 (1898). It appears, therefore, 
that this hydrocarbon is to be classed with those terpenes which occur 
in nature, and for this reason it may be briefly considered. 
Up to the present fenchene has been prepared artificially only by 
the abstraction of water from fenchyl alcohol or by splitting off hydro- 
i) Journ. f. pr. Chein. II, -19, p. 1. 
2) Journ. f. prakt. Chern. II, 49, p. 6. 
3) Compt. rend., 113, p. 553; 125, p. 112. 
*) Compt. rend., 120, p. 1418. 
5) Compt. rend., 126, p. 755. The More Commonly Occurring Constituents of Volatile Oils. 
113 
chloric acid from fenchyl chloride1 (Wallach 1891). It is a liquid 
terpene, recalling camphene in odor, and is known in both optically 
active modifications. As constants have been found: 
B. p. 154-155°; dis° = 0.8660; nois0 = 1-4693. 
B. p. 155-156°; di8°= 0.8670; udi8° -1.47047;2 ud- 4-21° (M .,3 
1898). 
Repeated experiments in the laboratory of Schimmel & Co. gave the 
following constants: 
B. p. 154-156° (765 mm.); di5° = 0.8660-0.86(55; 
udi6o -1.46733-1.46832. 
Fenchene yields no characteristic addition products with halogens, 
hydrohalogens, or nitrosylchloride which might be used for character, 
ization. Like camphene it can, however, be hydrated with glacial acetic 
acid and sulphuric acid to an alcohol CioHisO, isofenchyl alcohol 
(m. p. 61.5-62°) which with phenyl isocyanate yields a phenylurethane 
melting at 106-107°. 4 
Limonene. 
Limonene is a very widely 'distributed terpene. Besides the dextro 
and laevogyrate forms it also occurs in the inactive modification, called 
dipentene. As some of the dipentene derivatives are different in 
properties from the corresponding limonene derivatives it is usually 
considered as a separate hydrocarbon. d-Limonene (citrene) is contained 
in the citrus oils, in larger quantities in the oils of orange peel, lemon, 
and bergamot, in mandarin oil, in Italian limette oil, in neroli and 
petitgrain oils, further in caraway, dill and Macedonian fennel oil. in 
celery, erigeron and kuromoji oils. LLimonene does not occur as 
frequently. It has been found in the oil from the needles and cones of 
Abies alba, in Russian and American spearmint oil and American 
peppermint oil. 
Since the optically active limonenes could not be regenerated from 
solid derivatives, recourse had to be taken for their preparation to the 
fractional distillation of orange peel or caraway oils, and in the case of 
1-limonene, of oil of Abies alba. The most carefully purified hydrocarbon 
possesses a pleasant lemon like odor, which in the distillates obtained from 
caraway oil or oil of Abies alba changes after keeping for a short 
time, the odor then reminding of the oils used. This is probably due 
i) Liebig's Annalen, 263, p. 148. 
2) Liebig's Annalen, 300, p. 313. 
3) Liebig's Annalen, 302, p. 376-377. 
*) Bericht von S. & Co., October 1898, p. 56. 114 
General Part. 
to the presence of small quantities of foreign substances. The physical 
constants obtained from such fractions are as follows: 
B. p. 17o-1/6°; dis° = 0.8464; udit° -1.47568. 
For 1-limonene from pine needle oil Wallach found (1888): 
B. p. 175-176°; d2o° = 0.846; nD20° = 1.47459.1 
The rotatory power is not constant. The greatest deviation was 
found in the laboratory of Schimmel & Co. for a d-limonene fractionated 
in vacuum from caraway oil [<z]D - +123°40' (no solvent), consequently 
a still greater value than that found by Kremers2 (1895). For 
1-limonene from pine needle oil Wallach3 (1888 and 1889) has 
reported [a]n =-105° (in alcoholic or chloroformic solution), and 
Tilden and Williamson4 in 1893 found a, similar value [«],) =-106°. 
Quite recently Godlewsky5 has regenerated limonene from the tetra- 
bromide by reduction with zinc dust. The limonene resulting had the 
following properties: 
B. p. 177.5° at 759 mm.; d^ = 0.8585; dp -0.8584; dp° = 0.8425; 
[«]„ = +125° 36' at 20°. 
The regenerated limonene again added bromine to form the tetra- 
bromide melting at 104°. 
The two limonenes are completely alike in their chemical behavior; 
both give the same derivatives, differing only in their optical rotation. 
By mixing equal amounts of d- and 1-limonene dipentene results, which 
hydrocarbon is also formed when the optically active limonenes are 
heated to a- high temperature or treated with acids. In a completely 
dry state limonene absorbs one molecule of hydrohalogen with the 
formation of liquid, optically active compounds0 (Wallach). By 
replacing the halogen atom by the hydroxyl group this yields optically 
active terpineol7 (Semmler, 1895). Only in the presence of moisture 
does an addition of two molecules of hydrohalogen take place, with the 
formation of derivatives of dipentene. 
Limonene takes up four atoms of bromine and forms the optically 
active limonene tetrabromide (see p. 115) melting at 104-105°. By 
the addition of nitrosylchloride there result two (a- and /?-) nitroso- 
chlorides8 (Wallach. 1889) which are prepared in a similar manner to 
pinene nitrosochloride and are to be considered as physical isomers. 
i) Liebig's Annalen, 246, p. 222. 
2) Amer. Chem. Journ., 17, p. 692. 
3) Liebig's Annalen, 246, p. 222 ; Wallach 
& Conrady, ibidem 252, p. 145. 
+) Journ. Chem. Soc., 63, p. 293. 
3) Chem. Centrbl., 70i, p. 1241. 
») Annalen, 270, p. 188. 
7) Berichte, 28, p. 2190. 
8) Liebig's Annalen, 252. p. 109. The More Commonly Occurring Constituents of Volatile Oils. 
115 
The nitrosochlorides are perfectly alike in chemical behavior, both are 
changed to carvoxime melting at 72° by the abstraction of hydrochloric 
acid with alcoholic alkali, and yield when treated with bases the same 
(two) nitrolamines1 (Wallach, 1892). 
Limonene is converted by dilute permanganate solution into the 
saturated tetratomic alcohol limonetrite (m. p. 191.5-192°)2 (Wagner. 
1890). 
A characteristic derivative of limonene, which is often used for 
identification, the tetrabromide, is prepared according to Wallach's 
directions 3 (1887): 
The fraction is purified as much as possible and diluted with about four 
times its volume of glacial acetic acid. Bromine is added drop by drop to the 
well cooled solution as long as this is taken up with decoloration. The crystals 
separating after standing for some time are collected and recrystallized from 
acetic ether. The melting point of the pure tetrabromide is 104.5°. 
In the preparation of the tetrabromide it is to be observed that 
the use of absolutely anhydrous reagents is not necessary. In fact these 
give rise to the formation of an uncrystallizable tetrabromide. Never- 
theless the crystallized product is to be considered as the normal 
bromide.4 Wallach does not approve of using alcohol and ether as 
diluents, for they induce the formation of liquid by-products. The same 
difficulty is met with when the terpene fractions are impure. 
Small changes in the method of preparation have been recommended 
by other investigators. Baeyer and Villiger5 (1894) dilute the fraction 
to be investigated with an equal volume of amyl alcohol, and after the 
addition of twice the volume of ether cool and add the bromine drop 
by drop. As the ether evaporates the tetrabromide separates out. 
Power & Kleber6 (1894) allow the fraction to be tested for limonene 
to drop into a cooled mixture of glacial acetic acid and bromine until 
only a slight excess of bromine is present, then decolorize with an 
aqueous solution of sulphurous acid and precipitate with water; in this 
manner they want to avoid the formation of hydrobromic acid always 
noticed in the usual bromination method, and to prevent the formation 
of non-crystallizable bromides of isomeric terpenes. 
Finally, a combination of both methods has been recommended by 
Godlewsky7 (1898). who directs, to allow the solution of the terpene 
i) Liebig's Annalen, 270, p. 172. 
2) Berichte, 23, p. 2315. 
3) Liebig's Annalen, 239, p. 3. 
*) Liebig's Annalen, 264, p. 14. 
5) Berichte, 27, p. 448. 
Pharm. Rundschau, 12, p. 160; Archiv 
(1. Pharm., 232, p. G46. 
7) ('hem. Zeitung, 22, p. 827. 116 
General Part. 
in a mixture of equal parts by weight of amyl alcohol ami ether to 
drop into an ethereal solution of bromine, which is to be cooled with 
ice water during the reaction. 
Dipentene. 
Dipentene, the optically inactive modification of limonene has often 
been found occuring naturally, for instance in pine needle oil. 
citronella and palmarosa oils, in the oils of cubeb, pepper, cardamom, 
camphor, nutmeg, kuromoji, massoybark, bergamot, limette leaf, in 
fennel, golden rod, myrtle and kesso root, also in the oils from Satureja 
thymbra and Thymus capitatns, as well as in olibanum and elemi oils. 
In addition to its formation from equal parts of d- and 1-limonene it is 
obtained by the polymerization of the unsaturated aliphatic hydrocarbon 
isoprene CnHs; with terpinene by the abstraction of water from 
the aliphatic tertiary alcohol linalool CioHisO. It is also formed by 
isomerization of other hydrocarbons CioHie, for instance, from pinene, 
limonene, phellandrene; and results from oxygenated compounds by 
different transformations, for instance from cineol, terpineol and terpin 
hydrate. 
A relatively pure dipentene is obtained by the dry distillation of 
caoutchouc. After separating the first fraction containing the isoprene, 
the fraction boiling at 172-178° is carefully subjected to repeated 
fractional distillation from sodium. A less pure preparation is obtained 
from dipentene dihydrochloride by splitting off hydrochloric acid with 
aniline or sodium acetate and glacial acetic acid1 (Wallach, 1887) or 
from crystallized terpineol by the abstraction of water with potassium 
bisulphate2 (Wallach. 1893). 
Dipentene is distinguished from limonene in its physical properties 
only by its optical activity; boiling point,3 specific gravity, and index 
of refraction are identical with the data determined for limonene. For 
dipentene from caoutchouc the following data have been found in the 
laboratory of Schimmel & Co.: 
B. p. 175-176°; d2o° = 0.841; nD2o° = 1.47194. 
Dipentene is relatively stable, for upon heating it is not converted 
into an isomeric hydrocarbon CioHio, but yields polymers. Alcoholic 
sulphuric acid, however, on heating changes it to terpinene. Its deriva- 
1) Liebig's Annalen, 239, p. 3; 245, p. 
196. Comp, also Tilden and Williamson. 
Journ. Chern. Soc., 63, p. 294. 
2) Liebig's Annalen, 275, p. 109. 
3) Liebig's Annalen, 286, p. 138. The More Commonly Occurring Constituents of Volatile Oils. 
117 
tives are inactive and may be obtained from dipentene itself, as well as 
by combining' equivalent amounts of the corresponding' optically active 
compounds of limonene. They show a few small differences from those 
of the active limonenes, namely in respect to their melting points, on 
account of which it appears justifiable to treat dipentene as a separate 
hydrocarbon. Dipentene behaves like the active limonenes toward 
hydrohalogen, bromine and nitrosylchloride; the solid addition products 
formed with two molecules of hydrohalogen exist in two different forms, 
cis- and trans-modifications, of which the lower melting and more readily 
soluble is designated as the cis-form (Baeyer,1 1893). The higher 
melting trans-form is the more stable. It always forms, when the 
reaction takes place with heat. In the cold both forms usually result 
together. As the trans-form is usually obtained, the following data 
refer only to this modification. The dipentene dihydrohalides are 
obtained from limonene as well as from dipentene, when the cooled 
solutions of the hydrocarbons in ether, glacial acetic acid, etc., are 
saturated with the respective hydrohalogen. Upon evaporation of the 
solvent or upon dilution with water the compounds separate as oils 
which soon crystallize. The dihydrochloride melts at 50° and can be 
obtained in a crystalline form from its alcoholic solution by the careful 
addition of water; the dihydrobromide forms rhombic tablets of satin- 
like lustre and has the melting point 64°: the dihydroiodide crystallizes 
in different forms and melts at 77-81°. From all of these compounds 
dipentene may be regenerated by splitting off hydrohalogen. 
The nitrosylchloride compound is known in two modifications 
(a and /?) both of which yield inactive carvoxime by splitting off hydro- 
chloric acid with alcoholic potash. When acted upon by bases there 
are formed from each of the nitrosochlorides two nitrolamines. 
For the detection of dipentene the compound usually used is the 
tetrabromide, the formation of which results in the same manner as 
was described for limonene tetrabromide; it also forms when concentrated 
solutions of equal parts by weight of d- and 1-limonene tetrabromide 
are mixed. The crystals are distinguished by their habit, difficult 
solubility, and higher melting point, 124-125°, from those of the 
limonene compounds2 (Wallach, 1888). 
For identification the nitrosochloride, which can be changed to 
inactive carvoxime by heating with alcoholic potash, is also suitable. 
1) Berichte, 26, p. 2861. 
2) Liebig's Annalen, 246, p. 226. 118 
General Part. 
Sylvestrene. 
Sylvestrene is one of the rarely occuring terpenes. Up to the present 
time it has been found in German and Swedish pine needle oil from 
Pinus silvestris, in the oil from the leaves of Pinus montana, in pine 
tar oil and Finnish turpentine oil. In all of these it occurs in the 
dextrogyrate modification. 
It may be obtained in a comparatively pure state by preparing the 
dihydrochloride from fractious rich in sylvestrene and decomposing this 
by boiling with aniline1 (Wallach, 1885), or sodium acetate and 
glacial acetic acid2 (Wallach, 1887). The hydrocarbon thus obtained 
resembles limonene almost completely in its physical and chemical 
properties. Like this it possesses a pleasant odor, reminding of lemon 
and bergamot oil, and its specific gravity and boiling point are almost 
identical with those of limonene. 
Atterberg, the discoverer of sylvestrene, ascertained the following 
physical constants: 
B. p. 173-175°; die° = 0.8612; [*z]di6° - d-19.o°.3 
Wallach reports the following constants: 
B. p. 176-177°; die® - 0.851; nD - 1.47799.4 
B. p. 175-176°; 620° = 0.848; nD = 1.47573; [«]D = +66.32° (in 
chloroform).5 
When heated to 250° sylvestrene is polymerized, but is not changed 
by this physical agent nor by the action of alcoholic sulphuric acid 
into isomeric terpenes. This hydrocarbon is, therefore, one of the most 
stable of the terpene group. Like limonene, sylvestrene has two double 
bonds which may be wholly or partially broken by the addition of 
hydrohalogen, bromine or nitrosyl chloride. A peculiar behavior is 
shown by the dihydrochloride, which in opposition to the inactive 
dipentene dihydrochloride is optically active and by splitting off hydro- 
chloric acid yields active sylvestrene. The tetrabromide, prepared in 
the same manner as that of limonene, melts at 135-136°, but is 
obtained with difficulty in the solid form when, as is usually the case 
in terpene fractions, other hydrocarbons are present. Pure sylvestrene 
yields, when treated with amyl nitrite and hydrochloric acid, a nitroso- 
chloride melting at 106-107°. With benzylamine this forms a 
nitrolamine base of the melting point 71-72°. 
i) Liebig's Annalen, 230. p. 243. 
2) Liebig's Annalen, 239, p. 25; 245, 
p. 197. 
3) Berichte, 10. p. 1206. 
*) Liebig's Annalen, 245, p. 197. 
5) Liebig's Annalen, 252, p. 149. The More Commonly Occurring Constituents of Volatile Oils. 
119 
For the separation of sylvestrene from mixtures, as well as for 
identification,- the dihydrochloride is best suited and is prepared as 
follows: 
The fraction diluted with an equal volume of ether is strongly cooled and 
saturated with hydrochloric acid gas. After standing for about two days the 
ether is distilled off and the residue induced to crystallize by strongly cooling. 
The crystalline mass is freed from oily by-products on a porous plate, and the 
hydrochloride, first recrystallized from an equal weight of alcohol, is purified 
by fractional crystallization from ether; the melting point of the pure dihydro- 
chloride is 72° (W.,1 '85). It must be observed, that in the presence of dipentene 
or such terpenes as are changed to dipentene di hydrochloride, mixtures of 
dihydrochlorides are obtained, the melting point of which is the lower, the 
greater the amount of dipentene dihydrochloride present. 
If sylvestrene be dissolved in acetic anhydride and a few drops of 
concentrated sulphuric acid added to the solution, a beautiful blue 
coloration is produced. This reaction may be used for the easy detection 
of sylvestrene, but it is only successful when the tractions to be tested 
are rich in this hydrocarbon. 
Terpinene. 
This hydrocarbon is very similar to dipentene, yet sharply differ- 
entiated from it. According to Weber2 (1887) it is contained- in 
cardamom oil and recently it has also been found in marjoram oil by 
Biltz.3 It may, however, appear doubtful, whether this terpene is really 
found in nature, or whether it is formed by the influence of the heat 
during the distillation from other compounds contained in the respective 
oils. 
Artificially, this hydrocarbon, which distinguishes itself by its stability 
toward dilute mineral acids, is obtained by the action of boiling alcoholic 
sulphuric acid on terpenes, such as dipentene and phellandrene, or on 
oxygenated compounds, such as terpin hydrate, terpineol, dihydro- 
carveol and cineol. Besides dipentene it is also formed by the action 
of formic acid on linalool and geraniol. It is further formed, besides 
isomeric hydrocarbons CioHig and cymene, by the inversion of pinene 
with alcoholic sulphuric acid or when turpentine oil is shaken with 
small amounts of concentrated sulphuric acid, avoiding too violent a 
reaction4 (Wallach, 1887). The last named method is used when it is 
desired to obtain fractions containing terpinene. As terpinene has up 
i) Liebig's Annalen, 230, p. 241; 239, p. 25. 
2) Liebig's Annalen, 238, p. 107. 
3) Ueber das atherische Oel aus Or/ganwm majorana. Inaug.-Dissert. Greifswald, 1898. 
4) Liebig's Annalen, 239, p. 35. 120 
General Part. 
to the present not been regenerated from a solid derivative, the 
statement of the physical properties of this hydrocarbon refers not to 
the pure substance but only to terpinene-containing fractions. 
For a terpinene obtained from terpin hydrate and dilute sulphuric 
acid Wallach reports: 
B. p. 179-182°; d = 0.8554 
and for a purer preparation from dihydrocarveol and sulphuric acid: 
B. p. 178-180°; d = 0.847; nD = 1.48458.2 
Terpinene has an odor reminding of cymene and resinifies quite 
rapidly on standing; it has not yet been possible to convert it into 
isomers. It is therefore very similar to dipentene, but the two' hydro- 
carbons differ in their behavior toward bromine and the hydrohalogens, 
with which terpinene yields liquid addition products only. A nitroso- 
chloride of this terpene is not known, but nitrolamines can be prepared 
from the nitrosite mentioned later. 
By chromic acid mixture (prepared according to Beckmann) terpi- 
nene is readily attacked and completely destroyed (Baeyer,3 1894), even 
in the cold. This behavior may be made use of when terpinene is to be 
removed from mixtures of pinene, camphene, limonene, terpineols, cineol 
or pinol, as these compounds are fairly stable toward the oxidizing 
agent in the cold. 
The derivative of terpinene which may serve for the detection of this 
hydrocarbon is that formed by the addition of nitrous acid, terpinene 
nitrosite CioHioNaOs. It is obtained by the action of nascent nitrous 
acid on the terpene diluted with a solvent. In order to determine 
rapidly whether this hydrocarbon is present in a fraction of the 
boiling point of terpinene, Wallach (1887) directs4 to proceed as 
follows: 
A mixture of 2-3 g. of the fraction with an equal volume of petroleum 
ether is poured on top of an aqueous solution of 2-3 g. of sodium nitrite 
and the amount of acid necessary to decompose the latter is added in small 
portions; when all acid has been added the vessel is immersed for a moment 
in a hot waterbath and then allowed to stand in the cold. When terpinene is 
present, the insoluble nitrosite will separate in a few hours, or at latest in the 
course of two days. This is freed from accompanying oily products by spreading- 
on porous plates, dissolved in glacial acetic acid, again precipitated by water 
and finally recrystallized from hot alcohol. The purified compound melts at 155°. 
i) Liebig's Annalen, 230, p. 253 ; 239, p. 33. 
2) Berichte, 24, p. 3991. 
3) Berichte, 27, p. 815. 
*) Liebig's Annalen, 239, p. 36. The More Commonly Occurring Constituents of Volatile Oils. 
121 
The nitrosite reacts with bases, sucli as piperidine and benzylamine 
to form nitrolamines. The nitrolpiperidine base melts at 153-154°, the 
nitrolbenzylamine base at 137° 1 (Wallach). 
Phellandrene. 
Phellandrene occurs in nature in both optically active modifications. 
As d-phellandrene it has been found in bitter- and water-fennel oils, as 
well as in Macedonian fennel oil, in elemi and schinus oils and in the 
distillate of the wood of Caesalpinia sappan. As 1-phellandrene in 
Australian eucalyptus oil from Eucalyptus amagdalina, in pineneedle oil. 
the oil from the needles of Pinus montana, in star-anise and schinus oils. 
Besides these, it is contained in a large number of volatile oils, although 
in small quantities, for instance in the oils of ginger, curcuma, pepper, 
camphor, sassafras leaves, Ceylon cinnamon, angelica root and seed, 
in the oils of German and English dill, in that of dog fennel, wormwood, 
golden rod, lemon, bay and peppermint, as well as in the oils of Euca- 
lyptus risdonia and Andropogon laniger. 
It is one of the most unstable terpenes, and for this reason phel- 
landrene containing oils must never be redistilled under atmospheric 
pressure, but are best fractionated in a vacuum when it is desired to 
detect and isolate this hydrocarbon. The preparation of pure phel- 
landrene has not yet been accomplished; the only compound apparently 
suited for this purpose, the crystallized nitrosite, decomposes indeed, by 
treatment with alkali2 (Wallach, 1895), but no hydrocarbon CioHie is 
formed by the reaction. Fractions as rich as possible in phellandrene, 
viz. the portion boiling between 170-172° are therefore taken as 
representing fairly pure hydrocarbon. 
Pesci (1886), who found this hydrocarbon in water fennel oil and 
named it after its source, reports the following properties: 
B. p. 171-172° (760 mm.); dio = O.8558; [a]D10o-+17°64/;3 
nD - 1.484A 
For a preparation from Australian eucalyptus oil Wallach (1895) 
found :5 
B. p. 65° at 12 mm.; di»° = 0.8465; nDi»° = 1-488. 
The optical rotation for d-phellandrene has been found considerably 
higher than that given by Pesci; for a preparation from schinus oil «d 
was found to be + 60° 21'6 (Gildemeister and Stephan, 1897). 
i) Liebig's Annalen, 241, p. 315. 
2) Liebig's Annalen, 287, p. 374. 
3) Gazz chim. ital. 16, p. 225. 
*) Jahresber. f. Chern., 1883, p. 1424. 
5) Liebig's Annalen, 287, p. 383. 
6) Archiv (1. Pharm., 235, p. 591. 122 
General Part. 
Phellandrene is very readily changed; even by heating to its boiling 
temperature it polymerizes. Still more readily is it changed into inactive 
isomers by the action of acids, thus by hydrohalogen into dipentene, 
by alcoholic sulphuric acid into terpinene. Well characterized addition 
products with halogens or hydrohalogens cannot be prepared, the 
only known solid derivative is phellandrene nitrosite, which is formed 
by the addition of nitrous acid and which is therefore used for 
identification. 
A mixture of 5 cc. of oil and 10 cc. of petroleum ether is poured on a 
solution of 5 g. of sodium nitrite in 8 g. of water and the amount of glacial 
acetic acid (5 cc.) necessary to liberate the nitrous acid is added gradually 
with frequent shaking; the voluminous crystalline mass produced is filtered off 
with the aid of an air pump, washed first with water and then with methyl 
alcohol, and purified by repeatedly dissolving in chloroform and precipitating 
with methyl alcohol' (Wallach and Gildemeister, 1888). The brilliant white 
crystals thus obtained allow of being recrystallized from acetic ether without 
decomposition and melt at 105°2 (Wallach, 1895). The crude compound 
changes easily and is freed'from the oily by-products only with difficulty; by 
dissolving in a little acetic ether and precipitating with 60 percent alcohol the 
nitrite can be obtained at once in the form of white crystals3 (Bertram and 
Wal ban in, 1893). 
Both phellandrenes give nitrosites which are identical as to external 
appearance and in their melting point, but which differ in this respect, 
that the compound obtained from d-phellandrene is strongly laevo- 
gyrate. that from 1-phellandrene on the other hand, strongly dextro- 
gyrate. By piixing equal parts by weight. of d- and 1-phellandrene 
nitrosite in solution the inactive compound is formed, which in its 
properties is identical with the optically active modifications. Phellan- 
drene nitrosite, in opposition to terpinene nitrosite, cannot be changed 
to nitrolamines with bases. If the liquid reaction product formed by 
treatment with sodium ethylate is reduced there result, as well as by 
the direct reduction of the nitrosite, derivatives of the hydrocarvone 
series4 (Wallach, 1895). 
The presence of hydrocarbons of the formulas CioHis and C10H20 in 
volatile oils has not yet been definitely established. The statement 
made by Andres and Andreef5 (1892) that a hydrocarbon GioHis. 
presumably the menthene derivable from menthol, occurs in Russian 
peppermint oil has not been verified. 
1) Liebig's Annalen, 246, p. 282. 
2) Liebig's Annalen, 287, p. 374. 
s) Archiv d. Pharm., 231, p. 298, footnote. 
*) Liebig's Annalen, 287, p. 380. 
s) Berichte, 25, p. 616. The More Commonly Occurring Constituents of Volatile Oils. 
123 
Whereas menthene is a cyclic hydrocarbon with one double bond, 
Wassileef1 has recently prepared a chain hydrocarbon CioHis. an 
olefinic di hydroterpene as it were from active amyl alcohol. 
In addition to the terpenes CioHic many volatile oils contain 
sesquiterpenes, C15H24. Like the terpenes these hydrocarbons may be 
regarded as polymerization products of hemiterpene, CkHs. With few 
exceptions they have not yet been carefully examined. It seems 
probable, therefore, that some of them will prove identical. Most 
sesquiterpenes boil between 250 and 280°, have a specific gravity of 
over 0.90, as separated by fractionation are frequently slightly colored, 
are less mobile liquids than the terpenes, resinify as readily as do the 
terpenes and are difficultly soluble in alcohol. As unsaturated hydro- 
carbons they add halogens, hydrohalogens, nitrosylchloride and the 
oxides of nitrogen. They frequently occur in oils accompanied by 
alcohol-like compounds C15H26O (possibly also C15H24O) which stand 
in the same relation to the sesquiterpenes as do the terpineols to the 
terpenes. However, by treating the sesquiterpenes with the glacial acetic 
acid-sulphuric acid mixture, only one of them has so far been hydrated. 
Whether these sesquiterpene alcohols yield upon dehydration the same 
hydrocarbons C15H24 with which they are found in the oils has not yet 
been determined. 
Attention should also be called to the apparent existence of sesqui- 
terpenes corresponding to the olefinic terpenes. Semmler,2 in 1889 
obtained from asarum oil a hydrocarbon C15H24 boiling at about 255°, 
the specific gravity of which (0.873) is much lower than that of most 
sesquiterpenes. Thuja oils likewise contain fractions of the boiling point 
of the sesquiterpenes that are characterized by a very low specific 
gravity (0.85). 
Cadinene. 
The best known representative of the sesquiterpenes is the widely 
distributed cadinene. It has so far been found in cade oil (Oleum 
cadinum) from which source it has derived its name, further in the pine 
needle oils and of Pinus montana, the German and Swedish oils of Pinus 
silvestris, the oils of elderberry, savin, cedarwood, cubeb, betel, camphor, 
paracoto bark, asafetida, galbanum, olibanum, wormwood, golden rod, 
patchouli, peppermint, ylang-ylang and angosturo bark. As far as 
examined, cadinene has been found only in the laevogyrate modification. 
1) Chem. Centrbl., 70i, p. 775. 
2) Chem. Zeitung, 13, p. 1158. 124 
General Part. 
Cadinene can be prepared in a comparatively pure state, as it yields 
a solid well crystallized dihydrochloride, from which the hydrocarbon 
may be regenerated by splitting off hydrochloric acid by heating with 
aniline or sodium acetate and glacial acetic acid1 (Wallach, 1887). 
For the hydrocarbon purified in this manner Wallach found the 
following constants: 
B. p. 272° (uncorr.);2 274-275°; d2o° = 9.918; nD = 1.50647; 
[a]n = -98.56°.3 
Upon continued heating with dilute sulphuric acid cadinene is 
changed, while when treated with hydrohalogens no appreciable influence 
is noticed, as the optical activity remains unchanged. Especially 
characteristic are the crystallized addition products formed with two 
molecules of hydrohalogen, of which the dihydrochloride and the 
dihydrobromide are used for identification. 
For the preparation of the dihydrochloride the fraction boiling between 
260-280° is diluted with twice the volume of ether and saturated with hydro- 
chloric acid gas in the cold. After standing for some time the ether is partially 
removed by distillation. With the complete evaporation of the solvent, crystals 
of the dihydrochloride separate from the residue. These are freed from oily 
by-products by spreading on porous plates. They are then washed with 
alcohol, and recrystallized from acetic ether in which they are readily soluble 
while warm. The melting point of the pure compound is 117-118°. It is 
optically active. 
The dihydrochloride may also be prepared by using glacial acetic 
acid saturated with hydrochoric acid in the cold. This method of 
preparation-treating a glacial acetic acid solution of the sesquiterpene 
with a glacial acetic acid solution of the respective hydrohalogen-is 
suitable for the preparation of the dihydrobromide (m. p. 124-125°) 
and the dihydroiodide (m. p. 105-106°). 
The nitrosochloride and nitrosate have been prepared within the last 
year by Schreiner and Kremers.4 Of the latter the unusually large 
yield of over forty per cent was obtained. The nitrosochloride melts 
at 93-94°, the nitrosate at 105-110°, both with decomposition. 
Cadinene is characterized by a color reaction, which under some cir- 
cumstances may serve to show its presence in oils. The reaction * is 
prettiest when the hydrocarbon, slightly changed by standing for some 
time, is dissolved in glacial acetic acid and the solution treated with 
a little concentrated sulphuric acid. The greenish coloration first pro- 
duced soon changes through blue to red. 
1) Liebig's Annalen, 238, p. 84. 
2) Liebig's Annalen, 271, p. 303. 
3) Liebig's Annalen, 252, p.150; 271, p.297. 
4) Pharm. Arch., 2, p. 249. The More Commonly Occurring Constituents of Volatile Oils. 
125 
The second well characterized sesquiterpene is caryophyllene. So 
far it has been found in the oils of cloves and clove stems, the oil of 
copaiba balsam and that of Canella alba. It has not yet been prepared 
absolutely pure. The physical constants recorded pertain to distillates 
from clove oil and the oil of clove stems. Caryophyllene prepared from 
clove oil merely by fractionation contains some benzoyl eugenol1 which 
can be removed by saponification. In the sesquiterpene from the oil of 
clove stems this impurity is not found. The physical constants have 
been ascertained by several observers, viz.: 
Wallach2 (1892): b. p. 258-260°; di5° = 0.9085; Hd - 1.50094. 
Erdmann3 (1897): b. p. 119-120° at 9 mm.; 123-124° at 13 mm.; 
258-259° at 752 mm.; (I240 -0.9038. 
Kremers4 (1898): d2o° -0.9032, nD2o° 1.50019; [a]D2oo =- 8.74°. 
Schreiner and Kremers5 (1899): b. p. 136-137° at 20 mm.; [<z]d2oo = 
- 8.96; nD2o° -1.49976; d2o° = O.9O3O. 
The laevogyrate hydrocarbon yields optically active as well as 
inactive derivatives, the nitrosite e. g. being strongly dextrogyrate. 
With hydrogen chloride it yields a crystalline dihydrochloride6 (m. p. 
69-70°). It forms a crystalline nitrosochloride, apparently two nitro- 
sites (one blue, the other white), and a nitrosate. From several of these 
the benzylamine and piperidine bases have been prepared. From both 
the dihydrochloride and the nitrosochloride a hydrocarbon can evidently 
be regenerated (Schreiner & Kremers.7 1899). 
Caryophyllene hydrate which so far has been principally used for the 
identification of this sesquiterpene is prepared as follows: 
To a solution of 1000 g. glacial acetic acid, 20 g. cone, sulphuric acid and 
40 g. of water, 25 g. of caryophyllene or so much hydrocarbon as the mixture 
will retain in solution are added and the mixture heated for some time on a 
waterbath. When the reaction is completed the mixture is subjected to steam 
distillation. At first acetic acid and a mobile oil pass over, later a less volatile 
oil which congeals upon cooling. This is freed from oil by suction and further 
purified by crystallization from alcohol. Caryophyllene alcohol or hydrate melts 
at 94-96°. Its identification can be verified by the phenyl urethane derivative 
which melts at 136-137°. 
For the purpose of identification the nitrosite and the benzylamine 
base obtained from it are especially adapted: 
Caryophyllene. 
1) Journ. f. prakt. Chem. II, 56, p. 146. 
2) Liebig's Annalen, 271, p. 298. 
3) Journ. f. prakt. Chem. II, 56, p. 146. 
+) Pharm. Arch., 1, p. 211. 
5) Ibidem, 2, p. 282. 
6) Pharm. Archives, 2, p. 296. 
7) Pharm. Arch., 2. pp. 295, 296 126 
General Part. 
To a solution of 5 cc. of caryophyllene in 5 cc. of petroleum ether 5 cc. of 
glacial acetic acid and then 5 cc. of a saturated solution of sodium nitrite are 
added. The mixture while still warm from the reaction is rotated and then 
cooled in ice water with violent shaking. Crystallization usually takes place or 
may be induced with a fragment of nitrosite. The blue crystals are washed 
with water and then with alcohol. When recrystallized from hot alcohol, 
avoiding direct sunlight, the crystals melt at 113°. The benzylamine base 
from the nitrosite melts at 167°. 
Noteworthy is the fact that upon dehydration of caryophyllene 
alcohol, caryophyllene is not regenerated, but an isomeric hydrocarbon, 
Source. 
„ ... 
Boiling 
point 
d 
Ud 
«n 
Humulene1 
from hop oil 
263-266°' 
166-171° 
(60 mm) 
0,9001 
(20°) 
- 
- 
Cedrene 2 & 3 
from cedar oil 
261-262° 
131-132° 
(10 m m) 
0,9359 
(15°) 
1.5015 
- 60° 
-47°54' 
Cedrene4 
from cedrol & a) P2 O5 
b) formic acid 
237° (?) 
262-263° 
- 
- 
- 80° 
Cubebene5 
from cubebcamphor 
255-260° 
- 
- 
- 
Guajene6 
from guajol & ZnC12 
124-128° 
(13 mm) 
0,910 
(20°) 
1.50114 
- 
Ledene7 
from ledumcamphor & 
dil. sulphuric acid 
255° 
- 
- 
- 
Patchoulene8 
from patchoulicam ph or 
and KHSO4. 
254-256° 
0,939 
(23°) 
1.50094 
- 
Santalene9 
from santalol and 
P2O5 
260° 
- 
■ 1 
1) Chapman, Journ. chem. Soc., 67 (1895), p. 54- & 780. 
2) Chapman & Burgess, Chem. News, 74 (1896), p. 95. 
3) Rousset, Bull. Soe. chim, III, 17 (1897), p. 485. 
4) Walter, I.iebig's Annalen, 39 (1841), p. 247; 48 (1843), p. 35; Bericht von 
Schimmel & Co., October 1897, p. 12, footnote. 
s) Schmidt, Berichte, 10 (1877), p. 189. 
6) Wallach & Tuttle, Liebig's Annalen, 279 (1894), p. 396. 
7) Hjelt, Berichte, 28 (1895), p. 3087. 
8) Wallach & Tuttle. Liebig's Annalen, 279 (1894), p. 394. 
9) Chapoteaut, Bull. Soc. chim. II, 37 (1882), p. 303. The More Commonly Occurring Constituents of Volatile Oils. 
127 
clovene, is formed. This differs materially from caryophellene and has 
not yet been found in volatile oils. 
Besides these two sesquiterpenes may be mentioned the fairly well 
characterized humulene. It derives its name from hop oil from which 
it was prepared by Chapman1 who first prepared its nitrosochloride, 
its nitrosite (existing in a blue and a white variety) and nitrosate, 
also the nitro! benzylamine (m. p. 136°) and the nitro! piperidine 
(m. p. 153°) bases. It is characterized by the nitrosite, the blue 
variety of which (m. p. 120°) changes upon repeated recrystallization 
from alcohol to the white variety (m. p. 165-168°). Humulene also 
occurs in oil of poplar buds. Fichter and Katz2 identified it by means 
of the above mentioned derivatives. 
There remain to be mentioned cedrene occuring with cedrol in 
cedar oil, as well as other hydrocarbons C15H24 produced by splitting 
off water from sesquiterpene alcohols. Their properties are, so far as 
known, given in the table on the preceding page. 
Polyterpenes, namely di- and triterpenes, occur in vegetable balsams 
and resins. They are possibly formed by polymerization of hydrocarbons 
CgHs and CioHie and may therefore be found in the higher boiling 
fractions of volatile oils. The diterpenes are viscid liquids boiling above 
300°, the triterpenes resinous masses. Hence they do not invite examin- 
ation and their properties have been even less investigated than those 
of the sesquiterpenes. 
Alcohols. 
Of the monatomic alcohols of the paraffin series only those with less 
than eight carbon atoms have so far been found in volatile oils. They 
occur seldom as free alcohols and are mostly combined with fatty acids 
as esters. The occurrence of fatty alcohols and acids is mostly due to 
saponification of corresponding esters. Free alcohols may occur when 
the plant material containing carbohydrates has undergone partial 
fermentation before being distilled. Thus e. g. ethyl alcohol has been 
found in the distillate of rOses that had been stored for a short time. 
Maze,3 however, has recently shown that alcohol is formed not 
only in the process of germination of certain seeds, but also when they 
are soaked in water. The formation of alcohol in these cases is 
attributed to a diastatic process similar to that induced by yeast. 
1) Journ. Chem. Soc., 67, pp. 54 & 780. 
2) Berichte, 32, p. 3183. 
3) Compt. rend., 128, p. 1608. 128 
General Part. 
As esters and ethers methyl alcohol is widely distributed: as methyl 
salicylate in numerous plants, as methyl ether e. g. in eugenol which is 
likewise widely distributed. According to Goeppert (1859), ethyl alcohol 
as acetate is the odoriferous principle of Magnolia fuscata Andrews.1 
This statement has not yet been verified. It has been found as ethyl 
ester of caproic, caprylic, capric, lauric, palmitic and oleic acids in the 
volatile oil of saw palmetto by Sherman and Briggs.2 As butyrate ethyl 
alcohol is found in the oil of H. sphondilium. Isobutyl alcohol (isopropyl 
carbinol) occurs as ester of isobutyric and angelic acids in Roman 
chamomile oil; amyl alcohol (of fermentation) as caprinate in cognac 
oil and as ester of angelic and tiglinic acids also in Roman chamomile 
oil. Normal hexyl alcohol is found as acetate and butyrate in the oil 
of Heracleum giganteum, also as acetate in the oil of H. sphondylium. 
Optically active hexyl alcohol (methyl ethyl propyl alcohol) has been 
found combined with angelic and tiglinic acids in Roman chamomile oil. 
Octyl alcohol is found as acetate in the oils of H. sphondylium and 
H. giganteum', as butyrate it is the principal constituent of the oil of 
Pastinaca sativa. Besides hexyl alcohol it is also reported to occur in 
the oil of male fern. 
Of greater interest than the saturated fatty alcohols are the olefinic 
alcohol citronellol, CmHooO and the two diolefinic alcohols CioHisO. 
linalool and geraniol. 
Linalool. 
Linalool (''Licareol" of Barbier) is quite widely distributed. It is 
optically active and occurs in both modifications. So far d-linalool has 
been found in but one oil, viz. coriander oil and is, therefore, sometimes 
designated coriandrol: 1-linalool, alone or mixed with a little d-linalool, 
partly free, partly as ester, forms a constituent of the oils of lignaloe, 
bergamot, neroli, petitgrain, the Italian limette oil, Palermo lemon oil, 
of the oils of spike, lavender, muscatel sage, thyme, of Russian spear- 
mint oil, German and French basilicum oil, Cretian origanum oil. ylang- 
ylang oil and of sassafras leaf oil. 
To regenerate linalool from a crystallized derivative has so far been 
unsuccessful. Fractional distillation of the oils, which have previously 
been saponified, is used for its isolation. The constants given for linalool 
refer, therefore, always to the products obtained in this manner. If the 
alcohol obtained is to be freed from indifferent compounds, for instance 
terpinene, it may be converted into the sodium salt of the acid phthalic 
2) Pharm. Archiyes, 2, p. 110. 
i) Liebig's Annalen, 111, p. 127. The More Commonly Occurring Constituents of Volatile Oils. 
129 
ester according to Tiemann1 (1898). This is soluble in water and can 
be saponified by alcoholic potassa. The regenerated linalool must be 
removed from the alcoholic alkaline solution with ether, since it suffers 
changes when it is distilled from the alkaline solution by steam as the 
decrease in the rotatory power shows. 
According to the material employed and the method of preparation, 
products are obtained which show slight differences in their properties; 
in judging the purity of a preparation the following data may serve as 
a basis: 
for 1-linalool: b. p. 197-199°; 85-87° at 10 mm.; dis° = 0.870-0.875; 
ud2o° = 1-4630-1.4690 (Stephan,2 1898). 
B.p. 86-87° at 14 mm.; d2o° = 0.8622; no = 1.46108 (Tiemann,3 1898); 
for d-linalool: b. p. 85-86° at 12 mm.; 617.5° = 0.8726; no = 1.46455 
(Gildemeister.t 1895). 
The rotatory power is not constant, the greatest deviation so far 
observed for 1-linalool is [«]d = - 20°7',8 for- d-linalool (coriandrol) 
[a]d = +15° 1' (Barbier,8 1898). Tiemann reports for d-linalool [a]D = + 
13° 19'. 
Artificially, linalool is obtained, although only in the inactive state, 
when geraniol is heated with water to 200° in an autoclave, or when 
the different chlorides produced by the action of hydrochloric acid on 
geraniol, are treated with alcoholic potassa (Tiemann7, 1898). A 
third method of converting geraniol into linalool consists in passing 
steam through an aqueous solution of geranyl phthalate of an alkali 
which is either neutral or rendered slightly alkaline by the addition of 
an alkali carbonate (Stephan,8 1899). 
As unsaturated alcohol with two double bonds linalool also shows a 
capacity for addition. It combines with two molecules of bromine, as 
well as with the hydrohalogens. With the latter it forms compounds 
such as CioHisO.HCl, CioHisCla which, however, being liquid, are not 
suited for characterization. 
The unsaturated tertiary nature of this alcohol shows itself in its 
behavior toward reagents. Whereas alkalies scarcely act on it in the 
cold,9 organic acids change it either into geraniol or, especially in the 
presence of small amounts of sulphuric acid, into terpineol. Mineral 
i) Berichte, 31, p. 837. 
2) Jour. f. prakt. Chem., II, 58, p. 110. 
3) Berichte, 31, p. 834. 
*) Archiv d. Pharm., 233, p. 179. 
s) Compt. rend., 116, p. 1459. 
6) Bericht von S. &Co., April 1898, p. 25. 
t) Berichte, 31, p. 832. 
8) Journ. f. prakt. Chem., II, 60, p. 252. 
9) Bull. Soe. Chiin., 21, p. 549. 130 
General Part. 
acids, by the abstraction or addition of water, produce compounds 
with a cyclic structure. Thus terpin hydrate is produced by shaking 
with 5 percent sulphuric acid (Tiemann & Schmidt,1 1895). By heat- 
ing with glacial acetic acid and acetic acid anhydride there results 
besides geranyl acetate the acetate of solid terpineol, the rotation of 
which is opposite in direction of that of the linalool used. Formic 
acid, at the average temperature of 20°, also converts it into the 
esters of linalool and of the solid terpineol with opposite rotation 
(Stephan,2 1898). With moderate heat, however, (60-70°), water is 
split off with formation of the hydrocarbons dipentene and terpinene 
(Bertram & Walbaum,8 1892). 
Toward various oxidizing agents linalool behaves differently. With 
very dilute permanganate solution polyatomic alcohols are probably 
first formed with simultaneous addition of water. These cannot be 
isolated in a pure state, and are split up by further oxidation with 
permanganate or chromic acid mixture into acetone and laevulinic acid 
(Tiemann & Semmler,4 1893). In accordance with this result and in 
consideration of the fact that linalool is optically active and, therefore, 
must contain an asymmetric carbon atom, the formula of a dimethyl- 
2,6-octadiene-2,7-ol-6 
CH3. C(CH3): CH. CH2. CH2. C(CH3)(OH). CH: CH2 
has been suggested for this alcohol.5 If linalool is oxidized with 
chromic acid mixture only, it first suffers a rearrangement owing to the 
acidity of the oxidizing agent and is then changed to the aldehyde of 
geraniol, citral (Bertram & Walbaum,6 1892). The oxidation, how- 
ever, usually goes further and "Abbau" products of citral are also 
obtained, namely methyl heptenone, laevulinic acid, etc. The crystal- 
lized derivative observed by Bertram & Walbaum when oxidized with 
peroxide of hydrogen has been shown to be terpin hydrate, the forma- 
tion of which is in all probability, primarily due to the presence of 
mineral acid in the peroxide of hydrogen. 
Linalool does not add hydrogen when heated with reducing agents, 
but readily loses its oxygen with the production of the unsaturated 
hydrocarbon linaloolene CioHis. This is formed, when linalool is con- 
verted into its sodium compound, or treated with metallic sodium in 
alcoholic solution, or when heated with zinc dust to 220-230° (Semm- 
ler/ 1894). 
1) Berichte, 28, p. 2137. 
2) Journ. f. prakt. Chem., II, 58, p. 109. 
3) Journ. f. prakt. Chem., II, 45, p. 601. 
I) Berichte, 28, p. 2130. 
5) Ibidem, p. 2131. 
e) Journ. f. prakt. Chem., II, 45, p. 599. 
7) Berichte, 27, p. 2520. The More Commonly Occurring Constituents of Volatile Oils. 
131 
As already mentioned, linalool is found not only in the free state, 
but also as ester of fatty acids in volatile oils. Particularly important 
is the acetate, which possesses the characteristic odor of bergamot and 
constitutes the principal constituent of bergamot oil. In larger or 
smaller amounts linalyl acetate has been further found in French and 
English lavender oil, in Italian limette oil, in muscatel sage oil and sas- 
safras leaf oil. Of the other fatty acid esters, the butyrate and probably 
also the propionate and valerianate are contained in la vender oil. The 
valerianate also occurs in sassafras leaf oil. 
The esters of linalool that occur in volatile oils, are liquids of a more 
or less strong and pleasant odor. They cannot be distilled under atmos- 
pheric pressure without decomposition. Their synthetic preparation 
meets with difficulty in so far as linalool is fairly sensitive to acids and 
suffers rearrangement so that, while the products obtained by the 
heating of linalool with acid anhydrides or by the method of the German 
Imperial-Patent 80,711 consist for the main part of esters of linalool, 
they contain also those of geraniol and terpineol. 
For the acetic ester isolated from bergamot and lavender oils the 
following properties are recorded by Tiemann and Semmler1 (1892): 
B. p. 99-105° at 15 mm.; d2o° = 0.8951; b. p. 97-105° at 15 mm.; 
d2o° - 0.8972. 
For a preparation containing about 83 percent of acetate distilled 
from limette oil, Gildemeister2 (1895) found: 
B. p. 101-103° at 13 mm.; di5° = 0.898; <zdi5 - - 9°52'. 
Bertram and Walbaum3 (1892), however, determined the following 
constants for the acetate prepared by boiling linalool with acetic acid 
anhydride, which probably also contained the acetic esters of geraniol 
and terpineol: 
B. p. 105-112° at 11 mm.; di5° = 0.912. 
While the ester isolated from volatile oils rotates polarized light 
more or less strongly to the left, the synthetic preparation is either 
almost inactive or dextrogyrate. The dextrorotation increases with the 
quantity of linalool that has been changed to terpineol. 
As linalool yields no solid derivatives, which are suited for identifi- 
cation, it is necessary for this purpose to convert it into citral by 
oxidation, and to characterize the latter by the citryl-/?-naphtocinchoninic 
acid discovered by Doebner (see citral). 
i) Berichte, 25, pp. 1184 & 1187. 
2) Archiv d. Pharm., 238, p. 181. 
3) Jour. f. prakt. Chem., II, 45, p. 598. 132 
General Part. 
Geraniol. 
The diolefinic alcohol CioHisO geraniol ("Lemonol" Barbier and 
Bouveault; "Rhodinol" Erdmann and Huth, Poleck) is isomeric with 
linalool, but differs from it by its optical inactivity, higher boiling 
point and higher specific gravity. It is also found in the free state as 
well as in the form of esters and occurs rather frequently in volatile 
oils. While it constitutes the main part of palmarosa oil as well as of 
German and Turkish rose oil, and is contained in appreciable quantities 
in geranium, citronella and lemon grass oils, it is found in many oils 
only in small quantities, as in neroli and petitgrain oils, lavender oil 
and oil of spike, in lignaloe oil, ylang-ylang oil and sassafras leaf oil. 
As primary alcohol geraniol produces a crystalline double compound 
with anhydrous calcium chloride (Jacobsen,1 1871), which is insoluble 
in solvents like ether, ligroin, benzene, chloroform, and is decomposed 
by water into calcium chloride and geraniol. This property makes the 
preparation of chemically pure geraniol possible in a very simple 
manner (see below). For the isolation of this alcohol from mixtures 
with hydrocarbons, etc., several other methods have been reported. 
All of them involve the preparation of an acid ester of geraniol either by 
the action of phthalic acid anhydride on the sodium compound of the 
crude geraniol (Tiemann and Krueger,2 1896), or by heating geraniol 
with phthalic acid anhydride in a water bath (H. & E. Erdmann,3 1897), 
or in benzene solution (Flatau & Labbe,4 1898). This acid ester is 
saponified with alcoholic potassa either as such or its sodium salt 
which can be obtained from the silver salt purified by crystallization. 
These methods, however, possess no advantages over the calcium 
chloride method. On the contrary they are more complicated and 
yield no purer product than does the simpler method of Jacobsen. 
Geraniol prepared by one or the other of the above methods has a 
roselike odor and is a colorless, somewhat oily liquid which on longer 
standing in contact with the air changes through the absorption 
of oxygen. Its properties are reported as follows: 
B. p. 110-1110 at 10 mm.; 121° at 18 mm.; 230° under atmospheric 
pressure (Bertram and Gildemeister,5 1897). 
B. p. 120.5-122.5° at 17 mm.; d2o°~O.8894 (!); no2o° = 1.4766, 
(Tiemann and Semmler,6 1893). 
i) Liebig's Annalen, 157, p. 232. 
2) Berichte, 29, p. 901. 
3) Journ. f. prakt. Chem., II, 56, 
p. 17. 
*) Compt. rend., 126, p. 1725; Bull. Soc. 
chim., Ill, 19, p. 633. 
5) Journ. f. prakt. Chem., II, 56, p. 508. 
6) Berichte, 26, p. 2711. The More Commonly Occurring Constituents of Volatile Oils. 
133 
B. p. 110.5-111° (corr.) at 10 mm.; d^ = 0.8812, (H. and E. Erd- 
mann,1 1897). 
di5o = 0.880-0.883; nDiT°= 1.4766-1.4786, (Stephan,2 1898). 
As primary alcohol geraniol is converted by oxidation into the 
corresponding aldehyde citral, and can be again obtained from this by 
reduction (Tiemann,3 1898). Since citral can be prepared synthetically, 
geraniol must therefore be also classed with the compounds which can 
be obtained synthetically. Geraniol (besides terpineol) or its acetate 
are produced by isomerization from linalool, when this is heated for 
some time with acetic acid anhydride (Bouchardat,4 1893; Stephan,5 
1898). Obversely, geraniol can be changed to linalool by heating with 
water in an autoclave to 200°.0 At a higher temperature hydrocarbons 
and their r polymerization products are formed. The same result is 
obtained when the chlorides produced by the action of hydrochloric acid 
on geraniol are treated with alcoholic potassa (Tiemann,7 1898). A 
third method consists in decomposing the phthalate mentioned under 
linalool (Stephan,8 1899). 
In general, geraniol is not acted upon by acids to the same extent 
as linalool. Thus it is quantitatively changed into the acetate by 
boiling with acetic acid anhydride, but not isomerized. On shaking 
with dilute sulphuric acid it is changed like linalool, although with 
greater difficulty, to terpin hydrate (Tiemann and Schmidt,9 1895). 
Concentrated formic acid exerts, like potassium bisulphate or 
phosphoric acid anhydride, a dehydrating action on geraniol. While 
with potassium bisulphate a chain hydrocarbon is said to be formed 
(Semmler,10 1891), the other reagents produce terpenes. Formic acid 
produces dipentene and terpinene (Bertram and Gildemeister,11 1894 
and 1896). According to Stephan,12 formic acid, also a mixture of 
glacial acetic acid and sulphuric acid, convert geraniol as well as 
linalool into solid terpineol melting at 35°. Alkalies scarcely act on 
the alcohol in the cold. If, however, heated to 150° with a concen- 
trated alcoholic alkali solution, a tertiary alcohol CpHisO is said to 
be produced (Barbier,13 1898) by the splitting off of carbon dioxide. 
i) Journ. f. prakt. Chem., II, 56, p. 3; 
Berichte, 31, p. 359, note 1. 
2) Journ. f. prakt. Chem., Ig 58, p.110. 
3) Berichte, 31, p. 828. 
*) Compt. rend., 116, p. 1253. 
5) Journ. f. prakt. Chem., II, 58, p. 111. 
«) Bericht von S. & Co., April, 1898, 
p. 25. 
7) Berichte, 31, p. 832. 
s) Journ. f. prakt. Chern., II., 60, p. 252. 
9) Berichte, 28. p. 2138. 
io) Berichte, 24, p. 683. 
ii) Journ. f. prakt. Cheni., II, 49, p. 
185; 53, p. 236. 
12) Journ. f. prakt. Chem., II, 60, p. 244. 
13) Compt. rend., 126, p. 1423. 134 
General Part. 
This statement rests, however, on a mistake, as the alcohol produced 
is methylheptenol CsHieO (Schimmel & Co.,1 1898; Tiemann,2 1898). 
The compounds formed by the addition of bromine and the action 
of hydrohalogen on geraniol are all liquid and quite unstable. That 
the isomeric chlorides, produced by an excess of hydrochloric acid, yield 
linalool as well as geraniol when treated with alcoholic potassa, has 
already been mentioned. 
Like all primary alcohols, geraniol on oxidation with chromic acid 
mixture yields primarily an aldehyde, viz. citral CioHiuO (Semmler,8 
1891). Accompanying it are found further "Abbau" products of this 
aldehyde, so that the reaction does not at all take place quantitatively. 
On shaking with very dilute permanganate solution, polyatomic alcohols 
are propably first formed, which are oxidized by chromic acid mixture 
to acetone, laevulinic acid and oxalic acid (Tiemann and Semmler,4 
1895). Since geraniol is a primary alcohol and optically inactive, the 
following formula has been assigned to it,5 dimethyl-2,6-octadiene-2,6-ol-8 
CH3. C(CH3): CH. CH2. CH2. C(CH3): CH. CH20H. 
Like linalool geraniol occurs in volatile oils in the free state and 
also in the form of esters. As acetate it is contained (beside the normal 
capronate) in palmarosa oil, further in lemon oil. petitgrain oil and 
sassafras leaf oil; in the last also as valerianate. Combined with tiglic 
acid it occurs in geranium oil. As geraniol is fairly stable toward 
acids, its esters can be prepared artificially from acid anhydrides and 
geraniol, or also from acid chlorides and geraniol with the addition of 
pyridine (H. & E. Erdmann,0 1897 and 1898). The esters of the fatty 
acids are all liquid and the weaker in odor, the larger the molecule of 
the acid radical contained in it. For the acetate prepared by boiling 
geraniol with acetanhydride Bertram and Gildemeister,7 (1894) have 
determined the following constants: b. p. 127.8-129.2°; di5° = 0.9174; 
nDi5° = 1.4628. When distilled under ordinary pressure geranyl acetate 
decomposes, acetic acid being split off. 
Of the other esters of geraniol, diphenyl-carbaminic acid ester and 
the acid phthalic acid ester are worthy of mention, because both 
crystallize. The former is also a very suitable derivative for the identifi- 
cation of geraniol (see below), while the phthalic acid ester (m. p. 47°) 
(Flatau & Labbe,8 1898) can be used for the preparation of pure geraniol. 
i) Bericht von S. & Co., October 1898. 
p. 68. 
2) Berichte, 31, p. 2991. 
3) Berichte, 24, p. 203. 
4) Berichte, 28, p. 2130. 
5) Ibid., p. 2132. 
6) Journ. f. prakt. Chem., II, 56, p. 14; 
Berichte, 31, p. 356. 
7) Journ. f. prakt. Chem., II, 49, p. 189. 
s) Compt. rend., 126, p. 1725. The More Commonly Occurring Constituents of Volatile Oils. 
135 
If it is desired to separate the geraniol as such from a geraniol- 
containing oil, the following method of Bertram and Gildemeister1 
(1896 and 1897) is used: 
Equal parts of oil and very finely powdered calcium chloride are carefully 
triturated. The mixture, which as a result of the ensuing reaction acquires a 
temperature of up to 30-10°, is allowed to stand in a cool place in a desiccator. 
The resulting solid mass is then powdered, triturated with anhydrous ether, 
benzene or low boiling petroleum ether, transferred to a filter and freed by 
means of a pump from the compounds not combined with the calcium chloride 
by repeated washing with ether, etc. The mixture of geraniol calcium chloride 
and excess of calcium chloride thus obtained is decomposed by water, the 
separated oil washed several times with warm water and finally distilled with 
water vapor. 
The separation of the geraniol from mixtures by this method is not 
quantitative. Moreover, the oil to be worked with must consist at least 
one fourth of geraniol. The separation of geraniol from citronellol is 
described by Flatau and Labbe,2 that of geraniol from tertiary alcohols, 
e. g. terpineol, by Stephan.3 When only small amounts of material are 
available, it is better to use for characterization the diphenyl urethane 
of geraniol (CnHs^NCOOCioHi?, first recommended by Erdmann and 
Huth4 (1896) for this purpose. For the preparation of this compound 
the authors cited give the following directions:5 
1.0 g. of oil, 1.5 g. of diphenylcarbamine chloride and 1.35 g. of pyridine 
are heated for two hours in a boiling water bath. The product of the reaction 
is treated with water vapor and the residue solidifying on cooling recrystallized 
from alcohol. If much citronellol is present at the same time with the 
geraniol, it is difficult to obtain a pure preparation as citronellol also yields a 
diphenylurethane, which remains liquid. In this case urethanes are first 
obtained of a lower melting point (40-50°), which yield the pure diphenyl 
urethane of geraniol of the melting point 82.2° only after being recrystallized 
several times from alcohol. 
If geraniol is to be still further characterized, it may be converted 
into citral by oxidation and this into citryl-^-naphthocinchoninic acid 
(see citral). For this purpose the alcohol must, however, be already 
fairly pure, and must contain no linalool, as this also yields citral on 
oxidation with chromic acid mixture. 
Citronellol. 
Citronellol ("Reuni ol" Hesse, Naschold; "Rhodinol" Barbier and 
Bouveault) CioHooO, differs from linalool and geraniol by two atoms 
i) Journ. f. prakt. Chem., II, 53, 
p. 233; 56, p. 507. 
2) Chem. Centrbl., 70 >, p. 1094. 
3) Journ. f. prakt. Chem., II, 60, p. 254. 
4) Journ. f. prakt. Chem., II, 53, p. 45. 
5) Journ. f. prakt. Chem., II, 56, p. 28. 136 
General Part,. 
of hydrogen more in the molecule. Although it appears to stand in close 
relation to the alcohols cited and especially to geraniol, both being 
primary, the reduction of geraniol to citronellol has so far been unsuc- 
cessful. Geranic acid, however, has been reduced to citronellic acid 
(Tiemann,1 1898). 
Citronellol has only recently been obtained in a pure state and 
characterized as an individual chemical compound. Mixtures of it with 
geraniol have been formerly described under the name of "Rhodinol" 
(Eckart,2 1891; Barbier and Bouveault,3 1894) or "Reuniol" (Hesse,1 
1894). The "Roseol" of Markownikow and Reformatsky,5 (1893) which 
was said to be the main constituent of rose oil, has also shown itself to 
be a mixture of geraniol and citronellol. These mixtures, considered as 
individual compounds, were partly obtained from rose oil, partly from 
the true geranium oils. Now it is known, that there occurs in these 
oils, besides geraniol a second alcohol C10H200 in larger or smaller 
quantities, which on account of its identity with the alcohol C10H200 
prepared by Dodge by the reduction of citronellal has been called 
citronellol. In the geranium oils this alcohol occurs as a mixture of both 
optically active modifications, the laevogyrate predominating. Rose 
oil, however, contains only 1-citronellol. In addition to the free alcohol, 
its esters of the fatty acids have also been found. 
As geraniol and citronellol cannot be separated by fractional dis- 
tillation, either as such or after conversion into esters, it was difficult 
to obtain pure citronellol, especially since the calcium chloride method 
does not effect a quantitative separation. Pure citronellol was first 
prepared by Wallach, who noticed that geraniol when heated with water 
in an autoclave to 250° is completely decomposed with the formation 
of hydrocarbons, whereas citronellol remains unchanged.« A method 
of separation given by Tiemann and Schmidt7 (1896) depends on the 
fact that geraniol in etherial solution is changed by phosphorus tri- 
chloride partly to hydrocarbons, partly to geranyl chloride; citronellol, 
however, is converted into a chlorine-containing acid phosphoric acid 
ester, which is soluble in alkalies and therefore easily separated from 
the other compounds. The crude citronellol obtained by saponification 
of the ester is purified by distillation with water vapor. Separation is 
i) Berichte, 31, p. 2899. 
2) Archiv d. Phaj-m., 229, p. 355. 
31 Compt. rend., 119, pp. 281, 334. 
4) Journ. f prakt. Chem., II, 50, p. 
472. 
5) Journ. f. prakt. Cheni., II, 48, p. 293 ; 
Berichte. 27, Ref. p. 625. 
6) Nachrichten der Kgl. Ges. d. Wise, zu 
Gottingen, 1896, I, p. 64. 
7) Berichte, 29, p. 921. The More Commonly Occurring Constituents of Volatile Oils. 
137 
also successfully accomplished, when a mixture of both alcohols is heated 
to 200° with phthalic acid anhydride. Geraniol is destroyed by this 
treatment, while citronellol is converted into the acid phthalic acid ester, 
the sodium salt of which is soluble in water and can be saponified by 
alcoholic potassa. Another method of separating' citronellol and geraniol 
is described by Flatau and Labbe,1 who make use of the phthalic acid 
esters. 
Artificially, citronellol can be obtained from the corresponding alde- 
hyde, citronellal, by reduction with sodium amalgam and glacial acetic 
acid (Dodge,2 1889; and Tiemann and Schmidt,3 1896). The dextro- 
gyrate modification, however, is produced by this treatment. It may 
also be mentioned here that Wallach4 (189-1 and 1897) has obtained 
an alcohol C10H20C) by splitting the cycle of menthonitrile and inversion 
of the resulting aliphatic compound. This possesses great similarity to 
citronellol and is possibly identical with it. 
Pure citronellol is a colorless liquid of a pleasant rose-like odor, 
finer than geraniol. According to the manner of preparation, it shows 
slight variations in the physical properties. Wallach5 determined for 
a citronellol (reuniol) prepared by his method the following constants: 
B. p. 114-115° at 12-13 mm.; 622° = 0.856; 11022° = 1-45609; 
[a] o = - 1° 40'. 
According to Tiemann and Schmidt,6 (1896), d-citronellol formed by 
the reduction of citronellal possesses the following properties: 
B. p. 117-118° at 17 mm.; du-5° = 0.8565; ud17-5° = 1-45659; 
[«]d17-5° = + 4°. 
1-Citronellol, prepared from rose oil by the phosphorus trichloride 
method, boils under a pressure of 15mm. at 113-114°, has d2o°=O.8612, 
ud = 1.45789 and turns the plane of polarized light 4° 20' to the left.7 
For the alcohol obtained from geranium oil from the island of 
Reunion by a method similar to that of Wallach, Schimmel & Co.8 
found (1898): 
B. p. 225-226° at 764.5 mm.; du° = 0.862; 11022° = 1.45611 ; 
[a]D= -1°40'. 
J) Chem. Centrbl., 70t, p. 1094. 
2) Amer. Chem. Journ., 11, p. 463. 
3) Berichte 29, p. 906. 
4) Liebig's Annaien, 278, p. 316; 296, 
p. 129. 
5) Nachrichten d. Kgl. Ges. d. Wiss. zu 
Gottingen, 1896, I, p. 64; Nasehold, Bei- 
trage zur Kenntniss aliphatischer Terpen- 
verbindungen. Inaug. - Diss. Gottingen, 
1896, p. 56. 
6) Berlehte, 29, p. 906. 
7) Ibid., p. 923. 
8) Bericht von S. & Co., April 1898, 
p. 62. 138 
General Part. 
Citronellol is much more stable than geraniol and is not affected by 
heating with alkali. When shaken with 10 percent sulphuric acid it is 
converted by the addition of water into a diatomic alcohol, from which 
dehydrating agents regenerate citronellol (Tiemann and Schmidt,1 1896). 
To obtain from it a cyclic hydrocarbon CioHis by splitting off water 
has so far been impossible. As mentioned above several methods for its 
separation from other alcohols have been based on its stability toward 
phosphorus trichloride in the cold and the combined action of heat and 
pressure in the presence of water. 
On oxidation, citronellol as primary alcohol is first converted into 
the aldehyde citronellal CioHisO, which can be again changed to the 
alcohol by reduction with sodium amalgam. The change to the alde- 
hyde, however, is no more quantitative than that of geraniol to citral. 
Further oxidation products, like citronellic acid etc., are usually obtained 
(Tiemann and Schmidt,2 1897). If citronellol is first hydroxylized by 
cold dilute permanganate solution and the resulting polyatomic alcohol 
further oxidized with chromic acid mixture, acetone and /?-methyladipinic 
acid are obtained as decomposition products. The latter, according to 
the material used, is more or less optically active or inactive with 
the corresponding variation in melting point from 82-96°. Since 
citronellol can be converted into a cyclic alcohol, isopulegol, and from 
this into pulegone, citronellol has been regarded by Tiemann and 
Schmidt3 (1896) as dimet hyl-2,6-octene-2-ol-8, CH3.C(CH3) :CH.CH2. 
CH2. CH(CH3)CH2. CH20H. 
The esters of citronellol, of which the acetate occurs in volatile 
oils, are readily obtained by treatment of the alcohol with the respective 
acid anhydrides. The acetate is a colorless liquid of a pleasant odor, 
faintly suggesting bergamot oil. According to Naschold4 it boils 
under 15 mm. pressure at 121.5°; according to Tiemann and Schmidt5 
(1896) at 119-121° and has di7.5° = 0.8928; udi7-5° = 1.4456; 
[a]D = + 2°37'. 
The acid phthalic acid ester formed by heating citronellol with phthalic 
acid-anhydride is distinguished from that of geraniol by being liquid, 
but gives a well crystallized silver salt, from which pure citronellol can 
be regenerated (Erdmann and Huth,6 1897). 
The characterization of citronellol is effected by its oxidation to 
citronellal (see this) which is easily identified by conversion into 
1) Berichte, 29, p. 907. 
2) Berichte, 30, p. 34. 
3) Berichte, 29, p. 908. 
4) Diss., p. 49. 
5) Berichte, 29, p. 907. 
6) Journ. f. prakt. Chern., II, 56, p. 41. The More Commonly Occurring Constituents of Volatile Oils. 
139 
citronellyl-^-naphtocinchoninic acid or by the semicarbazone melting 
at 82.5° (Tiemann and Schmidt,1 1897). 
Of the aromatic alcohols but few have been found in volatile oils. 
Benzyl alcohol seems to occur as benzoate and cinnamate in Peru 
and tolu balsam, the cinnamate has also been found in storax. Small 
amounts of the free alcohol are reported to occur in Peru balsam and 
the oil of the cherry laurel. Cinnamic alcohol and its reduction product, 
phenylpropyl alcohol, occur as acetates in cassia oil; the former occurs 
also as cinnamate (styracin) in storax. 
More frequent is the occurrence of hydroaromatic alcohols, both as 
esters and in the free state. The following representatives of this group 
have been found: sabinol, CioHicO; thujyl alcohol, terpineol, borneol, 
all of the composition CioHisO; and menthol, C10H200. Whereas 
sabinol, thujyl alcohol and menthol have been found in but one oil 
each, terpineol and borneol have been found more frequently in volatile 
oils. 
Terpineol. 
By the action of dilute sulphuric acid on terpin hydrate the liquid 
terpineol of commerce is formed, which is not an individual substance, 
but a mixture of isomeric compounds CioHisO. From the results of the 
oxidation experiments carried out by Tiemann and Schmidt2 in 
1895 the conclusion may be drawn that the solid inactive terpineol 
of the melting point 35° is contained in it in considerable quantities. 
In nature, however, only the individual, solid, either optically inactive 
or active, terpineol appears to be found, the constitution of which was 
cleared up by the researches of Wallach3 (1893-1896), and of Semmler 
and Tiemann4 (1895-1896). Although liquid terpineols have been 
isolated from cardamom, kesso, and kuromoji oils and recently also 
from marjoram oil. it seems probable, however, that these may also be 
obtained in the solid state, especially since it has been found that the 
terpineol from cardamom oil can be obtained in a crystalline form.5 
Solid inactive terpineol occurs in cajuput oil; the laevogyrate 
modification is contained in niaouli oil, the dextrogyrate in lovage oil, 
cardamom and marjoram oil. in the latter, however, in the liquid form. 
1) Berichte, 30, p. 34. 
2) Berichte, 28, p. 1783. 
3) Liebig's Annalen, 275, pp. 103, 150; 277, p. 110; 291, p. 342; Berichte, 28, p. 1773. 
*) Berichte, 28, pp. 1778, 2189; 29, p. 2616. 
5) Bericht von S. & Co., Oct. 1897, p. 9. 140 
General Part. 
Besides these, liquid terpineol, in regard to the rotatory power of which 
no statements are made, has been found in camphor oil, kuromoji oil, 
kesso and erigeron oil. 
Artificially, inactive terpineol is formed according to a report by 
Bouchardat and Voiry1 (1887) by the action of very dilute sulphuric 
acid on terpin, but it is not easy to separate the solid from the liquid 
terpineol obtained. More successful is the preparation of the solid 
optically active modifications from d- or 1-limonene monohydrobromide 
by boiling with silver oxide or lead oxide according to the method 
given by Semmler2 (1895). In the simplest manner they can be 
obtained as acetates by the simultaneous action of glacial acetic acid 
and sulphuric acid (see under camphene, p. 112) on the limonenes, or 
glacial acetic acid and zinc chloride on the pinenes (Ertschikowsky,3 
1896). Further, the formation of optically active solid terpineols from 
linalool by acetic acid anhydride or formic acid (Stephan,4 1898), as 
well as of solid inactive terpineol from geraniol and formic acid5 are 
worthy of mention. 
The solid terpineol, which 'possesses the characteristic lilac odor 
of the liquid compound only to a small extent and is readily soluble in 
organic solvents, has the following properties: 
B. p. 217-218° at 760 mm.; 104-105° at 10 mm.; di5° = 0.935- 
0.940; nD20° = 1.48084;» m. p. 35°J (Wallach, 1893). 
The optical activity varies; the highest deviations observed are, 
for d-terpineol from cardamom oil [«]d = + 83°31' (Schimmel & Co.),8 for 
1-terpineol from niaouli oil [a]D =-2° 10' (Bertrand,0 1893). With 
artificially prepared 1-terpineol [a]D has been observed as high as 
-117.5° (Ertschikowsky30). 
In their chemical behavior the inactive and active modifications are 
completely alike; for a few derivatives, however, slight differences in 
the melting points have been observed. Terpineol is a tertiary unsatu- 
rated alcohol, which yields with bromine and nitrosyl chloride addition 
products, of which the latter as well as the nitrolamines produced from 
it by treatment with bases, are very well suited for characterization 
1) Coinpt. rend., 104, p. 997. 
2) Beriehte. 28, p. 2189. 
3) Journ. d. russ. phys.-chem. Ges., 28, p. 132; Abs. Bull. Soc. chlm., Ill, 16, p. 1584. 
*) Journ. f. prakt. Chern., II, 58, p. 109; II, 60, p. 242. 
5) Observations in the laboratory of 8. & Co. 
See p. 110. 
7) Liebig's Annalen, 275, p. 104. 
8) Bericht von S. & Co., Oct. 1897, p, 9. 
9) Bull. Soc. chlm., Ill, 9, p. 436; Comp, rend., 116, p. 1012. 
io) Loc. cit. Comp, also Godlewsky, Chern. Centrbl., 70', p. 1271. The More Commonly Occurring Constituents of Volatile Oils. 
141 
(see p. 142). By the action of hydrohalogen acids the corresponding 
dipentene dihydrohalides are produced, of which the dihydriodide 
C10H18I2 (m. p. 77-78°) formed by shaking with concentrated hydriodic 
acid may be used for the rapid detection of terpineol (Wallach,1 1885). 
Toward mineral acids and also some of the organic acids the alcohol is 
rather unstable. Whereas by shaking with dilute sulphuric acid it is 
converted into terpin hydrate (Tiemann and Schmidt,2 1895), by boiling 
with this reagent water is abstracted with the formation of terpinene, 
besides a little dipentene and cineol. Similar in action is potassium 
bisulphate, which yields mostly dipentene; further, phosphoric acid 
which, besides small amounts of terpinene and cineol, yields mostly 
terpinolene; and oxalic acid which likewise yields terpinolene (Wallach,3 
1893; Baeyer,4 1894). Acetic acid anhydride, especially on heating, 
also. acts as dehydrating agent with the formation of dipentene, so 
that it is impossible to convert terpineol quantitatively into its ester 
by boiling with this reagent (Ginzberg,5 1897). 
By oxidation with dilute permanganate solution terpineol is first 
converted into a polyatomic alcohol C10H2003 (m. p. 122°), from which 
by oxidation with chromic acid mixture a ketolactone CioHisOg 
(m. p. 64°) is produced. The study of this compound has been very 
useful in the determination of the constitution of terpineol, which 
accordingly is regarded as d1-terpene-8-ol.6 
ch3 ch3 
(LOH 
I 
CH 
ch2//x\ch2 
I I 
.1 I 
CH2\ , ch 
c 
CH« 
By the energetic oxidation of the terpineol, also of the ketolactone 
with chromic acid mixture or nitric acid terpenylic and terebic acids 
are formed (Tiemann and Mahla,7 1896; Godlewsky,8 1899). 
1) Liebig's Annalen, 230, p. 264. 
2) Berichte, 28, p. 1781. 
3) Liebig's Annalen, 275, pp. 104-108. 
4) Berichte, 27, p. 447. 
5) Chem. Centralbl., p. 417; Bericht von 
S. & Co., Oct. 1897, p. 69. 
6) For the literature seep. 139, foot- 
notes 3 & 4. 
7) Berichte, 29, p. 2621. 
s) Chem. Centrbl., 70i, p. 1241. 142 
Genera,! Part. 
Terpineol is of especial interest in so far as it can be converted 
into derivatives of carvone through the tribromide and nitrosochloride 
(Wallach,! 1894-96). 
The alcoholic hydroxyl group of terpineol reacts with phenyl 
isocyanate, when the two compounds are mixed and allowed to stand 
some time at room temperature. Sometimes crystals of diphenyl urea 
first separate, from which the remaining liquid mixture can be removed 
by treating it with cold anhydrous ether. On careful evaporation of 
the solvent the urethane separates out in fine needles. Recrystallized 
from alcohol it possesses the melting point 113° (Wallach,2 1893). The 
compound obtained from optically active terpineol is likewise optically 
active. The urethane can be used for identification. 
For the purpose of identification, the nitrosochloride is especially 
adapted. According to Wallach3 (1893) it is prepared in the following 
manner: 
15 g. of terpineol are dissolved in 15 co. of glacial acetic acid and 11 cc. of 
ethyl nitrite and after strongly cooling in a freezing mixture a solution of 6 cc. 
of hydrochloric acid in an equal volume of glacial acetic acid is added drop by 
drop and with constant shaking; when the reaction is completed the nitroso- 
chloride formed is precipitated by ice water. It separates as an oil, but soon 
becomes crystalline. The solid product can be purified by recrystallization from 
hot acetic ether or methyl alcohol and then melts at 112-113°. 
By treating the nitrosochloride with piperidine in alcoholic solution 
terpineol nitrolpiperidine CioHit(OH)NONC5Hio is obtained, which is 
difficultly soluble in ether and crystallizes from hot methyl alcohol in 
needles of the melting point 159-160°. This statement by Wallach 
refers to a preparation obtained from optically inactive terpineol; the 
nitrolpiperidine obtained from the optically active terpineol melts several 
degrees lower, namely at 151-152°.4 With aniline the nitrosochloride 
yields the terpineol nitrolaniline, m. p. 155-156°. 
In connection with terpineol terpin hydrate may be briefly con- 
sidered. This stands in close relation to terpineol and is formed from 
it by hydration in the presence of dilute acids. According to older 
statements it is said to occur in cardamom and basilicum oils. Recent 
observations, however, corroborating this statement have not been 
recorded. In all probability terpin hydrate was not originally contained 
in the oil, but was formed only after standing for some time. 
1) Liebig's Annalen, 281, p. 140; 291, 
p. 346. 
2) Liebig's Annalen, 275, p. 104. 
3) Liebig's Annalen, 277, p. 120. 
*) Bericht von S. & Co., April 1897, p. 9. The More Commonly Occurring Constituents of Volatile Oils. 
143 
Borneol occurs in the free state in both optically active modifications, 
in the form of ester mostly in the laevogyrate modification. The 
borneo-camphor from Dryobalanops camphora consists of d-borneol, 
while the Ngai-camphor (or Ngai-fen)1 from Blumea balsamifera is the 
laevogyrate modification of borneol found in nature. d-Borneol has 
also been found in spike and rosemary oils, as well as in Siam cardamom 
oil; 1-borneol occurs as esters and also in the free state in citronella oil 
and the oil of Matricaria parthenium as well as in valerian and kesso 
oils. In the two latter oils it occurs as acetate and isovalerianate. 
Further, borneol has been shown to be present in golden rod oil, in the 
oils from sage and thyme, as well as in the oils from Aristolochia 
serpentaria and A. reticulata, but no statements as to the direction of 
rotation of the borneol found are recorded. The acetate of this alcohol 
possesses the characteristic, fir odor and forms a large constituent of 
many coniferous oils. 
Artificially, borneol is most readily obtained from d- or 1-camphor 
by reduction with sodium in alcoholic solution (Wallach,2 1885) or in 
indifferent solvents (Beckmann,3 1888); the borneol thus prepared is, 
however, never pure, but is a mixture of borneol and isoborneol. In 
alcoholic solution less isoborneol is formed than in indifferent solvents. 
In the latter case there is obtained as by-product about 5 percent of 
camphor pinacone (Beckmann,4 1897). From the mixture of the two 
borneols pure borneol can, however, be separated by acetylization, and 
saponification of the bornyl acetate which crystallizes out. 
Pure borneol, recrystallized from ligroin, forms brilliant laminae or 
plates, which belong to the hexagonal system (Traube,5 1894). It 
possesses an odor somewhat similar to that of camphor, and reminding 
of amber. It melts at 203-204° (with preparations containing iso- 
borneol at 206-208°); the boiling point lies at 212°. Like camphor, 
borneol is also somewhat volatile at ordinary temperature, but not to 
the same extent. The specific gravity is reported by Plowman6 (1874) 
to be 1.011 for d-borneol, 1.02 for 1-borneol. 
Beckmann7 ('89 & '97) found the rotatory power of d-borneol to be 
4-37.44°. In agreement with this are the statements of Haller8 (1889) 
Borneol. 
i) Bericht S. & Co., April 1895., p. 74. 
2) Liebig's Annalen, 230, p. 225. 
3) Berichte, 21. Ref. p. 321. 
*) Journ. f. prakt. Chem., II, 55, p. 31. 
5) Journ. f. prakt. Chem., II, 49, p. 3. 
6) Pharm. Journ., III. 4, p. 710. 
Liebig's Annalen, 250, p. 353; 
Journ. f. prakt. Chem., II, 55, p. 31. 
8) Compt. rend., 109, 30; see also 
Haller, Compt. rend., 112 (1891), p. 143, 
on the influence of the solvent on optical 
activity. 144 
General Part. 
who determined for the alcohol regenerated from the crystallized 
acetate, [«]D 'to be 4-37.03°. Natural 1-borneol possesses according 
to Beckmann,1 [a]D = - 37.74°, according to Haller,2 (1889) [«]d = - 
37.77°. A slightly higher rotatory power, namely [a]D=: - 39° 25' was 
observed for the 1-borneol occuring under the name of Ngai fen 
(Schimmel & Co.3). 
The dextro- and the laevogyrate modifications of borneol are 
completely alike in their chemical behavior. Although borneol is a 
saturated alcohol, it forms loose addition products with bromine and 
hydrohalogens (Wallach,4 1885), which, however, are not suited for 
characterization. As secondary alcohol it is first converted by oxidation 
into the corresponding ketone CioHiuO, camphor, a reversal in rotation 
not taking place. By using nitric acid as oxidizing agent, oxidation 
products of camphor, like camphoric acid etc., also occur. Toward 
dehydrating agents, like zinc chloride and dilute sulphuric acid, borneol 
is very stable (Bertram and Walbaum,5 1894). In this respect it differs 
greatly from the isomeric isoborneol. Phosphorus pentachloride converts 
it into bornyl chloride. When this is boiled with aniline, hydrogen 
chloride is split off, and camphene is produced. 
As already mentioned, borneol also occurs in combination with fatty 
acids in volatile oils; more commonly as the acetate of 1-borneol, which 
has so far been shown to be present in the oil of Abies a,Iba, hemlock 
oil, oil of Picea nigra, in oil of Pinus ledebourii as well as in the 
oils of Abies balsamea and A. canadensis, further in valerian and kesso 
oils. In addition to these it has been shown to be present in the oils 
of Pinus montana, golden rod, Satureja thymbra and Thymus capitatus' 
but it is not known in which modification. 
Bornyl acetate is the only fatty acid ester of borneol which will 
crystallize. From petroleum ether it is obtained in rhombic hemihedral 
crystals, which melt at 29° (Bertram and Walbaum,0 1893). Since 
borneol is fairly stable toward acids, its esters can be prepared either 
from borneol and acid chlorides or anhydrides. They all possess 
an odor similar to the acetate, the intensity of which diminishes 
with increase in the molecular weight of the acid. Tschugaeff7 
(1898) reports on the properties of the fatty acid esters of 1-borneol as 
follows: 
, 1) Liebig's Annaien, 250, p. 353; Journ. 
f. prakt. Chem., II, 55, p. 31. 
2) Compt. rend., 108, p. 456; 109, p. 456. 
3) Bericht von S. & Co., April 1895, p. 74. 
A) Liebig's Annaien, 230, p. 226. 
5) Journ. f. prakt. Chem., II, 49, p. 8. 
6) Archiv d. Pharm., 231, p. 303. 
7) Berichte, 31, p. 1775. The More Commonly Occurring Constituents of Volatile Oils. 
145 
B. p. (15 mm) 
, 20° 
<3^5 
[«]d 
1-Borneol 
- 39.00° 
Formate 
97° 
1.0058 
- 40.46° 
Acetate 
107° 
0.9855 
- 44.40° i 
Propionate 
118° 
0.9717 
- 42.06° 
n-Butyrate 
128° 
0.9611 
- 39.15° 
n-Valerianate 
139° 
0.9533 
- 37.08° 
Similar statements were made by Bertram and Walbaum 2 in 1893. 
For the characterization of borneol the bornyl phenylurethane pro- 
duced by the action of carbanil is used. It melts at 138-139°3 and is 
optically active in the same direction as the borneol from which it is 
prepared. The addition products formed by the combination of borneol 
with chloral and bromal, of which that of the chloral melts at 56° 
(Haller,4 1891), that of the bromal at 105-109° (Minguin,5 1893), 
can also be used for the detection of borneol. Borneol may also be 
converted into camphor by oxidation with Beckmann's chromic acid 
mixture and this identified by its oxime. When acted on by formic 
aldehyde in the presence of sulphuric or hydrochloric acid, borneol is 
converted into diborneol formal (C10H17.0)aCH2 (Brochet,6 1899). 
Occasionally it is necessary to separate a mixture of borneol and 
camphor. The separation can be effected according to Haller's7 (1889) 
method by heating the mixture with succinic acid anhydride. Borneol 
is thereby converted into the acid succinic acid ester, the sodium salt 
of which is soluble in 'water and, therefore, easily separated from the 
camphor. Instead of succinic acid anhydride the corresponding deriva- 
tive of phthalic acid may be used. The esters of borneol formed by 
heating with benzoic or stearic acid anhydride are difficultly volatile 
and can be separated from camphor by distillation with water vapor. 
The camphor may also be converted into its oxime and this removed 
from the mixture by shaking with about 25 percent sulphuric acid. 
Menthol. 
Menthol is found only in the laevogyrate modification as the 
principal constituent of the peppermint oils, from which it separates in 
i) The same value was found by Haller 
In 1889 for the acetates of the borneol from 
valerian oil and Dryobalanops prepared by 
boiling with acetanhydride. Compt. rend., 
109, pp. 29 & 30. 
2) Archiv. d. Pharm., 231, p. 305. 
3) Journ. f. prakt. Chem., II, 49, p. 5. 
4) Compt. rend., 112, p. 145. 
s) Compt. rend., 116, p. 889; Bertram 
& Walbaum report 98-99° Joe. eit. 
s') Compt. rend., 128, p. 612. 
7) Compt. rend., 108, p. 1308. 146 
General Part. 
crystals on cooling. Artificially, it is obtained by reduction of menthone 
and pulegone (Beckmann and Pleissner,1 1891). With an excess of 
nascent hydrogen only menthol results from menthone. When solvents 
are used which do not themselves liberate hydrogen with sodium, some 
mentho-pinacone also is formed. 1- and d-Menthone yield by both 
methods, also with change in temperature, a strongly laevogyrate 
menthol mixture. From this 1-menthol, melting at 43°, and slightly 
dextrogyrate isomenthol, [a]n = + 2°, melting at 78-81°, can be 
separated (Beckmann,? 1897). 
Menthol crystallizes in colorless needles or prisms belonging to the 
hexagonal system. Lt is characterized by a strong peppermint odor 
and cooling taste. Its physical properties are reported as follows: 
M. p. 42°; b. p. 211.5° under 735 mm. pressure (Arth,8 1886); 
M. p. 42.3°; b. p. 212.5° under 742 mm. pressure (corr.); d^ = 0.890 
for solid, d^^ = 0.8810 for liquid menthol; [a]D46° - -49.86° for 
molten menthol (Long,4 1892); 
B. p. 215.5° under 758 mm. pressure; «D3o° - -43°45' for menthol 
in an overcooled molten condition (Power and Kleber.5 1894). 
M. p. 43°; [«]d = -49.3° (in 20 p. c. alcoholic solution); - 57.7° 
in 10 p. c. alcoholic solution (Beckmann,6 1889); nc48° - 1.4479 (Bruhl.7 
1888). 
Menthol is a saturated secondary alcohol, which by the abstraction 
of water with potassium bisulphate, zinc chloride, etc., is converted 
into the hydrocarbon menthene CioHis. By reduction with hydriodic 
acid and phosphorus, hexahydrocymene C10H20 is produced (Berken- 
heim,8 1892). Upon oxidation with chromic acid - mixture the corre- 
sponding laevogyrate ketone CioHisO, menthone, results (Beckmann,9 
1889). With potassium permanganate as oxidizing agent compounds 
are obtained which also result upon the oxidation of menthone, viz. 
ketomenthylic acid and /3-methyladipinic acid, m. p. 88-89°. In accord- 
ance with these results the accompanying formula 
i) Liebig's Annalen, 262, pp. 80 & 82. 
2) Journ. f. prakt. Chem., II, 55, pp. 19 & 30. 
3) Annales de Chim. et de Phys,, VI, 7, p. 438. 
*) Chem. Centralbl., 63 n, p. 525. 
5) Pharm. Rundschau, 12, p, 162; Archiv d. Pharm., 282, pp. 647 & 653 
6) Liebig's Annalen, 250, p. 327; Journ. f, prakt. Chem., II, 55, p. 15. 
7) Berichte, 21. p. 457. 
8) Berichte, 25, p. 688. 
a) Liebig's Annalen, 250, p. 325. The More Commonly Occurring Constituents of Volatile Oils. 
147 
CHaCHs 
XCH 
CH 
CH2//X\CH0H 
I 1 
I I 
I I 
CH2\ /CH2 
Vh 
I 
ch3 
has been given to menthol. Junger and Klages1 corroborated this 
formula in 1896 by the conversion of menthone into 3-chlorcymene. 
That menthol yields cymene when heated with anhydrous copper 
sulphate to 250-280°, had previously been found by Bruhl2 (1891). 
Of the fatty acid esters of menthol, which can be obtained in the 
same manner as those of borneol, the acetate and isovalerianate have 
been found in peppermint oil. They have been investigated by Tschugaeff3 
(1898) with special consideration of their rotatory power. According 
to this investigation, the lower esters possess the following properties: 
B. p. (15 mm) 
, 20° 
d 40 
[«]d 
Formate4 
98° 
0.9359 
- 79.52° 
Acetate 
108° 
0.9185 
- 79.42° 
Propionate ! 
118° 
0.9184 
- 75.51° 
n-Butyrate 
129° 
0.9114 
- 69.52° 
n-Valerianate 
141° 
0.9074 
- 65.55° 
Power and Kleber5 (1894) report that menthyl acetate boils at 
228° under 762 mm. pressure and that aD =- 72° 15'. With formic 
aldehyde menthol forms dimenthol formal CH2(OCioHig)2 melting at 
56.5° (Brochet6) The methyl ester of menthylxanthogenic acid (m. p. 
39°) and menthyldixanthogenate (yellow crystals) are of interest because 
they can be converted into menthene of a high rotatory power 
(Tschugaeff,7 1899). 
With its peculiar physical properties the identification of menthol 
will hardly offer any difficulty. If it does, however, the menthylphenyl 
1) Berichte, 29, p. 304. 
2) Berichte, 24,. p. 3374. 
3) Berichte, 31, p. 364. 
*) Solidifies at a low temperature and 
melts at + 9°. 
5) Pharm. Rundschau, 12, p. 162: 
Archiv d. Pharm., 232, p. 653. 
6) Compt. rend., 128, p. 612. 
7) Berichte, 32, p. 3332. 148 
General Part. 
urethane produced by the action of phenyl isocyanate may be used for 
this purpose. This compound, first prepared by Leuckart, melts at 
111-112°, and is optically active in the same direction as the menthol 
from which it is prepared. When heated with sodium ethylate menthol 
is regenerated, but also inactivated (Beckmann,1 1897). 
A further derivative, by means of which menthol is easily character- 
ized, is the menthyl benzoate produced by heating it with benzoic acid 
anhydride. The ester is difficultly volatile with water vapor and melts 
at 54.5° (Beckmann,2 1891 and 1897). 
The separation of a mixture of menthol and menthone may be 
accomplished in the same manner as that given for borneol (Beck- 
mann.3 1897). 
As previously stated, the sesquiterpenes are frequently accompanied 
by so-called sesquiterpene alcohols C15H26O, which upon dehydration yield 
hydrocarbons C15H24. They are colorless, and when pure mostly odorless. 
With the exception of the liquid santalol they have a marked tendency 
to crystallize. The following table contains a compilation of their 
physical properties together with those of several other alcohols of 
different composition. 
Formula 
M. p. 
B. p. 
Optical 
behavior 
Maticocamphor 
Ci2H2oO 
94° 4 
300-302° 
[aJD- - 28° 5 
Kessylalcohol6 
C14H24O2 
85° 
155-156° 
(11 mm) 
laevogyrate 
Santalcamphor 7 
C15H24O2 
104-105° 
- 
- 
Cedrol 
C15H26O 
85-86° 8 
282°9 
- 
Cubebcamphor 
C15H26O 
65-67°10 
248° 11 • 
laevogyrate 
Guaiol12 
Ci5H26O 
91° 
288° 
148° (10 mm) 
- 
Ledumcamphor13.... 
C15H26O 
104-105° 
282-283° 
[«]i = + 7.98° 
Patchoulialcohol 
Sesquiterpenhydrate 
C15H26O 
56°14 
- 
[a]D--U8°15 
from pepper16 
C10H16.2 h2oy 
164° 
- 
- 
Santalol17 
C15H26O 
liquid 
(dis°=0.980) 
167-169° 
(10-12 mm) 
[a]D to-31° 
Junipercam ph or18... 
Ylang-ylang- 
- 
165-166° 
- 
- 
camphor19 
- 
138° 
- 
- 
1) Journ. f. prakt. Chem., II, 55, p. 29. 5) Traube, Zeitschr. f. Krystallogr., 22, 
2) laebig's Annalen, 262, p. 31; Journ. p. 47. 
f. prakt. Chem., II, 55, p. 16. 6) Bertram & Gildemeister, Archiv d. 
3) Journ. f. prakt. Chem., II, 55, p. 17. Pharm., 228, p. 488. 
*) Kugler, Berichte, 16, p. 2841. 7-is) See next page. The More Commonly Occurring Constituents of Volatile Oils. 
149 
Aldehydes. 
Among the oxygenated constituents of volatile oils characterized by 
a strong odor are several aldehydes. Of the fatty aldehydes, acetaldehyde 
is found in the distillate of almost all seeds. Isovalerianic aldehyde and 
acetaldehyde have also been observed in the distillate of various 
eucalyptus oils, of cajeput oil and peppermint oil. The aldehyde of 
oleic acid has been found in orris oil. 
Of much greater importance, however, are the so-called aliphatic 
•terpene aldehydes, citral, CioHi«O and citronella!, CioHisO; and the 
aromatic aldehydes, benzaldehyde and cinnamic aldehyde. The former 
are also of special interest on account of their relation to important 
alcohols occuring in oils, the latter because of the laTge percentage 
present in some oils. 
Citral. 
Citral is the only aldehyde corresponding to the formula CioHiqO, 
which has so far been isolated from volatile oils. On account of its 
close relation to geranial, being its first oxidation product, it is also 
called geranial. It occurs quite frequently in nature. It was first20 found 
in the oil of Backhousia, citriodora and as it proved to be identical with 
the constituent to which lemon oil owes its odor, it was called citral. In 
larger quantity (70-80 percent) it is contained in lemongrass oil and 
occurs further in orange oil. mandarin and cedron oils, in West Indian 
limette oil. in the oils of verbena, balm, bay, pimenta, Japanese pepper, 
sassafras leaves and of Eucalyptus staigeriana. 
From all these oils citral can be isolated by means of the crystalline 
bisulphite double compound (see later), which, after previous purification 
by washing with alcohol and ether, yields citral in a pure state by 
decomposing it with alkali carbonate. 
7) Bericht von S. & Co., Oct. 1891, p. 
34; Berkenheim, Chern. Centralbl., 64', 
p. 986. 
8) Bericht von S. & Co., Oct. 1897, 
p. 12. Footnote. 
9) Walter, Liebig's Annalen, 39, p. 247; 
48. p. 35. 
io) Schaer & Wyss, Archiv d. Pharm., 
206, p. 316; Winckler, Liebig's Annalen, 
8, p. 230. 
ii) Schmidt, Berichte, 10, p. 189. 
12) Bericht von S. & Co., April 1892, p. 
42; Wallach, Liebig's Annalen, 279, p. 396. 
13) Hjelt, Berichte 28, p. 3087. 
i*) Wallach. Liebig's Annalen, 279, 
p. 394. 
is) Montgolfier, Conipt, rend., 84, p. 89. 
is) Peinemann, Archiv d. Pharm., 234, 
p. 241. 
it) Observations made in the labora- 
tory of Schimmel & Co. 
18) Bericht von S. & Co., Oct. 1895 
p. 46. 
19) Ibidem, April 1896, p. 62. 
20) For the history of citral see Tie- 
mann, Berichte, 31, p. 3278. 150 
General Part. 
Artificially, citral is obtained with a yield of 20-40 percent by the 
oxidation of geraniol with chromic acid mixture (Tiemann,1 1898). 
The tertiary alcohol linalool also yields the same oxidation product, 
since a transformation of the linalool to geraniol first takes place by 
the action of the acid oxidizing agent. In a purely synthetical way 
citral has been obtained by the distillation of a mixture of calcium 
gereniate and calcium formate (Tiemann,2 1898). 
Citral is a mobile, slightly yellowish, optically inactive oil of a 
penetrating lemon odor, which boils at 228-229° under atmospheric 
pressure, not entirely without decomposition. Its properties were given, 
by Tiemann and Semmler3 in 1893 as follows: 
B. p. 110-112° at 12 mm.; 117-119° at 20 mm.; 120-122° at 
23mm.; di5° = 0.8972; d22° = 0.8844; nm5° = 1.4931; ud22° = 1.48611. 
Observations made in the laboratory of Schimmel & Co. on an 
aldehyde carefully purified by means of the bisulphite compound gave 
the following results: 
B. p. 110-111° at 12 min.; di5° = 0.893; uDit° = 1.49015. 
As diolefinic aldehyde, citral takes up 2 molecules of bromine, but 
yields with it no solid compound. Toward acids and acid agents it 
is very sensitive and is greatly changed by them. Dilute sulphuric acid 
and potassium bisulphate act very energetically with abstraction of 
water and formation of cymene. Alkalies also act on citral. When 
boiled with potassium carbonate solution it is split up into acetaldehyde 
and methylheptenone CsHi40 (Verley,4 1897; Tiemann,5 1899). This 
ketone also accompanies citral, e. g. in lemongrass oil, and is also 
formed from it by gentle oxidation. 
Citral shows all the properties of an aldehyde; thus it is changed 
by reduction to geraniol (Tiemann,6 1898) and reacts with the well- 
known aldehyde reagents. It shows a peculiar behavior toward sodium 
bisulphite solution (Tiemann and Semmler,7 1893; Tiemann,8 1898). 
If the solution does not contain too great an amount of free 
sulphurous acid, there separates upon shaking at a low temperature the 
difficultly soluble, normal crystallized double compound C9H15. CH(0H)- 
SOsNa, which cannot be quantitatively split up by sodium carbonate or 
caustic soda. If the crystallized compound be allowed to stand with an 
excess of bisulphite solution at a moderate heat, it will again be dis- 
1) Berichte, 31, p. 3311. 
2) Berichte, 31. p. 827. 
3) Berichte, 26, p. 2709. 
4) Bull. Soc. chim., III. 17, p. 175 
5) Berichte, 32, p. 107. 
6) Berichte, 31, p. 828. 
7) Berichte, 26, p. 2710. 
8) Berichte, 31, p. 3310. The More Commonly Occurring Constituents of Volatile Oils. 
151 
solved with the formation of a dihydrosulphonic acid derivative of citral. 
C9H17. (S03Na)2. CHO. which no longer regenerates citral with alkali 
carbonate, but does so with caustic alkali. If the temperature rises too 
high during the solution of the crystallized compound, caustic alkali 
also fails to separate citral from the liquid, a sodium salt of a dihydro- 
sulphonic acid derivative which cannot be split up, having been formed. 
This compound is likewise formed, citral being simultaneously regenerated 
in part, when the normal bisulphite compound is suspended in water 
and treated for some time with water vapor until it is dissolved. If 
the solution of the citral-dihydrosulphonate of sodium is shaken with 
citral, this is taken up and the disulphonate is changed to citral- 
hydroxymonosulphonate of sodium which is readily decomposed by 
alkalies. 
The compounds of citral with hydroxylamine, phenyl hydrazine and 
ammonia, are all liquid and therefore cannot be used for the character- 
ization of citral. The oxime is changed to the nitrile of geranic acid 
by splitting off water with acetic acid anhydride. With semicarbazide, 
several well crystallizable semicarbazones (Wallach,1 1895; Tiemann 
and Semmler,2 1895; Tiemann,3 1898) are produced, which under certain 
conditions can be resolved into compounds of a definite melting point 
164° and 171°, and may therefore be used for the identification of citral 
(Tiemann4 1898). 
When oxidized with mild oxidizing agents, e. g. silver oxide in 
ammoniacal solution, liquid geranic acid is formed (Semmler,5 1890-'91), 
which has an odor similar to that of the higher fatty acids. Upon 
energetic oxidation with chromic acid mixture methylheptenone results 
(Tiemann and Semmler,6 1893), which on further oxidation with 
potassium permanganate and chromic acid mixture is decomposed to 
acetone and laevulinic acid.7 In harmony with these results citral is 
regarded as dimethy 1-2,6-octadiene-2.6-al-8. 
CH3. C(CH3): CH . CH2. CH2. C(CH3): CH. CHO. 
This formula corresponds with that of geraniol and agrees well with the 
reactions of citral. 
It is worth mentioning, that by condensation with acetone, citral 
yields a ketone Ci3H2oO, pseudoionone, which when heated with dilute 
sulphuric acid is converted into ionone, a compound isomeric with the 
1) Berichte, 28, p. 1957. 
2) Berichte, 28, p. 2133. 
3) Berichte, 31, pp. 821, 2315. 
Berichte, 31, p. 3331. 
5) Berichte, 23, p. 3556; 24, p. 203. 
6) Berichte, 26, p. 2718. 
7) Ibidem, p. 2128. 152 
General Part. 
irone of orris oil, and which like the latter has the odor of violets 
(Tiemann and Krueger,1 1893). 
Inasmuch as citral possesses a penetrating odor, this in itself 
attracts attention to its presence in volatile oils. For more positive 
proof the separation of the aldehyde by its bisulphite compound is 
tried. The regenerated citral is converted by condensation with pyro- 
tartaric acid and /5-naphthylamine into the a-citryl-/3-naphthocinchoninic 
acid discovered by Doebner2 in 1894 who directs this characteristic 
compound to be prepared as follows: 
20 g. of pyrotartaric acid and 20 g. of citral (or the oil in question) are 
dissolved in absolute alcohol, to this solution 20 g. of ^-naphthylamine, likewise 
dissolved in absolute alcohol, are added and the mixture boiled with a reflux 
condenser for about 3 hours on a water bath. After cooling, the citrylnaphtho- 
cinchoninic acid which has separated in a crystalline state is filtered off and 
purified by washing with ether. If the acid is too impure it is dissolved in 
ammonia a,nd separated from the filtered solution by neutralizing with acetic 
acid. The pure compound thus obtained crystallizes from alcohol in yellow 
leaflets. According to Doebner3 it melts at 197°, but the melting point will 
generally be found at 200° or slightly above. 
In the preparation of the naphthocinchoninic acid it must be re- 
membered that with a small citral content a-methyl-/3-naphthocinchoninic 
acid is formed, due to the decomposition of a part of the pyrotartaric 
acid used. This compound does not melt until 31(1° and is more diffi- 
cultly soluble in alcohol than the citrylnaphthocinchoninic acid. It 
therefore remains in the residue when the crude naphthocinchoninic acid 
is exhausted with hot alcohol. 
Further it must be remembered that when other aldehydes are 
present with citral the naphthocinchoninic acids resulting from these are 
formed at the same time. Thus Doebner found in fractions of lemon oil 
besides the citryl-compound also citronellyl- '-naphthocinchoninic acid 
(m. p. 225°). 
Citral-semicarbazone, m. p. 164°, is prepared in the following 
manner: 
To a solution of 4 parts of semicarbazide chlorhydrate in a little water a 
solution of 5 parts of citral (or of the fraction to be tested) in 30 parts of 
•glacial acetic acid is added. After a short time considerable quantities of a 
semicarbazone separate in needles, which after two or three recrystallizations 
from methyl alcohol have the constant melting point of 164°. From the mother 
liquid filtered from this semicarbazone the compound melting at 171° can be 
obtained (Tiemann,4 1898-'99). 
1) Berichte, 26, p. 2675. 
2) Berichte, 27, pp. 354, 2026. 
3) Loc. cit.; Berichte, 31. p. 1888 ; comp, 
also Berichte, 31. pp. 3197 & 3327. 
4) Berichte, 31, p. 3331: and 32, p. 115. The More Commonly Occurring Constituents of Volatile Oils. 
153 
A well crystallized derivative of citral, which is equally well suited 
for detection as for the approximate quantitative determination, is the 
citralidenecyanacetic acid C9H15. CH : C(CN). COOH melting at 122°, and 
produced by the condensation of citral with cyanacetic acid in the 
following manner: 
Two mol. of sodium hydroxide (as 30 percent soda solution) and one mol. 
of citral are added to a solution of one mol. of cyanacetic acid in about three 
times as much water. When pure, the citral dissolves completely on shaking. 
From the clear solution - purified if necessary by extracting with ether - acids 
separate the citralidencyanacetic acid in a crystalline form or as an oil which 
soon solidifies. By dissolving in benzol and precipitating with ligroin it can be 
obtained in compact yellow crystals (Tiemann.1 1898). 
Citral likewise forms a solid condensation product with acetyl 
acetone. 
It is obtained when 15.2 g. of citral are condensed with 20 g. of acetyl- 
acetone at room temperature with the aid of 10 drops of piperidine. After 
standing for three days the entire mixture congeals to a solid mass of crystals, 
from which, by recrystallization from a mixture of alcohol, ether and ligroin, 
the citralidenebisacetylacetone is obtained in light yellow warts melting at 
■16-48° (K. Wedemeyer,2 1897). 
Tiemann3 recommended to determine the presence of citral by con- 
densing it with acetone to pseudoionone and identifying this by its 
semicarbazone. This method, however, is more troublesome than the 
preparation of the citrylnaphtocinchoninic acid, so that the latter will 
undoubtedly be preferred as a means of identification. 
The ionone controversy has caused an unusual activity in the chemical study 
of citral during the year 1899. The results are of such a nature that it is 
impracticable to incorporate them into a work of this kind at least at present. 
Not only do different investigators interpret the same results differently, but 
different investigators obtained different results in what is supposed to be the 
same experiment. Furthermore, one and the same investigator has found it 
necessary to correct his own statements within a few months. It is necessary, 
therefore, not only to question the arguments made in the excitement of a 
controversy, but at times the experiments as well. For the benefit of those 
who desire to go into the details of the subject the following bibliography 
for 1899 is herewith appended. 
Bouveault: Isomeric aldehydes from lemon grass oils.4 
Nature of isomerism of the two lemonals.5 
Barbier: Lemonal from the essential oil of Lippia citriodora.^ 
Corie: Citral in pure oil of lemon.7 
1) Beriehte, 31, p. 3329. 
2) Ueber Condensationen mittelst aro- 
matischer Basen u. s. w. Inaug. Diss. 
Heidelberg, p. 24. 
3) Beriehte, 31, p. 822. 
4) Bull. Soc. Chim., 13], 21, p. 419. 
5) Ibidem, p. 923. 
6) Bull. Soc. Chim., [3], 21, p. 635. 
7) C. & D., 54, p. 650. 154 
General Part. 
Flatau: Essential oils of lemon-grass and citronella.1 
Flatau & Labbe: Method for separation of citronella! and citral.2 
Labbe: On lemongrass oil.3 
A polymeride of citral.4 
On barium acid sulphite addition products of citral and citronella!.5 
Stiehl : Three lemongrass aldehydes.6 
Tiemann: On the action of alkaline and acid reagents on citral.7 
On the behavior of citral purified according to different methods toward 
semicarbazide.8 
On the hydroxy sulphonates of cinnamic aldehyde, citronellal and citral.9 
On the separation of citral from citronellal and methyl heptenone.10 
On the three lemongrass aldehydes of Mr. W. Stiehl.11 
On natural citral and the composition of oil of lemon grass.12 
A number of these articles by the late Professor Tiemann have been 
published in book form. 
Vebley: Action of acids on citral.13 
Condensation of citral with cyanacetic acid.14 
Condensation of citral with malonic acid.15 
The report of Professor v. Baeyer as expert in the ionone proceedings has 
been published by A. W. Schade of Berlin. 
Citronellal. 
The second aliphatic aldehyde with ten carbon atoms found in 
volatile oils is citronellal CioHisO, which occasionally occurs accompany- 
ing- citral, the dihydroderivative of which it appears to be. Citronellal 
is distinguished from citral by being optically active, but has up to the 
present been found only in the dextrogyrate modification, it is probable 
that citronellal with a low rotatory power is a mixture of both optically 
active modifications. d-Citronellal is found in citronella oil and in the 
oil of Eucalyptus maculata var. citriodora. Its presence has also been 
shown in the oil of Eucalyptus deaIbata, in balm oil, and besides citral, 
in lemon oil. Whether it is contained in mandarin oil has not been 
definitely determined. 
The isolation of this aldehyde from the oils rich in citronellal 
(citronella oil, oil of Eucalyptus maculata) offers no difficulty, since 
citronellal can be readily separated in the form of its crystalline 
bisulphite compound. As citronellal is very sensitive to acids, as well 
i) Bull. Soc. Chim. [3], 21, p. 158. 
2) Chem. Centrbl., 70i, p. 1094. 
3) Bull. Soc. Chim. [3], 21, p. 77. 
4) Ibidem, p. 407. 
5) Ibidem, p. 1026. 
6) Johrn. pr. Chem., 167, p. 497. 
7)-Berichte, 32, p. 107. 
s) Ibidem, p. 250. 
9) Bull. Soc, Chiin. [3], 21, p. 196. 
io) Berichte, 32, p. 812. 
ii) Ibidem, p. 827. 
12) Ibidem, p. 830. 
13) Bull. Soc. Chim. [3], 21. p. 408. 
14) Ibidem, p. 413. 
is) Ibidem, p. 414. The More Commonly Occurring Constituents of Volatile Oils. 
155 
as to alkalies, alkali carbonate is used for the decomposition of the 
bisulphite compound. Artificially, citronellal can be obtained by the 
oxidation of the primary alcohol citronellol C10H200, but the yield in 
this case is still smaller than when geraniol is oxidized to citral. In 
this manner the laevogyrate modification which has so far not been 
found in nature Ims .been prepared from the 1-citronellol of rose oil. 
By splitting the cycle of menthoxime Wallach1 (1894 and 1897) 
has obtained an aldehyde CioHisO, designated by him as "Mentho- 
citronellal." which possesses great similarity to the naturally occurring 
citronellal and is probably identical with it. 
Citronellal boils under atmospheric pressure at 205-208°, under 
15 mm. pressure at 103-105°; its specific gravity was found at 17.5° 
to be 0.8538; the index of refraction nn = 1.4481 (Tiemann and 
Schmidt,2 1896). The optical rotation [a]n was found by Kremers3 
(1892) to'be + 8.18°. Recently, however. Tiemann and Schmidt2 have 
found [a]D=+ 12°30' for a preparation regenerated from the bisulphite 
compound. 
Citronellal has but one double bond. When reduced with sodium 
amalgam in alcoholic solution, being constantly kept slightly acid by 
the addition of acetic acid, it is converted into the primary alcohol 
citronellol CioHaoO (Tiemann and Schmidt4). Upon careful oxidation 
with silver oxide the corresponding oily citronellic acid C1OH18O2 is 
produced (Semnder,5 1891 and 1893). Like citral, citronellal is very 
sensitive toward alkalies and acids; but while citral, when treated 
with alkali, is split up into acetaldehyde and methylheptenone, citronellal 
is completely resinified. In contact with acids cymene is formed from 
citral, by splitting off water. Citronellal, however, is converted into the 
isomeric isopulegol (Tiemann and Schmidt,6 189(5-'97). This is 
isomeric, with the alcohol pulegol CioHisO, resulting upon reduction o^ 
pulegone, and yields when oxidized a ketone CioHioO, which can be 
inverted to natural pulegone. For corrected physical constants of pule- 
gone and isopulegone the more recent work of Harries and Roeder7 
should be consulted. Whether isopulegol, which has been found in 
commercial citronellal by Tiemann8 occurs in the natural oils from 
which citronellal is obtained or whether it is formed upon standing has 
not yet been determined. Labbe9 is of the opinion that whereas 
1) Liebig's Annalen, 278, p. 317; 296, p.131. 
2) Berichte, 29. p. 905. 
s) Amer. Chern. Journ., 14, p. 203. 
4) Loe. cit., p. 906. 
5) Berichte, 24, p. 208; 26, p. 2256, 
6) Berichte, 29, p. 913; 30, p. 22. 
7) Berichte, 32, p. 3357. 
s) Berichte, 32, p. 825. 
9) Bull. Soc Chim. [3J, 21. p. 1023. 156 
General Part. 
citronellal when mixed with terpenes and terpene alcohols is relatively 
stable, when pure it is easily converted into its isomeric cyclic com- 
pounds. 
Toward sodium bisulphite citronellal behaves much as does citral. 
Besides the crystallized normal addition product with one molecule of 
NaHSOs, in which the bisulphite has added itself to the aldehyde group, 
it also yields hydrosulphonic acid derivatives with one or two molecules 
of NaHSO.3. The addition may take place at the double bond only, or 
at both the double bond and the carbonyl group (Tiemann,1 1898). 
With hydroxylamine citronellal forms a liquid oxime, which by the 
abstraction of water is converted into the nitrile of citronellic acid 
(Semmler,2 1893). The semicarbazone resulting with semicarbazide is, 
so far as present observations show, a single substance, and is well 
suited for the identification of citronellal. It separates quantitatively 
when an alcoholic solution containing the aldehyde is shaken with a 
solution of semicarbazide chlorhydrate and sodium acetate. The crude 
compound, by recrystallization from chloroform and ligroin is obtained 
in white leaflets, melting at 84° (Tiemann and Schmidt,3 1897). 
By energetic oxidation citronellal yields the same products as 
citronellol, i. e., acetone and p'-methyladipinic acid (Tiemann and 
Schmidt,4 1896). Corresponding to citronellol the aldehyde is to be 
regarded as dimethyl-2,6-bctene-2-al-8 CHs . C(CHa) : CH . CH2 . CH2 . 
CH(CH3) . CH2 . CHO (T. & S5). 
Like citral, citronellal reacts with pyrotartaric acid and ^-naphthyl- 
amine yielding a-citronellyl-/?-naphthocinchoninic acid (Doebner,0 1894) 
which can be used for its detection. It is prepared like the citral 
compound. The crude naphthocinchoninic acid is recrystallized from 
alcohol containing hydrochloric acid, the hydrochloride obtained is 
dissolved in ammonia and the ammonium salt decomposed by acetic 
acid. The compound so purified crystallizes from dilute alcohol in 
colorless needles, and melts at 225°. By heating it above its melting- 
point it splits off carbon dioxide and is converted into citronellyl-?- 
naphthochinoline, a base crystallizing from dilute alcohol or ligroin in 
needles of satin-like lustre melting at 53°. 
Citronellal can be identified by the semicarbazone (see above) more 
rapidly thaft by the naphthocinchoninic acid. 
i) Berichte, 31, p. 3305. 
2) Berichte, 26, p. 2255. 
3) Berichte, 30, p. 34; 31, p. 3307. 
4) Berichte, 29, p. 908. 
5) Ibidem, p. 918. 
6) Berichte, 27, p. 2025. The More Commonly Occurring Constituents of Volatile Oils. 
157 
Of aldehydes with cyclic structure 
Furfurol C4H4O 
should first be mentioned, the occurrence of which in oil of cloves and 
oil of clove stems has been observed. Its formation is probably due to 
the decomposition of a carbohydrate-like compound. Inasmuch as it 
possesses the property of gradually becoming darker in color it is 
surmised that the darker color acquired by some oils upon standing 
is due to the presence of this substance. Furfurol has recently been 
also found in the oil from musk seed 1 and that of caraway seed.2 It is 
identified by means of its hydrazone and by the color reactions it 
produces with aniline and p-toluidine. 
The following carbocyclic aldehydes have been found: 
Benzaldehyde CeHs.CHO 
in the oils of bitter almond, cherry laurel, wild cherry bark and of Indigo- 
fern galegoides. It possibly also occurs in the oil of cinnamon leaves. 
Salicylic aldehyde C3H4 . OIF2]. CHOI1! 
(o-oxybenzaldehyde) in spirea oil from Spiraea ulmaria, Sp. filipendula, 
Sp. digitata, Sp. lobata, and in the oil of Crepis foetida. 
Anisic aldehyde C«H<. OCRs™. CHOW 
(p-oxybenzaldehyde-methylether) in old anise and fennel oils, in which 
it is formed by the oxydation of anethol. 
CUMINIC ALDEHYDE CeHi. C3H7M . CHO™ 
(p-isopropylbenzaldehyde) in cumin oil, in the oil of Cicuta virosa, also 
in various eucalyptus oils (E. haemastoma, odorata, oleosa, populifera). 
Vanillin 
(m-methoxy-p-oxy benzaldehyde) C«H3. OHM. OCH3M. CHOW and 
Heliotropin 
(protocatechnic aldehyde methylene ether) C3H3 . OOCHo™3! . CHOW in 
spirea oil. 
Cinnamic aldehyde CeHs ..CH: CH. CHO 
in cassia oil, Ceylon cinnamon oil, the oil of cinnamon leaves and roots, 
also in the oil of Cinnamonrum loureirii. 
O-CUMARIC ALDEHYDE METHYLETHER 
(o-methoxycinnamic aldehyde) CcH4.0CH3W . CH : CH . CHOW in cas- 
sia oil. 
i) Bericht S. & Co., Oet. 1899, p. 36. 
Ibidem, p. 32. 158 
General Part. 
Ketones. 
The aliphatic ketones are represented in volatile oils by a few 
members only. Of the saturated ketones only acetone CH3.CO.CH3, 
methyl amyl ketone CHs. CO. C5H11 and methyl nonyl ketone CH3. CO . 
C9H19; of the unsaturated only methyl heptenone CsHnO has been 
found. In the distillate, especially of leaves, acetone has frequently been 
observed together with methyl alcohol, e. g. in that of patchouli, coca, 
and tea leaves. Towhat reaction this ketone owes its origin is not known. 
Methyl amyl ketone is contained in the low-boiling fractions of clove 
oil and imparts to it a pleasant odor. Methyl nonyl ketone is the 
principal constituent of oil of rue and separates from this upon cooling 
(m. p. 15°), and can also be readily separated by shaking with 
bisulphite solution. 
Methyl heptenone. 
Of greater interest than the saturated ketones named is the 
unsaturated methyl heptenone CsHnO, which occurs as a constituent 
of some volatile oils and is also obtained as a decomposition product 
of related compounds. Accompanying the bodies closely related to it, 
linalool, geraniol and citral, it occurs in lignaloe, citronella and lemon- 
grass oils. It evidently owes its existence to the decomposition of these 
compounds, which can also be brought about artificially by mild 
oxidation. It can be easily isolated by means of its bisulphite addition 
product from the fraction 160-180° of the oils named. 
As a product of decomposition it was first observed by Wallach 
(1890) in the dry distillation of cineolic acid anhydride.1 It was also 
obtained as a saponification product of geranic acid nitrile (Tiemann 
& Semmler,2 1893) and as oxidation product of citral3 and finally by 
the splitting up of the latter with alkalies (Verley,4 1897), Synthetically, 
it has been prepared from amylene bromide and acetyl acetone (Barbier 
& Bouveault,5 1896) also from the iodide of acetopropyl alcohol, acetone 
and zinc dust (Verley,6 1897). 
It is a colorless, mobile, optically inactive liquid, with a penetrating 
amyl acetate-like odor. The physical constants, as given, do not wholly 
agree. Wallach7 (1890) found for the ketone formed from cineolic acid 
anhydride: 
1) Liebig's Annalen, 258, p. 323. 
2) Berichte, 2fi, p. 2721. 
3) Ibidem, p. 2719. 
4) Bull. Soc. chim. Ill, 17, p. 175. 
5) Gompt. rend., 122, p. 1422. 
6) Bull. Soc. chim. Ill, 17, p.-191. 
7) Liebig's Annalen, 258, p. 325. 77/e More. Commonly Occurring Constituents of Volatile Oils. 
159 
B. p. 173-174°; d20° = 0.853; un = 1.44003. 
Tiemann and Kruger3 (1895) determined for natural methylheptenone: 
B. p. 170-171°; d20° -0.8499; nD = 1.4380; 
and Verley2 (1897 ) reports for a preparation obtained by splitting up 
citral: 
B. p. 168°; 84° at 56 mm.; di<° = 0.910 (!); hdsio = 1-437. 
According to observations made in the laboratory of Schimmel & Co. 
methylheptenone, which had been isolated from lemongrass oil and 
regenerated from the bisulphite compound shows: 
B. p. 170-171° (758 mm); di5° = 0.858; nm 5° = 1.44388 
and a preparation made from citral by boiling with potassium carbonate 
solution : 
B. p. 173-174°; di5° = 0.8656. 
Upon reduction with sodium in alcoholic solution methyl heptenone 
is reduced to the secondary, alcohol, methyl heptenol (Wallach,3 1893), 
which is obtained as decomposition product of geraniol, also by the 
saponification of gerauic acid nitrile. It combines with bisulphites to 
form crystalline addition products; with hydroxylamine and phenyl- 
hydrazine to form liquid condensation products and with semicarbazide 
to form a crystallized semicarbazone, which can be used for identification. 
Upon oxidation, methylheptenone decomposes in correspondence with 
the formula 
CH8. C(CH8): CH. CH2. CH2. CO. CHS 
(methyl-2-heptene-2-one-6) into acetone and laevulinic acid CsHgOs 
(Tiemann and Semmler,4 1895). Dehydrating agents, like zinc chloride, 
etc., convert it into dihydro-m-xylene CsHi2 (Wallach,5 1890). 
Methylheptenone is easily recognized by its characteristic amyl 
acetate-like odor. For purposes of identification it is converted into the 
semicarbazone, which, like the corresponding citral compound appears 
to be a mixture of isomers, but is nevertheless obtained of a constant 
melting point when it is prepared according to the directions given by 
Tiemann and Kruger 6 (1895): 
A solution of 12 g. of semicarbazide hydrochloride and 15 g. of sodium 
acetate in 30 cc. of water is added to a mixture of 12 g. of methylheptenone 
and 20 cc. of glacial acetic acid and allowed to stand for some time (^ hour). 
Upon the addition of water the semicarbazone separates as an oil which soon 
solidifies and after recrystallization from dilute alcohol melts at 136-138°. 
1) Berichte, 28, p. 2123. 
2) Loc. cit., p. 176. 
3) Liebig's Annalen, 275, p. 171. 
4) Berichte, 28, p. 2128. 
5) Liebig's Annalen, 258, p. 326. 
6) Berichte, 28, p. 2124. 160 
Genera,! Part. 
A derivative which is also well suited for identification is obtained 
when methyl heptenone is treated with bromine in the presence of soda 
solution (Tiemann and Semmler,1 1893). Hypobromous acid is added 
and bromine is substituted with the formation of the well crystallized 
compound CsH^BrsO. OH. 
3 g. of ketone are shaken with a solution of 3 g. of sodium hydroxide and 
12 g. of bromine in 100 to 120 cc. of water. The compound separating as a 
heavy oil which soon solidifies is taken up with ether, the ethereal solution 
shaken with dilute soda solution and the residue remaining after evaporation 
of the ether is recrystallized from ligroin, with the addition of animal charcoal. 
The melting point of the pure white compound, gradually decomposing when 
kept, is 98-99°. 
With the exception of anisic ketone CeH^. OCH3W . CH2. CO. CH3W. 
which is reported to occur in anise and fennel oils, aromatic, ketones 
have not been found in volatile oils. Hydroaromatic ketones, however, 
are important constituents of these oils: viz. carvone C10H140, camphor, 
fenchone, thujone (tanacetone), pulegone, all having the formula CioHisO, 
menthone CioHigO, and irone C13H200. All of these possess a character- 
istic odor. Whereas irone has been found in orris oil only, to which it 
imparts the odor of violets, the other ketones occur more frequently, 
the camphor being of most common occurence. 
Carvone. 
Carvone occurs principally in its optically active variety in volatile 
oils. The earlier supposition of Wallach, that inactive carvone is con- 
tained in the high boiling fractions of thuja oil, has been corrected by 
this investigator, who has more recently shown that it is not carvone, 
but a hydrocarvone CioHiuO, which has probably resulted upon 
rearrangement from thujone. The dextrogyrate modification of carvone 
is found with d-limonene in caraway and dill oils, the laevogyrate in 
spearmint and kuromoji oils. 
In order to separate the ketone in a pure state from the respective 
oil. its property to combine with hydrogen sulphide to form a crystallized 
compound C10H140. H2S is made use of. 
A mixture of 20 parts of the carvone fraction, 5 parts of alcohol and 1 part 
of ammonia (sp. gr. 0.96) is saturated with hydrogen sulphide when carvone 
hydrosulphide separates out. This is collected and recrystallized from methyl 
alcohol and then decomposed by treating with alcoholic potassa. The regener- 
ated carvone is purified by steam distillation. 
1) Berichte, 26, p. 2723. '/'he More Commonly Occurring Constituents of Volatile Oils. 
161 
As an improvement Wallach1 suggests the following details for the 
preparation of 1-carvone: 
50 cc. of the carvone fraction of spearmint oil are diluted with 20 cc. of 
alcohol and the solution, kept cold with ice, is saturated with hydrogen 
sulphide. Then sufficient alcoholic ammonia, saturated at 0°, is added 
until the liquid smells strongly of ammonia. Upon passing more hydrogen 
sulphide into the solution it congeals shortly to a crystalline mass. The same 
process is repeated with the mother liquid. The carvone hydrosulphide, when 
recrystallized from a mixture of three parts of chloroform and one part of 
alcohol, melts at 190°. For the regeneration of the carvone, 50 g. of the 
hydrosulphide are digested with a solution of 80 g. of potassa in TOO g. of water. 
The oil is separated and dried with fused potassa either directly or after 
distillation with water vapor and finally rectified. 
Artificially, derivatives of carvone have been obtained in various 
ways. Thus, e. g. carvoxime has been obtained from limonene or dipen- 
tene nitrosochloride respectively (Goldschmidt and Ziirrer,2 1885); an 
oxydihydrocarvoxime from terpineol nitrosochloride (Wallach,3 1896); 
carveolmethylether from limonene tetrabromide and terpineol tribromide 
respectively and methyl alcoholic potassa (Wallach,4 1894). Pinene 
nitrosochloride is converted by hydrochloric acid in etherial solution 
into hydrochlorcarvoxime (Baeyer,5 1896); and by the decomposition 
of phellandrene nitrite, hydroderivatives of the carvone series result 
(Wallach,3 1895). 
Carvone is a colorless liquid, smelling strongly of caraway and 
solidifying when strongly cooled (Wallach,7 1889). Its physical properties 
are given as follows: 
for d-carvone: b. p. 224°; d|-o° = 0.9598 ; [«]d2° = + 62.07° (Beyer,8 1883); 
d2o° - 0.9538; nHa=1.4751 (Kanonnikoff,0 1881); 
dn° = 0.9667; no = 1.5020 (Gladstone,10 1886); 
d2o° = 0.9606; [«]d20° = +62.65 (Schreiner,11 1896); 
for 1-carvone: b. p. 223-224°; d^ = 0.9593; [«]d2° =- 62.41°.8 
According to observations made in the laboratory of Schimmel & 
Co., carvone boils at 230° (mercury completely in the vapor) and has 
the specific gravity 0.964 at 15°. 
i) Liebig's Annalen, 305, p. 224. 
2) Berichte, 18, p. 1732. 
3) Liebig's Annalen. 291, p. 346. 
4) Liebig's Annalen. 281, pp. 127 &140. 
5) Berichte, 29, p. 12. 
6) Liebig's Annalen, 287, p. 380. 
7) Liebig's Annalen, 252, p. 129, Footnote. 
8) Archiv d. Pharm., 221, p. 287. 
9) Berichte, 14, p. 1699. 
io) Jahresb. f. Chemie, 1886, p. 298. 
ii) Pharm. Review, 14, p. 78. 162 
General Part. 
Carvone is an unsaturated ketone, which forms with hydrochloric 
acid a liquid addition product, with hydrobromic acid a solid compound, 
melting- at 32° (Goldschmidt & Kisser,1 1887). By splitting- off hydro- 
bromic acid from the latter, a ketone CioHnO results, isomeric with 
carvone which has been termed eucarvone by Baeyer2 (1894). The 
bodies resulting- by the action of bromine, viz. the tribromide 
C1oH14O.HBr.Br2, the tetrabromide CioHnOBri and the pentabromide 
CioHisOBrs, have been investigated by Wallach3 (1895). 
Carvone does not add bisulphite, but with hydroxylamine yields a 
well crystallized oxime (Goldschmidt,4 1884) which, when prepared from 
the optically active ketone, melts at 72°. By the union of equal 
quantities of d- and 1-carvoxime, inactive carvoxime, melting at 93° 
results. Artificially, these oximes are obtained by splitting off hydro- 
chloric acid from limonene and dipentene nitrosochlorides (Goldschmidt 
& Ziirrer, 1885; Wallach,5 1888). With phenyl hydrazine carvone yields 
a phenyl hydrazone melting at 109-110° (Baeyer,6 1894); semicarbazide 
combines with d- and 1-carvone to form carbazones melting at 162-163° 
(Baeyer,7 1894). The semicarbazone of the inactive carvone melts 
lower than the active compounds, namely at 154-156° (Baeyer,8 1895), 
differing in this respect from i-carvoxime. 
On reduction carvone behaves differently from other ketones. 
Sodium in alcoholic solution does not convert it, as might be expected, 
into the corresponding alcohol carveol CioHisO, but 4 atoms of hydrogen 
are taken up at once with the formation of dihydrocarveol (Wallach,9 
1893). If the reduction is effected with zinc dust in alcoholic alkaline 
solution, but two atoms of hydrogen are added, yet the resulting 
compound is no alcohol, but a ketone CioHieO, dihydrocarvone (Wallach 
& Schrader,10 1894). Carvone is oxidized by potassium permanganate 
to' oxyterpenylic acid CsHiaOs (m.p. 190-192°) (Best,11 1894; Wallach,12 
1894). From oxidation results which Tiemann and Semmler (1895) 
obtained with dihydrocarveol and dihydrocarvone,13 they have deduced 
the following formula which had previously been suggested by Wagner, 
as the most probable one: 
i) Beriehte, 20, pp. 487 & 2071. 
2) Beriehte, 27, p. 811. 
3) Liebig's Annalen, 286, p. 119. 
*) Beriehte, 17, p. 1578. 
s) Beriehte, 18, p. 2220: Liebig's 
Annalen, 245, pp. 256, 268; 246, p. 226. 
e) Beriehte, 27, p. 811 ; see also 
Goldschmidt, Beriehte 17, p. 1578. 
7) Beriehte, 27, p. 1923. 
8) Beriehte, 28, p. 640. 
9) Liebig's Annalen, 275, p. 110. 
10) Liebig's Annalen, 279, p. 377. 
ii) Beriehte, 27, p. 1218. 
12) Beriehte, 27, p. 1495. 
13) Beriehte, 28, p. 2148. The More Commonly Occurring Constituents of Volatile Oils. 
163 
ch8 ch2 
c 
I 
CH 
ch2z X\CH2 
I I > 
I I 
CH - /CO 
c 
I 
ch3 
With phosphorus pentachlpride carvone yields the dichloride 
C10H14CI2 which, when heated with quinoline is converted into 2-chlor- 
cymene (KIages and Kraith,1 1899). 
Carvone suffers a remarkable rearrangement when it is heated with 
sulphuric acid, phosphoric acid, phosphorus oxychloride, zinc chloride 
or alkalies; it is thereby converted into carvacrol, a derivative of 
benzene: CeHg.CHgOl. OH f2l. C3H7 W. With hydrogen chloride the 
change is almost quantitative. Anhydrous formic acid also causes 
a like change (Klages2). A similar molecular rearrangement takes 
place with the oxime of carvone when it is boiled with alcoholic 
sulphuric acid or heated to 230-240° with a strong solution of 
alkali, being changed to carvacryl amine (Wallach,3 1893). By adding 
carvoxime to concentrated sulphuric acid it suffers rearrangement to 
p-amidothymol (Wallach,4 1894). 
When carvone is heated with ammonium formate dihydrocarvylamine 
is formed (Leuckart & Bach,5 1887; Wallach,6 1891); the same com- 
pound results when carvoxime is reduced with sodium in alcoholic solu- 
tion (Wallach,7 1893). If, however, the reduction is carried on in 
alcoholic solution with zinc dust and glacial acetic acid, carvylamine 
CioH]4NH2 results in two isomeric forms (Goldschmidt & Kisser,8 1887; 
G. & Weiss,9 1893; G. & Fisher,10 1897). 
Carvone has such a characteristic odor, that it can be recognized 
without difficulty. If it is to be separated in a pure state from fractions 
of a volatile oil it is converted into its hydrogen sulphide addition 
product (see above). It may be mentioned tha,t this compound does 
1) Berichte, 32, p. 2550. 
2) Berichte, 32, p. 1516. 
3) Liebig's Annalen, 275, p. 118 ; 279, p. 374. 
4) Liebig's Annalen, 279, p. 369. 
s) Berichte, 20, p. 113. 
6) Berichte, 24, p. 3984. 
7) Liebig's Annalen, 275, p. 119. 
s) Berichte, 20, p. 486. 
9) Berichte, 26, p. 2084. 
io) Berichte, 30. p. 2069. 164 
General Part. 
not melt at 187° as reported by Beyer,1 but at 210 to 211° (Claus & 
Fahrion,2 1889). 
In order to prove the presence of carvone, the simplest way is to 
prepare the oxime, taking care, however, that not too great an excess 
of hydroxylamine be employed, as in this case the oxime may add a 
Second molecule of hydroxylamine forming a compound C10H14N0H.- 
NH2OH (m. p. 174-175°) (Wallach & Schrader,3 1894; Harries,4 1898). 
If the freshly prepared oxime does not crystallize at once, it can some- 
times be brought to crystallize by distilling it over with steam. 
Camphor. 
In order to distinguish d-camphor from Borneo camphor (d-borneol), 
it is also called Japan or laurus camphor. Besides camphor oil, it is 
obtained in large quantities by steam distillation from the wood of 
Cinnamomum camphora. In smaller amounts it is contained in the oils 
of camphor leaves, sassafras leaves, cinnamon root, spike, rosemary, 
and in the oil from basilicum root from Reunion. 1-Camphor occurs 
only in the oils of feverfew and tansy. Like d-camphor it results upon 
oxidation of the corresponding borneol with nitric acid. 
Synthetically, camphor has been obtained by the dry distillation of 
the lead (Haller,5 1879 and 1896) or calcium (Bredt & Rosenberg,0 1896) 
salt of homocamphoric acid (Haller's hydroxycamphocarbonic acid). 
This synthesis is, however, only a partial one, since up to the present 
homocamphoric acid has been prepared only from a derivative of 
camphor. 
Camphor forms a granular, crystalline, colorless, transparent mass, 
with a great tendency to sublime. It is readily soluble in organic 
solvents and has a characteristic odor. Its properties, according to 
different observers are as follows : dis° = 0.9853 (determined on 1-camphor 
by Chautard7). 
M p. 176.3-176.5°; b. p. 209.1° at 759 mm. (mercury thread com- 
pletely in the vapor) (Forster,8 1890); 
M. p. 178.4°; [«]d = + 41.44° and - 42.76° (Haller,9 1887).-M. p. 175°; 
b. p. 204° (Landolt,10 1877). 
1) Archiv d. Pharm., 221, p. 285. 
2) Journ. f. prakt. Chem., If, 39, p. 365; 
Bericht von S. & Co., April 1898, p. 29. 
3) Liebig's Annalen, 279, p. 368. 
■i) Berichte, 31, pp. 1384, 1810. 
5) Contrib. h.l'£tudeducamphre. Thfise. Nancy 
1879, p. 34; Bull. Soc. chim., Ill, 15,-p. 323. 
6) Liebig's Annalen, 289, p. 5. 
7) Jahresbericht f. Chem., 1863, 
p. 555. 
8) Berichte, 23, p. 2983. 
9) Compt. rend., 105, p. 229. 
io) Liebig's Annalen, 189, p. 333. The More Commonly Occurring Constituents of Volatile Oils. 
165 
M. p. 175°; b. p. 204°; [a]D = + 44.22° in 20 percent alcoholic solution 
(Beckmann,1 1889). 
Camphor has always been of interest to chemists and the experi- 
mental material on it has grown to fairly large proportions. In harmony 
with the purpose of this work, only those compounds especially suited 
for its characterization will be considered. 
According to its chemical nature camphor CioHmO is a ketone, 
which does not combine with bisulphites. Hydroxylamine reacts upon 
it with the formation of an oxime, from which, however, the pure ketone 
cannot be regenerated, for when treated with acids water is split off 
and the nitrile of campholenie acid C9H15.CN is formed. 
If camphor oxime is reduced with sodium in ethyl or better amyl 
alcoholic solution, two isomeric bornylamines (-m. p. 163° and 180°) 
are formed (Forster,2 1898). A similar base, melting at 159-160° is 
obtained by heating camphor with ammonium formate to 220-230° 
(Leuckart & Bach,3 1887; Wallach & Griepenkerl,4 1892). 
Upon reduction camphor is converted into the alcohol CioHisO, 
borneol. In indifferent solvents there is also produced some isoborneol 
besides camphor pinacone (Beckmann,5 1894 and '96), while in alcoholic 
solution a mixture of borneol and isoborneol is principally obtained 
(Beckmann,6 1897). 
The oxidation with nitric acid leads to the dibasic camphoric acid 
CioHioOi (m. p. 187°) and further to the tribasic camphoronic acid 
C9H14O6 (m. p. 139°). From the constitution of the decomposition 
products of these acids many conclusions have been drawn as to the 
constitution of camphor. Of the many formulas suggested for this 
ketone, that of Bredt7 (1893) 
CH2 - CH - CH2 
I I I 
|CH8-C-CH3| 
I I I 
ch2 -c - co 
ch3 
is at present considered most favorably. 
1) Liebig's Annalen, 250, pp. 352-353.- 
On the influence of the concentration and the 
nature of the solvent on the rotatory power 
see Landolt loc. cit. and Rimbach, Zeitschr. 
L phys. Chern., 9 (1892), p. 701. 
2) Journ. Chern. Soc., 73, p. 386. 
s) Berichte, 20, p. 104. 
4) Liebig's Annalen, 269, p. 347. 
5) Berichte, 27, p. 2348; Liebig's 
Annalen, 292, p 1. 
6) Journ. f. prakt.Chem., 11,55, p. 35. 
7) Berichte, 26, p. 3049. 166 
General Part. 
Dehydrating agents act very energetically on camphor. Thus phos- 
phoric acid anhydride produces p-cymene; sulphuric acid and zinc chloride 
yield other substances besides this hydrocarbon. By the action of iodine 
carvacrol is obtained. 
For the identification of camphor the oxime is used. This com- 
pound, discovered by Nageli1 in 1883 is preferably prepared according 
to the method of Auwers,2 (1889): 
To a solution of 10 parts of camphor in 10-20 times the amount of 90 
percent alcohol a solution of 7-10 parts of hydroxylamine hydrochloride and 
12 to 17 parts of soda solution are added. The mixture is heated in a boiling 
water bath until the compound first precipitated by water dissolves completely 
in the soda solution. The oxime precipitated by water is recrystallized from 
alcohol or ligroin. It melts at 118-119° (Bertram & Walbaum,3 1894; Bredt 
& Rosenberg-,4 1896), and, when prepared from d-camphor is laevogyrate, 
whereas the oxime of 1-camphor is dextrogyrate (Beckmann,5 1889). 
For identification the semicarbazone of camphor melting at 236- 
238° may also be employed, further the compound produced witli 
p-bromphenylhydrazine melting at 161° (Tiemann,6 1895). 
Fenchone. 
Fenchone CioHmO is a compound very similar to camphor, but liquid. 
It occurs in both optically active modifications in volatile oils. d-Fen- 
chone is contained in fennel oil, while 1-fenchone is a constituent of thuja 
oil. For its preparation in a pure state the fenchone-containing fractions, 
boiling at about 190-195° are freed from impurities by oxidation with 
concentrated nitric acid or permanganate solution (Wallach,7 1891). 
Fenchone is very stable toward oxidizing agents and is only slightly 
acted upon by this treatment. If the fenchone has been fairly well 
purified by this treatment it will solidify in the cold and can then be 
completely purified by crystallization and removal of the liquid parts. 
Artificially, fenchone can be obtained by the oxidation of fenchyl 
alcohol. 
Absolutely pure fenchone is a limpid, somewhat oily liquid, which 
possesses an intense camphor-like odor and a bitter taste. Its physical 
properties are given by Wallach8 (1891-1893) as follows: 
M. p. 4" 5 to 6°; di9° - 0.9465, d23° - 0.943; ud19 - 1.46306; 
[a]D -71.97° and 66.94° resp. (in alcoholic solution). 
1) Berichte, 16, p. 497. 
2) Berichte, 22, p. 605 
s) Journ. f. prakt. Chem., II, 49, p. 10. 
*) Liebig's Annalen, 289, p. 6. 
5) Liebig's Annalen, 250, p. 354. 
6) Berichte. 28. p. 2191. 
7) Liebig's Annalen, 263, p. 130. 
8) Liebig's Annalen, 263, p. 131: 272, p. 102 The More Commonly Occurring Constituents of Volatile Oils. 
167 
With the exception of the character of rotation, the optically active 
modifications correspond completely both physically and chemically. 
Fenchone does not combine with bisulphites any more than does 
camphor, but is also indifferent toward phenyl hydrazine; with hydroxyl- 
amine, however, it yields an oxime melting at 164-165°. which can be 
used for characterization (Wallach1). The fenchone oxime behaves like 
camphor oxime in so far as by splitting off water it is converted into 
the nitrile of fencholenic acid C10H15N, isomeric with campholenic acid. 
Cockburn3 obtained two fencholenic acids. 
Upon reduction fenchone yields fenchyl alcohol CioHisO (Wallach2), 
which melts at 45°. By this treatment a change in rotatory power 
takes place, so that d-fenchone yields 1-fenchyl alcohol and the reverse. 
Upon oxidation with permanganate fenchone yields besides acetic and 
oxalic acids dimethylmalonic acid (CHs)2. C(C00H)2 (Wallach4). When 
concentrated nitric acid is used isocamphoronic and dimethyl tricarbal- 
lylic acids are also found. (Gardner & Cockburn,5 1898). 
Whereas camphor, when dehydrated with phosphoric acid anhydride, 
yields p-cymene; fenchone, upon like treatment yields m-cymene. 
Fenchone therefore appears to be the m-compound corresponding to 
camphor as the p-compound (Wallach6). Concentrated sulphuric acid 
acts on fenchone with the formation of acetyl xylene CeHs.CHgf1]. 
CH3U1. CHsCOM (Marsh ?). 
For the identification of fenchone the oxime is used, which is best 
prepared according to the directions given by Wallach.8 
To a solution of 5 g. of fenchone in 80 cc. of absolute alcohol a solution 
of 11 g. of hydroxylamine hydrochloride in 11 g. of hot water and 6 g. of 
powdered potash are added. After standing for some time when some of the 
alcohol has evaporated the oxime crystallizes out, which should be purified by 
recrystallization from alcohol, acetic ether, or ether, 
Thu jone. 
Thujone (ToHieO (tanacetone Semmler) together with 1-fenchone is 
a constituent of thuja oil, but has also been found in the oils of tansy, 
wormwood, and sage as well as in the oil of Artemisia, barrelieri. In all 
of them it occurs in the dextrogyrate modification only. From oils rich 
in thujone like tansy oil, and the oil of Artemisia barrelieri. the 
ketone is conveniently separated in the form of its bisulphite compound, 
which yields pure thujone by decomposition with soda. 
i) Liebig's Annalen, 263, p. 131; 
272, p. 102. 
3) Journ. Cnem. Soc., 75, p. 501. 
2) Ibidem, p. 146. 
4) Liebig's Annalen, 263. p. 134. 
5) Journ. Chem. Soc., 73, p. 708. 
6) Liebig's Annalen, 275, p. 157; 284, p. 324. 
7) Proc. Chem. Soc., 15, p. 196. 
s) Liebig's Annalen, 272, p. 104. 168 
General Part. 
Thujone is a colorless, pleasant smelling, somewhat oily liquid, for 
which Semmler reports the following properties: 
B. p. 84.5° at 13 mm.; d2o° -0.9126; no = 1-4495.1 
B. p. 203°; «d = about +68°.2 
For the ketone regenerated from the bisulphite compound and the 
semicarbazone Wallach found:3 
d 190 = 0.9175; nD -1-45109; 
d 20° - 0.916; n d --1.4507. 
As is seen from the physical constants thujone is a saturated ketone, 
yet it takes up bromine with decoloration and is readily affected by 
potassium permanganate. 
Differing from camphor and fenchone thujone combines with sodium 
bisulphite. With hydroxylamine it yields an oxime (Wallach,4 1893; 
Semmler,5 1892) melting at 54-55°, which upon heating with dilute 
sulphuric acid is changed to cymidine CaHs. CsHtI1! . NH2UJ. CH3W which 
yields carvacrol (Semmler6). Semicarbazide reacts on the ketone with 
the formation of a semicarbazone melting at 171-172° (Baeyer,7 1894). 
Upon reduction thujone yields the corresponding secondary alcohol 
CioHisO. thujyl alcohol (Semmler5), which had been found with thujone 
in wormwood oil. 
When oxidized with bromine and soda solution the monobasic 
tanacetogenic acid C9H14O2 results (Semmler8); with permanganate, 
however,* a mixture of two isomeric keto acids CioHigOs, is obtained 
(Wallach,9 1893 & 1897; Semmler,10 1892). When subjected to dry 
distillation, this yields a homologous ketone CgHieO possessing an odor 
similar to that of methyl hep ten one (Wallach,11 1893). By building 
down the keto acids to <5-(w-) dimethyl laevulinic acid the constitution 
of thujone has been fairly well cleared up (Tiemann & Semmler,12 
1897 and 1898). 
When thujone is heated to 280° in closed tubes for some time, it is 
changed to an unsaturated ketone of the same composition CioHioO, 
carvotanacetoue (Semmler,13 1889), which has an odor resembling that 
of carvone. The same rearrangement seems to take place even by 
1) Berichte, 25, p. 3343. 
2) Ibidem, 27, pp. 895 & 897. 
3) Berichte, 28, p. 1965. 
*) Liebig's Annalen, 277, p. 159. 
s) Berichte, 25, p. 3344. 
6) Ibidem, 3352. 
i) Berichte, 27, p. 1923. 
8) Berichte, 25, p. 3346. 
9) Liebig's Annalen, 272, p. Ill; Berichte, 
30, p. 423. 
10) Berichte, 25, p. 3347. 
11) Liebig's Annalen, 272, p. 116 ; 275, p. 164. 
12) Berichte, 30, p. 429; 31, p. 2311. 
is) Berichte, 27, p. 895. The More Commonly Occurring Constituents of Volatile Oils. 
169 
prolonged boiling of the thujone, as may be concluded from the decrease 
in rotatory power. Another isomeric ketone, isothujone, is formed by 
heating thujone witli dilute sulphuric acid (Wallach,1 1895). 
For the characterization of thujone the tribromide is well suited, 
and is best prepared according to Wallach2 (1893): 
5 g. of thujone are dissolved in a large beaker in 30 cc. of petroleum ether 
and to this solution 5 cc. of bromine are added at once. After several seconds 
a rather violent reaction takes place with liberation of considerable hydro- 
bromic acid. When this is ended, the solvent is allowed to evaporate and the 
tribromide separates slowly as a crystalline mass, which is to be freed from 
adhering oil by washing with cold alcohol and recrystallized from hot acetic 
ether; the melting point of the pure compound is 121-122°. 
Pulegone. 
The oil of European pennyroyal contains about 80 percent of a 
ketone CioHioO, pulegone, which has likewise been found in the penny- 
royal oil from Hedeoma pulegioides and in the oil of Pycnanthemum 
lanceolatum, in all of which it occurs in the dextrogyrate modification. 
As European pennyroyal oil consists principally of pulegone, this 
ketone can be obtained in a fairly pure state by fractional distillation. 
It can, however, be obtained much purer from the bisulphite compound 
which separates by shaking the oil diluted with some alcohol (% vol.) 
with sodium bisulphite solution (Baeyer,3 1895). The semicarbazone, 
decomposable by acids, can also be used for the purification of pulegone. 
Synthetically, pulegone has been obtained in a round-about way 
from citronellal (Tiemann & Schmidt,4 1896). Au isomeric ketone, but 
not identical with natural pulegone has been obtained by Wallach5 
(1896 & '98) by the condensation of methyl hexanone with acetone. 
Pulegone is at first a colorless liquid which on standing for some 
time becomes faintly yellow, and has a sweet peppermint-like odor. 
For the ketone purified only by distillation Beckmann and Pleissner 
(1891) found:0 
B.p. 130-131° at 60mm.; d2o°= 0.9323; nD = 1.47018; = + 22.89°. 
Barbier reports (1892): " 
B. p. 222-223°; d28° = 0.9293; [«]D-+ 25° 15'. 
i) Liebig's Annalen, 286, p. 101; Beriehte, 28, p. 1958; 30, p. 426. 
2) Liebig's Annalen, 275, p. 179. 
3) Beriehte, 28, p. 652. 
+) Beriehte, 29, p. 913; 30, p. 22. 
s) Beriehte, 29, pp. 1597, 2955; Liebig's Annalen, 300, p. 267. 
6) Liebig's Annalen, 262, pp. 3, 4, 20. 
t) Coinpt. rend., 114, p. 126. 170 
General Part. 
For the pulegone prepared from the bisulphite compound Baeyer 
and Henrich1 (1895) determined: 
B. p. 100-101° at 15 mm.; [«]d = +22.94° 
and Wallach2 (1895): 
B. p. 221-222°; d = 0.936; nD = 1.4846. 
As an unsaturated compound pulegone yields with bromine a liquid 
dibromide, with hydrochloric and hydrobromic acids crystallized addition 
products, which regenerate pulegone when treated with alcoholic potassa 
(Beckmann & Pleissner,3 1891; Baeyer & Henrich,4 1895). It also 
shows the character of a ketone. Upon careful reduction with sodium 
in alcoholic solution the alcohol CiqHisO, pulegol, which is difficult to 
obtain in a pure state, is first formed (Tiemann & Schmidt5). Upon 
further action of hydrogen 1-menthol C10H200 results (Beckmann & 
Pleissner6). 
Pulegone combines with hydroxylamine, two oximes being known, 
of which the one has the normal composition CioHieNOH and melts at 
118-119° (Wallach,7), while the other (m.p. 147°, Tiemann & Schmidt,8) 
described by Beckmann & Pleissner,9 contains an additional molecule of 
water. As has lately been determined the latter is produced by the 
addition of hydroxylamine to the double bond in the pulegone, so that 
the compound cannot be considered as an oxime (Harries & Roeder,10 
1898). The semicarbazone formed by the action of semicarbazide melts 
at 170° (Baeyer & Henrich,11 1895). 
When pulegone is boiled with anhydrous formic acid, or heated with 
water to 250° in an autoclave, it takes up water and is resolved into 
acetone and methyl hexanone C7H12O (Wallach,12 1896). The same 
decomposition is also brought about by concentrated sulphuric acid 
(Zelinsky,13 1897); also by the addition of bromine and splitting off 
hydrogen bromide with the aid of heat (Klages14). In the latter case 
m-cresol is also formed. 
Upon oxidation with potassium permanganate pulegone splits off 
acetone and yields /S-methyladipinic acid C7H1OO4. In harmony with 
this result the formula 
i) Berichte, 28, p. 653. 
2) Berichte, 28, p. 1965. 
3) Liebig's Annalen, 262, p. 21. 
4) Berichte, 28, p. 653. 
5) Berichte, 29, p. 914. 
6) Liebig's Annalen, 262, p. 30. 
7) Liebig's Annalen, 277, p. 160; 289, p. 347. 
8) Berichte, 30, p. 26. 
9) Liebig's Annalen, 262, p. 6. 
io) Berichte, 31, p. 180$). 
ii) Berichte, 28, p. 653. 
12) Liebig's Annalen, 289, p. 338. 
13) Berichte. 30, p. 1532. 
i<) Berichte, 32, p. 2564. More Commonly Occurring Constituents of Volatile Oils. 
171 
ch3ch3 
c 
II 
c 
h2c//x\co 
I I 
I 
■ I I 
H2C\ . /CH2 
CH 
I 
ch3 
has been assigned to pulegone (Semmler,1 1892) which also explains the 
ready decomposition into acetone and methyl hexanone. 
Pulegone has an odor very similar to that- of menthone. Both 
ketones can, however, be readily distinguished by their derivatives. For 
the characterization of pulegone the semicarbazone prepared in the 
usual manner, or the normal oxime may be used. For the preparation 
of the latter Wallach,2 1896, has given the following directions: - 
To a solution of 10 g. of pulegone in three times its volume of absolute 
alcohol a solution of 10 g. of potassium hydrate in 5 g. of water is added. 
To the liquid warmed to about 80° are added quite rapidly with constant 
agitation, 10 g. of hydroxylamine hydrochloride dissolved in 10 g. of water, 
and the mixture kept for 10 minutes more at 80°. If, after cooling, the 
mixture is poured into water, the oxime usually separates at once in the solid 
form. After recrystallization from ether or petroleum ether it melts at 
118-119°. 
According to Baeyer & Henrich3 (1895) the identification can be 
accomplished more rapidly with the characteristic bisnitrosopulegone. 
A solution of 2 cc. of pulegone or oil containing pulegone in 2 cc. of ligroin 
and 1 cc. of amyl nitrite is well cooled in a freezing mixture and treated with 
a very small amount of hydrochloric acid. In a very short time the bisnitroso 
compound separates in the form of fine needles, which are obtained pure by 
spreading on a porous plate and washing with petroleum ether. 
Menthone. 
1-Menthone occurs together with menthol in peppermint oil and 
probably also in the oil of buchu leaves. Recently it has been detected 
in geranium oil from Reunion. 
As it does not combine with bisulphite and cannot be freed from 
accompanying compounds by fractional distillation alone, it can be 
1) Beriehte, 25, p. 3515. 
2) Liebig's Annalen, 289, p. 347. 
3) Beriehte, 28, p. 654; compare Baeyer 
& Prentice, Beriehte, 29, p. 1078. 172 
General Part. 
isolated only by means of its oxime or semicarbazone. It should be 
remembered, however, that in the decomposition of these compounds, 
which is usually effected by means of dilute sulphuric acid, the rotatory 
power of the ketone is changed. 
By the oxidation of menthol with the chromic acid mixture recom- 
mended by Beckmann it is easy to obtain a 1-menthone with normal 
rotatory power (Beckmann,1 1889). 
Pure menthone is a mobile, limpid liquid, which possesses a peppermint 
odor and a cooling, bitter taste. For the ketone obtained by oxidation 
from menthol Beckmann found: 
B. p. 207°; d20° = 0.8960; dD12° = 1.4525; [a]D = - 28.18°.-' 
Binz records (1893): 
d24° - 0.8934; [^Jd--27.67°.3 
According to Wallach (1895) menthone regenerated from the semi- 
carbazone (m. p. 184°) possesses the following properties: 
B. p. 208°: d = 0.894; nD = 1.4496A 
If 1-menthone is treated at a low temperature with concentrated 
sulphuric acid, it is converted into the dextrogyrate isomer (Beckmann,5 
which has so far not been found in volatile oils. 
Menthone belongs to those ketones which do not yield addition 
products with bisulphites. Upon reduction with sodium in alcoholic 
solution it is converted into the corresponding secondary alcohol 
1-menthol, CioH2oO There are also formed small quantities of a slightly 
dextrogyrate isomenthol; by using indifferent solvents menthopinacone 
also results (Beckmann,6 1897). 
With hydroxylamine in alcoholic-aqueous solution it combines 
readily to form 1-menthoxime melting at 59° (Beckmann,7 1889; 
Wallach,8 1893). When this is treated with dehydrating agents it is 
converted into an aliphatic nitrile C9H17CN, which by further changes 
yields compounds which show great similarity to the members of the 
citronellal series (Wallach,9 1894 & '97). Semicarbazide reacts on 
menthone with the formation of the semicarbazone, which crystallizes 
in needles and melts at 184° (Wallach,10 1895; Beckmann,11 1896). 
i) Liebig's Annalen, 250, p. 325. 
2) Liebig's Annalen, 250, p. 327. 
3) Zeitschr. f. phys. Chem., 12, p. 727. 
*) Berichte, 28, p. 1963. 
s) Liebig's Annalen, p. 334. 
«) Journ. f. prakt. Chem., II, 55, pp. 
18 & 30. 
7) Liebig's Annalen, 250, p. 330. 
s) Liebig's Annalen, 277, p. 157. 
9) Liebig's Annalen, 278, p. 308; 296, 
p. 120. 
io) Berichte, 28, p. 1963. 
11) Liebig's Annalen, 289, p. 366. Hie More C ommonly Occurring Constituents of Volatile Oils. 
173 
If menthone is oxidized with a solution of chromic acid in glacial acetic 
acid, a liquid keto acid CioHisOs (keto- or oxymenthylic acid) is first 
produced (Beckmann & Mehrlander,1 1896), which, on further oxidation 
with potassium permanganate or chromic acid mixture is converted into 
the dibasic /?-methyladipinic acid (Arth's2/5-pimelinic acid) consequently 
into the same "Abbauproduct" which results from pulegone and 
citronellal (Beckmann and Mehrlander;3 Manasse and Rupe,4 1894). 
When oxidized with Caro's reagent (persulphate with concentrated 
sulphuric acid) it yields the corresponding s-lactone (Baeyer,5 1899). 
When isoamyl nitrite and hydrochloric acid are allowed to act on 
menthone in the cold, there is formed besides bisnitrosomenthone 
(C10H17C). N0)2, the oxime of keto-menthylic acid, the first oxidation 
product of menthone (Baeyer & Manasse,6 1894; B. & Oehler,7 1896). 
When bromine (2 mol.) acts on menthone (l'mol.) in chloroformic 
solution a crystallized dibrommenthone, CioHigBi^O (m. p. 79-80°) 
results, which can be converted into thymol by splitting off hydrobromic 
acid by means of chinoline (Beckmann & Eichelberg,8 1896). 
Those rearangements, as well as the conversion of menthone into 
3-chorcymene effected by Junger and Klages9 (1896) agree with the 
formula 
CHsCHa 
XCH 
CH 
h2cz X\co 
I 
I 
H2C\ /CH2 
. CH 
I 
ch3 
assigned to it. This also expresses the relation of menthone to pulegone. 
In order to identify menthone, the semicarbazone or the oxime is 
employed, the preparation of which is accomplished in the usual manner. 
For further characterization the ketone may be reduced to menthol and 
this converted into the benzoic acid ester (see menthol). 
1) Liebig's Annalen, 289, p. 368. 
2) Annates de Chiin, et Phys., VI, 7, p. 433. 
3) Liebig's Annalen, 289, p. 378. 
*) Berichte, 27, p. 1818. 
s'! Berichte, 32, p. 3625. 
6) Berichte, 27, pp. 1918 and 1914. 
7) Berichte, 29, p. 27. 
«) Berichte, 29, p. 418. 
9) Berichte, 29, p. 815. 174 
General Part. 
A diketone, viz. diacetyl CH3. CO. CO. CH3 remains to be mentioned. 
It has been isolated from the distillate from caraway seeds1 and in all 
probability occurs in the distillate from cloves and probably in other 
oils. It can be identified by its dioxime melting at 234.5°. 
Acids, Esters, Lactones, Oxides. 
The aqueous distillate obtained by the distillation of volatile oils 
with steam occasionally contains free fatty acids, viz. acetic, propionic, 
butyric or valerianic acid. These acids, like methyl and ethyl alcohol, 
are probably decomposition products of esters contained in the parts 
of plants subjected to distillation. 
Those acids contained in oils in the form of esters are obtained as 
salts when the oils are saponified. Formic acid is supposed to be con- 
tained in valerian oil as bornyl formate. Acetic acid occurs frequently 
in the form of esters as linalyl, geranyl, and bornyl acetates, which are 
characterized by their peculiar odor. Of the other fatty acids, propionic 
and butyric acids have been found in lavender oil; butyric acid as ethyl 
ester in the oil of Heracleum sphondyluun, as octyl ester in the oil of 
Pastinaca saviva; valerianic acid and its esters in the oils of valerian, 
citronella and angelica root; methyl ethyl acetic acid in the oil of angelica 
root and seed; n-capronic acid in palmarosa oil and the oil of H. 
sphondylium ; caprinic acid as ethyl and amyl ester in cognac oil; laurinic 
acid free in the oil of arnica flowers; myristic acid in orris oil and oil 
of nutmeg; and palmitic acid in the oils of ambrette seeds, vetiver, 
wormwood, celery and arnica flowers. 
Of the unsaturated acids, angelic and tiglinic acids occur as esters 
in cumin oil; tiglinic acid in geranium oil from Reunion; oleic acid in 
orris oil. • 
Of the aromatic acids, benzoic acid has been found in ylang-ylang 
oil and in the oil of tolu balsam ; cinnamic acid in storax oil, and as 
methyl ester in the oil of Alpinia malaccensis. Much more widely dis- 
tributed is salicylic acid which occurs as methyl ester in the oils of 
species of Gaultheria and Betula, also those of spiraea, senega root and 
tea. Methyl salicylate occurs in small amounts but is widely distributed 
in leguminous plants and in other plant families.2 In oil of cloves 
salicylic acid probably occurs as acetsalicylic ester of eugenol. 
t) Bericht S. & Co., Oct. 1899, p. 32. 
2) Comp. Bericht von Schimmel & Co., Oct. 1898, p. 51, also Jahresbericht des 
botanischen Gartens zu Buitenzorg, 1897, p. 37. The More Commonly Occurring Constituents of Volatile Oils. 
175 
Methyl salicylate is unquestionably one of the most widely distributed 
plant constituents. Its presence in a plant is not restricted to any one 
part. Probably the ester does not as a rule exist as such in plants, 
but in form of a glucoside, for frequently the distillate from fresh 
vegetable matter yields no reaction for methyl salicylate. 
Oxyacids and their anhydrides, the lactones, occur in volatile oils; 
oxymyristic and oxypentadecylic acid have been found in the oils of 
angelica root and of angelica seed respectively. 
Of the lactones, sedanolid from celery oil and cumarin and hydro- 
cumarin are characterized by their powerful odor. On the other hand, 
alantolactone (helenin) from alant oil and the lactone C1OH16O2 from 
peppermint oil have but a faint odor. 
The oxides are represented by but one compound, cineol or 
eucalyptol CioHisO. 
Cineol. 
Cineol (eucalyptol, terpane of Bouchardat and Voiry) like methyl- 
salicylate is widely distributed. It is the principal constituent of cajeput 
oil, the oils of Artemisia cina and Eucalyptus globulus and has been 
found in larger or smaller quantities in the following oils: galangal oil, 
zedoary oil, different cardamom oils, in the oil from the seeds of 
Amomum melegueta, kaempferia oil, camphor oil. laurel leaf and 
berry oils, myrtle oil, in the oils of Melaleuca leucadenclron var. lanci- 
folia, M. acuminata, M. decussata and M. uncinata, in cheken leaf oil, 
canella oil, in the oils of Eucalyptus odorata, cneorifolia, oleosa, 
dumosa, amygdalina, rostrata, populifera, corymbosa, resinifera, 
baileyana, microcorys, risdonia, leucoxylon, macrorrhyncha, capitellata, 
eugenioides, obliqua, punctata, loxophleba, crebra and hemiphloia, in 
oil of Artemisia vulgaris, milfoil oil, ivg oil. in sage and basilicum oil, 
in the oil of Lavandula dentata, L. stoechas and L. vera, in rosemary 
oil, as well as in peppermint and Russian spearmint oils. 
The preparation of this body from oils rich in cineol, like that of 
Eucalyptus globulus, is not difficult, insofar as the cineol, purified as 
far as possible by fractional distillation possesses the property of 
crystallizing when cooled. If the object is to detect and to isolate 
small quantities of cineol, the hydrobromic acid compound is used, 
which by decomposition with water yields cineol. 176 
General Part. 
Cineol has been observed as inversion product in the preparation of 
terpineol from terpin hydrate and dilute sulphuric acid; it results further 
by boiling terpineol with dilute sulphuric acid or oxalic acid. 
Pure cineol is a colorless liquid of camphor-like odor, which crystal- 
lizes in the cold and is optically inactive. For the cineol prepared from 
its hydrochloric acid addition product Wallach found: 
B. p. 176°; d2o° -0.9267; iid -1-45839.1 
According to observations made in the laboratory of Schimmel & Co. 
cineol purified by crystallization melts at -1°; it boils at 177° (764 mm.), 
and di5° = 0.930, udi7o = 1-45961. 
Cineol yields characteristic loose addition products with bromine, 
iodine, hydrochloric and hydrobromic acids,2 phosphoric acid, a- 
and 9-naphthol, and iodol, which can be used in part for its isolation 
and characterization. By the action of dehydrating agents it is 
converted into dipentene (Wallach & Brass,3 1884). It can also be 
converted directly into dipentene derivatives by proper treatment; thus 
for instance, dipentene hydriodide results by merely conducting dry 
hydriodic acid into cineol. The oxygen in cineol is combined as oxide 
oxygen and, therefore, this compound reacts neither with hydroxylamine 
nor with phenyl hydrazine, nor does sodium in alcoholic solution act 
upon it. 
When oxidized with warm solution of potassium permanganate 
dibasic cineolic acid, CioHicOb (m. p. 196 to 197°) is formed (Wallach & 
Gildemeister,4 1888). The cineolic acid anhydride produced by the 
action of acetanhydride on this acid yields, when subjected to dry dis- 
tillation, methyl heptenone, CsHi^O, which also occurs naturally. 
Cineol possesses a characteristic odor, which often directs the atten- 
tion to it. For rapid detection, the reaction with iodol given by 
Hirschsohn5 (1893) is especially suited. In a few drops of the oil to 
be tested a little iodol is dissolved by moderately heating; if cineol is 
present, the crystalline addition product consisting of equal molecules 
of the components soon separates. The melting point of the compound, 
recrystallized from alcohol or benzene, is about 112° (Bertram & Wal- 
baum,6 1897). 
1) Liebig's Annalen, 239, p. 22; 245. p. 195. 
2) Liebig's Annalen, 225, pp. 300, 303; 230, p. 227; 246, p. 280 
3) Liebig's Annalen, 225, p. 310. 
*) Liebig's Annalen, 246, p. 268. 
5) Pharm. Zeitschr. f. Russl., 32, pp. 49 & 67. 
6) Archiv d. Pharm., 235, p. 178. The More Commonly Occurring Constituents of Volatile Oils. 
177 
If the cineol is to be isolated as such, the cineol fraction diluted with 
about an equal volume of petroleum ether is well cooled and saturated 
with dry hydrobromic acid gas. The white crystalline precipitate which 
soon separates is filtered with a force-pump and washed with petroleum 
ether. The fairly stable hydrobromide thus obtained melts at 56-57° 
and is readily decomposed by water into cineol and hydrobromic acid. 
For the further characterization the cineolic acid produced by 
oxidation with warm potassium permanganate solution may be used. 
Phenols and Phenol ethers. 
Several of the phenols and their ethers have acquired considerable 
commelcial importance and are, therefore, prepared on a large scale. 
Thus thymol is largely used on account of its antiseptic properties, 
anethol is used in the manufacture of liquors, from eugenol and safrol 
the valuable vanillin and heliotropin are prepared. 
Of the simpler representatives, p-cresol methyl ether is found in 
ylang-ylang oil (cananga oil), phlorol (m-ethy 1 phenol?) is found as iso- 
butyric ester and as methyl ether in the oil of arnica root, the ethyl 
ether of hydroquinone occurs in star anise oil, and the methyl ether of 
thymohydroquinone in the oil of arnica root. 
Of the higher homologues of phenol, the two isomeric phenols 
C10H140, thymol and carvacrol are of special interest on account of their 
relationship to terpene derivatives. 
Carvacrol. 
Carvacrol (isopropyl-o-cresol), CeHs. CH3W . OH121. C3H7H], is the 
principal constituent of the Trieste and Smyrna origanum oil. It has 
also been found in the oils of Monarda fistulosa, of thyme and wild 
thyme, of Satureja hortensis, S. montana and of Pycnanthemum lanceo- 
latum, also in spearmint oil and the oil of Schinus mode. 
Artificially it can be obtained from the isomeric carvone by treat- 
ment with potassa, hydrochloric, sulphuric, phosphoric, and formic 
acids (comp. p. 163); also from camphor by heating it with iodine. 
When freshly distilled it is a colorless, thick oil, which solidifies in 
the cold. Its constants are reported as follows: 
B. p. 119° at 16 mm.; 620° = 0.9782; ud = 1.5228 (Semmler,1 1892). 
1) Beriehte, 25, p. 3353. 178 
General Part. 
For carvacrol from origanum oil, Gildemeister1 (1895) found: 
M. p.+0.5°; b. p. 235.5-236.2° (742 mm.); di5° = 0.980, d2o° = O.976; 
nD2o° = 1.52338; 
and for a preparation prepared from carvone: 
M. p. + 0.5°; b. p. 236-236.5° (742 mm.); 
di5° = 0.983, d2o° -0.979; ud2o° -1.52295. 
For the detection of carvacrol the phenyl carbaminic acid ester, 
first prepared by Goldschmidt2 (1893) can be used. According to 
Gildemeister1 it melts at 140°. For this purpose the nitroso derivative 
which can readily be prepared according to Klage's3 (1899) method 
should also prove serviceable. 
Thymol. 
Thymol (isopropyl-m-cresol) C0H3. CH3HI. OHJ31. C3H7W is found in 
considerable quantity besides p-cymene in ajowan oil, but also occurs in 
the oils of Monarda punctata, Morula japonica and Cunila mariana, in 
oil of wild thyme, and in thyme oil. 
Its artificial formation from dibrom menthone by splitting off hydro- 
bromic acid by means of quinoline is interesting. 
Thymol forms colorless, transparent crystals, having the odor of 
thyme which melt at 50-51° and distill at 232° (231.8°) (Pinette,4 
1886). Eykmann5 (1893) determined dg.6° = 0.9816, Nasini and Bern- 
heimer6 (1885) report d^ = 0.96895 and no = 1-51893. 
Chemically it can be readily characterized by its nitroso derivative 
(Klages,7 1899). 
The most phenols and phenol ethers as well as the most important 
ones belong to the olefinic phenols, i. e. phenols with olefinic side-chains. 
They mostly contain the group C3H5, either the allyl or propenyl group; 
myristicin alone apparently makes an exception, having a butenyl group. 
When heated with alcoholic potassa or sodium ethylate those substances 
containing an allyl group are converted into their isomers with a 
propenyl group. 
1) Arch. d. Pharm., 233, p. 188. 
2) Berichte, 26, p. 2086. 
3) Berichte, 32, p. 1518. 
4) Liebig's Annalen, 243, p. 46. 
5) Recueil des trav. chim. des P.-B., 12, 
p. 177. 
6) Gazz. chim. ital., 15, p. 59. Jahresb. 
f. Chem., 1885, p. 314. 
7) Berichte. 32, p. 1518. The More Commonly Occurring Constituents of Volatile Oils. 
179 
Chavicol. 
Chavicol (p-allylphenol), CgHr. CsH^C . OH W occurs in betel leaf oil 
from Java and in bay oil. 
It is a colorless liquid, boiling at about 237° and according to 
Eykmann1 has dis° = 1.033 and nD = 1.5441. 
Methyl chavicol. 
Methyl chavicol (estragol) was first found in anise bark oil and later 
also in estragon oil.2 Accompanying its isomeric propenyl compound 
anethol, it occurs in the oils of anise, star anise, and fennel, and has 
been shown to be present in bay oil, in German and French basilicum 
oils and in the oil of Persea gratissima. 
Methyl chavicol is a colorless^ liquid with a Jaint anise-like odor, 
which boils at 215-216° (corr.) (Grimaux,3 1893). At 11.5° d = 0.979 
and 110 = 1 5244 (Eykman,1 1890). The ether isolated from estragon 
oil has, according to the observations made in the laboratory of 
Schimmel & Co., the following properties: 
B. p. 97-97.5° at 12 mm., 86° at 7 mm.; di5° = 0.9714-0.972; 
iidi6° - 1.52355-1.52380. 
Methyl chavicol is characterized by changing it into the solid anethol 
by boiling with alcoholic potassa or by converting it into homoanisic 
(p-methoxyphenylacetic) acid melting at 86°. 
Anethol. 
Anethol (p-propenylanisol), CbHi. C3H5W . OCH3W, is the main con- 
stituent of anise and star anise oils and is also contained in considerable 
quantity in fennel oil. It has also been shown to be present in the oil of 
Osin orrh iza longistylis. 
It is a white crystalline mass, with a strong anise-like odor, the 
properties of which with slight disagreements are given as follows: 
M. p. 21.1°; b. p. 233-233.5° (751 mm.-); d^° = 0.9855 (Moreau & 
Chauvet,4 1897); 
M. p. 21°; d25° = 0.986; ud18° = 1.56149 (Stohmann,6 1892); 
du.5o = 0.999; ud = 1-5624 (Eykman1)- 
i) Berichte, 23, p. 862. 
2) Bericht von Schimmel & Co., April 
1892, pp. 17 &41; April, 1894, p. 28. 
3) Compt. rend., 117, p. 1089. 
4) Bull. Soo. chim., Ill, 17, p. 411. 
5) Sitzungsber. d. Akad.d.Wiss. Leipzig, 
1892, p. 307. 180 
General Part. 
When oxidized with chromic acid it is converted into anisic acid, 
with potassinin permanganate into p-methoxyphenylglyoxylic acid 
CoHwOCHs. W .CO.COOHi1] (in. p. 89°). With bromine the well crystal- 
lized monobrom anethol dibromide CoHgBr(OCH3). CsH5Br2 (m. p. 107- 
108°) results (Hell & Garttner,1 1895). 
Eugenol, betelphenol and safrol are derivatives of allyl- and propenyl- 
dioxybenzene respectively, which are not known as such. 
Eugenol. 
Eugenol (allylguaiacol), CeH.s. C3H5OJ. OCHsf3! . OHW, is contained 
in large amounts in the oil of cloves and clove stems. It is also found 
in the oils of cinnamon leaves, Ceylon cinnamon, sassafras, massoy 
bark, pimenta, bay, and canella, also in camphor oil and culilawan oil. 
It is a faintly yellow liquid, with an intense clove-like odor and 
burning taste with the following properties: 
B. p. 252° at 749 mm.; 123° at 12-13 mm. (Erdmann,2 1897); 
di<.5° = 1-072; ud = 1.5439 (Eykman,3 1890). 
With ferric chloride in alcoholic solution eugenol produces a blue 
coloration.' Upon oxidation (best as acetic acid ester) it yields vanillin 
and vanillic acid, besides small quantities of homovanillic acid. 
For its characterization the benzoic acid ester, m. p. 69-70°, which 
can be prepared with benzoyl chloride is well adapted. 
Besides eugenol some aceteugenol is also found in clove oil, but not 
in clove stem oil. It is frequently accompanied by its methyl ether 
(allyl veratrol) CeH.g. C3H5W . OCHgl^ . OCH3W, which occurs in bay and 
culilawan oils, in paracoto bark oil, in oil of Asamm europaeum. in 
citronella oil and probably in matico oil. The methyl ether possesses an 
odor reminding of eugenol but much weaker; it boils at 248-249° 
(128-129° at 11 mm.), du° = 1.041, iid = 1.5373 (Bertram & Gilde- 
meister,4 1889; Eykmann3). 
With bromine methyl eugenol yields the tribrom methyl eugenol 
CeH2Br. (OCHs^ . CsHgB^, crystallizing in pretty needles melting at 78° 
(Wassermann ;5 B. & G.4). By oxidation with potassium permanganate 
it is converted into dimethyl dioxybenzoic acid (veratric acid.) melting- 
at 179-180° (Comp. Wallach & Rheindorff,6 1892). Both compounds 
are well suited for the detection of methyl eugenol. 
i) Journ. f. prakt. Chem. II, 51, p. 424. 
2) Journ. f. prakt. Chem. II. 56, p. 146. 
3) Berichte, 23, p. 862. 
*) Journ. f. prakt. Chem. II, 39, p. 354. 
5) Jahresber. f. Chem., 1879, 520. 
6) Liebig's Annalen, 271, p. 306. The More Commonly Occurring Constituents of Volatile Oils. 
181 
Safrol. 
Safrol (shikimol of Eykman),the principal constituent of sassafras oil, 
is contained in considerable quantity in camphor oil and has been found 
in cinnamon leaf oil, star anise oil and massoy bark oil. It is the 
methylene ether of an allyl pyrocatechin CsHg. C3H5HJ . OOC^t3'41. 
It is a colorless or faintly yellow liquid which has the following' 
properties, according to observations made in the laboratory of 
Schimmel & Co.: 
B. p. 233° (759 mm.); di5° = 1.108; nr)i-° = 1.53836. 
On cooling it solidifies to a mass of crystals which do not melt 
until + 11°. Subjected to careful oxidation with potassium perman- 
ganate a glycol is first formed, which by further oxidation is converted 
into homopiperonylic acid C6H3.OOCH2.CH2.COOH (ni. p. 127°); 
when the oxidation is effected with chromic acid mixture piperonal 
(heliotropin) and piperonylic acid CeH3.OOCH2.COOH (m. p. 228°) 
are obtained. 
Asarone and myristicin are representatives of olefinic trioxybenzenes 
occurring in volatile oils. 
Asarone. 
Asarone 1 propenyl trimethoxybenzene) C«H2. C3H5II]. (OCHsjsf2'4'5'^, 
is contained in the oil of Asarum europaeum and has recently been found 
in matico oil. It melts at 62°, yields with bromine a well crystallized 
dibromide (in. p. 85-86°) and is converted by oxidation with potassium 
permanganate into'asarylic acid (trimethoxybenzoic acid. Ce^fOCHsjs- 
*COC)H, m. p. 144°). Its synthesis from asarilic aldehyde has been 
accomplished by Gattermann and Eggers 1 (1899). 
As derivatives of a tetratomic, unsaturated phenol the isomeric 
apiols C6H.C3H5. O2CH2. (0CH3)2 should be mentioned. The common 
(or parsley) apiol (m. p. 29.5-30°) is contained in the oil of parsley 
seed and in that of the Venezuelan camphor wood. The isomeric 
liquid (or dill apiol) is obtained from the high boiling fractions of the 
East Indian dill oil. The latter differs from the former by yielding 
isoapiol, m. p. 44°, when heated with sodium ethylate. 
i) Berichte, 32, p. 290. 182 
General Part. 
Compounds Containing Nitrogen and Sulphur. 
(Nitriles, Sulphides, Mustard Oils.) 
Compounds containing nitrogen and sulphur occur frequently when 
parts of plants rich in albuminous (protoplasm) and similar substances 
are distilled, e. g. fresh herbs or seeds. The more volatile compounds? 
such as ammonia, trimethylamine, sulphuretted hydrogen (given off in 
considerable quantity in the distillation of caraway), and hydrocyanic 
acid escape mostly in the course of the distillation, and are dissolved 
in small quantity in the aqueous distillate. Occasionally they combine 
with constituents of the oil. 
Hydrocyanic acid, the nitrile of formic acid, is formed during the 
distillation of a large number of plants.1 Together with benzaldehyde 
it occurs in Plectronia dicocca and Indigofera galegoides, in the oils of 
bitter almonds, cherry laurel and wild cherry bark. 
The nitrile of phenyl acetic acid constitutes the principal constituent 
of the oils of Tropaeolum majus and of Lepidium sativum; the nitrile 
of phenyl propionic acid in the oil of Nasturtium officinale. Gadamer,2 
however, has recently shown that several of the cruciferous oils contain- 
ing nitriles in place of isothiocyanates are products of decomposition 
rather than products of hydrolysis of the underlying glucosides. When 
nitriles are obtained upon distillation the ferment has not had an 
opportunity to act. 
Of carbon disulphide small amounts have been found in the oil of 
black mustard. Dimethyl sulphide has been isolated from the low 
boiling portions of American peppermint oil. Sulphides and poly- 
sulphides have been found besides other sulphur derivatives in the oils 
of garlic and onion. Vinyl sulphide and its polysulphides constitute the 
principal constituent of Allium ursinum. 
As a separate group should be mentioned the esters of isothiocyanic 
acid, which are characterized by their pungent odor, and which are 
commonly designated as mustard oils. Their typical representative is the 
common (allyl) mustard oil from Brassica nigra and B. juncea. It Ims 
also been found in the following plants: Alliaria officinalis, Capsella 
bursa pastoris, Cardamine sp., Sisymbrium sp., Cochlearia armoracia, 
and Thlaspi arvense. Secondary butyl mustard oil constitutes the 
principal constituent of the oil of spoonwort; p-oxybenzyl mustard oil 
(sinalbin mustard oil) is obtained from the seeds of Sinapis alba; 
phenyl ethyl mustard oil has been found in the oil of mignonette root. 
i) Jahresbericht des botanisehen Gartens zu Buitenzorg, 1897, p. 37. 
2) Archiv f. Phar., 237, p. 111. 3. THE EXAMINATION OF VOLATILE OILS. 
The-special methods of testing the more important volatile oils are 
described in detail in the following chapters. In order to avoid repetition, 
however, it will be expedient to discuss briefly in a special chapter the 
general methods used in the investigation and the most common 
adulterants met with. 
The practice of adulteration of the volatile oils, which is probably 
as old as the manufacture itself, had in the beginning a certain justifi- 
cation, as with the incomplete technical equipment of the early times 
the addition of fatty oils,, turpentine oil, or alcohol was often necessary 
in order to extract from the plants their odorous principle. Later, 
when the preparation of the pure oils was already known, the practice 
of making these additions was still retained. 
Even thirty years ago, it was customary to distill coriander with the 
addition of orange oil and to put the distillate on the market as 
coriander oil. Since pure coriander oil can now be prepared without 
difficulty, the product obtained by using orange oil, as it is found 
now and then even at the present time, must be considered as adulter- 
ated and if the foreign ingredient is not made known, its sale is a fraud. 
The adulteration need not always be* by the addition of a less 
valuable body, it sometimes consists i'n that the more valuable con- 
stituent of the oil has been partially removed. The effect is the same, 
whether from a caraway oil of the specific gravity 0.910 so much carvone 
be removed that an oil of the specific gravity 0.890 remains behind, or 
whether the same result is attained by the addition of limonene to the 
same oil. 
Although the adulterations themselves mostly find a sufficient 
explanation in the profitableness and the pecuniary advantage to the 
adulterator, it cannot, however, be denied, that often the ignorance of 184 
General Part. 
the consumer, and above all the desire to buy as cheaply as possible, is 
the cause of the spurious composition of many an oil. More than once 
the producer may have been induced to adulterate, because he found no 
buyers for his pure products at a reasonable price, while his adulter- 
ating- competitor was able to do a lucrative business at lower prices. 
♦ The main reason for the extensive adulteration to which volatile 
oils have been subjected at times, is to be sought in the fact that the 
detection of adulterants was very difficult and often entirely impossible. 
Owing to the development of the chemistry of the terpenes and their 
derivatives, great progress has been made during the last ten or fifteen 
years in the detection of adulterations. Knowing the composition of 
not a small number of volatile oils, it has become possible not only to 
distinguish between a pure and an adulterated oil, but also to judge 
the quality of these oils. This is effected by estimating the amount 
of the principal, or the most important constituent. In lavender oil, 
bergamot oil, petitgrain oil and others, the amount of esters present 
are therefore determined; in thyme oil, clove oil, bay oil, and Cretian 
origanum oil the amount of phenols are estimated; in cassia oil and 
lemongrass oil the amount of aldehyde. The assay of santalwood oil 
shows how much santalol, that of palmarosa oil, how much geraniol is 
contained in the oil. The quality of the oils named finds numerical 
expression in the percentage strength of the active constituents such as 
esters, phenols, aldehydes and alcohols. 
In a second class of oils, whose composition is likewise sufficiently 
known, an assay is not yet possible. The reason for this is twofold: 
first the value of the oil depends not upon a. single constituent but 
upon the blending of the properties of several; and, secondly the chemical 
methods of investigation are not sufficiently developed. 
With these oils, the examination is restricted as a rule to the 
determination of the normal composition of the oil and the absence of 
commonly used adulterants. Such oils are lemon oil, orange oil, rosemary 
oil and spike oil, which should be tested particularly for turpentine oil. 
The incomplete knowledge of the composition and the defectiveness 
of the methods of testing most of the oils, do not at present allow 
of an investigation resting on a rational chemical basis. With this 
class of oils the entire examination consists in determining the physical 
constants. As the average and limit values of specific gravity, optical 
rotation, solubility, etc., of the more common oils are well known 
through observations extending over many years, variations from these 
values call the attention of the investigator to adulterants. The Examination of Volatile Oils. 
185 
Indeed, the physical behavior of an oil is in general very well suited 
to indicate rapidly the addition of foreign substances: the investigation 
of volatile oils should therefore begin with the determination of the 
physical properties, no matter whether the investigation be for practical 
or for scientific purposes. After this, the special methods are to be 
used, su h as saponification, acetylization, aldehyde and phenol deter- 
minations, ami finally, if it appears necessary, the tests for turpentine 
oil, fatty oil, alcohol or petroleum should be applied. 
It is of course evident that when the practical value of an oil is to 
be considered the examination of the odor1 and the taste must 
accompany the chemical investigation, for these are the properties on 
account of which the volatile oils are used in the perfume and soap 
industries, in the manufacture of candies and liquors, and partly at 
least in medicine. 
It is necessary, or at least greatly to be desired, to have for 
comparison a sample of a. genuine, faultlessly distilled oil. A few drops 
each, of the genuine oil and of the oil to be tested, are put on a 
strip of filter paper, and compared by smelling alternately of both. 
This odor test is repeated after the larger part of the oil has volatilized, 
and in this manner easily volatile as well as more difficultly volatile 
foreign substances may be recognized. 
It is possible, however, to give only a very imperfect expression in 
language of odor and taste perceptions; moreover, odor and taste are 
purely subjective and are also quite differently developed faculties in 
each individual. The perceptions made with the sense of odor ami of 
taste do not admit of expression and comparison by means of figures 
like other observations. An adulteration may, therefore, be subjectively 
recognized, but cannot be objectively proven. A good sense of smell is 
in spite of this limitation of great value in the examination, as it often 
directs the investigation into the proper channel in the shortest time. 
Poorly distilled oils, possessing an empyreumatic odor or "Blasen- 
geruch," or oils carelessly kept but otherwise unadulterated are almost 
altogether recognized by the sense of smell, rarely by any other means 
of investigation. 
Determination of the Physical Properties. 
Specific gravity. On account of its ready determination the 
specific gravity is the most frequently taken and, therefore, the best 
1) Attention may here be called to the interesting work by H. Zwaardemaker, Die 
Physiologic des Geruchs, Leipzig, 1895. 186 
General Part. 
known property of the volatile oils. Even concerning the seldom and 
little investigated oils statements of their density are to be found. 
Further, as the maximum and minimum values of the more commonly 
used oils are fixed, the determination of the specific gravity belongs to 
the most important and also easiest means of investigation. The 
specific, gravity of an oil is changeable within certain limits, and de- 
pendent, outside of age, on the manner of the distillation and also 
upon the source and the state of ripeness of the plant material used. 
The'extent of this variation is so different in the individual oils that 
no general rules can be formulated. With normal bergamot oil, for 
instance, the specific gravity lies between 0.883 and 0.886. The difference 
between the highest and the lowest density, therefore, amounts in this 
case to only three places in the third decimal. As a ride, however, the 
limit values lie much further apart. 
