WITH COMPLIMENTS OF Tiff JjTHOR. 
Olestes and Oleo-Palmitates. 
FORMIC ACID AS AIN ANTISEPTIC. 
Cascara Sagrada. 
REPRINT OF PAF iERS 
Jj. WOLFF, M.D. 
TWELFTH AND CHESTNUT STREETS, 
PHILADELPHIA. 
PHILADELPHIA: 
Merrihew & Lippert, Printers, 501 Chestnut Street. 
1881. OLEATES AND OLEO-PAlMlTATES. 
L. Wolff, M.D. 
Head at the Pharna.eeutical Meeting, Phil. Coll. Pharm., October 1881. 
Since the publication of my article on Oleic Acid and the Oleates, 
u American Journal of Pharmacy,” 1879, page 8, there has been much 
written on the subject of the oleates and much complaint made of 
their instability, their indefinite character and, above all, their price. 
That the oleates were destined to play a most important part amongst 
therapeutics, and largely applicable for dermic medication instead of 
many of the unsightly and often inert ointments in use until now, is 
a fact that cannot well be disputed. That a substance which is 
applied to the cutaneous surface, dissolved in the vehicle containing it, 
will prove more efficacious, by penetrating deeper into the tissues 
than an insoluble powder distributed on the surface can also not be 
denied. 
When the oleates were first proposed on theoretical grounds, and 
introduced in medicine, they were thought to be the desiderata by 
which dermic medicatidn could be accomplished ; but alas, like many 
a priori conclusions, the practical results, while in many instances very 
satisfactory, left in general much to be desired. 
The cause of this is possibly largely attributable to the fact that, so 
far, our oleates have been of a character scarcely entitling them to 
that name, for a solution of a metallic oxide in acid without a reaction 
or the presence of water cannot be considered a salt according to the 
present views of chemical knowledge. That they are oleic solutions 2 
and, as such, of therapeutic value is, however, not to be disputed, 
though even as such they are of indefinite strength, if we take the 
so-called oleate of mercury as example, for when the proper amount 
of mercuric oxide is added only a small quantity of it remains in 
solution while the greater part, especially if the acid is not pure, is 
very soon reduced to metallic mercury and, as such, precipitated. If 
such is the case with pure oleic acid, it certainly is much more so with 
the oleic acids found in the market, of which the greater portion is 
the oleo-stearic acid of the candlemakers, deprived of its coloring 
matter, while others are oleo-palmitic acids derived from either pre- 
cipitating olive-oil or almond-oil soaps. Either of them soon gives 
rise to heavy precipitates, as the oleic acid itself has a tendency to 
take up the oxygen of the oxide and reduce it to the metallic state. 
Oleic acid, if pure and freshly made, will keep considerable of the 
oxides in solution, but the very excess of oleic acid present is the 
cause of its gradual change and deterioration, and though the appear- 
ances of the preparation may be saved by repeated filtration, the result 
is very soon that of an oleate containing no metallic salt in solution. 
Actuated by the desire to prepare true oleates, and to obtain them 
by a cheaper method than the retrograde process of first making acid 
from a true oleate and then making a series of oleic solutions, led me to 
experiments of which I already spoke in one of our last year’s meet- 
ings. 
I have already mentioned the fact in my former paper on this sub- 
ject, that petroleum benzin was a ready solvent for oleates, while it 
appeared to be a non-solvent, or at least a very limited one at ordinary 
temperature, of palmitates and stearates. I had utilized this to sepa- 
rate the lead oleate from the lead palmitate in making oleic acid. 
That chemically true oleates could be made in the same way as the 
lead oleate in that process was an inference which could be readily 
drawn, but which proved practically of not much success. As soaps, 
however, could be readily decomposed by metallic salts into sodium or 
potassium salts and oleo-stearates or oleo-palmitates of the metals 
there was no difficulty in obtaining the joint salts which could be sep- 
arated in turn by the use of benzin. After conducting experiments 
on that subject, I found that this method of preparing oleo-stearates 
had been proposed in an article—translated from a French journal—in 
the “ Medical Times,” and reprinted in the “ American Journal of 
Pharmacy,” January, 1874, page 28. 3 
In order to obtain true oleates, I saponified pure oleic acid, prepared 
according to my method, as published in my former article, with 
caustic soda until saponification was complete, dissolved the sodium 
oleates so obtained in water and precipitated with metallic salts with 
the results of obtaining oleates that were stable and definite in char- 
acter, possessing besides therapeutic properties of which I satisfied 
myself by the experiments which some of my medical friends con- 
ducted in hospitals and dispensaries. As oleates prepared in this 
manner, however, possessed the disadvantage of a high price, I used 
consecutively soap of the oil of sweet almonds, and ultimately the 
ordinary castile soap, with quite as much success. 
My process in general for obtaining oleates is as follows: One part 
of castile soap (sodium oleo-palmitate) is dissolved in eight parts of 
water, the solution so obtained is allowed to cool and stand for 24 
hours, when there will be a considerable deposit of sodium palmitate, 
while the supernatant liquor, containing mostly sodium oleate, is 
drawn off* and then decomposed with a concentrated solution of a 
metallic salt which, if obtainable, should contain no free acid to pre- 
vent the formation of free oleo-palmitic acid. The heavy deposit of 
•oleo-palmitate so derived is strained off*, pressed out in the strainer 
and the adherent water evaporated in a water-bath; after this it is 
dissolved in about six to eight times its quantity of petroleum benzin 
and the insoluble palmitate is left to subside while the solution of 
oleate decanted therefrom is filtered off*. The benzin evaporated will 
yield an oleate that is entitled to that name, as it is a chemical com- 
bination and will remain stable and efficacious. 