Most oils are lighter, some, however, heavier than water, especially 
those which contain larger amounts of oxygenated constituents of the 
aromatic series (e. g. wintergreen oil. clove oil, sassafras oil). The 
lowest specific gravity of all volatile oils is that of heracleum oil with 
0.800 and of rue oil with 0.833; the highest is that of wintergreen oil 
with 1.187. 
The determination is practically performed with an hydrostatic 
balance according to Mohr or Westphal,1 as the accuracy attained with 
this instrument, if rightly handled, is sufficient. When only small 
quantities of an oil are at disposal a pycnometer is used. 
In the determination the temperature is of course considered, and 
usually +15° C.2 is selected for reasons of convenience. Only with those 
oils which are viscous at +15°, or wholly or partly solidified, the 
density is determined at a correspondingly higher temperature. 
Optical rotation. The optical rotation is such a characteristic 
property of most of the volatile oils that its determination should never 
be omitted in an examination. Especially adapted for this purpose is 
the half-shadow polariscope according to Laurent.3 If the dark color 
of the oil does not allow of making the observation in a 100 mm. tube, 
which is tha,t usually employed, one of 50 or even 20 mm. may be 
i) The hydrostatic balance with steel axes by F. Sartorius, Gottingen, may be 
especially recommended. 
2) In this book, when not otherwise stated, the statements of the specific gravity 
are for a temperature of + 15° C. 
s) With regard to the manipulation of the polariscope the reader is referred to the well- 
known work by H. Landolt, "Das optische Drehungsvermogen organischer Substanzen", 
II. Edit., Braunschweig, 1898. The Examination of Volatile Oils. 
187 
used. In the following, an is the observed angle of rotation in a 
100 mm. tube with sodium light, and is the specific rotation as 
calculated by the formula [«]d= where a is the observed angle of 
rotation, 1 the length of the tube in millimeters and d the specific 
gravity of the liquid. When no special mention is made of the 
temperature, room temperature is to be understood. In general it is 
not necessary, although desirable, to make the observation at a fixed 
temperature, as the natural variations in the rotation of an oil are 
usually greater than the differences due to a variation in temperature 
of several degrees. Exceptions to this are the oils of lemon and orange, 
the rotation of which is relatively strongly influenced by even small 
changes in temperature. It is necessary, in order to get comparable 
figures, to determine the rotation of these two oils at + 20° or else to 
reduce the result to this temperature by calculation. The details of this 
will be found in the description of these oils in the special part. 
Refraction. The determination of the index of refraction ud has 
been recommended by several investigators for the examination of the 
volatile oils. Between chemical constitution and refraction there exist, 
as is well known, certain relations, and in many cases conclusions as to 
the position and number of double bonds may be drawn from the mole- 
cular refraction. Chemical individuals carefully purified are, however, 
necessary in order to obtain useful results. As the refractive coefficients 
of the constituents of the volatile oils are on the whole only slightly 
different from each other, they are not so well suited for the detection 
of adulterations as are other methods of examination. The addition of 
turpentine oil, for instance, infiuem es the refraction of lemon oil only 
slightly, but changes the rotation to a marked degree.1 As the refraction 
changes rapidly with the temperature, this must always be considered 
in making observations of the refractive coefficients of volatile oils. 
Congealing point. With certain oils, especially anise, star anise, 
fennel and rue oils, the congealing point gives a good basis for judging 
the quality. With the first three oils a high congealing point shows a 
large content of anethol, with rue oil one of methyl nonyl ketone. 
The determination of the congealing point can be very well performed 
with Beckmann's well-known apparatus for the determination of the 
molecular weight by the lowering of the freezing point. A few slight 
changes make it especially suited for this purpose. 
1) Bericht von S. & Co., October 1893, p. 50. 188 
General Part. 
Ihey consist principally in doing away with the cork connections which 
hinder the free inspection of the mercury thread of the thermometer. The 
laboratory of Schimmel & Co.1 has the form shown in fig. 52. The battery jar 
A serves as the receptacle for the cooling liquid or freezing mixture. The glass 
tube B hanging in the metal cover serves as an air jacket for the freezing tube 
C and prevents the premature congealing of the oil to be tested. The freezing- 
tube C is wider at the top and becomes narrower at the place where it rests 
on the edge of the tube B. In order to retain C in 
a fixed position three glass projections are fastened 
on the inside of the tube B, about 5 cm. below its 
upper edge. The thermometer, which is graduated 
into half degrees is held in position in a metal plate 
by three springs which allow of sliding the ther- 
mometer up or down. 
In conducting the determination with anise and 
star anise oil the battery jar is filled with cold 
water and pieces of ice, but with fennel oil a freezing- 
mixture of ice and salt is used. Then pour into the 
freezing tube so much of the oil to be tested that 
it stands at a height of about 5 cm. in the tube 
and bring the thermometer, which must not touch 
the sides of the tube at any place, into the liquid. 
During the cooling the overcooled oil is to be 
protected from disturbances, which would produce 
a premature congealation.2 When the thermometer 
has sunk about 10° below the congealing point, 
(with anise and star anise oil to about 6 to 8°) 
crystallization is to be induced by rubbing and 
scratching the thermometer against the sides of the 
tube. If this proceeding should not prove successful 
a small crystal of congealed oil or some solid 
anethol is brought into tRe liquid, when con- 
gealation will take place with liberation of heat. 
The solidification is hastened by continued stirring 
with the thermometer, the mercury thread of which 
rapidly rises and finally reaches a maximum which 
is called the congealing point of the oil. 
Behavior on boiling and fractional distillat on. Inasmuch 
as the volatile oils are mixtures of substances with different boiling- 
points it is improper to speak, as is so often done, of the boiling point 
of a volatile oil. It is more correct to speak of a boiling temperature, 
by which is meant the temperature interval within the limits of which 
the oil distills over in a single distillation from an ordinary distilling 
Fig. 52. 
i) Bericht von S. & Co.. October 1898, p. 49. 
2) A premature congeaJation often takes place when the oil has not been filtered 
clear, as suspended dust particles may give rise to congealation. The Examination of Volatile Oils. 
189 
flask (fig., 53) without the application of a fractionating arrangement. 
A thermometer with a shortened scale and with the entire mercury 
thread in the vapor is used. 
The observations recorded by different observers of the amounts of 
the same oil which distill over between certain limits of temperature, 
seldom agree, because 1 he results are not only greatly influenced by the 
form of the distilling flask, but also by the rapidity of the distillation 
and the height of the barometer. It is therefore necessary, in the 
'examination of certain fractions of individual oils, to use flasks of fixed 
dimensions and to observe a certain rapidity of distillation. Fortesting 
Fig. 53 
lemon oil, rosemary oil and spike oil, Schimmel & Co. use distilling1 
flasks according to Ladenburg of the dimensions given in fig. 54.1 
From 50 cc. of the oils mentioned, 5 cc. are distilled over in such a 
manner that about 1 drop falls in a second, and the distillate tested in 
the polariscope, as will be described more in detail under the individual 
oils. 
When the different constituents are to be isolated from an oil, the 
fractional distillation must be repeated many times and preferably by 
employing one of the well known distilling columns. It is best, in order 
i) Bericht von S. & Co., October 1898, p. 46. 190 
General Part. 
to avoid decomposition, to distill the fractions boiling above 200° in 
vacuum. Oils containing esters must first be saponified, as the acids, 
which are easily split off by the boiling, disturb the fractionation and 
may act upon the other constituents of the oils. 
Solubility. The volatile oils are readily soluble in the ordinary 
solvents, such as alcohol, ether, chloroform, benzene, acetic ether, carbon 
disulphide, petroleum ether, paraffin oil etc. Mention of this general 
property is not made in the description of the individual oils. A 
phenomenon which is sometimes considered as an incomplete solubility 
may be mentioned here. The turbidity noticed by mixing certain oils 
Fig. 54. 
with petroleum ether, paraffin oil or carbon disulphide is caused by the 
small amount of water which the oils have retained from their prepar- 
ation. The richer an oil is in oxygen, the more water it is capable of 
dissolving and the more cloudy does it become with petroleum ether.1 
The turbidity does not take place when the oil has been thoroughly 
dried with anhydrous sodium sulphate. 
i) When an oil rich in oxygen, such as bergamot oil, is mixed with one rich in 
terpenes, as turpentine oil or orange oil, the mixture becomes turbid by the separation 
of water. The Examination of Volatile Oils. 
191 
Although all oils are readily soluble m strong alcohol, only some of 
them are entirely soluble in dilute alcohol. For the last class this 
property becomes a practical and rapid means of examination. The 
presence of the difficultly soluble turpentine oil can, for instance, be 
readily shown in this manner in the oils soluble in 70 percent1 alcohol. 
The solubility determination is very simple. 
Bring into a small graduated cylinder (fig. 55) %-1 cc. of the 
oil to be tested and add small portions of the alcohol at a time 
until with vigorous shaking solution is effected. 
If an oil which is soluble under normal conditions does 
not dissolve, it is sometimes possible to draw conclusions as 
to the adulterant from the character of the turbidity and 
the separation of the insoluble part. Petroleum floats on 
the 70 percent alcohol, whereas fatty oil settles in-drops at 
the bottom. 
Dowzard2 suggests that the "solubility value" be deter- 
mined by dissolving 5 cc. of an oil in 10 cc. of alcohol, sp. gr. 
0.799, and diluting with water from a burette until the 
solution becomes turbid. By multiplying the number of cc. of water by 
100 the "solubility value" is obtained. 
Duyk3 recommends the use of a solution of sodium salicylate in 
water 1:1. The alcohols, aldehydes, and ketones, are much more soluble 
than the sesquiterpene hydrates, phenol ethers and esters. The hydro- 
carbons are practically insoluble. In special cases this solution may 
prove valuable. 
Fig. 55. 
Chemical Methods of Testing, 
The rational examination of a volatile oil in a chemical manner is 
only then possible, when its composition or at least its main constituents 
are known. The chemical investigation must be directed as much as 
possible toward the isolation and quantitative estimation of the con- 
stituents recognized as being the most valuable. The methods of testing 
must, therefore, conform to the analysis of the oil. If this really self- 
evident supposition had earlier been generally recognized, those methods 
of investigation, which are designated as quantitative reactions, as for 
instance the iodine absorption, or Maumen^'s sulphuric acid test, which 
i) The statements in this book always refer to volume percent. 90 percent alcohol 
corresponds to the Spiritus, and 70 percent to the Spiritus dilutus of the German 
Pharmacopoeia. 
2) Chemist & Druggist, 53, p. 749. 
3) Bull, de 1'Acad. Roy. de Med. de Belgique, 1899, p. 503; Ann. de Pharm., 5, p. 348. 192 
General Part. 
had given good results with the fatty oils, would not have'been applied 
offhand to the volatile oils. 
The fatty oils are a group of chemically closely related bodies; they 
are glycerides of the fatty and oleic acid series. The constituents of the 
volatile oils, however, recruit themselves from the greatest variety of 
classes of bodies. Among them may be found terpenes, sesquiterpenes, 
paraffins, alcohols, aldehydes, ketones, phenols, ethers, and esters. It 
should be no matter for surprise, therefore, that the methods of testing 
which are useful with the fatty oils, fail completely with the volatile 
oils. Nor is there any sense in subjecting the fatty and the volatile oils 
to the same reactions, just because they both bear the same designation 
"oils." 
The application of Hiibl's iodine addition method to volatile oils 
has been recommended by Barenthin1 (1886), Kremel2 (1888), Williams3 
(1889), Davies4 (1889) and Snow3 (1889). By a direct comparison of 
the results of these separate observers it could not have been difficult 
for Cripps6 (1889) to show the utter uselessness of this method. 
The use of bromine in place of iodine was first suggested by 
Levallois7 (1884) and later by Klimont8 (1894). 
In Maumene's test the fatty oil to be investigated is mixed in a 
certain proportion with concentrated sulphuric acid and the rise in 
temperature which takes place is observed. Its application to volatile oils 
was recommended by Williams9 (1890) as well as by Duyk10 (1897) 
but it has found just as little favor in practice as the others named 
abo've. 
With these methods are to be classed also the much recommended 
color reactions. They mostly consist in bringing together a volatile oil 
and e. g. sulphuric acid or nitric acid, whereby some coloration is pro- 
duced, which only in rare cases can be ascribed to a definite chemical 
change. As the shades of color produced are difficult to describe, and 
often cha.nge from one to the other and may therefore easily, give rise 
to mistakes, the color reactions in general are to be designated as use- 
less. This does not exclude, however, the occasional use of a color 
reaction in the detection of adulterants. It is, however, never to be 
considered as conclusive in itself. 
i) Archiv d. Pharm., 224, p. 848. 
2) Pharm. Post, 21, pp. 789, 821. 
s) Chem. News, 60, p. 175. 
1) Pharm. Journ., Ill, 19, p. 821. 
5) Pharm. Journ., Ill, 20, p. 4. 
6) Chem. News, 60, p. 236. 
t) Coinpt. rend., 99, p. 977. 
8) Chemiker Zeitung. 18, p. 641. 
9) Chem. News, 61, p. 64. 
io) Bull, de l'Acad. roy. de med. de Belgique. The Examination of Volatile Oils. 
193 
Besides the methods of testing already enumerated, many others 
have been suggested in the course of time, which however have acquired 
as little practical importance as these. Only such methods are here to 
be discussed as have really proven satisfactory in the investigation of 
volatile oils. 
Saponification. Through scientific investigation it has been 
established that many volatile oils contain ester-like compounds, the 
components of which are alcohols, usually of the composition CioHisO 
or CioHaoO on the one hand, and acid radicals of the fatty series, on 
the other. 
The esters, which are nearly without exception of a pleasant odor, are 
often to be considered as the most important constituents of the oils. 
Thus, linalyl acetate is the carrier of the odor in bergamot oil; the same 
ester is found in lavender oil and also occurs along with other compounds 
in petitgrain oil. The esters of borneol, found in the different pine-needle 
oils, play an important part in the formation of the pine aroma. 
Menthyl acetate is found in the peppermint oils and the geranyl ester 
of tiglic acid in the different geranium oils. The quantitative estimation 
of the ester is always valuable for judging the oils, even when the 
esters are of little consequence to the odor. But much more important, 
and really the only rational method as a test of quality is the determin- 
ation in all cases where the esters are the carriers of the characteristic 
odor, as with bergamot oil and with lavender oil. The estimation is 
made according to the method of quantitative saponification, as it has 
long been used in the analysis of the fats. Its application to the 
volatile oils was first made by A. Kremel1 (1888). This suggestion did 
not reach a practical importance until through scientific investigation 
the nature of the saponifiable compounds was learned. 
Kremel distinguishes acid number (S. Z.), ester number (E. Z.), and 
saponification number (V. Z.). The acid number expresses how many 
mg. KOH are necessary to neutralize the amount of free acid contained 
in 1 g. of oil. The ester number gives the amount of potassa in milli- 
grams used in the saponification of the ester contained in 1 g. of oil. 
The saponification number is the sum of acid number and ester number. 
As the volatile oils usually contain only a small amount of free acid, 
this may in general be neglected. Only old, partly spoilt oils, tend to 
show somewhat higher acid numbers. 
It must be mentioned that in all oils which contain aldehydes, the 
1) Pharm. Post, 21, pp. 789, 821. 194 
General Part. 
tester determination by saponification cannot be made, as a consumption 
of alkali takes place which increases with the length of the reaction, due 
to the decomposition of the aldehyde, but which gives no information 
as to the amount of aldehyde decomposed. 
The saponification is conducted in a wide necked flask of 
potash glass of 100 cc. capacity (fig. 56). A glass tube 
about 1 in. in length and passing through a stopper serves 
as a reflux condenser. About 2 g. of oil are weighed accur- 
ately to 1 eg. into such a flask and 10 to 20 cc.1 of an 
hemi normal alcoholic potassa solution are added. Previous 
to this the oil should be tested for free acid, an alcoholic 
solution of phenolphthalein being used as indicator. The 
flask provided with the condensing tube is heated for half an 
hour2 on a steam bath, and after cooling, the contents are 
diluted with about 50 cc. of water and the excess of alkali 
titrated back with half normal sulphuric acid. 
From the saponification number found, the percent- 
age content of esters of the formula C1OH17OCOCH3 
and CioHioOCOCHs may be read directly in the tables 
to be found on page 204 at the end of this chapter. 
Acetylization. Many volatile oils contain as im- 
portant constituents alcohols of the formula CioHisO 
and C10H200, for instance, borneol, geraniol, terpineol, 
linalool, thujylalcohol, menthol and citronellol. For the quantitative 
estimation their behavior toward acetic acid anhydride, with which they 
form acetic esters when heated, may be used. The reaction takes place 
according to'the equation: 
CioHi8O + (CH3CO)2O = CioH17OCOCH3 + CH3COOH. 
The reaction is quantitative with borneol, geraniol (Bertram and 
No. 56. 
i) In most cases 10 cc. are sufficient, only with unknown oils 20 cc of alkali solution 
are taken, 
2) With bergamot oil the saponification is complete within 10 minutes. In order 
to be certain in all cases, the heating can be continued somewhat longer, without 
detrimental effect. Compare Bericht von Schimmel & Co., October 1895, p. 16. The 
method used by Helbing (Helbing's Pharmacological Record, No. 30, p. 4) of saponifying 
in a closed vessel, consequently under pressure, gave, as the experiments by Schimmel & 
Co. show, for bergamot oil from 1-2 percent higher results than did the saponification 
in an open flask. The reason for this is, that when saponified under pressure the 
linalool is attacked by the potassa, which is thereby used up, while by boiling with 
potassa in an open flask the alcohol is not affected. Later (1895), Helbing and Pass- 
more (Chern. & Drug., 47, p. 585) coroborated that the saponification in an open vessel 
with a reflux condenser was preferable to saponification in an autoclave. Neither does 
the so-called cold saponification appear to be applicable to volatile oils. Moreover, it 
has the disadvantage of requiring a longer time. For, according to Henriques, (Zeit- 
schrift fiir angewandte Chemie, 1897, p. 399) linalool after 12 hours action of the 
alkali gave the saponification number 4.2, and geraniol by the same treatment one of 2.8. The Examination of Volatile Oils. 
195 
Gildemeister,1 1894) and menthol (Power and Kleber,2 1894) and makes 
an accurate determination of these bodies possible.3 Less fortunate are 
the conditions with linalool and terpineol as these on boiling with acetic 
acid anhydride are partly decomposed by splitting off water with the 
formation of terpenes. Comparative figures can, however, be also obtained 
with these alcohols, if the same amount of acetic acid anhydride is 
always used and the boiling continued for the same length of time. 
With linalool there was found as a favorable result after 2 hours of 
boiling, a deficiency of 15 percent of alcohol.4 
Terpineol behaves toward acetic acid anhydride as follows: 
Time of boiling: 
Terpinyl acetate formed 
10 minutes 
51.2 percent 
30 
75.5 
45 
84.4 
2 hours 
77.9 
With terpineol, therefore, heating longer than 45 
minutes has a detrimental effect. 
Acetic acid anhydride acts differently on aldehydes. 
While citronellal is converted quantitatively into iso- 
pulegol acetate, with citral there are formed indefinite 
amounts of saponifiable products5 as yet unknown. 
For the quantitative acetylization6 10 to 20 cc. of the 
oil, mixed with an equal volume of acetic acid anhydride 
and 1-2 g. of dry sodium acetate, are boiled uniformly from 
1-2 hours in a small flask provided with a condensing tube 
which is ground into the neck of the flask (fig. 57). After 
cooling, some water is added to the contents of the flask and 
then heated from % to % hour on a water bath, to decom- 
pose the excess of the acetic acid anhydride. The oil is then 
separated in a separating funnel, and washed with soda solution and water 
until the reaction is neutral. Of the acetylized oil dried with anhydrous 
sodium sulphate 2 g. are saponified according to the method described on 
Fig. 57. 
i) Journ. f. prakt. Chern., II, 49, p. 189. 
2) Pharm. Rundsch., 12, p. 162; Archiv d. Pharm., 232, p. 653. 
3) Even with these alcohols an indiscriminate application of this otherwise excellent 
method to all oils containing them should be avoided. It is known that acetic acid 
combines with terpenes to form acetates of corresponding alcohols. In fact preliminary 
experiments show that pinene and limonene may assay in part as alcohol when this 
method is used. E. K. 
4) Bericht von S. & Co., April 1893, p. 38. 
5) Bericht von S. & Co., Oct. 1896, p. 34. 
6) Bericht von S. & Co., Oct. 1894, p. 63. 196 
General Part. 
page 194. The amount of alcohol, based on the original unacetylized oil, 
corresponding to the saponification number, can be found in the tables on page 
20+ at the end of this chapter. 
Aldehyde determination. The quantitative determination of 
cinnamic aldehyde depends on its property to form a water soluble 
addition product with an excess of sodium bisulphite. When a known 
amount of an oil containing cinnamic aldehyde is shaken sufficiently 
long with a hot concentrated bisulphite solution, the aldehyde content 
of the oil is about equal to the decrease in volume. The manipulation 
of the aldehyde determination and the necessary apparatus are described 
in detail under cassia oil (see this). Citral behaves similar to cinnamic 
aldehyde, and is able to form a water soluble bisulphite addition pro- 
duct. 1 he same method is, therefore, applicable to oils rich in citral, 
as for instance, lemongrass oil. 
For the determination of the aldehydes in lemon oil this method 
is, however, not suited, on account of the formation of the citronella! 
addition product, which is insoluble in water and floats partly in the 
aqueous, partly in the oily layer and makes an accurate reading- 
impossible. Besides, the bisulphite method is hardly accurate enough 
for lemon oil, as this contains only 6-8 percent of aldehydes. 
Another method, to determine the carbonyl oxygen and thus the 
aldehyde and ketone content in volatile oils has been worked out by 
Benedikt and Strache1 (1893). The oil to be investigated is heated 
with a weighed amount of phenyl hydrazine, after some time the hydro- 
zone which has formed is separated by filtration, and the unchanged 
phenyl hydrazine in the filtrate oxidized with boiling Fehling's solution. 
By this treatment all the nitrogen of the phenyl hydrazine which has 
not taken part in the reaction is liberated as gas. From the volume 
of the collected nitrogen the amount of the unused phenyl hydrazine can 
be calculated. From this the amount which has gone into combination 
is known and consequently the amount of the ketone or aldehyde 
present. The amount of carbonyl oxygen, expressed in %o percents is 
designated as carbonyl number. 
With bitter almond oil (benzaldehyde), cumin oil (cuminic aldehyde), 
and rue oil (methyl nonyl ketone) this method yields fairly good results. 
With cassia oil, caraway oil, fennel oil and lemon oil, however, the 
determinations fall far too low.2 
i) Monatsh. f. Cheni., 14, p. 270. 
2) Beiicht von S. & Co., Oct. 1893, p. 48. The Examination of Volatile Oils: 
197 
The problem of a general method for determining the aldehyde and 
ketone content of volatile oils, is therefore not yet satisfactorily 
solved. Perhaps it is possible to reach better results by suitable changes 
in the method described. 
A method devised by Kremers and Schreiner specially for the 
estimation of carvone in carvone-containing oils will be discussed under 
caraway oil. 
Phenol determination. For an approximately accurate phenol 
determination in volatile oils, the property of the phenols to combine 
with alkalies to form compounds which are soluble in water, is used. 
If a measured quantity of an oil is shaken with a solution of alkali, 
the content of phenols can be approximately determined from the 
diminution in volume. The soda solution is to 'be five percent. A 
greater concentration is not allowable, as stronger phenol-alkali solutions 
take up relatively large amounts of the remaining constituents of the 
oil, and thus give results which are too high. The manipulation of 
such a determination is described under thyme oil. 
Thymol and carvacrol are determined by Kremers and Schreiner1 
(1896) quantitatively in volatile oils, by precipitating the phenols from 
the alkaline solution as.their iodine compounds and titrating back the 
iodine added in excess. The details of this method can be found under 
thyme oil. 
Schryver2 has based a new method for the determination of phenols 
on the fact that hydroxy compounds liberate ammonia from sodium 
amide. The determination of thymol in oil of thyme and of eugenol 
in clove oil is reported to give good results. 
According to Thoms3 (1891) eugenol is quantitatively changed to 
benzoyl eugenol and weighed as such. This method is especially to be 
recommended with clove oil and the oil of cinnamon leaves, as shaking 
out with alkali gives results which are too high. The manipulation for 
Thoms' method for estimating eugenol is given under clove oil. 
Methyl number. A number of volatile oils contain as important 
constituents methyl and ethyl ethers of phenols and acids, the alkyl 
groups of which can be determined according to Zeisel's method4 (1885). 
Benedikt and Griissner5 (1889) have recommended the quantitative 
methoxyl determination for the practical and scientific investigation of 
i) Pharm. Review, 14, p. 22. 
2) J. Soe. Ch. Ind., 18, p. 553. 
s) Berichte der pharm. Gesellsch., 1, p. 278. 
<) Monatsh. f. Chemie, 6, p. 989. 
a) Chem. Zeitung, 13, pp. 872, 1087. 198 
General Part. 
volatile oils, and shown its usefulness by a series of illustrations. They 
designate as methyl number that number which tells how many mg. of 
methyl 1 g. of substance splits off when boiled with hydriodic acid. 
Ethyl or propyl and isopropyl are here considered as having been 
replaced by the equivalent amount of methyl. The weighed amount of 
silver iodide is therefore in all cases calculated as methyl. 
The vapors of methyl iodide formed by boiling from 0.2 to 0.3 g. of the 
oil to be investigated with hydriodic acid (sp. gr. 1.70, to which, according 
to Herzig1 (1888) 8 percent of acetic acid is added) are first passed through 
some warm water in which some phosphorus is suspended, so as to retain any 
iodine vapors which may have been carried over. After the methyl iodide has 
passed through this apparatus it is passed into an alcoholic solution of silver 
nitrate and the separated silver iodide weighed. 
A very convenient apparatus has been designed by L. Ehmann2 
(1890) for carrying out this determination. 
Gregor3 (1898) has recently suggested to replace the phosphorus 
suspended in water by a solution of one part each of potassium 
bicarbonate and arsenous acid in 10 parts of water, by which not only 
the iodine vapors but also any hydriodic acid carried over is retained. 
For collecting the methyl iodide Gregor uses a normal silver nitrate 
solution which has been acidified with nitric acid and titrates back the 
silver not used for the precipitation of the silver iodide with %o normal 
potassium sulphocyanate solution according to Volhard. 
Of the oils investigated by Benedikt and Griissner the following 
gave no < methyl numbers: the oils of wormwood, bitter almond, 
angelica, bergamot, caraway, lemon, copaiba-balsam, coriander, cubeb, 
elemi, eucalyptus, geranium, juniper, cherry laurel, lavender, spearmint, 
peppermint, olibanum, oil of Pinus montana, savin, East Indian and 
West Indian sandalwood, turpentine and valerian. 
High methyl numbers were given by anise oil, star anise oil and 
fennel oil on account of their content of anethol and methyl chavicol, 
by clove oil, and oil of cinnamon leaves on account of their content of 
eugenol. With wintergreen oil the high methyl number is one to the 
methyl salicylate, with parsley oil to the apiol. 
The determination is only applicable with oils absolutely free from 
alcohol, as ethyl alcohol itself gives a methyl number, from which it 
follows, that this method may also be used for the quantitative 
i) Monatsh. f. Chemie, 9, p. 544. 
2) Chern. Zeitung, 14, p. 1767. 
3) Monatsh. f. Chemie, 19, p. 166. The Examination of' Volatile ()ils. 
199 
estimation of alcohol in those oils which in their pure condition do not 
contain any methoxyl groups.1 
The Detection of* Some of the More Common Adulterants 
Turpentine oil. Turpentine oil may be considered as the adulter- 
ant most often used. Very often it pan be recognized by its character- 
istic odor, especially in those oils which contain no pinene, as this is 
the main constituent of turpentine oil. In general, its presence causes 
changes in the specific gravity, solubility, boiling temperature and 
optical rotation. It must here be remembered that there are dextro- as 
well as laevogyrate turpentine oils. 
The positive proof of the presence of turpentine oil in oils, which in 
their pure state contain no pinene, is furnished by the isolation of and 
characteristic derivatives of pinene. The constituents boiling in the 
neighborhood of 160°, are fractionated out and, according to the method 
described on page 109, the pinene nitrosochloride, .as well as pinene 
nitrolbenzylamine or pinene nitrolpiperidine are prepared. 
If pinene is a normal constituent of the oil, the addition of turpentine 
oil can be recognized by a comparison of the physical properties of the 
lowest boiling fractions of the adulterated oil with the corresponding- 
portions of the pure oil. The detection of turpentine oil in rosemary 
oil furnishes an example (see this). 
Cedar wood, copaiba and gurjun balsam oils. On account of 
their cheapness and faint odor, these three oils belong to the most 
favored and the most dangerous of adulterants. They may, however, 
be detected without difficulty in most cases by means of their physical 
properties, which differ from those of many of the volatile oils, namely 
i) The methyl numbers of some of the oils investigated by Benedikt and Griissner 
can only be explained by the presence of alcohol. , It is greatly to be regretted, that the 
physical properties of the investigated oils are not given, and their purity cannot there- 
fore be judged. With the Ceylon cinnamon oil designated as No. 22 in the article cited, 
Benedikt and Griissner calculate from the methyl number found, 25.7, a eugenol content 
of 28.1 percent. As pure Ceylon cinnamon oil contains only 4-8 percent of eugenol, it 
follows from the determination (providing that the methyl number is due only to 
eugenol), that the oil was adulterated with the oil of cinnamon leaves, which is rich in 
eugenol. From this illustration it may be seen that the reported methyl numbers are 
to be used with care. It would therefore be a valuable piece of investigation to repeat 
these determinations on oils whose purity could be previously determined in another 
manner, in order to give to this really fine method the basis necessary for practical 
purposes. For the scientific investigation of the volatile oils the methoxyl determination 
s extremely valuable as it gives information of the presence or absence of phenol 
ethers or acid esters, which contain a methyl, ethyl, or propyl group. 200 
General Part. 
their difficult solubility in 70 to 90 percent or even stronger alcohol, 
their high specific gravity (above 0.900), their high boiling temperature, 
above 250°, and finally their rotatory power. 
All three oils turn the plane of polarized light more or less to the 
left. With copaiba balsam oil the angle of rotation «D lies between-7 
and -35°,1 with cedar wood oil between -30 and -40°, and with 
gurjun balsam oil between -35 and -130°(!). 
At present only copaiba balsam oil can be detected in a chemical 
way, in that the fraction boiling about 260° is converted into caryo- 
phyllene hydrate melting at 94-96°, or into caryophyllene nitrolpiper- 
idine (see p. 125) melting fit 141-143°, or into caryophyllene nitrosite 
and the corresponding nitrol benzylamine base (see p. 126). As yet no 
characteristic derivatives of the sesquiterpenes of cedar wood and gurjun 
balsam oils are known. 
Alcohol. The addition of alcohol to a volatile oil always results 
in a lowering of the specific gravity. When an oil containing alcohol is 
dropped into water, the drops do not remain clear and transparent, as 
is the case with pure oils, but become opaque and milky. 
For the definite identification of alcohol the suspected oil is heated 
until it just begins to boil,2 and the first few drops that come over are 
collected in a test tube and filtered, to remove any oil globules which may also 
have come over, through a filter moistened with water. The filtrate is made 
strongly alkaline with dilute potassa solution, and treated, after heating to 
50-60°, with a solution of iodine in potassium iodide, until the solution 
remains slightly yellow. If alcohol is present small crystals of iodoform will 
separate in a short time at the bottom of the liquid. It must here be remembered 
that other bodies, such as aldehydes, acetone and acetic ether also yield iodo- 
form under the given conditions. 
Larger amounts of alcohol may be removed from volatile oils by 
shaking with water, from which the alcohol may be again removed by 
distillation and identified by the iodoform reaction. If the shaking out 
is done in a graduated cylinder, the increase of the watery layer 
corresponds approximately to the amount of the alcohol. 
According to Hager it is better to use glycerin, because with this 
the two layers separate better, and a. more accurate reading is possible. 
The alcohol content may also be approximately calculated if the 
specific gravity is determined before and after shaking with water. 
i) Umney in 1895 (Pharm. Journ., Ill, 24, p. 215), found the oil of a socalled 
copaiba balsam from west Africa to be dextrogyrate, «D~ + 20°42'. Dextrogyrate 
gurjun balsam oils are also said to exist. 
2) All alcohol is not removed by heating on a water-bath. The Examination of Volatile Oils. 
201 
As already mentioned on page 198 the amount of the alcohol in an 
oil which in itself does not give a methyl number, may be determined 
quantitatively by Zeizel's methoxyl method. 
Fatty oil. The volatile oils adulterated with fatty oil leave a 
permanent fatty stain when evaporated on paper. With high boiling 
and difficultly volatile oils, however, similar residues are left, which may 
give rise to mistakes. Fatty oil is insoluble in 90 percent alcohol.1 For 
the separation of the fatty oil from the volatile oil the latter is distilled 
off by steam distillation or removed by evaporation in an open dish on 
the waterbath, where it must be remembered that some volatile oils, as 
bergamot, lemon, orange, anise and star-anise oil leave a residue of 
several percent even when they are not adulterated. 
The presence of the fat may be shown qualitatively in the residue 
by heating with potassium bisulphate in a test tube. Penetrating 
odors of acrolein show its presence. By igniting the residue on a 
platinum foil the characteristic odor of burning fat is noticed. 
As the fatty oils give saponification numbers which lie between 180 
and 200, the amount of the fat added can be determined quantitatively 
either directly in the volatile oil itself or in the distillation residue, by 
saponification. 
Oils that have been adulterated with cocoa nut oil solidify wholly 
or in part in a freezing mixture. Cocoa nut oil has been found in 
cananga oil, citronella oil and palmarosa oil and detected in this 
manner. 
Mineral oil, petroleum. Mineral oil, paraffin oil, kerosene, 
petroleum and petroleum fractions are insoluble in alcohol and can 
therefore be detected without difficulty in volatile oils; besides, they are 
often easily recognized by their low specific gravity. Palmarosa oil to 
which some mineral oil has been added is only partly soluble in 70 
percent alcohol. If the insoluble portion is successively treated with 
90 percent and absolute alcohol, an oil remains, which in the beginning 
it is true is colored brown by sulphuric or nitric acids, but in general 
resists the action of these acids and also of alkalies, and on saponi- 
fication with alcoholic potassa gives no saponification number. 
The mineral oils have different boiling points. The hydrocarbons 
of illuminating oil boil at about the same temperature as the terpenes. 
Lower boiling fractions are said to be sometimes used for adulterating 
turpentine oil. A higher boiling mineral oil, about 250°, has been 
O Only castor oil is soluble in 90 percent, but is insoluble in 70 percent alcohol. 202 
General Part. 
found in citronella and in gingergrass oils. The petroleum fractions 
of a lower boiling point are easily volatile with water vapor, the higher 
fractions not at all, or at least to only a small degree. 
A method for the quantitative estimation of mineral oils consists in 
weighing the residue left after having removed the volatile oil by 
oxidation with fuming nitric acid, as described under turpentine oil 
(see this). Attention should be called to the fact that some volatile 
oils, such as rose oil, chamomile oil, orange flower oil and others, 
contain larger or smaller amounts of paraffins as natural constituents. 
Chloroform. This body, which has been found occasionally in 
volatile oils (for instance, in cognac oil and sandalwood oil) can be 
isolated by distillation on a water bath and identified by the isonitrile 
reaction. This consists in that a small amount of the suspected 
distillate is treated with a few drops of aniline and alcoholic caustic 
soda solution, and gently heated. In the presence of chloroform the 
noxious and exceedingly disagreeable smelling vapors of phenylisonitrile 
are formed. 
Table 
for Calculating the Amount of Alcohols of the Formula CioHisO and C10H200, 
as well as acetic esters of these alcohols, from the saponification numbers, 
found before and after acetylizing. 
In order to save time-robbing calculations the following table, 
(p. 204 et seq.) has been worked out in the laboratory of Schimmel & 
Co.,1 from which the amounts of the alcohols CioHisO (geraniol, linalool, 
borneol, isopulegol, etc.) and C10H200 (menthol, citronellol) as well as 
their acetic esters, corresponding to the individual saponification 
numbers, can be read off. From this compilation it is further possible 
to see how much alcohol in the original oil corresponds to the saponifi- 
cation number of the acetylated oil. 
A few examples may serve to illustrate the above statements. 
The saponification number 109 has been found by saponifying a, 
bergamot oil. In the left half of the table headed CioHisO look up the 
number 109, and there will be found in the column which bears the 
heading "Acetate", the number 38.15, which gives the percentage content 
i) Bericht von Schimmel & Co., Oct. 1897, p. 82. 77m Examination of Volatile Oils. 
203 
of linalyl acetate in the bergamot oil. This 38.15 p. c. of acetate 
corresponds, as may be seen in the next column headed "Alcohol", to 
29.98 p. c. of linalool. 
By the saponification of a peppermint oil in the original unacetylated 
state, the saponification number 20 is found, and by the saponification 
after boiling with acetic acid anhydride, the saponification number 179. 
It is found that in the right half of the table the saponification number 
20 - 7.07 p. c. of acetate C1OH19OCOCH3, in this case menthyl acetate, 
and corresponds to 5.57 p. c. of menthol. The saponification number 
179 shows that 57.60 p. c. of total menthol are contained in this 
peppermint oil. If the total amount of menthol is 57.60 p. c., and that 
of menthol as ester 5.57, the peppermint oil contains 57.60 minus 5.57 
or 52.03 p. c. of free menthol. 
In the calculation of this table the following formulas were applied : 
196 X bap. No. 
1. = percent 01 ester 
56 
0 154 X Sap. No. 
2. - = percent of alcohol 
06 _ 
o a X lo.4 . . . . .. 
3. --n - percent of alcohol in the original oil 
s -(a X 0.042) , 
For the 
alcohol 
CioHigO 
198 X Sap. No. , 
1. -percent of ester 
5n 
9 156 X Sap. No. _ . . . , . 
2. - = percent of alcohol 
ab 
_ a X 15.6 
o. 7-o A »v - percent of alcohol m the original oil. 
s - (a X 0.012) K & 
For the 
alcohol 
CioH2oO 
In these formulas: 
a = the number of cubic centimeters of normal potassa solution used. 
s - the number of grams of the acetylated oil used for the saponification. 204 
General Part. 
CioHi8O 
C10H200 
Sap. 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
1 
0,35 
0,28 
0,27 
0,35 
0,28 
0,28 
1 
2 
0,70 
0,55 
0,55 
0,71 
0,56 
0,56 
2 
3 
1,05 
0,83 
0,83 
1,06 
0,84 
0,84 
3 
4 
1,40 
1,10 
l,io 
1,41 
1,11 
1,12 
4 
5 
1,75 
1,38 
1.38 
1,77 
1,39 
1,40 
5 
6 
2,10 
1,65 
1,66 
2,12 
1,67 
1,68 
6 
7 
2,45 
1.93 
1,94 
2,47 
1,95 
1,96 
7 
8 
2,80 
2,20 
2,21 
2,83 
2,23 
2,24 
8 
9 
3,15 
2,48 
2,49 
3,18 
2,51 
2,52 
9 
10 
3.50 
2,75 
2,77 
3,54 
2.79 
2,81 
10 
11 
3,85 
3,03 
3,05 
3,89 
3,06 
3,09 
11 
12 
4,20 
3,30 
3,33 
4,24 
3,34 
3,37 
12 
13 
4,55 
3,58 
3,61 
4,60 
3,62 
3,66 
13 
14 
4,90 
3,85 
3,89 
4,95 
3,90 
3,94 
14 
15 
5.25 
4,13 
4,17 
5,30 
4,18 
4,23 
15 
16 
5,60 
4,40 
4,45 
5,66 
4,46 
4,51 
16 
17 
5,95 
4,68 
4,74 
6,01 
4,74 
4,80 
17 
18 
6,30 
4,95 
5,02 
6,36 
5,01 
5,08 
18 
19 
6,65 
5,23 
5,30 
6,72 
5,29 
5,37 
19 
20 
7,00 
5,50 
5,58 
7,07 
5,57 
5,66 
20 
21 
7,35 
5,78 
5,87 
7,42 
5,85 
5,94 
21 
22 
7,70 
6.05 
6,15 
7,78 
6,13 
6,23 
22 
23 
8,05 
6,33 
6,44 
8,13 
6,41 
6,52 
23 
24 
8,40 
6,60 
6,72 
8,49 
6,69 
6,81 
24 
25 
8,75 
6,88 
7,01 
8,84 
6,96 
7,10 
25 
26 
9,10 
7.15 
7,29 
9,19 
7,24 
7,39 
26 
27 
9,45 
7,43 
7,58 
9,55 
7,52 
7,68 
27 
28 
9,80 
7,70 
7,87 
9,90 
7,80 
7,97 
28 
29 
10,15 
7,98 
8,15 
10,25 
8,08 
8,26 
29 
30 
10,50 
8,25 
8,44 
10,61 
8,36 
8,55 
30 
31 
10,85 
8,53 
8,73 
10,96 
8,64 
8,84 
31 
32 
11,20 
8,80 
9,02 
11,31 
8,91 
9,13 
32 
33 
11,55 
9,08 
9,31 
11.67 
9,19 
9,43 
33 
34 
11,90 
9,35 
9,59 
12,02 
9,47 
9,72 
34 
35 
12.25 
9,63 
9,88 
12.37 
9,75 
10.01 
35 
36 
12,60 
9,90 
10,17 
12 73 
10,03 
10.31 
36 
37 
12,95 
10,18 
10,47 
13,08 
10,31 
10,60 
37 
38 
13,30 
10,45 
10,76 
13,44 
10,59 
10.90 
38 
39 
13,65 
10,73 
11,05 
13,79 
10,86 
11,19 
39 
40 
14,00 
11,00 
11,34 
14,14 
11,14 
11,49 
40 The Examination of Volatile Oils. 
205 
CioHibO 
C10H200 
Sap. 
No. 
Acetate 
Alcohol 
Alcohol 
In the 
orig. oil 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Sap. 
No. 
41 
14,35 
11,28 
11,63 
14,50 
11.42 
11,78 
41 
42 
14,70 
11,55 
11,93 
14,85 
11,70 
12,08 
42 
43 
15,05 
11,83 
12,22 
15,20 
11,98 
12,38 
43 
44 
15,40 
12,10 
12,51 
15,56 
12,26 
12,68 
44 
45 
15,75 
12,38 
12,81 
15,91 
12,54 
12,97 
45 
46 
16,10 
12,65 
13,10 
16.26 
12,81 
13,27 
46 
47 
16,45 
12,93 
13,40 ■ 
16,62 
13.09 
13.57 
47 
48 
16,80 
13.20 
13,69 
16.97 
13 37 
13,87 
48 
49 
17,15 
13,48 
13,99 
17,32 
13,65 
14,17 
49 
50 
17,50 
13,75 
14,29 
17,68 
13,93 
14,47 
50 
51 
17,85 
14,03 
14,58 
18,03 
14,21 
14,77 
51 
52 
18,20 
14,30 
14,88 
18,39 
14,49 
15,07 
52 
53 
18,55 
14,58 
15,18 
18,74 
14,76 
15,38 
53 
54 
18,90 
14,85 
15,48 
19,09 
15,04 
15,68 
54 
55 
19,25 
15,13 
15,77 
19,45 
15,32 
15,98 
55 
56 
19,60 
15,40 
16,07 
19,80 
15,60 
16.28 
56 
57 
19,95 
15,68 
16,38 
20,15 
15,88 
16,59 
57 
58 
20,30 
15,95 
16,68 
20,51 
16,16 
16,89 
58 
59 
20,65 
16,23 
16,98 
■20,86 
16,44 
17,20 
59 
60 
21,00 
16,50 
17,28 
21,21 
16,71 
17,50 
60 
61 
21,35 
16,78 
17,58 
21,57 
16,99 
17,81 
61 
62 
21,70 
17,05 
17,88 
21,92 
17,27 
18,11 
62 
63 
22,05 
17,33 
18,18 
22,27 
17.55 
18,42 
63 
64 
22,40 
17,60 
18,49 
22.63 
17,83 
18,73 
64 
65 
22,75 
17,88 
18,79 
22,98 
18,11 
19,04 
65 
66 
23,10 
18,15 
19,10 
23,34 
18 39 
19,34 
66 
67 
23,45 
18,43 
19,40 
23,69 
18,66 
19,65 
67 
68 
23,80 
18,70 
19.70 
24,04 
18,94 
19,96 
68 
69 
24,15 
18,98 
20,01 
24,40 
19,22 
20,27 
69 
70 
24,50 
19.25 
20,32 
24,75 
19,50 
20,58 
70 
71 
24,85 
19,53 
20,62 
25,10 
19,78 
20,89 
71 
72 
25,20 
19,80 
20,93 
25,46 
20,06 
21,20 
72 
73 
25,55 
20,08 
21,24 
25,81 
20,34 
21,51 
73 
74 
25,90 
20,35 
21,55 
26,16 
20,61 
21,83 
74 
75 
26,25 
20,63 
21,85 
26,52 
20,89 
22,14 
75 
76 
26,60 
20,90 
22,16 
26,87 
21,17 
22,45 
76 
77 
26,95 
21.18 
22,47 
27,22 
21,45 
22.77 
77 
78 
27,30 
21,45 
22,78 
27,58 
21,73 
23,08 
78 
79 
27,65 
21,73 
23,09 
27,93 
22,01 
23,39 
79 
80 
28,00 
22,00 
23,40 
28,29 
22,29 
23,71 
80 206 
General Part. 
CioHtsO 
C10H200 
Sap. 
No. 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Sap. 
No. 
81 
28,35 
22 28 
23,72 
28,64 
22,56 
24,02 
81 
82 
28,70 
22,55 
24,03 
28,99 
22,84 
24,34 
82 
83 
29,05 
22,83 
24,34 
29.35 
23,12 
24,66 
83 
84 
29,40 
23,10 
24,65 
29,70 
23,40 
24,97 
84 
85 
29,75 
23,38 
24,97 
30,05 
23,68 
25,29 
85 
86 
30,10 
23,65 
25,28 
30,41 
23,96 
25,61 
86 
87 
30,45 
23,93 
25,60 
30,76 
24,24 
25,93 
87 
88 
30,80 
24,20 
25,91 
31,11 
24,51 
26,25 
88 
89 
31,15 
24,48 
26,23 
31.47 
24,79 
26,57 
89 
90 
31,50 
24,75 
26,54 
31,82 
25,07 
26,89 
90 
91 
31,85 
25,03 
26,86 
32,17 
25,35 
27,21 
91 
92 
32,20 
25,30 
27,18 
32,53 
25,63 
27,53 
92 
93 
32,55 
25,58 
27,49 
32,88 
25,91 
27,85 
93 
94 
32,90 
25,85 
27,81 
33,24 
26,19 
28,17 
94 
95 
33,25 
26,13 
28,13 
33,59 
26,46 
28,49 
95 
96 
33,60 
26,40 
28,45 
33,94 
26,74 
28,82 
96 
97 
33,95 
26,68 
28,77 
34,30 
27,02 
29,14 
97 
98 
34,30 
26,95 
29,09 
34,65 
27,30 
29,47 
98 
99 
34,65 
27,23 
29,41 
35,00 
27,58 
29.79 
99 
100 
35,00 
27,50 
29,73 
35,36 
27,86 
30,11 
100 
101 
35,35 
27,78 
30,05 
35,71 
28,14 
30,44 
101 
102 
35,70 
28,05 
30,37 
36,06 
28,41 
30,77 
102 
103 
36,05 
28,33 
30,70 
36,42 
28,69 
31,09 
103 
104 
36,40 
28,60 
31,02 
36,77 
28,97 
31,42 
104 
105 
36,75 
28,88 
31,34 
37,12 
29,25 
31,75 
105 
106 
37,10 
29,15 
31,67 
37,48 
29,53 
32,08 
106 
107 
37,45 
29,43 
31,99 
37,83 
29,81 
32,41 
107 
108 
37,80 
29,70 
32,32 
38,19 
30,09 
32,74 
108 
109 
38,15 
29,98 
32,64 
38,54 
30,36 
33,07 
109 
110 
38,50 
30,25 
32,97 
38,89 
30,64 
33,40 
110 
111 
38,85 
30,53 
33,30 
39,25 
30,92 
33,73 
111 
112 
39,20 
30,80 
33,62 
39,60 
31,20 
34,06 
112 
113 
39,55 
31,08 
33,95 
39,95 
31,48 
34,39 
113 
114 
39,90 
31,35 
34,28 
40,31 
31,76 
34,73 
114 
115 
40,25 
31,63 
34,61 
40,66 
32,04 
35,06 
115 
116 
40,60 
31,90 
34,94 
41,01 
32,31 
35,39 
116 
117 
40,95 
32,18 
35,27 
41,37 
32,59 
35,73 
117 
118 
41,30 
32,45 
35,60 
41,72 
32,87 
36,06 
118 
119 
41,65 
32,73 
35,93 
42,07 
33,15 
36.40 
119 
120 
42,00 
33,00 
36,26 
42,43 
33,43 
36,73 
120 The Examination of Volatile Oils. 
207 
CioHisO • 
Ci0H200 
Sap. 
No~ 
Alcohol 
Alcohol 
Sap. 
No.. 
Acetate 
Alcohol 
in the 
orig. oil 
Acetate 
Alcohol 
in the 
orig. oil 
121 
42,35 
33,28 
36,60 
42,78 
33,71 
37,07 
121 
122 
42,70 
33,55 
36,93 
43,14 
33,99 
37,41 
122 
123 
43,05 
33,83 
37,26 
43,49 
34,26 
37,75 
123 
124 
43,40 
34,10 
37,60 
43,84 
34,54 
38,08 
124 
125 
43,75 
34,38 
37,93 
44,20 
34,82 
38,42 
125 
12G 
41,10 
31,65 
38,27 
44,55 
35,10 
38,76 
126 
127 
44,45 
34,93 
35,20 
38,60 
44,90 
35,38 
39,10 
127 
128 
44,80 
38,94 
45,26 
35,66 
39,44 
128 
129 
45,15 
35.48 
39,27 
45,61 
35,94 
39,78 
129 
130 
45,50 
35,75 
39,61 
45,96 
36,21 
40,13 
130 
131 
45,85 
36,03 
39,95 
46,32 
36 49 
40,47 
131 
132 
46,20 
36,30 
40,29 
46,67 
36,77 
40,81 
132 
133 
46,55 
36,58 
40,63 
47,02 
37,05 
41,16 
133 
134- 
46,90 
36,85 
40,97 
47,38 
37.33 
41,50 
134 
135 
47,25 
37.13 
41,31 
47,73 
48,09 
37,61 
41,84 
135 
13G 
47,60 
37,40 
41,65 
37,89 
42,19 
136 
137 
47,95 
37,68 
41,99 
48,44 
38,16 
42,53 
137 
138 
48,30 
37,95 
42,33 
48,79 
38,44 
42,88 
138 
139 
48.65 
38,23 
42,67 
49,15 
38 72 
43.23 
139 
14-0 
49,00 
38,50 
43,02 
49,50 
39,00 
43,58 
140 
14-1 
49,35 
38,78 
43,36 
49,85 
39,28 
43,92 
141 
14-2 
49,70 
39,05 
43,71 
50,21 
39,56 
44.27 
142 
143 
50,05 
39,33 
44,05 
50,56 
39,84 
44,62 
143 
144 
50,40 
39,60 
39,88 
44,39 
50,91 
40.11 
44,97 
144 
145 
50,75 
44,74 
51,27 
40,39 
45,32 
145 
14G 
51,10 
40.15 
45,09 
51,62 
40,67 
45,67 
146 
147 
51,45 
40,43 
45,44 
51,97 
40,95 
46,02 
147 
148 
51,80 
40,70 
40,98 
45,78 
52,33 
41,23 
46,38 
148 
149 
52,15 
46,13 
52,68 
41,51 
46,73 
149 
150 
52,50 
41,25 
46,48 
53,04 
41,79 
47,08 
150 
151 
52,85 
41,53 
46,83 
53,39 
42,06 
47,44 
151 
152 
53,20 
41,80 
47,18 
53,74 
42,34 
47,79 
152 
153 
53,55 
42,08 
47,53 
54,10 
42,62 
48,15 
153 
154 
53.90 
54,25 
42,35 
47,88 
54,45 
42.90 
48,50 
154 
155 
42,63 
48.23 
54.80 
43,18 
48,86 
155 
156 
54,60 
42,90 
48,58 
55,16 
43,46 
49,21 
156 
157 
54,95 
43,18 
48,94 
55,51 
43,74 
49,57 
157 
158 
55,30 
43,45 
49,29 
55,86 
44,01 
49,93 
158 
159 
55,65 
43,73 
49,65 
56,22 
44,29 
50,29 
159 
160 
56,00 
44,00 
50,00 
56,57 
44,57 
50,65 
160 208 
General Part. 
CioHisO 
C10H200 
Sap. 
No. 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Acetate 
Alcohol 
Alcohol 
in the 
orig. oil 
Sap. 
No. 
161 
56,35 
44,28 
50,36 
56,92 
44,85 
51,01 
161 
162 
56,70 
4*4?, 
50,71 
57,28 
45,13 
51,37 
162 
163 
57,05 
44,83 
51,07 
57,63 
45,41 
51,73 
163 
164 
57,40 
45,10 
51,42 
57,99 
45,69 
52,09 
164 
165 
57,75 
45,38 
51,78 
58,34 
45,96 
52,46 
165 
166 
58,10 
45,65 
52,14 
58,69 
46,24 
52,82 
166 
167 
58,45 
45,93 
52,50 
59,05 
46,52 
53,18 
167 
168 
58,80 
46,20 
52,86 
59,40 
46,80 
53,55 
168 
169 
59,15 
46,48 
53,22 
59,75 
47,08 
53,91 
169 
170 
59,50 
46,75 
53,58 
60,11 
47,36 
54,28 
170 
171 
59,85 
47,03 
53,94 
60,46 
47,64 
54,64 
171 
172 
60,20 
47,30 
54,31 
60,81 
47,91 
55,01 
172 
173 
60,55 
47.58 
54,67 
61,17 
48,19 
55,38 
173 
174 
60,90 
47,85 
55,03 
61,52 
48,47 
55,75 
174 
175 
61,25 
48,13 
55,40 
61,87 
48,75 
56,12 
175 
176 
61,60 
48,40 
55,76 
62,23 
49,03 
56,48 
176 
177 
61,95 
48,68 
56,13 
62,58 
49,31 
56,85 
177 
178 
62,30 
48,95 
56,49 
62,94 
49,59 
57,23 
178 
179 
62,65 
49.23 
56,86 
63,29 
49,86 
57.60 
179 
180 
63,00 
49,50 
57,22 
63,64 
50,14 
57,97 
180 
181 
63,35 
49,78 
57,59 
64,00 
50,42 
58,34 
181 
182 
63,70 
50,05 
57,96 
64,35 
50,70 
58,71 
182 
183 
64,05 
50,33 
58,33 
64,70 
50,98 
59,09 
183 
184 
64,40 
50,60 
58,70 
65,06 
51,26 
59,46 
184 
185 
64,75 
50,88 
59.07 
65,41 
51,54 
59,84 
185 
186 
65,10 
51,15 
59,44 
65,76 
51,81 
60,21 
186 
187 
65,45 
51,43 
59,81 
66,12 
52,09 
60,59 
187 
188 
65,80 
51,70 
60,19 
66,47 
52,37 
60,97 
188 
189 
66,15 
51,98 
60,56 
66,82 
52,65 
61,35 
189 
190 
66,50 
52,25 
60,93 
67,18 
52,93 
61,72 
190 
191 
66,85 
52,53 
61,31 
67,53 
53,21 
62,10 
191 
192 
67,20 
52,80 
61,68 
67,89 
53,49 
62,48 
192 
193 
67,55 
53,08 
62,06 
68,24 
53,76 
62,86 
193 
194 
67.90 
53,35 
62,43 
68,59 
54,04 
63,24 
194 
195 
68,25 
53,63 
62,81 
68,95 
54,32 
63,63 
195 
196 
68,60 
53,90 
63,19 
69,30 
54,60 
64,01 
196 
797 
68,95 
54,18 
63.57 
69,65 
54,88 
64,39 
197 
198 
69,30 
54,45 
63,95 
70.01 
55,16 
64,78 
198 
199 
69,65 
54,73 
64,33 
70,36 
55,44 
65,16 
199 
200 
70,00 
55,00 
64,71 
70,71 
55,71 
65,55 
200 The Examination of Volatile Oils. 
209 
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No. The Examination of Volatile Oils. 
211 
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Sap, 
No. 
Acetate 
Alcohol 
Alcohol 
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Acetate 
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No. 
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- 4. LIST OF PLANTS, ARRANGED ACCORDING TO FAMILIES,1 
FROM WHICH VOLATILE OILS ARE OBTAINED. 
POLYPODIACEAE. 
Aspidium filix mas-Oil of male fern. 
PlNACEAE. 
Larix decidua-Oil of larch turpentine, larch needle oil. 
Pinus australis, P. taeda, P. cubensis, P. palustris-American turpentine oil. 
Pinus pinaster-French turpentine oil. 
Pinus laricio-Austrian turpentine oil. 
Pinus silvestris-Pine tar oil, and pine needle oil. 
Pinus ledebourii-Pine tar oil, Russian turpentine oil, and Siberian pine needle oil. 
Pinus khasya, P. merkusii-Burma turpentine oil. 
Pinus montana-Oil from needles. 
Pinus cembra-Oil from needles. 
Pinus sabiniana-Californian turpentine oil. 
Picea excelsa-Oil from oleoresin, oil from needles. 
Picea alba-Oil of needles. 
Picea, nigra-Oil of needles. 
Abies alba-Pine (white fir) needle oil, oil of cones of white fir, oil from oleoresin. 
Abies balsamea-Needle oil. 
Abies canadensis-Needle oil. 
Abies fraseri-Needle oil. 
Oil from Canada balsam. 
Abies reginae amaliae-Oil from cones. 
Cedrus libani-Lebanon cedar oil. 
Sequoia gigantea-Sequoia oil. 
Callitris quadrivalis-Sandarac oil. 
Thuja occidentalis-Thuja oil. 
Thuja orientalis-Oil from the roots. 
Cupressus sempervirens-Cypress oil. 
Chamaecyparis obtusa-Hinoki oil. 
Juniperus communis-Oil of juniper berries. 
1) According to Engler's Syllabus. Second edition. Berlin, 1898. List of Plants, Arranged According to Families, etc. 
213 
Juniperus oxycedrus-Oil of berries. 
Juniperus phoenicea-Oil of berries. 
Juniperus sabina-Oil of savin. 
Juniperus Virginian a-Oil of cedar wood (cedar oil), oil of cedar leaves. 
Pandanaceae. 
Pandanus odoratissimus-Oil of flowers. 
Gramineae. 
Andropogon schoenanthus-Palmarosa oil, and gingergrass oil. 
Andropogon citratus-Lemongrass oil. 
Andropogon muricatus-Vetiver oil. 
Andropogon nardus-Citronella oil. 
Andropogon odoratus-Oil of herb. 
Andropogon laniger-Camel grass oil. 
Palmae. 
Serenoa serrulata-Saw palmetta oil. 
Araceae. 
Acorus calamus-Calamus oil, oil from leaves, Japanese calamus oil. 
Liliaceae. 
Sabadilla officinalis-Sabadilla oil. 
Aloe vulgaris-Aloe oil. 
Xanthorrhoea hastile-Xanthorrhoea oil. 
Allium sativum-Garlic oil. 
Allium cepa-Onion oil. 
Allium ursinum-OW from entire plant. 
Iridaceae. 
Crocus sativus-Saffron oil. 
Iris florentina, I. pallida, 1. germanica-Orris oil. 
ZlNGIBERACEAE. 
Curcuma longa-Curcuma oil. 
Curcuma zedoaria-Zedoary oil. 
Kaempferia rotunda-Oil of root. 
Hedychium coronarium-Oil of flowers. 
Alpinia galanga- Galangal oil. 
Alpinia malaccensis-Oil of roots. 
Alpinia nutans-Oil of roots. 
Zingiber officinale-<Ginger oil. 
Elettaria cardamomum-Oil of cardamom (Ceylon), Malabar (Madras) carda- 
mom oil. . 214 
General Part. 
Amomum cardamomum Siam cardamom oil. 
Amomum melegueta-O'd of paradise grains. 
Amomum aromaticum-Bengal cardamom oil. 
Amomum spec.?-Kamerun cardamom oil. 
Amomum angustifolium-Korarima cardamom oil. 
PlPERACEAE. 
Piper nigrum-Oil of black pepper. 
Piper longum-Oil of long pepper. 
Piper ovatum-Oil of leaves. 
Piper lowong-Oil of fruit. 
Piper clusii-Aschanti pepper oil. 
Piper cubeba-Oil of cubebs. 
Piper angustifolium-Matico oil. 
Piper betle-Oil of betle leaves. 
Potomorphe umbellata-Oil of leaves. 
Artanthe geniculata-Oil of leaves. 
Ottonia anisum-Oil of roots. 
Salicaceae. 
Populus nigra-Oil of buds. 
My RIC ACE AE. 
Myriea gale-Oil of Dutch myrtle. 
Myriea cerifera-Oil of bay-berry. 
Myriea asplenifolia-Oil of sweet fern. 
JUGLANDACEAE. 
Juglans regia-Walnut leaf oil. 
Betulaceae. 
Betula lenta-Oil of sweet birch (wintergreen oil). 
Moraceae. 
Humulus lupulus-Oil of hops. 
Cannabis sativa-Hemp oil. 
Santalaceae. 
Santalum album-Oil of sandalwood (East Indian). 
Santalum preissianum-South Australian sandalwood oil. 
Santalum cygnorum-West Australian sandalwood oil. 
Santalum yasi-Fiji sandalwood oil. 
Unknown species-African sandalwood oil. 
Aristolochiaceae. 
Asarum europaeum-Oil of root. 
Asarum canadense-Oil of Canada snake root (wild ginger). List of Plants, Arranged According to Families, etc. 
215 
Aristoloehia serpentaria-Oil of Virginia snake root. 
Aristolochia clematitis-Oil of roots. 
Chenopodiaceae. 
Chenopodium ambrosioides var. anthelminticum-Oil of American wormseed. 
K ANUNCUL ACE AE. 
Paeonia moutan-Oil of roots. 
Nigella sativa-Oil of seeds. 
Nigella damascena-Oil of seeds. 
Magnoeiaceae. 
Micheha champaca-Champaca oil. 
Michelia longifolia-Oil of flowers. 
lllicium verum-Star anise oil. 
lllicium anisatum-Japanese star anise oil. 
Drimys winteri-Oil of Winter's bark. 
Anonaceae. 
Cananga odorata-Ylang ylang oil and cananga oil. 
Myristicaceae. 
Myristica fragrans-Oil of mace, od of nutmeg. 
Monimiaceae. 
Peumus boldus-Oil of boldo leaves. 
Atherosperma moschata-Atherosperina oil. 
Citriosma oligandra-Oil of leaves and bark. 
Citriosma cujabana-OW of leaves and bark. 
Citriosma apiosyce-O'A of leaves and bark. 
Unknown species-Oil of para coto bark. 
Lauraceae. 
Cinnamomum camphora-Camphor oil. 
Cinnamomum zeylanicum-Oil of cinnamon (Ceylon), oil of cinnamon leaves, oil 
of roots. 
Cinnamomum cassia-Cassia oil. 
Cinnamomum loureirii-Japanese cinnamon oil. 
Cinnamomum kiamis-Oil of bark. 
Cinnamomum culilawan-Culilawan bark oil. 
Cinnamomum wightii-Oil of bark. 
Cinnamomum oliveri-Oil of bark. 
Persea gratissima-Oil of leaves. 
Persea caryophyllata-Oil of clove bark. 
Nectandra puchury- Pichurim oil. 216 
General Part. 
Nectandra caparrapi-Caparrapi oil. 
Ocotea caudata-Guayana lignaloe oil. 
Ocotea species?-Ocotea oil. 
Nectandra myriantha. 
Nectandra or Ocotea species?-Venezuela camphor wood oil. 
Sassafras officina/e-Sassafras oil (bark), oil of sassafras leaves. 
Cryptocaria moschata-Cryptocaria oil. 
Cryptocaria pretiosa-Oil of bark. 
Laurus nobilis-Oil of laurel leaves, oil of fruit. 
Lindera sericea-Kuromoji oil. 
Oreodaphne californica-Oil of mountain laurel. 
Benzoin odoriferum-Spicewood oil. 
Tetranthera citrata-Tetranthera oil. 
Unknown species-Massoy bark oil. 
Cruciferae. 
Lepidium sativum-Pepper-grass oil. 
Thlaspi arvense-Oil of herb. 
Cochlearia officinalis-Oil of spoonwort. 
Cochlearia armoracia-Oil of horseradish. 
Alliaria officinalis-Oil of hedge garlic. 
Brassica nigra, B. juncea-Oil of mustard. 
Sinapis alba-Oil of white mustard. 
Nasturtium officinale-Oil of watercress. 
Raphanus sativus and R. niger-Oil of common radish. 
Resedaceae. 
Reseda odorata-Mignonette oil, oil of root. 
Hamamelidaceae. 
Liquidambar orientals-Oil of liquid storax. 
Liquidambar styracifluum-Oil of sweet gum, oil of leaves. 
Altingia excelsa-Rasamala oil (wood). 
ROS ACE AE. 
Spiraea ulmaria -Spiraea oil. 
Rosa damascena-Kose oil. 
Rosa centifolia-Rose oil. 
Prunus amygdalus, P. armeniaca, P. persica -Bitter almond oil. 
Prunus laurocerasus-Chevry laurel oil. 
Prunus virginiana-Oii of wild cherry bark. 
Leguminosae. 
Copaffera officinalis C. guajanensis, C. coriacea, C. langsdorfda, C. confertiflora, 
C. oblongifolia, C. rigida-Copaiba balsam oil. 
Myrocarpus fastigiatus-Cabriuva wood oil. List of Plants, Arranged According to Families, etc. 
217 
Genista tridentata-Carqueja oil. 
Indigofera, galegoides-Oil of leaves. 
Caesalpinia sappan-Sappan oil. 
Toluilera balsamnm-Tolu balsam oil. 
Myroxylon peruiferum-Oil of leaves. 
Glycyrrhiza glabra-Oil from root. 
Glycyrrhiza glandulifera-Oil from root. 
Geraniaceae. 
Pelargonium odoratissimum, P. capitatum, P. roseum-Oil of rose geranium. 
Tropaeolaceae. 
Tropaeolum majus-Oil of nasturtium. 
Erythroxylaceae. 
Erythroxylon coca-Oil of coca leaves. 
Zygophyllaceae. 
Bulnesia sarmienti-Guaiac wood oil. 
Rutaceae. 
Xanthoxylum piperitum-Japanese pepper oil. 
Xanthoxylum hamiltonianum-Oil of seeds. 
Ruta graveolens-Oil of rue. 
Boronia polygalifolia-Boronia oil. 
Barosma betulina, B. serratifolia-Oil of bucliu leaves. 
Empleurum serrulatum-Oil of leaves. 
Pilocarpus jaborandi-Jaborandi oil. 
Cusparia trifoliata,-Oil of angustura bark. 
Toddalia aculeata-Toddalia oil. 
Citrus limonum-Oil of lemon. 
Citrus aurantium-Oil of sweet orange, oil of neroli (Portugal). 
Citrus bigaradia-Oil of bitter orange^ oil of neroli, oil of petit grain. 
Citrus bergamia-Oil of bergamot. 
Citrus medica-Cedrus oil. 
Citrus medica var. acida-West Indian lunette oil. 
Citrus limetta-Italian limette oil, oil of leaves. 
Citrus nobilis-Oil of mandarins. 
Citrus decumana-Grape fruit oil. 
Schimmelia oleifera-West Indian sandalwood oil. 
Dacryodes hexandra-Oil from oleoresin. 
BurseracEae. 
Commiphora abyssinica, C. schimperi- Oil of myrrh 
Balsamodendron kafal-Opoponax oil. 
Boswellia carteri-Oil of frankincense. 218 
General Part. 
Canarium spec.?-Elemi oil. 
Idea heptaphylla-Conima resin oil. 
Bursera aloexylon-(Mexican) lignaloe oil. 
Mellace ae. 
Cedrela odorata and other species-Cedrela wood oil. 
POLYGALACE AE. 
Polygala, senega-Oil of senega root. 
Polygala variabilis, P. oleifera, P. calcarea, P. depressa, P. nemori vaga - 
Methyl salicylate. 
EUPHORBIACEAE. 
Croton eluteria-Cascarilla oil. 
Stillingia silvatica-Stillingia oil. 
An ACARDI ACE AE. 
Pistacia lentiscus-Mastic oil. 
Pistacia terebinthus-Chios turpentine oil. 
Schinus molle-Schinus oil. 
VlTACEAE. 
Vitis vinifera-Cognac oil. 
Tiliaceae. 
Tilia ulmifolig, T. platyphyllos-Oil of linden flowers. 
Malvaceae. 
Hibiscus abelmoschus-Oil of ambrette seeds. 
Theaceae. 
Thea chinensis-Tea oil. 
Dipterocarpaceae. 
Dryobalanops camphora-Borneo camphor oil. 
Dipterocarpus turbinatus and others-Gurjun balsam oil. 
Cistaceae. 
Cistus creticus, C. ladaniferus-Labdanum oil. 
Canellaceae. 
Canella alba-Canella oil. 
Turneraceae. 
Turnera aphrodisiaca, T. diffusa-Damiana leaf oil. List of Plants, Arranged According to Families, etc. 
219 
Lythraceae. 
Lawsonia inermis-Henna oil. 
Myrtaceae. 
Myrtus communis-Oil of myrtle. 
Myrtus cheken-Cheken leaf oil. 
Pimenta officinalis-Oil of pimenta. 
Pimenta acris-Oil of bay. 
Eugenia caryophyllata-Oil of cloves, oil of clove stems. 
Melaleuca leucadendron-Cajeput oil. 
Melaleuca viridiflora-^ia&uB oil. 
Melaleuca leucadendron var. lanCifolia, M. acuminata, M. decussata, M. ericifolia. 
M. genistifolia, M. Hnariifolia, M. squarrosa, M. uncinata, M. wilsonii-contain 
in th'e leaves cajeput-like oils. 
Eucalyptus globulus, E. odorata, E. cneorifolia, E. oleosa, E. dumosa, E. 
amygdalina, E. rostrata, E. populifera, E. corymbosa, E. resinifera, E. 
baileyana, E. microcorys, E. risdonia, E. leucoxylon, E. hemiphloia, E. crebra, 
E. macrorrhyncha, E. capitellata, E. eugenioides, E. obliqua, E. punctata, 
E. loxophleba, E. dextropinea, E. laevopinea, E. maculata, E. citriodora, 
E. dealbata, E. planchoniana, E. staigeriana, E. haemastoma, E. piperita, 
E. diversicolor, E. fissilis, E. goniocalyx, E. gracilis, E. lehmanni, E. longi- 
folia, E. occidentalis, E. paucidora, E. stuartiana, E. terreticornis, E. 
tessellaris-yield the various eucalyptus oils. 
Backhousia citriodora-Backhousia oil. 
Araliaceae. 
Aralia nudicaulis-Oil of rhizome. 
Umbellkferae. 
Coriandrum sativum-Coriander oil. 
Cuminum cyminum-Cumin oil. 
Apium graveolens-Oil of celery seed, oil of herb. 
Petroselinum sativum-Parsley oil, oil of root, oil of herb. 
Cicuta virosa-Cicuta oil. 
Cicuta maculata-Oil of fruit. 
Carum carvi-Caraway oil. 
Carum ajowan-Ajowan oil. 
Pimpinella anisum-Anise oil. 
Pimpinella saxifraga-Oil of root. 
Pimpinella nigra-Oil of root. 
Foeniculum vulgare-Fennel oil. 
Mourn athamanticum-Oil of root. 
Silaus pratensis-Oil of fruit. 
Oenanthe aquatica-Oil of water fennel. 
Levisticum officinale-Oil of lovage (root), oil of seed, oil of herb. 
Archangelica officinalis-Oil of angelica (root), oil of seed, oil of herb. 220 
General Part. 
Angelica refracta (anomala?)-Japanese angelica root oil. 
Ferula, asa foetida-Oil of asafetida. 
Ferula rubricaulis-Galbanum oil. 
Ferula sumbul-Oil of sumbul. 
Dorema ammoniacum-Ammoniac oil. 
Peucedanum oreoselinum-Oil of fresh herb. 
Peucedanum ostruthium-Oil of root. 
Peucedanum graveolens-Dill oil. 
Anethum sowa-East Indian dill oil. 
Peucedanum sativum-Pastinaca oil. 
Peucedanum grande-Oil of fruit. 
Peucedanum officinale-Oil of root. 
Heracleum sphondylium-Oil of fruit. 
Heracleum giganteum-Oil of fruit. 
Daucus carota-Oil of carrots. 
Osmorrhiza longistylis-Oi\ of root. 
PlROLACEAE. 
Monotropa hypopitys-Oil of stem. 
Ericaceae. 
Ledum palustre-Oil of Labrador tea. 
Gaultheria procumbens-Oil of wintergreen. 
Gaultheria punctata-Oil of leaves. 
Gaultheria leucocarpa-Oil of leaves. 
Primulaceae. 
Primula veris-Oil of root. 
CONVOLVULACEAE. 
Convolvulus scoparia, C. fioridus-Oil of rhodium. 
Verbenaceae. 
Verbena triphylla-Verbena oil. 
Lantana camara-Oil of herb. 
Vitex trifolia-Oil of leaves. 
Labiatae. 
Rosmarinus officinalis-Oil of rosemary. 
Lavandula vera-Oil of lavender. 
Lavandula spica-()il of spike. 
Lavandula stoechas-GW of herb. 
Lavandula dentata-Oil of herb. 
Lavandula pedunculata-Oil of herb. 
Nepeta cataria-Oil of catnep. 
Nepeta glechoma-Oil of gill-over-the-ground. 
Salvia officinalis-Oil of sage. List of Plants, Arranged According to Families, etc. 
221 
Salvia sclarea-Oil of herb. 
Monarda punctata-Horsemint oil. 
Monarda didyma-Oswego tea oil. 
Monarda fistulosa-Wild bergamot oil. 
Melissa officinalis-Balm oil. 
Hedeoma pulegioides-Pennyroyal oil. 
Hyssopus officinalis-Hyssop oil. 
Satureja hortensis-Oil of summer savory. 
Satureja, Montana-Oil of winter savory. 
.Satureja thymbra-Oil of herb. 
Origanum vulgare-Oil of wild marjoram. 
Origanum majorana-Oil of sweet marjoram. 
Origanum hirtum, 0. smyrnaeum and others-Oil of Cretian origanum. 
Thymus vulgaris-Oil of thyme. 
Thymus serpyllum-Oil of wild thyme. 
Thymus capitatus-Oil of herb. 
Lycopus virginicus-Oil of bugle weed. 
Mentha piperita, M. arvensis var. piperascens-Oil of peppermint. 
Mentha Silvestris var. crispa, M. viridis-Oil of spearmint. 
Mentha aquatica-Oil of herb. 
Mentha arvensis-Oil of herb. 
Mentha canadensis-Oil of Canada mint. 
Mentha pulegium-Oil of European pennyroyal. 
Pogostemon patchouly-Patchouly oil. 
Pogostemon comosus-Oil of leaves. 
Ocimum basilicum-Oil of sweet basil. 
Morula japonica-Oil of herb. 
Cunila mariana-Oil of herb. 
Lophantus anisatus-Oil of herb. 
Pycnanthemum lanceolatum-Oil of mountain mint. 
Pycnanthemum incanum-Oil of herb. 
a * ' 
SOL AN ACE AE. 
Fabiana imbricata-Oil from leaves. 
Caprifoliaceae. 
Sambucus nigra-Oil of flowers. 
Valerianace ae. 
Valeriana officinalis-Oil of valerian. 
Valeriana officinalis var. angustifolia-Kesso oil. 
Valeriana celtica-Oil of root. 
Nardostachys jatamansi -Oil of root. 
COMPOSITAE. 
Eupatorium foeniculaceum-OW of entire plant. 
Ageratum conyzo'ides-Oil of herb. 222 
General Part. 
Solidago odora-Golden rod oil. 
Solid ago rugosa-Oil of herb. 
Erigeron canadensis-Oil of flea bane. 
Blumea balsamifera, Bl. lacera-Blumea camphor. 
Helichrysum stoechas-Oil of herb. 
Inula helenium-Oil of elecampane. 
Osmitopas asteriscoides-Oil of herb. 
Ambrosia artemisiaefolia-Oil of rag weed. 
Anthemis nobilis-Oil of Roman chamomile. 
Anthemis cotula-Oil of mayweed or dog fennel. 
Achillea millefolium-Oil of milfoil. 
Achillea nobilis-Oil of herb. 
Achillea moschata-Oil of flowering herb. 
Achillea coronopifolia-Oil of herb. 
Achillea ageratum-Oil of herb. 
Matricaria chamomilla-Oil of German chamomile. 
Matricaria parthenium-Oil of flowering plant. 
Tanacetum vulgare-Oil of tansy. 
Tanacetum balsamita-Oil of herb. 
Pyrethrum indicum-Kiku oil. 
Artemisia vulgaris-Oil of mug-wort. 
Artemisia dracunculus-Esdragon oil. 
Artemisia cina-Wormseed oil. 
Artemisia absinthium-Oil of wormwood. 
Artemisia, gallica-Oil of herb. 
Artemisia barrellieri-Oil of herb. 
Artemisia glacialis-Oil of herb. 
Erechthites hieracifolia-Oil of fire weed. 
Arnica montana-Oil of arnica flowers, oil of arnica root. 
Saussurea lappa-Oil of root. 
Carliua acaulis-Oil of root. 
Spaeranthus indicus-Oil of root. SPECIAL PART. 1. Oil of Male Fern. 
Origin. The anthelmintic properties of the rhizome of male fern, 
Aspidium- dlix mas Sw., are said to be due in part to small quantities 
of a volatile oil, which was first prepared by Bock1" in 1851 by distil- 
lation with water vapor. The yield varies according- to the season in 
which the rhizome is collected. Ehrenberg-2 in 1893 obtained from air- 
dried rhizome freshly collected in June 0.025 p. c.; from rhizome collected 
in the months from September to November he obtained 0.04 to 0.015 
p. c. of volatile oil respectively. 
Properties. The volatile oil of male fern is a light yellow liquid, 
with an intense male fern odor, and an aromatic, afterwards burning- 
taste. It is readily soluble in ether and absolute alcohol. Its specific 
gravity lies between 0.85 and 0.86. Most of the oil boils between 140 
and 250°. Above this temperature decomposition takes place and dark 
colored products distil over. 
Composition.2 Besides free fatty acids (principally butyric acid) oil 
of male fern contains the hexyl and octyl esters of the fatty acids from 
butyric acid upwards, probably up to pelargonic acid. The substances 
to which the peculiar physiological action is due have not yet been 
isolated. 
2. Oil of Angiopteris Evecta. 
This fern, Angiopteris evecta Hoffm., yields an .aromatic oil, said to 
be used in the South Sea Islands for perfuming cocoanut oil (Maiden3). 
3. Oil of Polypodium Phymatodes. 
Polypodium phymatodes L. (Pleopeltis phymatodes G. Moore) like 
the above fern yields an oil also said to be used in the South Sea 
Islands for perfuming cocoanut oil.3 
i) Arch. cl. Pharm., 115, p. 262. 
2) Arch. d. Pharm., 281, p. 845. 
s) Useful native plants of Austr., p. 258. 226 
Special Part. 
OILS OF THE ABIETINEtE. 
Turpentine Oil, Pine Tar Oil ("Kienbl"), and the Pine 
Needle Oils ("Fichtennadelbl"). 
The term turpentine oil is applied in a more restricted sense to 
the product obtained by distillation of turpentine with water vapor. 
"Kienbl" is the product obtained by the dry distillation of coniferous 
roots rich in resin. The name turpentine oil, in a more general sense, 
is sometimes applied to these oils also,, but this use of the term should 
be avoided. The oils obtained by the distillation with water vapor of 
the leaves or one year old cones of various conifers are grouped under 
the collective term of pine needle oils. 
As to chemical composition, the oily distillates of the turpentine, 
the wood, and the leaves have in common one characteristic constituent, 
viz. pinene. The turpentine oils proper consist almost exclusively, the 
pine tar oils very largely of this hydrocarbon; whereas in the pine 
needle oils the place of the pinene is frequently taken by limonene or 
oxygenated substances, notably bornyl acetate. 
Turpentine Oils Proper. 
History. The oils obtained by the distillation of the oleoresins of 
various Abietinese were known to the ancients as cedar oil (Tricro-eXatov) i 
and later became known as turpentine oil. The oil as well as the resin, 
the colophonium, were used by seafaring people. Taking into consider- 
ation the perfection early reached by the Chinese a.nd Japanese in the 
preparation of varnishes and lacquers, it may be supposed that conifer- 
ous oils were distilled and used by them. However this may be, the 
oils of the Abietinese obtained in a crude manner have evidently been 
the first volatile oils that found commercial use and technical application. 
The name turpentine oil seems to have been introduced during the 
period of Greek civilization. Like the older synonyms (cedar oil, etc.) 
it apparently was used as a collective term. It is of Persian origin,2 
and may have been derived from the Cyprian species Pistacia tere- 
binthus L. 
As far as is known to history, the preparation of turpentine oil 
probably had its origin in the Caucausus and its south-western 
i) Herodoti, Historiae, Lib. II, p. 85. - Dioscorides, De mat. med., Lib. I, p. 34. 
Editio Kiihn-Sprengel, 1829, 1, p. 93. - Plinius, Naturalis historiae libri., Lib. 15, cap. 
6-7; and Lib. 16, cap. 22. 
a) Fliickiger, Pharmacognosie, p. 77. Oils of the Abietinese. 
227 
spurs. In central Europe it became known during- the middle ages, 
somewhat later also in northern Europe. The North American industry- 
had its origin in the dense and extensive pine forests of the South 
Atlantic States and developed in the beginning of the eighteenth century 
especially in Virginia and Carolina.1 
Inasmuch as the crude turpentine oil found little or no use in either 
household economy or in religious rites, it is but seldom mentioned in 
early literature. Attention has already been called on pp. 5, 20, 21, 
22 and 51 to mentionings by the older writers. Since its introduction 
into medicine, the mediaeval works on distillation and materia medica 
make mention of the oil. In addition to the references by Villanovus 
and LuIluS, who lived in the thirteenth century, to which attention has 
been called on pp. 20 and 21, mention is made of oil of turpentine by 
the following writers of the fifteenth century: Saladinus of Asculo2 and 
the canon Johann of Santo Amando of Doornyk;8 during the sixteenth 
century by Walter Ryff,4 Conrad Gesner,5 Job. Baptista Porta,6 Valerius 
Cordus7 and Adolphus Occo.8 
Attention lias already been called to the synonymous usage 
during the seventeenth century of the designations of alcohol and 
turpentine as aqua ardens and spiritus. The name Spiritus tere- 
binthinae has maintained itself as a popular term up to this time. As 
huile aetheree it seems to have been first designated in the year 1700. 
The early observations made in connection with oil of turpentine 
concerned its behavior at low temperatures. As early as 1794 
Margueron9 claims to have observed that the oil, when reduced to a 
temperature of -22° R. solidifies to a crystalline mass. Crystals had 
already been observed by Geoffroy in 1727 in the neck of the retort 
while distilling the oil. In conformity with the practice of designating 
as camphor all solid substances separating from volatile oils, these 
needle-like crystals, presumably pinol hydrate, were called turpentine 
camphor. 
i) Peter Kalm's Reise, etc., vol. 2, pp. 418, 556; vol. 3, pp. 293, 305, 523. 
Schopf, Reise, etc., vol. 2, pp. 220, 223, 273. 
Michaux, Histoire des arbres, etc. 
2) Saladini Asculani, Compendium, etc. 
s) Expositio Janis de Santo Amando. 
*) Ryff, Neu gross Destillirbuch, etc., fol. 180. 
s) Ein kostlicher theurer Schatz Euonymi Philiatri, vol. 1, p. 238. 
6) Gio. Batt. Portae, Magiae naturalis. 
7) Dispensatorium Noricum. 1546. 
8) Pharmacopoea pro Republica Augustana. 1564. 
9) Journ. de Chim. et de Phys., 2, p. 178; Crell's Chern. Annal., II, pp. 195, 310 
and 430. Special Pari. 
228 
While making the socalled Liquor antarthriticus Pottii, in the 
preparation of which hydrogen chloride is passed into turpentine oil, 
the apothecary Kind,1 of Eutin, in 1803 obtained a solid crystalline 
mass2 which he considered to be artificially prepared camphor. This 
compound was examined by Gehlen3 in 1819 and by Dumas4 in 1833. 
The first elementary analysis of the oil was made by Houton- 
Labilliardiere5 in 1817. In the same year this oil served as the first 
volatile oil of which the angle of rotation was ascertained. 
Origin. The various species of Pinus, Picea and Abies, of the family 
Pinaceae, growing in the temperate zones, contain in special ducts under 
the bark an oleoresin, which in some species collects in cavities. If the 
cambium under the bark is wounded, or if the cavities are tapped, the 
oleoresin exudes, sometimes turbid, sometimes clear. This oleoresin, 
which since antiquity has been known as turpentine, is a solution of 
resin in volatile oil. This solution is mostly rendered turbid by the 
intimate admixture of aqueous sap. Even when exposed to the air it 
mostly remains turbid and frequently congeals to a granular or crystal- 
line, honey-like mass. 
This turpentine, when distilled either by itself or with water vapor, 
yields the turpentine oil; and there remains a residue which, when 
remolten and strained, constitutes rosin or colophony. 
In former centuries, oil of turpentine-most likely in part also cedar 
oil-was distilled in the eastern countries bordering on the Mediter- 
ranean. especially in Asia Minor. When, with the development of the 
arts and industries as well as with that of navigation, it became more 
important and found wider application, greater advantage was taken 
of the coniferous forests in the more northern European countries. The 
principal producers were, and are in part to-day, the central European 
mountainous sections, rich in conifers, from Hungary and Galicia to 
Spain and Portugal; also the large coniferous forests of Russia, of 
eastern Germany, and of the southern provinces of the Scandinavian 
countries. In the course of the previous century, North America has been 
added with its apparently inexhaustible coniferous forests, and with its 
turpentine industry that surpasses that of all other countries. In spite 
of the economic waste of two centuries, America still is and, no doubt 
will continue to be the principal producer of these articles of commerce. 
i) Trommsdorff's Journ. der Pharm,, 11 n; p. 132. 
2) Pinene monohydrochloride, C10H17CI. 
3) Gehlen's allgem. Journ. f. d. Chern., 6, p. 462. 
4) Ann. de Chim. et Phys., II, 52, p. 400; Liebig's Annalen, 9, p. 56. 
5) Journ. de Pharmacie, II, 4, p. 5. Oils of the Abietinese. 
229 
With reference to geographical origin, the American and French 
oils only come into consideration in the world's commerce. The other 
commercial brands have only local significance. 
General Properties. Freshly distilled turpentine oil is a colorless 
limpid liquid of a peculiar odor which varies somewhat according to 
its source. The French oil, e. g. reminds somewhat of juniper and has a 
finer and milder odor than the American oil with its decided terebin- 
thinate odor. The sharp odor of old oil is said to be due to an aldehyde,1 
CioHiflOs, which is supposed to be formed by the exposure of the oil to 
the oxygen of the air. 
Turpentine oil is volatile at ordinary temperature. During evapo- 
ration, a part of the oil resinifies, taking up oxygen. The residue, which 
is sticky at first, gradually takes on the consistency of rosin. 
Owing to the presence of traces of free formic and acetic acids, crude 
oil of turpentine has a faint acid reaction. For this reason it has to 
be rectified with milk of lime for certain purposes. When air is not 
sufficiently excluded, oxidation products with an acid reaction are 
soon reformed. 
Of physiological interest is the fact that turpentine oil, when taken 
internally, or when the vapors are but inhaled, imparts to the urine a 
peculiar violet odor. This peculiarity is shared by all pinene-containing 
oils. Other terpenes do not possess this property. The inhalation of 
the vapors of turpentine oil for a longer period produces an unpleasant 
affection of the kidneys known as painter's disease. 
Solubility. Turpentine oil is difficultly soluble in alcohol, especially 
in dilute alcohol. Owing to this property, it can often be readily recog- 
nized when added to other oils as an adulterant. In the course of time, 
however, the solubility of turpentine oil in alcohol undergoes consider- 
able change. Whereas the solubility of most oils diminishes with age, 
that of turpentine oil increases.2 To effect a clear solution of freshly 
distilled oil, more alcohol is necessary, than for an old oil which has 
been exposed to the air. The plausible explanation for this observation 
lies in the formation of more readily soluble oxygenated compounds. 
i) If, according to Schiff (1896), the oil from which the aldehyde has been removed 
by shaking with sodium acid sulphite solution, be distilled in an atmosphere 
of carbon .dioxide, an almost odorless product is obtained. The odor, however, is 
again rapidly developed when the oil is exposed to the air. Chern. Ztg., 20, p. 361. 
2) A normal American turpentine oil which originally was soluble in not less than 
6 p. of 90 p. c. alcohol, after standing seven weeks gave a clear solution with 3 p.; 
French oil, which had been standing for four years in a bottle that was not completely 
filled, gave a clear solution with but 1 p. of 90 p. c. alcohol. Special Part. 
230 
On account of this changeability, little stress is to be laid on the 
solubility as a test. In general, a good turpentine oil will be soluble in 
from 5 to 12 parts of 90 p. c. alcohol. 
Solubility of turpentine oil in alcohol of different strength according 
to Ledermann and Godeffroy.1 
■ Variety of Oil. 
Strength of alcohol in percentage by volume 
70 
80 
85 
90 
95 
parts requisite to effect solution: 
1. French, crude 
6G 
18 
14 
7 
2 
2. French, rectified 
80 
16-17 
12 
6.5-7 
2-2.4 
3. American, crude 
56 
20 
12 
5 
2 
4. American, rectified 
60-64 
17-19 
12-14 
5-6 
2.2 
5. Austrian, crude 
- 
- 
- 
6 
- 
6. Au st ri an, recti fled 
- 
- 
13 
8 
3 
7. Polish ("Kienol") 
- 
- 
- 
5 
- 
8. Russian ("Kienol") 
49 
16 
11 
5.6 
2 
Turpentine oil is soluble in almost any proportion in ether, chloro- 
form, carbon disulphide, benzene, petroleum ether, glacial acetic acid, 
also in the fatty oils. When mixed with other volatile oils, turbidity 
occasionally results. Turpentine oil is an excellent solvent for fats, 
resins and most varieties of caoutchouc. 
Boiling Point. By far the greater portion of turpentine oil. namely 
from 75-80 p. c., boils between 155 and 162°. Above 162° the mercury 
rises rapidly and there remains in the flask a soft, colophony-like resin. 
Concerning the quantities that distill over at the various temperatures, 
also the specific gravity and rotatory power of these fractions of rectified 
American turpentine oil, Kremers2 has recently made a detailed report. 
On account of the oxidation and polymerization products formed, 
the boiling point of a resinified oil lies considerably higher. Of the pine 
tar oils also a larger portion boils above 162°, because of the presence 
of dipentene and sylvestrene. 
Rotatory Power. An important distinctive feature of the several 
oil varieties is their different rotatory power. French oil is always 
strongly laevogyrate, American oil mostly faintly dextrogyrate and but 
seldom laevogyrate. Austrian oils have been found to be dextro- as 
well as laevogyrate. The angle of rotation is given in connection with 
the respective oils. 
i) Zeitschr. d. allg. ost. Apt.-Ver., 15, p. 381: Jahresber. f. Pharm., 1877, p. 394. 
2) Pharm. Review, 15, p. 7. Oils of the Abietine;?. 
231 
Influence of Air and Light. It is a well-known fact that turpen- 
tine oil when allowed to stand in open vessels undergoes rapid change, 
especially if water is present. The oil becomes viscid, the specific gravity 
increases and the boiling point rises, the solubility in 90 p. c. alcohol 
increases, the originally neutral oil becomes acid, resinifi.es, it becomes 
"rancid" as this change is technically designated.1 Formerly such an 
oil was termed ozonized, because it acted like a strong oxidizing agent. 
Most of these changes are referable to a slow oxidation caused by 
the oxygen of the air. Schoenbein2 had assumed that in this process 
the oil was charged with ozone, the oxygen of the air being activated 
by the turpentine oil. It was shown later, however, by Kingzett,3 
Bardsky,4 and Papasogli5 that the turpentine oil contained no ozone0 
but hydrogen peroxide. 
1) A normal American turpentine oil, sp. gr. 0.867, which had been kept in a stop- 
pered but partly filled bottle, after standing seven weeks had a sp. gr. of 0.897. It 
was now soluble in 3.5 p. by volume of 90 p. c. alcohol, whereas the original oil had 
required 6 p. to effect a clear solution. 
Another sample of American oil, after having stood for some time had acquired a 
sp. gr. of 0.913 and gave a clear solution with but 3 p. of 90 p. c. alcohol. 
A French oil, which had been kept for four years in a partly filled but well stop- 
pered bottle, had undergone the following changes: 
Original normal oil. The same after 4 years. 
Specific gravity 0.871 1.009 
Optical Rotation -29° 55' -19° 18' 
Whereas the original oil required 20 13. by volume of 80 p. c. alcohol to effect a 
clear solution, the oxidized oil was soluble in 1 p. of the same alcohol and was mis- 
cible in all proportions in 90 p. c. alcohol. 
2) Liebig's Annalen, 102, p. 133. 
3} Journ. Chern. Soc., 27, p. 511 ; Pharm. Journ., Ill, 5, p. 84; ibidem, 6, p. 325; 
ibidem, 7, p. 261; ibidem, 9, pp. 772 and 811; ibidem, 20, p. 868;.Ch.N., 69, p. 143; 
comp, also Robbins, Pharm. Journ., Ill, 9, pp. 748, 792, 872. According to Kingzett. 
the ultimate products of the slow oxidation of turpentine oil, camphoric acid and 
hydrogen peroxide, do not result directly Peroxide of camphor, C10Hi4O4, is first 
formed which, in the presence of water, breaks up into camphoric acid and hydrogen 
peroxide. 
Ci0H14O4 + 2H3O = H2O3 + CioH1604 
Camphor peroxide Water Hydrogen peroxide Camphoric acid 
However, Kingzett did not succeed in isolating the hypothetical camphor peroxide. 
Later (1864) he tried to explain the change in a different way. Chern. News, 69, p. 143. 
4) Bardsky (Chern. Centralbl. 1882, p. 803) found hydrogen peroxide and, as he 
believes, nitrous acid in the water with which oxidized turpentine oil had been shaken. 
5) According to Papasogli (Chem. Centralbl. 1888, p. 1548) the water, which has 
stood in contact with turpentine for a longer period, contains hydrogen peroxide, 
camphoric acid (m. p. 176°), formic acid, acetic acid and an acid CioHi802, isomeric 
with campholenic acid. - The oxydized oil itself is said to contain oxysilvinic acid. 
6) The accuracy of these investigations have been questioned by no one, and the 
presence of hydrogen peroxide in oxidized turpentine oil can be definitely assumed. 
Nevertheless, many text-books contain the statement that old turpentine oil, in fact 
oils in general, contain ozone. Inasmuch, however, as ozone and hydrogen peroxide 
decompose each other according to the following equation 
O3 + H3o2 = H3O + 2 O2 
(Schoene, Liebig's Annalen, 196, p. 239), the presence of ozone is necessarily excluded. 232 
Special Part. 
As Loew1 lias first shown, turpentine oil which has been oxidized in 
the presence of moisture contains other substances besides hydrogen 
peroxide. Oxidized turpentine oil liberates iodine from potassium 
iodide, a behavior not attributable to hydrogen peroxide. This action, 
as was already assumed by Kingzett,2 must evidently be attributed to 
organic peroxides which decompose with water so far as ultimately to 
yield hydrogen peroxide. Presumably peroxide hydrates are formed as 
intermediate products. The explanation of this process has recently 
been given in a contribution by Engler and Weissberg.3 
These investigators demonstrate that, when absolutely dry turpen- 
tine oil is activated, neither hydrogen peroxide nor ozone results. They 
further show that turpentine oil activates oxygen most readily at a 
temperature of 100°; that above 3 00° no activated oxygen is formed, 
but that it is then used for the oxidation (destruction) of the oil. 1 ec. 
of turpentine oil can activate 100 cc' of oxygen at 100°. 
Turpentine oil, whether moist or dry, when charged with oxygen 
has a capacity to convey the oxygen to such substances as are not 
directly oxydizable with atmospheric oxygen. Thus, as has already 
been stated, iodine is liberated from potassium iodide, indigo solution 
is bleached, arsenous acid is oxidized to arsenic acid. Activated turpen- 
tine oil retains its properties for years if kept in the dark. But little 
is as yet known concerning the oxidation products resulting. 
The presence of the following substances has been definitely ascer- 
tained: formic acid, acetic acid and camphoric acid, CioHicOi.4 Besides 
these, a small amount of an aldehyde, corresponding in its composition 
with camphoric aldehyde, CioHicOs, has been found.5 It possesses a 
narcotic odor and is probably the cause of the peculiar odor of the old 
"rancid" turpentine oil. 
These oxidation processes, accompanied by the same changes of the 
oil, are accelerated when warm air saturated with water vapor is passed 
through the oil.0 
') Zeitschrift fur Chemie, II, 6, p. 609; Chern. Centralbl., 1870, p. 821. 
2) Loe. cit. 
3) Berichte, 31, p. 3046. 
4) Chem. Centralbl., 1888, p. 1548. 
5) Schiff, Chemiker Zeitung, 20, p. 361. The aldehyde seems to form most readily 
when turpentine oil is kept in partly filled, not well stoppered bottles in diffused light. 
The amount of the unstable aldehyde does not exceed 1 p. c. As has already been 
stated, it can be removed by shaking the oil with sodium acid sulphite solution. When 
exposed to the air in a watch glass, the aldehyde resinifies, loses its narcotic odor 
and no longer reacts with rosaniline sulphate. 
6) An oil, sp. gr. 0.864, after having been treated in this manner for 44 hours had 
a sp. gr. of 0.949. Kingzett also observed a considerable rise in the boiling point. Oils of the Abietineae. 
233 
By the action of direct sunlight on moist turpentine oil in the 
presence of air, or better still, of oxygen, pinol hydrate,CioHi8O2, results. 
According to the solvent used, pinol hydrate crystallizes in laminae or 
needles. Its inactive modification melts at 1310.1 
Composition. The first elementary analysis, referred to on p. 41, 
revealed the fact that turpentine oil consists of hydrocarbons CioHm. 
This was verified by later investigations, which also showed that 
different oils reveal physical differences in so far as some of them turn 
the plane of polarized light to the left, others to the right. Berthelot2 
designated the laevogyrate hydrocarbon terebenthene, the dextrogyrate 
one australene. Inasmuch as the two modifications are merely physical 
isomers, but chemicaly identical, Wallach 3 introduced the terms 1- and 
d-pinene. 
Since pinene is one of the most labile terpenes, it is not surprising 
that some of its decomposition products are formed during the pro- 
duction of turpentine oil, and thus get into the oil. As already stated, 
the oil contains traces of formic and acetic acids, also resin acids. At 
higher temperatures, these act on the pinene so that dipentene and 
presumably polymeric terpenes result. At least both are found as 
constant companions of the pinene in the turpentine oil. 
Certain observations and indications render it probable that 
camphene and fenchene belong to the normal constituents of turpentine 
oil. Since the boiling point of both of these lies very close to that of 
pinene, a direct proof to which no objection can be raised is impossible. 
Nevertheless, it may be assumed that the indirect proof for the presence 
of camphene has been furnished. 
Armstrong and Tilden4 found camphene in the so-called terebene, 
the product resulting by the action of concentrated .sulphuric acid on 
turpentine oil. They assumed that the camphene resulted according to 
a reaction analogous to the one by which it can be obtained from 
pinene hydrochloride, a possibility not to be denied off-hand. Power 
and Kleber,5 however, consider it more probable that the camphene 
is contained originally in the oil, and that its presence becomes notice- 
able only after the destruction and removal of the pinene. 
The results of the investigation by Bouchardat and Lafont6 also 
seem to permit a similar conclusion. They heated French turpentine oil 
Liebig's Annalen, 80, p. 106; ibidem, 
259, p. 313; Journ. Chem. Soc., 59, p. 315. 
2) Compt. rend., 55, pp. 496 and 544; 
Liebig's Annalen, Suppl. II, p. 226. 
3) Liebig's Annalen, 227, p. 300. 
Berichte, 12, p. 1753. 
5) Pharm. Rundschau, 12, p. 16. 
6) Compt. rend., 113, p. 551. 234 
Special Part. 
with benzoic acid anhydride for fifty hours. From the product of 
reaction they isolated camphene, also esters of isoborneol and fenchyl- 
alcohol, whose formation is probably due to the presence of camphene 
and fenchene. 
The same investigators1 obtained, by the action of sulphuric acid 
on French turpentine oil and the subsequent treatment with alcoholic 
potassa, two potassium salts of the composition C1OH17OSO2OK, which 
upon hydrolysis with acids yielded borneol and potassium hydrogen 
sulphate on the one hand, and 1-fenchyl alcohol and the same potassium 
salt on the other. The formation of these salts likewise indicates the 
presence of camphene and fenchene. 
The presence of 1-camphene in American turpentine oil was shown 
by Schimmel & Co.2 in the following manner. By treating fraction 
160-161° of American turpentine oil (sp. gr. 0.869; [a]D = + l°16') 
with glacial acetic acid and sulphuric acid according to Bertram's 
method,3 isobornyl acetate resulted which upon saponification yielded 
isoborneol (m. p. of the phenyl urethane derivative 138°). Inasmuch 
as pure pinene, regenerated from the nitroso chloride does not yield 
isoborneol when treated in the same manner, the formation of isoborneol 
is explained by assuming the presence of camphene in the American oil. 
Adulterations. On account of its cheapness, turpentine oil has 
been used largely as an adulterant. It itself has been subject to 
adulteration with petroleum and resin oils. 
Petroleum. Common illuminating oil. also the lighter as well as the 
heavier fractions of petroleum have been used. Illuminating oil and the 
lighter petroleum fractions are recognized by the lowering of the specific 
gravity; also by the lower flashing point, which lies at 33-34° for pure 
turpentine oil. The heavier fractions of petroleum are not volatile with 
water vapor and. therefore, remain behind, when the oil is rectified 
with water vapor, as a fluorescent residue which is not affected by 
concentrated nitric and sulphuric acids. 
Socalled patent turpentine oils are frequently mixtures of petroleum 
products with turpentine oil or camphor oil. Sometimes they are 
nothing but petroleum hydrocarbons brought upon the market under 
various fanciful names. Such designations are:4 Canadian turpentine 
oil, patent turpentine, turpentyne, turpenteen, larixolin, paint oil, and 
others. According to Dunwody,5 mixtures of turpentine oil and 
i) Conipt, rend., 125, p. 111. 
2) Bericht von S. & Co., Oct. 1897, p. 68. 
s) Journ. f. prakt. Chem., II, 49, p. 1. 
*) Pharm. Centralh., 33, p. 131. 
5| Amer. Journ. Pharm., 62, p. 288. Oils of the Abietmeae. 
235 
petroleum differ from pure turpentine oil by their different solubility in 
99 p. c. acetic acid. Absolute acetic acid (99.5 to 100 p. c.) is said to 
be miscible in all proportions with petroleum as well as with turpentine 
oil. An acetic acid prepared by mixing- 99 cc. of glacial acetic acid 
and 1 cc. of water makes a clear solution with turpentine oil in the 
ratio of 1:1, but not with petroleum. For the complete solution of 
turpentine oil-petroleum mixtures the following quantities of this acetic- 
acid (99 4-1) are required. 
Petroleum 12 3 4 5 7 8 cc. 
Turpentine oil....: 9 8 7 6 5 3 2 " 
Solution effected with acetic ac. (99 + 1) 40 60 80 110 150 230 270 cc. 
The Prussian Revenue Commission has recently1 directed the use of a 
test based on the different solubility of turpentine oil and mineral oils 
in aniline for the detection of patent turpentine oils.2 
"In a cylinder of 50 cc. capacity and calibrated in cc., also provided 
with a glass stopper, 10 cc. of the oil in question are poured and 10 cc. 
aniline are added. The cylinder is stoppered and the mixture thoroughly 
shaken. If after five minutes the solution is not uniform, but has separated 
into two layers, the oil is a patent turpentine oil." 
Conradson3 detects petroleum in turpentine oil in the following- 
manner : 
50 cc. of oil are evaporated on a waterbath down to from 1 to 2 cc. If 
the oil was free from petroleum, the residue should be soluble in from 5-10 cc. 
of glacial acetic acid. If 10 p. c. or more of petroleum was present, the 
mixture is turbid and separates into two layers upon standing. 
For the quantitative estimation of the petroleum, the turpentine oil 
is oxidized with fuming nitric acid and the residue, not acted upon by 
the acid, is weighed as mineral oil. 
According to Burton4 100 cc. of oil are carefully cooled in a spacious 
flask connected with a reflux condenser and 300 cc. of fuming nitric acid are 
• slowly added from a dropping funnel. The residual oil is washed with hot 
water and weighed. Control experiments with known mixtures showed that 
the determination is more accurate for the higher boiling fractions of petroleum 
than for the lower ones, for the latter are somewhat attacked by nitric acid. 
A petroleum product boiling at 250° yielded 34.1 p. c. in place of 35 p. c.; 
i) According to the former official directions for testing for purposes of revenue, an 
oil was to be regarded as pure if an increase in temperature of 25° C. resulted when 
the oil was shaken with an equal volume of fuming hydrochloric acid, or with one 
volume of hydrochloric acid (1.12) and % vol. of English sulphuric acid. As was to 
be expected, this process frequently yielded unreliable results and, as a consequence, 
was frequently criticised. 
2) Chern. Zeitung, 22, p. 834. 
3) Chern. Centralbl., 1897. II, p. 449. 
*) Amer. Chern. Journ., 12, p. 102. 236 
Special Part. 
a petroleum product boiling at 75° yielded 17.9 p. c. in place of 20 p. c.; and 
28 p. c. in place of 30 p. c. A similar method is described by Allen1 who 
employs 400 cc. of fuming nitric acid instead of 300 cc. for the same 
quantity of oil. 
The older method of Armstrong2 is based on the fact that turpen- 
tine oil is polymerized with concentrated sulphuric acid and thus largely 
converted into products not volatile with water vapor. Inasmuch as 
paraffin-like hydrocarbons as well as cymene, which are stable toward 
sulphuric acid, result, the process with nitric acid is to be preferred. 
Resin oil. X second adulterant of turpentine oil is the resin oil, a 
product of the destructive distillation of rosin. The adulteration is said 
to be practiced within moderate limits, since the addition of more than 
5 p. c. renders the turpentine oil sticky and imparts to it an unpleasant 
odor. According to Baudin,3 the adulteration can be detected by the 
fatty stain, which the adulterated oil leaves on paper upon evaporation. 
Aignan4 believes in the possibility of detecting resin oil both quali- 
tatively and quantitatively in French turpentine oil by means of the 
higher rotatory power of the former. The formula which he suggests 
for the calculation of the amount of the adulterant leads one to suppose 
that he assumed that resin oil as well as turpentine oil always has 
the same rotatory power. That this is not true at least for turpentine 
oil is shown by the variations in the angle of rotation recorded by 
various observers and enumerated under the description of the French 
oil. This, naturally, disposes of Aignan's formula. 
Aignan distinguishes between three kinds of resin oil: 
1) Huile blanche de choix rectifiee [«]d5=-72°. 
2) Huile blanche bine rectifiee [«]d=-32°. 
3) Huile blanche rectifiee - 21°. 
It is assumed that only No. 1 of these oils is used for the purpose 
of adulteration. This varies somewhat in its rotatory power from that 
of French turpentine oil, but could easily be given a normal rotation 
by a slight admixture of No. 2. 
An apparently better method for the detection of resin oil is given 
later in a contribution by the same author:6 The oil is distilled 
i) Chem. Centralbl., 1890n, p. 125. 
2) Journ. Soc. Chem. Industry, Dec. 1882; Pharm. Journ., Ill, 13, p. 584. 
3) Chem. Centralbl., 1891, I, p. 813. 
4) Comp., rend., 109, p. 944. 
s) As [«]n. Aignan apparently does not consider the specific rotatory power, but 
as becomes apparent from the rotatory power of turpentine mentioned later, the angle 
of rotation observed in a 250 mm. tube! 
6) Compt. rend., 124, p. 1367. Oils of the Abietines. 
237 
under 60 mm. pressure and the residue remaining above 100° is examined 
with the polariscope. The residue from pure French turpentine oil is 
laevogyrate; that of an oil adulterated with more than 5 p. c. resin 
oil is dextrogyrate. 
Zune1 employes the refractometer as a means of detecting resin oil. 
The oil is submitted to fractional distillation, three-fourths being- 
distilled over: the index of refraction of the first fourth and of the 
residue being determined. The difference in the two indices for a pure 
oil. amounts to from 0.0035 to 0.004; in the presence of resin oil, it is 
larger and amounts to 0.006 for 1 p. c. of adulterant. 
Production and Commerce. With reference to importance and 
value .of production of turpentine oil, the United States of North 
America occupy the first position as is shown by the total arrivals at 
the principal staple ports: 
From April 1, 1896, to March 31, 1897: 465,578 barrels; 
From April 1, 1897, to March 31, 1898: 439,304 barrels. 
The barrel contains 50 gallons or about 150 k. If an average 
production of 450,000 barrels per year is assumed, the grand total2 will 
be 67,500,000 bbls., with an approximate value of $7,500,000.00. 
The consumption of turpentine oil in the United States amounted to : 
From April 1, 1896, to March 31, 1897: 111,560 barrels; 
From April 1, 1897, to March 31, 1898: 130,722 barrels. 
Total export from the United States: 
1894: 12,618,407 gallons - abt. 252,000 barrels; 
1895: 14,652,738 " = " 293,000 
1896: 17,431,566 " = " 348,000 
1897: 16,820,000 " = " 336,000 
Thirty years ago, North and South Carolina only came into con- 
sideration in the production and export of turpentine oil. The forests 
in these states having been largely exhausted, the industry has gone 
farther south. Thus, e. g. Charleston, S. C., formerly the important 
port has ceased to export turpentine oil. The business has been trans- 
ferred to the ports Savannah and Brunswick, both in Georgia. 
Savannah is the most important port in the world's market for tur- 
pentine oil. It has exported more than one-half of the total American 
output. 
From New York turpentine oil is exported principally in cases to 
non-European countries. 
1) Compt. rend., 114, p. 490. 
2) For 150 years. 238 
Special Part. 
During the last three years the turpentine oil industry has largely 
developed in Florida and Alabama. It is feared that Pensacola will 
become a strong competitor of the present ports. 
The most important European markets for American turpentine 
oil are: 
London. 
Import 1896: 24,940 tons = abt. 165,000 bbls. 
" 1897: 25,140 " = 11 168,000 " 
Hamburg. 
Import 1896: 7,974,700 kilo = abt. 53,200 bbls. 
" 1897: 8,608,100 " = " 57,400 " 
Antwerp. 
Import 1896: 7,170,000 kilo = abt. 47,800 bbls. 
" 1897: 6,144,500 " = " 40,963 " 
The market price of American turpentine oil is not only affected by 
supply and demand, but is frequently influenced by speculations and, 
therefore, subject to considerable variation. In January, 1897, the 
price per 100 k. f. o. b. Hamburg was M. 43.50. It rose to M. 47.00 
in the beginning of June, and dropped again to M. 42.50 by the middle 
of July. It again rose to M. 54.00 by the beginning of October, but 
dropped to M. 50.50 by the end of September. Still greater were the 
variations in price in 1898. Beginning with M. 52.00 in January, the 
price gradually rose to M. 72.00. 
Of much lesser importance is the production of turpentine oil in 
France. Nevertheless, it is sufficient to supply the demand of that 
country for the importation of American turpentine oil has been made 
prohibitive by a duty of Fr. 24.00 per 100 k. The industry is confined 
to the Dep. des Landes. The principal commercial centers are Mont de 
Moreau, Bayonne and Bordeaux. 
Under these conditions but small quantities can be exported- 
According to official statistics, the export of turpentine oil from France 
amounted to: 
1896: 1,937,990 Kilo; 
1897: 1,411,500 " 
Of these amounts Hamburg received: 
1896: 430,100 Kilo; 
1897: 992,500 " 
Antwerp : 
1896: 970 Colli; 
1897: 530 " Oils of the Abietineae. 
239 
Qualitatively the French oil holds the first position among all com- 
mercial brands and in the arts is frequently preferred to the American. 
Its market value is, as a rule, from $2.00 to $2.50 higher per 100 kilo 
than the American. 
Among the commercial varieties of turpentine oil, the Russian1 
comes next in importance. 
According to the records published in "Die Productionskrafte 
Russlands" (1898), a work issued by the Imperial Russian Ministry of 
Finance the value of the oil of turpentine annually produced in Russia 
is Rb.2 1,500,000. The greatest part of this is used by the country itself. 
The industry has its seat in the gouvernements to the north of the 
Volga and in Poland. It is conducted on a small scale and is in the 
hands of the peasants. 
The export amounted to: 
1885: 160,000 Pud,2 value Rb. 498,000. 
1890: 295,000 " " " 811,000. 
1892: 365,000 " " " 826,000. 
1893: 300,000 " " " 853,000. 
1894: 258,000 " " " 717,000. 
Corresponding to the quality, the commercial value of the Russian 
turpentine oil is much less than that of the American and French. It 
is indeed the poorest of all the commercial varieties. 
The Russian import duty on turpentine oil of 60 kopeken 2 gold per 
pud, or of nearly $3.00 per 100 k. has the object of a duty for 
revenue only. 
In the Antwerp lists of imports there appears regularly for several 
years a Spanish turpentine oil. The importation amounted to: 
1896: 2,644 Colli: 
1897: 7,520 " 
4. American Oil (Spirit) of Turpentine. 
Oleum Terebinthinae Americanum.-Amerikanisches Terpentinol. - Essence de 
Terebenthine Americaine. 
History and Origin. The enormous areas which were at one time 
and in part are to-day densely covered with pine forests acquire their 
maximum luxury and broadest expanse in the South Atlantic States, 
i) The figures enumerated, in all probability, refer primarily to the pine tar oil 
obtained by destructive distillation. Whether turpentine oil proper, obtained from 
turpentine, is at all made on a commercial scale in Russia is not known. 
2) Rubel = 100 Kopeken = abt. 80^; Pud = 16.38 k. 240 
Special Part. 
from Virginia to the Gulf States, in the eastern part of Canada, in 
British North America and on the western slopes of the Pacific States. 
The first mentioned area, which is also the largest, comprises the 
states North and South Carolina, Georgia, and Alabama and within it 
there has developed the principal turpentine industry. Up to the middle 
of the last century the products of this industry were tar and pitch 
which were used principally in ship building and as naval supplies and 
hence were termed "naval stores."1 The preparation of turpentine oil 
seems to have begun as late as the middle of the eighteenth century in 
North Carolina and Virginia. Professor Kahn, the Swedish traveler, 
who is known as a careful observer, and who explored the Atlantic 
provinces of the then British colonies from Quebec to Virginia during the 
years 17-19 and 1750, reports concerning the preparation of tar and 
pitch only.2 Later travelers and reports first make mention of the 
preparation of turpentine, turpentine oil and colophony in Carolina. 
Among these are Dr. Johann David Schoepf, who traversed the Atlantic 
States from Canada to Florida3 in 1783 and 1784; also Francois 
Andre Michaux, who about twenty years after the longer stay of his 
father, the well known botanist Andre Michaux, traveled in North 
America at the beginning of this century.4 
Up to the year 1820 the consumption of turpentine, turpentine oil 
and colophony was restricted to the limited demands of the home- 
industries. The exportation of oil and rosin to England was un- 
important. Up to 1830 the manufacture of turpentine was restricted 
to the coast: between the Tar river in the north, and Cape Fair river 
in the south ;, while the ports New Bern. Wilmington and Washington 
in North Carolina served as collective points. The distillation of tur- 
pentine was conducted in cast iron stills. 
At the beginning of the thirties the application of turpentine in the 
industries experienced considerable extension. This was caused primarily 
by the increased use of paints accompanying the increase in wealth: by 
the development of the varnish, lacquer and caoutchouc industries; and. 
i) The oldest mention concerning- tar and pitch, and the preparation of turpentine 
in Virginia is to be found in vol. 1 of the "Calendar of State Papers. Colonial Series" 
for the year 1574 to 1660 in the Public Record Office in London. Of the year 1610 
this volume contains "Instructions for suche thinges as are to be sente from Virginia," 
also a printed pamphlet: "The Booke of the Commodities of Virginia." Both mention 
pitch, tar, rosin and turpentine among the products of Virginia. The former also 
■contains brief directions for the method of preparation of turpentine which is still in 
vogue. (Dan. Hanbury, in Proc. A. Ph. A., 19, p. 491.1 
2) Kalm, Reise, etc., vol. 2, pp. 418, 474; vol. 3, pp. 305, 523. 
3) Schbpf, Reise, etc., vol. 2, pp. 141, 247. 
*) Michaux, Histoire des arbres, tom. 1, p. 73. Oils of the Abietines. 
241 
finally, by the use of a mixture of turpentine oil and alcohol as an 
illuminating- agent, which was introduced since 1839 as camphine and 
under other fanciful names. Up to the introduction of petroleum 
products (kerosene) about 18(50, this was the cheapest illuminating- 
material. The improvements, made in the course of the thirties, by 
Comstock, Hancock, Macintosh, Chaffee and especially by Luedersdorff 
in the processes employed in the caoutchouc industry did much to 
bring about a larger consumption of turpentine oil. 
This increase in the consumption brought about an increase in the 
turpentine industry in 1834, and caused the introduction of better 
distilling apparatus which insured a larger yield (Ashe1). The expor- 
tation of American turpentine oil and colophony to England and 
other countries assumed large proportions only after the removal of 
the import duty in England in 1846. It was interrupted, however, 
during the years 1861 to 1865 of the civil war, the period of industrial 
and commercial stagnation. 
Up to the year 1837, the opinion prevailed in Carolina that the pine 
forests to the south were not adapted to the production of turpentine 
on account of differences in climate and soil. In the year mentioned, 
experiments conducted on a large scale showed this opinion to be 
erroneous. As a result of the great demand and of increasing speculation, 
the industry spread rapidly to South Carolina and Georgia, and later 
to Alabama and Mississippi (Mohr2). With the introduction of the more 
readily transportable copper stills, the distillation was more and more 
conducted at the place of production, so that the turpentine farms 
began to supply the finished though crude products of distillation, oil 
and rosin, in place of turpentine, to the ports along the coast. One 
other circumstance contributed to the transfer of the distillation to the 
immediate source of production of the crude material. This was the 
fact that the increased demand for turpentine caused a corresponding- 
overproduction of rosin. This could not be disposed of and consequently 
suffered a corresponding depreciation in value. 
'This disparity was equalized toward the end of the sixties. The 
opening up of new territories of production brought about an over- 
production in turpentine oil as well, which was felt all the more 
because petroleum products took its place as an illuminating agent and 
also superseded it in various branches of the arts and industries. On 
the other hand, colophony found new and large application. The 
1) The forests, forest lands and forest products, etc. 
2) The timber pines of the Southern U. S., p. 69; also Pharm. Rundschau, 2, p. 187. 242 
Special Part. 
turpentine industry in the Southern states thus developed unimpeded. 
With the establishment of cheap means of transportation by rail and 
by water, all the conditions were given for a prosperous growth to the 
enormous dimensions on which this industry is being conducted at 
present. 
At best, the larger pine trunks can be made to yield turpentine for 
from 15 to 20 years before they are exhausted. Of late years, the 
exhausted trees are no longer abandoned to wind and fire, but are 
taken to the mills to be sawed into logs and boards; to paper pulp 
factories; or are converted into charcoal. 
It is true that waste, the clearing of forests and temporary destruction 
by fire has driven the turpentine industry away from the coast into the 
interior. A diminution or exhaustion of the American turpentine 
industry, however, need scarcely be feared. Not only does there still 
exist an enormous wealth of pine forests, but the removed trunks are 
replaced by new shoots from the roots and also by more rational 
methods of cultivation. Former methods of waste have not been with- 
out their lessons. Manufacturers as well as the general population have 
become alive to the necessity of displacing former irrational methods and 
waste by more rational ones which insure a continuation of the industry. 
The pines which principally constitute the largest forests of the 
Southern states and which are used in the manufacture of turpentine 
are four in number: Pinus palustris Miller (P. australis Michaux), 
long-leaved or Southern pitch pine, which is the most important in this 
industry; P. taeda L., Loblolly or Rosemary pine; P. heterophylla 
Elliot (P. cubensis Griesebach), Cuban pine. Swamp pine, Slash pine; 
and P. echinata Miller (P. mitis Micheaux), short-leaved yellow pine. 
Preparation. The method of production is in general the same every- 
where. On account of the extent and density of the pine forests, the 
size and diameter of the trees, the larger yield due to a favorable 
climate, the lack of forest cultivation and the absence of control, the 
methods employed were those that insured the largest yield and quickest 
returns and had but little heed of the permanence of the forests. 
The operation, mostly by negroes, of the turpentine farms, begins- 
in the first dry days of spring, as a rule in April. The trees are "boxed" 
about 1 to foot above the ground (diagonally across the trunk of 
the tree). The length of such a box is about 14 inches, its greatest 
depth 6 to 7 inches, so that it has the capacity of more than a quart. 
If the trunk is very thick, a similar "box" is sometimes cut on the other 
side of the tree. Oils of the Abietines. 
243 
As soon as the sap begins to flow in spring, a strip of bark 2 inches 
wide and 8 inches long is removed from the trunk at either end of the 
box ("cornering"). Then the surface above the box between the two 
bare strips is deprived of its bark down to the splint (•'hacking," "chip- 
ping"). The exudation of the sap soon begins and varies with the 
temperature and the formation and secretion of the sap (•'bleeding"), 
the exposed surfaces above the boxes are increased every one or two 
Fis. 58. 
Beginning to Work in a Virgin Forest: Boxing 
weeks. In this manner the chipped surface above the box is lengthened 
or widened or both (fig. 58) as long as warm weather lasts, mostly to 
the end of October. 
In the beginning and during very warm weather, the boxes are filled 
every 2 to 4- weeks and are emptied by means of a flat ladle into 
wooden pails (fig. 59) and from these into barrels. With the advent of 
the cooler season the exudation ceases. The exposed surfaces and boxes 
are then freed from adhering and dried oleoresin ("scrape") and allowed 
to heal or they are again cut during the next spring. If allowed to heal, 244 
Special Part. 
the operation of bleeding is performed on another part of the trunk 
during the following or the third spring. 
The turpentine farms are usually laid out so as to supply one copper 
still with a capacity of 800 gallons or 20 bbls, of turpentine. For the 
operation of this, 4000 acres of forest with good growth are necessary. 
This is divided into 20 lots, of which each contains about 10,000 
boxes yielding olecresin. Inasmuch as many trunks according to their 
Fig. 59. 
Scraping and Dipping in a Turpentine Orchard. 
Tree to the right shows scarified surface. 
diameter contain two, three, sometimes even four boxes, the above 
number is distributed over about 4--5000 trees usually occupying- an 
area of two acres. 
With a rational treatment the yield from 10,000 boxes for each 
collection amounts to about 40 to 50 bbls, of turpentine of 280 lbs. each. 
During- the first years, and before the capacity of the trees has been 
reduced by excessive bleeding, the average yield of* a turpentine farm is Oils of the Abietinex. 
245 
about 270 bbls, of 280 lbs. each of dip turpentine and about 70 bbls, 
of scrapings at the end of the season. Each barrel of dip turpentine 
yields about 7 gal. of oil upon distillation, the scrapings about 3 gals. 
The total yield of a farm, therefore, amounts to about 2,200 gals., or 
50 bbls. @ 45 gals, of oil. and about 260 bbls, of rosin. 
During the first two or three months the collected turpentine is 
almost white and constitutes the best quality, ''virgin dip." This brand 
is brought into the market as ''water white" and '"window glass." 
Inferior, more or less yellow brands are marked N. or M. K. Minor 
shades are indicated by the various letters of the alphabet, so that A 
indicates the poorest, and N the best grades of the varieties next to 
the W. G. 
During the second year of the operations, the yield of the dip is 
about 10 bbls, less than during the first, whereas the scrapings increase 
to about 120 bbls. The quantity of turpentine oil during the second 
year amounts to about 40 bbls, of 45 gals, each, and about 200 bbls, 
rosin. The quality of the oil is the same as that of the first; the rosin, 
however is mostly darker. During the third year the yield of turpentine 
diminishes. 
The continued use of the same cups and exposures, and the annual 
increase of the latter bring about a deterioration of the oleoresin, due 
to evaporation and action of the air: a smaller yield of oil is obtained 
and the quality of the rosin is poorer. It is more advantageous, there- 
fore, to allow the trees to rest for several years and then to tap them 
at a different place. 
As has already been stated, the distillation of the turpentine has 
been conducted for years in copper stills on the larger turpentine farms. 
In the course of the distillation, and after the still has been heated, 
a thin but continous stream of water from the higher placed condenser 
is allowed to flow into the body of the still until the distillation is 
ended. The liquid rosin is allowed to flow off through an exit tube 
at jhe bottom of the still. It is strained through wire sieves and filled 
into barrels for shipment. 
The total average output of a farm of the described size, which is 
operated mostly for four years only, is about 120,000 gals, of turpentine 
oil, 52,000 bbls, of rosin of first quality, 4,000 bbls, of rosin of second 
grade, and 2,400 bbls, of poor quality (Mohr1). 
1) Pharm. Rundschau, 2, pp. 163, 187; 12, p. 211. 246 
Special Part. 
With the wasteful methods still largely in vogue, and in order to 
obtain the largest possible immediate returns from such a venture, the 
timber, after four years' production of oleoresin, is cut-either entirely 
or in part, provided a saw mill is located in the neighborhood or the 
wood can be disposed of to advantage in some other way*. Each acre 
yields about 25,000-30,000 ft. of lumber or 50-60 cords of fuel wood. 
According to the Forestry Division of the U. S. Department of 
Agriculture, the area involved in the turpentine industries of the Southern 
states during 1890 amounted to 2,300,000 acres of pine forests. 
Of late years, the distillation of the enormous wastes of the saw 
mills has increased largely. For this purpose the saw dust and other 
waste, especially of the older, dying trees are used. While gradually 
drying, the lower portion of these trees accumulate a larger amount 
of oleoresin. This wood, permeated by dried oleoresin, is known as 
"light wood" and is used for underground constructions, such as rail- 
road ties and as fuel for boilers and locomotives. Upon distillation, it 
yields about 2 to 2% p. c. of pine tar oil, also tar, pyroligneous acid, pitch 
and charcoal. The yield from 600 lbs. of fairly dried wood rich in resin 
from Pinus australis is about 21 to 22 lbs. of tar oil, 95 lbs. of pyrolig- 
neous acid, 150 lbs. of tar, and 127 lbs. of charcoal (Mohr1). 
Properties. The specific gravity of crude American turpentine oil 
lies as a rule between 0.865 and 0.870. However, lighter (sp. gr. 0.858) 
as well as heavier (up to 0.877, Kremers2) oils occur. Freshly distilled 
or rectified oil is mostly lighter than the crude or old oil. 
When fractionally distilled, about 85 p. c. distill over between 155 
and 163°. Inasmuch as the American species of pine yield dextro- 
gyrate3 as well as laevogyrate4 oils, the rotatory power of the com- 
mercial oils necessarily varies. According to the prevalence of the one 
or other species at the locality of production it may be more or less 
strongly dextrogyrate, or even laevogyrate. Armstrong5 observed in 
i) Pharm. Rundschau, 2, p. 199. 
2) Pharm. Review, 15, p. 8. 
3) of the olboresin from P. palustris = - 13.665°, 
[«]d of the oil from P. palustris = + 23.93°, 
[«]d of the oleoresin of P. cubensis = - 32.428°, 
[«]d of the oil from P. cubensis = + 9.6°. 
E. Kre ners, Pharm. Rundschau, 13, pp. 135. 136. 
4) According to Long (Journ. Amer. Chern. Soc., 16, p. 844; Abstr. Chem. Centralbl., 
1895, I, p. 156) the oil of Pinus glabra is strongly laevogyrate, aD = - 31.5° to-35°. 
According to the same author (Chem. Centralbl.. 1893, I, p. 835) the oil of Pinus 
palustris is also laevogyrate. This is contradictory to the observations made by 
Kremers (see footnote 3). 
5) Pharm. Journ.. III. 13, p. 584. Oils of the Abietineiv. 
247 
1883 that the rotatory power of 28 samples from Wilmington varied 
from + 13°33' to + 14° 17'; that of samples from Savannah from 
4- 9° 30' to + 12° 4'. Two samples from Savannah recently examined 
were slightly laevogyrate: «a= - 0°40' to -2° 5'. 
Oleum Terebintbinae Gallicuin. - Franzbsisches Terpentinbl. - Essence de 
Terebenthine Fran^aise. 
5. French Oil of Turpentine. 
Origin and Preparation. The. larger part of the turpentine oil pre- 
pared' in Europe is obtained from the turpentine from the Pin maritime, 
Pinus pinaster Solander (Pinus maritima Pqiret) and is obtained by 
steam distillation. This tree, which attains a height of 40 m., thrives best 
along the western half of the southern shore of the Mediterranean as far 
as the Bay of Biscay. The production takes place principally in the 
western French dune districts (Landes') of the Departments de la 
Gironde and des Landes. The principal commercial centers are Bordeaux 
and Bayonne. 
In order to obtain the turpentine, one or two narrow notches (carre) 
down to the splint are cut near the base of the trunk in spring when 
the sap begins to rise. These wounds are made 30 to 40 cm. long and 
10 cm. wide. Below the notch a tin or earthenware vessel is fastened 
so that the oleoresin as it exudes flows into it. According to temperature 
and duration of the flow, the incisions a,re extended upward from time 
to time (pinage), so that, in the course of 4 to 5 years they constitute 
parallel stripes, 4 m. in length, along the trunks of the trees. Only 
after the abandoned incision (carre) has healed, is another made on 
the opposite side in the following spring. The vessels in which the 
turpentine collects are emptied whenever necessary. The soft turpentine 
(gemme) is mostly distilled in the neighborhood of the place of col- 
lection. That which has dried along the carres is removed in fall and 
brought as galipot (barras) into the market. 
As a rule the trees are tapped (gem mage) only after they have 
reached an age of 20 to 30 years. Under rational treatment, a normal 
tree can then be used for the production of turpentine for almost 100 
years. Trees that show signs of exhaustion, after a final tapping made 
in such a manner as to produce the largest yield possible (gemmage a 
morte) are cut down at the end of the season for the wood. The trees 
are reproduced by shoots from the roots. 
100 Trunks of the Pin maritime in western France, on an average, 
yield 360 k. of turpentine, which upon distillation yields 15 to 18 p. c. 248 
Special Part. 
of turpentine oil.1 When the turpentine is to be distilled, it is first 
sufficiently heated in casks so that it can be strained through a wire 
sieve, which removes fragments of bark and leaves, into the copper stills 
of about 300 liters capacity. The distillation is conducted over 
direct fire while a current of steam is passed into the still. The residual 
resin (brai) is transferred to barrels and brought as yellow colophonium 
into the market. 
Properties. The specific gravity of French turpentine oil2 varies 
from 0.859 to 0.872, as a rule from 0.865 to 0.876. Formerly higher 
values were occasionally given. The optical rotation was first ascer- 
tained by Biot in 1818. Later the following angles were observed by 
different investigators: «d--20° to -400;3 -33° to 38° (Pereira,4 
1845); -30° to -30°30' (Armstrong,5 1883); and [«]d --39°50' 
(Lafont,6 1888). Tn its other properties as well as in its composition, 
the French turpentine oil agrees with the American oil. 
6. Austrian Turpentine Oil. 
Oesterreichisches (Neustadter) Terpentinol. 
Origin and Preparation. The turpentine industry in Austria is 
confined principally to the "Wiener Wald." In the vicinity of Moedling* 
Voeslau and Neukirchen, Pinus laricio Poiret serves for the production 
of turpentine. The method pursued is the same as that in America, 
but trees at least 50 years old only are tapped. Near the base, a 
cavity is cut into the trunk, into which the exuding oleoresin flows. 
Above this cavity (Grandel) the bark and splint are gradually removed 
by means of a bent hammer up to a height of about 15 inches. From 
time to time, when necessary, the turpentine is removed. During the 
following spring 15 inches more of bark are removed above the old 
wound. In order that the oleoresin may not flow too slowly and get dry. 
a gutter is made from the newly exposed surface to the cavity below. 
i) Comp, under Bibliography: Petzholdt, p. 88; Curie; Mathieu, pp. 537-540; 
Desnoyers. 
2) The Spanish turpentine oil mentioned on p. 239 can not be distinguished from 
the French. A sample of this oil examined in the laboratory of Schimmel & Co. 
possessed the following properties: sp. gr. 0.8478; [«]d = -28°4'; soluble in 7 parts 
of 90 p. c. alcohol. Upon distillation the following fractions were obtained : 157-159°, 
50 p. e.; 159-161°, 28 p. c.; 161-166°, 10 p. c.; 166-170°, 2 p. c.; 170-190°, 5 p. c.; 
residue 5 p. c. 
3) Bericht von S. & Co., April 1897, p. 47. 
4) Pharm. Journ., I. 5, p. 70. 
5t Ibid.. Ill, 13, p. 584. 
6) Compt. rend., 106, p. 140. Oils of the Abietinese. 
249 
The present annual production of turpentine oil in the "Wiener 
Wald'' is said to be about 4,000 cwt.1 The principal commercial center 
of this industry is Vienna (Neustadt). 
Properties. In the laboratory of Schimmel & Co. a single sample 
of oil of unquestionable source was examined. Sp. gr. 0.866; angle of 
rotation +3°46'; it was soluble in 6-8 parts of 90 p. c. alcohol. 
Upon distillation the following fractions were obtained: 
From 159-159°, 21 p. c. an - + 6° 18' 
" 159-160°, 56 " " = + 4°25' 
" 160-167°, 18 " " = + 0°18' 
Residue, 5 " " 
Ledermann and Godeffroy2 observed laevo-rotation in two Austrian 
turpentine oils. Taking into consideration the above, it would seem 
doubtful as to whether they had Austrian oil or not. 
7. Galician Turpentine Oil. 
Of this oil. of which the botanical source is unknown, but one 
sample appears to have been examined. It had a sp. gr. of 0.863; «d = 
+ 17° 18'; and was soluble in 4.5 parts of 90 p. c. alcohol. 
Upon distillation in a Ladenburg flask the following fractions were 
obtained: 
Up to 162°, 7 p. c., «d = +17° 15' 
from 162-165°, 18 " " = + 19°4' 
" 165-169°, 38 " " = +18° 7' 
" 169-173°, 13 " "=+17°28' 
" 173-177°, 10 " " - +15°37' 
" 177-210°, 12.5 " " = +12°2' 
Residue, 1.5 " 
Judging from the relatively large amount of high boiling fractions, 
the conclusion seems justified that this oil must have a different com- 
position from those previously enumerated. 
8. Turpentine Oil from Venetian (Larch) Turpentine. 
' History. Larch turpentine was known to the Romans. It is men- 
tioned in the writings of Vitruvius,3 a contemporary of Caesar, also in 
those of Dioscorides, Pliny,4 and Galen. During the middle ages, larch 
turpentine was one of the most highly prized balsams. The name 
i) According to a communication by A. Kremel of Vienna. 
2) Jahresber. d. Pharm., 1877, p. 894. 
3) Vitruvius, De architectura. Vol. 2, p. 9; Dioscorides, De mat. med., vol. 1, p. 95. 
*) Plinius, Historiae de plantis, p. 575. 250 
Special Part. 
Venetian turpentine was applied to it during the fifteenth century.1 
because it was brought from Venice, at that time the center of the drug 
commerce, into the market. 
The first mention of larch oil {Oleum laricis) in medical treatises is 
found in the works of Matthiolus2 and Conrad Gesner.3 
Origin and Preparation. Venetian turpentine is principally collected 
in southern Tyrol in the neighborhood of Meran, Mals, Bozen and TrienL 
also in Steiermark from Larix decidua Miller (L. europaea, D. C., Pihus 
larix, L.), a larch that flourishes in the central European mountainous 
districts. According to experience, and as has been demonstrated 
botanically by H. von Mold4 in 1859, the heart wood only contains 
numerous resin ducts, although they occur in limited numbers in all 
parts of the outer wood and bark. The production of larch turpentine, 
therefore, is different from that described heretofore. By means of a 
wide auger, one or several holes are bored in spring to the center of 
the tree. These are closed with a wooden stopper and opened in fall in 
order to remove the oleoresin which has collected, with an iron spoon. 
The hole is again dosed for the further accumulation of oleoresin during 
the next summer. 
If only one or two holes are drilled into the tree, the yield amounts 
to only several hundred grams, but remains the same for many years. 
If a larger number of holes are drilled into the tree, and the balsam is 
allowed to flow out, several pounds of balsam can be obtained in a 
single summer. In this case, however, the tree is exhausted after 
a number of years and the wood suffers considerable reduction in value. 
A more scientific management of the forests, for the production of 
turpentine is. therefore, more remunerative (Wesseley,5 1853). 
In the French Dauphine and about Briangon the oleoresin is reported 
to be obtained in a similar manner. The holes, however, are drilled in 
a straight up and down line and each hole is provided with a short tin 
or wooden tube. After the exudation ceases, the openings are closed 
and again opened after 2 to 3 weeks. After the first reopening the flow 
is said to be greater than when the holes are first drilled. The tapping 
goes on from March to September. Large trees yield about 3-4 k. of 
turpentine in a year. After 4(1-50 years the trees are exhausted.0 
i) Fliickiger, Pharmacognosie, p. 80. 
2) Matthioli, Opera, I, p. 103. 
3) Philiatri, Ein kostlicher Schatz, p. 289. 
*) Bot. Zeitung, 17, pp. 329 and 377. 
5) Die osterreichischen Alpenlander und ihre Forste, p. 369. 
6) G. Planchon et E. Collin, Les Drogues simples d'origine vggetale, Tom 1. p. 70. Oils of the Abietinea*. 
251 
Inasmuch as there is no real demand for Venetian turpentine oil, 
the distillation is not conducted on a large scale. The yield is about 
13.5 to 15 p. c. 
Properties and Composition.-The oil distilled from Venetian tur- 
pentine has a sp. gr. of 0.878 and a rotatory power «d = - 11°.1 The 
turpentine itself, according to Fliickiger, is dextrogyrate «d = + 9:5°.2 
Upon fractional distillation the oil comes over between 155-190°, the 
larger portion at 157°. If the lowest fraction is saturated with hydrogen 
chloride, crystallized chlorhydrate,- CioHie.HCl results, thus showing the 
presence of pinene. 
9. Turpentine Oil from Canada Balsam. 
History. Canada balsam, which was probably long known to the 
American Indians and enlployed by them, is first mentioned in European 
reports of travel by Marc Lescarbot3 who traveled in Canada during 
the years 1606 and 1607'. He declares the balsam equal in value to 
the Venetian. In the European market, however, it is not found before 
the eighteenth century (Fliickiger4). 
Origin and Preparation. Canada balsam, also known as balsa,in of 
fir. balsam of Gilead, is Used externally as well as in the preparation 
of elastic coilodium, for the mounting of microscopic preparations, etc. 
Its source is the balsam fir. Abies balsamea Miller (Pinus balsamea 
which grows in British America, the northern and northwestern United 
States. It is collected principally in the Laurentine hills in the province 
of Quebec. Somewhat farther south, in the northern Alleghanies, the 
double balsam hr, Abies fraseri Purch, and the hemlock spruce, Abies 
canadensis Michaux, Tsuga canadensis Carr, are also utilized.5 
These conifers secrete the oleoresin in resin ducts between the 
bark and the splint. The tedious collection is done mostly by descendants 
of the Indians, who camp in the forests during the summer. For the 
tapping of the pustules and the collection of the balsam they use small 
iron cans with a pointed lip. With this they puncture the bark covering 
the pustules readily recognizable on the trunk and the larger branches. 
1) Bericht von S. & Co., April 1897, table on p. 46. 
2) Neues Jahrb. f. Pharm., 31 (1869), p. 73; and Jahresber. d. Pharm., 1869, p. 37; 
Pereira (1845) states that the turpentine itself is laevogyrate (Pharm. Journ., I, 5, 
p. 71). 
3) Hist, de la Nouvelle-France, pp. 805, 811, 820. 
*) Documente zur Gesch. d. Pharm., p. 92. 
s) The latter constitutes large forests along the lower St. Lawrence, in Nova 
Scotia, New Brunswick and westward as far as Minnesota. 252 
Special Part,. 
The oleoresin exudes slowly into the cans, which are emptied daily and 
then thrust into a fresh pustule. One man collects little more than 
% gal., or 2% k., daily; with the aid of children he may collect double 
the amount. After every season the trees must be- allowed to rest 
for from one to two years, because of the insufficiency of the accumu- 
lation of oleoresin. The principal place of export for Canada balsam is 
Quebec. The annual production has been given at greatly varying 
figures. It probably does not exceed 20,000 k. during the best years. 
(Stearns,1 1859; Saunders,2 1877.) 
Upon distillation the balsam yields 16-24 p. c. of oil. 
Properties and Composition. The oil obtained from the dextro- 
gyrate balsam is laevogyrate. Its odor corresponds to that of the 
ordinary oil of turpentine. It begins to distill at 160°, the major 
portion coming over at 167°, a smaller amount even above 170°. 
When saturated with hydrogen chloride the oil does not yield a 
crystalline hydrochloride directly. A compound of the formula CioHio.HCl 
was obtained by Fliickiger3 only after treatment of the product of 
reaction with fuming nitric acid. The presence of pinene, rendered 
probable by this experiment, was proven by Emmerich4 (1895) by 
means of the nitrosochloride, and the nitrolbenzylamine base melting 
at 122°. The pinene of Canada balsam is 1-pinene. 
10. Turpentine Oil from Strassburg Turpentine. 
History. Strassburg turpentine, which was known and used at the 
time of the Romans, has long disappeared from the market being dis- 
placed by cheaper varieties of turpentine. The oil has probably never 
been distilled on any other than a small scale and principally for 
scientific purposes. 
Origin and Preparation. The oleoresin of Abies alba Miller [Abies 
pectinata I). C., Pinus picea L.) which is widely distributed in central 
Europe, is found in pustules like that of Abies halsamea Miller. Upon 
raising the bark, the pustules are readily recognizable and are opened. 
The exuding balsam is collected in small tin cans. The yield is small 
and the collection of larger quantities tedious. Up to the middle of the 
seventies. Strassburg turpentine was still collected near Mutzig and Barr 
in the Vosges mountains. For local trade and use, the collection 
may still take place; in general, however, this aromatic turpentine 
possesses historic interest only. 
1) Americ. Journ. Pharm., 31, p. 29. 
2) Proc. Amer. Pharm. Assn., 25, 
p. 337. 
3) Jahresber. f. Pharm., 1869, p. 37; 
Pharmacographia, p. 613. 
*) Amer. Journ. Pharm., 67, p. 135. Oils of the Abietineie. 
253 
Properties and Composition. The laevogyrate turpentine, accord- 
ing to its age, yields up to 24 p. c. of a laevogyrate oil which boils at 
163° and has asp. gr. of 0.861. Although no crystalline hydrochloride 
could be obtained (Fliickiger,1 1869) there can be little or no doubt but 
that this oil contains pinene. 
11. Burma Turpentine Oil. 
The distillate of the turpentines of two pines indigenous to and 
widely distributed in Burma, viz. the Pinus khasya and Pinus merkusii 
have been examined by Armstrong2 (1891 and 1896). Aside from 
the rotatory power, both are like the French oil of turpentine. 
Armstrong is of the opinion that India might supply its entire 
demand for turpentine oil from Burma if a turpentine industry could 
be established. 
The turpentine from Pinus khasya yielded upon distillation 13 
p. c. of oil of the sp. gr. 0.8627, and a specific rotatory power 
[«]d= + 36°28'. 
The turpentine from Pinus merkusii yielded almost 19 p. c. of oil, 
the sp. gr. of which was 0.8610 and the specific rotatory power 
[«]d= + 31°45'. 
12. Russian Turpentine Oil.3 
As shown in the communication of Schkatelow4 (1898), turpentine 
is collected from Pinus silvestris L. in the gouvernements Archangelsk 
and Wologda. Whether or not the oil is distilled from the oleoresin is 
not mentioned. 
Golubeff5 (1888) examined an oil distilled from Pinus sibirica^ with 
superheated steam. From fraction 162°, cooled to 0°, a solid, optically 
active camphene, CioHie, separated, which melted at 30° and boiled at 
159.° From fraction 230° a solid substance was also obtained, which, 
however, was not examined farther. 
i) Jahresber. f. Pharm., 1869, p. 38; Pharmacographia, p. 615. 
2) Pharm. Journ., Ill, 21, p. 1151; 56, p. 370. 
3) In commerce the pine tar oil distilled in Russian Poland is commonly designated 
as Russian turpentine oil. 
4) Journ. d. russ. phys.-chem. Ges., 20, p. 477; Jahresber. f. Pharm., 1888, p. 10; 
Chern. Centralbl., 1889, I, p. 106. 
a) Journ. d. russ. phys.-chem. Ges., 20, p. 585; Chern. Centralbl., 1888, II, p. 1622. 
s) Whether the oil was obtained from the oleoresin does not become apparent from 
the abstract available. This, however, may be assumed, since the oil from the needles 
of Pinus sibirica (Abies sibirica') does not contain camphene. 254 
Special Part. 
Rothtannenterpentiiiol. 
The turpentine from Picea excelsa Lk. (Pinus picea Duroi) col- 
lected in the neighborhood of Naples, being distilled for experimental 
purposes, yielded 18.3 p. c. of an oil of the sp. gr. 0.866. The optical 
rotation an was + 3° 5' at 18° and the saponification number = 0. The 
oil had the agreeable odor of pine needles.1 
14. Turpentine Oil from Pinus Sabiniana. 
The turpentine of the nut or digger pine, Pinus sabiniana, which is 
indigenous to California and the western slopes of the Sierra Nevada, 
yields upon distillation an oil that differs totally in properties and 
composition from the other turpentine oils. 
According to Wenzell2 (1872) the crude oil boils principally between 
101-105° and consists almost entirely of a hydrocarbon, abietene, the 
sp. gr. of which is 0.694 at 16.5°. At the beginning of the seventies it 
was sold in the San Francisco market under the names abietene, erasine, 
aurantine and theoline as a substitute for petroleum benzin for the 
removal of stains. 
Abietene is not affected by hydrochloric, sulphuric, and nitric acids 
in the cold and; according to Thorpe3 is identical with heptane. The 
examination by Schorlemmer 4 (1883), Venable5 (1880). render it 
probable that this hydrocarbon is normal heptane, identical with that 
from petroleum. 
The source of this oil has been a question of dispute, it having been 
referred to P. ponderosa and to P. jeffreyi as well; the oil has even been 
suspected of consisting merely of a petroleum fraction. The classification 
and synonomy of these pines is in an unsatisfactory condition and may 
well give rise to misunderstandings.0 
Pine Tar Oils. 
Kienole. 
Besides pyroligneous acid, pine tar oil is obtained in several districts 
of Europe rich in pine forests, as a by-product in the manufacture of 
charcoal and wood tar by the dry distillation of the resiniferous roots 
of the common pine, Pinus silvestris L. In Scotland Pinus lede- 
13. Turpentine Oil from Picea Excelsa. 
i) Bericht von S. & Co., Oct. 1896, p. 76. 
2) Americ. Journ. Pharm.. 44, p. 97: 
Pharm. Journ., Ill, 2, p. 789. 
3) Liebig's Annalen, 198, p. 364. 
4) Annalen, 217, p. 149. 
5) Berichte, 13, p. 1649. 
6) Pharm. Review. 18, p. 165. Oils of the Abietineiv. 
255 
bourii Endl. is also used (Tilden,1 1878). In continental Europe, most 
of the pine tar oil is made in eastern Germany, in Poland, in Finnland 
and in other parts of northern Russia, also in Sweden. 
The crude pine tar oil contains tarry, empyreumatic admixtures 
which are removed by rectification with milk of lime. Nevertheless, the 
oil retains an empyreumatic odor. Though resembling turpentine oil, 
this odor renders it inferior. 
In a general way it can be said that all pine tai' oils have like 
properties and like composition. Their components are dextro-pinene, 
dextro-sylvestrene, and dipentene.2 From turpentine oil they differ 
principally by their sylvestrene content.3 
15. German Pine Tar Oil. 
Deutsches Kienol. 
The distillation of tar is conducted only in a few places in the 
vicinity of Torgau (Province of Saxony); the production of charcoal, 
tar and pitch have become the prime object. While the trunks of the 
pines are converted into lumber or fuel, the roots rich in resin 
are submitted to dry distillation after the splint has been removed to 
be used as fuel. With the present rational method of production4 the 
distillation of tar is conducted in a sugarl oaf-like oven, built of fire- 
brick, which is heated by a wood fire circulating outside of these walls. 
The floor, which inclines toward the center, is provided with a large exit 
tube through which all of the liquid products of distillation escape into 
a pit of masonry. Through a lateral branch of the exit tube, the more 
volatile aqueous and ethereal products of distillation pass through a 
condenser and are collected in large Florentine flasks. In this manner 
the lighter oils are separated from the heavier pyroligneous acid. 
The crude pine tar oil is rectified over milk of lime and charcoal. It is 
used in the preparation of iron paints, for the cleaning of type and elec- 
tros, and in the preparation or dilution of the cheaper grades of paints. 
Pharm. Journ., Ill, 8, p. 539. 
2) In order to ascertain whether sylvestrene and dipentene are to be regarded as 
original components or as decomposition products due to destructive distillation, 
Aschan and Hjeit (Chem. Zeit., 18 [1894], p. 1566) distilled the tri^nk wood of the Scotch 
pine (fir) with water vapor. They found pinene and sylvestrene, but no dipentene. It 
would appear, therefore, that sylvestrene is an original constituent of the pine oil, but 
that dipentene must be regarded as a product of inversion of the pinene due to heat. 
3) So far, sylvestrene has been found in the roots, the wood and the needles of 
Finns silvestris L., also in the needles of Pinus montana Duroi. Apparently it is found 
in pinus species only and not in other'genera of the Abietineae. 
F, According to personal observations made at a large tar distillery in the neigh- 
borhood of Torgau. 256 
Special Part. 
Properties. German pine tar oil has a terebinthinate, empyreu- 
matic odor, a light yellow color, sp. gr. 0.865 to 0.870, and a rotatory 
power, «d, of +18 to +22°. Upon distillation of a normal pine 
oil the following fractions were obtained: 
From 160-165°, 21.6 p. c. From 175-180°, 6.4 p. c. 
" 165-170°, 50.4 " Residue, 6.4 " 
" 170-175°, 15.2 " 
Composition. German pine tar oil contains dextro-pinene, dextro- 
sylvestrene, and dipentene and does not differ in composition from either 
the Polish or Swedish oils. 
16. Polish or Russian Pine Tar Oil. 
Polnisches Oder Russisches Kienol. 
( Also known as Russian turpentine oil.) 
In Russia also, pine tar oil is but a by-product in the manufacture 
of charcoal in the tar distilleries. These are very common in Russia 
and to be found wherever there are large pine forests. The principal 
seat of the charcoal and tar industry is in Archangelsk, Wologda and 
the neighboring gouvernements,1 .also in Poland.2 It has almost 
invariably the character of an home industry and is conducted in a 
primitive manner in ovens made of clay. 
The crude pine tar oil of the smaller manufacturers is principally used 
for home consumption. The larger distilleries which also purchase the 
crude oil from the smaller plants, purify the oil by rectification over 
milk of lime and charcoal. The pyroligneous acid is mostly converted 
into calcium acetate. 
The sp. gr. of the Russian pine tar oil is 0.862-0.872, the angle of 
rotation aD = + 15°25' to +24° (Armstrong,3 1883). It boils between 
155-180° (Wallach,4 1885; Tilden,5 1877). Upon distillation of a 
normal Russian pine tar oil, Tilden obtained between 160-171°, 10 p. c.; 
between 171-172°, 63 p. c.; and between 172-185°, 24 p. c. 
Polish pine tar oil was examined in 1877 by Tilden and in 1887 by 
Flawitzky.6 Dextro-pinene was found present; a terpene boiling between 
i) Kowalewski, Die Produktivkrafte Russlands. German translation. Leipzig 1898, 
pp. 254. 255. 
2) According to a private communication (1896) from Prof. G. Wagner of Warschau 
there are in Russian Poland, particularly in the gouvernements Lublin, Lomza and 
Suwalki nearly 100 tar distilleries, each one of which produces on an average about 
1,500-2,500 kilo of pine tar oil. 
3) Pharm. Journ., Ill, 13, p. 586. 
*) Liebig's Annalen, 230, p. 245. 
5) Pharm. Journ., Ill, 8, p. 447; Journ. Chern. Soc., 33, p. 80. 
6) Berichte, 20, p. 1956. Oils of the Abietinete. 
257 
171-172° which Tilden supposed to be sylvestrene, though he did not 
succeed in preparing the chlorhydrate, m. p. 72°; and cymene, identified 
by means of bromine and sulphuric acid.1 Wallach in 1885 substantiated 
the presence of pinene.2 He also identified the sylvestrene in fraction 
170-180° by means of the crystalline hydrochloride, m. p. 72°. In the 
fractions boiling about 180°, he also identified dipentene by means of 
its tetrabromide, and a terpene which yielded a liquid addition product 
with bromine (terpinene?). 
17. Swedish Pine Tar Oil. 
Schwedisches Kienol. 
Swedish pine tar oil has a sp. gr. 0.871, and a rotatory power 
«d-+ 14°48'. According to the examination of Atterberg3 (1877) it 
contains dextro-pinene, b. p. 156.5-157.5° (pinene chlorhydrate, m. p. 
131°); and a hitherto unknown terpene, b. p. 173-175°, which Atter- 
berg characterized by a dichlorhydrate melting at 72-73° and which 
he termed sylvestrene. Wallach4 (1885) also examined this oil. 
18. Pine Tar Oil from Finnland. 
Finliindisches Kienol. 
Since closed ovens are used in the production of wood tar in Finn- 
land, a large quantity of pine tar oil is obtained as by-product from 
the trunks of the pines,5 spruces and firs. Two varieties of pine tar 
oil from Finnland have been examined by Aschan and Hjelt6 (1894). 
1. From southern Finnland. After five repeated fractionations the 
following fractions were obtained; 1) 155-160°, 7.1 p. c.; 2) 160-165°, 
30.2 p. c.; 3) 165-170°. 22.6 p. c.; 4) 170-175°, 20.1 p. c. 
The first fraction consisted of pinene (hydrochloride, m. p. 123-124°; 
nitrosochloride, nitrosopinene). In fraction 170-174° sylvestrene ('di- 
hydrochloride, m. p. 72°) and dipentene (dihydrochloride, m. p. 49-50°) 
were found. 
2. An oil from northern Finnland differed from the former in the 
relatively larger amount of higher boiling fractions. Fractions 160-165°, 
also 165-170° were insignificant, whereas fraction 170-174 represented 
32.2 p. c., and fraction 174-178°, 21.2 p. c. In the lower fractions 
i) In the presence of terpenes this reaction cannot be considered a positive proof. 
2) Liebig's Annalen, 230, p. 245. 
3) Berichte. 10, p. 1202. 
*) Liebig's Annalen, 230, p. 240. 
s) The forests of Finnland consist approximately of 77 p. c. pines and 12 p. c. spruce. 
6) Chem. Zeitung, 18, pp. 1566, 1699, 1800. 258 
Special Part. 
pinene was found, whereas the higher fractions consisted chiefly of 
dipentene. Sylvestrene, though probably present in small quantities, 
could not be identified. 
Mention has already been made (on p. 255, footnote 2) of the 
distillate with water vapor which was prepared in order to ascertain 
whether sylvestrene and dipentene are normal constituents of the 
original oil. 
Pine Needle Oils. 
Fichtennadelole. 
Distillates from the needles and cones of the Abietineae. 
The collective term pine needle oil comprises the fragrant oils from 
the fresh needles and young twigs, also the one year old cones of pines, 
spruces, larches and firs. 
If the above designation is not infrequently a misnomer, the names 
applied to specific oils in price lists are often no more correct, so that 
frequently no conclusion can be drawn from the name as to the source 
of the oil. Current names, though wrong, are difficult to displace. 
However, in the following presentation the correct names only will 
be used. 
This state of affairs is partly due to the confusion existing in the 
Latin as well as in the German (we might also add English) nomen- 
clature of the conifers. For this reason, the older literary references to 
coniferous oils must be cautiously accepted. 
On account of their balsamic and refreshing odor, these oils are 
being used in the preparation of various pine needle essences for sprays 
in living rooms and sick chambers, in the preparation of aromatic 
baths, and in finer perfumery and the soap industry. They have, there- 
fore, become current articles of commerce. 
The cheaper pine needle oils are frequently adulterated with tur- 
pentine oil. Inasmuch as pinene is a normal constituent of these oils, 
its mere presence does not signify adulteration. The addition of a large 
percentage of turpentine oil, however, can readily be demonstrated by 
comparing quantitatively the fractions of a suspected oil with those of 
a genuine oil. In the adulterated oil the fractions distilling about 160° 
or below 170° are much larger than in the pine needle oil. As a basis for 
comparison, quantitative fractionations are recorded in connection 
with the more important oils. Variations in specific gravity are not 
great and, therefore, of less importance than the examination of the 
rotatory power of the oils. Besides, the saponification number of the oils Oils of the Abietineae. 
259 
adulterated with turpentine oil is much smaller than that of the genuine 
oils and, therefore, may serve in a general way as a good test for the 
purity of the pine needle oils. 
19. Pine-Needle Oil from Abies Alba. 
Edeltannennadelol. 
This oil is distilled principally in Switzerland and Tyrol (in the 
Puster valley) from the needles and twigs of Abies alba Miller (Abies 
pectinata D. C., Abies excelsa Lk.) (Germ. Edeltanne, Weisstanne or 
Silbertanne}. 
Properties.1 This oil is a colorless liquid possessing a balsamic odor; 
sp. gr. 0.869-0.875; av =- 20° to -59°. It is soluble in 5 parts of 
90 p. c. alcohol. It contains 4.5 to 10.9 p. c. of ester (bornyl acetate). 
Upon distillation, 8 p. c. come over below 170°, and 55 p. c. between 
170-185°. Above this temperature partial decomposition results, the 
bornyl acetate splitting off acetic acid. 
Composition. Bertram and Walbaum1 ascertained the presence of 
the following constituents: 1-pinene (pinene nitrol benzylamine, m. p. 
122-123°), 1-limonene (tetrabromide, m. p. 104°), 1-bornyl acetate,2 
and a sesquiterpene not yet identified. 
20. Oil from Cones of Abies Alba. 
Edeltannenzapfenol. Teniplinol. 
This oil is obtained in several sections of Switzerland and the 
Thuringian forest by distilling the one year old cones of Abies alba 
Miller, collected in August and September, with water vapor. 
Properties. This oil is colorless and possesses an agreeable balsamic 
odor reminding somewhat of lemon and orange. Its sp. gr. is 0.853 
to 0.870; its an- - 60° to 76°. The amount of ester (calculated as 
bornyl acetate) is 0.5 to 4 p. c. With 6 parts of 90 p. c. alcohol, 
the oil gives a clear solution. It is characterized by a large percentage 
of 1-limonene. Inasmuch as this strongly optically active terpene is 
its most valuable constituent, the rotatory power of the oil is taken as 
a criterion of its value. The stronger the laevorotation and the lower 
the sp. gr., the more limonene the oil contains. 
i) Bericht von S. & Co., Oct. 1892, p. 21; April 1893, p. 29; Archiv d. Pharm., 
231, p. 291. 
2) Hirschsohn, Pharm. Zeitschr. f. Russland, 31, p. 593. 260 
Special Part. 
Upon distillation 11 p. c. came over between 150-170°, and 37 p. c. 
between 170-185°, Above this temperature partial decomposition 
accompanied by splitting off of acetic acid takes place. 
Composition. Of the older investigations of Templin oil those of 
Fliickiger1 (1856) and of Berthelot2 (1856) should be mentioned. These 
investigators studied the action of strong acids on the oil and obtained 
terpin hydrate, a terpene monohydrochloride and a terpene dihydro- 
chloride. The formation of these compounds is to be attributed to the 
presence of pinene and limonene as shown later. 
In 1885 Wallach3 examined a "templin oil" designated "Fichten- 
nadelol" and found its principal constituents to be pinene and 1-limonene. 
Bertram and Walbaum4 (1893) showed that the pinene also is laevo- 
gyrate and that "Templinbl" consists principally of 1-pinene and 
1-limonene. They also found a trace of an ester, the nature of which 
could not be ascertained, but which in all probability is bornyl acetate, 
also found in the oil from the needles. On account of the large per- 
centage of 1-limonene, this oil is the best source for this hydrocarbon. 
21. Pine Needle Oil from Picea Excelsa. 
Fichten- or Rothtaiineniiadelol. 
The "Fichtennadelol" proper is obtained by steam distillation from 
the fresh needles and twigs of the Norway spruce, the Picea excelsa Lk., 
(Picea vulgaris Lk.). The yield is about 0.15 p. c. (Bertram and 
Walbaum.5) As far as is known, it is not a commercial article. 
The odor of the colorless oil is as pleasantly aromatic as that of 
the oil from the needles and cones of Abies alba Miller. Its sp. gr. is 
0.880 to 0.888, and its «d - -21° 41/ to -37°. Upon fractional dis- 
tillation Bertram and Walbaum6 obtained 20 p. c. between 160-170°, 
ami 50 p. c. between 170-185°. Above this temperature decomposition 
took place. Umney7 (1895) obtained 41 p. c. between 163-173°, 16 
p. c. betw. 173-176°, 13 p. c. betw. 176-185°, 14 p. c. betw. 185-220°, 
and 16 p. c. residue. The amount of ester (calculated as bornyl acetate) 
is 8.3 to 9.8 p. c. 
Composition. Fraction 160-170° of "Fichtennadelol" contains 
1-pinene (nitrolbenzylamine, m. p. 122-123°; nitrosopinene, m. p. 132°). 
Fraction 170-175° consists of a mixture of 1-phellandrene (nitrite, m. p. 
i) Vierteljahrsschr. f. prakt. Pharm., 5, p. 1; 
Jahresber. f. Chern., 1855, p. 642. 
2) Journ. d. Pharm. etChim., Ill, 29, p. 38. 
3) Wallach, Liebig's Annalen, 227, p. 287. 
*) Archiv d. Pharm., 231, p. 293. 
5) Ibidem, p. 295. 
6) Ibidem, p. 296. 
7) Pharm. Journ., 55, p. 162. Oils of the Abietinese. 
261 
101°) and dipentene (dihydrochloride, m. p. 50°). The higher fractions 
contain 1-bornyl acetate and cadinene (dihydrochloride, m. p. 118°).1 
22. Pine Needle Oil from Finns Montana. 
Latchenkieferc Oder Krummliolzol. 
It is obtained by steam distillation from the needles and young 
twigs of Pinus montana Miller (Pinus pumilio Haenke, Pinus mughus 
Scop., Ger. Latschen- or Zwergkiefer, Legfohre) principally in the Austrian 
Alps, more especially in Tyrol (Punter valley), also in Hungary and 
Siebenbiirgen. 
Of the yield obtained at these places, no reliable data are on hand. 
An experimental distillation in Leipzig with fresh twigs obtained from 
Siebenbiirgen and Hungary yielded 0.26 p. c.2 and 0.68-0.71 p. c.3 of oil 
respectively. The young wood without the needles yielded 0.27 p. c. of oil. 
Properties. "Latschenkiefer" oil has a pleasant balsamic odor. It 
is colorless and has a sp. gr. of from 0.865 to 0.875. The oils, alluded 
to above, which had been distilled in Leipzig from material that had 
partly dried during the long transportation, could, therefore, not be 
considered as normal oils. Their sp. gr. was as high as 0.892.3 The 
optical rotation of the normal oil varies from -4°30' to -9°; the 
percentage of ester, calculated as bornyl acetate, varies from 5-7 p. c. 
Upon fractional distillation, nothing came over between 160-170°, but 
70 p. c. were obtained between 170-180° (Bertram & Walbaum4). 
An oil distilled by Umney5 (1895) yielded 2 p. c. betw. 155-165°, 
59 p. c. betw. 165-180°', 21 p. c. betw. 180-200° and 18 p. c. 
above 200°.6 
Composition. According to Bertram & Walbaum7 "Latschen- 
kieferol" contains but little 1-pinene8 in the lower fractions (pinene 
nitrolbenzylamine, m. p. 122-123°). In the following fractions 1-phel- 
landrehe (nitrite, m. p. 102°), sylvestrene0 (dihydrochloride, m. p. 72°) 
and bornyl acetate; in the highest fractions cadinene (dihydrochloride, 
m. p. 118°) have been found. 
i) Archiv d. Pharm., 231, p. 296. 
2) Bericht von S. & Co., Oct. 1893, p. 19. 
s) Ibidem, Oct. 1896, p. 76. 
Loe. clt., p. 297. 
5) Pharm. Journ., 55, p. 162. 
s') Tnis seems to show conclusively that the requirements of the seventh edition 
of the Austrian Pharmacopoeia, viz. sp. gr. 0.85, and b. p. 170°, are inaccurate. 
t) Loe. cit., p. 297. - Comp, also Liebig's Annalen, 116, p. 323. 
s) First found by Atterberg (1881) and described by him as terebentene. Berichte, 
14, p. 2531. 
9) Atterberg suspected the presence of sylvestrene in this oil. 262 
Special Part. 
23. Pine Needle Oil from Finns Silvestris. 
KiefernadeWl. 
From the needles of Pimis Silvestris L., Germ. Kiefer or Fbhre. 
German "Kiefernadelol". The needles from P. silvestris, which 
grows in all parts of Germany, have been repeatedly distilled for experi- 
mental purposes. Although but slightly inferior to other pine needle 
oils in odor, the oil has not found its way into perfumery and the soap 
industry and consequently is not an article of commerce. 
Fresh leaves distilled in July yielded 0.55 p. c.,1 leaves distilled in 
December 0.45 p. c. of volatile oil (Bertram & Walbaum2). 
Properties.2 The odor of the oil resembles that of the pine needle 
oils from Abies alba Miller and Pinus montana Miller but is less delicate. 
Its sp. gr. is 0.884-0.886 and its aD = + 7° 3' to 10°. Upon fractional 
distillation 10 p. c. came over between 160-170°, 46 p. c. betw. 
170-185°. With 10 p. of 90 p. c. alcohol the oil gives a clear solution. 
The ester content, calculated as bornyl acetate, is 3.2-3.5 p. c. 
Composition. The German oil, like the pine needle oils previously 
mentioned, contains pinene, but the pinene differs from that found in 
these oils in being dextrogyrate1 (nitrolbenzylamine, m. p. 122-123°). 
It also contains d-sylvestrene. Its dihydrochloride first melted below 
50° and only after repeated recrystallization acquired a constant melt- 
ing point of 72°. Inasmuch as, according to Wallach, dipentene 
dihydrochloride causes a material depression of the melting point of 
sylvestrene dihydrochloride, the assumption- that dipentene is present 
may be justified. 
Upon saponification, acetic acid was found which was evidently 
combined with an alcohol (probably borneol or terpineol) not yet 
identified. In the highest fractions cadinene (dihydrochloride, m. p. 118°) 
was found. 
Swedish "Kiefernadelol" is distilled in Sweden, more particularly in 
the district Jbnkoping, and is brought into the market as Schwedisches 
Fichtennadeldl. It is used for hygienic and medical purposes, in 
inhalations for affections of the lungs, as admixture to baths, and in 
sprays for sick chambers. 
Properties. The Swedish oil corresponds in its general properties 
with those of the German oil. Its sp. gr. is 0.872, its rotatory power 
+ 10°40', and upon distillation yields 44 p. c. distillate at 160-170° 
1) Archiv d. Pharm., 231, p. 300. 
2) Ibidem: and Ber. von S. & Co., Oct. 1896, p. 76. Oils oi the Abietines. 
263 
and 40 p. c. at 170-185°. It contains d-pinene (nitrolbenzylamine, 
m. p. 122-123°), d-sylvestrene (diliydrocldoride, m. p. 72°), and small 
amounts of an ester (3.5 p. c. calculated as bornyl ester), the nature of 
which has not yet been definitely ascertained but, judging- from the 
odor, appears to be bornyl acetate (Bertram and Walbaum,1 1893). 
English "Kiefernadeldl." From the German and Swedish oils, the- 
English is distinguished by its laevorotation. 
Umney2 (1895) distilled the needles of the Scotch fir, Pinus silvestris 
L. at different times of the year and'obtained 0.5 p. c. of oil in June, 
and 0.133 p. c. in December. Its sp. gr. varied from 0.885-0.889, and 
its rotatory power, ao =- 7.75° to -19°. The ester content, calculated 
as bornyl acetate, amounted to 2.9-3.5 p. c. Upon fractionation of 
the two oils, the following results were obtained: 
Oil distilled, 
In June. In December. 
157-167° 8 p. c. 13 p. c. 
167-177° 27 " 24 " 
177-187° 20 " 9 " 
187-197° 3 " 6 " 
197-240° 7 " 7 " 
240-252° 6 " 4 " 
Residue 29 " 37 " 
Composition. The lowest fraction deviated the ray of polarized light 
13° to the left (in a 100 mm. tube) and possessed all the properties of 
1-pinene. Fraction 171-175° was slightly dextro rotatory (+0.75°), 
and corresponds in its properties to dipentene3 and gave with glacial 
acetic and sulphuric acids the characteristic violet sylvestrene reaction. 
With the exception of the opposite rotation, it may be assumed 
that the English oil has the same composition as the German and 
Swedish oils. 
24. Hemlock or Spruce Needle Oil. 
Hemlock- or Spruce-Taiinennadelol. 
The needles and young twigs used in the distillation of this oil seem 
to be contributed by three different species: 1) Abies canadensis Michx., 
(Tsuga canadensis Carriere), the hemlock (Ger. Spruce- Hemlock- oder 
Schierlings-Tanne) which occurs throughout North America from Canada 
to Alabama and westward as far as the Pacific; 2) Picea alba Lk. or 
i) Archiv d. Pharm., 231, p. 299. 
2) Pharm. Journ.. 55, pp. 161, 542. 
3) Derivatives of this ^hydrocarbon were evidently not prepared. Neither did Umney 
succeed in obtaining the dihydrochloride of sylvestrene. 264 
Special Part. 
white spruce (Ger. weisse Tanne); and 3) Picea nigra, Lk., the black 
spruce (Ger. schwarze Tanne). The two latter are equally widely dis- 
tributed with the first. In the collection of the leaves and twigs it 
seems highly probable that no distinction is made between these three 
species, so that a commercial oil may contain variable amounts of the 
oils from all three. In fact the oils of these three species, being regarded 
as identical, are brought into the market under the common name of 
hemlock or spruce oil. Inasmuch as the oils are alike in propertiesand 
composition, quantitatively, the confusion in this case may be regarded 
as being of little or no consequence. 
Properties and Composition. Hemlock or spruce oil is colorless* 
of an agreeable balsamic odor,1 sp. gr. 0.907-0.913, «d = - 20° 54' 
(Bertram and Walbaum2) to -23° 55' (Power3). Fractional distillation 
yielded 11 p. c. between 150-170°, and 37 p. c. betw. 170-185°. Above 
this temperature decomposition sets in with the formation of acetic acid. 
Hemlock oil contains l-pinene (nitrolbenzylamine, in. p. 122-123°) > 
36 p. c. 1-bornyl acetate and sesquiterpenes not identified. 
Hunkel4 examined an oil distilled by himself from the fresh twigs of 
Abies canadensis Michx. Its sp. gr. at 20° was 0.9288, [«]d =-18.399°- 
It contained 51.5-52 p. c. of 1-bornyl acetate. 1-Pinene was identified 
by means of the nitrolbenzylamine base. m. p. 122°. 
An oil distilled in September consisted principally of about equal 
parts of 1-bornyl acetate and l-pinene. 
25. Needle Oil from Picea Nigra. 
Schwarzflchtennadelol. 
The oil from Picea nigra Lk. already mentioned under the previous 
heading is almost identical with hemlock oil. Its sp. gr. is 0.922 at 
20°, «d = - 36.367° at 20°, [«]d = - 39.45°. The oil distills between 
160-230°, the principal fraction between 212-230°. It contains 48.85 
p. c. bornyl acetate (Kremers,5 1895). 
26. Needle Oil from Balsam Fir. 
Balsaintannennadelol. 
The fresh twigs and young cones of the North American balm of 
Gilead fir yield upon distillation with water vapor an oil similar to the 
preceding ones. 
i) The oil with which Hunkel worked 
was by no means very agreeable as to 
odor, Kleber, however, regards to the odor 
of the commercial oil as very pleasant. E. K. 
2) Archiv. d. Pharm., 231, p. 294. 
3) Deser. Catalogue of ess. oils, p. 58. 
*) Pharm. Review, 14, p. 35. 
5) Pharm. Rundschau, 13, p. 135. Oils of the Abietine;?. 
265 
Properties and Composition. The sp. gr. of the oil is 0.8881 at 
20°; «d = - 28.91° at 20°; [a]D =- 32.55°. Upon distillation the 
following fractions were obtained: up to 160°, 1.5 p. c.; 160-170°, 
47.7 p. c.; 170-185°, 29.2 p.c.; 185-210°, 16.2 p. c.; residue 5.4 p. c. 
This oil contains 17.6 p. c. of bornyl acetate. Fraction 160-165°, 
which is laevogyrate, yielded a nitrosochloride melting at 101°. 
Although tlie yield was too small to make any of its derivatives it may 
be assumed that the fraction in question contains 1-pinene (Hunke!.1 
1895). 
37. Siberian Pine Needle Oil. 
Sibirisches Fichtennadelbl. 
This oil is distilled from the needles and young twigs of Abies sibi- 
rica2 (Ger. sibirische Fichte)', on a large scale in the gouvernement 
Wjatka, in northern Russia. On account of its strong, balsamic odor, 
the oil is used in perfuming "Fichtennadel" soaps and the cheaper 
"Tannenduft" preparations. 
Properties and Composition. The oil is colorless, has a sp. gr. of 
0.905-0.920; «d = - 40 to -42°. The ester content (bornyl acetate) 
varies from 29-36 p. c. With equal parts of a 90 p. c. alcohol it 
makes a clear solution. Fraction 160-163° contains 1-pinene (nitrol- 
benzylamine, m. p. 122-123°). Camphene could not be identified. In 
the higher fractions 1-borneol was contained as acetic ester (Hirsch- 
sohn,3 1892). Besides bornyl acetate, it contains the ester of another 
terpene alcohol, possibly terpineol.4 
28. Needle Oil from Pinus Cembra. 
Zirbelkiefernadelbl. 
The needles (without the branches) of the Siberian cedar. Pinus 
cembra L. (Ger. sibirische Ceder, Arve) yield upon distillation with 
water vapor 0.88 p. c. of oil. Its rotatory power, «d- + 29.1°. It con- 
sists chiefly of d-pinene (monohydrochloride, m. p. 125°). Fraction 156° 
has a very high specific rotatory power [a]o - + 45.04°. 
On account of this high rotatory power, the oil is very serviceable 
in the preparation of a strongly dextrogyrate pinene (Flawitzky,5 1892). 
1) Amer. Journ. Pharm., 67, p. 9. 
2) According to a statement of the firm of R. Koehler & Co., of Moscau; comp, 
also Bericht von Schimmel & Co., April 1886, p. 15. According to Prof. Menthin of 
Warsau, however, this oil is obtained from the needles of Larix sibirica Ledebour 
(Pinus ledebourii Endl.). 
s) Pharm. Zeitschr. f. Russl., 30, p. 593. 
*) Ber. v. S. & Co., Oct. 1896, pp. 42 & 76. 
5) Journ. f. prakt. Chem., II, 45, p. 115. 266 
Special Part. 
The fruit of Abies reginae amaliae Hei dr., which grows in the forests 
of Arcadia, contains so large an amount of volatile oil that it exudes 
when the fruit is compressed. Upon distillation of the crushed fruit more 
than 16 p. c. of volatile oil has been obtained (Buchner and Thiel,1 1864). 
Properties and Composition. The sp. gr. of the oil is 0.868, its 
rotatory power - 20°. It begins to boil at 156°, the boiling point 
remains constant for some time at 170° and finally rises to 192°. 
As shown by elementary analysis, the oil consists principally of 
hydrocarbons CioHie. A solid hydrochloride was not obtained. This 
is evidently due to the fact that besides pinene the oil probably contains 
limonene and dipentene. A mixture of hydrochlorides is thus obtained 
from which it is difficult to separate the individual compounds. 
30. Larch Needle Oil. 
Larchennadelol. 
The needles of the larch, Larix decidua Mill, upon distillation yield 
but 0.22 p. c. of oil of the sp. gr. 0.878; «d= + 0° 22'.2 It forms a 
clear solution with 5 and more parts of 90 p. c. alcohol. Saponification 
number 23.3, S. Z. after acetylization 46. 
If it is assumed that the ester of this oil is bornyl acetate, as is 
the case in most coniferous oils, and that the alcohol is borneol, the 
above figures indicate a percentage of 8.1 p. c. of bornyl acetate in the 
original oil and 16.1 p. c. in the acetylized oil. With reference to the 
alcohol, the same figures indicate 6.53 p. c. of borneol as ester, and 
6.14 p. c. of free borneol, a total of 12.67 p. c. 
Upon distillation the following fractions were obtained: 160-165°, 
30 p. c. («d = + 4° 15'); 165-170°, 24 p. c.; 170-180°, 16 p. c.; 
180-190°, 8 p. c.; 190-200°, 4 p. c.; 200-230°, 9 p. c.; residue 9 p. c. 
Larch needle oil has a pleasant, refreshing pine needle odor. The 
small yield and high price, as well as the difficulty of obtaining larger 
quantities prevent its practical application. 
31. Sequoia Oil. 
Upon distillation of the needles of the Californian giant, Sequoia 
gigantea Torrey {Wellingtonia gigantea Lindl.) which had been culti- 
vated in Zurich, Lunge and Steinkauler3 (1880) obtained a volatile oil 
which partly solidified at ordinary temperature. 
29. Oil from the Cones of Abies Reginae Amaliae. 
i) Journ. f. prakt. Chem., 92, p. 109. 
2) Bericht von S. & Co., Oct. 1897. p. 66. 
3) Beriehte, 13, p. 1656; 14, p. 2202. Oils of the Abietines?. 
267 
The greater portion of the distillate consisted of a, hydrocarbon 
CioHie, boiling at 155°, which possessed a pleasant terebinthinate odor, 
had a sp. gr. of 0.8522 and a rotatory power [«]j = + 23.8°. With 
hydrogen chloride, a white, camphor-like hydrochloride crystallizing in 
needles was obtained. Although these facts indicate pinene, Lunge and 
Steinkauler regard it as a new terpene on account of its high rotatory 
power.1 
Fraction 227-230° had a sp. gr. 1.04-5, angle of rotation + 6°, 
and its odor reminded of peppermint Oil. From the elementary analysis 
the formula CisH2oO8 was calculated. Between 280 and 290° a small 
amount of a heavy yellow oil of empyreumatic odor was obtained. 
Further there is contained in the oil a colorless hydrocarbon, which 
crystallizes in laminae melting at 105° and boiling between 290-300° 
(uncorr.). It is called sequojene and probably has the formula C13H10 
being isomeric with fluorene. 
32. Sandarac Resin Oil. 
According to Balzer2 (189(5) African sandarac from Callitris quad- 
rivalvis Vent, contains about 1 p. c. of volatile oil which can be obtained 
by steam distillation. The oil has a brownish color, a pleasant, 
strongly aromatic odor reminding of the odor of pines. In the cold it 
becomes viscid and apparently separates a stearoptene-like substance. 
33. Thuja Oil. 
Oleum Thnjae.-Thujaol.-Essence de Thuya. 
Origin and Production. Thuja oil obtained by distillation with 
water vapor of the leaves and twigs of the arbor vitae, Thuja occi- 
dentalis L. (Ger. Lebensbaumj. The yield varies according to the season 
from 0.4 to 0.65 p. c. It is largest in spring (March) and decreases 
toward summer (June, Jahns,3 1883). The small amount necessary to 
supply the demand, is distilled principally in North America. 
Properties. Thuja oil is a limpid, colorless liquid or of a yellowish 
or greehish-yellow color. It has a characteristic strong, camphor-like 
odor of tansy, and a bitter taste. Sp. gr. 0.915-0.935; aD - - 5 to 
- 14°. With 3-4 parts of 70 p. c. alcohol it forms a clear solution. 
It boils between 160 and 250°. The first runnings contain an acid liquid 
consisting principally of acetic acid with a little formic acid (Jahns3). 
i) Since then Flawitzky (1892) (Journ. f. prakt. Chem., II, 45, p. 115) has isolated 
a pinene with much higher dextro-rotation. See needle oil from Pinus cembra on p. 265. 
2) Archiv d. Pharm , 234, p. 311. 
3) Archiv d. Pharm., 221, p. 748. 268 
Special Part. 
Composition. Thuja oil was first examined by Schweizer1 in 1843 
without definite results. Jahns succeeded in separating three sub- 
stances by fractional distillation. He obtained a dextrogyrate terpene 
fraction between 156-161°, a dextrogyrate oxygenated fraction 
between 195-197°, and a laevogyrate oxygenated fraction between 
197-199°. The two latter fractions had the formula CioHieO and 
inasmuch as they appeared to be optical isomers, he named them 
d- and 1-th ujol. 
A few years later (1892) Wallach's2 investigation clearly revealed the 
composition of thuja oil. By means of the nitrosochloride the identity 
of fraction 160° with d-pinene was established. The fractions up to 
190° also contain a substance that is acted upon by potassa with 
the formation of potassium acetate and probably contains an acetic 
acid ester. Fraction 190-200° contains two chemically different ketones 
of the formula CioHisO, 1-fenchone, and d-thujone. The purification of 
1-fenchone, Wallach accomplished by acting on fraction 190-195° with 
potassium permanganate and nitric acid, thereby completely destroying 
the thujone whereas the very stable fenchone remained almost un- 
affected. The fenchone thus obtained corresponds in all its properties, 
with the exception of opposite optical rotation, with the ketone obtained 
from fennel oil (comp. p. 166). To the second ketone CioHieO, which 
boils slightly higher, Wallach applied the name thujone. Properties and 
derivatives of this substance are described on p. 167. 
From fraction 220° of the oil, Wallach3 (1894) obtained an inactive 
oxime melting at 93-94° which corresponded with optically inactive 
carvoxime. Upon hydrolysis with sulphuric acid it yielded an oil 
volatile with water vapor, which had the odor of carvone and which 
boiled between 220-230°. The properties of the hydro-sulphide addition 
product, however, did not agree with those of the corresponding com- 
pound obtained with inactive synthetic carvone. Later on it was shown 
by analysis that the oxime is not a derivative of i-carvone. as Wallach 
first supposed, but of hydrocarvone, CioHmO4 (1894). Inasmuch as 
Semmler5 has shown (1894) that thujone, when heated to higher tem- 
peratures, is converted into carvotanacetone= hydrocarvone, it seems 
probable that hydrocarvone is not contained in the original oil but is 
formed by fractional distillation from thujone. 
i) Journ. f. prakt. Cheni.. 30, p. 376; 
Liebig's Annalen, 52, p. 398. 
2) Liebig's Annalen, 272, p. 99. 
3) Liebig's Annalen, 275, p. 182. 
*) Liebig's Annalen, 279, p. 384. 
5) Berichte, 27, p. 895. Oils of the Abietines. 
269 
34. Thuja Root Oil. 
The oil from the root of Thuja occidentalis L. has a deep-brown 
color, an odor reminding' of that of thymoquinone, and a%sp. gr. 0.979. 
The yield is about 2.75 p. c.1 
35. Oil of Cypress. 
Oleum Cupressi. - Cypressenbl. - Essence de Cypres. 
Origin and History. Cypress oil which was recommended by Bravo 
in 1892 against whooping-cough, was introduced into commerce by 
Schimmel & Go. in 1894.2 It is distilled from the leaves and young- 
branches of Cupressus sempervirens L. According to the season and 
the freshness of the material the yield varies from 0.6 to 1.2 p. c. 
Properties. Cypress oil is a yellowish liquid, the odor of which is 
pleasant and reminds of cypress, but which after evaporation leaves an 
odor that reminds distinctly of labdanum and is ambra-like. Sp. gr. 
0,88-0.89, «d = + 4 to +14°. The oil is soluble in 4-5 parts of 
90 p. c. alcohol. 
Composition. Cypress oil consists chiefly of terpenes, principally of 
d-pinene (nitrolbenzylamine, m. p. 124°). Sylvestrene and sesquiterpenes 
appear also to be present. From the last runnings a crystalline 
substance occasionally separates, which crystallizes from alcohol in fine 
needles, from petroleum ether in compact crystalline masses. In its 
behavior, "cypress camphor" resembles cedar camphor or cedrol, from 
which it differs, however, by being optically inactive. Probably it is the 
optically inactive modification of cedrol. In addition, cypress oil con- 
tains small amounts of esters. 
36. Hinoki Oil. 
The white wood of the hinoki tree, Chamaecyparis obtusa Endl. 
(Retinospora obtusa, Sieb. et Zucc.), which is cultivated in Japan, is 
used in the construction of the Shinto temples and the manufacture of 
lacquered goods.3 The odor of the oil distilled from the leaves resembles 
that of the oil from the savin or thuja. It has a remarkably low 
boiling point. About half of the oil distills between 110 and 160°, the 
other half between 160 and 210°.4 
i) Bericht von S. & Co., Apr. 1892, p. 43. 
2) Ibidem, Oct. 1894, p. 70; and Apr. 1895. p. 22 
3) Rein, Japan, Leipzig, 1886, vol. 2, p. 277. 
Bericht von S. & Co., April 1889. p. 44. 270 
Special Part. 
Oleum Juniperi. - W. cholderbeerol. - Essence de Genievre. 
37. Oil of Juniper Berries. 
Origin and History. The several species of the genus Juniperus of 
the family Cupressineae are evergreen,trees or shrubs. Of these, Juniperus 
communis L. is distributed over the entire northern hemisphere, whereas 
the very similar Juniperus oxycedrus L. is found wild only in the 
Mediterranean countries east as far as the Caucasus and west as far as 
Madeira. The aromatic odor of all parts of the juniper, especially of its 
fruits, when burned has in all probability attracted early attention. 
It is also probable that the juniper tar oils, obtained by destructive 
distillation, were known and used previously to those obtained 
by water distillation from the wood and the fruits. Of the latter 
two that obtained from the wood seems to have been first known and 
used.1 
Apparently, juniper was first used as a domestic remedy by the Greeks 
and Romans. The fruits of both species, which grow together in the 
Mediterranean countries, were merely distinguished as the larger and 
smaller juniper berries. 
The empyreumatic oil obtained by the dry distillation of the juniper 
wood was already known to the Romans, and was used for medicinal 
purposes during the middle ages. The distilled juniper wood oil is 
repeatedly mentioned in the mediaeval treatises on distillation (Destillir- 
biicher), and is enumerated together with the oil from the fruits in 
medical treatises and price ordinances (Taxen) of the sixteenth century. 
The yield of the oil from the fruits was determined by Cartheuser2 
(1738). and Spielmann.3 
Production. The distillation of the berries and the preparation of 
the extract go hand in hand. After the mashed berries have been 
distilled with water, the residue in the still is extracted with hot water. 
The aqueous liquid is evaporated in vacuum pans to the consistency of a 
soft extract and is brought into the market as Succus* or Roob Juniperi. 
The yield of both oil and extract varies considerably in different years. 
The quality of the juice likewise varies considerably. In some years it 
is so rich in sugar that it congeals to a fairly solid mass. 
i) See p. 18. 
2) Fundamenta materia medicae, vol. 2, p. 346. 
3) Ibid., vol. 2, p. 272. 
4) The extract obtained in this manner does not correspond to the Suceus Juniper! 
of the German Pharmacopoeia since according to the method of preparation of the 
latter a part of the oil remains in the extract. Oils of the Abietinese. 
271 
On an average Italian berries yield 1-1.5 p. c., Bavarian 1-1.2 p. c., 
Hungarian 0.8-1 p. c. of oil. A smaller yield of oil, 0.6-0.9 p. c., is 
obtained from East Prussian, Polish, Thuringian and Frankish juniper 
berries. A distillation of Swedish berries yielded but 0.5 p. c. of oil. 
These data contradict the opinion expressed by Maier1 (1867) that 
the oil content of juniper berries grown in northern countries is greater 
than that of berries grown in southern countries. The above data 
indicate the opposite to be true. However, the collected data are not 
sufficient to settle this question finally. 
Fairly considerable quantities of oil of juniper berries are brought 
into the market from the Hungarian "Komitat" Trencsin. Judging 
from experience, this Hungarian oil is of minor quality and not normal 
in composition. It is probably obtained as a by-product in the manu- 
facture of gin. 
Oil of juniper berries is used principally in the preparation of gin 
(Steinhager, Genie we) and liquors, also to a limited extent medicinally, 
particularly in veterinary practice. 
Properties. Juniper berry oil is a limpid liquid, colorless or slightly 
greenish. Old oil is more viscid, reacts acid and smells more or less 
rancid. Fresh oil possesses a peculiar terebinthinate odor, and a 
balsamic, burning, somewhat bitter taste. In regard to its physical 
constants, it shows considerable variation according to origin and 
method of preparation. The sp. gr. lies between 0.865-0.882, and in a 
normal oil between the narrower limits of 0.867-0.875. The oil is 
mostly laevogyrate upto-11°, seldom inactive, now and then slightly 
dextrogyrate. In alcohol, particularly in dilute alcohol, it is but slightly 
soluble. To effect solution 8-10 parts of 90 p. c. alcohol are requisite. 
With some oils a clear solution cannot be effected with 90 p. c. alcohol 
in any proportion. The solubility further diminishes with increasing 
age. With chloroform, carbon disulphide, benzene- and amyl alcohol, 
juniper berry oil is miscible in all proportions. 
The previously mentioned Hungarian oil has a sp. gr. 0.862-0.868, 
and is optically active up to -18° 48'. In its solubility in alcohol it 
behaves like the German. So-called extra strong juniper oil, which is 
obtained either by fractional distillation or by shaking out with alcohol 
of varying strength, loses its original greater solubility within a short 
period. 
i) Die atherischen Oele, p. 102, 272 
Special Part. 
Composition. Fraction 155-162° contains pinene1 (Wallach, 1885); 
fraction 260-275° cadinene, as shown by the preparation of the 
dihydrochloride melting' at 118°.2 The fractions between 162 and 260° 
have not yet been specially examined, although they probably contain the 
characteristic constituents of the oil. The supposition that the peculiar 
odor of the oil is due to esters2 had to be dropped since the oil retains 
its odor after saponification. The amount of saponifiable substances is 
small, for the saponification figures are very low: e. g. 3.3, 3.4, 3.5, 3.7. 
Kremel3 (1888), however, has found figures as high as 7.4 and 16.4. 
Alcoholic constituents which can be converted into esters by boiling 
with acetic acid anhydride, are present in small quantity only. In three 
normal oils the following saponification numbers were found after esteri- 
fication: 18.3, 22.5, 22.9. Substances containing a methoxyl group 
are likewise not present. A further constituent is a substance obtained 
from the last runnings of a-n oil that had been standing in a cool 
place for a long time. It separated in the form of fine needles. After 
several recrystallizations from alcohol, fine needle-shaped crystals were 
obtained which melted at 165-166°.4 Similar crystallizations have 
been formerly observed and have been described in older literature5 as 
juniper camphor, juniper berry stearoptene, juniper berry hydrate.6 
Adulterations of juniper berry oil have seldom been definitely 
proven, because a moderate addition of turpentine oil cannot be 
readily established, since pinene is a regular constituent of the oil 
and since the addition of turpentine oil but slightly changes the physical 
constants of the oil. The addition of alcohol is ascertained according 
to tl^e method described on p. 200. 
38. Oil from Juniper Wood. 
The so-called juniper wood oil is nothing but turpentine oil distilled 
from juniper wood or branches, or turpentine oil to which some juniper 
berry oil has been added. The juniper wood oils of commerce correspond 
in their properties with such products. They are used externally as 
domestic remedies or in veterinary practice. 
1) Liebig's Annalen, 227, p. 288. 
2) Bericht von S. & Co., April, 1890, p. 43. 
3) Pharm. Post, 21, p. 823. 
4) Bericht von S. & Co., Oct. 1895, p. 46. 
s) Of the older contributions on juniper berry oil the following may here be men- 
tioned: Blanchet (1833), Liebig's Annalen, 7, p. 167; Dumas (1835), Liebig's Annalen, 
15, p. 159; Soubeiran and Capitaine (1840), Liebig's Annalen, 34, p. 324. 
6) Blanchet, loc. cit.; Buchner (1825), Repert. d. Pharm., 22, p. 425. From the 
insufficient data of the older authors it does not become apparent whether they had 
the same substance as Schimmel & Co. or possibly terpin hydrate. Oils of the Abietinese. 
273 
39. Oil from the Berries of Juniperus Phoenicea. 
A commercial variety of red juniper berries obtained from Smyrna 
and probably the fruit of Juniperus phoenicea L., yielded upon distil- 
lation 1 p. c. of oil. Its sp. gr. was 0.859, «d = - 4° 55" at 16°. The 
oil corresponds in all of its properties with those of the oil from 
Juniperus communis J 
4-0. Juniper Oil from Juniperus Oxycedrus. 
The reddish-brown berries of Juniperus oxycedrus L., growing in 
Dalmatia and Istria, yield about 1.32 to 1.5 1 p. c. of oil which is quite 
terebinthinate in odor, reminding but faintly of juniper. The sp. gr. of 
the oil is 0.8512 to 0.854;r «d --4°40'1 to -8°30'.2 It does not 
produce a clear solution with 10 p. of 95 p. c. alcohol. 
The odor of the oil distilled from the fresh twigs in Spain reminds 
of that of the finer pine needle oils.3 
41. Oil of Savin. 
Oleum Sabinae. - Sadebaumbl. - Essence de Sabine. 
Origin and History. Savin, Juniperus sabina L. is indigenous to 
the temperate zones of the old world, but is not widely distributed. 
Savin was used medicinally and in veterinary practice by the 
Romans. It seems probable that the name Sabina has been derived 
from the mountainous country of the Sabines lying to the north-east 
of Rome. Dioscorides and Pliny mention the plant among those being- 
used medicinally, but distinguish between two varieties. The differences, 
however, were probably those of source only and slight morphological 
variations. Charlemagne in the ninth century mentioned it in his 
Capitulare and thus caused its cultivation in the northern Alps. The 
abbess Hildegard of Bingen mentions savin as a remedy in her writings; 
it is also one of the 77 remedies praised by Otto of Mendon (Macer 
Floridus). In England the tree seems to have been cultivated and used 
before the Norman conquest. 
1) Bericht von S. & Co., Oct. 1895, p. 45. 
2) Observation in the factory of Schimmel & Co. 
3) Bericht von S. & Co., October 1889, p. 54. 
Cade oil, which is obtained in southern France by the dry distillation of the 
branches and the wood of Juniperus oxycedrus, and which is used medicinally, is of 
special interest because it contains a high percentage of cadinene. This sesquiterpene, 
which was named by Wallach (Liebig's Annalen, 238, p. 82: 271, p. 297) is widely 
distributed in volatile oils. 274 
Special Part. 
During the period in which distilled waters were in general use, 
Aqua sabinae was also officinal and is enumerated in the treatises on 
distillation mentioned on pp. 23 et seq. 
The distilled oil is first mentioned in the price ordinance of Frankfurt- 
on-the-Main for 1587 and was described by Begninus at the close of the 
seventeenth century.1 Concerning the yield of the oil Hoffmann seems 
to have made the first experiments about 1715.2 Wedel examined the 
oil in 1707 according to the methods in vogue at his time.3 The first 
chemical examination was made by Dumas in 1835.4 
Preparation. Oil of savin is prepared by distillation with steam of 
the leaves and twigs (Summitates sabinae). The yield varies between 
4 and 5 p. c. according to the time of collection and the freshness of 
the material. The leaves used for this purpose come principally from 
Tyrol. In southern France the oil is also distilled, but apparently the 
French oil of the market is invariably adulterated with large quantities 
of turpentine oil. 
Properties. Oil of savin is a colorless or yellowish liquid of an 
unpleasant narcotic odor and a bitter, pungent, camphor-like taste. 
Sp.gr. 0.910-0.930; «D = + 42to + 60°; saponification number 115-125. 
It is soluble in % part or more of 90 p. c. alcohol. Of 80 p. c. alcohol, 
15-20 volumes are requisite, but a perfectly clear solution is not 
always effected. The oil distills between 175 and 250° leaving con- 
siderable residue. Below 200° at most 25 p. c. distill over.5 
Composition. The principal constituent is an alcohol, ''sabinol", 
which occurs partly free, partly combined with acetic acid as ester.*1 
Sabinol, which can be obtained by fractionation of the saponified oil, 
boils at 210-213° (under 20 mm. pressure between 105-107°). Its 
odor reminds of thujone; the odor of the acetate reminds of savin. 
Inasmuch as oil of savin yields a. higher saponification number after 
acetylization than before, a part of the alcohol possibly exists in the 
free state. The acid combined with sabinol was shown to be acetic acid 
by the analysis of the silver salt. 
If the formula assumed for sabinol, CioHisO, is correct, the saponi- 
fication numbers 115-125 correspond to a content of 40-44 p. c. of 
acetate. The amount of free alcohol in an oil examined was about 
10 p. c. 
1) Tyroceyniuni chymicum, vol. Ill, p. 27. 
2) Opera omnia, Biber 65. Observatio 1. 
3) Dissertatio de Sabina. Jenae 1707. 
4) Liebig's Annalen, 15, p. 159. 
5) Pharm. Journ., Ill, 25 (1895),p. 1045. 
6) Bericht von S. & Co., Oct. 1895, p. 39. Oils of the Abietines'. 
275 
According to a more recent investigation by Fromm,1 (1898) the 
formula of the alcohol is not CioHisO, but CioHiaO. When pure 
it boils at 208-209°, its acetic ester CioHisOCOCHa at 222-224°. In 
small part the sabinol of the savin oil is combined with an acid that 
boils at 247°. Oxidized with potassium permanganate, sabinol yields 
quantitatively tanacetogen dicarbonic acid, C9H14O4, which melts 
at 140°. 
In the highest fractions of savin oil, Wallach2 (1887) found cadinene, 
C15H24. In addition, it is probable that terpenes are present, but 
nothing reliable as to their nature is known. From the results published 
by Dumas3 in 1835 the conclusion that either pinene or camphene is 
present might seem warranted. Dumas isolated a fraction 155-161° 
which had the composition CioHio. Gruenling4 (1878) obtained 
terephthalic and terebinic acids upon oxidation of fraction 161°. This 
also indicates pinene. Inasmuch, however, as savin oil does not 
contain any considerable quantities boiling below 1 75°, and since it is 
frequently adulterated with turpentine oil, these statements should be 
accepted cautiously. 
According to Umney5 oil of savin is said to contain a considerable 
amount of polyterpenes of the b. p. 226°. This, however, does not 
seem very probable since the boiling point of the polyterpenes lies in the 
neighborhood of about 300°. 
The chemists of Schimmel & Co.6 have isolated an aldehyde or ketone 
from fraction 220-250° which, when regenerated from the sodium acid 
sulphite addition product, possesses an odor which faintly reminds of that 
of cumin aldehyde. The unstable hydrazone melts at 40.45°; the more 
stable oxime at 85°. 
Examination. The principal adulterant of oil of savin is turpentine 
oil. The oil distilled in southern France seems to enter the market only 
after the addition of a large amount of turpentine oil. 
The addition- of French turpentine oil can be recognized by the 
lowering of the sp. gr., the reduction or inversion of the angle of rota- 
tion, the lowering of the saponification number and the diminution of the 
solubility in alcohol. Of an oil, adulterated with turpentine oil. more 
than 25 p. c. distills over below 200°. 
!) Berichte, 31, p. 2025. 
2) Liebig's Annalen, 238, p. 82. 
3) Liebig's Annalen, 15, p. 159. 
4) Beitrage zur Kenntniss der Ter- 
pene. Inaug. Diss., Strassburg, p. 27. 
- See also Levy (1885), Berichte, 18, 
p. 3206. 
fl) Loe. cit. 
6) Bericht von S. & Co., Apr. 1900, 
p. 40. 276 
Special Part. 
43. Oil of Red Cedar Wood. 
Oleum Ligni Cedri.-Cedernholzol.-Essence de Bois de Cedre. 
Origin and Preparation. The Virginia or red cedar, Juniperus vir- 
giniana L., a shrub or tree growing as high as 15 m., is distributed 
throughout the United States of North America. Its wood is used in 
the manufacture of cigar boxes, lead pencils and small ornaments. 
It is adapted to this purpose on account of its uniform structure, 
its mild sandal-wood-like odor and because it is not attacked by 
insects. 
For the distillation of the oil, the waste from the lead pencil 
manufactory is used, yielding from 2.5 to 4.5 p. c. The exhausted 
chips are then utilized by the furriers in the preparation of skins. 
A very inferior oil is obtained in this country as a by-product from 
the drying chambers of the lead pencil factories. These chambers are 
so constructed that the escaping vapors from the cedar wood can be 
condensed. In this case, however, the high boiling constituents of the 
wood remain behind and only the more volatile constituents are 
obtained. As a result the oil thus obtained is more mobile, its odor 
is both less fine and less permanent than that of the normal, and 
not serviceable for perfumery. 
Properties. Oil of cedar wood is almost colorless, somewhat viscid, 
and sometimes contains crystals of cedar camphor. It has a peculiar 
mild but persistent odor. The inhalation of the vapors causes the 
urine to acquire a violet odor. Sp. gr. 0.945-0.960; «u = - 30 to -40°; 
index of refraction iid - 1.505 at 17°. In alcohol it is rather difficultly 
soluble, for 1 p. of oil requires 10-20 p. of 90 p. c. alcohol to effect 
solution. 
Composition. The most interesting constituent of cedar wood oil, 
the so-called cedar camphor, was first examined by Walter1 (1841). 
He describes the oil as a soft, slightly reddish mass, . permeated with 
crystals. The camphor, purified by expression and by recrystallization 
from alcohol, melted at 74° and boiled at 282°. By the action of 
phosphoric acid anhydride, Walter obtained from it the hydrocarbon 
cedrene, which boiled at 237°. The formula, CieHssO, assigned to 
cedar camphor by Walter, was declared improbable by Gerhardt,2 who 
suggested C15H26O, the correctness of which was verified by more recent 
investigations." 
Liebig's Annalen, 39, p. 247. 
2) Lehrbuch d. org. Chemie, vol. 4, p. 378. Oils of the Abietinese. 
277 
The liquid constituents were examined by Chapman and Burgess.1 
By fractional distillation of the oil, they prepared cedrene (b. p. 261- 
262°; sp. gr. 0.9359; aD - - 60°) and compared it with the hydro- 
carbon obtained by the dehydration of fraction 301-306° of sandal 
wood oil, which according to the opinion of Chapoteaut2 (1882) was 
identical with the former. Chapman and Burgess, however, came 
to the conclusion that both hydrocarbons were very similar but not 
identical. 
In a recently conducted investigation of cedar wood oil, Rousset3 
(1897) obtained the following results: cedrene (obtained by fractional 
distillation of the volatile oil) is a sesquiterpene, C15H24, and boils 
under 10 mm. pressure at 131-132°; [<z]d = - 17° 54'. Attempts to 
establish the number of double bonds in the molecule, by the addition 
of hydrogen chloride and hydrogen bromide, failed on account of the 
lack of stability of the addition products. Upon oxidation of cedrene 
with chromic acid in glacial acetic acid, a liquid ketone, cedrone, results 
which boils at 147-151° under 7.5 mm. pressure. It has the com- 
position C15H24O and upon reduction is converted into the alcohol iso- 
cedrol, isomeric with the cedar camphor or cedrol (m. p. 84°). When 
heated with acetic acid anhydride in a sealed tube, only a part of the 
cedrol is converted into the acetic ester, another part is dehydrated 
yielding a sesquiterpene. Treated with benzoyl chloride, no ester is 
obtained but only the hydrocarbon C15H24. Inasmuch as neither 
aldehyde nor ketone result upon oxidation, cedrol is to be regarded as 
a tertiary alcohol. 
On account of the readiness with which cedrol loses a molecule of 
water, its quantitative estimation by means of acetylization is impossible. 
A stronger dehydrating agent than acetic acid is formic acid, with the 
aid of which cedrol can be quantitatively converted into the hydro- 
carbon in the cold.4 The latter boils at 262-263° and is strongly 
optically active, «d = - 80°. It has, therefore, almost the same boiling- 
point as the natural cedrene from the oil and is probably identical 
with it. 
Cedrol is not always contained in cedar wood oil. After having 
looked for this substance for years in vain in the laboratory of Schimmel 
& Co., it has recently been observed more frequently. The cause for 
this peculiar phenomenon has not yet been ascertained. 
i) Proc. Chern. Soc. 1896, p. 140. 
2) Bull. Soc. chim., II., 37, p. 303. 
3) Bull. Soc. chim., III.. 17, p. 485. 
4) Observation made in. the Laboratory 
of Schimmel & Co. 278 
Special Part. 
Examination. Adulterations of cedarwood oil have not yet been 
observed. This cheap oil, however, is frequently used for the adulteration 
of other oils, for which purpose it is well adapted on account of its feeble 
odor. It can be recognized by its high sp. gr., its high boiling point, its 
strong laevorotation, and by its slight solubility in alcohol. 
4-3. Oil of Cedar Leaves. 
Oleum Foliorum Cedri. - Cedernblatterol. - Essence des Feuilles de Cedre. 
According to the observations made in the laboratory of Fritzsche 
Bros.,1 the oil of cedar leaves of American commerce is never what it 
ought to be, namely the oil from the leaves of Juniperus virginiana L. 
This is partly due to the fact that the name cedar is applied in this 
country to two totally different trees, viz. Juniperus virginiana and 
Thuja, occidentalis. It is true, a distinction between them as red and 
white cedar is generally made, but the distillers of the oil evidently pay 
little or no attention to it. They not only use the leaves of both species 
indiscriminately, but also those of other conifers. It is not surprising, 
therefore, that the cedar leaf oils of commerce vary considerably in their 
properties. 
The specific gravities of a number of commercial oils varied from 
0.868 to 0.920, the optical rotation from -3° 40' to -24°10'. Some 
of these oils were soluble in 4 or 5 vols. of 70 p. c. alcohol, others not. 
All of these oils had a more or less thuja-like odor. 
Genuine cedar leaf oil seems to have been distilled but once.2 The 
yield was 0.2 p. c. This oil had the following properties:3 sp. gr. 0.887; 
an -+ 59° 25'; insoluble in lOparts of 80 p. c. alcohol. The odor was 
pleasant, somewhat sweetish. Upon fractional distillation most of the 
oil distilled below 180°, of this the greater part between 173°-176°. 
The sp. gr. of this fraction was 0.847; optical rotation +89° (at 20° 
in a 100 mm. tube). Upon bromination it yielded a tetrabromide melt- 
ing at 104-105°. This fraction, therefore, consisted almost entirely of 
d-limonene. Of the lower fractions but small quantities supposed to 
contain pinene were obtained. Although a nitrosochloride was success- 
fully prepared, no crystalline piperidine and benzylamine bases could be 
obtained. Possibly, as seems to be the case with lemon oil, there are 
here terpenes, closely related to those already known, but which have 
not yet been definitely characterized. 
1) Bericht von S. & Co., April 1898, p, 13. 
2) In the factory of Fritzsche Bros. Comp. Bericht von S. & Co., Apr. 1894, p. 56. 
3) Bericht von S. & Co., Apr. 1898, p. 13. Oils of the Pandanaceae. 
279 
The fractions boiling higher than limonene were treated with alcoholic 
potassa because they contained small amounts of saponifiable substances 
(saponification number of the original oil 10.9, of the acetylized 39.1). 
The acids thus obtained yielded a silver salt corresponding with silver 
valerianate upon analysis. The acid-free oil then yielded upon distilla- 
tion under diminished pressure a fraction which under ordinary pressure 
boiled at 210-21.5°. Upon cooling, this congealed to a crystalline mass 
which upon expression and sublimation, revealed itself as borneol melting 
at 203-204°. In the highest fractions cadinene could be readily identi- 
fied by means of its characteristic hydrochloride. 
Genuine cedar leaf oil, therefore, consists principally of limonene 
with cadinene, and some borneol, also small amounts of bornyl esters. 
4-4. Lebanon Cedar Oil. 
Origin and History. Whether cedar wood was distilled in antiquity 
or not does not become apparent, from the statements by Dioscorides 
and other writers. Dioscorides1 mentions as medicinal plants a number 
of pinus species, among them apparently also the cedar of Lebanon. 
The Cedrus libani Barr. (Finns cedrus L., Abies cedrus Poir, Larix 
cedrus Mill.) was considered during antiquity as one of the noblest 
trees. As such, and on account of its durable wood, it is often 
mentioned in the books of the Old Testament. 
Upon distillation, the comminuted wood yields 2.9 p. c. of oil.2 
Properties. The yellowish-brown oil has a very pleasant cedar 
odor and might find practical application if a sufficient quantity of the 
wood were to be had cheap. Sp. gr. 0.985; «d = -10° 48'.2 
4<5. Pandanus Oil. 
In India, Arabia and Persia, the flowers of Pandanus odoratissimus 
L. (Fam. Pandanaceae) are highly esteemed on account of their fragrance 
and their supposed medical virtue.3 The Mohammedan physicians use the 
aqueous decoction of the bruised stems against various diseases. 
Among the Hindoos, the aqueous distillate of the flowers is used as a 
preventive against small-pox. If the distilled water is to be used 
as a perfume, it is sometimes prepared with rose water and the addition 
of sandal wood oil. An odoriferous fatty oil, made by maceration of 
i) De mat. med. Editio Kiihn-Sprengel, Vol. 1, pp. 93, 140, 380. 
2) Bericht von S. & Co., Apr. 1892, p. 41. 
a) Dymock, Warden and Hopper, Pharmacographia indica. Part. VI, p. 535. 280 
Special Part. 
the flowers with sesame oil, is also much used. According to Holmes1 
(1880) the volatile oil has a very pleasant, decidedly honey-like odor. 
Concerning the other properties of the oil nothing is known. 
Andropogon Oils. 
Origin and History. The genus Andropogon of the family Gra- 
mineae is distributed well-nigh over all parts of the globe. A number of 
species, which are indigenous particularly to the East Indies, the islands 
of the Indian Archipelago and northern Africa, are odoriferous on 
account of the volatile oil they contain. The oils distilled within recent 
periods from these grasses, some of which are being cultivated, are: 
palmarosa or rusa oil, also known as Indian geranium oil; citronella 
oil; lemon-grass or Indian verbena oil; and vetiver oil. 
These aromatic grasses have been used on account of their fragrance 
for various purposes during antiquity: for the aromatization of wine; 
also of earthenware wine cups, the so-called Rhodian cups; in the 
preparation of ointments and oils; an incense in religious rites; and 
as couches during festivities. In Sanskrit writings, in the Old Testament, 
and in other documents of antiquity, these grasses are referred to under 
various names. The spices and annointing oils mentioned in the biblical 
translations and other ancient writings as narde, stakte, schonus, etc., 
apparently have been used synonomously for the fragrant andropogon 
grasses and their roots. Of these, it may be supposed that Andropogon 
laniger Desf. was the best known and most used during antiquity, 
inasmuch as it was more widely distributed throughout northern India, 
Thibet, Persia and Arabia as far as Egypt, Nubia and Ethiopia than 
the other species. Originally, however, and again in more modern 
times, the term narde was applied only to the aromatic'root of the 
valerianaceous Nardostachys jatamansi D. C., indigenous to the Hima- 
layas of northern India, perhaps also to Valeriana celticaV. indigenous 
to the European Alps. 
The Greek and Roman writers possibly referred to the same 
aromatic andropogon species when they used the words ^oivos or o-yoh-os, 
also juncus. In the Occident they apparently have never been cultivated 
nor introduced in the dried condition. 
The first mention of andropogon grasses by European travelers is 
to be found in the works of Garcia da Orta, van Rheede tot Draaken- 
stein,- who was governor of the Dutch East-India company on the 
i) Pharm. Journ., Ill, 10, p. 635. Oils of the Gramineae. 
281 
Malabar coast about the middle of the seventeenth century,- and of 
G. E. Rumpf (Rumphius, also Plinius indicus), Dutch governor in 
Amboyna during the second half of the seventeenth century. The first 
sample of a distilled andropogon oil, a lemon-grass oil, is said to have 
been brought to Europe from the Moluccas in 1717. However, the 
distillation of these oils on a large scale and their introduction into the 
commerce of the world and into industry apparently first began in 
1820. In this year the botanist William Roxburgh, who was Director 
of the Botanical Garden at Calcutta for a long time, mentions lemon- 
grass oil as coming from the Moluccas.1 In 1832 the first large assign- 
ment wras received in London. Since then, it, as well as the pahnarosa 
oil and somewhat later citronella oil, have been finding increased 
application in perfumery and especially in the soap industry. As a 
result of the ever increasing demand, the cultivation of these aromatic 
grasses, especially of the citronella grasses in Ceylon, has increased 
considerably so that these oils are now exported in large quantities. 
Besides Asia and Africa, several aromatic andropogon species thrive 
in Central and South America, on the 'West Indies and in Australia. 
With the increasing consumption of these oils in the soap industry, 
these countries as well as Italy may become producers in the course of 
time. Already samples of lemon-grass oil from southern' Brazil have 
been sent to Europe.2 
4-6. Pahnarosa (East Indian Geranium Oil. 
Oleum Palmarosae sen Geranii Imiieum. -Palmarosaol.-Essence de Geranium 
des Indes. 
Origin and Production. Pahnarosa oil, also known as Indian 
grass oil, rusa oil, Indian or Turkish geranium oil. is the oil from 
the leaves of Andropogon schoenanthus LJ (Family Gramineae). This 
plant is widely distributed in India proper and is also frequently found 
in tropical West Africa.3 The designation Turkish geranium oil, which, 
on account of its incorrectness, has now quite generally been dropped, 
has come down to us from a time when the oil entered the European 
market via Constantinople. From Bombay it was shipped to the ports 
of the Red Sea, and thence was conveyed over the land route through 
Arabia to Constantinople. After having been treated in a special man- 
ner, it was here used on a large scale for the adulteration of rose oil. 
i) Flora indica, vol. 1, p. 280. 
2) Bericht von S. & Co., Api*. 1896, p. 68. 
s) Berichte d. pharm. Ges., 7, p. 501. 282 
Special Part. 
The preparation of the oil is described in the Pharmacographia 
indica of Dymock, Warden and Hooper3 in the following manner: 
"The oil distillers in Khandesh2 call the grass Motiya, when the in- 
florescence is young and of a bluish-white color; after it has ripened 
and become red, it is called Sonfiya. The oil obtained from it in the 
first condition has a more delicate odor than that obtained from the 
ripened grass. The Motiya oil is usually mixed with the second kind, 
which by itself would not fetch a good price in the European market. 
The grass grows freely, though not very widely, on open hillsides in 
West Khandesh, especially in Akrani. The makers are Mussulmans, 
who, at the close of the rains, about September, when the grass is 
ripening, buy it from the Bhils, stack it, and set furnaces at the sides 
of brooks where wood and water are plentiful. A large pit, four feet 
long by two wide and two and a half deep, is dug, and a furnace (chula) 
prepared. Over this furnace is placed a copper or iron caldron, large 
enough to hold from 30 to 50 pots of water. After pouring in some 
water, the caldron is filled to the brim with chopped grass, and a little 
more water is added. The mouth of the caldron is carefully closed with 
an iron or copper plate, made fast with wheat dough. From a hole in 
this lid, a bamboo tube, wrapped in a piece of cloth, plastered with the 
flour of Udid [phaseohis nmngo, Linn., black var.), and bound with 
ropes, passes into a second closed caldron, sunk to the neck in running 
water. The steam from the grass is condensed in the second caldron, 
which, when full, begins to shake. The tube is then skillfully removed, 
and the contents of the caldron poured into a third similar vessel and 
stirred. Then the oil begins to appear on the surface, and is slowly 
skimmed off. The distillate is returned with fresh grass to the still." 
The yield amounts to about 0.3-0.4 p. c. 
Composition. The older statements concerning the botanical origin 
and physical properties of palmarosa or Indian grass oil are so contra- 
dictory that it seems doubtful as to whether the authors really had 
palmarosa oil.3 
1) Part. VI, p. 558; comp. Archiv d. Pharm., 234, p. 321. 
2) Bombay presidency. 
3) Stenhouse (Liebig's Annalen, 50, p. 157) in 1844 reports on an investigation of 
East Indian grass oil from Andropogon ivarancusa, the odor of which resembled that 
of rose oil, the taste that of oil of lemon. Upon distillation it yielded a hydrocarbon, 
CioHis. boiling at 170°. It may be assumed with some degree of certainty that this 
grass oil was not palmarosa oil, but citronella oil from Andropogon nardus L., some- 
times also designated Andropogon ivarancusa Roxb.; for citronella oil contains a 
terpene boiling at 160°, viz. camphene, whereas palmarosa oil does not contain such 
loxy boiling constituents. 
Gladstone (Journ. Chern. Soc., 17, p. 1; Jahresb. f. Chern., 1863, p. 548) describes Oils of the Gramineae. 
283 
The first examination with unobjectionable material was carried out 
by Jacobsen1 in 1871. He established the fact that the principal con- 
stituent of the oil is an alcohol, CioHisO, boiling at 232-233°, to 
which he gave the name geraniol. He further discovered the calcium 
chloride compound of geraniol, which is readily decomposed into its 
components by water, and which has become of such great importance 
in the purification of this alcohol. Semmler2 later (1890) verified the 
correctness of the formula CioHisO and.recognized geraniol as belonging 
to the unsaturated chain compounds. Geraniol thus became the first 
representative of a new and important class of constituents of volatile 
oils designated as aliphatic terpene alcohols. 
The amount of geraniol in palmarosa oil varies from 70-93 p. c. 
Of this the greater portion exists in the free state, and .about 5.5-If 
p. c. are present as ester. The acids of fhe ester content of the oil are, 
as was shown by Gildemeister and Stephan3 (1896), approximately like 
parts of acetic and normal capronic acids. Acetic acid was identified 
by means of its silver salt (calculated: 64.69 p. c. Ag.: found: 64.54 
p. c. and 64.37 p. c. Ag.). The capronic acid isolated from palmarosa 
oil boils at 205-206°, has a, sp. gr. of 0.935 at 15°, is optically inactive 
and, therefore, identical with normal capronic acid. (Analysis of silver 
salt: calculated: 48.43 p. c. Ag.; found: 48.24-48.55 p. c. Ag.) 
Of terpenes but a small amount is present in palmarosa oil, viz. about 
1 p. c. of dipentene (tetrabromide, m. p. 125°; nitrolbenzylamine, m. p. 
109-110°). Judging from the odor of the oil. traces of methyl heptenone 
are also present. 
Besides geraniol, Flatau and Labbe4 claim to have found a second 
alcohol, viz. citronellol. Their method of separation of these two alcohols 
is as follows: 
The oil is first saponified and the saponified product distilled under 
diminished pressure. Fraction 120-140°, under 30 mm. pressure, is boiled 
with an equal weight of phthalic acid anhydride and an equal volume of ben- 
zene for an hour in a flask connected with a reflux condenser. Soda, is then 
added, the product of reaction dissolved in water, and the solution extracted with 
ether. Hydrochloric acid is finally added whereby the acid phthalic acid esters 
of geraniol and Citronellol are liberated. 
an Indian geranium oil, sp. gr. 0.948 at 21°. which he considers identical with the 
East Indian grass oil from Andropogon ivarancusa. Which oil it was in reality does 
not become apparent from the statements of the author. 
1) Eiebig's Annalen, 157, p. 232. 
2) Berichte, 23, p. 1098. 
3) Archiv der Phar., 234, p. 321. 
Compt. rend., 126, p. 1725; Bull. Soc. chim., Ill, 19, p. 633. 284 
Special Part. 
These esters are now dissolved in ligroin and the solution cooled down to 
- 5°. At this temperature it is said that the geranyl ester crystallizes out 
quantitatively whereas the citronellyl ester remains in solution. The isolated 
acid esters are saponified with alcoholic potassa and the free alcohols purified 
by rectification. 
In this manner Flatau and Labbe claim to have demonstrated the 
presence of 63 p. c. of geraniol and 17 p. c. of citronellol in palmarosa oil. 
A repetition of this experiment in the Laboratory of Schimmel & Co.1 
has revealed the fact that the liquid ester regarded as the acid citronellyl 
phthalic Jacid ester was also fairly pure geranyl ester as was shown by 
the calcium chloride compound of the alcohol obtained by saponification. 
If citronellol is contained in palmarosa oil, the proof for which may be 
considered to be still wanting, it can be present in traces only. 
A second statement by the same chemists appears to be based on 
a similar weak foundation. Flatau and Labbe2 have claimed that 
palmarosa oil contains a saturated fatty acid CitHasOs, m. p. 28°. 
According to the investigations of Schimmel & Co.,3 pure palmarosa oil 
does not contain such an acid. The observation of the French chemists 
may possibly be referred to the presence of cocoa nut oil or some other 
fatty oil which had been added as adulterant. 
Properties. Palmarosa oil is colorless or light yellow, and has a 
pleasant odor reminding of roses. The optical rotation varies, some 
oils being slightly dextrogyrate, others slightly laevogyrate, still others 
inactive. Angles of rotation varying from 4-1° 41' to -1°55' have 
been observed. 
It is soluble in 3 or more parts of 70 p. c. alcohol. The saponifi- 
cation number lies between 20 and 40. After acetylization the saponifi- 
cation number lies between 230 and 270. Jeancard and Satie4 have 
recently observed that the amount of free acid increases if the oil is 
kept in partly filled containers. 
Examination. Palmarosa oil is frequently adulterated. The follow- 
ing adulterants have been found: gurjun balsam oil, cedar wood oil, turpen- 
tine oil, petroleum (kerosene, paraffin oil) and cocoa nut oil.5 They are 
all indicated by their solubility in 70 p. c. alcohol. Oils adulterated with 
cocoa nut oil solidify when exposed to the temperature of a freezing- 
mixture. Petroleum and turpentine oil lower the sp. gr., whereas fatty 
1) Bericht von S. & Co., Oct. 1898, p. 67. 
2) Compt. rend., 126, p. 1726. 
3) Bericht von S. & Co., Oct. 1898, p. 29. 
Bull. Soc. Chim., Ill, 23, p. 37. Comp, also Bericht von S. & Co., Apr. 1900, p. 26. 
5) Bericht von S. & Co., Apr. 1888, p. 22; Apr. 1889, p. 20; Oct. 1890, p. 23. Oils of the Gramineae. 
285 
oils raise it. In doubtful cases it is well to resort to an acetylization. 
Oils with less than 75 p. c. total geraniol content are to be rejected. 
Production and Commerce. For the last 20 years Bombay has 
been the principal center and port of exportation, whereas forrrierly almost 
the entire output was taken by caravans over land from East India to 
Cairo and Constantinople. From these places it was distributed to the 
brokers. 
The oil is distilled in the Khandesh district northeast of Bombay. 
Pimpalner, Akrani, Nandurbar, Shahada and Taloda are the principal 
places of production. In skins it is conveyed on the bullock's back over 
the Kundaibari pass to Surat, and by Dhulia and Manmad to Bombay. 
Here it is transferred to large tinned copper vessels of 100 to 200 lbs. 
capacity. These are not boxed, but surrounded by a network of ropes 
for the purpose of more easy handling. 
In 1879 the total production was estimated at 3,600 k. Since then 
it has risen enormously and may amount to about 20,000 k. at present. 
47. Ginger-grass Oil. 
Ginger-grass oil is an inferior quality of pahnarosa oil, or a mixture 
of the latter with much (up to 90 p. c.) turpentine oil or mineral oils. 
Occasionally other grasses are also used in the distillation (Andro- 
pogon laniger?}, for some' ginger-grass oils possess a phellandrene-like 
odor which is entirely wanting in the pahnarosa oil. Such an oil had 
the sp. gr. 0.897, «d =-2°8' and was soluble in 70 p. c. alcohol. Its 
petroleum ether solution gave a faint phellandrene reaction with sodium 
nitrite and glacial acetic acid (Gildemeister & Stephan.1 1896). 
48. Lemon-grass Oil. 
Olenin Andropogonis Citrati.-Lemongrasol.-Essence de Lemongrass. Essence 
de Verveine des Indes. 
Origin and Preparation. Lemon-grass, Andropogon citratus I). C., 
which is cultivated all over India, is used, in the form of an infusion, 
both internally and externally against all possible diseases. The oil, 
which is officinal in the Pharmacopoeia of India, is especially esteemed 
by the Hindoos as a remedy against cholera. For the production of the 
oil, the grass is cultivated on a large scale only on the Malabar coast 
in Travancore on the western slope of the mountains, north of Ajengo. 
The distillation is conducted in a primitive manner in plain stills.2 
1) Archiv d. Pharm., 234, p, 326. 
2) Pharmacographia indiea, Part VI. p. 564. Special Part. 
Lemon-grass oil is also distilled near Singapore and in Ceylon. Andro- 
pogon citratus is also cultivated in S. Thome, where oil has been 
distilled experimentally1 (1897). In Brazil (Porto Alegre) an attempt 
to produce the oil has also been made.2 
Composition. Nothing about the chemical composition of lemon- 
grass oil was known until 1888 when citral, an aldehyde CioHigO 
possessing a strong lemon-like odor, was recognized as the principal 
constituent in the laboratory of Schimmel & Co.3 Two years later 
Dodge4 described this substance as citriodoric aldehyde. He, however, 
did not have the aldehyde in a pure state inasmuch as he describes it 
as slightly dextrogyrate, boiling at 225°. Pure citral is inactive and 
boils between 228° and 229°. 
Inasmuch as Barbier and Bouveault5 obtained three semicarbazones6 
by the action of semicarbazide on lemon-grass oil, melting resp. at 
171°, 160° and 135°, they propounded the hypothesis that the citral 
from lemon-grass consists of three isomeric aldehydes. Since semicarba- 
zones of the same substance frequently occur in different modifications, 
which are distinguished by their melting points, solubility, and behavior 
toward acids, it must be considered in this case-as was, in fact, proven 
by Tiemann7-that there are no isomeric aldehydes but isomeric semi- 
carbazones. Flatau8 arrived at a like conclusion. 
W. Stiehl9 also assumes the presence of three isomeric aldehydes 
CioHigO in lemon-grass oil: of citral (geranial), 10 p. c.; citriodoric 
aldehyde, 40-50 p. c.; and of allolemonal 25-30 p. c. Judging from 
the method of preparation this citriodoric aldehyde, according to 
Schimmel & Co.,10 corresponds to the citral of commerce. Inasmuch as 
Semmler11 (1891) has shown that this is identical with the geranial 
from geraniol, citral and the citriodoric aldehyde of Stiehl may be 
regarded as identical. 
1) Ber. d. pharin. Ges., 7, pp. 353, 501; 8, p. 23. 
2) Bericht von S. & Co., Apr. 1896, p. 68. 
3) Bericht von S. & Co., Oct. 1888, p. 17. 
4) Amer. Chern. Journ., 12, p. 553. 
5) Compt. rend., 121 (1895), p. 1159. 
6) The formation of different semie.arbazones from citral was first observed by 
Wallach (1895). Berichte. 28, p. 1957; comp, also Tiemann & Semmler, Berichte, 28, 
p. 2133 and Tiemann, Berichte, 31, p. 821. 
7) Berichte, 32, p. 115. « 
s) Bull. Soc. Chiin., Ill, 21, p. 158. 
9) Journ. f. prakt. Chem., II, 58, p. 51. 
io) Bericht von S. & Co., Oct. 1898, p. 66. 
ii) Berichte, 24, p. 203; 31, p. 3001. Oils of the Gramineae. 
287 
Neither has Stiehl's third aldehyde stood the test of criticism. 
Doebner1 (1898) found that Stiehl's allolemonal consists of about 
equal parts of citral and a non-aldehyde substance. 
From the exhaustive investigations of Tiemann2 (1898) which can 
merely be referred to here, it becomes well nigh certain that the bulk of 
lemon-grass oil consists of citral. Besides citral, it contains traces of 
citronellal and possibly also of an isomer of citral (Doebner,3 1898). 
In the first fraction of lemon-grass oil Barbier and Bouveault4 
(189-1) found methyl heptenone. Inasmuch as they could not obtain 
hydro-m-xylene by means of zinc chloride, nor a solid bromide upon 
the addition of bromine, they declared this methyl heptenone different 
from the one obtained by Wallach5 from cineolic acid. 
However, according to Schimmel & Co.0 the methyl heptenone 
obtained from lemon-grass oil is identical with that obtained- by 
Wallach. The methyl heptenone regenerated from the bisulphite com- 
pound from lemon-grass oil boils at 173-171°, sp. gr. 0.853 at 20°, 
index of refraction, hd -1-43996. Wallach records the following physical 
constants for methyl heptenone from cineolic acid: b. p. 173-174°, 
sp. gr. 0.853 at 20°, ud 1.44003 at 20°. If the ketone from lemon- 
grass oil is heated with zinc chloride, hydro-m-xylene, CsHi2 (b. p. 132- 
135°) results in considerable quantity. Upon nitration this yields 
dinitro-m-xylene (m. p. 92°) and the very characteristic trinitro-m- 
xylene which melts at 181-182° and is difficultly soluble in alcohol. 
The same substances have been obtained from the methyl heptenone 
from cineolic acid so that a doubt as to the identity of the methyl 
heptenone from lemon-grass oil and of the compounds of like composition 
obtained by Wallach and by Tiemann and Semmler" tian no longer 
exist. 
Geraniol,8 the alcohol corresponding to the aldehyde citral, is con- 
tained in the highest fractions of the oil and has been isolated by 
means of its calcium chloride compound. The presence of linalool8 in 
fraction 198-^200° is also rendered probable. To furnish direct proof 
that the alcohol in this fraction is linalool is a difficult matter in the 
presence of citral and geraniol. Labbe9 has found capronic and caprinic 
acids, which he supposes are present in form of the geraniol ester. 
1) Berichte, 31, p. 3195. 
2) Berichte,31, pp. 3278, 3297, 3324: 
32, pp. 107, 115. 
3) Berichte. 31, p. 1891. 
*) Compt. rend., 118, p. 983. 
5) Liebig's Annalen, 258, p.( 319. 
6) Bericht von S. & Co. Oct. 1894, p. 32. 
Comp, also Tiemann & Semmler, Berichte, 
28, p. 2126, footnote. 
t) Berichte, 26, p. 2721. 
8) Bericht von S. & Co., Oct. 1894, p. 32, 
s») Bull. Soe. Chim., Ill, 21, p. 159. 288 
Special Part. 
The presence of a terpene, b. p. 175°, «d = - 5° 48', has been ob- 
served by Barbier and Bouveault in several oils. It yielded a liquid 
bromide from which small amounts of solid substance separated which 
melted at 85°. In other oils this terpene could not be found and 
possibly must be regarded as an adulteration. According to Stiehl1 
lemon-grass oil contains dipentene and possibly limonene. 
Properties. As the name indicates, lemon-grass oil has an intense 
lemon-like odor and taste. It is a reddish-yellow or brownish-red, mobile 
liquid of sp. gr. 0.899-0.903. On account of the dark color, the 
rotatory power mostly cannot be determined. In a few instances in 
which it was possible, an angle of from + 1° 25' to - 3° 5" was observed. 
The oil is readily soluble in alcohol, even in dilute alcohol, for it gives 
a clear solution with 2 and more parts of 70 p. c. alcohol.2 The citral 
content amounts to 70-75 p. c. 
Examination. Adulterations with fatty oil or petroleum are recog- 
nized by the incomplete solubility in 70 p. c. alcohol. The citral assay, 
which should not yield less than 70 p. c. aldehyde, supplies a further 
clue as to the quality of the oil. The method of assay is the same as 
the assay of cinnamic aldehyde in cassia oil: 
10 ce. of oil are shaken with bisulphite solution, the number of cc. of oil 
going into solution being regarded as citral. The necessary apparatus and the 
details of procedure are described under cassia oil. Inasmuch as methyl 
heptenone likewise reacts with bisulphite, one might suspect that the aqueous 
solution not only contains the citral, but also the methyl heptenone so that 
the apparent citral content was in reality that of citral + methyl heptenone. 
However, since the bisulphite compound of methyl heptenone is broken up into 
its components when heated in the waterbath, this ketone is contained in the 
oily layer, citral in the aqueous solution. The assay, therefore, shows the 
correct citral content.3 
Production and Commerce. Lemon-grass oil is principally produced 
in East India, more particularly in the province Travancore south of 
Cochin. The principal commercial center is Trivandrum. The total 
exports from the Malabar coast were: 
1) Loe. cit. 
2) An oil distilled in Porto Alegre, Brazil, showed a peculiar behavior in regard to 
solubility since it did not give a clear solution even with 98 p. c. alcohol. Its sp. gr. 
was 0.895, angle of rotation -0°8'. citral content 77 p. c. The oil, which has not 
yet become an article of commerce, is obtained from cultivated plants. In rainy years, 
four crops of this grass can be harvested; in dry years only three. The yield of oil 
from the fresh grass varies from 0.24 to 0.4 p. c. according to the season (Bericht von 
S. & Co., April 1896, p. 68.) 
3) Comp. Tiemann, Berlchte, 31, p. 3324. Oils of the Gramineae. 
289 
Season 1891.-92 1,4-50 Cases Season 1894-95 2,370 Cases 
" 1892-93 1,863 " " 1895-96 3,070 " 
" 1893-94 2,332 " " 1896-97 3,000 " 
Each case contains 12 wine bottles with a total net content of 
about 7% k. 
Some oil is also distilled in Ceylon, but only here and there and 
then only in small quantities. Statistics of production are wanting-. 
In the Straits Settlements the distillation is no longer conducted on 
as large a scale as formerly. The output is at most 2,000-3,00(1 lbs., 
for the total export of volatile oils from Singapore to England in 1896 
amounted to only 14,165 lbs. Engl., of which at least two-thirds was 
citronella oil. 
4>9. Oil of Vetiver. 
Oleum Andropogonis Muricati.-Vetiverol.-Essence de Vetiver. 
Origin and Preparation. Andropogon muricatus Retz., known in 
India as Vetiver or Cus-Cus, is a perennial grass the leaves of which 
are odorless, but the long fibrous roots of which possess a peculiar 
strong odor reminding somewhat of myrrh. The plant is found all 
along the Coromandel coast, in Mysore, in Bengal and in Burma in 
moist, heavy soil particularly along the shores of rivers. It grows also 
in Reunion, Mauritius and the Philippines, further in Porto Rico and 
Jamaica1 and in Brazil (Peckolt2). 
In India the root is used in the manufacture of artistic mats and 
wicker baskets. Inasmuch as the distillation of the oil is difficult on 
account of its sparing volatility and viscid consistency, it is usually 
conducted with sandal wood or sandal wood oil. This oil is seldom 
exported, whereas the root constitutes a regular article of commerce. 
Tuticorin (south Coromandel coast) is the principal place of export. 
The root is of a reddish color and often contaminated with red sand. 
A half distilled root is frequently found in commerce and can be 
recognized by its light color. The yield obtained in Europe from the 
Indian root varies from 0.4 to 0.9 p. c. In Reunion larger quantities 
of oil are distilled, but the root is not exported. 
Properties. Vetiver oil is the most viscid of all volatile oils. 
Its color is a dark yellow to dark brown. It has an intensive and 
very persistent odor which is not pleasant to some persons. On account 
!) Pharmaeographia indica, part VI, p. 571; Odorographia, vol. 1, p. 309. 
2) Catalogue of the National Exposition in Rio 1866, p. 22 and 48. - Pharm. 
Rundschau. 12, p. 110. v 290 
Special Part. 
of its sparing volatility it is used in finer perfumery primarily for fixing 
the more volatile odors. At 15° vetiver oil is heavier than water. Oils 
distilled in Germany had a sp. gr. of 1.015-1.030 at this temperature. 
On account of the tough consistency of the oil no claim for great 
accuracy can be made for these figures. At higher temperatures the oil 
is lighter than water. One sample had a sp. gr. of 0.99-1 at 44°. 
On account of the dark color, the angle of rotation cannot be ascer- 
tained in most instances. In one instance «d = + 27° 40' was observed, 
in another +25 to 26°.1 Vetiver oil forms a clear solution with 1% to 
2 p. of 80 p. c. alcohol. Upon the further addition of alcohol the 
solution becomes turbid. 
A vetiver oil distilled in Germany boiled between 144-200° under 
23 mm. pressure. Between 144-164°, 8 p. c. were obtained; from 
164-170°, 10 p. c.; 170-180°, 24 p. c.; 180-185°, 30 p. c.; 185-200°, 
20 p. c.; residue, 8 p. c. The saponification number lies between 60 
and 80. 
The oils distilled in Reunion are less viscid and specifically lighter. 
In a number of samples the sp. gr. varied from 0.982-0.998 at 30°. 
Being light in color the angle of rotation could be readily determined: 
«d = + 29° and + 36° being observed in two cases. These oils possessed 
the same solubility as those described above. Their faint odor and the 
difference in physical properties would lead one to suspect adulteration, 
but, owing to the want of knowledge of chemical composition, this 
cannot be decided. It is by no means excluded, however, that these 
differences are attributable to differences in the material distilled, for it 
seems but reasonable to assume that the Reunion oils are distilled from 
fresh roots. 
Peckolt2 found the sp. gr. 0.996 at 15° and 0.972 at 13° respectively 
for two oils distilled from fresh Brazilian root. It should be noted, 
however, that only 10 kilo of root were used and that it would be 
difficult to obtain the less volatile constituents from such small amounts. 
Examination. The examination is restricted to the determination 
of the sp. gr., solubility and, if possible, of the rotatory power. Under 
all circumstances it should yield a clear solution with two parts of 80 
p. c. alcohol. This permits of the recognition of fatty oils which are 
frequently used as adulterants.3 
The admixture of sandal wood oil would not be recognized by the 
solubility test, but by the lower sp. gr., also by the change in the 
i) Bericht von S. & Co., Oct. 1897, p. 62. 3) Bericht von S. & Co., Apr. 1893, p. 59. 
2) Footnote 2, p. 289. Oils of the Gramineae. 
291 
rotatory power. 1 nasmuch as sandal wood oil is laevogyrate, a vetiver 
oil adulterated with it will possess a lower rotatory power than a 
pure oil. 
50. Citronella Oil. 
Oleum Citronellae. - Citronellol. - Essence de Citronelle. 
Origin. Citronella oil is distilled from the grass Andropogon 
nardus L. This plant grows principally in Ceylon, the Malaccan penin- 
sula, also in India proper, and occurs frequently in tropical East Africa.1 
According to Winter,2 one of the largest distillers of citronella oil in 
Ceylon, two varieties of Andropogon nardus are used in the preparation 
of the oil. In Ceylon, which produces most of the oil, Lana Batu is the 
most widely distributed variety. It is said to have first been found in 
Matara, a city in the district of like name in southern Ceylon (comp, 
map). As will be shown later, this variety yields an oil relatively poor 
in geraniol, and contains methyl eugenol, has a high specific gravity 
and constitutes the. bulk of the oil of commerce. The second grass 
variety, which is cultivated in Ceylon only in the neighborhood of 
Baddagama, comes from Malacca and grows on good soil only. 
Apparently this variety is generally cultivated in the Straits Settle- 
ments, also in Java3 and is known as Maha pangiri. The oil from this 
variety has a lower specific gravity. At least the oil from Java has a 
lighter color and may in general be pronounced the finer oil.4 
Preparation.5 The cultivation of citronella grass in Ceylon is con- 
fined to the Southern Province, mainly between the Gin Ganga in the 
northwest and the Walawi Ganga in the east. It is found growing on 
the slopes of the hills. The individual tufts of grass grow at small, 
irregular intervals, attaining a height of 1 meter. According to the 
statement of competent dealers, as much as 40,000 to 50,000 acres 
are at present under cultivation. 
The plants require little or no care, provided the formation of seeds 
is prevented by regular harvests. Otherwise the tufts become too dense, 
become yellow within, and spoil. In general a distinction is made between 
two harvesting periods. The first and principal season is in July and 
August, the second lasts from December until February. The yield 
averages from 16-20 bottles (of 22 oz. each) per acre for the summer. 
1) Ber. d. pharm. Ges., 7, p. 501. 
2) Chemist and Druggist, 52, p. 646. 
s) Bericht v. S. & Co., Oct. 1899, p. 13. 
*) Bericht v. S. & Co., Apr. 1900, p. 11. 
5) According to the Bericht von S. & 
Co., Oct. 1898, p. 11. 292 
and from 5-10 bottles for the winter season. Exact data cannot be 
given, for the yield naturally varies with the weather, and the age and 
location of the plantation. Thus e. g. a plantation yields less and less 
oil with increasing age, though climate and soil conditions are favorable. 
When the plantation has reached the age of 15 years new plants have 
to be raised if the industry is to be profitable. 
The distilleries are mostly located at the base of ridges where cool 
water is to be had in sufficient quantity. 
The construction of the distilleries is not at all primitive, as is shown 
in the following sketch. The success of the natives, who constitute the 
majority of the producers, is really remarkable. The machinery is housed 
under a long roof which serves as a protection against the sun. The- 
Special Part. 
Elevation. 
Fig. 60. 
1. Chimney. 2. Boiler. 3. Stills. 4. Condenser. 5. Condensing basin. 6. Locked cellar 
for storage of the distillate. 7. Roof (fig. 61). 8. Water supply pipe (fig. 61). 
9. Basin for storage of distillate. 
regulation steam boiler, provided with safety valve and water gauge, 
rests on a solid foundation. The cylindrical iron stills, mostly 6-7 ft. 
high and 3-4 ft. in diameter, rest on a base and are'provided with a 
common, interchangeable alembic. This connects with a spiral cooler in 
a large wooden barrel resting on a lowered water basin. The conden- 
sation products of the cooler empty into a basin still lower than the 
one constituting part of the cooler, and in a locked compartment. The 
complete arrangement is shown by the accompanying sketches. (Fig. 
60; and fig. 61, p. 293.) The 
Citronella-Oil Districts 
OIL 
CEYLON. 
Scale 1 : 740 000. 
'EnglisTv Miles. 
11 1 Railway -- Telegraph 
=- Roads Steamer lines. 
Citronella districts. 
Lon^itud-e East of Greenwich. 81° 
Printed by EA.Brockhaus, Leipzig. Oils of the Gramineae. 
293 
The distillation is conducted with direct steam without the addition 
of water to the grass. The water in the barrel condenser, when warm, 
is used for feeding the boiler; whereas the water in the lower basin 
serves to effect complete condensation. The distillate is stored without 
effecting a separation of the oil. After a definite period, the proprietor 
visits his distilleries to remove the oil. The aqueous distillate is poured 
away. 
A charge of dry grass, for only such is used, is distilled in about 
6 hours. The exhausted grass, after being dried in the sun, is used as 
fuel. The Southern Province is extremely poor in wood. For this 
reason the distillation must be discontinued during the rainy season 
when the exhausted grass can no longer be dried. 
Ground-plan. 
Fig. 61. 
A still 7 ft. high and -1% ft. in diameter 'yields about 16-20 bottles 
of 22 oz. each per day, or about 360-440 oz. The work never being- 
controlled no accurate figures as to yield are obtainable. 
Besides the apparatus described above, such with direct fire are said 
to be in use in some districts. However, most of the citronella oil is 
to-day obtained by steam distillation. If the distillation is conducted 
over direct fire, water is added to the grass. It should be stated the 
grass is not dried before distillation. Nevertheless it is not moist when 
put into the apparatus, for as a rule, several hours elapse from the 294 
Special Part. 
time when it is cut to the time when it is distilled. With a temper- 
ature of about 65-70° in the sun, this suffices to remove a large portion 
of the moisture. 
The districts of production are more clearly indicated by the accom- 
panying map. The number of stills in operation in Ceylon is estimated 
at 600, with an annual output of 1,000,000 lbs. of citronella oil. 
Composition. The principal bearer of the citronella odor and, there- 
fore, the characteristic constituent of the oil is citronellal. It is an 
aldehyde of the formula CioHisO. Although present to the extent of 
from 10-20 p. c. only, it first attracted the attention of investigators. 
Owing to the instability of the aldehyde, its name as well as opinions 
regarding its composition have undergone repeated changes. 
Gladstone1 in 1872 found the boiling point of "citronellol," as he 
designated the substance, at 199-205° and assigned to it the formula 
CioHisO. Wright2 in 187-1 states that it boils at 210°. His analyses 
agree with the formula CioHisO. By shaking the oil with alkali bisulphite 
and regeneration with acid, Kremers3 obtained an aldehyde which 
decomposed when distilled. One of the fractions upon analysis yielded 
results corresponding with an heptoic aldehyde C7H14O. Schimmel & Co.4 
designated the compound, regenerated from the bisulphite derivative 
with soda and boiling between 205-210°, "citronellon," without decid- 
ing as to its ketone or aldehyde nature. Dodge5 then pronounced it an 
aldehyde without, however, bringing any proof as to the aldehyde nature 
of the "citronella aldehyde." This proof was supplied by Semmler3 
(1891) who oxidized the "citronellon'' to an acid with the same number 
of carbon atoms, the citronellic acid, CtoHisOs. For this reason the 
substance is now designated as citronellal, a more rational name desig- 
nating its chemical character. For the properties and derivatives of 
i) Journ. Chern. Soc., 25. p. 1; Phar n. Journ., Ill, 2, p. 746; Jahresb. f. Chemie, 
1872, p. 815. 
2) Pharm. Journ., Ill, 5, p. 233. Gladstone as well as Wright erroneously mention 
Andropogon schoenanthus as the plant from which citronella oil is derived. Their 
work, however, shows with sufficient certainty that the oils examined by them were 
true citronella oil from Andropogon nardus L. and not the oil from A. schoenanthus. 
On the other hand, the "Untersuchung des Oels von Andropogon ivarancusa" by Sten- 
house in 1844 (Liebig's Annalen, 50, p. 157), which he calls East Indian grass oil, does 
not pertain to palmarosa oil, but in all probability to citronella oil. Comp. "Ueber 
Palmarosaol" by G. E. Gildemeister and K. Stephan. Archiv der Pharm.. 234, p. 323. 
3) Proc. Am. Pharm. Assoc., 35, p. 571; Chern. Centralbl., 1888, p. 898. 
4) Bericht von S. & Co., Oct. 1888, p. 17. 
5) Dodge assigned' to it the correct formula CioHlsO. Amer. Chern. Journ., 11, 
p. 456; Chern. Centralbl., 1890, I, p. 127. 
6) Berichte, 24, p. 210. Oils of the Gramineae. 
295 
citronellal see p. 154. A detailed chemical examination of a Lana Batu 
oil has recently been made by Schimmel & Co.1 
Citronella oil contains but 10-15 p. c. of terpenes. In fraction 
157-164° camphene has been found (Bertram & Walbaum,2 1894). By 
passing hydrogen chloride into an ethereal solution of this fraction there 
is obtained, in addition to liquid products, a solid chloride, which, 
when heated under pressure with water at 100°, yields quantitatively 
camphene. By treating the same fraction with glacial acetic acid and 
sulphuric acid, isoborneol results. Furthermore there is present a second 
terpene of like boiling point which has not yet been identified.2 Fraction 
172-177° contains dipentene (tetrabromide, m. p. 124°).2 Limonene3 
also is present and has been identified as tetrabromide melting at 105°. 
Of oxygenated constituents of an alcoholic nature the presence of 
borneol and geraniol has been determined with certainty. On account 
of the small amount present (1-2 p. c.), the former can be isolated 
only with difficulty. The melting point was found at 203-204°, its 
specific rotatory power [a]D = - 31.82°, hence laevo borneol.4 Geraniol5 
constitutes about one-half of the citronella oil. The alcohol can be 
obtained pure by treating the corresponding fraction with calcium 
chloride and decomposing the calcium chloride geraniol with water.0 
Basing his conclusion on somewhat unsatisfactory analytical data, 
Dodge7 assumes the presence of an alcohol CiolLoO. b. p. 222°, identical 
with citronellol (citronellyl alcohol) obtained by the reduction of 
citronellal. This claim still requires verification.8 Methyl heptenone,9 
acetic and valerianic acids10 as esters and linalool9 have also been found. 
Another constituent, methyl eugenol, has been found by Schim- 
mel & Co.11 This probably occurs only in the Lana Batu oil, and to 
it the higher specific gravity of this variety possibly is due. From the 
highest boiling portion of the oil a fraction was obtained which pos- 
sessed the odor of methyl eugenol and .which upon oxidation with 
1) Bericht von S. & Co., Oct. 1899, pp. 13-22. 
2) Journ. f. prakt. Chem., II, 49, p. 16. 
3) Bericht von S. & Co., Oct. 1899, p. 15. 
4) Bericht von S. & Co., Apr. 1894, p. 15. 
s) Ibid.; Oct. 1893, p. 11. 
6) The preparation of geraniol from citronella oil is patented. G.I.P. 76,435. Chem. 
Zeitung, 18, p. 1356. 
7) Footnote 5, p. 294. 
s) Flatau and Labbe claim to have found 6 p. c. of citronellol in citronella oil. As 
shown on p. 284 under palmarosa oil, the method which they employed to effect the 
separation of citronellol and geraniol is altogether unreliable. 
9) Bericht von S. & Co., April 1895, 21. 
ie) Kremers, footnote 3, p. 294. 
11) Bericht von S. & Co., Oct. 1898, p. 17. 296 
Special Part. 
potassium permanganate yielded veratric acid melting at 179°. Accord- 
ing to a more recent investigation 8 p. c. of methyl eugenol was found 
present.1 
If this occurrence explains the higher sp. gr. of the Lana Batu 
variety, the cause for the higher optical rotation is to be sought in the 
larger content of strongly laevogyrate camphene. The lowest fractions 
of the oil in which the methyl eugenol had been found, had an angle of 
rotation «d =- 55° O'.2 
According to the recent investigation of Schimmel & Co. already 
referred to, the composition of the Lana Batu oil may be summarized 
as follows: a liquid camphene, dipentene, limonene, citronellal (28.2 p. c.), 
geraniol (32.9p. c. 1, linalool, borneol, terpineol (?),methyl eugenol (8p. c.), 
a light sesquiterpene (sp. gr. 0.8643), a heavy sesquiterpene (sp. gr. 0.912).3 
So far as examined the oil from the Mana pangiri variety has the 
same constituents, but the two oils differ decidedly in percentage com- 
position, the Mana pangiri variety containing up to 91p.c. of acetylizable 
constituents:4 50.45-55.34 p. c. citronellal, 38.15-31.87 p. c. geraniol, 
and only 0.78-0.84 p. c. of methyl eugenol. The low percentage of the 
last mentioned substance accounts for the low specific gravity. 
Properties. Citronella oil is a yellow or yellowish-brown liquid, 
sometimes green due to the presence of copper. Brownish oils frequently 
become green when exposed to the air. This change does not take place 
if the copper is removed by shaking the oil with acid.5 The odor of 
citronella oil is pleasant and lasting. Frequently the odor is described 
as resembling that of balm. This comparison is not pertinent inasmuch 
as the odor of balm resembles citral, and not citronellal, the bearer 
of the citronella odor. 
With regard to physical properties, the oils of the two varieties of 
grass previously described differ decidedly. 
The first kind, which may be designated as Singapore oil and which 
is regarded as the better quality, has a sp. gr. 0.886-0.900, rotatory 
power «d = - 0°34'to-3°, and a geraniol content of from 80-91 p. c. 
The oil distilled from Lana Batu constitutes the bulk of the com- 
mercial oil. Its sp. gr. is 0.900-0.920, «d - - 5° to-21°, the geraniol 
content varies from 50 to at most 70 p. c. 
1) Bericht von S. & Co., Oct. 1899, p. 22. 
2) Bericht von S. & Co., Oct. 1898, p. 17. 
3) No mention is made of the citral found by Flatau, who claims to have obtained 
25-30 p. c. of citronellal and 2-5 p. c. of citral. (Bull. Soc. Chim., Ill, 21, p. 158. 
4) Bericht von S. & Co., Apr 1900, p. 11. 
5) Pharm. Journ., Ill, 21, p. 922. Oils of the Gramineae. 
297 
The solubility of both oils is about the same. A good citronella oil 
yields a clear solution with 1-2 parts of an 80 p. c. alcohol. This 
solution, as a rule, remains clear if the quantity of alcohol is increased 
to 10 vols. Sometimes, however, the increase of the alcohol to 5-10 
vols. causes a slight turbidity, but even upon longer standing in a 
closed vessel no oily drops separate. 
Citronella oil does not yield a. definite saponification number. On 
account of the slow decomposition of the citronellal by means of alkali 
the results will vary with the length of boiling. 
Examination. In testing the oil, the main attention is to be directed 
against the most common adulterarfts, fatty oils and petroleum. The 
latter reduces the sp. gr. of the oil decidedly, whereas the fatty oils 
scarcely produce a change in this respect. Both adulterants can be 
detected by the behavior of the oil toward 80 p. c. alcohol. The follow- 
ing table1 shows the solubility of pure and intentionally adulterated 
citronella oils. 
Spec, 
gravity 
at 15° 
Proportion of oil to 80 p. c. of alcohol 
1 : 1 
3 : 1 
1 : 5 
1 : 10 
0.897 
soluble 
soluble 
soluble 
soluble 
Pure commercial oils 
0.908 
0.900 
4 4 
4 4 
44 
44 
4 4 
4 4 
0.905 
4 4 
4 4 
4 . 
German oil 
- 
0.895 
4 4 
4 4 
44 
44 
The same with 
10 percent 
petroleum 
0.887 
44 
4 4 
slightly 
milky 
20 percent 
0.877 
• < 
4 4 
milkv 
• > 
•30 percent 
0.868 
milkv 
4 4 
4 4 
Commercial oil adulterated 
with petroleum 
L 
0.883 
milky 
4 4 
4 4 
4 4 
Commercial oils adulterated 
with fatty oils 
0.893 
0.895 
0.898 
turbid 
4 ( 
44 
turbid 
4 4 
turbid 
44 
4 4 
turbid 
4 4 
4 4 
Conclusions as to the kind and quantity of the adulterant can be 
drawn from the appearance of the turbidity, also from the behavior of 
the substance separating. Petroleum produces a milky white turbidity, 
whereas fatty oils produce a turbid, but not a milky mixture. After 
prolonged standing, fatty oil collects in the form of drops at the 
bottom of the liquid, while petroleum rises to the surface. 
i) Bericht von S. & Co., Oct. 1889. p. 21. 
2) Distilled from dry citronella grass in Leipzig. 298 
Special Part. 
Citronella oil adulterated with fatty oils is soluble neither in 1-2 
parts nor in 10 parts of 80 p. c. alcohol. An oil adulterated with 
petroleum gives a clear solution with 1-2 parts, but becomes turbid upon 
the addition of more solvent and separates oily drops at the surface 
only after prolonged standing-. 
Strictly speaking, adulteration can be established only after the 
separation of oily drops, for a mere turbidity is frequently produced by 
pure commercial oils. The exact proof for adulteration with fatty oils 
and petroleum is described on p. 201. 
Acetylization will be found useful in passing judgment on an oil: the 
higher the geraniol content, the more valuable the oil. However, the 
geraniol content found upon acetylization does not correspond to the real 
alcohol content. Inasmuch as in the process of acetylization, citronellal is 
quantitatively converted into the acetic ester of isopulegol CioHisO (Tie- 
mann and Schmidt1), the citronellal content is determined with that of the 
geraniol. The term "geraniol content," therefore, is improper, but for the 
sake of simplicity is retained in practice. A method for the determination 
of geraniol in the presence of citronellal has not yet been worked out. 
Production and Commerce. Ceylon and the Straits Settlements on 
the Malaccan peninsula, are the countries which produce citronella oil. 
The accompanying map shows the producing districts in Ceylon. An 
area of 40,000-50,000 acres is said to be under cultivation in the 
island, with 600 stills in operation, which have an annual capacity of 
more than a million pounds of oil. 
At the time of publication of the German edition of this work the 
largest quantity of oil had been exported in 1898: viz. 1,365,917 lbs., 
valued at about $350,000.00. This record was broken in 1899 with a 
total of 1,478,756 lbs. The countries to which this oil was shipped, 
with the amounts, are: 
For 1898. 
For 1899. 
Fngla.mi 
696,869 lbs 
America 
618,999 " 
667'332 " 
Germany 
22,883 " 
1,3352 " 
India 
10,100 " 
7,537 " 
Australia 
10,633 " 
25,865 " 
France 
3,4-40 " 
1'467 
China 
2^249 " 
Singapore. 
504 " 
Africa 
250 " 
Total 
1,365,917 lbs. 
1,478,756 lbs. 
i) Berichte, 29, p. 913. 
2) These two figures are misleading inasmuch as the German importations amount- 
ing to about 250,000 lbs. are included in the English imports. Oils of the Gramineae. 
299 
The enormous increase in production and consumption is strikingly 
shown by the following statistics of exportation: 
Export of citronella oil from Ceylon. 
1887 551,706 lbs. 
1888 659,967 " 
1889 641,465 " 
1890 909,942 " 
1891 603,974 " 
1892 "844,502 " 
1893 668,520 " 
1894 908,471 " 
1895 1,182,255 " 
1896 1,132,141 " 
1897 1,182,867 " 
1898 1,365,917 " 
1899 : 1,478,756 " 
In comparison with these numbers the production of the Straits 
Settlements near Singapore is insignificant. The total area of the 
citronella estates in the peninsula is estimated at 2000 acres at the 
highest. The annual production of oil may not exceed 30,000 lbs. 
Qualitatively, however, this oil is preferable. 
51. Oil of Andropogon Odoratus. 
The grass Andropogon odoratus Lisboa, which serves the natives 
on the west coast of India proper as a domestic remedy, yields upon 
distillation as much volatile oil as Andropogon schoenanthus. 
Properties. According to Dymock,1 the oil is of a dark red color; 
sp. gr. 0.931 at 31°; «d = - 22.75°; [«]d = - 24.43°. 
An oil distilled from fresh grass possessed an odor resembling that 
of pine needle oil; sp. gr. 0.915; «D = - 23° 10'.2 
52. Camel-grass Oil. 
Origin. From Dioscorides up to the middle of the last century the 
herb of Andropogon laniger Desf. has been carried in apothecary shops 
as Herba. schoenanthi or Squinanthi, as Juncus odoratus or as Foenum 
camelorumA The plant is widely distributed throughout northern 
Africa and Arabia, also in northern India as far as Thibet. In the 
desert it constitutes the principal food of the camels. Upon distillation 
of the dried grass, as offered for sale in the Indian bazaars, Dymock4 
obtained 1 p. c. of oil. 
1) Pharmacographia indica, part VI, p. 571. 
2) Bericht von S. & Co., Apr. 1892, p. 44. 
3) Pharmacographia, II. edit., p. 728. 
4) Pharmacographia indica, part VI, p. 564. 300 
Special Part. 
Properties and Composition. Dymock observed the sp. gr. 0.905 
at 29.5° and the angle of rotation «d = - 4°. Schimmel & Co.1 found the 
sp. gr. 0.915 at 15° and the angle of rotation «D = + 34°38'. Theodor 
of camel-grass oil reminds of that of elemi oil. which resemblance 
appears to be due to its phellandrene content.1 The oil distills between 
170-250°. 
53. Oil of Saw Palmetto. 
Origin and History. The oil of saw palmetto is obtained from the 
berries of Serenoa semilata Michx. Hook, f., (Family Palmae), indigenous 
to the southern United States, especially to Florida. The oil is apparently 
first mentioned in 1894 by Sherrard,2 who claims to have obtained it 
from the chloroformic extract of the berries. Coblentz3 in 1895 obtained 
a small quantity of a volatile oil by distillation. The oil had, however, 
been distilled in much larger quantities as early as 1890 by J. U. Lloyd.4 
Preparation. The oil is obtained by distillation from the fresh 
berries. The yield of oil is about 1.2 p. c. The dried berries do not 
yield the oil.5 An oil has also been obtained by expressing the juice 
from the berries and collecting the oily layer (Sherman and Briggs6), 
and by siphoning off the oily layer which separates from the fluid 
extract (Lloyd5). 
Properties. The distilled oil of saw palmetto has a pleasant fruity 
odor, accompanied by a heavier, almost disagreeable odor. When 
distilled it is of a green to brownish color, which, however, disappears 
when distilled in a vacuum. The oil distilled in 1890 by J. U. Lloyd 
had in 1900 a sp. gr. of 0.8682 at 20°. The oil, when distilled under 
diminished pressure, was colorless and had the following properties: 
B. p. 60-170° at 18 mm.; d= 0.8679; ud2o° = 1.41233. 
The oil is optically inactive (Schreiner5). 
Two samples of oil obtained from the fluid extract had the sp. gr. 
0.8651 and 0.8775. They yielded by distillation with steam from 4 to 
5 p. c. of a green to brownish oil of the sp. gr. 0.8650 and 0.8653 
respectively. An oil obtained by Sherman and Briggs6 by expression 
from the berries preserved in alcohol boiled from 70-270° under a 
pressure of 16 mm. 
1) Bericht von S. & Co., Apr. 1892, p. 44. 
2) Proc. Am. Pharm. Assn., 42, p. 312. 
3) Proc. New Jersey Pharm. Assn., 1895, p. 63. 
*) Personal communication from J. U. Lloyd. 
5) Pharm. Rev., May, 1900. 
6) Pharm. Archives, 2, p. 101. Oils of the Pahnae and Araceae. 
301 
Composition. Sherman and Briggs1 have made a thorough chemical 
study of the oil of saw palmetto obtained by expression from the berries 
preserved in alcohol. The oil was subsequently fractionated under 
diminished pressure. They found this oil to consist to the extent of 
about 63 p. c. of free fatty acids, caproic, caprylic, capric, lauric, 
palmetic, and oleic acids, and about 37 p. c. of ethyl esters of these 
acids. No glycerides were found in the oil obtained from the pulp of 
the berries, although their presence was demonstrated in the fixed oil 
from the seeds, in which the same acids, with the addition of stearic acid, 
were found as in the oil from pulp. The fruity odor of the oil is due 
to the ethyl esters. The fact that the oil consists so largely of free 
fatty acids and of ethyl esters of these acids, and inasmuch as the 
berries are kept in alcohol, has led to the suspicion that the esters may 
be formed by the action of the alcohol on the free acids.2 This suspicion 
is supported by the fact that no volatile oil is obtained from the dry 
berries. 
54. Calamus Oil. 
Oleum Calami. - Calamusol. - Essence de Calamus. 
Origin and History. Calamus, Acorus calamus L., Family Araceae, 
though frequently found but in isolated places, occurs in the moderate 
zones of the entire northern hemisphere. It also occurs in Japan (Thun- 
berg) China, Cochin China (Loureiro), and Burma, the East Indies 
(Roxburgh), the Philippines a,nd some of the islands of the Indian 
Archipelago, and has, furthermore, been found on Tana lake in Abyssinia 
(Heuglin). Inasmuch as.the plant does not multiply by means of seeds 
(Kerner) in moderate and colder climates, but by the branching of the 
rhizome, it is assumed that the wide, but ofttimes isolated distribution 
of calamus may have been brought about by transplanting. 
Calamus is reported to have been cultivated in the thirteenth century 
in Poland; in Germany first during the sixteenth century; whence it 
became more widely distributed. Calamus is also indigenous to North 
America, being found from Nova Scotia south to Florida and westward 
to Minnesota, Iowa and Kansas. Of botanists Schbpf first observed it 
in 1783 in Pennsylvania and New Jersey. 
The distilled oil of calamus is first mentioned in the price ordinance 
of Frankfurt of 1582 and in the Dispensatorium Noricum of 1589. The 
yield of oil obtainable upon distillation of the rhizome was determined 
i) Pharm. Archives, 2, p. 101. 
2) Pharm. Rev., May 1900. 302 
Special Part. 
at the beginning of the eighteenth century by Hoffmann and Neumann; 
and about the middle of the eighteenth century by Cartheuser. The 
first investigations of the oil appear to have been made by Wedel in 
1718 and by Trommsdorff in 1808. Later examinations are by 
Martius in 1832, Schnedermann in 1842, Gladstone in 1863, and 
Kurbatow in 1873. 
Preparation. The rhizome, which contains oil in all its parts, is 
collected late in summer and in fall. Upon distillation the fresh root 
which contains 70-75 p. c. of water yields about 0.8 p. c., the dried 
unpeeled rhizome about 1.5-3.5 p. c. of oil. The root bark as well as 
the peeled roots when dried and distilled by themselves produce a smaller 
yield than the unpeeled rhizome. A plausible explanation seems to be 
that when peeled, the rhizome is cut into thin strips whereby oil is lost 
by both volatilization and resinification. A calamus oil of inferior 
quality, with properties deviating from those of the ordinary oil, is 
distilled in Galicia. 
On account of its aroma, calamus oil is used in the manufacture of 
liquors and of snuff, and finds less application than formerly in general 
medicine and the preparation of household remedies. 
Composition. Since 1832 calamus oil has been examined repeatedly.1 
The results obtained so far, however, do not afford a satisfactory in- 
sight into its chemical nature. It is not even known what substance 
constitutes the bulk of the oil, much less to what its peculiar properties 
are due. The investigation of Kurbatow2 (1874) revealed the presence 
of 5 p. c. of a terpene (CioHie) boiling at 158-159°, which yielded a 
solid derivative with dry hydrogen chloride melting at 63°. Though 
this melting point is extremely low-pinene hydrochloride melts at 125° 
-it is probable that this terpene is identical with pinene. 
Fraction 255-258°, sp. gr. 0.932 at 14° and constituting 2.5 p. c. 
of the oil, contains a sesquiterpene that does not combine to form a 
crystalline derivative with hydrogen chloride. At a still higher tem- 
perature a blue oil distills over. The highest boiling fractions contain 
a subtance (phenol?) which, in alcoholic solution, produces a greenish- 
brown color, with ferric chloride (Fliickiger3). 
i) Martins (1832), Liebig's Annalen, 4, pp. 264 & 266. - Schnedermann (1842), 
ibidem, 41, p. 374. - Gladstone (1864'1, Journ. Chem. Soc., 17, p. 1; Jahrb. f. Chem., 
1863, pp. 546, 547. 
2) Liebig's Annalen, 173, p. 4. The older statements are to be accepted with caution, 
for some of them, like those of Gladstone, are evidently based on adulterated oils. 
3) Pharmacognosie, p. 352. Oils of the Araceae. 
303 
Calamus oil also contains saponifiable substances and a small 
amount of an alcoholic substance as becomes apparent from the 
saponification number (40-50) after acetylization. 
Properties. Calamus oil is somewhat viscid in consistency, of a 
yellow to brownish-yellow color, possesses a camphor-like, aromatic 
odor and a corresponding bitter, burning, spicy taste. Its sp. gr. is 
0.960 to 0.970; angle of rotation «d= + 101 ^to +31°;2 saponification 
number 16-20, after acetylization 40-50. Calamus oil is soluble in 
almost all proportions in 90 p. c. alcohol, but rather difficultly soluble 
in more dilute alcohol. Of a 50 p. c. alcohol about 1,000 parts are 
necessary to effect a clear solution. (The solubility of the Japanese oil 
described below is very different.) Upon distillation of a normal calamus 
oil nothing came over below 170°; between 170-275° 32 p. c. were 
obtained; from 275-300°, 60 p. c.; leaving a residue of 8 p. c. 
Examination. Owing to the lack of knowledge of its chemical com- 
position, the examination of calamus oil is confined principally to the 
determination of its optical rotation, sp. gr., and solubility in 90 p. c. 
alcohol. 
Adulterations that cannot be readily recognized by their odor are 
turpentine oil, cedar wood oil and gurjun balsam oil. The first mentioned 
can be recognized by a lower sp. gr. and angle of rotation, and, if 
present in large quantity, by the diminution of solubility in 90 p. c. 
alcohol, and by fractional distillation. 
Cedar wood oil and gurjun balsam oil may influence the sp. gr. but 
little, but reduce the dextro-rotation materially or change it to laevo- 
rotation. Their presence may further be indicated by their sparing 
solubility in 90 p. c. alcohol.3 Inasmuch as the boiling points of both 
oils lie within the limits of those of calamus oil. they cannot be recog- 
nized by fractional distillation. 
55. Oil from Calamus Herb. 
The fresh green parts of calamus, Acorus calamus L., yield upon 
distillation with water vapor an oil which closely resembles that from 
the rhizome. Its sp. gr. is 0.964; aD = 4-20°44'.4 
t) Bericht von S. & Co., Apr. 1895, p. 15. 
2) The angle of rotation of the Galician oil is frequently lower than 4- 10°. 
3) Bericht von S. & Co., Apr. 1895, p. 16. 
4) Bericht von S. & Co., Apr. 1897, p. 8 of table. 304 
Special Part. 
Japanese calamus root, which does not differ morphologically from 
the ordinary rhizome, is probably derived from the same plant as the 
latter. It is possible, however, that it is derived from Acorus spuriosus 
Schott, which is common in Japan and the rhizome of which is said to 
scarcely differ from that of A. calamus L. (Holmes,1 1879). 
The Japanese root is much richer in oil than the common, con- 
taining 5 p. c. The oil has a sp. gr. 0.992 and boils from 210-290°. 
Collected in two fractions, the lower one possessed the characteristic 
calamus odor, whereas the higher boiling one had the odor of sesqui- 
terpenes.2 
Japanese oil is more readily soluble in alcohol than the German. 
1 p. of the Japanese oil dissolves in 500 p. of 50 p. c. alcohol, the 
German being soluble in not less than 1,000 parts.2 
57. Cevadilla Seed Oil. 
Sabadillsamenol. 
This oil is obtained by distillation of the comminuted seeds of 
Sabadilla officinalis (Liliaceae), or of the fat obtained by benzin extraction 
in the preparation of veratrine (Opitz,3 1891). The yield from the fresh 
seed is about 0.32 p. c., from old seed much less. The sp. gr. lies be- 
tween 0.902 and 0.928. Upon distillation the bulk passes over between 
190-250°, the esters present being largely decomposed. After saponi- 
fication the oil distills principally between 220-250°, [«]j = - 9° 10'. 
From the alkaline saponification liquid, oxymyristic acid C14H28O.3. 
(m. p. 51°), and veratric acid, C9H1OO4 (m. p. 179-180°), have been 
obtained. These acids seem to be present in the original oil as methyl 
and ethyl esters. Lower aliphatic aldehydes have also been found. 
58. Aloe Oil. 
The faint but characteristic odor of aloes is due to a minute quantity 
of volatile oil. Upon distillation of 500 lbs. of Barbadoes aloes from 
Aloe vulgaris Lam. var. Aloe barbadensis, T. and H. Smith & Co. of 
London in 1880 obtained 2 fl. dr. of oil. Lt was a light yellow, mobile 
liquid, sp. gr. 0.863, b. p. 266-271°.4 
56. Japanese Calamus Oil. 
1) Pharm. Journ., Ill, 10, p. 102. 3) Archiv d. Pharm., 229, p. 265. 
2) Bericht von S & Co., Apr. 1889, p. 7. 4) Pharm. Journ., Ill, 10, p. 613. Oils of the Liliaceae. 
305 
Upon distillation of the Australian yellow xanthorrhoea resin 
(acaroid resin, yellow grass tree gum) from Xanthorhoea hastile R. Br. 
Schimmel & Co.1 obtained 0.37 p. c. of a yellow oil, storax-like in odor. 
Sp. gr. 0.937, «D - 3° 14', saponification number 74.3, acid number 4.9. 
ester number 69.4. The free acid was isolated by shaking with dilute 
sodium hydroxide solution and recognized by means of its melting point 
133°, as cinnamic acid. From the saponification' lye cinnamic acid was 
separated in considerable quantity. 200 g. of oil yielding about 40 g. 
of cinnamic acid recrystallized from water. 
The saponified oil boiled between 145-240°. From the low boiling- 
portions a fraction 145-150° possessing the properties of styrene was 
isolated. Upon the bromination in a cold ethereal solution styrene 
dibromide, m. p. 74-75°, was obtained in fine needles. 
60. Garlic Oil. 
Upon distillation of the entire plant, Allium sativum L., 0.005-0.009 
p. c. of an oil2 are obtained, which is yellow in color and possesses a 
most disagreeable garlic-like odor. Sp. gr. 1.046-1.057; optically 
inactive. 
The oil was first examined chemically in 1844. Based upon this 
examination, Wertheim3 arrived at the conclusion that garlic oil con- 
sisted principally of allyl sulphide (CsHs^S. This view was held for 
almost 50 years and has passed into all text books without being put 
to a test in a single instance. 
When Semmler4 reexamined the oil in 1892 the fact was revealed 
that garlic oil does not contain a trace of allyl sulphide.5 
Analysis revealed the presence of sulphur besides carbon and hydro- 
gen, also the absence of oxygen and nitrogen. Inasmuch as the oil 
decomposed when distilled under ordinary pressure it was fractionated 
under reduced pressure. Under 16 mm. pressure it distilled between 
65-125°. Semmler isolated the following substances: 
1. A disulphide C0H12S2 (abt. 6 p. c.), b. p. 66-69° under 16 mm. 
It is probably allyl propyl disulphide, C3H5S - SC3H7. 
59. Xanthorrhoea Resin Oil. 
1) Bericht von S. & Co., Oct. 1897, p. 66. 
2) Bericht von S. & Co., Oct. 1889, p. 52; and Oct. 1890, p. 25. 
3) Liebig's Annalen, 51, p. 289. 
4) Archiv d. Pharm., 230, p. 434. 
s) This naturally disposes of the statements concerning other oils supposed to be 
Identical with garlic oil, such as those of Thlaspi arvense L. and AUiaria officinalis L. 306 
Special Part. 
2. A disulphide CoHioS2 (abt. 60 p. c.) constitutes the bulk of the 
oil and is the bearer of the pure garlic odor. Sp. gr. 1.0237 at 
14.8°; b. p. 79-81° under 18 mm. Its constitution probably is 
C3H5S -SC3H5. 
3. A substance CoHioSs (abt. 20 p. c.). Sp. gr. 1.0845 at 15°; 
b. p. 112-122° under 16 mm. Probable constitutional formula: 
C3H5S-S-SC3H5. 
The residue shows a still higher sulphur content and possibly has 
the composition C«HioS4. 
Inasmuch as allyl sulphide boils between 36-38° under 15.5 mm. 
pressure, and the first fraction of garlic oil between 60-65°, the presence 
of allyl sulphide in garlic is excluded. Neither could the sesquiterpene 
of Beckett and Wright,1 b. p. 253.9° be found in the oil examined by 
Semmler. 
61. Onion Oil. 
The pungent, persistent odor of the garden onion, Allium cepa L., is 
due to a volatile oil, of which a yield of 0.046 p. c. is obtained when the 
entire plant is distilled.2 
Onion oil is a dark brown, mobile liquid, sp. gr. 1.0410 at 8.7°3 or 
1.036 at 19°;2 an - - 5°. 
Inasmuch as the oil is decomposed by distillation under ordinary 
pressure, this operation must be conducted in vacuum. Under 10 mm. 
pressure the oil distills almost completely between 64-125°. According 
to Semmler3 the principal constituent is a disulphide C6H12S2 (b. p. 
75-83° under 10 mm., sp. gr. 1.0234 at 12°) which upon reduction with 
zinc dust is converted into a substance CcHi2S (b. p. 130°). Nascent 
hydrogen reduces C6H12S2 to C6H14S2 (b. p. 68-69° under 10 mm). 
The oil also contains a higher sulphide which zinc dust reduces to the 
compound CoHi2S. Finally, another sulphur compound was found in 
onion oil which is possibly identical with one of the high boiling com- 
pounds of asafetida oil. Neither allyl sulphide nor terpenes are contained 
in onion oil any more than in garlic oil. 
62. Oil from Allium Ursinum. 
Barlauchol. 
All parts of Allium ursinum L., leaves, flowers and corms, possess 
an extremely penetrating garlic odor. Upon distillation of the entire 
i) Journ. Chem. Soc., 1, p. 1. 
2) Berieht von S. & Co., Apr. 1889, p. 44. 
3) Archiv d. Pharm., 230, p. 443. Oils of the Iridaceae. 
307 
plant 0.007 p. c. of an oil is obtained which is highly refractive, and 
of a dark brown color and burning taste. Its odor, though garlic-like, 
is quite distinct. Sp. gr. 1.015 at 13°. It boils almost entirely between 
95 and 106°. According to Semmler1 it consists principally of vinyl 
sulphide, CHs:CH - S-CH:CH2 (b. p. 101°, sp. gr. 0.9125). In addition 
this oil contains vinyl polysulphides, also traces of a mercaptan, and 
an aldehyde not yet characterized. 
63. Saffron Oil. 
Origin and History. The spicy stigmas of the saffron, Crocus 
sativus L., N. 0. Iridaceae were used medicinally, and for their color and 
flavor during antiquity, and up to the middle ages were regarded as one 
of the more valued spices. 
The distilled oil of saffron is first mentioned by Ryff2 and Gesner,3 
and is enumerated in the municipal price ordinance of Nurnberg of 1613. 
The older medical treatises do not mention it. The yield was apparently 
first determined in 1670.4 Saffron and its constituents were further 
examined by Lagrange and Vogel in 1810.5 In 1821 Henry examined 
the coloring matter of saffron and arrived at the conclusion that the 
yield of oil was almost doubled if for every ounce of saffron 8 oz. of 
common salt and 4 oz. of potassa are added to the aqueous distillate.6 
Preparation, Properties and Composition. Upon distillation of 
saffron with water in a current of carbon dioxide a small amount of an 
oil is obtained which is but slightly yellow in color, and possesses an 
intense saffron odor. It readily absorbs oxygen, becoming viscid and 
brownish in color. 
An elementary analysis gave figures agreeing with the formula 
CioHis. The bulk of the oil, therefore, seems to consist of a terpene.7 
This also results when the aqueous solution of picroerocin, the bitter 
principle of saffron, is heated. The reaction is supposed to be expressed 
by the following equation: 
CssHgsOit + H2O - 3CgHi206 + 2C10H16 
Picroerocin Water Crocose Terpene. 
1) Liebig's Annalen, 241, p. 90. 
2) Neu gross Destillirbuch, fol. 188. 
3) Ein kbstlicher Schatz, fol. 222. 
4) Hertodt, Crocologia. Dissertatio, Jenae 1671. 
s) Ann. de Chim., 80, p. 185.-Trommsdorff's Journ. d. Pharm., 21, I, p. 206. 
6) Trommsdorff's Neues Journ. d. Pharm., 6, p. 65. - Berl. Jahrb. f. Pharm., 24, 
I, p. 160. 
7) Inasmuch as the terpenes possess but a slight odor it seems probable that the 
characteristic saffron odor is due to the presence of a small amount of an oxygenated 
substance. 308 
Special Part. 
64. Orris Oil. 
Oleum Iridis. - IrisoL - Essence d'lris concrete. Beurre de Violettes. 
Origin and Preparation. The steam distillation of the rhizome of 
white flag for the production of orris oil is a practice of modern times. 
Orris root itself, however, has been used since antiquity on account of 
its mild fragrance and taste. 
Zzvs germanica L., I. pallida L. and I. fiorentina are the three species 
of Iris, N. 0. Iridaceae, which are indigenous to the Mediterranean 
countries. In these as well as in central European countries they are 
cultivated and widely distributed as decorative plants. 
White hag, especially the first two species, is cultivated for com- 
mercial purposes principally in the province of Florence, the districts of 
Greve, Dicomano, Pelago, Regello. Bagno a Ripoli, Pontassieve, Galhizzo, 
S. Casciano in Vai di Pesa and Montespertoli being the principal centres. 
The best root is being cultivated in the communities S. Polo and 
Castellina belonging to the Greve district. 
The cultivation has gradually extended to the neighboring provinces 
of Florence which produce an equally good product: in Arezzo, Castel- 
franco di Sopra and Lore Ciuffenna in the province of Arezzo; in 
Grosseto in the province of like name; in Faenza in the province of 
Ravenna; and in Terui, in the province of Perugia. 
Orris root is cultivated on hills and the slopes of mountains-never 
in the valleys-mostly in large sunny clearings or in rows among the 
grape vines, and but seldom in extended fields. It flourishes in stony, 
dry soil. Usually the rhizome is harvested after three years, but if the 
price is high it is cut when two years old. The freshly cut rhizomes are 
laid in water to facilitate the peeling and then spread on terraces to 
dry, a process that requires about 14 days. 
When dry, the rhizome is turned into the form in which they are 
used for teething or into rosaries. The powder is used in the preparation 
of sachets. The less well-shaped roots, fragments and wastes from the 
peeling and cutting of the dried rhizome are sold for the distillation 
of orris oil. 
The principal places of export of Italian or Florentine orris root are 
Livorno, Verona and Triest. • 
For the purpose of distillation the Florentine root is almost 
exclusively employed. The Veronese root, derived from Iris germanica, 
is inferior and seldom used for distillation. Still poorer is the Morocco 
or Mogadore orris root, also derived from I. germanica. It is darker in Oils of the Iridaceae. 
309 
color and has but a faint odor. In order to render it lighter in color 
it is sometimes bleached with sulphur dioxide, thus rendering it unsuitable 
for distillation. 
Occasionally Indian root1 has appeared in the London market. 
It was, however, of such poor quality - due probably to poor methods 
of collection and treatment-as to be unfit for distillation. 
Upon steam distillation2 orris root yields but 0.1 to 0.2 p. c. of 
volatile oil. The distillation is rendered difficult and tedious by the 
frothing, due principally to the high starch content of the rhizome. To 
facilitate distillation, the addition of sulphuric acid has been suggested, 
whereby the starch is partly converted into sugar. This process, how- 
ever, did not stand the test of experience, inasmuch as it affected the 
odor of the oil. 
On account of the small yield and high price, the use of the oil is 
restricted principally to finer perfumery. In recent years, orris oil is 
used together with ionone in the preparation of artificial violet perfume. 
Properties. Orris oil is a yellowish-white to yellow mass, of rather 
firm consistency at ordinary temperature, and an intensive odor remind- 
ing of the dried orris root (Veilchenwurzeiy, it melts at about 44-50° 
to a yellow or yellowish-brown liquid.3 Orris oil is slightly dextro- 
gyrate. The acid number, about 213-222, corresponds to 85-90 p. c. 
of myristic acid. The saponification number is 2-6. 
Composition. The bulk of orris oil, about 85 p. c., is composed of 
the completely odorless myristic acid.4 The bearer of the violet odor is 
irone, a ketone of the formula C13H200 (Tiemann and Kruger,5 1893). 
Besides these two constituents, the oil contains small amounts of the 
methyl ester of myristic acid, oleic acid and its esters, also oleic 
aldehyde. 
For the preparation of the irone, the rhizome is exhausted with 
ether, and the ethereal residue is distilled with water vapor. In the 
') Bericht von Schimmel & Co., Oct. 1896, p. 45. 
2) Prof. H. Hirzel in his "Toiletten-Chemie," 4. ed. (1892), p. 215, states that orris 
oil cannot be the normal distillate of orris root, because myristic acid is not volatile 
with water vapor. The fact, however, is that the oil is obtained by steam distillation 
and since myristic acid is its principal constituent, there can be no doubt that the 
acid is volatile with water vapor under the conditions under which the distillation is 
conducted. 
3) In order to avoid detrimental over heating, the oil is melted by placing the bottle 
in warm water having a temperature of about 55-60°. 
*) Fliickiger (1876), Archiv d Pharm., 208, p. 481. Of older references comp. 
Vogel, Journ. de Pharm., II, 1, p. 483; Trommsdorff's Journ. d. Pharm., 24, II, p. 64; 
and Dumas, Journ. de Pharm., II, 21, p. 191; and Liebig's Annalen, 15, p. 158. 
5) Berichte, 26, p. 2675. 310 
Special Part. 
residue there remains a part of the myristic acid, iregenin, iridic acid, 
and esters of myristic and oleic acid, whereas part of the myristic acid 
and its methyl ester, oleic acid and one of its esters, and oleic aldehyde 
distill over with the irone. Upon repeated steam distillation of the first 
distillate, irone passes over first and can thus be separated somewhat 
from the other constituents. 
The irone is farther purified by converting it into its phenyl 
hydrazone and regenerating it by means of sulphuric acid. Perfectly 
pure irone is obtained by converting it into the crystallizable ironoxime 
and regenerating it by means of dilute sulphuric acid. 
In the preparation of irone from orris oil, the myristic acid is first 
removed by shaking with dilute potassa solution. This solution is 
shaken with ether, the ether extract distilled fractionally with water 
vapor and the irone purified as stated above. 
Irone has a sp. gr. of 0.939 at 20°, boils at 144° under 16 mm. 
pressure, and in a 100 mm. tube turns the plane of polarized light 
about 40° to the right. In water it is almost insoluble, but readily 
soluble in alcohol, ether, chloroform, benzene and ligroin. 
The odor of pure irone is pungent and in a concentrated state 
seems to differ entirely from that of the violet. The latter, however, 
becomes apparent when irone is dissolved in a large amount of alcohol 
and the solution evaporated. 
Adulteration. A liquid or semi-liquid oil is sometimes found in 
commerce under the name of orris oil, which has been obtained from 
orris root by distillation with cedar oil or other oils, or which is merely 
a mixture of such oils with some orris oil. Several years ago a mixture 
of 97.5 p. of acetanilid and 2.5 p. of orris oil was brought into commerce 
as "irisol" and sold at an enormous price. 
65. Curcuma Oil. 
Origin and Preparation. The curcuma plant, Curcuma longa L., 
N. 0. Zingiberaceae, is indigenous to southern Asia, and is cultivated 
on account of the yellow dyestuff which it contains, in India and in 
southern and eastern China. Upon distillation with water vapor, 
curcuma root yields 5-5.5 p. c. of volatile oil. 
Properties. Curcuma oil is an orange-yellow, slightly fluorescent 
liquid, which has a slight odor of curcuma and a sp. gr. of 0.942. With 
% to 1 vol. of 90 p. c. alcohol it produces a clear solution which is 
rendered milky upon the addition of more alcohol. Oils of the Zingiberaceae. 
311 
Composition. According to Bolley, Suida and Daube1 (1868) cur- 
cuma oil begins to boil at about 220° and is in complete ebullition at 
250°. Above this temperature decomposition takes place. Upon the 
addition of ammonium sulphide to fraction 230-250° they obtained 
crystals which were regarded as carvone hydrosulphide. Fliickiger2 
(1876), however, could not obtain a hydrogen sulphide addition product 
with any of the. fractions, thus indicating the absence of carvone. 
Jackson and Menke3 (1882) analysed the fraction distilling between 
193-198° under 60 mm. pressure, assigned to it the formula C19H28O, 
and called it turmerol. It is an alcohol which yields a chloride, turmeryl 
chloride, with strong hydrochloric acid. Its sp. gr. is 0.9016 at 17°. 
[a]D = +33.52°. Under ordinary pressure turmerol boils at 285-290° 
with decomposition. With an excess of hot permanganate solution it 
is oxidized to terephthalic acid. Chromic acid yields different oxidation 
products. Lvanow-Gajevsky 4 obtained valerianic and capronic acids 
from fraction 280-290°. The lowest boiling portion of curcuma oil 
consists of phellandrene.5 
66. Oil of Zedoary. 
Olenin Zedoriae.-Zitwerwurzelbl.-Essence de Zedoaire. 
Origin and History. The rhizome of the zingiberaceous plant 
Curcuma zedoaria Roscoe (C- zerumbet Roxburgh) is at present brought 
into commerce from Ceylon via Bombay. The plant has been cultivated 
in the island for a long period because some of the inhabitants are fond 
of it as a vegetable (Fliickiger;6 Dymock7). 
The distilled oil of zedoary is first mentioned in the price ordinance 
of Berlin of 1574,8 in those of Worms and Frankfurt-on-the Main of 
1582, also in the Dispensatorium Noricum of 1589. Examinations as 
to yield and properties of the oil were later made by Neumann9 (1785), 
Dehne10 (1779) and Geoffroy11 (1757.) 
i) Journ. f. pr. Chern., 103, p. 474. Jahresb. f. Pharm., 1868, p. 47. 
2) Berichte, 9, p. 470. 
3) Amer. C]jem. Journ., 4, p. 368. 
*) Berichte, 5, p. 1102. 
5) Bericht von S. & Co., Oct. 1890, p. 17. 
6) Pharmacognosie, p. 369. 
t) Materia medica of Western India, p. 772. 
8) Estimatio materiae medicae ... in gratiam et usum publicum civitatum Marchiae 
Brandenburgensis. Autore Matthaeo Flacco. Berolini 1574. 
9) Goettling's Almanach fur Scheidekiinstler, 1785, p. 118. 
io) Crell's Chemisches Journal, 3, p. 20. 
ii) Tractatus de materia medica, vol. 3, p. 265. 312 
Special Part. 
Properties and Composition. Oil of zedoary is a somewhat viscid, 
oily liquid. In thin layer its color is somewhat greenish, in thicker layer 
strikingly greenish black; in transmitted light its color is reddish. The 
odor reminds of that of ginger, but differs from the latter by a 
camphor-like odor due to the presence of cineol. Its sp. gr. is 0.990-1.01. 
The rotatory power has not yet been observed on account of the dark 
color of the oil. It it soluble in -2 vol. of 80 p. c. alcohol. 
Upon distillation only a small amount of oil comes over below 
240°. In this fraction cineol1 was shown to be present by means of the 
hydrobromide. The bulk of the oil distills between 240-300°, a small 
amount above 300°. 
' 67. Kaempheria Oil.. 
Kaempferia rotunda L., N. 0. Zingiberaceae, formerly supplied the 
Rhizoma zedoariae rotundae of the apothecary shops. Upon distillation 
the root yields 0.2 p. c. of a yellow colored oil.2 Its pleasant odor, at 
first camphor-like, is afterward decidedly estragon-like. The sp. gr. of 
the fresh oil varies from 0.886-0.8942 at 26°. Another sample, 
evidently older, had a sp. gr. of 0.9453 at 15°, «d= + 1304'at 14°. 
Upon distillation half of the oil distilled below 200°, and the greater 
portion of the other half about 240°.2 The oil contains cineol.3 
68. Hedychium Oil. 
The oil of the flowers of Hedychium coronariuni L., {Zingiberaceae}, 
which is cultivated in Java, has a pleasant, delicate, but faint odor. 
Sp. gr, 0.869, «d =- 0°28'.4 
From the flowers of the Brazilian plant, Peckolt5 obtained 0.026- 
0.029 p. c. of oil, sp. gr. 0.869. 
69. Oil of Galangal. 
Olenin Galangae. - Galgantol. - Essence de Galanga. 
Origin and History. Galangal, Alpinia officinarum Hance, (Zingi- 
beraceae}, is originally indigenous to the island Hai-nan. It is still 
cultivated in the same and in the opposite peninsula Lei-tscnou and the 
neighboring coasts, also in Siam. The spicy rhizome seems to have 
1) Bericht von S. & Co.. Oct. 1890, p. 53. 
2) S'Eands Plantentuln Buitenzorg, 1893, p. 55. 
3) Bericht von S. & Co., Apr. 1894, p. 57. 
O Bericht von S. & Co., Apr. 1894, p. 58. 
a) Pharm. Rundschau, 11, p. 287. Oils of the Zingiberaceae. 
313 
been used by the Chinese during' antiquity. It is mentioned in the 
Ayur-vedas Susrutas, by Plutarch and by the medical writers of the 
middle ages. In German literature it occurs since the eighth century. 
The rhizome is mentioned in the Dispensatorium Noricum, but the 
oil seems to have been distilled later. The first mention of the oil 
occurs in the price ordinance of Frankfurt-o.-M. of 1587. 
Production. Upon distillation of the comminuted root with water 
vapor 0.5-1 p. c. of oil is obtained. 
Properties. Galangal oil constitutes a greenish-yellow, slightly 
viscid liquid of a camphor-like odor, the taste of which is at first 
slightly bitter then somewhat cooling. The sp. gr. lies between 0.915 
and 0.925, the angle of rotation between -l°30' and -3° 30'. It is 
miscible with and more parts of 90 p. c. alcohol; of 80 p. c. alcohol 
10-20 parts are necessary to effect a clear solution. It boils between 
170 and 275°. 
Composition. The only known constituent of galangal oil is cineol1 
identified by means of the hydrogen bromide addition product. It is 
this constituent to which the camphor-like odor of the oil is due. 
70. Oil from Alpinia Malaccensis. 
The fresh rhizome of Alpinia malaccensis Roscoe (Ladja goah), which 
grows wild in Java, yields upon distillation X P- c. of an oil with a 
pleasant odor.2 Its sp. gr. varies between 1.039 and 1.017 at 27°. In 
a 200 mm. tube it deviates the plane of polarized light from 0.25 to 
1.5° to the right. Upon cooling, the oil becomes almost completely 
solid, handsome long needles of methyl cinnamate being formed. The 
leaves of the same plant also contain methyl cinnamate. 
71. Oil from Alpinia Nutans. 
Alpinia nutans, Roscoe, also contains in its rhizome a volatile oil,3 
the sp. gr. of which is 0.95 at 29°. A large portion of the oil distills 
below 230°. Fraction 255-265° yielded upon saponification with methyl 
alcoholic potassa an acid melting at 134° - probably cinnamic acid. 
72. Ginger Oil. 
Oleum Zingiberis.-Ing werbl.-Essence de Qingembre. 
Origin and History. The rhizome of Zingiber officinale Roscoe 
(Amomum zingiber L.), which is originally indigenous to southern Asia 
i) Bericht von S. & Co., Apr. 1890, p. 21. 
2) Kon. Akad. v. Wetensch. te Amsterdam 1898, p. 550. 
3) S'Lands Plant, te Buitenzorg, 1897, p. 36. 314 
Special Part. 
and which is cultivated there to-day as well as in the south Asiatic 
archipelago and in other countries, seems to have been used as a spice 
by the ancient Chinese and Indians. The Greeks and Romans with whom 
it was a favorite spice obtained it via the Red Sea route and, therefore, 
considered it an Arabian product. In the third century, however, it 
was already enumerated among the Indian products brought to Europe 
via the Red Sea and Alexandria. Ginger was introduced into the West 
Indies by the Spanish about the middle of the sixteenth century. As 
early as 1547 ginger was shipped from Jamaica to Spain, from San 
Domingo in 1585 and from Barbadoes in 1654. 
The first mention of distilled ginger oil is found in the spice ordinance 
of Copenhagen of 1672. The yield was determined in the course of the 
eighteenth century by Neumann,1 Gesner,2 Geoffroy,3 and Cartheuser.4 
The rhizome yields about 2-3 p. c. of volatile oil. At present 
African ginger is mostly used for the distillation of the oil. Of interest 
is the observation that ammonia is formed in the process. Its 
formation has not yet been satisfactorily explained. 
Properties. Ginger oil possesses the aromatic, not very strong, 
but persistent odor of the rhizome, but not the pungent taste of the 
latter. It is viscid and of a greenish-yellow color. 
The sp. gr., which lies between 0.875 and 0.885, seems very low,if 
the amount of high boiling constituents is taken into consideration. 
The angle of rotation varies between-25 and-45°. Ginger oil is one 
of the least soluble in alcohol, 50-100 parts of a 96 p. c. alcohol being- 
requisite to effect a clear solution. When distilled over a direct flame, 
the oil passes over between 155 and 300°, but a considerable residue 
of decomposition products remains in the flask. 
The distillate from Japanese ginger differed from the oil from 
African or Jamaica ginger. Inasmuch, however, as but a few kilos of 
the rhizome were used in the experiment, the oil may not have been 
normal. Its sp. gr. was as high as 0.894; its angle of rotation was 
dextrogyrate, viz. «d = 9° 40'; and it was soluble in 2 p. of 90 p. c. 
alcohol. No positive test for phellandrene was obtained. 
Moreover, an oil distilled in Japan,5 did not differ in its properties 
from the ordinary oils. Its sp. gr. was 0.883, «d - -26° 52'. With 
sodium nitrite and glacial acetic acid it yielded a positive test for 
phellandrene. 
1) Chymia medica, vol. 2, p. 638. 
2) Dissertatio de Zingibere. Altdorf, 
1723, p, 18. 
3) Tractatus de mat. med., vol. 2, p. 265. 
4) Elementa Chymiae, vol. 2, p. 62. 
5) Bericht von S. & Co., Oct. 1893, p. 46. Oils of the Zingiberaceae. 
315 
Composition. Of ginger oil only a few of the minor constituents are 
known;1 of the substances to which the characteristic odor is due 
nothing is known. In the lowest boiling portions terpenes are found. 
The angle of rotation of fraction 155-165° is 4-63° 13' (opposite in 
direction to that of the oil). This fraction contains dextro-camphene 
(Bertram & Walbaum.2) When treated with glacial acetic acid and 
sulphuric acid it yields an acetate which upon saponification yields 
isoborneol, m. p. 212°, the bromal derivative of which melts at 71°. 
Fraction 170° contains phellandrene2 and yields a nitrite melting 
at 102°. 
The bulk of ginger oil passes over between 256-266° and consists 
principally of a sesquiterpene (Thresh,3 1881) C15H24, not yet defined, 
which does not yield a solid compound with hydrogen chloride. 
73. Ceylon Cardamom Oil. 
Oleum Cardamomi.-Ceylon Cardamomenol.-Essence de Cardamome. 
History. Cardamoms, the capsular fruits of different species of 
Elettaria and Amomum, family Zingiberaceae, appear to have been 
widely used during antiquity, being known by the names Ela, (Ayur- 
vedas), Amomis, Amomum and Card-amomum, though some doubt 
exists as to the synonomy of these terms. 
Distilled oil of cardamom was known about 154-0; having been 
distilled by Valerius Cordus.4 The yield was determined by Neu- 
mann,5 Martins,6 Cartheuser and Spielmann.7 
Origin and Preparation. The cardamom oil of commerce is not 
distilled from the officinal Malabar cardamom from Elettaria carda- 
momum White et Matton. but from the long Ceylon cardamom. This 
variety was designated E. c. var. /? by Fliickiger.8 Formerly it was 
considered a separate species, the E. major Smith. 
The Ceylon cardamoms grow wild in the forests of the inner and 
southern provinces of the island. The ground fruits are distilled yield- 
ing A-6 p. c. of oil. In an experiment in which the seeds and the 
empty capsules were distilled separately, the former yielded 4 p. c., the 
latter 0.2 p. c. of oil. 
i) The first investigation of ginger oil 
by Papousek in 1852 threw no light on its 
composition. Sitzungsberichte der Akade- 
mie der Wissenschaften zu Wien, 9, p. 315. 
-Liebig's Annalen, 84. p. 352. 
2) Journ. f. prakt. Chemie, II, 49, p. 18. 
3) Pharm. Journ., Ill, 12, p. 243. 
4) De artiflciosls extractionibus, fol. 
226, 
5) Chemia mediea, vol. 1, p. 328. 
6) Schweigger's Journ. f. Chem. und 
Phys., 3, p. 311. 
7) Cardamomi historia et vindiciae. 
s) Pharmacographia, 2nd ed., p. 644. 316 
Special Part. 
Properties. The Ceylon cardamom oil is light yellow, somewhat 
viscid. It possesses the strong aromatic odor of the cardamoms, and 
a pleasant, cooling taste. Sp. gr. 0.895-0.905; «d = + 12 to + 15°. 
The oil is clearly soluble in 1-2 and more parts of 80 p. c. alcohol. 
With 70 p. c. alcohol it yields a turbid solution. The saponification 
number lies between 30 and 70. 
The above mentioned oil from the seed has the following properties: 
sp. gr. 0.908, «D = +13° 14'; that of the empty capsules: sp. gr. 
0.908, «d = +9° 48'. 
Composition. After repeated fractionation of Ceylon oil, Weber1 in 
1887 obtained the following four principal fractions: 1.) 170-178°; 
2.) 178-182°; 3.) 182-190°; 4.) 205-220°. By passing hydrogen 
chloride into fraction 1, a dihydrochloride, CioHie2HCl, melting at 52° 
was obtained. With bromine no crystalline bromide could be obtained. 
On account of the somewhat high melting point (2° higher than that 
of dipentene dihydrochloride), Weber leaves it undecided whether the 
dihydrochloride obtained is due to the presence of dipentene or not. 
Fraction 2) contains terpinene, a terpene which is characterized by 
the nitrosite melting at 155° and which had not' been found previously 
in any volatile oil. 
Fraction 4) consists of terpineol. Weber obtained with hydrogen 
chloride a chloride melting at 52°, and with hydrogen iodide an iodide 
melting at 76°. 
Although neither dipentene tetrabromide, obtained by Wallach2 from 
terpineol, nor phenyl terpinyl urethane3 could be obtained, the negative 
results of Weber must be attributed to impurities which act as disturbing 
factors in the test. 
In the course of the distillation water was split off, formic and acetic 
acid were also formed. The latter indicate the presence of esters, the 
amount of which according to the saponification number (comp, proper- 
ties) varies from about 10-20 p.c. From the residue of the fractionation 
a solid substance separated which, upon recrystallization from alcohol, 
constitutes light laminae of a silvery lustre melting at 60-61°. 
74. Malabar Cardamom Oil. 
Origin. On account of their high price, the officinal Malabar (and 
Madras) cardamoms from Elettaria cardamomum White et Matton are 
1) Liebig's Annalen, 238, p. 98. 
2) Liebig's Annalen, 230, p. 266. 
3) Ibid., p. 267. Oils of the Zingiberaceae. 
317 
seldom used in the manufacture of the volatile oil. The yield varies 
between 2 and 8 p. c. 
Properties. The odor of Malabar cardamom oil differs but slightly 
from that of the Ceylon oil. Sp. gr. 0.933 (HaenseP) to 0.943 
(Schimmel & Co.2); «d = + 26° 1 to + 34° 52'.2 It is soluble in 4 and 
more parts of 70 p. c. alcohol. Saponification number 132. 
Composition. In an old specimen of Malabar cardamom oil, Dumas 
and Peligot3 (1834) found prismatic crystals of terpin hydrate, 
CioHig - 3H2O. Their presence was undoubtedly due to their formation 
from terpineol shown to be present later. According to Schimmel & Co.,4 
the high saponification number is due to terpinyl acetate. The silver 
salt from the saponification liquid corresponds with silver acetate. 
(Found 64.8 and 65 p. c., Ag., calculated 64.69 p. c.) From the 
saponified oil crystallized d-terpineol was obtained by fractional distil- 
lation under diminished pressure (150-164° under 14 mm.). M. p. 
35-37°; aD = 4-81°37' (in the molten condition). It was chemically 
identified by means of dipentene dihydriodide (m. p. 78-79°); terpinyl 
phenyl urethane (m. p. 112-113°); (also optically active [a]D - 33°58' 
at 20° in 10 p. c. alcoholic solution); and terpineol nitrosochloride. 
The piperidide from the last melted at 151-152°, eight degrees lower 
than that of the inactive isomer. The oil also contains cineol. 
In a recent investigation Parry5 has also shown the presence of 
limonene. 
75. Siam Cardamom Oil. 
Origin. Under the name of "Camphor seeds," so called on account 
of their camphor-like odor, the seeds of the Siam cardamom from 
Amomum cardamomum L. occasionally find their way into the London 
market. Upon distillation, Schimmel & Co.4 obtained 2.4 p. c. of oil. 
Properties. At ordinary temperature, this oil constitutes a semi- 
solid mass having the odor of camphor and borneol. In order to redis- 
solve the crystals, the oil had to be heated to 42°, at which temperature 
the oil had a sp. gr. of 0.905 and an angle of rotation of +38° 4'. The 
saponification number was 18.8, after acetylization 77.2, corresponding 
to 22.5 p. c. of borneol in the original oil. The oil is soluble in 1.2 vol. 
of 80 p. c. alcohol. 
i) Sudd. Apoth.-Zeitung, 1896, p. 683. 
2) Bericht von S. & Co., Oct. 1897, p. 8. 
3) Ann. d. Chim. et Phys., II, 57, p. 335. 
4) Bericht von S. & Co., Oct. 1897, p. 9. 
5) Pharm. Journ., 63, p. 105. 318 
Special Part. 
Composition. In order to separate the stearoptene, the oil was 
cooled in ice and placed in a centrifuge. From 800 g. of oil, 100 g. of 
crystals were obtained. From the petroleum ether solution, about 40 g. 
of almost pure borneol separated upon cooling. When purified by means 
of the benzoyl ester, it melted at 204°, and in a 10 p. c. alcoholic 
solution had a specific rotatory power [a]D = + 42° 55' at 20°. 
The petroleum ether mother liquid, upon evaporation, left a granular 
mass which, after recrystallization from 80 p. c. alcohol, melted a-t 
176-178° and possessed all the properties of camphor. The oxime 
melted at 118°. The rotatory power determined in alcoholic solution 
at 20° was [«]d^ + 45°17'. 
Thus the crystals which separate from Siam cardamom oil1 consist 
of d-borneol and d-camphor, present in about equal parts. 
76. Oil from Grains of Paradise. 
Origin and History. The seeds of the zingiberaceous Amomum 
melegueta Roscoe, which is indigenous to the coast of tropical West 
Africa, were formerly much used as spice and were known in the apothecary 
shops as Grana paradisi, Semina cardamomi majoris or Piper melegueta. 
The plant grows from the Congo to the Sierra Leone and a part of 
this coast district is known by the name of the drug as the Pepper- or 
Melegueta coast. Upon distillation on a small scale of the grains of 
paradise, 0.3 p. c.2 were obtained, upon a larger scale 0.75 p. c. of oil.3 
This oil was distilled by Porta4 at the beginning of the seventeenth 
century and used medicinally. 
Properties. The oil from the grains of paradise is a yellowish 
liquid, of a spicy but scarcely characteristic odor. Sp. gr. 0.894 ;5 
an - - 3° 58'. It begins to boil at 236°, the principal portion passing- 
over between 257-258°. The results of an elementary analysis of this 
fraction corresponded with the formula C20H320. 
77. Bengal Cardamom Oil. 
Origin. Bengal cardamoms, from Amomum aromaticum Roxb.,8 
upon distillation yield 1.12 p. c. of volatile oil. 
1) The camphor mentioned by Fliickiger in Pharmacographia, 2nd ed., p. 647, 
should probably be referred to the oil from Siam cardamoms and not to that from 
Ceylon cardamoms. 
2) Pharmacographia, 2nd ed.. p. 653. 
3) Bericht von S. & Co., Oct. 1897, p. 10. 
4) De Destillatione, lib. IV, C. 4. 
5) Fliickiger (1. c.) gives the sp. gr. as 0.825, which may be due to a printer's error. 
6) According to E. M. Holmes, Bengal cardamoms are derived from Amomum 
aromaticum Roxb. and not as Fliickiger states in Pharmacographia from Amomum 
subulatum Roxb. Oils of the Zingiberaceae. 
319 
Properties. This oil1 has a light yellow color, and possesses a 
decided odor of cineol; sp. gr. 0.920 at 15°; «d = -12° 41'. It forms 
a clear solution with one and more parts of 80 p. c. alcohol. Upon 
distillation the bulk of the oil passes over below 220°, leaving, how- 
ever, considerable residue in the flask. 
Composition. The only known constituent of the oil is cineol. It 
was identified by means of the hydrobromide, regeneration of the pure 
cineol boiling at 175-176°, sp. gr. 0.924, and conversion into cineolic 
acid (m. p. 197°). 
Inasmuch as the characteristic cardamom odor is wanting, the 
Bengal oil cannot take the place of the Ceylon oil and is, therefore, 
without practical value. 
78. Cameroon Cardamom Oil. 
Origin. The plant from which the so-called Cameroon cardamom 
is obtained, is not yet known. Upon distillation of the fruit Schimmel & 
Co. obtained 2.33 p. c. of oil. 
Properties. The oil smells strongly of cineol and cannot, there- 
fore, be taken as a substitute for the Ceylon oil. Sp. gr. 0.9072 to 
0.9071 (Haensel8); «d =- 20°34'2 to -20° 30'.3 The oil forms a 
clear solution with 7-8 p. of 80 p. c. alcohol. 
Composition. The only known constituent is cineol, identified by 
means of the cineol-iodol reaction.2 
79. Korarima Cardamom Oil. 
Korarima cardamoms, formerly known as Cardamomum majus, have 
the form and size of a small fig. They come from the countries south 
of Abyssinia, but are seldom found in the European markets. The 
mother plant of this species, the Amomum angustifolium Sonnerat attains 
a height of 4-5 m. and has orange-yellow blossoms and scarlet fruits. 
The latter are eaten by the natives. The plant is common along 
the rivers in British Central Africa, and occurs also in the islands of 
Mauritius and Madagascar (Hanbury4). The roots have a slight 
ginger-like taste, the leaves are more aromatic.5 The oil from the fruits 
was distilled by Schimmel & Co.0 in 1877, a yield of 2.13 p. c. being 
obtained. 
1) Bericht von S. & Co., Apr. 1897, 
p. 48. 
2) Bericht von S. & Co., Oct. 1897, 
p. 10. 
3) Sudd. Apoth. Zeitung-, 36, p. 683. 
4) Science Papers, p. 112. 
5) Bull. Royal Gardens Kew., No. 142, 
p. 288.-Ref. Apt.-Zt., 13, p. 872 
6) Bericht von S. & Co., Jan. 1878, p. 7. 320 
Special Part. 
80. Oil of Black Pepper. 
Origin and History. The unripe, dried berries from Piper nigrum L.. 
a climber of the family Piperaceae, which was originally indigenous to 
southern India, are obtained from plants cultivated in different parts 
of southern India, in numerous islands of the Indian Archipelago, the 
Philippines and in the West Indies. 
The ripe berries, after the removal of the peri- and mesocarp, con- 
stitute the white pepper of commerce. 
Pepper has been highly prized since antiquity. Like gold it was used 
as a medium of exchange and as an article of tribute. Pepper was used 
as a symbol of the spice trade. Even in Rome the dealers in spices were 
known as Piperarii, later in France as Pebriers, and in England as 
pepperers. 
Inasmuch as the more common spices were frequently distilled, the 
distilled oil of pepper may have been known during the middle ages. 
It is first mentioned by Saladin and described by Valerius Cordus, later 
by Giov. Batt. Porta. Winther of Andernach, who distilled the oils of 
pepper, cinnamon, cloves etc., about 1750, first described the process of 
distillation. In medical treatises, it is first mentioned in the 1589 edition 
of the Dispensatorium Noricum, in the "Apothekertaxe" of Berlin for 
1574 and that of Frankfurt for 1582. . Rheede also described oil of 
pepper in 1688. 
The first examinations of the constituents of pepper were made by 
Neumann1 and by Gaubius,2 later by Willert,3 Oerstedt4 and Pelletier.5 
Preparation. The comminuted black pepper, the unripe fruit of 
Piper nigrum L., upon distillation with water vapor yields 1 to 2.3 p. c, 
of volatile oil. Worthy of notice is the formation of ammonia, which is 
also observed in the distillation of several other oils, viz. the oils of 
ginger, pimenta and cubebs. 
White pepper, which is obtained from the ripe berries, also the 
pericarp removed in its preparation, contains volatile oil.6 Whether 
this agrees with the oil from black pepper is not known. 
Oleum Piperis. - Pfefferol. - Essence de Poivre. 
i) Grundliche mit Experimenten erwiesene Chymie. Editio C. H. Kessel. 1789. Vol. 
2, Part 4, p. 9. 
2) Gaubii, Adversariorum varii argument! liber unus. 1771. Chap. 5, p. 55. 
3) Trommsdorff's Journ. der Pharniacie, 20, II, p. 44. 
Schweigger's Journ. fiir Chemie und Physik, 29, p. 80. 
5) Trommsdorff's Neues Journ. d. Pharm., G, II, p. 233. 
6) Luca (Trommsdorff's Taschenbuch fiir Chemiker und Pharmaceuten, 1822, p. 81) 
■obtained 1.61 p. c. of oil from white pepper. Oils of the Piperaceae. 
321 
Properties. A colorless or yellowish-green liquid of more or less 
distinct phellandrene-like odor, and a mild, by no means sharp taste. 
Sp. gr. 0.87 to 0.90. It deviates the ray of polarized light either to 
the right or left. The degree of deviation as observed on rather 
meagre material varies from -5° 2' to +2° 27'. In alcohol it is 
rather difficultly soluble, mostly requiring about 15 p. of 90 p. c. 
alcohol to effect a clear solution. On account of the large phellandrene 
content, the phellandrene test with sodium nitrite and acetic acid, 
is as a rule, though not invariably, successful directly without 
fractionation. 
Composition. As shown by the first analyses1 (1835) oil of pepper 
is almost free from oxygen. This fact was verified by the examination 
of Eberhardt2 (1887) who obtained 87.26 p. c. C. and 10.81 p. c. H. as 
the results of an elementary analysis. The highest fractions of the oil 
boiling between 170 to 310° were colored green. Fraction 169.5 to 171° 
had the composition of a terpene; fraction 176° yielded terpin hydrate 
when treated with alcohol and acid. 
Although fraction 176 to 180° upon bromination yielded dipentene 
tetrabromide melting at 122 to 123°, Eberhardt regarded the terpene 
as not identical with any of the known terpenes. As was shown later 
by Schimmel & Co.,3 oil of pepper contains phellandrene, which is 
evidently laevogyrate, the fraction from which it was obtained turning 
the plane of polarized light 10° to the left. 
The formation of the tetrabromide by Eberhardt from fraction 
176 to 180° reveals the presence of dipentene. It is still a question, 
however, whether dipentene is contained in the original oil or whether 
it was formed from the phellandrene by the repeated distillation of 
the oil.4 
• 
It also remains undecided to which terpene the terpin hydrate owes 
its origin. That dipentene can be converted into terpin hydrate is 
known. Whether phellandrene also will undergo this change has not 
yet been ascertained. 
!) An analysis of the oil by Dumas (Liebig's Annalen, 15, p. 159) yielded results 
agreeing with the formula Ci0Hi6 ; comp, also Soubeiran & Capitaine (1840), Liebig's 
Annalen, 34, p. 326. 
2) Archiv d. Pharm., 225, p. 515. 
3) Bericht von S. & Co., Oct. 1890, p. 39. 
4) Wallach states (Liebig's Annalen, 287, p. 372): that oils containing phellandrene 
should not be distilled, at least not repeatedly, under ordinary pressure, since phellan- 
drene undergoes changes when subjected to such treatment. 322 
Special Part. 
Origin and History. The spikes with the compact berries of two 
species of Piper or Chavira, viz. P. officinarum D. C. (C. officinarum 
Miqu.) and P. longum L. (C. roxburghii Miqu.) are known as long 
pepper. Both species grow in the islands of the Indian Archipelago, the 
latter also in the Philippines, in southern India, Bengal, Malabar and 
Ceylon. The fruit is collected while immature and dried. 
The distilled oil from long pepper is mentioned in the drug price 
ordinances of 1589 and was admitted to the Dispensatorium Noricum 
of 1589. The first examination of long pepper was made by Winckler 
in 1827.1 
Preparation and Properties. Upon distillation, long pepper yields 
1 p. c. of a viscid, yellowish-green oil of sp. gr. 0.861. It distills 
between 250 and 300°, has a mild taste like pepper oil and an odor 
reminding of ginger.2 
83. Oil from Piper Ovatum. 
Besides other constituents, the leaves of Piper ovatum (?) contain 
a terpene (Dunstan and Garnett,3 1895). 
83. Oil from Ashanti Pepper. 
According to Herlant4 the fruits of Piper clusii D. C, Ashanti pepper, 
contain 11.5 p. c. of volatile oil. 
84. Oil of Cubebs. 
Oleum Cubebarum.-Cubebenbl.-Essence de Cubebe. 
Origin and History. The berries from the piperaceous climber 
Piper cubeba L. (Cubeba officinalis Miquel) are mostly brought into 
commerce via Batavia and Singapore. The shrub is indigenous to the 
large Sunda islands and is there cultivated, also in Ceylon and other 
tropical islands. 
Cubebs were first examined by "Wedel5 in 1704, soon after by Neu- 
mann,6 in 1810 by Trommsdorff,7 and in 1821 by Vauquelin.8 The 
81. Pepper Oil from Long Pepper. 
i) Archiv d. Pharm., 26, p. 89. 
2) Bericht von S. & Co., Apr. 1890, p. 48. Comp, also Dulong (1825), Journ. de 
Pharm. II, 11, p. 59.-Trommsdorff's Neues Journ. d. Pharm., 11, I, p. 104. 
3) Chern. News, 71, p. 33. 
4) Acad. Roy. de M£d. de Belgique, 1894, p. 115; Jahresb. d. Pharm., 1895, p. 142. 
5) De cubebis. Dissertatio. Jenae 1705. 
6) Lectiones chymici. 
7) Trommsdorff's Journ. der Pharm., 20, I, p. 69. 
8) Trommsdorff's Taschenb. fur Chern, und Pharm., 1822, p. 195. Oils of the Piperaceae. 
323 
volatile oil was known to Valerius Cordus before 1540 ;x in price 
ordinances it first receives mention in that of Frankfurt-on-the-Main 
in 1582. 
Preparation. Comminuted cubebs upon distillation with water- 
vapor yield 10-18 p. c. of oil. In the course of the distillation ammonia 
is given off, the formation of which is no more understood in this case 
than in the distillation of ginger, pepper, pimenta and other drugs. 
Properties. Cubeb oil is a viscid, light green or bluish-green oil. 
It is colorless only when the last portions of the distillation, which 
are blue, have not been added to the product. It possesses the character- 
istic cubeb odor and a warm, camphor-like taste, which finally becomes 
grating. Sp. gr. 0.915 to 0.930; «d = - 25 to -40°. 
The solubility in 90 p. c. alcohol varies greatly. Some oils, pre- 
sumably from old cubebs, are soluble in an equal part, others require 
10 p. c. of this alcohol to effect solution.2 
The bulk of the oil distills3 between 250-280°. A quantitative 
fractionation yielded the following result:4 
1) from 175-250° = 9.2 p. c. 
2) " 250-260° = 26.8 " 
3) " 260-270° = 47.6 " 
4) " 270-280° = 7.2 " 
above 280° = 9.2 " 
100.0 p. c. 
Oils distilled from old cubebs, which contain the cubeb camphor 
described below, are heavier than the normal and can be recognized by 
their behavior toward potassium. A piece of potassium or sodium, 
immersed in such an oil, loses its lustre and is covered with a crust, 
whereas an oil distilled from fresh cubebs does not attack the metal 
(Schmidt,5 1870). 
Composition. From the behavior toward potassium it becomes 
apparent that the oil from fresh cubebs is almost devoid of oxygen, 
consisting only of terpenes and sesquiterpenes. On the other hand the 
reaction of the oil from old cubebs is to be attributed to cubeb camphor. 
1) Annotationes, 1561, fol. 226. 
2) The requirement of the U. S. P., according to which the oil is to be soluble in 
an equal volume of 90 p. c. alcohol is, therefore, too exacting. 
3) Oils containing cubeb camphor undergo, on distillation, partial decomposition with 
the elimination of water. Schaer & Wyss (1875), Archiv d. Pharm., 206, p. 322. 
4) Pharm. Journ., Ill, 25, p. 951. 
5) Archiv d. Pharm., 191, p. 23. 324 
Special Part. 
From the lowest boiling fractions a small amount can be collected 
between 158-163° by systematic fractionation. It consists of a laevo- 
gyrate terpene (Oglialoro,1 1875), («d -- 35.5°) presumably pinene or 
camphene. Furthermore dipentene was identified (dihydrochloride, 
m. p. 48-49°) in the fraction below 200° (Wallach,2 1887). 
As already stated, the bulk of the oil distills between 250 and 280° 
and consists of two laevogyrate sesquiterpenes.2 The one, b.p. 262-263°, 
has the lesser rotatory power, does not combine with hydrogen chloride, 
and has not yet been further examined. The second yields a dihydro- 
chloride,3 C15H24.2HCI, melting at 118° and is identical with cadinene. 
Although pure cadinene boils at 274-275°, almost the total amount 
of the hydrocarbon is obtained in lower boiling fractions from which the 
dihydrochloride separates upon saturation with hydrogen chloride. 
Cubeb camphor4 is a sesquiterpene hydrate, possibly an alcohol of 
the composition5 C15H25OH. It is laevogyrate, crystallizes in rhombic 
forms and melts according to different authors at 65°,6 67° 7 and 70°.8 
It is rather unstable, decomposing when kept over sulphuric acid into 
sesquiterpene and water.6 It boils at 148° giving off part of its water.9 
The dehydration is complete when heated for some time to 200-250°. 
The resulting sesquiterpene has not yet been examined. 
The fact that cubeb camphor is found only in old cubebs, leads to 
the supposition that it is formed by the hydration of the oil when the 
berries are exposed to a moist atmosphere. 
85. Oil from Piper Lowong. 
From the fruit of Piper lowong BL, known as false cubebs, Peine- 
mann10 in 1896 obtained by distillation with water vapor 12.4 p. c. of 
an almost colorless oil with a sp. gr. of 0.865. 
i) Gazz. chini. ital., 5, p. 467; Berichte, 8, p. 1357. 
2) Liebig's Annalen, 238, p. 78. 
3) This was first obtained by Soubeiran and Capitaine in 1840 (Liebig's Annalen, 
34, p. 323), and recognized by them as sesquiterpene dihydrochloride. Later it was 
examined by Schmidt, Schaer & Wyss, also by Wallach. 
<) Cubeb camphor was first observed by Tesehemacher at the beginning of this 
century. It was also examined by Muller in 1832, Liebig's Annalen, 2, p. 90; by 
Blanchet & Sell in 1833, Liebig's Annalen, 6, p. 294; by Winckler in 1833, Liebig's 
Annalen, 8, p. 203; bjr Schmidt in 1870, Archiv d. Pharm., 191, p. 23, and Berichte, 
10, p. 188; also by Schaer & Wyss in 1875, Archiv d. Pharm., 206, p. 316. 
5) Schmidt, Schaer & Wyss, loc. cit. 
6) Schmidt, loc. cit. 
7) Schaer & Wyss, loc. cit. 
s) Winckler, loc. cit. 
9) This low boiling point for a sesquiterpene is rather remarkable and probably due 
to the partial decomposition. 
io) Archiv d. Pharm., 234, p. 238. Oils of the Piperaceae. 
325 
Upon distillation it can be resolved into two principal fractions, but 
partial decomposition takes place whether distilled under ordinary or 
diminished pressure. 
Fraction 1, constituting 40 p. c. of the oil, boils between 165-175°, 
and is colorless; sp. gr. 0.854 at 20°; «d = +22°. 
Fraction 2, constituting 34 p. c. of the oil, boils between 230-255°, 
and is colored yellow; sp. gr. 0.9218; optically inactive. 
At 270° a bluish-green fraction is obtained. 
From a fraction 110-148° under 17 mm. small crystals separated 
upon standing, which after recrystallization from chloroform melted 
at 164°.1 An elementary analysis yielded results corresponding with the 
rather improbable formula CioHic . 2HoO. 
86. Matico Oil. 
Oleum Foliorum Matico.-Maticool.-Essence de Matico. 
Origin. Piper angustifolium Ruiz et Pavon, indigenous to South 
America, is stated to be the mother plant of the matico leaves. Inas- 
much, however, as the term Matico is applied to a number of plants, 
the leaves of which can hardly be distinguished from the genuine, it is 
not surprising that mistakes are frequent and that the genuine article 
cannot be had at times. Recently imported matico leaves differ but 
little in appearance from those formerly in commerce, but considerably 
in the amount of oil they contain and in the properties of this oil. 
Whereas formerly 1-3.5 p. c. of an oil lighter than water was obtained, 
now 3-6 p. c. of an oil heavier than water results. 
Properties. The matico oil of former years had a sp. gr. of 
0.93-0.99 and was slightly dextrogyrate. It was a viscid, more or 
less dark colored liquid the odor of which reminded of cubebs and mint. 
The more recent matico2 oil is yellowish-brown; has asp. gr. lt06- 
1.13; slightly laevogyrate [«]d = -0°25', or dextrogyrate up to + 5° 34'. 
The odor reminds of that of Asarum europaeum. The oil is soluble in 
10 p. of 80 p. c. alcohol and in equal parts of 90 p. c. alcohol. 
Composition. Matico camphor which was discovered by Fliickiger8 
and which has been examined as to its physical properties only, is the 
only known constituent of the old matico oil. It was obtained by distil- 
ling off those portions of oil boiling below 200°. From the residue 
i) Possibly this substance is identical with the stearoptene, of like melting point, 
found in juniper oil. 
2) An oil, which evidently was obtained from a third variety of leaves (yield 0.3 p. c.), 
had a sp. gr. of 0.922 and a rotatory power aD =-27° 28'. 
3) Pharmacognosie. Ill ed., p. 747. 326 
Special Part. 
the camphor crystallized out in hexagonal prisms 2 cm. long and 
5 mm. thick. Frequently it also crystallized from the oil when exposed 
to the cold. 
Matico camphor, which when pure is odorless and tasteless, is readily 
soluble in alcohol, ether, chloroform, benzene and petroleum ether. The 
melting point of the crystals lies at 94° (Hintze1). It is optically 
active (Traube2). In chloroformic solution [a]D =- 28.73° at 15°. 
In a molten condition, calculated for 15°, [«]d = -29.17°. The specific 
rotatory power of the crystals is about eight times as great, being 
- 240° for a plate 100 mm. thick. 
The identity of'matico camphor with ethyl camphor, CioHi5(C2H5)O, 
was regarded probable by Kugler3 who based his supposition on an 
elementary analysis. The fact, however, that ethyl camphor4 is a liquid 
having the odor of camphor, whereas matico camphor is odorless with 
a great tendency to crystallize, seems to speak against this assumption.4 
The new matico oil contains no matico camphor. From an oil 
distilled by Schimmel & Co.5 (sp. gr. 1.077; «d- - 0°25') a substance 
separated which, after repeated crystallization from petroleum ether 
melted at 62° and which proved to be asarone. The dibromide melted 
at 85-86°, and the asarylic acid, obtained by oxidation with perman- 
ganate, at 144°. The oil possibly also contains methyl eugenol, for 
upon oxidation with permanganate it yielded an acid melting at 174° 
which probably was identical with veratric acid. 
87. Oil from Artanthe Geniculata. 
The leaves of Artanthe geniculata Miq., known in Brazil as "false 
jaborandi," yield small amounts of a light greenish oil, of a spicy, 
somewhat mint-like odor and pungent, burning taste.0 
88. Oil of Betel Leaves. 
Oleum Folioruin Betle. -Betelol.-Essence (les Feuille des Betel. 
Origin. The ancient custom of betel chewing practiced in the Malayan 
Archipelago and in southern China consists in chewing a betel leaf (Sirih) 
i) Tschermak's Mineral. Mitth., 1874, p. 227. 
2) Zeitschr. f. Kryst., 22, p. 47. 
3) Berichte, 16, p. 2841. 
4) Conipt. rend.. 63, p. 222. 
s) Berieht von S. & Co., Oct. 1898, p. 37. 
6) Peekolt, Pharm. Rundschau, 12, p. 286. - Artanthe geniculata Mlq. and Piper 
angustifolium Ruiz et Pavon are according to Liirsse i. Medic. Pharm. Botanik, vol. 2, 
p. 514, synonymous terms. This oil, therefore, is probably identical with one of the 
oils described under matico oil. Oils of the Piperaceae. 
327 
from Piper betle L. {Chavira betle Miq.) with some lime, gambier (from 
Uncaria gambir Roxb.) and a piece of betel nut from Areca catechu L.1 
The betel leaves owe their spicy, burning taste to a volatile oil which 
has been repeatedly prepared and investigated, but which has not yet 
found any practical application worth mentioning. 
History. When and by whom betel oil was first distilled is not 
known: it is highly probable that the preparation of the oil by 
Kemp2 in 1885 was not the first. A superficial examination of Siam 
betel oil in the laboratory of Schimmel & Co.3 in 1887 revealed the 
presence of a phenol in fraction 250-260°, which seemed to correspond 
with eugenol. Eykman,4 who in 1888 examined an oil distilled by him- 
self in Java, found no eugenol, but a new phenol which he called chavicol. 
A second examination in the laboratory of Schimmel & Co. revealed the 
fact that Siam betel oil contains neither eugenol nor chavicol, but a 
third phenol, a previously unknown isomer of eugenol, which Bertram 
and Gildemeister5 in 1889 termed betel phenol. 
Properties. Betel oil is a light yellow to dark brown liquid of 
aromatic, somewhat creosote-like odor, reminding of tea, and with a 
pungent taste. 
The sp. gr. varies between 0.958 and 1.044; the oil from fresh leaves 
being lighter both in weight and color than that distilled from the dried 
material. The rotatory power was observed on three samples of oil from 
fresh leaves. Of these two were laevogyrate («d up to-1°45') and one 
dextrogyrate (aD=+2°45')- 
With ferric chloride the alcoholic solution of betel oil produces a 
greenish to bluish-green color. 
Source, yield, physical properties and composition of the betel oils 
thus far examined are given in the following table (see next page). 
Composition. Of the two phenols found in betel oil. betel phenol and 
chavicol, only the former has been found in all oils and may, therefore, 
be regarded as the characteristic constituent of betel oil. Chavicol, 
which so far has been found only in the Java oil, does not occur in the 
Manila or Siam oils. 
i) The details concerning' betel chewing and the constituents of the ''Betel-Apotheke" 
owned by almost every Malay family are described in Tschirch's work. "Indische Heil- 
und Nutzpflanzen" (Berlin 1892) p. 138. See also True, Pharm. Review, 14, pp. 130, 177. 
2) Pharmacographia indica, part VI, p. 188. 
3) Bericht von S. & Co., Oct. 1887, p. 34. 
4) Chemiker-Zeitung, 12, p. 1338. 
5) Journ. f. prakt. Chemie, II, 39, p. 349. 328 
Special Part. 
Origin, Material used 
and Yield 
Sp. Gr. 
an 
Constituents 
I. 
Siam.1 
Leaves dried on hot 
plates. Yield 0.6 p. c. 
1.024 
at 15° 
- 
Betel phenol, 
Cadinene. 
II. 
Siam.1 
Leaves dried by ex- 
posure to the sun. 
Yield 0.9 p. c. 
1.020 
at 15° 
- 
III. 
Manila.2 
Fresh leaves. 
Yield 0.27 p. c. 
1.044 
at 15° 
- 
Betel phenol. 
IV. 
Java.3 
Fresh leaves. 
0.959 
at 27° 
-1°45' 
Chavicol, 
Betel phenol, 
Sesquiterpene. 
V. 
Java.4 
Probably fresh leaves. 
0.958 
at 15° 
+ 2° 45' 
Not examined. 
VI. 
Bombay.5 
Fresh leaves. 
0.9404 
at 28° 
Slightly 
laevogyrate 
Betel phenol (chavibetol), C1OH12O2, contains the same side chains 
as its isomer eugenol, but in different positions. 
C3H5 C3H5 C3H5 
I I I 
c c c 
HC/Z^XCH HC/^^\CH HC//^\CH 
I I . 
I 
I I 
HC\ /COH HC\ /COCH3 HC\ /CH 
COCHs COH COH 
Eugenol. Betel phenol. Chavicol. 
Betel phenol6 is a liquid with marked refractive power, and possesses 
a peculiar, not unpleasant but persistent betel odor, which differs greatly 
i) Bertram & Gildemeister, Journ. f. prakt. Chemie II, 39, p. 349.-Bericht von 
S. & Co., Apr. 1888, p. 8; Apr. 1889, p. 6; Oct. 1889, p. 6: Apr. 1890, p. 6; Oct. 1891, p. 5. 
2) Bericht von S. & Co., Apr. 1891, p. 5, and Oct. 1891, p. 5. 
3) Berichte, 22, p. 2736. 
Bericht von S. & Co., Oct. 1893, p. 45. 
5) Pharm. Journ., Ill, 20, p. 749. 
6) Bertram & Gildemeister, loc. eit. Oils of the Piperaceae. 
329 
from that of the closely related eugenol. When pure, betel phenol boils 
without apparent decomposition at 254-255° (at 131-132° under 
12-13 mm. pressure) and has a sp. gr. of 1.067 at 15°. In alcoholic 
but not in aqueous solution it yields an intensely bluish-green color 
with ferric chloride. 
Betel phenol can be identified by means of its benzoyl derivative, 
which crystallizes in laminae and melts at 49-50°. (Benzoyl eugenol 
melts at 69-70°). Acetyl betel phenol boils at 275-277° and melts at 
- 5° (acetyl eugenol melts at 30-31°), and upon oxidation with perman- 
ganate yields acet-isovanillic acid, m. p. 207°. 
Chavicol,1 also a phenol, has so far been definitely shown to be 
present only in betel oil from Java. Chavicol or para hydroxy allyl 
benzene (comp. p. 179) boils at 237° and has a sp. gr. of 1.041 at 13°. 
Its aqueous solution is colored intensely blue with ferric chloride, the 
alcoholic solution but faintly blue. 
An oil distilled by de Vrij in Java, when examined in the laboratory 
of Schimmel & Co.2 was found to contain in addition to betel phenol a 
second phenol, which is probably identical with chavicol. The benzoyl 
compound crystallized in long needles and melted at 72-73°. 
Another oil distilled in Manila from fresh leaves and examined by 
Schimmel & Co.3 contained no other phenol than betel phenol. The 
phenol separated from the soda solution had a constant boiling point 
of 128-129° under 11 mm. pressure and yielded exclusively a benzoyl 
compound crystallizing in laminae and melting at 50°. 
Another constituent, possibly to be found in all betel oils, is cadinene, 
C15H24. So far this hydrocarbon has been isolated from the Siam oil4 
only (dihydrochloride, m. p. 118°). Probably the sesquiterpene (b. p. 
abt. 260°, sp. gr. 0.917) found by Eykman in the betel oil from Java 
is also cadinene. The Java oils from fresh leaves contain a considerable 
amount of low boiling constituents. Eykman3 did not succeed in 
isolating of identifying a pure terpene of constant boiling point from 
the fractions between 173-190°. Probably several terpenes are present, 
but apparently no pinene. Fraction 173-175° (sp. gr. 0.848 at 16°; 
aD = - 5° 20') yielded neither a solid bromide nor a crystalline hydro- 
chloride. Fraction 190-220° contains substances having a minty odor 
(menthone or menthol?). 
1) Eykman, loc. cit. 
2) Bericht von S. & Co., Apr. 1890, p. 7. 
3) Bericht von S. & Co., Oct. 1891, p. 5. 
4) Bertram & Gildemeister, lot. cit. 
5) Loc. cit. 330 
Special Part. 
The oil distilled from dried Siam leaves was devoid of low boiling- 
fractions, only a few drops coming over below 200°. Whereas the 
absence of terpenes in this oil may be accounted for by the character 
of the crude material, the absence of chavicol in Siam and Manila oils 
and the occurrence of this substance in Java oil may be accounted for 
by differences in climate and soil of the respective countries. 
89. Oil from Potomorphe Umbellata. 
The fresh leaves of Potomorphe umbellata Miq. (Family Piperaceae) 
contain 0.05 p. c. of an oil, the taste and odor of which remind of 
pepper (Peckolt1). 
90. Oil from Ottonia Anisum. 
From 12 kilo of the air-dried root of wild jaborandi, Ottonia. anisum 
Spreng. (Serronia jaborandi Guill.) 10.54 g. (-0.088 p. c.) of a viscid 
oil were obtained. It possesses a peculiar, somewhat pepper-like odor 
and a burning taste which benumbs the tongue. Sp. gr. 1.035 (Peckolt2). 
91. Oil from Poplar Buds. 
The leaf-buds of the black poplar, Populus nigra L., (Family Salica- 
ceae), which were formerly found in apothecary shops under the name 
of Oculi populi and used in the preparation of ointments, yield about 
% p. c. of volatile oil upon distillation with water vapor. It is light yellow 
in color and has a pleasant odor reminding somewhat of chamomile. 
It is insoluble in 70-90 p. c. alcohol, but yields a clear solution with 
% p. or more of 95 p. c. alcohol. Sp. gr. 0.900-0.905; an - + 1° 54'3 
to +5° 54'; saponification number 13. 
Poplar bud oil distills between 255-265°3 and consists principally 
of a hydrocarbon (C.5Hs)x boiling at 260-261°. Piccard4 (1873) judges 
from its vapor density that it is a diterpene, C20H32, whereas its boiling- 
point indicates a sesquiterpene. 
Fichter and Katz5 in a recent investigation of this oil, found it to 
consist principally of a sesquiterpene boiling at 263-269°. The com- 
pound was identified as humulene by means of its nitrosochloride, 
nitrosate, both the blue and the white nitrosite, and the piperidine and 
benzylamine bases prepared from these. Besides humulene there is pro- 
i) Pharm. Rundschau, 12, p. 241. 
2) Pharm. Rundschau, 12, p. 287. 
3) Bericht von S. & Co., Apr. 1887, p. 36. 
4) Beriehte, 6, p. 890; 7, p. 1486. 
5) Beriehte, 32, p. 3183. Oils of the Myricaceae. 
331 
bably contained in the oil a second sesquiterpene, and about % P- c. of 
paraffin, C24H50, m. p. 53-68°. The bodies to which the pleasant odor 
of the oil is due passed over in the lowest fraction. 
92. Dutch Myrtle Oil. 
Upon distillation of the fresh leaves of Jfyrica gale L. (Family 
dfyricaceae), 0.65 p. c. of a brownish-yellow oil (Rabenhorst,1 1837), 
sp. gr. 0.876, are obtained. At 17.5° it congeals partly, at 12.5° com- 
pletely to a crystalline mass. The odor is peculiar balsamic, pleasant; 
the taste mild at first, then temporarily burning and permanently 
astringent. It is said to contain 70 p. c. camphor (?). 
93. Bayberry Oil. 
The leaves of Myrica cerifera L. (Family Myricaceae) yield 0.021 
p. c. of volatile oil,2 of greenish color, and very pleasant aromatic, spicy 
odor. Sp. gr. 0.886; «d -- 5° 5'. 
94s Sweet Fern Oil. 
The dried leaves of Myrica asplenifolia Endl. (Comptonia aspleni- 
folia Aiton) yield upon distillation about 0.08 p. c. of volatile oil. It 
has a strong spicy, cinnamon-like odor. Sp. gr. 0.926. When cooled 
in a freezing mixture the oil congeals.3 
95. Oil from Walnut Leaves. 
The aromatic odor of the fresh leaves of Juglans regia L. (Family 
Juglandaceae) is attributable to the volatile oil they contain. Upon 
distillation of 800 k. of fresh leaves, Schimmel & Co.4 obtained 235 g. 
of oil. It is yellowish-green in color, solid at ordinary temperature, and 
has a pleasant tea-like odor. 
96. Sweet Birch Oil (Wintergreen Oil). 
Oleum Betnlae Lentae. - Birkenrindenol. - Essence de Betula. 
Origin and History. Cherry birch or sweet or black birch, Betula 
lenta L. (Family Betulaceae} is a tree 15-20 m. high which grows on 
good forest soil throughout southern Canada and the northern United 
i) Repert. Pharm., 60, p. 214. Gmelin, Organ. Chemie, IV Ed., Vol. 7, p. 335. 
2) Bericht von S. & Co., Oct. 1894, p. 73. Comp, also Hambright (1863), Am. 
Journ. Pharm., 35, p. 193. 
3) Bericht von S. & Co., Oct. 1890, p. 50. 
4) Bericht von S. & Co., Oct. 1890, p. 49. 332 
Special Part. 
States, westward as far as Minnesota and Kansas, and to the south as 
far as Georgia and Alabama. When chewed its reddish-bronze colored 
bark develops a peculiar fragrance and taste, and on this account has 
been used by the natives for chewing and in the preparation of refresh- 
ing and medicinal beverages. Next to turpentine oil, the oils of sas- 
safras, wintergreen and birch bark are among the first oils obtained 
by distillation in the United States. The similarity in odor and taste 
of birch bark oil with true oil of wintergreen from Gaultheria procum- 
bens was known before 1818 (Bigelow1). The chemical identity of the 
principal constituent of both, however, was demonstrated by Proctor2 
in 1843. As the demand for wintergreen oil increased, sweet birch bark 
was distilled indiscriminatly with wintergreen leaves or even distilled 
alone as substitute3 so that the commercial natural oil is at present 
obtained almost exclusively from the bark of Betula lenta L. 
Preparation. For purposes of distillation, the young trunks and 
branches were formerly used. These were cut into pieces 1-4 inches in 
length which were macerated for 12 hours previous to distillation. For 
the latter operation stills like those described under wintergreen oil 
were used. More recently the bark of the trunk and the larger branches 
is peeled off in late summer and either cut, or torn by means of 
toothed rollers, and freshly distilled with water from copper stills. 
If wintergreen grows abundantly in the neighborhood it is added to the 
bark in the still. According to the abundance and the convenience with 
which the one or the other can be obtained, preference is given to the 
cheaper material. According to Kennedy, maceration for 12 hours is 
considered indispensable to a good yield. A ton of 2,240 lbs. of birch 
bark yields about 5 pounds of oil - 0.23 p. c. A like amount of 
wintergreen yields about 18 lbs. of oil.4 Upon rational distillation, 
however, as much as 0.6 p. c. of oil can be obtained from the bark. 
Proctor already recognized in 1843 that the oil did not preexist in 
the bark, but results upon the interaction of two constituents in the 
presence of water, similar to the formation of the oils of bitter almonds, 
1) American Medical Botany, vol. 2, pp. 28 and 241. 
2) Am. Journ. Pharm., 15. p. 241. 
3) Betula lenta and Gaultheria procumbens grow together in the wooded mountain- 
ous regions of the North Atlantic states. In a report on the wintergreen oil industry, 
Kennedy (Am. Journ. Pharm., 52. p. 49) in 1882 called attention to the fact that the 
cost of collection of birch bark was but i/7 of that of wintergreen leaves; also that the 
yield of oil from the bark was but 0.25 p. c., whereas that from wintergreen was 
0.80 p. c. According to these figures the cost of production of the oil from birch bark 
is but half as great as that of wintergreen leaves. 
4) Am. Journ. Pharm., 54, pp. 49-53. mustard, etc.1 According to more recent investigations by Schneegans2 
these substances are betulase, a ferment, and the glucoside gaultherin3 
which crystallizes with one molecule of water: 
Ci4H1808 + H2O - + CqHiaOe 
Gaultherin Water Methyl salicylate Grape sugar. 
Properties. Oil of sweet birch is a colorless or yellowish colored 
oil sometimes colored red due to the presence of traces of iron. As to 
odor and taste, it can scarcely be distinguished from pure methyl 
salicylate, but differs decidedly in both respects from the oil of Gaul- 
theria, procumbens. Sp. gr. 1.180 to 1.187. It is optically inactive, 
differing in this respect from the slightly laevogyrate gaultheria oil. 
It forms a clear solution with 5 p. of 70 p. c. alcohol at ordinary 
temperature, and with aqueous potassa or soda solution upon gentle 
heating. Water shaken with a drop of the oil produces a deep violet 
color with ferric chloride. By distillation over a free flame, swee't birch 
oil passes over between 218-221°. 
Composition. Inasmuch as no commercial distinction is made 
between birch oil and gaultheria oil, it remains doubtful whether the 
discovery of salicylic acid by Cahours4 (1844) was made in connection 
with an oil of sweet birch, a true wintergreen oil, or a mixed oil. 
Proctor possibly distinguishes between the two. It is quite certain that 
the oil examined by Cahours must have been adulterated for he found 
10 p. c. of a terpene boiling at 160° which he terms "gaultherilene" and 
which presumably was pinene from admixed turpentine oil. Recent examin- 
ations of genuine oils have shown the absence of terpenes in both oils. 
According to Power and Kleber5 (1895) sweet birch oil contains as 
much as 99.8 p. c. of methyl salicylate.0 If the oil diluted with ether is 
shaken with an aqueous 7.5 p. c. potassa solution, the methyl salicylate 
passes into the aqueous solution as potassium methyl salicylate and 
can readily be separated from the other constituents remaining in 
ethereal solution. 
Oils oi the Betulaceae. 
333 
!) Am. Journ. Pharm., 15, p. 241. 
2) Journ. d. Pharm. v. Elsass-Lothr., 23, p. 17. 
3) Arch. d. Pharm. 232, p. 437. 
4) Ann. de Chim. et Phys., III. 10, p. 327.-Liebig's Annalen, 48, p. 60; 52, p. 327. 
5) Pharm. Rundschau, 13, p. 228. 
6) The statement by Trimble & Schroter (Am. Journ. Pharm., 61, p. 398, and 67, 
p. 561), that the oils of gaultheria and sweet birch contain benzoic acid, ethyl alcohol 
and a sesquiterpene was not substantiated by the examination of a large amount of 
authentic oil. See Power (Pharm. Rundsch., 7, p. 283), also Power & Kleber (Pharm. 
Rundschau, 13, p. 228). These constituents evidently do not occur in the genuine oil. 334 
Special Part. 
The residue remaining- upon evaporation of the ether was separated 
into two parts by steam distillation. The non-volatile residue congealed 
upon cooling. It was readily soluble in ether, more sparingly in alcohol, 
and crystallizes in laminae which are not attacked by sulphuric or nitric 
acids. They consist of paraffin which, judging from an elementary 
analysis and m. p. determination (m. p. 65.5°) may be regarded as 
triacontane, CsoB^. The portion volatile with water vapor is readily 
soluble in 80 p. c. alcohol, boils between 230-235° (under 25 mm. 
pressure a.t abt. 135°), and has the composition C14H24O2. It is an 
ester and upon saponification is resolved into its compounds; an alcohol 
CsHieO and an acid C«HioO2. 
Examination. Inasmuch as the oils of sweet birch and gaultheria 
are the heaviest of all known oils, the presence of foreign oils or of 
petroleum causes a lowering of the specific gravity. The solubility in 
70 p. c. alcohol is also diminished by the presence of most adulterants. 
The property of methyl salicylate to form water soluble salts with the 
alkalies (e. g. CoHifOKjCOOCHa) affords a convenient means of detect- 
ing adulterations. A suitable method is that directed by the U. S. 
Pharmacopoeia: 
If to 1 cc. of oil contained in a capacious test-tube, 10 cc. of sodium 
hydrate T. S. be added, and the mixture agitated, a bulky, white, crystalline 
precipitate will be produced; then if the test tube, loosely corked, be allowed 
to stand in boiling water for about five minutes, with occasional agitation, the 
precipitate should dissolve, and form a clear, colorless or faintly yellowish 
solution, without the separation of any oily drops, either at the surface or at 
the bottom of the liquid (absence of other volatile oils or of petroleum). 
Still more convenient is the use of a 5 p. c. caustic potash solution 
which dissolves methyl salicylate immediately without the formation of 
a precipitate, leaving other oils undissolved. 
Chloroform can also be detected in this way. Five percent of foreign 
constituents can be recognized in this way. Inasmuch as the odor of 
methyl salicylate disappears completely in the alkaline solution, the 
nature of the adulterant can usually be recognized by its odor. 
The amount of methyl salicylate can be determined by isolating and 
weighing the salicylic acid or volumetrically. 
For the gravimetric determination Ewing1 (1892) recommends the 
following process: 
1.5-2 g. of the oil are saponified in a flask of 50 cc. capacity with a slight 
excess of soda solution. To the liquid, transferred to a separating funnel, 
i) Proc. Am. Pharm. Ass., 40, p. 196. Oils of the Betulaceae. 
335 
hydrochloric acid is added in excess and the liberated salicylic acid shaken out 
with ether. In order to remove traces of sodium chloride from the ethereal 
solution, this is shaken with water. The ethereal solution is evaporated in a 
tared capsule on a waterbath. The residual salicylic acid is weighed after 
having been dried to constant weight over sulphuric acid. 
This method of assay presupposes a pure oil, for foreign additions 
such as sassafras oil, would pass into the ethereal solution with the 
salicylic acid and remain upon evaporation of the solvent. 
For the volumetric estimation, E. Kremers and M. James 1 give the 
following directions: 
5 g. of oil to be dissolved in an excess of standard soda solution and,the 
solution to be boiled for five minutes to effect saponification. The excess of 
soda solution is ascertained with the aid of normal acid and the number of ccs. 
of normal alkali consumed in the saponification multiplied by 0.152, the methyl 
salicylate factor. 
The assay can also be effected by determining the amount of salicylic 
acid present according to the method of Messinger and Vortmann.2 
This method is based upon the supposed fact that in the presence of 
much alkali salicylic acid is converted by iodine into a diiodo salicylic 
acid iodide. The excess of iodine is ascertained by titration with 
standard thiosulphate solution. The reaction is supposed to take place 
according to the following equation: 
CoH4(OH)COOK + 3NaOH + 61=C6H2I2(0I)C00K + 3KI + 3H2O 
The application of this method to wintergreen oil has been suggested 
by Kremers and James:1 
A weighed quantity of oil (abt. 3 g.) is saponified with normal alkali, care 
being taken to employ at least 7 molecules of potassium hydroxide for every 
molecule of methyl salicylate. The saponified liquid is diluted to either 250 or 
500 cc. Of this solution 5 or 10 cc. respectively are heated in a flask to 
60°. Decinormal iodine solution is then added until the color is permanently 
yellow. Upon shaking a deep red precipitate results. Upon cooling, the solution 
is acidified with dilute sulphuric acid and diluted with water to 250 or 500 cc. 
In an aliquot part (abt. 100 cc.) of the filtrate the excess of iodine is ascer- 
tained by means of N/10 thiosulphate solution. 
1 Mol. Methyl salicylate 151.64 
= = 0.19974314. 
6 Atoms Iodine 759.2 
By multiplying the amount of iodine found (in ccs.) with the factor 
0.19974314 the amount of methyl salicylate present is found, from which the 
percentage of ester in the oil can be calculated. 
A good oil should contain at least 98 p. c. of methyl salicylate. 
D Pharm. Review, 16, p. 130. 
2) Berichte, 22, p. 2321; 23, p. 2755. 336 
Special Part. 
Oleum Huniuli Lupuli.-Hopfenol.-Essence de Houblon. 
97. Oil of Hops. 
Origin and History. On account of their peculiar aromatic odor 
and taste, the fruit of Humulus lupulus L. (Family Moraceae), which is 
cultivated in most countries, has been used since the middle ages for 
the aromatization of barley beer. Hops, therefore, are mentioned in 
literature since the eighth century.1 Medicinally hops are being used only 
comparatively recently. The medical use of lupulin was suggested in 
1820 by Ives,2 a New York physician. 
The volatile oil of hops seems to have been first distilled from the 
glands by Payen and Chevallier,3 but thus far has found but little 
application. 
Preparation. Oil of hops is prepared from the strobiles as 
well as from the lupulin. The yield from hops varies from 0.3-1 p. c., 
from lupulin as much as 3 p. c. are obtained. The latter, however, is 
less pleasant and, therefore, inferior. The aqueous distillate-especially 
that from lupulin - is strongly acid and contains valerianic acid (Per- 
sonne) and probably also butyric acid (Ossipow). Unbleached hops 
must be used for distillation, otherwise the oil has an unpleasant 
sulphurous odor. 
Properties. Oil of hops is a light yellow to reddish-brown thin 
liquid which becomes viscid upon prolonged standing. It has an 
aromatic odor and its taste is not bitter. Sp. gr. 0.855-0.880; 
«d = +0° 28' to +0°40'. In alcohol it is very difficultly soluble, especially 
older oils do not yield a clear solution with even 95 p. c. alcohol. This 
may possibly be attributed to polymerization products resulting from 
so-called olefinic terpenes present in the oil. 
Composition. Although oil of hops has frequently been examined 
chemically,4 not a single constituent had been isolated and characterized 
until recently. 
In 1895 Chapman5 showed that, aside from small amounts 
of olefinic terpenes, oil of hops consists principally of a sesquiterpene, 
humulene. The oxygenated constituents, however, to which the oil 
evidently owes its peculiar aroma, were not investigated by Chapman. 
i) Pharmacographia, p. 551. 
2) Silliman's Journ. of Sc. & Arts, 1820, p. 302. 
3) Journ. de Pharmacie, 8, pp. 214 & 533. 
4) Payen & Chevallier, loc. cit. - Wagner (1853), Journ. f. prakt. Chem., 58, p. 351. 
- Personne (1834), Compt. rend., 38, p. 309.-Kiihnemann (1877), Berichte, 10, p. 2231. 
- Ossipow (1883 & '86), Journ. f. prakt. Chem., II, 28, p. 48, and 34, p. 238. 
5) Journ. Chem. Soc., 67, pp. 54 & 780. Oils of the Moraceae. 
337 
The fact that the analysis of fraction 166-171 (sp. gr. 0.789) 
agrees with the formula C10H17, seems to render it probable that it 
consists of a mixture of two hydrocarbons, viz. CioHis and CioHie. 
The latter is possibly identical with one of Semmler's 1 olefinic terpenes. 
Bromine and hydrochloric acid are absorbed energetically, but do not 
yield crystalline derivatives. Upon oxidation, oxalic acid alone was 
obtained. 
Almost two-thirds of the oil consist of humulene, a sesquiterpene 
boiling at 263-266°, sp. gr. 0.9001 at 15°. Isolated by fractionation 
it is obtained either slightly laevo- or dextrogyrate. When perfectly 
pure it is probably inactive. 
With bromine and hydrogen chloride liquid addition products only 
are obtained. A characteristic derivative was obtained by passing 
nitrosyl chloride into the chloroform solution. This nitrosochloride 
melts at 164-165° and may serve for its characterization. The humu- 
lene nitrolpiperidide obtained from it melts at 153°, the nitrolbenzylamine 
base at 136°. 
Caryophyllene from oil of cloves yields similar derivatives which are, 
however, quite different in melting point. Caryophyllene also readily 
yields a crystalline hydrate, whereas humulene does not. The latter, 
therefore, is to be regarded as a new distinct representative of the class 
of sesquiterpenes.2 
Adulteration. Oil from copaiba balsam is mentioned as an 
adulterant of hop oil. The higher sp. gr. and larger angle of rotation 
should, however, readily betray its presence. 
According to Chapman,3 the statement made by Personnes that 
the oil upon oxidation yields valerianic acid is incorrect. This acid, 
however, results upon oxidation of the extract of hops with per- 
manganate. 
98. Oil of Hemp. 
The various statements concerning the properties and composition 
of the volatile hemp oil differ considerably. 
According to Personne4 (1857) the oil from Cannabis indica is 
lighter than water and congeals at 12-15° to a butyraceous mass. 
It is said to consist of two hydrocarbons: the liquid canabene, CisHao, 
1) Berichte, 24, p. 682. 
2) For a detailed comparison of these two hydrocarbons see Phatm. Arch., 2, p. 273. 
3) Chern. Centralbl., 1898, II. p. 360. 
4) Journ. de Pharm. et de Chim., Ill, 31, p. 48. 338 
Special Part. 
which boils at 235-240°, and cannabene hydride, C12H24, which 
crystallizes from alcohol in scales with a fatty lustre. 
Valente1 (1880) examined an oil that was obtained from Italian 
Cannabis indica. It consisted principally of a sesquiterpene, C15H24; 
b. p. 256-258°; sp. gr. 0.9299 at 0°; [a]D = -10.81°. With hydrogen 
chloride it yielded a solid hydrochloride. The same sesquiterpene is 
found in the oil from the male inflorescence of Cannabis gigantea. 
Upon steam distillation of the female flowering plant, Vignolo2 (1885) 
obtained a mobile aromatic oil which boiled between 248 and 268° and 
did not congeal when cooled to -18°. When distilled over sodium, a 
stearoptene remained behind which was not further examined, whereas a 
sesquiterpene (b. p. 256°; sp.gr. 0.897 [?] at 15.3°) passed over. The 
formula C15H24 was established by elementary analysis and vapor 
density determination. A crystalline hydrochloride was not obtained. 
Schimmel & Co.3 obtained upon distillation of the non-flowering herb of 
Cannabis indica 0.1 p. c. of a mobile oil with narcotic but not unpleasant 
odor. At 0° it congealed to a butyraceous mass. Sp. gr. 0.932. 
Whether the sesquiterpene found in the oil is identical with any of 
the known compounds does not become apparent from the scant 
literature on the subject. The cannabene hydride of Personnes is 
possibly nothing more or less than paraffin which is frequently found 
in volatile oils. 
99. Sandalwood Oil. 
Oleum Ligni Santali. - Ostindisches Sandelholzol.-Essence de Santal. 
History. On account of its peculiar, very pleasant odor, as well as 
on account of its durability, sandalwood from Santalum album L. has 
been used since antiquity. Medicinally and economically it has an 
important and very interesting history. 
In mediaeval writings and in the later treatises on distillation, 
however, sandalwood is but seldom mentioned, the oil having' been 
used only in recent periods for medicinal and other purposes. Previous 
to this century the oil has been distilled by Saladin4 (1488), Gesner5 
(1555), and Hoffmann6 (1722). Neumann and Dehne7 (1780) ascer- 
tained the yield, and Chapoteaut8 first examined the oil in 1882. 
i) Gazz. chim. ital., 10, p. 540, & 11, p. 
191.-Berichte, 13, p. 2431, & 14, p. 1717. 
2) Gazz. chim. ital., 25, I, p. 110. 
3) Bericht von S. & Co., Oct. 1895, p. 57. 
4) Compendium aromatariorum, fol. 349. 
5) Ein kostlicher Schatz, p. 246. 
6) Observatonum physico-chemicarum, 
p. 69. 
7) Crell's Chemisches Journal, 3, p. 18. 
8) Bull. Soc. chim., II, 37, p. 303. Oils of the Santalaceae. 
339 
In Ceylon, distilled sandalwood oil is reported to have been used for 
the embalming1 of the dead bodies of native princes since the ninth 
century.1 
Origin and Preparation.2 Sai it alum album!;. (Family Santalaceae), 
a tree 6-10 m. high with dense foliage, is indigenous to the mountains 
of India and either grows wild or is cultivated in dry open places, 
rarely in forests.3 The wood of the trees growing in dry rocky 
mountainous soil is harder and richer in oil than that of trees cultivated 
in fertile soil. The territory which produces sandalwood is a strip 250 
miles long which extends from the Nilgiri mountains to the north and 
northwest through Mysore and Coimbatore to Canara. The tree 
grows from sea-level up to altitudes of 1000 m. The trees 
are property of the state. In the presidencies of Madras ' and 
Mysore the wood and the roots are arranged according to grade into 
18 classes4 and sold at auction. Wood destined for the European 
market is shipped via Tellichery or Bombay. A considerable amount is 
used in Asia for ritualistic purposes, and some of it is used in the 
primitive distillation of the oil at the place of production. Bidie5 
describes the process as follows: 
"The body of the still is a large globular clay pot, with a circular mouth, 
and is about 2% feet deep by about 6 feet circumference at the bilge. No 
capital is used, but the mouth of the still, when used, is closed with a clay lid, 
having a small hole in its centre, through which a bent copper tube about 5% 
feet long is passed for the escape of the vapor. The lower end of the tube is 
conveyed inside a copper receiver, placed in a large porous vessel containing- 
cold water. When preparing the sandalwood for distillation the white or sap 
wood is rejected, and the heart wood is cut into small chips, of which about 
2 maunds or 50 lbs. are put into the still. As much water is then added as 
will just cover the chips, and the distillation is carried on slowly for ten days 
and nights, by which time the whole of the oil is extracted. As the water from 
time to time gets low in the still, fresh supplies are added from the heated 
contents of the refrigerator." 
According to another report6 the distillation lasts 21 days and 
yields 2.5 p. c. of oil of a sp. gr. 0.980 and higher. The prolonged 
distillation is sufficient explanation for the dark color and high specific 
i) Pharmacographia, II ed., p. 599. 
2) J. L. Pigot, conservator of forests in Mysore, India, has written an interesting 
pamphlet on the sandalwood cultivation in India accompanying the exhibition of the 
British Colonial Governments at the Paris Exposition 1900. 
3) Holmes, Pharm. Journ., Ill, 16, p. 819.- Petersen, ibid., p. 757.-Kirkby, ibid., 
p. 857.-Sawer, Odorographia, vol. I, p. 315. 
*) Bericht von S: & Co., Oct. 1898, p. 44. 
5) Holmes, loc. cit. 
e) Chemist and Druggist, May 26, 1894. 340 
Special Part. 
gravity1 of this oil contaminated with decomposition products. Only 
a small part of it is brought to Europe, most of it being exported to 
China and Arabia. 
Sandalwood is also produced in eastern Java, and in the islands 
Sumba (Soemba or Tjendana) and Timor. This variety is brought 
into the market as Macassar sandalwood via Macassar (in the Celebes). 
It does not contain as much oil as the East Indian wood, but the oil 
can hardly be said to be inferior. 
Owing to a more complete comminution as well as to perfected 
apparatus for distillation a larger yield of oil is obtained in Europe 
than in India: from East India sandalwood 3-5 p. c., from Macassar 
wood 1.6-3 p. c. The European oil is light colored, has a pleasant 
odor and compares favorably with the Indian oil which is contaminated 
with empyreumatic products. 
Properties. East Indian sandalwood oil is a rather viscid, light 
yellowish to yellow liquid of peculiar, faint but persistent odor, and of 
an unpleasant, resinous, harsh taste. The sp. gr. of a normal oil lies 
between 0.975 and 0.980. The Indian oils, as already stated, have a 
higher specific gravity and a darker color due to decomposition pro- 
ducts. The angle of rotation varies between narrow limits, viz. -17 to 
-19°. With 5 p. of 70 p. c. alcohol, sandalwood oil yield a clear 
solution which is not rendered turbid by the further addition of alcohol. 
Upon age, especially under the influence of light and air, its solubility 
diminishes and it then yields turbid mixtures in the ratio mentioned. 
The santalol content determined by acetylization and calculated for 
C15H26O is 93-98 p. c. Under 14 mm. pressure about 95 p'. c. of the 
oil passes over between 155-170°,2 under ordinary pressure between 
275-295° (Umney,3 1895). The saponification number is 5-15. 
Composition. According to the investigation of Chapoteaut1 (1882) 
sandalwood oil consists almost exclusively of two substances C15H24O 
and C15H26O. The former boils at 300° and is regarded as an aldehyde, 
whereas C15H26O, with a boiling point of 310° is supposed to be the 
corresponding alcohol. Phosphoric acid anhydride abstracts, water 
from the oil, two hydrocarbons resulting: to the one boiling at 245° 
i) Conroy has shown experimentally that the sp. gr. of an oil is increased from 
0.989 when heated with water to 50° for ten days (Chemist and Druggist, Aug. 19, 
1893). 
2) Bericht von S. & Co., Oct. 1893, p. 37. 
3) Pharm. Journ., Ill, 25, p. 1044. The statement of Chapman arid Burgess, how- 
ever, (see under composition) do not fully agree with these data. 
*) Bull. Soc. chim., II, 37, p. 303. Oils of the Santalaceae. 
341 
the formula C15H22 is assigned; and to the other, b. p. 260°, the 
formula C15H24. When the oil is heated with glacial acetic acid to 150° 
the acetic ester of santalol, C15H25O. COCH3 results, also a substance 
C30H460 (?). 
Inasmuch as the low specific gravity of Chapoteaut's oil (0.945) 
would seem to indicate that it was adulterated, the above results should 
be accepted with caution. Furthermore he did not prepare a single 
crystalline derivative with which to prove the correctness of his formulas. 
For the aldehyde character of the substance C15H24O he does not supply 
a single proof. 
Chapman and Burgess1 have more recently published a preliminary 
report on santalol and the hydrocarbon obtained by its dehydration. 
Santalal, which they also regard as an aldehyde, was isolated by 
fractional distillation from the oil. The substance thus obtained boils 
at 301-306° and upon oxidation with potassium permanganate yielded 
santalenic acid, which crystallizes in thin laminae and melts at 76°. 
The hydrocarbon obtained by the dehydration of santalal with phos- 
phorus pentoxide boils at 140-145° under 25 mm. pressure; sp. gr. 
0.9359 at 15°; [<z]D- 4- 5°45'. It is unsaturated and combines directly 
with the hydrides of chlorine and bromine. Nitroso and nitrosochloride 
derivatives could not be obtained. 
As was first shown by Parry 2 (1895) sandalwood oil contains saponi- 
fiable substances. It is, therefore, assumed that part of the santalol 
occurs in the oil as ester. The acetylization of the oil, described under 
the next heading, shows that the bulk of the oil consists of an alcohol. 
Whether the formula, used in the calculation, viz. C15H26O, which was 
assigned to santalol by Chapoteaut is correct or not will have to be 
decided by further investigation. Schimmel & Co.3 have recently obtained 
saponification numbers with acetylized santalol which had been regener- 
ated from the phthalic acid compound which do not agree with the 
formula C15H26O. The results agree better with C15H22O, or else 
santalol is a mixture of different alcohols. 
Von Soden and Muller4 found in the non-alcoholic portion of the oil 
a sesquiterpene boiling from 261-262°; sp. gr. 0.898; aD --21°. It 
could not be identified as one of the known sesquiterpenes. It adds 
hydrochloric and hydrobromic acid and bromine, but yields no crystalline 
derivative. By hydration with glacial acetic acid and sulphuric acid a 
i) Proc. Chem. Soc., 1896, p. 140. 
2) Pharm. Journ., 55, p. 118. 
3) Bericht von S. & Co., Apr. 1900, p. 44 
4) Pharm. Ztg., 44, p. 258. 342 
Special Part. 
small amount of an alcohol boiling at 160-165° under 7 mm. pressure 
was obtained. They also found an acid melting at 154° in the oil. 
Guerbet1 has recently investigated sandalwood oil. but his results 
must be taken with caution as the oil investigated had a very low 
sp. gr. and was therefore either adulterated or else an abnormal 
distillate. He found the following constituents: 1. Two sesquiterpenes: 
a-santalene, b. p. 252-252.5°, sp. gr. 0.9134 at 16°, aD =-13.98°; 
/5-santalene, b. p. 261-262°, sp. gr. 0.9139 at 0°, «d - - 28.55°. The 
latter is identical with that found by Von Soden and Midler. 2. A 
mixture of two alcohols, C15H26O, of different rotatory power. 3. An 
aldehyde, C15H24O, santalal, b. p. 180° at 40 mm.; it has a strong 
pepperdike odor. Its semicarbazide melts at 212°.» 4. An acid. C15H24O2, 
santalic acid, a viscid, colorless liquid boiling at 210-212° at 20 mm. 
5. An acid, C1OH14O2, teresantalic acid, m. p. 157°. Small amounts of 
strongly smelling substances, to which the odor of the oil is principally 
due were found in the more volatile portions of the oil. 
Examination. Inasmuch as the physical constants of sandalwood oil 
are subject to slight changes only, additions of almost any nature can 
usually be detected by means of the specific gravity, optical rotation, 
and solubility in 70 p. c. alcohol. Cedar wood oil, the principal adulterant, 
is readily recognized by an increase in the optical rotation, lowering of 
the sp. gr. and the diminution of solubility. Very similar changes are 
produced by the oils from copaiba- and gurjun balsam; the former, 
however, usually diminishes the angle of rotation. 
West Indian sandalwood oil, which is sometimes used as adulterant, 
is dextrogyrate and is very difficultly.soluble in alcohol. It is reported 
that the oil distilled in India is sometimes adulterated with castor oil 
or with the fatty oil from the seeds of the sandalwood tree, which is 
used as illuminating oil. Additions of sesame oil, paraffin oil and 
linseed oil are also reported as not being infrequent. All of these, no 
doubt, betray their presence by their insolubility in 70 p. c. alcohol 
and by their high saponification number (naturally with the exception 
of paraffin oil). 
The best means of ascertaining the purity of a sandalwood oil. or 
the amount of an adulterant, is to determine the santalol content. Good 
oils mostly contain from 93-98 p. c., never less than 90 p. c. santalol. 
Parry2 first suggested the conversion of santalol, C15H26O, into 
its acetic ester, C15H25O .COCH3, by heating it with glacial acetic acid 
1) Compt. rend., 130, p. 417; Journ. de Pharm. et Chim., VI, 9, p. 224. 
2) Pharm. Journ.. 55. p. 118. Oils of the Santalaceae. 
343 
Fig. 62. 
Santa!wood Tree. 344 
in a- closed vessel to 150°; and to saponify the ester with alcoholic 
potassa. According to Schimmel & Co.,] however, it is more expedient 
to make the alcohol assay of volatile oils with acetic anhydride. 
The process is conducted as follows :2 
About 20 g. of sandalwood oil are gently boiled for 1% hour with an equal 
volume of acetic acid anhydride and a small amount of fused sodium acetate. 
The product is washed with water and soda solution and the resulting oil 
dried with anhydrous sodium sulphate. Of the dried oil, 2-5 g. are boiled 
with an excess of N/l potassa V. S. and the excess of alkali ascertained by 
titration with N/l sulphuric acid V. S. 
The amount of santalol is calculated with the aid of the following formula: 
a X 22.2 
P = 
s-(a X 0.12) 
P = Santalol content of the original oil. 
a - Number of cc. N/l potassa V. S. consumed. 
s - Amount of acetylized oil, expressed in grams, used for saponification. 
In most instances the determination 'of the physical constants will 
suffice to distinguish a pure oil from one adulterated. Positive assur- 
ance can, however, be had by making a determination of the santalol 
content. It is, therefore, as unnecessary as it is unscientific to resort to 
color reactions which have been suggested. 
100. South Australian Sandalwood Oil. 
Santalum preissianum Miq. known as "quandong" in Australia 
bears edible fruits known as native peaches. The wood is dark brown, 
of very dense and tough texture and unusually hard and heavy. It 
contains 5 p. c. of a viscid, cherry-red oil. sp. gr. 1.022. The odor is 
pleasantly balsamic reminding somewhat of roses. Upon standing the 
oil separates crystals, which by recrystallization are obtained in prisms 
melting at 104-105°.3 
Composition. The crystalline constituent of the oil has been examined 
by Berkenheim4 (1892). He found the melting point 101-103° and 
assigned to it the formula C15H24O2. The substance is an alcohol, the 
acetic ester of which crystallizes in hexagonal plates melting at 68.5 to 
69.5°. With phosphorus trichloride it yields a chloride, C15H23OCI, 
m. p. 119-120.5°; phosphorus pentachloride does not act on the 
Special Part. 
i) Bericht von S. & Co., Oct. 1895, p. 41. 
2) Bericht von S. & Co., Apr. 1897, p. 40. 
3) Bericht von S. & Co., Apr. 1891, p. 49; and Oct. 1891, p. 33. 
*) Zeitschr. d. Russ. phys. chem. Ges., 24, p. 688; Abstr. Chem. Centralbl., 1893, 
I, p. 986. Oils of the Santalaceae. 
345 
alcohol. The methyl ether obtained by means of the sodium compound 
of the alcohol is liquid. Potassium permanganate oxidizes it to a liquid 
acid C7H14O2. 
101. West Australian Sandalwood Oil. 
The wood of Santalum cygnorum Miq. (Fusanus spicatus R. Br.) 
is exported from Freemantle, W. Austr., and is known in the Singapore 
market as Swan river sandalwood. In India and China it is used as 
substitute for the Indian sandalwood from Santalum album. The wood 
contains 2 p. c. of oil having an unpleasant resinous odor; sp.gr. 0.9531- 
0.965 (Parry2); aD -+ 5°20'. 
West Australian sandalwood oil, therefore, has .very different proper- 
ties from those of the East Indian oil and cannot be used as a sub- 
stitute for the latter. 
The oil was distilled as early as 1875 by Schimmel & Co.; recently 
the distillation of the oil has been taken up in Freemantle.3 
Parry 2 found the saponification numbers 1.1-1.6. After acetylization 
he obtained saponification numbers which seemed to indicate an apparent 
santalol content of 75 p. c. Whether the alcohol of this oil is identical 
with that of S. album has not yet been established. 
103. Fiji Sandalwood Oil. 
The wood of Santalum yasi Seem4 from the Fiji islands was 
exhibited at the Colonial Exposition at South Kensington in 1886. 
Upon distillation it yielded 6^ p. c. of a volatile oil with a faint but 
not very delicate odor, thus rendering it unfit for perfumery.5 Sp. gr. 
0.9768; «□ =-25.5° (Mac Ewan.6 1888). 
103. African Sandalwood Oil. 
The botanical origin of this oil is not known. The wood designated 
sandalwood, from which this oil was distilled, was dark brown in color, 
very hard and tough and had been brought to Europe from Tamatave 
(Madagascar) via Zanzibar. Upon distillation it yielded 3 p. c. of a 
ruby red oil of the consistency of East Indian sandalwood oil, which it 
also resembled in odor.7 Sp. gr. 0.969. 
1) Bericht von S. & Co., Oct. 1888, p. 36; and April 1891, p. 43. 
2) Notes on Santal Wood Oil, p. 9; Chem. & Drug., 53, p. 708. 
3) Bericht-von S. & Co., Oct. 1898, p. 45. 
*) rharm. Journ., Ill, 16, p. 757 & 820. 
s) Bericht von S. & Co., Apr. 1888, p. 39. 
6) Pharm. Journ., Ill, 18, p. 661. 
7) Bericht von S. & Co., Apr. 1891, p. 49. 346 
Special Part. 
The wood is possibly identical with Hasoranto, a wood occurring in 
northern Madagascar which is said to possess properties similar to 
those of sandalwood.1 
104. Oil of Asarum Europaeum. 
Oleum Asari Europaei. -Haselwurzol.-Essence d'Asaret. 
The root of Asarum europaeum L. (Family Aristolochiaceae), which 
grows in the shady hard wood forests of Europe, Siberia and the 
Caucasus, upon distillation yields 1 p. c. of a viscid brown oil heavier 
than water with an aromatic odor and a peppery, burning taste. Often 
the oil congeals soon after distillation, sometimes crystals of asarone 
separate only after prolonged standing. Sp. gr. 1.018-1.068. On 
account of its dark color, the angle of rotation has not yet been 
observed. 
Composition. The separation of a solid substance from the oil was 
first observed by Gorz2 in 1814. Lassaigne and Feneulle3 (1820) seem 
to have regarded the stearoptene obtained by the distillation of the 
root with water vapor, as camphor. Further reports on this substance 
were made by Grager4 in 1830 and by Blanchet and Sell5 in 1833 
who made the first elementary analysis of asarum camphor. Schmidt0 
(1845) studied principally the crystallographic characters of the sub- 
stance to which he assigned the name asarone which is still in use. 
Rizza and Butlerow7 recognized that asarone contains three 
methoxy groups and assigned to it the formula C12H16O3, which was 
later shown to be correct. Poleck and Staats,8 however, found at first 
the formula CsHioOo, later C13H17O3 and finally C13H18O3. 
The relative position of the three methoxy groups was ascertained 
by Will9 in 1888 who showed that asarone is a derivative of oxy- 
hydroquinone. The recently accomplished synthesis of asarone by Gat- 
termann10 shows it to have the formula CgH2 . C3H5. (0CH3)3 = 1:2 :4: 5. 
i) Odorographia, vol. 1, p. 325. 
2) Pfaff, System der Mat. Med., vol. 3, p. 230. 
3) Journ. de Pharm., 6, p. 561.-Trommsdorff's Neues Journ. d. Pharm., 5, II, p. 71. 
4) Dissertatio de Asaro Europaeo. Gotting. 
s) Liebig's Annalen, 6, p. 296. 
6) Liebig's Annalen, 53, p. 156. 
7) Berichte, 17, p. 1159.-Zeitschr. d. Russ. phys. chem. Ges., 19, I, p. 1; Berichte 
20, Referate, p. 222. 
8) Berichte, 17, p. 1415.-Chem. Zeitung, 9, p. 1464.-Jahresb. f. Pharm., 1885. 
p. 331.-Tagebl. der 59. Versammlung deutscher Naturforscher, 1886, p. 127.-Jahresb. 
f. Pharmacie, 1886, p. 233. 
9) Berichte, 21, p. 614. 
io) Berichte, 32, p. 289. Oils of the Aristolochiaceae. 
347 
Eykman1 made a study of the structure of the CsHs-radical in 1889. 
From the index of refraction and the dispersion he came to the con- 
clusion that asarone was a propenyl and no allyl-derivative. Properties 
and derivatives of asarone are described on p. 181. 
Upon fractionation of the constituents accompanying- the asarone, 
Petersen2 obtained a laevog'yrate fraction boiling at 162-165° which 
contained 1-pinene. Upon direct bromination it yielded a liquid mono- 
bromide; after heating to 250° dipentene tetrabromide melting at 122° 
was obtained. 
The higher boiling constituents distilled principally at about 250° 
yielding a fraction of the composition C11H14O2. With sodium nitrite 
and acetic acid a nitrite melting at 118° was obtained. When heated 
with hydrogen iodide, methyl iodide was split off. Upon oxidation with 
potassium permanganate, veratric acid was formed. Petersen (1888), 
therefore, regarded the substance boiling at 250° as methyl eugenol. 
Mittmann3 (1889), however, is of the opinion, that it is not methyl 
eugenol, but methyl isoeugenol, basing his conclusion on comparisons 
made with the synthetic methyl ether prepared from bay oil eugenol; 
also with the natural ether occurring in bay oil. Inasmuch, however, 
as the phenol from bay oil, from which Mittmann prepared the methyl 
ether, must have been a mixture of eugenol and chavicol, as was shown 
later, the methyl ether of Mittmann can hardly have been pure and 
thus his comparisons are rendered valueless. It, therefore, still remains 
an open question whether asarum oil contains the methyl ether of 
eugenol or of isoeugenol. 
The highest boiling fraction is colored green by a substance not yet 
examined. 
105. Oil of Canada Snake-root. 
Oleum Asari Canadensis.-Canadisches Schlangenwurzelol.-Essence de 
Serpentaire du Canada. 
Asarum canadense L. is known in the United States as Canada snake- 
root, wild ginger, and Canadian asarabacca. The rhizome contains a 
fragrant volatile oil which is used extensively in perfumery in North 
America. Upon distillation, the dry rhizome yields 3.5-4.5 p. c. of oil. 
The rootlets contain somewhat less oil than the rhizome. 
i) Berichte, 22, p. 3172. 
2) Arehiv d. Pharm., 226, p. 89. 
3) Arehiv d. Pharm., 227, p. 543. 348 
Special Part. 
Properties. The oil has a yellow to yellowish-brown color and a 
strong but pleasant aromatic odor and taste. It is soluble in 2 p. of 
70 p. c. alcohol; sp. gr. 0.93-0.96. 
Composition. According to Power1 (1880) the oil contains the 
following subtances: 
1. A very small amount of an inactive terpene, CioHie, boiling at 
163-166° which possibly is identical with pinene.2 
2. Asarol alcohol CioHisO; b. p. 196-199°; sp. gr. 0.874 at 17°; 
«d= + 4°. Its odor reminds of coriander and in the oil it is partly 
combined with acetic and valerianic acids as ester. It appears to be 
identical with linalool. 
3. An alcohol CioHisO, isomeric with the former but boiling betw- 
222-226°. Its odor resembles that of geranium oil and possibly con- 
sists largely of geraniol. 
4. Methyl eugenol. Fraction 254-257° has the composition 
C11H14O2, and upon oxidation with permanganate yields an acid which 
Petersen has recognized as veratric acid. Methyl eugenol may, therefore? 
be considered as one of the constituents of the oil of Asarum eanadense L. 
5. Fraction 275-350° is blue, has no constant boiling point, and 
is indefinite in composition. 
106. Oil of Virginia Snake-root. 
The rhizome and roots of Aristolochia serpent aria Tj. and of J. reti- 
culata Nutt. (Family Aristolochiaceae') are official in the U. S. Phar- 
macopoeia under the title of Serpentaria. As the rhizomes of both plants 
are similar morphologically and as to their therapeutic properties, so 
the oils from both are closely related. 
Aristolochia serpentaria L. upon distillation yields 1-2 p. c. of oil 
of valerian-like odor and a sp. gr. of from 0.98-0.99. Spica3 (1887) 
has shown the principal constituent to be borneol. 
Aristolochia reticulata Nutt., distilled in small quantities by Peacock4 
(1891) yielded but 1 p. c. of a golden-yellow oil of camphor- and 
valerian-like odor. Sp. gr. 0.974-0.978; - 4°. The oil contained a 
terpene boiling at 157°, probably pinene; also borneol, which is com- 
bined with an acid not yet identified. 
1) On the constituents of the rhizome of Asarum eanadense L. Dissertation, Strass- 
burg; Proc. Am. Pharm. Assoc., 28, p. 464. 
2) Comp. Petersen, Arch. d. Pharm., 226, p. 123; Berichte, 21, p. 1064; also 
Power, Pharm. Rundschau, 6, p. 101. 
3) Gazz. chim. ital., 17, p. 313; Jahresb. f. Pharm., 1887, p. 45. 
4) Am. Journ. Pharm., 63, p. 257. Oils of the Chenopodiaceae. 
349 
Osterluzeibl. 
The oil from the •rhizome of Aristolochia clematis L. was prepared 
by Winckler1 in 1849 and by Frickhinger2 in 1851, the former obtaining 
0.4 p. c. Walz3 in 1853 distilled the entire plant and obtained a 
golden-yellow, viscid oil of acid reaction and a sp. gr. of 0.903. 
108. American Wormseed Oil. 
Oleum Chenopodii Anthelmintici. - Chenopodinmbl oder amerikanisches Wurm- 
samenbl.-Essence de Semen Contra d'Ambrique. 
Origin. In the neighborhood of Baltimore the oil is distilled from 
the entire plant, Chenopodium ambrosioides L. var. anthelminticum 
Gray.1 Westminster in western Maryland is the center of production. 
The fruits are said to owe their anthelmintic properties to the oil they 
■contain. Upon distillation, the fruit yields 0.6-1 p. c., the leaves 
about 0.35 p. c. of volatile oil. 
Properties. The odor of the colorless or yellowish oil is very 
penetrating, offensive, camphor-like; the taste bitter and burning. 
The sp. gr. of good commercial oils has been found to be 0.97; the 
rotatory power between -5 and -6°. A clear solution resulted with 
10 p. of 70 p. c. alcohol. 
Oils with a lower sp. gr. and slight dextro rotation were not soluble 
in 70 p. c. alcohol and were shown to be adulterated with American 
turpentine oil. The data obtained from an oil distilled by Schimmel & 
Co. show that a lower sp. gr. and a lesser solubility alone cannot be 
regarded as proof of adulteration. In order to justify the conclusion 
that turpentine oil is present, pinene, which does not appear to occur 
in the pure oil, should be shown to be present. 
An oil distilled by Schimmel & Co. from the seed5 had a sp. gr. of 
0.900; «d =-18° 55'. The oil from the leaves had a sp. gr. of 0.879;° 
and an angle of rotation of -32° 55'. Neither of these two oils was 
clearly soluble in 70 p. c. alcohol. 
The seed of Chenopodium ambrosioides L., a closely related plant, 
are used in Brazil as a popular anthelmintic. According to Peckolt7 
they contain a volatile oil with a strong aromatic odor, bitter, burning 
taste, sp. gr. 0.943. 
107. Oil from Aristolochia Clematis. 
i) Jahrb. f. prakt. Pharm., 19, p. 71. 
2) Repert. f. d. Pharm., III., 7, p. 1. 
3) Jahrb. f. prakt. Pharm., 26, p. 65. 
4) Am. Journ. Pharm., 22, p. 304; 26, p. 503. 
5) Bericht von S. & Co., Apr. 1894, p. 56. 
6) Ibid., p. 57. 
7) Pharm. Rundschau, 13, p. 89. 350 
Special Part. 
Fig. 63. 
Wormseed Oil Distillation in Maryland. Oils of the Ranunculaceae. 
351 
The leaves of this plant yielded upon distillation 0.25 p. c. of a 
volatile oil with a repulsive camphor-like, narcotic odor, reminding- of 
tri methylamine, and sp. gr. 0.901.1 
Composition. The constituents of American wormseed oil have as 
yet been but little investigated. According to an examination conducted 
by Garrigues2 in 1854 the oil contains a hydrocarbon boiling at 176° 
(possibly limonene), and a liquid substance CioHigO. 
109. Oil from Paeonia Moutan. 
The rootbark of Paeonia moutan Sims. (Family Ranunculaceae~) is 
much used as a drug in Japan and China. On the inner surface as well as 
on surfaces made by fracture, white prismatic crystals of paeonol are 
found. These can be obtained by distillation with water vapor, or 
better by extraction with ether. The crude oil (yield 3-4 p. c.)3 is 
purified by shaking the ethereal solution with soda solution, which 
takes up the impurities only; then combining- the paeonol with sodium 
hydrate and regenerating it with sulphuric acid. 
Paeonol was first isolated by Martin and Jagi4 (1878). Basing 
their conclusions on the elementary analysis of a calcium derivative, 
these chemists regarded it as a fatty acid closely related to caprinic 
acid. According to Nagai5 (1891) paeonol has an aromatic odor, 
crystallizes in colorless, shining needles melting- at 50°, and has the 
composition CgHioO.6 It is sparingly soluble in cold water, readily in 
hot water, alcohol, ether, benzene, chloroform and carbon disulphide. 
The aqueous as well as the alcoholic solution is colored reddish-violet 
by ferric chloride. Aqueous solutions of the caustic alkalies dissolve 
paeonol and form well crystallizable derivatives. 
According to Nagai, paeonol is p-methoxy-o-hydroxyphenyl methyl 
ketone: CgHs. COCH3. OH. 0CH3 = l: 2 :4. When fused with potassa, 
or when boiled with hydriodic acid, paeonol yields resacetophenone, 
CgH.3 . COCH3. OH: OH = 1:2:4, m. p. 142°. Acetyl paeonol, m. p. 46.5° 
is oxidized with permanganate to p-methoxysalicylic acid, CgH3 . C00H. 
OH . OCH3 = 1:2:4. The oxime of paeonol crystallizes in fine needles, the 
phenyl hydrazone in light yellow needles melting at 170°.6 Tahara7 in 
1891 prepared paeonol synthetically by methylation of resacetophenone. 
1) Bericht von S. & Co., Apr. 1891, 
p. 49. 
2) Am. Journ. Pharm., 26, p. 405. 
3) Berichte, 19, p. 1776. 
4) Archiv d. Pharm., 213, p. 335. 
5) Berichte, 24, p. 2847. 
6) Tiemann in 1891 (Berichte, 24, p. 
2854,) found the m. p. of pure paeonol at 
48°. Further derivatives of paeonol are 
described: Berichte, 25, pp. 1284, 1306, 
and 29, p. 1754. 
7) Berichte, 24, p. 2459. 352 
Special Part. 
IIO. Oil of Nigella Sativa. 
The seeds of Nigella, sativa L. (Ger. Schwarzkiimmel) yield 0.46 p. c. 
of a volatile oil of a yellow color, which does not fluoresce and has 
an unpleasant odor. Sp. gr. 0.875; aD = + l°26'. It boils between 
170-260°.1 
111. Nigella Oil from Nigella Damascena. 
The seeds of Nigella damascena L., which are sometimes also called 
Schwarzkiimmel, yield upon distillation2 0.5 p. c. of an oil with a 
beautiful blue fluorescence, that possesses the agreeable odor and taste 
of the wild strawberry. Sp. gr. 0.895 to 0.906; aD = + l°4/. In 90 p. c. 
alcohol the oil is imperfectly soluble, but miscible with absolute alcohol 
in all proportions. 
The fluorescence of the oil is due to damascenine, C1OH15NO3, which 
boils at 168° and melts at 27°. According to Schneider3 it belongs to 
the alkaloids: with acids it forms crystallizable salt, with the chlorides 
of platinum, gold and mercury it forms double salts. With the general 
alkaloidal reagents it yields the reactions characteristic of alkaloids: 
with iodine potassium iodide a purplish-brown precipitate; with potas- 
sium bismuth iodide a brown; with potassium mercuric iodide and 
phospho molybdic acid white precipitates. Solutions of damascenine 
containing an excess of nitric acid are colored a beautiful violet upon 
standing (damascenine red). Upon heating of the nitrate, damascenine 
blue results.4 
Pommerehne5 has recently studied damascenine which was isolated 
by extracting with dilute hydrochloric acid, making alkaline with soda 
and shaking out with petroleum ether. The blue fluorescent petroleum 
ether solution is then again shaken with hydrochloric acid and the acid 
solution evaporated. Pommerehne sets up the formula CsH^OCHs^NO, 
based on an analysis of the platinum double salt and a methyl deter- 
mination. 
1) Bericht von S. & Co., Apr. 1895, p. 74. 
2) Bericht von S. & Co., Oct. 1894, p. 55. 
3) Pharm. Centralh., 31, pp. 173 and 191. Comp, also Inaug. Dissertation of the 
same author, Erlangen 1890. 
4) The earlier reports are frequently contradictory, because the examinations were 
conducted m part with the seeds of Nigella damascene L., in part with those of Nigella 
sativa L.-Greenish (1882), Pharm. Journ., Ill, 12, p. 681.-Reiusch (1841), Jahrbuch 
f. prakt. Pharm., II, 4, p. 384.-FJiickiger (1854), ibid.. Ill, 2. p. 161. 
5) Archiv d. Pharm., 237, p. 475. Oils of the Magnoliaceae. 
353 
112. Champaca Oil. 
The oil distilled from the flowers of the champaca tree, Michelin cham- 
paca L. (Family Magnoliaceae), which grows in Java and the Philippine 
islands, possesses decided fragrance, which strongly resembles that of the 
flowers of Acacia farnesiana Willd., but also reminds of that of violet and 
ylang-ylang.1 Inasmuch as the oil is very costly it can be had, if at 
all, in comparatively small quantities only. 
The rather mobile oil is of a light yellow, or reddish-yellow to 
brownish color. Sp.gr. 0.907-0.935; «d = -12°18' to-52°. Saponi- 
fication number 77 (one determination). In alcohol it is difficultly 
soluble, for it does not even give a clear solution with 10 p. of 90 p. c. 
alcohol. 
As to its composition, hardly anything is known. Like ylang-ylang 
oil it has a rather high ester content, and like this oil contains benzoic 
acid (m. p. 121°) which sometimes crystallizes from the oil.2 
113. Oil from Michelia Longifolia. 
The flowers of Michelia longifolia Bl. (Family Magnoliaceae), which 
grows in Java, yield upon distillation a limpid, very volatile oil. the 
odor of which reminds of basilicum. Sp. gr. 9.883; «d - -12° 50'.3 
114. Star Anise Oil. 
Oleum Anisi Stellati. - Steruanisol. -Essence de Badiane.1 
The various species of Illicium are indigenous to middle and 
southern East-Asia, Japan, and the islands of the Chinese and 
Indian seas. On account of the similarity of the fruits of the different 
species, the statements concerning the origin of the various commercial 
varieties have been contradictory up to the present time. Linne first 
called the tree, which belongs to the Magnoliaceae, Badanifera anisata,5 
later Illicium anisatum.® A variety cultivated in Japan, especially in 
i) Guaiac oil from Bulnesia sarmienti (see this) which has recently been intro- 
duced into the market as champaca wood oil has nothing in common with genuine 
champaca oil. 
2) Bericht von S. & Co., Apr. 1882, p. 7; Apr., 1894, p. 58; Oct. 1894, p. 10; Apr. 
1897, p. 11. 
3) Bericht von S. & Co., Apr. 1894, p. 59. 
4) In Europe, star anise was formerly known as Anis de la Chine, de la Sib^rie, 
Foenieulum sinense, Badian. The last name, taken from the Arabian BAdiyAn for 
fennel, was employed by Pierre Pomet, the author of the Histoire general des drogues 
(livre 1, p. 43), published in 1694, and remained in use for a long time. . 
s) Mat. med. e regno vegetabile, lib. 1, p. 180. 
s) Species plantarum, p. 664. 354 
Special Part. 
Fig. 64. 
Star Anise Plantation in the Vicinity of Langson (Tonkin). Oils of the Magnoliaceae. 
355 
the groves of Buddhist temples, was described in 1690 by Kampfer,1 
in 1781 by Thunberg2 and again in 1825 by von Siebold,3 who termed 
Fig. 65. 
Tonkin Distilling Apparatus. 
it Illicium japonicum, which term he changed to I. religiosum in 1837. 
Jos. Hooker the younger, showed in 1886 that the official and com- 
i) Amoenitates exoticae, p. 880. 
2) Flora japonica, p. 235. 
3) Het gezag van Kampfer, Thunberg, Linnaeus en anderen, omtrent den botanischen 
oorsprong van den steranijs des Handels. Leiden, 1837, p. 19. - Rein, Japan, 1886^ 
vol. 2, pp. 160 and 307. 356 
Special Part. 
mon star anise is not derived from the species termed 1. anisatum by 
Linne, and named the tree I. verum. 
The volatile oil was distilled in the course of the eighteenth century, 
but did not find wider application until the nineteenth century. As to 
its constituents and percentage of volatile oil, star anise was examined 
by Neumann and Cartheuser,1 later in 1818 by Meissner.2 
Preparation. At present, star anise oil is imported principally 
from the northwestern provinces of China and from the French colony 
Tonkin. In both districts it is prepared- on a large scale. 
The distillation is conducted in a primitive manner. According to 
English3 and French reports the method in Tonkin is the same as in 
the Chinese provinces. 
Fig. 6G. 
Chinese Distilling Apparatus. 
The still (fig. 65) consists of a strong, vapor-tight wooden barrel or of an 
iron cylinder, the bottom of which is frequently perforated. This rests on an 
hemispherical or flat iron kettle fastened in a hearth of masonry and heated 
by direct fire. The upper part of the barrel or cylinder is so constructed 
that the charging and discharging can take place from above, and that the 
vapors escape through a central opening and tube into the condenser situated 
above. This consists usually of an earthenware jar covered by a tin kettle. 
The latter is filled with water, supply and exit tubes consisting of bamboo. 
The barrel or cylinder is filled with comminuted star anise. After all 
joints have been sealed, the water in the kettle below is heated. The vapors 
i) Elementa chymiae-medicae, vol. 2, p. 327. 
2) Buchholz, Taschenb. f. Seheidekiinstler. u. Apoth. auf das Jahr 1818 und 1819, p. 1. 
3) Decennial Reports on the trade, etc., in China and Corea. Statistical series No. 6, 
1882 to 1891, p. 659. Oils of the Magnoliaceae. 
357 
of water and oil condense on the lower surface of the hemispherical upper wall 
of the condenser and flow through a tinned tube from the condenser basin 
into a basin usually made of wood and lined with tin. 
The Chinese apparatus is not essentially different. The receiver, however, 
consists of two chambers and is so arranged that the lighter oil flows into the 
second chamber, whereas the water is prevented from flowing over by means 
of a siphon (tig. 66). 
In Tonkin a kind of Florentine flask is used and the aqueous distillate is 
allowed to flow back into the still. 
As a rule, the stills contain 3 piculs = 180 k. of star anise. The distillation 
lasts about 45 hours. The yield averages 5% k. or about 3 p. c. of oil, which 
is shipped in lead canisters of 7.5 k. 
Composition. Anethol is the most important and valuable con- 
stituent of star anise oil. The congealing point shows whether the oil 
is relatively rich in anethol; an exact method of assay has not yet 
been devised. Inasmuch as from 80 to 90 p. c. of anethol can be 
obtained from good anise oil by repeated freezing, the true content may 
be regarded as somewhat higher. Anethol was first recognized in 
star anise oil by Cahours1 in 1841, who established the identity between 
the stearoptene of fennel, anise and star anise oils. Shortly after- 
ward, Persoz2 obtained anisic acid from anethol by oxidation with 
chromic acid. He called the acid badianic acid. For properties and 
derivatives of anethol see p. 179. 
The remaining 10-20 p. c. of the oil consist of a mixture of at 
least five different substances. The lowest fraction 157-175° contains 
two terpenes.3 
1) d-Pinene: b. p. 157-163°; «d = + 21° 30'; m. p. of the nitrol- 
benzylamine 122-123°. 
2) 1-Phellandrene: b. p. 170-175°; aD=-5°40'; m. p. of the 
nitrite 102°. 
3) Methyl chavicol (para, methoxy allyl benzene), the isomer of 
anethol (para methoxy propenyl benzene), has not yet been isolated in 
a pure form from star anise oil. Judging from the properties of the 
corresponding fraction its presence can not well be doubted.1 If star 
anise oil is freed as far as possible from anethol by repeated freezing, 
a mobile oil is obtained which suffers striking changes when boiled with 
alcoholic potassa (Eykman's method). The boiling point rises, the 
index of refraction is increased, and upon freezing large amounts of 
1) Conipt, rend., 12, p. 1218; Liebig's Annalen, 35, p. 313. 
2) Conipt, rend., 13, p. 433; Liebig's Annalen, 44, p. 311. 
3) Bericht von S. & Co., Apr. 1893, p. 56. 
4) Bericht von S. & Co., Oct. 1895, p. 6. 358 
Special Part. 
anethol are again separated. This has evidently been formed by the 
action of the potassa on the preexisting methyl chavicol. 
4) Hydroquinone ethyl ether,1 CeH^OH). OC2H5, but mere traces of 
which are present, can only be obtained by shaking out large amounts 
of star anise oil with aqueous alkali. When pure it crystallizes in color- 
less laminae of pearly lustre which melt at 64°. 
5) Safrol is considered to be present though a satisfactory proof of 
its presence has not yet been given. Oswald2 (1891) attributes the 
difference in odor of star anise oil from that of anise oil to safrol. 
Two substances, which are found not only in star anise oil, but in 
every oil containing anethol are anisic aldehyde and anisic acid. They 
are said not to preexist in the oil but are formed by oxidation due to 
exposure to air. The older the oil. the larger the amount of these two 
substances present. 
Properties. Star anise oil is a colorless or yellowish liquid of 
great refractive power. On account of the high percentage of anethol 
it congeals in the cold. It has an anise-like odor; an intensely sweetish1 
taste; sp. gr. 9.98 to 0.99; rotation slightly laevogyrate, «p up to 
- 2°.3 The oil forms a clear solution with three or more parts of 
90 p. c. alcohol. The congealing point lies between +14 and + 18°.4 
Under certain conditions, especially in closed vessels and when slowly 
cooled, star anise oil can be cooled far below its congealing point with- 
out being solidified and may then remain liquid for a long time. The 
congealing is usually induced by some external impetus, by a particle 
of dust or by shaking, and takes place the more readily the lower the 
temperature of the oil. The best way to cause a cooled oil to solidify 
is to drop into it a particle of anethol or to scratch the inner side of 
the dish with a glass rod. 
It is noteworthy that an old oil which has been kept for a longer 
period in partly filled containers or which has been exposed to the air 
by repeated melting, gradually loses its power to congeal on account 
of the partial oxidation of anethol to anisic aldehyde and anisic, acid. 
i) Bericht von S. & Co., Oct. 1895, p. 6. 
2) Arehiv d. Pharm., 229, p. 86. 
3) In a few instances slight dextro rotation has been observed. 
4) Recently oils have found their way into the market that had a lower congealing 
point but were unadulterated. The properties of five of such oils were as follows: 
sp. gr. 0.988-0.998; «d=+0°11' to +0°32'; congealing point +8% to 13%°; all 
soluble in 1% p. of 90 p. c. alcohol. These "flower oils," as they ha ve been designated, 
are not, however, obtained from the flowers of the star anise tree, but from the unripe 
fruits which are picked to facilitate the ripening of the other fruits. Though not 
adulterated, these oils cannot be regarded as the equivalent of the oil from the ripe 
fruit and should not be sold in its place. (Bericht von Schimmel & Co., Oct. 1898, p. 47.> Oils of the Magnoliaceae. 
359 
In order to distinguish between star anise oil and anise oil a color 
reaction1 with alcoholic hydrogen chloride has been recommended, 
which, however, does not yield reliable results. Star anise oil is said 
to give a yellowish to a brownish color with this reagent, whereas 
anise oil is colored blue or red according to the degree of concentration 
of the acid. 
Examination. In order to detect adulterations and to test for 
a normal anethol content, the specific gravity, solubility and congealing 
point should be determined. 
Formerly adulterations were never observed and it is only in recent 
years that it has occurred to the Chinese to add petroleum to the oil. 
This addition causes a lowering of the specific gravity and of the con- 
gealing point and also influences the solubility in 90 p. c. alcohol. 
Whereas pure oil dissolves without turbidity in three or more parts of 
90 p. c. alcohol, oil adulterated with petroleum produces a turbid 
mixture from which the petroleum separates in the form of drops upon 
prolonged standing. 
In order to isolate the petroleum, the oil is distilled with water vapor and 
the first distillate collected separately, and treated first with concentrated 
sulphuric acid and then with concentrated nitric acid. The volatile oil is thus 
destroyed whereas the petroleum remains almost unchanged and can be 
recognized by its general properties. High boiling mineral oils are non-volatile 
with water vapor and will be found in the residue. 
The following table2 shows in how far'the properties of star anise 
oil are modified by the addition of from 5 to 10 p. c. of petroleum. 
Sp. gr. 
Congealing 
point 
Solubility in 90 p. c. alcohol 
Pure oil 
0.986 
+ 18° 
1:2.2 and more. 
The same with 5 p. e. 
petroleum 
The same with 10 p. c. 
petroleum 
0.978 
0.970 
+ 16%° 
+ 14%° 
( not clearly soluble in 10 parts 
1 of 90 p. c. alcohol. 
From the above data it becomes apparent that adulteration with 
petroleum' is more readily recognized by the determination of the specific 
gravity and solubility than by the congealing point. For this reason 
an oil should be required to stand the tests of specific gravity and 
solubility even if it conforms with the requirements made with regard 
to the congealing point. 
i) Eykman (1881), Mittheil. d. deutsch. Gesellsch. f. Natur- und Volkerkunde Ost- 
asiens, 23.-Umney, Pharm. Journ., Ill, 19, p. 647.-Squire, ibid., Ill, 24, p. 104.- 
Umney, ibid., Ill, 25. p. 947. 
2) Bericht von S. & Co.. April 1897, p. 42. 360 
Special Part. 
On the other hand, unadulterated oils that are normal with regard 
to specific gravity and solubility, may be defective as to anethol content. 
Inasmuch as the oil is valuable in the ratio of its anethol content, and 
as the congealing point rises with the latter, the congealing point may 
be regarded as a direct measure of the quality of the oil. 
Determination of the congealing point. When taking a 
sample of the oil, care should, be taken that the contents of the canister 
are completely melted and well mixed. 
200 g. of oil are transferred to a flask and filtered if necessary.1 An 
accurate thermometer, indicating half degrees, is dipped into the oil and this 
cooled by means of chopped ice or ice water. During the process of cooling 
shaking is to be avoided, neither is the liquid to be stirred with the thermometer 
in order to avoid premature congealing. After the oil has been cooled to about 
+ 6 to 8°, crystallization is induced by the addition of a particle of solid 
anethol or solid star anise oil, or by scratching the inner wall of the flask with 
the thermometer. During the solidification, the mixture is continuously stirred 
in order to facilitate the process of congealing. In the course of this operation 
the temperature rises rapidly. The highest point which the mercury reaches is 
the congealing point. 
The determination can be made with less material with the aid of 
Beckmann's apparatus for the determination of molecular weights 
described on p. 187. 
In order to obtain uniform results, care should be exercised to 
induce crystallization at a temperature of about 6 to 8°. The melting- 
point of the oil would be just as serviceable as the congealing point 
were it not for the fact that the latter can be ascertained much more 
accurately. The congealing point of star anise oil should not be below 
15°. The oil imported from Tonkin usually has a higher congealing point. 
Production and Commerce. The production of star anise is restricted 
to the Chinese districts Lung-chow (province Kwang-si), Po-se (province 
Kwang-tung), and to the neighborhood of Lang-son in the French 
colony of Tonkin. The yield is subject to considerable fluctuations, being- 
only 1,922 piculs in 1895, whereas it was 16,138 piculs in 1892. During 
the last 10 years between 3,000 and 13,000 piculs of star anise, or 
180,000 to 780,000 k., taken for export, were shipped exclusively via 
Pak-hoi to Hong-kong which is the world's market for this drug. 
A still larger quantity of star anise is used for the distillation of the 
oil. The two Chinese districts mentioned above produce about 1,500 to 
i) Oils that are not perfectly clear can be cooled below the congealing point only 
with difficulty. The suspended solid particles induce crystallization as soon as the 
temperature has been reduced to several degrees below the congealing point. Oils of the Magnolia,ceae. 
361 
2.000 piculs or 3,000--1,000 cases which are also shipped to Hong-kong 
via the port Pak-hoi. The Tonkin-Chinese border district has produced 
about 400 piculs or 800 cases in recent years. This is taken by rail 
and steamer to the Tonkin-Chinese port Hai-phong whence, favored by 
special duty regulations, it is shipped exclusively to France. On account 
of its high anethol content, it has met with special favor in recent years 
and is preferred to the Chinese oil. 
Total export of star anise oil during the last 10 years: 
Year 
From Pak-hoi and Lappa 
(Macao) 
From Hai-phong 
(Tonkin) 
Total 
1888 
976 Piculs1 
150 Piculs 
1126 Piculs 
1889 
810 " 
200 " 
1010 " 
1890 
1294 " 
230 " 
1524 " 
1891 
507 " 
288 " 
795 " 
1892 
1803 " 
44 
1803 " 
1893 
862 " 
* 4 
862 " 
1894 
1998 " 
1998 " 
1895 
489 " 
13 " 
502 " 
1896 
2369 " 
435 " 
2804 " 
1897 
1398 " 
399 " 
1797 " 
The price of the oil is also subject to considerable fluctuations. 
During the last twenty years it has varied between $1.30 and $2.25 
per pound. Since several years the congealing point serves as basis for 
its valuation. The principal Hongkong and Tonkin firms are familiar 
with the method and have the necessary equipment. 
115. Star Anise Leaf Oil. 
The natives of the Pe Se district obtain an oil by distilling the 
leaves and even the branches of star anise trees. The yield is about 
0.75 p. c. (Simon2). 
In odor the oil differs slightly from that of the fruit, the odor of 
anisic aldehyde being far more pronounced. It has a higher sp. gr. than 
the oil 'from, the fruit, 0.9878 at 15.5°; «d= + 1°.3 According to 
Umney3 the proportion that boils above 230° is quite different from 
that of the oil from the fruit. 
Star anise fruit oil. 
Star anise leaf oil. 
Below 225° 
20 p. c. 
10 p. c. 
226-230° 
65 " 
60 " 
Above 230° 
15 " 
30 " 
!) 1 Picul = 2 <-ases with a net content of 30 kilo. During the years 1897 and 
1898 the total export has been valued at $5.50,000.00 and $375,000.00 respectively. 
2) Chern. & Druggist. 53, p. 875. 
3) Chem. & Druggist, 54, p. 323. 362 
Special Part. 
The anethol content is small and its congealing point correspondingly 
low, for which reason it has been designated as liquid star anise oil1 and 
appears to be used as an adulterant and a substitute for the oil from 
the fruit. 
116. Japanese Star Anise Oil. 
The oil from the leaves of Illicium religiosum Sieb. (Japanese Shikimi), 
the Japanese star anise tree, which is ill-famed on account of its poisonous 
fruits, was examined by Eykman2 in 1881. Upon distillation of the 
leaves he obtained 0.44 p. c. of volatile oil, sp. gr. 1.006 at 16.5°, 
[«]d = - 8° 6'. It contains a terpene (b. p. 173-176°; sp. gr. 0.855; 
«d =- 22.5°) and 25 p. c. of a liquid anethol which yields nitroanisic 
acid melting at 174°. 
According to a second contribution by the same author3 (1885) the 
shikimi leaf oil consists of eugenol, a terpene "shikimene", (b. p. 170°; 
sp. gr. 0.865) and "shikimol" or safrol. It is noteworthy that Eykman 
determined on "shikimol" the constitution of safrol CsHs: C^CH^CsHs). 
The fruits of the Japanese star anise tree also contain a volatile 
oil4 of a disagreeable odor, which has nothing in common with that of 
the true star anise oil. Sp. gr. 0.984; «d =- 4° 5'. 
117. Winter's Bark Oil. 
According to Arata and Canzoneri5 (1889), the genuine Winter's 
bark of Drimys winter! Forst, contains 0.64 p. c. of a dextrogyrate 
volatile oil. This consists principally of a hydrocarbon, "winterene" 
boiling at 260-265°, which the authors regard as a triterpene. Probably, 
however, it is a sesquiterpene. 
118, 119. Ylang-Ylang Oil and Cananga Oil. 
Oleum Anonae. Oleum Canangae.-Ylang-Ylangol. Canangaol.-Essence de 
Ylang-Ylang. Essence de Cananga. 
Origin and History. Ylang-ylang oil is obtained by the distillation 
of the flowers of Cananga odorata, Hooker et Thomson (Family 
Anonaceae). This tree occurs in the Malay Archipelago and in the 
Philippines and is cultivated in the latter and throughout southern 
1) Chem. & Druggist, 53, pp. 840, 875. 
2) Mitth. d. deutseh. Ges. fur Natur- u. Volkerkunde Ostasiens, 23; Berichte, 14, Ref., 
p. 1720. 
3) Rec. trav. chim. des P. B., 4, p. 32; Berichte, 18, Ref., p. 281. 
*) Bericht von S. & Co., Sept. 1885, p. 29; Oct. 1893. p. 46. 
5) Jahresb. f. Pharm., 1889. p. 70. Oils of the Anonaceae. 
363 
Asia. The first statement in European literature concerning this tree is 
made by the English botanist John Ray (born 1628, died 1705), who 
described the tree under the name Arbur Saguisen. Rumpf, a contem- 
porary of Ray described and illustrated it as Borga Cananga. Lamarck 
called the tree Uvaria or Unonia odorata. Roxburgh became acquainted 
with the tree, which had been transplanted from Sumatra to the 
botanical garden in Calcutta, in 1797. The first correct illustrations of 
flower and fruit were published by Blume in 1829. 
Notwithstanding the exceeding fragrance of the blossoms and the 
desire of the European colonial powers to find profitable commercial 
articles in the Malay Archipelago, the manufacture of ylang-ylang oil 
was first conducted by Germans in the island of Luzon in the early 
sixties. The oil became known to wider circles through its exhibition 
at the Paris Industrial Exposition in 1878 by the Manila merchants 
Oskar Reymann and Adolf Roensch. 
Ylang-ylang oil is distilled in the islands of Luzon and Java. The 
blossoms of the trees growing in dense forests are said to be less 
fragrant and poorer in oil than those of cultivated trees or trees stand- 
ing in clearings. 
In the process of distillation, the oxygenated constituents and the 
esters, the substances to which the fragrance of the cananga blossoms 
is due, pass over first; later the sesquiterpenes predominate. In Luzon, 
and recently also in Java, the first part of the distillate is kept separate 
and brought into the market as ylang-ylang oil, whereas the second 
part of the distillate or the entire oil is sold as cananga oil. 
On account of the delicacy of the flavor, the collection and distil- 
lation of the blossoms requires special knowledge and care. For this 
reason but few distillers have succeeded so far in manufacturing a 
uniformly good article of like qualities. 
Composition. Although the ylang-ylang oil consists principally of 
the lower and cananga oil of the higher fractions, the difference between 
these two oils is of a quantitative rather than a qualitative nature. 
The first examination of ylang-ylang oil was made by Gal1 in 1873. 
Upon saponification of the oil with alcoholic potassa he obtained ben- 
zoic acid, thus indicating the presence of a benzoic ester. Reychler,2 
who later (1894) made a more careful examination of both oils, also 
found acetic acid to be present as ester. 
i) Compt. rend., 76, p. 1482. 
2) Bull. Soe. chim., Ill, 11, pp. 407, 576 and 1045; ibid. 13, p. 140. 364 
Special Part. 
Of the alcoholic constituents which are possibly combined with these 
acids, the following have been identified: 1-linalool (b. p. 196-198°; 
sp.gr. 0.874 at 20°; «D --16° 25') and geraniol (b. p. 230°; sp. gr. 
0.885 at 20°) which was separated from the corresponding fraction by 
means of the calcium chloride compound. 
In addition to these esters, the characteristic odor of the oil 
is partly due to the presence of the methyl ether of para cresol, 
CH3.CaH4.OCH3, which boils at 175° and upon oxidation yields anisic 
acid melting at 178c. 
The high boiling fractions, especially of the cananga oil, contain 
cadinene (dihydrochloride, in. p. 117°). This sesquiterpene is accom- 
panied by a colorless and odorless substance1 crystallizing in needles 
that melt at 138°. which evidently belongs to the class of ses- 
quiterpene hydrates. Ln the lower boiling portions a very small amount 
of a terpene, presumably pinene.2 is contained. 
Besides these substances, the oil contains a very small amount of 
a compound that combines with acid sulphite, the chemical nature of 
which, however, has not yet been determined. The violet color reaction, 
which the oil produces with ferric chloride, indicates the presence of 
a phenol (Fliickiger,8 1881) the isolation of which would demand a 
large quantity of this costly oil. 
Properties of Ylang-Ylang Oil. The ylang-ylang oil from 
Manila, which alone is of importance commercially, constitutes a light 
yellow liquid of exceeding fragrance. Sp. gr. between 0.930 and 0.950; 
«d = - 38 to-45°. In alcohol the oil is but difficultly soluble. Generally 
a clear solution is obtained with to 2 volumes of 90 p. c. alcohol 
but, as a rule, this solution becomes turbid upon the addition of more 
alcohol. Inasmuch as the odor is largely dependent on the esters 
present, the determination of the saponification number (between 75 
and 120 for good oils) is to be recommended. With ferric chloride the 
alcoholic, solution of the oil produces a violet color reaction. 
Ylang-ylang oils of other sources vary considerably in their physical 
properties from those of the Manila oil. The oil examined by Gal,4 
which is reported to have been obtained from the West Indies, had 
a sp. gr. of 0.980 at 15° and «d = - 28°. An oil distilled in Reunion5 
had a sp. gr. of 0.974. 
i) Bericht von S. & Co., Apr. 1896, p. 62. 
2) Bericht von S. & Co., Apr. 1896, p. 67. 
3) Arch. cl. Pharm., 218, p. 24; also Reychler, loc. cit. 
Co npt. rend., 76, p, 1482. 
5) Bericht von S. & Co., Oct. 1890, p. 47. Oils of the Anonaceae. 
365 
The differences existing in the properties of pure oils render difficult 
the detection of adulterations. To pass judgment on the quality of 
ylang-ylang oil is, therefore, often a matter to be decided by the per- 
fumer rather than by the chemist. 
Properties of Cananga Oil. The odor of Cananga oil is similar 
to that of ylang-ylang oil. but not as fine. Owing to the different 
methods of preparation, the physical properties are subject to con- 
siderable variations: sp. gr. 0.91-0.94; «d --17 to-55°. 
In 90 p. c. alcohol cananga oil is not completely soluble. Of 95 p. c. 
alcohol to 2 vols. are mostly necessary, but the solution becomes 
turbid on the further addition of alcohol. However, no drops separate 
from the resulting opalescent liquid upon standing. 
The saponification number is 10-30. In general an oil with a high 
saponification number may be regarded as the best, provided this is 
not due to the presence of cocoa nut oil. 
Cananga oil from dried flowers.1 Dried cananga blossoms 
from Samoa, known there as Mosoi yielded 1 p. c. of oil upon distil- 
lation. Its odor was somewhat different from that of the oil from fresh 
blossoms but had the same general character. Like ordinary cananga 
oil, it contained benzoic acid and had a sp. gr. of 0.922. 
Adulteration. In recent years adulteration with cocoa nut oil has 
been observed repeatedly in connection with oils coming via Amsterdam.2 
Such addition can readily be recognized. Specific gravity and rotatory 
power are influenced but little, but the saponification number is con- 
siderably increased and the oil ceases to be soluble in 95 p. c. alcohol; 
From the turbid mixture of oil and alcohol drops of oil separate upon 
standing. 
Cocoa nut oil can also be recognized without difficulty by exposing 
the suspected oil to the temperature of a freezing mixture of ice and 
salt. Whereas a pure oil remains liquid, an oil adulterated with larger 
amounts of cocoa nut oil congeals to a butter-like mass. This test ean 
readily be carried out by anyone and should never be omitted. 
Small amounts of fat as well as other oils that do not congeal at 
low temperatures remain behind upon distillation with water vapor 
and will be found in the residue. It should be borne in mind, however, 
that undulterated oils also leave a residue of about 5 p. c., which amount 
should be deducted in an approximate quantitative determination. 
1) Bericht von S. & Co., Oct. 1890, p. 48. 
2) Bericht von S. & Co., Oct. 1897, p. 8. 366 
Special Part. 
120, 121. Oils of Mace and Nutmeg. 
Olenin Macidis. Olenin Nncis Moschati.-Macisol. Muskatnnssol.-Essence de 
Macis. Essence de Muscade. 
Origin and History. The nutmeg- tree, Myristica, fragrans Hout- 
thuyn (M. officinalis L., M. moschata Thunberg), which belongs to the 
family Myristicaceae and which attains a height of 20 meters, is in- 
digenous to the Molucca, Banda and Sunda islands. It has been 
cultivated extensively in these islands and also in other countries. 
The distilled oils of nutmeg and mace were well known to the 
authors of the "Destillirbiicher" about the middle of the sixteenth 
century and later Cordus1, Ryff2, Gesner3, Porta4, Winther5 and 
others repeatedly mention the oils. Both oils are first mentioned in the 
apothecaries' price ordinances of Berlin of 1574, those of Frankfurt and 
Worms of 1582, and in the 1589 edition of the Dispensatorium Noricum. 
These oils were first examined by Neumann.6 (1749), Valentini7 
(1719), and Bonastre8 (1824). Upon distillation nutmegs yield 
8-15 p. c., in ace 4-15 p. c. volatile oil. 
Properties of Oil of Mace. It is colorless or yellowish, becoming 
reddish-yellow with time. It has a pleasant though strong mace odor 
which with age becomes unpleasant and terebinthin ate. The taste is mild 
at first, then pungent, aromatic. As a rule the specific gravity of oil of 
mace is somewhat higher than that of oil of nutmeg and varies between 
0.890 and 0.930; «D = + 10to +20°. The oil is clearly soluble in 
3 parts of 90 p. c. alcohol. 
Properties of Oil of Nutmeg. This is a mobile, colorless liquid 
which, owing to the absorption of oxygen, becomes viscid with age, has 
a characteristic nutmeg odor and a spicy taste. According to the 
nature of the crude material, the sp. gr. of the distillate varies between 
0.865 and 0.920; «d= + 14 to + 28°. The oil is clearly soluble in 
3 parts of 90 p. c. alcohol. When distilled, about 60 p. c., pass 
over below 180°. When evaporated, a small amount of a fatty sub- 
stance, consisting principally of myristic acid, remains behind. 
Oil of nutmeg clearly resembles oil of mace in all of its properties 
and is scarcely distinguishable from the latter. 
i) Annotationes, etc., De artifl. extr. lib., fol., 226. 
2) Neu gross Destillirbueh. Ed. Frankf.-a.-M., fol. 181. 
3) Ein kostlicher Schatz, etc., p. 215. 
*) Magiae naturalis. Lib. de dest., pars 1, p. 378. 
•I) Guintheri, Andernacei de iriedieina veteri et nova. Basilae 1571, pp. 630-635. 
6) Chymia medica, vol. 2, part 3, p. 437. 
t) Macis vulgo sed perperam, Muskatenblume dicta. Dissertatio. Giessen 1719. 
s) Trommsdorff's N. Journ. der Pharm., 8, II, p. 231. Oils of the Myristicaceae. 
367 
Composition. On account of the great similarity between the two 
oils, frequently no commercial distinction is macle. As a result, the true 
origin of the various oils that have been examined is not ascertainable. 
For this reason it will be expedient to discuss the composition of both 
at the same time. This can be done without hesitation because so far no 
qualitative difference has been observed.1 Quantitatively they vary in so 
far as oil of nutmeg generally contains more terpenes than oil of mace. 
Although numerous older examinations are recorded,2 individual 
constituents were but recently definitely characterized and determined. 
However, there are still a number of problems which demand further 
investigation. 
The following constituents have thus far been found: 
1. Pinene. This terpene was found by Wallach3 in the lowest 
boiling fraction of the oil (pinene nitrolbenzylamine, m. p. 123°). It is 
present as an almost inactive mixture of dextro- and laevogyrate pinene. 
As early as 1862 Schacht had isolated pinene, his "macene" and prepared 
from it the solid hydrochloride. 
2. Dipentene.4 This is present in fraction 175-180° and has 
been identified as tetrabromide.5 
3. Myristicol. The contradictory statements concerning this 
substance make a revision very desirable. According to Gladstone, 
myristicol has the composition C10H140, boils at 224°, has the sp. gr. 
0.9466 and a rotatory power of +31°. Wright gives the boiling point 
as 212° and considers the formula CioHiuO to be correct. This formula 
at least explains the formation of cymene by the action of zinc chloride 
or phosphorus pentachloride on myristicol. Distilled under a pressure 
of 10 mm., myristicol is found in fraction 70-144° (about 15 p. c.) of 
the oil, sp. gr. 0.913 (Semmler5). 
i) Koller pronounces both oils identical (N. Jahrb. Ph arm , 23, p. 136; Jahresb. 
f. Chem., 1864, p, 536). 
2) John (1821), Chemische Schriften, 6, p. 61. Abstr. in Journ. f. Chem. u. Phys, 
von Schweigger u. Meinecke, 33, p. 250. - Mulder (1839), Journ. f. prakt. Chem., 17, 
p. 102, and Liebig's Annalen, 31, p 71. - Schacht (1862) Archiv d. Pharm., 162, 
p. 106. - Cloez (1864), Compt. rend., 58, p. 133. - Gladstone (1872), Journ. Chem. 
Soc., 25, p. 1. Abstr. in Jahresb. f. Chem., 1872, p, 816. - Wright (1873), Journ, 
Chem. Soc., 26, p. 549. Abstr. in Jahresb. f. Chem., 1873, p. 369. - Pharm. Journ., 
Ill, 4, p. 311. 
3) Liebig's Annalen, 227, p. 288; 252, p. 105. 
4) The so-called myristicene of Gladstone, like the terpene (b. p. 165°) of Cloez, was 
a mixture of dipentene and pinene. Wright's statement that oil of mace contains 
cymene is open to question inasmuch as he used concentrated sulphuric acid in order 
to identify it. This reagent, however, is not permissible when terpenes are present. 
Semmler could not find cymene in the oil. 
5) Beriehte, 23, p. 1803; 24, p. 3818. 368 
Special Part. 
4. Myristicin,1 C12H14O3.2 After treatment with metallic sodium, 
the highest boiling fraction (b. p. 142-149° under 10 mm. pressure) 
contains a substance that melts at 30°, has a sp. gr. of 1.1501 at 25°. 
an intense odor of mace and has been termed myristicin. According to 
Semmler it is oxymethyl oxymethylene butylene benzene. 
ZC4H7 [i] • ZC4H7 m 
r tj -0\en [31 r w "OCH3 [3] 
C«H2_0/CH2 [4] 01 C6H2_0 [4] 
\0CH3 [5] \0/LI12 15] 
Whether the position of the side chains is as indicated in the first or 
second formula has not yet been ascertained. 
According to a private communication by Professor Semmler, more 
recent observations seem to agree with those made in the laboratories 
of Schimmel & Co., viz. that the oil originally contains a phenyl ether 
which undergoes modifications in the processes to which the oil is sub- 
mitted during its examination. 
The fact that the fraction which after the treatment with sodium 
yields myristicin, in its original state does not solidify when exposed to 
a freezing mixture,3 and the coefficient of refraction being much less before 
than after the treatment, renders it highly probable that the C^HT-group 
changes its position under the influence of sodium. The same change 
evidently takes place here that eugenol undergoes when converted into 
isoeugenol, of safrol into isosafrol, of methyl chavicol into anethol. 
Should this prove to be the case, the solid substance should properly 
be termed isomyristicin, whereas the name myristicin should be made 
to apply to the original liquid substance. 
5. Myristinic acid. According to the duration of the process of 
distillation, more or less of this acid is found in the oil and will some- 
times crystallize out. 
6. Phenol-like substance. The last portions obtained by 
fractional distillation produce an emerald green color with ferric 
chloride, thus indicating the presence of a phenol.1 
132. Oil of Boldo Leaves. 
The fragrant, dried leaves of Peumus boldus Mol. (Monimiaceae), a 
tree indigenous to Chili, yield upon distillation 2 p. c. of an aromatic 
i) Not to be confounded with the stearoptene myristicin, so called by John and 
Mulder, which sometimes crystallizes from old oils and which, as has been shown by 
Fluckiger in 1874 (Pharm. Journ., Ill, 5, p. 136), consists of myristic acid. 
2) Wright assumed the formula C1OH13O2 for myristicin. 
s) Observation in the laboratories of Schimmel & Co. 
4) Semmler, loc. cit. Oils of the Monimiaceae. 
369 
oil, the odor of which is cymene-like and reminds slightly of peppermint. 
Sp. gr. 0.915 to 0.945; slightly laevogyrate, aD=-l°40'; it boils 
between 175 and 250° and produces a green color with ferric chloride.1 
The oil contains terpenes and oxygenated substances that have not yet 
been closer examined (Hanausek2). 
123. Atherosperma Oil. 
The bark of Atherosperma moschata Labillard. (Monimiaceae) yields 
upon distillation 1 p. c. of volatile oil (Maiden3). On account of its 
sassafras-like odor the tree is also called Victorian' sassafras. According 
to Gladstone,4 the oil has a yellowish-brown color and a sp. gr. of 
1.0386 at 20°. It is slightly dextrogyrate, 4- 7° in a 10 inch tube. It 
begins to distill at 221° and passes over almost completely at 224°. 
124,. Oil of Citriosma Oligandra. 
On account of its unpleasant odor, the tree Citriosma oligandra Jul., 
(Monimiaceae) is known in Brazil as Negra. Mina, Catinga de negra, or 
Catingueira. The leaves upon distillation yield 0.54 p. c. of volatile oil 
which is of a light yellow color with greenish fluorescence and an odor 
that faintly reminds of bergamot. Sp. gr. 0.899 (Peckolt5). 
125. Oil of Citriosma Cujabana. 
Citriosma cujabana Mart, is known in Brazil as Limoeiro domato, 
and L. bravo or wild lemon tree. The fresh leaves yield 0.18 p. c., the 
fresh twigs 0.07 and the fresh bark 0.22 p. c. of volatile oil. The oil is 
a mobile liquid, sp. gr. 0.894, the odor of which resembles that of a 
mixture of bergamot and lemon oils (Peckolt5). 
126. Oil of Citriosma Apiosyce. 
Citriosma apiosyce Mart, is known in Brazil as Limoeiro bravo, 
Cidreira melisse, or Cafe bravo, wild coffee tree. All parts of the shrub, 
especially the leaves and unripe fruits, have a strong odor of melissa 
(lemon balm) or lemon. From the fresh leaves Peckolt obtained 0.14 
p. c., from the twigs 0.06 p. c. of volatile oil.5 
1) Bericht von S. & Co., Apr. 1888, p. 43. - Claude Verne, Etude sur le Boldo. 
Th&se pr£sent£e et soutenue A 1'Ecole SupSrieure de Pharmacie de Paris. Paris 1874. 
According to Pharm. Journ., Ill, 5, p. 405. 
2) Jahresb. f. Pharm., 1877, p. 79. 
s) Useful native plants of Australia, p. 254. 
*) Journ. Chern. Soc., 1864, 17, p. 5. Ref. Jahresb. f. Chem., 1863, p. 545. - 
Chem. News, 1871, 24, p. 283. 
s) Berichte d. deutsch. pharm. Ges., 6, p. 93. 370 
Special Part. 
Paracoto bark is brought into commerce from Bolivia and derived 
from an unknown species of the Monimiaceae.1 The oil which is obtained 
as a by-product in the preparation of cotoin, was first examined by 
Jobst and Hesse2 in 1879, later (1892) by Wallach and Rheindorff.3 
Properties. Paracoto bark oil is a mobile, colorless liquid of a 
very pleasant odor. Sp. gr. 0.9275; «d = - 2.12°.2 
Composition. 1. According to Jobst and Hesse, fraction 160t> 
(sp. gr. 0.8727; [«]d = + 9.34°) is a hydrocarbon C12H18 named 
a-paracotene by them. 
2. Fraction 170-172° (sp. gr. 0.8846; [«]D = - 0.63°) has the 
formula CnHis assigned to it and is designated ^-paracotene. 
Both fractions, which evidently consisted of slightly impure terpenes, 
were wanting almost entirely in the oil examined by Wallach and 
Rheindorff. 
3. The principal fraction of the oil consists of laevogyrate cadinene 3 
(m. p. of the dihydrobromide 121°, of the dihydrochloride 118°). 
4. After the dihydrobromide has been removed there remains an oil 
which contains methyl eugenol (m. p. of the bromide 78°, of the veratric 
acid obtained by oxidation 179-180°). 
According to Wallach, the and Z-paracotol of Jobst and Hesse, 
to which the formulas C15H24O and C28H4OO2 had been assigned, are 
not chemical individuals but mixtures principally of laevogyrate 
sesquiterpene and inactive methyl eugenol. As to a-paracotol, the 
possibility is not excluded that it may be a natural hydrate of cadinene. 
In this case, however, the formula would have to be C15H26O, not 
C15H24O. 
128. Oil of Camphor. 
History. In China, camphor has been prepared and used in early 
antiquity. The first documental reference to it is found in the writings 
of the Arabian prince Imru-l-Kais of the sixth century; also in the 
Koran, in which it is mentioned as a refrigerant in connection with the 
beverages of the blessed in paradise. Aetius of Amida, also in the sixth 
century, mentions camphor as a remedy. When the palace in Madain 
of Choroes II, king of the Sassanides was pillaged in 636, much camphor 
127. Oil of Paracoto Bark. 
1) Moller (Anatomie tier Baumrinden) is of the opinion that the bark is that of a 
Monimiacea, whereas Vogl (Conimentar zur bsterreich. Pharmacopbe) believes that it 
belongs to a Lauracea. 
2) Liebig's Annalen, 199, p. 75. 
3) Liebig's Annalen, 271, p. 300. Oils of the Lauraceae. 
371 
was taken in addition to musk, ambra, sandalwood and other oriental 
aromatics.1 Later, when Arabian sailors and merchants sailed to India 
and through the Indian Archipelago to China, they became acquainted 
not only with the principal ports from which the camphor was shipped 
from southeastern Asia to the Mediterranean countries, but also with 
the sources of supply. Thus the Arabian merchants and physicians 
became acquainted with the different varieties which entered the world's 
market in part from China, in part from Sumatra. Marco Polo, in the 
thirteenth century, also became acquainted with the camphor in Sumatra 
and Borneo. E. Kaempfer was the first to describe the mode of pre- 
paration in Japan. Medicinally camphor was used by the Arabians, 
also in Italy as early as the eleventh century and during the twelfth 
century in Germany. 
Origin and Preparation of Camphor Oil. This oil which is a 
by-product in the Japanese camphor industry, has but recently been 
introduced into the European market. The camphor laurel, Cinnamomnm 
(■amphora Fr. Nees et Ebermaier (Laurus camphora L.) is a stately 
forest tree found in several provinces of southern China, in the islands 
Hai-nan, Formosa and several other Japanese islands. 
In the older trees camphor is found in a crystalline condition in 
cavities of the trunk. Principally, however, it is found dissolved in a 
volatile oil that permeates the entire tree. This oil occurs most 
abundantly in the roots, less abundantly in the trunk and still less in 
the branches and leaves. The amount of oil also seems to vary with 
'the height of the trunk, diminishing with increasing height. With the 
age of the tree and the density of the wood, the amount of oil, how- 
ever, increases. 
The ratio of solid camphor and camphor oil seems to vary with the 
age of the tree, the season and the temperature. The younger trees 
yield upon distillation more camphor oil and less camphor. The same 
is true with increasing temperature, so that the yield of oil is greater 
in summer than in winter. 
In recent times, and more particularly since the acquisition of 
Formosa, Japan has become the principal producer of camphor and 
camphor oil. The method of preparation is generally as follows:2 
On Ilie slope of a hill near a supply of water a sufficient area is leveled. 
On this a stove is erected with crude stones having a height of about 1 m. 
i) Weil, Geschichte der Chalifen. Mannheim, 1846, p. 75. 
2) D. E. Grassmann. Der Campherbaum. Mittheilungen der Deutsehen Gesellschaft 
fur Natur- u. Volkerkunde Ostasiens. Tokio, 1895, 6, pp. 277-328. 372 
Special Part. 
and an inner diameter of 0.70 m. The opening for the fuel supply is rather 
small, 0.40x0.30, and covered with a roof. On this the distilled chips 
(fig."67 b) are dried to be used later as fuel. A flat kettle provided with a. 
strong, perforated, wooden cover is placed on top of the stove (fig. 68 b) and 
over this a barrel or tub. This has the shape of a truncated cone (fig. 67 c) 
and is 1.15 in. high; the upper diameter being 0.30 m. the lower 0.87 m. 
The cover to the kettle fits as a bottom to the tub. To one side, just over the 
cover of the kettle there is a rectangular opening in the tub 0.30 in. high and 
0.25 m. wide (fig. 68 e). The head-piece of the barrel or tub consists of a 
Fig. 67. 
Fig. 68. 
removable, well fitting cover provided with an opening that can be closed by 
a plug. The tub is coated with a layer of clay 0.15 m. thick and held together 
by a network of bamboo. Near the top a bamboo tube 2 m. long is carefully 
inserted, which leads to a condenser farther up on the slope. This condenser, Oils of the Lauraceae. 
373 
in its simplest form (fig-. 69), consists of two boxes of which the upper serves 
for the condensation of the camphor and the lower for the reception of the 
cooling water. The upper box is 1.60 m. long, 0.90 m. broad and 0.42 m. 
high. The inverted bottom is covered with water, the sides projecting 
10-12 cm. over the bottom. The camphor vapors enter the box over the 
surface of the water. To pass them through the water has not proved suc- 
cessful. By means of partitions 18.5 cm. apart the condenser is divided into 
sections. These partitions are each provided wdth a rectangular opening at 
the top, one in the right corner, the other in the left corner, etc , so that the 
camphor vapors must pursue a circuitous path. From the last chamber the 
vapors can pass out through a bamboo tube slightly plugged with straw'. A 
lateral tube allows the water to flow' from the bottom (= cover) of the upper 
box into the lower. The upper box inverted with its opening downward is 
placed into the lower box which is somewhat longer and W'ider but not as 
high, so that the water in the latter rises to about one-half of the height of 
the former on all sides. A lateral exit tube allows the excess of water to flow 
out. In order to avoid a rapid heating of the 
water in the condenser, this is protected by a roof 
made of boards. 
Frequently a third smaller box, 0.80 m. long, 
0.54 in. broad and 0.25 m. high, is placed over 
the upper one. This box is likewise open on the 
lower side, standing in w'ater 10 cm. deep. The 
sides likewise project over the top so that a layer 
of w'ater 5 cm. high remains on it. The vapors 
from the last chamber of the larger condenser pass 
through a tube (fig. 68 A) into this smaller box 
where more camphor is condensed. This small 
upper condenser is provided with a small exit tube 
for the vapors. 
The following utensils are used in connection 
with this apparatus: a w'ooden shovel of the shape of 
a spoon-oar for shoveling the distilled chips into the 
fire place; also an iron poker. In order to protect the stove and tub a roof 
of straw and reed is constructed, also a wall of straw' matting to the wind- 
ward (valley) to protect against draft and rain. 
The production of camphor is conducted as follow'S. After the kettle has 
been filled with water, the chips are introduced through the upper opening 
into the tub, and all cracks and crevices carefully luted so that the vapors 
cannot escape. Only a moderate fire is maintained. 
In the course of the distillation the kettle is frequently refilled through the 
opening c (fig. 68). The vapors pass through the perforation into the tub 
(fig. 68 d) and convey the camphor vapors from the heated chips through the 
bamboo tube (fig. 68 f) into the condenser w'here they are deposited. In the 
early part of the distillation, camphor oil only is found in the condenser, later 
also solid camphor. Most of the camphor condenses behind the 3rd, 4th and 
5th chamber of the seven-part condenser. The tub will hold 112.5 k. of chips, a 
Fig. 69. 374 
Spacial Part. 
quantity that can be distilled in 24 hours. The exhausted chips are removed 
from the lateral opening (fig. 68 e). Every week the condenser is opened and 
the camphor and camphor oil contained therein removed. 
On the surface of the water in the condenser there collects a granular 
crystalline mass resembling a mixture of snow and ice, which in the first few 
chambers is mixed with camphor oil and is colored yellow. On the walls of the 
condensing chambers the pure, white crystalline camphor is deposited. The 
yellowish or brownish-black camphor oil floats on the surface where it mixes 
with the granular camphor. 
Properties. Normal camphor oil, i. e. the oil with all constituents 
as it is obtained by the distillation of the camphor wood, is a semi-solid 
mass, or a liquid mixed with camphor. Usually, however, the product 
which remains after the camphor has been removed by filtration and 
expression is known as camphor oil. This was the oil that came into 
the market about the middle of the eighties. It still contained large 
quantities of camphor which could be obtained by fractionation and 
cooling. At present this operation appears to be carried out in Japan 
as well, for the oil now found in the market is almost free from camphor. 
Distinction is made between two kinds of oil which often vary 
largely in their composition. The measure of their value is their 
specific gravity. 
1. White Camphor Oil. This consists of the lowest boiling 
fractions and contains terpenes almost exclusively, also some cineol. 
Sp. gr. up to about 0.890. 
2. B lack Camphor Oil. It is that portion of the oil that boils 
higher than camphor and contains safrol, eugenol and sesquiterpenes. 
Sp. gr. mostly from 0.900 up to over 1.000. 
The normal oil, as well as the individual fractions, is dextro- 
gyrate. All fractions have the odor of camphor. In the so-called black 
oils, however, this odor becomes subordinate to that of safrol. 
The oil from the roots and leaves is like that obtained from the 
wood. Camphor roots 1 yielded upon distillation 4 p. c. of an oil that 
was partly solid at ordinary temperature. When completely liquified 
its sp. gr. at 45° was 0.957. The liquid portion of the oil boiled between 
165-270° and possessed the properties of ordinary camphor oil. 
An oil obtained from dry leaves1 (yield 1.8 p. c.) also contained 
solid camphor. The liquid portion boiled between 170-270° and could 
not be distinguished from ordinary camphor oil. 
Two oils distilled from fresh leaves were reported on by Hooper2 in 
1896. The leaves from which the first oil was distilled were obtained 
i) Bericht von S. & Co., Oct. 1892, p. 7. 2) Pharm. Journ., 56, p. 21. Oils of the Lauraceae. 
375 
from a tree in the government garden at Utakamand (India) and yielded 
1 p. c. of oil: sp. gr. 0.9322 at 15°; aD= + 4°32'. It contained about 
10-15 p. c. of camphor. The second batch of leaves was from Nadu- 
vatam, in the Nilgiri mountains. The oil contained 75 p. c. of camphor, 
by far more than did the first oil. After the camphor had been removed, 
the oil had a sp. gr. of 0.9314; «d = +27°. 
Composition. Camphor oil is an exceedingly complex mixture of 
hydrocarbons and oxygenated substances, which belong to a large 
number of classes of chemical compounds. Aldehydes are represented 
by acet-aldehyde; the ketones by camphor; the alcohols by terpineol; 
the phenols and the phenol ethers by eugenol and safrol; the oxides 
by cineol; the terpenes by pinene, phellandrene and dipentene; and 
finally the sesquiterpenes by cadinene. 
Arranged according to their boiling points, they may be enumerated 
in the following order: 
1. Acet-aldehyde, CH3CHO. This substance, which is possibly 
found in all oils to the extent of mere traces, makes its presence known 
when large quantities of oils are rectified. In part it is removed with 
the aqueous distillate, in part it is also found in the lowest terpene 
fractions. 
2. Dextro-pi ne ne,1 CioHiq, has been found in the fraction boil- 
ing below 160° and was identified by means of its nitrosochloride and 
conversion into nitrosopinene melting at 130°. 
Yoshida2 (1885) obtained a strongly laevogyrate fraction. 
[«]j = - 71.1°, which was identified as 1-pinene (chlorhydrate, nitroso- 
chloride, nitrosopinene). Inasmuch as the lowest boiling fractions have 
always been found to be dextrogyrate, Yoshida's observation is rather 
remarkable and arouses the suspicion that the oil examined was not 
a normal oil (Bertram & Walbaum,3 1894). 
Whether camphene, the presence of which seems to be indicated, is 
really present or not has not yet been decided.4 
3. Phellandrene,1 CioHiq. This is present in such small quantity 
that its identification by means of the nitrite (m. p. 102°) caused 
difficulties. 
1) Bericht von S. & Co., April 1889, p. 8. 
2) Journ. Chem. Soc., 47, p. 779. 
3) Journ. f. pract. Chem., II, 49, p. 19. 
*1 It is also noteworthy that Yoshida does not mention any fraction boiling above 
230°, of which a considerable quantity is contained in camphor oil. 376 
Special Part. 
4. Cineol, CioHisO, constitutes 5-6 p. c. of the camphor oil. It 
has been isolated by means of the hydrobromide.1 
5. Dipentene, CioHm, has been found by Wallach2 and was 
identified by means of the tetrabromide melting at 123°. An impure 
dipentene dihydrochloride (m. p. 42° instead of 49°) had been isolated 
by Lallemand3 by passing hydrochloric acid into the fraction boiling 
at 180°. 
6. Camphor, CioHieO, which is economically the most important 
constituent, crystallizes in the receiver when the thermometer rises 
to 200°. 
7. Terpineol, CioHisO. Inasmuch as it was impossible to obtain 
this alcohol in such a degree of purity by fractional distillation to 
enable its identification as such, its presence in fraction 215-220° was 
determined in several ways. Upon boiling with dilute sulphuric acid, 
terpinene and dipentene resulted. Upon standing with dilute acids 
terpin hydrate was formed.4 When shaken with concentrated hydriodic 
acid, dipentene dihydriodide5 melting at 77° was formed. 
8. Safrpl, CioHioC>2, b. p. 232°, was found by J. Bertram in 
1885 in Schimmel & Co.'s laboratory. This firm has since then prepared 
it in large quantities from camphor oil.6 
. 9. Eugenol,7 C1OH12O2, is present only in relatively small amounts. 
It is obtained by shaking the higher fractions with dilute soda solution. 
10. Cadinene, C15H24, is the principal constituent of the high 
boiling portions. By passing hydrogen chloride into fraction 260-270° 
a good yield of cadinene dihydrochloride melting at 117° is obtained.3 
11. Blue oil. The portions distilling over last, consist of a blue 
oil which has been frequently observed in volatile oils and of which no 
characteristic derivative has yet been prepared. 
A few words about the so-called "camphorogenol," which is reported 
to boil at 212-213° and is said to have the formula CioHisO2- remain 
to be said. According to Yoshida9 it polymerizes when boiled, but at 
the same time separates camphor. When acted upon by dilute nitric 
acid, acetic acid anhydride or benzoic acid, camphor is said to be 
formed; and when heated with sodium and alcohol, it is converted into 
borneol. 
i) Bericht von S. & Co., Oct. 1888, p. 8. 
2) Liebig's Annalen, 227, p. 296. 
3) Liebig's Annalen, 114, p. 196. 
4) Bericht von Schimmel & Co., Apr. 
1888, p. 9. 
5) Bericht von S. & Co., Apr. 1889, p. 8. 
6) Ibidem, Sept. 1885, p. 7. 
7) Ibidem, Apr. 1886, p. 5. 
8) Ibidem, Apr. 1889, p. 9. 
9) Yoshida, loc. cit. Oils of the Lauraceae. 
377 
As a matter of fact, such a substance evidently does not exist in 
camphor oil. "Camphorogenol" apparently is a mixture consisting 
principally of camphor and terpineol. Such a mixture behaves toward 
the above mentioned reagents like "camphorogenol."1 When boiled, the 
terpineol decomposes into terpenes and water and the camphor, which 
•is less soluble in the terpenes, partly separates out. If the terpineol is 
oxidized with nitric acid, the more resistant camphor remains behind. 
Treatment with sodium reduces the camphor to borneol. 
Use. The oil from which the camphor has been removed is used by 
the poorer classes in Japan for illuminating purposes. It is also used as 
a solvent for resins in the manufacture of lacquer. From the soot, 
obtained by burning the oil, India ink is made. 
In Europe camphor oil is used for the safrol it contains. The waste 
oil that results in the isolation of safrol is utilized as light and heavy 
camphor oil. 
Light camphor oil, sp. gr. 0.89 to 0.92 consists of the low 
boiling fractions. Inasmuch as it has the property of hiding the pene- 
trating odor of the cheap fats and tallow, it is used for perfuming 
ordinary soaps. It is also used as a substitute for turpentine oil over 
which it has some advantages. Thus e. g. it surpasses other cleansing 
media in the cleaning of types, plates and parts of machinery. It is 
further a good solvent for resins2 and caoutchouc and is used in the 
manufacture of lacquers and varnishes. 
Heavy camphor oil, sp.gr. 0.96 to 0.97, boils between 240 and 
270° and is likewise added to cheap soaps and lubricants. 
139. Oil of ( Ceylon) Cinnamon. 
Oleum Cinnamomi Zeylanici.-Ceylon ZimmtoL -Essence de Canelle de Ceylan. 
Origin and Preparation. The genus Cinnamomum, Fam. Lauraceae, 
consists of evergreen, aromatic trees and shrubs. Its several species 
yield volatile oils that are much used. The Ceylon cinnamon, C. zeylani- 
cum Breyne contains volatile oil in the underground portions of the 
shrub as well as in those overground. Whereas the oils obtained from 
the various parts of the cassia, C. cassia BL, seem to be almost 
identical, the oils obtained from the bark, leaves and root respectively 
of the Ceylon cinnamon vary considerably. 
i) Bericht von S. & Co., Apr. 1888, p. 9. 
2) G. Bornemann, Teehnische Mittheil. f. Malerel, 1892, 9, p. 5. 378 
Special Part. 
C. zeylanicum is indigenous to the forests of Ceylon. The bark, 
which was originally collected from the wild shrub, is at present collected 
from the cultivated plant only.1 
For the distillation of the oil, the waste that results in the peeling 
of the bark, is used. These shavings and fragments have been exported 
as "chips" since 1867. The preparation of the oil from chips was intro- 
duced into Germany in 1872 by the firm of Schimmel & Co. of Leipzig. 
The yield from the chips is about 0.5 to 1 p. c. 
The oil produced in Ceylon is but rarely the pure distillate from the 
bark. Commonly it contains much oil from the leaves, which are 
possibly distilled with the bark. It is also possible that the oil from 
the bark is subsequently adulterated with leaf oil. 
History. Cinnamon and cassia are among the oldest spices, and 
the history of the drug as such is a very interesting one. The history 
of the oil, however, is of more recent date. 
When in the course of the fifteenth century the distillation of aromatic 
waters for medicinal purposes became a common practice, cinnamon 
bark was undoubtedly distilled for the preparation of its water. The 
heavy oil which sinks to the bottom of the distillate was in all proba- 
bility observed by the apothecary or chemist. The Canon St. Amando 
of Doormyk seems to have been the first to isolate besides bitter 
almond oil and oil of rue, a number of other volatile oils, among them 
the oil of cinnamon. Valerius Cordus had prepared the oil about 
1540. At that time it may already have found application in medicine, 
so that it was included in the first edition of the Dispensatorium 
Noricum. Lonicer soon afterward distilled the oils from the spices, 
among them cinnamon oil. in a new peculiar apparatus. In the price 
ordinances cinnamon oil is first mentioned in that of Berlin of 1574, 
also in that of Frankfurt-o.-M. of 1582. Winter of Andernach distilled 
and described the oil in 1570, and J. B. Porta in 1589. 
The early observations made on cinnamon oil, like those made on 
other oils, restricted themselves to the crystalline deposit formed upon 
prolonged standing. ' Such crystal formations were observed (among 
others) by Ludovici about 1670, later by Slare in England, by Boer- 
haave and Gaubius in Holland. The latter regarded them as camphor; 
Du Menil and Stockmann supposed them to be benzoic acid, Dumas and 
Peligot in 1831 recognized them to be cinnamic acid. C. Bertagnini 
prepared pure cinnamic aldehyde in 1852. 
i) The cultivation, preparation and packing of Ceylon cinnamon is described in 
detail in A. Tschirch's Indische Heil- und Nutzpflanzen, p. 86. Oils of th a Lauraceae. 
379 
The yield of volatile oil from cassia and cinnamon barks was deter- 
mined by the following observers: G. W. Wedel in 1707; Fr. Cartheuser, 
C. Neumann and Ph. F. Gmelin in 1763; J. F. A. Goettling about 1803; 
by Dehne about the same time; also by Buchholz in 1813. 
Properties. The oil is a light yellow liquid which has the agreeable' 
fine delicate odor of the Ceylon cinnamon, and a spicy, sweet, burning 
taste. 
The sp. gr. lies between 1.021 and 1.040; optically it is slightly 
laevogyrate, aD = up to -1°. The oil is clearly soluble in 2 parts of 
70 p. c. alcohol. It contains between 65-75 p. c. of cinnamic aldehyde. 
Composition. Blanchet1, in 1833 observed that in the distillation 
of Ceylon cinnamon two oils separate in the receiver, one being lighter 
than water, the other heavier, whereas Chinese cinnamon yielded only 
the heavy oil. The older chemists, however, concerned themselves only 
with the heavy oil. Dumas and Peligot2in 1834 ascertained, that like 
the oil of cassia, the heavy oil of the Ceylon cinnamon consisted 
principally of cinnamic aldehyde. That the heavy oil of the Ceylon 
cinnamon contains eugenol as well was observed later. The amount of 
eugenol in the oil from the bark is but 4-8 p. c., much less than in 
the leaf oil. 
Of the constituents of the light oil but one is known, viz. phellan- 
drene, which has been isolated from the fraction boiling about 175° and 
has been identified by the nitrite3 melting at 102°. The substance to 
which the characteristic odor of the Ceylon cinnamon oil is due is not 
yet known. 
Adulteration and Examination. Ceylon cinnamon oil is frequently 
adulterated with the much cheaper oil from the leaves. None of the 
oils from Ceylon appear to be pure bark oils, for all of the oils from 
this source examined thus far contained considerable quantities of leaf 
oil. Whether the two oils are mixed, or whether the leaves have been 
distilled with the bark, naturally cannot be decided. 
Inasmuch as the addition of leaf oil increases the eugenol content 
and diminishes that of the cinnamic aldehyde, its recognition is not 
difficult. All that is necessary is to determine with approximate quanti- 
tativeness the amount of both substances present. After the deter- 
mination of the specific gravity, which is increased by the addition of 
larger amounts of leaf oil. the aldehyde content is determined according 
i) Liebig's Annalen, 7, p. 163. 
2) Ann. de Chim. et Phys., 57, p. 305; Liebig's Annalen, 14, p. 50. 
3) Bericht von S. & Co., Oct. 1892, p. 47. 380 
Special Part. 
to the method described under cassia oil on p. 390. If the aldehyde 
content is less than 65 p. c. or more than 75 p. c., the oil is suspicious. 
If the oil contains less than 65 p.c. of aldehyde, the amount of eugenol 
in the non-aldehyde portion is determined according to one of several 
ways. The most accurate results are obtained according to the somewhat 
complex method of Thoms,1 the eugenol being converted into benzoyl 
eugenol and weighed. (Comp, under oil of cloves.) Umney2 has suggested 
to shake the oil with 10 p. c. potassa solution and to determine the 
eugenol content from the diminution in the volume of the oil. Inasmuch, 
however, as the strong potassa solution dissolves appreciable amounts 
of non-phenol constituents, the results are inaccurate and about 10 p. c. 
higher than those obtained 'according to Thoms' method. The error can 
be reduced by using a 5 p. c. potassa solution. • For ordinary purposes 
at least, this method can be considered of sufficient accuracy to ascertain 
whether an oil is pure or adulterated. Adulteration may be assumed if 
the eugenol content of the original oil exceeds 10 p. c. 
The extent to which the adulteration with leaf oil is carried on 
becomes apparent from the result of examinations published by Umney2 
and Schimmel & Co.3 Every one of the seven oils was strongly adulter- 
ated with leaf oil, three containing at least 30 p. c., the other four 
not less than 50 p. c. The four last mentioned oils had the following 
properties: 
Percentage of 
Percentage of 
Sp. gr. 
«D 
cinnamic aldehyde 
Eugenol (according to Thoms) 
1) 1.039 
-0°55' 
29 p. C. 
41.9 p. c. 
2) 1.040 
-0°28' 
28 " 
39.1 " 
3) 1.041 
-0°57' 
29 " 
47.7 " 
4) 1.049 
-0°22' 
24 " 
45.7 " 
The following reaction enables the qualitative distinction between 
the bark and leaf oils:2 
A drop of genuine cinnamon oil dissolved in 5 drops of alcohol produces a 
pale green color with ferric chloride, whereas leaf oil and oil adulterated there- 
with produce a deep blue color. 
The cinnamon oils adulterated with cassia oil have a higher specific 
gravity and, as a rule, also a higher cinnamic aldehyde content. Oils 
with more than 75 p. c. aldehyde, if not suspicious, are of inferior value. 
Whereas the cinnamic aldehyde content is the criterion of value of the 
cassia oil. this is not the case with the cinnamon oil, for in the latter 
1) Berichte der pharm. Ges., 1, p. 279. 3) Bericht von S. & Co., Oct. 1895, p. 48. 
2) Pharm. Journ., Ill, 25, p. 949. Oils of the Lauraceae. 
381 
the non-aldehyde constituents are the more valuable as is shown by the 
fact that the cinnamon oil with the smaller aldehyde content commands 
several times the price of the cassia oil. 
130. Oil of Cinnamon Leaves. 
Oleum Foliorum Ciunamomi.- Zimmtbliitterol.-Essence de Feuilles de Cannelle 
de Ceylan. 
For a time the oil from the leaves of the genuine cinnamon, Cinna- 
momum zeylanicum Breyne, was designated commercially as cinnamon 
root oil. After Schimmel & Co. had shown in 1892 that an oil. distilled 
by themselves from Ceylon cinnamon leaves (yield 1.8 p. c.) corresponded 
in all its properties with the so-called root oil, the erroneous designation 
could no longer be retained. Two oils, which corresponded in every 
respect with the home distillate and which were correctly designated as 
cinnamon leaf oil, .had previously been obtained from the Seychelles and 
from the botanical garden in Buitenzorg, Java.1 
The oil formerly exported as cinnamon leaf oil was a thick, viscous 
oil of the consistency of West Indian sandalwood oil. It has since dis- 
appeared from commerce and nothing definite is known as to its origin. 
Properties. Cinnamon leaf oil is of a light color, rather mobile, 
and has the odor of cloves and cinnamon. Sp. gr. 1.044-1.065; 
«d =- 0°5' to 4-1° 18'. With 3 parts of 70 p. c. alcohol it forms a 
clear solution, which, however, sometimes becomes turbid upon the 
further addition of alcohol. 
Composition. Stenhouse2 (1855) found large amounts (70-90 p. c.) 
of eugenol in cinnamon leaf oil. Schaer3 (1882) later confirmed this 
report. In the oil distilled by themselves, Schimmel & Co. found cinnamic 
aldehyde (0.1 p. c.). Weber4 made a detailed examination of two 
different oils. The first, obtained from bhe Seychelles, had a sp. gr. of 
1.0552 at 18.5° and contained eugenol (benzoyl eugenol, m. p. 69-70°), 
cinnamic aldehyde (phenyl hydrazone, m. p. 167°), and terpenes that 
were not identified. The other, still purchased by Schimmel & Co. under 
the erroneous name of cinnamon root oil, was also leaf oil. Its sp. gr. 
was 1.041 at 19°. It varied somewhat in its composition from the 
preceding. Weber found eugenol, safrol (piperonylic acid, m. p. 226 to 
227°), terpenes and benzaldehyde (phenyl hydrazone, m. p. 150-151°), 
but no cinnamic aldehyde. 
1) Bericht von S. & Co., Apr. 1892, p. 
45; Oct. 1892, p. 47. 
2) Liebig's Annalen, 95, p. 108. 
3) Archiv d. Pharm., 220, p. 492. 
*) Archiv d. Pharm., 230, p. 232. 382 
Special Part. 
Stenhouse had found benzoic acid which is probably combined with 
an alcohol. Later investigators do not mention this constituent. 
Whether the benzaldehyde found by Weber is an original constituent of 
the oil or an oxidation product of the cinnamic aldehyde, remains 
undecided. 
131. Oil of Cinnamon Root. 
The oil of cinnamon root is an almost colorless liquid with a strong 
odor of camphor. Even at ordinary temperature a part of the camphor,1 
which is identical with the ordinary laurus camphor, separates out. 
Other constituents are cinnamic aldehyde and a hydrocarbon (Holmes,2 
1890). That the roots contain camphor has long been known. It was 
mentioned by Trommsdorff,3 also by Dumas and Peligot4 (1835). 
Cinnamomum zeylanicum affords an interesting illustration of a 
plant, the root, leaves and bark of which afford oils of totally different 
composition. In the root oil we find camphor as characteristic consti- 
tuent. in the leaf oil eugenol predominates and in the bark oil cinnamic 
aldehyde. 
133. Oil of Cassia. 
Oleum Cinnamomi Cassiae. - Cassiabl, Chinesisches Zimtol, Zinitbluthenbl. - 
Essence de Cannelle de Chine. 
Origin and Preparation. Although the plant which yields the oil 
of cassia, the Cinnamomum cassia BL, has been known for a long time,' 
considerable uncertainty existed as to the part of the plant from which 
the oil was obtained. It was supposed, by way of illustration, that the 
unripe fruits, the Flores cassiae of commerce, were the source of the oil 
which for this reason was called "Zimtbliithenbl. " As early as 1881,5 
however, it became known that near In-lin, north of Pak-hoi, the leaves 
of the cassia bush were distilled for oil. The oil was, however, reported 
as being thicker, darker and less fragrant than the cassia oil. H. 
Schroeter,6 in the description of his travels through the cassia district 
in 1886, also mentions the production of oil from leaves. It was sup- 
posed, however, that the leaves yielded but a small amount of an 
inferior oil. In order to ascertain the properties of the leaf oil, Schimmel 
& Co. secured, with the aid of Melchers & Co. of Canton, not only the 
leaves, but all parts of the cassia shrub that might come into consider- 
1) Bericht von S. & Co., Oct. 1892, p. 46. 
2) Pharm. Journ., Ill, 20, p. 749. 
3) Handbuch der Pharmacie, p. 666. 
4) Liebig's Annalen, 14, p. 50. 
5) Deutsches Handels-Archiv, Sept. 2, 
1881, p. 262. 
6) Bericht fiber elne Reise nach Kwang- 
si. Im Herbst 1886 uuternommen. Oils of the Lauraceae. 
383 
ation in the distillation of the oil.1 Upon distillation, the bark, flowers, 
flower stalks, twigs and leaves yielded oils that were similar in proper- 
ties and aldehyde content. Inasmuch as the bark, the flowers and 
flower-parts are excluded on account of their high price, the leaves and 
branches alone can come into consideration as far as the production 
of the commercial oil is concerned. As a matter of fact, the leaves 
only, with possibly some waste from the bark, are used for distillation. 
Fig. 70. 
Cassia Oil Distillation in China. 
This was definitely ascertained by 0. Struckmeyer, who made a trip 
through the Cassia district in 1895 at the request of Siemssen of 
Hongkong-.2 
The distillation is conducted in the valleys of the provinces Kwang-si 
and Kwang-tung at points where a sufficient water supply can be had. 
i) Bericht von S. & Co., Oct. 1892, p. 12. 
2) Ibidem, Oct. 1896, p. 11. 384 
Special Part. 
The apparatus in use1 (fig. 70) consists of a brick oven with an iron pan 
let into the masonry. On this rests a wooden cylinder lined on the inside with 
sheet-iron and open above. After the cylinder has been charged with leaves 
and half filled with water, the opening is closed with a peculiar shaped helmet 
of sheet-iron. The joint is sealed with wet cloths pressed between. The helmet 
has a groove on the inner side into which the condensed vapors flow and 
thence through a tube into the receivers. The receivers are arranged cascade- 
like and in them is deposited the heavy oil. The water is used for the next 
distillation. 
Cassia oil is shipped in lead canisters with a capacity of 7.5 k., of 
which 4 are packed in a case. The interstices are filled with the glumes 
of rice. The form and color of the labels on the canisters have long 
remained unchanged. 
History. The history of cassia oil will be found with that of Ceylon 
cinnamon on p. 378. 
Properties. Chinese cinnamon oil or cassia oil, when pure, is a 
mobile liquid, yellowish to brownish in color, and strongly refractive. 
Its odor is cinnamon-like, the taste burning and intensely sweet, with- 
out the unpleasant, grating after-taste that is perceptible in oils adulter- 
ated with rosin. Sp. gr. 1.055-1.065. Inasmuch as the specific gravity 
of the cinnamic aldehyde and the other constituents of the oil is almost 
the same, differences in the aldehyde content are not revealed by 
changes in the specific gravity. 
Cassia oil is optically inactive or has but a slight rotatory power 
either to the right or to the left. It is readily soluble in 1-2 p. of 80 
p. c. alcohol. Its behavior toward 70 p. c. alcohol varies in so far as 
most oils yield clear solutions with 3 parts of the solvent, whereas 
some otherwise good oils produce turbid, opalescent solutions. This 
peculiar behavior is possibly traceable to zinc cinnamate which is 
frequently present in the oil. The oil boils with partial decomposition 
between 240-260°; acetic acid is split off, and a viscid residue of 6-8 
p. c. remains. For further details see under Examination. 
If four drops of cassia oil, well cooled with ice water, are mixed with 
a like amount of nitric acid, they unite forming a crystalline mass. 
This reaction, which is mentioned in the German Pharmacopoeia as a 
reaction of identity, depends on the union of the nitric acid with the 
cinnamic aldehyde to an unstable addition' product, which is readily 
split up into its component parts by water. The reaction cannot be 
used as a test of purity for even strongly adulterated oils will produce 
crystals. In order to carry out the reaction, the oil must be well cooled, 
1) Bericht von S. & Co., Apr. 1893, p. 11; Oct. 1896, p. 13. Oils of the Lauraceae. 
385 
for if the heat of the reaction becomes too great, only oily products 
result. The principal constituent of the oil, which supplies a criterion 
for its valuation, is the cinnamic aldehyde. A good oil contains as 
much as 75-90 p. c. 
Composition. The principal constituent of cassia oil as well as of 
cinnamon oil is the cinnamic aldehyde. The differences in the two oils 
due to the accompanying constituents were known to the chemists 
who investigated the Chinese and Ceylon oils during the first half of 
this century. Blanchet1 (1833) e. g. calls attention to the fact that 
cassia oil has a much more pungent odor than the Ceylon cinnamon 
oil. Dumas and Peligot2 (1834) also point out differences in the oils. 
With oils distilled by themselves they came to the conclusion that the 
cinnamic acid, obtained by the oxidation of the oil, stood in the same 
relation to the cinnamon oil or cinnamic aldehyde, as benzoic acid does 
to bitter almond oil or benz-aldehyde. In other words they recognized 
that cinnamon oil consists essentially of cinnamic aldehyde. The same 
investigators discovered the interesting, though unstable substance 
CpHsO. NO3H, ■ which results upon the addition of nitric acid to 
cinnamic aldehyde in the cold, and which is remarkable on account of 
its tendency to crystallize. 
Of other investigations of the same period, those of Mulder3 (1840) 
and of Bertagnini4 (1853) may be mentioned. Bertagnini investigated 
the compounds resulting by the action of the acid alkali sulphites upon 
the aldehyde, the composition of which has only recently been definitely 
established by Heusler5 (1891). 
Cinnamic aldehyde, CgHs . CH : CH . CHO, is a light yellow, strongly 
refractive liquid with an intensely sweet taste. At low temperatures it 
solidifies and melts at -7.5°.6 Sp. gr. 1.064 at 15° (1.0497 at ^).7 
Only under greatly diminished pressure does it boil without decom- 
position: at 128-130° under 20 mm. pressure.8 For purposes of identi- 
fication the phenyl hydrazone, which melts at 168°, is well adapted.9 
The "cassia stearoptene" of Rochleder10 is a crystalline deposit only 
seldom found in old cassia oil. Its constitution was determined by 
i) Liebig's Annalen, 7, p. 164. 
2) Ann. de Chim. et Phys., 57, p. 305; 
Abstr. in Liebig's Annalen, 12, p. 24; 13, 
p. 76; 14. p. 50. 
s) Liebig's Annalen, 34, p. 147; Journ. 
f. prakt. Chem., 15, p. 307; 17, p. 303; 
18, p. 385. 
*) Liebig's Annalen, 85, p. 271. 
5) Beriehte, 24, p. 1805. 
6) Zeitschr. f. phys. Chern., 16, p. 24. 
7) Liebig's Annalen, 285, p. 18. 
§) Berichte, 17, p. 2110. 
9) Berichte, 17, p. 575. 
io) Ber. d. Academ. d. Wissensch. zn 
Wien, mathem. phys. KI., 1850, p. 1. 
(Abstr. Chem. Centrbl., 1851, p. 46), and 
ibid., vol. 12, p. 190. (Abstr. Chem. 
Centrbl.. 1854, p. 701). 386 
Special Part. 
Bertram and Kuersten^in 1895. This particular specimen crystallized 
out of the last fraction obtained in the rectification of an oil of cassia. 
In the pure 'state it consists of well formed, hexagonal, yellow plates 
which melt at 45-46°. They have a very persistent, unpleasant odor 
and are identical with methyl ortho cumaric aldehyde, CpH^OCHs) 
CH: CH. CHO, a substance that can be obtained synthetically by the 
condensation of methyl salicylic aldehyde and acet-aldehyde. 
A constituent that has no very favorable influence on the odor and 
taste of the cassia oil is the cinnamyl acetate which was found in the 
oil by Schimmel & Co.2 in 1889. Upon saponification of the non-aldehyde 
constituents oUthe oil with alcoholic potassa cinnamic alcohol is obtained 
on the one hand and acetic acid on the other. The former crystallizes 
from ether in hard, white crystals (b. p. 137° at 11 mm.). Cinnamyl 
acetate boils between 135-140° under 11 mm. pressure and has 
an unpleasant odor' and a grating taste. Besides this, small amounts 
of a second ester seem to be. present, viz. the phenyl propyl ester of 
acetic acid. This conclusion is drawn from the boiling point of an 
alcohol that accompanies the cinnamic alcohol after saponification. 
On account of the readiness with which cinnamic aldehyde oxidizes, 
cassia oil always contains free cinnamic acid, but the amount is much 
less than one might expect from the changeability of the pure aldehyde. 
It is present to the extent of about 1 p. c.3 The free acid has the 
undesirable property of dissolving the lead of which the canisters are 
made. A crystalline sediment observed by Hirschsohn4 in 1891 con- 
sisted of lead cinnamate. Subsequently he examined a number of com- 
mercial oils and out of twelve samples eleven were found to contain 
lead. The test for lead is made by shaking a few drops of the oil with 
sulphuretted hydrogen water. According to the amount of lead present, 
the oil is colored red to black. For medicinal or culinary purposes only 
the rectified oil, free from lead, should be used. 
Adulterations and their Detection. Formerly cassia oil was 
adulterated only with fatty oils, cedar wood oil and gurjun balsam oil. 
i) Journ. f. prakt. Chem., II, 51, p. 316. 
2) Bericht von S. & Co., Oct. 1889, p. 19. 
3) Evidently the cinnamyl acetate largely prevents the oxidation as is shown by 
the following experiment. A very old oil of cassia containing 77.7 p. c. of aldehyde was 
set aside for a year in shallow dishes covered with perforated filter paper. Heat, light 
and air had free access. At the end of this period? the cinnamic acid content had 
increased from 0.7 p. c. to 8.5 p. c. Resiniflcation had been but slight, for the non- 
volatile residue (comp, tests), was but slightly greater after the experiment than before. 
Under like conditions pure cinnamic aldehyde would rapidly lyive been converted into 
a mass of crystals of cinnamic acid.-(Ber. of S. & Co., Oct. 1890., p. 10.) 
4) Pharm. Zeitschr. f. Russland, 30, p. 790. Oils of the Lauraceae. 
387 
The detection of these adulterants was very simple, since the specific 
gravity was lowered and the oil was no longer soluble in 80 p. c. 
alcohol. The presence of the oils of cedar wood and gurjun balsam could 
furthermore be readily ascertained by their strong laevo-rotation. Less 
easy of detection was the adulteration with rosin and petroleum which 
was much practiced in Macao and Hongkong especially during the late 
eighties. At first colophonium only seems to have been used, but inas- 
much as larger additions of rosin thickened the oil and increased its 
specific gravity, this discrepancy was equalized by the addition of 
petroleum. Inasmuch as this method of adulteration did not influence 
the solubility in 80 p. c. alcohol any more than the specific gravity, it 
was not discovered for some time. Detection, however, followed when 
the addition of rosin became too large. The commercial oils of that 
period had a very unpleasant odor, a dark brown color and the con- 
sistency of a thick lacquer. The taste which was but slightly sweetish 
soon gave way to an unpleasant and persistently grating sensation in 
the mouth. Upon rectification with water vapor, as much as 40 p. c. 
of a resinous mass remained in the still. The distillate separated in 
two layers: one -sank to the bottom of the water, the other floated on it. 
The latter consisted, as was found upon examination, of petroleum. 
The demand to be able to detect on a' small scale this form of 
adulteration, led to the distillation test of Schimmel & Co.1 This test 
consists in distilling a weighed or measured quantity of the oil and 
weighing the residual rosin. * 
Fifty grams of cassia oil are weighed in a tared fractionation flask of 
100 cc. capacity (fig. 53, p. 189). A tube 1 m. in length is attached as con- 
denser and the oil distilled with the aid of a direct flame. At first water 
passes over with "cracking," the thermometer then rises rapidly to 240° and 
the bulk of the oil distills between 240 and 260°. The end of the distillation 
is indicated by the appearance of white fumes arising from the decomposition 
of the residue. The thermometer at the same time rises to 280-290°. Upon 
cooling the residue in the flask is weighed. The residue of a good oil is viscid 
and tough and constitutes 6-8, at most 10 p. c. of the oil. The residue of an 
oil adulterated with rosin is hard and brittle and correspondingly larger. 
Instead of weighing the oil, 50 cc. can be measured in a pipette and the 
distillate be collected in a graduated cylinder. By deducting the number of cc. 
of distillate from 50, the amount of residue can be ascertained with sufficient 
accuracy. 
The petroleum Can be detected in the distillate. The distillate from pure 
oils forms a clear solution with 70-80 p. c. alcohol. If petroleum is present, 
Berlcht von S. & Co., Oct. 1889, p. 15. 388 
Special Part. 
no perfect solution results:1 the liquid is turbid at first, but upon standing the 
supernatant petroleum can be removed and its behavior toward sulphuric and 
nitric acids be tested (comp. p. 201.) 
In order to detect rosin in cassia oil without material loss, Gilbert2 
suggests that several grams of oil be heated in a watchglass in a 
drying oven at a temperature of 110-120° until of constant weight. 
According to Gilbert, the determination of the acid number also yields 
useful results for the detection of rosin. An oil which upon distillation 
yielded 6 p. c. of residue had an acid number of 13. After 20 p. c. of 
rosin (acid number 150) had been dissolved in the oil, 
the acid number rose to -10. A cassia oil with 28 p. c. 
of residue yielded an acid number of -17. 
According to Hirschsohn3 (1890), an alcoholic 
solution of lead acetate, which has the property of 
producing precipitates with a solution of rosin, can be 
used for the detection of rosin in cassia oil. 
To a solution of 1 p. of cassia oil in 3 p. of 70 p. c. 
alcohol, a freshly prepared solution of lead acetate in 70 p. c. 
alcohol, saturated at ordinary temperature, is added drop 
by drop to the extent of one-half the volume of the oil 
solution. If a precipitate is produced, the oil was adulter- 
ated with rosin. As little as 5 p. c. of rosin can be detected 
in this way. 
Aldehyde Assay. Inasmuch as the value of cassia 
oil depends on its cinnamic aldehyde content, the 
aldehyde assay is of the greatest importance in deter- 
mining the value of the oil. The method worked out 
by Schimmel & Co.4 is universally recognized5 and the 
oil is sold according to the results obtained by it in 
the principal markets of the world, such as Hongkong, 
London, Hamburg and New York. 
For the assay a special flask (cassia flask, aldehyde flask, fig. 71) of about 
100 cc. capacity is used. The neck of the flask is about 13 cm. long, has an 
Fig. 71. 
% natural size. 
i) As already stated, cassia oil that contains rosin as well as petroleum, is soluble 
in 80 p. c. alcohol, whereas otherwise pure cassia oil to which petroleum has been 
added does not form a clear solution with 80 p. c. alcohol, the petroleum separating 
in the form of oily drops. 
2) Chern. Zeitung, 18, p. 1406. 
3) Pharm. Zeitschr. f. Russl., 29, p. 255. 
*) Bericht von S. & Co., Oct. 1890, p. 12. 
5) In the description of his travels through the cassia districts, O. Struckmeyer 
relates that he found the implements for the aldehyde determination according to 
Schimmel & Co. on a plantation near Loting-chow in the interior of China. Bericht 
von S. & Co., Oct. 1896, p. 12. Oils of the Lauraceae. 
389 
inner diameter of 8 mm., and is calibrated into Mo cc. The neck has a 
capacity of about 6 cc. The zero mark is fixed slightly above the point 
where the flask is narrowed into the neck. 
By means of a pipette, 10 cc. of oil are transferred to the flask and an 
equal volume of 30 p. c. sodium acid sulphite solution is added. The mixture 
is shaken and the flask placed in a boiling water bath. After the solid mass 
has become liquid more acid sulphite solution is added, the mixture being 
constantly heated and occasionally shaken, until fully three-fourths of the flask 
is filled. The solution is heated until no more solid particles are visible and 
the odor of cinnamic aldehyde has disappeared. When the clear oil floats upon 
the salt solution, flask and contents are allowed to cool and sufficient acid 
sulphite solution is added to raise the lower limit of the oily layer to the zero 
point of the scale. The number of cc. of oil is read off, and by deducting 
this number from ten, the aldehyde content is ascertained. Accurately speaking, 
percentage by volume and not percentage by weight is determined in this manner. 
Inasmuch, however, as the specific gravity of the aldehyde and the non- 
aldehyde constituents is almost the same, the two are practically identical. 
The chemical reactions involved can be explained by means of the 
following equations (Heusler,1 1891): At first the insoluble aldehyde 
addition product is formed. 
C«H5 . CH : CH . CHO + NaHS03 = C0H5 . CH : CH . CHO . NaHS03 
Cinnamic aldehyde Acid sulphite of sodium Clnnamal hydroxy sulphonate of sodium. 
When boiled with water, two molecules of this addition product 
break up into a molecule of cinnamic aldehyde and one of sulpho 
cinnamal hydroxy sulphonate of sodium. 
2C6H5. CH : CH. CHO. NaHSOs = C6H5. CH. CH. CHO + 
Cinnamal hydroxy sulphonate of sodium Cinnamic aldehyde 
CgH5CH2 . CH(SOsNa). CHO. NaHSOs 
Sulpho cinnamal hydroxy sulphonate of sodium.; 
In order to convert all of the aldehyde into the second compound 
soluble in water it is necessary to use an excess (2 mol.) of sodium 
acid sulphite. The salts of the sulpho cinnamal hydroxy sulphonic acid 
are readily soluble in water, and not decomposed by boiling water. They 
are decomposed by destructive distillation or when heated with caustic 
soda or sulphuric acid. 
The aldehyde content of a good cassia oil amounts to at least 
75 p. c., and only in rare instances is higher than 90 p. c. However, 
oils have been obtained from China which contained only 35-50 p. c. 
of aldehyde, yet no adulteration could be detected. According to the 
Chinese, these oils were distilled from young leaves, an assertion the 
correctness of which cannot be ascertained. 
i) Berichte, 24, p. 1805; Bericht von S. & Co., April 1890, p. 13. 390 
Special Part. 
Iii order to be able to assay oils with but 35 p. c. of aldehyde 
according' to the method given above, it is necessary to use 5 cc. of 
oil instead of 10 cc. and to make corresponding changes in the calculation. 
Oils obtained from the different parts of the Cassia Shrub. 
All parts of the cassia shrub yield oils with a high aldehyde content.1 
The differences in the specific gravity, though they are but slight, 
indicate that the non-aldehyde constituents vary somewhat as to com- 
position. In the distillation of the commercial oil only the leaves and 
twigs 'are commonly used. The bark and the so-called cassia buds 
command too high a price, whereas the flower stalks cannot be obtained 
in sufficient quantity. However, it may happen occasionally that all 
of these parts are distilled. 
1. Oil from the bark, the Cassia lignea of commerce. Yield 1.5 p. c.; 
sp. gr. 1.035; aldehyde content 88.9 p. c. 
2. Oil from the cassia buds, the Flores cassiae of commerce. Yield 
1.6 p. c.; sp. gr. 1.026; aldehyde content 80.1 p. c. 
3. Oil from the stalks of the cassia buds. Yield 1.7 p. c.; sp. gr. 
1.046; aldehyde content 92 p. c. 
4. Oil from the leaves. Yield 0.54 p. c.; sp. gr. 1.056; aldehyde 
content 93 p. c 
5. Oil from the twigs. Yield 0.2 p. c.; sp. gr. 1.045; aldehyde 
content 90 p. c. 
6. Oil from a mixture of leaves, petioles and young twigs. Yield 
0.77 p. c.; sp. gr. 1.055; aldehyde content 93 p. c. 
Inasmuch as the commercial oil is distilled from the materials 
enumerated under No. 6, its properties should correspond with those 
found and recorded above. The fact that the commercial oils never 
equal the above in quality is probably due to the crude method common 
in China, namely the distillation over a free flame. 
Production and Commerce. Cassia, also known commercially as 
Cassia lignea in order to distinguish it from other cinnamon varieties, 
is produced in a comparatively limited territory, namely in the provinces 
Kwang-si and Kwang-tung. The cassia district lies between the degrees 
110 and 112 eastern longitude. It is bounded on the north by the 
Si-kiang or West river, and extends to the south as far as the 23° 3' 
northern latitude. The principal plantations are in the vicinity of 
Tai-wo, Yung and Sih-leong on the Sang-kiang, also at Loting-chow on 
the Lintan river. 
i) Bericht von S, & Co., Oct. 1892, p. 12. Oils of the Lauraceae. 
391 
The Tai-wo product is preferred in the market. The annual output 
of cassia varies between 50,000 and 80,000 piculs or 3,000,000 and 
4,800,000 k. Canton and Hongkong are the principal markets. From 
the latter point 54,032 piculs were exported during 1896. 
The distillation is conducted in the district outlined above. As 
material for distillation the leaves, petioles and twigs, which result as 
waste in the production of the Cassia, lignea, are used. Whereas the 
cassia bark is transported down the Si-kiang, the natural water route, 
to Canton, the oil is conveyed in lead containers over the mountains 
to Pak-hoi and then by ship to Hongkong. This is done to avoid the 
high tariff levied at the Likin stations on the way to Canton. 
The annual production of cassia oil varies between 2,000 and 3,000 
piculs, or 4,000 and 6,000 cases of 30 k. each, with a value of $250,000 
to $375,000. Hongkong is the principal center. The aldehyde content 
serves as criterion of the value of the oil. Following the example of 
Schimmel & Co., the principal firms in Hongkong are equipped to make 
the aldehyde assay and have acquired a considerable degree of accuracy 
in making the test. 
133. Japanese Cinnamon Oil. 
The various parts of Cinnamomum loureirii Nees are used in Japan 
as cinnamon, the root bark Komaki being especially esteemed. Upon 
distillation Shimoyama1 obtained 1.17 p. c. of a light yellow, strongly 
refractive oil, sp. gr. 0.982 at 15°. Like the genuine cinnamon oil it 
contains cinnamic aldehyde. The non-aldehyde oil has the odor of 
lavender, boils at 175-176° and, as shown by analysis, consists 
principally of a terpene. 
134. Oil from the Bark of Cinnamomum Kiamis. 
From the massoy bark of Cinnamomum kiamis JNees Bonastre2 
(1829) distilled an oil that separated into a light and a heavy oil and 
from which a camphor crystallized out. The light oil was almost 
colorless, mobile, and its odor reminded of sassafras. The heavy oil 
was thicker, less volatile, had a fainter odor and a strong taste of 
sassafras. The massoy camphor, which is likewise heavier than water, 
consists of a white, soft, odorless and tasteless powder which is soluble 
in hot alcohol and ether. 
i) Mitt, der med. Fak. Tokio, vol. 3, No. 1. Abstr. Apoth.-Zeit., 11, p. 537. 
2) Journ. de Pharm., 15, p. 204. 392 
Special Part. 
135. Culilawan Oil. 
The oil from culilawan bark from Cinnamomum culilawan Bl. Was 
first prepared by Schloss1 in 1824 who describes it as an oil having the 
odor of the oils of clove and cajeput. The yield is 4 p. c.; sp. gr. 1.051. 
With 3 or more parts of 70 p. c. alcohol it produces a clear solution. 
The principal constituent is eugenol (benzoyl eugenol, m. p. 70-71°) 
of which the oil, assayed according to Thoms' method contains about 
62 p. c. (Gildemeister & Stephan,2 1897). A fraction 249-252° con- 
tained methyl eugenol (monobrom methyl eugenol dibromide, m. p. 
78-79°; veratric acid, m. p. 179-180° 5). Fraction 100-125° under 
10 mm. pressure possibly contains terpineol. 
136. Oil from Cinnamomum Wightii. 
The bark of Cinnamomum wightii Meissn. which grows in the 
mountainous districts of southern India, yielded upon distillation 0.3 
p. c. of oil, which boiled from 130-170° and the sp. gr. of which was 
1.010 at 15°. The plant that yields this bark was formerly falsely 
designated Michelia nilagirica^ 
137. Oil from Cinnamomum Oliveri. 
From the bark of Cinnamomum oliveri Bail., a. tree known in 
Australia as black, brown or white sassafras, R. T. Baker4 obtained 
upon distillation with water vapor 0.75-1 p. c. of an oil of a, golden- 
yellow color and a very agreeable odor. Sp. gr. 1.001; «d = +22 to 
22.3°. The oil distilled between 213-253°, 54 p. c. passing over 
between 230-253°. 
The lowest fraction gave the iodol reaction for cineol. With alkali 
a small amount of a phenol, presumably eugenol, was separated, which 
gave a blue color with ferric chloride. Acid sulphite removed from the 
oil about 2 p. c. of an aldehyde, having the odor of cinnamon and 
which presumably is cinnamic aldehyde. Upon cooling the oil to -12°, 
crystals separated which, however, dissolved again in the oil when 
removed from the freezing mixture (safrol?). 
The leaves of this tree, which was formerly incorrectly designated 
as Beilschmiedia obtu^ifolia, yield upon distillation (770 oz. to the 
ton) an oil which has a decided odor of sassafras.5 
i) Trommsdorff's Neues Journ. der Pharm., 8, II, p. 106. 
2) Archiv d. Pharm., 235, p. 583. 
3) Bericht von S. & Co., Oct., 1887, p. 36; Apr. 1888, p. 46. 
Proc. Linnean Soc. of N.'-S.-Wales, 1897, part 2, p. 275; abstr. Pharm. Ztg;., 42, 
p. 859. 
a) Bericht von S. & Co., Apr. 1887, p. 38. Oils of the Lauraceae. 
393 
138. Oil from Persea Gratissima. 
The leaves of Persea gratissima Gaertn. (from the botanical garden 
in Genoa) yielded upon distillation 0.5 p. c. of a light greenish oil which 
closely resembles estragon oil in odor and taste.1 Sp. gr. 0.9607; 
aD= + lo50'; ud at 18.2° = 1.5164. These data indicated the presence 
of fairly pure methyl chavicol. Anethol was excluded because of the 
absence of a sweet taste and because no crystals separated when the 
oil was exposed to a freezing mixture. 
An attempt to convert a part of the oil, of which but 10 g. were 
obtainable, into anethol by means of alcoholic potassa failed on account 
of an accident. The remaining oil. when oxidized with permanganate, 
yielded an acid melting at 183° which possessed the properties of 
anisic acid, thus indicating methyl chavicol. 
139. Oil from Clove Bark. 
The bark of the Brazilian tree Persea caryophyllata Mart. (Dicy- 
pelliuin caryophydatum Nees) was formerly used in the apothecary 
shops as Cortex, caryophyllati. It was also known as Cassia caryo- 
phyllata (Ger. Nelkenrinde, Nelkenzimt,2 Nelkencassie and Nelkenholz). 
Upon distillation of the powdered bark, Trommsdorff3 (1881) 
obtained 4 p. c. of a light yellow oil heavier than water which had the 
odor of cloves. With potassa, soda, and ammonia the oil formed 
crystalline compounds from which it could be regenerated upon the 
addition of sulphuric acid. This property as well as odor and density 
render it probable that this oil, like the oil of cloves, contains eugenol. 
I 
14>0. Oil of Pichurim Beans. 
The volatile oil of the cotyledons of Nectandra pichury major Nees 
and A7, p. minor Nees, the pichurim beans of commerce, was first prepared 
by Robes4 in 1799 and then by Bonastre5 in 1825. It was examined 
by Mueller6 in 1853. On account of the large amount of starch present 
he added sulphuric acid to prevent the formation of starch paste and 
obtained 0.7 p. c. of an oil of greenish-yellow color and the characteristic 
pichurim odor. 
i) Bericht von S. & Co., Oct. 1894, p. 71. 
2) The oil from the leaves of the Ceylon cinnamon was for a time designated as 
Nelkenzim tol. 
s) Trommsdorff's Neues Journ. d. Pharm.. 23, I, p. 7. 
4) Berlin. Jahrb. d. Pharm., 5, p. 60. 
5) Ibidem, 37, p. 160; Repert. f. d. Pharm., I, 21, p. 201. 
«) Journ. f. prakt. Chem., 58, p. 463. 394 
Special Part. 
The oil distills between 180-270°. After repeated fractionation, 
Mueller obtained a hydrocarbon (pinene?) with a constant boiling point 
at 150°. Fraction 165-170° had an orange odor and seems likewise 
to have been a terpene. Fraction 255-256° had a deep indigo blue 
color. From the highest fractions crystals of "pichurim Fettsaure" 
(lauric acid) separated. Inasmuch as the pichurim beans have a distinct 
safrol odor, this substance is probably a constituent of the oil. 
141. Caparrapi Oil. 
According to B. F. Tapia1 (1898) the oil of Nectanclra caparrapi is 
long known in Columbia as caparrapi oil. The tree is popularly known 
as Canelo, probably on account of the cinnamon-like odor of the bark. 
The oil is obtained according to a method similar to that in vogue in 
this country for the production of turpentine, and is used as a substitute 
for copaiba in this country. 
In commerce the oil is found more or less colored in accordance 
with the temperature employed in the removal of the water. It contains 
a monobasic acid, C15H26O3, which melts at 84.5° and which can be 
obtained in a crystalline form only from the light colored oils. The acid 
free oil consists in large part of a sesquiterpene alcohol, C15H25OH, 
called caparrapiol, which is converted into caparrapene, C15H24, by 
dehydrating agents. The alcohol as well as the hydrocarbon are readily 
polymerized, especially by heat, so that in the water distillation about 
three-fourths of the oil is resinified. 
142. Guayana Linaloe Oil. 
The oil from Ocotea ca,udata is described together with Mexican 
linaloe oil, which see. 
143. Ocotea or Laurel Oil from Guayana. 
An oil designated laurel oil from Demerara (British Guayana) was 
examined by Stenhouse2 in 1842. According to Christison, it is obtained 
from a species of the genus Ocotea. Incisions are made near the root, 
penetrating the oil cavities beneath the bark. The exuding oil is a 
yellowish liquid which has a pleasant terebinthinate odor, sp. gr. 0.864 
at 13.3° and boils between 149-162.5°. Upon standing, a mixture of 
1) Bull. Soc. chim., Ill, 19, p. 638. 
2) Philos. Magaz. and Journ. of Science, 20, p. 273; 25, p. 200. Liebig's Annalen, 
44, p. 309; 50, p. 155. Comp, also Hancock, Bull, des sciences, math. phys. et chim. 
F^vr. 1825, p. 125. Abstr. Trommsdorff's Neues Journ. d. Pharm., 11, I, p. 171. Oils of the Lauraceae. 
395 
oil, alcohol and dilute nitric acid yielded crystals which upon recrystal- 
lization were obtained in the form of white, rhombic prisms melting 
at 150°. The oil, therefore, appears to consist of pinene and the 
crystals obtained by Stenhouse were probably terpin hydrate although 
the melting point of this substance lies at 116-117° and not at 150°.1 
144% Venezuelan Camphor wood Oil. 
Through the kindness of Professor H. H. Rusby,2 Fritzsche Bros, of 
New York obtained some Venzuelan camphorwood, the botanical origin 
of which has not been determined, but which probably belongs to either 
the genus Nectandra or Ocotea (Family Lauraceae). The wood, which 
was in the form of large billets, was rather soft and easily split, has a 
silky lustre and possesses a faint odor reminding somewhat of borneol. 
Upon distillation of the comminuted wood, 1.15 p. c. of a light 
yellow oil was obtained that had an unusually high sp. gr., viz. 1.155, 
and «d=+ 2° dO'.3 The oil had a faint odor reminding of that from 
Asarum canadense and congeals at ordinary temperature to a crystalline 
mass. Drained and recrystallized this was obtained in the form of 
handsome, colorless prisms which melt at 28.5°. Concentrated sulphuric 
acid dissolves these with a blood-red color. When boiled with alcoholic 
potassa they are converted into a substance which recrystallizes from 
alcohol in plates and melts at 55-56°. These properties show that the 
crystals which separate from the oil, and which constitute about 90 
p. c. of it, consist of apiol. A careful comparison showed them to be 
identical in all respects with the apiol from parsley oil. 
145. Sassafras Oil. 
Oleum Sassafras. -Sassafrasol.-Essence de Sassafras. 
Origin and History. The sassafras tree, Sassafras officinalis Nees 
(Family Lauraceae) is widely distributed in North America from Canada 
to Florida and Alabama, and westward as far as Kansas4 and the 
northern part of Mexico. In the southern states it frequently attains 
a height of 15 m., the trunk occasionally having a diameter of % m. 
Numerous older statements to the contrary, the older bark and 
wood are odorless. The green parts of the tree, when crushed, smell 
faintly aromatic, but not of safrol. The wood of the roots and especially 
the root bark are more rich in oil cells. 
1) Gmelin, Organ. Chem., IV ed., vol. 7, p. 282, the melting point of the substance 
obtained by Stenhouse Is given as 125°. 
2) Comp. Rusby, Botany of Venezuela, Pharm. Journ., 57, p. 292. 
3) Bericht von Sj & Co., Apr. 1897, p. 52. 
4) Proc. Am. Pharm. Assoc., 29, p. 446. 396 
Special Part. 
As already mentioned under the oils of sweet birch and wintergreen 
(p. 331) next to turpentine oil, the oil of sassafras was the first 
volatile oil distilled in a primitive fashion in North America. On 
account of the pleasant aroma, the root bark was chewed by the 
natives as Pavame. It was also mixed with smoking tobacco 
(Rafinesque1), and added as aromatic to refreshing beverages and 
was used as a remedy. On account of its peculiarity, the sassafras 
tree is said to have attracted the attention of the Spaniards at 
their first landing in Florida under Ponce de Leon in 1512, also 
under de Soto in 1538. They are said to have regarded it as a kind 
of cinnamon tree. Afterward the sassafras tree soon came to be 
regarded as a valuable medicinal plant and article of luxury of the new 
world, not only by the Spaniards and French in Florida, but also in 
Mexico. As late as the first half of this century the bark, leaves and 
buds were used in the middle and central states as a substitute for 
Chinese tea (Lloyd2). 
As early as 1582 sassafras wood and bark became known in 
Germany as a new American drug and were used under the name of 
Lignum pavanum, L. tioridum, L. xylomarathrum (Ger. Fenchelholz}.^ 
In 1610 young plants were brought to England and cultivated.4 Bark 
and wood were apparently first distilled by Angelus Sala in 1620, who 
mentions that the oil is heavier than water.5 Schroeder's Pharmacopoea 
medico-chymica, published in Frankfurt-on-the-Main in 1641, is the first 
pharmacopoeia that gives directions for the distillation of the oil, 
whereas the municipal price ordinance of Frankfurt-on-the-Main of 1587 
already enumerates Oleum ligni sassafras. Hoffmann in Halle distilled 
the oil in 1715 and describes it as being colorless and specifically heavy.6 
In 1738 Maud, an Englishman, observed the formation of large crystals 
of sassafras camphor.7 Early examinations of the oil were made by 
Muschenbroeck, by Neumann,8 and by Dehne,9 the first. thorough one 
was made by Grimaux and Ruotte10 in 1869. 
A detailed historic account of the sassafras tree as a drug-yielding 
plant was given by J. U. Lloyd2 in 1898, who, however, does not enter 
into the history of the volatile oil. Schoepf,6 who was a careful observer 
i) Med. Flora or Manual of the Med. 
Bot. of the U. S. of N. Am., vol. 2, p. 235. 
2) Historical study of Sassafras. Pharm. 
Review, 16, p. 450 ; Pharm. Era, 20, p. 608. 
s) Documente zur Gesehichte der Phar- 
macie, p. 30. 
Pharmacographia, p. 537. 
5) Opera physico-medica, p. 84. 
6) Observationes physico-chymici. Obser- 
vatio 1, p. 13. 
7) Phil. Trans, of the Roy. Soc., 8, 
p. 243. 
si Chym. med., vol. 2, pars 3, p. 248. 
0) System d. Mat. med., vol. 4, p. 242. 
10) Compt. rend., 68, .p. 928. Oils of the Lanraceae. 
397 
and who traveled through the Atlantic states in 1783 and 1784 
repeatedly refers to the sassafras tree, but does not mention the oil. 
Evidently the distillation of the oil did not become an industry until 
the close of the last or the early part of this century. Possibly it was 
fostered by the growth of the industry in medical specialties ("patent 
medicines"), as was the case with the oils of sweet birch and wintergreen. 
The process of distillation seems to have been generally very 
primitive,1 
The still consisted of a barrel with a perforated bottom, firmly fitted into 
a conical iron kettle. The top of the barrel could be removed to charge the 
still. It is provided with an opening for the reception of a tin tube which 
passes through a barrel of cold water and serves as condenser. 
In recent years the distillation is conducted in a somewhat more 
rational manner. 
The stills, made of 3 in. pine planks, are 4-5 ft. high, about 12 ft. square 
and strengthened by iron bands. One of the sides is provided with two close 
fitting doors, an upper one for charging the still, and a lower one for removing 
the exhausted material. The wood is split, or sawed into thin pieces. The 
steam, generated in a boiler, enters the still at the bottom and the distillate is 
cooled in a coil condenser and collected in a large copper flask of 20 gal. 
capacity. About 2 in. from the bottom this flask is provided with a stopcock 
through which the oil is drawn off from time to time. The exhausted wood is 
dried and used as fuel. Such a still has a capacity for 20,000 lbs. of -wood 
and the distillation of this quantity lasts about 48-50 hours. The root bark 
yields 6-9 p. c. of oil, the woody part of the root less than I p. c. 
Up to the middle of this century the oil was distilled principally in 
Pennsylvania, Maryland and Virginia, and Baltimore and Richmond 
were the principal commercial centers for the oil. At the beginning of 
the war in 1860, not less than 50,000 lbs. of sassafras oil were sold 
annually in Baltimore alone (Sharp2). Since the sixties, considerable 
quantities of the oil have also been distilled in New Jersey, New York, 
Ohio, Indiana, Tennessee and the New England states, until the practical 
extinction of the tree rendered the industry unprofitable. 
Properties. Sassafras oil is a yellowish or reddish-yellow liquid 
having the odor of safrol and an aromatic taste. Sp. gr. 1.070-1.080; 
an = + 3 to + 4°; soluble in all proportions in 90 p. c. alcohol. If, 
according to the U. S. Pharmacopoeia, 5 drops of oil are mixed with 
5 drops of nitric acid, a violent reaction results: the oil is first colored 
red and is later converted into a red resin (Bonastre3). 
i) Proc. Am. Pharm. Assoc., 14, p. 211: Am. Druggist 1887, p. 45; New Remedies. 
1883. p. 224; Oil, Paint & Drug Reporter, Sept. 14, 1891; Pharm. Journ., Ill, 22, p. 491. 
3) Am. Jour. Pharm., 35, p. 13. Comp, also W. Procter, ibid. 33, p, 1; 38, p. 484. 
3) Comp. p. 400, footnote 2. 398 
Special Part. 
Fig. 72. 
Distillation of sassafras on a small scale in Virginia. Oils of the Lauraceae. 
399 
Fig. 73. 
Comminuting apparatus and stills in Lexington, Va. 400 
Special Part. 
Composition. To its principal constituent, the safrol, CioHioOa, the 
oil owes its odor as well as its principal properties. This substance 
was observed by Binder1 in 1821, it having crystallized out of the oil. 
The earlier investigators2 contented themselves by studying the action 
of chlorine, bromine, etc. on the oil as well as on the safrol. Upon satur- 
ating the oil with chlorine, then neutralizing the mixture with lime and 
distilling with water vapor, Faltin3 observed another constituent of the- 
oil, the ordinary camphor. 
The terra safrol was introduced by Grimaux and Ruotte4 (1869) 
who ascertained its composition to be represented by the formula 
CioHioO2. They also isolated a hydrocarbon CioHie, b. p. 155-157°, 
and named it safrene. They further observed the presence of a phenol 
which had the. odor of eugenol and produced a green color with ferric 
chloride. The identity of this phenol with eugenol was later established 
by Pomeranz5 (1890). 
A detailed study of the composition of the oil was made by Power 
and Kleber6 in 1896. From the air-dried root bark 7.4 p. c. of oil were 
obtained, sp. gr. 1.075, aD = + 3°16'. After most of the safrol had 
been removed by freezing, the eugenol (benzoyl eugenol, m. p. 69°) was 
shaken out with caustic alkali solution. The oil thus deprived of safrol 
and eugenol was fractionated. Fraction 155-160° was found to consist 
of pinene (pinene nitrolbenzylamine, m. p. 123°); fraction 160-1750, 
contained phellandrene (nitrite). The so-called safrene of Grimaux 
and Ruotte is, therefore, pinene. From a higher fraction dextro 
camphor (oxime, m. p. 115°) was isolated. The quantitative reduction 
of the camphor to borneol and the acetylization of the latter 
showed that camphor was present to the extent of 6.8 p. c. in the 
oil. Inasmuch as fraction 260-270° gave the characteristic sesquiter- 
pene reaction with sulphuric and glacial acetic acids, the presence of 
such a hydrocarbon is assumed, though a solid hydrochloride could not 
be obtained. 
According to the investigation of Power and Kleber, the composition 
of sassafras is as follows: 
1) Buchner's Repert. f. d. Pharm., 11, p. 346. 
2) Bonastre, 1828, Journ. de Pharm., II, 14, p. 645. Abstr. Trommsdorff's Neues 
Journal, 19, I, p. 210; Saint Evre, 1844, Ann. de Chim. et Phys., Ill, 12, p. 107; 
Compt. rend., 18, p. 705. Abst. Liebig's Annalen, 52, p. 396. 
3) Liebig's Annalen, 87, p. 376. 
*) Compt. rend., 68, p. 928. 
5) Monatsh. f. Chern., 11, p. 101. 
6) Pharm. Review, 14, p. 101. Oils of the Lauraceae. 
401 
Safrol 80.0 p. c. 
Pinene 
Phellandrene) 
d-Camphor 6.8 " 
Eugenol 0.5 " 
High boiling substances (sesqui- 
terpene and residue) 3.0 " 
100.3 " 
Adulteration. Sassafras oil is frequently adulterated with camphor 
oil. A perfectly pure article appears to be of rare occurrence. Inasmuch 
as camphor oil contains all of the constituents found in sassafras oil, 
the detection of the former is exceedingly difficult, but its presence may 
be indicated by strong variations in the specific gravity and other 
physical properties. Under the name of artificial sassafras oil, fractions 
of camphor oil having a specific gravity similar to that of true sas- 
safras oil are sold. 
146. Oil of Sassafras Leaves. 
As far as is known, the oil of sassafras leaves has been prepared 
but once. Power and Kleber1 obtained upon the distillation of fresh 
sassafras leaves 0.028 p. c. of an oil with a very agreeable odor remind- 
ing of that of lemons. Sp. gr. 0.872, «D = + 6°25'. 
The low boiling fractions consist of a mixture of pinene (nitrol- 
benzylamine) and myrcene. This representative of the olefinic terpenes 
which have been found e. g. in the oils of bay, hops, origanum 
and rosemary, was hydrated according to Bertram's method. The 
resulting alcohol had the odor and boiling point of linalool. This 
alcohol was further identified by its oxidation product citral and the 
condensation product of the latter with naphthylamine and pyrotartaric 
acid. The third terpene identified is phellandrene (nitrite). In addition, 
the presence of a paraffin melting at 58° and of a sesquiterpene was 
established. Of oxygenated constituents the oil contains citral (citral-/?- 
naphtho cinchoninic acid) and the two isomeric alcohols linalool and 
geraniol. These alcohols occur free as well as in the form of acetic and 
valerianic esters. 
147. Cryptocaria Oil. 
Cryptocaria moschata Mart, is a tree 10-15 m. high and is known 
in Brazil by the popular name Nos moscado do Brasil, Brazilian 
10.0 " 
i) Pharm. Review, 14, p. 103. 402 
Special Part. 
nutmeg. The ripe fruits are somewhat smaller than nutmegs, and have 
a strong aromatic odor reminding of laurel, sassafras, cajeput and 
nutmeg. 
Ten kilos of the powdered fruit deprived of their pericarp yielded upon 
distillation 37 g. of volatile oil (Peckolt1). This is a mobile liquid, light 
yellow in color, of a penetrating, aromatic odor and a burning, spicy 
taste. Sp. gr. 0.917. It is soluble in 90 p. c. alcohol in all proportions. 
14-8. Oil of Cryptocaria Pretiosa. 
The bark of Cryptocaria pretiosa Mart., (Mespilodaphne pretiosa 
Nees et Mart., Family Lauraceae), which is indigenous to northern Brazil 
on the Rio Negro, has a pleasant aromatic, cinnamon-like odor. Upon 
distillation the bark yielded 1.16 p. c. of an oil of cinnamon-like odor and 
a sp. gr. of 1.118. Although the odor seems to indicate the presence of 
cinnamic aldehyde, no crystalline addition product was obtained with 
sodium acid sulphite solution.2 
149. Oil of Laurel Leaves. 
Oleum Lauri Foliorum.-Lorbeerblatterbl. -Essence de Laurier. 
Origin and History. The laurel, Lauras nobilis L. is indigenous 
to Asia Minor, Syria and the Silician Taurus and has been extensively 
cultivated. During classical antiquity it acquired great significance as 
a symbol of victory but apparently found no other application than 
as a decorative plant. During the middle ages bark and leaves were 
used medicinally. The laurel oil of commerce is distilled from the leaves. 
The yield varies from 1-3 p. c. according to the quality of the leaves. 
Properties. The oil of the laurel leaves is a light yellow liquid 
with a pleasant odor, which first reminds of that of cajeput oil, and 
later becomes sweetish. Sp. gr. 0.920-0.930; «d = - 15 to -18°; 
2-3 p. of 80 p. c. alcohol are requisite to effect solution. 
Composition. The oil begins to boil at 158°, the thermometer rising 
rapidly to 168°. This fraction contains pinene (nitrolpiperidine base, 
m. p. 118°). Fraction 176° contains cineol as shown by the hydrobrom 
addition product. The fractions above 180° had a decided odor of 
anethol.3 Inasmuch, however, as the oil has no sweetish taste, which 
ought to be the case if anethol were present, this odor seems to indicate 
methyl chavicol, the isomer of anethol. The oil also contains small 
amounts of eugenol (benzoyl eugenol, m. p. 70°).3 
1) Pharm. Review, 14, p. 248. 
2) Bericht von S. & Co., Apr. 1893, p. 63. 
s) Bericht von S. &Co., Apr. 1899, p. 31. Oils of the Lauraceae. 
403 
150. Laurel Oil from ferries, 
History. Upon boiling and expression of the laurel berries a 
green mixture of fatty and volatile oil is obtained (Oleum laurinum) 
which is semi-liquid at ordinary temperature. It was used during 
antiquity and in older literature is mentioned among the substances 
employed in the preparation of ointments; also among the aromatics. 
It was contained in the first edition of the Dispensatorium Noricum 
of 1543. The volatile oil also seems to have been used medicinally. 
It is also mentioned in the price ordinances of Frankfurt of 1582 as 
well as in later ones. At present it seems to find little or no practical 
application and is only now and then prepared for scientific purposes. 
The yield from the berries is about 1 p. ,c. 
Properties. The oil from the berries is somewhat more viscid than 
that from the leaves; its odor is less agreeable. On account of the 
lauric acid which it contains, some specimens solidify at temperatures 
above 0°. Sp. gr. 0.915-0.935. The angle of rotation of a single oil 
was found to be -14° 10'. The same oil was insoluble in 80 p. c. 
alcohol, but was soluble in and more parts of 90 p. c. alcohol. 
Composition.1 The lower fractions contain the same constituents 
as the leaf oil (Wallach,2 1889), viz. very little pinene (pinene nitrol- 
benzylamine, m. p. 122-123°) and much cineol (cineol hydrobromide). 
The supposed laurene of Bruhl3 (1888) has revealed itself as a mixture 
of the above two constituents. Fraction 250°, sp. gr. 0.925, «d =- 7.2°, 
has the composition C15H24 and is therefore a sesquiterpene (Blas,4 
1865). 
Another constituent of the oil, the amount of which will vary 
according to the duration of the distillation, is lauric acid. It can be 
removed by shaking the oil with lye and melts when pure at 43°.5 In 
addition the oil contains ketones and alcoholic constituents which form 
solid compounds with sodium. Liberated by means of water they form 
a viscid oil which distills between 71-184° under 20 mm. pressure. 
The statement made by Gladstone6 that this oil contains eugenol 
has not been substantiated by the investigations of Blas and Muller. 
J) The first investigations were carried out by Bonastre, 1824, Journ. de Pharm., 
10, p. 36; 11, p. 3; Abstr. Repeat, f. d. Pharm., I, 17, p. 190; and by Brandes, 
1840, Archiv d. Pharm., 72, p. 160. 
2) Liebig's Annalen, 252, p. 97; also Muller, Berichte, 25, p. 547. 
3) Berichte, 21, p. 157. 
4) Liebig's Annalen, 134', p. 1. 
5) Blas and Muller, loc. cit. 
6) Journ. Chem. Soc., II, 2, p. 1. Abstr. in Jahresb. f. Chern., 1863, p. 545. 404 
Special Part. 
Although Gladstone designates his oil as "Bay oil from the berries of 
Laurus nobilis" it seems rather probable that he examined genuine 
bay oil which consists largely of eugenol.1 
151. Kuro-moji Oil. 
Oleum Kuromoji.-Kuromojiol.-Essence de Kuro moji. 
Lindera sericea Bl. is a shrub quite generally distributed throughout 
the mountainous regions of Japan.2 All parts of the plant contain 
small amounts of volatile oil, even the wood which is used in the 
manufacture- of tooth-picks. The oil, which was introduced into the 
market in 1889 by Schimmel & Co., is obtained from the leaves and 
young twigs. The distillation is conducted on a small scale by farmers 
who are satisfied to work up the material growing on their farms. 
Properties. Kuro-moji oil is of a dark yellow color and has a fine 
aromatic, balsamic odor. Sp. gr. 0.890 to 0.905; a-Q -- 0°4'. 
Composition. According to Kwasnik3 (1892) the oil contains two 
terpenes and two oxygenated constituents, viz. d-limonene (tetrabromide, 
in. p. 104°), dipentene (tetrabromide, m. p. 124°), terpineol (phenyl- 
terpinyl urethane, m. p, 109.5°), and 1-carvone (hydrosulphide, m.p. 214). 
153. Mountain Laurel Oil. 
All parts of the Mountain laurel or California bay tree4 Umbellularia 
californica Nutt. (Oreodaphne californica Nees, Tetranthera californica 
Hook, et Arn., Californischer Lorbeerbaum} contain volatile oil, 
especially the leaves which yield 2.45 to 4 s p. c. The oil is of a light 
yellow color and has a pungent aromatic odor reminding of nutmeg 
and cardamom. Strongly inhaled it attacks the mucous membrane 
and causes the flow of tears. The taste is warm and camphor-like. 
Sp. gr. 0.936 to 0.940. 
According to Heany6 the oil boils between 175 and 245° and con- 
tains a hydrocarbon boiling at 175°, also an oxygenated constituent 
called oreodaphnol, b. p. 210°, sp. gr. 0.960. 
Stillmann5 found in fraction 167-168° a substance of the com- 
position of the "terpinol" of Wiggers and List,7 also umbellol, boiling 
at 215-216° and having the composition CsHi20. 
1) Even much more recently no difference 
has been made in England between bay 
oil and the oil from laurel or bay berries. 
Comp. e. g. Ashton in Chemist and Druggist, 
July 2, 1892. 
2) Chemist and Druggist, 47. p. 502. 
3) Archiv d. Pharm., 230, p. 265. 
4) Ber. d. pharm. Ges., 6, p. 56. 
5) Berichte, 13, p, G30. 
6) Am. Journ. Pharm., 47, p. 105; 
Pharm. Journ., Ill, 5, p. 791. 
7) As shown by Wallach, terpinol is 
no chemical unit, but a mixture of dipen- 
tene, terpinene, terpinolene and terpineol 
(Liebig's Annalen, 230, p. 251). Oils of the Lauraceae. 
405 
153. Spicewood Oil. 
All parts of the North American spicewood, spice bush or fever bush 
{Benzoin odoriferum Nees, Laurus benzoin L., Benzoelorbeer-Strauch), 
but especially the bark and the berries contain volatile oil.1 The bark 
is used as a domestic remedy. 
1. The oil of the bark and twigs which was introduced into the market 
as spicewood oil by Fritzsche Bros, in 1885, has the odor of winter- 
green, sp. gr. 0.923 and boils between 170-300°. It consists of hydro- 
carbons and 9-10 p. c. of methyl salicylate. By treating 200 g. of oil 
with caustic soda, 10 g. of salicylic acid were obtained. 
2. The berries contain 4-5 p. c. of an aromatic, spicy oil with a 
camphor-like odor; b. p. 160-270°; sp. gr. 0.850-0.855. 
3. The leaves contain about 0.3 p. c. of oil with a very agreeable 
odor. Sp. gr. 0.888. 
154. Tetranthera Oil. 
The fruits of Tetranthera citrata Nees (Family Lanraceae), some- 
times called citronella fruits, are regarded as a panacea in India. Upon 
distillation they yield about 5.5 p. c. of an oil which has a strong odor 
resembling that of verbena oil and for this reason has been designated 
Japanese verbena oil. Sp. gr. 0.890-0.896. It boils between 180-240°, 
and contains in addition to a terpene, citral as principal constituent.2 
155. Oil of Massoy Bark. 
The botanical origin of the New Guinea bark, from which Schimmel 
& Co. have since 1888 distilled their massoy bark oil. is not known. 
Upon comparison of this bark with that of the genuine bark from 
Massoia aromatica Beccari, Holmes3 (1888) arrived at the conclusion 
that the two were not identical, but that the bark of Schimmel & Co. 
was very similar to the Cortex cvlilabani papuanus of Hanbury's col- 
lection, the botanical origin of which is also unknown. Wender4 (1891), 
on the other hand is of a different opinion. He states that according to 
its anatomical structure, the massoy bark of Schimmel & Co. is un- 
questionally that of a lauraceae, and that in other respects it corresponds 
best with the bark of Sassafras goesianum or Massoia aromatica. 
i) Bericht von S. & Co., Oct. 1885, p. 27; Oct. 1890, p. 49. 
2) Bericht von S. . & Co., Oct. 1888, p. 44. The sp. gr. 0,980 mentioned in the 
report is evidently due to a printer's error and should be 0.890. Two later distillates 
had the sp. gr. 0.894 and 0.896 respectively. 
3) Pharm. Journ., Ill, 19, pp. 465 and 761. 
4) Zeitschr. d. allgem. osterr. Apoth. Ver., 29, p. 2. 406 
Special Part. 
The massoy bark from German Guinea yields upon distillation 6.5-8 p. c. 
of a volatile oil of a pleasant clove- and nutmeg-like odor. Sp. gr. 
1.04-1.06. 
Composition. According to Schimmel & Co.1 the oil consists princi- 
pally of eugenol (75 p. c.) and safrol. In addition to these substances 
Woy2 isolated a fraction boiling at 172° in which he supposed he had 
found a new terpene, "massoyene." Wallach3 (1890), however, showed 
that it consisted of a mixture of three terpenes: pinene (nitrolbenzyl- 
amine, m. p. 123° and nitrosopinene, m. p. 133°), limonene (nitrol- 
benzylamine, m. p. 93°), and dipentene (tetrabromide, m. p. 123°). 
156. Oil of Garden Cress. 
In 1846 Pless4 demonstrated that the oils of Lepidium rudera^e L., 
L. sativum L., and L. campestre R. Br. are heavier than water and 
contain sulphur. He states that the oil is ready formed in the herb 
but not in the seeds, where it results through the action of the water. 
The composition of the oil from garden cress, L. sativum L. was 
ascertained by Hofmann5 in 1874. The herb was collected immediately 
after flowering and distilled in wooden vats6 with water vapor. The 
oil being completely dissolved in the aqueous distillate was extracted 
by shaking with benzene. The yield was 0.115 p. c. The crude oil was 
of a light yellow color but became colorless upon rectification. Three- 
fourths of the oil boiled at 231.5°, the boiling point of benzyl cyanide, 
CeH5.CH2.CN. The identity of this substance was established by its 
conversion into phenyl acetic acid melting at 77°, and by the analysis 
of the silver salt of this acid. The lower fractions contained a small 
amount of sulphurated compounds, the composition of which was not 
determined. Gadamer 7 has recently investigated this oil and found it to 
be identical in composition with the oil from Troepoelum majus. It con- 
sists principally of benzyl isocyanate, CeHs.CHo.NiCS, and small amounts 
of benzyl cyanide. The oil is formed by the action of a ferment on the 
glucoside ghicotropaeolin, K0.S02.0.C(:N.CH2.C6Ho).S.C6Hn05 + 2H20. 
The fresh herb of Lepidium latifolium L. yields upon distillation an 
oil which is heavier than water and contains sulphur. (Steudel8). 
i) Bericht von S. & Co., Oct. 1888, p. 42. 
2) Archiv d. Pharm., 228, pp. 22 and 687. 
3) .Liebig's Annalen, 258, p. 340; Archiv 
d. Pharm., 229, p. 116. 
*) Liebig's Annalen, 58, p. 39. 
5) Berichte, 7, p. 1293. 
6) During the distillation of this and 
other sulphur-containing oils, the use of 
copper vessels is to be avoided, for the 
copper will cause partial decomposition 
of the oils with formation of copper 
sulphide. 
7) Berichte, 32, p. 2326; Archiv d. 
Pharm., 237, p. 508. 
8) Dissert, de Acredine nonnull. Vege- 
tabil. Tubingen 1805. Oils of the Cruciferae. 
407 
157. Oil of Thlaspi Arvense. 
According to Pless1 (1846) this oil is obtained by first macerating 
the herb or seed with water and then distilling. It is colorless, possesses 
a peculiar penetrating odor and leek-like taste, reminding alike of 
garlic and mustard. 
If the oil is saturated with ammonia and the product distilled with 
water, there remains a residue of thiosinamine (m. p. 72°), thus indi- 
cating the presence of allyl sulphocyanate. This distillate yielded with 
platinum chloride the same addition product obtained by Wertheim2 
(1844) from garlic oil. I'less, therefore, regarded it as allyl sulphide. 
Semmler8 (1892), however, has shown that Wertheim's conclusions 
are erroneous, that oil of garlic contains a group of different sulphides, 
but does not contain allyl sulphide. The presence of allyl sulphide in 
the oil of Thlaspi arvense L. is, therefore, highly improbable. 
158. Oil of Spoonwort. 
Oleum Cochleariae.-Loffelkrautbl.-Essence de Coclilearia. 
Origin and History. Spoonwort. Cochlearia officinalis L. grows 
wild in the neighborhood of the coast-line of the northern continents 
and in several mountain ranges of the central European Alps. It is 
also largely cultivated. Upon distillation the plant yields an oil pos- 
sessing a faint mustard odor. 
During the middle ages spoonwort was regarded as a remedy against 
scurvy. The distilled oil of spoonwort seems to have been known and 
to have been used medicinally since the middle of the sixteenth century. 
This use, however, does not appear to have been general, for the oil is 
not mentioned in any edition of the Dispensatorium Noricum, neither 
in the Pharmacopoea Augustana nor in Schroeder's Pharmacopoea 
medicochymica of Frankfurt-on-the-Main. It occurs, however, in the 
municipal ordinance of Frankfurt of 1587. Later it occurs also in 
inventories of apothecary shops of Braunschweig and Dresden of 1640 
and 1683 respectively. At the beginning of the eighteenth century it 
was distilled by Hoffmann in Halle and described by him. 
Preparation. According to Gadamer4 (1898), the dried herb, which 
need not be in blossom, is macerated with water to which powdered 
white mustard has been added and then distilled. The yield is about 
0.23 p. c. or more. 
i) Liebig's Annalen, 58, p. 36. 
2) Liebig's Annalen, 51, p. 298. 
3) Archiv d. Pharm., 230, p. 434. 
4) Apotheker Zeitung, 13, p. 679; Arch, 
d. Pharm., 237, p. 92. 408 
Special Part. 
Properties. Spoonwort oil is optically active; Gadamer observed 
the angle «d = -f- 55.27°. Upon distillation of 42.8 g. the following- 
fractions were obtained: 150-154°, 6.3 g.; 154-156°, 12.2 g.; 
156-158°, 10.0 g.; 158-162°, 12.0 g.; residue 2 g. The sp. gr. of 
these fractions varied from 0.941 to 0.943; the angle of rotation from 
4- 51.41° to + 62.87°. ■ 
Composition. Simon1 (1840) gives the boiling point of the oil 
at 156-159°. He found that it contains sulphur and yields a thiosin- 
amine-like derivative with ammonia. Gieseler2 regarded the oil as being 
free from nitrogen but containing oxygen and pronounced it an oxy- 
sulphide of allyl. Hofmann3 (1869) showed the oil to have the com- 
position of secondary butyl isosulphocyanate. From the bruised fresh 
herb4 mixed with water he obtained 0.034 p. c. of an oil distilling 
between 158-165°. After repeated fractionation, fraction 161-163° 
upon analysis yielded results corresponding with those for butyl mustard 
oil. Comparison with synthetic secondary butyl isosulphocyanate, 
CH3CH2. (CHs) .CH.N:C:S, revealed the identity of the two. It is a 
colorless liquid, sp. gr. 0.944 at 12°, b. p. 159.5°, and possesses the 
characteristic odor of the oil of spoonwort. When heated with ammonia 
to 100° it yields a thio-urea5 which melts at 133° and is optically 
active. 
According to Moreigne,0 spoonwort oil contains raphanol. Inas- 
much as the commercial, so-called artificial spoonwort oil is not 
secondary but isobutyl mustard oil it should not be substituted for the 
natural product in medicinal preparations. 
159. Oil from Horse Radish. 
The investigations of Gadamer7 have rendered it highly probable 
that the formation of the oil of the root of Cochlearia armoracia L., 
to which the pungent taste of horse radish is due, is caused by the 
presence of sinigrin. When the juicy root is grated, the glucoside is 
broken up by a ferment present with the formation of mustard oil. 
When distilled in glass vessels, the root yields about 0.05 p. c. of oil. 
The crude oil is light yellow in color and has the consistency of 
cinnamon oil; the rectified oil is colorless. Sp. gr. 1.01. The odor is 
i) Poggend. Annalen, 50, p. 377. 
2) De Cochlearia officinal! ejusque oleo 
dissertatio. Berol. 1857. 
3) Berichte, 2, p. 102; 7, p. 508. 
4) According to Simon, dry herb yields 
an oil upon distillation only when white 
mustard meal has been added. 
s) Gadamer, loc. cit. 
6) See under radish oil, p. 417. 
7) Archlv d. Pharm., 235, p. 577. Oils of the Cruciferae. 
409 
penetrating, causes tears to flow and cannot be distinguished from that 
of mustard oil. Like the latter, the oil of horse radish causes burning 
and blistering when brought in contact with the skin. 
Oil of horse radish contains sulphur. Based on the results, of 
elementary analyses as well as the formation of thiosinamine, Hubatka1 
(1843) concluded that the oil has the same composition as mustard oil. 
The statements of Hubatka have later been verified by Sani.2 When 
kept in contact with water in a closed vessel for years, the oil dis- 
appeared and in its place acicular crystals were formed that had a 
silvery lustre and the odor first of horse radish, then of peppermint 
and finally of camphor (Einhof,3 1807). 
160. Oil of Hedge Garlic. 
From the roots of Alliaria officinalis Andr. (Sisymbrium alliaria 
Scop., Ger. Lauchhederich}, Wertheim4 (1844) obtained upon distillation 
0.033 p. c. of an oil that could not be distinguished from mustard oil 
and which yielded thiosinamine melting at 74°. Judging from the odor 
the herb contains the same constituents as garlic oil. According to 
Pless5 (1846), the oil of the seeds consists of about %o mustard oil 
and lio garlic oil. 
161. Oil of Mustard. 
* Oleum Sinapis. - Senfol. - Essence de Montarde. 
Origin and History. As black mustard are designated the seeds of 
several mustard plants belonging to the Cruciferae, viz. Brassica nigra 
Koch (Sinapis nigra L.) and B.juncea Hooker fil. et Thompson (S.juncea 
L.). B. nigra, belongs to the European-Asiatic flora and is culti- 
vated in most civilized countries, especially in those of central Europe; 
whereas B. juncea, is cultivated on a larger scale in southern Russia, 
India and North America. The largest amount of seeds are used in the 
manufacture of table mustard, less for medicinal purposes and for the 
distillation of mustard oil. 
The first statement which indicates a knowledge of the fact that 
mustard oil can be obtained by distillation with water, is found in the 
writings of Porta; another in the writings of the Parisian apothecary 
Nic. Ie Febvre. Boerhaave, however, seems to have been the first to 
prepare the volatile mustard oil in 1732 and to have called attention 
i) Liebig's Annalen, 47, p. 153. 
2) Aecacl. Line., 1892; Abstr. Bericht 
von S. & Co., Apr. 1894. p. 50. 
3) Neues Berlinisches Jahrbuch, 5, p. 365. 
4) Liebig's Annalen, 52, p. 52. 
5) Liebig's Annalen, 58, p. 38. 410 
Special Part. 
to its properties. That it contains sulphur was observed by Thibierge 
of Paris in 1819. Boerhaave and Murray observed the great density 
of the oil; Jul. Fontenelle determined the specific gravity in 1824. 
Undoubtedly those who prepared mustard oil knew that the volatile 
oil does not preexist in the seed but is produced by the action of water. 
Yet the first to call attention to this fact were Glaser1 in 1825, Boutron 
and Robiquet2 in 1831, and independently of these Faure3 as well as 
Guibourt,4 both in 1831. Shortly after (1833), Dumas and Pelouze5 
made the first elementary analysis of the oil and discovered the thio- 
sinamine, which mustard oil forms with ammonia. That mustard oil is 
produced by the action of a ferment was noticed by Boutron and 
Fremy6 (1840). They isolated myrosin by extracting the seed with 
alcohol and obtained mustard oil by allowing this substance to act on 
the aqueous extract of the seed which had previously been extracted 
with alcohol. Sinigrin or inyronate of potassium, was first prepared 
by Bussy7 (1840). He termed the underlying acid acide myronique 
and with Robiquet8 determined its physical constants and its behavior 
toward reagents. The knowledge of the chemical composition of the 
oil was advanced by Will9 (1844) and simultaneously by Wertheim10 
who regarded the mustard oil as allyl sulphocyanate. Ludwig and 
Lange11 in 1860 confirmed the existence of sinigrin and its decom- 
position by ferment action into mustard oil, sugar and potassium acid 
sulphate. This reaction was made more clear by the detailed studies 
of Will and Koerner12 (1863). Artificial mustard oil had been prepared 
by the action of allyl iodide on potassium sulphocyanate by Zinin13 in 
1855 and by Berthelot and de Luca14 also in 1855. The natural oil 
was therefore regarded as an ester of thiocyanic acid. Oeser,15 however, 
showed in 1865 that allyl thiocyanate and natural mustard oil possess 
different properties. 
The true constitution of mustard oil as the ester of the isothiocyanic 
acid was recognized by Billeter10 and Gerlich17 in 1875. They showed 
1) Repert. f. d. Pharm., I, 22, p. 102. 
2) Journ. de Pharm., II, 17, p. 294; 
Geiger's Magazin f. Pharm. und Exper. 
Kritik, 36, pp. 64 and 67. 
3) Journ. de Pharm., II, 17, p. 299: 
21, p. 464. 
i) Journ. de Pharm., II, 17, p. 360. 
5; Ann. de Chim. et Phys., II, 53, p. 
181: Liebig's Annalen, 10, p. 324. 
6) Journ. de Pharm., II, 26, pp. 48 
and 112; Liebig's Annalen, 34, p. 230. 
7) Journ. de Pharm., II, 26, p. 39; 
Liebig's Annalen, 34, p. 223. 
8) Journ. de Pharm., II, 26, p. 110. 
9) Liebig's Annalen, 52, p. 1. 
io) Liebig's Annalen, 52, p. 54. 
n) Zeitschr. f. Chemie und Pharm., 3, 
pp. 430, 577. 
12) Liebig's Annalen, 125, p. 257. 
is) Journ. f. prakt. Chem.. 64, p. 504; 
Liebig's Annalen, 95, p. 128. 
1*) Compt. rend.. 41, p. 21. 
is) Liebig's Annalen, 134, p. 7. 
16) Berichte, 8, pp. 464 and 820. 
it) Berichte, 8, p.650; Liebig'sAnnalen, 
178, p. 89. Oils of the Cruciferae. 
411 
that by the interaction of allyl iodide and potassium sulpho- 
cyanate, allyl sulphocyanate is first formed and that upon heating this 
is converted into its isomer, the allyl isosulphocyanate. As an expla- 
nation of this form of isomerism, Hofmann1 in 1868 had suggested that 
in the true thiocyanates the carbon is directly united with the sulphur, 
but in the iso compounds with the nitrogen. 
Inasmuch as the possibility was not excluded that by the ferment 
action on sinigrin allyl sulphocyanate may first be formed, Schmidt2 
allowed this action to take place at low temperature. He ascertained 
that even at 0° allyl isosulphocyanate is formed and only traces of the 
normal isomer. The last uncertainty in connection with the hydrolysis 
of sinigrin was removed by Gadamer3 (1897). He showed that the 
formula of sinigrin is CtoHiqNSoKOp and not CioHisNSsKOio as was 
supposed by Will and Koerner, also that the hydrolysis takes place by 
the addition of the elements of one molecule of water. 
Preparation. The mustard which is used in the manufacture of 
mustard oil is obtained either from Brassica nigra K. (Sinapis nigra L.) 
which is cultivated in Holland, Apulia or the levant, or more frequently 
from B. juncea Hook. fil. et Thomson (S. juncea L.), a species which is 
cultivated on a large scale in Sarepta, in the Russian gouvernement 
Saratow, also in East India. 
Mustard oil is not contained as such in the seeds, but is formed by 
ferment action. The ground mustard seed is deprived of its fatty oil 
with the aid of hydraulic presses. The press-cakes are mixed with tepid 
water and allowed to undergo fermentation, and then distilled with water 
vapor. The yield varies between 0.5-0.75 p. c. of the original seed.4 
i) Berichte, 1, p. 28. 
2) Berichte, 10, p. 187. 
3) Archiv d. Pharm., 235, p. 44. 
<) For the quantitative estimation of mustard oil in the seed, the method of 
Dieterich (Helfenberger Annalen, 1896. p. 332) can be employed: 5 g. of the bruised 
seed are allowed to ferment for two hours at a temperature of from 20-25°, when 
10 g. of alcohol are added. The flask is connected with a condenser, the tube of which 
dips into the receiver containing 30 cc. of ammonia. The distillation is continued 
until 50-60 cc. have passed over. To the ammoniacal liquid an excess of silver 
nitrate solution is added, the precipitated silver sulphide is collected on a filter, washed, 
dried and heated to a red heat. The reduced silver is then weighed and its weight 
multiplied by 0.4938. The product gives the amount of mustard oil in 5 g. of seed. 
Gadamer (Arch. d. Pharm., 235, p. 58) has modified thepjocess somewhat. Before 
the distillation he adds a definite quantity of N/10 silver nitrate V. S. known to be 
in excess to the ammonia. After the distillation, the distillate is diluted to a definite 
volume, set aside for 12 hours and filtered through a dry filter into a dry flask. In an 
aliquot part of the filtrate, acidulated with nitric acid, the excess of silver is titrated 
back with potassium sulphocyanate. 412 
Spacial Part. 
At a temperature exceeding 70° no fermentation takes place, because 
the myrosin is coagulated and rendered inactive. 
The fermentation is brought about by the albuminoid ferment, 
myrosin, which acts on the sinigrin in the presence of water with the 
formation of mustard oil, dextrose and- potassium acid sulphate. 
Ci0Hi6NS2K09 + H20 = CSNCsHs + C6Hi206 + KHSO4 
Sinigrin Water Mustard oil Dextrose Potassium acid sulphate. 
Beside this reaction others take place resulting in the formation of 
allyl cyanide and carbon disulphide, which are never entirely wanting 
in the oil. Contact with the copper of the still, or prolonged contact 
with water cause the separation of sulphur and the formation of allyl 
cyanide. 
C3H5NCS + Cu - C3H5CN + CuS 
Mustard oil Copper Allyl cyanide Copper sulphide. 
When the distillation has been conducted in a careless manner, the 
amount of allyl cyanide can be so large that the oil becomes lighter 
than water (Will,1 1863). (Sp. gr. of allyl cyanide is 0.835 at 17.5°). 
How the carbon disulphide always found in the oil (in the artificial 
oil as well) is formed has not yet been clearly demonstrated. It has 
been shown2 that when mustard oil is boiled with water for an hour in 
a flask connected with a reflux condenser no carbon disulphide is formed. 
This substance, however, is formed in appreciable quantities together 
with carbon dioxide when mustard oil is heated for several hours with 
water in sealed tubes under pressure at a temperature of 100-105°. It 
may be assumed that in the nascent state mustard oil has a greater 
capacity for reaction and that in this condition water may effect its 
decomposition in a manner expressed by the following equation. 
2C8H5NCS + 2H20 = 2C3H5NH2 + C02 + CS2 
Mustard oil . Water Allyl amine Carbon dioxide Carbon disulphide. 
Carbon disulphide is also formed by prolonged contact of water 
with mustard oil. For the detection of this substance see under 
Examination. 
As to the time requisite to complete the fermentation, 80 minutes 
are required for the hydrolysis of pure sinigrin.3 
Inasmuch as the potassium acid sulphate, which is split off in the 
course of the reaction, acts on the mustard oil in the process of forma- 
tion, a better yield can be obtained by neutralizing with alkali (when 
i) Liebig's Annalen, 125, p. 278. 
2) Arehiv d. Pharm., 235, p. 53. 
3) Gadamer, loc. cit. Oils of the Cruciferae. 
413 
pure sinigrin is used). Au excess of alkali is to be carefully avoided, 
because it also diminishes the yield. Calcium carbonate has also been 
found serviceable. With mustard meal, however, it is quite different. 
The addition of calcium carbonate not only is of no advantage, but 
its presence acts detrimentally. The cause for this has not yet been 
explained. Possibly the base sinapine, which is contained in the mustard 
enters into the reaction by being liberated by the calcium carbonate, 
forming a non-volatile thiosinamine-like compound with the mustard oil.1 
Composition. Besides small variable amounts of allyl cyanide and 
carbon disulphide, mustard oil consists almost entirely of allyl mustard 
oil or allyl isothiocyanate, C3H5NCS. Possibly traces of the isomeric 
allyl thiocyanate, and higher boiling (polymeric?) unknown compounds 
are present. 
The chemical reactions of mustard oil are, therefore, largely those of 
allyl isosulphocyanate which can be found in any chemical reference 
work. Here only those will be mentioned that are necessary to under- 
stand the tests. 
For the quantitative determination of allyl isosulphocyanate in 
mustard oil, its property of forming a solid, non-volatile compound with 
ammonia is utilized. If to mustard oil an excess of ammonia and 
alcohol are added, the odor of both mustard oil and ammonia dis- 
appears, gradually in the cold but more rapidly when heated, while 
crystals of thiosinamine are formed. 
H ZNH.CsHs 
C^A • C3H5 + H _ C_NH2 
-b nh2 xg 
Mustard oil Ammonia Thiosinamine 
Thiosinamine or allyl thio urea crystallizes in rhombic prisms which 
melt at 74°, possess a faint leek-like odor and taste, and are readily 
soluble in water, alcohol and ether. When a small amount of mustard 
oil is mixed with twice its volume of concentrated sulphuric acid a 
violent reaction sets in with the formation of carbon oxysulphide,2 
sulphur dioxide3 and allylamine sulphate. The last remains as a 
faintly colored liquid which sometimes solidifies in the test tube. 
Artificial mustard oil is obtained by the interaction of allyl 
iodide and potassium thiocyanate in alcoholic solution. Allyl thio- 
cyanate is first formed which under the influence of heat rearranges 
itself to the isothiocyanate. 
i) Gadainer, loc. cit. 
2) Berichte, 1. p. 182. 
3) Archiv d. Pharin., 196, p. 214. 414 
Special Part. 
C3H51 + NCSK = C3H5NCS + KI 
Allyl iodide Potassium thiocyanate Mustard oil Potassium iodide. 
Mustard oil also results by the dry distillation of potassium allyl 
sulphate and potassium thiocyanate. 
C3H5KSO4 + CNSK = C3H5NCS + K2SO4 
Potassium allyl sulphate Potassium thiocyanate Mustard oil Potassium sulphate. 
Properties. Mustard oil is a mobile, colorless or yellowish, strongly 
refractive liquid, which is optically inactive and which has a very strong- 
odor causing tears to flow. When brought in contact with the skin it 
draws blisters. The specific gravity varies in accordance with the 
method of preparation between 1.016 and 1.022 and sometimes rises 
up to 1.030. Mustard oil is soluble in 160-300 p. of water, and in 
10 p. of 70 p. c. alcohol. With 90 p. c. alcohol, with ether, amyl 
alcohol, benzene and petroleum ether it is miscible in all proportions. 
It boils principally between 148-156° (b. p. of pure allyl isothiocyanate 
is 150.7°). Exposed to light, mustard oil gradually becomes of a 
reddish-brown color. At the same time a film, consisting of a sub- 
stance composed of carbon, nitrogen, hydrogen and sulphur, is deposited 
on the inner wall of the bottle. 
Examination. The German Pharmacopoeia contains a series of tests, 
that have been taken almost unchanged from the U. S. Pharmacopoeia 
of 1890, which generally suffice for the characterization of a good 
mustard oil. 
1. The sp. gr. is to be 1.018-1.029 according to the U. S. P., 
1.016-1.022 according to the Ph. Ger. A slight variation either way, 
however, is not sufficient indication of adulteration, for the reasons 
mentioned under Preparation. 
2. The requirement of both pharmacopoeias that the boiling point 
is to lie between 148-150° cannot be construed literally inasmuch as 
allyl isothiocyanate boils at 150.7° (mercury in vapor). Furthermore, 
a slight decomposition invariably takes place during the distillation, 
so that some of the oil distills above 152°. Inasmuch as allyl cyanide 
is always present, the first fractions cannot have the same specific 
gravity as the original oil. Large differences in this respect will be 
accompanied by a lowering of the boiling point of the first fractions 
and should not be tolerated. 
3. Sulphuric acid test. If to 3 g. of the oil 6 g. of sulphuric acid 
be gradually added, the liquid being kept cool, the mixture, upon 
subsequent agitation, will evolve sulphur dioxide, but will remain of a 
light yellow color, and at first perfectly clear, becoming afterwards thick Oils of the Cruciferae. 
415 
and occasionally crystalline, while the pungent odor of the oil will 
disappear. In the presence of petroleum, petroleum ether, chloroform 
or undue amounts of carbon disulphide, the mixture of mustard oil and 
sulphuric acid is rendered turbid and upon standing forms two layers. 
Other volatile oils would be rendered dark in color by the sulphuric 
acid. 
4. Ferric chloride test. Diluted with 5 p. of alcohol, mustard oil is 
not changed by ferric chloride. Adulteration with oil of cloves would 
be recognized by the production of a bluish-green color. 
5. The thiosinamine test according to the U. S. P. is to be made 
as follows: 
"If a mixture of 3 g. of the oil and 3 g. of alcohol be shaken in a small 
flask with 6 g. of ammonia water, it will become clear after standing for some 
hours, or rapidly when warmed to 50° 0. (122° F.) and usually deposit with- 
out becoming colored, crystals of thiosinamine [allyl-thio-urea, CS.NsHsfCsHs)]. 
"To determine the proportion of thiosinamine obtainable from the oil, de- 
cant the mother-water from the crystals, and evaporate it gradually in a tared 
capsule, on a water-bath, adding fresh portions only after the ammoniacal odor 
of each preceding portion has disappeared. Then add the crystals from the 
flask to those in the capsule, rinsing them out of the flask with a little alcohol, 
and heat the capsule on a waterbath until its weight remains constant. The 
amount of thiosinamine thus obtained from 3 g. of the oil should be not less 
than 3.25 g., nor more than 3.5 g. After cooling, thiosinamine forms a 
brownish, crystalline mass, fusing at 70° C. (158° F.) and having a leek-like, 
but no pungent, odor. The mass should be soluble in 2 parts of warm water, 
forming a solution which should not redden blue litmus paper, and which 
possesses a somewhat bitter, not persistent taste." 
Attention should be called to the fact that, by following this test, 
carbon disulphide is included in this estimation since it also unites with 
ammonia according to the following equation: 
CS2 + 4NH3 = NH4SCN + (NH4)2S 
Carbon disulphide Ammonia Ammonium sulphocyanate Ammonium sulphide. 
Inasmuch as the products of the reaction remain behind upon 
evaporation, the residue may weigh more than 3.5 g. If this is the 
case and especially if the residue has the odor of ammonium sulphide 
an unwarranted amount of carbon disulphide was probably present. 
Kremel1 (1888) has suggested the use of ammonia of definite 
strength and to determine the excess with N/2 acid. As yet no practical 
test of this method seems to have been made. 
According to Gadamer2 (1899) mustard oil can be assayed titrimetri- 
cally according to a method that is also applicable to spirit of mustard. 
i) Pharm. Post, 21, p. 828. 
2) Archiv d. Pharm., 237, pp. 110, 372. 416 
Special Part. 
A solution of 2 p. of mustard oil in 98 p. of alcohol (Spiritus sinapis Ph. G.) 
is first prepared. 5 cc. of this spirit (4.2 g.) are transferred to a 50 cc. 
measuring flask, and 25 cc. of N/10 silver nitrate V. S. and 5 cc. ammonia are 
added. The flask is well stoppered and set aside for 24 hours. The liquid is 
then diluted to the 50 cc. mark and filtered. 25 cc. of the filtrate, after the 
addition of 4 cc. of nitric acid and a few drops of ferric chloride T. S., should not 
require more than 4.5 cc. and not less than 4.1 cc. of N/10 ammonium sulpho- 
cyanate to produce a permanent red color. These numbers-4.1 and 4.5- 
correspond to the requirements of the Ph. G., viz. a content of 92.6 to nearly 
100 p. c. of allyl mustard oil. 
Griitzner1 converts the allyl isothiocyanate into thiosinamine and 
oxidizes this with sodium peroxide. The resulting sulphuric acid is 
estimated as barium sulphate, either gravimetrically or volumetrically. 
Determination of Carbon Disulphide in Mustard Oil. For the 
detection of not too small amounts of carbon disulphide, i. e., in case 
of adulteration, it can be converted into copper ethyl xanthate2 and 
determined quantitatively. 
20-25 g. of mustard oil are heated on a water bath while a slow current 
of air is passed through the oil. The vapors of carbon disulphide are thus 
carried over, cooled by passing through a condenser and conducted into 
alcoholic potassa where they are converted into potassium ethyl xanthate. 
After the alkaline solution has been neutralized N/10 copper sulphate V. S. is 
added until a drop produces a reddish-brown color with potassium ferro- 
cyanide, i. e., until a slight excess of copper sulphate has been added and all 
potassium ethyl xanthate has been converted into the cuprous salt. From 
the amount of the consumed copper solution (1 cc. corresponds to 0.0152 g. of 
carbon disulphide) the percentage of carbon disulphide present can be ascer- 
tained. This volumetric process can be supplemented by a gravimetric one. 
The precipitate of cuprous ethyl xanthate can be collected on a filter, washed, 
dried and heated to a red heat in a crucible, and the residue of cupric oxide 
weighed. 1 g. of the oxide corresponds to 1.918 g. of carbon disulphide. 
For the quantitative estimation of traces of carbon disulphide which 
occur in every mustard oil, the method of Hofmann3 can be used 
according to which it can be converted into a compound with triethyl 
phosphine, PfHaHsls + CS2, and weighed. 
163. Oil of White Mustard. 
Sinalbin is the glucoside from the white mustard (Sintipis alba, L.) 
corresponding to the sinigrin from the black mustard. Robiquet and 
Boutron-Charlard 4 (1831) first extracted it with boiling alcohol from 
the seed deprived of its fatty oil. Its properties, including its hydrolysis 
i Archiv. <1. Pharm., 237, p. 185. 
2) Zeitschr. f. anal. Chem., 21, p. 133. 
3) Berichte, 13, p. 1732. 
4) Journ. de Pharm., II, 17, p. 279. Oils of the Cruciferae. 
417 
by myrosin, were examined by Will and Laubenheimer1 (1879) and 
recently by Gadamer2 (1897). The identity of the white mustard 
oil with para hydroxy benzyl isothiocyanate was established by 
Salkowski3 (1889). 
Sinalbin mustard oil, Ccdlj. OHM. CH2NCSM, is but sparingly 
volatile with water vapor and for this reason cannot be prepared from 
white mustard by distillation. It is an oily liquid of a burning taste, 
w'hich draws blisters when in contact with the skin but much slower 
than allyl mustard oil. The pungent mustard oil odor is noticeable 
only when heated; when cold it possesses only a faint anise-like odor. 
It is soluble in dilute alkalies. It is prepared by the hydrolysis of 
sinalbin, dextrose and sinapine sulphate resulting ap by-products. 
C3OH42N2S2O15 + H2O = C7H7ONCS + C6Hi20« + Ci6H24N205HS04 
Sinalbin Sinalbin mustard oil Dextrose Sinapine acid sulphate. 
Artificially it is prepared by the action of carbon disulphide on 
p-hydroxy benzylamine and by treating the resulting product with 
mercuric chloride. 
163. Oil of Water-cress. 
The oil of Nasturtium officinale L. was examined by Hofmann4 in 
1874, who extracted the aqueous distillate (600 k.) from 600 k. of fresh 
herb with petroleum ether. Upon evaporation of the ether he obtained 
40 g. (=0.0066 p. c.) of oil. The oil no longer had the odor of water- 
cress, sp. gr. 1.0014 at 18° and distilled between 120 and 280°. The 
principal fraction came over at 261° and was shown to be the nitrile 
of phenyl propionic acid, C0H5. CH2. CH2. ON. Moreigne found raphanol5 
in the oil. 
164. Oil of Radish. 
The roots and seeds of Raphanus sativus L., (Family Cruciferae) 
yield upon distillation with water vapor a small amount of a colorless, 
sulphuraceous oil, heavier than water, which possesses the taste but 
not the odor of the radish.6 
Upon the distillation of the roots of Raphanus niger, Moreigne7 
obtained besides a small amount of oil, 0.0025 p. c. of a substance 
which crystallized in laminae melting at 62°. It was called raphanol 
1) Liebig's Annalen, 199, p. 150 
2) Archiv d. Pharm., 235, p. 83. 
3) Berichte, 22, p. 2143. 
4) Berichte, 7, p. 520. 
s) See under radish oil. 
6) Pless, Liebig's Annalen, 58, p. 40. 
Comp, also Bertram & Walbaum, Journ. f. 
prakt. Chern., II, 50, p. 560. 
7) Journ. de Pharm. et Chim., VI, 4, p. 
10; Bull. Soc. chim., Ill, 15, p. 797. 418 
Special Part. 
or, because it possessed the properties of a lactone, raphanolid. It is 
free from nitrogen and sulphur, elementary analysis and molecular 
weight determination indicating the formula C29H58O4.1 When boiled 
with acetic acid anhydride, it yields an acetyl derivative melting at 
122-123°. The liquid portion of the oil was found to contain sulphur 
but was free from nitrogen and did not combine with ammonia. 
165. Oil from Mignonette Flowers. 
Upon steam distillation of the fresh flowers of Reseda odorata L. 
(Family Resedaceae) an oil yield of but 0.002 p. c. is obtained. Remark- 
able is the strong development of carbon disulphide2 during the process 
of distillation. The oil is of a dark color, and solid at ordinary tem- 
perature, having the consistency of orris oil. When greatly diluted it 
has the odor of fresh mignonette.3 
In order to obtain the oil in a more suitable form for use it is 
distilled with geraniol (1 k. of geraniol to 500 k. of flowers), the product 
being brought into the market as "Reseda Geraniol."4 
166. Oil from Mignonette Root. 
The fresh roots yield upon distillation with water vapor 0.014- 
0.035 p. c. of oil. It is a light brownish liquid which has the odor of 
radish, sp. gr. 1.010-1.084, aD = + l°30'. It begins <to boil at 255° 
with decomposition. Even under diminished pressure it does not boil 
without decomposition. 
The oil was first examined by Vollrath5 in 1871, who recognized 
its character as that of a mustard oil. His surmise that it was identical 
with allyl mustard oil was, however, shown to be erroneous by Bertram 
and Walbaum6 (1894), who identified it as phenyl ethyl mustard oil, 
C6H5CH2. CH2NCS. 
The odor of this substance is that of the mignonette root oil. Upon 
heating with ammonia, the well crystallizing thiourea, NH2. CS. - 
NHC2H4C6H5 is formed, which melts at 137°. If this thiourea is treated 
with silver nitrate and baryta water, silver sulphide and phenyl ethyl 
urea, crystallizing in long needles and melting at 111-112°, are formed. 
If phenyl ethyl mustard oil is heated with concentrated hydrochloric acid 
i) Raphanol has also been isolated by 
Moreigne from the following plants: the 
radish, turnip, water-cress, spoonwort and 
gilly-flower. 
2) Bericht von S. & Co., Oct. 1891, p. 40. 
3) Ibidem, Oct; 1898, p. 43. 
4) Ibidem, Oct. 1894, p. 69. 
5) Archiv d. Pharm., 198, p. 156. 
6) Journ. f. prakt. Chemie, II, 50, p. 555. Oils of the Hamamelidaceae. 
419 
in a sealed tube, crystalline laminae of phenyl ethylamine chlorhydrate 
melting- at 217° are obtained. With oxalic acid ethyl ester, phenyl 
ethylamine combines to form diphenyl ethyl oxamide melting at 186°. 
These derivatives were prepared by Bertram and Walbaum from 
the oil of the root as well as from the synthetic phenyl ethyl mustard 
oil1 obtained by the action of phenyl ethylamine on carbon disulphide, 
and were found to be identical. 
167. Oil of Storax. 
Oleum Styracis. - Storaxol.-Essence de Styrax. 
Origin and History. The storax, Liquidambar orientate Miller 
(Family Hamamelidaceae) is a tree sometimes as high as 30 m. which 
resembles the plane and is indigenous to southern Asia Minor. The tree 
sheds its bark annually. In the tissue of the bark it secretes a 
fragrant balsam which hardens on exposure to the air. This balsam is 
obtained by boiling the bark with water and thus prepared constitutes 
the Styrax liquidus of commerce. This is a dirty greyish or greenish, 
resinous mass of peculiar aromatic odor and a pungent, spicy taste. 
The Styrax calamita, the present solid storax of the market is 
storax balsam mixed with sawdust so as to render it almost dry. 
Storax is already mentioned among the aromatics by the ancients, 
e. g. by Herodotus, Theophrastus and Dioscorides. Mediaeval literature 
mentions storax varieties of different sources, some of which were used 
medicinally at times. 
The volatile oil from the storax was distilled by Ryff, Gesner and 
by Porta who moistened the resin with alcohol. Upon distillation with 
water, storax yields 0.5 p. c. of volatile oil, when distilled with super- 
heated steam about 1 p. c. of oil. 
Properties. Oil of storax is a light yellow to dark brown liquid 
of a pleasant odor. The specific gravity varies from 0.89 to 1.1, 
according as the hydrocarbons or the cinnamic esters predominate. 
It is laevogyrate, «d =-3 to -38°. It boils between 150-300° with 
partial decomposition, cinnamic acid remaining behind. 
Composition. The peculiar odor of the oil, reminding somewhat of 
petroleum, is due to the presence of styrene, CgHo . CH: CH2, or phenyl- 
ethylene (Simon,2 1839). This hydrocarbon boils at 116°, is optically 
inactive and can be identified by means of its dibromide, CeHCs.CHBr.- 
CH2B1'. (Comp. p. 103). According to van't Hoff3 (1876), the optical 
i) Berichte, 19, p. 1824. 
2) Liebig's Annalen, 31, p. 265. 
3) Berichte, 9, p. 5. 420 
Special Part. 
activity of the oil is referable to an oxygenated constituent, the styro- 
camphene, CioHieO or CioHisO. The oil also contains more or less of 
the cinnamates of ethyl/ benzyl,2 phenyl propyl1 and cinnamic alcohols.1 
168. Oil from American Storax. 
Origin and History. Ocosotl, an aromatic balsam from Mexico 
and Central America is one of the drugs from the new world which 
attracted interest in Europe. In almost all of its properties it clearly 
resembled the Styrax liquidus, the storax coming from the levant and 
known since antiquity. Its origin, like that of the levant article and 
especially that of the other American balsams (Tolu, Peru, Copaiba etc.) 
was for a long time uncertain and created much confusion. The first 
description of American storax is found in the works of Monardes, 
Garcia ab Orto and Matthiolus, who lived during the first half of the 
sixteenth century. 
Liquidambar styraciduum L. (Family Hamamelidaceae) is a tree 
found in the middle and southern United States, in Mexico and Central 
America. The resinous balsam of the consistence of honey exudes from 
the splintwood beneath the bark of the trunk and branches. The 
excretion is either spontaneous or may be caused by incisions, but occurs 
abundantly only in hot climates. For this reason it enters the market 
principally from the Central American countries. According to the 
method of preparation, the balsam varies in appearance and con- 
sistency. In North America it is known as sweet gum and is used as 
a chewing gum and in the preparation of popular remedies.3 
The first examination of American storax was made by Bonastre4 
in 1830 and 1831. Upon distillation of an apparently fresh balsam, 
he obtained 7 p. c. of oil. Further investigations were made by Proctor5 
in 1857 and by Harrison6 in 1874. 
Properties and Composition. According to v. Miller,7 the oil from 
American storax differs from that of the levant by being dextrogyrate 
(an = + 16° 33'), and contains styrene (bromide, m. p. 73°) and an 
optically active substance having the odor of turpentine oil, which 
i) Liebig's Annalen, 188, p. 184. 
2) Liebig's Annalen, 164, p. 289. 
3) Pharm. Rundschau, 13, p. 57. 
4) Journ. de Pharm., II, 16, p. 88; II, 17, p. 338; Trommsdorff's Neues Journ. 
d. Pharm., 21, II, p. 242, and 24, II, p. 236. 
5) Am. Journ. Pharm., 29, p. 261; 38, p. 33.-Proc. Am. Pharm. Assoc., 13, p. 160. 
6) Am. Journ. Pharm., 46, p. 161; Arch. d. Pharm., 206, p. 541. 
7) Archiv d. Pharm., 220, p. 648. Oils of the Hamamelidaceae. 
421 
was not further examined. American storax contains the cinnamates 
of cinnamyl (styracin) and phenyl propyl alcohols, but not of ethyl 
and benzyl alcohols. 
The leaves of the American storax have a peculiar terebinthinate 
odor. Upon distillation1 they yielded 0.085 p. c. of a mobile oil, which 
was greenish-yellow; sp. gr. 0.872; «d =-38°45'; saponification 
number 5.9; acetylization number 25.2. The odor of the oil reminds 
of the pine needle oils. It probably contains borneol and bornyl acetate 
in addition to terpenes. 
169. Oil from Rasamala Wood. 
Upon distillation of a wood coming from the Dutch East Indies 
and designated Rasamala,, Schimmel & Co.2 obtained 0.17 p. c. of a 
volatile oil. At ordinary temperature, this oil is a light brownish, 
crystalline mass, which melts between 30-40° and the odor of which 
reminds alike of cinnamon and rhubarb. The principal constituent of 
the oil is a crystalline substance which melts at 54-55°. It is probably 
a ketone, since it combines with hydroxylamine to a crystalline compound 
melting at 106-107°. The other constituents of the oil are liquid. 
According to a communication by Dr. van Romburgh of Buitenzorg 
the term Rasamala is not only applied to the genuine but rare rasamala 
tree, Altingia excelsa, Nor. (Liquidambar altingia BL, Family Hama, 
melidaceae) but also to different Indian drugs, namely to the liquid 
storax from Liq. orientale (Getah Rasamala) as well as to other fragrant 
balsams and to the fragrant wood from Canarium microcarpum Willd. 
(Kaju Rasamala). 
Whether the oil distilled by Schimmel & Co. was derived from any 
one of the above named trees is uncertain. Possibly it may have been 
the so-called aloe or eagle wood (Ger. Aloeholz) from Aquillaria agal- 
loeha Roxb. which is sold in the Indian markets as Kaju lakka and the 
characteristic rhubarb-like odor3 of which corresponds with that of the 
wood distilled by Schimmel & Co. 
170. Oil of Spiraea. 
Oil from the flowers. In 1835 Pagenstecher4 obtained upon 
distillation of the flowers of Spiraea ulmaria L. a small amount of oil 
i) Bericht von S. & Co., Apr. 1898, p. 58. 
2) Bericht von S. & Co., Apr. 1892, p. 43. 
3) Bericht von S. & Co., Apr. 1892, p. 43. According to a recent investigation by 
Prof. Moller (Pharm. Post, 1898) aloewood is odorless and developes a peculiar odor 
only when burnt. 
4) Repert. f. d. Pharm., 49, p. 337. 422 
Special Part. 
heavier than water which he gave to Loewig1 for examination. 
Dumas2 (1839), to whom the oil was shown, recognized its similarity 
with the salicylic aldehyde obtained from salicin by Piria shortly before. 
Ettling3 (1839) verified Dumas' surmise by showing that salicylic 
aldehyde is one of the two or three volatile substances of which the oil 
is composed. Ettling had obtained a yield of 0.2 p. c. of oil upon 
distillation of the flowers. According to Wicke4 (1852) the cultivated 
variety produces a larger yield than the wild plant. The oil is heavier 
than water and congeals completely at -18 to -20°. 
The investigations of Schneegans and Gerock5 (1892) have shown 
that besides salicylic aldehyde (formerly known as spiroyl hydride, 
spiraeic acid, salicyl hydride, spiroylic or spiric acid) the oil also 
contains methyl salicylate, also traces of heliotropin (piperonal) and 
vanillin. Ettling had also found a small amount of white, crystalline 
matter of a pearly lustre (paraffin?) and an oil of the composition 
CoHs (terpene or sesquiterpene?). According to Schneegans and Gerock, 
the flowers do not contain salicylic aldehyde as such, but an unknown 
substance (not salicin, however, as supposed by Buchner6) which is 
decomposed during the process of distillation by a ferment. In 
addition to methyl salicylate, the flowers contain free salicylic acid. 
Oil from the roots. The statement of Wicke, that the roots 
of Spiraea ulmaria L. contain salicylic aldehyde, is incorrect. According 
to Nietzki7 (1875) the oil consists principally of methyl salicylate with 
traces of another substance, probably a hydrocarbon. 
Oil from the herb. In the distillate from the herb, Wicke has 
shown the presence of salicylic aldehyde. 
According to Wicke the herb of S. digitata, S. lobata, S. filipendula 
and the flowers of S', aruncus yield salicylic aldehyde upon distillation. 
The'herb of S. aruncus, the leaves of S. japonica, the herb and flowers 
of S. sorbi folia yield hydrocyanic acid but no salicylic aldehyde. 
Neither aldehyde nor acid were found in the oil from S. laevigata, 
S. acutifolia, S. ulmifolia, and S. opulifolia. 
i) Poggend. Ann., 36, p. 383; Pharm. Centralbl., 1839, p. 129. 
2) Liebig's Annalen, 29, p. 306. 
3) Liebig's Annalen, 29, p. 309: 35, pp. 1, 24. 
4) Liebig's Annalen, 83, p. 175. 
s) Journ. d. Pharm. f. Elsass-Lothr., 19, pp. 3 and 55. Abstr. Jahresb. f. Pharm 
1892, p. 164. 
6) Liebig's Annalen, 88, p. 284. 
7) Archiv d. Pharm., 204, p. 429. Oils of the Rosaceae. 
423 
171. Oil (Otto) of Rose. 
Oleum Rosarum. - Rosenol. - Essence de Rose. 
History. Since the earliest periods the charm and fragrance of the 
rose has led to its appreciation and use. This is shown by the entire 
older literature, and of all the flower perfumes that from the rose has 
always received preference. In Chinese and Sanskrit writings the 
fragrance of the rose is much praised. Fats and oils saturated with 
the rose perfume have been used since earliest antiquity in perfumery. 
Thus Aphrodite anointed the dead body of Hector with rose oil. The 
Greeks and Romans celebrated annually a rose festival, at which the 
graves of the dead were decorated with roses and their tombstones 
were anointed with rose oil. Of the various flower cults that of the 
roses has been the most eminent since antiquity. 
The earliest description of the method of preparation of the oil of 
rose of the ancients is found in the writings of Dioscorides. It was an 
aromatised fatty oil as were the majority of the rose oils of the middle 
ages, such as Oleum rosarum, 0. rosatum or 0. rosaceum, etc. 
Aside from apocryphal Persian and oriental traditions, the earliest 
definite directions for the preparation of roses and the use of the distil- 
late is found in the writings of the Arabian historian Ibn Chaldun. 
He mentions that during the eighth and ninth centuries rose water was 
an important article of commerce, being carried as far as China and 
India. In a codex of ceremonies of 946 by the East Roman emperor 
Constantine VII., Persian rosewater is mentioned as a toilet water. At 
the beginning of the tenth century, Nonus Theophanes, the physician 
of emperor Michael VIII., recommended and used rose water as a 
medicament. Avenzoar, the physician of the calif Ebn Attafir of 
Morocco, who lived at the beginning of the twelfth century; also his 
contemporary, Joannes Actuarius, a physician of Constantinople, used 
rose water as an ophthalmic, and rose sugar as an internal remedy. 
During this period, Persia seems to have supplied most of the rose 
water. During the fourteenth century it was also exported from Meso- 
potamia. After the prime of the levant commerce, the Portuguese and 
Dutch were the principal carriers of goods between Aden, the ports of 
the Persian bay, India and the Occident. Rose water constituted one 
of their principal articles of merchandise. During the tenth century the 
distillation of roses was introduced into Spain by the Arabs. 
Throughout the middle ages, the distillation of rose water seems to 
have been an important industry of Persia. Unless strongly alcoholic 424 
Special Part. 
wine was used in the process, one would expect that in the distillation 
of large amounts of rose water the separation of oil of rose at low 
temperatures in the form of a butyraceous mass had been noticed at an 
early date and probably used to perfume fats and fatty oils. 
The first statements concerning rose oil, which possibly refer to the 
distilled oil, is found in the writings of Mesues, and in the almanac of 
Harib for the year 961, which mentions the time suitable for the pre- 
paration of rose water and a rose preserve. In his Compendium aroma- 
tariorum written about the middle of the fifteenth century, Saladin of 
Asculi, the body physician of a prince of Tarentum, describes the 
distillation of roses for the preparation of rose water and rose oil. 
According to a statement by Langles, distilled rose oil is twice 
definitely mentioned in Mohammed Achem's history of the great moguls 
of 1525 to 1667: also in the annals of the Mongolian empire written by 
Manucci, a Venetian physician who lived 40 years in India. Unquestioned 
mention of the butyraceous oil of rose is made in 1574 by Hieronymus 
Rubens, body physician of Pope Clemens III.; also in the writings of 
Porta of the year 1563 and again in 1604. 
In the apothecary tax-ordinances of Worms of 1582 and of 
Frankfurt-on-the-Main of 1587, Oleum rosarum verum is mentioned 
in the list of distilled oils. About the same time Angelus Sala describes 
the distillation of rose oil and designates it strikingly as candiscente 
pinguidine, instar spermatis ceti. In his Pharmacopoeia of 1641, 
Schroeder enumerates the oil under the Olea destillata usitatoria. 
Up to the seventeenth century and beyond, however, Persia princip- 
ally seems to have supplied the market with rose water and rose oil. 
In the course of the century, however, the cultivation of the rose and 
the oil industry spread to India, Arabia, Tunis, Algiers, and Morrocco 
to the south, also to Asia Minor, Turkey and Bulgaria to the north. 
On the island of Chios also considerable rose oil was distilled at the 
beginning of this century, which entered commerce via Smyrna. 
The cultivation of roses in Bulgaria, which became of such import- 
ance in later years, was begun about the beginning of the seventeenth 
century. It seems to about coincide with the founding of Kezanlyk, a 
city on the southern slope of the Balkan mountains in East Roumelia. It 
was not until the nineteenth century, however, that the rose industry of 
Bulgaria became a dangerous competitor of the Persian rose distillation. 
In recent years Bulgaria, in turn, has found successful competitors in 
Germany and France. Oils of the Rosaceae. 
425 
Since the fourteenth century, rose water and with it small quantities 
of rose oil, have been distilled for popular and medicinal use, also for 
perfumery, in the north European countries, especially in France, Germany 
and England. The amount of oil, however, was so small that rose oil 
was mostly bouhgt from the orient and later from the Balkan states. 
The cultivation of roses for the purpose of distilling rose oil on a large 
scale was begun in France about the middle of this century, in Germany 
in 1883.1 
The high price of rose oil and the ease with which it can be adulter- 
ated seems to have brought about adulteration in Persia in the course 
of the seventeenth century. Engelbert Kaempfer from Lemgo, who 
traveled in Persia in the years 1682 to 1684, mentions that rasped 
sandalwood is added to the roses in the process of distillation. This 
observation was verified in 1787 by Archibald Keir in Chatra in the 
Ramgur, whereas Polier observed in Cashmere during the same year 
that in this country not sandalwood, but the fragrant Indian grass 
(Andropogon) is added to the roses for distillation. 
Aside from its use during antiquity, the use of Andropogon 
schoenanthus L. for the purpose of adulteration of rose distillates, 
dates back more than a century. As a more convenient adulterant, 
pahnarosa oil is more recently used in place of the grass from which it 
is distilled in India. 
At an early period oil of rose was used as a perfume and, filled in 
fancy flasks, became a much sought for article in the bazaars of Con- 
stantinople, Smyrna, the levant and the entire orient. The demand 
being greater than the supply, both, manufacturers as well as dealers, 
early learned to increase the supply in a manner profitable to them- 
selves. The former added palmarosa oil to the roses in the process of 
distillation, the latter still further diluted it with indifferent oils and 
spermaceti, the latter being necessary to maintain the proper congealing 
point. 
Origin. Only a few of the 7,000 cultivated varieties of roses are 
used in the production of the oil. For the purpose of distillation, hand- 
some appearance is of less importance than hardiness and a rich yield 
of flowers. Both these qualities are possessed by the Rosa damascena 
Miller, which is cultivated in the Balkan provinces and in recent years 
also in Germany for the production of rose oil. This variety does not 
occur wild, but is a product of cultivation and originally may have been 
a hybrid between R. gallica and R. canina. 
i) I'harm. Rundschau, 12, p. 92. 426 
Special Part. 
The Bulgarian rose-plant is armed with numerous not strongly 
recurved prickles. The glabrous, obtuse three paired lateral leaflets and 
the terminal leaflet are pure bright green, the calyx smooth and 
slightly primrose. In many cases the ordinarily racemose clusters - of as 
many as twenty-seven flowers - are almost cymes. In the fully expanded 
condition the roses attain a maximum width of 7 cm. and, though 
double, they are nevertheless provided with numerous stamens with 
large yellow anthers. In many flowers the outer petals are almost 
white, becoming redder and redder toward the center and under the 
most favorable conditions chiefly pure rose-red. 
Fig. 74. 
Bulgarian Rose Oil Distilling Apparatus. 
In Bulgaria and in Germany the roses are grown in fairly dense 
hedges, about the height of a man. In Bulgaria a white rose, R. alba L. 
is planted to indicate the divisions of the rose fields. It is said to yield 
an oil of poorer quality which is richer in stearoptene. 
In southern France R. centifolia L. is principally cultivated for the 
production of rose water and rose pomade. It is planted in rows but 
forms less dense and lower hedges than the Bulgarian. It is uncertain 
which species of rose was cultivated in the famous rose gardens of 
Schiras. Possibly it was R. gallica, the dried petals of which are even 
to-day exported from Persia in large quantities. 
In India where rose oil distilleries have existed for two centuries in 
Gazipour on the Ganges and in other places of Bengal, R. damascena 
is likewise used. The oil distilled there, however, is never pure, but Oils of the Rosaceae. 
427 
Fig. 75. 
Rose Fields at Miltitz near Leipzig. 428 
Special Part. 
always .contains sandalwood oil. As already stated, the roses are 
generally distilled with sandalwood. 
Production of Bulgarian Rose Oil. The rose stills used in Bulgaria 
are very simple, and are to-day much the same as the ones described 
by Baur1 30 years ago. 
The copper still (Lambic) of 110 liters capacity rests on a fire-place built 
of stone (fig. 74) which is heated by wood from the near forests of the Balkan 
mountains. The conical still is 1.1 m. high and provided with handles with 
which it can be removed from the fire-place. The middle diameter of the still 
is 0.8 m., at the neck it is 0.25 m. The helmet which is 0.3 m. high and 
which has the form of a toad-stool fits closely to the neck of the body of the 
stilb The joints are made tight with clay and strips of cloth. The helmet is 
provided with an exit tube which is inclined to the ground at an angle of 45° 
and which connects with the condenser tube proper. The latter is straight, 
about as thick as a thumb, 2.5 m. long and passes through a tub of oak or 
beech wood filled with water. The cooling water is conveyed by means of a 
wooden gutter. 
A number of these stills are usually mounted under one shed. Each 
apparatus is charged with 10 k. of freshly picked roses and 75 1. of water. 
The distillation is continued until two five liter flasks are filled with aqueous 
distillate. The water remaining in the still is used for the next charge, a pro- 
ceeding that is irrational inasmuch as the salts and extractive matter which 
accumulate cannot be without influence on the delicate perfume. 
When a sufficient amount of rose water has accumulated, 40 1. are 
transferred to a still and 5 1. are distilled off. This second distillate is at first 
a white, turbid liquid, which becomes clear upon standing, the oily constituents 
separating at the surface. For the separation of the oil, a small funnel-shaped 
instrument of tin is employed in Bulgaria. The tube has but a very fine 
opening through which the water will pass but not the semi-congealed oil. 
According to unreliable and improbable statements 3,000 k. of flowers yield 
1 k. of oil in Bulgaria. In all probability a much larger quantity of roses is 
necessary, though 3,000 k. of flowers with a sufficient amount of palmarosa oil 
may yield 1 k. of Bulgarian rose oil. 
After the oil (Bulgarian Giiljag) has received another addition of 
palmarosa oil, which for this purpose is exposed to the sun in shallow 
dishes, by the broker, it is transferred to the well known tinned copper 
flasks (Estagnons) and is brought into the market as Bulgarian rose 
oil. The designation Turkish is no longer correct, for in Turkey no 
rose oil is distilled. 
Production of German Rose Oil. The first attempts by Schim- 
mel & Co. to distill rose oil on a large scale were made in 1883. At 
first Rosa centifolia L. from the neighborhood of Leipzig was used. 
i) Neues Jahrbuch fur Pharmacie und verwandte Facher, 27, p. 1. Abstr. Jahresb. 
f. Pharm., 1867, p. 350. Oils of the Rosaceae. 
429 
In 1888 the firm obtained a considerable number of rose bushes from 
Bulgaria which, by skillful treatment were rapidly multiplied. At the 
present time 35 hectares (=86.4 acres) are being cultivated with this 
rose variety near Miltitz, a station 12 km. from Leipzig on the Thuringian 
R. R. The detrimental influence of the transportation on the freshly 
picked roses, made their distillation on the spot a necessity. Now there 
stands in the midst of the rose plantation a large factory building 
equipped with the best modern apparatus. The freshly picked roses are 
at once taken to the large copper stills, which have a capacity for 
1,500 k. of roses in addition to the requisite amount of water (fig. 50, 
p. 81). From 5,000 to 6,000 k. yield 1 k. of oil. 
It goes without saying that here the crudities of the Bulgarian 
process are not tolerated. The stills are not heated with direct fire but 
with steam. For every new charge of roses fresh water is used and 
the oil is collected in a cascade-like series of Florentine flasks like 
all other oils. Owing to the greater care exercised, the odor of the 
German oil is by far superior to that of the Bulgarian oil. Although 
the stearoptene content is much higher, the intensity of its odor is 
again as great as that of the latter. A product, similar in intensity of 
odor and stearoptene content to the Bulgarian rose oil, is the r'ose 
geraniol of Schimmel & Co. which is made by distilling 2,500 k. of fresh 
roses with 1 k. of pure geraniol. 
Properties. The commercial Bulgarian rose oil is light yellow in 
color, and sometimes has a greenish tint. At 21-25° it is of the con- 
sistency of sweet almond oil, has a strong odor of fresh roses, and 
a pungent, balsamic taste. At about 18-21° acicular crystals or 
shining crystalline laminae separate out, which, on account of their 
lighter sp. gr. collect in the upper portion of the oil and coat the sur- 
face with a thin film that readily parts when the oil is disturbed. 
When cooled the oil congeals to a translucent, soft mass, which is again 
liquified by the warmth of the hand. 
The sp; gr. varies as a rule between 0.855-0.870 at 20°, being 
lowered by a higher stearoptene content. The oil is slightly laevo- 
gyrate, «o = up to - 40.1 On account of the difficultly soluble 
paraffins which rose oil contains, it yields only turbid mixtures with 
even very large amounts of 90 p. c. alcohol. The liquid portion, the 
so-called oleoptene forms a clear solution with 70 p. c. alcohol. The 
i) Baur, whose statements, however, are not always reliable (comp. p. 430), 
found «D = +4°. 430 
Special Part. 
saponification number is 10-17. Rose oil has a slightly acid reaction, 
its acid number being 0.5-3. For this reason the test of the German 
Pharmacopoeia, that the chloroform-alcoholic solution should not 
redden blue litmus paper, is untenable. The temperature at which the 
rose oil begins to congeal, the congealing point, lies between 15 and 
22°, mostly between 17 and 21°. The stearoptene content varies from 
10-15 p. c. 
On account of its larger stearoptene content, German rose oil from 
Rosa damascena Mill, is at ordinary temperature a greenish mass inter- 
mingled with crystals. The odor is much stronger and more persistent 
than that of the Bulgarian oil. The congealing point lies between 27 
and 37°, the sp. gr. between 0.845-0.855 at 30°; «d = +1 to -1°. 
The stearoptene content varies between 26-34 p. c. 
An oil distilled in Leipzig from Rosa, centifolia L. had the following 
properties: sp. gr. 0.8727 at 25°; aD = + 0°49'; congealing point +28; 
saponification number 7.8. 
According to Dupont and Guerlain1, two French oils distilled in 
1895 and 1896 had the following properties: sp. gr. 0.8225-0.8407 
at 30° ; «□ at 30° = - 6° 45' to - 8° 3'; stearoptene content 35 and 
26 p. c. 
Composition. Shortly after the introduction of elementary analysis 
the first combustion of rose oil and its stearoptene was made by Saus- 
sure2 in 1820. A second analysis was made by Blanchet3 in 1833. 
The analysis of the oil merely indicated that it contained oxygen, that 
of the stearoptene that it was a hydrocarbon. Blanchet supposed the 
latter to be a terpene, CioHie, whereas Fliickiger4 in 1869 first 
recognized in it a representative of the paraffin series. The vapor 
density determination made by Power5 in Fliickiger's laboratory indi- 
cated the formula C16H34. Baur,6 who has made numerous observations 
on the distillation of rose oil in Bulgaria and who made detailed reports 
in 1867 and 1872, claimed that the odorless stearoptene could be con- 
verted into fragrant oleoptene by oxidation, and also that the reverse 
reaction could be made to take place. Later investigations, however, 
have not confirmed these statements. About the same time (1872) 
Gladstone7 examined the liquid portion of the oil and found its boiling 
i) Compt. rend., 123, p. 750. 
2) Ann. de Chim. et Phys., II, 13, p. 337. 
3) Liebig's Annalen, 7, p. 154. 
4) Pharm. Journ., II, 10, p. 147. 
s) Pharmakognosie, 3rd ed., p. 170. 
6) Neues Jahrb. f. Pharm., 27, p. 1; 
28, p. 193. 
7) .Tourn. Chein. Soe., 25, p. 12. Oils of the Rosaceae. 
431 
point to be 216°. The first detailed investigation was made by Eckart1 
in 1890, who showed that the principal constituent of both Bulgarian 
and German rose oil was an alcohol CioHisO, to which he gave the name 
rhodinol. Although he ascertained the great similarity between the new 
alcohol and geraniol, he declared the two to be distinct and suggested two 
formulas indicative of their difference. Like Gladstone, he found the boiling 
point of the rhodinol to be 216° (instead of 229°) and it is, no doubt, due 
to this reason that Eckart did not recognize the geraniol as such. 
Shortly afterward (in 1893) Markownikoff and Reformatzky2 claimed 
that the principal constituent of Bulgarian rose oil, to which they gave 
the name roseol, had the formula C10H200. At the same time, how- 
ever, Barbier3 arrived at the conclusion that Eckart's formula CioHisO 
was correct. This was further confirmed by Tiemann and Semmler4 
who recognized the identity of Eckart's rhodinal and citral, the aldehyde, 
CioHieO, corresponding to geraniol. These differences led Bertram 
and Gildemeister5 to take up the investigation of rose oil. They 
ascertained that the principal constituent of German as well as Bul- 
garian rose oil is geraniol, the alcohol CioHisO (b. p. 229-230°) 
discovered by Jacobsen in 1870 in palmarosa oil, and that ''rhodinol" 
is impure geraniol.6 
However, geraniol is not the only alcohol contained in rose oil. 
Hesse7 (1891) expressed the surmise that the alcohol "reuniol," 
CioHaoO, found by him in the pelargonium oils, might also be con- 
tained in rose oil. Tiemann and Schmidt8 demonstrated the identity 
of "reuniol" with citronellol, the reduction product of citronellal. 
i) Archiv d. Pharm., 229, p. 355; also Berichte, 24, p. 4205; Poleck, Berichte, 23, 
p. 3554. 
2) Journ. f. prakt. Chem., II, 48, p. 293. 
3) Compt. rend,, 117, p. 177. 
Berichte, 26, p. 2708. 
s) Journ. f. prakt. Chem., II. 49, p. 185. 
6) As to whether this alcohol is to be designated "geraniol," the name assigned to 
it by its discoverer, or "rhodinol," the name suggested by Eckart for the impure 
compound, has given rise to a lively controversy. Without entering upon this dis- 
cussion, a mere reference to the literature will here be made: H. Erdmann & Huth: 
"Zur Kenntniss des Rhodinols und Geraniols." Journ. f. prakt. Chem., II, 53, p. 42; 
Bertram & Gildemeister: "Ueber Rhodinol und Geraniol." Journ. f. prakt. Chem., II, 
53, p. 225; A. Hesse: "Ueber die vermeintliche Identitat von Rhodinol und Geraniol." 
Journ. f. prakt. Chem., II, 53, p. 238; H. Erdmann: "Untersuchungen iiber die Be- 
standtheile des Rosenols und verwandter atherischer Oele." Journ. f. prakt. Chem., II, 
56, p. 1; Bertram & Gildemeister: "Die Bestandtheile des Rosenols und verwandter 
atherischer Oele," Journ. f. prakt. Chem., II, 56, p. 506; Th. Poleck: "Zur Rhodinol- 
frage." Journ. f. prakt. Chem., II, 56, p. 515; Berichte, 31, p. 29; Bertram & Gilde- 
meister: "Zur Rhodinolfrage." Berichte, 31, p. 749. 
7) Journ. f. prakt. Chem., II, 50, p. 472. 
s') Berichte, 29, p. 922. 432 
Special Part. 
As already stated, the greater portion of rose oil consists of geraniol. 
If the stearoptene is removed by dissolving the oil in dilute alcohol or 
by vacuum distillation, there remains an oil which distills under ordinary 
pressure between 228-232°. When treated with carefully dried and 
very finely powdered calcium chloride, this oil solidifies to a solid mass 
of geraniol calcium chloride. This is freed from oil by washing with 
ether, petroleum ether or benzene, and then decomposed with water, 
yielding chemically pure geraniol.3 For the identification of geraniol 
the well crystallizing diphenyl urethane derivative (m. p. 83-84°) dis- 
covered by Erdmann and Huth2 can be employed. Properties and 
derivatives of geraniol are described on p. 132. 
The second alcohol, the 1-citronellol, is quantitatively of less im- 
portance. Tiemann and Schmidt3 estimate the amount in Turkish 
rose oil to be about 20 p. c. For the identification and isolation of 
citronellol phosphorus trichloride is allowed to act on a well cooled 
ethereal solution of the alcohols of rose oil. The geraniol is hereby 
converted partly into geranyl chloride, partly into hydrocarbons, 
whereas the citronellol is converted into a citronellyl chlorophosphorous 
acid, which can be removed from the ethereal solution by shaking with 
caustic soda solution. The aqueous solution of this citronellyl acid 
ester is shaken out with ether, saponified with strong caustic soda 
solution, and the free citronellol distilled with water vapor. 
The two alcohols, geraniol and citronellol, occur in rose oil princi- 
pally in the free state and only in small part as ester. The oleoptene 
of Bulgarian rose oil contains about 90 p. c. of alcohols (calculated as 
CioHisO). Normal Bulgarian oil, including the stearoptene, contains 
on an average 2.5-3.5 p. c. of ester (calculated as geranyl acetate); a 
sample of German oil contained 3 p. c. 
According to Dupont and Guerlain4 (1896) the esters deviate 
polarized light more than the underlying alcohols. The liquid portion 
of a French oil which deviated the ray of polarized light 10° 30' to the 
left, after saponification had an angle of only-7° 55'. The acids which 
are probably partly combined with geraniol, partly with citronellol, 
have not yet been investigated. Dupont and Guerlain are of the 
opinion that the esters play an important role in the production of the 
rose perfume. 
i) Bertram & Gildemeister, loc. cit. 
2) Journ. f. prakt. Chem., II, 53, p. 45; also Tiemann & Schmidt, Berichte, 29 
p. 920; further H. Erdmann, Journ. f. prakt. Chem., II, 56, p. 6. 
3) Loc. cit. 
4) Compt. rend., 123, p. 750. Oils of the Rosaceae. 
433 
As shown by Fluckiger1 the stearoptene of oil of rose belongs to 
the series of paraffin hydrocarbons. It is not, however, a single hydro- 
carbon, bat consists of at least two, possibly of a number of 
homologous paraffins. This is shown by the fact that on proper treat- 
ment of a large amount of stearoptene, fractions melting at 22° and 
40-41° respectively are obtained.2 
The ethyl alcohol found by Eckart results, according to Schim- 
mel & Co.,3 only when the roses have become heated on their way 
from the fields to the stills and have thus undergone fermentation. 
Inasmuch as neither geraniol and citronellol, nor their esters either 
alone or mixed possess the characteristic honey-like odor of the rose 
oil, it must be assumed that other substances are present in very small 
amounts which assist in producing the fine aroma of the rose. The 
different odors of the various varieties would seem to indicate chemical 
differences. 
Examination. Since the danger of adulteration of as expensive an 
oil as rose oil is very great, a number of empirical tests have been 
suggested by means of which it was supposed the presence of foreign 
additions, especially of palmarosa oil (so-called Turkish geranium oil) 
could be detected. Though these tests were never received with much 
confidence, their value became even more problematic when it was 
shown that geraniol constituted the principal constituent of rose oil as 
well as of palmarosa oil. It is true that some characteristic constituent 
of the palmarosa oil not contained in rose oil might produce a particular 
reaction with the proposed reagents and thus betray the presence of the 
adulterant. A recent investigation, however, of palmarosa oil by Gilde- 
meister and Stephan4 has not ^een productive of any result in this 
direction. In addition, it should be remembered that the Bulgarians 
subject the palmarosa oil to special treatment before they use it as 
adulterant. Thus e. g. by shaking the oil with lemon juice and by 
exposing it to the sun, they try to make the palmarosa oil resemble 
the rose oil in odor and other properties as far as possible. 
Besides palmarosa oil, the true geranium oil is used as an adulterant 
of rose oil. If the adulteration is at all skillful not only do the numerous 
suggested color reactions with iodine, sulphuric acid, fuchsin sul- 
i) See footnote 4, p. 430. 
2) Bericht von S. & Co., Oct. 1890. p. 42.-Eckart, Dupont & Guerlain, loc. cit. 
3) Bericht von S. & Co., Oct. 1892, p. 36. 
<) Archiv d. Pharm., 234, p. 321. 434 
Special Part. 
phurous acid,1 etc. fail, but even the rational physical and chemical 
examination proves of no avail. This is caused partly by the great 
similarity of rose oil and its adulterants, partly by the fact that rose 
oil varies especially in paraffin content according to climate, atmospheric 
conditions, soil and method of distillation to such an extent that a 
comparison of physical properties usually proves of no avail in the 
attempt to detect adulteration. 
For this reason there is no positive foundation for the claim that 
the commercial Bulgarian rose oil is the pure distillate from the roses. 
Several indications render it improbable. First of all, the large imports 
of palmarosa oil into Bulgaria create suspicion. Further, the enormous 
differences between the Bulgarian and German distillates is very striking 
and not to be explained by mere reference to climatic differences. Rather 
startling is also the fact that Bulgarian manufacturers have repeatedly 
exhibited as especially fine products, oils that agreed closely with the 
German distillate in odor, congealing point and stearoptene content. 
On the other hand the oil which is obtained by distilling 2,500 k. 
of roses with 1 k. of geraniol,2 cannot be distinguished from the 
Bulgarian oil of commerce. Intensity of odor, congealing point and 
stearoptene content are alike. 
In order to guard against gross adulteration, specific gravity, 
optical rotation, congealing point, stearoptene content, saponification 
number, and eventually the amount of alcoholic constituents should be 
determined. If the data thus obtained correspond with those of a good 
average oil, and if the odor is delicate and rich, it may be pronounced 
unsuspicious. No chemist, however, can guarantee an oil on the strength 
of its physical and chemical properties. 
Specific gravity. Inasmuch as the oil is partly solidified at 15°, 
the determination must be carried out at 20, 25 or 30°. Palmarosa 
oil has but little effect on the density; alcohol, which has been observed 
occasionally, lowers it; sandalwood oil, which is added during the 
distillation in India, increases it. 
Optical rotation. The angle of rotation is scarcely influenced by 
palmarosa oil. It is remarkable that the rotation of the French oil is 
much greater than that of the German or Bulgarian. 
l) Panajotow, Berichte, 24, p. 2700; Bericht von S. & Co., April 1892, p. 32. 
Comp, also Jedermann, Zeitschr. f. analyt. Chemle, 36, p. 96; Bericht von S. & Co., 
Apr. 1897, p. 39. 
2) Bericht von S. & Co., Oct. 1896, p. 66. Oils of the Rosaceae. 
435 
Congealing point. With reference to rose oil, it is that point 
at which the first crystals separate when the oil is slowly cooled. 
Raikow.1 who considers the congealing point as the point of super- 
saturation of the oleoptene with stearoptene, determines it in the follow- 
ing manner: 
About 10 cc. of rose oil are introduced into a test tube of about 15 mm. 
diameter. A thermometer is so inserted that it touches neither the bottom nor 
the sides of the tube, but floats freely. The oil in the tube is warmed 4-5° 
above the saturation point by means of the hand and well shaken. The tube 
is then securely supported and the oil allowed to cool spontaneously until the 
first crystals appear. At this point the temperature is read, and the operation 
repeated. 
The congealing point of good commercial Bulgarian oil lies as a 
rule between 18 and 21°, but deviations upward as well as downward 
occur. Formerly rose oil was valued according to its congealing point 
alone. Although the odorless paraffin was valueless the oil demanded 
a higher price according to its higher congealing point. It was originally 
and correctly considered that the addition of palmarosa oil would lower 
the congealing point. Later, when the congealing point was artificially 
raised by the addition of spermaceti, the test lost its significance and 
value. It has already been stated that the genuine, normal' Bulgarian 
oil of rose probably contains much more stearoptene than the commercial 
oils from that source. 
Stearoptene assay.2 
50 g. of oil are heated to 70-80° with 500 g. of 75 p. c. alcohol. When 
cooled to 0° the stearoptene separates almost quantitatively. It is separated 
by filtration, again treated with 200 g. of 75 p. c. alcohol and the operation 
repeated until it has become perfectly odorless. As a rule two such treatments 
of the crude stearoptene suffice. 
Test for spermaceti in the stearoptene. 
3-5 g. of the stearoptene are boiled for a short time with 20-25 g. of a 
5 p. c. alcoholic solution of potassa. The alcohol is evaporated and the 
residue treated with hot water. Upon cooling most of the stearoptene separates 
as a solid crystalline mass on the surface. The alkaline solution is removed, 
the stearoptene melted with some hot water, again allowed to cool, the water 
again removed, the operation being repeated until the wash water is neutral. 
The united aqueous liquids are twice extracted with ether in order to remove 
any suspended stearoptene. The alkaline aqueous solution is then acidified 
with dilute sulphuric acid and the acid solution extracted again with ether. 
Upon evaporation, the-ether should leave no residue (fatty acids). By way of 
control, the recovered stearoptene, dried at 90°, is weighed. Allowance should 
be made for a slight loss resulting from evaporation while drying. 
1) Chemlker Zeitung, 22, p. 149. 
2) Bericht von S. & Co., Apr. 1889, p. 37. 436 
Special Part. 
The spermaceti content can be determined in a simpler manner by 
saponifying* the separated stearoptene with alcoholic potassa of known 
strength and titrating back with N/2 sulphuric acid. The saponification 
number of spermaceti is 108. 
Saponification. The saponification number of a good commercial 
oil varies from 10-17, the acid number from 0.8-2.7. Palmarosa 
oil according to Gildemeister and Stephan1 has a saponification number 
of 30-50, the genuine geranium oils 45-100. Additions of the latter 
may, therefore, become noticeable. 
Acety lization. In order to make the examination of the oil 
complete, it will often be advisable to ascertain the alcohol content 
(geraniol and citronellol) by acetylization. The amount present will 
be inversely proportional to the percentage of stearoptene present. 
Umney2 found 70-72.5 p. c. (calculated as geraniol) in good rose oil. 
Palmarosa oil contains 76-92 p. c. of geraniol.1 
As latest adulterant, guaiac wood oil from Bulnesia sarmienti, which 
has an agreeable tea-rose-like odor, has been employed in Bulgaria.3 
It can be recognized by the microscopic examination of the form of the 
crystals of guaiol which separate from the oil upon cooling. Guaiol 
forms needle-shaped crystals which are characterized by a channel-like 
middle line. The crystals of the rose oil paraffin are smaller and thinner 
and possess less sharply outlined forms (Dietze4). 
The positive presence of guaiac wood oil in rose oil should be estab- 
lished by the isolation of guaiol melting at 91°. The new adulterant 
increases the specific gravity and the optical rotation, and raises the 
congealing point of the oil; it lowers the saponification number 
but very little, and upon evaporation leaves a resinous residue.4 
172. Oil of Bitter Almond. 
Oleum Amyg'dalaruin Amararum.-Bittermandelbl.- Essence d'Amandes Ameres. 
Origin and History. Prunus amygdalus Stokes (Amygdalus com- 
munis L.) which belongs to the family of the Rosaceae is cultivated in 
Europe, Asia and northern Africa, recently also in California. In the 
course of time several cultivated varieties have been formed, which are 
distinguished by larger or smaller fruits and seeds. The trees which 
produce the bitter almond do not reveal any permanent botanical 
1) Archiv d. Pharm., 234, p. 326. 
2) Chemist and Druggist, 49, p. 795. 
3) Bericht von S. & Co., Oct. 1898, p. 43. 
4) Siiddeutsche Apoth. Zeitung, 38, pp. 672 and 680. Oils of the Rosaceae. 
437 
differences from those that produce the sweet almond. It is possible 
that the wild almond tree originally produced none but bitter almonds 
which gradually became sweet upon cultivation. Both varieties have 
been known since antiquity. 
Bitter almond oil is first mentioned in the writings of Saladin of 
1488 and those of Sancto Amando in the sixteenth century. The distil- 
lates from bitter almonds and of other Prunoideae, seem to have received 
but little attention during the period of general use of distilled waters. 
It is also uncertain whether the poisonous character of bitter almond oil 
was generally known. Even Scheele, when he discovered hydrocyanic acid 
in 1782 does not seem to have fully realized its poisonous properties. 
Murray appears to have been the first in 1784 to have emphasized its 
very poisonous character. 
The presence of hydrocyanic acid in bitter almond oil was first 
surmised by Render, an apothecary in Erfurt, in 1785. Its presence 
was, however, first established by Bohm, an apothecary in Berlin, in 
1803. Bitter almond oil and its hydrocyanic acid content were in- 
vestigated by Schaub, Schrader, Ittner, Gay-Lussac1 (1831), Robiquet 
und Vogel,2 Boutron-Charlard3 (1837), Liebig and Wohler4 (1837), 
Winckler5 (1839), and others. 
The separation of hydrocyanic acid from the benzaldehyde was first 
accomplished by Vogel in 1822 by shaking the oil with baryta water.2 
Liebig and Wohler6 (1837) shook the oil with ferric sulphate or chloride 
and milk of lime, a method that is still in use, and thus first prepared 
pure benzaldehyde. Bertagnini in 1853 suggested the use of sodium 
bisulphite.7 The separation of benzoic acid from bitter almond oil upon 
exposure to air was observed by Stange in 1823.8 
Preparation. Only a very small amount of the bitter almond oil 
of commerce is prepared from bitter almonds. For the manufacture of 
the oil the seeds of the apricot, Prunus armemaca L., serve almost- 
exclusively and the oil thus obtained does not appear to differ in any 
respect from the oil obtained from bitter almonds. The seeds of the 
apricot are brought from Asia Minor, the home of the tree, into 
i) Poggendorff's Annalen der Physik. New series. 23, pp. 1 and 138. 
2) Journ. de Pharm.. II, 8, p. 293; Ann. de Chim. et Phys., 15, p. 29; 21, p. 250. 
3) Ann. de Chim. et Phys., 44, p. 352.-Liebig's Annalen, 25, p. 175. 
4) Liebig's Annalen, 22, p. 1. 
5) Repert. f. d. Pharm., I, 17. p. 156.- Pharm. Centralbl., 1839. p. 634. 
6) Liebig's Annalen, 3, p. 252. 
7) Ibidem, 85, p. 183. 
8) Repert. f. d. Pharm., I, 14, pp. 329, 361; 16, p. 80. 438 
Special Part. 
European commerce as "peach kernels." The seed of the peach, Primus 
persica Jess, likewise yields an oil that may be regarded as the equiva- 
lent of bitter almond oil. 
Previous to the distillation of the volatile oil, the seeds must be 
deprived of their fatty oil. They are ground to a coarse powder and 
the oil is expressed by means of hydraulic presses, a pressure of 350 
atmospheres being applied. Upon cold expression, bitter almonds yield 
about 50 p. c., apricot seeds about 25-38 p. c. of fatty oil. 
The press-cakes are finely ground and are then ready for the 
manufacture of the volatile oil. This is not present as such in the 
seeds but is formed by a process of fermentation similar to that pro- 
ducing mustard oil and oil of wintergreen. In the presence of water 
the glucoside amygdalin which is contained in these seeds is decomposed 
by a ferment known as emulsin into benzaldehyde, hydrocyanic acid 
and dextrose according to the following equation: 
C2OH27NO11 + 2H2O = C6H5CH0 + CNH + 2CflHi206 
Amygdalin Water Benzaldehyde Hydrocyanic acid Dextrose. 
Inasmuch as the emulsin coagulates at the boiling temperature 
of water, and thereby loses its activity, the fermentation must be 
completed before the distillation is begun. The powder is therefore 
mixed with 6-8 parts of water of about 50-60° and the mixture set 
aside for about 12 hours. The oil formed is then distilled over with 
water vapor. 
According to the directions of Pettenkofer1 (1862) 12 parts of the ground 
seeds, deprived of their fatty oil, are added to 100-120 parts of boiling water 
while stirring. The mixture is kept at this temperature for about 15-30 
minutes and is then set aside to cool. To the cool mixture 1 part of fresh 
bitter almond powder, mixed with 6-7 parts of water, is added and allowed 
to macerate for 12 hours. 
By treating the larger portion of the almond powder with boiling water, 
a more complete solution of the amygdalin is supposed to be accomplished. 
In order to hydrolyse the amygdalin of 12 parts of the powder, the emulsin 
of 1 part will suffice. 
During the process of distillation, care is to be exercised not to allow the 
vapors of the very poisonous hydrocyanic acid to escape into the room. Not 
only should good condensation be provided, but the receiver should be joined 
air-tight to the condenser by means of bladder or parchment paper. All 
escaping gases should be conducted into the open atmosphere. 
Inasmuch as benzaldehyde is rather readily soluble in water, especially in 
such containing hydrocyanic acid, the bulk of the oil is obtained only after 
cohobation of the aqueous distillate. The yield of oil from bitter almond seed 
varies from 0.5-0.7 p. c., that from apricot seeds from 0.6-1 p. c. 
i) Liebig's Annalen, 122, p. 81. Oils of the Rosaceae. 
439 
Inasmuch as the hydrocyanic acid is objectionable in many instances, 
a part of the oil is deprived of this poisonous acid. 
For this purpose the oil is shaken with milk of lime and ferrous sulphate 
whereby the hydrocyanic acid is precipitated as calcium ferrocyanide. The 
unchanged benzaldehyde is rectified by means of water vapor. If the operation 
has been carefully conducted no trace of hydrocyanic acid remains, as may be 
shown by the tests described under Examination. 
In place of the oil deprived of its hydrocyanic acid, the cheaper 
artificial benzaldehyde is largely used. Inasmuch as the latter article 
usually contains chlorinated products which possess an unpleasant odor 
and taste, it can be used only in the manufacture of the cheaper grades 
of soap, but not in perfumery and in liquors. Artificial benzaldehyde 
is made by boiling benzyl chloride with lead or copper nitrate, or by 
heating benzylidene chloride with soda lye or milk of lime. Benzaldehyde 
obtained in this manner can be detected by means of its chlorine con- 
tent as described on p. 442. 
Properties. Bitter almond oil containing hydrocyanic acid is at 
first a colorless liquid 'which later becomes yellow. It is strongly 
refractive and posesses the well-known odor of bitter almonds. 
In smelling of the bitter almond oil great care should be exer- 
cised on account of the strongly poisonous hydrocyanic acid. The 
sp. gr. of the normal oil is 1.045-1.06. A higher specific gravity 
may be due to an abnormally high hydrocyanic acid content or of 
phenyl oxyaceto-nitrile. (Comp, under Composition on p. 440.) Freshly 
prepared oil is neutral. Upon standing it acquires an acid reaction 
owing to the oxidation of benzaldehyde to benzoic acid. The oil is 
optically inactive. 
In water it is relatively soluble: 1 part of oil requires somewhat 
over 300 parts of pure water for solution. In water containing hydro- 
cyanic acid, however, it is more soluble. The oil is soluble in 90 p. c. 
alcohol in all proportions, of 70 p. c. alcohol it requires -2 parts. 
Nitric acid dissolves bitter almond oil at ordinary temperature without 
the generation of nitric oxide vapors. 
Upon distillation of the oil over a direct flame an oil rich in hydro- 
cyanic acid comes over first, later a weaker distillate is obtained. 
On account of the hydrocyanic acid vapors given off, special care must 
be taken in conducting this operation. The residue contains benzoin 
which results from the polymerization of the benzaldehyde under the 
influence of the hydrocyanic acid. 440 
Special Part. 
Bitter almond oil deprived of its hydrocyanic acid, or benzaldehyde, 
is a colorless, optically inactive liquid; sp. gr. 1.050-1.055; b. p. 179°. 
It is much more readily acted upon by atmospheric oxygen than the 
oil containing hydrocyanic acid, which seems to act as a preservative. 
Atmospheric oxygen quite readily oxidizes benzaldehyde to benzoic 
acid. Compare under Preservation on p. 442. 
Composition. Bitter almond oil consists of benzaldehyde, hydro- 
cyanic acid and phenyl oxyaceto-nitrile (benzaldehyde cyanhydrin or the 
nitrile of mandelic acid). Upon the hydrolysis of amygdalin, benzalde- 
hyde and hydrocyanic acid result which, upon prolonged contact, unite 
to form phenyl oxyaceto-nitrile: 
C6H5CH0 + CNH = C6H5CH(0H)CN. 
Benzaldehyde Hydrocyanic acid Phenyl oxyaceto-nitrile. 
The proof that bitter almond oil contains this nitrile was brought 
by Fileti1 in 1818. Upon reduction of bitter almond oil he obtained 
phenyl ethyl amine whereas a fresh mixture of hydrocyanic acid and 
benzaldehyde yielded only methyl amine. 
Phenyl oxyaceto-nitrile is readily decomposable, breaking up into its 
components when distilled with water vapor or in a vacuum. It must, 
therefore, be formed after the distillation of the oil. It is formed in large 
quantities when the oily distillate remains in contact with the aqueous 
distillate containing the hydrocyanic acid for a long time. 
Inasmuch as the sp. gr. of the nitrile of mandelic (phenyl glycoIlic) 
acid is high, viz. 1.124, the density of an oil will increase with the 
amount of nitrile present. Whereas normal oils having a sp. gr. of 
from 1.052-1.058 contained 1.6-X p. c. of hydrocyanic acid, oils 
having a density of from 1.086-1.096 were found to contain 9-11.4 p. c. 
of hydrocyanic acid. To further clear up these relations it was observed 
that the sp. gr. of pure benzaldehyde changed from 1.054 to 1.074 
when allowed to stand two days in contact with a 20 p. c. aqueous 
solution of hydrocyanic acid.2 
From the above it becomes apparent that the hydrocyanic acid 
content of an oil will vary considerably with, the method of preparation. 
For medicinal purposes, therefore, a definite percentage strength should 
be required.3 
Examination. Qualitative test for hydrocyanic acid. In 
order to distinguish a bitter almond oil containing hydrocyanic acid from 
one which does not contain this acid the following test is made use of: 
i) Gazz. chlm. ital. 8, p. 446; Be- 
richte, 12, Ref. p. 296. 
2) Bericht von S. & Co., April 1893, p. 40. 
3) Phar.n. Zeitung, 41, p. 780. Oils of the Rosacea e. 
441 
10-15 drops of the oil to be examined are shaken with 2-3 drops of a 
strong (or a corresponding amount of dilute) soda solution. Several drops of 
ferrous sulphate solution containing some ferric salt are then added, the 
mixture thoroughly shaken and acidulated with dilute hydrochloric acid. Upon 
solution of the precipitate of ferrous and ferric oxide a precipitate of Prussian 
blue results if hydrocyanic acid was present. The reaction is so delicate that 
even minute traces of hydrocyanic acid can be detected in this way. 
Assay of hydrocyanic acid. The best results are obtained by 
the gravimetric method according to the following directions. 
1 g. of oil carefully weighed is dissolved in 10-20 g. of alcohol and 10 g. 
of alcoholic ammonia (free from chlorine) are added. After standing for a 
short time 1 g. of silver nitrate is added and the mixture acidulated with 
nitric acid. After the liquid has become clear, the silver cyanide is collected on 
a dried and weighed filter, carefully washed with water and dried at a temper- 
ature of 100°. 
The silver precipitate obtained in this way represents all of the 
hydrocyanic acid contained in the oil. If the oil is not previously 
treated with ammonia only the free hydrocyanic acid is estimated. 
The ammonia decomposes the phenyl oxyaceto-nitrile.1 
More convenient is the volumetric method of Vielhaber2 but it is 
less accurate because the end-reaction cannot be recognized with 
certainty. Liebig's method for the estimation of hydrocyanic acid in 
bitter almond water is not at all applicable to the oil. The following 
directions are given by Kremers and Schreiner:1 
1 g. of oil is carefully weighed in a small Erlenmeyer flask, and 10 cc. of 
a mixture of freshly prepared magnesium hydroxide and several drops of 
potassium chromate solution are added. Sufficient N/10 silver nitrate 
V. S. is added with constant shaking until the formation of the red silver 
chromate indicates the end of the reaction. In order to obtain the percentage 
of hydrocyanic acid, the number of cc. of the deci-normal solution used are 
multiplied by 0.0027. 
The presence of foreign oils can readily be detected by converting 
the benzaldehyde into its sodium acid sulphite addition product and 
thus separated from the non-aldehyde constituents. 
In a test tube of fully 100 cc. capacity 5 g. of the oil to be examined and 
45 g. of acid sulphite solution are thoroughly shaken. 60 cc. of water are added 
and the tube placed in hot water. If the oil was pure a clear solution will 
result, whereas foreign substances will rise to the surface and can be examined. 
In order to test for nitro-benzene (oil of mirbane), either the original oil or 
the oil floating on the sulphite solution is dissolved in 20 times its volume of 
alcohol and the solution diluted with water until it becomes turbid. Zinc and 
sulphuric acid are then added and the solution set aside for several hours. 
The solution is filtered, the alcohol evaporated and the remaining solution 
2) Archiv d. Pharm., 213, p. ^08. 
id Pharm. Review. 14, p. 196. 442 
Special Part. 
boiled with a drop of potassium bichromate solution. The presence of aniline, 
resulting upon the reduction of any nitro-benzene in the original oil, will be 
recognized by the violet color of the solution. 
The most common adulterant of bitter almond oil, whether deprived 
of hydrocyanic acid or not, is artificial benzaldehyde. Inasmuch as the 
latter is almost invariably accompanied by chlorinated products the 
determination of chlorine affords the easiest method of detection in the 
following manner:r 
In a small porcelain capsule, placed within a larger one of about 20 cm. 
diameter, a folded strip of filter paper saturated with oil is placed and ignited. 
A large beaker of about 2 1. capacity, the inner surface of which has been 
moistened with distilled water, is immediately placed over the burning oil. 
The products of combustion condense on the moistened surface of the beaker 
and with the aid of a little distilled water are washed on to a filter. The 
filtrate should not be rendered turbid, much less yield a precipitate with silver 
nitrate T. S. Genuine oil, i. e., oil prepared from almonds or apricot seeds 
never yields a chlorine reaction. It may be well, however, to make a duplicate 
test with a known pure oil inasmuch as the water and the utensils employed 
may at times be contaminated with some chlorine. 
Inasmuch as a benzaldehyde free from chlorine has recently been 
brought into the market, the ' absence of chlorine is by no means a 
sign of the absolute purity of an oil. In all cases, however, where 
chlorine is found the presence of artificial benzaldehyde may be regarded 
as being established. The presence of alcohol, which is not infrequently 
found, can be determined in the usual manner. 
Preservation. If a small amount of benzaldehyde be exposed to 
the air in an open dish, crystals are soon formed and after a short 
time the oil will be converted into a magma of crystals of benzoic acid. 
The same change takes place if the oil is kept in half-filled bottles. 
Bitter almond oil should, therefore, be kept in well-filled bottles. Ex- 
periments have shown that the addition of 10 p. c. of alcohol will act 
as a preservative.2 If but 5 p. c. of alcohol are added, the oxidation 
will take place even more rapidly than when undiluted. Bitter almond 
oil containing hydrocyanic acid is not as readily oxidized as the oil 
free from acid. The hydrocyanic acid evidently acts in a manner 
similar to the alcohol when 10 p. c. are used. 
173. Oil of Cherry-laurel. 
Oleum Laurocerasi. - Kirschlorbeerol. - Essence de Laurier-Cerise. 
Origin, History and Preparation. Cherry-laurel, Prunus lauro- 
cerasus L.. which is indigenous to Persia and the Caucasus and which 
i) Bericht von S. & Co., Apr. 1890, p. 29. 
2) Bericht von S. & Co., Apr. 1895, p. 47. 443 
is cultivated in countries with a temperate climate, appears to have 
become known in Europe since the beginning of the sixteenth century. 
The aqueous distillate from the leaves has been used medicinally since 
the first half of the- eighteenth century and its poisonous properties 
were repeatedly observed. The distilled oil is mentioned in medical 
treatises since 1780. The presence of hydrocyanic acid in the oil was 
observed simultaneously by Schaub and by Schrader at the beginning 
of this century. 
The oil from the leaves closely resembles the oil from bitter almonds 
but has a slightly different odor. The method of preparation is likewise 
similar to that of the bitter almonds. The cut leaves are macerated 
with water and the mash set aside. The oil thus formed is distilled 
with water vapor. The yield is about 0.5 p. c. (Umney1). 
The oil is formed by the hydrolysis of laurocerasin, a glucoside 
closely related to amygdalin, but not identical with it.2 Being hygro- 
scopic it is not readily obtained in the crystalline state, but results as 
a thick syrup or an amorphous mass upon evaporation of the alcoholic 
extract. Laurocerasin, CioHstNOso is made up of one molecule of 
amygdalin, C2OH27NO11, one molecule of amygdalic acid, C20H28C13, and 
six molecules of water. In contact with emulsin, the amygdalin of the 
laurocerasin is broken up into hydrocyanic acid, benzaldehyde and 
grape sugar. The amount of oil obtainable from the laurocerasin is, 
therefore, much smaller than that obtained from an equal weight of 
amygdalin. 
Properties. Oil of cherry-laurel can only be distinguished from 
bitter almond oil by its odor. The difference in odor is emphasized by 
first uniting the benzaldehyde with an acid sulphite. Its other properties 
agree with those of bitter almond oil. Its sp. gr. is 1.054-1.066, it is 
optically inactive and forms a clear solution with 2 parts of 70 p. c. 
alcohol. 
Inasmuch as cherry-laurel oil is very poisonous on account of the 
hydrocyanic acid contained therein sufficient regard should be had for 
this property in the use of the oil. 
Composition. Like bitter almond oil, cherry-laurel oil contains 
benzaldehyde, hydrocyanic acid and phenyl oxyaceto-nitrile (Fileti,3 
Oils of the Rosaceae. 
i) Pharm. Journ., Ill, 5, p. 761. 
2) Lehmann (1874), Neues Repert. f. <1. Pharm.. 23, p. 449; and (1885) Pharm. 
Zeitsehr. f. Russl., 24, pp. 353, 369, 385, 401. - Berichte, 18, p. 569 Referate. 
3) Gazz. chim. ital., 8, p. 446; Berichte, 12, p. 296. 444 
Special Part. 
1878). According to Umney1 (1869) hydrocyanic acid is present to the 
extent of 2 p. c. It is probable, however, that the percentage varies 
as in bitter almond oil. 
According to Tilden2 (1875), traces of another substance are 
present, to which the peculiar odor of this oil is probably due. If the 
oil is shaken with sodium acid sulphite solution, a dark colored oil 
remains which upon oxidation with chromic acid yields benzoic acid. 
Tilden supposes this substance to be identical with benzyl alcohol. 
Adulteration and Examination. Oil of cherry-laurel is subjected 
to the same kind of adulteration as bitter almond oil. The tests are 
the same as those described on p. 440. 
171. Oil of Wild Cherry Bark. 
The bark of the wild cherry, Primus virginiana, Mill. (P. serotina 
Ehrh.), which is indigenous to North America, has been used for a long- 
time by the natives in the preparation of aromatic beverages and 
household remedies and was made official in the early editions of the 
U. S. Pharmacopoeia. That the distillate from the bark contains 
hydrocyanic acid was observed by Procter3 in 1834. In 1838 he 
showed that the oil does not preexist in the bark but results by a 
process similar to that taking place in the formation of bitter almond 
oil.4 A more detailed examination of the oil was made by Power and 
Weimar5 in 1887. 
The powdered bark when macerated yields 0.2 p. c. of oil, which 
resembles the oil of bitter almonds, consists largely of benzaldehyde, 
and contains hydrocyanic acid.*5 Sp. gr. 1.045-1.050. 
According to Power and Weimar the bark contains no amygdalin, 
but a substance that behaves like laurocerasin. The ferment does not 
consist of emulsin, at least no emulsin can be isolated according to 
the usual method. The leaves of the wild cherry tree also yield an 
aqueous distillate containing hydrocyanic acid.7 
Hydrocyanic acid and benzaldehyde have been obtained from parts 
of other rosaceous plants. Thus, e. g. from the leaves, branches and 
seeds of the peach, Primus persica Jess., from the seeds and the fleshy 
1) Pharm. Journ., II, 10, p. 467. 
2) Pharm. Journ., Ill, 5, p. 761. 
3) Americ. Journ. Pharm., 6, p. 8. 
4) Ibidem, 10, p. 197. 
5) Pharm. Rundschau, 5, p. 203. 
6) Bericht von S. & Co., Apr. 1890. p. 48. 
7) Pharmacognosie, 3rd ed., p. 765. Oils of the Leguminosae. 
445 
pericarp of the cherry, P. cerasus L., from the seeds of the plum, P. 
domestica L., from the bark, leaves, flowers and seeds of P. padus L., 
from the young leaves and flowers of P. spinosa L. 
175. Oil of Copaiba. 
Oleum Balsami Copaivae.-Copai vabalsainol.-Essence de Baume de Copahu. 
Origin. Copaiba balsam, which has been used in Europe since the 
beginning of the sixteenth century, is obtained from a number of species 
of Copaifera (Family Leguminosae) which are indigenous to the territory 
of the Amazon and its tributaries as far north as Guayana, Venezuela 
and Columbia. The principal species are Copaifera officinalis L., C. 
guaianensis Desf., C. coriacea Martins, C. Langsdorffii Desf., C. conferti- 
flora, C. oblongifolia Martins and C. rigida Bentham. The balsam is 
allowed to flow from the cavity made in the trunk of the tree by means 
of tin tubes into the vessels used for its transportation. Occasionally 
the trees are so charged with balsam that the receptacles burst and the 
balsam exudes from the vertical cracks. 
Commercially, the balsam is distinguished according to the ports of 
export. The most important varieties are the Maracaibo balsam 
(derived principally from Copaifera officinalis} and the Para balsam. 
The latter is more fluid and inasmuch as it yields the larger percentage 
of oil, abt. 60-90 p. c., is preferred for distillation. Maracaibo balsam 
which is more viscid yields upon distillation about 40 p. c. of oil. A like 
yield was obtained from a Maranhao balsam. 
Properties. Copaiba oil from Para or Maracaibo balsam is a 
colorless, yellowish or brownish liquid possessing the characteristic 
pepper-like odor of the balsam, and a bitter, grating and persistent 
taste. Sp. gr. 0.900-0.910; «d = - 7 to -35°. The boiling temper- 
ature lies between 250 and 275°. It is not completely soluble in 90 
p. c. alcohol. Of absolute alcohol, usually equal parts are requisite to 
form a clear solution. According to Kremel,1 two samples of para oil 
yielded no saponification number. Duliere2 examined an oil of unknown 
origin and of a high specific gravity, viz. 0.9155, and found a saponifi- 
cation number corresponding to 4 p. c. of sesquiterpene acetate 
(C15H25OCOCH3). After acetylization a saponification number was 
obtained corresponding to 6.5-7.35 p. of acetate.3 
An oil from Maranhao balsam had the sp. gr. 0.889 and «d = - 20°- 
1) Pharm. Post, 21, p. 822. 
2) Ann. de Pharm. (Louvain), 3, p. 553; 4, p. 11. 
3) Bericht von S. & Co., Oct. 1895, p. 42; Apr. 1898, p. 49. 446 
Special Part. 
Composition. The. only known and well defined constituent of 
copaiba oil is the sesquiterpene caryophyllene, C15H24, which also occurs 
in oil of cloves. If fraction 250-270° is treated according- to Wallach1 
with glacial acetic acid and sulphuric acid, caryophyllene hydrate 
C15H25OH is obtained in handsome crystals melting at 96°. By the 
action of phosphorus pentachloride on caryophyllene hydrate the 
chloride C15H25CI melting at 63° is obtained. The nitrosochloride, 
characteristic of caryophyllene and melting at 161-163° with decom- 
position, has also been obtained. 
Blanchet2 (1833), also Soubeiran and Capitaine8 (1840), obtained 
a solid hydrochloride by passing hydrochloric acid into copaiba oil. 
One product melted at 77°, another at 54°. The analysis agreed with 
the formula (CioHie2HCl). Later investigators have been unable to 
obtain a solid hydrochloride from either Para or Maracaibo oil.4 
Neither Posselt5 1(1896) nor Strauss6 (1868) obtained definite results 
by oxidizing both oils with nitric acid. Levy and Englander7 (1887), 
who oxidized Para oil with potassium bichromate and sulphuric acid, 
were more successful. They obtained a crystalline acid melting at 140° 
which was identified as a symmetric dimethyl succinic acid, CeHioO^. 
The small yield of but p. c. renders it doubtful whether this acid 
owes its origin to caryophyllene or to some other minor constituent of 
the oil. According to Brix, Maracaibo balsam oil yields upon oxidation 
small amounts of terephthalic acid. The same oil when dried over 
sodium yields a blue oil which has the composition C20H32 + H20. 
Adulteration. Copaiba oil is more frequently used as an adulter- 
ant than adulterated itself. As adulterant gurjun balsam oil only 
comes into consideration, which, however, can be readily recognized 
on account of its higher specific gravity and greater optical activity. 
The oil of the African copaiba balsam (see next oil) is not soluble in 
an equal volume of absolute alcohol like the genuine oil. 
176. African Copaiba Balsam Oil. 
Under the above designation there appeared several years ago a 
balsam from West Africa. Although its botanical origin is not known, 
its resemblance to the South American balsam renders its derivation 
1) Liebig's Annalen, 271, p. 294. 
2) Liebig's Annalen, 7, p. 156. 
3) Liebig's Annalen, 34, p. 321. 
4) Brix (1882), Monatsh. f. Chern., 2, p. 507; 
Umney (1893), Pharrn. Journ., Ill, 24, p. 215. 
5) Liebig's Annalen, 69, p. 67. 
6) Liebig's Annalen, 148, p. 148. 
Liebig's Annalen, 242, p. 189; 
Berichte, 18, pp. 3206, 3209. Oils of the Leguminosae. 
447 
from a copaifera species probable. Upon distillation, Umney1 obtained 
37-40 p. c. of oil. Sp. gr. 0.917-0.918; «D-+ 20°42'. Upon passing 
hydrogen chloride into fraction 240-270° no solid hydrochloride was 
obtained. Neither could caryophyllene hydrate be obtained by treat- 
ment with glacial acetic acid and sulphuric acid. 
177. Cabriuva Wood Oil. 
Cabriuva, Myrocarpus fastigiatus Fr. All. (Family Leguminosae) is 
a handsome tree native to Brazil that acquires a height of 8 meters 
and more. The yellowish-white flowers are very fragrant, the odor 
resembling that of a mixture of vanilla and tolu balsam. The wood is 
counted among the most valuable of Brazil. 
The oil from the wood was examined by Schimmel & Co.2 It is of a 
light yellow color and has a faint, not unpleasant odor. Sp. gr. 0.9283; 
«d = - 8° 29'. From 100 k. of sawdust, Peckolt3 obtained 4.3 g. of oil. 
Sp. gr- 0.925 at 13°. 
178. Carqueja Oil. 
Genista tridentata is supposed to be the plant from which this oil is 
obtained. This leguminous plant grows wild in Brazil and is used as 
a domestic remedy.4 
Carqueja oil is yellow, has a somewhat narcotic, camphor-like, not 
unpleasant odor. Sp.gr. 0.9962; «d=-31° 15' at 17°; saponification 
number 190.5. Upon distillation three-fourths of the oil distill over 
between 200-300° while ucetic acid is split off. In the first fraction 
cineol could be identified. A viscid mass remained in the flask. 
179. Indigofera Oil. 
According to van Romburgh, the leaves of Indigofera, galegoides 
D. C. (Family Leguminosae') contain a substance (possibly amygdalin 
or laurocerasin) which with emulsin yields hydrocyanic acid and benz- 
aldehyde. Upon distillation of the fresh, macerated leaves, 0.2 p. c. of 
oil were obtained. 
Indigofera oil is light yellow in color, its odor resembles that of 
bitter almond oil but differs from it in being herbaceous. Sp. gr. 1.046.5 
Besides benzaldehyde and hydrocyanic acid, the oil contains traces of 
i) Pharm. Journ., Ill, 22, p. 452; 24, p. 215. 
2) Bericht von S. & Co., Apr. 1896, p. 69. 
3) Catalogue of the Nat. Exhib. in Rio, 1866, p. 48. 
4) Bericht von S. & Co.. Apr. 1896, p. 70. 
5) Bericht von S. & Co., Oct. 1894, p. 75. 448 
Special Part. 
ethyl alcohol and also small amounts of methyl alcohol. The latter 
was identified by its conversion into methyl iodide and into the methyl 
ester of oxalic acid melting- at 54°. If the leaves were digested for 
24 hours at a temperature of 50° before being distilled, the first distil- 
late contained larger amounts of ethyl alcohol which, however, was 
formed during the process of maceration.1 
180. Sappan Leaf Oil. 
The leaves of Caesalpinia sappan L., a leguminous tree, from which 
the sappan wood used for dyeing is obtained, yields according to 
van Romburgh 0.16 to 0.2 p. c. of an almost colorless oil, sp. gr. 0.825 
at 28°. It is strongly dextrogyrate, aD= + 37°30' to +50° 30' and 
boils principally at 170°. The odor is pepper-like, reminding of phel- 
landrene. With sodium nitrite and glacial acetic acid so large an 
amount of phellandrene nitrite was obtained, that the bulk of the oil 
may be regarded as d-phellandrene. Upon distillation of the leaves, 
van Romburgh observed the occurrence of methyl alcohol.2 
181. Oil of Tolu Balsam. 
Oleum Balsami Tolutani.-Tolubalsamol.-Essence de Baume de Tolu. 
Origin and History. The statements made on p. 420 concerning 
the origin and preparation of American storax apply in general to tolu 
balsam from Toluifera balsamum Mill. It is prepared in the southern 
states of South America and has been used for a long period, in Europe 
since the middle of the sixteenth century. 
Upon distillation with water vapor, the solid balsam yields 1.5-3 p.c. 
of oil. Slow distillation yields a light oil, whereas rapid distillation 
with superheated steam yields more oil of a higher density. The sp. gr., 
therefore, varies between 0.945-1.09. The oil is slightly laevo- or 
dextrogyrate, «d =- 0°58' to + 0°54'. The odor is pleasant, highly 
aromatic and reminds of hyacinth. 
Composition. The older, somewhat contradictory statements give 
but imperfect information concerning the composition of tolu balsam 
oil.3 According to Kopp the hydrocarbon boiling at about 170° and 
having an elemi-like odor is a terpene (possibly phellandrene?). Inas- 
i) Bericht von S. & Co., Apr. 1896, p. 75. 
2) Bericht von S. & Co., Apr. 1898, p. 57. 
3) Deville (1841), Ann. de Chim. et Phys., Ill, 3, p. 151; Liebig's Annalen, 44, 
p. 304.-Kopp (1847), Journ. de Pharm. et Chim., Ill, 11, p. 425.- Scharling (1856), 
Liebig's Annalen, 97, p. 71. Oils ol the Leguminosae. 
449 
much as Busse1 (1876) has shown the presence of benzoic and cinnamic 
esters of benzyl alcohol in the balsam, these esters are probably also 
contained in the oil. As a matter of fact the oil has a high saponification 
number (abt. 180) and from the alkaline saponification liquor crystalline 
acids (presumably cinnamic and benzoic acids) can be precipitated. 
182. Oil of Myroxylon Peruiferum. 
From the leaves of the leguminous Myroxylon peruiferum L. f.. a 
tree closely related to the Peru balsam tree,-' Peckolt3 obtained a small 
amount of oil with a faint but pleasant odor and a sp. gr. of 0.874 at 
14°. The bark yielded two oils, one having the sp. gr. 1.139 at 15°, 
the other 0.924 at 17°. The oil from the wood had a faint sassafras 
odor and a sp. gr. of 0.852 at 15°. 
183. Oil of Rose Geranium.5 
Oleum Geranii. - Geranium- or Pelargonin mol. - Essence de Geranium Rose. 
Origin and History. The pelargoniums which are indigenous to 
South Africa and which are now largely cultivated as decorative plants 
were introduced into Europe in 1690 (Piesse4). Recluz6 in 1819 first 
obtained a volatile oil from the leaves. However. Demarson of Paris, 
in 1847 was the first to cultivate pelargoniums for the distillation of 
the oil. Since then their cultivation throughout France has been largely 
extended and was introduced into Algiers by Chiris and Monk. The 
production in the latter colony now exceeds that of any other country. 
In Spain pelargoniums were cultivated in the vicinity of Valencia by 
Robillard. Later they were also cultivated in the province of Almeria. 
The island of Reunion has entered upon the cultivation of these plants 
since the eighties and now holds the second position in the manufacture 
of the oil. Of much less importance are the plantations in Corsica. 
Preparation. Three species and their varieties are principally 
■cultivated, viz., Pelargonium odoratissimum Willd., P. capitatum Ait., 
and P. roseum Willd. The last is regarded as a variety of P. radula Ait. 
(Sawer 7). 
i) Berichte, 9, p. 880. 
2) Inasmuch as the so-called Peru balsam oil cannot be obtained by steam distil- 
lation it is not included among the volatile oils in this treatise. 
3) Zeitschr. d. ost. Apt.-Ver., 17, p. 49; Jahresb. f. Pharm., 1879, p. 59. 
4) The Art of Perfumery, 4th ed., p. 124. 
a) This oil is not to be confounded with palmarosa oil from Andropogon schoen- 
■anthus L. which is misnamed Indian geranium oil. 
6) Pharm. Journ., I, 11, p. 325. 
7) Odorographia, vol. 1, p. 42. 450 
Special Part. 
The oil is to be found in all green parts of the plant, especially in 
the leaves. The flowers are perfectly odorless. The plants are harvested 
before they blossom, when the leaves begin to get yellow and after the 
lemon-like odor has given way to the more rose-like odor. It is- 
reported that the plants grown on dry soil give a smaller yield but a 
finer oil than those grown in irrigated soil. The yield varies from 
0.15 to 0.33 p. c. 
Properties. Geranium oil is a colorless, greenish or brownish 
liquid of a pleasant, rose-like odor. Sp. gr. 0.89-0.906; = -6 to- 
-16°. With the exception of the Spanish oil, .all varieties are soluble 
in 2-3 parts of 70 p. c. alcohol. The saponification number varies 
from 45 to 100 and the percentage of ester calculated as geranyl 
tiglinate from 19 to 42 p. c. • 
The constants of the different oil varieties are as follows: 
1. French oil. Sp. gr. 0.897 - 0.905; «d - - 7°30' to -9°.. 
Geranyl tiglinate 25-28 p. c. Forms a clear solution with 2-3 parts 
of 70 p. c. alcohol. 
2. African (Algerian) oil. Sp. gr. 0.892-0.90; aD = - 6°30' 
to -10°. Geranyl tiglinate 19-29 p. c. Solubility same as No. 1. 
3. Reunion oil. Sp.gr. 0.889-0.895 ; «d =-8° to-11°. Geranyl 
tiglinate 27-33 p. c. Solubility same as No. 1. This oil usually has 
a green color which does not result from the presence of copper but 
from one of the compounds contained in the highest fractions winch 
when pure is possibly blue in color. 
4. Spanish oil. Sp. gr. abt. 0.897; «d =-10 to-11°. Geranyl 
tiglinate 35-42 p. c. As to solubility this oil differs from the others 
inasmuch as the solution in 2-3 or more parts of 70 p. c. alcohol is 
rendered turbid by the presence of minute crystals of paraffin which rise- 
to the surface. The separation of oily drops at the bottom of the tube 
would indicate adulteration with fatty oil. 
5. German oil.1 This oil has been distilled by way of experiment 
but is not an article of commerce. Yield 0.16 p. c. Sp. gr. 0.906; 
«d = -16°. Geranyl tiglinate 27.9 p. c. 
Of the commercial varieties, the Spanish oil is rated highest. French 
and African oil are about alike in quality, while the price of Reunion oil 
is somewhat lower. 
The oil is mostly transported in tin cans and often acquires a 
brownish color and an odor of rotten eggs. This disagreeable odor^ 
1) Bericht von S. & Co., Apr. 1894, p. 32. Oils of the Leguminosae. 
451 
however, is easily removed by exposing- the oil to the air in shallow 
dishes for several days. As soon as possible the oil should be filled into 
glass containers. 
Composition. The principal constituent is geraniol,1 CioHisO, which 
is contained in all commercial varieties of the oil. It can be isolated 
by treating the saponified and dried oil with very fine calcium chloride. 
The addition product is. carefully washed with ether and the -pure 
geraniol separated by decomposing the compound with water.2 
Besides geraniol, a second alcohol, CioHaoO, which has been identified 
as citronellol by Tiemann and Schmidt3 has been found in the oil. It 
occurs to a larger extent in the oil from Reunion. Mixtures of these 
alcohols have been described as "Rhodinol de Pelargonium" by Barbier 
and Bouveault4 and as "Reuniol" by Hesse.5 
The percentage of geraniol and citronellol in the various commercial 
varieties has been determined by Tiemann and Schmidt:3 The Spanish 
oil contains 70 p. c. of alcohols, of which 65 p. c. are geraniol and 
35 p. c. citronellol. The African oil contains 75 p. c. alcohols of which 
80 p. c. is geraniol and 20 p. c. citronellol. The Reunion oil contains 
80 p. c. of equal parts of geraniol and citronellol. In all of these oils 
the citronellol is a mixture of the dextro- and laevogyrate modifications. 
The lower fractions of the oil contain a third alcohol, in all probability 
linalool. (Barbier and Bouveault).6 
The acids which were separated from the lye after saponification 
boiled between 100 and 210°, and in part solidified. The solid acid 
melted at 64-65°. Its silver salt and its dibromide melting at 87° 
identify it as tiglinic acid.7 The liquid acid mixture apparently consists 
of valerianic, butyric7 and acetic6 acids. 
Jeancard and Satie8 have found that the amount of free acid in 
geranium oil increases when the oil is kept in partly filled bottles. An 
oil which originally showed an acid number of 56, after two months 
standing had increased to 66.73. The same authors also made a 
comparative examination of the different commercial varieties of the oil. 
i) Jahresb. d. Chern., 1879, p. 942. 
2) Journ. f. prakt. Cheni., II, 49, p. 191. 
3) Beriehte, 29. p. 924. 
*) Compt. rend., 119, pp. 281 & 334. 
5) Journ. f. prakt. Chem., II, 50, p. 472; 53, p. 238. 
6) Conipt, rend., 119, p. 281. 
7) Bericht von S. & Co., Apr. 1894, p. 31. It would be of interest to reexamine 
the aqueous distillate of Pelargonium roseum in order to ascertain whether or not the 
pelargonic acid of Pless (1846) (Liebig's Annalen, 59, p. 54), may reveal itself as a 
mixture. 
8) Bull. Soc. ehim. Ill, 23, p. 37. 452 
Special Part. 
Geraniol and citronellol are contained in the oil both free and 
combined with acids. The esters of citronellol are more strongly 
optically active than the alcohol. If geranium oil is saponified with 
alcoholic potassa the angle of rotation is less after the saponification 
than before.1 
Of minor constituents 1-menthone remains to be mentioned. It was 
identified by Flatau and Labbe2 by means of the semicarbazone melting 
at 179.5°. In the highest fractions a crystalline substance melting at 
63° has been found which resembles the stearoptene from oil of rose. 
Judging from the behavior of the oil to 70 p. c. alcohol, this paraffin 
occurs in largest amounts in the Spanish variety. 
Adulteration and Examination. Geranium oil is adulterated with 
turpentine oil, cedar wood oil and fatty oils, all of which can be recog- 
nized by their insolubility in 70 p. c. alcohol. Fatty oil remains behind 
upon distillation with water vapor and can be detected without 
difficulty. 
184-. Oil of Garden Nasturtium. 
* 
The odor of the leaves of Tropaeolum majus L. (Family Tropaeola- 
ceae) having an odor similar to that of the cress, induced Hofmann 3 in 
1874 to examine the oil. 300 k. of flowering herb and unripe seeds were 
distilled with water vapor. The aqueous distillate was shaken with 
benzene and upon evaporation of the benzene 75 g. (=0.025 p. c.) of 
oil were obtained. 
The oil boiled between 160-300° leaving a not inconsiderable residue. 
Only the first fractions contained sulphur and had an unpleasant odor, 
the others not. The bulk of the oil distilled at about 231.9°. This 
fraction was a liquid of strong refractive power, sp. gr. 1.0146 at 
18°, and when acted upon with caustic potassa gave off large quantities 
of ammonia. Analysis showed it to be the nitrile of phenyl acetic acid. 
The principal constituent of the oil, therefore, is the same as that of 
Lepidium sativum L. The same substance was found in the lower and 
higher fractions of the oil together with a hydrocarbon not farther 
investigated. 
Quite different results were obtained recently by Gadamer.4 He 
prepared the oil by extracting the juice from the comminuted herb with 
ether, also by distilling the carefully comminuted herb and extracting 
the aqueous distillate with ether. 4 k. of herb yielded 1.3 g. of a 
i) Compt. rend., 119, p. 281. 
2) Bull. Soc. chini., Ill, 19, p. 788. 
s) Beriehte, 7, p. 518. 
4) Archiv d. Pharm., 237, p. 111. Oils of the Erythroxylaceae. 
453 
brownish colored oil the cress-like odor of which became especially 
marked when warmed. With ammonia the oil yields almost quanti- 
tatively benzyl thiourea melting at 162°, thus showing that the oil 
consists almost entirely of benzyl mustard oil. 
This mustard oil owes its origin to the decomposition of a glucoside, 
the glucotropaeolin, C14H18KNS2O9 + XH2O by means of a ferment. 
Inasmuch as the glucoside and ferment are contained in separate cells, 
the formation of the benzyl mustard oil takes place only when the 
cell walls are ruptured and both substances can act on each other. 
If the cell wall is not destroyed before distillation, the ferment is 
rendered inactive by the heat before it can act on the glucoside. This 
is then decomposed during the process of distillation with the formation 
of the nitrile of phenyl acetic acid (benzyl cyanide). If it is assumed 
that Hofmann did not sufficiently comminute his crude material, the 
results obtained by him are explained. 
185. Oil of Coca Leaves. 
The presence of an oil in the coca leaves was first observed in 1860 
by Niemann1 and Lossen.2 The leaves of Erythroxylon coca Lam. 
var. spruceanum Brck. (Family Erythroxylaceae) contain variable 
amounts of oil according to their development. Van Romburgh3 
obtained from young, undeveloped leaves 0.13 p. c., from fully developed 
leaves only 0.06 p. c. of oil. It consisted principally of methyl salicylate 
with small amounts of acetone and methyl alcohol. 
186. Oil of Guaiac Wood. 
Olenin Ligni Gnajaci. - Gnajakholzol.-Essence de Bois Gaiac. 
Origin and Preparation. Bulnesia sarmienti Lor. is, according to 
Grisebach,4 a tree 40-60 feet in height, belonging to the family 
Zygophyllaceae, and is indigenous to the Argentine province of Gran 
Chaco about half way up the Rio Berjemo. The wood, very similar to 
the ordinary guaiac wood from Guajacum officinale L., occurs since the 
year 1892 as Palo balsamo in commerce. It is exceedingly solid and 
tenacious, and is colored greenish blue on exposure to the air, which 
allows of drawing the conclusion that guaiac resin is present. By distil- 
1) De foliis Erythroxyli, Dissertatio. Gottingen 1860. 
2) Ueber die Blatter von Erythroxylon Coca, Lam., Dissertation, Gottingen 1862. 
s) Ree. ties trav. chim. des Pays Bas, 13, p. 425. - S'Lands Plantentuin te Buiten- 
zorg, 1894, p. 43.-Bericht von S. & Co., Oct. 1895, p. 47; Apr. 1896, p. 75. 
4) Abhandl. d. Konigl. Ges. d. Wissensch. zu Gottingen. Vol. 24, p. 75. 454 
Special Part. 
lation the wood yields 5-6 p. c. of oil, which was first prepared by 
Schimmel & Co.1 and brought into commerce as oil of guaiac wood.2 
Properties. Oil of guaiac wood is a viscous, heavy oil, which at 
ordinary temperature gradually solidifies to a crystalline mass. When 
it has solidified, it does not melt again until between 40 and 50°. The 
odor of the oil is very pleasant, being violet- and tea-like. The specific 
gravity lies between 0.965 and 0.975 at 30°, the angle of rotation 
is -6 to -7° at 30°. The oil is soluble in 70 p. c. alcohol. The 
saponification number found of an oil was 3.9, the ester number 2.4 
and the acid number 1.4.3 
Composition. The crystalline constituent of the oil is guaiac alcohol 
or guaiol (Wallach4), a-sesquiterpene hydrate C15H26O. Guaiol is an 
odorless body, crystallizing in large transparent prisms, and melting 
at 91°.5 It boils under ordinary .pressure at 288°, under 10 mm. 
pressure at 148°. Its solution in chloroform is laevogyrate. With 
dehydrating agents a hydrocarbon C15H24 is formed, accompanied by 
an intensely blue substance. On boiling guaiol with acetic acid an- 
hydride a liquid acetyl compound is produced which boils at 155° under 
a pressure of 10 mm. The odoriferous constituent of the oil has not 
yet been investigated. 
The oil is used in the perfume industry for the purpose of producing 
a tea-rose odor. Recently it is being employed in Bulgaria as an 
adulterant for oil of rose (p. 436). 
187. Japanese Oil of Pepper. 
The fruit of Xanthoxyhun piperitum D. C. (Family Rutaceae} known 
as Piper japonicum or Sansho (Japanese), yields upon distillation6 with 
water 3.16 p. c. of a yellowish oil of a pleasant odor reminding of 
lemon. Sp. gr. 0.973; b. p. 160-230°. 
The oil was investigated by Stenhouse7 in 1857, who established 
the presence of a terpene boiling at 162°, xanthoxylene (pinene or 
camphene?), as well as a crystalline body CioHgO4. The main con- 
stituent of the oil is citral,6 CioHigO. 
i) Bericht von S. & Co., Apr. 1892, p. 42; Apr. 1893, p. 32; Apr. 1898, p. 26; 
Oct. 1898, p. 30. 
2) The fanciful name "Champaca oil" was later given to this same oil although it 
has not the slightest resemblance to the genuine champaca oil from Michelia champaca L. 
(Bericht von S. & Co., Apr. 1893, p. 33.) 
3) Dietze, Stiddeutsche Apoth. Zeitung, 38, p. 680. 
4) Liebig's Annalen, 279, p. 395. 
s) The designation champacol (Chemiker-Zeitung Repert., 17, p. 31) for this alcohol 
is of course as little justified as the name champaca oil for the oil. 
R) Bericht von S. & Co., Oct. 1890, p. 49. 
7) Pharm. Journ., I, 17, p. 19. - Liebig's Annalen, 104, p. 236. Oils of the Rutaceae. 
455 
188. Oil of Xanthoxylum Hamiltonianum. 
The seeds of Xanthoxylum hamHtonianum1 yield according to 
Helbing2 3.84--5 p. c. of volatile oil of the sp. gr. 0.840. It is colorless 
and has a pleasant persistent odor, reminding of a mixture of geranium 
and bergamot oils. 
189. Oil of Rue. 
Oleum Riitae.-Rautenol. -Essence de Rue. 
Origin and History. Garden rue, Ruta graveolens L., belonging to 
the family Rutaceae, is indigenous to the Mediterranean countries 
and is cultivated in different countries having a moderate climate. 
It contains about 0.06 p. c. of volatile oil, which gives to the plant 
a peculiar aromatic odor and taste which gave rise to its use as 
a kitchen spice. In ancient times the plant was employed as a remedy, 
especially for scurvy and snake bites. 
The first mention of oil of rue (although possibly of the fatty oil) 
is found in Saladin's writings. Gesner distilled the oil about the middle 
•of the sixteenth century and the same is mentioned in the price ordi- 
nances of the cities of Berlin for the year 1574 and of Frankfurt for the 
year 1582, and in the Dispensatorium Noricum of the year 1589. 
The yield of volatile oil from rue was first determined by Cartheuser 
in the beginning of the eighteenth century. The oil was investigated 
by Neumann and Mahl in Rostock in the year 1811,3 by Will in the 
year 1840,4 Cahours in 1845,5 Gerhard in 1848,6 Williams in 1858," 
Hallwachs in 1859,8 Harbordt in 1862.9 Giesecke in 1870 10 and Gorup- 
Besanez and Grimm in 1871.11 
Properties. Oil of rue is a colorless to yellow liquid of an intensive 
persistent rue odor, which is pleasant only when greatly diluted. 
Its specific gravity is lower than that of all known volatile oils and 
lies between 0.833 and 0.840. Oil of rue is slightly dextrogyrate 
(«D = -|- 0°13' to + 2° 10') and solidifies at a low temperature. Its solidi- 
fication point lies between + 8 and + 10°.12 During the distillation 
very little passes over up to 200°, the largest portion boils from 
i) Evodia fraxinifolia was originally 
given as. the source of this oil. 
2) Jahresb. f. Pharm., 1887, p. 157; 
and 1888, p. 128. 
s) Trommsdorff's Journ. d. Pharm., 
20, II, p. 29. 
4) Liebig's Annalen, 35, p. 235. 
5) Compt. rend., 26, p. 262. 
6) Liebig's Annalen, 67. p. 242. 
7) Liebig's Annalen, 107. p. 374. 
8) Liebig's Annalen, 113, p. 107. 
9) Liebig's Annalen, 123, p. 293. 
io) Zeitschr. fiir Chemie, 13. p. 428. 
11) Liebig's Annalen, 157, p. 275. 
12) Bericht von S & Co., Oct. 1896, p. 65. 456 
Special Part 
215 to 232° (Umney,1 1895). The oil forms a clear solution with 
2-3 parts of 70 p. c. alcohol. 
Composition. The only constituent which has been positively identified 
is methyl nonyl ketone,2 CH3CO.C9H19. Besides this body, which forms 
about 90 p. c. of the oil, there is contained in it according to Williams3 
laurinic aldehyde, C12H24O (b. p. 232°). This assertion is. however, too 
little supported by facts and, therefore, makes the presence of this 
aldehyde in oil of rue appear still doubtful. 
The terpene found by different investigators can in all probability 
be traced to adulteration with turpentine oil. 
For the preparation of pure methyl nonyl ketone the oil is shaken 
with sodium bisulphite solution, the resulting mixture made fluid with 
ether, then pressed, and the operation of washing out and pressing- 
repeated several times. The disintegrated press cakes are decomposed 
by alkali solution. The separated oil is purified by distillation with 
steam. 
Methyl nonyl ketone has the specific gravity 0.8295 at 17.5°; it boils 
at 224° and melts at + 15°.4 According to H. Carette5 it boils at 
226° under 766 mm. pressure (corr. 230.65°) and at 121-122° under 
a pressure of 24 mm. (corr. 122-123°). Carette also prepared the 
oxime by treatment with hydroxylamine hydrochloride and alkali. 
M. p. 46°. 
Examination. As the value of the oil of rue depends on the amount 
of the methyl nonyl ketone present, the determination of its solidification 
point gives a valuable criterion for judging the oil. This determination 
is conducted as described on page 187. 
All foreign additions lower the solidification point which lies at + 8 
to +10° with good oils, they also raise the specific gravity (with the 
single exception of petroleum). 
Petroleum like turpentine oil is detected by it insolubility in 70 p. c. 
alcohol. Turpentine oil can be further identified by fractional distillation. 
The portions boiling below 200° are collected separately and tested for 
pinene. With a pure oil not more than 5 p. c. distill over below 200.6 
Adulterants may also be separated from the methyl nonyl ketone by 
the bisulphite method described under Composition and then identified 
as such. 
i) Pharm. Journ.. Ill, 25, p. 1044. 
2) Liebig's Annalen, 157, p. 275. 
3) Liebig's Annalen, 107, p. 374. 
*) Zeitschr. f. Chemie, 13, p. 428. 
5) Journ. de Pharm. et Chini. VI, 10, p. 255 
6) Pharm. Journ., Ill, 25, p. 1044. Oils of the Rutaeeae. 
457 
190. Boronia Oil. 
An oil distilled1 in Victoria. (Australia) from Boronia, polygalifolia 
(Family Rutaceae) had a sweet odor, reminding of estragon and some- 
what of rue. Specific gravity 0.839 (!); an = + 10°. 
Upon fractional distillation of the oil. there came over from 150-170° 
31 p. c., from 170-180° 38 p. c., from 180-190° 15 p. c., and 
above 190° 16 p. c. 
191. Oil of Buchu Leaves. 
Olenin Bnccn Folioruin. - Bnccublatterdl.-Essence de Fenilles de Buco. 
Origin and History. The genus Barosma belonging to the family 
Rutaceae is distributed in southern Africa in various species. The resin- 
and oil-containing leaves of these shrubs appear to have been used for 
a long time by the natives as a medicine. In the year 1820 the leaves 
were brought from Capetown through London into the European market 
(Reece2). Since the latter twenties they have been made official in most 
of the pharmacopoeias. 
In commerce, round and long buchu leaves are distinguished: the 
first are the leaves of Barosma betulina Barth, and B. crenuhita L., 
the second those of B. serratifolia Willd. The latter are sometimes 
adulterated with the leaves of Empleurum serrulatum Ait.3 
The volatile oil of buchu was prepared in 1827 by Brandes.4 It 
was investigated by Fliickiger in 1880, by Spica in 1884, by Shimoyama 
in 1888 and by Bialobrzeski in 1896. From the leaves of Barosma 
betulina there are obtained by distillation 1.3-2 p. c. of oil,5 from 
which separate even at ordinary temperature crystals of diosphenol. 
The liquid portion separated from this has the sp. gr. 0.957-0.97 at 
15°. The density of a norjnal oil which had been warmed to 27° in 
order to dissolve all the diosphenol, was 0.943. 
The leaves of Barosma serratifolia yield only 0.8-1 p. c. The oil, 
poor in diosphenol and liquid at the ordinary temperature, has the 
sp. gr. 0.944-0.961 at 15°. 
Oil of buchu leaves is dark in color and has a strong camphor- and 
mint-like odor and a bitter, cooling taste. 
i) Imperial Institute Journal, 2, p. 302; Pharm. Journ., 57, p. 199. 
2) Monthly Gazette of Health, London, Feb. 1821, p. 799. 
3) Prantl'g Lehrbueh der Botanik, von Ferd. Pax, p. 336; Pharmacographia, p. 110. 
Archiv der Pharm., 22, p. 229. 
s) Bericht von S. & Co., Apr. 1891. p. 6; Pharm. Journ., Ill, 25, p. 796. 458 
Special Part. 
Composition.1 The stearoptene crystallizing from oil of buchu leaves 
in the cold is a phenol of the formula CioHieOs. Diosphenol, as the 
body has been called, melts at 82°, boils under 14- mm. pressure at 
112°, under ordinary atmospheric pressure at 232° with partial decom- 
position, and is optically inactive. With ferric chloride it gives a dark 
green color reaction. Besides its properties as a phenol, diosphenol 
shows the behavior of an aldehyde as it reacts with hydroxylamine 
and phenyl- hydrazine. Opposed to the supposition that an aldehyde 
group is present in diosphenol is the fact that by the action of alcoholic 
potassa and heat an acid CioHisOsd- H2O, diolic acid m. p. 96°, is pro- 
duced, whereas from an aldehyde CioHieO2 the acid CioHieOs and the 
alcohol CioHisOa would be expected. Upon reduction diosphenol yields 
diolalcohol, CioHisC^, crystals melting at 159°; upon oxidation with 
moist silver oxide or permanganate, a liquid acid CioHicOg results. 
The remaining constituents of the oil boil lower than diosphenol. 
In the first portion is contained a hydrocarbon CioHis of the boiling 
point 174 to 176° (at 14 mm. from 65-67°). This hydrocarbon forms 
a mobile, strongly active liquid of a pinene-like odor. Sp. gr. 0.8647; 
[«]D= 4. 60° 40'. 
The fraction boiling from 206-209° consists of a slightly laevo- 
gyrate ketone ([«]d =- 6° 12') CioHisO, which possesses a pure pepper- 
mint-like odor. With hydroxylamine it yields a viscous oxime, slightly 
dextrogyrate and boiling between 134-135° under a pressure of 15 mm. 
The ketone is probably identical with laevogyrate menthone, as its 
reaction with bromine also indicates, with which it forms an oily com- 
pound of the composition CioHuBrOB^. 
192. Oil of Empleurum Serrulatum. 
The leaves of Empleurum serrulatum Ait., which are now and then 
mixed in with the long buchu leaves, contain 0.64 p. c. of volatile oil,2 
the odor of which reminds of rue and is quite different from that of 
buchu leaves. Sp. gr. 0.9464. It boils between 200 and 235°, for the 
greater part between 220 and 230°. From this fraction a crystalline 
compound is obtained by treating with sodium bisulphite, which seems 
to indicate the presence of methyl nonyl ketone, the main constituent of 
oil of rue. 
1) Fliickiger (1880), Pharm. Journ., Ill, 11, pp. 174 and 219 -Spica (1885) Gazetta 
chim. ital., 15, p. 195; Abstr. Jahresb. f. Chem., 1885, p. 56.-Shimoyama (1888), 
Archiv. d. Pharm., 226, p. 403.-Bialobrzeski (1896), Pharm. Zeitschr. f. Russl., 35, 
pp. 401, 417. 433, 449.-Kondakow (1896), Journ. f. prakt. Chem., II, 54, p. 433. 
2) Pharm. Journ., Ill, 25, p. 796. Oils of the Rutaceae. 
459 
193. Oil of Jaborandi Leaves. 
Olenin Foliornm Jaborandi.-Jaborandiblatterbl.-Essence de Feniiles 
de Jaborandi. 
The genuine jaborandi leaves from Pilocarpus jaborandi Holmes1 
(Family Rutaceae) yield upon distillation 0.2-1.1 p. c. of volatile oil,2 
the yield depending upon the freshness of the material. It has a strong- 
odor reminding somewhat of rue and a mild, fruity taste. Sp. gr. 0.865- 
0.895; aD= + 3°25'. It dissolves in 2 parts of 80 p. c. alcohol to a 
clear solution. It boils from 180-290° and sometimes solidifies on 
cooling. 
By fractionation a hydrocarbon called pilocarpene (Hardy3) (sp. 
gr. 0.852 at 18°, [«]d - +1-21°) can be isolated, which forms with 
hydrochloric acid a solid dihydrochloride. According to this, pilocarpene 
appears to be dipentene accompanied by small amounts of an optically 
active substance. Kleber4 has also found methyl nonyl ketone and 
homologous ketones. 
The fractions boiling above 260° solidify in the cold and contain a 
compound melting at 27-28° which is evidently a hydrocarbon as it is 
capable of taking up considerable amounts of bromine in petroleum 
ether solution and probably belongs to the olefinic series.5 
Jaborandi bark contains but very little volatile oil. 
194. Oil of Angostura Bark. 
Origin and Properties. The genuine angostura bark from Cusparia 
trifoliata Engl. (Galipea cusparia St. Hih. G. officinalis Hancock) 
(Family Rutaceae) coming from Venezuela and the upper Orinoco 
districts, yields by distillation with steam 1.56-1.97 p. c. of volatile 
oil of an aromatic odor and taste. It is slightly yellow at first, but 
later becomes much darker. Sp. gr. 0.93-0.96; angle of rotation «d - 
- 36° to -50°. 
Composition. According to an extensive investigation by Beckurts 
and Troeger8 the sesquiterpene alcohol, galipol, C15H23O, is the aromatic 
principle of angostura oil. It boils between 260 and 270°, has the 
i) Pharm. Journ., 55, pp. 522, 539. 
2) Bericht von S. & Co., Apr. 1888, p. 44 
3) Bull. Soc. chim., II, 24, p. 497; Abstr. Chern. Centralbl., 1876, p. 70. 
*) Private communication. 
5) Bericht von S & Co., Apr. 1899, p. 28. 
6) Bericht vop S. & Co.. Apr. 1890, p. 47. 
7) Journ. de Pharm. etChim., IV, 26, p. 130; Abstr. Jahresb. d. Pharm., 1877, p. 178. 
8) Archiv d. Pharm., 235, pp. 518 and 634; ibid., 236, p. 392.- Comp, also 
Beckurts & Nehring, Archiv d. Pharm., 229, p. 612; also Herzog, ibid., 143, p. 146. 460 
Special Part. 
sp. gr. of 0.9270 at 20° and is optically inactive. The highly unstable 
alcohol when heated splits off water, and is contained in the oil to the 
extent of about 14 p. c. 
A prominent constituent of the oil is cadinene C15H24, which is the 
cause of the laevogyrate rotation; it was characterized by its crystal- 
line hydrochloric acid addition product. 
Besides the laevogyrate cadinene and the inactive alcohol there is 
contained in angostura oil an inactive sesquiterpene, called galipene. 
This boils at 255-260° and has the sp. gr. 0.912 at 19°. It forms 
liquid, easily decomposed compounds with the hydrohalogens. 
A terpene is found in small amounts in angostura oil. which appears 
to be pinene. 
195. Toddalia Oil. 
Toddalia aculeata Pers. (Family Rutaceae) is a shrub which grows 
wild in the Nilgiri mountains (India) and which is there called wild 
orange tree. All parts of the plant have a sharp, aromatic taste. 
The root, which was already known in the seventeenth century under the 
name of Radix Indica Lopezianiad is called by the natives Malakarun- 
nay and is employed as a domestic remedy for indigestion. The bark 
of the root contains a volatile oil, which is described by Schnitzer2 as 
having a cinnamon and'melissa-like odor. The ripe berries are used in 
India as a spice in place of black pepper; the bark and leaves are also 
said to possess medicinal properties. 
The oil of the leaves has been distilled by D. Hooper.3 It is very 
fluid and has a pleasant odor, reminding at the same time of verbena 
and basilicum, and contains considerable quantities of citronellal and an 
alcoholic constituent boiling above 200°. 
The oil would be useful for purposes of perfumery if it could be 
furnished at a reasonable price. 
THE OILS OF THE AGRUMEN FRUITS 4 
Origin and History. The subfamily Aurantieae of the Rutaceae is 
indigenous to central Asia. The large number of varieties of the citrus 
fruits, known by the collective term of agrumen (acid) fruits is indicative 
of a very long period of cultivation. As far as oils that are expressed 
from the rinds of the fruits are concerned, the following species come 
into consideration: 
i> Pharmacographia, p. 111. 
2) Wittstein's Vierteljahrsschrift f. prakt. 
Pharmacie, 11, p. 1. 
3) Bericht von S. & Co., Apr. 1893, 
p. 64. 
<) Acid fruits. Oils of the Rutaceae. 
461 
for lemon oil: Citrus limonum Risso, 
for bergamot oil: Citrus bergamia Risso. 
for grape fruit oil: Citrus decumana L., 
for cedro oil: Citrus medica Risso, 
for limette oil: Citrus medica, var. acida Brandis, and Citrus 
limetta Risso, 
for mandarin oil: Citrus madurensis Loureiro, 
for orange oil: Citrus aurantium Risso, and Citrus bigaradia 
Risso. 
During the process of ripening of the fruit the oil is secreted in cells of 
the outer layer of the rind. When ruptured the oil exudes and can be 
collected. This oil must have been known early although it does not 
seem to have found application. 
The earliest statements concerning distilled lemon and orange oils 
were made by Gesner in 1555. Besson followed in 1571, Porta in 1589. 
The latter described the preparation of the two oils by distilling the 
fresh, grated rinds. During the sixties of the last century Gaubius 
recommended the same process. 
The method of the mechanical preparation of the agrumen oils by 
rupturing the oil cells by means of a grate was described by Geoffroy 
in the beginning of the eighteenth century. Evidently this method was 
practiced before this date. 
In the price ordinances, the oils of lemon and orange appear first in 
that of Frankfurt-on-the-Main of 1582. Both oils are mentioned in the 
Dispensatorium Noricum of 1589 and in the Pharmacopoea Augustana 
of 1613. Oil of bergamot apparently came into use about 1690. 
In 1786 Remmler1 tried to prepare rosin from oil of lemon. About 
the same time Liphard2 mentions that the yield of lemon oil is larger 
when the fruit is allowed to stand until decay sets in. In 1789 the 
apothecary Heyer of Braunschweig, upon cooling bergamot oil, obtained 
crystals which he termed bergamot camphor.3 
Preparation. The preparation of the volatile oils from the agrumen 
fruits is not effected by the otherwise usual method of distillation, but 
by expressing the rinds of the fruit. The distilled oil is inferior and 
valueless. The oil is contained in the cells of the outer layer which 
need only be ruptured in order that they may yield their odorous 
content. 
i) Gottling-'s Taschenb. f. Scheidekiinstler, 1786. 
2) Crell's Chemisehe Annalen, 1787, II, p. 250. 
3) Ibidem, 1789, I, p. 320. 462 
Special Part. 
In southern Italy, i. e. in Sicily and the southern point of Calabria, 
three different methods are in use for obtaining lemon, orange and 
bergamot oils, the Spugna process, the Scorzetta process and the 
manufacture with the Macchina. 
In the Processa. alia Spugna1 the worker cuts the fruit into quarters, 
removes the acid fruit pulp and presses the rind of the fruit against a 
sponge which he holds firmly in his right hand. The oil cells are broken 
and give their content to the sponge, which is expressed by the hand 
as soon as it has absorbed a sufficient quantity of oil. The sponges- 
belong to that kind which are usually designated as medium horse 
sponges; after such a sponge has been used for about 10 days it loses 
its usefulness, it is now coarse and unable to further absorb any oil. 
Somewhat different from the method just described is the Scorzetta 
process.2 In this the fruit is cut transversely into halves and the 
content removed by a kind of spoon. Both halves of the rind are then 
pressed on all sides against the sponge by continually turning them in 
the hand. This method of obtaining the oil has the advantage that 
the rinds so treated are not broken, but retain their original appearance 
and can be salted and exported as so-called Salato. Besides, the whole 
inner part of the fruit remains intact and can be worked more 
economically into lemon juice than is possible with the fruit sections 
treated by the Spugna process. After a double expression for oil and 
juice these can only be used as food for cattle. 
The Macchina is an ingeniously constructed, fairly complicated 
machine, in which the outer layer of the fruit is first ruptured and then 
pressed against sponges which absorb the volatile oil. The machines 
are now almost wholly used in the manufacture of bergamot oil, as the 
round, uniform shape of the bergamot is especially suited for this 
method of preparation. For the production of lemon oil the machine 
is useless for two reasons. First, the irregular form of the lemon 
prevents all parts of the rind from coming in contact with the sponges, 
and second, the lemon oil thus obtained is green and is, therefore, not 
marketable as such. The lemon oil sometimes prepared with the 
machines is used for adulterating bergamot oil. 
The Ecuelle a piquer is an instrument employed in Nice for the 
preparation of the oil. It consists of a bowl, provided with upright 
brass needles, which is prolonged into a tube at the bottom. The fruit 
pricked by the needles allows its oil to run into the bowl and collect 
in the tube from which it is filled into vessels. 
i) Archiv d. Pharm., 227, p. 1065. 
2) Bericht von S. & Co., Apr. 1896, p. 26. Oils of the Rutaceae. 
463 
In southern France hardly any oil is at present obtained from 
agrumen fruits. The EcueUe method is said to be still used in the West 
Indies for the preparation of limette oil. 
Sometimes the unripe fruit which has fallen from the trees, as well 
as the expressed residues or the filter pulp, are distilled with water. 
The oil obtained is without exception of a very poor quality and serves 
for mixing with only the poorest kinds of the pressed oils. 
The finished oil, previously purified by filtration, comes into commerce 
in copper flasks of 50 k. capacity. 
Production and Commerce. The following figures, taken from the 
official reports (Statistics del Commercio Speciale), give an interesting- 
exposition of the enormous extent and the increase in the production 
and export of bergamot, lemon, mandarin and orange fruits during the 
last few years. 
The production of Italy amounted to: 
1892 3,163 million fruits 
1893 3,140 
1894 3,320 
1895 3,550 
1896 3,337 
of these were exported: 
1892 1,704,628 double hundred weights 
1893 1,978,134 
1894 2,148,011 
1895 2,206,870 
1896 2,372,369 " " 
The harvest of the campagne 1895/96 was: 
Agricultural 
regions 
Oranges 
Lemons 
Cedros, Man- 1 
darins, Berga- 
mots etc. 
Total Agrumens 
Number of 
trees 
Number of 
fruits in 
thousands 
Number of 
trees 
Number of 
fruits in 
thousands 
Number of 
trees 
Number of 
fruits in 
thousands 
Number of 
trees 
Number of 
fruits in 
thousands 
Lombardy 
755 
39 
21,242 
1,918 
3,350 
83 
25,347 
2,040 
Venice 
144 
5 
L210 
156 
12 
0.2 
1,366 
162 
Liguria 
Marken and 
1 4,950 
12,045 
409,652 
15,777 
38,750 
9,131 
553,352 
36,953 
Umbria 
5 ,509 
1.452 
17,842 
237 
460 
4 
70.811 
1,693 
Tuscany 
2,203 
320 
16.486 
819 
759 
29 
19,448 
1,168 
Latium 
South. Adriatic 
11,760 
1,478 
19,873 
2,411 
1,370 
79 
33,003 
3,969 
region 
South. Mediter- 
343,730 
70,136 
134,913 
23,022 
13,482 
1,029 
492,125 
94,486 
rani an region.. 
2,666,693 
541,634 
1,031*16 
193,588 
1,023,450 
179,784 
4,721.259 
915,003 
Sicilv 
4,359,203 
544,350 
6,243,158 
1,661,994 
318,779 
57,043 
10,921,143 
2,263,386- 
Sardinia 
187,797 
14,649 
40,786 
3,237 
18,132 
693 
246,715 
18,580- 
Total 
7,729,747 
1,186,408 
7,936.278 
1,903,159 
1.418,544 
247,875 
17,084,569 
3,337,443- 464 
Special Part. 
If 800 fruits are calculated to a double hundred weight the year 
1896 would give the following result: 
Total production 3,337,443,000 fruits 
Total export 2,372,360 double hundred weights@800pieces 1,897,888,000 " 
Remain for Italian consumption inclusive of the essence 
manufacture 1,439,555,000 fruits 
Among the consumers in 1896 the most prominent are the United 
States and Canada with nearly 50 percent of the total exports. Then 
follows Austria-Hungary with about 20 percent, Great Britain with 
about 14 percent, Russia with 6 percent and Germany with about 5 
percent. 
The total export of bergamot, lemon and orange essences of the 
individual centers of production during the last two years was as 
follows: 
1897 
Export from Messina 560,788 k. having a value of 7,570,618 lire 
" " Reggio 87,095 " " " 1,306,425 " 
" " Catania 12,016 " " " 120,160 " 
" " Palermo 72,193 P " " 721.153 " 
Total essence export 1897... 732,092 k. hav g a value of 9,718,356 lire 
1898 
Export from Messina 524,099 k. having a value of 6,813,287 lire 
" " Reggio 85,069 " " 1,446,117 " 
" " Catania 6,366 " " " 82,758 " 
" " Palermo 51,759 " " " 672,867 
Total essence export 1898... 667,293 k. having a value of 9,015,039 lire 
During the last 10 years the essence export amounted to: 
1889 277,599 k. having a value of 4,206,258 lire 
1890 301,879 " " " 5,056,214 " 
1891 264,150 " " " 4,954,655 " 
1892 359.378 " " " 5,543 358 " 
1893 588,334 " " " 9,356,814 " 
1894 666,740 " " " 8,308,148 " 
1895 554,191 " " " 8,081,870 " 
1896 514,067 " " " 7,579,424 " 
1897 732,092 " " " 9,719,133 " 
1898 667,293 " " " 9,015,083 " 
The manufacture of the essences produced by expression is almost 
entirely carried on in Calabria and Sjply. The only exception is the 
preparation of the West Indian limette oil at Montserrat. 
It is true that now and then samples of expressed essences from the 
West Indies and from Florida appear, but one cannot yet speak of a Legend: (Calabria.) 
I I Districts of Bergamot. 
Essence of Lemon. 
Essence of Bergamot. 
Essence of Orange. 
The Districts of Production 
of 
ORANGE-, LEMON-AND BERGAMOT- 
ESSENCES 
in Southern Italy, 
CAOBRM UTO SICTLX 
Scale 1:1100 000. 
5 0 5 10 15 K) O 10 20 30 
** ™ Italiaax Miies.1 Kflometers. 
- ■ High, - roads. 
Railroads. EtnaRaiLroad. Telegraph Cables. Light-Tuxuses. 
Legend: (Sicily.) 
Essence of Orange. 
Essence of Lemon with regard, 
to its optical rotation. 
I I +59° - t 61° 
I "I +61° - + 63° 
I I +63° - + 64° 
F I +63° ~ + 67° 
East of Greenwich 
Printed, by F. A.Brockhans,Leipzig. Oils of the Rutaceae. 
465 
manufacture in these places. It is hardly to be expected that one will 
arise, as the high wages there paid .cannot compete with the low wages 
of Italy. The preparation of expressed agrumen oils formerly conducted 
on a small scale appears to have been entirely given up. 
The districts of production can be seen on the accompanying map, 
which was prepared in 1896 by a representative of the firm of Schimmel 
& Co. Bergamots are only cultivated in Calabria. The principal center 
for the oil is Reggio. Lemons and oranges are planted on the continent 
as well as in Sicily. 
In Calabria lemon oil is made in the same places as bergamot oil. 
In Sicily the principal productive centers of lemon oil are in the provinces 
of Messina, Catania, Syracuse and Palermo. The oils from the different 
districts often show quite important variations in their optical rotation. 
The angle of rotation of the Calabrian oils lies between +59 and +62°30'. 
In Sicily the principal places of production, arranged according to 
the angle of rotation of their oils are as follows: 
«d-+ 59° to +61°. Messina and vicinity, Nizza di Sicilia. 
«d= + 61° to +63°. Acireale, S. Teresa di Riva, Scaletta, S. Lucia, 
Patti, S. Agata, S. Stefapo. 
md= + 63° to +64°. Catania, Giarre, Giardini, Acireale, Leutini. 
«d= + 64° to +67°. Barcellona, Siracusa. 
In the province of Palermo the places colored yellow on the map 
produce only fruit but no oil, the manufacture of which is restricted to 
the immediate vicinity of Palermo to which the fruit is transported. 
The angle of rotation of the oils there produced lies between +59° and 
+ 61°; rotations of +61 to 63° are very rare. 
196. Oil of Lemon. 
Oleum Citri.-Citronenbl.-Essence de Citron. 
Properties. Oil of lemon is a light yellow liquid of the pleasant 
odor of fresh lemons and an aromatic, mild, somewhat bitter after-taste. 
Sp. gr. 0.858-0.861. The angle of rotation lies as a rule between 60 
and 64° at 20°.1 Oils with a rotatory power of + 64 to 67° are rare.2 
i) It will be well to make the rotation determinations for lemon oil at 20° or to 
reduce to 20° by calculation, for the same reason as that given under orange oil 
(remark 6 on page 471). If the rotation is determined at a temperature below 20°, 
9 minutes are to be subtracted from the result found for every degree of temperature 
below 20°. On conducting the investigation at a temperature above 20°, 8.2 minutes 
are, however, to be added for every degree in temperature in order to find the angle of 
rotation for +20°. 
2) The oils obtained in the vicinity of Siracusa and Barcellona (Sicily) distinguish 
themselves by a high rotatory power. The lemon oils from the province of Palermo 
are the weakest in rotatory power (4-5 9 to 61°). Compare with above. 466 
Special Part. 
The gummy and vegetable wax-like constituents present often 
prevent the clear solubility of lemon oil in 90 p. c. alcohol. Rectified 
oil requires about 5 p. of 90 p. c. alcohol to form a clear solution. 
Absolute alcohol, ether, chloroform, benzol and amyl alcohol dissolve 
lemon oil in all proportions. The solutions in carbon disulphide and 
in benzene are usually somewhat cloudy on account of a little water 
contained in the oil. Oil of lemon, like all essential oils obtained by 
expression, gives on standing a more or less crystalline deposit. 
Inasmuch as rectified and distilled oils decompose rapidly and have 
an unpleasant, penetrating odor, it is irrational to rectify a lemon oil. 
Oil of lemon is rapidly changed by the action of light and air. It 
loses its color and a thick, brown deposit separates. At the same time 
the specific gravity and the solubility in 90 percent alcohol increase. 
This is the same phenomenon that can be observed with old, poorly 
kept turpentine oil. 
Preservation. Oil of lemon is to be kept in carefully closed vessels, 
filled to the neck, in the dark and in a cool place. 
Composition. Although a large number of investigators have worked 
on oil of lemon since the first quarter of the present century, its compo- 
sition is for all that not yet satisfactorily cleared up. 
A critical examination of the rather extensive literature,1 the details 
of which cannot here be considered, shows that a part of the oils 
investigated were adulterated with turpentine oil. This is not surprising, 
as it is only now possible, by means of the recent proof2 that lemon 
oil contains no pinene, to distinguish pure lemon oil from that adulter- 
ated with turpentine oil. 
Even by the first analyses of the oil its small amount of oxygen 
was recognized. Some chemists, however, went so far as to declare it 
free from oxygen and consisting only of hydrocarbons. This mistake 
arose from the fact that rectified oils were mostly used in the investi- 
gation, in which the much higher boiling oxygenized compounds 
remained in the residue of the flask. 
!) Saussure (1820). Ann. de Chim. et Phys., II, 13, p. 262; Liebig's Annalen. 3, 
p. 157. - Dumas (1833), Ann. de Chim. et Phys.. II, 52, p. 45; Liebig's Annalen, 6, 
p. 255, and ibid., 9, p. 61. - Blanchet & Sell (1833), Liebig's Annalen, 6, p. 318.- 
Soubeiran & Capitaine (1840), Journ. de Pharm., II, 26, p. 1; Liebig's Annalen, 34, 
p. 317.-Gerhardt (1843), Compt. rend., 17, p. 314.-Berthelot (1853), Ann. de Chim. 
et Phys., Ill, 37, p. 233; ibid. 38, p. 44; ibid., 40, p. 36.-Liebig's Annalen, 88, p. 346. 
- Oppenheim (1872), Berichte, 5, p. 628. - Lafont (1887), Bull. Soc. chim., II, 48, 
p 777, and 49, p. 17. 
2) Bericht von S. & Co., Apr. 1897, p. 19; Oct. 1897, p. 22. Oils of the Rutaceae. 
467 
Iii reality about %o of the oil consist of hydrocarbons, of which 
dextrogyrate limonene (Wallach,1 1885), (tetrabromide, in. p.124-125°) 
is the most important. 
Tilden2 (1877) has called attention to the fact that this terpene is 
contained in a far less pure state in lemon oil than in orange oil. By 
the oxidation of the limonene fraction designated by him as "citrene" 
he obtained paratoluic and terephthalic acids, two acids which do not 
result by the oxidation of the corresponding fractions from orange oil. 
"Citrene" behaves likewise different than limonene when treated with 
concentrated sulphuric acid. Besides resinous polymerization products 
some cymene is formed. It does not follow, however, that cymene is 
contained in the original oil. It is much more likely that the cymene 
resulted from a second terpene by the action of sulphuric acid. As a 
matter of fact neither cymene nor pseudo-cumene3 have up to the 
present been found in lemon oil which had not been treated with 
sulphuric acid.4 
The reason for the differences between "citrene" and limonene may 
probably be found in part in the presence of phellandrene in lemon oil. 
This terpene has only recently been discovered in the oil and recognized 
as such by its nitrite melting at 102°.4 
The behavior of the fraction boiling below 170° observed by 
Wallach5 can in all probability be also traced to phellandrene. This 
fraction gave no solid addition product by direct bromination6 but 
after heating from 250-270° it readily yielded dipentene tetrabromide. 
Although the terpenes make up by far the greater part of the lemon 
oil, the odor is largely due to the comparatively small amount of 
oxygenated compounds. The constituent of greatest importance as to 
odor is citral, CioHieO, an aldehyde, which was found by Bertram in 
oil of lemon in 1888.7 The amount of the citral is estimated at 7-10 
percent. 
Besides citral lemon oil contains a second aldehyde, citronella]. 
When condensed with pyrotartaric acid and /3-naphthylamine this yields 
1) Liebig's Annalen, 227, p. 290. 
2) Pharm. Journ., Ill, 8, p. 190; 9, p. 654. 
3) Bouchardat & Lafont (Journ. de Pharm., V, 27, p. 49) found, after treating 
citrene with sulphuric acid, pseudo-cumene besides cymene. They seem to consider 
these substances as preexisting in lemon oil. 
41 Bericht von S. & Co., Oct. 1897, p. 23. 
5) Wallach, loc. cit. 
6) Oliveri claims to have obtained a tetrabromide of the melting point 31° from the 
fraction of lemon oil boiling at 170 to 170.5° (Gazz. chim. ital., 21, I, p. 318; Berichte 
24, p. 624, Ref.). 
t) Bericht von S. & Co., Oct. 1888, p. 17. 468 
Special Part. 
according to Doebner1 citronellal , -naphtho cinchoninic acid, in. p. 225°. 
Apparently the statements of Ladell2 who investigated so-called terpene- 
free lemon oil, refer also to citronellal. He isolated by fractionation a 
dextrogyrate body CioHisO boiling at 206°. 
Tilden3 in 1877 described as a constituent of lemon oil a dextro- 
gyrate substance of the composition CioHisO, boiling a little above 
200°, which, with the exception of its rotatory power, agreed in 
its principal properties with "terpinol." It is probable that Tilden 
also had citronellal under consideration. Barbier and Bouveault,4 how- 
ever, deny the presence of citronellal in lemon oil. 
According to Umney and Swinton5 geranyl acetate is also contained 
in the lemon oils from Messina and Palermo. They removed from 
so-called concentrated lemon oil, i. e. from the high boiling fractions 
rich in oxygen, the aldehyde with hot bisulphite solution, and saponified 
the non-aldehydes. From the alkaline solution acetic acid was separated 
and from the oil a fraction was obtained which combined with calcium 
chloride to form a solid compound, which yielded citral on oxidation, and 
consequently consisted of geraniol, which must have existed originally in 
the oil.as acetic ester. From Palermo lemon oil, besides geraniol, a 
fraction of the properties of 1-linalool was isolated. Umney and Swinton 
are of the opinion that the differences in odor which exist between the 
lemon oils from Palermo and Messina can be attributed to a different 
ratio of the quantities of citral and citronellal, as well as to the presence 
of linalyl acetate in the Palermo oil. 
A sesquiterpene, C15H24, of the boiling point 240-242° is contained 
according to Oliveri (7oc. cit.) in the highest boiling fractions of lemon oil. 
The statements found in literature6 referring to the so-called lemon 
camphor or citraptene, the non-volatile constituent of lemon oil, vary 
so much both as to composition and properties (m. p. from 45-144°) 
that the body must at present be considered as a mixture of different 
substances. 
Adulteration and Examination. Turpentine oil, the adulterant 
mostly employed, can be readily detected by means of the polariscope, 
i) Archiv d. Pharm., 232, p. 688; Berichte. 27, p. 352. 
2) Pharm. Journ., Ill, 24, p. 586. 
3) Footnote 2 on p. 467: comp, also Wright, Journ. Chem. Soc., II, 12, pp. 2 and 
317; Berichte, 6, p. 1320. 
4) Compt. rend., 122, p. 85. 
5) Pharm. Journ.. 61, pp. 196 and 370. 
6) Mulder (1839), Liebig's Annalen, 31, p. 69. - Berthelot, loc. cit.- Tilden & Beck 
(1890), Journ. Chem. Soc., 57, p. 328; Berichte, 23, p. 500, Ref.-Crismer (1891), 
Bull. Soc. chim., Ill, 6, p. 30; Berichte, 24. p. 661, Ref. Oils of the Rutaceae. 
469 
as it decreases the rotatory power of the lemon oil to a considerable 
extent. In order to determine approximately the amount of the 
addition, it must first be determined whether French or American 
turpentine had been employed. As turpentine oil (pinene) boils lower 
than the constituents of normal lemon oil, it is to be sought for in 
the fraction which distills over first. The lemon oil to be investigated 
is therefore fractionated several times and the rotatory power of the 
fraction boiling at about 160-165° determined. If the first distillate 
finally becomes laevogyrate, French turpentine oil is under consideration, 
but if it remains slightly dextrogyrate, American turpentine oil has 
been employed. 
For the approximate calculation of the amount of turpentine oil 
from the rotatory power, the mean angle of rotation -30° for 
French and + 6° for American turpentine oil may be taken. 
A lemon oil consisting of half turpentine oil would rotate in a 100 
_|_ gQ° _| 30° 
mm. tube in the one case 3 -= +15°, and in the other case 
+ 6W= + 83O . 
According to this it is not difficult to calculate the approximate 
amount of the addition, providing that it is known whether this 
addition was French or American turpentine oil. 
Detection of Turpentine oil in the presence of orange oil. 
Lemon oils, in spite of their normal rotatory power, may be adulterated 
with turpentine oil, when orange oil has been added to compensate the 
decrease in rotatory power. Even this manipulation is detected in the 
polariscope by testing individual fractions of the oil. 
By numerous experiments it has been determined that by the distil- 
lation of pure oils the angle of rotation of the 10 p. c. which distill 
over first is at most 4-5° smaller than that of the original oil. With 
oils containing turpentine oil this difference is of course much greater. 
For the distillation a so-called Ladenburg fractionating flask with three 
bulbs (fig. 54 on p. 190) is used and from 50 cc. of the oil to be inves- 
tigated, just 5 cc. are slowly distilled off. At first a few drops of water 
distill over, which make the distillate turbid and are removed by 
shaking with some anhydrous sodium sulphate. After filtering, the 
distillate is investigated in a 50 mm. tube in the polariscope with the 
proper consideration of the temperature. The result is reduced by 
calculation to 20° in the manner given in footnote 1 on page 465 and 470 
Special Part. 
deducted from the rotatory power, likewise reduced to 20°, of the 
original oil.1 
In some cases, especially when only small quantities of oil are at 
command, the modification of Soldaini and Berte2 is preferable. This 
consists in that from 25 cc. of the oil one-half is distilled off. The 
rotation of the 50 p. c. distilled over from pure oil is higher than that 
of the original oil and higher than that of the residue. When turpentine 
has been used as adulterant the first half will always show a lower 
rotatory power. 
It should be mentioned that the addition of turpentine oil produces 
only a very slight increase in the specific gravity. 
Fatty oil remains in the residue when the oil is evaporated; the 
residue of normal lemon oil does not amount to more than 4-5 p. c. 
For its determination see under bergamot oil on page 476. 
Citral Determination. A. very dangerous adulterant which up 
to the present has defied definite detection, consists in the terpenes 
obtained in the manufacture of the so-called terpene-free lemon oil. As 
by the addition of these hydrocarbons to the lemon oil the relative 
amount of the oxygenated constituents, that is of citral and citronella!, 
is decreased, such an adulteration might be detected by an accurate 
citral or aldehyde determination. On the other hand it has been claimed 
that a citral determination is not an absolute standard of purity.3 
Thus, an oil of high citral content might be nothing more than the 
terpenes resulting from the preparation of so-called concentrated lemon 
oil, mixed with citral from some other source, for instance, from lemon 
grass oil. Attempts to establish methods for the estimation of citral 
have not been wanting, but so far they have all failed on account of 
insufficient accuracy. 
Thus, for instance, it has been tried to determine the amount of 
aldehyde present in the manner employed for cassia oil,4 which is indeed 
very rational, since citral like cinnamic aldehyde forms with bisulphite 
a compound soluble in water. Citronellal, however, does not possess 
this property, and its double salt separating partly in the oily and 
partly in the aqueous layer makes an accurate reading impossible. 
1) Bericht von S. & Co., Oct. 1896, p. 30. 
2) Gazz. chim. ital., 27, II, p. 25. 
3) Chemist & Druggist, 53, pp. 120, 292, 94-9; 54, pp. 495, 545. 
4) See Soldaini and Bert€. Boll. chim. farm., 38, p. 537; Berichte von S. & Co., 
Apr. 1900, p. 22. Oils of the Rutaceae. 
471 
Garnett1 tried to convert the aldehydes by reduction with sodium 
into alcohols, and determine these by acetylization. Unfortunately, as 
thorough examinations have shown, the reduction does not take place 
quantitatively and the results are therefore useless.2 
Walther3 has published a method for the estimation of citral in 
lemon oil by treating the latter in alcoholic solution with hydroxylamine 
hydrochloride and sodium bicarbonate and then titrating back the 
excess of hydroxylamine. Schimmel & Co.4 have tested the method and 
found that the results are too high. 
Parry 5 has based a method on the formation of citralidene cyanacetic 
acid. From 200 co. of oil 175 cc. are distilled off under 15 mm. pressure. 
10 cc. of the residue are shaken in a cassia flask with 5 g. of cyanacetic acid 
and 5 g. of sodium hydrate in 30 cc. of water. The part insoluble in water 
is read off on the scale. No determinations were made on known mixtures 
of citral and terpenes, so that the accuracy of the method is unknown. 
197. Oil of Sweet Orange. 
Oleum Aurantii Dulcis. - Susses Pomeranzenschalenbl. Susses Oraugeuschaleubl. 
Apfelsinenschalenbl. - Essence d'Orange Portugal. 
Properties. Oil of orange is a yellow to yellowish-brown liquid of 
a characteristic orange odor and a mild, aromatic, not bitter taste. 
Specific gravity 0.848-0.852; 4) = +00 to +98° at 20°.6 
On account of the presence of wax-like, non-volatile substances of 
unknown composition, which partly separate on standing for some time, 
the oil as a rule does not form a clear solution with 90 p. c. alcohol. 
It begins to boil at 175°; up to 180° nine-tenths distill over. 
The rectified oil is colorless; its sp.gr. is somewhat lower, the rotatory 
power slightly higher than that of the original oil. Rectified orange oil 
is kept with .difficulty, it deteriorates rapidly and acquires thereby a 
stale, grating odor. 
1) Chemist and Druggist, 48, p. 599. 
2) Bericht von S. & Co., Oct. 1896, p. 32. 
3) Pharm. Centralh., 40, p. 621. 
i) Bericht von S. & Co.. Apr. 1900, p. 20. 
5) Chemist & Druggist, 56, p. 376. 
6) Since the angle of rotation of orange oil, like that of lemon oil, varies greatly 
with changes in temperature, decreasing with an increase in temperature, it is neces- 
sary, in order to obtain comparable numbers, to ascertain accurately the temperature 
and to reduce the result to 20° by calculation. As the difference in the angle of rotation 
between 4-10° and 4-20° is 14.5 minutes and between 4-20° and 30° it is 13.2 minutes 
for one degree of change in temperature, the reduction to 20° is made by deducting 
14.5 minutes for each degree in temperature, when the polarization was effected at a 
temperature below 20°. If the determination was made at a temperature above 20°, 
13.2 minutes are to be added to the number found in order to find the angle of 
rotation for 4-20°. 472 
Special Part. 
Composition. Orange oil consists, as Wallach1 (1884) has shown, 
of at least'90 p. c. of d-limonene (dihydrochloride, m. p. 50° (Soubeiran 
and Capitaine,2 1840), tetrabromide, m. p. 104-105°1). On this 
account, especially as other hydrocarbons are completely absent, it is 
well suited for the preparation of this terpene in a pure state. The 
absence of pinene is of importance for the detection of adulteration 
with turpentine oil. 
Of oxygenated compounds, aldehydes are present in orange oil. By 
shaking with sodium bisulphite solution crystals of a double compound 
are formed, which can be isolated by filtration and pressing; by decom- 
posing with soda an oil is obtained which is purified by steam distillation. 
A part of this boils at 224-228° and consists of citral (Semmler,3 1891). 
The lower boiling fraction contains likewise an aldehyde, the composition 
of which has not yet been determined. 
The assertion made by Wright4 in 1873 that oil of orange peel 
contains 0.3 percent of a body boiling at 212-218° identical with the 
somewhat mystic myristicol (CioHigO) of the oil of nutmeg, is too little 
supported by facts. 
The most recent and not yet completed investigation of orange oil 
is that of Flatau and Labbe.5 They obtained by shaking orange oil 
with bisulphite solution a double compound, which yielded besides traces 
of citronellal, a small amount of a new aldehyde that had a very 
characteristic orange odor. In addition an acid of possibly twenty-one 
carbon atoms was isolated. Like the acid, its ethyl ester is difficultly 
soluble in alcohol and can be precipitated by this solvent from the 
residue of the oil after 95 p. c. have been distilled off. When purified it 
melts at 64-65° and has a pleasant and characteristic orange odor. 
Further communications on this ester are promised. 
Parry6 suspects the presence of the methyl ester of anthranilic acid 
in sweet orange oil. This observation is confirmed by Schimmel & Co." 
who have definitely shown its presence. 
Of the nature of the orange oil stearoptene, which finds its way into 
the oil by expressing the peel of the fruit and which remains in the 
residue when the oil is rectified, nothing is known. 
i) Liebig's Annalen, 227, p. 289. Comp, 
also Volckel (1841), ibid, 39, p. 120; and 
Wright & Piesse (1871), Chem. News, 24, 
p. 147. 
2) Liebig's Annalen, 34, p. 319. 
3) Berichte, 24, p. 202. 
4) Chem. News, 27, p. 260; Berichte, 
6, p. 148. 
5) Bull. Soc. chim., Ill, 19, p. 361. 
6) Chemist &, Druggist, 56, p. 462. 
t) Bericht von S. & Co., Apr. 1900, 
p. 18. Oils of the Rutaceae. 
473 
Examination. On account of the low specific gravity and the 
extraordinarily large rotatory power of orange oil, all kinds of foreign 
additions can be readily and accurately detected, as there is no 
adulterant by which these two properties would not be changed. 
Formerly, when the polariscope was not so generally used as it is 
to-day the oil was greatly adulterated with turpentine and sometimes 
even with lemon oil. 
Recently1 the terpenes remaining from the manufacture of terpene-free 
lemon oil are used to an enormous extent in Messina for the adulteration 
of orange oil. 
For the detection of turpentine oil the lowest boiling portions of the 
oil are repeatedly fractionated by employing a dephlegmator, and the 
pinene may then be recognized by its boiling point, as well as by its 
rotatory power (strongly laevogyrate with French and slightly dextro- 
gyrate with American turpentine oil). Should such a test be considered 
as not conclusive, the pinene must be converted into pinene nitroso- 
chloride and into the characteristic pinene nitrolbenzylamine or nitrol- 
piperidine base. 
198. Oil of Bitter Orange. 
Oleum Aurantii Amari. - Bitteres Pomeranzenschalenol.-Essence d'Orange 
Bigarade. 
The oil of bitter orange, which plays only a subordinate role in 
commerce in comparison with oil of sweet orange, differs from this 
mainly in its bitter taste. The rotatory power2 is sometimes slightly 
lower and varies from 4- 92° to + 98°. 
All other properties are the same as those of the sweet oil. and it 
is impossible to distinguish between the two oils in any other manner 
than by them odor and taste. 
199. Oil of Bergamot. 
Oleum Bergamottae. -Bergamottol. - Essence de Bergamotte. 
Properties. Oil of bergamot is a brownish-yellow or honey-colored 
liquid often colored' green by the presence of copper.3 It has a bitter 
taste and a very pleasant odor. Specific gravity 0.882-0.886. The 
angle of rotation, which on account of the dark color of the oil can 
mostly be determined only in a 50 or 20 mm. tube, varies from +8 to 
+ 20°. 
1) Bericht von S. & Co., Oct. 1899, p. 25. 
2) Bericht von S. & Co., Apr. 1896, p. 29. 
3) Ibidem, Apr. 1889, p. 16. 474 
Spacial Part. 
The oil yields a clear solution with about % to volume of 90 p. e. 
alcohol and the solution does not become turbid on the addition of 
more alcohol. All oils do not dissolve clearly in 80 p. c. alcohol. 
Many, and especially those of a high ester content, often give turbid 
mixtures, from which fatty globules separate on the bottom by standing. 
The reason for this phenomenon has not yet been determined, but can 
probably be sought in the wax-like constituents, which get into the oil 
by expressing the peel. This non-volatile substance, which partly 
separates as a deposit when the oil is kept for some time, consists 
principally of bergaptene. It remains in the residue when the oil is 
evaporated on a water bath or by rectification; it amounts to 5-6 p. c. 
Rectified oil of bergamot is colorless and has a lower specific gravity 
(0.870-0.880) as well as a slightly higher rotatory power than the 
original oil. The rectified oil is as a rule less valuable, because during 
the steam distillation part of the ester is always decomposed. 
The amount of ester present is a measure of the value of bergamot 
oil, i. e. the oil is the better, the more linalyl acetate it contains. The 
average content in ester varies somewhat in different years; it usually 
amounts to between 36 and 4-0 percent, but sometimes rises as high as 
45 percent. Even within the limits of the same harvesting period great 
variations occur. The oils obtained at the beginning of the harvest 
from less ripe fruit contain less (down to 30 percent linalyl acetate); 
with increasing ripeness the ester content increases, for which reason 
the oil expressed from ripe fruit is the best. 
Composition. As early as 1840 Soubeiran and Capitaine1 called 
attention to the presence of different terpenes in bergamot oil. Wallach2 
showed in 1884 that d-limonene was contained in the fraction boiling 
from 175-180°. When he heated the fraction of the oil boiling from 
180-190°, which, indeed, absorbed bromine but yielded no solid bromide, 
to a higher temperature, high boiling condensation products were formed, 
and on again fractionating, the portion going over up to 190° gave 
dipentene tetrabromide melting at 124-125°. It does not follow from 
this, whether the dipentene detected in this manner is to be considered 
as an original constituent of the oil, or whether it has been produced 
by heating the fraction 180-190° which no doubt contained linalool. 
Likewise, the observation made by Semnder and Tiemann3 in 1892 
according to which the oil boiling 17° higher than the limonene fraction 
i) Liebig's Annalen, 35, p. 313. 
2) Liebig's Annalen, 227, p. 290. 
3) Berichte, 25, p. 1182. Oils of the Rutaceae. 
475 
yielded dipentene tetrabromide cannot be considered as a proof of the 
presence of dipentene in bergamot oil. 
Our knowledge of the most important constituent as far as the 
odor of the bergamot oil is concerned, is due to two investigations, 
published at nearly the same time, by Semmler and Tiemann1 and by 
Bertram and Walbaum.2 By these investigations it was shown that 
the principal carrier of the bergamot odor is the acetic ester of 1-linalooL 
In addition to this ester, free 1-linalool and possibly substances not 
yet isolated take part in the formation of the aroma. The properties 
and derivatives of linalool and linalyl acetate have been described on 
pp. 1.28-131. 
Charabot3 has made a comparative study of the oils of bergamot 
from the green and the ripe fruit. The oil from the green fruit had a 
sp. gr. of 0.882 at 14°, «d = 4-14° 38'; 0.289 p. c. of free acid, 33.8 
p. c. of linalyl acetate. 13.9 p. c. of linalool, and 5.9 p. c. of bergaptene. 
The oil from the ripe fruit had a sp. gr. of 0.883, «d - + 20° 30', 0.283 
p. c. of acid, 37.3 p. c. of ester. 5.9 p. c. of linalool and 5.5 p. c. of 
bergaptene. He draws the conclusion that in ripening the original 
linalool is changed to the ester and that during this process some 
of the linalool is dehydrated with the formation of terpenes. 
The bergaptejie contained in the oil to the extent of about 5 percent 
is completely odorless. A whole series of investigations has been carried 
out on this compound.4 Pomeranz5 in 1891 succeeded in clearing up 
its constitution. Bergaptene C12H8O4 forms soft, white, satin-like, 
tasteless needles, which are odorless at ordinary temperature, but on 
heating give off aromatic vapors and melt at 188°. Bergaptene 
is the monomethyl ether of a dioxycumarin which is traceable to phloro- 
glucin. By treating with methyl iodide and alcoholic potassa methyl 
bergaptenic acid and its methyl ester result. According to this bergap- 
tene is the inner anhydride of bergaptenic acid. 
Examination. The determination of the purity of bergamot oil is 
not difficult because adulterations of all kinds change the physical 
constants to a considerable extent. As the specific gravity of pure oils 
1) Berichte, 25, p. 1182. 
2) Journ. f. prakt. Chem., II, 45, p.%02. 
3) Bull. Soe. chim. Ill, 21, p. 1083. 
4) Mulder (1839), Liebig's Annalen, 31, p. 70.- Ohme (1839), ibid., 31, p. 320.- 
Franke, Dissertation. Erlangen, 1880. - Godefroy (1881), Zeitsehr. d. allgem. osterr. 
Apoth. Ver., 19, p. 1; Chem. Centralbl., 1881, p. 372. - Tilden & Beck (1890), Journ. 
Chem. Soo., 57. p. 323; Chem. Centralbl., 1890, I, p. 719. - Crismer (1891), Bull. Soc. 
chim., Ill, 6, p. 30; Chem. Centralbl., 1891, II, p. 379. 
5) Monatsh. f. Chem., 12, p. 379; 14, p. 28. 476 
Special Part. 
varies within the comparatively narrow limits of 0.882-0.886, the 
addition of turpentine oil,1 lemon oil, orange oil, as well as distilled 
bergamot oil produce a decrease, fatty oil, cedar wood oil or gurjun 
balsam oil an increase in the density. A part of these adulterants 
would also change the angle of rotation which lies between +8 and 
+ 20° with pure oils. 
The solubility determination with 90 percent alcohol gives with 
bergamot oil results of only slight value, as by it only very extensive 
adulterations can be recognized. Only a part of pure bergamot oils, as 
already mentioned, are soluble in 80 percent alcohol. If a bergamot oil 
dissolves to a clear solution in this solvent it is free from fatty oil, 
turpentine oil and orange oil. If, however, it does not dissolve, this 
may be due either to an adulterant, for instance, fatty oil, or also to 
the presence of large quantities of bergaptene or wax-like constituents. 
The detection of fatty oil is effected by weighing the residue left by 
evaporating the oil at 100°, which with normal oil amounts to 5-6 p. c. 
About 5 g. of oil (weighed accurately to 1 eg.) are weighed off in a glass 
or porcelain dish and heated on a waterbath until that which remains has 
lost all odor of bergamot oil. After cooling, the dish, previously tared, is 
weighed with the residue. If this amounts to more than 6 p. c. of the oil 
used, fatty oil is present. Each additional percent represents one percent of 
adulterant. Thus e. g. a bergamot oil adulterated with 5 percent of olive oil 
will leave a residue of from 10 to 11 p. c. 
In the oils adulterated with turpentine oil, orange oil or distilled 
bergamot oil the residue will in certain cases amount to considerably 
less than 5 or 6 percent. 
The determination of the residue is of special importance as fatty 
oil gives a high saponification number and may therefore easily give 
rise to mistakes. 
Ester Content. The determination of the ester content2 which is 
described in detail on page 193, not only allows of the detection of 
adulterations, but also furnishes a. criterion of the quality of the oil. 
This is the better, the greater the amount of linalyl acetate. 
By the saponification the addition of the essence obtained by the dis- 
tillation from the press residues or the small rejected fruit,3 which shows a 
much smaller saponification number than theexpressedoil, isalso detected. 
1) As bergamot oil contains no pinene, the presence of this hydrocarbon can be 
considered as a proof of the adulteration with turpentine oil. 
2) As according to Borntrager (.Zeitsehr. f. anal. Chein., 35, p. 35) the evaporation 
residue on saponification gives numbers which correspond to an amount of 2 p. c. of 
linalyl acetate, this number ought by right to be deducted from the result found. This is> 
however, not done, as the method would thereby be only made unnecessarily complex. 
3) An oil obtained in Messina by distillation from the expressed bergamot peel Oils of the Rutaeeae. 
477 
The oil offered in commerce under the name of cedro oil or cedrate 
•oil is nothing more than a mixture of lemon oil and other oils. 
Genuine cedro oil, obtained by expression from the rind of Citrus 
medica Risso {Cedro ordinario, Cedratier ordinaire), is a yellow liquid 
of a pleasant odor reminding of citral or lemon oil. 
In physical as well as chemical behavior cedro oil differs but little 
from lemon oil. Its specific gravity is 0.871 at 15°, = + 67°8,.'l 
Upon distillation the larger part of the oil passes over from 177 to 
220°. By boiling with an alcoholic solution of /9-naphthylamine and 
pyrotartaric acid citryl-/?-naphtho-cinchoninic acid was obtained in yellow 
crystalline leaflets, melting at 197-200°, by which the presence of citral 
in cedro oil was shown. 
201. Oil of Limette. 
Olenin Li mettae. - Limettol. - Essence de Limette. 
Two oils coming from different plants and of entirely different 
properties are designated by the common name of limette oil2 which 
according to their source may be called West Indian and Italian 
limette oils. 
West Indian Limette Oil. The West Indian limette or lime, 
Citrus medica L., var. acida Brandis.3 is cultivated on Montserrat, 
Dominica, Jamaica and Trinidad on account of its acid juice, com- 
mercially known as lime juice. 
The oil obtained from the peel of the fruit by expression {oil 
of limette) is of a golden yellow color and can hardly be distinguished 
from a good lemon oil by its odor, if the greater intensity of the 
limette oil is not considered. Sp. gr. 0.8734 at 29° to 0.882 at 15°; 
«D - + 35 to 4- 38°. The most important constituent of the oil is citral. 
Entirely different from the expressed oil is the distilled oil which is 
obtained as a by-product in the evaporation of the juice and is known 
in commerce under the name of oil of limes. Its odor is unpleasant, 
terebinthinate, and no longer reminds of citral. Probably this aldehyde 
200. Oil of Cedro. 
possessed an ester content of only 12 p. c. (sp. gr. 0.865). Two oils distilled from the 
peel of fallen unripe bergamot fruit contained 6.3 and 23.5 p. c. of ester (sp. gr. 0.868 
and 0.889). (Bericht von S. & Co., Oct. 1894, p. 15.). 
1) Bericht von S. & Co., Oct. 1895, p. 18. 
2) Arch. d. Pharm., 233, p. 174. 
3) Bulletin of Miscellaneous Information, Royal Gardens Kew, 1894, p. 113. 
*) Pharm. Journ., Ill, 15. p. 322. 478 
Special Part. 
is completely destroyed by the boiling of the acid liquid. Sp. gr. 0.8651 
-0.868 ;2 «d = +38° 52'. It boils between 175 and 220°. 
Italian Limette Oil.2 The fruit of the South European limette, 
Citrus limetta Risso (Citrus limetta vulgaris, Lima dulcis, Lima di 
Spagna dole., Limettier ordinaire') distinguishes itself from that of the 
West Indian by its sweet juice. 
The oil obtained by expression from the peel is of a brownish-yellow 
color, has an odor reminding strongly of bergamot oil, and forms a 
yellow deposit in considerable amounts on standing. Sp. gr. 0.872; 
«d = +58° 19'; saponification number 75. 
The composition of the Italian limette oil is very similar to that of 
bergamot oil, only the limette oil contains more limonene and less 
linalyl acetate. 
The limonene is the dextrogyrate modification («p - +81° 45', 
sp. gr. 0.848) and yields a dihydrochloride3 melting at 50°, as well as 
a tetrabromide melting at 105°. 
In the oil investigated by Gildemeister 26.3 p. c. of linalyl acetate 
were present (b. p. 101-103° at 13 mm., sp. gr. 0.898, «d = -9°52'). 
• , After saponification with alkali, acetic acid was found in the alkaline 
solution, while from the oil 1-linalool (b. p. 88.3-89.5° at 13 min., 
sp. gr. 0.870, [«]d =-20°7') was separated by fractional distillation. 
From it citral was formed on oxidation.4 Linalool is present in the 
oil partly in the free state, partly as acetic acid ester. 
The limettin which separates from the oil on standing melts according 
to Tilden5 at 121-122°. It has the composition C6H3(0CHb)2• C3HO2 
and yields on melting with potassa, besides acetic acid, phloroglucin. 
302. Oil of Limette Leaves. 
The oil of the leaves from Citrus limetta contains according to 
Watts6 (1892) an inactive terpene, boiling at 176-177°, which yields 
with hydrochloric acid a crystalline hydrochloride melting at 49-50° 
i) Pharm. Journ., Ill, 14, p. 1005. 
2) Gildemeister, loc. cit. 
3) The same dihydrochloride was obtained by de Luca in 1860 (Compt. rend., 51, 
p. 258) from the terpene boiling at 180° of an oil, which is designated as coming from 
Citrus lumia, but which in all probability was Italian limette oil. Comp. Gildemeister, 
loc. cit. 
*) To which compound the "Limettsaure," CnH^Oe obtained by Vohl in 1853 upon 
the oxidation of the oil (Archiv d. Pharm., 124, p. 16) owes its origin, is uncertain. 
s) Journ. Chem. Soc., 61, p. 344; also Tilden & Beck, Journ. Chern. Soc., 57, p. 323. 
6) Journ. Chem. Soc., 49, p. 316. Oils of the Rutaceae. 
479 
and is, therefore, dipentene or limonene. Fraction 220-230° yielded 
upon oxidation with chromic acid, acetic acid and pelargonic acid, on 
account of which it is considered as methyl nonyl ketone. 
303. Oil of Mandarins. 
Oleum Mandarinae. - M'andarinenol. - Essence de Mandarines. 
Origin. The peel of the pleasant tasting fruit of Citrus madurensis 
Loureiro1 known as mandarins contains a very pleasant smelling oil, 
which is obtained like the oils of the other agrumen fruits, by expression. 
Properties. Mandarin oil is a golden yellow liquid with a slight 
bluish fluorescence, which becomes more prominent when the oil is 
diluted with alcohol. The odor, although similar to tha.t of lemon oil, 
is more pleasant and distinctly different from it. Sp. gr. 0.854- 
0.858 ; «d - + 05 to + 75°. 
Two mandarin oils2 distilled in Porto Alegre (Brazil) had the 
following properties: Sp. gr. 0.8515 and 0.8510; angle of rotation 
+ 74° 16' at 17° and +74° 20' at 16°. Both oils were distinguished by 
a beautiful blue fluorescence. 
Composition. The oil began to boil at 175° and all except a 
small residue went over up to 179°. The fraction boiling at 175-177° 
(«d = + 76° 45') gave on bromination in glacial acetic acid solution a 
tetrabromide melting at 104-105° (Gildemeister and Stephan,3 1897). 
By conducting hydrochloric acid into the same fraction dipentene 
dihydrochloride, in. p. 49°, resulted (de Luca,4 1857). According to 
this the greater part of the mandarin oil consists of ddimonene. 
If the portion which did not distill over up to 177° be treated with 
bisulphite solution, an addition product is obtained, from which an 
oil is separated by alkali. This behaves like a mixture of citral and 
citronellal when condensed with pyrotartaric acid and ,3-naphthylamine. 
The melting point of the naphtho-cinchoninic acid formed is not constant. 
At 197° (the melting point of the pure citral compound) the body 
begins to run together, but does not melt completely until 222° 
(melting point of the citronellal compound 225°). The positive identi- 
fication of these two aldehydes in the oil has, therefore, not yet been 
made. 
i) According- to de Lucca ^see footnote 4) the mandarin Is obtained from Citrus 
bigaradia sinensis and C. b. myrtifolia, according- to Sawer (Odorographia, vol. 1, 
p. 74) and v. Muller (Select Extra-Tropical Plants, 9th ed., p. 129) however, from 
Citrus nobilis Loureiro. 
2) Bericht von S. & Co., Apr. 1896, p. 68. 
3) Archiv d. Pharm., 235, p. 583. 
4) Compt. rend., 45, p. 904. 480 
Special Part. 
According to Flatau and Labbe1 the expressed mandarin oil con- 
tains the same ester, difficultly soluble in alcohol, as does orange oil 
(comp, page 472). 
204-. Oil of Grape Fruit. 
The fruit of Citrus decuinana L., known as shaddock or grape fruit, 
contains in its peel a small - amount of volatile oil, which can be 
obtained by expression or by distillation. 
An oil2 expressed from fruit which came from Orlando in Florida 
possessed an exeedingly pleasant odor, reminding of bitter oranges, the 
sp. gr. was 0.860 and rotatory power «d = + 94° 30'. 
205. Oil of Neroli. 
Oleum florum Aurantii. - Orangenbluthenol.-Essence de Neroli. 
Origin and History. The oil of neroli is obtained by the distillation 
with water from the fresh blossoms of the bitter orange, Citrus bigaradia 
Risso. 
Oil of orange flowers was known as early as the sixteenth century. 
Its distillation was described for the first time by Porta. About a 
century later, in the year 1680, it appears to have been made the 
fashionable perfume by the Duchess Flavio Orsini, Princess of Neroli, 
hence the name of essence of neroli. On account of its delicate pleasant 
odor, the oil has been able to hold its reputation as one of the finest 
flower perfumes. This is also true of the distilled orange flower water, 
or Aqua naphae, which is used extensively for the aromatizing of food, 
confections and beverages, also for toilet purposes. The distillation of 
orange flower oil was described by Benatius in 1806. The oil was 
investigated in 1825 by Bonastre3 and in 1828 by Boullay.4 
Preparation. Oil of neroli is obtained exclusively in southern 
France from the blossoms of the bitter orange. The oil is not pro- 
duced in Italy. 
Properties. The oil of neroli of commerce is a yellowish, slightly 
fluorescent liquid, which becomes brownish-red when exposed to light, 
of an intensive, highly pleasant odor reminding of orange blossoms, 
and a bitter aromatic taste. Sp. gr. 0.870-0.880. The rotatory power 
is slightly dextrogyrate, aD= + l°30' to +.5°. The oil is soluble in 
1^-2 vols. of 80 p. c. alcohol.- On the further Addition of alcohol the 
liquid becomes turbid, and on standing crystalline flakes consisting 
1) Bull Soe. chim., III. 19, p. 364. 
2) Berieht von S. & Co., Apr. 1894, p. 27. 
3) Journ. d. Pharm. II, 11, p. 529. 
4) Journ. d. Pharm. II, 14, p. 496. Oils of the Rutaceae. 
481 
of paraffin collect on the surface. The alcoholic solution of neroli oil 
distinguishes itself by a beautiful violet-blue fluorescence, which becomes 
especially prominent when some alcohol is poured in a layer above 
the oil. 
On strongly cooling, the oil becomes turbid on account of the 
separation of paraffin. At times it even solidifies to a butter-like mass. 
The saponification number of good oils lies between 20 and 52. 
corresponding to an amount of 7-18 percent of linalyl acetate. Oils 
with a saponification number higher than 55 are suspicious. Details 
are mentioned under Examination. 
In order to ascertain the properties of oils which were undoubtedly 
genuine, fresh orange blossoms which were partly preserved with salt, 
partly with sea water, for transportation, were distilled by the firm of 
Schimmel & Co.1 and about 0.1 percent of oil obtained which possessed 
the following properties: 
No. 
Specific gravity 
«D 
Sap. 
number 
Behavior in a freezing mixture 
1. 
0.887 
inactive 
41 
solidifies to a butter-like mass. 
2. 
0.881 
- 
36 
1 
3. 
0.876 
- 0°52' 
21 
J viscous, but not becoming solid. 
4. 
0.872 
- 0°40' 
21 
The rotatory power of No. 2 could not be determined on account 
of its dark color. Nos. 3 and 4 are distillates of the same shipment 
of blossoms. No. 4 consists only of the oil which separated directly in 
the receiver on distillation. Its preparation corresponds to the method 
usually employed in southern France, where orange blossom oil is 
obtained as a by-product in the manufacture of orange blossom water. 
No. 3 is a normal product, i. e. a mixture of oil separating at once 
and that obtained by cohobation from the water. The oils obtained 
by these two methods differ but slightly. 
Of still greater importance for the determination of the constants 
of pure commercial oils than these experiments with preserved blossoms, 
are the distillations of fresh material by Charabot and Fillet2 in 
southern France. The oils distilled in May 1898 in Cannes and Antibes 
behaved as follows: The sp. gr. was between 0.8720 and 0.8757, the 
5) Bericht von S. & Co., Oct. 1891, p. 26; Oct. 1894, p. 40. 
2) Bull. Soc. chim., II, 19, p. 853. 482 
Special Part. 
angle of rotation. «d, between 4-1.42° and 4-4.06°. 1 part of the oil 
dissolved in 1.3 to 1.6 parts of 80 p. c. alcohol at 20°. The amount 
of ester (C1OH17OCOCH3) present was 13.4-18.0 p. c. 
Some interesting quantitative distillations were made by Jean Gras 
in Cannes during the last liarvest (1899). 30 samples were distilled at 
different periods throughout the harvest. The yield increases as the 
season advances, from 0.80 to 1.23 p. c. 25 of the 30 samples were 
investigated by Schimmel & Co.1 No marked differences were noted. 
The sp. gr. varied from 0.873-0.877 at 15°, saponification number 
35.3-44.8, «D = + 3°22't to 4-5° 24' at 20°. All the oils were soluble in 
V/2 and more parts of 80 p. c. alcohol. 
Composition. Neroli oil was investigated by Tiemann and Semmler2 
in 1893 and subjected to fractional distillation under diminished pressure 
at 15 mm. in order to effect a separation of the individual constituents. 
At 75° a terpene came over which was identified as limonene by means 
of its tetrabromide melting at 105°. 
Between 88 and 94° boiled an optically laevogyrate alcohol 
corresponding to the formula CioHisO of the sp. gr. 6.8671 at 20°, 
which possessed the properties of 1-linalooL 
At 97-104° the acetic acid ester of linalool came over, sp. gr. 0.8972 
at 20°, likewise laevogyrate. It was split up into acetic acid and 
linalool by boiling -with potassa. 
In the fraction boiling from 110-120° a second alcohol, almost 
optically inactive and corresponding to the formula CioHisO was con- 
tained, which consisted principally of geraniol. 
The methyl ester of anthranilic acid occurring in small quantities in 
the oil and found in 1894 in the laboratory of Schimmel & Co.,3 plays 
an important part in the formation of the orange blossom perfume. 
The fluorescence of the oil is due to the presence of this substance. 
The methyl ester of anthranilic acid NH2.C6H4.COOCH3 boils at 
132° under a pressure of 14 mm., melts at 25° and in an overcooled 
state at 15°, it has the sp. gr. 1.168. The odor in the undiluted state is 
unpleasant. It reminds of the fragrance of the orange blossom only 
when greatly diluted. 
The stearoptene of the orange blossom oil, also called neroli camphor 
or aurade was first found by Boullay1 in 1828. It is one of the 
1) Bericht von S. & Co. Oct. 1899, p. 42. 
2) Beriehte, 26, p. 2711. 
3) Bericht von S. & Co., Apr. 1899, p. 35. See also Walbaum, Journ. f. prakt. 
Chemie, II, 59, p. 350; see also Erdmann, Beriehte, 32, p. 1213. 
4) Journ. de Pharm., 14, p. 497; Trommsdorff's Neues Journ. d. Pharm., 19, 1, p. 227. Oils of the Rutaceae. 
483 
paraffins which occur in almost all oils obtained from blossoms and in 
the pure state is completely odorless and tasteless. Its melting- point 
is 55°.1 
Inasmuch as the decomposition of the paraffin is wholly improbable, 
the assertion by Plisson2 (1829) that the amount of the stearoptene in 
the oil decreases with age, evidently rests on a wrong observation. 
Examination. The most common and .most dangerous adulterants 
are the oils of bergamot and petitgrain. As these for the greater part 
possess the same constituents as oil of neroli - linalool and linalyl 
acetate-the detection of small amounts is impossible. Larger additions 
cause an increase in the specific gravity and the amount of esters, which 
in pure neroli oil is 7-18 percent (saponification number 20-52), in 
bergamot oil 35-45 p. c. (s. n. 100-130), in petitgrain oil 38-85 p. c. 
(s. n. 110-245). 
Orange flower oils which show a saponification number higher than 
55 are therefore to be rejected as suspicious. 
The property of neroli oil to separate paraffin in a freezing mixture 
has been employed as a test, which is not wholly irrational, as the 
addition of paraffin free oils might decrease the relative amount of 
paraffin to such an extent that a separation no longer takes place on 
cooling. It must, however, be remembered in employing this test that 
some unadulterated oils may in certain cases be poor in paraffin. When, 
for instance, at the time of the harvest a large amount of blossoms is 
to be quickly distilled, it happens, that the distillation is not carried 
on to its complete exhaustion and that a smaller amount of the 
difficultly volatile paraffin gets into the oil. For the rest it is necessary 
in testing to depend on the comparison of the physical properties with 
those of good oils, especially of the odor. 
306. Oil of Neroli Portugal. 
Oleum Aurantii Floruni Dulce.-Susses Orangenbluthenbl.-Essence de Neroli 
Portugal. 
Oil of sweet orange blossoms, Neroli Portugal, i. e. the oil distilled 
from the blossoms of the sweet orange does not occur at all in commerce 
in a pure state. The goods sold under the above designation are always 
a mixture of different aurantiaceous oils. 
An oil distilled in Germany from the fresh blossoms of the sweet 
orange Citrus aurantium Risso, had entirely different properties from 
i) Pharmacographia, 2nd ed., p. 127. 2) Journ. de Pharm., II, 15, p. 152. 484 
Special Part. 
that procured from southern France.1 The blossoms used for the 
distillation were transported from southern Spain in iron caskets from 
which the air was pumped out after having been filled. 
0.154 p. c. of oil was obtained having the sp. gr. 0.893 and the 
angle of rotation «d - + 16° 8'. 
207. Oil of Petitgrain. 
Oleum Petitgrain. - Petitgrainol. - Essence de Petit-grain. 
Origin and Preparation. Petitgrain oil is obtained from the leaves, 
twigs and immature fruit of the bitter orange, Citrus bigaradia Risso, 
by distillation with water. Formerly the oil was principally produced 
in southern France, until toward the end of the seventies French 
colonists began the distillation in Paraguay. The poor quality of the 
oils there produced in the beginning improved in the course of the 
years to such an extent that the South American oil is now generally 
preferred on account of its greater reliability and uniformity to the 
often adulterated French product. The market for the Paraguay oil is 
Asuncion; the principal place of distillation is said to be the little town 
of Yaguaron.2 r 
Properties. The odor of petitgrain oil is similar to that of neroli, 
but far less delicate, the taste is aromatic and somewhat bitter, the 
color yellowish. Sp. gr. 0.887-0.900. It turns the polarized ray of 
light either slightly to the right, or to the left; an = + 3°43' to -1°22'. 
The oil is soluble to a clear solution in 2 parts of 80 p. c. alcohol. 
Saponification number 110-245 = 38-85 p. c. of linalyl acetate. 
Eight different petitgrain oils recently distilled from the leaves of the 
bitter orange by Charabot and Pillet3 in Cannes, had the following; 
properties: Sp. gr. 0.8910-0.8934; «d = -5° 12' to -6° 15'. Soluble in 
1-1.1 parts of 80 p. c. alcohol. The amounts of ester varied from 
51.5-69.6 p. c. 
It may be remarked, that oils with so strong a rotatory power as 
these have not yet been met in commerce. Moreover, as a general rule, 
petitgrain oil is not distilled exclusively from the leaves, but also from 
the unripe fruit, by which the deviations of the commercial oils are 
explained. 
Composition. Semmler and Tiemann4 in 1892 fractionated petit- 
grain oil under 15 mm. pressure. The first portions contained a 
1) Bericht von S. & Co., Oct. 1889. p. 38. 
2) Chemist and Druggist, 51, p. 110. 
3) Bull. Soc. chim., Ill, 21, p. 73. 
Berichte, 25, p. 1186. Oils of the Rutaceae. 
485 
hydrocarbon which was recognized as limonene. The main fraction, 
amounting to 70 p. c. of the crude oil, contained oxygen, boiled from 
102-106° and had the sp. gr. 0.8988 at 20°. The composition cor- 
responded to the formula C12H2OO3. By treatment with potassa the oil 
was decomposed to acetic acid and linalool (aurantiol) and consisted 
therefore of linalyl acetate. 
According to Passy1 linalool is not the only alcohol CioHisO 
contained in petitgrain oil, but also geraniol in the free state as well 
as in the form of the acetic acid ester. 
Besides the bodies named other oxygenized, not yet isolated com- 
pounds are present in the oil, which take part in developing the specific 
petitgrain odor. 
The amount of esters, linalyl acetate and geranyl acetate, varies 
between -40 and 85 p. c. and usually amounts to about 50 p. c. The 
last fractions of the petitgrain oil contain a sesquiterpene. 
Charabot and Pillet2 have recently shown that only the petitgrain 
oils distilled from the leaves and twigs contain no limonene, so that 
the occasional presence of d-limonene comes from the accompanying 
small fruit in the distillation. According to the authors named, petit- 
grain oil (from the leaves) contains about 70-75 p. c. of 1-linalool and 
10-15 p. c. of geraniol, as well as small amounts of a sesquiterpene. 
Adulteration and Examination. Petitgrain oil is adulterated with 
orange oil, lemon oil and turpentine oil. These additions are readily 
recognized by the lowering of the specific gravity, decrease in the 
saponification number and the solubility, and finally by the change in 
rotatory power. 
Petitgrain citronnier. By this name an oil is designated which 
is obtained now and then from the twigs, leaves and unripe fruit of the 
lemon tree. Its odor is similar to that of the petitgrain oil, but the 
lemon-like odor accompanying it betrays the source of the oil. Sp. gr. 
0.868 - 0.874; «d = 4-22° 5' to + 34°12'. Saponification number 
14.5-32.2. The odor, also the property of forming a crystalline com- 
pound with bisulphite solution caused the presence of citral to be 
suspected. In fact the citryl /3-naphtho cinchoninic acid was obtained, 
and the presence of this aldehyde thereby proven.3 
1) Bull. Soc. chim., Ill, 17, p. 519. 3) Bericht von S. & Co., Oct. 1896, p. 59. 
2) Bull. Soc. chim.. Ill, 21, p. 74. 486 
Special Part. 
208. Oil of West Indian Sandalwood. 
Olenin Santali ex India Occidental!. - Westindisches Sandelholzol. - Essence 
de hois de Santal des Indes Occidentales. 
The botanical source of the West Indian santalwood was unknown 
until recently. Through a study of the wood and the leaves Holmes, 
Kirkby and Petersen came to the conclusion, that the plant must 
belong to the family of the Rutaceae, and by no means be classed 
with the family of the SantalaceaeA More than this could not be 
ascertained on account of the want of blossoms. In compliance with a 
request by E. M. Holmes of London, Schimmel & Co. finally succeeded 
in 1898 in obtaining flowering branches of the tree from Puerto Cabello 
in Venezuela, from whence the wood is brought into commerce. In the 
investigation Holmes came to the conclusion, that the plant belonged 
to the family of the Rutaceae. He believed it to be a representative of 
a hitherto unknown genus and named it Schimmelia oleifera.2 Later, 
however, he agreed with Urban of Berlin, who determined the plant as 
Amyris balsamifera L. The mistake was caused by the fact, that the 
genus Amyris has hitherto been classed by the English botanists with 
the family of the Burseraceae, while in Germany, and according to 
Holmes' view with perfect right, it is classed with the Rutaceae. Now, 
as no species of the Rutaceae in English botanical literature corresponded 
to the description of the West Indian sandalwood plant, Holmes had 
considered it as a new species. 
The wood, which has no similarity with the East Indian sandal- 
wood, consists of sticks from a thumb to an arm in thickness'. It is 
white and hard and covered with a gray bark. The anatomical build 
of the wood has been studied and described by Petersen and Kirkby. 
The well comminuted wood yields upon distillation 1.5-3.5 p. c. of 
a thick, viscous oil of a weak not pleasant odor. 
The sp. gr. lies between 0.960 and 0.967, the angle of rotation 
between + 24 and + 29c. Of the composition of the West Indian 
sandalwood oil nothing is known. 
209. Oil of Myrrh. 
Oleum Myrrhae. -MyrrheniM. -Essence de Myrrhe. 
Origin and History. Myrrh is the dried up emulsion-like juice, 
originally contained in the parenchyma of the bark, of several species of 
the genus Commiphora which belongs to the family of the Burseraceae. 
i) Pharm. Journ., Ill, 16, pp. 757. 821 and 1065. 
2) Pharm. Journ., 62, pp. 53, 137 and 205. Oils of the Burseraceae. 
487 
These shrubs grow partly wild, and are partly cultivated in the coast 
districts of the Red Sea especially on the Somali coast of East Africa, 
and appear to flourish in many parts of Arabia as far as Persia. 
The distilled oil of myrrh was well known to Ryff, Cordus and 
Gesner. In the drug and spice ordinances it is first mentioned in those 
of the city of Frankfurt-on-the-Main of 1587, and taken up in the 
Dispensatorium Noricum of 1589. 
Observations on the methods' of preparation and yield were made 
in the course of the eighteenth century by Hoffmann, Neumann, Spiel- 
mann, Thielebein, and later by Braconnot, Pelletier and Brandes. 
The officinal (Ph. G. III.) or Herabol myrrh is derived from Com- 
miphora abyssinica Engl, and C. schimperi Engl, from southern Arabia 
and the coast districts of Somali-land. It can be distinguished from 
other varieties in that the extract made with petroleum ether is colored 
red by bromine vapors. This color reaction is also peculiar to the volatile 
oil which is obtained by distillation in yields of 2.5-8. p. c. 
Properties. Oil of myrrh is a thick fluid, of a yellow to greenish 
color and has a strong myrrh odor. 
Sp. gr. 0.988-1.007. Kohler1 in 1890 found a density of only 
0.9621 at 17.5° due possibly to the fact that in the preparation on a 
small scale the heavier parts are likely to remain in the resin and only 
the lighter oil conies over. Angle of rotation «d = - 67° 54' (Kohler) to 
- 90°, Gladstone2 observed in a 10 inch (25 cm.) tube a rotation 
of -136. 
Oil of myrrh boils according to Kohler from 220-325°, according 
to Tucholka3 (1897) from 260-280°. It dissolves to a clear solution 
in 10 parts of 90 p. c. alcohol. 
Composition. Of the constituents of oil of myrrh not one has been 
isolated and identified. An elementary analysis made by Ruickhold which 
had yielded numbers nearly corresponding with the formula C10H140, 
induced Fliickiger4 (1876) to investigate the oil for carvone. It was 
found, however, that this body is not contained in oil of myrrh. 
Bisabol Oil of Myrrh.5 Bisabol, or Bissabol myrrh comes from 
the interior of the Somali-lands and according to Holmes is identical 
with the opopanax (see this) now occurring in commerce. It does not 
give the color-reaction with bromine vapors as described for Herabol 
myrrh. 
i) Archiv d. Pharm., 228, p. 291. 
2) Journ. Chern. Soe., 17, p. 1. 
3) Archiv d. Pharm., 235, p. 298. 
Berichte, 9, p. 471. 
5) Archiv d. Pharm., 235, p. 289. 488 
Special Part. 
If 6 drops of the petroleum ether extract of Bisabol myrrh (1:15) are 
mixed with 3 cc. of glacial acetic acid and this liquid poured in a layer on top 
of 3 cc. of concentrated sulphuric acid, a rose colored zone is formed at the 
place of contact of the two layers, and in a short time the entire acetic acid 
layer will become pink. Herabol myrrh gives under the same conditions only 
a very slight pink coloration to the acetic acid layer. The zone of contact of 
the two liquids is green. 
Oil of Bisabol myrrh is mobile and light yellow. Sp. gr. 0.8836 at 
24°; ["-]d =-14° 20 at 24°. It boils from 220-270°. 
By conducting hydrochloric acid into the ethereal solution of the 
oil an optically active dihydrochloride (CioHic,2HC1)2, melting at 79.3° 
is formed, the yield being about 6.5 p. c.; [«]d = - 35°17' at +7° in 
chloroform solution. 
By boiling with sodium acetate in glacial acetic acid solution hydro- 
chloric acid is split off, and a hydrocarbon "bisabolene" is formed 
which is not identical with any of the known terpenes. B. p. 259- 
260.5; sp. gr. 0.8914; ud = 1.4608. 
210. Oil of Opopanax. 
The botanical source of the genuine opopanax is still unknown but 
presumably comes from Opoponax chironium Koch {Ferula opoponaxC.)- 
The opopanax now found in commerce, from which the volatile oil is 
distilled, is according to Holmes1 the gum-resin of Commiphora kataf 
Engl. {Balsamodendron kafal Kunth). In the collection of Chinese 
drugs it is commonly designated as myrrh and has probably been often 
mistaken for this. According to Holmes it may probably be the myrrh 
of the Scriptures. 
Upon distillation opopanax yields 6-10 p. c. of oil of a greenish- 
yellow color and a pleasant balsamic odor. It resinifles readily on ex- 
posure to air. Sp. gr. 0.870-0.905; -10 to -12°.2 It dissolves 
to a clear solution in an equal part of 90 p. c. alcohol. 
Oil of opopanax boils with decomposition between 250 and 300° 
(Baur,3 1895). The carrier of the characteristic odor is found in the 
lower boiling portions.4 
Recently Knitl5 has made an investigation of undoubtedly genuine 
oil. The oil was prepared by shaking out the alcoholic solution of the 
1) Pharm. Journ., Ill, 21, p. 838; 25, p. 500; 61, p. 565. 
2) An oil distilled in the laboratory of Schimmel & Co., was probably obtained 
from the oleoresin of another plant. Yield 6.7 p. c.; sp. gr. 0.861; «d =+42° 30'. 
3) Arch. d. Pharm., 233, p. 235. 
■i) Bericht von S. & Co., Apr. 1890, p. 34. 
s Arehiv d. Pharm., 237, p. 256. Oils of the Burseraceae. 
489 
resin with petroleum ether. With bisulphite solution a brownish mass 
was separated, which on sublimation gave white colorless needles melt- 
ing at 133-134°. The body corresponded with the formula CsoHioOt 
and was called oponal. The oil itself, when distilled under diminished 
pressure gave at first colorless distillate having the odor of lovage oil 
and later a blue distillate came over. Crystals of oponal separated in 
the neck of the retort. 
211. Oil of Olibanum (Frankincense). 
Olenin Olibani. - Weihraucliol. - Essence d'Oliban. 
History. The distilled oil of olibanum was known to Valerius 
Cordus, but was seldom mentioned in literature. In the treatises on 
distillation of the sixteenth century frankincense is mentioned as one of 
the many constituents used in the distillation of the complex balsams. 
Oil of frankincense is first found as Oleum thuris in the drug ordinances 
of the city of Berlin for 1574, and of Frankfurt-on-the-Main for 1587; 
further in the Dispensatorium Noricum of the year 1589. 
The older investigations of frankincense as to content of volatile 
oil as well as the properties of the oil were mostly made in connection 
with like investigations of oil of myrrh of which the more important 
have been mentioned on p. 487. 
Origin and Preparation. Frankincense is obtained from Boswellia 
carterii Birdw. and other species of the genus Boswellia (Family 
Burseraceae) in Somali-Iand and in south-eastern Arabia. If the bark 
of the frankincense tree is cut, a white emulsion oozes out, which 
solidifies after some time and then forms yellow granules (tears or 
drops) which are separated from the tree trunks or picked up from 
the ground. 
Frankincense yields u'pon distillation with steam 3-8 p. c. of volatile 
oil. It is colorless or yellowish and has a pleasant balsamic and 
slightly lemon-like odor. Sp. gr. 0.875-0.885; «D - -11° to -17° 
(Stenhouse,1 1840). 
Composition. Oil of olibanum, consisting for the greater part of 
terpenes, when distilled comes over principally about 162°.1 After 
fractionating several times a laevogyrate hydrocarbon of the formula 
CioHie is obtained, which boils a-t 157 to 160°. It yields with hydro- 
chloric acid a monohydrochloride melting at 127° (Kurbatow,2 1874); 
with amyl nitrite and hydrochloric acid a nitrosochloride melting at 
i) Liebig's Annalen, 35, p. 306. 
2) Liebig's Annalen, 173, p. 1. 490 
Special Part. 
100-101°. The latter when boiled with alcoholic potassa is readily 
converted into nitroso pinene C10H15NC) melting- at 130°, from which 
it follows, that the terpene boiling at 157 to 160° (the olibene of 
Kurbatow) is 1-pinene (Wallach,1 1889). 
The fraction boiling between 177 and 179° yields on bromination 
dipentene tetrabromide.1 The second constituent of the oil is therefore 
di pentene. 
As oil of olibanum gives with sodium nitrite and glacial acetic 
acid the phellandrene reaction, phellandrene is the third terpene con- 
tained in the oil.2 
The oxygenized fractions boiling above 175° have not yet been 
carefully investigated. 
212. Oil of Elemi. 
Olenin Elemi. - ElemiQl. - Essence d'Elemi. 
History. Elemi is a dried up resin juice, comparable with turpen- 
tine, of a number of different trees belonging to the family of the 
Burseraceae. At the present time elemi resin comes mainly from the 
Philippines, especially from Luzon. Besides this, now and then Central 
American, Brazilian, West African and other varieties occur in the 
market. 
The distilled elemi oil was first mentioned in the ordinance of 
Frankfurt-on-the-Main of 1587 and included in the Pharmacopoea 
Augustana of 1613, likewise in the Frankfurt Pharmacopoeia of 1649. 
The first determination of the yield of volatile oil was made by 
Neumann about 1730; Bonastre in 1823 and Manjeau in 1824 repeated 
the experiment. 
Origin and Preparation. The Manila elemi exclusively used for the 
preparation of elemi oil consists of a thick, turpentine-like, white mass 
enclosing many small fragments of bark. On keeping for some time it 
takes on a wax-like appearance on the exterior, due to drying out. by 
which the outer layer becomes of a yellow color and loses its odor. 
When treated with 90 p. c. alcohol in the cold a part dissolves, 
while a crystalline residue remains. From the solution prepared by 
boiling, needle-shaped crystals of amyrin separate in large quantity on 
cooling (Vester berg,3 1887). 
1) Liebig's Annalen, 252, p. 100. 
2) Observation made in the laboratory of Schimmel & Co 
3) Berichte, 20, p. 124-2. Oils of the Burseraceae. 
491 
The botanical source of the Manila elemi is not definitely known; it 
is, however, supposed that its source is a species of Canarium. Neither 
Canarium commune L. the resin of which forms a dry mass,3 nor Cana- 
rium muelleri need be considered in discussing the source of Manila 
elemi, as the turpentine of the latter plant contains according to 
Maiden,2 (1892) no crystalline constituents, and its solutions deposit no 
crystals on evaporation. Up to 30 p. c. of oil are obtained from 
Manila elemi by distillation. 
Properties. Oil of elemi is colorless or pale yellow and has a 
decided phellandrene odor. The specific gravity of the oil prepared on 
a large scale lies between 0.87 and 0.91. Distilled on a small scale 
terpenes principally come over. Hence the specific gravity is found to 
be lower, as for instance by Fliickiger3 who determined 0.860. 
Manila elemi oil is optically dextrogyrate;4 aD = +44°3'. With 
sodium nitrite and glacial acetic acid it gives a strong phellandrene 
reaction. 
Composition. The fraction of the oil boiling below 175° contains 
according to Wallach5 (1888) d-phellandrene. In fraction 175-180° 
dipentene is present to such an extent that it is very well suited for the 
preparation of dipentene derivatives. The dipentene was identified by 
means of the tetrabromide m. p. 125°, and by the nitrosochloride and 
its conversion into carvoxime melting at 93°. 
The elemi oil investigated by Deville3 in 1819 also contained 
dipentene, as it yielded a solid hydrochloride. 
Besides these terpenes and polyterpenes elemi oil also contains 
oxygenized products, which readily split off water, even when distilled 
by themselves, but especially when distilled with potassium acid 
sulphate.5 
In the preparation of the oil on a large scale a portion was 
obtained which sank in water. This boiled in, a vacuum of 10 mm. 
pressure between 153 and 163°, the main portion from 160-161°. 
Under ordinary atmospheric pressure this fraction boiled at 279-280°, 
was optically inactive and had the sp. gr. 1.043 at 15°. Upon oxidation 
with potassium permanganate an acid of the melting point 170° was 
i) Pharniacographia Indica, vol. 1, p. 321. 
2) Pharm. Journ., Ill, 23, p. 15. 
3) Pharmaeognosie, 3rd ed , p. 86. 
<) An oil examined by Deville in 1849 (Liebig's Annalen, 71, p. 353) was strongly 
laevogyrate and probably obtained from a different variety of elemi. Comp, also 
Stenhouse. Liebig's Annalen, 35 p. 304. 
s) Liebig's Annalen. 246, p. 233; 252, p. 102. 
6) Liebig's Annalen, 71, p. 353. 492 
Special Part. 
obtained, the silver salt of which, stable toward light, after being 
purified by recrystallization from boiling water, was analysed, 29.58 p. c. 
of silver being found.1 The composition of the acid, which no doubt 
represents the direct oxidation product of an oxygenized compound 
has not yet been determined. 
213. Oil of Conima Resin. 
The resin known under the name of conima resin or Hyawa gum 
from Idea heptaphylla Aubl. is used in place of frankincense as incense 
in British Guayana. 
It contains small amounts of volatile oil (Stenhouse and Groves,2 
1876) which can be obtained by distillation with steam. The oil is 
yellowish and on distillation comes over mainly between 260 and 270°• 
The highest boiling portions have a bluish-green color. When distilled 
from sodium a hydrocarbon, conimene, of the boiling point 264° was 
isolated. Conimene is a sesquiterpene of the formula C15H24. 
214. Oil of Linaloe.3 
Oleum Linaloes. - Linaloeol. - Essence de Linaloe. Essence de Licari. 
History. Since the eighteenth century woods with a pleasant odor 
have come into commerce from Mexico and French Guayana under the 
name of aloe wood, because they were first considered to be identical 
with the earlier known aloe wood. Mexican linaloe oil was first intro- 
duced into France in the year 1866. Guayana linaloe wood came for 
the first time to Marseille in the seventies where it was used for making 
the oil. The oil is distilled in Cayenne itself only since 1893. 
Origin.4 On account of the great similarity of their physical and 
chemical properties the oils from the wood of entirely different trees are 
designated by the common name of linaloe oil. 
The Mexican linaloewood, called in Mexico Lignaloe or 
Linalue, also Bois de citron de Mexique conies from Bursera delphechiana 
Poiss. belonging to the family of Bur. eraceae, and probably also from 
Bursera aloexylon Engler (Elaphrium aloexylon Schiede, Amyris linaloe 
La Llave). 
It occurs in commerce in the form of thick trunks, which are usually 
free from bark and more or less weathered on the surface and of an 
ash gray appearance. The quite spongy and light wood shows in 
section a moire-like figure of brown, close, concentric rings. 
1) Beiicht von S. & Co., Oct. 1896, p. 95. 
2) Liebig's Annalen, 180, p. 253. 
3) Also spelled lignaloe. 
4) Pharm. Journ., Ill, 18, p. 132. Oils of the Burseraceae. 
493 
Upon distillation, which is carried on in a primitive manner by 
native Indians in the province of Guerrero, south from the capital of 
Mexico, the wood of old trunks is said to give a yield of 10-12 p. c. 
of oil. Wood distilled in Europe gave only 7-9 p. c. of oil. 
The linaloewood from French Guayana, or Cayenne 
linaloewood is called by the natives Likari, by the French colonists 
Bois de rose male. It is further designated as Bois de ro e femelie, 
Bois jaune, Bois de citron de Cayenne. Cedre jaune or Copahu. 
The botanical source has not yet been definitely determined, but 
according to Moeller1 Ocotea caudata Mez., a tree belonging to the 
Lauraceae may, with considerable probability, be considerd as its source. 
The wood is hard and heavy, readily cleavable, on fresh surfaces 
yellow, on older ones of a, reddish color. It is exported from Cayenne in 
logs deprived of bark, the size of which indicate enormous trees. 
Properties. Although both oils are in general very similar, 
differences do exist, especially in the specific gravity and optical 
rotatory power. 
The linaloe oil of commerce is almost exclusively the Mexican. 
This is a colorless to yellowish liquid of pleasant linalool odor.2 
Sp. gr. 0.875 to 0.895; «d =- 5 to-12°; saponification number 1-10. 
With two and more parts of 70 p. c. alcohol the oil yields a clear 
solution. 
Cayenne linaloe oil can be readily distinguished from the former by 
its odor. Sp. gr. 0.870-0.880; «d =-15° to -20°. Its solubility is 
the same as that of the Mexican oil. 
Composition. Linaloe oil consists almost entirely of an alcohol 
CioHisO, boiling at 198-199°, which was first isolated from the 
Cayenne oil and called licareol by Morin3 in 1881. Semmler4 in 1891 
found it in the Mexican oil. He ascertained that it belonged to the 
aliphatic series and gave it the name of linalool. Barbier5 (1892) at 
first considered linalool and licareol as different bodies, but later 
admitted their identity.6 
Two further constituents, of subordinate importance, as they are 
present in only small quantities, and affect the odor but slightly, have 
1) Pharm. Post, 29, Nos. 46-48. 
2) The odor, which is usually described as lemon- or rose-like, has not the slightest 
resemblance either to that of rose or that of lemon. 
3) Compt. rend., 92, p. 998; 94, p. 733; Ann. de Chim. et Phys., V, 25, p. 427. 
4) Berichte, 24. p. 207. 
5) Compt. rend., 114, p. 674; 116, p. 883. 
6) Compt. rend., 121, p. 168. 494 
Special Part. 
been found by Schimmel & Co.1 in the oil. They are geraniol and 
methyl heptenone, which so often accompanies the aliphatic terpene 
alcohols. According to Barbier and Bouveault2 linaloe oil contains 
also 3 percent of a sesquiterpene, 0.1 percent of a monatomic and a like 
amount of a diatomic terpene. 
Examination. The adulteration of linaloe oil with fatty oil. which 
has been observed several times, can be readily determined by its 
insolubility in 70 p. c. alcohol, by the increase in the specific gravity 
and by the high saponification number. 
215. Oil of Cedrela Wood. 
About 12 different species of the genus Cedrela. (Family Meliaceae) 
indigenous to America, yield a pleasantly odorous wood, which is used 
for making cigar and sugar boxes. It is incorrectly called cedar wood 
Volatile oils have been distilled from a number of these woods, the 
botanical sources of which are unknown. 
1. Cedrela wood from Corinto (Nicaragua).3 Yield 2.3 p. c. 
Yellow oil of the sp. gr. 0.906 and the angle of rotation ap = -17° 23'. 
2. Cedrela wood from Cuba.3 Yield 1.75 p. c. Slightly yellow 
oil of the sp. gr. 0.923 and the angle of rotation aD = + 18°6'. It 
contains large amounts of cadinene, the laevogyrate hydrochloride of 
which, melting at 118° was prepared. 
3. Cedrela wood from La Plata.3 Yield 0.59 p. c. Optically 
inactive oil of a light blue color and the sp. gr. 0.928. 
4. Cedrela wood from Punta Arenas (Costa Pica).3 Yield 
3.06 p. c. Light blue oil, boiling from 265-270°. Sp. gr. 0.915; 
«d = - 5° 53'. Consists principally of cadinene, as was shown by the 
preparation of the dihydrochloride melting at 118°. 
5. Cedrela wood from Cedrela. brasiliensis (Cedrela odorata, L.?) 
from Porto Alegre.4 From the sawdust of this wood only 0.5 
p. c. of a. light blue oil of the sp. gr. 0.9348 and the angle of rotation 
«d - - 0°22' were obtained. The oil may perhaps be identical with the 
La Plata cedrela wood oil mentioned above. 
216. Oil of Senega Root. 
The senega belonging to eastern North America, Polygala senega L. 
(Family Polygalaceae) contains according to Reuter5 in its root 0.25 
>) Bericht von S. & Co., Apr. 1892, 
p. 24; Oct. 1894. p. 35. 
2) Compt. rend., 121, p. 168. 
3) Bericht von S. & Co., Apr. 1892, p. 41. 
Bericht von S. & Co., Apr. 1896, p. 69. 
s) Archiv d. Pharm., 227, p. 313. Oils of the Euphorbiaceae. 
495 
to 0.33 p. c. of volatile oil, which consists of a mixture of methyl 
salicylate and an ester of valerianic acid. 
Quite a number of other species of the genus Polygala also yield 
methyl salicylate when distilled. Van Romburgh1 found this ester in 
the roots of Polygala variabilis H. B. K. albiflora 1). C., of P. oleifera 
Heckel and P. j avail a. 
Bourquelot2 showed the presence of methyl salicylate in the roots 
of P. vulgaris L., P. calcarea F. Schultz and P. depressa Wenderoth. 
The investigations of Bourquelot render it probable that the methyl 
salicylate does not exist as such in the root, but is formed by the action 
of a ferment, which he designates as gaultherase,3 on the glucoside 
gautherin. 
217. Oil of Cascarilla. 
Oleum Cascarillae.-Cascarillol.-Essence de Cascarille. 
Origin. The cascarilla bark, coming from the Bahama islands and 
principally used in pharmacy, is derived from Croton eluteria Bennet 
(Family Euphorbiaceae}. Upon distillation it yields 1.5-3 p. c. of 
volatile oil. 
Properties. Cascarilla oil is yellow to greenish and has a slight 
aromatic odor and taste. Sp. gr. 0.890-0.925; «d= + 2 to +5°. In 
90 p. c. alcohol it is readily soluble. 
Composition. Of the but incompletely investigated oil not a single 
constituent has been definitely determined. Volckel4 in 1840 separated 
the oil by fractionation with water vapor into two portions. The first 
part was mobile, boiled at 173°, had the sp. gr. 0.8G2 and was almost 
free from oxygen. The oil which distilled over later was viscous and 
contained oxygen. According to Gladstone5 (1864) the oil consists 
of two hydrocarbons, of which the one has a lemon-like odor, boils at 
172°, and is probably dipentene (Bruhl,6 1888). The second hydro- 
carbon is described as being similar to calamus oil and is probably a 
sesquiterpene. 
i) Rec. des trav. ehim. des Pays-Bas., 13, p. 421. 
2) Compt. rend., 119, p. 802; Journ. de Pharm., V, 30, pp. 96, 188, 433; VI. 3, p. 577. 
3) Termed betulase by Schneegans in 1896 (Journal der Pharmacie von Elsass 
Lothringen, 23, p. 17). 
4) Liebig's Annalen, 35, p. 307; comp. Trommsdorff, Trommsdorff's Neues Journ. 
d. Pharm., 26, II, p. 136. 
5) Journ. Chem. Soc., 17, p. 1. 
6) Berichte, 21, p. 152. 496 
Special Part. 
The purgative root of Stillingia silvatica I. Midi. (Family Euphor- 
biaceae) indigenous to North America from Virginia to Florida, and 
westward to Kansas and Texas, yields upon distillation 3.25 p. c. of a 
light yellow oil, lighter than water (Bichy,1 1885). 
219. Oil of Mastiche. 
Oleum Masticis.-Mastixol.-Essence de Mastice. 
Origin and History. Mastiche is the dried resinous juice of the 
evergreen tree Pistacia lentiscus L. (Family Anacardiaceae). This tree 
grows on several of the islands of the Mediterranean and on the 
southern coasts of the Mediterranean as far as Morocco and the Canary 
Islands. The collection of the resin is, however, principally carried on 
in the island of Chios, where the tree is cultivated for this purpose. The 
resinous juice oozes out slowly from the slight incisions made in the 
bark of the trunk, and dries up to form round, colorless granules. 
Distilled oil of mastiche, probably obtained by dry distillation, 
is first mentioned about the middle of the fifteenth century. Such 
an empyreumatic oil of mastiche is also mentioned in the inventory 
of the "Rathsapotheke" at Braunschweig of the year 1518. Ryff and 
Gesner distilled mastiche with wine. In the drug ordinances oil of 
mastiche is first mentioned in that of Berlin of 157-4. in books on 
medicine in the Pharmacopoea Augustana of 1580 and in the Dispensa- 
torium Noricum of 1589. Later the oil went almost altogether out of 
use. Recently it is used in Turkey for the preparation of a liquor. 
Preparation and Properties. Mastiche yields upon distillation 
1-2 p. c. of volatile oil. This is colorless and smells strongly balsamic 
like mastiche.2 Sp. gr. 0.858-0.868; «d= + 22 to +28°. It begins 
.to boil at 155°3 and on distillation goes over at 1(50°. With dilute 
acids it yields terpin hydrate. According to this the principal constituent 
of oil of mastiche appears to be d-pinene. 
220. Oil of Chios Turpentine. 
Chios turpentine, already known to the ancients,4 is obtained by 
making incisions in the trunk of Pistacia terebinthus L. (Family Ana- 
218. Oil of Stillingia. 
i) Amer. Journ. Pharm., 57, p. 531. 
2) Bericht von S. & Co., Apr. 1893, p. 61. 
3) Archiv d. Pharm., 219, p. 170. 
Chios turpentine is the of Theophrastus and the of other 
authors. From this designation the word "Turpentine," at present used for the resinous 
juice of the different species of Pinus, is derived. Fliickiger & Hanbury, Pharmaco- 
graphia, p. 166. Oils of the Anacardiaceae. 
497 
carJiaceae) widely distributed in the orient, especially in the island of 
Chios. Chios turpentine has the consistency of the ordinary turpentine 
of the conifers and like it consists of a mixture of resin and volatile oil. 
Upon distillation with steam about 14 p. c. of oil are obtained 
from this turpentine. The oil has a pleasant, mild, turpentine-like odor, 
which reminds somewhat of mace and of camphor. Sp. gr. 0.868- 
0.869; «d= + 12°6'1 to +19°45'.2 
When treated with sodium the oil boils at 157° and has, as shown 
by an elementary analysis, the composition of a hydrocarbon CioHic,. 
The distillate saturated with hydrochloric acid yielded a solid compound.1 
From this it follows without a doubt that Chios turpentine oil. like 
ordinary turpentine oil. consists for the greater part of pinene. 
. 221. Oil of Schinus. 
Origin. Schinus molle L. indigenous to South America, is often 
planted in southern Europe on account of its fine feathery leaves and 
fragrant yellow clusters of blossoms. The aromatic berries serve for the 
preparation of a wine-like drink. They taste at first sweet, later spicy 
and at last sharply pepperish and are used quite extensively in Greece 
in place of pepper. In odor they are similar to elemi, but also remind 
of pepper and juniper and yield upon distillation 3.35 3 to 5.2 p. c.4 of 
volatile oil. * 
Properties. A mobile oil, having the odor of phellandrene; sp. gr. 
0.850; «d = +46°4/ at 17°, soluble in 3.3 and more parts of 90 p. c. 
alcohol. 
Composition. By copducting hydrochloric acid into the lowest 
boiling fractions Spica5 in 1884 obtained a solid monohydrochloride 
melting at 115°, the formation of which can probably be traced to 
pinene. A nitrosochloride could be obtained in only very small quanti- 
ties from a fraction boiling up to 170° of an oil investigated by Gilde- 
meister and Stephan.6 from which it follows, that only a small part of 
the oil estimated, at most % p. c., can consist of pinene. The largest 
amount boils from 170-174° («d = + 60°21', sp. gr. 0.839) and gave 
with sodium nitrite and glacial acetic acid a strong phellandrene 
reaction. As follows from the optical behavior of the fractions of the 
nitrite, the phellandrene in schinus oil is a mixture of much dextrogyrate 
and very little laevogyrate phellandrene. 
1) Arehiv d. Pharm., 219, p. 170. 
2) Bericht von S. & Co., Oct. 1895, p. 57. 
3) Jahresb. der Pharm.. 1887, p. 25. 
4) Bericht von S. & Co., Apr. 1897, p.49. 
5) Gazz. chini. ital., 14, p. 204. 
6) Archiv di Pharm., 235, p. 589. 498 
Special Part. 
With alkali a phenol can be shaken out of the oil, which Spica 
regarded as thymol1 on account of the melting point 156° of its nitrite. 
In the oil investigated by Gildemeister and Stephan, carvacrol, (iso- 
cyanate compound, m. p. 140°) was present, but no thymol. 
Spica observed in the fraction boiling from 180-185°, which had 
been exposed for some time to the light, a crystalline body, melting at 
160° and supposed it to be identical with pinol hydrate CioHniO. H2O 
first found by Sobrero. This, however, is excluded, as pinol hydrate 
melts at 131°. 
222. Oil of Cognac. 
Oleum Vitis Viniferae. - Cognacol. - Huile Volatile de Cognac mi de Li de Vin. 
Origin and Preparation. The specific aroma, peculiar to wine and 
cognac is produced by the ethereal fusel oil. It is also called oil of 
cognac (Ger. Drusendl, Weinbeerol, Weindl) and is a product, of the 
fermentation action of wine yeast. For this reason it is principally 
found in the yeast deposited from the wine on the bottom after com- 
pletion of the fermentation. The wine itself contains only minute 
amounts of it in solution, namely 1 part of oil in 40,000 parts. 
For the preparation of oil of cognac either the residues (liquid wine 
yeast) remaining in the barrels after removing the clear wine, are 
distilled, or the yeast cakes remaining after expression of the liquid are 
utilized. 
The distillation is conducted in a very primitive manner in the wine 
districts. Formerly a barrel, lined with lead and provided with a con- 
denser, the contents of which were heated with direct steam, served as 
distilling apparatus.2 
According to a more recent description,3 ordinary whiskey stills are 
used, which are heated by fire and provided with a stirring arrange- 
ment to prevent the burning of the yeast. 
Before the distillation additions of various kinds are sometimes 
made to the yeast mixed with water, the purposes of which are not 
clearly understood. 
According to Rautert2 to 50 k. of lees 250 g. of sulphuric acid are 
added, by which the mass is said to become more fluid. In the 
Palatinate to a mixture of 1 part of lees with 5 parts of water, 2 p. c. 
of freshly slacked lime, 1 p. c. of potassa and 1 p. c. of salt are added. 
i) Nitrosoearvacrol melts at 153°. 
2) Dingl. polytechn. Journ., 143, p. 71. 
3) Chemist and Druggist, 50, p. 183. Oils of the Vitaceae. 
499 
The oil collected in the receiver floats on top of the alcohol con- 
taining water, from which liquid still further amounts of oil can be 
obtained by cohobation. The yield of cognac oil from yeast cakes is 
given as 0.036-0.066 p. c. Schimmel & Co. obtained, however, from 
the wine yeasts from the Rhine and Palatinate 0.07-0.12 p. c. of 
cognac oil. 
Properties. The crude cognac oil, usually colored green by copper, 
contains large amounts of free fatty acid, which, because odorless, may 
be considered as a worthless constituent. For purification the oil is 
first freed from copper by shaking with tartaric acid solution, then 
freed from fatty acids by treatment with soda solution, and in this 
condition forms the second quality of cognac oil. The finest quality is 
prepared by the rectification of the oil so purified. In this process a 
part of the slightly odorous esters of the higher fatty acids are kept 
back, on account of which the distillate of course becomes stronger. 
The physical properties of these three varieties, the crude, purified and 
rectified oil, are of course different. As, however, the observation material 
at hand is insufficient, general means of differentiation cannot at present 
be given. 
Oil of cognac possesses a stupifying odor, which is unpleasant and 
even offensive in the undiluted state. Often an empyreumatic odor is 
perceptable, due to careless preparation. 
The specific gravity of different crude cognac oils coming from the 
Moselle, from Tyrol, from the Rhenish Palatinate and the Rheingau 
varied between 0.875 and 0.8854 Optically they were slightly laevo- 
or dextrogyrate, «D = 0° 3' to + 0° 43'. The oil is but sparingly soluble 
in 70 p. c. alcohol; of 80 p. c. alcohol 1.5 to 3.5 parts are necessary to 
form a clear solution. The ester number varies between 140 and 250, 
the acid number between 50 and over 100.2 
Composition. As the result of an investigation made by Pelouze3 
and Liebig in 1836 the oenanthic acid ethyl ester CisHisOs was con- 
sidered as the principal constituent of wine fusel oil. Later Delffs4 
asserted that the "oenanthic acid" of the ester was identical with pelar- 
gonic acid. Fischer5 then showed on a Palatinate cognac oil, that the 
"oenanthic acid" which had been considered as a single substance, was 
i) Judging from the low sp. gr. 0.85 at 20° the oil examined by Grimm (see 
following page) must have contained alcohol. 
2) Bericht von S. & Co., Apr. 1899, p. 13. 
3) Liebig's Annalen, 19, p. 241. 
4) Poggendorff's Annalen, 84, p. 505; Liebig's Annalen, 80, p. 290. 
5) Liebig's Annalen, 118, p. 307. 500 
Special Part. 
a mixture of much caprinic with a little caprylic acid. In Hungarian 
cognac oil Grimm1 (1871) likewise found caprinic and caprylic acid, 
the caprinic acid being present in larger amount. From the non-acid 
portions of the saponified oil, Halenke and Kurtz2 were able to separate 
only ethyl and amyl alcohol, but no butyl nor propyl alcohol. 
According to this, cognac oil consists principally of amyl caprinate 
and ethyl caprinate. These esters, however, are not its most important 
constituents, as the specific odor is due to other, not yet isolated 
compounds. 
An investigation made by Morin3 in 1887 of a genuine cognac, 
which had been distilled in 1883 in Surgeres in lower Charente, is of 
interest. He found in 100 liters of cognac the following constituents in 
the stated amounts: 
Aldehyde Traces. 
Ethyl alcohol 50,837.00 g. 
Normal propyl alcohol 27.17 " 
Isobutyl alcohol 6.52 " 
Amyl alcohol 190.21 " 
Furfuroll 3.19 " 
Bases J 
Pleasant smelling oil of wine4 7.61 " 
Acetic acid Traces. 
Butyric acid " 
Isobutylene glycol 2.19 " 
Glycerin 4.38 " 
In the investigation of another cognac, Ordonneau5 in 1886 found 
218 g. of normal butyl alcohol in a hectoliter, and considered this as 
the characteristic product of the fermentation of the elliptical yeast. 
Later, however, it was found, that the cognac investigated by Ordon- 
neau had probably been prepared from a wine, which had contained 
the Bacillus butyricus, and the presence of the butyl alcohol, which 
does not form under normal conditions is to be traced to this source. 
From these investigations it follows, that the cognac oil, when it is 
obtained in the manner described above, is far from containing all of 
the constituents of cognac. It is therefore never possible to obtain 
with such an oil a product that can be compared to a genuine cognac 
prepared by distillation from wine. 
1) Liebig's Annalen, 157, p. 264. 
2) Ibid., p. 270. 
3) Compt. rend., 105, p. 1019. 
4) Probably identical with the cognac oil obtained from yeast. 
5) Compt. rend., 102, p. 217; comp, also Claudon & Morin, Compt. rend., 104, 
p. 1109; further Sell, Arbeiten aus dem kais. Gesundheitsamte, 6, p. 335. Oils of the Malvaceae. 
501 
Examination. The tests are at present restricted to the determina- 
tion of a possible presence of alcohol. For this purpose a certain 
quantity of cognac oil is shaken in a, graduated cylinder with an equal 
volume of water or glycerin. The presence of alcohol is shown by an 
increase in the water or glycerin layer. 
223. Oil of Linden Flowers. 
Oil of linden flowers is prepared by treating the water obtained by 
distilling fresh linden flowers with common salt and shaking out with 
ether. On evaporating the ether 0.038 p. c. of oil remain. Oil of linden 
flowers is colorless, very fluid, quite volatile and possesses the odor of 
the fresh flowers in a high degree. It is soluble in all proportions in 
ether and alcohol (Winckler1). 
224-. Oil of Ambrette Seeds. 
Olenin Abelmoschi Seminis.-Moschuskbrnerol.-Essence de Graines d'Ambrette. 
Hibiscus abelmoschus Xj., (Abelmoschus moschatus^XoencXi), (Family 
Malvaceae), yields the ambrette seeds, formerly officinal in the German 
Pharmacopoeia, and no longer used in medicine, but which are still 
employed in perfumery. The herb-like plant is indigenous to India, 
but has lately been cultivated in Java and in the West Indies 
(Martinique). s 
The oil was first prepared by Schimmel & Co.2 in 1887. Upon 
distillation of the comminuted ambrette seeds a yield of 0.2 p. c. of oil 
is obtained. Furfurol has been isolated from the distillation water.3 
Oil of ambrette seeds is solid at ordinary temperature; it begins to 
solidify at about 30-35° and has an agreeable, musk-like odor. Sp. gr. 
about 0.900 at 25-35°. The oil is inactive or only slightly dextro- 
gyrate. This property can be used to advantage, when it is required 
to distinguish the mixtures with cedar or copaiba balsam oil found in 
commerce, from genuine oil. 
The compound which causes the solidification of the oil is a fatty 
acid, most probably palmitic acid. As the result, the oil has a high 
saponification number lying between 180 and 200. 
225. Oil of Tea. 
By extracting dried tea leaves, Thea chinensis L. (Family Theaceae), 
with ether, 0.6-0.98 p. c. of a citron-yellow extract, solidifying on 
1) Pharmaceut. Centralblatt, 1837, p. 781. 
2) Bericht von S. & Co., Oct. 1887, p. 35; Apr 1888, p. 29; Oct. 1893, p. 45. 
3) Bericht von S. & Co., Oct. 1899, p. 36. 502 
Special Part. 
cooling-, and smelling and tasting strongly of tea, is obtained. Mulder1 
has wrongly called this extract, volatile oil of tea, as it consists for 
the greater part of non-volatile extractive matter. Upon distillation 
of dried tea leaves Mulder obtained only a turbid water, but no oil. 
The real oil of tea was prepared by van Romburgh2 by the dis- 
tillation of fresh fermented tea leaves. The yield was only 0.006 p. c. 
The oil appears to be formed during the fermentation, probably by the 
decomposition of a glucoside under the influence of a body similar to 
the ferment laccase. Oil of tea has the sp. gr. 0.866 at 26°; angle of 
rotation (200 mm.) -0°ll'. 
By repeated fractionation a liquid boiling at 153-154° (740 mm. 
pressure), of a penetrating fusel-like odor, strongly reminding of tea, is 
obtained. Its principal constituent is an alcohol of the formula CoHiaO, 
the acetic acid ester of which boils at 160-165°. 
Oxidation with potassium bichromate converts the alcohol into an 
oil of the composition and the properties of butyric acid. By heating 
the alcohol with hydrochloric acid in a sealed tube to 100°, a chloride 
boiling at 120° is formed. 
The fraction of oil of tea which on distillation passes over between 
220-225° is methyl salicylate. 
The presence of methyl alcohol (b.p. 66°. nitro methyl meta-phenylene- 
diamine compound and oxalic acid methyl ester, m. p. 51°) in the aqueous 
distillate was shown. This is, however, not a product of fermentation, 
but is, as van Romburgh had previously shown, a constituent of the 
fresh, unfermented tea leaves. 
226. Oil of Borneo Camphor, 
Origin and Preparation,3 The Borneo-camphor tree, Dryobalanops 
aromatica. Gartn., is a large and beautiful tree, indigenous to the north- 
western coast of Sumatra and to northern Borneo. In the cavities and 
cracks of the wood of old trees is found the valuable Borneo camphor, 
also called Baros camphor, Sumatra camphor, or Malay camphor. It is 
used by the Malays for the embalming of the dead and for ritualistic pur- 
poses, and well paid for. Besides the camphor, the trees contain also a 
volatile oil, which is obtained, either by tapping the tree or by the 
distillation of the wood. 
1) Poggendorff's Annalen der Physik, 43, p. 163; Liebig's Annalen, 28, p. 314. 
2) Verslag omtrent den Staat van S'Lands Plantentuin te Buitenzorg, 1895, p. 119, 
and 1896, p. 166: Berichte von S. & Co., Apr. 1897, p. 42, and Apr. 1898, p. 53. 
s) For History see under camphor oil, p. 370. Oils of the Dipterocarpaceae. 
503 
Properties. Oil of Borneo camphor is a liquid, sometimes colored 
green by copper, of the sp. gr. 0.882-0.909 (Macewan,1 1885). 
Composition. The lack of an investigation along modern lines is 
probably due only to the fact, that this interesting oil can not be 
obtained in the market. • 
From older investigations of Martins2 (1838), Pelouze3 (1840) and 
Gerhardt4 (1843) it can be seen that borneol5 is the characteristic 
constituent of the oil. More recent investigators, however, like Lalle- 
mand6 (1860) and Macewan1 (1885) deny the presence of this alcohol 
in the oil. 
According to Pelouze3 the liquid part of the oil has the same 
composition as the supposed terpene "borneen," which is obtained by 
the action of phosphoric acid anhydride on borneol. As Wallach" has 
shown (1885), there result by this treatment several hydrocarbons; 
"borneen" is therefore a mixture of several substances. Although 
nothing positive can be drawn from this statement of Pelouze, it is. 
nevertheless, probable also from other considerations that camphene is 
contained in the liquid parts of the oil of Borneo camphor. 
The oil investigated by Lallemand had been brought by Junghuhn 
from Sumatra, and had been obtained by distilling various comminuted 
parts of the tree. It turned the plane of polarization to the right (a for 
red light = +7°) and on distilling began to boil at 180°. The fraction 
going over at this temperature was relatively small (sp. gr. 0.86, <zd+13°) 
and yielded after passing hydrochloric acid through it and treating the 
resulting product with fuming nitric acid, a solid hydrochloride (dipen- 
tene?). The principal part of the oil went over from 260-270°, had 
the sp. gr. 0.90-0.92 and yielded a compound C15H242HCI melting at 
125°. Overlooking the somewhat high melting point the body might 
be looked upon as cadinene hydrochloride. As already mentioned this 
Borneo camphor oil contained no borneol. 
227. Oil of Gurjun Balsam. 
Origin and History. Gurjun balsam, called wood oil in India, has 
been known there for a long time and used as an excellent varnish. 
i) Pharm. Journ., Ill, 15, pp. 795 and 1045 
2) Liebig's Annalen, 27, p. 63. 
3) Compt. rend., 11, p. 365; Liebig's Annalen, 40, p, 326. 
Liebig's Annalen, 45, p. 38. 
5) The borneol from the Borneo camphor tree is dextrogyrate. Fliickiger, Pharm. 
Journ., Ill, 4, p. 829. 
6; Liebig's Annalen, 114, p. 193. 
7) Liebig's Annalen. 230, p. 237. 504 
Special Part. 
The balsam is obtained in East India, in a manner similar to 
turpentine, from several species of Dipterocarpus (Family Dipterocarpa- 
ceae), especially from D. turbinatus Gaertn. til., I), incanus Roxb. and 
I), alatus Roxb. The Dipterocarpus trees belong to the most magnificent 
trees of the Indian mountain forests, and are so productive, that full 
grown trees yield up to 180 liters of balsam during a summer. 
The collection is as follows: At the end of the dry season a 
transverse slit 2 inches in length and 6 inches in width is made 
with an axe through the bark into the wood, just above the 
ground. At the base of this a deep cavity is made, which is capable 
of holding at least 1 liter of balsam. This is heated by means of a 
coal fire which has been started in it, until the walls are charred. The 
cavity is then emptied and cleaned. The balsam soon begins to flow 
at such a rapid rate from the slit, that the cavity serving as a reser- 
voir has to be emptied several times a day. When the flow diminishes 
or is retarded by drying on the walls, the crusts are scraped off or the 
walls are again heated. When exhausted, the same operation is repeated 
on the opposite side of the trunk.1 
The principal places of export of the gurjun balsam are Saigon, 
Singapore, Moulmein in Tenasserim and Akyab. 
Gurjun balsam, according to its source and manner of collection, 
differs in consistency, color, and behavior to solvents. The better 
varieties are of a greenish gray color; with reflected light somewhat 
turbid and slightly fluorescent, with transmitted light it appears entirely 
clear and reddish brown. Odor and taste remind of copaiba balsam. 
Its sp. gr. is 0.96-0.97. By steam distillation up to 70 p. c. of oil are 
obtained. 
In Europe attention was called to gurjun balsam in 1811 by 
Franklin2 and in 1813 by Ainslie,3 but its source and manner of 
collection was first described accurately by Roxburgh about 1827.4 
The similarity of the action of gurjun balsam to that of copaiba balsam 
was made known in India about the year 1812 by the physician 
O'Shaughnessy.5 The balsam also gained in India a considerable 
reputation as a cure against leprosy and was used later in England in 
dermatology.6 
i) Pharm. Journ., Ill, 5, p. 729; III, 18, p. 161; D. Hanbury, .Science Papers, p. 118. 
2) Tracts on the dominions of Ava. London, 1811, p. 26. 
3) Materia medica of Hindoostan. Madras, 1813, p. 186. 
4) Plants of the coast of Coromandel, 1828, vol. 3, p. 10. 
s) Bengal Dispensatory, Calcutta, 1842, p. 22. 
6) Pharmac. Journ., Ill, 5, p. 729. Oils of the Cistaceae. 
505 
Properties. Gurjun balsam oil is a yellow, somewhat viscous 
liquid, of the sp. gr. 0.915-0.930. It has at times a very high 
rotatory power, namely - 35° to -130°. Most of the balsams 
give laevogyrate oils, but strongly dextrogyrate oils have also been 
observed.1 The oil is not completely soluble in 90 p. c. alcohol, and 
even in 95 p. c. alcohol the solubility is limited. It contains no saponi- 
fiable constituents, but probably small amounts of alcoholic bodies, for 
after acetylization the saponification number 9.6 was obtained. 
Gurjun balsam oil boils for the greater part at 255-256° and 
appears to consist almost wholly of sesquiterpene,2 015024- With 
hydrochloric acid this does not give a solid hydrochloride, but only a 
fine dark blue coloration. Whether this hydrocarbon is identical with 
one of the known sesquiterpenes has not yet been determined. 
Oil of gurjun balsam is on account of its weak odor a very dangerous 
adulterant for ot her volatile oils. On account of its high boiling point, 
its strong rotatory power, and its difficult solubility in alcohol, its 
detection, however, usually offers no great difficulties. 
228. Oil of Ladanum. 
Origin and History. The ladanum3 resin, used since antiquity as 
incense and embalming agent, is an exudation of the bush-like plants 
Cistus creticus L., C. ladaniferus L. and others (Family Cistaceae) 
indigenous to Asia Minor, Crete, Cyprus and a few other islands off the 
coast of Asia Minor. Up to the beginning of this century it was an 
officinal drug, valued for its pleasant odor, and is often mentioned along 
with the ancient aromatics storax, myrrh and frankincense in literature 
and has often, especially in the translations of the Bible, been confounded 
with galbanum. Lately it has gone almost altogether out of use. 
Ladanum oil, distilled at first with wine or spirits of wine (aqua 
vitae) was already known to Ryff, Gesner, Rubens, and to Porta. It 
was taken up in medical books, first in the Dispensatorium Noricum of 
the year 1589 and in the Pharmacopoea Augustana of the year 1613. 
Properties. The oil distilled from the leaves of Cistus ladaniferus 
L. has an unpleasant, narcotic odor. It has the sp. gr. 0.925 and 
boils from 165-280° with decomposition and splitting off of acetic acid.4 
i) Pharmacographia Indiea, vol. 1, p. 193. 
2) Pharmacognosie, 2nd ed., p. 102. Comp, also Werner, Zeitschr. f. Chem. und 
Pharm., 5, p. 588; Jahresb. f. Chem., 1862, p. 461. 
3) Also spelled labdanum. 
4) Bericht von S. & Co., Oct. 1889, p. 53. 506 
Special Part. 
Upon distillation of ladanum resin Schimmel & Co.1 obtained a 
golden yellow oil, of a fine strong amber odor. After standing for 
about half a year, magnificent crystals separated out, which made 
up about the fourth part of the oil.2 
229. Oil of Canella. 
Origin and History. The evergreen bush Canella alba Murray 
(Family Canellaceae}, indigenous to the West Indies, has a pleasant 
aromatic bark, which, when it was brought with other drugs from the 
new world to Europe, was considered as a variety of cinnamon bark, 
and later was confounded with other medicinal barks, especially with 
Winter's bark, from Drimys winter! Forst. 
The volatile oil of canella bark was probably first distilled in 1707 
by Sloane in England, and later, in 1820, by Henry, but appears to 
have found no application. It was investigated in 18-13 by Meyer and 
von Reiche and later by Bruun and Williams. 
Properties. Upon distillation of canella bark, 0.75 to 1.25 p. c, 
of volatile oil are obtained, the odor of which is similar to that of a 
mixture of clove and cajeput oil. Sp. gr. 0.920 to 0.935. Optically it 
is slightly dextrogyrate «d = + 1° 8'. 
Constituents. By shaking out with alkali, a phenol, eugenol3 
(benzoyl eugenol, Bruun4) could be separated. 
By the distillation of the remaining portion the lowest fraction went 
over from 165-170.° (Sp. gr. 0.888; «d =- 3.38°). The presence of 
1-pinene (Williams5) was demonstrated by preparing the pinene nitroso- 
chloride and the pinene nitrolbenzylamine base, melting at 122-123°. 
The next highest fraction consists of cineol6 (cineolic acid, m. p. 197°).2 
The highest boiling parts of the oil contain caryophyllene,5 the presence 
of which was shown by preparing the crystalline caryophyllene hydrate, 
melting at 92-95°. 
230. Oil of Damiana Leaves. 
Several species of Turnera (Family Turneraceae), especially Turnera 
aphrodisiaca Ward and Turnera diffusa Ward have been named as the 
botanical sources of damiana leaves, used medicinally since 1875 in 
America. The leaves of other plants, however, are also sent into the 
market as damiana leaves, for instance those of Bigelovia veneta Gray 
1) Bericht von S. & Co., Apr. 1893, p. 63. 
2) Ibidem, Oct. 1893, p. 24. 
3) Liebig's Annalen, 47, p. 224. 
4) Proc. Wise. Pharm. Assoc., 1893, p. 36. 
5) Pharm. Rundschau, 12, p. 183. 
6) Bericht von S. & Co., Oct. 1890, p. 53. Oils of the Myrtaceae. 
507 
(Aplopappus discoideus D. C.). The differences in the material employed 
no doubt, explain also the differences noticed in the oils obtained by 
distillation at different times. 
Pantzer1 obtained in 1887 0.5 p. c. of a yellow oil of an aromatic 
odor and a warm, camphor-like, bitter taste. Schimmel & Co.2 obtained 
0.9 p. c. of a green visebus oil, of a chamomile-like odor. It had the 
sp. gr. 0.970 and boiled between 250 and 310°. The highest boiling 
fractions were blue. From another consignment of leaves the same firm 
obtained3 in 1896 1 p. c. of oil of the following properties: sp. gr. 
0.943; «D = - 23° 25'; saponification number 41.8. On standing in 
the cold, the separation of crystals on the upper surface could be 
noticed, similar to those which are observed at the beginning of the 
solidification of rose oil. According to this it is probable, that paraffins 
are also present in oil of damiana leaves. 
231. Oil of Henna. 
The blossoms of the henna shrub. Lawsonia inermis L. (Family 
Lythraceae) used in the Orient for dyeing, contain according to Holmes4 
a volatile oil. which is said to have an odor closely resembling that 
of tea rose. 
a 232. Oil of Myrtle. 
Oleum Myrti.-Myrtenol. -Essence de Myrte. 
Origin. The myrtle, Myrtus communis L. (Family Myrtaceae), very 
widely distributed in the mountainous districts of Spain, Italy and 
southern France, is distinguished for its fragrant blossoms and leaves. 
Only the leaves are used for the preparation of the volatile oil5 giving 
a yield of 0.3 p. c. The myrtle oil of commerce is usually of French or 
Spanish origin. The Corsican oil is especially valued. 
Properties. Oil of myrtle is a yellow to greenish liquid, of a 
pleasant and refreshing aroma. Sp. gr. 0.890-0.915; «d -+ 10 to +30°. 
Composition. The fraction boiling between 158-160° consists of a 
dextrogyrate terpene CioHig ([a] = + 36.8°), the chemical behavior of 
which pointed to pinene.6 That the substance under consideration was 
really d-pinene, was shown by Jahns in 1889 by the preparation of 
pinene nitrosochloride.7 
1) Am. Jouru. Pharm., 59, p. 69. 
2) Bericht von S. & Co., Apr. 1888, p. 44. 
3) Bericht von S. &Co., Apr. 1897, p. 13. 
4) Pharm. Journ., UI, 10, p. 635. 
5) The fresh fruits likewise contain 
volatile oil. Raybaud, Journ. de Pharm, 
II, 20, p. 463. 
6) The "Myrtene" of Gladstone (1864), 
Journ. Chern. Soc., 17, p. 1; 25, p. 1. 
7) Archiv d. Pharm., 227. p. 174. 508 
Special Part. 
The oil boiling about 176° contains cineol, CioHisO. By conducting 
into it hydrochloric or hydrobromic acid, the characteristic addition 
products are formed, by the decomposition of which by water the cineol 
can be readily obtained in a pure form. 
The fraction collected at 180° consists of dipentene.1 This terpene 
was identified by the preparation of dipentene nitrosochloride and 
tetrabromide of the melting point 125°. 
The fraction boiling from 195-200° acts on sodium with liberation 
of hydrogen. Jahns suspects it to be a camphor CioHic.O. According 
to the boiling point linalool might be contained in this fraction. In a 
later investigation of oil of myrtle by Bartolotti,2 to whom the investi- 
gations of Jahns and Schimmel & Co. were evidently unknown, not a 
single constituent was identified. 
Oil of myrtle was formerly much used for the preparation of myrtol, 
as the fraction boiling from 160-180° was called. The reputed anti- 
zymotic and deodorizing properties3 of "myrtol" can no doubt be 
traced to its content of cineol. 
233. Oil of Cheken Leaves. 
The cheken leaves, often recommended for medicinal use, the leaves 
of Myrtus cheken Spr. indigenous to Chili, contain about 1 p. c. of an 
oil very similar to ordinary myrtle oil (Weiss,4 1888). 
It is quite mobile, of a yellowish green color and has a pleasant odor, 
reminding of eucalyptus and sage., Sp. gr. 0.8795 at 15°; «j = + 23.5°. 
The principal part of the oil, about 75 p. c., boils from 155-157° 
(sp. gr. 0.8635; aj = -r 31.28°), has the composition CioHm and yields 
with hydrochloric acid a monohydrochloride melting at 120°. On 
heating this fraction to 260-270° dipentene resulted (tetrabromide, 
m. p. 125-126°). From this it follows that the hydrocarbon boiling 
from 155-157° is d-pinene. 
The fraction boiling about 176° (15 p. c.) consists of cineol, as was 
shown by the formation of the cineol bibromide CioHisOBrs, which 
separates in red crystals from the petroleum ether solution on the 
addition of bromine. 
About 10 p. c. of the oil pass over, on distillation, from 220-280°. 
The composition of this fraction has not yet been determined. 
1) Bericht von S. & Co., Apr. 1889, p. 28. 
2) Gazz. chini. Itai., 21, p. 276; Berichte, 24, Referate, p. 572. 
3) Pharmaceut.isehe Zeitung, 35, p. 224. 
*) Archiv d. Pharm., 226, p. 666. Oils of the Myrtaceae. 
509 
Oleum Amomi sen Pimentae.-Pimentel. - Essence de Piment. 
234% Oil of Pimenta. 
Origin and Preparation. The evergreen shrub Pimenta. officinalis 
Lindl. (Family Myrtaceae), indigenous to the West Indies, grows on 
calcareous soil near the coast, in Cuba, Hayti, San Domingo, Trinidad, 
Antigua, and especially in Jamaica, further in Central America, Mexico, 
Costa Rica and Venezuela. 
For obtaining pimenta valued as an aromatic or allspice,1 the 
unripe berries are gathered and dried in the sun. The ripe fruit contains 
a sweet jelly, but is almost odorless and has therefore no commercial 
value. 
Pimenta yields on distillation, which is at first accompanied by a 
strong evolution of ammonia, 3-4.5 p. c. of volatile oil. 
Properties. Oil of pimenta is of a yellow to brownish color and 
has a pleasant aromatic odor, similar to clove oil, although sharply 
differentiated from it, and a piercing, sharp taste. Sp. gr. 1.0242 to 
1.050. Slightly laevogyrate. It is soluble in all proportions in 90 p. c. 
alcohol, and soluble to a clear solution in 2 parts of 70 p. c. alcohol. 
Composition. The experiments of Bonastres,3 (1825) who prepared 
the alkali salts of the acid constituents of pimenta oil, already indicated 
that the similarity of this oil to clove oil was due to the eugenol which 
was common to both. The proof of the identity of these two phenols 
was furnished by Oeser4 in 1864, who separated the eugenol from the 
oil by means of an alkali solution, and analysed it. 
That part of the oil which did not combine with the alkali, boiled 
at 255° and was slightly laevogyrate. The analysis gave results 
agreeing with CsHs. This is therefore a sesquiterpene. 
The odor of oil of pimenta indicates that eugenol and sesquiterpene 
are not the only constituents. An investigation of the oil according to 
modern methods might be a profitable and a not too difficult problem. 
Oil of pimenta leaves. An oil distilled in Trinidad from the 
leaves of an undetermined species of Pimenta, is a yellow liquid, smelling 
strongly of lemon, of the sp. gr. 0.882 at 25°; aD --0°37'. The 
lemon-like odor is due to citral, the presence of which was demonstrated 
by forming the citryl ^-naphtho cinchoninic acid.3 
i) Odorographia, vol. 2, p. 51. 
2) Bericht von S. & Co., Apr. 1899, p. 39. 
3) Journ. de Pharm., 13, p. 466. Comp, also ibid., 11, p. 187; Trommsdorff's 
Nejies Journ. d. Pharm., 11, I, p. 127. 
4) Liebig's Annalen, 131, p. 277. 
a) Bericht von S. & Co., Oct. 1896, p. 77. 510 
Special Part. 
235. Oil of Bay. 
Oleum Myrciae. - Bayol. - Essence de Myrcia. 
Origin and Preparation. As the numerous species of the genera 
Myrcia and Pimenta are very variable and very similar to each other, 
it is highly probable that these small botanical differences are not 
observed in collecting, and therefore the bay leaves of commerce are not 
always derived from one and the same plant,1 but are rather mixtures 
of the leaves of several species. According to Holmes2 the botanical 
source of the genuine bay leaves is Pimenta acris Wight {Eugenia acris 
Wight et Arnott) and not Myrcia acris D. C. as is given in the U. S. P. 
The bay tree is indigenous to the West Indies and flourishes 
especially on Jamaica, St. Thomas, Antigua, Guadeloupe, Dominica 
and Barbadoes. The oil is obtained only in part from the fresh material 
on the islands themselves; the larger part is probably prepared in 
New York from the dried leaves. 
On distilling, part of the oil separates in the receiver on top of the 
water and another part sinks to the bottom. They must be mixed 
if a normal oil is to be obtained. This appears not always to be done, 
as bay oils of a specific gravity greater than water often appear in the 
market. The yield from dried leaves is 2-2.5 p. c. 
• Properties. Bay oil is a yellow liquid, soon becoming brown on 
exposure to the air, of a pleasant odor reminding of clove and a sharp 
spicy taste. The sp. gr. of the normal oil varies from 0.965 to 0.985 
and is as a rule above 0.970; optically it is slightly laevogyrate, «d - 
up to -2°. The freshly distilled oil is soluble to a clear solution in an 
equal volume of 90 p. c. alcohol; on standing, however, it soon loses 
its solubility and then gives only turbid mixtures, a behavior which is 
due to the polymerization of an olefinic terpene, myrcene, contained in 
the oil. The content in phenols (eugenol and chavicol) amounts to 
59-65 p. c. according to volumetric determinations with dilute potassa 
solution. 
Composition. The identity of the main constituent of greater 
specific gravity of the oil with eugenol appears to have been first 
recognized by Markoe3 in 1877. The first complete investigation of the 
oil was made by Mittmann4 in 1889. He found besides eugenol a 
small amount of methyl eugenol, which statement was later corroborated. 
By fractional distillation he obtained a small fraction, boiling from 
i) Odorographia, vol. 2, p. 56. 
2) Pharm. Journ., Ill, 21, p. 837. 
3) Proc. Am. Ph. Assoc., 25, p. 488. 
4) Archiv d. Pharm., 227. p. 529. Oils of the Myrtaceae. 
511 
160-185°, which according to him. consisted of two terpenes, of which 
lie believed the lower boiling to be pinene, and suspected dipentene 
in the higher boiling portion. According to a more recent investigation 
by Power and Kleber1 neither of these terpenes, but a whole series of 
other bodies, overlooked by Mittmann, are contained in oil of bay. 
Upon distillation under 20 mm. pressure of the oil separated from 
the phenol 80 p. c. went over between 67 and 68°, the remainder 
at 160°. The first fraction had the sp. gr. 0.8023 and was a colorless 
liquid of a characteristic odor, but quite different from that of 
the known terpenes. Analysis and molecular weight determination 
corresponded with the formula C;oHis. From the index of refraction, 
ud = 1.4673, the molecular refraction 47.1 was calculated, according 
to which the compound contains three double bonds. As with 
such an arrangement of the atoms a ring configuration is excluded, the 
atoms must form an open chain, which is also in harmony with the 
low sp. gr. A so-called olefinic terpene, which was called myrcene was, 
therefore, under consideration. 
Myrcene is very susceptible to change and polymerizes even after 
standing for only one week to a thick oil. By treating myrcene with 
glacial acetic acid and sulphuric acid (Bertram's hydration method) 
there resulted (besides dipentene) an oil of a lavender-like odor, which 
yielded linalool after saponification. This alcohol was identified by its 
conversion into citral. Myrcene bears therefore the same relation to 
linalool, as does camphene to isoborneol, and pinene or dipentene to 
terpineol. Besides myrcene, bay oil contains 1-phellandrene. Other 
terpenes have not been found by Power and Kleber. 
The fractions of bay oil freed from phenols and terpenes, gave a 
solid compound with sodium bisulphite, the decomposition of which 
yielded citral (citryl :-naphtho cinchoninic acid). 
After separating the citral an oil, smelling like anise, remained, 
which consisted in part of methyl chavicol. By oxidation it was con- 
verted into anisic acid, by treatment with alcoholic potassa into anethol. 
The highest boiling fractions of the oil contained methyl eugenol. 
By treating the phenols separated from the oil by means of Alkali 
with methyl iodide, Power & Kleber obtained a mixture of methyl 
eugenol and methyl chavicol, from which it follows, that besides eugenol, 
chavicol is also present in oil of bay. 
1) Pharm. Rundschau, 18, p. 60. 512 
Special Part. 
The constituents of oil of bay arranged according to the amounts 
present are as follows: 
1. Eugenol, C1OH12O2, 
2. Myrcene, CioHio, 
3. Chavicol, C9H100, 
4. Methyl eugenol, C11H14O2, 
5. Methyl chavicol, C10H12C), 
6. Phellandrene, CioHie, 
7. Citral, CioHioO. 
Examination. As oil of bay contains no pinene, any turpentine oil 
which may have been added, can be detected without difficulty. 
From 10 cc. of bay oil 1 cc. is sloWly distilled off from a fractionating 
flask, and the distillate mixed with 1 cc. of amyl nitrite and 2 cc. of glacial 
acetic acid. To this is added drop by drop with agitation, while the whole is 
kept well cooled in a freezing mixture, a mixture of equal parts of glacial acetic 
acid and hydrochloric acid as long as a blue coloration results. If pinene is 
present a white precipitate of pinene nitrosochloride is formed. In this manner 
10 p. c. of turpentine oil in bay oil can be detected. 
236. Oil of Cloves. 
Oleum Caryopliyllorum. - Nelkenbl. - Essence de Girofle. 
History. Oil of cloves appears to have been distilled for the first 
time in the fifteenth century, but probably, like other aromatics, with 
wine or the addition of spirits of wine. This method of distillation was 
described by Ryff, Gesner, Lonicer and others. Gesner also mentions 
the distillation of the oil. per descensum. The pure oil was, however, 
shortly afterwards distilled by Cordus, by Winther of Andernach and 
by Porta. In the Dispensatorium Noricum, oil of cloves was not 
admitted until the edition of 1589. In drug ordinances it was first 
mentioned in that of the city of Berlin of 1574. 
The yield of volatile oil from cloves was determined by Boerhaave, 
Hoffmann. Neumann and Trommsdorff. Boerhaave remarked that the 
quite different yield obtained on distillation was sometimes due to the 
adulteration with cloves which had been exhausted of their oil by 
distillation and then dried again. 
Bonastre1 in 1827 recognized the acid nature of clove oil and 
investigated the salt-like compounds of eugenol that were formed with 
alkalies. Ettling and Liebig2 in 1834 first showed that besides Nelken- 
saure, eugenic acid, there is alsojpresent in the oil an indifferent body. 
i) Journ. de Pharm., II, 13, pp. 464, 513; Poggendorff's Annalen, 10, pp. 609, 611. 
2) Liebig's Annalen, 9, p. 68. Oils of the Myrtaceae. 
513 
Of the older investigations, which were restricted mostly to eugenol, 
those of Dumas1 (1833), Bockmann2 (1838), Stenhouse3 (1843), Calvi4 
(1856), Bruning5 (1857), Williams6 (1858), Hlasiwetz and Grabowski 7 
(1866) and Erlenmeyer8 (1866) may be mentioned. 
Origin and Preparation. The ever-green clove tree, Eugenia caryo- 
phyllata, Thunb. (Caryophyllus aromaticus L.) (Family Myrtaceae}, was 
originally indigenous to the Philippines and is now cultivated on 
Amboina, Reunion, Mauritius, Madagascar and Malacca (Penang). 
The plantations on the largest scale are, however, found on the east 
African islands Zanzibar and Pemba, which taken together produce 
about % of the total clove production of the world. 
Cloves are the undeveloped blossoms, dried in the air, of the clove 
tree, which is aromatic in all its parts. Its inflorescence is a perfect 
cyme containing as many as 35 individual blossoms. Each blossom 
has a pulpy receptacle nearly 1 cm. in length, which at first is of a 
light color, later green, and just before blossoming becomes dark red. 
When this color appears, the blossoms are gathered, because they are 
then richest in oil, and dried in the air. The flower buds of the culti- 
vated trees contain more oil than those of the trees growing wild. 
The berry-like fruit collected just before ripening, formerly came into 
commerce under the name of Anthophylli, mother-cloves. 
Only the Zanzibar cloves (under which designation are included the 
cloves coming from Pemba) are used for distillation. The cloves from 
Amboina and Reunion are indeed richer in oil, but on account of their 
better appearance command a much higher price than the difference in 
the oil content justifies. The most expensive is the Madagascar clove, 
from St. Marie on the southern point of the island. It yields 18 p. c. 
of oil, which is considered as finer by the Parisian perfumers, but from 
other considerations no especial advantages can be assigned to it.1 
The cloves are distilled either whole or in a comminuted condition; 
according to the method of distillation (water or dry steam) there is 
obtained an oil of higher specific gravity and richer in eugenol, or a 
lighter oil, in which the non-phenol constituents are relatively larger. 
The oil collecting in the receivers partly sinks in the water and partly 
floats upon it. By mixing both parts normal oil of cloves is obtained. 
The yield from Zanzibar cloves amounts to 15-18 p. c. 
1) Ann. de Chim. et de Phys., II, 53, p. 
165; Liebig's Annalen, 9, p. 68. 
2) Liebig's Annalen, 27, p. 155. 
s) Ibidem, 95, p. 103. 
*) Ibidem, 99, p. 242. 
5) Ibidem, 104, p. 202. 
6) Ibidem, 107, p. 238. 
7) Ibidem, 139, p. 95. 
8; Zeitschr. f. Chemie, 9, p. 95. 514 
Special Part. 
Properties. Oil of cloves is, when freshly distilled, an almost 
colorless to yellowish, strongly refracting liquid, which becomes darker 
with age. The odor is strongly aromatic, the taste persistently bnrning. 
The specific gravity varies according to the method of distillation from 
1.045 to 1.070. The optical rotation is slightly to the left, «d - up to 
-l°10'. The oil dissolves to a clear solution in 2 parts of 70 p. c. 
alcohol. 
The chemical reactions are partly those of eugenol, several color 
reactions are. however, produced by the traces of furfurol present. 
Upon distillation oil of cloves goes over between 250 and 260°. 
Composition. Of the constituents of oil of cloves, eugenol, which is 
present to the extent of 70-85 p. c., was the first to attract the 
attention of chemists (comp. History, p. 512). 
Eugenol, a phenol of the formula C1OH12O2, boils under ordinary 
pressure with slight decomposition at 253-254°1 (thermometer com- 
pletely in the vapor). It is the most characteristic and valuable 
constituent of clove oil; its quantitative determination is described on 
page 516, its properties and compounds on page 180. 
Pure eugenol is obtained by treating oil of cloves with weak 
(2-5 p. c.) soda solution and after shaking out the alkaline solution 
several times with ether, decomposing it with dilute sulphuric acid. 
Besides free eugenol, there is contained, according to Erdmann,2 
in oil of cloves also 2-3 p. c. of acet-eugenol, which is found in the oil 
not attacked by the alkaline solution. In this the acet-eugenol can be 
detected and removed by saponification with alcoholic potassa or by 
heating with a concentrated aqueous solution of potassa. 
The oil remaining after removing the acet-eugenol consists principally, 
as was already recognized by Church3 in 1875, of a sesquiterpene, 
which was more closely investigated by Wallach4 in 1892 and called 
caryophyllene. 
Caryophyllene, C15H24, is a colorless liquid boiling from 258-260°, 
of a weak odor which does not resemble cloves and the sp. gr. 0.9085. 
By taking up a molecule of water it is converted into the nicely 
crystalline alcohol, caryophyllene hydrate, C15H26O, melting at 96°. 
For further information see page 125. 
Scheuch5 in 1863 pointed out the presence of small amounts of 
salicylic acid. The correctness of this statement was, however, rendered 
i) Bericht von S. & Co., Apr. 1892, p. 28. 
2) Journ. f. prakt. Chern., II, 56, p. 143. 
s) Journ. Cheni. Soc., 28, p. 113. 
Liebig's Annalen, 271, p. 287. 
5) Liebig's Annalen, 125, p. 14. Oils of the Myrtaceae. 
515 
■doubtful by Wassermann 1 in 1875. Erdmann2 definitely showed the 
presence of salicylic acid in oil of cloves and found that it did not exist 
free but probably as acet-salicylic acid ester of eugenol. Of other minor 
constituents of oil of cloves, methyl alcohol must be mentioned, which 
is best obtained by collecting the first portions in working up the 
■cohobation waters and fractionating this repeatedly. Finally a liquid 
boiling at 65.5-66° is obtained which can be identified as methyl 
alcohol3 by means of its oxalic acid ester, melting at 54°. 
By continuing the distillation a liquid boiling at 162° is obtained, 
which consists of furfurol3 and was identified by its intense color reaction 
with aniline and p-tohiidine, by converting it into its phenyl hydrazone 
melting at 96°, as well as by splitting it into pyromucic acid and 
furfurol alcohol. Furfurol is probably partly the cause of the darkening 
of oil of cloves. 
In the fraction boiling at 150-155°, which cannot be completely 
separated from furfurol by distillation, is contained methyl amyl ketone,4 
CH3.CO.C5Hu. If from the fraction mentioned, the furfurol be removed 
by shaking with permanganate solution, the pure ketone, boiling at 
151-152° remains. The elementary analysis corresponded to C7H14O. 
By heating with chromic acid mixture it was gradually oxidized to 
valerianic acid (together with some capronic acid) and acetic acid. 
Although the^methyl amyl ketone is present in oil of cloves only in a 
fraction of one percent it, nevertheless, has a considerable effect on the 
odor of the oil, as it gives rise to the peculiar fruity odor which 
accompanies the heavy eugenol odor. 
A further substance, which has been found in the oil, vanillin,5 may 
have been formed by the oxidizing influence of the air on the eugenol. 
It is worthy of notice that vanillin is already present in the cloves. 
Examination. As nearly all adulterants which can be considered, 
are specifically lighter than clove oil, the determination of the specific 
gravity is not to be omitted. When it is found less than 1.045 it is to 
be tested by means of fractional distillation for turpentine and similar 
low boiling oils. Its solubility in 2 parts of 70 p. c. alcohol is also to 
be observed. Oils of cedar wood, copaiba and gurjun balsam would 
show themselves by their difficult solubility and simultaneous increase 
of the rotatory power. The German Pharmacopoeia gives a test for 
the highly improbable presence of carbolic acid, in that it£directs 1 cc. 
i) Liebig's Annalen, 179, p. 369. 
2) Journ. f. prakt. Chemie, II, 56, p. 143. 
3) Bericht von S. & Co., Oct. 1896, p. 57. 
4) Bericht von S. & Co., Apr. 1897, p. 50. 
s) Chem. Centralbl., 1890, II, p. 828. 516 
Special Part. 
of oil to be shaken with 20 co. of hot water, and that the filtrate 
obtained after allowing the mixture to cool, be treated with ferric 
chloride. A blue coloration would indicate the presence of carbolic acid_ 
Much more common than the adulteration of clove oil, is the sub- 
stitution of the cheaper and less pleasantly odorous oil of clove stems, 
the sure detection of which is only possible to a well trained nose. 
Investigations on a physical or chemical basis are entirely inadequate. 
Perhaps the recently found fact that only oil of cloves, but not oil of 
clove stems, contains acet-eugenol, might be used as a means of dis- 
tinguishing between these oils. 
It may often be desirable to know how much eugenol is contained 
in a clove oil (or clove stem oil). For this purpose H. Thoms1 has 
worked out a method of determination which depends on converting 
the eugenol into its benzoyl derivative, separating and weighing as 
such. The method is as follows: 
In a fared beaker of about 150 cc. 5 g. of clove oil are treated with 20 g. 
of sodium hydrate solution (15 p. c.) and then 6 g. of benzoyl chloride added. 
The mixture is well shaken, when a considerable amount of heat will be 
liberated, until it is uniformly mixed up. After cooling, 50 cc. of wrater are 
added, and then heated until the crystalline ester has again become oily and 
again allowed to cool. The clear supernatant liquid is filtered off and the 
crystalline mass remaining in the beaker is again treated with 50 cc. of water, 
heated on a water bath until the ester is melted and filtered after cooling. This 
operation is repeated with 50 cc. more of water. The excess of soda as well 
as of sodium salt has then been removed. 
After having returned any crystals which may have been washed on to the 
filter to the beaker, the still moist benzoyl eugenol is at once treated with 
25 cc. of alcohol of 90 p. c. by weight, and heated with agitation on a, water 
bath until solution is effected; the beaker is now removed from the waler bath 
and the agitation continued until the benzoyl eugenol has separated in fine 
crystals. This takes place in a few minutes. The mass is then cooled to 17°, 
the precipitate transferred to a filter of 9 cm. diameter and the filtrate collected 
in a graduated cylinder. About 20 cc. of filtrate are usually obtained; the 
alcoholic solution which is held in the crystalline mass is forced out by adding 
so much of 90 p. c. alcohol by weight until the total filtrate measures 25 cc. 
The still moist filter with its precipitate is transferred to a weighing tube (the 
latter with the filter having previously been dried at 101° and weighed) and 
dried at 101° until the weight is constant. 25 cc. of 90 p. c. alcohol dissolve 
at 17° 0.55 g. of pure benzoyl eugenol, which amount must be added to the- 
result obtained. 
If a is the amount of benzoic acid ester, b the amount of clove oil used 
(about 5 g.), and if 25 cc. of the alcoholic solution of the ester are filtered off 
i) Ber. der pharm. Gesellschaft, 1, p. 283. Oils of the Myrtaceae. 
517 
as above described, the percentage content of eugenol in the oil of cloves is 
found by the following formula: 
4100 (a. + 0 55) 
67 . b 
This formula results from the two equations: 
(Benzoyl eugenol) (Eugenol) 
268 : 164 = (a+ 0.55): Amount of eugenol found 
164 . (a + 0.55) 
Eugenol - 
h 268 
164. (a+ 0.55) 
Hence b: - 100 : x 
268 
_ 164 (a + 0.54) . 100 _ 4100 (a + 0.55) 
268 . b ~~ 67 . b 
Mixtures of pure eugenol with caryophyllene yielded by this method results 
which agreed within 1 p. c., an accuracy which is probably sufficient for 
most cases.1 
By Thoms' method only the free eugenol and not that which is in 
the form of acet-eugenol is determined. If the content of acet-eugenol is 
also to be found, two determinations must be made; one as before 
described, and the other after saponifying the oil.2 
For this purpose the oil is heated with concentrated aqueous potassa 
solution for a-short time to 100°. The saponification must not be made with 
alcoholic potassa as the alcohol which is removed only with difficulty, would 
form ethyl benzoate and thus affect the results. 
The eugenol content of a good oil of cloves amounts to 70-85 p. c. 
Umney3 has recommended a much simpler and more rapidly con- 
ducted eugenol determination by using a Schimmel cassia flask with 
graduated neck.4 
A known amount of clove oil is put in the flask, 10 p. c. aqueous potassa 
solution added, and heated. The oil floating on top (non-phenols) is brought 
into the neck by filling up the flask, cooled to 15° and its amount read off on 
the scale. 
According to Umney's own statement the results thus obtained by 
Thom's method are 11-12 p. c. too high, which is explained in that 
the strong alkali solution dissolves a part of the caryophyllene. By 
using a more dilute lye (4-5 p. c.) the determinations are more correct 
and perhaps may then serve for comparative tests as to the eugenol 
content of several clove oils. 
1) Bericht von S. & Co., Apr. 1892, p. 28. 
2) Journ. f. prakt. Chern., II, 56, p. 143. 
s) Pharm. Journ., Ill, 25, p. 950. 
4) Comp, under cassia oil, p. 388, fig. 71. 518 
Special Part. 
Oleum Caryophyllorum e Stipitibus.-Nelkenstielbl.- Essence de Tiges de Girofle. 
337. Oil of Clove Stems. 
Clove stems, the flower stems of the cloves already mentioned, are 
less aromatic than these, and yield on distillation 5-6 p. c. of oil. 
Oil of clove stems was distilled as early as the middle of the six- 
teenth century. At the beginning of the second decade of this century 
clove stems were distilled together with cloves for the purpose of 
cheapening the oil of cloves.1 
Properties. Oli of clove stems is very similar in its properties to 
oil of cloves. Its odor, however, is less agreeable, for which reason the 
oil is not to be used in finer perfumery and in pharmacy; sp. gr. 1.040- 
1.065; «d = up to-1°10'. It has the same solubility as oil of cloves, 
i. e. it is soluble to a clear solution in 2 parts of 70 p. c. alcohol. 
Composition. The amount of free eugenol contained in oil of clove 
stems is as a rule somewhat higher than in oil of cloves. The fact 
that oils of clove stems show a higher content of eugenol by the benzoyl- 
chloride method than clove oils of the same specific gravity,2 is ex- 
plained in that the specifically heavier acet-eugenol of oil of cloves is 
absent in oil of clove stems.3 
Caryophyllene, methyl alcohol and furfurol have been shown to be 
present in oil of clove stems. Judging from the color, methyl amyl 
ketone is also present in the oil, however, in much smaller quantity 
then in oil of cloves. 
Tests and eugenol determination are the same as for oil of cloves. 
338. Oil of Cajeput. 
Oleum Cajeputi.-Cajeputol.-Essence de Cajeput. 
Origin and History. Oil of Cajeput is distilled from the fresh leaves 
and twigs of various species of Melaleuca (Family Myrtaceae) especially 
Melaleuca leucadendron L. and the variety known as M. minor Smith 
(M. cajeputi Roxb., M. virididora Gaertn.). These trees, growing to a 
height of 15 meters, are indigenous to upper India, the islands of the 
Indian Ocean, to northern Australia, Queensland and New South Wales. 
Oil of cajeput appears not to have been brought to Europe until 
the beginning of the seventeenth century, when the Dutch took posses- 
sion of the Moluccas. The first accurate account of the source of this 
oil was made known by the missionary Valentyn and the merchant 
i) Buchner's Repert. f. d. Pharm., 
26, II, p. 278. 
2) Comp. Ber. d. pharm. Ges., 1, p. 283. 
3) Jour. f. pract. Chem., II, 56, p. 143. Oils of the Myrtaceae. 
George Eberhard Rumpf of Hanau, both living in Amboina. The latter 
was an enthusiastic plant collector, and author of the first flora of the 
island Amboina. According to Rumpf's statement the Malays and 
Javanese were acquainted with oil of cajeput long before the Moluccas, 
the Banda and the Sunda islands were taken possession of, and used it 
as a diaphoretic. In Europe, the oil at first appears to have found no 
application. The first notice of. such is by a physician Lochner in 
Nurnberg and the apothecary Link in Leipzig. The former mentioned 
the oil in 1717, the latter had bought the oil about the same time as 
a novelty from the physician of a ship which had just returned from 
the East Indies. From this time on cajeput oil wras used medicinally in 
Germany and was introduced into the apothecary shops and mentioned 
in price ordinances and in medical works. It remained, however, for 
some time rare and expensive and not until 1730 did larger quantities 
of the oil come into the European market through Amsterdam. In 
Germany, it was at first called Oleum Wittnebianum after a merchant 
E. H. Wittneben of Wolfenbiittel, who lived several years in Batavia 
and had recommended the oil as a valuable remedial agent in German 
writings. In France and in England oil of cajeput was not used until 
the beginning of this century. 
The first detailed account of the simple methods of distillation of 
cajeput oil "used on the Moluccas, was given by the French traveler 
Labillardiere, who visited the island of Burn in 1792. The use of 
copper stills and condensers gave rise to a green color due to a small 
amount of copper in the oil. When perfectly pure, the oil is colorless. 
The cause of this coloration was first detected by the apothecaries 
Hellwig in Stralsund in 1786, Westrumb in Hameln in 1788 and 
Trommsdorff in Erfurt in 1795. 
Preparation, Production and Trade. Oil of cajeput is obtained in 
a primitive manner by the natives of some of the Molucca islands. 
According to Reinwardt the oil was prepared formerly only on Buru. 
In 1821 there were only 3 distilling apparatus on this island, in 1855 
there were 50. Recently the distillation is also carried on in Ceram. 
Martin, who in 1891-92 visited Ceram and Buru, described the method 
of preparation, illustrated in the accompanying figure, as follows: 
"Above a crudely mortared fire-place stands a barrel a, 1 meter in height, 
which serves as a distilling vessel; into this are pressed the leaves of the 
Melaleuca and the container is half filled with water. A metallic helm (b) 
which is obtained from Ambon or Java, is mounted on top, and its elongated 
tube passed through a second, somewhat larger barrel (e), serving as a 
519 520 
Special Part. 
condenser. Water is conducted into the latter from the top by means of a 
bamboo tube (d) from some small channel on the side of a hill. The volatile 
oil of the plant passes over with the water vapor and separates again after 
condensation. Water and oil flow into a vessel made of a cocoanut shell, which 
in turn is connected by means of a short tube with a bottle. Usually one sees 
a four-cornered brandy flask, as they are frequently seen in India, used for this 
purpose. This flask is provided at the bottom with a small opening, and 
stands in a small trough (e). filled with water, so that it is likewise filled with 
Fig. 76. 
Cajeput Oil Distillation on Ceram (Moluccas). 
water at the beginning. The distillation product gradually replaces the water 
in the flask, and the water which has passed over with the oil, likewise flows 
through the opening into the trough, until finally the entire flask is filled with 
oil, and can be removed by putting a finger on the opening while under water. 
The yield of oil as obtained with such an arrangement amounts to about 
1% liters per day. As is well known the light bluish-green liquid is valued in 
Europe as a stimulant, in Burn it is used as a domestic remedy for all 
imaginable ills." 
The oil is filled into empty wine and beer bottles. 25 bottles are 
packed at a time into a box made of the stems of the leaves of the 
sago palm1 (Metroxylon). The exhausted cajeput leaves serve as packing 
material. Macassar on Celebes is the principal commercial center for 
oil of cajeput. 
i) An illustration of sueh a case is to be found in Tschirch's Indische Heil- und 
Nutzpflanzen, plate 75 and p. 127. Oils of the Myrtaceae. 
521 
The total export of this oil from Macassar was:1 
1894 34,075 kilos. 
1895 49,301 " 
1896 57,800 " 
1897 78,543 " 
The greater part of the oil is consumed in the orient, especially in 
British India. A smaller part comes through Amsterdam, Hamburg 
and London into the European market. 
The import of Amsterdam amounted to: 
1894 about 10,700 bottles - about 6,420 kilos. 
1895 " 13,300 " = " 7,980 " 
1896 " - " - . " - 
1897 " 3,500 " = " 2,100 " 
The oil is not sold by weight but by bottles. As these, in the course 
of time, became smaller and smaller, and as considerable loss was 
experienced by breakage in transporting, Schimmel & Co. tried the more 
rational proceeding of shipping the oil in iron containers. This practical 
innovation, which was to establish the trade on a firmer basis, has up 
to now been unsuccessful on account of the conservatism of the Dutch. 
Properties. Crude oil of cajeput is a green to bluish-green liquid, 
due to the presence of copper, while the rectified oil is colorless or 
yellowish. -It has the pleasant, camphor-like odor of cineol and an 
aromatic, somewhat burning, later cooling taste. Sp. gr. 0.920-0.930; 
«d = - 0°10' to -2°. The oil dissolves in I part of 80 p. c. alcohol, 
but often gives clear solutions even with 3-5 parts of 70 p. c. alcohol. 
On strongly cooling with liquid carbonic acid and ether, it solidifies 
to a crystalline mass. The copper can be removed from the oil by 
shaking with a concentrated solution of tartaric acid. As can be seen 
from its spectroscopic behavior, chlorophyllan,2 oxidized chlorophyll, is 
contained also with the copper in the crude oil. 
Composition. The first chemical investigations dealt almost exclu- 
sively with the principal constituent of cajeput oil. the elementary com- 
position of which, CioHisO, was correctly recognized as early as 1833 
by Blanchet.3 The identity of this body, which was called 'cajeputene 
hydrate by Schmidt,4 cajeputol by Gladstone,5 also by Wright and 
1) Berieht von S. & Co., Apr. 1898, p. 10; Apr. 1899, p. 8. 
Pharm. Zeiischr. f. Russl., 27, p. 548; Jahresb. f. Pharm., 1888, p. 317. 
3) Liebig's Annalen. 7, p. 161. 
4) Journ. Chem. Soo., 14, p. 63; Journ. f. prakt. Chem., 82, p. 189. 
s) Journ. Chem. Soc., 25, p. 1; Pharm. Journ.. Ill, 2, p. 746; Jahresb. f. Chemie, 
1872, p. 815. 522 
Special Part. 
Lambert,1 with cineol was shown by Wallach2 in 1884. He prepared 
the halogen and hydrohalogen compounds. A further proof was fur- 
nished by Wallach and Gildemeister 3 by the oxidation of the fraction in 
question to cineolic acid CioHieOs, melting at 196-197°. 
Another important constituent of cajeput oil which in regard to the 
amount present takes second place, is the solid terpineol,4 CioHisO, 
discovered by Voiry,5 which is present in the free state, as well as in 
the form of its acetic acid ester. 
Terpenes are present in the oil to only a small extent; the laevo- 
gyrate fraction, boiling at 155-165°, gives with hydrochloric acid a 
solid laevogyrate monohydrochloride CioHieHCl5 melting at 126-128°. 
1-Pinene is therefore present. 
Several aldehydes are present in the first fraction. Voiry obtained 
by separation with sodium bisulphite a liquid of the properties of valeric 
aldehyde. The second aldehyde, smelling like oil of bitter almonds, is 
probably benzaldehyde. 
239. Oil of Niaouli. 
Oil of niaouli, the distillate obtained from Melaleuca viridiflora 
Brongn. et Gris, called Niaouli in New Caledonia, is very similar to oil 
of cajeput in its properties and composition. The oil is also called 
Gomenol on account of its preparation in the neighborhood of Gomen. 
Sp. gr. 0.908-0.922 at 12°. Optically it is either inactive or slightly 
dextro- or laevogyrate. 
Composition.6 In place of the 1-pinene in cajeput oil, niaouli oil 
contains d-pinene of which a dextrogyrate solid monohydrochloride 
CioHiqHCl was obtained. Cineol is the principal constituent (about 
66 p. c.), and is accompanied by a laevogyrate compound of the same 
boiling point (1-limonene?). Crystallized • terpineol, CioHisO, and its 
valerianic acid ester are present to the extent of about 30 p. c.; there 
are also present traces of acetic and butyric acid esters.7 Bertrand 
separated by means of bisulphite two aldehydes from the oil, of which 
the one had the odor of valeric aldehyde, the other that of bitter 
1) Berich^e, 7, p. 598; Pharm. Journ., Ill, 5, p. 234. 
2) Liebig's Annalen, 225, p. 315. 
3) Liebig's Annalen, 246, p. 276. 
•t) Bericht von S. & Co., Apr. 1892, p. 7. 
5) Compt. rend., 106, p. 1538; Bull. Soc. chim., II, 50, p. 108; Journ. de Pharm., 
V, 18, p. 149. 
6) Bertrand, Bull. Soe. chim., Ill, 9, p. 432; Compt. rend., 116, p. 1070. - Voiry, 
Contribution h i'^tude chimique des huiles essentielles de quelques Myrtac^es. Th&se de 
1'Ecole de Pharmacie de Paris 1888. 
7) Bericht von S. & Co., Apr. 1892, p. 44. Oils of the Myrtaceae. 
523 
almond oil and boiled at 180° (benzaldehyde?). The unpleasant odor 
of the crude oil is due to sulphur compounds. 
240. Oil of Melaleuca Acuminata F. v. Mull. 
Colorless oil, with an odor reminding slightly of juniper berries. 
Sp. gr. 0.892; «D = -15° 20'. It contains much cineol.1 
241. Oil of Melaleuca Decussata R. Br. 
Distillate of the branches and leaves. Yield 0.037 p. c.; sp. gr. 
0.938; b. p. 185-209°. Odor and taste are very similar to cajeput 
oil (Maiden2). 
242. Oil of Melaleuca Ericifolia Sm. 
The leaves yield 0.033 p. c. of oil which is also similar to cajeput 
oil. Sp. gr. 0.899-0.902. It boils between 149 and 184°2 and is 
dextrogyrate.4 
243. Oil of Melaleuca Genistifolia Sm. 
From the leaves and twigs 0.062 p. c. of oil are obtained. It is 
yellowish-green in color, and has a mild odor and taste.3 
244. Oil of Melaleuca Leucadendron var. Eancifolia. 
Sp. gn 0.955; «d = - 3° 38'. It consists principally of cineol.1 
245. Oil of Melaleuca Linariifolia Sm. 
Fresh leaves give a yield of 0.17 p. c. of oil which is of a pleasant 
cajeput-like odor, and has first a mace-like, later a minty taste.6 It is 
dextrogyrate,4 has the sp. gr. 0.898-0.903 and boils from 175-187°. 
246. Oil of Melaleuca Squarrosa Sm. 
Yield 0.002 p. c. The oil is green and has an unpleasant taste.6 
247. Oil of Melaleuca Uncinata R. Br. 
Sp. gr. 0.925; aD = 4-l°40'. The principal part boils between 175 
and 180°. The lower boiling fraction has a decided spike- or rosemary- 
1) Bericht von S. & Co., Apr. 1892, p. 44. 
2) The useful native plants of Australia, p. 275. 
3) Ibidem, p. 276. 
*) Journ. Chem. Soc., 25, p. 1; Pharm. Journ., Ill, 2, p. 746; Jahresb. f. Chemie. 
1872, p. 815. 
5) Bericht von S. & Co., Apr. 1892, p. 44. 
6) Useful native plants, etc., p. 279. 524 
Special Part. 
like odor. The second fraction smells strongly of cineol which is the 
main constituent of the oil. The highest boiling portions consist 
probably of terpineol.1 
248. Oil of Melaleuca Wilsonii F. v. Miill. 
The leaves yield 0.024 p. c. of an oil similar to cajeput, of the 
sp. gr. 0.925.2 
EUCALYPTUS OILS. 
History. The oil of Eucalyptus piperita Sm., is the oldest oil of 
eucalyptus leaves, being mentioned as early as 1790.3 In 1853 the 
botanist Ferdinand von Muller recommended to the Province of Victoria 
the distillation of the leaves of the eucalyptus species.4 Bosisto,5 who 
had distilled experimentally the dried leaves in London, established in 
1854 the first factory in Australia,6 and is, therefore, to be considered 
as the founder of this extensive industry. 
Australian eucalyptus oil came into the German market about 18GG 
without any botanical reference as to its source. It probably was 
principally the distillate from Eucalyptus amygdalina. 
Eucalyptus globulus was discovered in Tasmania in 1792 by Labil- 
lardiere and introduced into Europe in 1856 by Ramel. The oil of 
this species was obtained on a large scale, first in southern France, 
Algiers and California, and is a staple article of commerce only since 
the early eighties. 
Production. The Australian eucalyptus oil industry soon spread 
from Victoria to South Australia, then to Tasmania and Queensland. 
The principal places of production are in Victoria, Melbourne and 
vicinity, the shores of Lake Hindmarsh and Bendigo; in South Australia, 
Adelaide and Kangaroo Island; in Queensland, Brisbane, Gladstone, 
Rockhampton, Inghamstown and Wallaroo; on Tasmania, Hobart. 
In Australia the leaves of the various species used for distillation 
are not kept separate with the required care, so that the designations 
of botanical sources are sometimes unreliable. 
According to a report by Maiden7 the so-called bulk oil is obtained 
1) Bericht von S. & Co., Apr. 1892, p. 44. 
2) Useful native plants, etc., p. 280. 
3) Journal of a Voyage to New South Wales by John White, Surgeon-General to 
the Settlement, published 1790. 
*) Eucalyptographia, Melbourne, 1879; Select Extra-Tropical Plants. 9th ed., p. 184. 
5) Transact. Royal Soc. Victoria, 1861-64. 
«) Bericht von S. & Co., Oct. 1886, p. 13. 
7) Bericht von S. & Co., Apr. 1893, p. 27. Oils ot the Myrtaceae. 
525 
in Bendigo (Victoria), where five firms are engaged in the distillation 
of eucalyptus oil, from a mixture of the leaves of Eucalyptus sideroxylon 
with those of E. leucoxylon, E. melliodora, E. polyanthema and others, 
while for the preparation of the finer qualities, the leaves of E. sideroxylon 
are exclusively used. The leaves stripped from the felled trees are usually 
packed into bags by common laborers and transported by them. It is 
readily seen that with such a system of collection the bags might often 
contain mixed leaves, and this is also the reason why the quality of 
the resulting eucalyptus oil often varies so widely. 
The distillation is performed in Australia1 by passing steam through 
the stills2 filled with the leaves without the addition of water. 
The crude oil from the leaves of Eucalyptus cneorifolia, E. gonio- 
calyx and E. incrassata is of a dark color, that of E. odorata is bright 
yellow. For purification the oil is treated with sodium hydrate solution, 
which removes the irritating aldehydes and saponifiable bodies, and is 
then rectified. The removal of the readily volatilized aldehyde is, how- 
ever, only partially accomplished by this method. The resulting distil- 
late is the ordinary eucalyptus oil of commerce. Ten percent of the 
original oil remain in the still and form with the sodium hydrate a 
kind of soap, of a deep dark brown color and syrupy consistency. This 
distillation residue is used under the name of eucalyptus tar or resin oil 
as a cheap'disinfecting agent or for perfuming common soaps. Frequently, 
however, it is discarded altogether. 
The California eucalyptus oil from E. globulus was for a time 
obtained in considerable quantities as a side product in the manu- 
facture of an anti boiler deposit remedy in Alameda County near San 
Francisco Bay. This oil no longer occurs in the European market. 
The closest competitor of the Australian globulus oil is Algiers, 
where considerable amounts are produced. In southern France and also 
in Spain some eucalyptus oil is obtained. What part the oil recently 
distilled in Portugal3 will play in the markets of the world cannot yet 
be estimated. The oil (E. globulus) prepared in India in the Nilgiri 
mountains is exclusively consumed there and not exported.4 
The eucalyptus oils can, according to their constituents or their 
odor, be divided into 5 groups. 
i) Pharin. Journ,, III, 25, p. 501. 
2) These distilling apparatus are often constructed of wood, and have a capacity 
up to 20,000 liters. They are capable of distilling 47 tons of leaves per week. (Bericht 
von S. & Co., Oct. 1886, p. 13). 
3) Bericht von S. & Co., Oct. 1897, p. 24. 
*) Bericht von S. & Co., Apr. 1891, p. 18. 526 
Special Part. 
First Group: Cineol- (Eucalyptol-) containing Oils. 
This group includes primarily all those eucalyptus oils which are of 
■commercial interest. Among these the oil from E. globulus is the most 
important on account of its high content of cineol. The oils from 
E. odorata, E. oleosa, E. cneorifolia and E. dumosa which are likewise 
prepared in larger quantities are to be considered as substitutes for the 
globulus oil, which they resemble in their properties. 
249. Oil of Eucalyptus Globulus. 
Origin. Of all the eucalyptus species that of Eucalyptus globulus 
Labillardiere is the best known and the most highly valued outside of 
Australia. On account of its rapid growth and the enormous water 
evaporation connected therewith, the tree has been planted with success 
in marshy districts. The beneficial influence which its cultivation exerts 
in malarial districts, is in all probability principally due to the drying- 
up of the marshes and less to the balsamic exhalation produced by the 
oil in the leaves. 
The tree known in Australia as the blue gum-tree of Victoria and 
Tasmania requires for its growth about the same climate as the oranges. 
Its excellent properties are the cause of its cultivation in all parts of 
the world. It is found in Algiers, southern France, Italy, Spain and 
Portugal, in California, Florida, Mexico, on Jamaica, in Transvaal and 
Pretoria, in India and many other places. 
According to F. von Midler the fresh leaves yield 0.71 p. c. of oil. 
Schimmel & Co. obtained a yield of 1.6-3 p. c. from the dried leaves. 
Properties. The oil of Eucalyptus globulus is a light yellow, 
mobile liquid, of a pleasant, refreshing cineol odor, and spicy cooling- 
taste. Aldehydes, (especially valeric aldehyde), make themselves unpleas- 
antly noticeable in the crude oil by their tendency to produce coughing. 
Well rectified oils do not possess this disagreeable property, or at least 
only to a very slight degree. Sp. gr. 0.910-0.930; «d = + 1 to + 15°. 
The more cineol (eucalyptol) the oil contains, the higher is its 
specific gravity and the lower its rotatory power. Oils containing much 
•eucalyptol solidify to a white crystalline mass when they are cooled in 
a freezing mixture of ice and salt. The oil gives a clear solution with 
3 parts of 70 p. c. alcohol. 
Composition. The first investigation of' eucalyptus oil was under- 
taken by Cloez1 in. 1870. He separated from the oil by fractional 
i) Compt. rend., 70, p. 687; Liebig's Annalen, 154, p. 372. Oils of the Myrtaceae. 
527 
distillation a body boiling at 175°, which he called eucalyptol. From 
the low specific gravity (0.905 instead of 0.930) as well as the optical 
activity of the fraction it can be seen that it was still contaminated 
with terpenes, on account of which the elementary analysis led Cloez 
to the incorrect formula C12H22O. 
A few years later, in 1874, Faust and Homeyer1 investigated a 
eucalyptus oil, the source of which is not mentioned by them. The fact 
that the fraction of this oil boiling at 171-174° contained no oxygen, 
shows that it could not have been the oil of Eucalytus globulus. 
The correct composition of eucalyptol as CioHisO was recognized 
by Jahns2 in 1884. He demonstrated its identity with cineol. He 
employed the method recommended shortly before by Wallach and 
Brass3 for the isolation and purification of cineol, by conducting hydro- 
chloric acid into the cineol fraction. For the properties of cineol com- 
pare p. 175. 
The hydrocarbon accompanying the cineol, and formerly called 
eucalyptene, is d-pinene. Wallach and Gildemeister4 obtained solid 
pinene monohydrochloride by conducting dry hydrochloric acid gas into 
the fraction boiling about 165°. A nitrosochloride was formed with 
amyl nitrite and hydrochloric acid, which on boiling with alcoholic 
potassa was converted into nitrosopinene (m. p. 129-130°), and by 
heating with piperidine into pinene nitrolpiperidine melting at 116°. 
According to a further observation it is probable that eucalyptus 
oil contains other terpenes besides pinene. Bouchardat and Tardy5 
obtained by the action of formic acid on the terpene fraction of the 
oil boiling at 156-157°, terpineol, isoborneol and fenchyl alcohol. The 
formation of the terpineol is explained by the presence of pinene, whereas 
the formation of isoborneol and fenchyl alcohol can probably be traced 
to the presence of camphene and fenchene. 
The unpleasant, penetrating and irritating odor of the crude 
eucalyptus oil is occasioned by different aldehydes, principally valeric 
aldehyde, besides butyric and capronic aldehydes.6 According to 
Bouchardat and Oliviero.7 there are found in the first fraction ethyl 
and amyl alcohols, and according to WTallach and Gildemeister8 fatty 
acids not definitely determined. 
i) Berichte, 7, p. 63. 
2> Berichte, 17, p. 2941; Arehiv d. 
Pharm., 223, p. 52. 
3) Liebig's Annalen, 225, p. 291. 
4) Liebig's Annalen, 246, p. 283. - Comp, 
also Voiry, Bull. Soc. chim., II, 50, p; 106. 
5) Coinpt. rend., 120, p. 1417. 
6) Bericht von S. & Co., Apr. 1888, 
p. 18. 
7) Bull. Soc. chim., Ill, 9, p. 429. 
8) Liebig's Annalen, 246, p. 283. 528 
Special Part. 
The fraction of the oil boiling- above 200° is laevog-yrate and on 
distillation splits off an acid (acetic acid?); it contains therefore an 
ester. After saponifying- there is obtained a laevogyrate alcohol 
("d - -17°) boiling- at 215-220° of the sp. gr. 0.96. This alcohol has 
not yet been investigated. 
Quantitative Determination of Cineol in Eucalyptus Oils. As 
the value of the eucalyptus oils of this group depends entirely on the 
amount of cineol present, the quantitative determination of this body 
is of importance. It is to be regretted that control experiments for the 
following three methods mostly employed have not been made on 
mixtures of known cineol content, so that at present nothing can be 
said as to the degree of accuracy of these methods. As the results of 
the different methods of determination do not agree, they are only of 
value when, in stating the cineol content, the method is mentioned by 
which the latter was determined. The distillation method as well as the 
phosphoric acid method described in the following are only applicable 
to oils rich in cineol, while the hydrobromic acid method yields results 
even when the cineol is present in smaller amounts. 
I. The Hydrobromic Acid Method. Dry hydrobromic acid is conducted 
into the well cooled solution of the eucalyptus oil in an equal or greater 
volume of petroleum ether as long as a precipitate is formed. The hydro- 
bromide of cineol formed is rapidly filtered off with a suction pump and washed 
with cold petroleum ether. Hydrobromic acid is again conducted into the 
filtrate in case a further precipitation takes place. The total hydrobromide of 
cineol after being dried in a vacuum is decomposed with water, transferred to 
a burette and the amount of cineol read off on the scale. By multiplying the 
number of cubic centimeters found by 0.93 (the sp. gr. of the cineol) the weight 
of the cineol separated from a certain amount of oil is obtained. 
II. The Distillation Method.1 The oil to be investigated is fractionated, 
and the fractions collected at intervals of 2 degrees, are placed in a freezing- 
mixture and cooled to -15 to -18°. Crystallization is then induced by shaking 
or by bringing into contact with a crystal of cineol. The portion remaining 
liquid after standing for one hour in the freezing mixture is removed with a 
finely pointed pipette. With a little experience an almost dry mass of crystals 
is obtained from which the last traces of liquid can be removed by a repeated 
shaking together of the crystals. The melted cineol of all fractions is collected 
and weighed. 
As a certain amount of the cineol remains dissolved in the terpene, it is 
of course evident, that not all of the compound can be separated in this 
manner. This method is, therefore, only applicable, when it is desired to know 
which one of a number of oils is richest in cineol. 
D Helbing's Pharmacological Record, VIII, 1892. Oils of the Myrtaceae. 
529 
III. The Phosphoric Acid Method. This depends on the property of phos- 
phoric acid to combine with cineol to form a compound analogous to the 
addition products of hydrobromic and hydrochloric acids. According to 
Helbing and Passmore1 the method is as follows: 
Concentrated phosphoric acid (sp. gr. 1.75) is added drop by drop with 
constant stirring to 10 g. of eucalyptus oil in a beaker. During this operation 
the beaker must be kept cold with water, and care must be taken that the 
contents do not warm up. By the careful addition of the phosphoric acid 
scarcely a yellow or reddish color is developed. The reaction is complete as 
soon as a drop of the acid produces a dark red coloration of the mass. 
The crystalline mass formed is sharply pressed between filter paper, for 
which purpose an ordinary copying press may be used. The pressing is repeated 
with fresh filter paper until no grease spots are visible on the latter. The 
crystals are then weighed in a beaker and by multiplying by 6.11 the percent 
of the cineol is obtained. 
The factor 6.11 is gotten from the following equation, based on the as- 
sumption as yet unproven, that the double compound is an addition product of 
1 mol. each of phosphoric*acid and of cineol. 
CioHisO + H3PO4 = CioHisOHaPOi. 
The results obtained by the phosphoric acid method are about X 
higher than those obtained by the freezing method, but are still con- 
siderably from the true value. Kebler2 obtained with pure cineol only 
62.14 p. c. instead of 100. He, therefore, recommends the following 
modification of the method. 
4 cc. Of phosphoric acid (1.75) are added to 8 g. of oil contained in a 
beaker cooled with ice water. It is then slowly but thoroughly stirred and the 
cineol phosphate expressed, decomposed with hot water and the acid titrated 
with normal alkali. In this manner Kebler found for pure cineol, instead of 
100, 103.75 p. c. 
Experiments with mixtures of known cineol content were not ma.de, 
and there is, therefore, no basis for judging the applicability of the 
method to eucalyptus oils. When it is considered how difficult it is to 
remove quantitatively the excess of the viscid phosphoric acid, no con- 
fidence can be extended even to this modification of the phosphoric 
acid method. 
Allen3 has recently tested the method by making mixtures of pure 
eucalyptol with the eucalyptol-free constituents of a globulus oil. In oil 
containing more than 50 p. c. the experimental result differed from the 
theoretical by at most 1^ p. c. With a content of from 20 to 50 p. c. 
the highest difference was only 2^ p. c. With oils containing less than 
20 p. c. the method was found to be inapplicable. 
i) Helbing's Pharmacological Record, 
XXIV, 1893. 
2) Am. Journ. Pharm., 70, p. 492. 
3) Chemist & Druggist, 54, p. 641. 530 
Special Part. 
Eucalyptus odorata Behr, is a tree indigenous to South Australia, 
Victoria and New South Wales. The yield of oil from fresh leaves 
amounts to 1.4 p. c. The light yellow oil has an aromatic camphor-like 
taste and smells after cineol and Roman caraway oil. Sp. gr. 0.899 to 
0.925; slightly laevogyrate. It boils from 157-199° (Maiden1) and is 
often so rich in cineol (identified by the hydrobromic acid compound) 
that it solidifies in a freezing mixture without being fractionated. 
From the rectification residue a considerable amount of cuminic alde- 
hyde was separated by means of its bisulphite compound. It was 
identified by oxidation to cuminic acid.2 
351. Oil of Eucalyptus Cneorifolia. 
The oil of this bush-like eucalyptus species, growing on Kangaroo 
island in South Australia has only lately appeared in the market. Its 
accompanying odor reminds of dill and caraway. Sp. gr. 0.899-0.923; 
[a]D = - 4 to -14° (Wilkinson3). 
A firm in Adelaide, which had introduced the oil into the market, 
at first designated it as coming from Eucalyptus oleosa. This is due 
to the fact that E. cneorifolia is now considered as a separate species, 
whereas it was formerly considered as a variety of E. oleosa.4 
252. Oil of Eucalyptus Oleosa. 
Eucalyptus oleosa F. v. Mull, likewise belongs to the bush-like 
eucalyptus species. The yield of oil is 1.25 p. c.;1 sp. gr. 0.906-0.926 ; 
[a]D=d-4 to 5°.3 It contains cineol and cuminic aldehyde. 
253. Oil of Eucalyptus Dumosa. 
Eucalyptus dumosa5 is found in northern Victoria, in southern New 
South Wales and in South Australia. Yield about 1 p. c.; sp. gr. 0.884 
to 0.915 ; «d - + 0° 6' to + 6° 30'. It contains large amounts of cineol.6 
254. Oil of Eucalyptus Amygdalina. 
Origin. The tree, known in south-eastern Australia as white and 
brown peppermint tree, Eucalyptus amygdalina Labill., is one of the 
250. Oil of Eucalyptus Odorata. 
1) The useful native plants of Australia, p. 272. 
2) Bericht von S. & Co., Apr. 1889, p 19. 
3) Proc. Royal Soc. of Victoria, 1893, p. 195. 
*) Bericht von S. & Co., Apr. 1892, p. 44. 
5) The useful native plants of Australia, p. 267. 
6) Bericht von S. & Co.. Oct. 1889, p. 26. Oils of the Myrtaceae. 
531 
tallest of the eucalyptus species. According to F. von Muller it reaches 
a height of over -400 feet. Its leaves contain more oil than any other 
species, yielding on distillation over 3 p. c. of oil. Formerly it came 
in great quantities into the market, but it has recently been replaced 
more and more by the oils richer in cineol. 
According to Baker & Smith1 the commercial oil of Eucalytus 
amygdalina Labill. is not obtained from this species but from E. amyg- 
dalina var. latifolia Maiden et Deane. The true oil of E. amygdalina 
Labill. contains according to Baker and Smith, when the leaves are 
distilled at the proper time, about 45 p. c. of cineol. 
Properties. The oil is light yellow or colorless. Its cineol odor is 
almost masked by the terpene odor; sp. gr. 0.850-0.886; «d =- 25 
to -70°. The higher the specific gravity and the lower the rotation, the 
more cineol and less phellandrene does the oil contain. The phellandrene 
reaction mentioned below is characteristic for the oil. It is much less 
soluble in alcohol than oil of Eucalyptus globulus. As a rule more than 
6 parts of 90 p. c. alcohol are necessary for solution, which in most 
cases is not even perfect. 
Composition. According to Wallach and Gildemeister2 the oil of 
Eucalyptus amygdalina consists principally of phellandrene. 
If the oil diluted with twice its volume of petroleum ether be treated with 
a concentrated aqueous solution of sodium nitrite, and then acetic acid be 
added in small portions, the quantities of phellandrene nitrite formed are so 
large, that often the entire liquid solidifies to a pasty mass. 
It may be interesting to note that the phellandrene is laevogyrate 
and that this optical modification was found for the first time during 
the investigation of this oil. 
Cineol is present only in small quantities in the amygdalina oil. 
Its presence cannot be shown by the hydrochloric acid reaction; on the 
other hand, its hydrobromic acid addition product can be readily 
obtained from the petroleum ether solution of the oil.2 
255. Oil of Eucalyptus Rostrata. 
Eucalyptus rostrata Schlechtd., indigenous to Australia and there 
distributed from South Australia to northern Queensland, is much 
cultivated in southern France as well as in Algiers, where the tree is 
said to be better able to withstand the heat than E. globulus. The 
1) Chemist and Druggist, 54, p. 864. 
2) Liebig's Annalen, 246, p. 278. 532 
Special Part. 
yield of oil from fresh leaves amounts to only 0.1 p. c.1 The oil is 
yellowish in color and reminds in odor of the oil of E. odorata. 
Sp. gr. 0.912-0.925; «D = -l°8'to + 13°.2 
It is soluble in 2 parts of 70 p. c. alcohol, boils according to Witt- 
stein and Muller from 137°(?)-181° and contains valeric aldehyde and 
large quantities of cineol,3 but no phellandrene.0 
256. Oil of Eucalyptus Populifera. 
Eucalyptus populifera Hook, is distributed over New South Wales, 
Queensland and North Australia. 
The bright red oil smells of cajeput.1 Lt contains besides cuminic 
aldehyde a fair amount of cineol.4 
257. Oil of Eucalyptus Corymbosa. 
Eucalyptus corymbosa Sm. is found in the coast districts of New 
South Wales and in northern Queensland. 
According to Wittstein and Muller the oil smells slightly of lemon 
and rose (?) and has a bitter, somewhat camphor-like taste.5 Sp. gr. 
0.881. According to Schimmel & Co. it contains much cineol.4 
258. Oil of Eucalyptus Resinifera. 
Eucalyptus resinifera Sm. grows in New South Wales and Queens- 
land. According to Gladstone0 the oil consists principally of a hydro- 
carbon smelling of turpentine oil; Schimmel & Co., however, found in it 
much cineol. An oil, coming from Portugal, and probably obtained 
from E. resinifera, had the sp. gr. 0.893, and the rotatory power 
ud~ -17° 8'. It was not soluble in 70 and 80 p. c. alcohol and con- 
tained besides cineol (iodol reaction) also phellandrene.7 
259. Oil of Eucalyptus Baileyana. 
Eucalyptus Baileyana F. v. Miill. occurs in the neighborhood of 
Brisbane in Queensland. The fresh leaves yield on distillation 0.9 p. c.5 
of oil of the sp. gr. 0.940. It boils from 160-185° and contains about 
30 p. c. of cineol.8 
1) Maiden, The useful native plants of Australia, p. 273. 
2) Wilkinson, Proc. Roy. Soc. of Victoria, 1893, pp. 197, 198. 
3) Bericht von S. & Co., Oct. 1891, p. 40. 
4) Bericht von S. & Co., Apr. 1893, p. 28. 
5) Maiden, loo. cit., p. 266. 
6) Journ. Chem. Soc., 17, p. 1; Jahresb. f. Chemie, 1863, p. 541 
i) Bericht von S. & Co., Oct. 1898, p. 26. 
s) Bericht von S. & Co., Apr. 1888, p. 19. Oils ot the Myrtacepe. 
533 
Eucalyptus microcorys F. v. Miill. is distributed in the northern 
coast districts of New South Wales to Cleveland Bay (Queensland). 
Yield from the fresh leaves 1-2 p. c., sp. gr. 0.896-0.935. The oil boils 
from 160-200° and contains besides terpenes about 30 p. c. of cineol.1 
261. Oil of Eucalyptus Risdonia.2 
Under this name a pleasant and mild smelling eucalyptus oil was 
introduced in 187-1 in London. Sp.gr. 0.915-0.916; «d - - 4°49'. It 
contained cineol and phellandrene.3 
262. Oil of Eucalyptus Leucoxylon. 
Eucalyptus leucoxylon F. v. Miill. (F sideroxylon A. Gunn.) grows 
in South Australia, Victoria, New South IVales and in southern Queens- 
land. Bosisto4 reports about 1 p. c. of oil, but remarks that the leaves 
used for its preparation had lost a part of their oil through heating. 
Odor and taste are said to be similar to those of the oil from E. oleosa. 
Sp. gr. 0.915-0.927; [«]d= + U5° to +2.7°.5 
263. Oil of Eucalyptus Hemiphloia. 
Eucalyptus hemiphloia F. v. Miill. is common in eastern South 
Australia. Victoria. New South Wales, and in southern Queensland. The 
reddish-brown oil contains cineol and large amounts of cuminic aldehyde.6 
264. Oil of Eucalyptus Crebra. 
Eucalyptus crebra. F. v. Miill. (Iron Bark) is indigenous to the coast 
districts of Queensland and New South Wales. The oil is light yellow, 
very similar in its odor to the oil of E. globulus, and like this is rich 
in cineol.7 
265. Oil of Eucalyptus Macrorrhyncha. 
The oil of the leaves of Eucalyptus macrorrhyncha F. v. Miill. a 
tree known in New South Wales as red stringybark8 has been investi- 
gated by Baker and Smith.9 
260. Oil of Eucalyptus Microcorys. 
i) Bericht von S. & Co., Apr. 1888, p. 19. 
2) According to Maiden Eucalyptus risdoni Hook, is identical with E. amygdalina 
Labill. or at least closely related. 
3) Bericht von S. & Co , Apr. 1894, p. 2'.). 
*) Maiden, The useful native plants etc., p. 270. 
5) Wilkinson, Proc. Roy. Soc. of Victoria. 1893, p. 198. 
6) Bericht von S. & Co., Apr. 1892, p. 28. 
7) Bericht von S. & Co., Apr. 1893, p. 28. 
s) In Australia the following species ol^Eucalyptus are designated as stringybark : 
E. obliqa Herit., E. baileyana F. v. Miill., E. macrorrhyncha F. v. Mull., E. capitellata 
Sm„ E. eugenioides Sieb , and E. fastigata Deane et Maiden. 
9) Journ. and Proc, of the Royal Soc. of N S. Wales, 32, p. 104. 534 
Special Part. 
They obtained by distillation a yield of 0.28-0.31 p. c. of oil. The 
oil is reddish-brown, has the sp. gr. 0.924-0.927 at 22°, and begins to 
boil at 172°. It contains a trace of phellandrene, cineol, and the 
■crystallized eudesmol1 described under oil of E. piperita on p. 538. 
266. Oil of Eucalyptus Capitellata. 
Baker and Smith2 suggest the name of brown stringybark for 
Eucalyptus capitellata Smith. 
The leaves yield on distillation only 0.1 p. c. of a dark red oil of 
the sp. gr. 0.9153 at 18°. It contains cineol and a trace of phellandrene. 
267. Oil of Eucalyptus Eugenioides. 
Eucalyptus eugenioides Sieb. is known in Australia as white stringy- 
bark. Baker and Smith2 obtained from the leaves 0.68-0.79 p. c. of 
oil. The sp. gr. of the oils of two distillations was 0.907 and 0.908; 
[«]d= + 3.7 and +5.2°. The oil contains cineol, but no phellandrene. 
268. Oil of Eucalyptus Obliqua. 
Eucalyptus obliqua Herit. is found in the southern coast districts 
of New South Wales, principally, however, in Tasmania, Victoria and 
South Australia. Yield 0.5 p. c. A reddish-yellow oil of mild odor and 
bitter taste; sp. gr. 0.899. It boils from 171-195°.3 
An oil obtained in Portugal had the sp. gr. 0.914 and the rotatory 
power «d =- 7° 28'. It was soluble in an equal part of 80 p. c. alcohol 
and contained cineol (iodol reaction) and phellandrene4 (nitrite). 
269. Oil of Eucalyptus Punctata. 
The tree from which the oil was obtained, Eucalyptus punctata I). C. 
(E. tereticornis Sm. var. brachy coris), is called grey gum in Australia, 
and yields besides kino a useful hard wood. It is found in the coast 
districts of New South Wales, of Queensland as far as the border of 
Victoria. 
For the preparation of the oil, the leaves and twigs were used. 
Altogether nine distillations were made of material collected in different 
districts. The yield varied between 0.63 and 1.19 p. c. The sp. gr. 
was between 0.9122 and 0.9205 at 17°. Two oils were laevogyrate 
i) Journ. and Proc, of the Roy. Soc. of N. S. Wales, 33, p. 86; Bericht von S. & Co., 
Apr. 1900, p. 24. 
2) Journ. and Proc, of the Royal Soc. of N. S. Wales, 32, p. 104. 
») Maiden, The useful native plants etc., p. 272. 
*) Bericht von S. & Co., Oct. 1898, p. 27. Oils of the Myrtaceae. 
535 
([«]d - 0.92° and - 2.52°), the other seven were dextrogyrate ([a] d + 0.54° 
to 4.44°). A sample mixture of all the distillates had the following- 
properties: sp. gr. 0.915 at 16°, [^]d = + 0.927°. According to the 
phosphoric acid method the cineol content of the oil was from 46.4-64.5 
p. c. No phellandrene is present in the oil of E. punctata.1 
270. Oil of Eucalyptus Loxophleba. 
Eucalyptus loxophleba Benth.2 is called by the people York gum, 
on account of its frequent occurrence in the vicinity of the city of York. 
The oil has a highly unpleasant odor, and produces fits of coughing 
when inhaled. Sp. gr. 0.8828 at 15.5°; angle of rotation about + 5°. 
Upon distillation the following fractions were obtained: 168-171° 
68 p. c.; 171-176° 14 p. c.; 176-182° 2 p. c.; 182-187° 8 p. c.; 
residue 8 p. c. 
The oil contains phellandrene and cineol. The amount of the latter 
is estimated at 15-20 p. c. On shaking with bisulphite the oil diminished 
in volume 20 p. c., which allows oi concluding that a considerable 
amount of aldehydes and ketones is present. Amyl alcohol, of which 
small quantities were found in the oil-of E. globulus, and to which, no 
doubt, are partly due the irritating action of this oil, is not present. 
r 271. Oil of Eucalyptus Dextropinea. 
The oil of Eucalyptus dextropinea Baker3 has been prepared by 
Baker and Smith,4 as has also the oil of E. laevopinea Baker, from the 
fresh leaves of these trees. Both are indigenous to New South Wales. 
The yield was in one case 0.825, in another 0.850 p. c. The deep red 
colored and strongly dextrogyrate oil has the sp. gr. 0.8743-0.8763 
at 17°. By distillation the following fractions were obtained: 156-162° 
62 p. c.; 162-172° 25 p. c. 
The oil consists almost entirely of d-pinene.4 The main fraction, 
finally boiling at 156-157° had the sp. gr. 0.8629; [«]d = +41.2° 
at 18°. 
i) On "Grey Gum" {Eucalyptus punctata D. Cj, particularly in regard to its 
essential oil, by R. T. Baker F. L. S and H. G. Smith F. C. S , Technological Museum, 
Sydney. Journ. and Proc, of the Royal Society of N. S. Wales, 31, p. 259; Bericht 
von S. & Co., Oct. 1898, p. 27. 
2) Pharm. Journ., 61, p. 198. This article by Parry gives the species name 
as toxophleba. 
3) The two new species Eucalyptus dextropinea and E. laevopinea have been 
described by Baker in Proc, of the Linnean Soc. of New South Wales, 27, p. 414. 
4) Journ. and Proc, of the Royal Soc. of N. S. Wales, 32, p 195. 536 
Special Part. 
For the identification of the pinene the following derivatives were 
prepared: pinene nitrosochloride (in. p. 103°) and from this nitroso- 
pinene (m. p. 128-129°), further terpin hydrate, as well as pinene 
monohydrochloride (m. p. 121-124°). 
Besides pinene the oil contains small amounts of cineol, which was 
recognized by the behavior of the higher boiling fractions toward iodol 
and bromine. 
272. Oil of Eucalyptus Laevopinea. 
From the fresh leaves of Eucalyptus laevopinea Ba^er,1 silver top 
stringybark, Baker and Smith2 obtained 0.66 p. c. of a reddish oil 
having the sp. gr. 0.8732. The following fractions were collected: 
157-164° 60 p. c.; 164-172° 28 p. c. Just as the foregoing oil con- 
sisted almost entirely of d-pinene, this oil consists almost entirely of 
1-pinene. The fraction boiling at 157-158°, which can probably be 
considered as fairly pure pinene, had the sp. gr. 0.8626 at and 
[«]d =- 48.63°. The same derivatives of the pinene were prepared as 
with the foregoing oil. This oil likewise contains only small amounts 
of cineol. 
273. Oil of Eucalyptus Smithii. 
The leaves of Eucalyptus smithii yield on an average 1.353 p. c. of 
oil which contains over 70 p. c. of cineol.4 The oil contains d-pinene, 
but no phellandrene. The eudesmol, described under the oil of Euca- 
lyptus piperita on p. 538 has also been found in this oil.5 
Second Group: Citronellal-contaiiiing Oils. 
274. Oil of Eucalyptus Maculata. 
The spotted gum-tree, Eucalyptus maculata. closely related to 
E. citriodora Hook., grows in New South Wales and Queensland, but 
has also been transplanted to Ceylon and Algiers. The oil, of citronellal- 
like odor,0 has the sp. gr. 0.900, boils from 210-220° and cannot be 
distinguished from the following oil. 
i) See footnote 3 on p. 535. 
2) See footnote 4 on p. 535. 
3) According to Smith almost all of the oils obtained from species closely related to 
E. globulus contain pinene, such as the oils from E. bridgesiana, E. gonioealyx, etc. 
*) Proc, of the Linnean Soc of N. S. Wales, 1899, II. p. 292; Bericht von S. & Co., 
Apr. 1900, p. 24. 
5) Journ. and Proc, of the Roy. Soc. of N. S. Wales, 33, p. 86; Bericht von S& Co., 
Apr. 1900, p. 24. 
6) Bericht von S. & Co., Apr. 1888, p. 19. Oils of the Myrtaceae. 
537 
275. Oil of Eucalyptus Citriodora. 
Eucalyptus citriodora Hook, is probably only a variety of E. macu- 
lata Hook, and is for this reason sometimes designated as E. maculata 
Hook. var. citriodora. The tree grows best in stony ground. It is 
indigenous to Queensland and has also been planted with success in 
India, in Zanzibar and on the Magdalene River.1 The leaves are distilled 
in Gladstone (Queensland) and give in the fresh state 1-1.5 p. c., in 
the dried state 3-1 p. c. of oil. 
The oil, distinguished through its pleasant citronellal-like odor, is 
much used as a perfume for soap. Sp. gr. 0.870-0.905. It is inactive 
or slightly dextrogyrate («d up to +2°) and is soluble in 4 to 5 parts 
of 70 p. c. alcohol. 
It consists to the extent of 80-90 p. c. of citronellal, CioHisO. 
The remainder of the oil. judging from the odor, consists of geraniol 
and citronellol. Cineol is not contained in it.2 
276. Oil of Eucalyptus Dealbata. 
Eucalyptus dealbata A. Cunn. (E. viminalis Labill.3) grows in Tas- 
mania, South Australia, Victoria and New South Wales. The oil has 
an exceedingly fine, melissa-like odor, due to citronellal. Besides this 
there is present another body of pleasant odor, reminding of geranium 
(geraniol?). ^The oil boils from 206-216° and has the sp. gr. 0.871- 
0.885.4 
An oil of E. viminalis (no author) described by Wittstein and Midler 
is so different from that just given, that it is impossible that it should 
have come from the same plant. The odor was unpleasant ; it had the 
sp. gr. 0.921 and boiled between 159 and 182°, that is, at a tem- 
perature at which the oil of E. dealbata had not begun to boil.5 
277. Oil of Eucalyptus Planchoniana. 
The fresh leaves of the tree, Eucalyptus planchoniana F. v. Mull., 
occurring in northern New South Wales and in southern Queensland, 
yield according to Staiger6 only 0.06 p. c. of volatile oil. It has a 
peculiar, citronella-like odor and the sp. gr. 0.915. 
i) v. Muller, Select Extra-Tropical Plants, 9th ed., p. 187. 
2) Bericht von S. & Co., Apr. 1888. p. 20; Oct. 1890, pp. 1(5 and 20; Apr. 1891, 
p, 19; Apr. 1893, p. 27; Oct. 1893, p. 17. 
3) Maiden, The useful native plants etc., p. 527. 
4) Bericht von S. & Co., Apr. 1888, p. 19. 
5) Maiden, loc. cit., p. 274. 
6) Maiden, loc. cit., p. 273. 538 
Special Part. 
Third Group: Citral-containing Oils. 
278. Oil of Eucalyptus Staigeriana. 
Eucalyptus staigeriana F. v. Mull, grows in northern Queensland. 
Its leaves yield upon distillation 2.75-3.36 p. c. of an oil, smelling 
pleasantly like lemon and verbena. It has the sp. gr. 0.880-0.901 and 
boils from 170-230°. The lemon-like odor is due to citral, which 
besides terpenes forms the principal constituent of the oil.1 
279. Oil of Backhousia Citriodora. 
.Backhousia citriodora F. v. Mull. is indigenous to southern Queens- 
land. The leaves yield 1 p. c. of volatile oil, which in odor and proper- 
ties is similar to the foregoing one, and appears to consist almost 
entirely of citral. Sp. gr. 0.900; boiling temperature 223-233.2 
Fourth Group: Oils with a Peppermint-like Odor. 
280. Oil of Eucalyptus Haemastoma. 
Eucalyptus haemastoma Sm. is distributed from Illawarra (New 
South Wales) to Wide Bay (Queensland). From the fresh leaves 1.8- 
1.9 p. e. of oil are obtained. It has a peppermint-like odor, but at the 
same time reminds of geranium and cumin. Sp. gr. 0.880-0.890; 
boiling temperature 170-250°. It contains cineol, terpenes and 
probably also cumin aldehyde and menthone.1 
281. Oil of Eucalyptus Piperita. 
The oil from the leaves of Eucalyptus piperita Sm. was already 
known in 1788. It is mentioned on page 266 of White's "'Journal of a 
Voyage to New South Wales." The name pepperm|nt-tree3 was given to 
this plant, on account of the great similarity of the oil of its leaves 
with that of peppermint (Mentha piperita), which grows in England. 
The oil has recently been prepared and investigated by Baker and 
Smith.4 The leaves and twigs yielded on distillation 0.78 p. c. of oil. 
It has a light color and a decided peppermint-like odor, which, however, 
becomes fainter even after several weeks. Sp. gr. 0.909 at 17°; 
[a]D = - 2.97°. It boils between 170 and 272°. In the lower boiling 
1) Berieht von S. & Co., Apr. 1888, p. 20. 
2) Berieht von S. & Co., Apr. 1888, p. 20; Oct. 1888, p. 17. 
3) This tree is also designated Sydney peppermint in order to distinguish it from 
the white and brown peppermint tree, the E. amygdalins,. 
*) Journ. and Proc, of the Royal Soc. of N. S. Wales, 31, p. 195. Oils of the Myrtaceae. 
539 
fraction^ phellandrene and cineol were found. From the fractions boiling 
at 266-272° there separated a compound in well formed crystals, which 
was called eudesmol. Eudesmol boils at 270-272° and melts at 
74-75°. Eudesmol has lately been subjected to a more thorough study 
by Smith.1 It crystallizes in white milky needles melting at 79-80°. 
its analysis corresponds with the formula CioHioO, but contains neither 
an hydroxyl nor a ketone group. It yields a dinitro compound melting 
at 90° and a dibromide melting at 55-56°. 
Wilkinson2 found for an oil distilled from E. piperita the sp. gr. 
0.913 and [«]d= + 1.6°. 
Fifth Group: Oils Less Known and of Indefinite Odor. 
382. Oil of Eucalyptus Diversicolor. 
Eucalyptus di versicolor F. v. Mull, grows in south-western Australia, 
Ceylon and Algiers. The oil has the sp. gr. 0.924; [a]D= +9.7°.2 
283. Oil of Eucalyptus Fissilis. 
The oil from the leaves of Eucalyptus fissilis8 has the sp. gr. 0.928 
and is optically inactive.2 
284. Oil of Eucalyptus Goniocalyx. 
Eucalyptus goniocalyx F. v. Midi, is indigenous to Victoria and 
New South Wales. Yield from the leaves 0.9 p. c. The light yellow oil 
has a penetrating, quite unpleasant odor and obnoxious taste. Sp. gr. 
0.918-0.920; [a]D = - 4.30;2 boiling temperature 152-175°.4 
According to Smith1 the oil contains eudesmol. 
285. Oil of Eucalyptus Gracilis. 
The oil of Eucalyptus gracilis F. v. Mull., growing in Queensland, 
Victoria and south-western Australia, has the sp.gr. 0.909; [«]d = + 9.30.5 
286. Oil of Eucalyptus Lehmanni. 
Eucalyptus Lehmanni Preiss. occurs in south-western Australia. The 
oil obtained from it has the sp. gr. 0.923; [«]d - + 5.9°.2 
!) Journ. and Proc, of the Roy. Soc. of N. S. Wales, 33, p. 86; Bericht von S. & Co., 
Apr. 1900, p. 24. 
2) Proc, of the Royal Soc. of Victoria, 1893, p. 198. 
3) According' to Maiden, Eucalyptus fissilis F. v. Miill. is synonymous with E. amyg- 
dalina Labill., the oil of which is strongly laevogyrate. Its specific gravity also does 
not agree with that obtained by Wilkinson from E. iissilis. 
*) Maiden, The useful native plants etc., p. 268. 
5) Wilkinson, loc. cit., p. 197. 540 
Special Part. 
Eucalyptus longifolia Lk. is distributed in Victoria and in New 
South Wales as far as Port Jackson. The oil is viscid, has an aromatic 
cooling' taste and camphor-like odor. Sp. gr. 0.940; boiling temperature 
194-215° J 
288. Oil of Eucalyptus Occidentalis. 
The leaves of Eucalyptus occidentalis End! growing in south-western 
Australia give an oil of the sp. gr. 0.9236; [«]d = + 2.7°.2 
289. Oil of Eucalyptus Pauciflora. 
Eucalyptus pauciflora Sieb. is found in Tasmania, Victoria and 
New South Wales. The oil of the leaves has the sp. gr. 0.894-0.920; 
[«]d - 4-6 to -f-17°.2 
290. Oil of Eucalyptus Stuartiana. 
Eucalyptus stuartiana F. v. Mull., distributed from Tasmania to 
Queensland, contains a golden yellow oil, smelling strongly of cymene, 
but not of cineol.3 Sp. gr. 0.917-0.932; [a]D =- 7° to -16°.2 
291. Oil of Eucalyptus Tereticornis. 
Eucalyptu'i tereticornis Sm. or red gum is found in Victoria and 
Queensland, and contains a red oil, of a difficultly definable odor, 
reminding somewhat of zedoary root. It contains no cineol.3 
292. Oil of Eucalyptus Tessellaris. 
Eucalyptus tessellaris F. v. Mull. (E. viminalis Hook, f.), Morton 
bay ash, grows in South Australia, New South Wales to North Australia. 
The dark brown oil has an entirely distinct balsamic benzoin-like odor. 
It contains no cineol.3 
293. Oil of Eucalyptus Dawsoni. 
Eucalyptus dawsoni, called slaty gum. was recognized as a separate 
species by Baker.4 The yield of oil amounted to only 0.172 p. e. Its 
sp. gr. was 0.9414 at 15°. The oil contains no cineol, but much phel- 
landrene. Its principal constituent appears to be a sesquiterpene. 
287. Oil of Eucalyptus Longifolia. 
1) Maiden, The useful native plants etc., p. 270. 
2) Wilkinson, Proe. Roy. Soc. of Victoria, 1893, p. 198. 
3) Bericht von S. & Co., Apr. 1893, p. 28. 
4) Proc, of the Linnean Soc. of N. S. Wales, 1899, II, p. 292; Bericht von S. & 
Co., Apr. 1900, p. 24. Oils of the Umbelliferae. 
541 
294. Oil of Eucalyptus Camphora. 
The leaves of Eucalyptus camphora, known as sallow or swamp 
gum, give an average yield of 0.398 p. c. of oil. Sp. gr. 0.916. It 
contains pinene, cineol and much eudesmol.1 
295. Oil of Chervil. 
By the distillation of the fresh fruit of garden chervil, Anthriscus 
cerefolium Hoffm. (ChaerophyUum sativum Lam., Family Unibelliferae) 
Charobot and Fillet2 in 1899 obtained 0.0118 p. c. of a light yellow 
oil of an anise-like odor, reminding of estragon. It consists principally 
of methyl chavicol. On treating the oil with alcoholic potassa, anethol 
(m. p. 20-21°) was formed, which was converted into anisic aldehyde 
by oxidation. 
Gutzeit3 in 1875 had distilled the unripe chervil fruit and obtained 
from 10 k. 27 g. of oil. He showed the presence of ethyl and methyl 
alcohol in the distillation water. 
296. Oil of Coriander. 
Olenin Coriandri. - Corianderol. - Essence de Coriandre. 
Origin and History. The coriander plant, Coriandrum sativum L. 
(Family Umbelliferae), cultivated in many countries and in nearly all 
climates, was used as a kitchen spice even before the Christian Era. 
As such, coriander fruit is mentioned several times in Sanscrit writings, 
in the Bible and in later Roman writings. Coriander fruit has also 
been found in old Egyptian monuments of the tenth century B. C. 
among other still recognizable offerings. 
Coriander is also mentioned among the useful plants recommended 
for cultivation by Charlemagne, but it appears to have received, 
as with the Arabians, so also with the Germans in the middle ages, 
only slight consideration. The fruit is again mentioned in the medical 
and distilling books of the sixteenth century, although it had been 
employed now and again as a kitchen spice. 
The distilled oil of coriander appears to have been first obtained 
by Porta in the sixteenth century. In the price ordinances of spices, 
the oil is first included in that of Berlin of 1574 and Frankfurt-on-the- 
Main of 1587 and in the 1589 edition of the Dispensatorium Noricum. 
1) See footnote 4 on p, 540. 
2) Bull. Soc. ehim., Ill, 21, p. 368. 
3) Liebig's Annalen, 177, p. 382. 542 
Special Part. 
Coriander, oil was investigated in 3 785 by Hasse, in 1835 by 
Trommsdorff,1 in 1852 by A. Kawalier2 and in 1881 by B. Grosser.8 
A true insight into its composition, however, was brought about by 
the investigations of Semrnler (1891) and of Barbier (1893). 
Preparation,. Coriander oil is distilled from the fruit4 which has 
been crushed between rollers. For the preparation on a large scale, 
only the coriander from Moravia, Thuringia and Russia is used, the 
yield being 0.8-1.0 p. c.5 Only in cases of necessity is the fruit of other 
districts, which are all much poorer in oil, used. Of these may be 
mentioned: French (yield about 0.4 p.c.), Dutch (0.6 p. c.) and Italian 
(0.5 p. c.) coriander. Still less oil is given by the large grained Morocco 
fruits, namely 0.2-0.3 p. c., while the East Endian fruit with only 
0.15-0.2 p. c. gives the lowest yield. 
The exhausted and dried fruit is used as cattle food. It contains 
11-17 p. c. of proteids and 11-20 p. c. of fat (Uhlitzsch,6 1893). 
Properties. Oil of coriander is a colorless or slightly yellowish 
liquid of a characteristic coriander odor, and an aromatic, mild taste. 
Sp. gr. 0.870-0.885; ao - + 8 to +13°. The oij is soluble in 3 parts 
of 70 p. c. alcohol at 20°. 
Composition. Through the investigations of Kawalier2 a body of 
.the" formula CioHisO was recognized as the principal constituent of the 
oil. The alcoholic nature of this compound was later shown by Grosser.3 
Semrnler7 in 1891 designated it as coriandrol and found that it was a 
chain compound belonging to the so-called "olefinic camphors." Barbier8 
in 1893 showed that linalool and coriandrol had the same physical 
properties with the exception of being opposite in rotation, and that 
they were also completely alike in their chemical behavior. Both yield 
on oxidation the same aldehyde viz. citral, split off water in the same 
manner, and can be converted by proper treatment into geraniol. For 
these reasons coriandrol must be considered as the dextrogyrate 
modification of linalool. 
For the investigation of the terpene9 contained in coriander oil, the 
more volatile portion coming over on rectification by steam distillation 
1) Arehiv d. Pharm., 52; p. 114. 
2) Liebig's Annalen, 84, p. 351; Journ. fiir prakt. Chern., 58, p. 226. 
3) Berichte, 14, p. 2485. 
The umbelliferous fruits are commonly, though erroneously designated seeds. 
5) A yield of 1.1 p. c., as reported by Eck in 1897 (Pharm. Ztg., 32, p. 423) has 
never been obtained on a large scale. 
6) Die landwirthschaftliehen Versuchsstationen, 42, p. 60. 
7) Berichte, 24, p. 206. 
8) Conipt, rend., 116, p. 1460. 
9) Bericht von S. & Co., Apr. 1892, p. 11. Oils of the Umbelliferae. 
543 
was repeatedly fractionated with the use of a distilling- column. A 
fraction boiling- between 156 and 160° was obtained. Lt has the sp. gr. 
0.861 and «d= + 32°42/. The nitrosochloride gave with benzylamine 
pinene nitrolbenzylamine melting at 123-124°. Accdrding to this the 
terpene of coriander oil, the amount of which is about 5 p. c., is d-pinene. 
As a mixture of pinene with linalool has by no means the odor of 
coriander oil, another body, at present unknown, must be contained'in 
the oil, to which is due the specific coriander odor. 
Examination. Coriander oil is often adulterated with orange or 
turpentine oil. These additions are readily recognized by the specific 
gravity and the rotatory power. The solubility test with 70 p. c. 
alcohol is also very serviceable for detecting adulterations; oils which 
do not form a clear solution with this solvent are to be rejected. 
Ln order to make a study of the changes which the oil undergoes 
in the ripening process of the plant, Schimmel & Co.1 distilled coriander 
at different stages of its growth. First of all the fresh flowering herb 
was distilled with the roots immediately after being collected. The plant 
in this condition had a highly disagreeable, stupefying bed-bug odor. 
Later, when the herb was half ripe and had already begun to go to 
seed, the second distillation was untertaken. The bed-bug odor was 
less prominent and the true coriander odor was more noticeable. As 
the herb, when the fruit is ripe, is nearly devoid of odor, only the ripe 
fruits were used immediately, after harvesting. 
1) Oil from the fresh, flowering plant. 
Yield 0.12 p. c. Sp. gr. 0.853. Not soluble in 70 p. c. alcohol. 
Highly unpleasant' bed-bug odor. After 2% months the sp. gr. had 
increased to 0.856. The angle of rotation (which had at first not been 
determined) amounted to + 1°2'. The bed-bug odor had almost entirely- 
disappeared ; the compound appears, therefore, to have suffered poly- 
merization or to have been changed or inverted in some oilier way.1 
2) Oil from the fresh, half ripe coriander herb with fruit. 
Yield 0.17 p. c. Sp. gr. 0.866; aD= + 7°10'. Soluble in 3 parts 
of 70 p. c. alcohol. The odor is coriander-like accompanied by a slight 
bed-bug odor. After one month the sp. gr. had risen to 0.869. 
i) Bericht von S. & Co.. Oct. 1895, p. 12. 544 
Special Part. 
3) Oil from ripe coriander fruit distilled immediately after 
the harvest. 
Yield 0.83 p. c. Sp. gr. 0.876; «d- +10°48'. Soluble in 3 parts 
of 70 p. c. alcohol. True coriander odor. 
297. Oil of Cumin. 
Oleum Cumini.-Cuminol.-Essence de Cumin. 
History, Origin and Preparation. The Roman or mother caraway 
of the orient, Cuminum cyminum L has been used together with the 
common caraway as a spice in antiquity. Both have been often con- 
fused, the one with the other and also with the seeds of the black 
caraway, Nigella, in literature. They were used in England toward the 
end of the thirteenth century and in Germany in the fifteenth century. 
The volatile oil of cumin is included in the price ordinances of Berlin 
for 1574, of Frankfurt for 1582, and in the 1589 edition of the 
Dispensatorium Noricum. 
Oil of cumin is distilled from the seed of the Roman caraway. 
Syria, Morocco, Malta and East India are of commercial interest as 
places of production. The individual varieties gave according to deter- 
minations in the manufacture on a large scale the following yields: 
Maltese cumin 3.5 percent 
Morocco " 3 " 
East Indian '• 3-3.5 " 
Syrian " 2.5-4 " 
Properties. Oil of cumin is at first a colorless, later a yellowish 
liquid, of the unpleasant bug-like, but characteristic odor of cumin, and 
an aromatic, somewhat bitter taste. 
The specific gravity of the oil distilled from cumin from the levant, 
is 0.91-0.93. With an East Indian oil, as well as with two oils of 
unknown source, the density was found to vary from 0.893-0.899; 
«d = + 4 to 4" 8°. 
The solubility varies as much as the specific gravity, which rises 
and falls with the amount of cumic aldehyde in the oil. The heavy 
oils dissolve in 3 parts of 80 p. c. alcohol, the lighter oils require as 
much as 10 parts of this solvent. 
Composition. Cumic aldehyde, or cuminol1 is the constituent to 
which cumin oil owes its odor and its more prominent properties. 
Cymene and a terpene CioHic accompany this aldehyde in the oil. 
i) In accordance with the aldehyde character of this substance it should be desig- 
nated cumin al. • Oils of the Umbelliferae. 
545 
Gerhardt and Cahours1 in 1841 separated the hydrocarbons from 
the oxygenated constituents for purposes of investigation by distilling 
the oil with caustic potassa. The aldehyde was thereby changed to 
cumic acid and cumic alcohol and was at the same time retained by 
the alkali. Bertagnini2 in 1853 found that cuminol combined with 
sodium bisulphite and thus recognized its aldehyde nature. This gave 
at the same time a rational way for the preparation of the body in a 
pure form. According to Kraut3 (1854) the lower boiling portions are 
distilled off and the residue shaken with sodium bisulphite. After 
standing 24 hours the thick mass is expressed and decomposed by 
distillation with soda solution or dilute sulphuric acid. 
Cumic aldehyde, C10H120, has the sp. gr. 0.972 at 13° (Kopp,4 
1855), boils at 109.5° under 13.5 mm. pressure, at 232° under 760 
mm.5 and is optically inactive. 
The presence of a terpene in cumin oil boiling at 156° and having 
the sp. gr. 0.865 at 15° was first shown by Warren6 (1865) and later 
confirmed by Beilstein and Kupfer7 (1873). Wolpian8 (1896) prepared 
the terpene in its purest form. He found the boiling point 157-158° 
•under 768 mm. pressure, sp. gr. 0.8604, au= + 25°25'. His attempts 
to prepare a crystallized derivative and thus to identify the hydro- 
carbon with one of the known terpenes, were fruitless. He believed, 
therefore, to have found a new terpene which yielded onljT liquid com- 
pounds and gave it the name of hydrocuminene. In order to justify 
such assumptions, much stronger proofs are necessary then the almost 
exclusively negative results of Wolpian. 
The second hydrocarbon of cumin oil is cymene, the identity of 
which with cymene from camphor as well as that obtained from other 
volatile oils was shown by Beilstein and Kupfer, and also by Wolpian. 
298. Oil of Celery Seed. 
Oleum Apii Graveoleutis Seminis.- Selleriesamenol.-Essence <Ie Semences 
de Celeri. 
Origin and Properties. The volatile oil which is present in all 
parts of the celery plant, Apium graveoJens L., is especially well 
!) Liebig's Annalen, 38, p. 70. 
2) Liebig's Annalen, 85, p. 275. 
3) Liebig's Annalen, 92, p. 66. 
*) Liebig's Annalen, 94, p. 317. 
s) Anschutz & Reitter, Die Destination unter 
vermindertem Druck. Bonn, 1895, p. 73. 
6) Zeitschr. f. Chemie, 1. p. 667. 
7) Liebig's Annalen, 170, p. 282. 
s) Pharm. Zeitschr. f. Russl., 35, 
pp. 97. 113, 129, 145, 161. 546 
Special Part. 
represented in the fruit, somewhat sparingly, but still in quantities 
sufficient for preparation, in the green herb, while the roots give an 
aromatic water upon distillation, but no oil. 
By distillation with water vapor about 2.5-3 p. c. of a very mobile 
and colorless oil are obtained from the seed. It smells and tastes 
strongly of celery, has a sp. gr. of 0.870-0.895 and «d = +67 to +79°. 
Composition. Celery oil consists of about 90 p. c. of hydrocarbons. 
In an investigation in the laboratory of Schimmel & Co. a fraction 
boiling constant at 176-177° was obtained, the rotation of which was 
«d = + 107°. By the action of bromine a solid bromide was formed 
which melted at 105°. According to this, d-limonene1 is a constituent 
of celery oil. Other terpenes, it appears, are not present, in any case, 
pinene is excluded, as nothing came over before 170° when distilled. 
This is of interest, as adulteration with turpentine oil can now be 
readily recognized. 
The amount of the oxygenated constituents to which are due the 
celery odor is very small compared with the terpenes. Sometimes a 
separation is effected during distillation, in that the heavier portions 
settle at the bottom of the receiver. Usually, however, no heavy oil is 
obtained. This is only difficultly volatile with water vapor and there- 
fore often partially remains as residue in the still when the oil is 
rectified. 
Such a residue, as well as the so-called heavy oil was used by 
Ciamician and Silber2 in 1897 for their investigations. They found the 
following compounds: 
1) Palmitic acid; 2) a phenol possessing the properties of guaiacol; 
3) a second phenol, white needles, melting at 66-67°, of the com- 
position CioHaoOg; 4) a liquid boiling from 262 to 269°, probably a 
sesquiterpene; 5) sedanolid, a lactone C12H18O2. It boils at 185° under 
a pressure of 17 mm. The corresponding oxy acid, sedanolic acid 
C12H2OO3, melts at 88-89° and is easily changed to sedanolid. From 
the oxidation results it follows that sedanolic acid is o-oxyamyl-J5-tetra- 
hydrobenzoic acid. 6) Sedanonic acid anhydride, Ci2HiflO2. Sedanonic 
acid, C12H18O3, is an unsaturated ketone acid (m. p. 113°), o-valeryl- 
J1-tetra hydrobenzoic acid. Sedanolid and the anhydride of sedanonic 
acid are to be considered as the constituents giving the characteristic 
odor to celery oil. Their constitution is shown by the following 
structural formulas: 
1) Bericht von S. & Co., Apr. 1892, p. 35. 
2) Berichte, 30, pp. 492, 501, 1419, 1424, 1427 Oils of the Umbelliferae. 
547 
CH.C4H9 C:C4H8 
C8H8 ° CeH8 \^/ 0 
co co 
Sedanolid Sedanonic acid anhydride. 
299. Oil of Celery Leaves. 
Oleum Apii Graveoleutis Foliorum.-SellerieblStterol.-Essence de Feuilles de 
Celeri. 
The oil prepared from the fresh herb1 (yield about 0.1 p. c.) has a 
strong odor of the fresh celery leaves. It is very fluid and of a greenish- 
yellow color, has the sp. gr. 0.848-0.850 at 15°, the rotatory power 
ab=+48 to +52° and is soluble to a clear solution in 10 parts of 
90 p. c. alcohol. 
300. Oil of Parsley. 
Oleum Petroselini.- Petersiliensamenbl.- Essence de Persil. 
Origin and History. Parsley, Petroselinum sativum Hoffm. (Apium 
petroselinum L., Caruni petroselinum Benth. et Hook.) (Family CmbeUi- 
ferae), was originally indigenous to the Mediterranean countries and to 
Asia Minor, but is cultivated as a spice in nearly all moderate climates. 
Distilled parsley water was during the time of the distilled waters a 
much used remedy and is often described in the distilling books of the 
fifteenth and sixteenth centuries. 
Distilled oil of parsley does not appear to have come into use 
until about the middle of the sixteenth century. It is first mentioned in 
the drug ordinances of Frankfurt-on-the-Main of 1587 and later in the 
1589 edition of the Dispensatorium Noricum. 
The apiol contained in the oil. and crystallizing out at a low 
temperature, was observed as early as 1715 by Link, apothecary in 
Leipzig,2 and in 1745 by Walther.3 
The oil from the fresh herb and the fruit was prepared by Pabitzky4 
in 1754. Further, the oil and the crystals separated from it were 
mentioned by Dehne5 in 1778, by Bolle" in 1829 and by Bley" in 1827. 
i) Bericht von S. & Co., Oct. 1895. p. 59. 
2) Sammlung von Natur und Medicin, wie auch von Kunst- und Liiteraturgewhich- 
ten. Leipzig; and Budissin, 1716. 
s) De oleis vegetabilium essentialibus. Dissertatio. Leipzig-. 1745. p. 17. 
*) Braunsch weiger Anzeiger. 1754, p. 1205. 
5) Crell's chemisches Journal. 1778, I, p. 40. 
Archiv d. Pharm.. 29. p. 168. 
t) Trommsdorff's Neues Journ., 14, II, p. 134. 548 
Special Part. 
The first elementary analysis of the "parsley camphor'' was made by 
Blanchet and Sell1 in 1833. It was further investigated by Lbwig and 
Weidmann2 in 1839. 
Preparation, The volatile oil contained in all parts of the plant 
is particularly well represented in the fruits. These give upon distillation 
2-6 p. c. of oil, which is simply designated in commerce as parsley oil 
or parsley seed oil. 
Properties. A colorless, yellowish or yellowish-green, thick liquid, 
the odor of which, in spite of any similarity, is quite different from 
that of the herb. It has the sp. gr. 1.05-1.10 and is slightly laevo- 
gyrate. The oil from German seed is usually so rich in apiol, that it is 
half solid at ordinary temperature. French seeds, however, give an oil 
much poorer in apiol. 
Composition. Apiol can be considered as the principal constituent 
of parsley oil. It has been studied by v. Gerichten3 in 1876, by Gins- 
berg 4 in 1888 and Ciamician and Silber5 in 1888 and later. The some- 
what complicated structure of the compound was almost completely 
cleared up by the two last named investigators. It only remains to be 
decided, which of the two formulas proposed6 belongs to the apiol 
from dill oil and which to the apiol from parsley oil. 
Apiol, C12H14O4, melts at 30° and boils under ordinary pressure at 
29-1°, under a pressure of 33-34 mm. at 179°. It contains an allyl 
group, which is changed to the propenyl group by boiling with alcoholic 
potassa. The resulting isoapiol melts at 55-^56° and boils at 304°. 
By the oxidation of isoapiol is formed: 1) Apiolaldehyde, CioHioOs, 
small needles melting at 102°. 2) Apiolic acid, CioHioOu, m. p. 175°. 
3) Apiolketonic acid, CiiHioOt, crystallizing in long, yellow needles, 
which melt at 160-172°. 
The terpene fraction of parsley oil boiling at 160-164°" has, accord- 
ing to v. Gerichten the sp. gr. 0.865 at 12° and the angle of rotation 
in a 100 mm. tube -30.8°. By conducting into it hydrochloric acid 
no solid hydrochloride was obtained immediately; by diluting with 
alcohol and pouring on a large surface one was obtained in small 
quantity melting at 115-116°. According to this it is probable that 
1-pinene is a constituent of parsley oil. 
1) Liebig's Annalen, 6, p. 301. 
2) Liebig's Annalen, 32, p. 283. 
3) Berichte, 9, pp. 258, 1477. 
i) Berichte, 21, pp. 1192, 2514; ibid., 
23, p. 323. 
s) Berichte, 21, pp. 913, 1621; 22, p 
2481; 23, p. 2283. 
«) These are mentioned under dill oil. 
7) Griinling (Dissertation, Strassburg, 
1879) found the boiling point of the terpene 
at 158°. Oils of the Umbelliferae. 
549 
301. Oil of Parsley Root. 
The root of parsley contains only very little oil. According to 
Schimmel & Co.1 the yield on distillation from the dry root was 
0.08 p. c., from the fresh 0.05 p. c. 
The oil had the sp. gr. 1.049 and separated crystals even at the 
ordinary temperature (probably apiol). 
302. Oil of Parsley Leaves. 
The yield of oil obtained by distillation from fresh parsley herb 
amounts to only 0.06-0.08 p. c.2 
Properties. Oil of parsley leaves is very fluid and of a greenish 
yellow color. It has the full odor of fresh parsley which is cnly slight 
in the oil from the seed. Sp. gr. 0.900-0.925; «d = T0°16 tu+3°10'. 
The oil distilled at 68-170° under a pressure of 12 mm.; the 
principal part boiled from 78-96°. By means of Zeisel's methoxyl 
determination made on the fractions which corresponded to the boiling 
point of apiol, it was ascertained, that only small quantities of this 
body were contained in the oil. 
303. Oil of Water Hemlock. 
The fruit as well as the root of the poisonous water hemlock. Cicut a 
virosa L.r contain volatile oil. 
Oil of the fruit. Trapp3 obtained from the fruit collected in the 
autumn and dried, by distillation 1.2 p. c. of an almost colorless, quite 
fluid oil, lighter than water and having the odor and taste of Roman 
caraway oil. 
By shaking with sodium bisulphite solution a solid compound was 
obtained which had the composition of cuminal hydroxy sulphonate of 
sodium. The oil not acted upon by the bisulphite solution consists of 
cymene; by treatment with fuming sulphuric acid cymene sulphonic acid 
was obtained. 
The oil of the fruit of water hemlock contains therefore the same 
constituents as the Roman caraway oil from Cuminum cyminum L., 
cumic aldehyde and cymene. 
Oil of the root. The roots yield on distillation 0.124-0.365p. c. 
of an oil smelling of water fennel and celery and having the sp. gr. 0.870 
i) Bericht von S. & Co., Apr. 1894, p. 55. 
2) Bericht von S & Co., Oct. 1895, p. 59. 
3) Journ. f. prakt. Chemie, 74, p. 428: Archiv <1. Pharm., 231, p. 212 
±) Liebig's Annaien, 31, p. 258. 
5) Journ. f. prakt. Chemie, 105, p. 151. 550 
Special Part. 
at 18°. It is entirely different from that of the fruit, as it contains 
neither cymene nor cumic aldehyde. Upon fractional distillation a 
dextrogyrate terpene boiling at 166° "cicutene" was isolated. By con- 
ducting hydrochloric aeid into cicutene a hydrochloride was formed, 
which solidified when cooled. Cicutene is probably not an individual 
hydrocarbon, but rather a mixture of several terpenes (pinene and 
phellandrene?). 
The oil from the root of the water hemlock was formerly considered 
as poisonous. That this is not the case was shown by Simon,1 who 
experimented on animals. 
304. Oil of American Water Hemlock. 
The fruit of the poisonous plant, Cicuta maculata L., widely dis- 
tributed in North America, gives on distillation (Glenk2) 3.8--1.8 p. c. 
of an oil smelling like Chenopodium anthelminticum and having the 
sp. gr. 0.840-0.855. The larger part boils between 176 and 183° and 
consists, as is seen from the elementary analysis of the two fractions 
176-178.5° and 178-183°, of terpenes. 
305. Oil of Caraway. 
Oleum Carvi.-KummeloL-Essence de Carvi. 
Origin and History. The caraway plant, Carum carvi L. (Family 
Umbelli ferae), is cultivated largely in Europe and Asia,. 
Distilled oil of caraway is first mentioned in the price ordinances of 
Berlin for 1574 and that of Frankfurt for 1589, as well as in the 
1589 edition of the Dispensatorium Noricum. 
Preparation. If all the oil contained in the caraway is to be 
extracted, it, like all other seeds, must be crushed between rollers before 
distillation. The crushed fruit must be distilled at once, as a great loss 
of oil is experienced by exposure to the air. At the beginning of the 
distillation considerable quantities of sulphuretted hydrogen are liberated. 
The cause of this has not yet been satisfactorily explained. This 
phenomenon, which also takes place with a few other umbelliferous 
seeds has been noticed as early as 1823 by Planche.3 Schimmel & Co.4 
have found methyl alcohol, furfurol and diacetyl in the distillation water. 
Acetaldehyde is also liberated in large quantities during the distillation. 
1) Liebig's Annalen, 31, p. 258; comp, also Pharm. Rundschau, 13, p. 103. 
2) Amer. Journ Pharm.. 63, p. 330: Stroup, ibid., 68, p. 236. 
3) Trommsdorff's Neues Journal, 7, I. p. 358. 
Bericht von S. & Co., Oct. 1899, p. 32. Oils of the Umbelliferae. 
551 
The modern distilling apparatus (fig 48 on p. 79) will hold about 
2,500 k. of caraway, which yields its oil completely in 6-8 hours. 
Formerly it was customary-and is even done now and then at the 
present time - to distil caraway in the uncomminuted state. The 
exhausted seeds are dried, and used in cheese manufacture or for pur- 
poses of adulteration. Of course, the seeds are not entirely deprived of 
their oil by this treatment, and the yield of oil is therefore less, which 
is, however, more than counterbalanced by the sale of the dried seeds. 
Caraway which has been exhausted by distillation, is distinguished from 
the fresh seed by its darker color, by the very faint odor and taste, 
and the shrivelled appearance of the seed. Under the microscope, the 
broken, empty oil cells, and the torn upper layers of cells can be seen 
in a cross-section. 
The exhausted, comminuted caraway is also dried in special 
apparatus1 and then used as a cattle food, which is highly prized for 
its nourishing qualities. According to a series of analyses made at the 
Royal Saxon Agricultural station at Mockern,2 dried caraway fodder 
contains 20-23.5 p. c. of crude protein (of which 75-85 p. c. is 
digestable) and 14 to 16 p. c. of fat. 
The yield of oil varies according to the source of the seeds. Schim- 
mel & Co.3 found as an average the following yields for the different 
commercial varieties: 
Bavarian, wild 6.5-7 p. c. 
German, cultivated 3.5-5 " 
Finnish, wild 5 -6 " 
Galician 4.5 " * 
Hessian, wild 6 -7 ' 
Dutch, cultivated 4 -6.5 " 
Moravian 4 " 
Norwegian, wild 5 -6.5 " 
East Frisian 5.5-6 " 
East Prussian, cultivated 5 -5.5 " 
Russian, wild 3.2-3.6 " 
Swedish, wild 4 -6.5 " 
Styrian 6 " 
Tyrolese, wild... 6.5 " 
Wurttemberg, wild 5.5-6 " 
The Dutch, Norwegian and East Prussian are the commercial 
varieties principally used for distillation. The caraway cultivated in 
i) Muspratt-Stohmann, Technische Chemie, -4th ed., vol 1, p. 69. 
2) Uhlitzsch, Die landwirthschaftlichen Versuchsstationen, 42, p. 48. 
3) Berieht von S. & Co., Apr. 1897, Suppl. p. 26. 552 
Special Part. 
other places of northern Germany, is, in spite of its fine appearance, 
not suitable for oil distillation, on accouht of the low yield. 
How extremely large the consumption of caraway is in Germany is 
seen from the following figures.1 
Imported through Hamburg: 
1896. 
From the Netherlands 1,661,900 kilos 
" Norway 41,000 " 
" France 14,500 " 
Further import from the sea 13,400 " 
By rail and from the upper Elbe 105,700 " 
Total 1,836,500 kilos 
Add to this: 
Import to Germany by rail via Groningen.... 316,600 kilos' 
2,153,100 kilos 
Of this came from Holland: 
Conveyed by sea 1,661,900 kilos 
" by land 316.600 u 
Total 1,978,500 kilos 
a quantity equivalent to 39,570 bales or fully 60 p. c. of the yield of 
a normal Dutch harvest. Several thousand bales, which were trans- 
ported to Austria, are indeed included in these figures. These are. 
however, more than compensated for by the caraway grown in Germany 
itself. The consumption of the Leipzig factories is probably not over- 
estimated at 10,000 to 12,000 bales per year. 
As to profit, the yield is not the only factor that comes into con- 
sideration, but the quality of the oil as well. This depends largely on 
its carvone content, which is indicated by the specific gravity of the 
oil. It might happen, that the distillation of a consignment of caraway 
with a lesser yield of oil of high specific gravity would be more profitable 
than that of another of higher yield but lighter oil. 
For the preparation of carvone (carvol, Oleum Carvi of the German 
Pharmacopoeia), the caraway oil is either fractionated in a vacuum 
or with water vapor. The fractions from the sp. gr. 0.960 on are 
collected separately as carvone. The limonene (carvene) obtained as a 
by-product has the sp. gr. 0.850 and is used as a cheap soap perfume. 
Properties. Normal caraway oil is a colorless liquid, becoming- 
yellowish in time, of a caraway odor and mild spicy taste. The sp. gr. 
i) Bericht von S. & Co., Oct. 1897. p. 31. Oils of the UmbeHiferae. 
553 
lies between 0.907 and 0.915. Oils of lower sp. gr. rarely occur and 
are less valuable, as they contain less carvone. Its optical rotation «d 
is +70 to +80°. Specific gravity and angle of rotation are in inverse 
ratio. 
Oil of caraway is but sparingly soluble in 70 p. c. alcohol, but 
yields clear mixtures with 3-10 volumes of 80 p. c. alcohol as well as 
with an equal volume of 90 p. c. alcohol. It boils from 175 to 230°. 
Carvone of carvol (Oleum Carvi oi the German Pharmacopoeia) has 
the sp. gr. ' 0.903-0.960 and the rotation ud = +57 to 60°. The 
advantage of carvone over caraway oil lies, aside from its greater 
intensity of odor and taste, in its ready solubility in dilute alcohol. 
It is miscible in all proportions with 90 p. c. alcohol. At 20°, 1^-2 
parts of 70 p. c. alcohol, and 10-20 parts of 50 p. c. alcohol are 
sufficient for complete solution. The solubility in 50 p. c. alcohol is a 
good criterion of the purity of the carvone, as carvone containing 
2 p. c. of limonene will not dissolve clearly in 20 parts of 50 p. c. 
alcohol. 
Caraway oil, and especially carvone, is colored yellow by exposure 
to the air. The oil becomes thereby more viscous and of a higher 
specific gravity. 
If 1 cc. of such a carvone be dissolved in an equal volume of alcohol and a 
few drops of a very dilute solution of ferric chloride be added, a reddish-violet 
coloration will be produced which, however, vanishes on the further addition 
of ferric chloride. 
Freshly distilled oil does not give this reaction. This reaction may 
perhaps be due to the formation of a phenol by the decomposition of 
the carvone.1 The proof, however, that a phenol is indeed formed, is 
still wanting. 
Composition. Volckel2 in 1840 recognized that caraway oil was a 
mixture of two bodies, an oxygenated body and one free from oxygen. 
The carrier of the caraway odor, and therefore the most important 
constituent, is oxygenated. It has the composition C10H14C) and was 
formerly called carvol;3 Wallach.4 however, in 1893 changed the name 
to carvone in order to express the ketone nature of the compound. 
Pure carvone, liberated from its hydrogen sulphide addition product, 
has the sp. gr. 0.961 and the specific rotatory power5 [v.]d = +62.07° 
1) Archiv d. Pharm., 222, p. 362. 
2) Liebig's Annalen, 35, p. 308. 
3) Liebig's Annalen, 85, p. 246. Glad- 
stone, Journ. Chem. Soe., 25, p. 1; Pharm. 
Journ., Ill, 2, p. 746; Jahresb. f. Chem., 
1872, p. 815. 
*) Liebig's Annalen, 277, p. 107. 
5) Archiv d. Pharm., 221. p. 283. 554 
Special Part. 
and boils at 229-230° (thermometer completely in the vapor). Good 
caraway oil contains 50-60 p. c. of carvone. For the chemical behavior 
and derivatives of carvone see page 160. 
The hydrocarbon of caraway oil boiling at 175° and called carvene 
by Schweizer.3 is, according to Wallach's2 investigation, d-limonene 
(tetrabromide, m. p. 104-105°). 
The odor of the carvene obtained by fractionation is quite different 
from that of pure limonene. It can be changed to the characteristic 
lemon-like odor of limonene by removing the last traces of carvone by 
means of the acetate of phenyl hydrazine and then shaking the 
preparation repeatedly with a dilute solution of potassium per- 
manganate. 
Examination. Caraway oils are often met with in commerce from 
which part of the valuable carvone has been removed. On the other 
hand under the designation "carvone" are found oils from which a 
part, but not all limonene has been removed. 
Such products are readily recognized by their abnormal specific 
gravity. In judging'carvone its solubility in 50 p. c. alcohol is also to 
be considered. 
The carvone content, and thus the value of a caraway oil, can be 
calculated from its density, by taking the specific gravities 0.964 for 
carvone and 0.850 for limonene as a basis. 
If a is the specific gravity of the oil investigated, b the specific gravity 
of one of the components (limonene), and c the difference of the specific gravity 
of carvone (0.964) and limonene (0.850), the amount of the other component 
(carvone) x in percents is given by the following formula: 
a - b . 100 
c 
This method of determination, which is sufficient for practical 
purposes, rests on the assumption, that carvone and limonene are the 
only constituents of caraway oil. 
An adulteration often found is that with alcohol, which, moreover, 
gives the impression that the consumer has under consideration a 
readily soluble oil, especially suited for the liquor manufacture. For 
this reason the specific gravity determination and the test for alcohol 
should never be neglected. 
For the direct determination of carvone in volatile oils, Kremers 
and Schreiner3 have recommended a method in which the carvone is 
1) Journ. f. prakt. Chern., 24, p. 257. 3) Pharm. Review, 14, p. 76 
«) Liebig's Annalen. 227, p. 291. Oils of the Umbelliferae. 
555 
converted into its oxime, and separated from the terpene by steam 
distillation. The method is as follows: 
To a solution of 10 g. of the oil to be tested in 25 cc. of alcohol is added 
5 g. of hydroxylamine hydrochloride (in case more than 50 p. c. of carvone is 
supposed to be present, the amount of hydroxylamine is correspondingly 
increased) and 0.5 g. of sodium bicarbonate and the mixture boiled on a water 
bath in a flask connected with a reflux condenser for % hour. 25 cc of water 
are then added and the alcohol, which carries over a large quantity of limonene, 
is distilled off from a water bath. Steam is then passed slowly through the liquid 
until traces of carvoxime come over. In order that these are not lost for the 
determination, the last portions of distillate are collected separately in test- 
tubes, and when traces of crystals of carvoxime appear on the surface the 
distillation is interrupted. The tube of the condenser is then washed with a 
little hot water and this, as well as the last collected distillate, containing 
some carvoxime. returned to the flask. When thoroughly cold the solidified 
carvoxime is collected on a force filter, washed, and dried by suction. The air- 
dried carvoxime is then transferred to a fared glass evaporating dish and 
heated for one hour on a water-bath, and when cool weighed. To the weight 
thus obtained 0.1 g. is added as this is about the quantity lost during the 
heating. The weight of oxime found gives by multiplying by the factor 0.9088 
the amount of carvone present. 
It is to be regretted that this method, which can, perhaps, be 
improved, gives only approximate results. In order to determine the 
extent of the error, Schimmel & Co.1 prepared mixtures of pure carvone, 
prepared, from its hydrogen sulphide addition product, with carefully 
prepared limonene, and found differences of nearly 7 p. c. between the 
found and the real carvone content: 
A 50 p. c. mixture gave 43.18 p. c. carvone. 
" 25 " " " 19.36 " 
" 12.5 " " " 8.54 " 
The source of error lies in that the exact point at which the distil- 
lation is to be interrupted, is difficult to determine. Moreover, a mix- 
ture of oxime and limonene, which remains liquid for some time, goes 
over and is lost for the determination, before crystals are noticed on 
the distillate. 
The details of this method have been more carefully studied and the 
above results refuted by Kremers.2 
Walter3 has also based a method on the action of hydroxylamine 
on carvone. He treats the oil with hydroxylamine and determines the 
excess by titration with iodine. The applicability and accuracy of the 
method can not be judged from the available abstract. 
1) Berirht von S. & Co., Oct. 1896, p. 49. 3) Chern. Zeitung. Repert., 23, p. 264. 
2) Pharm. Archives, 2, p. 81. 556 
Special Part. 
In order to see in what succession the formation of the individual 
constituents of caraway oil takes place in the plant, Schimmel & Co.1 
distilled caraway plants at different stages of growth and examined the 
oils obtained. 
Oil No. 1. From long cut, fresh plants, partly in bloom and partly 
in seed. Sp. gr. 0.882; ud at 17° 1.48306; «d = + 65° 12'. 
Oil No. 2. From fresh plants of the same cutting, but after 
removing the inflorescence and fruits. Sp. gr. about 0.88 (not accurately 
determined as the amount was small); ud at 17° 1.5083; «d = + 20°36'. 
Oil No. 3. From fresh plants in an advanced state of development, 
but in which the seeds were not yet fully ripe. Sp. gr. 0.9154; ud at 
17° 1.48825; aD = + 63°6'. 
Oil No. 2 had an odor reminding but slightly of caraway; it con- 
tained neither carvone nor limonene in amounts that could be detected. 
The small specimen for examination was only sufficient to make a 
boiling point determination. The boiling began at 195°, the thermometer 
rose rapidly to 230° and about 65-70 p. c. distilled over between 
230 and 270°. A resinous residue remained in the flask. 
The oils No. 1 and 3, which are comparable, as they were both 
distilled from the whole herb, show a considerable difference in their 
specific gravities. The fractional distillation of both gave the following- 
results : 
No. 1. 
No. 3. 
175-178° 45.0 percent 1 . 
178-185° 21.0 " 1 ^.1 percent. 
185-190° 4.5 
^178 " 
190-220° 5.6 
| Li.O 
220-235° 4.8 
46.6 
235-240° 6.4 
5.5 " 
240-270° 9.2 
I AH u 
Residue and loss 3.5 " 
1 O.v 
The distillation residue of both oils solidified to a crystalline mass 
and contained besides resinous products a hydrocarbon, probably 
belonging to-the paraffin series, crystallizing from hot alcohol in white 
scales melting at 64°. 
The differences between the oils are at once -apparent. While the 
terpene fraction is the larger in No. 1 and the carvone fraction com- 
paratively small, this is quite large in No. 3. It was possible to obtain 
from the entire carvone fraction of the first oil only about 0.2 g. of 
1) Bericht von S. & Co., Oct. 1896, p. 47. Oils of the Umbelliferne. 
557 
pure crystallized earvoxime, which speaks for the low carvone content 
of the oil. On the other hand the corresponding fraction of No. 3 gave 
earvoxime in good yield. 
The result of the fractional distillation indicates that the carvone 
content of the oil is the lower, the more undeveloped the caraway plant 
is when distilled; it is highest in the oil distilled from ripe material. 
The reverse is true for the terpene content. According to this it seems 
probable, that, the terpene is first formed in the plant and from this 
the oxygenated constituent. 
In both oils, the fraction boiling from 240 to 270° contains a body 
of quite high specific gravity, which is absent in normal caraway oil. 
This compound, which does not possess the properties of a phenol, and 
gives with ferric chloride no color reaction, has not been prepared in 
a pure state, and its relations to the other constituents of the oil are 
unknown. 
306. Oil of Ajowan. 
Origin and History. < Carum ajowan Ben th. et Hook. (Ptychotis 
ajowan I). C.) is an annual belonging to the UmbeUiferae, and is culti- 
vated in India from Punjab to Bengal and the South Decan. It also 
grows in Egypt, Persia, and Afghanistan. The grayish-brown fruits 
are similar to those of parsley but are distinguished from these by their 
rough surface and different odor. The ajowan seeds found in Europe 
are almost exclusively of Indian source and enter commerce from 
Bombay. Marwar in Rajputana is reported as the principal Indian 
market. The plant is called in India Ajwan, Ajwain or Omain. The 
thymol crystals separating from the oil are known in the bazaars as 
Ajwan Ka-phul, that is, flower of ajowan. The thymol as well as the 
distillation water (Omum water) are used medicinally in India, especially 
in cholera. 
Ajowan oil mixed with fatty oil is used medicinally like ajowan 
water in India. 
Preparation. The comminuted fruit yields 3-4 p. c. of oil by 
distillation. The exceedingly large amount of fat in the distilled and 
dried seeds, makes them very good fodder for cattle. They contain 
15-17 p. c. of protein and 25-32 p. c. of fat (Uhlitzsch1). 
Properties. Ajowan oil is an almost colorless or brownish liquid of a 
decided thyme odor and a sharp, burning taste. Sp. gr. 0.900-0.930; 
it is slightly dextrogyrate. 
i) Die landwirthschaftlichen Versuchsstationen, 42, p. 52. 558 
Special Part. 
Composition. In Europe, ajowan oil is distilled exclusively for the 
preparation of its principal constituent, thymol, of which it contains 
45-55 p. c. 
Thymol, CioHnO, was found in the oil by Haines1 and Stenhouse2 
almost simultaneously in 1855-56. It crystallizes in part from the oil 
and can be completely separated by shaking with sodium hydrate 
solution. 
The remaining part of the oil, about one half, consists of hydro- 
carbons, which are sold in commerce under the name of thymene as a 
soap perfume. 
Thymene is a mixture of cymene,1 and a terpene boiling at 172°, 
but not further investigated.2 Thymene is the cheapest source for the 
preparation of cymene. 
307. Oil of Anise. 
Oleum Anisi.-Anisol. - Essence d'Anis. 
Origin and History. The anise plant, Pimpinella anisuin L. (Family 
Umbelliferae} comes originally from the orient, but is now cultivated in 
nearly all parts of the world. The European market is principally 
supplied by Russia. Germany, Scandinavia, Bohemia, Moravia, France, 
the Netherlands and Spain. The greater part of this anise seed is used 
for distillation for the preparation of anise oil and anethol. 
Distilled oil of anise has, on account of its property to solidify, no 
doubt been noticed as long as anise has been used for the preparation 
of anise water. The distillation of the oil has, however, been first 
described in the works of Brunschwig, Lonicer, Ryff. Gesner, Rubens and 
Porta. Valerius Cordus in 1540 called attention to the ready solidifi- 
cation of the oil. Nearly a century later Robert Boyle again described 
the "butter-like" solidification of anise oil. 
Anise oil is mentioned in medical books and ordinances first in the 
Pharmacopoea Augustana of 1580, the Dispensatorium Noricum of 1589. 
and the Berlin ordinance of Matthaeous Flacco of 1574. 
The first accurate investigations of anise oil were undertaken by 
Saussure3 in 1820, by Dumas4 in 1833, by Blanchet and Sell5 in 1833, 
t) Journ. Chern. Soc., 8, p. 289; Jahresb. d. Chem.. 1856, p. 622. 
2) Liebig's Aunalen. 93, p. 269; 98, p. 309.. 
3) Ann. de Chim. et Phys., II, 13, p. 280; Schweigger's Journal f. Chem. und Phys., 
29, p. 165. 
4) Liebig's Annalen. 6, p. 245. 
5) Ibidem, 6, p. 287. Oils of the Umbelliferae. 
559 
Cahours1 in 1841, by A. Laurent2 and Gerhardt3 in 1842. Gerhardt 
called the stearoptene of anise oil anethol and Cahours again pointed 
out the identity of the stearoptenes of anise and fennel oils, previously 
recognized by Blanchet.4 
Production. The anise used for distillation comes at present 
principally from Russia. The cultivation is particularly carried on in 
the gouvernements Woronesh, (districts Walcysk, Birjutschensk and 
Ostroy), Kursk, Charkow, Chersson, Podolia and Taurida. 
A part of the anise is used for the preparation of the oil at the 
place of production, the rest is for home consumption and export. The 
average export for the last 10 years amounted to 150,032 puds valued 
at 453,721 rubels per annum. The suburbs Krassnaja and Alexejewskaja 
(gouvernement Woronesh) are the commercial ('enters for anise. The 
cultivation is principally done by the peasants. 
Anise oil was produced in Russia in 1893 to the value of 105,500 
rubels.5 
The yearly average of anise exported from Russia during the years 
1882-1891 amounted to 137,000 puds6 at a value of 235,000 rubels. 
The increase during this interval of time is interesting:7 
Export 1882, 69,000 puds, value 169,000 rubels 
1891. 176,000 " *' 504,000 " 
One desjatine8 usually yields 50 puds and under favorable conditions 
of weather as much as 100 puds of anise. If, however,- the weather is 
cloudy and rainy at the time of blossoming, the yield sinks to 20-25 puds. 
The harvest in Russia was estimated in 1896 at 4,380,000 kilos. 
The exports of the different anise cultivating countries in 1896 was 
as follows: 
Russia 
Export over Libau 722,600 kilos 
" Riga 396,000 " 
Levant " from Chios 400,000 " 
" Cadiz 24,200 " 
" " Malaga 102,000 " 
Spain 
Bulgaria 402,463 " 
i) Liebig's Annalen, 41, p. 56; 56, p. 177. 
2) Ibidem, 44, p. 313. 
3) Ibidem, 44, p. 318; 48, p. 234; Journ. f. prakt. Chern., 36, p. 267. 
4) Liebig's Annalen, 41, p. 74. 
5) W. J. Kowalski, Die Produktivkrafte Russlands. German edition by E Davidson. 
Leipzig, 1898, p. 322. 
6) 1 Pud = 16.375 k. 
t) From "Odoriferous plants and volatile oils," a book in the Russian language by 
A. Bazaroff and N. Monteverte. 
8) 1 Desjatine - 109.25 Ar = 2.68 acres. 560 
Special Part. 
Preparation. The odor and taste of anise seed is due to its 
volatile oil. They yield their oil only completely when they are distilled 
in a comminuted condition. The yield obtained from the different 
commercial varieties is seen from the following table: 
Chilian anise Yield 1.9-2.6 p. c. 
Italian (Bologna) " " 3.5 " 
" (''puglieser") " " 2.7-3.0 " 
Macedonian " .. " 2.2 " 
Moravian " *• 2.4-3.2 " 
Mexican " " 1.9-2.1 " 
East Prussian " " 2.4 
Russian " " 2.4-3.2 
Spanish " " 3.0 u 
Syrian " " 1.5-6.0 '' 
Thuringian " " 2.4 " 
The rather marked differences in yield are not always due to the 
differences in the seeds themselves, but more often to the accidental or 
intentional admixture with stems, other seeds, earth and small stones, 
sometimes amounting to 30 p. c. In Russia and Moravia, earthy 
particles, very similar to anise in size and color are said to be especially 
manufactured. They are readily recognized and separated when a 
sample ■ of the seeds is treated with chloroform or a concentrated 
solution of salt in a test-tube. The seeds will rise to the surface, 
whereas the earth particles settle at the bottom. The amount of 
inorganic admixture can be determined by means of an ash deter- 
mination. Pure anise gives 7-10 p. c. of ash. 
The distilled anise is dried in special apparatus1 and sold as fodder 
for cattle, for which purpose it is highly valued on account of its high 
protein and fat content. According to analyses made in the Royal 
Saxon Experiment Station at Mockern, the anise residues contain 
17-19 p. c. of protein and 16-22 p. c. of fat (Uhlitzsch2). 
It might be metioned that during the distillation, sulphuretted 
hydrogen is given off. 
Properties. Anise oil is, at medium temperature (above 20°), a 
colorless, highly refractory liquid of characteristic odor, and pure, 
intensely sweet taste. In the cold it solidifies to a snow-white, 
crystalline mass, which begins to melt at 15° and becomes completely 
liquid at 19-20°. The oil can under certain conditions be cooled far 
below its solidification point, without becoming solid and can be kept 
i) Musspratt-Stohmann, Technische Cheniie, 4th ed., vol. 1, p. 69. 
2) Die landwirthHchaftlichen Versuchsstationen, 42, p. 29. Oils of the Umbelliferae. 
561 
for a long while in this over-cooled condition. The falling in of a 
particle of dust, touching with a crystal of anethol, a sharp agitation, 
or scratching of the walls of the flask with a glass rod, produces a 
sudden solidification of the entire mass, with considerable rise in 
temperature, the thermometer rising up to the true solidification point 
of the oil. This is, as it is dependent on the anethol-content of the oil, 
a good indicator of the quality of the oil. In normal oils it lies between 
15 and 19°.' The method for determining the solidification point is 
described'in detail on p. 187. 
The sp. gr. of the liquid oil is 0.980-0.990 at 15°. The plane of 
polarized light is slightly turned to the left, aD = -1° 50'. (Different 
from fennel oil and fennel stearoptene which turn the light toward the 
right.) 
For complete solution 1%-5 vol. of 90 p. c. alcohol are required. 
Anise oil can be distinguished from star anise oil only by the odor and 
taste. The reaction with alcoholic hydrochloric acid, recommended for 
this, which was discussed under star anise oil on p. 359, does not give 
reliable results. * 
If anise oil be exposed for some time to the light, in contact with 
air (especially in the liquid state), its crystallizing tendency is diminished 
and finally disappears altogether.1 The phenomenon is due to the 
formation of oxidation products (anisic aldehyde and anisic acid) as 
well as polymers2 (metanethol and photo anethol?). At the same time 
the sp. gr. is increased, which may go so far as to make the oil heavier 
than water. The oil becomes also more readily soluble in 90 p. c. alcohol. 
When anise oil, star anise oil, or anethol (about 2 g.) are evaporated 
in a small dish on a water bath, a comparatively large amount, 9-10 
p. c., of a non-volatile residue remains. This is viscous, odorless, no 
longer tastes sweet, and propably consists mainly of photo anethol, a 
polymer, which, according to the investigations of de Varda3 is formed 
by'the action of light on anethol. / 
Composition. Anise oil consist principally of two isomeric com- 
pounds CioIIiaO, namely, of the anethol, solid at ordinary temperature, 
and of the liquid methyl chavicol.4 
0 This was known at the beginning of this century and is mentioned by Hagen, 
Lehrbuch der Apothekerkunst, 6th ed. (1806), vol. 2, p. 411. 
2) According to Grimaux anethol loses its tendency to crystallize by prolonged 
heating (Bull. Soc. chim., Ill, 15, p. 778). 
3) Gazz. chim. ital., 21, I, p. 183; Berichte, 24, Ref., p. 564. 
4) Bericht von S. & Co., Oct. 1895, p. 6. Bouchardat & Tardy later substantiate the 
occurrence of methyl chavicol (estragol) in Russian anise oil (Compt. rend., 122, p. 624). 562 
Special Part. 
The characteristic properties of the oil are due to the anethol, 
present to the extent of 80-90 p. c., which is therefore its most 
valuable constituent. It forms snow-white laminae and melts at 21.5° 
to a colorless, highly refractory, optically inactive liquid of pure anise 
odor, and an intense sweet taste. The sp. gr. is 0.98(5 at 25°. 
Methyl chavicol is likewise optically inactive and has an anise-like 
odor, without, however, possessing the sweet anise taste. The properties 
and characteristic derivatives of anethol and methyl chavicol are 
described on page 179. In the first runnings of the anise oil, there are 
contained besides acetaldehyde, bad smelling sulphur compounds, and 
possibly small amounts of terpenes. In how far these compounds are 
due to the impurities always accompanying the seeds, cannot be stated. 
Attention may briefly be called to a recent observation by Bouchardat 
and Tardy.1 It was undoubtedly made on an anise oil adulterated 
with fennel oil, and might therefore give rise to a false notion of the 
composition of pure anise oil. The oil investigated by the authors cited 
was %o solid at 10° and turned the ray of polarized light to the right. 
The dextrorotation was almost entirely due to a body, CioHieO, which 
could only be separated from the anethol by oxidation of the latter, 
and which was identical with the fenchone of Wallach. From the liquid, 
freed as much as possible from anethol by repeated freezing, two further 
substances were obtained with bisulphite, anisic aldehyde and a ketone, 
C1OH12O2. The "anise ketone" boiled at 263° and was oxidized by 
permanganate to anisic acid. 
Schimmel & Co.2 remark on this, that the presence of fenchone in 
anise oil has never been observed by them, although they had used up 
many thousand kilos of the oil in making anethol, and that it would have 
been impossible to overlook so stable a body of so penetrating an odor 
as fenchone. Furthermore it would follow, from the statements of 
Bouchardat and Tardy (melting point and rotation) that the anise oil 
had been adulterated with fennel oil to a marked extent. 
In regard to the "anise ketone" it must also remain an open 
question as to whether this body came from the anise oil or the fennel 
oil. This can only be decided by repeating the experiment on un- 
objectionably pure material. 
Adulteration and Examination. The cruder adulterations observed 
so far consisted in the addition of turpentine oil, cedar wood oil, 
copaiba- and gurjun balsam oil, alcohol, spermaceti and fatty oil. All 
i) Compt. rend., 122, p. 198; Bull. Soc. chim.. Ill, 15, p. 612. 
2) Bericht von S. & Co., Apr. 1896, p. 7. Oils of the Umbelliferae. 
563 
these adulterants are detected by the determination of the physical 
properties, as specific gravity, optical rotation, solubility, and solidi- 
fication point (see p. 187). 
The admixture with fennel oil or fennel stearoptene is frequently 
practiced. Even small amounts can, however, be recognized by the 
dextrogyration in the polariscope. Dextrogyrate anise oils are, there- 
fore, in all cases to be rejected. In taking the sample for investigation, 
care must be taken that all the oil is melted and mixed to a homo- 
geneous liquid. 
Attention is here again called to the changes described on p. 561 
under the heading "Properties," which a normal oil may suffer when 
carelessly kept and which must be considered in certain cases when the 
genuineness of an oil is to be determined. 
The best criterion for the quality of anise oil is its solidification 
point, which lies normally between 15 and 19°, usually, however, 
at + 17°. 
308. Oil of Pimpinella Root. 
The oil of the white pimpinella root of Pimpinella saxifraga L. 
(Family Umbelliferae) is a golden yellow liquid of a penetrating and 
unpleasant odor, reminding somewhat of parsley oil, of a disagreeable 
bitter, scratching taste.1 Sp. gr. 0.959 at 15.° It begins to boil at 
240®, then rises to about 300°, a part even passing over above 300°, 
with considerable decomposition.2 
The oil of the black pimpinella root, Pimpinella nigra Willd. (yield 
0.38 p. c.) is light blue, floats on water and smells less penetrating 
than the preceding. It is changed in the sunlight even in closed vessels 
to a green color.3 
309. Oil of Fennel. 
Olenin Foemculi.-Fenchelol.-Essence de Fenouil. 
History. The oil of fennel has no doubt been known since the time 
of the preparation of the distilled waters. In the sixteenth century it 
appears to have been introduced along with fennel water as a remedy 
and its preparation described by Brunschwig and by Porta. In the 
municipal ordinances of drugs and spices it is first mentioned in that 
of Berlin of 1574 and of Frankfurt-on-the-Main of 1582; also in the 
Pharmacopoea Augustana of 1580 and the Dispensatorium Noricum 
of 1589. 
1) Trommsdorff's Neues Journ. d. Pharm., 12, II, p, 63. 
2) Berk'ht von S. & Co., Apr. 1890, p. 37. 
3) Trommsdoj-ff's Neues Journ. d. Pharm., 13, II, p. 43. 564 
Special Part. 
Early investigations of fennel oil were made in 1779 by Heyer of 
Braunschweig,1 in 1792 by Gertinger of Eperies in Hungary,2 and in 
1793 by Gbttling of Jena and Giese of Dorpat. Further observations, 
which like the above deal mainly with fennel camphor (anethol), were 
made by Buchner3 and by Goebel. Blanchet and Sell4 recognized in 
1833 the identity of the stearoptenes from fennel and anise oils. This 
was corroborated in 1842 by Cahours.5 Wallach6 investigated fenchone, 
a body characteristic for fennel oil, which possesses considerable theore- 
tical interest on account of its similarity to camphor. 
Origin. Fennel, Foenicuhun vulgare Gaertn. {F. capillaceum Gilib., 
Anethum /beniculum L.) is a fine umbelliferous plant, which is cultivated 
in Germany (vicinity of Lutzen), Moravia, Galicia, Roumania and Mace- 
donia, in France and Italy, also in India and Japan, partly on account 
of its edible root, but principally on account of its much used fruit. 
The fruits of the fennel cultivated in the various countries differ not 
only externally,7 in form, size and color, but the oils distilled from them 
show greater differences than is the case with the different varieties of 
any other plant. 
The oils of the fennel from Lutzen, Roumania, Galicia, Moravia and 
Japan, are distinguished by the bitter tasting fenchone, which, together 
with anethol, produces the characteristic fennel odor. Fenchone is not 
found in the sweet Roman (French) and Macedonian fennel, anethol. on 
the other hand, is either entirely absent, or present only in traces in 
the wild bitter fennel. 
In the individual fennel oils the greatest variety of terpenes is found. 
The oil of the fennel from Lutzen contains pinene and dipentene, wild 
bitter fennel phellandrene and Macedonian fennel limonene. From this 
it follows that under the name of fennel oil are understood oils of 
entirely different properties. 
In the following the term "fennel oil" applies to the ordinary fennel 
oil of commerce, the Oleum Foeniculi of the Pharmacopoeia, as it is 
obtained by distillation from the fennel from Lutzen, Roumania, Moravia 
and Galicia. 
1) Crell's Chern. Journal. 3, p. 102. 
2) GSttling's Almanack fiir Scheidekiinstler und Apotheker, 14, p. 149. 
3) Buchner's Repert. f. die Pharm., 15, p. 163. 
4) Liebig's Annalen, 6, p. 287. 
s) Liebig's Annalen, 41, p. 74; Journ. fiir prakt. Chem., 24, p. 359. 
6) Liebig's Annalen. 259, p. 324; 263, p. 129. 
7) In an article on the commercial varieties of fennel and their essential oils (Pharm. 
Journ., 58, p. 225) Umney in 1897 described and illustrated the different varieties of 
commerce. Oils of the Ombelliferae. 
565 
Upon distillation of crushed seeds, the principal varieties give the 
following yield: 
Saxon fennel (Lutzen) Yield 4.4-5.5 p. c. 
Galician " " 4.5-6 " 
Moravian " " 4 " 
Roumanian " " 4.6 " 
The distillation residues, which form a valuable cattle food (comp, 
under caraway oil, p. 551) contain after drying 34-22 p. c. of protein 
and 12-18.5 p. c. of fat.1 
Properties. At a medium temperature oil of fennel is a colorless 
or slightly yellow liquid of the peculiar fennel odor, and a taste, which 
is at first bitter and camphor-like, but having a sweet after taste. 
Sp. gr. 0.965-0.975; «d= + 12 to +24°. The solidification point of 
the normal fennel oil, determined as described on p. 187, lies between 
+ 3 and +6°. As with anise oil, so also here, the oil of the highest 
solidification point is the best. 
Fennel oil is soluble in an equal volume of 90 p. c. alcohol, while 
5-8 vol. of 80 p. c. alcohol are required to dissolve 1 vol. of fennel oil. 
Composition. The constituent of fennel oil longest known is anethol, 
crystallizing out in the cold. (See p. 179.) Good oils contain about 
50-60 p. c. of this body. A second compound is also characteristic of 
the oil.2 It is found in the fracticp 190-192°, and has an intensely 
bitter, camphor-like taste. According to the investigations of Wallach 
and Hartmann3 it is a ketone, which was first called fenchol, later 
fenchone. Fenchone, CioHieO, is isomeric and closely related to camphor, 
and giveg a series of analogous derivatives. It boils at 192-193°, has 
the sp. gr. 0.9465 at 19°, is strongly dextrogyrate, [a]D= + 71.97°, 
solidifies at a low temperture and melts again at + 5 to 4- 6°. By 
reduction with sodium it is converted into fenchyl alcohol, CioHisO.4 
For further information see p. 166. 
Of terpenes, d-pinene and dipentene are contained in common fen- 
nel oil. Pinene was detected in the fraction boiling at 157-160° 
(aD=:-^-41o58,) by converting it into pinene nitrosochloride and pinene 
benzylamine, melting at 122°. The fraction boiling at 180° after ten 
t) Die landwirthschaftlichen Versuehsstationen, 42, p. 36. 
2) Bericht von S. & Co.. Apr. 1890, p. 20. 
3) Liebig's Annalen, 259, p. 324; 263, p. 129. 
•i) Laboring under the supposition that this reaction is a quantitative one, Umney 
has elaborated an assay method by converting fenchone into fenchyl alcohol and this into 
the acetate. Inasmuch, however, as it requires repeated treatment with sodium to 
completely reduce the fenchone to fenchyl alcohol, Umney's results must be much too low 
(Pharin. Journ., 58, p. 225). 566 
Special Part. 
fractionations gave, on shaking with hydrobromic acid in glacial acetic 
acid solution, dipentene dihydrobromide, melting at 94°; by bromina- 
tion, dipentene tetrabromide, melting at 123-124°, was obtained. 
The presence of pinene, fenchone and anethol is corroborated by a 
more recent investigation by Tardy*1 on an oil from French, cultivated 
bitter fennel. Newly found were methyl chavicol, as well as anise ketone. 
Anise ketone combines with bisulphite and boils between 260 and 265°. 
Upon oxidation with potassium permanganate, acetic and anisic acids 
result. These meager results, together with an elementary analysis, the 
results of which do not agree very well, hardly justify the assumption 
of a new body of the formula 
The product obtained by Tardy by conducting dry hydrochloric acid 
gas into fraction 176-177° could be separated by distillation in a 
vacuum into two portions, of which the one consisted of cymene, the 
other of dipentene dihydrochloride. Although the original fraction 
yielded no phellandrene nitrite, Tardy, nevertheless, proclaims it as a 
mixture of phellandrene and cymene, assuming that the latter prevents 
a positive phellandrene reaction. In order to make this explanation 
more plausible, it would first have to be proven that the cymene was 
originally in the oil. and that it did not result by the treatment with 
hydrochloric acid. . 
The oxidation products present in all anethol-containing oils, namely 
anisic aldehyde and anisic acid, were also found in this fennel oil. 
Examination. The principal test is that for oils deprived of a part 
of their anethol by fractionation or freezing. The solidification of such 
oils is then below + 3°, which can be considered as the lowest allowable 
limit. The addition of alcohol, which has sometimes been observed, is 
recognized by the lowering of the specific gravity. The same is true 
for turpentine oil. 
The fennel oils described in the following paragraph have more 
scientific than practical interest. 
Oil from the Sweet or Roman Fennel. 
The variety of fennel cultivated in southern France, and formerly 
designated as Fomiculum dulce D. C., yields on distillation 2-3 p. c. 
of oil. It distinguishes itself by its high anethol content and by the 
absence of fenchone. Sp. gr. 0.976-0.980;2 «d = + 7° 50' to + 16° 30' ;2 
solidification point +10 to +12°. 
1) Bull. Soc. chim., Ill, 17. p. 660. 
2) Umney, Pharm. Journ., 58, p. 226. Oils of the Umbelli ferae. 
567 
Oil from Macedonian Fennel. 
The Macedonian fennel oil is very similar to the oil from the sweet 
fennel. It has a purely sweet taste and high anethol content. Yield 
3.4-3.8 p. c. Sp. gr. 0.970-0.980; <zd= + 5 to +12°; solidification 
point +7 to +12°. 
Fenchone is entirely absent in Macedonian fennel oil. The terpenes 
boil from 170-180°. The fraction 170-175° - + 57° 53') gave 
with glacial acetic acid and sodium nitrite a faint, but pronounced 
phellandrene reaction. The fraction 175-180° (aD - J- 64° 33") gave 
by bromination, limonene tetrabromide melting at 104-105°. According 
to this the oil contains d-phellandrene and d-limonene.1 
Oil from the Wild Bitter Fennel. 
The bitter fennel growing wild in France, Spain and Algiers gives 
by distillation about 4 p. c. of a volatile oil. Sp. gr. 0.905-0.925; 
«D = + 48°. 
The principal constituent of bitter fennel oil is a terpene, found by 
Cahours2 and more closely studied by Bunge.3 Wallach4 found this 
terpene to be identical with the d-phellandrene found in water fennel oil 
by Pesci. The higher boiling fractions are slightly bitter, and appear 
therefore to contain some fenchone. Anethol is either entirely absent or 
present only in small amount. 
Oil from the Indian Fennel. 
Distilled from the Indian variety, Foeniculum panmorium I). C. Yield 
0.72 (Umney5) to 1.2 p. c. Sp. gr. 0.968-0.973; «d=+21°; m. p. 
8.2°.5 It contains fenchone and anethol. 
Oil from the Japanese Fennel. 
The Japanese fennel is recognized by its small seeds, and therefore 
sometimes designated in commerce as Japanese anise. The oil is very 
similar to the German fennel oil. Yield 2.7 p. c. (Umney6); sp. gr. 
0.975 7-0.976; «d= + 107 to +16°; solidification point +7°. Fen- 
chone and anethol are constituents of the Japanese fennel oil. 
1) Observation in the laboratory of 
Schimmel & Co. 
2) Liebig's Annalen, 41, p. 74. 
3) Zeitschr. f Chemie, 5, p. 579. 
4) Liebig's Annalen, 23!), p. 40. 
5) Pharm. Journ., 58, p. 226. 
6) Pharm. Journ., 57, p. 91. 
7) Berieht von S. & Co., Oct. 1893, p. 46. 568 
Special Part. 
Oil from the Sicilian Ass Fennel. 
The sharp tasting fruit of the Foeniculum piperitum D. C. \Finocchio 
d'asino) used in southern Italy as a spice, yields upon distillation 2.9 
p. c. of oil. The sp. gr. of the oil is 0.951. It can contain only traces 
of anethol, as on cooling to -5° no separation of anethol took place. 
Oil of Fennel from Asia Minor.1 
Yield 0.75 p. c.; sp. gr. 0.987. 
Oil from the Syrian Fennel.1 
Yield 1.6 p. c.; sp. gr. 0.972. 
Oil from the Persian Fennel.2 
Yield 1.7 p. c.; sp. gr. 0.977; «d= + 14°; m. p. 11.2°. 
Oil from Russian Fennel.2 
Yield 4.8 p. c.; sp. gr. 0.967; an = + 23°; m. p. 4.4°. 
310. Oil of Meum Athamanticum. 
Barwurzbl. 
The dry roots of Meum athamanticum Jacq. (Germ. Barwurz), gave 
on distillation 0.67 p. c. of a dark yellow oil, very similar in odor to 
lovage oil. Its sp. gr. at 21° is 0.999. It began to boil at 170° and 
above 300° greenish-blue fractions, smelling like celery, came over. By 
distillation from a glass flask about half the oil resinified.3 
311. Oil of Silaus Pratensis. 
Silanol. 
The fruit4 of Silaus pratensis Besser (Family Umbelliferae), growing 
wild in Germany, gives by distillation 1.4 p. c. of oil, the odor of which 
reminds strongly of estragon. A stearoptene separates in fine needles 
when exposed to the cold. Sp. gr. 0.982; «d=;+0o7'. Saponification 
number 20.8. 
312. Oil of Water Fennel. 
Oleum Phellandrii Aquatici. - Wasserfenchelbl. - Essence de Fenouil d'Eau. 
The fruit of the water fennel, Oenanthe aquatica Lain. {Oenanthe 
phellandrium Lam., Phellandrium aquaticum L.), contains 1-2.5 p. c. of 
i) Bericht von S. & Co.,'Apr. 1897, p. 20 of Suppl 
2) Pharm. Journ., 58, p. 226. 
3) Bericht von S. & Co., Apr. 1889, p. 43. 
*) Bericht von S. & Co., Oct. 1895, p. 59. Oils of the UmbelUferae. 
569 
volatile oil. Oil of water fennel is at first a colorless to wine yellow 
liquid, becoming darker with age. It has a strong penetrating odor 
and burning taste. The sp. gr. is 0.85-0.89; «□= 4- 12° 42' to + 15° 30'. 
It begins to boil at about 170° and about 50-60 p. c. go over up to 
172°. On further heating the thermometer rises gradually to 300°. and 
finally a black resin remains in the flask (Bauer1). 
According to an investigation by Pesci2 in 1886 the oil consists to 
the extent of 80 p. c. of a terpene, characterized by a nitrite melting at 
103°, which has been called phellandrene, after the name of the plant 
yielding the oil.3 For the properties and derivatives of this hydrocarbon 
see p. 121. 
Haensel4 has observed the separation of a small amount of a heavy 
oil on the bottom of the Florentine flask during distillation. 
313. Oil of Lovage. 
Oleum Levistici.-Liebstockbl. -Essence de Liveche. 
Origin and History. The original habitat of the umbelliferous 
plant Levisticum officinale Koch (Angelica levisticum Baillon, Ligusti- 
cum levisticum L.), now much cultivated as a kitchen spice, has not 
been determined, nor has the plant been definitely found growing wild. 
The distillates from lovage root are often mentioned in rhe later 
treatises on distillation. 
The oil distilled from the root appears to have come into use about 
the middle of the sixteenth century. It is mentioned as Oleum Levistici 
in the price ordinance of Frankfurt-on-the-main of 1587 and as Oleum 
Ligustici in the 1589 edition of the Dispensatorium Noricum. 
All parts of the lovage plant contain volatile oil. Formerly only 
that from the root was prepared, but lately the oil from the fruit and 
herb is also made. 
Preparation. The aromatic, fresh roots of lovage yield upon 
distillation with water vapor 0.3 to 0.5 p. c., the dried roots 0.6-1 p. c. 
of oil, the odor of which resembles that of angelica oil. According to 
whether the fresh or dried roots are used in the distillation, a yellow 
or a brown oil is obtained. These oils show but a slight difference in 
specific gravity, but behave differently during the process of distillation.5 
When dry lovage root is distilled there appears together with the oil, 
i) Ueber das atherische Oel von Phellan- 
drium aquaticum. Inaug. Dissertat. Frei- 
burg, 1885. 
2) Gazz. chim. itai., 16, p. 225. 
3) Liebig's Annalen. 239, p. 40. 
Pharm. Zeitung, 43, p 760. 
5) Bericht von S. & Co., Apr. 1895, p. 9. 570 
Special Part 
from the very beginning of the distillation, but especially toward the 
end, a yellow, sticky, resinous body, which in part separates in the 
outflow tube of the receiver, but the larger part of which remains dis- 
solved in the oil. When the green root is distilled this resin is scarcely 
noticeable. If the root has just been collected this resin is altogether 
absent. When the oil from the fresh root is rectified, almost the entire 
oil is volatile; the oil from the dry root, however, leaves behind a large 
amount of resin. 
Properties. Sp. gr. 1.0(H) to 1.040. The oil is inactive (Braun1) 
or slightly (up to + 5°) dextrogyrate.2 It dissolves to a clear solution 
in 2-3 p. of 80 p. c. alcohol. 
Composition. If the oil saponified with alcoholic potassa be distilled 
with water vapor and then fractionated there will be obtained, accord- 
ing to Braun,1 a fraction boiling at 176° under ordinary atmospheric 
pressure (sp. gr. 0.8534, «d-+ 5°) and having the composition of a 
terpene. Schimmel & Co. isolated as principal fraction a liquid boiling 
between 107 and 115° under 15 mm. pressure. From this could be 
separated at ordinary pressure a fraction boiling at 217-218°, which 
solidified to a crystalline mass and had all the properties of solid 
d-terpineol; 3 «d (in over-cooled condition) = +79° 18'at 22°. M. p. of 
terpinyl phenyl urethane 112°, of terpineol nitrolpiperidine. 151-152°. 
The dihydriodide prepared from the terpineol melted at 77-78°. 
314. Oil of Lovage Fruit. 
The fruit of lovage yields upon distillation 1.1 p. c. of a distillate 
very similar to that obtained from the root. Sp. gr. 0.935.4 
315. Oil of Lovage Herb. 
The fresh herb and flower stems of Levisticum officinale yield 
0.05-0.15 p. e. of oil, which is very similar in odor to that of the root. 
It has the sp. gr. 0.904-0.940, «d= + 16 to + 46°. It is soluble in 
an equal part of 90 p. c. alcohol. 
316. Oil of Angelica. 
Oleum Angelicae. -Angrlicawurzelol. - Essence d'Ang&iqne. 
Origin and History. Angelica (Ger. Engelwurz), Archangelica offici- 
nalis Hoffm. (Angelica archangelica L.) (Family Umbelli ferae}, grows 
i) Archiv d. Pharm., 235, pp. 2 and 18. 
2) Fliickiger (Pharmacognosie, 3rd ed., p. 460) found an oil, the source of which is 
not mentioned, to be laevogyrate. 
3) Bericht von S. & Co., Apr. 1897, p. 27; Oct. 1897, p. 9, footnote 3. 
*) Bericht von S. & Co., Apr. 1890, p. 48. Oils of the Umbelliferae. 
571 
here and there throughout northern Europe as far as Siberia and is 
much cultivated as a drug and for the manufacture of liquors. The 
plant is the finest of the north European umbellifers and contains in 
all parts a peculiar aromatic volatile oil, especially in the root and 
fruit. The fresh green parts of the plant serve as a much liked vegetable 
in the northern parts of Europe, Sweden and Finnland, and on Iceland 
and Greenland. 
Angelica appears to have first come into use as a spice plant during 
the fifteenth century, and was no doubt first used for the preparation 
of the distilled angelica water, the preparation of which is described in 
Brunschwig's and in later treatises on distillation. 
The distilled oil of the roots was not prepared until the second half 
of the sixteenth century and first mentioned in the price ordinance of 
Frankfurt in 1582 and in the Dispensatorium Noricum of 1589. 
Recently the oil from the fresh roots, the stems and leaves and 
that of the fruit, have also come into use. 
In composition the oils of the various parts, and of the fresh and 
dried plants, are on the whole identical. Marked differences exist, how- 
ever, in the quality of the aroma. The aroma, as with so many plants, 
appears to be affected by the place of growth, the moisture of the 
atmosphere and the intensity of the light during the time of develop- 
ment of the plant. 
Oil of angelica root was investigated by Buchner in 1842,1 by 
Beilstein and Wiegand in 1882,2 by Naudin in 1883,3 and by Ciamician 
and Silber in 1896.4 
Preparation. The oil of the roots as well as that of the fruit 
(oil of angelica seed) finds practical application. The distillation 
material comes mostly from Thuringia and Saxony (Erz-Gebirge), 
although sometimes the fruit from France, from Moravia and the Harz 
are used for the preparation of the oil. 
The yield from the dry root is 0.35-1 p. c.; from the fresh root, 
which gives a finer oil, 0.2-0.37 p. c. 
Properties. The oil from the root is, when freshly distilled, an 
almost colorless liquid of a pleasant balsamic odor. It becomes yellow 
to brownish when kept, due to the action of light and air. The odor 
is very aromatic, pepper-like with a slight admixture of musk. The 
taste is spicy. Sp. gr. 0.857-0.918; «d = + 16 to +32°. 
1) Buchner's Repert. f. d. Pharm., 76, p. 167. 
2) Berichte, 15, p. 1741. 
3) Bull. Soc. ehim., 39, p. 114 
4) Berichte, 29, p. 1811. 572 
Special Part. 
Composition. The oil investigated by Beilstein and Wiegand1 gave 
on distillation a principal fraction at 160-175°; a small part boiled 
between 175 and 200°, and still less above 200°. The lowest fraction 
had after repeated fractionation the constant boiling point 158° and 
the composition CioHie. The terpene absorbed 1 mol. of hydrochloric 
acid gas, but did not separate a solid hydrochloride. The fraction 
going over between 170 and 175° formed the principal product and 
likewise corresponded to the formula CioHie. From this fraction a 
hydrochloride melting at 127° crystallized out, after passing hydro- 
chloric acid gas into the oil. After repeated treatment with sodium the 
fraction boiling originally at 175-200° boiled constant at 176°. The 
analysis indicates a mixture of terpenes and cymene. From the diffi- 
cultly volatile portions a hydrocarbon boiling at 250°, probably a 
sesquiterpene, was obtained. 
Naudin2 obtained by fractionation a pepper-like smelling terpene of 
the boiling point 166°, which he called 3-terebangelene. 
Schimmel & Co.3 showed the presence of phellandrene in the oil by 
the preparation of the nitrite. As the solution of the phellandrene 
nitrite in chloroform turns the ray of polarized light to the left, and 
as the rotation of the nitrite is in the opposite direction to that of the 
hydrocarbon, it follows that d-phellandrene is contained in angelica 
root oil. 
From the investigations of Beilstein, Wiegand and Naudin it can be 
concluded that other terpenes (probably pinene) are also present. No 
doubt the /3-terebangelene of Naudin can be considered as a mixture of 
phellandrene with a lower boiling terpene. 
The high boiling fractions, in which the carrier of the musk-like 
odor is present, were investigated by Ciamician and Silber.4 
From the fraction obtained last during a st^am distillation, fine 
crystalline leaflets of the melting point 74-77° separated. The amount 
was too small for a detailed investigation; it was probably the an- 
hydride of an oxy acid. The oil distilled in a vacuum was saponified 
with alcoholic potassa. The non-saponiflable part had the characteristic 
odor of the sesquiterpenes and boiled between 240 and 270°. Sulphuric 
acid separated two acids from the alkaline solution; 1) a valerianic 
acid, methyl ethyl acetic acid, the calcium salt of which crystallizes with 
five mol. of water; 2) oxy penta decylic acid, C15H3.O3, which when 
crystallized from ether, forms star grouped needles of the m. p. 84°. 
1) Berichte, 15, p. 1741. 
2) Bull. Soc. chim., II., 39, p. 407. 
3) Bericht von S. & Co., Apr. 1891, p. 3. 
*) Berichte, 29, p. 1811. Oils of the Umbelliferae. 
573 
Of the derivatives of this acid were prepared the barium salt, the acet- 
penta decylic acid of the m. p. 59°, the brom-penta decylic acid, m. p. 
65°, and finally the iod-penta decylic acid, m. p. 78-79° and crystal- 
lizing in pearly scales. It may be mentioned that the next lower 
homologue of oxy penta decylic acid, oxy myristinic acid, is contained 
in the oil from angelica seed. 
317. Oil of Angelica Seed. 
Angelikasamenol. 
Angelica seed yields upon distillation 1-1.2 p. c. of oil. 
Properties. The oil is very similar to that obtained from the root. 
Sp. gr. 0.856-0.890; «d = + 11 to +12°. 
Composition. Neither of the investigations for the terpenes of the 
oil from the seed made by Muller1 in 1881 and by Naudin2 in 1882 
yielded positive results. 
The only hydrocarbon definitely determined is phellandrene.3 It is 
probable that, as in the case of the oil of the root, phellandrene is not 
the only terpene. 
Of oxygenated constituents Muller found after saponifying the oil 
with alcoholic potassa two acids. 1) A valerianic acid, namely methyl 
ethyl acetic acid, as was shown by the properties of its barium salt. 
2) Oxy myristinic acid, pearly leaflets of the m. p. 51°. It is found in 
the highest boiling and in the non-volatile portions. A number of salts 
were prepared and analysed. Benzoyl oxy myristinic acid, crystallizing 
in small white leaflets and melting at 68°, was also prepared. 
318. Oil of Angelica Herb. 
Augelikakrautol. 
Fresh angelica herb yields about 0.1 p. c. of oil4 on distillation. 
In odor it differs but slightly or not at all from the root oil. Sp. gr. 
0.870-0.890; «D = + 8 to +21°. 
319. Japanese Oil of Angelica. 
Japanisches Angelikaol. 
Two species of angelica are cultivated in Japan for their roots. 
They are Angelica refracta Fr. Schmidt (Japanese Senkiyu) and Angelica, 
anomala Lail. = Angelica japonica A. Gray (Japanese Biyakushi) 
(Rein5). 
1) Berichte, 14, p. 2476. 
2) Bull. Soe. chim., II, 37, p. 107; 
•Compt. rend., 93, p. 1146. 
3) Bericht von S. & Co., Apr. 1891, p. 8. 
+) Bericht von S. & Co., Apr. 1895, p. 10. 
5) Japan. Leipzig, 1886. vol. II, p. 159. 574 
Special Part. 
* The Japanese angelica root1 is somewhat poor in oil, containing 
only 0.07-0.1 p. c. Sp. gr. 0.910 at 20°. At 4-10° the oil separates 
crystals and at 0° it solidifies. The crystal mass obtained by freezing 
and suction filtering has the property of a fatty acid, the melting point 
of which, after several recrystallizations, was 62-63°. (Impure oxy 
penta decylic acid?) 
The boiling point of the oil lies between 170-310°. The fractions 
coming over last are of a fine bluish-green color. The residue solidifies 
upon cooling and consists mainly of the non-volatile acid. 
The odor of the Japanese oil is exceptionally intensive and persistent, 
also sharper than that of the German oil. It also has the characteristic 
admixture of musk odor. 
From the fruit of the Japanese angelica Murai obtained 0.67 p. c. 
of oil.1 
320. Oil of Asafetida. 
Oleum Asae Foetidae. - Asantol, Oel von Asa foetida. - Essence d'Ase Fetide. 
Origin and History. Asafetida (Ger. Asant, Stinkasant or Teufels- 
dreck) is the dried-up milk sap of several species of Ferula and Peuce- 
danum, especially of Ferula asa foetida. L. growing in Persia, Afghanistan 
and the table lands of northwestern Asia. 
In the mediaeval distilling books, asafetida is not used by itself, 
but as an addition in the distillation of alcoholic balsams. The volatile 
oil of asafetida is apparently first mentioned in the price ordinance of 
Strassburg for 1685. 
Asafetida yields upon distillation 3-6.7 p. c. of volatile oil, which 
possesses to a high degree the unpleasant odor of the drug, reminding 
of onions and garlic. Its color is yellow to brown. Sp. gr. 0.975-0.990; 
optical rotation2 «d = - 9° 15' (single observation). 
Composition. According to an investigation by Hlasiwetz3 in 1849 
the oil is free from oxygen and nitrogen and contains (CgHh)2S, hexenyl 
sulphide, and (CeHi 1)282, hexenyl disulphide. 
Semmler,4 however, in 1891 reached entirely different conclusions. 
He found a small amount of oxygenated compounds and an entirely 
i) Bericht von S. & Co., Apr. 1889, p. 4. 
2) Fliickiger (Pharmacognosie, 3rd ed., p. 59) observed +13 to +19° which led 
Semmler to suppose that the oils examihed by Fliickiger consisted only of the lower 
dextrogyrate fractions. This would also explain the low sp. gr. (0.9515 at 25° - abt. 
0.96 at 15°) of Fluckiger's oils. 
3) Liebig's Annalen, 71, p. 23. 
4) Archiv d. Pharm., 229, p. 1; Berichte, 23, p. 3530; 24, p. 78. Oils of the Umbelliferae. 
575 
different composition for the sulphides. He separated from the lowest 
boiling fractions, by repeated distillation from metallic potassium, two 
terpenes: 
A hydrocarbon apparently identical with pinene. Sp. gr. 0.8602 at 
10°; av - + 32° 30'. It formed a liquid dibrom addition product 
CioHujBra. A second terpene in smaller amount, which gave a solid 
tetrabromide CioHi6Br4. 
From the higher boiling portions the following compounds were 
isolated: 
A disulphide C7H14S2, b. p. 83-84° at 9 mm.; sp. gr. 0.9721 at 15°; 
«d = -12° 30'; it is present to the extent of 45 p. c. in the crude oil. 
A disulphide C11H20S2, which makes up 20 p. c. of the oil. Sp. gr. 
1.0121 at 14°; b. p. 126-127° at 9 mm.; «d = -18° 30'. The 
repulsive odor of asafetida oil is due principally to this compound. 
A body (CioHi6O)n- Sp. gr. 0.9639 at 22°; b. p. 133-145° at 9 mm.; 
«d =-16°. It is contained to the extent of 20 p. c. in the crude oil. 
By treatment with sodium, cadinene C15H24, results. 
A compound CsHniS?. B. p. 92-96° under 9 mm. pressure. 
A disulphide CioHi8S2. B. p. 112-116°. 
321. Oil of Galbanum. 
Galbanumol. 
Origin and History. Galbanum, a gum resin, is the dried milky 
juice exuding from the trunks and larger branches of the umbelliferous 
plant Ferula rubricaulis Boissier, F. galbaniflua Boissier et Buhse 
(Peucedanum rubricaule H. Bailion, P. galbanifluum H. Baillon and 
probably also of Ferula ^Peucedanum} Schair growing in Persia. 
Distilled oil of galbanum was prepared by Ryff, by Gesner, and by 
Rubens. It was included in the 1589 edition of the Dispensatorium 
Noricum and in the Pharmacopoea Augustana of 1580, and mentioned 
in apothecary and spice ordinances about 1560. Early cursory in- 
vestigations of the oil were made by Neumann about 1728, by Walther 
in Leipzig about 1744, by Fiddichow in 18151 and by Meissner in 1816.2 
Preparation and Properties. The aromatic, not unpleasant odor 
of galbanum is due to its large content of volatile oil. The yield on 
distillation is different according to the age of the drug and varies 
between 14 and 22 p. c. 
i) Berl. Jahrbuch der Pharmacie, 1816, p. 230. 
2) Trommsdorff's N. Journ. d. Pharm., 1, I, p. 3. 576 
Special Part. 
Oil of galbanum is yellowish, has the sp. gr. 0.910-0.940 and turns 
the ray of polarized light either to the right or to the left, «d -+ 20° 
to -10°. According to Hirschsohn1 Persian galbanum yields a dextro- 
gyrate, levant galbanum, however, a laevogyrate oil. 
Composition. An oil investigated by Mossmer.2 which boiled almost 
completely between 160 and 165° cannot be considered as normal, as 
the distillation with water from a glass retort will yield only the lower 
boiling portions and not the difficultly volatile, higher hydrocarbons. 
The dextrogyrate hydrocarbon CioHie, boiling at 160-161°, gave 
with hydrochloric acid a crystalline compound, which agreed completely 
in its properties with the corresponding body from turpentine oil. 
Mossmer did not succeed in obtaining terpin hydrate with nitric acid, 
but Fliickiger3 was successful in preparing it in this manner. The terpene 
of galbanum oil, is therefore, d-pinene. 
Fraction 270-280° contains, according to Wallach,4 cadinene, 
C15H24, the presence of which was shown by the preparation of its 
dihydrochloride, melting at 117-118°. 
322. Oil of Sumbul. 
Oleum Sumbuli. - Moschnswurzel- Oder Sumbulwurzelbl.-Essence de Sumbul. 
In East India the roots of several aromatic plants are designated 
as sumbul. The root of Nardostachys jatamansi D. C. is known as 
Sumbul Hindi, the root of Valeriana celtica L. as Sumbul Ekleti, Sumbul 
Ekelti, Sumbul Kumi and Sumbul italicus.^ The root of Dorema 
ammoniacum Don. often used for adulterating the genuine sumbul root, 
is known as Bombay sumbul or Boi* 
The genuine sumbul root comes from Ferula sumbul Hooker fil. 
Euryangium sumbul Kauffmann) and was first brought into Europe in 
1835. On distillation it yields 0.2-0.4 p. c. of a viscous, dark colored 
oil of musk-like odor, and a sp. gr. of 0.954-0.964. The saponification 
number of the oil is 92 (single determination). It is not soluble in 10 
vol. of 80 p. c. alcohol but in an equal volume of 90 p. c. alcohol. 
Nothing is known as to the composition of the oil. 
323. Oil of Gum Ammoniac. 
Ammoniakgummibl. 
Origin and History. The flow of a gum resin from the umbelliferous 
plant Dorema ammoniacum Don. (Peucedanum ammoniacum H. Baillon), 
i) Jahresb. f. d. Pharm., 1875, p. 113. 
2) Liebig's Annalen, 119, p. 257. 
3) Pharmacognosie, 3rd ed., p. 65. 
4) Liebig's Annalen, 238, p. 81. 
s) Pharm. Journ., I. 7, p. 546. 
6) Pharmacographia, 2nd ed., p. 313. Oils of the Umbelliferae. 
577 
rich in milky sap, is produced by insects. The gum resin, hardened by 
contact with the air, was used in antiquity on account of its pleasant 
odor, as incense, and together with other resins for embalming and 
probably also as a remedy. The plant grows on sterile ground in many 
parts of anterior Asia and in eastern North Africa. The botanical source 
of the gum resin was determined in 1829 by David Don of London.1 
The oil of gum ammoniac was distilled by Ryff, Cordus and Gesner 
and is included in the Frankfurt tax for the year 1587 and in the 
Dispensatorium Noricum of 1589. 
Earlier investigations were made by Buchholz2 and by Calmeyer3 
in 1808, by Braconnot4 in 1809, and by Hagen5 in 1814. 
Properties. The ammoniacum of commerce gives on distillation 
0.3 p. c. of a dark yellow oil, smelling strongly of the crude material, 
and reminding vividly of angelica.6 
It is slightly dextrogyrate,7 has the sp. gr. 0.891 at 15° and boils 
principally from 250 to 290°. Between 155 and 170° only a small 
portion goes over.8 It is free from sulphur. 
324-. Oil of Peucedanum Oreoselinum. 
Berg-petersilienol. 
Schnedermann and Winkler9 in 1844 prepared from the fresh herb 
of Peucedanum oreoselinum Moench (Athamanta oreoselinum L.) a 
volatile oil by water distillation. It had a strong, aromatic odor, some- 
what similar to juniper. Sp. gr. 0.843. It boiled at 163° and consisted, 
as is seen from the analysis, almost entirely of terpenes. With hydro- 
chloric acid a liquid monohydrochloride CioHiuHCl was obtained. 
Which terpene or terpenes are the basis for this compound cannot 
be decided from the meagre results given. 
325. Oil of Peucedanum Ostruthium. 
From the dry root of Peucedanum ostruthium Koch [Imperatoria 
ostruthium Lj 0.2-0.8 p. c. of oil are obtained by distillation. It has 
i) Buchner's Bepert., 37, p. 115; Trans, of the Linnean Soc. of London, 16, p. 601. 
2) Taschenb. f. Scheidekiinstler u. Apoth., 1809, p. 170. 
3) Trommsdorff's Journ. d. Pharm., 17, II, p. 82. 
4) Ann. de Chim., 68; Trommsdorff's Journ. d. Pharm., 18, I, p. 202. 
5) Berl. Jahrbuch d. Pharmacie, 1815, p. 95. 
6) Bericht von S. & Co., Apr. 1890, p. 47. 
7) Pharmacognosie, 3rd ed., p. 73. 
8) Archiv d. Pharm., 233, p. 553. 
9) Liebig's Annalen, 51, p. 336. 578 
Special Part. 
an odor reminding strongly of angelica oil, and a biting aromatic 
taste. It has a sp. gr. of 0.8771 and boils from 170 to 190°. 
The investigations2 made up to the present have thrown no light 
on the composition of the oil. 
326. Oil of Dill. 
Oleum Anethi. - Dillol. - Essence d'Aneth. 
Origin and History. The fruit of the dill, Peucedanum graveolens 
Benth. et Hook. (Anethum graveolens L.), an umbelliferous plant, 
indigenous to the Caucasus and Mediterranean countries, but now 
cultivated in many other places, has been known since antiquity. 
In the treatises on distillation of the fifteenth and sixteenth century 
the distillation of dill is often mentioned. In German apothecary and 
spice ordinances, dill oil is first mentioned in that of Frankfurt-on-the- 
Main for 1587. 
Preparation. Dill, which on account of its aromatic seed is culti- 
vated in Bavaria, Thuringia and Roumania, yields on distillation 3-4 
p. c. of oil. The dried distillation residues contain 14.5-15.6 p. c. of 
protein and 15.5-18 p. c. of fat and are used as cattle food.3 
Properties. The oil, though colorless at first, soon becomes yellow 
on keeping. The odor reminds strongly of caraway oil, yet can be 
distinguished from this by its peculiar dill aroma. The taste is at first 
mild, later sharp and burning. Sp. gr. 0.895 (as a rule above 0.900) 
to 0.915; «d = + 75 to +80°. Dill oil is soluble in 5-8 parts of 80 
p. c. alcohol to a clear solution. 
Composition. Carvone,4 present to the extent of 40-60 p. c. is the 
most important constituent of dill oil. As dill carvone has the same 
rotatory power, as well as the other properties of the carvone from 
caraway oil, the two are to be considered as entirely identical (Beyer5). 
(Com. p. 160.) 
As far as the terpenes in the oil are concerned, Wallach6 has shown 
the presence of limonene in fraction 175-180° by preparing its tetra- 
bromide melting at 104-105°. 
1) Bericht von S. & Co., Oct. 1887, p. 35. 
2) Hirzel (1849), Journ. f. prakt. Chem., 46, p. 292; Pharm. CentralbL, 1849, p. 37. 
Wagner (1854), Journ. f. prakt. Chem., 62, p. 280. 
3) Die landwirthschaftlichen Versuchsstationen, 42, p. 62. 
*) Journ. Chem. Soc., 25, p. 1; Jahresb. f. Chem., 1872, p. 816. 
5) Archiv d. Pharm., 221, p. 283. 
3) Liebig's Annalen, 227, p. 292. Oils of the Umbelliferae. 
579 
Limonene is the principal hydrocarbon of dill oil. Other terpenes 
are, however, present. Nietzki1 in 1874 isolated 10 p. c. of a hydro- 
carbon, CioHio, boiling at 155-160°, which yielded on treatment with 
dilute acid terpin hydrate, but gave no crystalline hydrochloride. 
Schimmel & Co.2 report on an oil distilled in England, in which a 
decided phellandrene reaction was obtained with sodium nitrite and 
glacial acetic acid. On repeating, this test on German oil, the reaction 
for phellandrene failed completely, using the oil as a whole. By using 
the first fraction, * however, the phellandrene could also be detected by 
the formation of the nitrite. Spanish oil, like the English, readily gives 
the reaction for phellandrene.3 
Dill-apiol, boiling at 285° and found in the East Indian dill oil, does 
not occur in the German oil. In a fractional distillation, made for the 
purpose of detecting this body, it was found that the oil contains no 
constituents boiling higher than carvone.2 In the flask remained a 
slight residue, solidifying to a solid mass, which crystallized from 
petroleum ether in colorless laminae, melting at 64°. As must be con- 
cluded from its indifference to concentrated sulphuric acid, it consisted 
of paraffin. 
337. East Indian Dill Oil. 
The oil obtained from the East Indian and Japanese dill of Anethum 
sowa D. 0., differs from that of Anethum graveolens L. not only physi- 
cally but also in its chemical compostion.4 
The East Indian dill oil (yield 2-3 p. c.) has the sp. gr. 0.9485 to 
0.970 6 and the rotatory power «d -+ 41°30' 7 to +47° 30'.5 For the 
Japanese oil, Umney observed the sp. gr. 0.9G4 and the angle of 
rotation «d = + 50° 30'. 
In the distillation a part heavier than water separated at the 
bottom of the receiver, a phenomenon which has never been noticed 
with the common dill oil.6 This specifically heavier portion consists, 
i) Archlv d. Pharm., 204, p. 317. 
2) Bericht von S. & Co., Apr. 1897, p. 13. 
s) Bericht von S. & Co., Oct. 1898, p. 20. 
*) Although Fliickiger and Hanbury (Pharmacographia) do not regard East Indian 
dill as a separate species, more recently scientists are more inclined to regard the 
Indian (and Japanese) dill as a distinct species (Anethum sowa D. C.) on account of the 
botanical as well as on the decided chemical differences. (Comp. Umney, Pharm. Journ., 
61, p. 176; also Bericht von S. & Co., Oct. 1898, p. 18.) 
5) Pharm. Journ., Ill, 25, p. 977. 
6) Bericht von S. & Co., Oct. 1891, p. 12. 
7) Berichte, 29, p. 1799. 580 
Specia l Part. 
according to an investigation of Ciamician and Silber,1 of a body 
closely related to and isomeric with the apiol from parsley oil, called 
dill-apiol. 
Dill-apiol, C12H14O4, is a thick oily fluid which boils at 162° under 
11 mm. pressure, and at 285° under atmospheric pressure. By the 
action of bromine in excess the dibromide of monobrom-apiol, crystal- 
lizing in colorless prisms and •melting at 110°, is formed. 
Dill-isoapiol is obtained, analogous to isoapiol, by heating dill-apiol 
with dry sodium ethylate to 150-170°. It forms colorless, shining 
prisms melting at 44° and boiling at 296° with slight decomposition. 
By oxidation of the dill-isoapiol with potassium permanganate the 
following substances were obtained: 1) Apiol aldehyde, CioHioOs, white 
needles, m. p. 75°; 2) apiolic acid. CioHioOg, m. p. 151-152°. 3) apiol 
ketonic acid, CiiHioOt, light yellow laminae, m. p. 175°. 
By fusing the dill-apiolic acid with potassa, dimethyl apionol carbonic 
acid is formed, which by dry distillation yields quantitatively dimethyl 
apionol, boiling at 283°. This can be readily changed by methyl iodide 
into tetramethyl apionol melting at 89° and identical with that obtained 
from parsley-apiol. 
OH EC 
P w OH(3] 
UH20H [2] 
OHIO 
Apionol. 
OCH3M 
p M OCH3[3] 
b6n20UH3f2] 
OCH3H] 
Tetramethyl apionol. 
0>LH2L4] 
C6H0CH3 [3] 
OCH3 121 
C3H5 hi 
Aplol I. 
OCH8 E51 
°>chJ4J 
C6H0>LH2E3] 
OCH3 [2] 
C3H5 IB 
Aplol II. 
Which of these two formulas belongs to the apiol from parsley oil 
and which to that from dill oil is still to be determined. 
328. Oil of Peucedanum Sativum. 
Pastinakol. 
The dried fruit of Peucedanum sativum (Pastinaca sativa L.) yields 
by distillation with water vapor 1.5 to 2.5 p. c. of oil.2 The oil is 
yellowish and has a penetrating, persistent odor. Sp. gr. 0.87-0.89; 
«d -- 0°15'to-0°30'; saponification number about 170. 
Composition. The chemical composition of the oil appears to change 
with the ripening of the fruit. 
Van Renesse8 in 1873 found that the greater part of an oil, distilled 
from the ripe fruit, boiled between 244 and 245° and consisted of the 
1) Berichte, 29, p. 1799. 
2) Wittstein in 3 839 (Buchner's Repert. f. d. Pharm., 68, p. 15) obtained a yield, 
of but 0.7 p. c. 
3) Liebig's Annalen, 166, p. 84. Oils of the Umbelliferae. 
581 
octyl ester of normal butyric acid. The acid contained in the portion 
distilling over below 244° gave on the analysis of its silver salts figures 
which point to a mixture of butyric acid with an acid of less carbon 
content. Whether this is propionic acid, as van Renesse suspects, or 
some other acid, cannot at present be decided. 
An oil distilled by Gutzeit1 from ripe and half ripe fruit was less 
simple in composition: It consisted for the greater part of the following 
three fractions: 
195-210° 58.6 p. c. 
233-240° 29.3 " 
240-270° 12.1 " 
The presence of ethyl alcohol was shown by Gutzeit in the distil- 
lation water. 
329. Oil from the Fruit of Peucedanum Grande. 
The oil from the fruit of Peucedanum grande C. B. Clarke has an 
exceedingly strong, spicy odor,2 reminding of the carrot oil. Sp. gr. 
0.9008 at 15.5°; «d -+ 36°. It boils from 185-228°, leaving a quite 
large residue.3 
330. Oil of Peucedanum Root. 
The dry root of Peucedanum officinale L. gives 0.2 p. c. of a 
yellowish-brown oil4 of an intensive, persistent odor, hardly pleasant 
and reminding most of senega root. 
Sp. gr. 0.902; «D =: + 29° 4'; saponification number 62. Upon 
standing in the cold the oil separated a solid body, which when twice 
recrystallized from alcohol formed somewhat yellowish laminae melting 
at 100°. 
331. Oil of Heracleum. 
Barenklauol. 
The oils obtained from the fruits of different species of Heracleum 
are of no practical importance, but are very interesting from a scientific 
point of view. On the one hand because the esters of the fatty acids 
of alcohols of the paraffin series, otherwise difficult to obtain, are con- 
tained in them, and on the other hand, because the predominant con- 
stituents in different stages of the development of the fruit allow of 
drawing certain conclusions in plant physiology. It has namely been 
1) Liebig's Annalen, 177, p. 372. 
2) Bericht von S. & Co., Apr. 1891, p. 50. 
3) Pharmacographia Indica, vol. 2, p. 126. 
4) Bericht von S. & Co., Apr. 1895, p. 73. 582 
Special Part. 
determined that not only the oil content, bat also the chemical com- 
position of the oil is dependent on the stage of ripeness of the seed. 
In the oils distilled from half ripe fruit, compounds of low carbon con- 
tent are found which are absent from the oil of the ripe fruit, and 
which seem to disappear in the course of the ripening. From this it 
appears that the bodies of low carbon content are first formed in the 
fruit, and are then used for the building up of the compounds of higher 
carbon content. 
The yield of oil varies1 with the fruit of Heracleum sphondylium L. 
from 0.32-3 p. c.3 The oil is a yellowish, acid reacting liquid, of a 
penetrating and persistent odor and a sharp taste. Sp. gr. 0.80 to 
0.88. The rotatory power observed on two oils was 4q0°15' and 
4-0° 16'; saponification number 260-290. 
Composition. An oil investigated by Zincke2 in 1869 boiled from 
190-270° and consisted principally of acetic and capronic acid esters of 
normal octyl alcohol. The free octyl alcohol' also shown to be present 
is probably not a normal constituent of the oil, but a decomposition 
product of the ester, formed during the steam distillation of the oil. 
Two oils distilled by Moslinger4 in 1876 were somewhat more 
complex in composition. They boiled from 110-291° and contained the 
following constituents: 1) Ethyl butyrate; 2) an hexyl compound, 
probably hexyl acetate; 3) esters of octyl alcohol, principally the 
acetate, caprinate and laurinate and possibly also esters of the acids 
between capronic and laurinic acids; 4) methyl and ethyl alcohol, as 
well as ammonia, were found in the distillation water. 
332. Oil from the Fruit of Heracleum Giganteum. 
The oil investigated by Franchimont and Zincke5 in 1872 had been 
distilled from a foreign heracleum species, most probably from H. gigan- 
teuni L. Its principal constituents were hexyl butyrate and octyl acetate. 
By the distillation of the not fully ripe fruit of H. giganteum L., 
Gutzeit6 in 1875 obtained 0.56 p. c., from the ripe and partly dried 
fruit, however, 2 p. c. of oil. Upon fractional distillation it boiled from 
130-250°. Fraction 130-170° contained ethyl butyrate. 
1) The great variation in the yield obtained by different investigators is not so 
much due to differences in the oil content of the fruit as to differences in the percentage 
of water, i. e., differences in the stage of drying. 
2) Liebig's Annalen, 152, p. 1. 
3) Bericht von S. & Co., Oct. 1886, p. 33. 
*) Befichte, 9, p. 998; Liebig's Annalen, 185, p. 26. 
5) Liebig's Annalen, 163, p. 193. 
6) Liebig's Annalen, 177, p. 344 Oils of the Umbelliferae. 
583 
Methyl and ethyl alcohol were found in the distillation water. 
The methyl alcohol was more prominent in the distillation of the ripe 
fruit, whereas with the unripe fruit the ethyl alcohol was present in 
larger quantity. 
333. Oil of Daucus Carota. 
Molirenol. 
The oil distilled from the fruit of the wild carrot, Daucus carota L. 
is colorless to yellow and has a pleasant, carrot-like odor. Yield 0.8-1.6 
p. c.; sp. gr. 0.870-0.923; «d = -13 to -37°. 
According to Landsberg1 (1890) the principal constituent of the 
oil is a 'terpene, CioHw, boiling at 159-161°, sp. gr. 0.8525 at 20°, 
«d -+ (?) 32.3°. By direct bromination it yields a liquid dibromide, 
after heating to 280°, dipentene tetrabromide, melting at 123-125° 
results. It is therefore to be considered as pinene. 
Upon fractionation of the parts boiling above 200°, the splitting 
off of water and acetic acid was noticed. The chemical nature of the 
compounds giving rise to this phenomenon has not been determined. 
Carrot root gives only 0.0114 p. c. of a colorless oil by distillation. 
Sp. gr. 0.8863 at 11.2° (Wackenroder,2 1831). 
334. Oil of Osmorrhiza Longistylis. 
The root of the umbelliferous plant Osmorrhiza lougistylis Rafinesque, 
known in North America as sweet cicely, sweet root or sweet anise, 
smells distinctly of anise and fennel (Green,3 1882). Induced by this, 
Eberhardt4 in 1887 subjected the root to distillation and obtained 
0.63 p. c. of oil having a sp. gr.. of 1.0114 at 10°. It solidified at 
10-12° and again became liquid at 16°. 
On distillation the oil began to boil at 189°; the thermometer then 
rose rapidly to 225°, the main portion going over from 225-230°, 
while only a small part went over from 230-280°. The fraction 
226-227° consisted, as its properties show, of anethol. By oxidation 
anisic acid melting at 184° was obtained. 
The fraction boiling about 250° gave with bromine a bromide 
crystallizing in rhombic plates, melting at 139°. The nature of the 
compound forming the basis of this bromide was not determined. 
1) Archiv d. Pharm., 228, p. 85. 
2) Magaz. d. Pharm., 33, p. 145. 
3) Am. Journ. Pharm., 54, p. 895. 
Pharm. Rundschau, 5, p. 149. 584 
Special Part. 
335. Oil of Monotropa Hypopitys. 
The volatile oil of Monotropa hypopitys L. (Family Pirolaceae), often 
found parasitic on roots in forests, was first prepared in 1857 by 
Winckler.1 From the plant almost in full bloom, Winckler distilled an 
oil which was identical with wintergreen oil from Gaultheria procumbens. 
More recently (1894) Bourquelot2 again showed the identity of this oil 
with that of wintergreen. From his investigation it follows, that the 
oil does not exist in the plant as such, but is present as a glucoside, 
which is probably identical with the gaultherin isolated by Schneegans 
and Gerock3 from the bark of Betula lenta. This glucoside splits up 
under the influence of a ferment contained in the plant, or by dilute 
sulphuric acid, into methyl salicylate and glucose. Neither the emulsin of 
almonds, nor the diastase of malt, nor the ferment of saliva are capable 
of splitting up the gaultherin. 
336. Oil of Labrador Tea. 
Oleum Ledi Palustris. - Porschol. - Essence de Ledon. 
All parts of Ledum palustre L. (Family Ericaceae) yield on distil- 
lation 0.3-2 p. c. of volatile oil, which is usually so rich in stearoptene 
that it solidifies at ordinary temperature. Sometimes, however, no 
crystalline separation can be effected, even by placing separate fractions 
into a freezing mixture.4 The reason for this fluctuation in yield, as 
well as in composition, of the oil, lies according to Trapp in the different 
stages of development of the plant parts subjected to distillation. If 
a large yield and an oil rich in stearoptene is desired, the twigs must 
be distilled before, during, or immediately after blossoming. Hjelt on 
the other hand could notice no decided influence of the season or growth 
on the amount of volatile oil. 
Properties. Oil of Labrador tea is a greenish or reddish viscid 
liquid of a penetrating narcotic odor and sharp, unpleasant, persistent 
taste. Sp. gr. 0.93-0.96. The portions of the oil not consisting of 
ledum camphor boil between 180-250°. 
Composition. The oil first prepared by Rauchfuss5 in 1796 has 
i) Neues Jahrb. d. Pharm., 7, p. 107; Vierteljahrsschrift f. prakt. Pharm., 6, p. 571; 
Jahresb. f. Chemie, 1857, p. 520. 
2) Journ. de Pharm. et Chim., V, 30, p. 435; and VI. 3, p. 577; Conipt, rend., 119, 
p. 802; and 122, p 1002. 
3) Archiv d. Pharm., 232, p. 437. 
4) Bericht von S. & Co., Oct. 1887, p. 35. 
s) Troinmsdorff's Journ. d. Pharm., 3, p. 189. Oils of the Ericaceae. 
585 
since been investigated by numerous chemists.1 The chemical nature of 
ledum camphor, however, has only lately been cleared up by Rizza2 
and Hjelt.3 
Ledum camphor crystallizes from alcohol in fine long needles melting 
at 104-105°. It boils at 282-283° and is slightly dextrogyrate in 
alcoholic solution, [«]j = +7.98°. Ledum camphor is a sesquiterpene 
hydrate C15H26O, the hydroxy group of which is so labile, that its 
alcoholic nature cannot be directly proven. By treatment with benzoyl 
chloride or sulphuric acid ledene, C15H24, results with splitting off of 
water. Ledene is a sesquiterpene boiling at 255°. Oxidation with 
nitric acid produces oxalic acid. Potassium permanganate does not act 
upon it, which indicates that ledum camphor is a tertiary alcohol. 
According to experiments by Sundvik. ledum camphor is a poison, 
acting strongly on the central nervous system. 
337. Oil of Wintergreen. 
Oleum Gaultheriae. - Winter griinbl. - Essence de Gaultheria. 
Origin and History. Wintergreen, Gaultheria procumbens L. 
(Family Ericiceae} grows from the New England States to Minnesota 
and south as far as Georgia and Alabama. On account of the peculiar 
pleasant odor and taste which develops when the plant is chewed, it was 
early used by the natives. The distillation of the oil was probably 
begun in the first decades of this century along with that of sassafras 
bark (p. 395) and birch bark (p. 331) in the states of Pennsylvania, 
New Jersey and New York. At first these aromatics were used for 
chewing, later for the preparation of refreshing beverages and home 
remedies, and especially for the much used, supposed blood purifiers' 
When the preparation of the volatile oils was successful, these were often 
used instead of the aqueous extraction of the drug. This use is of con- 
siderable importance to the history of the introduction of wintergreen 
and sassafras oils, as both of these were used as popular remedies in 
the United States since the beginning of this century under the title of 
patent medicines. The preparation and use of these remedies soon 
i) Meissner (1812), Berl. Jahrb. d. Pharm.. 13. II, p. 170. - Grassmann (1831), 
Rep. f. d. Pharm., 38, p. 53. - Buchner (1856), ibid., p. 57, and Neues Rep. f. d. Pharm., 
5, p. 1. - WiDigk (1852), Wiener Academ. Berichte, 9, p. 302. - Frohde (1861), Journ. 
f. prakt Chem., 82, p. 181. - Trapp (1869), Zeitschr. f. Chem., 5, p. 350; Berichte, 
8 (1875), p. 542; Pharm. Zeitschr. f. Russl., 34 (1895), pp. 561 and 661. - Ivanov 
(1876), Pharm. Zeitschr. f. Russl., 5, p. 577. - Hjelt & Collan (1882), Berichte, 15, 
p. 2500. - Rizza (1883), Berichte, 16, p. 2311. 
2) Zeitschr. der russ. phys.-chem. Ges., 19, I, p. 319. Chem. Centralbl., 1887, p. 1257. 
s) Berichte, 28, p. 3087. 586 
Special Part. 
became general and with it came a greater demand for the oils. Winter- 
green oil was especially in demand for the preparation of one of the 
oldest popular remedies in the United States, namely Swaim's Panacea, 
introduced in 1815, which at that time had an enormous sale and in 
the efficiency of which great confidence was placed. 
Wintergreen oil appears not to have been used at that time for 
other purposes. The first mention of it in literature is found in a 
botanical work1 by Bigelow, a physician of Boston, published in 1818. 
In it, gaultheria oil is mentioned as a stable article of the drug stores, 
and also that this oil occurs, besides in Gaultheria, also in Spiraea 
ulmaria, the root of Spiraea, lobata, and especially in the bark of 
Betula leuta.2 In pharmacopoeias, the oil was first taken up in that of 
the United States of 1820. The medicinal use of the oil did not become 
general until after 1827, when the New York Medical Society made 
known its use in the preparation of the popular specific mentioned above.3 
Although the similarity of the volatile oil from Gaultheria procum- 
bens L. with that from the bark of Betula lenta L. was known before 
1818,1 the identity of their principal constituent.was shown scientifically 
about the same time by Wm. Procter jr.4 of Philadelphia in 18-12 
and Cahours5 in 1811. From that time on the oil was no longer 
distilled exclusively from wintergreen, but often from this together with 
birch bark, .or only from the latter. The oil came more and more into 
use as an aromatic for pharmaceutic and cosmetic preparations, for 
beverages and medicinal remedies,6 and thus became- an important 
article of commerce. In recent times, however, it was often adulterated 
with kerosene and alcohol.7 
Besides the investigations mentioned above, the oil has been more 
recently examined by Pettigrew8 in 1883, by Power and Werbke9 in 
1) American Medical Botany, vol. 2, p. 28. 
2) According to the investigations of Bourquelot (Compt. rend., 119, p. 802, and 
122, p. 1002), Schneegans and Gerock (Archiv d. Pharm.. 232, p. 439), methyl salicy- 
late is produced by the decomposition of the glucoside gaultherin by the ferment 
betulase. This glucoside seems to occur not only in wintergreen and sweet birch, but 
also in a number of other plants, e. g., in the roots of various polygala species, in those 
of Spiraea ulmaria, S. filipendula, S. salicifoUa, S. lobata, and the flowers of Azalea, in 
Monotropa hypopitys. and many other plants. As to Gaultheria procumbens, a part of 
the oil seems to occur as such in the leaves, for by crushing them a strong odor of 
methyl salicylate is developed. 
3) Pharm. Review, 16, p. 179; Am. Journ. Pharm., 3, p. 199. 
*) Am. Journ. Pharm., 14, p. 211. 
5) Annal. de Chim. et Phys.. III., 10, p. 327; Liebig's Annalen, 48, p. 60: 52, p. 327. 
6) New York Medical Record, 22, p. 505; Squibb's Ephemeris, 3, p. 950. 
t) Pharm. Rundschau, 7, p. 286. 
8) Am. .Journ. Pharm., 55, p. 385; and 56, p. 266. 
9) Pharm. Rundschau, 6, p. 208; 7, p. 283; 8, p. 38; 10, p. 7. Oils of the Ericaceae. 
587 
Fig. 77. 
Wintergreen Oil Distillery in Virginia. 588 
Special Part. 
1888-1892 and finally by Power and Kleber1 in 1895, who determined 
the nature of the constituents other than methyl salicylate. 
Methyl salicylate is prepared on a large scale and brought into the 
market as artificial oil of wintergreen since 1886 by the firm of Schim- 
mel & Co. It is official in the U. S. Pharmacopoeia. 
Preparation. The preparation of oil of wintergreen has always 
been carried on in a primitive manner, the distillation being conducted 
by smaller farmers at the place of growth. This was first done in the 
New England states2 and later in the mountain and forest districts of 
the states of New York, New Jersey, Pennsylvania, Virginia, and Mary- 
land. Usually old copper whisky stills of various sizes, mostly from 
200 to 100 gals, capacity, serve as stills.3 Sometimes the distillation 
is done in boxes of oak wood about 8 ft. long, 4 ft. high, and 4-5 ft. 
broad, mostly, however, in larger alcohol barrels, held together by strong 
iron hoops, the perforated bottom of which is placed as tightly as 
possible into a suitable cast iron kettle, which is filled with water for 
distillation. On the upper part of the barrel is placed a copper helm, 
which is connected with a condensing worm in a large wooden tub. 
In the distillation, which is carried on for only a few months in the 
year, the still, barrel or box, is filled with finely chopped, well wetted 
plants. The charge is allowed to stand over night and firing begun in 
the morning. The distillation is usually complete in eight hours. About 
90 p. c. of the oil pass over during the first 2-3 hours, the remaining 
10 p. c. in the course of the next 3-4 hours. The crude oil is colored 
dark by the iron of the condenser. The small producers sell the crude 
oil obtained to wholesale druggists, who purify it by rectification.4 
Properties. Gaultheria oil is a colorless, yellow or reddish liquid 
of a characteristic, strongly aromatic odor, which is distinctly different 
from that of the oil from Betula lenta. The sp. gr. is 1.180-1.187, 
the boiling temperature lies between 218 and 221°. 
Gaultheria oil differs from the inactive betula oil in being slightly 
optically active, «d - - 0° 25' to - 1°. It yields a perfectly clear solution 
with 6 p. of 70 p. c. alcohol at 20°. This property, together with the sp. 
gr. and the optical rotation, allows of the ready detection of most of the 
adulterants, especially the frequent one with petroleum. Mixtures with the 
otherwise equal oil of Betula lenta, or with artificial methyl salicylate, can 
only be detected by the depression of the rotatory power below -0°25'. 
J) Pharm. Rundschau, 13, p. 228. 
2) Proc. Amer. Pharm. Assoc., 28, p. 269; 
30, p. 184. 
s) Am. Journ. Pharm., 51, p. 439. 
4) Am. Journ. Pharm., 56, p. 264. Oils of the Ericaceae. 
589 
The details for further tests have been described under oil of birch 
bark, page 334. 
Composition. The principal constituent of wintergreen oil, the- 
methyl salicylate, was recognized by Cahours and Proctor1 at the- 
beginning of the forties. Quite contradictory views existed as to the- 
nature of the other constituents. Power and Kleber2 in 1895 cleared 
up the nature of the constituents other than methyl salicylate in 
wintergreen and also in birch bark oil. In order to prevent any possible 
decomposition, these chemists did not employ the saponification method, 
which had been used so far in the investigation of this oil, for the 
separating of the unknown compounds. They took advantage of the 
property of the methyl salicylate to form a solid salt with potassa, 
potassium methyl salicylate. The total amount of salicylic ester was- 
removed from the oil by shaking repeatedly with 7.5 p. c. potassa 
solution. Only 1.05 p. c. of the oil did not combine with the potassa and 
remained as a semi-solid mass at ordinary temperature. This consisted 
of the following compounds: 1) A paraffin, CnH2n+2, which on account 
of its melting point, 65.5°, must be considered as tricontane, C30H62- 
2) An aldehyde or ketone, which when separated in a pure form from 
its bisulphite compound, has an odor like oenanthic aldehyde, and on 
oxidation with potassium permanganate yields an acid, the silver salt 
of which corresponds to the formula CoH»O2Ag. 3) An alcohol, CsHioO, 
boiling between 160 and 165°, which corresponds to the ketone or 
aldehyde mentioned. 4) An ester, C14H24O2, boiling at 230-235° (1350- 
at 25 mm.). This on saponification splits up into the alcohol, CsHieO, 
and the acid, C6H1OO2, resulting by oxidation from the ketone. The- 
alcohol and also the ester possess the very penetrating characteristic 
odor, by which wintergreen oil is distinguished from artificial methyl 
salicylate. 
338. Oil of Gaultheria Punctata. 
The leaves of Gaultheria punctata. Blume (G. fragrantissima Wal- 
lich, G. fragrans Don, Arbutus laurifolia, Hamilton,3 give upon distil- 
lation 1.15 p. c. of a volatile oil, which seems to be identical with 
that of wintergreen. De Vrij4 in 1859 prepared the oil from plants- 
which he found in the exhausted volcano Patoea on Java, and in 1871 
ascertained that it consisted almost exclusively of methyl salicylate. 
1) See p. 586, footnotes 4 and 5. 
2) Pharm. Rundschau, 13, p. 228. 
3) Sawer. Odorographia, vol. 2, p. 340. - 
Comp. also Kremers and James, Pharm. 
Review, 16, p. 105. 
4) I'harm. Journ., Ill, 2, p. 503. 590 
Special Part. 
The same oil distilled by de Vrij was again investigated in 1879 by 
Kohler1 apparently without the knowledge of the statements of its 
composition made by de Vrij in 1871. The inactive oil boiled at 
221-222°; on saponification an amount of salicylic acid, melting at 
155-156°, corresponding to the pure methyl ester, was obtained. 
Andromeda leschenaultii, growing profusely in the Nilgiri mountains 
in India, in the leaves of which Broughton2 in 1867 found methyl 
salicylate, is probably identical with G. punctata Bl. 
339. Oil of Gaultheria Leucocarpa. 
According to de Vrij3 the fresh leaves of Gaultheria leucocarpa 
Blume, indigenous to Java, yield on distillation 0.012 p. c. of an oil 
consisting chiefly of methyl salicylate. Kohler1 investigated the same 
oil and confirmed the result obtained by de Vrij. It was inactive and 
boiled at 221-223°. 
340. Primula Root Oil. 
The root of Primula veris L. (Family Primulaceae), contains, besides 
cyclamin, a glucoside probably identical with saponin, the so-called 
primula camphor (Mutschler,41877) which can be obtained by distillation. 
It separates from the distillate in fine, shining, hexagonal laminae, 
or as a semi-solid mass, has a fennel- or anise-like odor, and a taste 
at first burning, then sweetish, fennel-like. 
Primula camphor is only difficultly soluble in water; the aqueous 
solution is colored deep violet to violet-blue by ferric chloride. Its 
elementary composition corresponds to the formula C22H24O1O. Upon 
oxidation with chromic acid, carbon dioxide and salicylic acid resulted; 
by boiling with potassa there resulted, besides salicylic acid, a very 
small amount of a second acid, which gave a beautiful dark blue 
coloration with ferric chloride. 
341. Oil of Jasmine. 
The general method of obtaining the volatile oils by water or steam 
distillation is not applicable to a large number of blossoms, as at best 
only traces of the volatile oil are obtained by it. To these belongs the 
jasmine blossom of Jasminum grandiflorum L. (Family Oleaceae). In 
1) Berichte, 12, p. 246. 
2) Pharm. Journ., Ill, 2, p. 281. 
3) Pharm. Journ., Ill, 2, p. 503. 
*) Liebig's Annalen, 185, p. 222. - Comp. 
also Hiinefeld (1836), Journ. f. prakt. Chem., 
7, p. 57, and 16, p. 111. Oils of the Oleaceae. 
591 
order to isolate the odorous principles of the jasmine blossoms, Verley1 
shook the jasmine pomade obtained by Enfleurage a froid with vaseline 
oil and exhausted the oil from this by treatment with acetone. On 
evaporation of the acetone a reddish colored oil smelling intensively of 
jasmine remained behind. Its principal portion came over at 100-101° 
under 12 mm. pressure and had the composition C9H1OO2. Upon 
oxidation the compound yielded benzaldehyde, benzoic acid and form- 
aldehyde. By boiling with oxalic acid solution, styrolene alcohol, 
CgH.5 . C2H3(0H)2, was formed. This led to the conclusion that the body 
was the methylene acetal of phenyl glycol CeHg .C2Hs~q>CH2. Verley 
called the compound jasmal and considered it as the odorous principle 
of the jasmine blossoms.2 
Jasmal can be prepared synthetically by heating phenyl glycol with 
formaldehyde and sulphuric acid. It boils at 101° under 12 mm., at 
218° under atmospheric pressure. Sp. gr. 1.1334 at 0°. 
Hesse and Muller3 reached entirely different conclusions in their 
investigation of the oil, which had been prepared in a manner similar 
to Verley's and purified by steam distillation. They obtained from each 
kilo of jasmine pomade 4-5 g. of oil having the following properties: 
sp. gr. 1.007-1.018; «D = +2°30'to +3° 30'. The ester-content was 
69.1 to 73 p. c., calculated as benzyl acetate, and 90.3 to 95.4 p. c., 
calculated as linalyl acetate. 
According to Hesse and Muller jasmine oil contains large amounts 
of benzyl acetate, as well as linalool and its acetate. According to a 
quantitative determination made by a method worked out by them for 
this purpose they found the following approximate composition for 
jasmine oil: 
65.0 p. c. Benzyl acetate. 
7.5 " Linalyl acetate (including possibly other alcohol esters). 
6.0 " Benzyl alcohol. 
5.5 " other odorous principles. 
16.0 " Linalool (eventually also other constituents). 
Benzyl acetate, C6H5CH2OCH3CO, boils at 215-216° and has the 
sp. gr. 1.069.3 
i) Compt. rend., 128, p. 314; Bull. Soc. chim.. Ill, 21, p. 226. 
2) According to Verley the homologues of jasmal, the ethylidene, isobutylidene and 
amylidene acetals of phenyl glycol have a jasmine-like odor. 
3) Berichte, 32, pp. 565, 765. 592 
Special Part. 
Benzyl alcohol, CeHsCHsOH, boils at 88° under 9 mm. pressure. 
For identification the phenyl urethane melting at 77-79° is well suited.1 
The jasmal of Verley was not present in the oil investigated by 
Hesse and Muller. As the phenyl glycol methylene acetal is stable 
toward alcoholic potassa, it ought to be possible to detect its presence 
after the saponification of the oil. This, however, was not the case, 
nor did so much as a trace of styrolene alcohol result by boiling the 
oil with oxalic acid solution. On the ground of these observations 
Hesse and Miiller came to the conclusion that the volatile oil of 
jasmine blossoms contained no phenyl glycol methylene acetal. 
Schimmel & Co.2 in their investigation of jasmine oil in 1895 also 
found benzyl acetate, benzyl alcohol and linalyl acetate, but no com- 
pound of the properties of jasmal. 
More recently, Hesse3 has found three further constituents: 
2.5 p. c. Indol, C8H7N. 
0.5 p. c. Anthranilic acid methyl ester, CsHpNCH. 
3.0 p. c. Jasmone, ChHigO. 
Jasmone, ChHigO has an intensive, pleasant jasmine odor when 
diluted. It boils at 257-258° at 755 mm. and has a sp. gr. of 0.945 
at 15°. It yields an oxime, by means of which it was separated from 
the oil, melting at 45°, and a mixture of semicarbazones melting at 
200-204°, from \vhich by recrystallization a compound was obtained 
melting at 204-206°. 
312. Oil of Rhodium. 
Oleum Ligni Rhodii.-Rosenholzol.-Essence de Bois de Rose,4 on de Rhodes. 
The so-called rosewood, i. e. the wood of the roots of the shrubs 
Convolvulus scoparius L. and C. fioridus L. (Family Convolvulaceae), 
indigenous to the Canary Islands, is generally reported as the material 
used for the preparation of oil of rhodium. 
The oil of rhodium at present in the market is often nothing more 
than a mixture of rose oil with sandalwood or cedar wood oil. 
Oil of rhodium was investigated by Gladstone5 in 1864. The 
source of this oil can naturally not be be determined at present. It 
was viscid, had the sp. gr. 0.906 at 15.5° and the rotatory power 
i) Bericht von S. & Co., Apr. 1899, p. 27. 
2) Bericht von S. & Co., Apr. 1899. p. 27. 
3) Berichte, 32, p. 2611. 
*) The wood designated Bois de rose femelle or male by the French is Guayana 
linaloe wood. Comp. p. 493. 
s) Journ. Chem. Soc., 17, p. 1; Jahresb. f. Chemie, 1863, p. 546. Oils of the Verbenaceae. 
593 
- 16° in a 250 mm. tube. Four fifths of it consisted of a hydrocarbon 
Ci0Hi6 (more probably C15H24) boiling- at 249°, which had an odor of 
sandalwood and rose. 
The source of an oil distilled by Schimmel & Co.1 in 1887 is also 
unknown. The oil had a fine golden-yellow color, with a pleasant rose- 
like odor. It solidified at + 12° to a mass of needle shaped crystals. 
A rose wood from Tenerife2 recently used by the same firm for 
distillation, corresponded fairly well with the description of the root 
wood of Convolvulus scoparius L. The odor of the oil did not fulfill 
the expectations. Sp. gr. 0.951 at 15°; «d=:+1o30'; saponification 
number before acetylization - 0, after acetylization -151.3. The oil 
dissolved with a slight turbidity in 10 p. of 95 p. c. alcohol. 
343. Oil of Verbena. 
The true verbena oil from the leaves of Verbena triphylla L. (Aloysia 
citriodora Ort., Lippia citriodora Kth., Family Verbenaceae') cultivated 
as an ornamental plant in Spain, northern France and Central America 
is, as its high price stands in no relation to its true value, no regular 
article of commerce. It can in most cases be replaced by the much 
cheaper lemon-grass oil which is similar in odor, and has therefore 
been called East Indian verbena oil. As genuine verbena oil is so 
difficult to obtain the statements concerning it have to be taken with 
some reserve. 
Verbena oil has a fine, very pleasant, lemon-like odor, resembling 
that of lemon-grass oil. An oil distilled in Grasse, according to the 
statement of the manufacturers, from the leaves of Lippia citriodora 
(yield 0.09 p. c.), had the following properties: Sp. gr. 0.900; 
«d =-12° 38'; soluble in 1-5 volumes of 90 p. c. alcohol, on the 
further addition of alcohol it became turbid. It contained 35 p. c. of 
aldehyde, which, as was shown by the preparation of /?-citryl naphtho 
cinchoninic acid (m. p. 195-197°), was citral (Schimmel & Co.) 
An oil described as "Oil of true Vervain,"3 the sp. gr. of which is 
given as 0.902 and aD as -12.7°, agrees very well with the above. It 
was not soluble in 10 p. of 80 p. c. alcohol, but in equal parts of 
90 p. c. alcohol, and contained 28 p. c. of aldehyde. After acetylization 
a decided odor of linalyl acetate was noticed. By saponification of the 
acetylized oil an alcohol content (CioHisO) of 30 p. c. was determined. 
O Bericht von S. & Co., Apr. 1887, p. 28. 
2) Bericht von S. & Co., Apr. 1899, p. 41. 
3) Chemist and Druggist, 50, p. 218. 594 
Special Part. 
Umney1 reports on an oil distilled in Dunolly (Victoria, Australia) 
"probably" from Lippia, citriodora. The sp. gr. after removing the 
alcohol which had been added, was 0.894, «d = -16°. It contained 
74 p. c. of citral. 
An oil early investigated by Gladstone2 (1864) and said to have 
come from Aloysia citriodora was much lighter, its sp. gr. at 15.5° 
being 0.881; its angle of rotation in a 250 mm. tube was -6°. 
344. Oil of Lantana Camara. 
The volatile oil of Lantana camara L. (Family Verbenaceae), widely 
distributed as a weed in Java, has been distilled in the botanical garden 
at Buitenzorg. Its odor is not especially pleasant, has a sp. gr. of 
0.952 and turns the ray of polarized light 0°24' to the left in a 
100 mm. tube.3 
345. Oil of Vitex Trifolia. 
The leaves of Vitex tri folia L. (Family Verbenaceae) are used in 
India for bathing purposes and as a remedy against various diseases. 
They contain a volatile oil, which was prepared in the botanical garden 
at Buitenzorg.4 
Its odor is pleasantly aromatic, somewhat camphor-like. The latter 
property is due to cineol, which was shown to be present by the iodol- 
cineol reaction. 
34.6. Oil of Rosemary. 
Oleum Rorisinarini.- Rosmarinol. - Essence de Romarin. 
Origin and History. The rosemary bush, Rosmarinus officinalis L. 
belonging to the Labiatae, grows in the Mediterranean countries and 
islands from Greece to Spain. 
The first mention of the distillation of rosemary is found in the 
writings of Arnoldus Villanovus of the thirteenth century. He distilled, 
probably for medicinal purposes, turpentine oil and rosemary oil. An 
alcoholic distillate of both or only of rosemary was in use for centuries 
as the first popular perfume under the name of Hungarian water. The 
distillation of the oil is described more fully by Raimund Lullus, a 
disciple of Villanovus. 
1) Pharm. Journ., 57, p. 257. 
2) Journ. Chem. Soc., 17, p. 1; Jahresb. f. Chern., 1863, pp. 546 and 549. 
s) Bericht von S. & Co., Oct. 1896, p. 77. 
Bericht von S. & Co., Oct. 1894, p. 74. Oils of the Labiatae. 
595 
Oil of rosemary was a much used oil in the middle ages and is often 
mentioned in the writings of that period. It is described in the index 
of the Compendium of Saladin at the end of the fifteenth century and 
in the works of Brunschwig, Ryff, Gesner, Porta, and others, and is 
mentioned in drug and spice ordinances of the fifteenth century. In 
several of the treatises on distillation and in medical works of the 
fourteenth and fifteenth centuries, an empyreumatic oil of rosemary is 
also mentioned. 
One of the first investigations of rosemary oil was made by the 
Parisian apothecary Geoffroy1 in 1720. A century later it was more 
fully investigated by Saussure2 and in 1837 by Kane.3 Cartheuser in 
1734 determined the yield of oil.4 
The so-called rosemary camphor was first noticed by Kunkel of 
Berlin in 18655 and a century later (1785) by Arezula of Cadix.6 
Proust prepared it in 1800.7 
Preparation.8 In commerce, two rosemary oils are principally 
distinguished, the Italian and the French. 
The Italian or more correctly the Dalmatian rosemary oil is obtained 
on the islands of Lissa, Lesina and Solta on the Dalmatian coast, where 
the rosemary grows wild and covers large tracts of land. It is surprising 
that rosemary grows neither on the mainland nor on the neighboring 
islands Brazzo, Curzola, Melada and Lagosta. The most pleasant 
smelling rosemary is that on Solta, where it is, however, more and 
more suppressed by vineyards, so that distillers come but seldom to 
this island for the preparation of the oil. 
Most of the oil is produced in Lesina, which is also the commercial 
center for rosemary oil, Lissa is second in importance. Both islands 
are covered with bushes about a meter in height. The "Rosemary 
forests" are the property of the community, which gives the license for 
distillation to the highest bidder at auction. The use of the forests is 
regulated by law, so that a full harvest is made only once in three 
years; in the two following years very little oil is distilled. The dis- 
tillation takes place in July and August, consequently after the flowering 
period, which lasts from February to April. After the cut twigs have been 
1) Mem. de l'Acad. de sc. de Paris, 1721, p. 163. 
2) Ann. de Chem. et de Phys., II, 13, p. 278. 
3) Trans, of the Roy. Irish Acad., 18, p. 135. - Journ. f. prakt. Chem., 15, p. 156. 
Elementa Chymiae, II, pp. 83 & 106. 
s) Probierstein. p. 397. 
6) P. 39; Resultado de las experiencias, p. 8. 
7) Trommsdorff's Journ. d. Pharm., 8, II, p. 221. 
8) Dingier's Polytechn. Journal, 229, p. 466.-Bericht von S. & Co., Oct. 1896, p. 69. 596 
Special Part. 
dried for eight days in the sun, the leaves are stripped off and distilled 
with water vapor. The distilling apparatus is very primitive, old copper 
whisky stills being mostly employed.1 From the port Cittavechia the 
oil is shipped in tin cans to Triest. From here, often adulterated with 
turpentine oil, it enters into the world's commerce. 
No statistics of the production of the Dalmatian rosemary oil exist. 
According to inquiries made at the place of production, 20,000 k. of oil 
are said to be obtained in those years when a full harvest is made. 
This estimate agrees with a statement made by Fliickiger2 in 1884. 
As far as the yield of oil is concerned, it has probably been but 
seldom determined in Dalmatia, as it may be assumed that the distillers 
do not weigh the material before putting it into the still. Schimmel & 
Co.3 obtained from Dalmatian rosemary leaves 1.4-1.7 p c. of oil. 
The French rosemary oil is finer in odor and correspondingly higher 
in price. It is principally obtained in the Departements du Gard, 
du Herault, de la Drome, des Alpes Maritimes and des Basses Alpes. 
Here the erect shrub grows to a height of 2 m. and together with 
Thymus vulgaris forms the brushwood of clearings.2 The distillation is 
done in itinerant stills in the same manner as described under lavender 
oil (p. 602). Schimmel & Co.4 obtained by distillation from the dry 
French rosemary leaves 2 p. c., from the flowers 1.4 p. c. of oil. 
Whether the better quality of the French oil depends on the plant itself 
or on the more careful selection of the material is difficult to state. 
Inasmuch as rosemary is also found in Spain, the oil is now and 
then distilled in that country.5 It appears, however, to be almost 
always adulterated with turpentine oil. The properties of the pure 
Spanish oil are the same as those of the Dalmatian or French oil, as 
was shown by the recent examination of a Spanish oil in the laboratory 
of Schimmel & Co. 
The English rosemary oil, which is obtained in Mitcham and Market 
Deeping in small amounts from cultivated plants, is no more important 
commercially than is the Spanish oil.6 
Properties. Rosemary oil is a colorless or slightly greenish-yellow 
liquid of a penetrating camphor-like odor and an aromatic, bitter, 
i) See p. 67. 
2) Archiv d. Pharm., 222, p. 476. 
3) Archiv d. Pharm., 235, p. 586; Bericht von S. & Co., Oct. 1897, p. 54. 
*) Bericht von S. & Co., Oct. 1893, table in appendix, p. 34. 
5) Bericht von S. & Co., Oct. 1889, p. 55. 
6) Comp. Holmes, Pharm. Journ., Ill, 12, p. 238; III, 20, p. 581.- Sawer, Odoro- 
graphia, vol. 1, p. 370. Oils of the Labiatae. 
597 
cooling taste. The, sp. gr. of the French as well as the Italian oil is 
always higher than 0.900 and sometimes rises to 0.920. The ray of 
polarized light is always rotated to the right, an = + 0° 45' to +15°. 
The first 10 p. c. obtained by fractional distillation are likewise dextro- 
gyrate. One part of oil gives a clear solution with % and more parts 
of 90 p. c. alcohol, and sometimes with 2, but often as many as 9-10 
parts of 80 p. c. alcohol are required. Saponification number 12-20. 
The oils distilled by Schimmel & Co. from five different shipments of 
Dalmatian rosemary leaves had the following properties: Sp. gr. 0.904- 
0.913; «D = +3° 40' to +8°52'.1 Two oils were distilled in Leipzig 
from French material.2 1) From flowers: sp. gr. 0.920; «d = + 1°38'. 
2) From leaves: sp. gr. 0.914; «D = +14°35'. 
The content of bornyl acetate in two authentic oils was found to be 
5.4 and 5.8 p. c. The amount of borneol determined by acetylization 
was 16.8 and 18.8 p. c. 
A Spanish oil recently investigated in the laboratory of Schimmel 
& Co. had the sp. gr. 0.905 and «d = +7° 40'. It was soluble with 
slight turbidity in 10 parts of 80 p. c. alcohol. The angle of rotation, 
«d, of the first 10 p. c. going over on distillation was 4-4°l'. Another 
sample,3 investigated later, had the sp. gr. 0.932, «d - + 17° 37' at 20°. 
Spanish distillates which had been investigated at an earlier time4 wTere 
lighter in sp. gr. and laevogyrate, and probably were adulterated with 
turpentine oil. 
The English oil obtained from cultivated plants shows differences in 
properties, especially in rotatory power. The sp. gr. of three English 
oils was found by Cripps3 (1891) to be 0.901, 0.911 and 0.924, the 
rotatory power, «d, determined on one of these oils was -9° 35'. 
Symes6 (1879) determined on another, doubtless adulterated English 
oil the sp. gr. 0.881 and the angle of rotation «d =-16°47'. As the 
English oils are commercially unimportant, all laevogyrate oils found 
in commerce can safely be declared as adulterated. 
Composition. • The following compounds have so far been found in 
rosemary oil: 1) pinene, 2) camphene, 3) cineol, 4) camphor, 5) borneol. 
Up to the present all investigations have been directed toward 
individual constituents. A thorough investigation of the oil as a whole 
may therefore result in finding still other substances. 
i) Bericht von S. &.Co.. Oct. 1897, p. 56. 
2) Ibidem, Apr. 1891, p. 41. 
3) Ibidem, Apr. 1900, p. 40. 
4) Ibidem, Oct. 1889, p. 55. 
5) Pharm. Journ., Ill, 21, p. 937. 
6) Pharm. Journ., Ill, 10, p. 212. 598 
Special Part. 
Pinene. According to the statement of Bruylants1 (1879) oil of 
rosemary contains 80 p. c. of a laevogyrate hydrocarbon C10H16 boiling 
at 157-160°. From the low sp. gr. 0.885 and the laevo-rotation, as 
well as the large amount of the terpene found, it is evident that the 
oil investigated was adulterated with French turpentine oil. On 
account of the frequent adulteration with turpentine oil it became a 
matter of interest to know whether pure rosemary oil contained pinene 
or not. Gildemeister and Stephan,2 therefore, investigated the lower 
boiling fractions of an oil distilled by themselves from Dalmatian 
rosemary leaves. The portion boiling at 156-158° after repeated 
fractionation (sp. gr. 0.867, «d - 4-2° 30') gave on treating with amyl 
nitrite and hydrochloric acid in glacial acetic acid solution a nitroso- 
chloride. This yielded with benzylamine pinene nitrolbenzylamine 
(m. p. 122-123°), from which it follows that pinene -probably a 
mixture of d- and 1-pinene-is a constituent of rosemary oil. 
Camphene. The fraction boiling at 160-162° (sp. gr. 0.875, 
«d - - 0°45') was treated with glacial acetic and sulphuric acids. After 
saponification of the product of the reaction, isoborneol, of the melting- 
point 211-212°, was obtained. The latter was reconverted into 
camphene, boiling at 159-160° and melting at about 50°, by boiling 
with zinc chloride in benzene solution. According to this a second 
terpene, camphene, is contained in rosemary oil, and judging from the 
slight rotation of the fraction, it is inactive camphene. 
A commercial rosemary oil distilled in Dalmatia gave the same 
results; pinene and camphene were identified. The first runnings (from 
40 k.) of this oil had an odor of acetaldehyde, boiled below 150°, 
decolorized fuchsin sulphurous acid and was partly soluble in water. 
The insoluble oil was hydrated with glacial acetic and sulphuric acids, 
whereby a decided odor of linalyl acetate was developed. This behavior 
indicates the presence of olefinic terpenes, similar to those occurring in 
bay, hops, and origanum oils.2 
Cineol. In the fraction boiling at 176-182° Weber3 in 1887 found 
cineol, CioHisO, and isolated this body by means of its hydrochloric 
acid addition product. The identification was made by preparing the 
dipentene tetrabromide, CioHioBr^, (m. p. 123.5-124°) as well as 
dipentene dihydriodide, C10H18I2, (m. p. 78.5-79°). 
1) Journ. de Pharm. et Chim., IV, 29, 
p. 508; Pharm. Journ., Ill, 10, p. 327; 
Jahresb. f. Chemie, 1879, p. 944. 
2) Archiv d. Pharm., 235, p. 585 
3) Liebig's Annalen, 238, p. 89. Oils of the Labiatae. 
599 
By conducting hydrochloric acid gas into the ethereal solution of 
fraction 171-176° Weber obtained dipentene dihydrochloride melting 
at 49-50°. This compound owes its formation either to cineol, or to 
dipentene, but as the fraction mentioned contained according to the 
analysis considerable terpene, its formation is probably due to dipentene 
(terebene of Bruylants?). 
Camphor and borneol. Camphor was first observed in rosemary 
oil by Lallemand1 in 1860. Montgolfier2 in 1876 showed that the 
rosemary camphor was a mixture of the dextro- and laevogyrate 
modifications. Bruylants3 found that the stearoptene crystallizing from 
the high boiling fractions of the oil consisted not only of camphor, but 
also of borneol. In the oil, which, as mentioned above, was strongly 
adulterated, Bruylants determined 4-5 p. c. of borneol and 6-8 p. c. 
of camphor. Pure oil must therefore contain considerably more of these 
compounds. Gildemeister and Stephan5 determined the borneol content 
by acetylization and found in two cases 16.8 and 18.8 p. c. It was 
assumed that rosemary contained no other alcohols, such as linalool or 
geraniol. 
According to Haller4 (1889) camphor is separated from borneol by 
converting the latter into bornyl acid succinate by heating with succinic 
acid. The borneol contained in rosemary oil is, as was shown by 
Haller, like the camphor, a mixture of both optical modifications. 
Judging from the saponification number obtained by boiling with 
potassa, rosemary oil contains small amounts of esters, presumably of 
borneol. The acid combined with the alcohol has not yet been determined. 
Examination. In testing rosemary oil, especial attention should be 
paid to the specific gravity and rotatory power which should agree 
with those mentioned under Properties. Turpentine oil, no matter of 
what source, will cause a decrease in the specific gravity. French 
turpentine oil is recognized, providing the amount is not insignificant, 
by the inversion of the angle of rotation to the left. In order to 
recognize small additions, which do not cause inversion to the left, and 
do not lower the sp. gr. below 0.900, from 100 cc. of oil 10 cc. are 
slowly distilled off in the flask described on p. 190 and the distillate 
tested in the polariscope.5 With pure rosemary oil the lowest boiling- 
10 p. c. will always be found dextrogyrate, while if only small amounts 
of French turpentine oil are present it will be laevogyrate. 
1) Liebig's Annalen, 114, p. 197. 
2) Bull. Soe. chim., II, 25, p. 17. 
s) See p. 598, footnote 1. 
<) Conipt rend., 108, p. 1308. 
5) Arehiv d. Pharm., 235, p. 585. 600 
Special Part. 
Fractions of camphor oil are also often used for adulteration.1 
These, however, usually affect one of the characteristic properties of the 
rosemary oil. Either the rotatory power (which is usually increased) 
or the specific gravity, or the solubility in 80 p. c. alcohol is changed. 
347. Oil of Lavender. 
Olenin Lavandulae.-Lavendelbl.-Essence de Lavande. 
Origin and History. The species of lavender used since antiquity 
on account of their pleasant odor, are indigenous to the northern 
Mediterranean countries, but flourish especially on the slopes of the 
French Cevennes and Sea Alps. Whereas formerly the oils of the different 
species of lavender were known by the general name of spike oil, they 
have, since a little more than a century ago, been separated into 
lavender oil and spike oil. 
The different lavender species were formerly gathered indiscriminately 
for oil distillation. In the eighteenth century they were more accurately 
determined and distinguished botanically. The species determined as 
Lavandula, spica a by Linne, (L. officinalis Chaix, L. angustifolia Mdnch, 
L. vulgaris a Lamarck, L. vera De Candolle) yields the lavender oil. 
The spike oil, which is decidedly different in aronia and constituents, 
is obtained from the more tender L. spica D. C. (L. vulgaris ,3 Lamarck, 
L. latifolia Villars) growing in the lower hilly and coast districts. 
The history of the lavender species and their distillates is given 
under the earlier known spike oil (p. 607). 
Preparation. The French lavender oil is obtained in the higher 
mountainous regions of southern France in the Departements des Alpes 
Maritimes, des Basses Alpes, du Herault, de la Drome, du Gard and de 
Vaucluse. As the lavender blossoms cannot be transported, the distil- 
lation is carried on as near as possible to the place of collection, as a 
general rule in portable stills. At the beginning of the flowering period in 
July, the distillers take their apparatus to the mountains on mules. In 
the neighborhood of a spring or creek the still is erected on a fire place 
constructed of stones, and heated with wood, which is abundant. The 
collection is always begun in the lowest regions where the lavender 
blooms first. When all obtainable material has been collected and 
distilled in the neighborhood of the place of distillation the apparatus 
is carried' to a higher point. The oil distilled in the lower regions is 
considered inferior in value to that distilled toward the end of September 
at an altitude of 1,500 m. 
3) Bericht von S. & Co., Apr. 1898, p. 46. Oils of the Labiatae. 
601 
Fig. 78. 
Distillation of Lavender Oil near Escragnolles (Departement des Alpes Maritimes), Southern France. 602 
Special Part. 
The accompanying illustration (fig. 78) shows such a DistiUerie 
aaibulante1 in the neighborhood of the village Escragnolles, on the 
road from Grasse to Paris,. thirty kilometers from Grasse. The two 
copper stills are supported on a fire place made of stones laid in the 
form of a horse shoe. The condenser consists of an old petroleum 
barrel, from which the head has been removed, and into which the con- 
densing worm is fitted. The condensing water is furnished by the 
neighboring spring. Tn the foreground a laborer is busy turning the 
pile of lavender flowers with a hay fork, to prevent fermentation. The 
exhausted blossoms are spread out behind the still. After completion 
of the distillation the laborer removes the still from the fire, empties it 
by turning it over, and replaces it by another which had meanwhile 
been filled. 
H. Laval2 in 1886 made an interesting and exhaustive report on the 
distribution, collection and distillation of lavender in the Departement 
de Vaucluse. Although not of very recent date, some of his figures may 
here be mentioned, in order to give an idea of the importance of this 
industry in southern France. 
On the southern slope of the Ventoux mountains lavender is found 
at a height of 700-1,150 m., together with thyme and satureja. On 
the northern slope the lavender begins at 450 m., but rises here no 
higher than 900 m. The ground covered by the plants (lavandieres) on 
the Ventoux is approximately 11,000 hectares (27,000 acres); of these, 
7,000 hectares (17,200 acres) are property of the communities, the 
remainder is of private ownership. At the time of flowering, in July and 
August, the men, women and children go up the mountains. The flower 
clusters are cut off above the leaves with a sickle and are carried on 
the head in bundles to the places of distillation. The collection of the 
lavender is commonly free on the properties of the communities, some, 
however, make an annual charge of one franc for each family. The 
amount of fresh lavender flowers collected annually in the Ventoux is 
estimated at 1,700,000 k. Of these 1,200,000 k. are used for the dis- 
tillation of the oil (about 6,000 k.) the balance is dried. 
Laval describes from personal inspection three different methods of 
distillation. In a small factory at Sault the distillation was effected by 
means of steam which was generated in a separate vessel and fed four 
cylindrical, copper stills. Each had a capacity for 150 k. of fresh 
1) See pp. 26 and 67. 
2) Journ. de Pharm. et de Chim., V, 13, pp. 593 and 649. Oils of the Labiatae. 
603 
flowers. The warm water from the condenser was used for feeding the 
boiler. A distillation lasted 1% hours. Each still was filled 14 times in 
24 hours and thus 8,400 k. of material were distilled daily. 
In a second factory in Villes the distillation was also with steam 
from two egg shaped stills, each of which held a charge of 100 k. of 
fresh flowers. , 
A third factory in Bedoin had cylindrical stills, 3 m. high and 1^ m. 
in diameter, which were heated by direct fire; the flowers were supported 
on a false bottom, so that they were not in contact with the water 
but only with the steam. 75 k. were placed on the lowest false bottom, 
then a second false bottom was put in which carried the same amount 
of flowers. Alternately a false bottom and flowers followed until the 
still contained 250 k. Five distillations were made daily. 
In the third kind of distillation the flowers are put into the still 
with water and without sieve bottoms. This method is common to the 
itinerant stills, and is the one most generally used. 
The most rational method of preparation is probably the one with 
the false bottoms, as this is the most suitable for delicate oils. By the 
distillation with steam as well as with the water without false bottom 
no doubt more of the valuable ester is decomposed than in the method 
used at Bedoin. According to Laval in order to obtain 1 k. of oil, 
200 k. of fresh flowers are necessary, which corresponds to a yield of 
0.5 p. c. From dried French flowers Schimmel & Co. obtained 1.2 p. c., 
from German flowers as much as 2.8 p. c. of oil.1 
The English lavender oil industry is quite insignificant in com- 
parison with the French. Whereas in France only the wild plant is 
used for distillation in England the cultivated plant is used exclusively. 
The lavender plantations2 are found in Surrey county in Mitcham, 
Carshalton and Beddington, further in Canterbury (Kent), Hitchin 
(Hertfordshire) and in Market Deeping (Lincolnshire). The distillation, 
which usually begins in the first weeks of August, is done in the same 
stills used for the peppermint. The yield from the fresh flowers is given 
as 0.8 to 1.5 p. c. Both figures appear to be rather high. 
1) Bericht von S. & Co., Oct. 1893. Table in the appendix, p. 24. 
2) More detailed accounts of the cultivation and distillation of English lavender can 
be found in the following journals and works: Holmes, Pharm. Journ., Ill, 8 (1877), 
p. 301; Fluckiger and Hanbury, Pharmacographia, p. 477; Sawer, Pharm. Journ., 
Ill, 20 (1890), p. 659, and Odorographia, vol. I, p. 356; Chemist and Druggist, 39 
(1891), p. 398; Pharm. Journ., 58 (1897), p. 52; Brit, and Colon. Druggist, 34 
(1898), p. 338. 604 
Special Part. 
Properties. French oil of lavender is a yellowish or yellowish- 
green 1 liquid of the pleasant, characteristic odor of the lavender flowers, 
and of a strong aromatic, slightly bitter taste.' Sp. gr. 0.885-0.895; 
«d =- 3 to-9°. It is soluble to a clear solution in three and more 
parts of 70 p. c. alcohol. The linalyl acetate content is as a rule 
30-40, seldom 45 p. c. According to the amount of ester the lavender 
oils can be divided into two classes. First, those oils with 36 and 
more p. c. of ester. They come from the highest regions of the southern 
French Alps, possess the finest and most intense aronia, and con- 
sequently bring the highest prices. Second, those with 30-36 p. c. of 
ester. Oils with less than 30 p. c. of linalyl acetate are mostly 
adulterated, much more seldom is the low ester content due to im- 
perfect distillation by which a part of the ester was decomposed. 
The English lavender oil differs from the French by a camphor- or 
cineol-like odor which accompanies it, as well as by its low ester con- 
tent. Sp. gr. 0.885 to 0.900; «d -- Ito-10°. The solubility is the 
same as that of the French oil, the amount of linalyl acetate is only 
5 to 10 p. c. 
Composition. According to the earlier works of Saussure2 (1817- 
1832), Proust and Dumas3 (1833), the ordinary laurus camphor, 
CioHiqO, had to be considered as a normal constituent of lavender oil. 
As recent investigations have shown that the oil from Lavandula vera 
D. C, contains no camphor, these statements refer no doubt to oils of 
other lavender species.4 
The results of Lallemand5 (1860) and of Bruylants6 (1879) in part 
do not agree with the most recent investigations. Lallemand found 
a laevogyrate hydrocarbon CioHie (?) boiling from 200 to 210°, and 
was the first to observe the presence of esters in lavender oil. According 
i) The finest oils with a high ester content mostly have a green tint, whereas 
rectified oils are colorless. To rectify lavender oil is irrational, because this process 
decomposes in part the principal constituent, viz. the linalyl acetate. As a result the 
flavor of the rectified oil is inferior (Bericht von S. & Co., Oct. 1894, p. 30). 
2) Ann. ('him. et Phys., II, 4, p. 318; II, 13, p. 273; II, 49, p. 225; Liebig's 
Annalen, 3, p. 163. 
3) Liebig's Annalen. 6, p. 248. 
*) In the literature quoted above, Spain is several times mentioned as the country 
from which the examined oil was obtained. As is shown in an article published by 
Charabot in 1897 (Bull. Soc. chim., Ill, 17, p. 378) the Spanish oil, of which the origin 
is not known, has different properties and is different in composition. Sp. gr. 0.912- 
0.916; aD = +13°20' to 4-16° 25'; ester content 3.15-3.4 p. c. The oils contained 
44.5 to 50.5 p. c. of alcohols as determined by acetylization. In the higher boiling 
fractions borneol (m. p. 204°) was found. The Spanish oil, therefore, resembles oil of 
spike more closely than the oil of lavender. 
5) Liebig's Annalen, 114, p. 198. 
6) Journ. de Pharm. et Chim., IV, 30, p. 139. Oils of the Labiatae. 
605 
to Bruylants the oil contains a terpene, CioHm, boiling at 162°, which 
yields a solid monohydrochloride. The principal part (45 p. c.) is said 
to be a mobile oil, the composition of which corresponds to a mixture 
of borneol. CioHisO. and camphor, CioHigO. On cooling to - 25° 
no solid constituents separated out; on oxidation with potassium 
dichromate and sulphuric acid, ordinary camphor was obtained. This 
would seem to show conclusively that Bruylants could not have had 
genuine lavender oil for examination. 
The most recent investigation of French lavender oil was made by 
Bertram and Walbaum.1 According to it, the principal constituent is 
1-linalyl acetate, which is present to the extent of 30-45 p. c. Besides 
linalyl acetate the ester of butyric acid and perhaps also those of 
propionic and valerianic acids are present in small amounts. The 
presence of formic acid could not be shown. 
Linalool is present in lavender oil not only as ester, but also in the 
free state. After acetylization, 67 p. c. of ester were found in an oil 
which originally contained only 34 p. c. As linalool cannot be quanti- 
tatively determined by acetylization, the results always being too low, 
it might be assumed that the amount of linalool present in lavender 
oil is about as great in the free state as in the form of ester. 
While an oil distilled by Schimmel & Co. from the dried flowers con- 
tained no pinene, a small amount of pinene (nitrosochloride, m. p. 102°, 
nitrolbenzylamine, m. p. 122-123°) was found in the first runnings 
boiling at 160-170° of a larger quantity of French oil. Cineol is like- 
wise only present in traces. In one case it could only be detected after 
the linalool contained in the proper fraction had been destroyed by 
heating with formic acid.2 
If larger amounts of pinene can be separated from lavender oil, the 
suspicion of adulteration with turpentine is justified, especially when 
supported by the ester determination, the sp. gr., the optical rotation, 
and the solubility in 70 p. c. alcohol. On the other hand a larger 
cineol content in the French oil indicates adulteration with spike oil., 
The linalool is accompanied in lavender oil by a second alcohol 
CioHisO, geraniol. From the fraction boiling at 110-120° under 
13 mm. pressure by treatment with calcium chloride, an oil could be 
separated, from which the diphenyl urethane of geraniol, melting at 
82° could be obtained.3 
1) Journ. f. prakt. Chem., II, 45, p. 590. 
2) Bericht von S. & Co., Oct. 1893, p. 25. 
3) Bericht von S. & Co., Apr. 1898, p. 32. 606 
Special Part. 
The English oil of lavender has been investigated by Semmler and 
Tiemann.1 From the first runnings of this oil they obtained a tetra- 
bromide melting at 105°, and thus showed the presence of limonene. 
The fraction boiling at 85-91° under 15 mm. pressure, consisted of 
1-linalool, that boiling at 97-105° of 1-linalyl acetate. In the last 
boiling fractions a sesquiterpene, C15H24, was found but not examined. 
The English oil differs from the French in its larger content of cineol,2 
as well as its low ester content, amounting to only 5-10 p. c. 
Examination and Valuation. The value of lavender oil depends on 
its- content of linalyl acetate. Although the amount of ester alone is 
not an absolute standard for the quality of the oil, the fineness and 
value of the oil stands, however, in direct ratio to it, providing, of 
course, that the oil is a normal distillate, free from any empyreumatic 
odor due to careless preparation. Such a case is, however, very unlikely 
to occur, as with an irrational distillation a part of the ester is 
destroyed. For this reason a carefully prepared oil must always show 
a comparatively high ester content. If the high linalyl acetate is partly 
decomposed during the distillation, the free acid acts detrimentally on 
the linalool and thus influences the odor also in this manner to an 
appreciable extent. 
By adulterations of any kind the ester content is of course also 
lowered. For these reasons the quantitative saponification is absolutely 
necessary in testing the value of an oil. The method has been described 
in detail on p. 193. 
In testing for foreign additions, the specific gravity, rotatory power 
and solubility in 70 p. c. alcohol must be considered. 
The more common adulterants are turpentine oil, cedar wood oil, 
and spike oil. Turpentine oil decreases the specific gravity and the 
solubility in 70 p. c. alcohol. The presence of pinene can also be readily 
shown (see under Composition). Spike oil does not influence the 
solubility, but decreases, as it contains but a small amount of linalyl 
acetate, the ester content. Besides, spike oil differs by its larger cineol 
content. 
There remains to be mentioned the adulteration of lavender oil with 
the ethyl ester of succinic acid, which, it is true, has been observed but 
once.3 It is, however, worthy of mention, as the addition of compara- 
tively small amounts of this succinic ester to lavender oil, produces a 
1) Berichte, 25, p. 1186. 
2) Bericht. von S. & Co., Oct. 1894, p. 31. 
3) Bericht von S. & Co., Apr. 1897, p. 25. Oils of the Labiatae. 
607 
high saponification number and thus the amount of linalyl acetate is 
apparently increased. 8 p. of ethyl succinate give the same saponifi- 
cation number as 18 p. of linalyl acetate. Apart from the large, 
apparent increase in the ester content, the ethyl succinate is a 
dangerous adulterant, because it has only a faint odor, which is 
almost completely covered by that of the lavender oil, and also because 
it influences but slightly the solubility and rotatory power. The specific 
gravity of the succinic ester is, however, much higher than that of 
lavender oil and may thus indicate its presence. 
In testing the lavender oil for the esters of succinic, oxalic or similar 
acids which may here be employed, the property of the acids to form 
difficultly soluble salts with barium is made use of. 
For this purpose about 2 g. of the oil are saponified, the portion insoluble 
in water separated by shaking with ether and the aqueous solution neutralized 
with dilute acetic acid. The solution is diluted to 50 cc. and 10 cc. of a cold 
saturated barium chloride solution added. It is then warmed for two hours 
on a waterbath and allowed to cool. If a crystalline deposit is formed, the 
oil is to be considered adulterated, as the acids contained in normal lavender 
oil, acetic and butyric acids, give soluble barium salts. 
34.8. Oil of Spike. 
Oleum Spicae.-Spikol.-Essence d'Aspic. 
Origin. Lavandula spica I). C. (L. spica p L., L. vulgaris ft Lam., 
L. latifolia Vill., Ger. Spiklavendel), has about the same distribution in 
the Mediterranean countries as the true lavender. It grows, however, 
mostly in the lower mountainous regions, not exceeding 700 m., at an 
altitude where Lavandula vera 1). 0. just begins. The oil is distilled 
exclusively in southern France in the same manner as lavender oil. 
160 k. of flowers yield 1 k. or 0.62 p. c. of oil (Laval1). 
History. As was mentioned under lavender oil (p. 600) the dis- 
tillates of various species of lavender have since antiquity been desig- 
nated as spike oil. It was not until the end of the sixteenth century 
that lavender oil and spike oil were differentiated. In antiquity, 
probably the Lavandula stoechas L. indigenous to the Mediterranean 
coast and distinguished by its aromatic, violet-red blossoms, was 
commonly used for the preparation of spike oil. The spike or stoechas 
oil mentioned in the writings of Dioscorides, Pliny, Scribonius Largus 
and other contemporaries was in all probability only aromatized fatty 
oil, like the rose and spikenard oil and other aromatic oils much used 
in antiquity. 
i) Journ. de Pharm. et Chim., V, 13, p. 599. 608 
Special Part. 
The distilled spike or spikenard oil was probably known in the 
fifteenth century. Besides cedar (turpentine) oil it is the only distilled 
oil mentioned by Brunschwig in his "Destillirbuch" of 1500 as Oleum 
de Spica from "Provinz" (Provence). Saladin also mentioned spikenard 
oil at the end of the fifteenth century. 
Valerius Cordus mentioned in his Dispensatorium Noricum of 1543 
only three distilled oils: turpentine oil, juniper oil and spike oil. Ryff 
described in his treatise on distillation published somewhat earlier, the 
distillation of "Spik und anderen fiirnemen Olen" and added the state- 
ment that, ''das Spiken- oder Lavendelol gemeygklich aus der Provinz 
Frankreich gebracht wird in kleinen glasslin eingefasst und theuer ver- 
kaufft." In the sixteenth century the several species of lavender were 
cultivated in Germany and in England. 
Gesner used the name spike oil only and described the distillation 
of the spike blossoms, whereas Porta at the end of the sixteenth century 
described also the distillation of lavender blossoms and especially 
emphasized the superiority of the oil from the French lavender. An 
interesting description of the preparation of the French spike or lavender 
oil is contained in the works of Demachy of 1773. 
In medical works Oleum spicae has been mentioned as early as the 
thirteenth century. It was included in the first edition of the Dispensa- 
torium Noricum of 1543, and Oleum lavandulae is also mentioned 
together with spike and other essential oils in the 1589 edition. The 
Pharmacopoea Augustana of Occo, contains up to 1613 only Oleum 
spicae, from that date on also Oleum lavandulae. 
Spike oil is mentioned in the oldest drug and price ordinances of 
German cities, Oleum lavandulae, however, is not found until 1582 in 
the Frankfurt ordinance. 
The statements of Demachy and other writers of his time agree 
with the assertions of later authors, that the spike oil found in 
commerce in the eighteenth century was probably only a distillate or 
mixture of turpentine and lavender oils. 
The yield of oil from the distillation of spike and lavender blossoms 
appears to have been first mentioned by Lewes,1 also by Cartheuser.2 
The so-called "lavender camphor" was observed in 1785 by Arezula,3 
and in 1800 by Proust. The first investigations of lavender oil were 
made by Saussure.4 
i) The new. Dispensatory, 1746. 
2) Elementa chymiae, vol. 2, pp. 133 
and 149. 
») Resultado de las experiencias, etc. 
4) Annal. de Chiin, et Phys., 4, p. 318; 
13, p. 273; 49, p. 159. Oils of the Labiatae. 
609 
Properties. Spike oil is a yellowish liquid, of a camphordike odor, 
reminding at the same time of lavender and rosemary. The specific 
gravity lies between 0.905 and 0.915. Spike oil is always dextrogyrate. 
As a rule the angle of rotation aD is up to + 3°, rarely up to + 7°. 
It is clearly soluble in 2-3 and more parts of 70 p. c. alcohol. The 
saponification number is about 15, corresponding to 5 p. c. of linalyl 
acetate (bornyl or terpinyl acetate, resp.). 
Composition. The first constituent identified with certainty in spike 
oil is camphor (Kane,1 1838). This compound does not occur in 
genuine lavender oil, as was shown in the preceding article, although 
the older authors claim to have found it. It is, therefore, highly 
probable that a part of the earlier investigations were made on spike 
oil and not on lavender oil. Besides camphor, Bruylants2 (1879) also 
found borneol in spike oil. 
The oil was thoroughly investigated, partly by Bouchardat3 alone 
in 1893, partly in co-operation with Voiry4 in 1888. By repeated 
fractionation a very insignificant amount (0.2-0.25 p. c.) of .an oil 
boiling about 160° was finally obtained, which yielded a solid hydro- 
chloride melting at 129°. On boiling with alcoholic potassium acetate 
this was decomposed for the greater part, and gave dextrogyrate 
camphene, solidifying in the cold. Whether or not d-pinene is present 
together with the d-camphene, could not be definitely shown. Bouchardat 
believed that the portion of the solid hydrochloride which was not 
decomposed by boiling for a short time with alcoholic potassium 
acetate, was pinene hydrochloride. The fraction boiling about 175°, 
about 10 p. c. of the oil, solidified in a freezing mixture, and consisted of 
cineol, CioHisO, of which the hydrochloride and dibromide, CioHisOBr2, 
were prepared. 
The portion going over at about 200° was a mixture of 1-linalool, 
d-camphor and d-borneol. The linalool (b. p. 198-199, «d = -16°44'), 
was converted into geranyl acetate by boiling with acetic acid anhydride. 
The camphor oxime prepared from the camphor had all the properties 
of the oxime obtained from ordinary camphor. The borneol, after it 
had been separated from the camphor by means of benzoic acid anhyd- 
ride, likewise turned the ray of polarized light to the right. 
Spike oil may also contain terpineol, for Bourchardat obtained 
dipentene dihydrochloride on conducting hydrochloric acid gas into the 
i) Journ.f. prakt. Chem., 15, p. 163. 
Comp, also Lallemand (1860), Liebig's 
Annalen, 114, p. 198. 
2) Chem. Centralbl., 1879, p. 616. 
3) Compt, rend., 117, pp. 53 and 1094. 
4) Compt. rend., 106, p. 551. 610 
Special Part. 
fraction having the boiling point of terpineol. The formation of this 
hydrochloride cannot, however, be definitely traced to terpineol, as it 
might also have been formed from linalool or geraniol. The geraniol 
also has not been positively identified. Hydrochloric acid yielded with 
the fraction boiling at 145-160° in a vacuum and smelling like 
geraniol, a liquid hydrochloride of the properties of geranyl chloride.1 
The analysis of the portion of the oil going over at 250°, gave results 
agreeing with C15H24, which indicates a sesquiterpene. 
Examination. Turpentine oil, with which spike oil is probably most 
often adulterated, is recognized by the lowering of the specific gravity, 
the diminution in solubility, and, when French turpentine is present in 
larger amount, by the inversion of the rotation to the left. If the 
amount of this oil is so small that only a decrease but no inversion 
of the angle of rotation takes place, while sp. gr. and solubility of the 
oil appear suspicious, the first 5-10 p. c. going over on fractional 
distillation should be tested in the polariscope. 
As*with rosemary oil (p. 594) the lowest boiling portions of spike 
oil are always dextrogyrate, while even a small addition of French 
turpentine oil produces laevorotation. Moreover, with genuine spike oil 
the amount of the terpenes boiling at about 160° is very small, so 
that the oil can also be declared adulterated (American turpentine oil, 
camphor oil) when at this temperature larger amounts of dextrogyrate 
terpenes distill over. 
The addition of rosemary oil is more difficult to recognize. This is, 
however, much more rarely used as adulterant, as the difference in price 
is not great. Sp. gr., rotation and boiling temperature of spike and 
rosemary oils are about alike, only the solubility in 70 p. c. alcohol is 
different. Mixtures of these two oils often dissolve in 2-3 parts of 
70 p. c. alcohol to form a clear solution, but it becomes turbid on the 
further addition of 70 p. c. alcohol. 
Schimmel & Co.2 have shown that spike oil contained more than 
30 p. c., rosemary oil only up to 15 p. c. of alcoholic constituents 
which could be determined by acetylization. Umney,3 therefore, 
suggests for judging the purity of the oil and for detecting the presence 
of rosemary oil, to acetylize the suspected oil, and to reject oils which 
show a content of less than 30 p. c. of alcohols as adulterated with 
i) According to Tiemann (Berichte, 31, p. 832) geranyl chloride prepared in this 
way is a mixture of different isomeric chlorides and not a definite chemical unit. 
2) Bericht von S. & Co., Oct. 1894, p. 65. 
3) Chemist and Druggist, 52, p. 166. Oils of the Labiatae. 
611 
rosemary oil. It must here be remembered that the alcoholic con- 
stituents of spike oil consist for the greater part of linalool, and that 
this body cannot, as is well known, be quantitatively acetylized, as it is 
partly decomposed with the formation of terpenes. Inasmuch as the 
acetylization- result depends on the length of time the acetic acid 
anhydride reacts on the oil, the results obtained can be used for 
judging- the purity of spike oil, only when the exact conditions under 
which the acetylization gives uniform results have been determined. 
Furthermore, the limits between which the apparent alcohol content 
thus determined varies with normal spike oil, ought to be ascertained 
by a series of experiments. 
349. Oil of Lavandula Stoechas. 
Lavandula stoechas L. is known in Spain as Romero santo (holy 
rosemary) (p. 607). Its volatile oil and also that of Lavandula dentata 
L. is there obtained for domestic use, by hanging the fresh, flowering 
plants with the flower heads downward in bottles, which are sealed and 
exposed to the sun. On the bottom a mixture of water and volatile 
oil collects, which is used as a styptic for washing wounds, and also 
for eruptions. 
The odor of the oil does not in the least remind of lavender, but is 
rather more similar to rosemary, having the camphor-like properties 
of the latter. The sp. gr. of a sample of oil was 0.942. It boiled from 
180-245°; the lower boiling portions contained cineol.1 
350. Oil of Lavandula Dentata. 
The oil of Lavandula, dentata L. is very similar to that of Lavandula 
stoechas L. Its odor reminds strongly of rosemary oil and camphor. 
It has the sp. gr. 0.926, distills almost completely between 170-200° 
and contains cineol.1 
351. Oil of Lavandula Pedunculata. 
An oil of Lavandula pedunculata Cav. coming from Portugal, is 
described by Schimmel & Co.2 as follows: "The oil has a difficultly 
definable, not pleasant odor, and is, therefore, useless for practical 
purposes. Sp. gr. 0.939; «d =-44° 54'. It is soluble in an equal part 
of 80 p. c. alcohol. The high saponification number 111.7 corresponds 
to a content of 39 p. c. of an acetic acid ester of an alcohol CioHisO. 
i) Bericht von S. & Co., Oct. 1889, p. 54. 2) Ibidem, Oct. 1898, p. 33. 612 
Special Part. 
On distilling the saponified oil with steam a light yellow liquid came 
over. The first fraction contained cineol, as was shown by the cineol- 
iodole compound. The odor of this fraction suggests the presence of 
thujone, together with the cineol." 
353. Oil of Catnep. 
The oil of Nepeta cataria L. indigenous to North America and used 
as a domestic remedy, has a not pleasant, mint- and camphor-like 
odor. Sp. gr. 1.041A 
353. Oil of Ground-ivy. 
From the dried herb of the ground-ivy, Nepeta glechoma Benth. 
(Glechoma hederacea L.), Schimmel & Co.2 obtained 0.3 p. c. of volatile 
oil. It had a difficultly definable, not pleasant odor, and was dark in 
color. Sp. gr. 0.925. 
354. Oil of Sage. 
Oleum Salviae. - Salbeiol.- Essence de Sauge. 
Origin and History. The somewhat shrub-like sage, Salvia officinalis 
L., is indigenous to the northern countries of the Mediterranean, and is 
cultivated in many countries of moderate climate as a garden plant for 
medicinal purposes. The plant will grow as far north as the northern 
part of Norway. 
Sage appears to have been used as a medicinal herb at the time of 
the Romans and was one of the plants recommended by Charlemagne for 
cultivation. In the "Destillirbuch" by Brunschwig of 1500 a distinction 
is made between large and small sage for the distillation of sage water 
The distilled oil of sage is first mentioned in the price ordinances of 
Worms of 1582 and of Frankfurt of 1587 and is included in the 1589 
edition of the Dispensatorium Noricum. The distillation of the oil has 
been described by Begnini in 1688, and the yield of oil from the leaves 
was determined by Wedel in 1715 and Cartheuser about 1732.3 
In 1720 Geoffroy observed a stearoptene which had crystallized from 
the oil and which he termed sage camphor.4 The same substance was 
again observed by Arezula in 1789 and described by him.5 The first 
i) Bericht von S. & Co., Oct. 1891, p. 40. 
2) Bericht von S. & Co., Apr. 1894, p. 55. 
3) Elementa chymiae, vol. 2, p. 87. 
a) Mem. de l'Acad. roy. des sciences de Paris, 1721, p. 168. 
s) Resultado de las experiencias hechas sobre el alcanfor de Murcia non licencia. 
Segovia, 1789, p. 8. Oils of the Labiatae. 
613 
examination of the leaves appears to have been made by Ilisch1 in 
1810; whereas the oil was investigated by Herberger2 in 1829 and by 
Rochleder3 in 1841. 
Preparation. For the distillation of the oil the wild Dalmatian 
herb, which grows abundantly and is brought into the market in large 
compressed bales, alone seems to be used. The yield from Dalmatian 
leaves is 1.3-2.5 p. c. German leaves upon distillation yielded 1.4 p. c. 
of oil. 
Properties. Oil of sage is a yellowish or greenish-yellow liquid 
possessing the peculiar odor of 'the herb while at the same time re- 
minding somewhat of tansy and camphor. Sp. gr. 0.915-0.925; «d = 
+ 10 to + 25°. The oil is soluble in two and more parts of 80 p. c. 
alcohol. Saponification number 107. 
Composition. The presence of the following substances has been 
definitely determined: pinene, cineol, thujone and borneol. 
1) Pinene. From the laevogyrate fraction boiling at 156-158°, 
Tilden,4 also Muir and Sugiura5 obtained a nitrosochloride. Wallach 
converted the nitrosochloride into nitrosopinene6 (CioHisNO, m. p. 130°) 
and the original fraction into dipentene7 (tetrabromide, m. p. 124-125°) 
and thus established the identity of the hydrocarbon present with pinene. 
With regard to the optical rotation, the statements vary.- Muir and 
Sugiura found the fraction at one time laevogyrate, at another dextro- 
gyrate; Wallach found it optically inactive. The fraction, therefore, 
seems to consist of a mixture of the two optical isomers, in which at 
times the one, at times the other isomer predominates. 
2) Cineol. Fraction 174-178° yielded no nitrosochloride. By 
means of the hydrobrom addition product, Wallach was able to isolate 
pure cineol.8 
3) Thujone (tanacetone, salviol, salvone), CioHieO. Fraction 
198-203° was regarded by Muir and Sugiura as having the com- 
position CioHieO, later CioHisO and was termed salviol. Semmler in 
i) Trommsdorff's Journ. der Pharm., 20, II, p. 7. 
2) Buchner's Repert. f. d. Pharm., 34, p. 131. 
3) Liebig's Annalen, 44, p. 4. 
*) Journ. Chern. Soc., 1877, I, p. 554; Abstr. Jahresb. f. Chem., 1877, p. 427. 
5) Philosoph. Magaz. and Jou-rn. of Science, V, 4, p. 336. - Pharm. Journ., Ill, 8, 
pp. 191, 994; Journ. Chem. Soc., 1877, II, p. 548; Abstr. Jahresb. f. Chem., 1877, 
p. 957. - Chem. News, 37, p. 211; Journ. Chem. Soc., 33, p. 292; Abstr. Jahresb. f. 
Chem., 1878, p. 980. - Journ. Chem. Soc., 37, p. 678; Chem. News, 41. p. 223; Abstr, 
Jahresb. f. Chem., 1880, p. 1080. 
6) Liebig's Annalen, 252, p. 103. 
t) Liebig's Annalen, 227, p. 289. 
s) Liebig's Annalen, 252, p. 103. 614 
Special Part. 
1892 declared salviol, which constituted 50 p. c. of the oil of sage, as 
identical with tanacetone.1 Two years later, however, he expressed his 
doubt as to their identity.2 By a comparison of the physical properties 
of the compounds regenerated from their acid sulphite addition products, 
Schimmel & Co.3 established the identity of the corresponding ketones 
from the oils of sage, thuja, tansy and wormwood. Wallach4 also 
obtained identical derivatives from thujone, tanacetone, salvone and 
absinthol. For the properties and derivatives of thujone see p. 167. 
4) Borneol. Upon oxidation of oil of sage, Rochleder5 had 
obtained camphor which evidently had existed in the oil as such or had 
been derived from borneol by oxidation. Sugiura and Muir had observed 
that the higher boiling fractions of the oil separated crystals upon 
cooling, which resembled camphor but did not agree with it in all of 
its properties. In order to decide whether camphor is contained in the 
oil or not, Schimmel & Co.6 fractionated an oil which they had distilled 
from Dalmatian herb, and submitted to a freezing mixture those 
fractions which ought to have contained the camphor if present. No 
solid substance separated. Acetylization, however, indicated the presence 
of an alcohol (abt. 8 p. c. calculated as CioHisO). A part of the 
fraction was, therefore, treated with benzoyl chloride. The benzoate was 
separated and saponified and a substance corresponding with borneol 
in all of its properties resulted. After repeated crystallization it melted 
at 204°. In 10 p. c. alcoholic solution it deviated the ray of polarized 
light 0°23' to the right. The borneol of oil of sage is, therefore, a 
mixture of the dextrogyrate and laevogyrate modifications. Camphor 
could not be found in the oil examined. This does not, however, 
exclude its presence in other than the Dalmatian oils. 
According to Muir, English oil of sage contains much cedrene, 
b. p. 260°, some terpene and only traces of oxygenated constituents (?). 
355. Oil of Salvia Sclarea. 
This oil is distilled from the dry herb, or better from the fresh herb 
of the muscatel sage Salvia sclarea L. Its odor is pleasant, lavender- 
like and, after evaporation of the more volatile portions, reminds of 
ambra. Sp. gr. 0.907-0.928; «d = -19°22' to -24°1/; saponification 
number 144, corresponding to 50.4 p. c. of linalyl acetate. Judging 
1) Berichte, 25, p. 3350. 
2) Berichte, 27, p. 895. 
3) Bericht von S. & Co., Oct. 1894, p. 51. 
*) Liebig's Annalen, 286, p. 93. 
s) Liebig's Annalen, 44, p. 4. 
6) Bericht von S. & Co., Oct. 1895, p. 40. Oils of the Lnbiatae. 
615 
from the odor, this ester is a constituent of the oil,1 but its presence 
has not yet been chemically established. 
356. Oil of Monarda Punctata. 
The American labiate, Monarda, punctata L., commonly known as 
horsemint, yields upon distillation about 3 p. c. of volatile oil which 
is yellowish-red or brownish in color and of a pungent thyme-like and 
minty odor. Sp. gr. 0.930-0.940; slightly dextrogyrate. Upon 
prolonged standing thymol separates in large crystals or crusts. 
Composition. Thymol was discovered in the oil by Arppe2 in 1846. 
It is present in such quantity that the oil has served for its preparation 
on a large scale.3 According to Schroter4 (1888), the oil is reported 
to contain 50 p. c. of a laevogyrate hydrocarbon, b. p. 170-173°, 
25 p. c. of a dextrogyrate (!), non-crystallizable thymol, and a 
substance CioHisO (?), b. p. 240-250°. These statements, which do 
not inspire confidence, throw doubt both upon the results and the 
material. 
From material, identified by botanical authority, Schumann and 
Kremers5 obtained an oil which contained as much as 61 p. c. of thymol 
when assayed according to the iodine method described under oil of 
thyme. The non-phenol portion of the oil contained cymene, C10H14, 
identified by the oxypropyl benzoic acid, m. p. 155-156°. Fraction 
186-202° contains oxygen and consists possibly of linalool. In addition 
to thymol, Hendricks and Kremers6 found a phenol fraction' which 
would not solidify upon cooling and possibly contains carvacrol. They 
also found traces of d-limbnene identified by means of its nitrol- 
benzylamine base melting at 94°. 
357. Oil of Monarda Fistulosa. 
Wild bergamot or Monarda fistulosa. L. yields according to Kremers 
upon distillation an oil similar to that of M. punctata.7 The sp. gr. 
of a number of oils distilled from the entire plant at different periods 
from June to September varied from 0.916 to 0.941. Optical rotation 
is slightly to the left. The amount of phenol varies from 52-58 p. c. 
The phenol of this species, however, is not thymol but carvacrol. This 
isomer was identified by means of dicarvacrol (m. p. 147-148°), carva- 
i) Bericht von S. & Co., Apr. 1889, 
p. 44: Oct. 1894, p. 38. 
2) Liebig's Annalen, 58, p. 41. 
3) Bericht von S. & Co., Oct. 1885, 
p. 20. 
*) Am. Journ. Pharm., 60, p. 113. 
5) Pharm. Review, 14, p. 223, 
6) Pharm. Archives, 2. p. 73. 
t) Pharm. Rundschau, 13, p. 207; 
Pharm. Review, 14, p. 198. 616 
Special Part. 
crol sulphonic acid (m. p. 58-59°), nitroso carvacrol (m. p. 153-154°) 
and dinitro carvacrol (m. p. 117-119°). Other constituents are cymene, 
identified by means of oxypropyl benzoic acid (m. p. 156°), and limo- 
nene, identified by means of its nitrolbenzylamine base (m. p. 93°).1 
Upon steam distillation of the phenol separated from its alkaline 
solution by acid, in one instance a red substance crystallized in the 
cooler. Purified by sublimation, it melted at 256-266° and behaved 
toward alkalies like alizarin. 
358. Oil of Monarda Didyma. 
This oil is presumably similar in composition to that of the two 
previous oils. Concerning it Fliickiger2 makes the following statement: 
"In 1796 Brunn, apothecary in Gustrow, observed a crystalline deposit 
(evidently thymol) in the oil from Monardi didyma L., which it seems 
had been imported from America." 
359. Oil of Balm. 
Oleum Melissae. - Melissenol. - Essence de Melisse. 
Origin and History. The labiate, Melissa officinalis L. is indigenous 
to the northern Mediterranean countries from Spain to the Caucasus, 
and is cultivated as a garden plant and for medicinal purposes in Europe 
a,nd North America. 
On account of its fragrance, balm was cultivated by the Greeks, 
Romans and Arabs, and during the middle ages in Italy, Germany and 
Scandinavia. During the period of distilled waters, from the fifteenth 
to the seventeenth centuries, balm water was a current article. Oil of 
balm appears to have come into use about the middle of the sixteenth 
century. It is first mentioned in the ordinance of Frankfurt-on-the-Main 
for 1582 and in the Dispensatorium Noricum of 1589. 
Comparable to the distillate from rosemary of the sixteenth century 
which was the precursor of the Eau de Cologne of the eighteenth and 
nineteenth centuries, the fragrant distillate from balm, lemon peel and 
lavender of the seventeenth century developed later into a very popular 
perfume. It was first prepared by the Carmelite monks of Paris in 1611 
and became famous as Eau de Cannelites (Ger. Karmelitergeist'). Later 
the alcoholic distillate was made officinal as Spiritus Melissae com- 
positus. 
The earlier investigations of the oil were made by Schultz in 1739, 
by Hoffmann about the same time, and by Dehne in 1779. 
1) Pharm. Archives, 2, p. 76. 
2) Archiv d. Pharrn.. 212, p. 488. Oils of the Labiatae. 
617 
The balm oil of commerce is no pure distillate from the balm. It 
may be an oil of lemon distilled over balm (Oleum melissae citratum),' 
or a citronella oil treated in the same way, or merely a fractionated 
citronella oil. The yield from the herb Melissa officinalis L. is so small 
that the price of the oil would have to be extremely high. An oil 
distilled from the dry herb by Schimmel & Co. was solid at ordinary 
temperature and contained citral1 as was shown by Doebner's reaction. 
Later the same firm subjected the fresh herb of two varieties of balm 
to distillation.2 
1) Fresh herb, just beginning to blossom. Yield 0.014 p. c.; 
sp. gr. 0.924; an = + 0°30'. The oil had a very pleasant balm odor. 
2) Fresh herb in full blossom. Yield 0.104 p. c.; sp. gr. 0.894; 
optically inactive. The odor was less pleasant than that of the first 
oil and distinctly indicated the presence of citral and citronella!. 
The attempt to prove the presence of these two aldehydes by means 
of Doebner's reaction yielded no positive result. The resulting acids 
from both oils began to melt at about 208° and were completely 
liquified at 225°. Evidently the mixture consisted of the citral com- 
pound (m. p. 197-200°) and the citronella! compound (m. p. 225°). 
' 360. Oil of Pennyroyal. 
Oleum Hedeomae.-Pennyroyal- oder amerikanisches Poleiol. - Essence 
d'Hedeoma. 
Origin and History. The oil from the American labiate, Hedeoma 
pulegioides Persoon is so similar to the oil from the European Mentha 
pulegium L., that it is frequently substituted for the latter. Pennyroyal 
is found from the Atlantic states to the Rockies. For its distillation 
very simple apparatus are used and the operation is, therefore, con- 
ducted in various regions. The bulk of the oil is reported as being* 
distilled in North Carolina (Harris3) and in the southern and eastern 
sections of Ohio.4 The primitive stills, like those used for the distil- 
lation of sassafras and wintergreen (pp. 397 and 588), consist of a 
barrel resting on a kettle used as boiler. The boiler is placed over a 
fire-place dug into the ground and provided with a chimney. The barrel 
is connected with a tube condenser resting in a trough through which 
i) Bericht von S. & Co., Oct. 1894, p. 37. 
2) Bericht von S. & Co., Oct. 1895, p. 58. 
3) Pharm. Journ., Ill, 17, p. 672. 
*) Comp. Kremers, Proceed. Am. Pharm. Assoc , 35, p. 546.-J. F. Patton, Proc. 
Penn. Pharm. Ass., 1890; and Proc. Am. Pharm. Assoc., 39, p. 548. 618 
Special Part. 
■cool water flows. The fresh herb is distilled, a ton yielding about 
10-12 pounds of oil. The dry leaves1 yield about 3 p. c., the dry 
stems and leaves only 1.3 p. c. oil. 
Properties. American pennyroyal oil is a light yellow liquid, of a 
■characteristic minty and sweetish odor and an aromatic taste. Sp. gr. 
0.925-0.940; «d= + 18 to +22°. It is soluble in two or more parts 
of 70 p. c. alcohol. By means of this property, adulterations with 
petroleum, turpentine oil and other essential oils can readily be detected. 
Composition. The principal constituent of pennyroyal oil is pule- 
gone, the presence of which was established by Habhegger2 by means 
of the hydrated pulegone oxime, CioHiuNOH. H2O, m. p. 147°. and by 
the benzoyl ester of the latter melting at 141°. 
Kremers3 found in the oil heated with potassa two ketones, CioHisO. 
The one boiled at 1G8-171° and yielded an oxime melting at 41-43°; 
the other boiled at 206-209° and yielded an oxime melting at 52°. 
The latter is possibly identical with menthone. Formic, acetic and 
isoheptoic acids were also found. 
361. Oil of Hyssop. 
Oleum Hyssopi. - Isopol.-Essence d'Hysope. 
Hyssop oil was formerly used medicinally and is mentioned in the 
drug ordinances of Berlin for 1574' and of Frankfurt-on-the-Main for 
1582. It is distilled from the herb of Hyssopus officinalis L.1 The 
yield from the dry herb is about 0.3-0.9 p. c. The oil has a pleasantly 
aromatic odor reminding of male fern. Sp. gr. 0.925-0.94; «d H 17 
to -23°. It forms a clear solution with 2-4 parts of 80 p. c. alcohol, 
while with 70 p. c. alcohol even 10 parts will render only a turbid 
solution.5 The saponification number of one oil was 1.4, after acetyli- 
zation 45. 
The oil begins to boil at about 170°; but little passes over below 
175°, the bulk distills between 200 and 218° and has a strong odor of 
thujone or thujyl alcohol. 
An examination by Stenhouse6 was restricted to the analysis of 
various fractions from which no conclusions as to the composition of 
1) Bericht von S. & Co., Oct. 1893, p. 33. 
2) Proc. Wis. Pharm. Assoc., 1893, p. 51; Am. Journ. Pharm., 65, p. 417. 
3) Proc. Am. Phar. Assoc., 35, p. 546; Am. Journ. Pharm., 59, p. 535.-Pharm. 
Rundschau, 9, p. 130. 
4) Comp, also oil from Origanum vulgare. 
5) Chemist and Druggist, 50, p. 218. 
«) Liebig's Annalen, 44, p. 310; Journ. f. prakt. Chemie, 27, p. 255. Oils of the Labiatae. 
619 
the oil could be drawn. Besides, the oil examined by Stenhouse appears 
to have been adulterated with turpentine oil. One of his fractions 
began to boil at 160°, whereas pure oil begins to boil at 170°. 
Several French oils had properties that deviated materially from 
those of pure oils. The sp. gr. of one of these oils was 0.95 and the 
angle of rotation + (!) 45°. They had a strong odor of fenchone, thus 
leading to the supposition that they consisted principally of the first 
runnings of fennel oil. 
362. Oil of Satureja Hortensis. 
Origin and History. Satureja hortensis L. (Ger. Bohnen- or Pfeffer- 
kraut) owes its odor and pungent taste to a volatile oil obtained by 
steam distillation. The yield from the fresh herb is about 0.1 p. c. 
The oil is enumerated in the Frankfurt ordinance of 1582 among the 
medicinal volatile oils. 
Properties. The oil possesses the strong aromatic odor of the 
plant and a sharp, biting taste. The sp. gr. of the oil distilled from 
the fresh herb lies between 0.900 and 0.925; «D = + 0°4' (determined 
on a single oil); phenol content 38-42 p. c. The oil forms a clear 
solution with 10 parts of 80 p. c. alcohol.1 An oil examined by Jahns2 
in 1882 and distilled from the dry herb had a sp. gr. 0.898 ; «d = - 0.62°; 
phenol content 30 p. c. 
Composition. According to Jahns, this oil contains carvacrol, also 
traces of a second unknown phenol which gives a blue color reaction 
with iron salts. 
Of the hydrocarbon fractions, about one-third consists of cymene 
(b. p. 173-175°; cymene sulphonate of barium). The other two-thirds 
(b. p. 178-180°; sp. gr. 0.855; «d =- 0.2°) consist of a terpene or 
terpenes as shown by analysis. 
363. Oil of Satureja Montana. 
The oil of >8. montana L. has much the same properties as that of 
S. hortensis. The two oils cannot be distinguished by their odor. 
Fresh, cultivated herb1 yielded upon distillation 0.18 p. c. of oil. 
Sp. gr. 0.939; «d=-2° 35'; soluble to a clear solution in 4.5 parts of 
70 p. c. alcohol, and in 1.5 parts of 80 p. c. alcohol; phenol content 
65 p. c. 
t) Bericht von S. & Co., Oct. 1897, p. 65. 2) Berichte, 15, p. 816. 620 
Special Part 
An oil examined by Haller1 in 1882 had been distilled from wild 
herb growing on the Maritime Alps in the neighborhood of Grasse. 
Sp. gr. 0.93942 at 17°; «d =- 3° 25'. He found 35-40 p. c. carvacrol 
and a small amount of phenol boiling above 235°. The hydrocarbons 
boiled between 172-175° and 180-185° and appeared to be terpenes. 
364-. Oil from Satureja. Thymbra. 
Satureja thymbra, L. was dedicated to Priapos by the ancient Greeks. 
In Spain it is used commonly as a spice and has the reputation of being 
a stimulant and disinfectant. These properties are said to be due to 
its volatile oil. Such an oil was obtained from Spain by Schimmel & Co.3 
and examined by them. It had a sp. gr. 0.905. The oil remaining after 
the removal of the thymol (abt. 19 p. c.) was fractionated. A fraction 
boiling abt. 160° contained pinene (nitrolbenzylamine base, m. p. 121°); 
fraction 175° contained cymene; the following fraction contained traces 
of dipentene. The fraction above 200° yielded after saponification 
borneol and acetic acid 'which are contained in the oil as bornyl acetate. 
In composition, the oil is therefore closely related to oil of thyme. 
365. Oil of Origanum Vulgare. 
Origanum vulgare L. is one of the spice plants of antiquity. The 
hyssop of Luther's translation does not refer to a Hyssopus but to 
Origanum. The volatile oil was used during the latter part of the 
middle ages and is mentioned in the German ordinances of the sixteenth 
century. The yield from the dry herb is 0.15-0.4 p. c. The oil possesses 
a strong aromatic odor and a spicy, bitter taste;4 sp. gr. 0.870-0.910; 
«d = - 34.4°.5 
According to Kane6 (1839) the oil contains a stearoptene about 
which nothing is known. The bulk of the oil is reported by him to boil at 
161°. Jahns5 in 1880 found two phenols in an oil distilled from the fresh 
herb. One of these gave a green coloration with ferric chloride, and is 
possibly identical with carvacrol; the other gave a violet color. The 
oil contained not more than about 0.1 p. c. of combined phenols. 
The French oils of commerce are mostly mixtures of a pennyroyal- 
like odor which possibly contain not a trace of the genuine oil. 
5) Archiv d. Pharm., 216, p. 277. 
6) Liebig's Annaien, 32, p. 284; 
Journ. f. prakt. Chemie, 15, p. 157. 
i) Compt. rend., 94, p. 132. 
2) 0.7394 is evidently a printer's error. 
3) Bericht von S. & Co., Oct. 1889, p. 55. 
Bericht von S. & Co., Apr. 1891, p. 49. 366. Oil of Sweet Marjoram. 
Oils of the Labiatae. 
621 
Oleum Marjoranae.-Majoranol.-Essence de Marjolaine. 
Origin. The fresh, flowering herb of Origanum majorana L. yields 
upon distillation 0.3-0.4 p. c., the dry herb 0.7-0.9 p. c. of oil. The 
oil of commerce is mostly obtained from Spain. 
Properties. Oil of sweet marjoram is a yellow or greenish-yellow 
liquid of a pleasant odor reminding of the herb and of cardamom. The 
taste is spicy but mild. Sp. gr. 0.89-0.91; aD = + 5 to +18°. The 
saponification number of a single oil was 21.5. As a rule the oil 
produces a clear solution with 2 vol.,of 80 p. c. alcohol. 
Composition. Oil of sweet marjoram has been repeatedly examined. 
The stearoptene described and analyzed by Mulder1 in 1839 possibly 
was terpin hydrate or pinol hydrate. 
According to Bruylants2 (1879) the oil contains 5 p. c. of a dextro- 
gyrate hydrocarbon CioHie, and 85 p. c. of a dextrogyrate mixture of 
borneol and camphor. This statement has not been confirmed. 
Beilstein and Wiegand3 in 1882 isolated a terpene boiling at 178°, 
sp. gr. 0.846 at 18.5°, which absorbed one molecule of hydrogen chloride, 
without yielding a crystalline compound. Fraction 200-220° was 
analyzed and regarded as a sesquiterpene hydrate, C15H24H2O. The low 
boiling point, however, renders this conclusion very improbable. 
. According to a recent investigation by Biltz4 (1898), the oil con- 
tains 40 p.c. of terpenes, principally terpinene (nitrosite m. p. 155-156°); 
also d-terpineol which, however, could not be obtained crystalline. 
Fractions 215-218° (sp. gr. 0.930) had the composition CioHisO. 
Oxidized with permanganate it yielded trioxy hexahydro cymene 
CioHaoOa (m. p. 129-130°).5 Further oxidation with chromic and 
sulphuric acids yielded the keto lactone, CioHicOg (m. p. 61°), obtained 
by Wallach from terpineol. Fraction 215-218° must, therefore, be pro- 
nounced as terpineol. The alcohol is present principally in the free state 
and only small portions are present in the form of ester. The nature 
of the substance that produces the peculiar marjoram odor is still 
unknown. 
i) Liebig's Aanalen, 31, p. 69.-Journ. f. prakt. Chern., 17, p. 103. 
2) Journ. de Pharm. et Chim., IV, 30, p. 138; Jahresb. f. Pharm., 1879; p. 160.- 
Chem. Centralbl., 1879, p. 616. 
3) Berichte, 15, p. 2854. 
4) Ueber das atherische Oel von Origanum majorana. Inaugur.-Dissertat., Greifs- 
wald, 1898; Berichte, 32, p. 995. 
5) The substance obtained by Wallach in 1893 from inactive terpineol melted at 
121-122° (Liebig's Annalen, 275, p. 152). 622 
Special Part. 
367. Oil of Cretian Origanum. 
Oleum Origani Cretici. - Spanisch Hopfenol. - Essence d'Houblon d'Espagne. 
The carvacrol-containing oils of several species of Origanum growing 
in Mediterranean countries are known in the German market as 
Spanisch Hopfendl and Kretisch Dostendl. At present there are two 
varieties in the market which differ in properties and composition, the 
Triest oil and the Smyrna oil. The former is dark in color, has a high 
specific gravity and a corresponding high carvacrol content. The latter 
is lighter in color, has a milder odor and a lesser carvacrol content in 
correspondence with its lower specific gravity. 
1. Triest Origanum Oil. 
Origin. The oil enters the market from Triest. It is uncertain whether 
the oil is distilled at that place or in the Mediterranean islands which 
supply the herb. The oil corresponds in all its properties with that 
distilled in Germany from the dry herb of Origanum hirtum Lk. It is 
probable, therefore, that this is the species yielding the Triest oil. The 
yield from the dry herb is 2-3 p. c. 
Properties. The oil possesses a strong, thyme-like odor and a 
pungent, persistent taste. Freshly distilled it is of a golden-yellow 
color, which upon exposure to air is changed to dark brown to greyish- 
black. The darkening begins at the surface and gradually proceeds 
downward. Sp. gr. 0.94-0.98. On account of the dark color, the 
angle of rotation in most instances cannot be observed. In a few 
instances, when observation was possible, the oil was found inactive or 
a slight laevorotation, less than 1°, was observed. With 3 p. of 70 p. c. 
alcohol the oil forms a clear solution. The carvacrol content varies 
from 60-85 p. c. 
Composition. The Triest oil was examined by Jahns1 in 1879. He 
showed the presence of carvacrol which previously had been prepared 
artificially but had not been found in an oil. Properties and derivatives 
of carvacrol are described on p. 177. 
If the oil is treated with dilute soda solution and the solution of 
the phenylate shaken with ether, all of the carvacrol can be removed. 
If the alkaline solution which no longer yields anything to the ether 
is acidulated, a small amount - about 0.2 p. c. - of a second phenol is 
obtained which produces a violet color with ferric chloride. 
The non-phenol portions of the oil, after several rectifications over 
sodium, boiled principally between 172-176° and consist principally 
i) Arehiv d. Pharm., 215, p. 1. Oils of the Lahiatae. 
of cymene as shown by the formation of cymene sulphonic acid. The- 
fact that the fraction when shaken with sulphuric acid developed the 
odor of sulphur dioxide and became strongly heated indicates that in 
addition to cymene other substances, presumably terpenes, are present.. 
2. Smyrna Origanum Oil. 
Origin. The oil is distilled in Asia Minor1 from Origanum smyrnaeum 
L. and enters the world's market from Smyrna. 
Properties. The oil is of a golden-yellow color and of a mild odor 
reminding somewhat of linaloe oil or linalool. Sp. gr. 0.915-0.945; 
«d = - 3 to -13°. It forms a clear solution with 3 parts of 70 p. c. 
alcohol and has a carvacrol content of from 25-60 p. c. 
Composition. According to Gildemeister2 (1895) the Smyrna oil 
differs from the Triest oil principally as to the linalool which the 
former contains in appreciable amount. As a result it contains less, 
phenol than the Triest oil. Besides much carvacrol (phenyl isocyanate, 
m. p. 140°), but very little of the phenol which gives a violet reaction 
with ferric chloride is present. Fraction 155-163° («n = -3° 28') has 
a remarkably low sp. gr., viz., 0.826 at 15°, thus leading to the sup- 
position that so-called olefinic terpenes may be present. 
Fraction 175° contains cymene (oxypropyl benzoic acid, m. p. 156- 
158°; and isopropyl benzoic acid, m. p. 257-262°); fraction 198-199°^ 
having a sp. gr. of 0.870 and «d = -15° 56', possessed all of the 
properties of 1-linalool. The presence of this alcohol was proven by 
oxidizing it to citral and identifying this aldehyde by converting it into 
citryl-/9-naphtho cinchoninic acid, m. p. 198-199°. 
Examination. The solubility of the oil in 70 p. c. alcohol should 
be tested, by means of which the addition of turpentine oil and other 
cheap oils can be detected. Of importance is the determination of the 
carvacrol content as described under oil of thyme. Oils rich in carvacrol 
command a higher price than those poor in phenol. 
368. Oil of Thyme. 
Oleum Thymi. - Thymianol. - Essence de Thym. 
History. The labiate Thymus vulgaris L., which is indigenous to 
the countries bordering on the Mediterranean, is now cultivated in 
most countries with a temperate climate. During the middle ages the 
623 
1) This is possibly the same oil which is prepared in Konia in Anatolia in primitive 
apparatus and sold in small flasks in the streets of Constantinople as a remedy against, 
rheumatism. Comp. Bericht von S. & Co., Apr. 1891, p. 44, 
2) Archiv. d. Pharm., 23, p. 182. 624 
Special Part. 
distinction between T. vulgaris and T. serpyllum does not appear to 
have always been made. Though thyme has always been a rather 
unimportant remedy, it and the oil of thyme have been officinal since 
the sixteenth, century in most medicinal treatises and in drug and spice 
ordinances. The oil is enumerated in the Dispensatorium Noricum of 
1589. Thyme-camphor was first observed by Neumann in 1719, and 
by Cartheuser in 1754. It was examined and named thymol by Lalle- 
mand in 1853.1 
Origin. Oil of thyme is distilled principally from the fresh, flowering 
herb of Thymus vulgaris L. which grows abundantly in the wild state 
in the mountains of southern France. The small knotty and woody 
stems of the thyme are found in clearings and in the shadeless coast 
districts of the Riviera, also in the mountainous regions of the Maritime 
Alps up to an altitude of 1,000 m. It is not definitely known what 
plant yields the Spanish oil of thyme. Inasmuch as it resembles the 
Cretian origanum oil in properties and composition, it is not improbable 
that it is derived from a species of origanum. The yield is known for 
the oil obtained from the cultivated herb from which the commercial 
oil, as a rule, is not obtained. Fresh German herb yields 0.3-0.4 p. c., 
dry German herb 1.7 p. c. of oil; fresh French thyme, cultivated in 
Germany, yielded 0.9 p. c., dry French herb 2.5-2.6 p. c. of oil. 
Properties. Both French and German oil of thyme are of a dirty, 
dark reddish-brown color, of a pleasant, strong thyme odor and a 
biting, persistent taste. The sp. gr. of a pure oil is always above 
0.900, good French oils having a sp. gr. of 0.905-0.915. Schimmel & 
Co. observed the sp. gr. 0.909-0.935 on their own distillates. The 
optical rotation is faintly laevogyrate, but in most instances cannot be 
observed on account of the dark color bf the oil. It is soluble in part 
of 90 p. c., and in 1-2 parts of 80 p. c. alcohol; of 70 p. c. alcohol 
15-30 parts are mostly requisite to form a clear solution. The phenol 
content of normal oils varies, as a rule, between 20-25 p. c. and in 
rare instances rises to 42 p. c. The phenol of the French and German 
oils is mostly thymol, sometimes, however, carvacrol or a mixture 
of both. 
Oil of thyme rectified in the ordinary manner readily resumes the 
dark color of the crude oil. In order to obtain a light yellow colored 
oil with full phenol content special precautions are necessary for its 
rectification. Many consumers lay unnecessary stress on the light color 
1) Journal de Pharm. et Chim., Ill, 24, p. 274; Compt. rend., 37, p. 498. Oils of the Labiatae. 
625 
of the oil. In southern France such a "white oil of thyme" is produced 
by distilling the crude oil with several times its volume of turpentine 
oil. Such an oil frequently contains less than five per cent, from 1-2 
p. c., of thymol. This explains why rectified oil of thyme is frequently 
quoted for less than the crude oil. 
Spanish oil of thyme is quite different from the French and German. 
Its color is often dark green, sp. gr. 0.93-0.95; phenol content 
50-70 p. c. (carvacrol but no thymol). It is also more soluble than 
either the French or German oils, rendering a clear solution with 
2-3 parts of 70 p. c. alcohol. These great differences render it very 
probable that the Spanish oil is obtained from a different plant. 
Composition. As the amount of cinnamic aldehyde determines the 
value of cassia oil, eugenol that of oil of cloves and linalyl acetate that 
of bergamot, so the amount of thymol (or carvacrol) is indicative of 
the value of oil of thyme. Although thymol was observed as early as 
1719 and therefore belongs to those compounds from volatile oils 
longest known, its composition was first correctly determined by Lalle- 
mand1 in 1853. By analysis he determined the formula C10H140, which 
took the place of the formula C10H15C), found by Doveri2 a few' years 
earlier. 
Occasionally thymol crystallizes from old oils in the cold; it can 
be removed completely only by shaking with lye. It melts at 50-51° 
and boils at 232°. Its properties and characteristic derivatives are 
mentioned on p. 178. 
Of other constituents Lallemand found cymene, C10H14, b. p. 175°; 
and thymene, CioHie, b. p. 160-165° and laevogyrate. Inasmuch as 
Schimmel & Co.3 have shown the identity of this hydrocarbon with 
1-pinene, the name thymene should be dropped. 1-Pinene occurs in the 
oil in such small quantities only, that its presence cannot be determined 
without the use of large quantities of oil. 
Labbe4 in 1898 did not succeed in obtaining a solid hydrochloride 
from fraction 155-158°. With amyl nitrite and hydrochloric acid he 
obtained a nitrosochloride melting at 106.5°. Inasmuch as the melting 
point of pinene nitrosochloride is given as 103°, he concludes that 
pinene is not contained in oil of thyme, w'hereas the preparation of the 
benzylamine base would have removed all doubt. In fraction 165-169° 
i) Compt. rend., 37, p. 498; Liebig's Annalen, 101, p. 119; Ann. de Chim. et Phys., 
Ill, 49, p. 148; Liebig's Annalen, 102, p. 119. 
2) Ann. de Chim. et Phys., Ill, 20, p. 174; Liebig's Annalen, 64, p. 374. 
3) Bericht von S. & Co., Oct. 1894, p. 57. 
*) Bull. Soc. chim., Ill, 19, p. 1009. 626 
Special Part. 
Labbe claims to have found menthene. He obtained a nitrosochloride, 
m. p. 113-113.5°, and upon oxidation with permanganate cymene. It 
is known, however, that the melting points of the nitrosochlorides can- 
not be safely used for the identification. The supposed oxidation to 
cymene is also inconclusive, for cymene is already present in the oil and 
may have been contained in the fraction. 
Of the more difficultly volatile fractions, the one boiling between 
195-230°1 had a decided odor of borneol and linalool. Inasmuch as 
their boiling points lie so close, their separation could not be effected 
by fractional distillation, but was accomplished by oxidizing the fraction 
with chromic acid and distilling the products of oxidation in a vacuum. 
A part of the distillate solidified and was proven to be camphor by 
means of its oxime melting at 117-118°. The liquid portion yielded 
with sodium acid sulphite a crystalline derivative from which citral 
could be regenerated (citryl-/3-naphtho cinchoninic acid, m. p. 197°). 
The formation of camphor indicates the presence of borneol in the oil, 
that of citral the presence of linalool. The presence of the latter was 
further demonstrated by Labbe2 by converting it into geraniol (m. p. of 
geranyl phthallate of silver 133°). Upon oxidation of the borneol 
fraction Labbe likewise obtained camphor. 
Thymol is not the only phenol in oil of thyme. At times thymol is 
partly, at times wholly replaced by its isomer carvacrol (see properties 
on p. 177). What conditions favor the one or the other phenol is not 
known. Schimmel & Co. have made the following observations: French, 
dried thyme yielded an oil tha£ contained much thymol, but little 
carvacrol; French thyme, cultivated in Germany an oil the phenol of 
which consisted exclusively of carvacrol; both fresh and dried German 
thyme yielded an oil containing only thymol. In the Spanish oil carva- 
crol only is found, and this oil has a much larger phenol content than 
the other oils. 
That oil of thyme probably contains a third phenol is indicated by 
the fact that the oil produces a greenish-black color with ferric chloride. 
Examination. The adulteration of oil of thyme is most commonly 
accomplished with turpentine oil. In the preparation of "white oil of 
thyme," such an adulteration has become an established custom in 
southern France. The addition of oil of turpentine reduces the specific 
gravity below 0.900 and diminishes the solubility in alcohol. A reduction 
of the phenol content also results from -the addition of turpentine oil 
i) Bericht von S. & Co., Oct. 1894, p. 57. 2) Bull. Soc. chim., Ill, 19, p. 1009. Oils of the Labiatae. 
627 
thus rendering a phenol assay of the greatest importance. A simple 
method, which is sufficiently accurate for most practical purposes, is 
applied in the following manner: 
A burette of 60 co. capacity calibrated into tenths is almost completely 
filled with 5 p. c. caustic soda solution. 10 cc. of the oil to be examined are 
then added, the burette stoppered with a well fitting cork, well shaken and set 
aside for 12-24 Jiours. Drops of oil adhering to the side of the burette are 
loosened by tapping and rotating the burette. After the alkaline solution 
has become clear the amount of non-phenol oil is read off. 
In order to determine at the same time whether the oil contains thymol or 
carvacrol, the alkaline solution of phenylate is separated from the oil, trans- 
ferred to a separating funnel and acidulated with sulphuric acid. After the 
phenol has completely separated, the aqueous solution is runoff and the oil set 
aside in a capsule in a cool place. If the oil consists of thymol it solidifies 
upon standing, or crystallization may be induced by adding a fragment of a 
thymol crystal. If it consists of carvacrol, the oil remains liquid. If both 
phenols are present it crystallizes partially. 
This method yields approximate results only. On the one hand the 
alkaline solution of phenols dissolves some of the hydrocarbons, on the 
other hand a part of the phenol remains dissolved in the oil. Both 
errors probably compensate each other. To remove the hydrocarbons 
dissolved in the alkali by shaking with ether, would simply increase the 
error inasmuch as thymol and still more carvacrol can be partly 
extracted from their alkaline solutions by ether. 
More rational, though more complicated, is the assay method 
devised by Kremers and Schreiner.1 It is a modification of the method 
suggested by Messinger and Vortmann,2 and is based upon the fact 
that in alkaline solution thymol combines with iodine to a red insoluble 
compound and that the excess of iodine can be titrated back by standard 
thiosulphate after the solution had been* acidified. Each molecule of 
thymol requires four atoms of iodine for precipitation. The process 
is carried out in the following manner: 
5 cc. of the oil to be examined are weighed and transferred to a burette 
provided with a glass stopper and calibrated into tenths. The oil is diluted 
with about an equal volume of petroleum ether. 5 p. c. soda solution is added 
and the two solutions shaken. After the two solutions have separated upon 
standing, the aqueous solution is drawn off into a 100 cc. flask. This operation 
is repeated as long as the ethereal solution diminishes in volume. The alkaline 
phenol solution is diluted to 100 cc. or if necessary to 200 cc. 
10 cc. of this solution are transferred to a measuring flask of 500 cc. 
capacity and N/10 iodine solution added in slight excess whereby the thymol 
is precipitated as a dark brown iodine compound. In order to ascertain 
i) Pharm. Review, 14, p. 221. 
2) Berichte, 23, p. 2753. 628 
Special Part. 
whether sufficient iodine has been added, a few drops are transferred to a test 
tube and acidulated with hydrochloric acid. An excess of iodine is indicated by 
a brown color of the solution, an insufficient amount of iodine by milkiness 
produced by thymol. An excess of iodine having been established, the entire 
alkaline solution is acidulated and diluted to 500 cc. In 100 cc. of the filtrate 
the excess of iodine is ascertained by titration with N/10 hyposulphite solution. 
The number of cc. of hyposulphite solution are deducted from the volume 
of iodine used and the resultant multiplied by five, this product indicating the 
total amount of iodine used by the thymol. 
Each cc. of N/10 iodine solution corresponds to 0.003741 g. of thymol. From 
the amount of thymol found in the alkaline solution the percentage of phenol 
in the original oil can readily be ascertained. 
The reaction involved is expressed by the following equation: 
C10H140 + 41 + 2NaOH = Ci0Hi2I20 + 2NaI + 2H20. 
The carvacrol assay should be slightly modified, because the carvacrol 
iodide separates in a milky state. In order to obtain a precipitate the 
mixture is thoroughly shaken after the addition of iodine and then 
filtered. Then the solution is acidulated with hydrochloric acid and the 
process continued as directed under thymol. The calculation is the same. 
369. Oil of Wild Thyme. 
Oleum Serpylli. - Quendeldl. - Essence de Serpolet. 
Origin. Wild thyme, Thymus serpyllum L. (Ger. Quendel, Feld- 
thymian, Feldkiimmel) is indigenous to Europe, North America, central 
and northern Asia and Abyssinia, and yields upon distillation but little 
oil. The yield from the dry herb is 0.15 to 0.6 p. c., that from the 
fresh herb less. 
Properties. Oil of wild thyme is a colorless or golden yellow 
colored liquid of a pleasant odor, somewhat balm-like, also reminding 
faintly of thyme. Sp. gr. 0.890-0.920; =-10 to 21°. 
As Essence de serpolet mixtures of origanum oil, pennyroyal oil 
and oil of thyme are frequently sold in southern France which naturally 
possess quite different properties from those of the genuine oil of 
wild thyme. 
Composition. The bulk of the oil distills between 175-180° and, 
according to Febve3 (1881), consists of cymene, C10H14, with traces of a 
dextrogyrate hydrocarbon CioHio. With alkalies about 1 p. c. of phenol 
can be removed. This phenol, however, is not a definite chemical body, 
but according to Jahns2 consists of a mixture of carvacrol, thymol and 
i) Compt. rend., 92, p. 1290. 
2) Archiv d. Pharm., 216, p. 277 ; Beriehte, 15, p. 819. Oils of the Labiatae. 
629 
a phenol which in alcoholic solution produces a violet color with ferric 
chloride.1 The higher boiling fractions (200-250°) presumably also 
contain sesquiterpenes. 
An oil examined by Gladstone2 in 1864, which had a sp. gr. of 0.884 
and = - 31.6°, consisted almost exclusively of a hydrocarbon 
resembling turpentine oil. The explanation is not difficult, for specific 
gravity and angle of rotation indicate a very liberal adulteration with 
French oil of turpentine. 
370. Oil of Thymus Capitatus. 
An oil, distilled from the fresh herb of Thymus capitatus Lk. in the 
province of Granada in southern Spain, was examined by Schimmel 
& Co.3 Its odor was strongly thyme-like, reminding somewhat of 
origanum. In its composition it closely resembles the oil of Satureja 
thymbra. Sp. gr. 0.901 at 15°; thymol content is small, about 6 p. c. 
A liquid phenol is also present, the boiling point of which lies close to 
that of thymol (carvacrol?). Pinene, cymene, dipentene and bornyl 
acetate are also present. 
371. Oil of Bugle Weed. 
The dried herb of the American bugle weed, Lycopus virginicus 
Michx. yields upon distillation 0.075 p. c. of an oil with a characteristic 
but difficultly definable odor. Sp. gr. 0.924 at 15°.4 
MENTHA OILS. 
History. The mints, which are indigenous to temperate climates 
and some of which are cultivated, yield several valuable and much used 
oils: viz. oil of peppermint, oil of spearmint, German and American, and 
oil of pennyroyal, European and American. 
The mints have the peculiarity of readily forming varieties by 
differences in cultivation, soil and climate conditions. These botanical 
variations have a rather decided influence on the volatile oils. The 
varieties of Mentha piperita L. also of M. ar vensis D. 0. var. piperascens 
Holmes yield peppermint oil, M. crispa yields the Krauseminzbl of the 
Germans and M. viridis the American spearmint oil. 
Although several mints have been in use for culinary or medicinal 
purposes since antiquity, no well defined distinction is made even in the 
1) Archiv d. Pharm., 212, p. 485. 
2) Journ. Chem. Soc , 17, p. 1; Jahresb. f. Chem., 1863, pp. 546 and 549. 
3) Bericht von S. & Co., Oct. 1889, p. 56. 
4-) Bericht von S. & Co., Oct. 1890, p. 49. 630 
Special Part. 
treatises on distillation of the fifteenth and sixteenth centuries during 
which period they were extensively used for the preparation of distilled 
waters. The oils enumerated in price ordinances and older medical 
treatises are also of uncertain origin. Thus the Berlin ordinance of 
1571 mentions Oleum menthae, the Frankfurt ordinance of 1582 
mentions Oleum menthae, Oleum polemii and Oleum pulegii. 
372,. Oil of Peppermint. 
Oleum Menthae Piperitae.-Pfefferminzol.- Essence de Menthe Poivree. 
Origin. As peppermint, Mentha piperita, are designated a group 
of botanically unstable species, subspecies and varieties of mint that 
produce menthol or an oil possessing the properties of peppermint oil. 
In Europe and North America several varieties are cultivated for the 
distillation of the oil. The Japanese peppermint is usually not regarded 
as belonging to Mentha piperita. It is supposed to be derived from 
Mentha arvensis D. C. var. piperascens Holmes. 
Origin and Preparation. Whether or not peppermint was among 
the mints used during the middle ages can no longer be determined. 
In the oldest German treatise on distillation the "Liber de arte 
distillandi" of Brunschwig of the year 1500, the following mints are 
mentioned as being used in the preparation of distilled waters: Mentha 
aquatica, M. rubra, M. balsamica, M. sarcenica and M. crispa, but no 
distinguishing characteristics are given. Neither is it definitely known 
whether the kinds of mint used formerly agree with those now in use. 
As far as known, the only specimens of Mentha piperita which are 
several hundred years old, are found in the herbarium of the British 
Museum in London. John Ray,1 the English naturalist, had obtained 
them from the county of Hertfordshire of southern England in 1696 
and described them as Mentha palustris, "peper mint." The well pre- 
served specimens correspond in all essential characteristics with the 
peppermint which is to-day cultivated in Mitcham, county of Surrey, 
near London (Fluckiger2). The cultivation of peppermint in Mitcham 
seems to have begun about the middle of the eighteenth century and 
was of some importance toward the end of the century. Up to 1805, 
however, the distillation of peppermint oil was not conducted in 
Mitcham but in London (Lysons3). 
The English peppermint industry reached its height about 1850. 
From that time on American competition caused a decided set-back in 
1) Historia plantarum, vol. Ill, p. 284. 3) Environs of London, 1800, p. 254. 
2) Pharmacognosie, 3rd ed., p. 726. Oils of the T^abiatae. 
631 
the production.1 On the continent, peppermint was evidently not 
cultivated earlier for purposes of distillation than in England. Accord- 
ing to the Leyden botanist David Gaubius, it was cultivated for this 
purpose near Utrecht in 1770. He also mentions the menthol, the 
camphora europaea menthae piperitidis. Meanwhile Linnaeus had named 
the plant Mentha piperita. 
About the same time peppermint was cultivated in Germany. Fol- 
lowing the example of the London Pharmacopoeia, in which peppermint 
Fig. 79. 
Distillation of Peppermint Oil in Japan. 
was officinal since 1721 as Mentha piperitis sapore it was mentioned in 
medical and botanical treatises. The treatise by Knigge2 seems to 
have made it better known in professional circles. 
In Japan, however, the cultivation of peppermint appears to anti- 
date that of any other country. It is reported to have begun before 
i) Chemist and Druggist, 1891, p. 405. 
2) De mentha piperitide commentatio. Dissertatio. Erlangae. 1780. 632 
Special Part. 
the Christian era. Even menthol is supposed to have been known 
almost as long and to have been used medicinally.1 The cultivated 
varieties used in Japan for the distillation of the oil can no longer be 
traced back to the species from which they have been derived. They 
differ from the varieties used in Europe and America and in their 
general characteristics are more closely related to the European Mentha 
arvensis L. and the American M. canadensis var. glabrata Benth., than 
to M. piperita. 
A Japanese outfit was described by E. Marx2 in 1896. The arrange- 
ment, however, is not the same everywhere. 
It consists of cast iron kettles with broad rims (A, I, H, fig. 79), of wooden 
casks (B) and coolers (C). As a rule three apparatus are so arranged that they 
can be heated by a common fire. The kettles A, I, H are first filled with 
water. The casks B with perforated bottoms are placed over the kettles, filled 
with dry herb and luted with rims of straw and soft clay. The condensers C 
are then placed in position and the fire started in F. The vapors saturated 
with volatile oil condense on the lower surface of the condensers C and collect 
in the cups K. From here the mixture of oil and water passes through the 
bamboo tube L into the receiver O. The separated water flows through P 
back into the kettles A, I, H and replaces in part the evaporated water. As 
soon as the water in C becomes hot it is removed by a bamboo syphon G. 
Sometimes the rims of the kettles are overheated so as to cause a charring of 
the straw rims. This imparts an empyreumatic odor to the oil which is 
frequently observable in the Japanese oil. 
Another description of the Japanese distillation of peppermint with 
illustrations is given by T. Asahiva3 which, however, agrees in the main 
with the above. 
The distillation of peppermint oil on a commercial scale had its 
origin in Wayne Co., New York, in 1816. It was here conducted on a 
small scale by individuals and later also in neighboring counties. In 
1835 the cultivation of peppermint was begun in Michigan in St. Josephs 
Co. and was extended to Ohio and northern Indiana.4 
For a long time the distillation was conducted in copper stills with 
direct heat. In 1846 several of the larger planters and distillers intro- 
duced steam distillation with large wooden stills, experience having 
shown that the conditions were favorable for this peppermint oil in- 
dustry. With the older stills but 15 lbs. of oil could mostly be obtained 
^rom a charge. Steam distillation from wooden stills allows of the distil- 
lation of 75 to 100 lbs. of oil per charge without great increase of cost. 
1) Pharmacognosie, 1891, p. 726. 
2) Mittheil. d. d. Gesell. ftir Narar- und Volkerkunde Ostasiens, 6, p. 355. 
3) Journ. d. pharm. f. Elsass-Lothringen, 23, p. 314. 
4) Proc. Am. Pharm. Assoc., 34, p. 121. Oils of the Labiatae. 
633 
Wherever modern distilling apparatus are not used, two or three vats are 
used in connection with each boiler. The plants are packed on a perforated 
bottom which is lowered by means of chains to within a short distance of the 
true bottom. For purposes of discharging the false bottom merely has to be 
raised. The vat is filled by two men, one throwing in the dry mint while the 
other stamps it down. By admitting some steam from time to time, the herb 
is moistened somewhat and in better condition to be firmly packed. After the 
vat is closed steam is admitted from below until the herb is exhausted. 
The renewal of the peppermint plantation is accomplished in spring 
by means of roots and sprouts of the previous year's plants. The 
largest yield of oil is obtained from the plants cut in September. 
Formerly it was supposed that a larger yield of oil was obtained by 
distilling the fresh plant. Experience, however, has taught that it is 
better to let the herb dry for a short period.1 
Formerly several labiates and composites growing with peppermint 
were distilled indiscriminately with the latter and produced a poorer 
quality of oil.2 The more important of these plants were Erigeron 
canadensis L., Erechthites hieracifoiia, Raf., Hedeoma pulegioides L. 
and Ambrosia species (ragweed). By more careful cultivation and 
selection these have been largely removed. 
Aside from the early cultivation in Japan, the first observations of 
the crystallization of menthol from the oil (peppermint camphor) were 
made about 1770 by Gaubius,3 by Glendenberg about 1784,4 and by 
Trommsdorff in 1795.5 The first examinations of peppermint oil and 
menthol were made by Dumas6 in 1832, Blanchet & Sell7 in 1836, 
by Walter8 in 1839 and by Oppenheim9 in 1861 and 1864. 
Production and Commerce. In the following list the countries are 
arranged with reference to the amount of oil produced. 
America. The principal places of production are in the states of New 
York, Michigan and Indiana. Whereas formerly the state of New York 
controlled the market, Michigan has superseded it during the last ten 
years and produces at present at least four to five times as much. On 
the other hand the oil from the former state and especially that from 
Wayne county with Lyons as the market, is still preferred qualitatively 
to the Michigan or "Western" oil. 
1) Proc. Am. Pharm. Assoc., 34, p. 
121; Amer. Druggist, Sept. 1886, p. 
161, and June 1888: Proc. N. Y. State 
Pharm. Assoc., 1888: Pharm. Journ., 
Ill, 19, pp. 3 and 4. 
2) Proc. Am. Pharm. Assoc., 7, p. 
449.-Am. Journ. Pharm., 42, p. 120; 
Archiv d. Pharm., 192, p. 252. 
3) Adversariorum varii argument! liber 
unus, p. 99. 
*) Crell's Chem. Ann., 1785, II, p. 427. 
5) Trommsdorff's Journ. d. Pharm., 3, p. 120. 
fi) Annal. de Chiin, et Phys., 50, p. 232. 
7) Liebig's Annalen, 6, p. 293. 
8) Ibidem, 32, p. 288. 
9) Ibidem. 120, p. 350; 130, p. 176. 634 
Special Part. 
Fig. 80. 
Peppermint Harvest in Michigan. Oils of the Labiatae. 
635 
Fig. 81. 
American Peppermint Distillery. 636 
The largest yearly production of peppermint oil was reached in 1897 
and was distributed as follows. 
Eastern Michigan 13,000 lbs. 
Western " 79,000 " 
Northern " 25,000 " 
Southern " 55,000 " 
Indiana 32,000 " 
Various localities 10,000 " 
Total 214,000 lbs. 
Add to this: 
State of New York 37,000 lbs. 
Total 251,000 lbs. 
As the result of this enormous production an entirely unexpected 
drop in price has taken place, which must necessarily lead to restriction 
in the peppermint culture. 
The oldest and best known American trademarks are those of 
"H. G. Hotchkiss" under which only crude, natural oil is shipped, and 
"F. S. & Co.," under which rectified American peppermint oil is brought 
into the market since 1872. Both of these are found in the market 
exclusively in 1 and 5 lb. glass bottles. Large amounts of crude 
American oil come into the market in tins or cans. The largest 
purchasers of these are New York wholesale houses who have agents 
in the producing districts. 
Japan. The peppermint oil production originally had its seat in 
the vicinity of Yonezawa, but since a few years has also started in the 
province Bingo Bitchu - both on Hondo - and recently also on the 
northernmost island Hokkaido (Yezo). The largest production in 
Japan was probably reached in 1896 with more than 220,000 catties 
(1 catty = 605 g.). This enormous amount was distributed in the 
different localities as follows: 
Uzen with Yonezawa as principal place abt. 1,200 piculs 
Bingo " 800 " 
Bitchu " 150 " 
Bizen..: 50 " 
Aki " 5 " 
Yamato " 7 " 
Yramashiro " 5 " 
Shinano u 5 " 
Suruga " 5 " 
Island of Shikoku " 5 " 
Total abt. 2,232 piculs.1 
Special Part. 
1) 1 Picul = 100 catties = 60.479 k., 1 catty = 605 g. Oils of the Labratae. 
637 
' Here, likewise, the necessary result was a corresponding decrease in 
price and a restriction in the peppermint cultivation. The production 
of peppermint oil decreased as a result in 1897 to about 1,400 piculs, 
in 1898 to about 1,000 piculs. The principal commercial center for 
peppermint oil in Japan is Yokohama; Kobe ranks next in importance. 
Hamburg has, on account of the splendid steamer connections, be- 
come the principal market in Europe for Japan peppermint oil. London 
and New York are second and third in importance. The great importance 
of Hamburg for the entire peppermint commerce is seen from the fol- 
lowing official statistics: 
Import 
18 
k. 
97 
Mk.i 
Average 1 
value 
18 
k. 
96 
Mk. 
From the United States and 
the Atlantic Ocean 
34,190 
480.380 
14 
31,840 
542,130 
From Japan 
30,470 
303,860 
10 
24,000 
286,410 
" Australia (Mainland).... 
240 
7,480 
31 
- 
- 
" China 
- 
- 
190 
3,110 
" Great Britain 
7,060 
181,250 
26 
8,020 
222.080 
" Spain 
- 
- 
- 
200 
4.700 
' ' F rance 
- 
- 
- 
210 
2.950 
Other import by water 
100 
1,200 
12 
140 
1.470 
Total by water ; 
72,060 
974,170 
14 
64,600 
1,062,850 
England. The peppermint culture and oil distillation have their 
seat in Surrey, Hertfordshire and Lincolnshire, in the vicinity of the 
towns Mitcham, Waddon, West Croyden, Wallington, Carshalton and 
Market Deeping. The total area under peppermint cultivation in the 
Mitcham districts is estimated at 300 acres. About 50 acres are planted 
with the preferred, so-called white mint. The total production of the 
districts named is estimated at about 20,000 lbs.; statistics do not exist. 
Not entirely unimportant is the peppermint oil production in France, 
amounting to several thousand kilos. It has its seat exclusively in the 
Departement des Alpes Maritimes. The French oil belongs to the better 
commercial varieties. 
Germany. In Germany the production of peppermint oil has con- 
siderably decreased during the last four decades; in Thuringia it has 
stopped almost altogether. On the other hand the peppermint cultivation 
has been started on a large scale in the vicinity of Leipzig. A distillery 
equipped with modern apparatus is in the midst of the fields and, by 
means of special purifying processes, a product of superior quality is 
1) Mark = 23.8 cts. 638 
Special Part. 
Fig. 82. 
Campania Farm of A. M, Todd near Kalamazoo, Michigan, Oils of the Labiatae. 
639 
Fig. 83. 
Peppermint Distillery in Decatur, Michigan. 640 
Special Part. 
obtained. The annual production lias up to the present not exceeded 
400 k. ( 
Italy and Russia produce peppermint oils to a similar extent, 
which are used almost exclusively for home consumption. In Italy the 
article is protected by a comparatively very high import duty. 
An estimation of the annual world production of peppermint oil 
under normal conditions, leads to the following result: 
North America abt. 90,000 k. 
Japan " 70,000 " 
England " 9,000 " 
France " 3,000 " 
Germany " 800 " 
Italy " 600 " 
Russia " 1,200 " 
Various other countries " 400 " 
Total abt. 175,000 k. 
This quantity appears to considerably exceed the world demand. The 
principal varieties have so decreased in price, that only a restriction in 
the production can gradually restore a normal state. 
Properties. As already mentioned, the peppermint oils produced 
in the various countries are not obtained from a single botanical 
species. This explains why the individual varieties of the oil show such 
a great diversity in properties and composition. For all practical 
purposes, the odor and taste give an indication of the quality of the 
oil. By these properties an experienced connoisseur is able to distinguish 
between the three principal commercial varieties, the English, American 
and Japanese. This is of importance on account of the great differences 
in price. It is to be regretted that the origin of an oil cannot always 
be definitely recognized by a physical examination, it is usually com- 
pletely impossible when a mixture of different oils is under consideration. 
Peppermint oil is colorless, yellowish or greenish-yellow, of a 
pleasant, refreshing odor and a cooling persistent taste. It is fairly 
fluid, but thickens and darkens with age. 
Specific Gravity. The specific gravity of the different varieties 
does not vary greatly, but the differences are, nevertheless, great 
enough, that sometimes a conclusion as to the origin of the oil can be 
reached. The lightest oil is the dementholated Japanese oil with a 
density of 0.895-0.905. The sp. gr. of the English oil lies between 
0.900 and 0.910, that of the American mostly between 0.910-0.920. 
With the German oil a sample as high as 0.930 was found. Oils of the Labiatae. 
641 
Rotation. To a certain extent the rotation of the different varieties 
is characteristic; it is least with the French (up to -6°) and greatest 
with the Japanese (up to -42°) oil. 
Solubility. The solubility in alcohol of various strengths offers a 
good means of distinguishing American from English and Japanese oil. 
English peppermint oil dissolved to a clear solution in 3-5 vol. of 70 
p. c. alcohol at 20°. With a further addition of alcohol the solution 
as a rule remains clear, although sometimes showing a slight opalescence, 
but with a pure oil never a separation of oil drops. The solubility of 
the Japanese (dementholated) oil in 70 p. c. alcohol is usually the same 
as that of the English, often, however, somewhat less. It must be 
remembered that in this case a normal distillate is not under consider- 
ation, but rather a by-product of the menthol manufacture, which varies 
according to the method employed for the preparation of the menthol. 
Of the American oils the cheap Western oil shows the same solubility 
as the English; the better oil from Wayne Co., N. Y., is not clearly 
soluble in 70 p. c. alcohol. Of 90 p. c. alcohol, % vol. is requisite for 
making a clear solution with the latter oil. If larger quantities of this 
same strength of alcohol are added, there appears sometimes, especially 
with unrectified oils, a bluish opalescence, which is undesirable for 
purposes of liquor manufacture. According to Kennedy1 this opalescence 
is due to a decomposition produced by the light. The air appears not 
to affect the oil detrimentally in this case, as a long continued passage 
of the air through the oil did not give rise to this phenomenon. 
Observations which were made during a distillation of Saxon pepper- 
mint oil, indicate that the oils are soluble in 70 p. c. alcohol when they 
have been distilled from the fresh, and insoluble when distilled from the 
dry, herb. This would explain the differences in solubility of the English 
and the American oil, inasmuch as it is known that the former is 
distilled from the fresh, the American (Wayne Co.) from the previously 
dried, herb. Whether or not other influences play a part, cannot at 
present be stated. 
Menthol Separation in the Cold. The normal Japanese oil is so 
rich in menthol, that even at ordinary temperature it forms a crystalline 
mass saturated with oil. American oil solidifies completely in a freezing 
mixture, while the English as well as the Saxon oil very often shows 
crystalline separations only after standing for a long while in the 
freezing mixture. As the two last named oils command the highest 
i) Proc, of the Texas State Pharm. Assoc., 1888, p. 37. 642 
Special Pai't. 
price, it follows, that the amount of menthol which can be separated 
from an oil by cooling, is not a criterion of the value of a pepper- 
mint oil. 
Color Reactions. Numerous color reactions have been suggested 
for the identification of peppermint oil, of which that produced by acids 
is the prettiest and most striking. 
.If 5 drops of American or English peppermint oil are mixed with 1 cc. of 
glacial acetic acid, a blue coloration will be noticed after several hours, which 
gradually increases in intensity and reaches its maximum in about 24 hours; 
the mixture with American oil then shows a deep dark blue with transmitted 
light, and a fine copper-colored fluorescence with reflected light. With the 
English oil these phenomena are less intense, often only a light blue coloration 
with a faint reddish fluorescence appears. Japanese oil1 does not show this 
reaction, the mixture remaining colorless. 
Slight warming hastens the appearance of the reaction. The color obtained 
in this manner is, however, not so pure a blue, but rather of a violet shade. 
Contact with the air is necessary for the reaction. If the air be excluded, no 
coloration is noticed, even after several days. The reaction is therefore to be 
considered as an oxidation phenomenon. The reaction is very quickly produced 
when, according to the U. S. Pharmacopoeia, 2 cc. of oil are mixed with 1 cc. 
of glacial acetic acid and 1 drop of nitric acid. By this treatment the Japanese 
oil is also colored slightly violet. 
The cause of the color reaction is, according to Polenske,2 , to be 
found in a nitrogen-free, volatile body accompanying the oil. The colors 
which this forms with acids show a characteristic spectroscopic 
behavior. The body itself is decomposed by light, for an oil which has 
been exposed for some time to the sunlight no longer gives the color 
reaction. 
Other color reactions are produced as follows: 
A solution of 1 cc. of oil in 5 cc. of alcohol is heated with 0.5 g. of sugar 
and 1 cc. of hydrochloric acid. The mixture assumes a deep blue, violet or 
bluish-green color.3 
A red color is produced when some chloral hydrate and hydrochloric acid 
are added to French peppermint oil.4 German and English oils are said to be 
colored light brown by this reaction. 
The cause of these color phenomena are as little known as the 
composition of the bodies which produce them. From a practical 
standpoint but little importance can be attached to these reactions. 
i) Pharm. Journ., Ill, 1, p. 682; III, 2, p. 321. 
2) Arbeiten a. d. kaiserl.. Gesundheitsamte, Berlin (1890), 6, p. 522. - Pharm. 
Zeitung, 35, p. 547. 
3) Chemiker-Zeitung, 13, p. 264. 
4) Archiv d. Pharm., 203, p. 29; 205, p. 326. Oils of the Labiatae. 
643 
Composition. Menthol, which is found in all varieties of peppermint 
oil, must be considered as its characteristic constituent. On account of 
its ready crystallization it was early observed and repeatedly investi- 
gated by the older and the newer chemists. The properties and 
chemical derivatives of this interesting compound have been described 
in detail on page 145. Menthol occurs in peppermint oils for the 
greater part in the free state, in smaller quantities in the form of its 
acetic and valerianic acid ester. A further constituent supposed to be 
common to all peppermint oils is menthone, which appears to have been 
first observed by Beckett and Wright.1 
The formation of menthol and other constituents of peppermint oil 
during various stages in the development of the plant has been investi- 
gated by Eugene Charabot.2 The oils examined were derived from plants 
at three different stages of growth; the first as soon as the inflorescence 
appeared, and before the formation of flower buds, the second when flower 
buds were formed, the third when the flowers were fully expanded. 
Before forma- 
tion of flower 
buds. 
After formation of 
flower buds 
Flowering 
plants. 
Sp. gr. at 18° C 
0.9025 
a) leaves. b) inflores- 
cences. 
0.9016 0.9081 
0.9200 
Opt. rot. at 18° C 
-24° 10' 
-26° -20° 15' 
-2° 37' 
Esters (as menthyl acetate). 
3.7 percent 
2.9 " 
10.3 percent 7.5 percent 
8.1 " 5.9 " 
10.7 percent 
8.4 *• 
■Combined menthol 
Free menthol 
44.3 " 
42.2 " 29.9 " 
32.1 " 
Total menthol 
47.2 " 
50.3 " 35.8 " 
40.5 " 
Menthone 
5.2 " 
4.2 " 16.7 " 
10.2 " 
It will thus be seen that at the first stage the plant yields an oil 
rich in menthol, but containing a relatively small proportion of esters, 
and in which menthone is only present in small quantity; as, however, 
the development of the green parts of the plant progresses, the 
proportion of esters increases, and this esterification takes place in the 
leaves, for the oil from the inflorescences is less rich in esters. Menthone, 
however, would appear to be chiefly formed in the flowers, where it 
increases during the development of the inflorescences, while the pro- 
portion of the total menthol diminishes. It is concluded, therefore, that, 
as in the case of lavender, esterification is confined to the chlorophyll- 
bearing parts, and that menthone is formed in the flowers by the 
oxidation of menthol. 
i) Journ. Chem. Soc., 1876, I, p. 8. 2) Compt. rend., 130, p. 518. 644 
Special Part. 
The more recent investigations are always confined to a single oil 
of definite origin. Inasmuch as the differences between the various oils 
depend without doubt on a difference in chemical composition, the 
results obtained with one oil cannot offhand be applied to another. 
For this reason the chemical composition will have to be discussed 
under each individual oil. 
American Peppermint Oil. 
There are two varieties of American oil, that from Wayne County on 
Lake Ontario, in New York, which is considered as the finer oil, and the 
cheaper and less valued oil distilled in Michigan and Indiana, in Wayne, St. 
Joseph and Van Buren Counties, and known as Western or Michigan oil. 
Properties. The sp. gr. of the peppermint oil from the state of 
New York lies between 0.91 and 0.92, the angle of rotation «d between 
- 25 and -33°. The oil is not soluble in 70 p. c., but in % and more 
parts of 90 p. c. alcohol, to a clear solution. In a freezing mixture it 
solidifies quite rapidly to a crystalline mass. It contains a total of 
50-60 p. c. of menthol, of which 40-15 p. c. are in the free state and 
8-14 p. c. as esters. The amount of menthone present is about 12 p. c. 
The Michigan oil has a less fine odor than the preceding oil, but 
has the advantage, that it is clearly soluble in 4-5 p. of 70 p. c. 
alcohol. The sp. gr. of the oils so far investigated varied between 
0.905 and 0.913. the rotatory power aD between -18 and -29°. A 
menthol determination made on four oils gave the following results: 
Free menthol, 43.6-50.3 p. c.; menthol as ester, 4.3-8.5 p. c.; total 
menthol, 48.6-58 p. c. Two other oils of the same source were, as 
could be seen from their low total menthol content of 32.6 and 35.8 p. c., 
adulterated or dementholated. 
Power and Kleber1 have published a very detailed investigation of 
the constituents of American peppermint oil. The oil had been distilled 
from the dried herb, free from weeds, collected in Wayne County, New 
York. The yield was 0.67 p. c.; sp. gr. 0.9140; «d = -32°0'. Menthol 
as ester, 14.12 p. c.; free menthol, 45.5 p. c.; total menthol, 59.6 p. c. 
By distillation from a fractionating flask the following fractions were 
obtained; 
Up to 200° 2.6 p. c. 
200-205° 2.4 " 
205-210° 8.6 " 
210-215° 18.8 " 
215-220° ..24.0 " 
220-225° 19.6 p. c. 
225-230° 9.0 " 
230-235° 3.6 " 
Residue 12.2 " 
1) Pharm. Rundschau, 12, p. 157; Arch. d. Pharm., 232, p. 639. Oils of the Labiatae. 
645 
' On account of the greater care taken in the. collection of the 
material, and on account of the more perfect distilling arrangements, 
the oil had a much purer and more pleasant odor than the ordinary 
commercial oil. 
In American peppermint oil there have been found so far no less 
than 17 different, well characterized chemical compounds, a number 
which has up to the present not been found in any other oil. The 
bodies found can be here given with but a brief mention of their 
detection. For the details and the course of the analysis the original 
must be consulted. 
American peppermint oil contains: 
1) Acetaldehyde, CH.3COH, abt. 0.044 p. c., yielded acetic acid on 
oxidation. 
2) Isovaleric aldehyde, (CH3j2.CH.CH2.COH, abt. 0.048 p. c., 
b. p. 92°, gave valerianic acid on oxidation. 
3) Free acetic acid, CH3COOH. 
4) Free isovalerianic acid, (CH3)2. CH. CH2. CO OH. 
5) Pinene,2 CioHm, inactive, perhaps a mixture of d- and 1-pinene 
(pinene nitrolpiperidine, m. p. 118°, pinene nitrolbenzylamine, 
m. p. 123°). 
6) Phellandrene. CioHih (nitrite, m. p. 100°). 
7) Cineol, CioHisO, b. p. 174-177° (cineol hydrobromide, cineolic 
acid, m. p. 196°). 
8) 1-Limonene, CioHie, (tetrabromide, m. p. 104°). 
9) Menthone, CioHisO, (conversion into menthol). 
10) Menthol, CioHaoO, b. p. 215.5°. 
11) Menthyl acetate, C10H19C). C2H3O. 
12) Menthyl isovalerianate, C10H19C). C5H9O. 
13) Menthyl ester of an acid C8H12O2, CioHigO. CsHnO. 
14) A lactone C1OH16O2, m. p. 23°, of a stale odor, reminding 
slightly of borneol. The corresponding oxy acid crystallizes 
from petroleum ether in shining needles, melting at 93°. 
15) Cadinene,1 C15H24 (dichlorhydrate, m. p. 118°). 
16) Amyl alcohol. C5H12O, (acetate). 
17) Dimethyl sulphide,3 S(CH3)2. 
Besides these there appear to be present in peppermint oil other 
higher boiling, unstable sulphur compounds, as during the middle of 
1) Bericht von S. & Co., Apr. 1894, p. 42. 
2) First observed by Halsey (Proc. Wisconsin Pharm. Assoc., 1893, p. 90). 
3) Bericht von S. & Co., Oct. 1896, p. 61. 646 
Special Part. 
the rectification of. the oil, there is frequently noticed a penetrating 
odor, reminding of putrifying ruta-baga. 
The presence of dimethyl sulphide in peppermint oil, is shown as 
follows: 
From 50 cc. of the crude oil about 1 co. is distilled off, and this poured on 
an aqueous solution of mercuric chloride. In a short time the formation of a 
soft skin can be observed at the zone of contact of the two liquids. On account 
of its volatility the dimethyl sulphide collects in the first portions on rectifi- 
cation of the oil. Oils from which the first runnings of the rectification have 
been removed, no longer show the reaction. 
Menthene, CioHis, b. p. 158-160°, which according to Andres and 
Andreef1 occurs in Russian peppermint oil, could not, in spite of a 
diligent search, be found in the American oil. Likewise unsuccessful 
was the search for a terpene CioHis, boiling at 175° and having the 
properties of Bruhl's2 so-called menthene. 
English Peppermint Oil. 
The English oil, mostly designated as Mitcham peppermint oil, is 
very highly valued on account of its fine aroma and pleasant taste. 
It is obtained from two varieties, the black and the white mint. 
The former gives by distillation the larger yield, but the oil from the 
white mint is considered as superior in quality. 
Properties. English peppermint oil has the sp. gr. 0.900-0.910, 
the rotatory power «D = - 22° to -33°. Total menthol, 58-66 p. c.; 
free menthol, 50-60 p. c.; menthol as ester, 3-Id p. c.; menthone 
9-12 p. c. The oils of the two English varieties differ, according to 
Umney,3 in their content of menthol as esters. Whereas the oil of the 
white mint contains 14 p. c. of menthol as esters, the oil of the black 
mint contains only 7 p. c. The oil of a black mint cultivated in America 
had, however, a content of 12.2 p. c. of menthol as esters, from which 
it follows that the difference in the ester content is not decisive. Umney 
observed great differences on fractionation of the oil of the white and 
of the black mint. 
Black mint. 
White mint. 
Below 200° 
5 p. c. 
24 p. c. 
200-205° 
27 " 
15 " 
205-210° 
31 " 
15 " 
210-215° 
22 " 
15 " 
215-220° 
7 " 
13 " 
Above 220° 
8 " 
18 " 
t) Berichte, 25, p. 609. 
2) Berichte, 21, p. 157. 
3) Pharm. Journ., 56, p. 123; 57, p. 103. Oils of the Labiatae. 
647 
«The color reaction with glacial acetic acid is less intense than 
with the American oil; according to Umney the intensity of coloration 
increases with the amount of esters present. 
Although the menthol content found by acetylization is higher in 
the English oil than in the American, often only a slight separation of 
crystals takes place in the freezing mixture. This behavior makes it 
probable that besides menthol there are present other alcohols (isomeric 
liquid menthols?) which are estimated as menthol in the acetylization 
method. 
Composition. Fliickiger and Power1 isolated from the English 
peppermint oil two laevogyrate terpenes, boiling at 165-170° (mixture 
of pinene and phellandrene?), as well as a dextrogyrate sesquiterpene 
boiling at 255-260° (probably cadinene). Umney2 showed the 
presence of phellandrene by the nitrite reaction and ascertained that 
the acids combined with the menthol as esters are the same as 
in the American oil, namely, acetic and isovalerianic acids. He 
further determined quantitatively the amount of menthone present in 
the oil. 
There is no doubt but that with a thorough investigation a great 
number of the same substances occurring in the American oil would be 
found. 
Japanese Peppermint Oil. 
Properties. The normal Japanese oil is at ordinary temperatures 
a solid mass of crystals saturated with oil. In commerce occurs the 
normal oil {unseparated), the crude menthol, forming a loose crystal 
mass {crystals), or the liquid oil separated from the latter {oil). 
The Japanese oil is the cheapest of the peppermint oils, but cannot 
be used for all purposes on account of its bitter taste. Normal oil has 
the sp. gr. 0.895-0.900 at 24°; solidification point3 +17 to +28°; 
angle of rotation an =- 30 to -42°. It is soluble in 3-5 p. of 70 
p. c. alcohol. Total menthol, 70-91 p. c.; free menthol, 65-85 p. c.; 
menthol as ester, 3-6 p. c. The liquid oil obtained in the prepar- 
ation of menthol has the sp. gr. 0.895-0.905, «d =- 26 to -35°. It 
is not always soluble to a clear solution in 3-5 p. of 70 p. c. alcohol. 
The color reaction with glacial acetic acid described bn p. 642 is not 
given by the Japanese oil, or only to a slight degree. 
i) Pharm. Journ., III. 11, p. 220; Archiv d. Pharm., 218, p. 222 
2) Pharm. Journ., 56, p. 123; 57, p. 103. 
3) Determined as described on p. 187. 648 
Special Part. 
Composition. Japanese peppermint oil was investigated in 1876 by 
Beckett and Wright.1 They found in the fraction boiling at 210-215° 
of the part remaining liquid on cooling, a body CioHisO isomeric with 
borneol, which in all probability was menthone. In the fraction boiling 
at 245-255° they suspected a compound CsoHgoO, which, according to 
their view, was formed by the splitting off of water from 3 molecules 
of the body CioHisO. 
3CioHi8O = C3oH5oO + 2H2O. 
As this formula is not very probable, it must be assumed that the 
fraction 245-255° consisted of impure menthol, mixed with sesquiterpene. 
Saxon Peppermint Oil. 
The Saxon peppermint oil is unsurpassed by all other commercial 
varieties in fineness' of aroma and taste. It is the highest priced of all 
the peppermint oils. As its annual production amounts to only a few 
hundred kilos, it plays no important part in the world's market. 
Sp. gr. 0.900-0.915; «d =- 25 to -33°. The solubility is mostly the 
same as with the English oil, sometimes, however, a slight opalescent 
turbidity results on the further addition of 70 p. c. alcohol. Total 
menthol, 54.7-67.6 p. c.; free menthol, 46.5-61.2 p. c.; menthol as 
ester, 5.7-8.2 p. c.; menthone, 15.7 p. c. On cooling a crystal separ- 
ation or solidification takes place only after standing for several days 
in a freezing mixture.2 
German Peppermint Oil. 
The oil distilled in Gnadenfrei, Silicia, in small amounts, belongs to 
the best peppermint oils and is similar in its properties to the Saxon oil. 
From the refuse, not suitable for medicinal purposes, of the pepper- 
mint plants cultivated in Colleda, Ringleben (Thuringia) and other 
places, an oil of inferior quality, accompanied by an unpleasant spear- 
mint-like odor, is obtained. Sp. gr. 0.899-0.930; =-27 to -33°. 
The oil is usually not soluble to a clear solution in 70 p. c. alcohol. 
French Peppermint Oil. 
The peppermint oil produced in southern France appears to be 
principally used in France itself. It distinguishes itself by a high sp. gr. 
and low rotatory power. Sp. gr. 0.918-0.920 «d = - 5° 54' to -8° 20'. 
A sample investigated was not soluble in 70 p. c. alcohol. Total 
i) Journ. Chem. Soc., 1876, I, p. 3; Jahresb. f. Chem., 1876, p. 397. 
2) Bericht von S. & Co., 1896, I, p. 50. Oils of the Labiatae. 
649 
menthol 43.7-46 p. c.; free menthol 35.7-39.4 p. c.; esters 7.1-10 p. c.; 
menthone 8.8-9.6 p. c. The acids combined with the menthol are the 
Bame as those in the American and English oil, namely, acetic and 
isovalerianic acid.1 
Charabot,1 together with C. Ebray, has studied an interesting 
•change in the inflorescence of Mentha piperita, which is known to the 
•cultivators and distillers of south-western France as Menthe basiliquee. 
This variety of Mentha piperita, shows besides the normal inflorescence 
also some which appear like racemes, similar to the inflorescence of the 
basilicum after the petals have fallen off. These changed shoots do not 
blossom; but rather appear as though carrying seed, although in their 
place are found only bunches of leaves. A microscopic examination of 
a section through the base of the changed sprout has shown, that the 
change is brought about by the sting of an insect. The oil obtained 
from this changed plant has an unpleasant odor and distinguishes 
itself from the normal oil by a higher sp. gr. and rotatory power, as 
well as by the lower content of menthol and menthone. For such an 
oil were determined: sp. gr. 0.924 at 18°; «d = +7°; esters, 8.2 p. c.; 
total menthol, 41 p. c.; menthone, 3 p. c. 
. Russian Peppermint Oil. 
The Russian peppermint oil likewise plays no part in the world's 
market, and like the French, is principally distilled for home consumption. 
Sp. gr. 0.905-0.910; «d = -17 to -22°. The amount of total menthol 
determined in a single case was 50.2 p. c. (free menthol 46.8, menthol 
as ester 3.4). Crystallization took place only after standing for a long 
while in the freezing mixture.2 
Russian peppermint oil has been investigated by Andres and 
Andreef.3 Besides menthol, it contains dextrogyrate menthone, probably 
a mixture of both optical modifications, in which the dextrogyrate 
modification predominates. The fraction 158-160° gave on analysis 
numbers which indicate a mixture of a hydrocarbon CioHis with a 
terpene (pinene?). The authors therefore assume the presence of a 
menthene,4 which, however, they were unable to isolate in a pure form. 
The fraction 173-175° contains 1-limonene (tetrabromide, m. p. 102°, 
nitrosochloride, m. p. 103°, dichlorhydrate, m. p. 49.5-50°. 
i) Bull. Soc. chim., Ill, 19, p. 117. 
2) Bericht von S. & Co., Apr. 1896, p. 50; ibidem, Apr. 1889, p. 35. 
3) Beriehte, 25, p. 609; Pharm. Ztsch. f. Russl., 29, p. 341. 
4) The menthene, CioHi8, resulting by splitting off water from menthol, boils at 
167-168°. 650 
Special Part. 
Italian Peppermint Oil. 
The oil distilled in the provinces of Piemont and Padua is not 
exported, at least not in appreciable quantities. Sp. gr. 0.911-0.926; 
«d = -13 to -18°; b. p. 195-222°. In a freezing mixture none or 
only a slight menthol separation takes place. Total menthol, 44.1-46.6 
p. c.; free menthol, 36.7-41 p. c.* menthol as ester, 5.6-7.4 p. c. 
Bohemian Peppermint Oil. 
An oil distilled in Bohemia had the following properties: sp. gr.. 
0.905; «d = -27°22'. Soluble in 70 p. c. alcohol. TotaPmentholr 
59.9 p. c.; ester menthol, 8.7 p. c.; free menthol, 51.2 p. c.1 
Chilian Peppermint Oil. 
An oil distilled in Osorno (Chili) of the sp. gr. 0.916, had an 
intense odor of pennyroyal.2 
Reunion Peppermint Oil. 
An oil prepared on the island of Reunion had an odor more of 
lavender than of peppermint. With iodole it gave Hirschsohn's cineol 
reaction, had the sp. gr. 0.887, the rotatory power = -6° 9', and 
was soluble in 4 p. of 70 p. c. alcohol. 
Examination. For the detection and identification of the numerous 
adulterants of peppermint oil it is necessary, above all. to determine 
the physical constants, as by them the attention is called to grosser 
adulterations with alcohol, turpentine oil, and other volatile oils. For 
distinguishing the different varieties the solubility determination in 
70 p. c. alcohol is very useful. All peppermint oils are soluble in equal 
parts of 90 p. c. alcohol, but only a part of them form clear solutions- 
with 70 p. c. alcohol. 
The U. S. Pharmacopoeia requires that peppermint oil solidify at 
- 8 to -20°. If American oil is allowed to stand in a good freezing 
mixture of ice and salt until thoroughly cooled, and then a small 
crystal of menthol added, it will crystallize in a short while to a solid 
mass. With English peppermint oil a good menthol separation usually 
takes place, but as a rule it does not solidify. The behavior of the 
other oils in a freezing mixture has been mentioned under their 
i) Bericht von S. & Co., Apr. 1896, p. 50. 
2) Bericht von S. & Co., Oct. 1894, p. 75. Oils of the Labiatae. 
651 
description. American oil lias been repeatedly found in the market from 
which a part of the menthol had been removed; the solidification test 
is therefore of importance for this variety. With the English oil the 
separation of menthol is hardly profitable as the oil commands a higher 
price than menthol. 
Inasmuch as adulterations with other oils decrease the menthol 
content, a quantitative menthol determination is often of great value. 
According to Power and Kleber the method is as follows:1 
20 g. of peppermint oil are heated to boiling with 20 g. of alcoholic normal 
soda solution (or normal or % normal potassa solution) for about an hour, in 
a flask provided with a reflux condenser (fig. 56, p. 194), in order to decpmpose 
the menthol esters. After cooling, the unconsumed alkali is titrated back with 
normal sulphuric acid, using phenol phthalein as indicator. The saponified oil 
is repeatedly washed with much water and then heated with an equal volume 
of glacial acetic acid and 2 g. of anhydrous sodium acetate in a flask provided 
with a glass-ground tube condenser (fig. 57, p. 195). After cooling, the oil is 
washed several times with water and dilute soda solution, dried with calcium 
chloride and filtered. 8-10 g. of this oil are then saponified, as described 
.above, with 50 cc. of alcoholic normal soda solution and the excess of alkali 
titrated back. 
Each cc. of the normal soda solution corresponds to 0.156 g. of menthol or 
0.198 g. of menthyl acetate. In order, therefore, to obtain the percentage of 
menthol in the original oil (not acetylized. but freed from ester) it is necessary 
to deduct 0.042 g. (the difference between 0.156 and 0.198) for every cc. of 
normal alkali consumed. If, e. g., s g. of acetylized oil require a cc. of normal 
soda solution, the total menthol content P (free and ester) can be calculated 
according to the following formula: 
a X 15.6 
" s - (a X 0.042) 
The result thus obtained does not express exactly the menthol content, 
inasmuch as it is assumed for purposes of calculation that all the menthol is 
present as acetic ester whereas some of it is combined with isovalerianic acid. 
The resulting error, however, is so small that it can be disregarded. 
The amount of menthone is determined in the following manner: 
After the menthol content has been determined with a part of the saponified 
oil, another part is diluted with twice its volume of alcohol and boiled for 
some time with metallic sodium. Thereby the menthone is reduced to menthol 
which can be assayed as described above. 
373. Oil of Spearmint. 
Oleum Menthae Crispae. - Krauseminzol.-Essence de Menthe Crepue. 
Origin and Preparation. Distinction is made between three kinds 
of spearmint oil, American, German and Russian. The American oil is 
1) Pharm. Rundschau, 12, p. 162. 652 
Special Part. 
distilled in New York and Michigan from the fresh herb of Mentha 
viridis L. The herb is cultivated to a not inconsiderable extent, as 
much as 12,000 lbs. of oil being obtained in the two states mentioned.1 
In England (Mitcham) also some oil is distilled from the same plant. 
The German oil is distilled in small amounts, in Thuringia only, 
where spearmint is cultivated for medicinal purposes. The waste resulting- 
in the process of drying is used for this purpose. The plant cultivated 
is the Mentha crispa L. which is regarded as a cultural variety of 
M. aquatica L., whereas M. viridis L. is probably a cultural variety of 
M. silvestris L.2 
The botanical source of the Russian oil is not known. 
Properties. American and German spearmint oil resemble each 
other so closely that no distinction is made in commerce. The oil is 
a colorless, yellowish, or greenish-yellow liquid and possesses the char- 
acteristic, penetrating and disagreeable odor of spearmint. With age 
and upon exposure to the air, the oil becomes viscid and darker. 
The American oil has a sp.gr. of 0.920-0.940 and «d = - 36 to - 48°. 
It is soluble in equal parts of 90 p. c. alcohol, but the solution is 
rendered turbid upon the addition of more solvent. An oil distilled by 
Fritzsche Bros, had somewhat different properties. The spearmint had 
been cultivated on the factory grounds at Garfield, N. J., and was 
just in blossom when distilled. The yield was 0.3 p. c. The oil had 
a sp. gr. of 0.980, consequently higher than that of the ordinary 
oils; an--42°30'. The odor was quite different from that of the 
commercial oil, not at all minty or pennyroyal-like, but reminded 
distinctly of carvone. Upon cohobating the aqueous distillate a con- 
siderable amount of oil heavier than water was obtained. It is possible 
that in the distillation of the commercial oil a part of this heavy oil is 
lost, thus accounting for the lower specific gravity.1 After the first 
harvest toward the close of July, a second was made early in October. 
The yield from the fresh herb was only 0.18 p. c. The odor of this oil 
was less delicate, its specific gravity and rotatory power were lower, viz. 
0.961 and «d =- 37° 20'. Nevertheless, this oil was still heavier than 
the commercial oils, though no fraction was obtained heavier than water.3 
Composition. According to Kane4 the oil of Mentha viridis is sup- 
posed to contain a crystalline constituent, but none of the later 
i) Bericht von S. & Co., Oct. 1896, p. 45. 
2) Pharmacognosie, 3rd ed., p. 727. - See also p. 629. 
3) Bericht von S. & Co., Apr. 1897, p. 49. 
4) Journ. f. prakt. Chem., 15, p. 163; Liebig's Annalen, 32, p. 286. Oils of the Labiatae. 
653 
investigators observed such a substance. Gladstone1 found carvone in 
spearmint oil. With sulphuretted hydrogen he obtained a solid com- 
pound which upon treatment with alkalies yielded an oil of the com- 
position C10H140. This turned the plane of polarized light as far to 
the left as dill carvone turned it to the right. Gladstone gave to this 
substance the inappropriate name of menthol. 
From German spearmint oil Fliickiger2 in 1875 obtained 1-carvone 
of low rotatory power. Beyer,3 on the other hand, found in 1883 
that the angle of rotation of the carvone of the German oil is as great 
as that of carvone from dill and caraway oils. The amount of carvone 
in spearmint oil was determined by Schreiner and Kremers4 as 56 p. c. 
According to Trimble5 spearmint oil contains a terpene boiling at 
160-167.5°, according to Beyer a laevogyrate hydrocarbon boiling at 
168-171°. Bruhl6 concludes from the statements of Gladstone that 
d-pinene is present. According to Gilman7 the oil contains 1-limonene 
and probably 1-pinene. To which constituent the oil owes its char- 
acteristic odor is not yet known. 
Russian spearmint oil is reported to be distilled in large quantities 
but it is principally consumed in Russia. It differs from the American 
and German oils by its stale odor reminding but slightly of spearmint. 
Specific gravity and optical rotation are much lower than of the first 
two varieties, viz.,0.8838-0.885; «d - - 23°12' at 17°. The oil under 
examination gave a clear solution with 2 parts of 70 p. c. alcohol and 
had a saponification number of 25.9. It was shown to consist of 
50-60 p. c. of 1-linalool.9 Fraction 196-200°. with an =-17° 37' 
at 17°, upon oxidation yielded citral (citryl-?-naphtho cinchoninic acid, 
m. p. 197°). Fraction 170-175° («□ = - 24°54'), which constituted 
about 20 p. c. of the oil, yielded the iodole reaction (iodole-cineol, 
m. p. 113°) for cineol; and also yielded a nitrosochloride melting at 100°, 
thus indicating the presence of 1-limonene. The highest fraction yielded 
carvone hydrosulphide melting at 210-211° ([«]d = - 36°O', at 17° 
and in 5 p. c. chloroform solution). The amount of 1-carvone in Russian 
spearmint oil is estimated at 5-10 p. c. 
The difference between American and German spearmint oil on the 
i) Journ. Chern. Soc., 25, p. 1; 
Jahresb. f. Chern., 1872, p. 816. 
2) Berichte, 9, p. 473. 
3) Archiv d. Pharm., 221, p. 283. 
Pharm. Review, 14, p. 244. 
s) Am. Journ. Pharm., 57, p. 484. 
6) Berichte, 21, p. 156. 
7) Proc. Wis. Pharm. Assoc., 1893, p. 53. 
There also seems to be an alcohol CioHi80 
present as indicated by the CaCh compound 
and analysis of the regenerated oil. Unpub- 
lished results of L. Sumner. E. K. 
s) Bericht von S. & Co., Apr. 1889, p. 23. 
9) Bericht von S. & Co., Apr. 1898, p 28 654 
Special Part. 
one hand, and Russian oil on the other, lies principally in the linalool 
content of the latter accompanied by a small percentage of carvone. 
Examination. For the detection of adulterations Kremers and 
Schreiner1 suggest the carvone assay of the oil according to the method 
previously described.2 As principal adulterants cedarwood and gurjun 
balsam oils are taken into consideration. Both of them have about 
the same specific gravity as spearmint oil; both are also laevogyrate. 
Individually these oils can be added to the extent of 10-15 p. c., com- 
bined however in much larger quantity before being detected by the 
determination of physical constants. To determine the carvone content 
of oils thus adulterated is not feasable because the boiling points of 
carvone and the sesquiterpenes are too close together. The oxime 
method alluded to above also yields results that are too low. This is 
attributed to the circumstance that the sesquiterpenes when distilled 
with water vapor carry some of the carvoxime over and retain it in 
solution. 
Qualitatively the presence of the two adulterants can be ascertained 
by Wallach's sesquiterpene reaction (p. 124). The test is made with 
the oily distillate obtained in the carvone assay. 
374. Oil of Watermint. 
The dry herb of Mentha aquatica, L. yielded upon distillation 
0.34 p. c. of volatile oil of a yellowish-green color and pennyroyal-like 
odor.3 Sp. gr. 0.880; «d - - 2° 14'. 
375. Oil of Mentha Arvensis. 
From the dry herb of Mentha arvensis L. 0.22 p. c. of oil was 
obtained. Sp.gr. 0.857; «d = - 2° 44'. 
376. Oil of Wild Mint. 
Mentha, canadensis L., which grows wild in North America, yielded 
upon distillation an oil of reddish-yellow color the odor of which 
reminded of pennyroyal. The yield from the dry herb was 1.23 p. c.4 
Sp. gr. 0.943 at 15°,4 0.927-0.935 at 20°;5 aD = +16° 11' to + 20° 32'. 
It forms a clear solution with twice its volume of 70 p. c. alcohol.4 
According to Gage,5 the oil contains pulegone, the presence of 
which was determined by means of the bisnitroso compound suggested 
1) Pharin. Review, 14, p. 244. 
2) See under caraway oil p. 554. 
3) Berlcht von S. & Co., Oct. 1889, p. 55 
A) Bericht von S. & Co., Oct. 1893, p. 45. 
5) pharin. Review, 16, p. 412. Oils of the Labiatae. 
655 
by Baeyer. The melting point of the compound, not mentioned by 
Baeyer, is 81.5°. Besides pulegone, this oil contains small amounts of 
thymol or carvacrol. 
377. Oil of European Pennyroyal. 
Oleum M'enthae Pnlegli. - Poleiol.-Essence de Pouliot. 
Origin and History. European pennyroyal (Ger. Polei) is derived 
from Mentha pulegium L. (Pulegium vulgare Mill.) or its hybrid 
varieties, and has been used medicinally since the middle ages and 
possibly earlier. The distilled Oleum pulegii is mentioned in the price 
ordinance of Frankfurt for 1582 and appears to have been used 
medicinally like the plant and its distilled water in the sixteenth and 
seventeenth centuries. 
The commercial European oil of pennyroyal is distilled in Spain, 
southern France and Algiers from the fresh herb. The Spanish oil is 
favored on account of its greater purity, whereas the oil from the two 
other countries is less reliable on account of being frequently adulterated. 
Properties. European pennyroyal oil is of a yellowish or reddish- 
yellow color and of a strong, aromatic, minty odor. Sp. gr. 0.930- 
0.960; «d = +17° to +23°. It forms a clear solution with 2 and 
more parts of 70 p. c. alcohol. Inasmuch as the addition of turpentine 
oil renders the oil less soluble, this test is a valuable one. Turpentine 
oil also lowers the boiling temperature and the specific gravity. 
Composition. European pennyroyal oil has a boiling temperature 
of limited range. Up to 212° about 5 p. c. pass over; the bulk of the 
oil, abt. 80 p. c., distills over between 212-216° apd consists of a 
ketone, CioHisO, named pulegone by Beckmann and Pleissner.1 The 
properties and derivatives of this compound, which boils at 221-222° 
when pure, are described on p. 169. 
The oil examined by Kane2 in 1839 cannot have been a pure oil, 
neither can the fraction 183-185°, the composition of which agreed 
with either of the formulas CioHir.O or CioHisO, have consisted of 
pulegone. 
Russian Pennyroyal Oil. 
The only reference concerning this oil is by Butlerow8 in 1854. 
According to him it is distilled from the herb of Pulegium micranthum 
Claus, growing on the steppes of southern Russia, especially near 
i) Liebig's Annalen, 262, p. 1. 
2) Liebig's Annalen, 32, p. 286; Journal f. prakt. Chem., 15, p. 160. 
s) Jahresb. f. Chemie, 1854, p. 594. 656 
Special Part 
Sarepta and Astrachan. Sp. gr. 0.934. It begins to boil at 202°, the 
bulk coming over at 227°. It has the composition CioHisO and pre- 
sumably consists principally of pulegone. 
378. Oil of Patchouly. 
Oleum Foliorum Patchouli. - Patchouliol. - Essence de Patchouli. 
Origin and Preparation. Genuine patchouly, Pogostemon patchouli 
Pellet, is cultivated principally in the Straits Settlements, in Penang, 
also in the province Wellesley. It is either directly distilled or dried 
and brought into commerce from Singapore. Comparatively little herb 
is produced on Mauritius and Reunion.1 Attempts to cultivate it have 
been made in Paraguay,2 also on the West Indian islands Dominica, 
Guadeloupe and Martinique. No appreciable amounts, however, seem 
to be produced. Formerly a considerable amount of the drug was also 
supplied by Java, but in recent years this source of supply has given 
out entirely. The botanical origin of the plant from Java is not yet 
known.3 
The drug shipped from Calcutta and Bombay is of poor quality, 
containing a large amount of stems and yielding an inferior distillate.4 
The herb cultivated in Assam (Silhet and Khasia mountains) is obtained 
from Microtaena cymosa Prain3 (Plectranthus patchouli Clarke) and 
probably enters commerce via Calcutta. This would explain the difference 
of this commercial variety. Whether the herb exported from Bombay 
is derived from Pogostemon patchouli is not known. 
Concerning the cultivation and the distillation J. Fisher of Singa- 
pore makes the following report:5 
"The variety selected for cultivation is known locally as Dhelum Wangi, 
which was originally obtained from a small island south of Penang, called 
Rhio (probably one of the Bindings). The soil most suitable is a rather stiff 
clay, containing only a small percentage of silica. Land of this description is 
found near the coast (containing traces of inarine deposits), and is planted in 
rows of 4 or 5 feet apart. The plants are propagated by cuttings struck in 
the open air, which, until rooted, are sheltered from the sun by pieces of cocoa- 
nut shell. The harvest is made in dry weather, and when the sun has drawn 
up the dew from the leaves; the tops and green parts of the plant are taken 
off, rejecting all yellow and decayed leaves, and as much as possible the woody 
stems. The selected parts are then dried in the shade, under large sheds (as 
the sun would draw out the perfume), and to ensure evenness in drying they 
are spread on bamboo racks, allowing the air to penetrate from beneath. 
1) Bericht von S. & Co., Oct. 1890, p. 36. 
2) Bericht von S. & Co., Oct. 1887, p. 24. 
3) Pharm. Journ., 56, p. 222. 
4) Bericht von S. & Co., Apr. 1887, p. 25. 
s) Odorographia, vol. 1, p. 297. Oils of the Labiatae. 
657 
During this process they are frequently turned over, and when so far dried as 
to leave just sufficient moisture to permit of a slight fermentation they are 
piled in heaps and allowed to heat gently;1 after this they are again spread 
out and dried - but not to absolute dryness - and are immediately distilled. 
The addition of about 25 p. c. of the wild herb Dhelum Outan is said to 
increase the fragrance of the distillate. The distillation is effected by passing 
steam, generated in a boiler apart, through the leaves in the stills. The 
pressure of steam is not allowed to rise above 20 lbs., the yield under these 
conditions being about % oz. per pound of leaves; by high-pressure steam the 
yield would be a little increased, but rank in quality. The stills are sometimes 
jacketed, and, by passing a separate current of steam into the jacket conden- 
sation in the body of the still at the commencement of the operation is avoided."2 
The bulk, however, of patchouly oil, which is used exclusively for 
perfumery, is probably distilled in Europe. With the perfect equipment 
there in use, the yield is as high as 4 p. c. 
The purchase of patchouly herb requires considerable care inasmuch 
as it is frequently adulterated. The most common adulterant is the 
leaves of Ocimurn basilicum L. var. pilosum (Family Labiatae) known 
as Ruku by the Malays. The peculiar odor of these is lost entirely in 
the presence of patchouly leaves. Frequently the leaves of Urena 
1 obata L. var. sinuata (Family Malvaceae) are also found, which are 
called Perpulut by the Malays. It is a weed, common in cocoanut 
plantations. Other - adulterants are the leaves of Plectranthus fructi- 
cosus, of Lavatera olbia and of Pavonia weldenii (Paschkis3). In 
addition to these foreign herbs, which sometimes make up 80 p. c. of 
the bales, as much as 50 p. c. of sand and earth and up to 35 p. c. of 
moisture have recently been found. 
Properties. Patchouly oil is a yellowish or greenish-brown to 
dark brown liquid from which crystals occasionally separate upon 
standing. The odor of the oil is exceedingly intensive and persistent. 
Sp. gr. of pure oils distilled in Europe varies from 0.970 to 0.995; 
«d varies from - 50 to - 68°. The oil renders a clear solution with 
equal parts of 90 p. c. alcohol which as a rule remains clear upon the 
addition of more alcohol. Occasionally, however, the solution becomes 
turbid upon the addition of 2 volumes, but this turbidity disappears 
when as much as 4-5 volumes have been added. 
Inasmuch as the fresh patchouli herb is odorless, it is to be assumed that the 
oil is formed during this process of fermentation. 
2) Further interesting communications concerning the cultivation and distillation 
of patchouly on the Malaccan peninsula from the pen of Wray, curator of the govern- 
ment museum at Perak, are to be found in the Kew Bulletin for June 1889 and are 
reproduced in the detailed account in Sawer's Odorographia, vol. 1, pp. 293-308. 
3) Zeitschr. des bst. Apt. Ver., 17, p. 415; Pharm. Journ., Ill, 11, p. 813. 658 
Special Part. 
Of the imported oils many possess the same properties, some, how- 
ever, differ materially. Of a number of oils imported from Singapore 
the sp.gr. lies between 0.957 and 0.965; a d varied from-44 to-50°. 
These oils were soluble in not less then 3 or 7 volumes of 90 p. c. 
alcohol. Whether these were adulterated or not cannot be determined 
at present. They must, however, be regarded as suspicious, for by the 
addition of cedar wood oil or cubeb oil to patchouly oil distilled in 
Europe, oils of the just enumerated properties were obtained. 
Composition. Concerning the substances that produce the character- 
istic odor of patchouly oil nothing whatever is known. Thus far. but 
two constituents, which are inessential as far as the odor is concerned, 
have been isolated, namely patchouly alcohol and cadinene. 
The patchouly alcohol, formerly known as patchouly camphor, 
occasionally separates upon prolonged standing and therefore, first 
attracted the attention of chemists. Gal1 in 1869 proposed the formula 
C15H28O, Montgolfier2 in 1877, C15H26O. The latest investigation is 
by Wallach3 (1894) who introduced the more rational term patchouly 
alcohol. 
Patchouly alcohol, C15H26O, crystallizes in transparent, colorless, 
hexagonal prisms which end in six-sided pyramids and melt at 56°. It 
is strongly laevogyrate, [a]D =-118°.2 The elements of water are so 
loosely bound that even weak dehydrating agents such as hydrochloric 
acid, sulphuric acid and acetic acid anhydride in the cold, or acetic 
acid, potassium acid sulphate or zinc chloride with the aid of heat, form 
the hydrocarbon C15H24. This patchoulene boils at 254-256°, has a 
sp. gr. 0.939 at 23° and has a cedar-like odor. By the exchange of 
halogen for the hydroxy group of the patchouly alcohol very unstable 
halides result which at once lose the elements of hydrogen halide. The 
entire behavior of patchouly alcohol seems to indicate that it is a 
tertiary alcohol (Wallach). 
In fraction 270° Gladstone4 found a sesquiterpene similar to that 
obtained from oil of cubeb. In the highest fraction he found a portion 
the vapors of which were blue, the so-called azulene or coeruleine which 
also occurs in other oils. According to Wallach,5 the oil is rich in 
cadinene, C15H24, the hydrochloride of which melted at 117-118°. 
1) Compt. rend.. 68, p. 406; Liebig's Annalen, 150, p. 374. 
2) Compt. rend., 84, p. 88. 
3) Liebig's Annalen, 279, p. 394. 
4) Journ. Chem. Soc., 17, p. 3; Jahresb. f. Chemie, 1863, p. 545. 
5) Liebig's Annalen, 238, p. 81. Oils of the Labiatae. 
659 
379. Oil of Dilem. 
As Dilem the Malays designate a number of plants with patchouly 
odor. The leaves from Java distilled by Schimmel & Co.1 were identical 
with the "flowering patchouly herb" of the botanical garden at Buiten- 
zorg and, according to Holmes,2 are derived from Pogostemon como- 
sus Miq. 
These dilem leaves upon distillation yielded 1 p. c. of oil. the odor 
of which resembled that of patchouly oil, but was much finer. It is 
yellowish-green, rather viscid, sp. gr. 0.960, and boils between 250-300°.1 
Upon distillation of the flowering patchouly leaves acetone was 
observed.3 An oil distilled in Buitenzorg had a green color and an 
odor similar to that of patchouly, the intensity of which was agreeably 
subdued by an anise-like by-odor. Sp. gr. 0.961; «d = - 32° 17'.4 
380. Oil of Sweet Basil. 
Oleum Basilic!. - BasilicumoL - Essence de Basilic. 
History. Oil of sweet basil appears to have been in use during the 
middle of the sixteenth century. It is enumerated among the oils of 
the Frankfurt price ordinance for 1582 and in the Dispensatorium 
Noricum of 1589. The distilled water was used as early as the fifteenth 
century. 
Origin. Oil of sweet basil is distilled in southern France and Spain, 
occasionally also in Germany from the fresh herb of Ocimum basili- 
cum L. The yield from the German herb is only 0.02-0.04 p. c. On 
Reunion also oil of sweet basil is distilled. The differences in properties 
and composition of this oil, however, render it probable that some 
other species or variety of Ocimum is used. 
Properties. French and German oil of sweet basil are yellowish, 
of an aromatic, penetrating odor reminding of estragon. The sp. gr. 
varies from 0.905-0.930; aD from- 6 to - 22°. It is soluble in 1-2 
parts of 80 p. c. alcohol. The Reunion oil differs from the French in 
having a camphor-like by-odor, also a higher sp. gr., viz. 0.945 to 0.987. 
Whereas the French and German oils are laevogyrate, the Reunion oil 
is dextrogyrate, «d = + 7° to + 12°. The Reunion oil as a rule is 
soluble in 7 or more parts of 80 p. c. alcohol. In some instances 3 parts 
will suffice to produce a clear solution. 
1) Bericht von S. & Co., Oct. 1888, p. 42. 
2) Pharm. Journ., 56, p. 223. 
3) Verslag omtrent den Staat van s'Eands Plantentuin te Buitenzorg, 1894, p. 43. 
A) Ibidem, 1893, p. 55. 660 
Special Part. 
Composition. Bonastre1 in 1831 found in oil of sweet basil a solid 
constituent, the so-called basilicum camphor. An analysis made by 
Dumas and Peligot2 in 1835 agreed with the formula C1OH22O3, i. e. 
with terpin hydrate. In all probability this substance was formed by 
the addition of water to pinene or linalool. The French oil was ex- 
amined more recently (1897) by Dupont and Guerlain3 who found as 
principal constituents methyl chavicol and linalool. 
Of similar composition is the German oil as shown by Bertram and 
Walbaum4 (1897). The lowest boiling fraction contains cineol5 (cineol 
iodole, m. p. 112°). Fraction 215° contains methyl chavicol (homo- 
anisic acid, m. p. 85°). Judging from the methoxy determination, the 
oil contains 24- p. c. of this compound. Fraction 200° was of an 
alcoholic nature and probably contains linalool which was found in the 
French oil. Neither the German nor the French oil contains camphor. 
In the Reunion oil Bertram and Walbaum found : 1) d-pinene (pinene 
nitrolbenzylamine, m. p. 123°); 2) cineol (hydro brom cineol, iodole 
cineol, m. p. 112°); 3) d-camphor (camphor oxime, m. p. 118°); 
4) methyl chavicol, which constitutes the bulk of the oil. It was 
identified by means of its oxidation to homoanisic acid and anisic acid, 
also by inversion into its isomer anethol. Judging from a methoxy 
determination according to Zeisel's method, the Reunion oil contains 
67.8 p. c. of methyl chavicol. Linalool was not contained in this oil. 
From a small sample of Reunion oil Dupont and Guerlain obtained 
a crystalline substance, m. p. 64-65°, the amount of which was too 
small for investigation. 
The oil from a large leaved variety of 0. basilicum known to the 
natives as Selasih Mekah, contained 30-40 p. c. of eugenol.3 
381. Oil of Mosla Japonica. 
According to Shimoyama7 (1892), Mosla japonica Maxim, which 
is indigenous to Japan yields, when dry, 2.13 p. c. of a reddish-brown, 
laevogyrate oil, the specific gravity of which is 0.820 (?). It contains 
44 p. c. of thymol and a fraction 170-180°, probably cymene. 
i) Journ. de Pharm., II, 17, p. 647. 
2) Liebig's Annalen, 14, p. 75. 
3) Coinpt. rend., 124, p. 300; Bull. Soc. chim., Ill, 19, p. 151. 
4) Archiv d. Pharm., 235, p. 176. 
s) The presence of cineol in oil of sweet basil was previously demonstrated by 
Hirschsohn in 1893 by means of the iodole reaction (Pharm. Zeitschr. f. Russl., 32, p. 419). 
6) Annual report of the botanical garden at Buitenzorg, 1898, p. 28; Bericht von 
S. & Co., Apr. 1900, p. 5. 
7) Apt. Ztg., 7, p. 439; Jahresb. f. Pharm., 1892, p. 465, where the plant is named 
Mosula, whereas Hartwig (Die neuen Arzneidrogen aus dem Pflanzenreiche, p. 220) 
designates it Morula. Oils of the Labiatae. 
661 
The dry herb of the North American Cunila mariana L. yields 
0.7 p. c. of a reddish-yellow oil, sp. gr. 0.915, the odor of which 
resembles oil of thyme. A preliminary investigation shows it to contain 
40 p. c. of phenol, probably thymol.1 
383. Oil of Lophantus. 
The oil of Lophantus anisatus Forst, has a pure, pleasant anise 
odor, reminding somewhat of the honey-like odor of Solidago odora Ait. 
Sp. gr. 0.943 at 20°; aD = - 7°10'.2 
384-. Oil of Pycnanthemum Lanceolatum. 
The odor of the oil distilled from the herb of Pycnanthemum lan- 
ceolatum Pursh3 is scarcely to be distinguished from that of American 
pennyroyal oil. Sp. gr. 0.9184-0.9365 at 15?; 0.914-0.935 at 20°; 
an = - 0.566° to + 11.083°.« 
According to Correll5 it contains 7-9 p. c. of carvacrol (carvacrol 
sulphonic acid, m. p. 56-57°, dicarvacrol, m. p. 145-147°). The oil 
deprived of phenol distills between 180-230°. The analysis of fraction 
220-230° (sp. gr.. 0.922 at 20°, [«]D = + 14.88°) corresponded with 
the formula CioHkjO and indicated the presence of pulegone. Its identity 
with pulegone was established by Alden0 by means of the pulegone 
oxime hydrate melting at 151°. The molten oxime, after having been 
allowed to cool, then melted at 117-118°. The melting point of the 
pulegone oxime hydrate of Beckmann and Pleissner melts at 156-157°, 
that of the normal oxime of Wallach at 118°. 
385. Oil of Pycnanthemum Incanum. 
The dried herb of the North American labiate, Pycnanthemum 
incanum Michx. yields 0.98 p. c. of a reddish-yellow oil7 with a strongly 
aromatic odor, sp. gr. 0.935. It produces a clear solution with twice 
its volume of 70 p. c. alcohol. 
382. Oil of Dittany. 
1) Berieht von S. & Co., Oct. 1893, p. 44; comp, also, Millemann, Am. Journ. 
Pharm., 38, p. 495. 
2) Berieht von S. & Co., Apr. 1898, p. 58. 
3) Pycnanthemum lanceolatum and Pycnanthemum linifoliam were formerly regarded 
as one species and described as Thymus virginicus L. 
*) Amer. Journ. Pharm., 66, p. 65. 
&) Pharm. Review, 14, p. 32. 
6) Pharm. Review, 16, p. 414. 
7) Berieht von S. & Co., Oct. 1893, p. 45. 662 
Special Part. 
386. Oil of Fabiana Imbricata. 
Kunz-Krause1 obtained from the ethereal extract of the leaves of 
Fabiana imbricata Ruiz et Pavon, by steam distillation and shaking- 
out the distillate with ether, a small amount of volatile oil. Upon 
distillation a small fraction came over at 130°, the principal fraction 
boiling at 275°. Upon analysis this fraction had the composition 
C54H9OO4 and was called fabianol. 
387. Oil of Chione Glabra. 
Origin. On account of the aromatic odor of its flowers, Chione glabra, 
a tree belonging to the Rubiaceae, is known as Violette on the West 
Indian island Grenada. On Porto Rico it is known as Palo bianco. 
The wood and the bark possess an unpleasant, faecal odor which 
gradually disappears when exposed to the air. 
Preparation and Properties. Distilled with water vapor the bark, 
according to Paul and Cownly2 yields 1.5 p. c. of a light yellow oil 
which is heavier than water and which, when cooled to -20°, congeals 
to a mass of acicular crystals. This oil, which possesses to a remarkable 
degree the odor of the bark, has been examined by Dunstan and Henry.3 
Its consists principally of a liquid which congeals at low temperatures, 
boils at 160° under 34 mm. pressure, has a sp. gr. of 0.850 at 15° and 
the composition CsHsO2. Its odor is aromatic and slightly faecal. 
With acetic acid anhydride it yields an acetic ester melting at 88°. 
With hydroxylamine and phenyl hydrazine it yields derivatives indicating 
the presence of a carbonyl group. The oxime melts at 112°, the phenyl 
hydrazone at 108°. When fused with potassa, salicylic acid and then 
phenol are obtained, while nitric acid produces picric acid. These 
reactions reveal the substance to be o-hydoxy aceto phenone, Cc>H4. OH. 
CO. CHs = l: 2. As a matter of fact the properties of this substance agree 
with those of the artificial compound prepared in a round-about manner 
from o-nitro cinnamic acid. 
In addition to o-hydoxy aceto phenone, the oil contains a crystalline 
substance that melts at 82°'and which possibly is an alkyl derivative 
of the phenol. On account of the small amount it could not be further 
examined. The oil also contains traces of nitrogenous compounds, but 
neither indole nor its derivatives, the presence of which are indicated by 
the odor, could be obtained. 
1) Archiv d. Pharm., 237, p. 10. 
2) Pharm. Journ., 61, p. 51. 
3) Journ. Chem. Soc. 75, p. 66. Oils of the Caprifoliaceae. 
663 
388. Oil of Elder Blossoms. 
The oil from the flowers of Sambucus nigra L. (Family Caprifoliaceae} 
has been prepared from the fresh as well as the dried material.1 It was 
usually obtained by saturating- the aqueous distillate with salt, shaking 
out with ether, and allowing the ether to evaporate spontaneously. In 
this way Pagenstecher obtained 0.32 p. c. of oil. Schimmel & Co. obtained 
without the use of ether 0.037 p. c. from the fresh flowers, and 0.0027 
p. c. from the dried ones. 
At ordinary temperature, elder blossom oil as a rule is a butyraceous 
or wax-like mass of light yellow or greenish-yellow color. It has an 
intensive elder blossom odor which becomes especially prominent in 
great dilutions. The oil is occasionally liquid and congeals when cooled. 
According to Gladstone2 (1864) the oil contains a terpene CioHic 
and a crystalline substance which is difficultly soluble in alcohol, but 
not in alkalies and which appears to be a paraffin. 
389. Oil of Valerian. 
Oleum Valerianae.-Baldrianol.-Essence de Valeriane. 
Origin and History. Valeriana officinalis L. and several of its 
varieties are found wild and. cultivated in most of the temperate 
and more northern countries of Europe and Asia. 'The peculiar 
oil contained in the roots, presumably has early attracted attention 
and brought about its medicinal use. For commercial purposes and 
for distillation, the plant is recently cultivated in Germany (Thuringia), 
in France (Dep. du Nord), Holland, England and North America. 
The treatises on distillation of the sixteenth century contain 
directions for preparing distillates of valerian with wine or water. The 
distilled oil was obtained by Hoffmann, Boerhaave and Geoffroy, in 
part from the dry, in part from the fresh root. Later Graberg (1782) 
described the oil, and Trommsdorff investigated the root in 1808. In 
1830 he named the acid obtained from the aqueous distillate valerianic 
acid. 
Preparation. For purposes of distillation the dried root and more 
rarely the fresh root is employed. While Trommsdorff claims that the 
dried root yields relatively more oil, Zeller is of the opinion that the 
fresh or dry state has no appreciable effect on the yield. From dried 
i) Eliason. Trommsdorff's Neues Journ. d. Pharm., 9, I, p. 246; Winckler, Pharm. 
Centralbl., 1837, p. 781; Repert. f. d. Pharm., 73 (1841), p. 35; Muller, Archiv d. 
Pharm., 95 (1846), p. 153. 
2) Journ. Chem. Soc., 17, p. 1; Jahresb. f. Chern., 1863, p. 545. 664 
Special Part. 
Thuringian root, Schimmel & Co. obtained 0.5-0.9 p. c,, from Dutch 
root about 1 p. c. of oil. The strongly acid aqueous distillate contains 
valerianic acid which presumably is formed from the bornyl valerianate 
of the oil during the process of distillation. 
Properties. When fully distilled, oil of valerian is a yellowish-green 
to brownish-yellow liquid which is slightly acid, and possesses a pene- 
trating, characteristic, not unpleasant odor. Old oil is dark brown and 
viscid. It has a strongly acid reaction and, on account of the large 
amount of free valerianic acid it contains, has a disagreeable odor. 
The stearoptene which occasionally separates from old oil consists of 
borneol. 
As a rule the sp. gr. varies from 0.93 to 0.96. Abnormally light 
were the oils of Oliviero mentioned under "Composition." They were 
distilled from the fresh roots of plants growing wild in the Departements 
Vosges and Ardennes. Their sp. gr. is given as 0.880-0.912 at 0°, 
corresponding to a density 0.875-0.900 at 15°. Oil of valerian is 
laevogyrate, aD =- 8 to -13°. Acid number = 20-50; ester number 
= 80-100; saponification number = 100-150. 
Composition, Although oil of valerian has been examined repeatedly 
since the beginning of this century,3 its composition has become known 
but comparatively recently through the investigations of Bruylants2 in 
1878 and Oliviero3 in 1893. 
Of the constituents valerianic acid, which derives its name from the 
plant, is longest known. It was also known that upon oxidation of the 
oil camphor results. 
For the systematic investigations of the oil the esters must first be 
saponified so that the acids which otherwise result during the process 
of fractionation do not act on the terpenes and terpene alcohols. The 
saponified oil begins to boil at 155° and up to 160° a liquid passes 
over which in its physical properties corresponds to 1-pinene, but which 
consists of two terpenes. By passing dry hydrogen chloride into this 
fraction a solid dextrogyrate hydrochloride results, which when 
boiled with potassium acetate is in part decomposed to 1-camphene. 
The part not affected consists of laevogyrate pinene hydrochloride. 
i) Trommsdorff (1809)', Trommsdorff's Journ. d. Pharm., 18, I, p. 3; Liebig's An- 
nalen, 6 (1833), p. 176, and 10 (1834), p. 213.- Ettling (1834), ibid., 9, 40.- 
Gerhardt & Cahours (1841), Ann. de Chiin, et Phys.. Ill, 1, p. 60. - Roehleder (1842), 
Liebig's Annalen, 44, p. 1.-Gerhardt (1843), ibid., 45, p. 29, and Journ. f. prakt. 
Chern., 27 (1842), p. 124. - Pierlot (1845), Ann. de Chiin, et Phys., Ill, 14, p. 295, 
and 56 (1859), p. 291. 
2) Berichte, 11, p. 452. 
s) Compt. rend., 117, p. 1096; Bull. Soc. chim., Ill, 11, p. 150; 13, p. 917. Oils of the Valerianaceae. 
665 
The lowest fraction, therefore, consists of 1-camphene1 and 1-pinene. 
Oliviero is of the opinion that "citrene" (?) is also present, but 
furnishes no positive proof. 
When that portion of the oil which distills under ordinary pressure 
above 180° is distilled under reduced pressure, fraction 130-140° under 
50 mm. pressure largely solidifies on account of the 1-borneol present. 
This alcohol is present in the oil as esters of formic, acetic, butyric and 
valerianic acids, the largest part being combined with valerianic acid. 
According to Gerock2 (1892), the oil contains about 9.5 p. c. of valeri- 
anic acid ester and 1 p. c. each of the esters of the other three acids. 
Fraction 132-1-10° (50 mm.) probably contains terpineol, which 
•could not be isolated in the crystalline state. The formation of dipen- 
tene dihydrochloride, however, renders its presence probable. 
Fraction 160-165° (50 mm.) contains a laevogyrate sesquiterpene, 
F15H24, and fraction 190° a substance C15H26O which, judging from its 
behavior to benzoic acid anhydride and hydrochloric acid, is an alcohol. 
From the water obtained in washing the oil after saponification, 
Oliviero obtained a crystalline alcohol of the formula C10H2002. It is 
strongly laevogyrate and melts at 132°. According to Fliickiger,3 the 
highest fractions (300°) are blue in color. 
Basing his claims merely on an elementary analysis, Bruylants4 
supposes fraction 285-290° to contain bornyl ether or bornyl oxide 
C10H17.0 .C10H17. an assertion still wanting proof. 
Mexican Oil of Valerian. 
A Mexican valerian root, probably derived from Valeriana mexicana 
D. C. was distilled by Schimmel & Co.5 The distillation yielded only a 
•clear water from which no oil separated. Only after cohobation of the 
aqueous distillate an oily liquid with disagreeable odor and sp. gr. 0.949 
at 15° was obtained. It was optically inactive and when shaken with 
soda solution was dissolved with the exception of a few flakes. Titra- 
tion with alcoholic potassa yielded as acid number 415, corresponding 
to 89 p. c. of valerianic acid hydrate C5H1OO2 + H2O. 
i) The claim made by Oliviero that the oils of valerian and spike are the first in 
which camphene has been found is not correct. The occurrence of camphene in citronella 
oil and ginger oil was reported in the Bericht of Schimmel & Co. of October 1893, 
pp. 11 and 22. The first publication of Oliviero (also that of Bouchardat on oil of 
spike) appeared in the Comptes rendus dated December 23, 1893. 
2) Journ. d. Pharm. f. Els iss-Lothringen, 19, p. 82. 
3) Archiv d. Pharm., 209, p. 204. 
Berichte, 11, p. 452. 
s) Bericht von S. & Co., Apr. 1897, p. 47. 666 
Special Part. 
Mexican valerian root, therefore, yields scarcely a trace of volatile 
oil, but only free valerianic acid. Inasmuch as the root has a strong 
odor of the acid, it is to be supposed that it is contained as such in 
the root and is not formed during- the process of distillation. 
390. Oil of Kesso Root. 
Origin and Preparation. Japanese valerian root is not derived, 
as was first supposed, from Patrinia scabiosaefolia Link, but from 
Valeriana officinalis L. var. angustifolia Miq.. which is known as Kesso 
or Kanokoso in Japan. Upon distillation it yields 8 p. c. of oil and 
is, therefore, much richer in oil than the common valerian root. 
Properties. Tne odor of the optically laevog-yrate oil is barely 
distinguishable from that of valerian oil. The oil. however, is much 
heavier, having a sp. gr. of 0.990-0.996. 
Composition. In composition also kesso oil closely resembles valerian 
oil for it contains almost all constituents found in the latter. In 
addition it contains kessyl acetate which causes the higher specific 
gravity (Bertram and Gildemeister,1 1890). 
When kesso oil is distilled a first fraction is obtained that is strongly 
acid, has the disagreeable odor of decayed cheese and contains acetic 
and valerianic acids and probably valerianic aldehyde. 
Fraction 155-160°is strongly laevogyrate and like the corresponding- 
fraction of valerian oil contains Lpinene (nitrosopinene, m. p. 101°) and 
Lcamphene2 (isoborneol, m. p 212°). Fraction 170-180° contains, 
dipentene (tetrabromide, m. p. 123°). It is questionable whether this 
terpene is an original constituent of the oil or whether it is formed by 
the action of the acids on pinene or terpineol. 
The borneol of kesso oil. like that of valerian oil, is laevogyrate 
and is present as acetate and isovalerianate. Bornyl formate found in 
oil of valerian is not contained in kesso oil. 
Terpineol was identified by the formation of dipentene dihydriodide 
(m. p. 76°) from fraction 200-220°. Other reactions, more characteristic 
for terpineol, could not be applied on account of the borneol which is- 
difficult to remove. 
Fraction 260-280° had a decided sesquiterpene odor but did not 
yield a solid hydrochloride. The highest boiling fractions contain in 
addition to a blue oil, the acetate of an alcohol C14H24O2., the kessyl 
acetate. 
1) Archiv d. Pharm.. 228, p. 483. 
2) Journ. f. prakt. Chem., II, 49. p. 18.. Oils of the Valerian aceae. 
667 
Kessyl acetate, C14H23O2COCH3, is a viscid liquid which does not 
solidify at -20°. Under 15-16 mm. pressure it boils between 178 
and 179°; under atmosperic pressure at about 300° with slight decom- 
position ; «d = - 70° 6'. 
Kessyl alcohol, C14H24O2, crystallizes in large, well formed crystals 
of the rhombic system. It is odorless, insoluble in water, readily soluble 
in alcohol, ether, chloroform, benzene and petroleum ether. It melts at 
85° and under 11 mm. pressure boils between 155 and 156°, under 
ordinary pressure between 300 and 302°. Its alcoholic solution is 
laevogyrate. Upon oxidation with potassium bichromate and sulphuric 
acid a substance with two hydrogen atoms less is obtained, which 
crystallizes in thick needles melting at 104-105° and turns the plane 
of polarized light to the left. 
391. Oil of Valeriana Celtica. 
The small Valeriana celtica L. of the Styrian alps formerly yielded 
a drug known as Spica celtica (Ger. Alpenspik, celtischer Spik). The root 
yields upon distillation 1.5-1.75 p. c. of volatile oil of a strong odor 
reminding more of Roman chamomile and patchouly than of valerian. 
Sp. gr. 0.967 ; boiling temperature 250-300°.1 
392. Oil of Nardostachys Jatamansi. 
The rhizomes of Nardostachys jatamansi D. C. (Patrinia jatamansi 
Wallich) and of N. granditiora D. C., (Family Valeria,naceae) which are 
indigenous to the Himalaya mountains of northern India have an 
odor reminding faintly of musk but more strongly of patchouly. On 
account of its fragrance this root was highly prized during antiquity 
and was used for perfuming ointments and fatty oils Later other 
roots were used as substitutes, notably that of Ferula sumbul Hook. fil. 
(p. 576) and still later that of Valeriana celtica L. (see above). 
According to Kemp2 the root of Nardostachys jatamansi D. C. 
yields upon distillation 1 p. c. of a volatile oil of light yellow color. 
Sp. gr. 0.9748 at 22°; «d=- 19° 5'. 
393. Oil of Dog Fennel. 
Eupatorium foenicnlaceum Willd. (Family Compositae) known as 
dog fennel on account of its fennel-like leaves, is found along the 
Virginia coast and in other southern states of North America. An oil 
1) Bericht von S. & Co.. Oct. 1887, p. 36. 
2) Pharmacographia indica. vol. 2, p. 237. 668 
Special Part. 
distilled in Florida from the entire plaut was light in color and had an 
aromatic, pepper-like odor not at all resembling fennel. Sp. gr. 0.935; 
aD= + 17°50'. It contained a large amount of phellandrene.1 
394. Oil of Ageratuni Conyzoides. 
This oil was distilled in the Botanical Garden at Buitenzorg. The 
presence of methyl alcohol in the aqueous distillate was observed. 
Sp. gr. 1.015 at 27.5°; optical rotation -5.5° (in 200 mm. tube). 
It boils at about 260° and probably contains sesquiterpene.2 
395. Oil of Golden Rod. 
In the United States east of the Rocky Mountains there are found 
about fifty species of Solidago known as golden rod, some of which are 
so common as to be regarded as weeds. Several possess more or less 
aromatic properties. 
The oil of golden rod so-called is derived from Solidago odora Aiton. 
It has a strongly aromatic, but not especially pleasant odor and a 
sp. gr. of 0.963.3 
The fresh, flowering herb of Solidago canadensis L. yields 0.63 p. c. 
of oil. It is of a light yellow color and has a very agreeable, sweetly 
aromatic odor. Sp. gr. 0.859; «d = -11° 10'.4 
This oil contains about 85 p. c. of terpenes, especially pinene with 
some phellandrene and dipentene, possibly also limonene. The higher 
boiling portions consist of borneol (total 9.2 p. c.), bornyl acetate 
(3.4 p. c.) and cadinene. It is remarkable that this golden rod oil 
should so closely resemble, as to composition, the pinene needle oils of 
an entirely different family.5 
The odor of the oil of Solidago rugosa Mill, is said to resemble that 
of origanum oil. 
396. Oil of Erigeron (Fleabane). 
Olenin Erigerontis.-Erigeronol. - Essence d'Erigeron. 
Origin. Erigeron canadensis L. is a very common weed which is 
known in America as fleabane, horseweed or butterweed. It is frequently 
found in peppermint fields. The fresh herb yields upon distillation 
0.2-0.4 p. c. of oil which finds limited medical application in the 
United States and which was made official in the U. S. Pharma- 
copoeia of 1890. 
i) Bericht von S. & Co., Apr. 1896, p. 70. 
2) Ibidem, Apr. 1898, p. 57. 
3) Ibidem, Oct. 1891, p. 40. 
4) Ibidem, Apr. 1894, p. 57. 
5) Bericht von S. & Co., Apr. 1897, p. 53. Oils of the Compositae. 
669 
PROPfcRTiES. When fresh, erigeron oil is a colorless or light yellow, 
mobile liquid, and possesses a peculiar aromatic, persistent odor and a 
somewhat prickly taste. Exposed to the air it rapidly resinifies and 
becomes viscid and darker. Sp. gr. 0.850-0.870; aD = + 52°.1 With 
an equal volume of 90 p. c. alcohol it forms a clear solution. 
Composition. Erigeron oil boils almost completely at 175° (Power2) 
and consists very largely of d-limonene. Vigier and Cloez3 (1881) 
prepared a dihydrochloride, which Beilstein and Wiegand4 (1882) found 
to melt at 47-48°; Wallach5 (1885) prepared the tetrabromide melt- 
ing at 104-105°; Meissner6 (1893) the nitrosochlorides, and from the 
a-nitrosochloride the benzylamine base melting at 90-92°. 
In fraction 205-210° Hunkel7 found terpineol which he identified by 
means of its nitrosochloride and the nitrolpiperidine base melting at 
159-160°. 
397. Oil of Blumea Balsatnifera. 
The semi-shrub-like composite Blumea balsamifera D. C. is indigenous 
to India and is found from the Himalayas to Singapore and in the 
Malay Archipelago. It likewise grows in the Islands Hai-nan and 
Formosa. In Hai-nan and in the Chinese province Kwang-tung con- 
siderable quantities of the so-called Ngai camphor, Ngai-fen, are obtained 
from it by distillation. From Hoi-han on Hai-nan annually 15,000 lbs. 
are said to be exported. The crude Ngai camphor is rectified in Canton 
and is then called Ngai-p-ien (Holmes8). In Burma also this camphor 
is prepared.9 
Ngai camphor is used in China for ritualistic and medicinal purposes. 
It is also added to the better qualities of india ink.10 
Formerly this camphor was rarely brought to Europe. In 1895 
Schimmel & Co. obtained a sample in the form of a yellowish-white, 
crumbly mass consisting almost entirely of 1-borneol.11 (See p. 143.) 
The identity of Ngai camphor with 1-borneol was first established in 1874 
by both Plowman12 and Fliickiger.18 
1) Bericht von S. & Co., Oct. 1894, 
p. 73. 
2) Pharm. Rundschau, 5, p. 201. 
3) Journ. de Pharm., V, 4, p. 236. 
4) Berichte, 15, p. 2854. 
5) Liebig's Annaien, 227, p. 292. 
o) Amer. Journ. Pharm., 65, p. 420. 
i) Pharm. Rundschau. 13, p. 137. 
s) Pharm. Journ., Ill, 21, p. 1150. 
9) Buchner's Neues Repert. f. d. Pharm., 
28, p. 321; Hanbury, Science Papers, 1876, 
p. 394. 
io) Pharmacognosie, 1891, p. 158; Phar- 
macographia, 1879, p. 518. 
ii) Bericht von S. &Co., Apr. 1894, p. 74. 
12) Pharm. Journ., Ill, 4, p. 710; Neues 
Repert. f. d. Pharm., 23, p. 325. 
13) Pharm. Journ., IJI, 4, p. 829. 670 
Special Part. 
398. Oil of Blumea Lacera. 
Blumea lacera D. C. is a perennial plant which is widely distributed 
in India. It possesses a strong camphor-like odor and is therefore used 
by the natives against flies and other insects. 
Dymock1 obtained by the distillation of 150 lbs. of fresh, flowering- 
herb about 2 oz. of a light yellow oil, sp. gr. 0.9144 at 26.7° and 
= - 66°. 
399. Oil of Helichrysum Stoechas. 
The oil of the flowering herb of Helichrysum stoechas D. C. is used 
in Spain as a remedy against diseases of the bladder and kidneys. It 
has the odor of inferior coniferous oils and about three-fourths boil 
between 155 and 170°, the remaining fourth between 170 and 260°. 
Pinene is probably the principal constituent.2 
400. Oil of Elecampane. 
Oleum Helenii.-Alantol.-Essence de Racine d'Aunde. 
Origin and History. Upon distillation of elecampane, the root of 
Inula helenium L., with water vapor, 1-2 p. c. of a solid, crystalline 
mass permeated by some liquid oil is obtained. Aqueous distillates were 
used medicinally during the middle ages. Oleum radicis helenii is first 
mentioned in the Frankfurt ordinance of 1582. Oil of elecampane is 
used principally for the preparation of alanto-lactone, the helenin of 
Gerhardt3 (1839). 
Composition. Oil of elecampane consists almost entirely of alanto- 
lactone with which are mixed small amounts of alantolic acid, alantol 
and a substance (CgHsO)x, the helenin4 of Kallen.5 
0 
Alanto-lactone CijHsox | was formerly regarded by Kallen as 
TO 
alantolic acid anhydride. Bredt and Posth recognized its character as 
lactone and changed the name correspondingly. 
i) Pharm. Journ., Ill, 14, p. 985. 
2) Bericht von S. & Co., Oct. 1889, p. 54. 
3) Ann. de Chiin, et Phys., II, 72, p. 163; and III, 12, p. 188. - Liebig's Annalen, 
34, p. 192, and 52, p. 389. 
*) Bredt and Posth (Liebig's Annalen, 285, p. 349) in 1895 suggested to drop the 
term helenin because it is used to designate three different substances. Gerhardt 
designated his impure alanto-lactone as helenin ; Kallen so designates the substance 
(CgHgOlx; finally the inulin from elecampane is someti ues called helenin. The helenin 
of commerce is almost pure alanto-lactone. 
5) Berichte, 6, p. 1506. Compare also Kallen, Ueber Alantolacton und die Anlage- 
rung von Blausaure an ungesattigte Lactone. Inaug.-Dissertation. Rostock, 1895. Oils of the Compositae. 
671 
Recrystallized from dilute alcohol, the lactone is obtained in color- 
less, prismatic needles melting at 76°, of faint odor and taste. Under 
10 mm. pressure it boils between 205-210°. It is readily soluble in 
alcohol, ether, chloroform, glacial acetic acid, benzene, petroleum ether, 
sparingly soluble in water. In sodium carbonate solution it is insoluble 
in the cold. When heated with solutions of the alkalies, it dissolves to 
form the salts of the corresponding oxy acid, the alantolic acid. 
O OH 
Ci4H20<| +K0H = Ci4H20< 
CO COOK 
Alantolic acid, Ci4H2o(OH)COOH, crystallizes in fine needles which 
melt at 94°, splitting off water. It is readily soluble in sodium carbonate 
solution, also in alcohol and ether. When heated with water it is 
largely decomposed. The hot aqueous solution upon cooling separates 
fine crystals of alantolic acid which are contaminated with the lactone. 
The easy change from the one to the other explains why the crude oil 
contains alantolic acid besides the lactone. 
The helenin of Kallen, (CeHsO)x, crystallizes in four sided prisms 
which melt at 110°. Under ordinary pressure it does not distill without 
decomposition; under 14 mm. pressure, however, it distills at 240° 
without decomposition. It is indifferent toward ordinary reagents. 
Since it is contained in the root in small amounts only, it has not yet 
been farther examined. 
Alantol is an oil that boils at about 200°, and apparently occurs 
in small quantities in the fresh root only. It is a yellowish liquid, and 
an isomer of common camphor, CioHioO. Upon distillation with phos- 
phorus pentasulphide it yields cymene, CioHi4, b. p. 175°. 
401. Oil of Osmitopsis Asteriscoides. 
An alcoholic infusion of Osmitopsis asteriscoides (Osmites bellidi- 
astrum Thbg., Bellidiastrum osmitoides Less.) is used in Cape Colony 
as a remedy against lameness. 
The volatile oil of the plant was examined by Gorup-Besanez1 in 
1854. It is a mobile, yellowish-green liquid of a not pleasant odor, 
reminding of camphor and cajeput oil; sp. gr. 0.931 at 16°. The oil 
began to boil at 176°, two-thirds passed over between 178-188°, the 
remainder between 188-208°. When the thermometer rose to 206° a 
sublimate, possibly of camphor, was deposited in the neck of the retort. 
1) Liebig's Annalen, 89, p. 214. 672 
Special Part. 
Fraction 178-182° had the composition CioHisO and probably con- 
sisted of cineol, which is also indicated by the cajeput-like odor and 
specific gravity. 
402. Oil of Ambrosia Artimisiaefolia. 
Ambrosia artimisiaefolia. is a common weed in North America and 
is known as ragweed, hogweed, bitterweed and Roman wormwood. 
The fresh, flowering herb yielded upon distillation 0.07 p. c. of a. 
dark green oil possessing an aromatic, not unpleasant odor. Sp. gr. 
0.870; aD = - 26°.i 
403. Oil of Roman Chamomile. 
Oleum Chamomillae Romanae. Oleum Anthemidis. - Romiseh Kamillenol. - 
Essence de Camomille Romaine. 
Origin and History. Anthemis nobilis L. occurs wild only in 
scattered districts of western Europe. In Europe and America it is 
cultivated as garden plant'and for commercial purposes. Occasionally 
it escapes cultivation. 
Owing to the similarity of several species of Anthemis, Chrysanthemum 
and Matricaria it is not known what plant was designated as Anthemis 
by the writers of antiquity. In the German treatises on distillation 
the common chamomile seems to have been preferred for medicinal 
purposes, whereas in England the Roman chamomile was almost 
exclusively used as chamomile flowers. Distilled oil of Roman chamomile 
is first mentioned along with Oleum chamomillae vulgaris in the price 
ordinance of Frankfurt for 1587. 
Preparation. Up to quite recent times Roman chamomile was 
cultivated to a considerable extent in the neighborhood of Leipzig, but 
has been dropped for several years because no longer profitable. At the 
present time the oil is distilled principally in Mitcham near London, where 
the plant is cultivated and where it also grows wild. The dried flowers 
yield about 0.8-1 p. c. of oil. 
Properties. Freshly distilled Roman chamomile oil has a light 
blue color, which under the influence of air and light changes to greenish 
and brownish-yellow. The odor is strong but pleasant, the taste 
burning. Sp. gr. 0.905 to 0.915, «d = + 1 to +3° '(Umney,2 1895). 
The oil has usually a faintly acid reaction, saponification number 
250-300. As a rule it forms a clear solution with 6 parts of 70 p. c. 
t) Bericht von S. & Co., Oct. 1894, p. 73. 2) Pharm. Journ., Ill, 25, p. 949. Oils of the Compositae. 
673 
alcohol. ' A lesser solubility is occasionally due to a larger paraffin 
content, and does not necessarily indicate adulteration. 
Composition. The oil of Roman chamomile consists principally of a 
mixture of esters of butyric acid, and the isomeric angelic and tiglinic1 
acids which are present as esters of isobutyl, amyl and hexyl alcohols. 
Angelic acid was discovered in the oil by Gerhardt2 in 1848, and 
has thus become readily accessible to chemists. The other statements 
by Gerhardt concerning the presence of angelic aldehyde and a terpene 
boiling at 175°, chamomillene, have been shown to be wrong. 
Demar^ay3 in 1873 showed that angelic acid is not free but com- 
bined with butyl and amyl alcohols. He supposed that he had found 
valerianic acid, but this was not verified by later investigators. 
More detailed examinations of the oil were made by Fittig and 
Kopp4 in 1876 and by Fittig and Kobig5 in 1879. Kopp saponified 
the oil and isolated and identified the acids, whereas Kobig fractionated 
the oil and examined the various fractions. The two investigations, 
therefore, supplement each other. 
Upon repeated fractionation, five large fractions are obtained: 
1) 147-148°; 2) 177-177.5°; 3) 200-201°; 4) 204-205°;- 5) above 
220° decomposition sets in and about one-third of the oil remains in 
the residue. 
Fraction 1, b. p. 147-148°, contains an ester of isobutyric acid, 
probably that of isobutyl alcohol, C4H7O. OC4H9, with which is mixed 
a small amount of a hydrocarbon. In the lowest fraction of the acids, 
150-160°, after separation of the alcohols, a white amorphous powder 
separated which was not isolated in a pure state but which, judging 
from its properties, consisted of methacrylic acid CH2 :C(CH3)C00H. 
The first fraction of the non-saponified oil, therefore, may be regarded 
as an ester of this acid. 
Fraction 2 consists of fairly pure angelic acid isobuty] ester, 
C5H7O. OC4H9. The isobutyl alcohol obtained from it boils at 107-108°, 
the angelic acid melted at 45°. 
Fraction 3, b. p. 200-201°, consisted of a colorless, rather viscid 
oil having the odor of chamomile. Upon saponification it was resolved 
i) It is doubtful whether tiglinic acid is contained as such in the oil or is formed 
from the angelic acid. 
2) Compt. rend., 26, p. 225; Ann. de Chim. et Phys., Ill, 24, p. 96; Liebig's 
Annalen. 67, p. 235; Journal f. prakt. Chemie, 45, p. 235. 
3) Compt. rend., 77, p. 360; ibid., 80, p. 1400. 
*) Berichte, 9, p. 1195; ibid., 10, p. 513. 
5) Liebig's Annalen, 195, pp. 79, 81 and 92. 674 
Special Part. 
into inactive amyl alcohol of fermentation, C5H12O, b. p. 129-130°, 
and angelic acid. It, therefore, consists of angelic acid amyl ester, 
C5H70. OC5H11. 
Fraction 4 consists of a mixture of the amyl esters of angelic and 
tiglinic acids. 
Fraction 5. The portion above 220° was saponified with potassa. 
Among the volatile acids, tiglinic and angelic acids were found. The 
oil distilled from the lye was separated into a smaller fraction, 152- 
153°, and into a larger one, 213.5-214.5°. 
Fraction 152-153° upon analysis revealed itself as a hexyl alcohol 
which upon oxidation yielded a capronic acid. VanRomburgh1 showed, 
in 1886 that this acid is identical with methyl ethyl propionic acid, and 
that the alcohol, which was also prepared synthetically, has the formula 
C2H5(CH3)CH. CH2. CH20H. The methyl ethyl propyl alcohol of Roman 
chamomile oil boils at 154°, has a sp. gr. of 0.829 and is dextro- 
gyrate, [«]D = +8.2°, whereas the synthetic alcohol is optically inactive. 
The oil contains about 4 p. c. of this hexyl alcohol. 
Fraction 213.5-214.5° is a colorless, viscid liquid of camphor-like 
odor, which does not distill without decomposition under ordinary 
pressure. It is isomeric with camphor, having the formula CioHieO, 
and was named anthemol. The acetate of this alcohol boils at 234- 
236°, and upon saponification yields the original alcohol. Chromic acid 
destroys the alcohol entirely, dilute nitric acid oxidizes it to p-toluic 
and terephthalic acids, also a more soluble acid, possibly terebinic acid. 
There remains to be mentioned that Naudin2 obtained from the 
flowers of Roman chamomile, by the extraction with petroleum ether a 
paraffin, "anthemene", CisHae, which melted at 63-64°. 
404. Oil of Anthemis Cotula. 
Upon distillation of the fresh flowers of Anthemis cotula L. and 
shaking the aqueous distillate with ether, Hurd3 in 1885 obtained. 
0.013 p. c. of oil. The entire fresh plant, when treated in like manner, 
yielded 0.01 p. c. of a reddish oil with acid reaction and bitter taste; 
sp. gr. 0.858 at 26°. Upon cooling a crystalline acid separated, which 
melted at 58° after purification. The same acid was obtained upon 
saponification of the oil. The saponified oil boiled between 185-2900, 
and left a residue of 20 p. c. 
i) Rec. des Trav. chim. des Pays-Bas, 5, 
p. 219, and 6, p. 150; Berichte, 20, pp. 375 
and 468. Referate. 
2) Bull. Soc. chim., II, 41, p. 483. 
3) Am. Journ. Pharm., 57, p. 376. Oils of the Compositae. 
675 
405. Oil of Milfoil. 
The fresh flowers of Achillea millefolium L. yield upon distillation 
0.07-0.13 p. c. of volatile oil of a dark blue color and a strongly 
aromatic, camphor-like odor, sp. gr. 0.905-0.925. It was first prepared 
by Bley1 in 1828. The only known constituent is cineol, the presence 
of which was demonstrated by Schimmel & Co.2 The high boiling blue 
fraction is possibly identical with the so-called azulene or coeruleine of 
chamomile oil. 
From the roots of milfoil, Bley3 in 1828 obtained 0.032 p. c. of an 
almost colorless oil possessing an unpleasant taste and a peculiar, 
faintly valerian-like odor. In the aqueous distillate ascetic acid was 
found. The root contains traces of volatile sulphur compounds. 
406. Oil of Achillea Nobilis. 
Bley4 in 1835 prepared the oil from the flowers (0.24 p. c.), dry 
herb (0.26 p. c.) and the seeds (0.19 p. c.) of Achillea nobilis L. The 
oil from the herb had a sp. gr. of 0.970. It had a strong camphor- 
like odor similar to that of milfoil, but finer, and a spicy, bitter taste. 
407. Oil of Achillea Moschata. 
The iva herb used in the manufacture of iva liquor is obtained 
from Achillea moschata L. and owes its agreable odor to a volatile oil 
of which about 0.5 p. c. are obtained upon distillation. 
The oil has a greenish-blue to dark blue color and a strongly 
aromatic odor and taste. Sp. gr. 0.932-0.934. It boils between 
170-260°. The only substance characterized so far is cineol,5 identified 
by Hirschsohn's cineol reaction. The so-called ivaol of Planta- 
Reichenau,'5 C24H4OO2, boiling from 170-210°, cannot be an individual 
substance, as is shown by its boiling temperature. 
408. Oil of Achillea Coronopifolia. 
Schimmel & Co.7 obtained from Spain a deep blue, mobile oil of 
Achillea coronopifolia Willd., possessing a strong but pleasant odor 
reminding of tansy. Sp. gr. 0.924. 
i) Trommsdorff's N. Journ. d. Pharm., 16, II, p. 96. 
2) Bericht von S. & Co.. Oct. 1894, p. 55. 
3) Trommsdorff's N. Journ. d. Pharm., 16, I, p. 247. 
*) Archiv d. Pharm., 52, p. 124. 
5) Bericht von S. & Co., Oct. 1894, p. 27. 
6) Liebig's Annalen, 155, p. 148. 
t) Bericht von S. & Co., Apr. 1893, p. 64. 676 
Special Part. 
The oil of Achillea ageratum L. was distilled by de Luca1 in 1875 
from the flowering plant. Sp. gr. 0.849 at 24°. Upon distillation two 
fractions were obtained: the first boiling between 165-170°; the 
second between 180-182° and yielding upon analysis results agreeing 
with the formula C26H1403- 
410. Oil of German Chamomile.2 
Oleum Cliamomillae. - Kamillenol. - Essence de Camomille. 
Origin and History. The common chamomile, Matricaria chamo- 
milla L. {Chrysanthemum chamomilla Bernh.) grows throughout 
Europe with the exception of the extreme north, and has migrated to 
North America and Australia. 
Chamomile was used medicinally by the Greeks and Romans, and 
was highly valued during the middle ages. Brunschwig describes the 
distillation of the flowers. 
The oil, which attracted attention on account of its blue color, 
seems to have been known since the middle of the fifteenth century. 
Saladin mentions it in his list of 1488, and the Nurnberg physician 
Joaohim Camerarius prepared it in 1588. Gesner and Porta distilled 
the oil after moistening the flowers with aqua, vitae. In the price 
ordinances it is first mentioned in that of Berlin for 1574 under the 
title of Oleum matricariae and of Frankfurt-on-the-Main for 1587. In 
the Dispensatorium Noricum of 1589 it is mentioned as Oleum 
chamomillae vulgaris besides Oleum matricariae. 
The blue color of the oil was attributed to a copper content due to 
the distilling vessels, until Pauli and Herford of Copenhagen showed in 
1664 that the oil distilled from glass vessels likewise possessed a blue 
color.3 On a large scale by steam distillation, chamomile oil was first 
distilled in 1822 by the apothecary Franz Steer of Kaschau in 
Hungary.4 The oil was first examined by Zeller5 in 1827. 
Preparation. For purposes of distillation the more unsightly 
blossoms, which are not as serviceable for pharmaceutical purposes, are 
employed. The drug used for distillation comes from Hungary. The 
409. Oil of Achillea Ageratum. 
i) Ann. de Chiin, et Phys., V, 4, p. 132; Jahresb. f. Chem., 1875, p. 849. 
2) In the United States and England the term "oil of chamomile" is also used to 
designate the oil of Roman chamomile, Anthemis nobilis. 
8) Quadripartitum botanicum, p. 282. 
4) Buchner's Repent, f. d. Pharm., 61, p. 85. 
5) Buchner's Repert. f. d. Pharm., 25, p. 467. Oils of the Compositae. 
677 
yield Varies from 0.2 to 0.36 p. c. On account of the small yield of oil, 
chamomile was formerly distilled with lemon oil and thus the Oleum 
chamomillae citratum of the apothecary shops was obtained. 
Properties. At middle temperature, chamomile oil is a rather 
viscid liquid of a dark blue color, which when carelessly exposed to 
light and air, passes into green and finally into brown. The odor of 
the oil is strong and characteristic, the taste bitter and aromatic. 
Sp. gr. 0.930-0.940 at 15°, at which temperature the oil begins to 
deposit crystals. When cooled the oil becomes butyraceous and at 0° has 
congealed to a solid mass. The saponification number averages about 
45. On account of the large paraffin content, the oil yields but turbid 
mixtures with 90 p. c. alcohol. 
Composition. Very little is known about the composition of oil of 
chamomile for, with the exception of the odorless paraffin, not a single 
constituent has been isolated. The older investigations of Borntrager1 
(1844) and Bizio2 (1861) contain nothing worth mentioning. The 
examination by Gladstone3 (1864) was restricted principally to the 
blue fraction, the "coeruleine." The statements made concerning the 
properties and composition of this substance differ greatly from those 
of Piesse4 (1863) and Kaehler5 (1871). 
An oil distilled- by Kaehler himself began to boil at 105°. Up to 
180° about 4.5 p. c. of a faintly bluish fraction was obtained which 
possessed a strong chamomile odor; 8.3 p. c. boiled between 180-250°; 
between 255-295° 42 p. c. were obtained, distilling with blue vapors. 
The fraction obtained above 295° (25 p. c.) was very viscid, the vapors 
becoming violet at last; a residue of 20 p. c. of a pitchy, brownish 
mass remained. The distillation was accompanied by decomposition, 
for all of the fractions had an acid reaction. By shaking with aqueous 
potassa an acid was extracted the silver salt of which gave figures 
agreeing with caprinic acid, C10H2002. After a second fractionation of 
the two lower fractions an oil was obtained between 150-165°, the 
composition of which accidentally agreed with the formula CioHieO. 
A fraction boiling within a range of 15 degrees cannot represent a 
chemical individual. The analyses of the following fractions are of no 
interest for the same reason. 
i) Liebig's Annalen, 49, p. 243. 
2) Wiener akadem. Ber., 43, 2nd part, p. 292; Jahresb. f. Chemie, 1861, p. 681. 
3) Journ. Chein. Soe., 17, p. 1; Jahresb. f. Chem., 1863, p. 550. 
*) Compt. rend., 57, p. 1016; Chem. News, 8, pp. 245, 273; Chem. Centralbl., 
1864, p. 320. 
5) Berichte, 4, p. 36. 678 
Special Part. 
The blue oil named azulene by Piesse, boiled between 281-289° and 
was regarded by Kaehler as a polymer of camphor of the formula 
(CioHi«O)3. By treatment with potassium a hydrocarbon boiling 
between 250-255° was obtained. The formula C30H48 assigned to it is 
not very probable if the boiling point is taken into consideration. (The 
sesquiterpenes C15H24 boil at about the above temperature). Anhydrous 
phosphoric acid acts on the blue substance with the formation of a 
hydrocarbon (CioHiOn- In its general properties, the blue fraction of 
chamomile oil agrees with the blue oil obtained by Mbssmer1 (1861) 
upon the destructive distillation of galbanum. Possibly the high boiling, 
blue fractions of other oils, such as those of milfoil, kesso, valerian, 
Roman chamomile, wormwood and others are identical with the blue 
fractions of the oil of German chamomile. None of the others, however, 
have such a deep blue color and it would, therefore, seem probable that 
the substance involved is contained in the purest condition in chamomile 
oil. It certainly is worthy of careful investigation. 
The congealing of chamomile oil at low temperatures is due to its 
paraffin content. The paraffin, which remains in the flask when the oil 
is fractionated, as a dark colored mass, is difficultly soluble in alcohol, 
but readily in ether and persistently retains the blue color of the oil. 
In the pure state it is white as snow, melts at 53-54°, and shows all 
the properties of the paraffin hydrocarbons.2 Whether it is an individual 
hydrocarbon or a mixture of several homologues, has not yet been 
determined. 
Examination. It is reported that oil of milfoil is used for the 
adulteration of chamomile oil, it being specially suited to this purpose 
on account of its blue color.3 Larger quantities, however, are excluded 
on account of its totally different odor. More frequently oil of cedar- 
wood4 seems to be used which has no marked odor of its own. The 
addition of this oil, however, or of other oils reduces the congealing 
point. Genuine oil begins to get viscid at +15° and becomes solid 
at 0°. Adulterated oils remain liquid. 
411. Oil of Feverfew. 
Origin. Matricaria parthenium L. (Pyrethrum parthenium Sm., 
Chrysanthemum parthenium Pers., Ger. Mutterkraut) is frequently 
cultivated in Germany and also occurs wild. It supplied the Herba 
Matricariae formerly officinal in Germany. Upon distillation of the 
i) Liebig's Annalen, 119, p. 262. 
2) Bericht von S. & Co., Apr. 1894, p. 13. 
3) Chem. Ztg., 8, p. 268, and 19, p. 385. 
Bericht von S. & Co., Apr. 1895, p. 19. Oils of the Compositae. 
679 
fresh, 'flowering plant 0.02-0.07 p. c. of a yellow to dark green oil is 
obtained. Sp. gr. 0.908-0.960. At times the oil deposits crystals at 
ordinary temperature. According to Chautard the budding herb yields 
more oil than the flowering herb, but that of the former contains less 
stearoptene. 
Composition. Oil of feverfew is of special interest because the rare 
1-camphor1 was first found in it by Dessaignes and Chautard2 in 1848. 
In order to obtain this substance the oil is fractionated, and fraction 
200° is subjected to the temperature of a freezing mixture, and the 
■crystals separated by means of a force filter. 1-Camphor melts at 175°, 
boils at 204® and deviates the ray of polarized light as far to the left, 
([a]D = - 33.1°) as ordinary camphor does to the right. 
Feverfew cultivated in the neighborhood of Leipzig yielded 0.068 
p. c. of oil, sp. gr. 0.960. At ordinary temperature a considerable 
quantity of hexagonal crystals separated, which, when recrystallized 
from petroleum ether, melted at 203-204° and consisted of 1-borneol, 
[a]D = - 36°. Camphor was not to be found in the oil.3 
It seems probable that the oil examined by Dessaignes and Chautard 
also contained borneol besides camphor, for the mother liquor from the 
■crystals, after treatment with nitric acid, yielded more camphor. It is 
but rational to assume that the further amounts of camphor obtained 
after the treatment with nitric acid owed their origin to the borneol 
present. 
According to Chautard4 the oil further contains a terpene boiling 
below 200°, which did not yield a solid derivative with hydrogen 
•chloride; and a liquid dextrogyrate constituent boiling above 200° 
which contained more oxygen than camphor. In connection with the 
oil mentioned above, Schimmel & Co. obtained the saponification 
number 131 which indicates a rather high ester content. 
412. Oil of Tansy. 
Oleum Tanaceti. - Rainfarnol. -Essence de Tanaisie. 
Origin and History. Tanacetum vulgarelj. (Chrysanthemum tana- 
cetum Karsch) is found wild in most European countries, likewise in the 
Atlantic states of North America, and is also cultivated. It is one of 
the strongly aromatic composites. The oil, which is especially contained 
i) 1-Camphor occurs also in one other oil, namely in oil of tansy. 
2) Journ. f. prakt. Chern., 45, p. 45. 
3) Bericht von S. & Co., Oct. 1894, p. 71. 
4) Journ. de Pharm., Ill, 44, p. 13; Jahresber. f Chemie, 1863, p. 555. 680 
Special Part. 
in 'the flowers, has been used as an anthelminthic since the middle ages. 
In the United States the leaves und flowers are official. 
The distilled water from the flowers and leaves was a common 
remedy during the sixteenth and seventeenth centuries. The oil is first 
mentioned in the price ordinance of Frankfurt for 1582 and in the 
Dispensatorium Noricum of 1589. The oil was first examined by 
Persoz1 in 1841. 
Preparation. Fresh, flowering tansy yields upon distillation 0.1 to 
0.2, dry herb 0.2-0.3 p. c. of oil.2 The commercial oil is obtained 
principally from North America. It should be noted that the oil from 
different sources varies somewhat. 
Properties. Oil of tansy is a yellowish liquid, which becomes brown- 
under the influence of air and light. The sp. gr. of the oil from fresh 
herb is 0.925-0.940, that from dried herb 0.955; «d = + 30 to +45°. 
The American oil, when pure, forms a clear solution with 3 parts of 70 
p. c. alcohol. An oil distilled in Germany gave no clear solution with 
70 p. c. alcohol. 
An English oil from cultivated tansy3 had but little resemblance, as; 
to odor, to ordinary oil of tansy but resembled oil of rosemary and 
had a decided odor of camphor; upon evaporation of the oil a delicate- 
ambra odor was finally developed. Its camphor content was so large 
that a part of it crystallized out at 0°. Very remarkable was its 
optical behavior for it was strongly laevogyrate, «D = - 27°. 
Composition. The bulk of oil of tansy consists of thujone or tana- 
cetone to which the oil owes its characteristic odor. It was first isolated 
in a pure state by Bruylants4 in 1878. If the oil is shaken according 
to his directions with an equal volume of sodium acid sulphite solution 
and two parts of alcohol, a compound CioHieO. NaHSOs is formed 
upon prolonged standing, from which the pure thujone can be separated 
by means of soda. That this substance, which Bruylants regarded as- 
an aldehyde and named tanacetyl hydride, is a ketone and identical 
with the thujone isolated by Wallach from thuja oil, was shown 
by Semmler.5 Properties and derivatives of thujone are described 
on p. 167. 
1) Compt. rend., 13, p. 436; Journ. fiir prakt. Chem., 25, pp. 55, 60. 
2) The yield mentioned by Leppig (Beriehte, 15, p. 1088, Ref.), viz.. 1.49 p. c. from 
the flowers and 0.66 p. c. from the herb can not well refer to the oil obtained by 
distillation. 
3) Berieht von S. & Co., Oct. 1895, p. 35. 
*) Beriehte, 11. p. 449. 
s) Beriehte. 25, p. 3343. Oils of the Compositae. 
681 
Fraction 203-205° upon oxidation with chromic acid yielded a 
small amount of camphor. Bruylants supposed that this fraction 
contained the alcohol CwHisO corresponding to thujone and regarded 
the camphor as its oxidation product. Inasmuch as it is now known that 
thujyl alcohol does not yield camphor, this ketone must be regarded 
either as a constituent of the oil or as a product of oxidation from 
some substance other than thujyl alcohol. Persoz1 (1841), also Vohl2 
(1853) had observed that the oil, after having been oxidized with 
chromic acid, contained camphor. Persoz did not answer the question 
whether this camphor was contained in the oil as such or whether it 
was a product of the oxidation. 
In order to decide this question Schimmel & Co. removed the thujone 
as completely as possible by shaking with bisulphite solution, and 
fractionated the remaining oil. At 205° the distillate congealed partly 
in the receiver. The crystalline mass was separated by suction and 
crystallized from 80 p. c. alcohol. Odor and other properties indicated 
a mixture of camphor and borneol. For their separation Haller's 
method3 was employed and a relatively large amount of camphor with 
little borneol obtained. The camphor was identified by means of the 
oxime melting at 116°. The optical properties showed that it was not 
the common dextro camphor, but the very rare laevo camphor. The 
amount of borneol was too small to determine its rotation. 
It remains to be determined whether thujyl alcohol is contained in 
the oil, its presence being probable according to Bruylants; also whether 
the terpene of Bruylants, boiling about 160°, is pinene or camphene. 
According to Peyraud,4 oil of tansy is exceedingly poisonous. In 
animals it produces a condition similar to rabies, la rage tanacetique. 
413. Oil of Tanacetum Balsamita. 
The fresh, flowering herb of Tanacetum balsamita L. yielded upon 
distillation 0.064 p. c. of oil.5 The odor is agreeably balsamic, but little 
characteristic, reminding of tansy. Sp. gr. 0.943-0.949; aD =- 43° 40' 
to -53° 48'; sap. number = 21. In the cold, paraffin-like crystals are 
formed at the surface. The oil was not soluble in 80 p. c. alcohol. 
With 1-2 parts of 90 p. c. alcohol, however, it gave a clear solution, 
but this was rendered turbid upon the addition of more alcohol, white 
flakes (paraffin?) separating. The oil boiled between 207-283°. 
1) Compt. rend., 13, p.436; Liebig's 
Annalen, 44, p. 313; Journ. f. prakt. 
Chern., 25, p. 55. 
2) Arehiv d. Pharm., 124, p. 16. 
3) Compt. rend., 108, p. 1308. 
4) Compt. rend., 105. p. 525. 
5) Bericht von S. & Co., Oct. 1897, p. 66. 682 
Special Part. 
Kiku oil is distilled in large quantities in the western part of Japan 
from the leaves and flowers of Pyrethrum indicum Cass. (Jap. Abura- 
Kuku). The production in 1887 amounted to about 1,400 k. It is used 
as a popular remedy.1 
The oil of the leaves is colorless and has a camphoraceous odor 
reminding somewhat of eucalyptus. Sp. gr. 0.885; boiling temperature 
165-175°. 
The oil of the flowers is likewise colorless and has an unpleasant 
odor. The first fraction distilling at about 180° has a pleasant odor, 
the higher fractions are camphoraceous but not agreeable.2 
4-15. Oil of Artemisia Vulgaris. 
Artemisia vulgaris L. (Ger. Beifuss) is a common weed found along 
hedges and roadsides and contains volatile oil in all its parts, the root 
.yielding 0.1 p. c., the herb 0.2 p. c. 
The root oil is greenish-yellow, butyraceous, crystalline.3 It has a 
nauseating, bitter taste, first burning then cooling. 
The oil from the herb is but little characteristic as to odor. 
Sp. gr. 0.907. According to an observation made in the laboratory of 
Schimmel & Co. it contains cineol. 
416. Oil of Estragon. 
Oleum Dracunculi. - Esdragonbl.-Essence d'Es ragon. 
Origin. Estragon oil. which is used in the preparation of aromatic 
vinegars, is distilled from the flowering herb of Artemisia dracuuculus L. 
The dry herb yields 0.25-0.8 p. c.; the fresh herb 0.1-0.4 p. c. 
Properties. Estragon oil is a colorless to yellowish-green liquid of 
peculiar, anise-like odor and strongly aromatic, but not sweetish taste. 
The sp. gr. varies greatly, 0.900-0.945. An oil distilled from the dry 
Thuringian herb had a sp. gr. of but 0.890. The oil is dextrogyrate, 
= 4-2 to 4-9°. It is soluble in 10 parts of 80 p. c. alcohol. 
Composition. Estragon oil was first examined by Laurent4 in 1842. 
Upon oxidation he obtained an acid melting at 175° which he termed 
•dragonic acid. Gerhardt5 (1844) identified this acid with anisic acid 
414-. Kiku Oil. 
1) Berieht von S. & Co., Apr. 1888, p. 46. 
2) Berieht von S. & Co., Apr. 1887, p. 37. 
3) Bretz & Elieson, Taschenbuch fur Chemiker und Apotheker, 1826, p. 61. 
*) Liebig's Annalen, 44, p. 313. 
s) Conipt, rend., 19, p. 489; Liebig's Annalen, 52, p. 401. Oils of the Compositae. 
683 
and showed that estragon oil behaved toward reagents like anise oil, 
and concluded that the two oils were identical. Since then anethol was 
regarded as the principal constituent of estragon oil. When in 1892 
Schimmel & Co. found methyl chavicol (p-methoxy allyl phenol), the 
isomer of anethol (p-methoxy propenyl phenol) for the first time in a 
volatile oil, viz. oil of anise bark, the estragon-like odor attracted 
attention. This suggested a new investigation of estragon oil which 
showed that the bulk of this oil consists of methyl chavicol.1 
Upon energetic oxidation, methyl chavicol like anethol yields anisic 
acid, milder oxidation with permanganate, however, yields homoanisic 
acid. The statement by Gerhardt that the acid obtained by the oxid- 
ation of anise oil was anisic acid was correct, but his conclusions were 
wrong. 
Somewhat later (1893) Grimaux2 likewise found methyl chavicol in 
estragon oil and named it estragol. 
The properties and derivatives of methyl chavicol are described on 
p. 179. In addition to the inactive methyl chavicol, estragon oil con- 
tains several other constituents to which the optical activity of the oil 
is due, but these have not yet been examined. 
417. Oil of Levant Wormseed. 
Origin. The unexpanded flowers of Artemisia maritima var. stech- 
manni are used as a popular anthelmintic. The bulk of the levant 
wormseed is used in the manufacture of santonin, whereby the oil was 
obtained as by-product. Since the manufacture of this by-product has 
been dropped the price of the oil has risen and its consumption decreased. 
To this circumstance should be added that the principal constituent of 
the oil. the cineol or eucalyptol, can be had pure and at a low price. 
The yield varies from 2-3 p. c. 
Properties. Oil of levant wormseed is a yellowish liquid possessing 
the camphoraceous odor of cineol, but also the unpleasant by-odor 
characteristic of the drug. Sp. gr. 0.915-0.940. The oil is slightly 
laevogyrate. 
Composition. Up to 1884 oil of levant wormseed had been 
repeatedly examined but the results were unsatisfactory because they 
were more or less contradictory, particularly those pertaining to the 
dehydration products of the constituent CioHisO. Whereas Volckel3 
*) Bericht von S. & Co., Apr. 1892, p. 17. 
2) Compt. rend., 117, p. 1089. 
3) Liebig's Annalen, 38. p. 110; 87, p. 312; 89, p. 358. 684 
Special Part. 
(1841, 1853 and 1854), Hirzel1 (1854), Kraut and Wahlforss2 (1864) 
and Graebe3 (1872) claimed that phosphoric acid anhydride produced 
a hydrocarbon CioHie, Faust and Homeyer4 (1874) showed that this 
hydrocarbon "cynene" was identical with cymene, CioHi4- These con- 
tradictory points, however, were cleared up by two contributions 
published at almost the same time, viz. those of Wallach and Brass5 
and Hell and Stiircke.6 
Wallach and Brass were the first to isolate the oxygenated con- 
stituent in a pure state, by making its hydrogen chloride addition 
product and decomposing this with water. This substance, which they 
called cineol, is dehydrated by hydrogen chloride or benzoyl chloride 
yielding a terpene, cynene, which later was termed dipentene. They 
also showed that dipentene under the influence of concentrated sulphuric 
acid or phosphorus pentachloride yields cymene. This explains the 
contradictory statements of earlier chemists who according to the 
strength and character of the dehydrating agents obtained a mixture 
in which either dipentene or cymene predominated. 
In addition to cineol, the oil contains an unknown hydrocarbon, 
either a terpene or cymene, the boiling point of which lies very close to 
that of cineol; also an oxygenated substance boiling higher than cineo 
and optically laevogyrate. 
418. Oil of Wormwood. 
Oleum Absynthii. - Wermutol. - Essence d'Absynthe. 
Origin and History. Artemisia absinthium L. is indigenous to 
many European countries and has been introduced into North America. 
For commercial purposes the plant is frequently cultivated. 
The distilled oil of wormwood was known to Porta about 1570, 
who called attention to its blue color. It was first examined by 
Hoffmann in 1722 and recommended by him for medicinal purposes. 
It was also examined by Geoffroy (1721), Kunzemiiller (1784), Buchholz 
(1785), and Margueron (1798). In the price ordinances it occurs in 
that of Frankfurt for 1587, also in the Dispensatorium Noricum 
of 1589. 
Preparation. Whereas the French oil formerly controlled the 
market, it is now replaced more and more by the cheaper but less 
i) Jahresb. f. Chemie, 1854, p. 591; 
1855. p. 655. 
2) Liebig's Annalen, 128, p. 293. 
3) Berichte, 5, p. 680. 
4) Berichte, 7, p. 1429. 
5) Liebig's Annalen, 225, p. 291. 
6) Berichte,'17, p. 1970. Oils of the Compositae. 
685 
prized American oil from New York (Wayne Co.), Michigan, Nebraska 
and Wisconsin. Similar in quality to the French are the Spanish and 
Algerian oils, also the oil prepared in small quantities on Corsica. The 
Russian oil which for a time was to be had. has again disappeared 
from the market. The consumption of wormwood oil has decreased 
considerably, due possibly to the toxic properties of the oil to which 
attention has been directed. 
From the fresh herb cultivated in Germany % p. c. of oil at most is 
obtained, which at first is dark brown, the color changing to green 
after prolonged exposure to the air. 
Properties. Oil of wormwood is & somewhat viscid liquid of a 
dark green or occasional blue color. It has the not pleasant odor of 
the plant and a bitter, grating and persistent taste. Sp. gr. 0.925- 
0.955. On account of the dark color the angle of rotation cannot be 
determined. Inasmuch as the principal constituent of the oil, the 
thujone, is strongly dextrogyrate, the oil itself must be dextrogyrate. 
The oil is soluble to a clear solution in 2-4 p. of 80 p. c. alcohol. 
Composition. The first chemical examination of the oil was made 
by Leblanc1 in 1845. After repeated rectification over lime, he obtained 
a principal fraction boiling at 205° which had the composition CioHieO. 
By treating this with phosphoric acid anhydride he obtained a hydro- 
carbon CioHn. These results were confirmed by the later investigations 
of Cahours2 (1847), Schwanert3 (1863) and Gladstone4 (1864). 
Beilstein and Kupffer5 (1873) called the substance CioHioO absynthol 
and identified its dehydration product with cymene. They also verified 
Gladstone's statement that the high fraction 270-300° is identical 
with the corresponding fraction of oil of chamomile. 
By washing the various fractions with aqueous potassa, Beilstein and 
Kupffer obtained an acid, the barium salt of which indicated acetic acid. 
The identity of absynthol with tanacetone or thujone was pointed 
out by Semmler6 (for properties see p. 167). 
Fritzsche Bros.7 recently examined an oil distilled in their Garfield 
laboratories. The thujone was removed as completely as possible by 
0 Compt. rend., 21, p. 379; Ann. de Chim. et Phys., Ill, 16, p. 383; Chem. 
Centralbl., 1846, p. 62. 
2) Compt. rend., 25, p. 725. 
3) Liebig's Annalen, 128, p. 110. 
*) Journ. Chem. Soc., 17, p. 1; Jahresb. f. Chem., 1863, p. 549. 
s) Liebig's Annalen, 170, p. 290. 
6) Berichte, 25, p. 3350. Comp, also ibid., 27, p. 895, and Bericht von S. & Co., 
Oct. 1894, p. 51; and Wallach, Liebig's Annalen, 286, p. 93. 
t) Bericht von S. & Co., Apr. 1897, p. 51. 686 
Special Part. 
means of sodium acid sulphite solution and alcohol, and the remaining 
oil saponified with alcoholic soda. The saponified oil was distilled with 
water vapor, but a viscid residue remained which was only partly 
soluble in ether. The portion not soluble in ether proved to be the 
sodium salt of an acid which was identified with palmitic acid by 
means of its melting point and the analysis of its silver salt. Of the 
volatile acids acetic and isovalerianic acids were identified. 
The saponified oil was distilled in vacuum and the lower boiling 
portions fractionated under ordinary pressure. A small fraction 158- 
168° resulted in which the presence of phellandrene was demonstrated. 
An attempt to prepare pinene nitrosochloride resulted in the formation 
of the characteristic blue color and a few crystals were obtained, but 
the amount was too small to make possible the identification of pinene.1 
Fraction 200-203° was found to consist of thujone which cannot 
be removed completely from the oil by means of the bisulphite. It was 
characterized by means of the bisulphite addition product, also by its 
tribromide melting at 121-122°. Neither of these compounds could be 
obtained from the following fraction 210-215° which was shown to be 
of alcoholic nature by means of acetylization and subsequent saponifi- 
cation. Careful oxidation with chromic acid converted it almost 
completely into thujone, thus demonstrating the presence of thujyl 
(tanacetyl) alcohol. 
In the higher, fairly large fraction 260-280° the presence of cadinene 
was demonstrated by means of the hydrochloride melting at 117-118°. 
By saponification of the original and of the acetylized oil it was 
shown that the oil contains 17.6 p. c. of thujyl acetate (==13.9 p. c. of 
thujyl alcohol) and 24.2 p. c. of total thujyl alcohol (free and combined). 
Oil of wormwood, therefore, consists of the following substances: 
1) thujone, CioHibO; 2) thujyl alcohol, CioHisO, free and combined 
with acetic, isovalerianic and palmitic acids; 3) phellandrene and 
possibly pinene; 4) cadinene; 5) blue oil, the elementary composition 
of which has not yet been definitely determined. 
Examination. Oil of wormwood is principally adulterated with 
turpentine oil. Inasmuch as oil of wormwood itself contains but little 
of this terpene, its presence is readily ascertained. If a first fraction of 
10 p. c. is distilled over, this should be soluble in 2 p. of 80 p. c. 
alcohol. 
1) Wright (1874) (Pharm. Journ., Ill, 5, p. 233) found two hydrocarbons in the 
oil, the one boiling at 150°, the other between 170-180°. Briihl (1888) (Berichte, 21, 
p. 156) is of the opinion that the physical properties mentioned by Gladstone indicate 
d-pinene. Oils of the Compositae. 
687 
According to Heckel and Schlagdenhauffen3 (1885). Artemisia 
gallica Willd., which is widely distributed throughout France, contains 
besides santonin 1 p. c. of volatile oil. In its preparation a small 
amount of a crystalline substance (camphor?) was obtained. Concerning 
the composition of the oil nothing is known. 
430. Oil of Artemisia Barrelieri. 
The oil distilled from the flowering herb of Artemisia barrelieri Bess, 
is used in Spain as a popular remedy against colic, and hysteric and 
epileptic attacks. It is also said to be used in the preparation of 
Algerian absynthe. 
The odor is pleasant, strong, aromatic and reminds strongly of 
tansy.2 Sp. gr. 0.923. It boils between 180-210° and consists almost 
entirely of thujone,3 thus explaining its similarity to wormwood and 
tansy. If it could be obtained in large quantities it would be admirably 
suited for the preparation of pure thujone. 
431. Oil of Artemisia Glacialis. 
The dry herb of Artemisia glacialis L. (Genepi des Alpes) (Ger. Alpen- 
beifuss, Genepikraut) yields upon distillation 0.15-0.3 p. c. of volatile 
oil with a strongly aromatic odor. Sp. gr. 0.964 at 20°. It boils 
between 195 and 310°. At 0° it solidifies to a butyraceous mass due- 
to the presence of a fatty acid melting at 16°.4 
433. Oil of Fireweed. 
Erechthitis hieracifolia Raf. is frequently found wild in burned forest 
districts, hence the name. According to Todd5 its sp. gr. is 0.845-0.855, 
according to Power3 0.838 at 18.5°. It is either dextro- or laevo- 
gyrate, aD = - 2 to +2°.6 
According to Beilstein and Wiegand7 (1882) the oil consists princi- 
pally of a terpene boiling at 172°, sp. gr. 0.838 at 18.5° which absorbs 
a molecule of hydrogen chloride without forming a crystalline derivative. 
Fraction 240-310° also has the elementary composition CioHie. The 
fractions boiling above 190° are, according to Power, polymerization, 
products due to boiling. 
419. Oil of Artemisia Gallica. 
i) Compt. rend., 100, p. 804. 
2) Bericht von S. & Co., Oct. 1889, p. 53. 
3) Bericht von S. & Co. Oct. 1894, p. 51. 
■*) Bericht von S. & Co., Apr. 1889, p. 43. 
5) Am. Journ. Pharm., 59, p. 312. 
6) Pharm. Rundschau, 5, p. 201. 
7) Berichte, 15, p. 2854. 688 
Special Part. 
Petasites officinalis Moench, (Ger. Pestwurz), yields upon distillation 
0.1 p. c. of volatile oil which does not form a clear solution with even 
10 parts of 90 p. c. alcohol. Sp. gr. 0.944; aD= + 2°18'. 
4,24. Oil of Arnica Root. 
Origin and Properties. This oil is obtained from the freshly dried 
root of Arnica montana L., with a yield of 0.5-1 p. c. It is at first 
light yellow in color and darkens with age. It has an odor reminding 
of radish, and a pungent aromatic taste. Sp. gr. 0.990-1.000; 
«d =- 1° 58'. 
Composition. Arnica root oil was first examined by Walz1 in 1861, 
who claimed to have found capronic and caprylic esters in the oil and 
capronic and caprylic acids in the aqueous distillate. Entirely different 
results were obtained by Sigel2 in 1873. He found isobutyric acid in 
the aqueous distillate, also traces of formic acid and a small amount 
of an acid the silver salt of which gave results agreeing with either 
angelic or valerianic acids. 
The oil boiled between 214 and 263° with decomposition, leaving a 
brown resinous residue. 
For the investigation of the individual constituents the oil was 
saponified with alcoholic potassa, and the alkaline solution neutralized 
with dilute sulphuric acid. A phenol, b. p. 224-225°, and sp. gr. 
1.015 at 12° was thus obtained, the elementary analysis of which agreed 
with the formula CsHioO. Sigel, therefore, regards the substance as 
phlorol (ethyl phenol) without, however, bringing any proof. The ethyl 
ether of this phenol is a colorless liquid of agreeable aromatic odor, 
sp. gr. 0.9323 at 18° and b. p. 215-217.° The alkaline liquid also 
contained isobutyric acid, thus rendering the presence of isobutyric acid 
phloryl ester in the original oil probable. 
The oil separated from the alcoholic alkaline solution by means of 
water boiled between 224-245° and upon oxidation with chromic acid 
yielded thymoquinone, C1OH12O2. When heated with hydriodic acid in 
a sealed tube, methyl iodide, thymohydroquinone, C1OH14O2, and a 
phenol boiling at 225-226° and of the composition of phlorol, CsHioO, 
were obtained. These results indicate the presence of hydrothymo- 
quinone methyl ether and phloryl methyl ether in the oil. 
423. Oil of Petasites Officinalis. 
i) Neues Jahrb. der Pharm., 15, p. 329; Archiv d. Pharm., 158, p. 1; Jahresb. f. 
Cheinie, 1861, p. 752. 
2) Liebig's Annalen, 170, p. 345. Oils of the Compositae. 
689 
According to Sigel the oil of arnica root consists one-fifth of iso- 
butyric acid ph'loryl ester, the remaining four-fifths consisting largely 
of the methyl ether of hydrothymoquinone and of a small amount of 
the methyl ether of a phlorol. 
• 425. Oil of Arnica Flowers. 
Origin and Properties. The flowers of Arnica montana L. give 
upon distillation a small yield, 0.04-0.07 p. c., of oil. It is of a 
reddish-yellow to brown color and has a strong aromatic odor and 
taste. At normal temperature it is usually a butyraceous mass, some- 
times, however, it congeals only when cooled. In one instance1 the 
sp. gr. was found 0.906 at 15°; in another2 0.900 at 25°; a third oil 
had the sp. gr. 0.8977 at 15°. Acid number 75.1, saponification number 
29.9. It was not completely soluble in 10 parts of 90 p. c. alcohol. 
Composition. The oil has not yet been examined. In the petroleum 
ether extract Borner3 found lauric and palmitic acids, also hydro- 
carbons of the paraffin series. Inasmuch as these three substances are 
volatile with water vapor they must be contained in the oil, and are 
undoubtedly the cause of its congealing. Schimmel & Co. isolated an 
acid melting at 61° from the oil. 
426. Oil of Costus Root. 
Origin. The root of Saussurea lappa Clarke (Aplotaxis lappa 
Decaisne, A. auriculata, D. C., Aucklandia costus Falconer) was known 
to the Greeks as kootos and was used in the preparation of a fragrant 
ointment. The plant is indigenous to the northwestern Himalaya 
mountains and grows at an altitude of 7,000 to 13,000 ft. The root 
is fully developed in fall and is collected in September and October. In 
Cashmere as much as 2 million lbs. are said to be collected annually. 
They are used principally to protect the Cashmere shawls against insects. 
Large quantities of the root are also exported to China where they are 
used as incense under the name of Putchuc. Upon distillation the root 
yields 0.8-1 p. c. of volatile oil. 
Properties. The oil of costus root is viscid and of a light yellow 
color.4 The odor reminds first of elecampane5 and later of violet. The 
oil from old roots sometimes has an unpleasant odor. Sp. gr. 0.982 to 
0.987; «ij = + 15 to +16°. The oil begins to boil at 275°. About 
i) Berieht von S. & Co., Oct. 1889, p. 5. 
2) Berieht von S. & Co., Oct. 1891, p. 4. 
3) Inaug.-Dissertation. Erlangen, 1892. 
4) Bericht von S. &Co., Apr. 1896, p. 42. 
a) Elecampane was used during anti- 
quity as adulterant of costus root. 690 
Special Part. 
half passes over by 315° when complete decomposition sets in. By 
treatment with soda lye a part of the oil is dissolved and is again set 
free from the salt solution by means of acids.1 
427. Oil of Carline Thistle. 
The root of Carlina acaulis L. (Ger. Eberwurz) yields upon distillation 
1.5-2 p. c. of an oil with a narcotic odor, and sp. gr. 1.030 at 18°. 
Upon distillation under ordinary pressure, one-half passes over between 
265-300°, then decomposition and complete resiniflcation sets in.2 
By distillation over sodium in a vacuum, Semmler3 isolated a 
fraction 139-141° (20 mm.) which was a hydrocarbon of the com- 
position (CbHs)x (b. p. under ordinary pressure 250-253°). According 
to its boiling point it might be a sesquiterpene, but for such its sp. gr., 
0.8733 at 22.8°, is low (sp. gr. of all known sesquiterpenes 0.90-0.92) 
The principal constituent of the oil is an oxygenated, specifically 
heavy substance boiling at 169-171° under 21 mm. pressure. The oil 
also contains a substance which separates in white, shining laminae 
upon cooling. 
428. Oil of Sphaeranthus Indicus. 
The composite Sphaeranthus indicus L. with its rose-like odor is 
used in India as a medicine. According to Dy mock4 (1884) it yields 
upon distillation a dark red, viscid oil which is rather soluble in water. 
From 150 lbs. of the fresh herb about oz. of oil was obtained. 
OIL OF UNKNOWN BOTANICAL ORIGIN. 
429. Oil of Anise Bark. 
As anise bark Schimmel & Co. obtained in 1891 a bark from 
Madagascar,5 which resembled massoy bark in exterior appearance, 
but differed materially as to odor. The aroma was more anise- than 
estragon-like, and reminded somewhat of safrol. The supposition of the 
importer that it is the bark of the star-anise tree is not probable, 
inasmuch as Illicium verum does not occur on Madagascar. It may be 
the bark of another species of Illicium, possibly of I. parviflorum Michx., 
which is reputed to have a sassafras-like odor. Upon distillation the 
i) Bericht von S. & Co., Apr. 1892, p. 41. 
2) Bericht von S. & Co , Apr. 1889, p. 44. 
3) Chemiker-Zeitung, 13, p. 1158. 
*) Pharm. Journ., Ill, 14, p. 985. 
5) Bericht von S. & Co., Apr. 1892, p. 40. Oils of Unknown Origin. 
691 
anise'bark yielded 3.5 p. c. of a light yellow oil of anise-like odor but 
without a sweet taste. Sp. gr. 0.969; «u =-0°46'. In addition to 
small amounts of anethol, the oil consisted largely of methyl chavicol, 
which had been prepared artificially by Eykman. 
4-30. Oil of Quipita Wood. 
This Venezuelan wood is of a light color, dense in texture but not 
very hard, and enters commerce in billets several meters in length and 
5-20 cm. in diameter. The thicker stems have a thin, white outer bark 
and somewhat resemble birch stems; the bark of the younger stems is 
grayish-brown. 
Upon distillation of the rasped wood, Schimmel & Co.1 obtained 
1 p. c. of a light yellow oil, with terebinthinate odor. Sp. gr. 0.934; 
«d = - 34° 31'. Saponification number of the original oil 2.9; after 
acetylization 40.2. This shows that in addition to a small amount of 
ester there are alcoholic constituents in the oil. 
i) Bericht von S. & Co., Oct. 1896, p. 75. BIBLIOGRAPHIC NOTES. 
Those who desire further information than that here given concerning 
the writings mentioned in the historical chapters of this work, or about 
their authors, may consult the historical appendix to Fliickiger's 
Pharmacognosie des Pflanzenreiches and the works there mentioned. 
The translator desired to make these bibliographic notes more complete, 
but time did not permit to do so at present. 
Aetius. A Christian physician, born in Amid, now Diarbekr, on the 
upper Tigris, who was educated in Alexandria. Between 540 and 550 
he wrote a medical treatise in sixteen books or section. The following 
editions are referred to in the historical chapters of this work: 
Aetii medici graeci ex veteribus medicinae tetrabiblos. Editio Aldina. 
Veneti 1547. 
Aetius larptKa. eKKcuSeKa'. Libri medicinales sedecim. Editio Aldina 
1533. 
Anschutz, R. and H. Reitter. Dr. Anschutz was in 1895 Professor 
of Chemistry at Bonn, when Dr. Reitter was laboratory assistant. 
Die Destination unter vermindertem Druck im Laboratorium. Zweite neu 
bearbeitete Aufiage. Ein Bd., pp. IV, 86. Verlag von Fr. Cohen, Bonn, 1895. 
Arabian Physicians. The writings of the Arabian physicians and 
scientists are preserved principally in a collective edition printed in Venice 
in 1502. The following works are contained in this volume: 
Uni Joannis Mesne Liber de consolatione medicinarum simplicium et cor- 
rectione operationem earum canones universales: cum expositione preclarissimi 
medici magistri Bondini de lentiis felicitur incipiunt. 
Additiones Petri Apponi medici clarissimi, et Francisci de Pedemontium. 
Joannis Nazareni filii Mesue Grabaddin medicinarum particularium incipit. 
Antidotarium Nicolai cum expositionibus, et glossis clarissimi magistri 
Platearii. 
Expositio Joannis de Santo Amando supra antidotarrii Nicolai incipit 
feliciter. 694 
Bibliographic Notes. 
Tractates de synonymis quid pro quo. 
Liber Servitoris seu libri XXVIII Bulchasin Ben-aherazern: translatus a 
Simone Januensi: interprete Abraamo Judeo Tortuosienzi. 
Uni Saladini de esculo Servitati principis Tarenti physici principalis com- 
pendii aromatiorum opus feciliter incipit. 
Quae omnia supradicta hie finem habent ad laudam dei. Veneti impressa 
anno Domini 1502, die 23 Junii. 
The oldest single editions of these works date up to 1-L71, about the 
time of the introduction of the printing of books. * 
Askinson, George Wm. Manufacturer of perfumes. The following 
works are of A. Hartleben's chemisch-technische Bibliothek. 
Die Fabrikation der atherischen Oele. Anleitung zur Darstellung der 
atherischen Oele nach den Methoden der Pressung, Destination, Extraction, 
Deplacirung, Maceration und Absorption, etc. Zweite vermehrte und verbesserte 
Auflage. Ein Bd., pp. VIII, 215, mit 36 Abbildungen. A. Hartleben's Verlag, 
Wien, 1887. 
Die Parfumerie-Fabrikation. Vierte, vermehrte und verbesserte Auflage. 
Ein Bd., pp. 376, mit 35 Abbildungen. A. Hartleben's Verlag, Wien, 1895. 
Avenzoar. (Averrhoes, Averroes.) Abul-Welid Muhammed Ben 
Ahmed Ibn Roschd el-Maliki was born (1126) and educated in Cordova. 
A famous Arabian philosopher and physician. Of his numerous works 
the following is referred to on p. 19. 
Liber Theizir Dahalmodana Vahaltadabir prooemium Averrhoi Cordubensis 
ab Jacobo Hebraeo. Anno 1281. Colliget Veneti 1553. 
Ayurvedas. See Susruta. 
Bergmann, Torbern. Swedish chemist, born 1735, died 1784. 
De primordiis chemiae. Upsala 1779. Editio Hebenstreit. Lipsiae 1787. 
Historiae chemiae medium seu obscurum aevum. Editio Hebenstreit. 
Lipsiae 1787. 
Bessonius. 
Jacobi Bessonii, De absoluta ratione extrahen di aquas et olea ex medica- 
mentis simplicibus a quodarn empirico accepta et a Bassonio locupletata, 
experimentis conflrmata. Tiguri 1559. - French edition, Paris 1573. 
Boerhaave, Hermann. Born 1668 near Leiden. Since 1709 Pro- 
fessor of medicine, botany and chemistry at Leiden. Died there 1738. 
Elementa chemiae, quae anniversario labore docuit, in publicis, privatisque 
scholis, Hermannus Boerhaave. Tomus primus, qui continet historiam et artis 
theoriam. Tomus secundus, qui continet operationes chemicas. Lugduni Ba- 
tavorum 1732 - Londini 1732 et 1735 - Parisii 1732, 1733, 1753 - Lipsiae 
1732 - Basileae 1745 - Veneti 1745 et 1759. Bibliographic Notes. 
695 
Bornemann, Georg. 
Die fliichtigen Oele des Pflanzenreichs, ihr Vorkommen, ihre Gewinnung und 
Eigenschaften, ihre Untersuchung und Verwendung. Ein Bd., pp. XII, 441, mit 
einem Atlas von '8 Foliotafeln, enthaltend 83 Abbildungen. Verlag von B. V. 
Voigt. Weimar 1891. 
Brunfels, Otto. 1488-1534. Carthusian friar, then teacher in 
Strassburg, died as city physician in Basel. 
Spiegel der Arznei. Strassburg 1532.-Reformation der Apotheken. Strass- 
burg 1536. 
Brunschwig, Hieronymus. About 1450-1530. Born in Strassburg, 
physician. 
Liber de arte distillandi. For the complete title see title pages of both 
volumes on pp. 23 and 25, reproduced half size. 
Burghart, G. H. 
Die zum allgemeinen Gebrauch wohl eingerichtete Destillirkunst. Auch die 
Bereitung verschiedener destillirter Wasser und Oele. Von G. H. Burghart. 
Breslau 1736. - Neue Auflage mit vielen Zusatzen von J. Christian Wiegleb. 
1754. 
Das Brennen der Wasser, Oele und Geister. Wohleingerichtete Destillirkunst 
und nene Zusatze. Von G. H. Burghart. Breslau 1748. 
Cartheuser, Joh. Friedr. 1704-1769. Professor of medicine, 
botany and chemistry at the University of Frankfurt-on-the-Oder. His 
contributions on volatile oils are contained in the following works: 
Fundamenta materiae medicae. . Francofurt. ad Viadr. 1738 and Paris 
edition 1752. 
Elementa Chymiae dogmatico-experimentalis, una cum synopsi Materiae 
medicae selections. Halae 1736. Editio secunda priore longe emendatior. 
Dissertatio chymico-physica de genericis quibusdam plantarum principiis 
hactenus neglectis. Francof. ad Viadr. 1754. Editio secunda 1764. 
Dissertatio physico-chemica medica de quibusdam Materiae medicae subjectis 
exarat. ac publice habet nunc iter, resus. Francof. ad Viadr. 1774. 
Dissertationes nonnullae selectiores physico-chemicae ac medicae. varii argu- 
menti post novam lustrationem ad prelum revocat. Francof. ad Viadr. 1778. 
Pharmacologia theoretico-practica praelectionibus academicis accommodata. 
Berolini 1745. 
Charaka. See Susruta. 
Cordus, Valerius. Born 1515 near Erfurt, died 1544 in Rome. 
See pp. 27 and 30. His lectures on Dioscorides were published after 
his death and reedited by Conrad Gesner with the following title: 
In hoc volumine continentur Valerii Cordi Simesusii Annototiones in Pedacii 
Dioscoridis Anazarbei de medica materia hbros quinque longe aliae quam antea 
sunt hac sunt evulgatae. 696 
Bibliographic Notes. 
Ejusdem Vai. Cordi Historiae stirpium libri quatuor posthumi nunc primum 
in lueem editi, adjectis etiam stirpium iconibus et brevissimis Annotatiunculis. 
Sylva qua rerum fossilium in Germania plurimarum. Metallorum, Lapidum et 
Stirpium aliquot rariorum noticiam brevissime persequitur, nunc hactenus visa. 
De artificiosis extractionibus liber, - Compositiones medicinales aliquot non 
vulgares. - Hie accedunt Stockhornii et Nessi in Bernatium Helvetiorum ditione 
montium, et nascentium in eis stirpium, descriptio Benedicti Aretii, Graecae et 
Hebraicae linguarum in schola Bernensi professoris clarissimi. Item Conradi 
Gesneri De Hortis Germaniae liber recens una cum descriptione Tulipae Tur- 
carum, Chamaecerasi montani, Chamaeopiti, Chamaeuerii et Conizoidis. - Omnia 
summo studio atque industria doctissima atque excellentis viri Conr. Gesneri 
medici Tigurini collecta et praefationibus illustrata. - 1561 Argentorati excude- 
bat Josias Sibelius. 
An earlier edition referred to on p. 65 bears the following title: 
Valerii Cordi Annotationes in Pedacei Dioscoridis de Materia medica libros 
quinque. Liber de artificiosis extractionibus. Liber II. De destillatiorie oleo- 
rum. Anno dei 1540. 
The title of the pharmacopoeia compiled at the request of the 
Nurnberg council and published 1546 is: 
Pharmacorum omnium, quae quidem in usu sunt, conficiendorum ratio. 
Vulgo vocant Dispensatorium pharmacopolarum. Ex omni genere bonorum 
authorum, cum veterum turn recentium collectum, et scholiis utilissimis illustra- 
tum in quibus obiter, plurium simplicium, hactenus non cognitorum vera 
noticia traditur. Authore Valerio Cordo. Item de collectione repositions et 
duratione simplicium. De adulterationibus quorundam simplicium. Simplici 
aliquo absolute scripto, quid sit accipiendum, 'Ai/rt^aXXogeiza, id est, Succedanea, 
sive Quid, pro Quo. Qualem virum Pharmacopolam esse conveniat. Cum indice 
copioso. Norimbergae, apud Joh. Petreium. 
Other editions of this Dispensatorium Noricum used in the com- 
pilation on p. 32 are enumerated on p. 51, footnote 3. 
CONRINGIUS. 
Hcrmannus Conringius, De hermetica Aegyptiorum vetere et Paracelsiorum 
nova medicina libri duo. Helmstadt 1648. 
Crato von Krafftheim. 
Conciliorum et epistolarum libri vii. Francofurti 1589. 
C. C. CUNRATHH, 
Medulla destillatoria et medica, oder Bericht, wie man den Spiritus vini zur 
Exultation bringen soil. Leipzig 1549. 
Demach v. 
Laborant im Grosser! oder die Kunst die chemischen Producte fabrikmassig 
zu verfertigen. Aus dem Franzdsischen iibersetzt, mit Zusatzen versehen von 
Samuel Hahnemann, der Arzneikunde Doctor und Physikus des Amtes Gommern. 
Leipzig 1784. Bibliographic Notes. 
697 
Dejean. 
Traite raisonne de la destination, ou la destination reduite en principes avec 
un traits des odeurs. Par Dejean. Paris 1753.-German edition, Altenburg 1754' 
Traits des odeurs, Suite du traite de la destination. Par Dejean. Paris 1764. 
Destillirbucher. See p. 24. Also Brunschwig, Ulstad and Reiff. 
For more recent works see Burghart, Dejean, and Demachy. 
Dioscorides. Pedanius Dioscorides is the first medical writer of 
importance of the Christian era. He was born about the beginning of 
the first century in Anazarbus in the southeastern part of Asia Minor. 
In the capacity of a physician he traveled with the Roman army. His 
"Materia Medica" written in the second half of the first century is the 
most thorough work of its kind produced in antiquity. It was regarded 
as authority throughout the middle ages. Even during Luther's time 
it was made the basis for lectures and printed commentaries, e. g. by 
Melanchthon and Valerius Cordus at the University of Wittenberg about 
the middle of the sixteenth century. 
Dioscorides' most important writings are his five books "De materia 
medica," and his "Alexipharmaca et theriaca," remedies against vege- 
table and animal poisons, which were added as books six and seven. 
These and others, more or less apocryphal writings, have been frequently 
published and commented upon in many languages. Some of the oldest 
editions are to be found in the library at Leyden. They are a manu- 
script in the Arabic language, written about the year 940; a very rare 
Greek edition printed by Aldum Manutium in Venice in 1499; and a 
Latin edition by J. Allemanum de Medemblich printed in Colle in 1503. 
Some of the better translations and commentaries are: 
Pedanii Dioscoridis Anazarbensis: de materia medica libri quinque. Jano 
Coronario medico physico interprete. Basiliae 1529. 
Valerii Cordi Simesusii Annotationes in Pedacei Dioscoridis Anazarbei de 
medica materia libros quinque, longe aliae quam ante liac sunt emulgatae. 
Ejusdem Historiae stirpium libri quatuor, et de artificiosis extractionibus liber. 
Tiguri 1540. 
Valerii Cordi Simesusii Annotationes in Pedanii Dioscoridis Anazarbei de 
materia medica libros quinque, longe aliae quam antea sunt baec sunt emul- 
gatae. Ejusdem historia stirpium libri quatuor, et de artificiosis extractionibus 
liber etc. Translatio Riillii. Francofurtum ad Moenum 1549. Editio Gessnerii 
1561. 
Pedanii Dioscoridis Anazarbei de medicinale materia medica libri sex, 
Joanno Riillio Suessionensi interprete. Accesserunt priori edition! Valerii Cordi 
Simisusii Annotationes dfictissimi in Dioscoridis de medica materia libros Euricii 
Cordi judicium de herbis et simplicibus medicinae; ac eorum quae apud medicos 
controverruntur explicatio. Francofurti 1543. 698 
Bibliographic Notes. 
Petri Andreae Matthioli Opera quae extant omnia. Commentarii in sex 
libros Pedacei Dioscoridis de materia medica. Veneti 1554. 
Petri Andreae Matthioli, Medici Caesarii et Fernandi Archiducis Austriae, 
Opera qnae extant omnia: hoc est Commentarii in sex libros Pedacei Dioscoridis 
Anazarbei de medica materia. Post diyersarum editionem collationem infinitis 
locis aucti: De ratione destillandi aquas ex omnibus plantis; et quomodo 
genuini odores in ipsis aquis conseryare possint. Veneti 1544. - Basilae 1565 
HeSaKtou AiosxoptSou 'Ava£ap/?ew$ Trepi uXiys laTpiKr/s /3l/3Xm or Pedacei 
Dioscoridis Anazarbei opera quae extant omnia. Ex nova interpretatione. 
Jani-Antonii Saraceni, Lugduni Medici, Francofurti 1578 and 1598. 
A Latin translation of the Dioscorides' "Materia Medica" had 
appeared as early as 1478, and a Greek edition about the same time 
in Cologne. 
• A later edition of Dioscorides' "Materia Medica" which has been 
used in this work is the edition of Prof. Curtius SprengeL It constitutes 
volume 25 of Kilim's collection: "Medicorum graecorum opera quae 
extant," and consists of two parts. The first part contains: "De 
Materia medica libri quinquae"; the second part: "Liber de venenis 
eorumque precautione et medicament!one" (pp. 1-338), and "Cominen 
tarius in Dioscoridem" (pp. 340-675). 
Dispensatorium Brandenburgicum. The edition of 1698 was con- 
sulted . See p. 31, footnote 3. 
Dispensatorium Noricum. See Cordus and Gesner. 
Fluckiger, F. A. Born May 15, 1828, in Langenthal, Switzerland, 
died Dec. 11, 1894, in Bern. Professor of Pharmacy and Pharmacog- 
nosy at Strassburg from 1873-1892. 
Pharmacognosie des Pflauzenreiches. Dritte Auflage. Ein Bd., pp. XVI, 
1117. Verlag von Hermann Heyfelder, Berlin, 1891. 
Fluckiger and Hanbury. 
Pharmacographia, a history of the principal drugs of vegetable origin met 
with in Great Britain and British India. Second edition. One vol., pp. XX, 
803. Macmillan & Co., London, 1879. 
Fourcroy, A. F. Born 1755, died 1809. An influential French 
teacher of chemistry. 
Systeme des connaissances chimiques, et de leur applications aux phenomenes 
de la nature et de l'art. Paris 1801. 
Fuchs, Leonhard. 1501-1566. Professor of medicine in Ingolstad 
and Tubingen. 
De componendorum miscendorumque medicamentorum ratione. 1549. Bibliographic Notes. 
699 
Fuchs, Remaclius. Born 1510 in Limburg-, died 1587 in Brussels. 
■Remaclii Fuchsji, Historia omnium aquarum, quae in commune hodie 
practicantium sunt usu, vires et recta destillandi ratio. Veneti 1542. - 
Parisii 1542. 
Galenus. Born 131 in Pergamon, educated in Smyrna, Alexandria 
and Rome as physician. Died between 201 and 210. His numerous 
writings have been edited by Kuhn under the title: 
Claudii Galeni Opera omnia, in 20 Banden, Lipsiae 1821-1833. Special 
mention may here be made of De simplicium medicamentorum temperaturis et 
faculthtibus libri XI. 
Geber. Abou Moussah Dschafar al Sofi, known in western countries 
as Geber, was active as Arabian physician and scientist during the 
second half of the eighth century. 
In addition to the original writings of Geber which were written in 
Arabic, a number of works which evidently were written later in the 
Greek and Latin languages, have been attributed to him up to a com- 
paratively recent date. The apocryphal character of these later works 
has recently been proven by M. Berthelot ("Introduction a 1'etude de la 
chimie des anciens et du moyen-age." Paris, 1889; also "Revue des deux 
mondes," Sept. 15 and Oct. 1, 1893). 
Some of the works written by Geber or at least attributed to him 
and referred to in this book are: 
Gebri "de alchimia libri tres." Argentorati arte et impensa. Io. Griegningeri 
anno 1529. 
Gebri "Summa perfectionis magisterii." Ex bibliotheca vaticana exemplari. 
Gedani 1682. 
Alchimiae Gebri Arabis libri excud. Joh. Petrins, Niirembergensis. Bernae 
1545. 
Gesner, Conrad. (Euonymus Philiatrus.1) Born 1516 in Zurich, 
died there in. 1565. Studied in Bourges, Paris and Basel. Was city 
physician and later Professor of the natural sciences in Zurich. Edited 
the works of Cordus (see Cordus). More important than these 
"Anuotationes" is the following: 
Thesaurus Euonymi Philiatri, de remediis secretis; liber physicus. medicus 
et partim etiam chymicus et oeconomicus in vinorum diversi sapores apparatur: 
medicis et pharmacopolis omnibus praecipue necessarius. Tigur. 1552. Liber I- 
De destillatione ejusque differentiis in genere. Auctor est Conradus Gesnerus. 
Tiguri A 
i) The pseudonym of Gesner is possibly derived from Euonymus (Ger. Pfaffenhiitchen) 
and philiatros. larpos) friend of medicine. 
2) Another reference contains after the sentence ending with "necessarius" the 
following data: Tiguri 1552 - Lugduni 1557-1566 - Francof. 1578. 700 
Bibliographic Notes. 
A German edition appeared in 1555 under the title: 
"Eiu kostlicher theurer Schatz des Euonymus Philiatrus, darinnen behalten 
sind vil heymlicher gutter stuck der arzney. fiirnemmlich aber die art und eygen- 
schafften der gebrannten wasseren und dien, wie man dieselbigen bereiten solle: 
desgleychen yeder wasseren und olen art und eygenschafft, nutz und brauch. 
Item alles mit schbnen lieblichen figiirlinen angezeigt unnd Item wie man 
mancherley weyn bereiten solle, auch den abgestandenen durch hilff der gebrann. 
ten wasseren, gewiirtzen unnd anderley materi widerumb helffen moge fur die 
augen gestellt, ganz lustig, nutzlich und gut alien Alchemisten, haushalten, 
insbesonders den Balbiererern, Apothekern und alien liebhaberen der Arztney.- 
Erstlich in Latin beschrieben durch Euonymum Philiatrum, unn newlich ver- 
teutscht durch Johannem Rudolphum Landenberger zu Zurich: vormals in 
Teutsche sprach niemals gesahen. Getruckt in Zurich bei Andrea und Jacobo den 
Gessneren gebruder im jar als man zalt von Christi unseres Heylands geburtl555.'' 
For more than a century this work was frequently reprinted and 
translated. The English translation by Moroyng appeared in 1559 
under the title: 
New book of distillation called the treasure of Euonymus, London 1559, 
1564-1565. 
A French translation appeared in 1555 in Lyon. 
In 1583, after the death of Gesner, this volume was reprinted with 
a second volume (also written by him and published by Caspar Wolf in 
the original Latin in 1565) translated into German by Jacob Niischeler. 
The title of this second volume is: 
Ander Theil des Schatzes Euonymi von allerhand kiinstlichen und bewerten 
olen, wasseren und heymlichen Arzneyen, sampt ihrer ordentlichen bereytung 
und dienstlichen Figuren. Erstlich zusammen getragen durch Herrn Doctor 
Cunrat Gesner, Demnach von Capar Wollfen der Arzneyen Doctor. Zurich; in 
Latin beschrieben und in Truck gefertiget, jetzt aber newlich von Johann Jacobo 
Niischeler Doctoren, in Tiitsche Sprach vertolmetschet. 1583. 
Glauber, Johann Rudolf. 1604-1668. A representative of techni- 
cal chemistry during the iatrochemical period. 
Johanni Rudolphi Glauberi Furui novi philosophic! oder Beschreibung der 
neu erfundenen Destillirkunst. Amsterdam 1648 - Leiden 1648 - Prag 1700. 
Gren, F. A. C. 1760-1798, studied pharmacy, was professor of 
chemistry at Halle. Founded with Gilbert the Annalen derPhysik in 1798. 
Gren's Grundriss der Chemie nach den neuesten Entdeckungen entworfen 
und zum Gebrauch akademischer Vorlesungen eingerichtet. Halle 1796. 
Hanbury, D. Born Sept. 11, 1825, died March 27, 1875. Phar- 
macist and writer on numerous pharmacognostical subjects. 
Science Papers. Edited with memoir by Joseph Ince. One vol., pp. XI, 
543. Macmillan & Co., London, 1876. 
Ph arm acographi a-See Fliickiger. Bibliographic Notes. 
701 
Heusler, Fr. For several years Professor Wallach's assistant at 
Gottingen, later Privatdocent at Bonn. 
Die Terpene. Braunschweig 1896. Reprint from the new "Handworterbuch 
dei' Chemie." Published by Vieweg und Sohn, Braunschweig, 1896. 
Hirzel, Heinrich. 
Die Toiletten-Chemie. Leipzig 1864. 
Hoefer. 
Histoire de la chimie. 2nd ed. 1866. 
Hoffmann, Fr. Born 1660 in Halle, died 1742. Professor of 
medicine in Halle. A representative of the phlogistic school of chemistry. 
Frederici Hoffmannii, Opera omnia physico-medica. Denuo revisa, correcta 
et aucta. In sex tomos distributa. Genevae 1740-1761 - Veneti 1745, 17 
Volumina - Neapel 1753, 25 Volumina. 
Fr. Hoffmannii Opera omnia physico-medica. Suppiementum secundum. 
Geneve 1760. 
Ibn Khaldun. 
Notices et extraits des manuscripts de la bibliotheque imperiale a Paris. 1862. 
JO ANNI RHENANI, 
Medici, Solis e puteo emergentis: sive dissertationis chymia technice practica, 
materia lapidis philosophici et clavis operum Paracelsi, qua abstrusa impli- 
cantur deficientia supplentur. Francofurti 1613. Pars 1. Theoremata chymio 
technica. 
Kliemont, J. M. Vienna. 
Die synthetischen und isolirten Aromatica. Verlag von Eduard Baldamus, 
Leipzig) 1899. 
Kopp, Hermann. Born 1817 in Hanau, studied under Liebig, and 
since 1841 Professor at Heidelberg. Known as physical chemist and 
author of several historical treatises: 
Geschichte der Chemie, 1843-1847. 
Entwickelung d. Chem. in der neueren Zeit. 1873. 
Beitrage zur Geschichte der Chemie, 1869-1875. 
Largus. See Scribonius Largus. 
Lewis, William. 
The new Dispensatory: Containing the theory and practice of pharmacy, a 
description of medicinal simples, according to their virtues and medicinal 
qualities, the description, use and dose of each article, etc. Intended as a, 
correction and improvement of Quincy. London 1753. 
Lonicer, Adam. 1528-1586. 
Adami Loniceri, der Arzney Doctor und weiland Ordinarii Primarii Physici 
zu Francfurt am Meyn, Krauterbueh und kiinstliche Conterfeyungen der Bau- 
men, Stauden, Hecken, Krautern, Getrayde, Gewiirzen und niitzlichen Kunst zu 702 
Bibliographic Notes. 
destilliren. ... - Auf das allerfleissigste iibersehen, corrigirt und verbessert 
durch Petrum Uffenbachium, Ordin. Physicus in Francfurt am meyn. Ulm, 
anno dei 1551, 1573 und 1589. 
Adami Loniceri. Krauter Buch und kiinstliche Conterfeyungen sammt der 
schbnen und niitzlichen Kunst zu destilliren. Von Petrus Uffenbach in's Teutsche 
iibertragen. Ulm 1703. 
Lullus. Raymundus Lullus, born about 1235 of family of Spanish 
nobility, alchemist, was killed as missionary in Africa in 1315. 
Raimundi Lulli, "Experimenta nova" in Mangel's Bibliotheca chemica 
curiosa. Genf 1702. 
Matthiolus. Born 1501 near Siena, studied medicine in Padua, 
body physician of Emperor Maximilian II, succumbed to the pest in 
Trient in 1577. 
Petri Andreae Matthioli, Opera quae extant omnia. Suppiementum: De 
ratione destillandi aquas ex omnibus plantis: et quomodo genuini odores in 
ipsis aquis conservari possint. Basilae 1565. 
Maier, Julius. 
Dr. Julius Maier, Die atherischen Oele, ihre Gewinnung, chemischen und 
physikalischen Eigenschaften, Zusammensetzung und Anwendung. Verlag von 
Paul Neff. Stuttgart. 1867. 
Mierzinski, Stanislaus. 
Die Fabrikation der atherischen Oele und Riechstoffe. Berlin 1872. 
Die Riechstoffe und ihre Verwendung zur Herstellung von Duftessenzen, 
Haarolen, Pomaden, Riechkissen etc., sowie anderer kosmetischer Mittel. 
Siebente A ullage. Ein Bd., pp. XX, 331, mit 70 Abbildungen. Verlag von 
B. F. Voigt, Weimar, 1894. (Sechster Band von Neuer Schauplatz der Kiinste 
und Handwerke.) 
Mesue, the Younger. Yahya ben Masawaih ben Hamech ben Ali 
ben Abdallah, body physician of the Chalifa el-Hakim in Cairo, died 
about 1015 when more than 90 years old. His "Antidotarium" was 
the most renowned pharmaceutical treatise of the middle ages. 
Mesue, Antidotarium seu Grabaddin medicamentorum compositorum libri 
XII. Editio Veneti 1502. 
Mesue, Simplicia et composita, et antidotarii novem posteriores sectiones 
adnotationes. Venetiae 1602. 
Neumann, Caspar. Born 1683, died 1737. Apothecary in Berlin. 
His work on distilled oil is contained in the second volume of his 
Chymia medica dogmatico-experimentalis, oder Griindliche mit Experimenten 
bewiesene Medicinische Chemie. Herausgegeben von Christ. Heinr. Kessel. 
4 Bande. Ziillichau 1749-1755. Hibliographic Notes. 
703 
Nonus Theophanus. Body physician of Emperor Michael VIII in 
Constantinople. - 
Nonus Theophanus. Editio Bernardi. Praefatio ad Synesius de febribus. 
Amstel odami, 1749. 
Comp. Synesius. 
Occo, Adolph. Second half of sixteenth century, author of the 
famous Augsburg Pharmacopoeia. 
Pharmacopoea seu Medicamentarium pro Republica Augustana. Author 
Adolphus Occo. Augusta Vindelicorum 1564. 
Ortolff. Adolph Megtenberger or Meydenberger, also Ortolph or 
Ortolff von Bayernland, born 1450, author of the first pharmacopoeia 
in Germany. 
Ortloff von Bayrland. Arzneibuch. Hie fahet an eyu buchelin von maniger- 
ley Artzeney. Mainz 1485. 
Pharmacopoea Augustana. See Occo. The editions of 1580, 1597 
and 1640 were consulted in preparing the list on p. 32. 
Philippe.. 
Histoire des Apothicaires. One vol., pp. VII, 452. A la Direction de 
Publicite Medicale, Paris, 1853. 
Translated into German by Ludwig. 
Philippe & Ludwig, Geschichte der Apotheker. 1858. 
PlESSE, S. ' 
The Art of Perfumerie. London 1862. 
Plinius. Caius Plinius Secundus, born in the year 23 A. D. near 
Como, died in the year 79 near Stabiae (Castellamare) at the time of 
the famous eruption of Vesuvius. Compiled the natural scientific 
information of his time in 47 books. Most references in this work are 
to the following edition: 
Plinii Secundi Naturalis Historiae libri 37. Recognovit atque indicibus 
instruxit Ludovicus Janus. Lipsiae 1859. Littre. 2 vols. Paris 1877. 
Porta. Giovanni Battista della Porta, 1537-1615. A Neapolitan 
nobleman, known especially for his researches in physics. 
Joh. Baptistae Portae, Neapolitan]', Magiae naturalis libri viginti, in quibus 
scientiarum naturalium divitiae et deliciae demonstrantur. lam de novo, ab 
omnibus mendis repurgati, in lucem prodierunt. Romae 1565. Antwerp. 1567. 
Editio: Hanoviae 1619. Liber decimus: Destillat, destillata ad fastigia virium 
sustollit.1 
Power, F. B. See Schimmel & Co. 
i) Other editions are Romae 1563, Antwerpiae 1564 and [1567, Ravennae 1565, 
Hanoviae 1619. 704 
Bibliographic Notes. 
Price Ordinances. See also p. 31. 
"Ita sunt nomina medicinarum sitnplicium sive materialium quae ad 
apothecam requirentur. In genere et in specie." Prof. F. A. Fliickiger under 
the title "Die Frankfurter Liste." 
Register Riles Apothekischen Simplicien und Compositen, so in den beiden 
Messen zu Frankfurt am Main durch Materialisten, Kauffleut, wurzeltrager, 
Krautler und durch die Apotheker daselbst verkauft werden. Frankfurt a. M. 
1582. 
Reformatio oder erneute Ordnung der heilig Reichsstadt Frankfurt a. M., 
die Pflege der Gesundheit betreffend. Den Medicis, Apothekern und Materia- 
listen zur Nachrichtigung gegeben. Darneben den Tax und Werth der Arzneien, 
welche in den Apotheken allda zu linden. 1587. 
Phases. Abu Bekr .Muhammed Beu Zakerijja el-Raze. Born and 
educated in Raj, at one time director of the hospital in Bagdad, author 
of numerous works, called the Galen of his time. Died 923 or 932. 
Das Buch der Geheimnisse des Abu Bekr Ben Zakartja Er-Razi. Fleischer's 
Catalog No. 266. Leipziger Stadtbibliothek. Codex K. 215. 
Extracts of Phases' writings and the unimportant illustrations of 
several Arabian distilling apparatus were published in 1878 by Prof. 
E. Wiedemann in vol. 32 (p. 575) of the Zeitschrift der deutschen 
morgenlandischen Gesellschaft. 
Reiff. Walther Hermann Ryff, during the first half of the sixteenth 
century surgeon in Strassburg. 
H. Gualtherus Ryff, New gross Destillirbuch, wohl gegriindeter kiinstlicher 
Destination, sainpt underweisung und bericht, kiinstlich abzuziehen oder Sepa- 
riren die furnembste destillirte Wasser, kostliche aquae vitae, Quintam essentiam, 
heilsame oel, Balsam und dergleychen vielgiiter Abziige. Recht kiinstlich und 
viel auff bequeme art dann bisher, auch mit bequemerem Zeug der Gefass und 
Instrument, des ganzen Destillirzeugs von Kreutern, Bliimen, Wurzeln, Friichten, 
Gethier unnd anderen stucken, darinnen natiirliche feuchte unnd Elementische 
krafft, einfach oder mancherley gestalt vermischt und componirt; durch H. 
Gualtherum Ryff, Medicum & chirurgum Argentinensem, getruckt zu Frankfurt 
a./m. bei Christian Egenolff's seligen Erben im jar 1556. 
Reformirte deutsche Apothek. Frankfurt a./M. 1563. 
Saladinus Asculanus. Italian physician. Wrote, probably between 
1442 and 1458, a rather remarkable pharmaceutical treatise entitled: 
Compendium aromatiorum Saladini. principis Tarenti dignissimi, raedici 
diligenti, correctum et emendatum. Bononae 1488. Editio Veneti 1471, 1488 
and 1502. 
Sancto Am ANDO. 
Expositio Joannis de Sancto Amando supra Antidotarium Nicolai incipit 
feliciter. With the edition of Mesue's works. Veneti 1502. Bibliographic Notes. 
705 
Sawer, J. Ch. 
.Odorographia, a natural history of raw materials and drugs used in the 
perfume industry. One vol., pp. XXIII, 383. Gurney, Jackson, London 1892. 
Second series 1894. 
■ Rhodologia. A discourse on roses and the odor of rose. One vol., pp. 93. 
W. J. Smith, Brighton 1894. 
Schmieder, Chr. G. 
Geschichte der Alchemie. Halle 1832. 
Scribonius Largus. Roman physician of the first century of the 
Christian era, who in the year 43 accompanied the Emperor Tiberius 
Claudius to Britannia. 
Scriboni Largi, Compositiones medicamentorum. Editio Schneider. 
Schimmel & Co. Since January 1877 the firm of Schimmel & Co., 
Leipzig, has published a report on volatile oils, at first annually, since 
1880 semi-annually. The character of this report was at first com- 
mercial, but soon became scientific as well until it became a semi-annual 
repertory of everything pertaining to volatile oils. The title of the 
German edition is: ' 
Bericht von Schimmel & Co. (Inhaber Gebr. Fritzsche) in Leipzig. Fabrik 
ather. Oele, Essenzen und chemischer Praparate. April and October. 
Since Oct. 1890 an English translation is also published: 
Semi-Annual Report of Schimmel & Co. (Fritzsche Brothers). Leipzig and 
New York, 
The title of the French edition which appears since Oct. 1896 is: 
Bulletin Semestriel de Schimmel & Cie (Fritchzse Freres). Leipzig and 
New York. 
In 1893 this firm published: 
The factories of Schimmel & Co., Leipzig-Prag and Fritzsche Brothers, 
New York-Garfield. Text by Professor Dr. F. A. Fliickiger-Bern. 
An elegant work with 32 heliogravure plates. The text gives a 
brief account. of the history of the volatile oils. A year later the New 
York branch published a 
Descriptive catalogue of essential oils and organic chemical preparations 
compiled by Frederick B. Power, Ph. G., Ph, D., Director of the laboratories 
of Fritzsche Brother^, at Garfield, N. J. 
Scholtz, Max. 
Die Terpene. Sonderabdruck, pp. 189-246. 
Susruta. The name, possibly pseudonym of the author1 of a book 
on health Ayurvedas of Sanskrit literature. It was formerly supposed 
that this book had been written centuries before Christ, but it is now not 
1) Hippocrates has been suggested. 706 
Bibliographic Notes. 
placed back farther than the twelfth century of the present era. It was 
translated into German by Hessler between 1844 and 1855 in Erlangen. 
The Charaka is a similar older treatise possibly of the eighth century. 
Susrutas Ayur-vedas, id est medicinae systema a venerabili D'hanvantare 
demonstratum a Susruta discipulo compositum. Nunc primum ex Sanscrita in 
Latinum sermonem vertit, introductionem, annotationes et rerum indicem 
adjecit Dr. Fr. Hessler, Erlangae 1844. 
The Susruta, or System of medicine, taught by Dhanvantari and composed 
by his disciple Susruta. Published by Sri Madhusudana-Gupta, Prof, of medicine 
at the Sanscrit College at Calcutta. Calcutta 1835. 2 vol. 
With regard to the age of these works consult: 
Lassen, Indische Alterthumskunde. 1. Aufl., Band 2, p. 551. 
J. F. Royle, An essay on the antiquity of Hindoo medicine. London 1837. 
Deutsche Ausgabe von Wallach und Heusinger, Das Alterthum der indischen 
Medicin. Cassel 1839, p. 45. 
Allan Webb, The historical relations of ancient Hindoo with Greek medicine. 
Calcutta 1850, p. 45. 
Zeitschrift der Deutsch. Morgenland. Gesellsch. Bd. 30 (1876), p. 617; 
also Bd. 31, p. 647. 
Synesius. Born 375 in Cyrene, a disciple of Hypatia in Alexandria, 
elected Bishop of Ptolemais in 410, alchemist, died 415. 
Synesii Tractatus chymicus ad Dioscoridem. In Fabricii biblia graeca. 
Tom. 8. 
Theophrastus. Born 370 or 392 B. C. in Eresos on the island of 
Lesbos, disciple of Aristotle, died between 288 and 286 in Athens. 
Theophrasti Eresii opera, quae supersunt omnia. Historia plantarum. 
Editio Wimmer. Parisii 1866. 
Ulstad, Phieipp. Professor of medicine in Nurnberg during the 
first half of the sixteenth century. 
Philippi Ulstadii, patris nobilis Coelum Philosophorum seu liber de secretis 
naturae, id est: quomodo non solum e vino, sed etiam ex omnibus metallis, 
fructibus, radicibus, herbis etc. Quinta essentia, sive aqua vitae, ad conser- 
vationem humani corporis educi debeat. Argentor. 1526 und 1528 - Lugduni 
1540 und 1553 - Parisii 1543 - August. Treboc. 1553 - Francofurti 1600. 
The title of the German edition is: 
Dess Edlen und Hocherfahrenen Herrn Philippi Ulstadii von Niirmberg 
Biichlein von Heimligkeiten der Natur, jetzund verdeutischt. Frankfurt am 
Mayn 1551. 
That of the French edition which appeared in 1547: 
Le Ciel des philosophes on secrets de la nature. Paris 1547. Bibliographic Notes. 
707 
Victories Faventinus. The Bologna physician and professor 
■Bennedetto Vettori was born 1481, died 1561. 
Victorii Faventini, Practicae magnae de morbis curandis ad tirones. tomi 
duo. Veneti 1562. Tom. 1, cap. 21. fol. 144. 
Villanovus. Little is known about Arnaldus Villanovus as to 
nativity. Was physician in Barcelona during the second half of the 
thirteenth century, suffered shipwreck on his way to Avignon to Pope 
Clemens V about the year 1313. Alchemist. 
■ Arnoldi Villanovi Opera omnia. Veneti 1505. Liber de vinis. 
Arnoldi Villanovi Breviarium practicae, proemium in operis omnibus cum 
N. Taurelli in quos libros annotationibus. Basiliae 1587. 
Winther, Johann. Born 1487 in Andernach, died 1574 as professor 
of medicine in Strassburg. 
Guintheri Andernaci Liber de veteri et nova medicina turn cognoscenda turn 
facienda. Basiliae 1571. 
Zeise, H. Born 1793 in Holstein, died 1863, apothecary in Altona. 
Beitrage zur Nutzanwendung der Wasserdampf'e. Pamphlet. Altona 1826. 
- Arch. d. Pharm. Bd. 16 (1828), p. 69. 
Zeller, G. H. Apothecary. 
Studien uber die atherischen Oele. I. Heft. Des chemischen Theils erster 
Abschnitt. Landau 1850. - II. Heft. Die physischen und chemischen Eigen- 
schaften der officinellen atherischen Oele. Stuttgart 1855. - III. Heft. Die 
Ausbeute und Darstellung der atherischen Oele aus officinellen Pflanzen. 
Stuttgart 1855. 
Zosimos of Panopolis. an encyclopaedic writer of the fourth century 
and one of the principal authorities of the alchemists. 
"Et quid plura moramur? Unus Zosimos Panopolites libro Trepi opyavcuv 
Kal Ka/Mvwv loculente ad oculos nobis sistit antiquorum ilia vasa destillationibus 
accommodata; postquam enim jussisset candidates artis id agere ut ipsis ad 
manus esset /3lko$ vcXlkos aoi^v oaTpaKcvos Xottos Kat ayyos arevosrovov, 
mandassetque ctti aKpa rwv cruXT/vow /3lkov<; veXov pceyaXovs Trayefs €7ri'9e?vai, 
iva p.fj paywsiv airo Tr]^ '>eppr]^ tov vSaros, tandem, ut clarius sese explicit, 
ipsas vasorum figuras appingit, quarum nonnullas licet rudiori manu exaratas 
ex bibliotheca regis christianissimi, et ilia D. Marci Venetiis, libuit hie in 
gratiam curiosorum adjicere." (0. Borrichius "Hermetis Aegyptiorum et 
chemicarum sapientia" ab Hermanni Conringii animadversionibus vindicata. 
Hafniae 1674, p. 156.) 
A detailed account of Zosimos' discussion on distillation is found in 
Hofer's Histoire de la chimie. 2. Edit. 1866. Tom 1, pp. 261-270. INDEX. 
Abelmoschus moschatus, 501 
Abies alba, 252, 259 
balsamea, 251, 252 
canadensis, 251, 263 
cedrus, 279 
excelsa, 259 
fraseri, 251 
pectinata, 252, 259 
reginae amaliae, 266 
sibirica, 265 
Abietene, 254 
Abietineae, 226 
Absinthium, 684 
Absynthe, 684 
Absynthol, 685 
Abura kuku, 682 
Acaroid resin oil, 305 
Acetylization, 194, 202 
Acid number, 193 
Acids, 174 
Achillea ageratum, 676 
coronopifolia, 675 
millefolium, 675 
moschata, 675 
nobilis, 675 . 
Acorus calamus, 301, 303, 304 
spuriosus, 304 
Adulterations, 199 
Ageratum conyzoides, 668 
Argumen fruits, 460 
Ajowan oil, 557 
Ajwain, 557 
Ajwan, 557 
ka-phul, 557 
Alantol, 670 
Alantol, 670 
Alantolactone, 670 
Alantolic acid, 670 
Alcohol as adulterant, 200 
Alcohols, 127, 148 
Aldehyde assay, 196 
determination, 196 
in cassia oil, 388 
Aldehydes, 149 
Alembic, 52 
voyageant, 67 
Alliaria officinalis, 409 
Allium cepa, 306 
sativum, 305 
ursinum, 306 
Allolemonal, 286 
Allspice, 509 
Allyl cyanide, 412 
Almond oil, bitter, 436 
Aloe barbadensis, 304 
Aloe oil, 304 
Aloe vulgaris, 304 
Aloewood oil, 421 
Aloexylon agallochum, 421 
Aloysia citriodora, 593 
Alpenbeifussbl, 587 
Alpenspik, 667 
Alpinia malacensis, 313 
nutans, 313 
officinarum, 312 
Altingia excelsa, 421 
Amandes ameres, 436 
Ambrosia artemisifolia, 672 
Ambrosia oil, 672 
American -wormseed oil, 349 Index. 
710 
Anisbl, 558 
Anise oil, 558 
Anisic aldehyde, 157 
Anisrindenol, 690 
Anonaceae, 215, 362 
Anthemene, 674 
Anthemis cotula, 674 
nobilis, 672 
Anthemol, 674 
Anthophylli, 513 
Anthranilic acid methyl ester, 592 
Anthriscus cerefolium, 541 
Apfelsinenschalenbl, 471 
Apiol, 181, 548 
Apium graveolens, 545, 547 
petroselinum, 547 
Aplopappus discoideus, 507 
Aplotaxis auriculata, 689 
■_ lappa, 689 
Aqua ardens, 227 
naphae, 480 
sabinae, 274 
vitae, 20 
Aquillaria agalloeha, 421 
Araceae, 213, 301 
Araliaceae, 219 
Arbor vitae, 267 
saguisen, 363 
Arbutus laurifolia, 589 
Archangelica officinalis, 570 
Aristolochiaceae, 214, 346 
Aristolochia clematitis, 349 
reticulata, 348 
serpentaria, 348 
Arnica flower oil, 689 
Arnica montana, 688, 689 
Arnica root oil, 688 
Arnikabliithenbl, 689 
Arnikawurzelbl, 688 
Aromatic balsams, 24 
waters, 20, 21, 27 
Aromatized fatty oils, 22 
Arome, 35 
Artanthe geniculata, 326 
Artemisia absinthium, 684 
barrelieri, 687 
dracunculus, 682 
gallica, 687 
Amomum angustifolium, 319 
aromaticum, 318 
cardamonium, 317 
melegueta, 318 
zingiber, 313 
Amygdalin, 438 
Amygdalus communis, 437 
Amyris balsamifera, 486 
linaloe, 492 
Anacardiaceae, 218, 496 
Analysis of oils, 98 
Andromeda leschenaulti, 590 
Andropogon citratus, 285 
ivarancusa, 282, 294 
laniger, 299 
muricatus, 289 
nardus, 282, 291, 294 
odoratus, 299 . 
Andropogon oils, 22, 294 
Andropogon schoenanthus, 281, 294, 
299 
Aneth, 578 
A net hoi, 179 
Anethum foeniculum, 564 
graveolens, 578 
sowa, 579 
Angelic aldehyde, 673 
Angelica anomala, 573 
areha^ngalica, 570 
herb oil, 573 
Japanese oil, 573 
japonica, 573 
■ levisticum, 569 
oil, 570 
refracta, 573 
root oil, 573 
- seed oil, 570 
Angelikakrautol, 573 
Angelikasamenbl, 573 
Angelikawurzelol, 57 0 
Angglique, 570 
Angiopteris evecta, 225 
Angostura bark oil, 459 
Angosturarindenol, 459 
Anis de la Chine, 353 
Sibgrie, 353 
Anisebark oil, 690 
Anise ketone, 160, 562 Index. 
711 
Artemisia glacialis, 687 
maritima var. stechmanni, 683 
vulgaris, 682 
Asafetida oil, 574 
Asafoetidabl, 574 
Asantol, 574 
Asarabacca, Canadian, 347 
Asaret, 346 
Asarol, 348 
Asarum camphor, 346 
Asarum canadense, 347 
europaeum, 346 
Ase f etide, 574 
Ashanti pepper oil, 322 
Aspic, 607 
Aspidium filix mas, 225 
Athamantha oreoselinum, 577 
Athanor, 62 
Atherosperma moschata, 369 
Aueklandia costus, 689 
Aunee, 670 
Aurade, 482 
Aurantiaceae, 460 
Aurantine, 254 
Aurantium amarum, 473 
dulce, 471, 483 
Austra camphene, 45, 110 
Australene, 45, 106 
Azulene, 678 
Backhousia citriodora, 538 
Badanifera anisata, 353 
.Badiane, 353 
Bhdiyan, 353 
Baldrianol, 663 
mexikanisches, 665 
Balm oil, ,616 
Balm of Gilead fir, 264 
Balneum arenae, 54 
Mariae, 54, 57 
per cinerem, 57 
Balsam copaiba oil, 445 
Balsam fir, 264 
Balsamkrautbl, 681 
Balsamodendron kafal, 488 
Balsam of fir, 264 
Balsam of Gilead, 264 
Balsam Peru, 449 
Balsams, aromatic, 24 
Balsamtannennadelol, 264 
Balsam tolu, 448 
Barenklaubl, 581. 
Barlauchol, 306 
Baros camphor, 502 
Barosma species, 457 
Barras, 247 
Barwurzel, 568 
Basil oil, 659 
Basilic, 659 
Basilicumol, 659 
Basil, sweet, 659 
Baume de copahu, 445 
tolu, 448 
Bayberry oil, 331 
Bay oil, 510 
Beifussbl, 682 
Beilschmiedia obtusifolia, 392 
Bellidiastrum osmitoides, 671 
Benzaldehyde, 157 
Benzaldehyde cyanhydrin, 440 
Benzoelorbeerstrauchol, 405 
Benzoin odoriferum, 405 
Benzyl acetate, 591 
Benzyl alcohol, 444, 591 
Benzyl cyanide, 453 
Benzyl mustard oil, 453 
Bergamot oil, 473 
Bergamotte, 473 
Bergamottbl, 473 
Bergaptene, 475 
Bergpetersilienol, 577 
Betel, 326 
Betelol, 326 
Betelphenol, 328 
Betel oil, 326 
Betulaceae, 214, 331 
Betula lenta, 331, 588 
Betulase, 333 
Beurre de violettes, 308 
Biglovia venata, 506 
Birch, black, cherry, sweet, 331 
Birkenrindenol, 331 
Bisabol myrrh oil, 487 
Bisabolene, 487 
Bitter almond oil, 21, 436 
Bitterfenchelol, 567 712 
Index. 
Bitterfennel, old of wild, 567 
Bittermandelol, 436 
Bitter orange oil, 473 
Bitterweed, 672 
Bituminous oils, 35 
Biyakushi, 573 
Black birch oil, 331 
Black pepper oil, 320 
Black spruce oil, 264 
Blue gum tree, 526 
Blumea balsamifera, 669 
lacera, 670 
Bohnenkrautol, 619 
Boiling point, determination of, 188 
Bois de cedre, 276 
citron de Cayenne, 493 
citron de Mexique, 492 
gaiac, 453 
Rhodes, 592 
rose, 592 
rose femelle, 493, 592 
rose male, 493, 592 
jaune, 493 
Boldoblatterol, 368 
BoldoJeaf oil, 368 
Borga cananga, 363 
Borneo camphene, 110 
camphor, 143, 502 
camphor oil, 502 
Borneol, 143 
Boronia oil, 457 
Boronia polygalifolia, 457 
Boswellia carteri, 489 
Boxing of turpentine orchard, 243 
Brai, 248 
Brassica juncea, 409 
nigra, 409 
Brazilian nutmeg, 401 
Bromine addition method, 192 
Brown peppermint tree, 530 
stringy bark, 534 
Brunnenkressenol, 417 
Buccublatterol, 457 
Buchu oil, 457 
Buco, 457 
Bugle weed, 629 
Bulnesia sarmienti, 353, 453 
Burseraceae, 217, 486 
Bursera species, 492 
Butterweed, 668 
Butyl mustard oil, 408 
Cabrinoa wood oil, 447 
Cade oil, 273 
Cadinene, 123 
Caesalpinia sappan, 448 
Cafb bravo, 369 
Cajeput oil, 528 
Cajeputene hydrate, 521 
Cajeputol, 521 
Calamus herb oil, 303 
Calamus, Japanese, 304 
Calamus oil, 22, 301 
California bay tree, 404 
Callitris quadrivalvis, 267 
Calmuskrautbl, 303 
Calmusol, 301 
japanisches, 388 
Camel-grass oil, 299 
Camomille, 676 
Romaine, 672 
Camphene, 45, 46, 110 
Campherholzbl from Venezuela, 395 
Camphol alcohols, 46 
series, 46 
Camphora europaea menthae pipe- 
ritis, 631 
Camphor, 39, 41, 143, 148, 227, 270, 
276, 326, 346, 370, 468, 482, 502, 
608, 612 
artificial, 40, 42, 43, 108, 228 
Baros, 502 
Borneo, 502 
Laurus, 164 
liquid, 41 > ' 
-- Malay, 502 
oil, black, 374 
Borneo, 502 
heavy, 377 
light, 377 
- white, 374 
olefinic, 542 
seeds, 317 
Sumatra, 502 
wood oil, Venezuelan, 395 
Camphorogenol, 377 Index. 
713 
Canada balsam oil, 251 
mint oil, 654 
snakeroot oil, 347 
Canadian asarabacca, 347 
Cananga odorata, 362 
Canarium microcarpum, 421 
spec., 491 
Canella alba, 506 
Canellaceae, 218, 506 
Canelle de Ceylan, 377 
feuilles, 381 
Chine, 381 
Canelo, 394 
Cannabene, 334 
hydride, 338 
Canabis gigantea, 338 
indica, 337 
sativa, 337 
Caparrapene, 394 
Caparrapiol, 394 
Caparrapi oil, 394 
Caprifoliaceae, 221, 663 
Caraway oil, 550 
Carbon disulphide, 181, 412 
Carbonyl oxygen, determination of, 196 
Cardamome, 315 
Cardamom oil, 315 
Bengal, 318 
Cameroon, 319 
Ceylon, 315 
Korarima, 319 
Malabar, 316 
Siam, 317 
Cardamomum majus, 319 
Carlina acaulis, 690 
Carline thistle, 690 
Carqueja oil, 447 
Carre, 247 
Carrot oil, 583 
Carum ajowan, 557 
carvi, 550 
petroselinum, 547 
Carvacrol, 177 
, determination of, 554 
Carvene, 554 
Carvi, 549 
Carvol, 160 
Carvone, 160 
Carvone, determination of, 554 
Caryophyllene, 125 
Caryophylli, 512 
Caryophyllus aromaticus, 513 
Cascarilla oil, 495 
Cascarille, 495 
Cassia, 382 
buds, 382, 390 
caryophyllata, 393 
chips, 378 
leaf oil, 390 
lignea, 390 
oil, 382 
stearoptene, 385 
twigs, 390 
Catinga de negra, 369 
Catingueira, 369 
Catmint, 612 
Catnep, 612 
Cedar camphor, 148, 276 
Cedar leaf oil, 278 
Lebanon, 279 
, red, 276 
, Siberian, 265 
, white, 278 
Cedarwood oil as adulterant, 199 
from Juniperus virginiana, 
276 
Cedrate oil, 477 
Cedratier ordinaire, 477 
Cfidrejaune, 493 
Cedrelawood oil, 494 
Cedrene, 126, 614 
Cedrol, 148 
Cedro oil, 477 
Cedrone, 356 
Cedro ordinario, 477 
Cedrus libani, 279 
Celeri, 545, 547 
Celery root oil, 547 
seed oil, 545 
Celtischer Spik, 667 
Cevadilla seed oil, 304 
Ceylon cinnamon oil, 377 
Chaerophyllum sativum, 541 
Chamaecyparis obtusa, 269 
Chamomile oil, 672 
, German, 676 714 
Index. 
Chamomilla, 672 
romana, 672 
Champaca oil, 353 
Chavibetol, 328 
Chavica betle, 327 
officinarum, 322 
roxburghii, 322 
Chavicol, 179, 328 
Cheken leaf oil, 508 
Chenopodiaceae, 215, 349 
Chenopodium ambrosioides, 349 
var. anthelmintica, 349 
Chenopodium oil, 349 
Cherry birch, 331 
laurel, 442 
Chervil, 541 
Chione glabra, 662 
Chios turpentine, 496 
Chloroform as adulterant, 202 
Chrysanthemum chamomilla, 676 
parthenium, 678 
tanaeetum, 679 
Chula, 282 
Gicily, sweet, 583 
Cicuta maculata, 550 
virosa, 549 
Cicutene, 550 
Cidreira melisse, 369 
Cineol, 175 
assay in eucalyptus oils, 528 
Cinnamic aldehyde, 157 
Cinnamomum camphora, 371 
cassia, 377, 382 
culilawan, 392 
kiamis, 391 
loureirii, 391 
oliveri, 392 
whigtii, 392 
zeylanicum, 377, 381, 382 
Cinnamon oil, 21, 377 
Cinnamon leaf oil, 381 
Cinnamon root oil, 381, 382 
Circulation, 56 
Circulatoria, 56 
Cistaceae, 218, 505 
Cistus spec., 505 
Citral, 149 
assay, 470 
Citrapiene, 46S 
Citrene, 113, 467 
Citr;pdora aldehyde, 286 
Citriosma apiosyce, 369 
cujabana, 369 
oligandra, 369 
Citron camphor, 468 
Citronella aldehyde, 294 
Citronella oil, 291 < 
Citronellal, 154 
Citronelle, 291 
Citronellic aldehyde, 294 
Citronellol, 135, 294 
Citronellone, 294 
Citronenol, 465 
Citrus aurantium, 461, 471, 483 
bergamia; 461, 473 
bigaradia, 461, 473, 480, 484 
myrtifolia, 479 
sinensis, 479 
decumena, 461, 480 
limetta, 478 
vulgaris, 478 
limonum, 461, 465 
madurensis, 461, 479 . 
medica, 461, 477 
var. acida, 461 
nobilis, 479 
Clove oil, 512 
bark oil, 393 
stem oil, 516, 518 
Coca leaf oil, 453 
Cochlearia, 407 
- armoracia, 408 , 
officinalis, 407 
Coerulein, 677 
Cognac oil, 498 
Colophene, 46 
Colophony, 228 
Color reactions, 192 
Commiphora spec., 486, 488 
Compositae, 221, 667 
Comptonia asplenifolia, 331 
Comptonia oil, 331 
Condensation, 51, 58, 94 
Congealing point, determination of, 187 
Coniferous oils, 226 
Conima resin oil, 492 Index. 
715 
Conimene, 492 
Constituents of oils, 97 
Convolvulaceae, 220, 592 
Convolvulus floridus, 592 
scoparius, 592 
Copahu, 493 
Copaiba balsam, 445 
, African, 446 
oil, 445 
as adulterant, 199 
Copaifera species, 445 
Copaivabalsamol, 445 
Coriander oil, 541 
Coriandrol, 129, 542 
Coriandrum sativum, 541 
Cortex caryqphyllati, 393 
culilabani papuanus, 405 
Costuswurzelbl, 689 
Cress, garden, 406 
water, 417 
Cretian origanum oil, 622 
Crocose, 307 
Crocus sativus, 307 
Croton eluteria, 495 
Cruciferae, 216, 406 
Cryptocaria moschata; 401 
oil, 401 
pretiosa, 402 
Cuban pine, 242 
Cubeba officinalis, 322 
Cubebe, 322 
Cubebene, 126 
Cubeb camphor, 148 
Cubeb oil, 322 . 
Cucurbita, 52, 54 
Cuminic aldehyde,'157 
Cumaric aldehyde methyl ether, 157 
Cumin oil, 544 
Cuminum cyminum, 544 
Cunila n^ariana, 661 
Cupressus sempervirens, 269 
Curcuma longa, 310 
oil, 310 
zedoaria, 311 
zerumbet, 311 
Cus-cus, 289 
Cusparia'trifoliata, 459 
Cymene, 104 
Cymol, 104 
Cypress oil, 269 
Cypress camphor, 270 
Cypres, 269 
Damascenine, 352 
Damiana leaf oil, 506 
Daucus carota, 583 
Destillationsbucher of the 16th cent., 
23-37. 
Destillatio panis, 57 
per ascensum, 18, 28, 35 
per descensum, 18, 28, 35, 36, 60, 
62 
per ventrem equinum, 57 
solis, 57, 62 
Dhelum outan, 657 
wangi, 656 
Diatomic series of terpenes, 46 
Dicypellium caryophyllatum, 393 
Digger pine, 254 
Dilem oil, 659 
Dill apiol, 181, 579 
Dill oil, 578 
East Indian, 579 
Diosphenol, 458 
Dipentene, 116 
Dipping in turpentine orchard, 244 
Dipterocarpaceae, 218, 504 
Dipterocarpus spec., 504 
Dissertations on volatile oils, 37 
Distillation, 18, 19 
after fermentation, 36 
, destructive, 18 
, definition by Brunschwig, 24 
, definition of, in historical writ- 
- ings, 22 
, downward, 18, 35, 59 
, fractional, 19, 44, 188 
over burnt lime or chalk, 39 
, history of, 51 
, treatises on, 23, 30, 37 
under diminished pressr^e, 69 
, upward, 18, 35 
with acetic acid, 19 
with acids and salts, 36, 40, 66 
with alcohol, 19 
--■- with steam, 69, 85 716 
Index. 
Distillation with water, 18, 19 
Distillerie ambulante, 602 
Distilling apparatus, history of, 51 
Diterpene, 46, 127 
Dittany oil, 661 
Dog fennel oil, 667 
Dorema ammoniacum, 576 
Dostenbl, 620 
Double balsam fir, 251 
Dragonic acid, 682 
Drimys winteri, 362, 506 
Drusenbl, 498 
Dryobalanops spec., 502 
Dutch myrtle oil, 331 
Eau de Carmelites, 616 
de Cologne, 34, 616, 
Eberwurzol, 690 
Ecuelle a piquer, 462 
Edelscharfgarbenol, 67 5 
Edeltannennadelbl, 259 
Edeltannenzaphenbl, 259 
Elaoptene, 41 
Elaphrium aloexylon, 492 
Elder blossom oil, 663 
Elecampane oil, 670 
Elemi oil, 490 
Elettaria cardamomum, 315 
cardamomum, White et Maton, 
315 
Empleurum serrulatum, 457, 458 
Empyreumatic oils, 18, 24, 35 
Enfleurage a froid, 591 
Erasine, 254 
Erechthites hieracifolia, 587 
Ericaceae, 220, 584 
Erigeron canadensis, 668 
oil, 668 
Erythroxylaceae, 217, 453 
Erythroxylon coca, 453 
Esdragonbl, 682 
Esels-Fenchel, 568 
Essence d?absynthe, 684 
d'amandes amhres, 436 
d'aneth, 578 
■ d'angelique, 570 
d'anis, 558 
d'asaret, 346 
Essense d'ase f etide, 574 
d'aspic, 607 
-»- de badiane, 353 
-- basilic, 659 
baume de copahu, 445 
baume de tolu, 448 
bergamotte, 473 
betula, 331 
bois de cedre, 276 
- bois de Rhodes, 592 
rose, 592 
-- -- bois de santal des Indes Oc- 
cidentales, 486 
bois guiac, 453 
cajeput, 518 
calamus, 301 
camomille,*676 
-; camomille romaine, 672 
cananga, 362 
canelle de Ceylon, 377 
canelle de Chine, 382 
cardamome, 315 
carvi, 550 
cascarille, 495 
- citron, 465 
citronelle, 291 
cochlearia, 407 
coriandre, 541 
cubebe, 322 
cumin, 544 
cypres, 269 
d'elemi, 490 
d'erigeron, 668 
d'estragon, 682 
- de fenouil, 563 
fenouil d'eau, 568 
feuilles de betel, 326 
feuilles de bucco, 457 
feuilles de c&dre, 278 
feuilles de celeri, 547 
feuilles de jaborandi, 457 
galanga, 312- 
gaultheria, 585 
- genibvre, 270 
--- geramium des Indes, 281 
girofle, 512 
; - graines d'ombrette, 501 
d'hedeoma, 617 Index. 
717 
Essence d'houblon, 336 • 
d'houblon d'Espagne, 622 
d'hysope, 618 
d'iris concrete, 308 
de kuro moji, 404 
laurier, 402 
laurier cerise, 442 
r- lavande, 600 
- ledon, 584 
licari, 492 
limette, 477 
linaloe, 492 
liveche, 569 
macis, 366 
-- -~- mandarines, 479 
- marjolaine, 621 
mastice, 496 
*- matico, 325 
melisse, 616 
menthe crgpue, 651 
menthe poivree, 630 
moutarde, 409 
■-■ muscade, 366 
myreia, 510 
- myrrhe, 486 
myrte, 507 
neroli, 480 
neroli Portugal, 483 
d'oliban, 489 
d'orange blgarade, 473 
d'orange Portugal, 471 
de patchouli, 656 
persil, 547 
petit-grain, 484 
piment, 509 
poivre, 320 
pouliot, 655 
racine d'aunee, 670 
romarin, 594 
rose, 423 
- rfte, 455 
■ santal, 338 
sassafras, 395 
sauge, 612 
semen contra d'Amerique, 
349 
semences de celeri, 545 
serpelot, 628 
Essence de serpentaire du Canada, 347 
■ sombul, 576 
- sty rax, 419 
tanaisie, 679 
terebenthine Americaine, 239 
terebenthine Francaise, 247 
' thuya, 267 
thyme, 623 
tiges de girofle, 518 
valeriane, 663 
vetiver, 289 
ylang-ylang, 362 
zedoire, 311 
Essences, pine needle, 258 
Estagnons, 428 
Ester number, 193 
Esters, 174 
Estragol, 561 
Estragon oil, 682 
Ethyl alcohol, 127 
as adulterant, 200 
camphor, 326 
Eucalyptol, see cineol. 
Eucalyptus amygdalina, 524, 530, 539 
baileyana, 532, 533 
bridgesiana, 536 
camphora, 540 
capitellata, 533, 534 
citriodora, 536, 537, 538 
cneorifolia, 525, 530 
corymbosa, 532 
crebra, 533 
dealbata, 537 
dawsoni, 540 
dextropinea, 535 
diversicolor, 539 
dumosa, 530 
eugenioides, 533, 534 
fastigata, 533 
fissilis, 539 
globulus, 524, 526 
goniocalyx, 525, 536, 539 
gracilis, 539 
haemastoma, 538 
hemiphloia, 533 
incrassata, 525 
laevopinea, 535, 536 
lehmanni, 539 718 
Index. 
Eucalyptus leucoxylon, 525, 533 
longifolia, 340 
loxophleba, 535 
macrorrhyncha, 533 
maculata, 536 
var. citriodora, 537 
melliodora, 525 
microcorys, 533 
obliqua, 533, 534 
occidentalis, 540 
odorata, 525, 530 
Eucalyptus oils, 524 
cineol containing, 526 
citral containing, 538 
citronellal containing, 536 
with peppermint-like odor, 
538 
with indefinite odor, 539 
Eucalyptus oleosa, 530 
pauciflora, 540 
piperita, 524, 538 
planchoniana, 537 
polyanthema, 525 
--- populifera, 532 
punctata, 534, 535 
resinifera, 532 
risdonia, 533 
rostrata, 531 
--■ sideroxylon, 525, 533 
smithii, 536 
staigeriana, 538 
stuartiana, 540 
tereticornis, 540 
tereticornis var. brachycbris, 534 
tesselaris, 540 
viminalis, 537 
Eudesmol, 539, 541 
Eugenia acris, 510 
caryophyllata, 513 
Eugenol, 180 
assay, 516 
Eupatorium foeniculaceum, 667 
Euphorbiaceae, 218, 495 
Euryangium sumbul, 576 
Examination of oils, 184 
Fabiana imbricata, 662 
Fatty oils as adulterants, 201 
Faule Heinz, 62 
Feldkiimmelol, 628 
FSldthymianbl, 628 
Fenchelholzol, 396 
Fenchelol, 563 
Fenchene, 112 
Fenchone, 166 
Fennel, Asia Minor, 568 
Bitter, 567 
Dog, 667 
Indian, 567 
oil, 563 
Persian, 568 
Roman, 567 
Russian, 568 
Sicilian, 568 
Syrian, 568 
wild, 567 
water, 568 
Fenouil, 563 
d'eau, 568 
Fermentation as preliminary to distil- 
lation, 36 
Ferula asa foetida, 574 
galbaniflua, 575 
--- opoponax, 488 
rubricaulis, 575 
s chair, 575 
sombul, 576, 667 
Feuerkrautbl, 587 
Feuilles de cedre, 278 
Feverbush, 405 
Feverfew, 678 
Fichtennadelol, 226, 258, 260 
from Picea excelsa, 260 
Siberian, 265 
Swedish, 262 
Fidschi Sandelholzbl, 345 
Fiji sandelwood oil, 345 
Finocchio d'asino, 568 
Fire weed, 587 
Fleabane, 668 
Florentine flask, 70 
Flores cassiae, 382, 390 
Foehre, 262 
Foeniculum capillaeeum, 564 
dulce, 566 
panmorium, 567 Index. 
719 
Foeniculum piperitum, 568 
sinense, 353 
vulgare, 564 
Foenum camelorunp 299 
Folia cedri, 278 
Fractional distillation, 44, 188 
.Frankincense, 489 
Furfurol, 157 
Furnus acediae, 62 
Fusahus spieatus, 345 
Gagelbl, 331 
Gai'ac, bois, 453 
Galanga, 312 
Galangal oil, 312 
Galbanum oil, 575 
Galgantbl, 312 
Galipea cusparia, 459 
officinalis, 459 
Galipene, 460- 
Galipol, 459 
■Galley furnaces, 63 
Garden cress, 406 
nasturtium, 452 
■Garlic oil, hedge, 409 
Garlic oil, 305 
Gaultherase, 495 
Gaultheria fragrans, 589 
fragrantissfima, 589 
leucocarpa, 590 
procumbens, 332, 585 
punctata, 589 
Gaultherilene, 333 
Gaultherin, 333, 495, 584, 586 
Gebrannte Waesser, 24 
Weine, 24 
Gemmage, 247 
h morte, 247 
Gemme, 247 
Genepi des Atpes, 587 
Genepikraut, 587 
Genievre, 270 
Genista tridentata, 447 
Geraniaceae, 217, 449 
Geraniol, 131 
Geranium des Indes, 281 
Geranium, East Indian, 281 
indieum, 281 
Geranium oil, 449 
, Turkish, 281 
Geranium, rose, 449 
Getah rasamala, 421 
Gingembre, 313 
Gingergrass oil, 285 
Ginger oil, 313 
, wild, 347 
Girofle, 512 
Glechoma hederacea, 612 
Glucotropaeolin, 453 
Golden rod, 668 
Gomenol, 522 
Graines d'ambrette, 501 
Grains of paradise oil, 318 
Gramineae, 213, 280 
Grana moschata, 501 
paradisi, 318 
Grandel, 248 
Grape fruit, 480 
Grey gum, 534, 535 
ivy, 612 
Griinminzbl, 629, 652 
Guaiac wood oil, 453 
Guaiene, 126 
Guaiol, 148, 454 
Guajacholzol, 453 
Guayana laurel oil, 394 
linaloe oil, 394 
Giiljag, 428 
Gum ammoniac, 576 
blue, 526 
grey, 534, 535 
slaty, 540 
sweet, 420 
York, 535 
Gundermannkrautol, 612 
Gurjun balsam oil, 503 
as adulterant, 199 
Hamamelidaceae, 182, 419 
Hanfol, 337 
Haselwurzol, 346 
Hasoronto, 346 
Hedeoma pulegioidds, 617 
Hedge garlic, 409 
Hedychium coronariuni, 312 
oil, 312 720 
Index. 
Helenin, 670 
Helichrysum oil, 670 
stoechas, 670 
Heliotropin, 157 
Helm, 55, 58 
Hemlock needle oil, 263 
spruce, 251 
tannennadelol, 263 
Hemp oil, 337 
Henna oil, 507 
Heracleum giganteum, 581 
sphondylium, 582 
Herba matricariae, 678 
--- schoenanthi, 299 
squinanthi, 299 
Hibiscus abelmoschus, 501 
Hinoki oil, 269 
Hopfenbl, 336 . 
Hop oil, 336 
Horse, mint, 615 
radish; 408 
Houblon, 336 
d'Espagne, 622 
Hiibl's iodine method, 192 
Huile aetheree, 227 
blanche de choix rectifiee, 236 
fine rectifiee, 236 
rectifiee, 236 
volatile de cognac, 498 
de li de vin, 498 
Humulene, 126 
Humulus lupulus, 336 
Hundefenchelbl, 667 
Hungarian water, 20, 34 
Hyawa gum, 492 
Hydrocarbons, 112 
Hydrocuminene, 545 
Hydrocyanic acid, 182, 437, 443, 444, 
447 
assay, 441 
, detection of, 440 
Hydroquinone ethyl ether, 358 
Hydroxy acetophenone, 662 
Hysope, 618 
Hyssop oil, 618 
Hyssopus officinalis, 618 
Icica heptaphylla, 492 
lllicium anisatum, 353 
japonicum, 355 
parviflorum, 690 
religiosum, 355, 362 
verum, 356, 690 
Imperatoria ostruthium, 577 
Indian hemp, 337 
Indigofera galegoides, 447 
Indigofera oil, 447 
Indol, 592 
Ingwerbl, 313 
Inula helenium, 670 
Iodine addition method, 192 
Iridaceae, 313, 307 
Iregenin, 310 
Iridic acid, 310 
Iris florentina, 308 
germanica, 308 
pallida, 308 
Irisol, 308 
Iron bark, 533 
Irone, 310 
Isoborneol, 111 
phloryl ester, 688 
Isopbl, 618 
Iva oil, 675 
Ivaol, 675 
Jaborandiblatterbl, 459 
Jaborandi, false, 326 
Jaborandi leaf oil, 459 
Jasmal, 591 
Jasmone, 592 
Jasminium grandiflorum, 590 
Jasmin oil, 590 
Juglandaceae, 214, 331 
Juglans regia, 331 
Juncus odoratus, 299 
Juniper, 270 . 
berry oil, 270 
from J. phoenicea, 273 
- from J. oxycedrus, 273 
camphor, 148, 272 
wood, oil of, 24, 272 
Juniperus communis, 270 
oxycedrus, 270, 273 
phoenicea, 273 
sabina, 273 
virginiana, 276, 278 Index. 
Kadeol, 273 
Kaempheriaol, 312 
Kaempheria rotunda, 312 
Kamelgrasolj 299 
Kamillenol, deutsches, 676 
romisch, 672 
Kanokosp, 666 
Kapuzinerkressenbl, 452 
Karmeliter Geist, 34, 616 
Katzenminzol, 612 
Kaju rasamala, 421 
lakka, 421 
Kerbelol, 541 
Kesso, 666 
Kesso l oot oil, 666 
Kessowurzelol, 666 
Kessyl acetate, 667 
alcohol, 148, 667 
Ketones, 158 
Kiefer, 262 
Kiefernadelbl, 262 
English, 263 
German, 262 
Swedish, 262 
. Kienol, 226, 254 
Finnish, 257 
German, 255 
Polish, 256 
Russian, 256 
Swedish, 257 
Kiku oil, 682 
Kirschlorbeerbl, 442 
Knoblauchol, 305 
Komaki, 391 
Krauseminzol, 651 
Kressenol, 406 
Kretisch Dostenol/622 
Krummholzbl, 261 
Kummelbl, 550 
Kuromoji oil, 404 
Labiatae, 220, 594 
Labrador tea oil, 584 
Lactones, 174 
Ladanum oil, 505 
Lambic, 428 
Lana batu, 291 
oil, 296 
721 
Langpfefferol, 322 
Lantana camara, 594 
Liirchennadelol, 266 
Larch needle oil, 266 
turpentine oil, 249 
Larix cedrus, 27 9 
decidua, 250, 266 
europsea, 250 
sibirica, 265 
Larixolin, 234 
Latschenkieferol, 261 
Lauchhederichbl, 409 
Lauraceae, 215, 377, 493 
Laurel berry oil, 403 
leaf oil, 402 
oil from Guayana, 394 
. mountain, 404 
Laurene, 403 
Laurier, 402 
t cerise, 442 
Laurinic aldehyde, 456 
Laurinic acid, 403 
Laurocerasin, 443, 444 
Laurus benzoin, 405 
camphora, 371 
nobilis, 403 
Lavande, 600 
Lavendelol, 600 
Lavender camphor, 608 
Lavender oil, 26, 600 
Lavatera olbia, 657 
Lavandula angustifolia, 600 
-1 dentata, 611 
latifolia, 600, 607 
officinalis, 600 
pedunculata, 611 
spica, 600, 607 
stoechas, 607, 611 
vera, 600, 604 
vulgaris, 600 
Lawsonia inermis, 507 
Lebanon cedar oil, 279 
Lebensbaum, 267 
Ledene, 126 
Ledone, 584 
Ledum camphor, 148, 585 
palustre, 584 
Legfohre, 261 722 
Index. 
Leguihinosae, 216, 445 
Lemon camphor, 468 
Lemongrasol, 285 
Lemongrass oil, 285 
Lemon oil, 465 
Lemonol, 132 
Lepidium campestre, 406 
latifolium, 406 
ruderale, 406 
sativum, 406 
Levant worm seed, 683 
Levisticum officinale, 569, 570 
Licareol, 128 
Licari, 492 . 
Liebstock friichte, 570 
Liebstock kraut, 570 
Liebstockol, 569 
Lie de vin, 653 
Lignaloe, 492 
Lignum aloes, 492 
cedri, 276 
flbridum, 396 
pavanum, 396 
Rhodii, 592 
santali, 338 
xylomarathrum, 396 
Ligusticum levisticum, 569 
Likari, 493 
Liliaceae, 213, 304 
Lima di spagna, 478 . 
dulcis, 478 
Lime oil, 477 
Limettblatterol, 478 
Limette, 477 
Limettier ordinaire, 478 
Limettol, 477 
Limoeiro bravo, 369 
domato, 369 
Limonene, 113 ■ 
Linaloe, 492 
Linaloe oil, 492 
, Guayana, 394 
Linalool, 128 
Linalue, 492 
Linden blossoms, oil of, 501 
Lindenbliithenbl, 501 
Lindera sericea, 404 
tippia eitnodora, 593 
Liquidambar altinga, 421 
orientale, 419 
styracifluum, 420 
Liveche, 569 
Loblolly pine, 242 
Loffelkrautol, 407 
Long-leaved pine, 242 
Long pepper, oil of, 322 
Lophanthus anisatus, 661 
Lophanthus oil, 661 
Lorbeerbeerenol, 403 
Lorbeerblatterol, 402 
Lorbeerbl, californisehes, 404 
Lovage, 569 
Lycopus virginicus, 629 
Lythraeeae, 219, 507 
Macchina, 462 
Mace oil, 366 
Magnoliaceae, 215, 353 
Majoranol, 621 
Malakarunnay, 460 
Male fern oil, 225 
Malvaceae, 218, 494 
Mana pangiri, 291 
oil, 296 
Mandarinenoel, 479 
Mandarin oil, 479 
Mandelic acid nitrite, 440 
Marjorlaine, 621 
Marjoram, sweet, 621 
Massoya aromatica, 405 
Massoy bark oil, 405 
Massoyene, 405, 
Massoyrindenol, 405 
Mastice, 496 
Mastiche, 496. 
Mastix oil, 496 
Matico camphor, 148, 326 
Matico oil, 325 
Matricaria chamomilla, 676 
parthenium, 678 
Maumene's sulphuric acid test, 192 
Meerrettigol, 408 
Meisterwurzbl, 577 
Melaleuca acuminata, 523 
cajeputi, 518 
decussata, 523 Index. 
723 
Michelia nilagirica, 392 
Microtaena cymosa, 656 
Mignonette flower oil, 418 
root oil, 418 
Milfoil, 675 
Mineral oil as adulterant, 201 
Mint, Canadian, 653 
mountain, 661 
pepper, 630 
wild, 654 
Mohrenkopf, 54, 58 
Mohrenol, 583 
Monarda didyma,«616 
fistulosa, 615 
punctata, 615 
Monatomic series of terpenes, 46 
Monimiaceae, 215, 368 
Monotropa hypopitys, 584 
Moraceae, 214, 336 „ 
Moschuskornerol, 501 
Moschuswurzelol, 576 
Mosla japonica, 660 
Mosoilbliithenol, 365 
Motiya, 282 
Mountain laurel oil, 404 
mint oil, 661 
Moutarde, 409 
Muscade, 366 
Muscatnussol, 366 
Muskatelier Salbei, 614 
Mustard oils, 182 
oil, black, 409 
white, 416 
Mutterkrautbl, 67 8 
Myrcene, 511 
Myrcia asplenifolia, 331 
cerifera, 331 
gale, 331 
Myricaceae, 214, 331 * 
Myristica fragrans, 366 
moschata, 366 
officinalis, 366 
Myristicaeeae, 215, 366 
Myristicin, 368 
Myristicol, 367 
Myristic acid, 310, 368 
methyl ester, 310 
Myrocarpus fastigiatus, 447' 
Melaleuca ericifolia, 523 
genistifolia, 523 
leucadendron, 518 
var. lancifolia, 523 
linariifolia, 523 
minor, 518 
squarrosa, 523 
uncinata,- 523 
viridiflora, 518, 522 
wilsonii, 524 
Meliaceae, 218, 494 
Melissa officinalis, 616 
Melisse, 616 
Melissenol, 616 
Mentha aquatica, 630, 652, 654 
-•- arvensis, 630, 654 
- var. piperascens, 629, 630 
balsamica, 630 
canadensis, 630, 654 
var. glabrata, 632 
crispa, 629, 630, 652 
oils, 629 
palustris, 630 
pulegium, 617, 655 
-r- rubra, 630 
sarcenica, 630 
silvestris, 629, 652 
viridis, 629, 652 
Menthe basiliqufee, 649 
crepue, 651 
poivree, 630 
Menthene, 122 
Menthol, 145 
assay, 651 
Menthone, 171 
assay, 651 
Mespilodaphne pretiosa, 402 
Metanethol, 561 
Methacrylic acid, 673 
Methyl alcohol, 128 
Methyl chavicol, 179 
Methyl heptenone, 158 
Methyl nonyl ketone, 456, 458, 479 
Methyl number, 197 
Methyl ortho cumaric aldehyde,'386 
Meum athamanticum, 568 
Michelia champaca, 353 
longifolia, 353 Index. 
724 
Myronate of potassium, 410 
Myroxylon peruiferum, 449 
Myrrh oil, 486 
Myrrhenol, 486 
Myrtaceae, 219, 507 
Myrtenol, 507 
Myrtle oil, 507 
Dutch, 331 
Myrtol, 508 
Myrtus cheken, 508 
communis, 507 
Napha, 480 
Nardostachys grandiflora, 667 
jatamansi, 576, 667 
Nasturtium, garden, 452 
officinale, 417 
Nectandra caparrapi, 394 
puchury, 393 
Negra mina, 369 
Nelkencassie, 393 
Nelkenholz, 393 
Nelkenol, 512 
Nelkenrinde, 393 
Nelkensiiure, 512 
Nelkenstielol, 518 
Nelkenzimmtbl, 393 
Nepeta cataria, 612 
glechoma, 612 
Neroli, 480 
Neroli camphor, 482 
Neroli oil, 480 
Neroli Portugal, 483 
Ngai-camphor, 143, 669 
fen, 143, 669 
p'ien, 669 
Niaouli oil, 522 
Nigella damascena, 352 
- oil, 352 
sativa, 352 
Nitriles, 182 
Nitrogen-containing oils, 182 
Norway spruce, 260 
Nos moscado do Brasil, 401 
Number, acid, 193 
ester, 193 
iodine, 192 
methyl, 197 
Number, saponification, 193 
Nussfichte, 254 
Nutmeg oil, 366 
Nut pine, 254 
Nux moschata, 366 
Ocimum basilicum, 659 
var. pilosum, 657 
Ocosotl, 420 
Ocotea caudata, 394, 493 . 
oil, 394 
Oculi populi, 330 
Oenanthe aquatica, 568 
phellandrium, 568 
Oil-containing plants, 212 
Oils, analysis of, 98 
attempted synthesis, 41 
bituminous, 35 
classification by Dumas, 42 
constituents of, 97 
containing nitrogen, 182 
containing sulphur, 182 
empyreumatic, 18, 35 
known to Arnaldus Villanovus, 
Lullus, Sto. Amando and Sala- 
dinus of Aesculo, 20, 21 
known up to 1730, 32 
mentioned in Brunschwig's Destil- 
lirbuch, 24 
Ryff's Destillirbuch, 26 
7 -the Annotations of Cor- 
dus, 28 
the Dispensatorium Nor- 
icum, 34 
- the Thesaurus of Ges- 
ner, 28 
purification of, 94 
treatises on, 50 
Olea aerea, 28 
Oleaceae, 220, 590 
Olefinic camphors,' 542 
sesquiterpenes, 123 
terpenes, 103 
Oleum absynthii, 684 
amygdalarum amararum, 437 
andropogonis muricati, 289 
anisi stellati, 353 
anonae, 362 Index. 
725 
Oleum anthemidis, 672 
asari canadensi, 347 
europaei, 346 
aurantii amari, 473 
dulcis, 471 
floruni dulce, 483 
balsami copaivae, 445 
'tolutani, 448 
basilici, 659 
benedictinum compositum, 24 
bergamottae, 473 
betulae lentae, 331 
buccu foliorum, 457 
- cadinum, 273 
calami, 301 
-- canangae, 362 
cardamomi, 315 
-- cascarillae, 495 
chamomillae, 676 
chamomillae eitratum, 677 
chamomillae romanae, 672 
chamomillae vulgaris, 676 
chenopodii anthelmintici, 349 
' cinnamomi cassiae, 382 
Zeylanici, 377 
citri, 465 
- citronellae, 291 
cochleariae, 407 
cubebarufn, 322 
cupressi, 269 
draeunculi, 682 
elemi, 490 
erigerontis, 668 
floruni aurantii, 480 , 
foliorum betle, 326 
cedri, 278 
jaborandi, 459 
matico, 325 
patchouli, 656 
,galangae, 312 
geranii indicum, 281 
helenii, 670 
humuli lupuli, 336 
iridis, 308 
juniperi, 270 
kuromoji, 404 
ligni cedri, 276 
-: guajaci, 453 
Oleum ligni santali, 338 
sassafras, 396 
--- limettae, 477 
linaloes, 492 
lauri foliorum, 402 
laurinum, 403 
lauro cerasi, 442 
macidis, 366 
mandarinae, 479 
. masticis, 496 
matricariae, 676 
Menthae, 630 
crispae, 651 
piperitae, 630 
pulegii, 655 
mirabile, 20 
myrrhae, 486 
nucis moschati, 366 
olibani, 489 
palmarosae, 281 
petit grain, 484 
piperis, 320 
polemii, 630 
pulegii, 630, 655 
radicis helenii, 670 
rosaceum, 423 
rosarum, 423 
-- verum, 424 
rosatum, 423 
rutae, 455 * 
sabinae, 273 
santali ex India Occidentalis, 486 
serpylli, 628 
sinapis, 409 
styracis, 419 
tanaeeti, 679 
terebinthinae amerieanum, 239, 
gallicum, 247 
thujae, 267 
thuris, 489 
valerianae, 663 
vini, 36 
witthebianum, 519 
zedoariae, 311 
Olibene, 492 
Omani, 557 
Omum water, 557 
Onion oil, 306 726 
Index. 
Oponal, 489 
Opopanax chironium, 488 
oil, 488 
Optical rotation, determination of, 186 
Orange, bigarade, 473 
bitter, 473 
group of terpenes, 47 
Orangenbluthenbl, bitteres, 480 
susses, 483 
Orangenschalenbl, susses, 471 
Orange, Portugal, 471 
sweet, 471 
Oreodaphne californica, 404 
Oreodaphnol, 527 
Origanum hirtum, 622 
major ana, 621 
oil, Smyrna, 623 
oil, Trieste, 622 
smyrnaeum, 623 
vulgare, 620 
Orris oil, 308 
Osmitis bellidiastrum, 671 
Osmitopsis asteriscoides, 671 
Osmorrhiza longistylis, 583 
Osterluzeibl, 349 
Ottonia anisum, 330 
Otto of rose, 423 
Oxides, 174 
Oxybenzyl mustard oil, 417 
Oxmyyristic acid, 304 
Paeonia moutan, 351 
Paeonol, 351 
Paint oil, 234 
Palmae, 213, 300 
Palmarosa oil, 281 
Palo balsamo, 453 
Pandanaceae, 213, 279 
Pandanus odoratissimus, 279 
oil, 279 
Pappelknospenbl, 330 
Paracota bark oil, 370 
Paracotol, 370 
Paradieskbrnerbl, 318 
Para oxybenzyl mustard oil, 417 
Parsley leaf oil, 549 
oil, 547 
root oil, 549 
Parsley seed oil, 547 
Paschkis, 657 
Pastinaca oil, 580 
sativa, 580 
Patchoulene, 126 
Patchouliol, 656 
Patchouly alcohol, 148, 658 
oil. 656 
Patent turpentine, 234 
Patrinia jatamansi, 667 
scabiosaefolia, 666 
Pavanie, 395 
Pavonia weldenii, 657 
Pelargonium oil, 449 
spec., 449 
Pennyroyal, European, 655 
Pennyroyal oil, 617 
Russian, 655 
Pepper, oil of black, 320 
Pepper oil, Japanese, 454 
Peppermint oil, 630 
oil, American, 633 
Bohemian, 650 ■ 
Chilian, 650 
English, 637, 646 
French, 648 
German, 637, 648 
Italian, 640, 650 
Japanese, 636, 647 
Reunion, 650 
Russian, 640, 649 
' Saxon, 648 
tree, 538 
brown, 530 
white, 530 
Perpulut, 657 
Persea caryophyllata, 393 
gratissima, 393 
Persil, 544, 549 
Peru balsam oil, 449 
Pestwurzelol, 688 
Petasites officinalis, 688 
Petersilienbliitterol, 549 
Petersiliensamenbl, 547 
Petersilienwurzelol, 549 
Petitgrain citronnier, 485 
Petitgrain oil, 484 
Petroleum as adulterant, 201, 234 Index. 
727 
Petroselinum sativum, 547, 549 
Peucedanum ammoniacum, 576 
galbanifluum, 575 
grande, 581 
graveolens, 578 
officinale, 581 
oreoselinum, 577 
ostruthium, 577 
root oil, 581 
rubricaule, 575 
sativum, 580 
schair, 575 
spec., 574 
Peumus boldus, 368 
Pfefferkraut, 619 
Pfefferminzbl, 630 
Pfefferbl, 320 
Phellandrene, 121 
Phellandrium aquaticum, 568 
Phenol, 177 
• determination, 197 
Phenols, 177 
Phenyl ethyl mustard oil, 418 
acetic acid nitrile, 452 
glycol methylene acetal, 591 
oxyaceto nitrile, 443 
propionic acid nitrile, 417 
Phlogiston, hypothetical constituent of 
oils, 58 
Phlorol and isobutyric ether, 688 
Photoanethol, 561 
Physical properties, determination of, 
185 
Picea alba, 263 
excelsa, 254, 260 
nigra, 264 
vulgaris, 260 
Pichurim bean oil, 393 
Picrocrocin, 307 
Pilocarpus jaborandi, 459 
Pimenta acris, 510 
Pimentablatterbl, 509 
Pimenta officinalis, 509 
oil, 509 
Pimpinella anisum, 558 
nigra, 563 
--- root oil, 563 
saxifraga, 563 
Pimpinellwurzelbl, 563 
Pinaceae, 212, 226 
Pinage, 247 
Pine, Cuban, 242 
long-leaved, 242 
loblolly, 242 
needle essences, 258 
needle oils, 226, 258 
oil from Abies alba, 259 
oil from Larix decidua, 266 
- oil from Picea excelsa, 260 
oil from Pinus montana, 261 
oil from Pinus silvestris, 
262 
oil from hemlock or spruce, 
263 
oil from Picea nigra, 264 
oil from balsam fir, 264 
oil from Abies siberica, 265 
oil from Pinus cembra, 265 
rosemary, 242 
short-leaved, 242 
slash, 242 
southern pitch, 242 
swamp, 242 
Pinene, 45; 106 
Pine tar oils, 226, 254 
oil, Finnish, 257 
German, 255 
Polish, 256 
Russian, 256 
Swedish, 257 
Pin maritime, 247 
Pinol hydrate, 227 
Pinus, australis, 242, 246 
balsamea, 251 
cedrus, 279 
cembra, 265 
cubensis, 242, 246 
echinata, 242 
glabra, 246 
heterophylla, 242 
jeffreyi, 245 
khasya, 253 
laricio, 248 
larix, 250 
ledebourii, 254, 265 
maritima, 247 Index. 
728 
Pinus merkusii, 253 
mitis, 242 
montana, 261 
mughus, 261 
palustris, 242, 246 
picea, 252, 254 
pinaster, 247 
ponderosa, 254 
pumilio, 261 
sabiniana, 254 
sibirica, 253 
silvestris, 253, 254, 262 
taeda, 242 
Piper angustifolium, 325 
betle, 327 
clusii, 322 
cubeba, 322 
japonicum, 454 
longum, 322 
lowong, 324 
melegueta, 318 
nigrum, 320 
officinarum, 322 
ovatum, 322 
Piperaceae, 214, 320 
Pirolaceae, 220, 584 
Pistacia lentiscuS', 496 
terebinthus, 226, 496 
Plants containing oils, 212 
Plecthranthus fructicosus, 657 
patchouli, 656 
Pleopeltis phymatodes, 225 
Pogostemon comosus, 659 
patchouli, 656 
Poivre, 320 
Poleiol, 655 
Amerikanisches, 617 
Polygala senega, 494 
spec., 495 
Polygalaceae, 218, 494 
Polypodiaceae, 212, 225 
Polypodium phymatodes, 225 
Polyterebene, 46 
Polyterpene, 46, 127 
Pomeranzensehalenol, bitteres, 473 
siisses, 471 
Pompelmusol, 480 
Poplar bud oil, 330 
Populus nigra, 330 
Porschol, 584 
Potomorphe umbellata, 330 
Pouliot, 655 
Price ordinances, 22 
Primelwurzelbl, 590 
Primulaceae, 221, 590 
Primula veris, 590 
Processa alia spugna, 462 
Prunoideae, 437 
Prunus amygdalus, 436 
armeniaca, 437 
eerasus, 445 
domestica, 445 
laurocerasus, 442 
padus, 445 
persica, 438, 444 
serotina, 444 
spinosa, 445 
virginiana, 444 
Ptychotis ajowan, 557 
Pulegium micranthum, 655 
vulgare, 655 
Pulegone, 169 
Putchue, 689 
Pycnanthemum incanum, 661 
lanceolatum, 661 
linifolium, 661 
Pyrethrum indicum, 682 
parthenium, 678 
Quandong, 344 
Quendelol, 628 
Quipita wood oil, 691 
Radish oil, 417 
Radix Indica Lopeziana, 460 
Rainfarnol, 679 
Ranunculaceae, 215, 351 
Raphanol, 417 
Raphanolid, 418 
Raphanus niger, 417 
sativus, 417 
Rasamala wood oil, 421 
Rautenol, 455 
Receivers, 55, 70 
Receptacula, 55 
Red cedar wood oil, 276 Index. 
Refraction, determination-.of, 187 
Resedabluthenol, 418 
Resedaceae, 216, 418 
Reseda-Geraniol, 418 
odorata, 418 
Resedawurzelol, 418 
Resin oil, 236 
Retinosperma bbtusa, 269 
Rettigbl, 417 
Reuniol, 135, 431 
Rhizoma zedoariae rotundae, 312 
Rhodinal, 431 
Rhodinol, 132, 135, 431 
-- de pelargonium, 431 
Rhodium oil, 592 
Romarin, 594 
Romero santo, 611 
Romisches Kamillenbl, 672 
Roob j uniperi, 270 
Rosa alba, 426 
canina, 425 
centifolia, 426, 428, 430 
damascena, 425, 430 
gallica, 425 
Rosaceae, 216, 421 
Rose geranium, 449 
Rose oil, 19, 21, 22, 423 
Bulgarian, 428 
German, 428 
Rose water, 18 
Rosemary forest, 595 
Rosemary oil, 22, 24, 594 
Rosenhut, 58, 62 
Rosengeraniol, 429 
Rosenholzol, 592 
Rosenol, 423 
Roseol, 431 
Rosin, 228 
Rosmarinol, 594 
Rosmarinus officinalis, 594 
Rothtannennadelbl, 254, 260 
Rubiaceae, 221, 662 
Rue oil, 21, 455 
Ruku, 657 
Rutaceae, 216, 454 
Ruta graveolens, 455 
Sabadilla officinalis, 304 
Sabadillasamenbl, 304 
Sabine, 273 
Sabinol, 274 
Sadebaumol, 273 
Safranol, 307 
Saffron oil, 307 
Safrene, 400 
Safrol, 181, 400 
Sage camphor, 612 
Sage oil, 21, 22, 612 
Salbeiol, 612 
Salicaceae, 214, 330 
Salicylic aldehyde, 157 
Salt, hypothetical constituent of oils, 
38 
combustible, 39 
volatile, 39 
Salvia officinalis, 612 
sclarea, 614 
Salvrol, 613 
Salvone, 613 
Sambucus nigra, 663 
Sandalwood, 16, 338, 486 
oil, 21, 338 
African, 345 
Australian, 344, 345 
East Indian, 338 
Fiji, 345 
South Australian, 344 
Swan River, 345 
West Australian, 345 
West Indian, 486 
Sandarac resin oil, 267 
Sansho, 454 
Santal, 338, 486 
Santal camphor, 148 
Santalaceae, 214, 338, 486 
Santalal, 341 
Santalene, 126, 342 
Santalol, 148, 341 
Santalum album, 338 
cygnorum, 345 
preissianum, 344 
yasi, 345 
Saponification, 193, 202 
number, 193 
Sappanblatterol, 448 
Sassafras, black, brown, white, 392 
729 Index. 
730 
Sassafras leaf oil, 401 
goesianum, 405 
officinale, 395, 401 
oil, 395 
artificial, 401 
Safureja hortensis, 619 
montana, 619 
thymbra, 620 
Sauge, 612 
Savin oil, 273 
Saw palmetto oil, 300 
Sehimmelia oleifera, 486 
Schinus molle, 497 
oil, 497 
Schlangenwurzelbl, canadisches, 347 
virginisches, 348 
Schierlings Tanne, 263 
Schwarzfichtennadelbl, 264 
Schwarzktimmelol, 352 
Schwarze Tanne, 264 
Scorzetta process, 462 
Scotch fir, 263 
Scrape, 243 
Scraping in turpentine orchard, 244 
Sedanolid, 547 
Sedanonic acid anhydride, 547 
Selasih Mekak, 660 
Selerieblatterbl, 547 
Seleriesamenol, 545 
Semen abelmoschi, 501 
contra d'Amerique, 349 
Semina cardamomi majoris, 318 
Senega root oil, 494 
Senegawurzelol, 494 
Senfol, 409 
Senkiyu, 573 
Sequoia gigantea, 266 
oil, 266 
Seronoa serulata, 300 
Serpentaria, 348 
Serpentina, 18, 54, 55 
Serpolet, 628 
Serpyllum, 628 
Serronia jaborandi, 330 
Sesquiterebene, 46 
Sesquiterpene, 46 
hydrates, 148 
Sesquiterpenes, 123 
Shaddock, 480 
Shikimene, 362 
Shikimi, 362 
Shikimol, 362 
Short-leaved yellow pine, 242 
Siberian cedar, 265 
Silanol, 568 
Silaus pratensis, 568 1 
Silbertanne, 259 
Silver top stringy bark,- 536 
Sinalbin mustard oil, 416 
Sinapis alba, 416 
juncea, 409 
nigra, 409 
Sinigrin, 412 
Sirih, 326 
Sisymbrium alliaria, 409 
Slash pine, 242 
Slaty gum, 540 
Snake root, Canada, 347 
Virginia, 348 
Solanaceae, 221, 662 
Solidago canadensis, 668 
odora, 668 
rugosa, 668 
Solubility, 190 
Sonfiya, 282 
Southern pitch pine, 242 
Spanish Hopfenbl, 622 
Spearmint oil, 651 
Specific gravity, determination of, 185 
Speikbl, 667 
Sphaeranthus indicus, 690 
Spice bush, 405 
wood, 405 
Spik, celtischer, 667 
lavendel, 607 
Spike oil, 22, 25, 26, 607 
Spikenard, 667 
Spikol, 607 
Spiraea acutifolia, 422 
aruncus, 422 
digitata, 422 
filipendula, 422 
japonica, 422 
laevigata, 422 
lobata, 422 
opulifolia, 422 Index. 
731 
Spiraea sorbifolia, 422 
species, 586 
ulmaria, 421 
ulmifolia, 422 
Spiraea oil, 421 
Spirit of turpentine, 239 
Spiritus melissae comp., 616 
rector, 34 
terebinthinae, 227 
Spoonwort, 407 
Spruce, 264 
Spruce-Tannennadelol, 263 
Spugna process, 462 
Star anise oil, 353 
oil from leaves, 361 
oil, Japanese, 362 
Stearoptene, 41 
Sternanisol, 353 
Stillingia oil, 496 
Stillingia silvatiea, 496 
Stinkasant, 574 
Stipites caryophyllorum, 518 
Storax, American, 420 
Strassburg turpentine oil, 252 
Stringy bark, 533 
brown, 534 
white, 534 
silver top, 536 
Styracin, 421 
Styrax, 419 
calamita, 419 
liquidus, 419, 420 
Styrocamphene, 420 
Styrene, 103, 419 
Succus juniperi, 270 
Sulphides, 182 
Sulphur-containing oils, 182 
Sulphur, hypothetical constituent, 35, 
38 
Sumatra camphor, 502 
Sumbul Ekelti, 576 
Hindi, 576 
Italicus, 576 
Kunis, 576 
oil, 576 
root oil, 576 
Sumbulwurzelbl, 57 6 
Swamp pine, 242 
Swan river sandal wood, 345 
Sweet anise, 583 
basil, 659 
birch, 331 
- cicely, 583 
fern, 331 
gum, 420 
orange oil, 471 
root, 583 
Sylvestrene, 118 
Tanacetone, 167, 613 
Tanacetum balsamita, 681 
-- vulgare, 679 
Tanacetyl hydride, 680 
Tanaisie, 679 
Tannenduft, 265 
Tansy, 679 
Tea, Labrador, 584 
Templinol, 259 
Terebene, 45 
Terebangalene, 572 
Terebentene, 45, 46, 106 
Terebenthine americaine, 230 
francaise, 247 
Terebinthina americana, 239 
gallica, 247 
Terecamphene, 45, 110 
Terpane, 175 
Terpene, name suggested by Kekule, 46 
alcohols, 664 
synthesis by Bouchardat, 47 
Terpenes, classification by Berthelot, 45 
by Gladstone, 46 
by Tilden, 47 
by Wallach, 48 
constitution of, 46 
Terpentinbl, see turpentine oil 
Terpil series, 46 
Terpilene, 46 
Terpin hydrate, 43, 47 
Terpinene, 119 
Terpineol, 139 
Testing oils, chemical methods of, 191 
Tetranthera, californica, 404 
citrata, 405 
Teufelsdreck, 574 
Thea chinensis, 501 Index. 
732 
Theaceae, 218, 501 
Theebl, 501 
Theoline, 254 
Thiosinamine, 413 
Thlaspi arvense, 407 
Thuja occidentalis, 267, 278 
oil, 267 
orientalis, 269 
root oil, 269 
Thujone, 167 
Thym, 618 
Thyme oil, 618 
white oil of, 625, 626 
wild, 628 
Thymianol, 623 
Thymol, 178 
assay, 627 
Thymus capitatus, 629 
serpyllum, 628 
virginicus, 661 
vulgaris, 623 
Tiges de girofle, 518 
Tilia spec., 501 
Tiliaceae, 218, 501 
Toddalia aculeata, 460 
oil, 460 
Tolu balsam oil, 448 
Toluifera balsamum, 448 
Tricyclene, 108 
Triterpene, 127 
Tropaeolaceae, 217, 452 
Tropaeolum majus, 452 
Tsuga canadensis, 251, 263 
Turkish geranium oil, 281 
Turmer61, 311 
Turnera spec., 506 
Turneraceae, 218, 506 
Turpenteen, 234 
Turpentine, American, 239 
camphor, 227 
farms, 242 
French, 247 
group of terpenes, 47 
Strassburg, 252 
Venetian, 249 
Turpentine oil, 20, 22, 24, 36, 41, 226, 
228 
American, 239 
Turpentine oil as adulterant, 199 
Austrian, 248 
Burma, 253 
:- French, 247 
from Canada balsam, 251 
Picea excelsa, 254 
Pinus sabiniana, 254 
Strassburg turpentine, 
252 
- Venetian turpentine, 249 
Galician, 249 
Russian, 253, 256 
oils, patent, 234 
proper, 226 
Turpentyne, 234 
Udid, 282 
Uinbelliferae, 219, 541 
Umbellol, 404 
Umbellularia californica, 404 
Unonia odorata, 363 
Urena lobata, 657 
Uvaria odorata, 363 
Valerian, 663 
oil, 663 
Mexican, 665 
Valerianaceae, 221, 663 
Valeriana celtica, 667 
mexicana, 665 
officinalis, 663 
var, angustifolia, 666 
Valeriane, 663 
Valerianic acid, 664 
Vanillin, 157 
Veilchenwurzelol, 309 
Venetian turpentine oil, 249 
Venezuelan camphor wood oil, 395 
Veratric acid, 304 
Verbena oil, 593 
triphylla, 593 
Verbenaceae, 220, 593 
Vervain, 593 
Verveine des Indes, 285 
Vetiver, 289 
Vetiver oil, 289 
Vettiver, 289 
Vinyl sulphide, 307 Index. 
733 
Violette, 662 
Violettes, beurre de, 308 
Virginia snake root, 348 
Vitaceae, 218, 498 
Vitex trifolia, 594 
Vitis vinifera, 498 
Volatile salt, 39 
Wacholderbeerbl, 270 
von Juniperus oxycedrus, 273 
von Juniperus phoenicea, 273 
Wacholderholzbl, 273 
Wachsmyrtenol, 331 
Walnussblatterbl, 331 
Wanderdestillirgerathe, 67 
Wasserfenchelol, 568 
Wasserminzbl, 654 
Wasserschierlingbl, 549 
Water cress oil, 417 
fennel oil, 568 
hemlock, American, 550 
European, 549 
mint oil, 654 
Weihrauchbl, 489 
Weinbeerbl, 498 
Weinbl, 498 
Weisse Tanne, 264 
Weisstanne, 259 
Weisszimmtol, 506 
Wellingtonia gigantea, 266 
Wermutol, 684 
White cedar, 278 
peppermint tree, 530 
spruce, 264 
stringy bark, 534 
Wild bergamot oil, 615 
cherry bark oil, 444 
ginger, 347 
lemon tree, 369 
mint, 654 
thyme, 362 
Wildkirschenrindenol, 444 
Winterene, 362 
Wintergreen oil, 585 
(Gaultheria), 585 
(sweet birch), 331 
Winter's bark oil, 362 
Wintersrindenbl, 362 
Wood oil, 503 
Wormseed, American, 349 
Levant, 683 
Wormwood oil, 684 
Roman, 672 
Wurmfarnol, 225 
Wurmsamenol, amerikanisch^s, 349 
Xanthorrhoea hastile, 305 
resin oil, 305 
Xanthoxylene, 455 
Xanthoxylum hamiltonianum, 455 
piperitum, 454 
Yellow grass tree gum, 305 
Ylang-ylang camphor, 148 
oil, 362 
York gum, 535 
Ysop, 620 
Zedoire, 311 
Zedoaria rotunda, 311 
Zedoary, 311 
Zimtblatterol, 381 
Zimtbluthenbl, 382 
Zimtol, chinesisches, 382 
japanisches, 391 
Zimtwurzelol, 382 
Zingiber officinale, 313 
Zingiberaceae, 213, 310 
Zirbelkiefernadelbl, 265 
Zitwerwurzelol, 311 
Zwergkiefer, 261 
Zwiebelol, 306 
Zygophyllaceae, 217, 453