The oleates, so prepared, present an amorphous appearance, while 
the palmitates are of a crystalline character. While I have noticed a 
marked affinity of some of the metallic salts for palmitic acid, the 
absence of it in others is remarkable. Thus, mercury, zinc, bismuth 
and lead combine with palmitic acid abundantly, but iron and 
copper seem to form an exception herefrom, and while the oleates of 
mercury, iron and copper seem to be desirable as therapeutic agents, 
the oleo-palmitates of zinc, bismuth and lead appear preferable. To 
take up each one. of the above-named alone, I would state that the 
oleo-palmitate of zinc is a pulverulent substance, imparting a greasy 
touch, not unlike that of powdered soapstone, and will readily dissolve 
in warm oils, cosmolin, etc., imparting to them a semi-diaphanous 
appearance on cooling. One part dissolved in five of cosmolin 4 
makes an ointment of zinc oleate, of which I have heard much 
praise in eczema and other dermic affections. Applied dry to excori- 
ated and erythematous surfaces it acts mechanically by relieving fric- 
tion, and by its astringent properties it helps to correct and heal the 
parts. It is prepared by precipitating the soap solution with zinc 
sulphate. 
The oleo-palmitate of bismuth is of an unctuous consistence, and I 
am advised has yielded very good results in chronic skin affections 
where an alterative action seems desirable. To prepare it the solution 
of soap was decomposed by a glycerin solution of the crystallized 
nitrate of bismuth. 
The oleo-palmitate of lead is nothing more than the lead plaster of 
old, but it is free from glycerin, beautifully white, and dissolved in 
olive oil makes a litharge ointment more elegant and quicker than the 
recently-proposed process of precipitating the hydrated oxide of lead 
from the basic lead acetate solution, and saponifying it with olive oil 
in the presence of water. It affords also a very excellent substitute 
for the old lead plaster, and can readily be made in a very short time 
at an expense not exceeding that of the old method. It is best pre- 
pared by precipitating the soap solution with the officinal solution of 
lead subacetate. 
The oleate of mercury is well-known for its therapeutic application, 
and I dwell on it no further than to state that it should be diluted 
with cosmolin, unless it is needed to make a marked mercurial impres- 
sion. -It should be prepared by precipitating the soap solution by a 
concentrated watery solution of mercuric chloride. The precipitate so- 
formed should be heated to the boiling point to insure its subsidence. 
It is then deprived of its water in a water-bath, dissolved in benzin 
and filtered, and the filtrate left to evaporate. 
The oleate of copper is as yet not used, but I should think would, if 
diluted with oil or cosmolin, make an excellent stimulant application 
to indolent ulcers, lupus, etc. The soap solution, precipitated with 
a solution of cupric sulphate, yields it readily. 
The oleate of iron lias as yet found no use, to my knowledge, though 
in the formulas proposed for ferrated codliver oil this is evidently' 
formed. That a definite quantity of it dissolved in codliver oil would 
serve quite as well, seems obvious, though its odor and taste is not 
encouraging. I have made it by precipitating the soap solution with a solution of ferrous sulphate, but found that from a ferrous the new- 
formed salt readily changed to the ferric state. 
I have still a number of other metallic salts under experimentation,, 
the results of which I intend to make the subject of another paper. 
While I do not consider that I have by far exhausted the research in 
the direction of these valuable therapeutic agents, I trust that I have 
re-awakened the interest therein which, from incompleteness, began to 
flag, and that hereafter the oleates will be considered rather as chemi- 
cally defined bodies than mere unstable solutions of metallic oxides in 
oleic acids. 
Philadelphia, October, 1881. 
5 FORMIC ACID AS AN ANTISEPTIC. 
L. Woeff, M.D. 
Read at the Meeting of the Pennsylvania Pharmaceutical Association, 
June 15, 1881. 
Query No. 13.—It has been asserted that “ formic acid ” is a powerful 
antiseptic. Can these claims be sustained by a series of experiments, test- 
ing it by comparison with thymol, carbolic acid and others? 
The answer to this query involves the consideration of the processes 
known as fermentation and putrefaction, which bring about such 
changes of organic compounds that their atomic relations as well as 
their chemical character are totally altered or destroyed. 
Agents destined to preserve them from these metamorphoses are 
termed, as a contradistinction of septic change, antiseptics. 
If we look at the septic process in organic bodies we always find 
two factors as conditions for its existence. The first, the passive, is the 
base, while the second is constituted as an exciting cause or foreign 
element in the process, and is termed the ferment. 
These ferments, although the object of speculation and observation 
of many able investigators and scientists are as yet not clearly under- 
stood as regards their intimate action on, or chemical relation to, fer- 
menting bases. While some are claimed to belong to the lowest type 7 
of animal life, others are distinctly vegetable in their existence. While 
they are again argued to be creations of extraneous influences, chemi- 
cal, atmospherical, electrical and otherwise, the reasons for conceiving 
them as part of the result of a process of oxidation are not to be 
rejected. That they are minute living organisms is certain, as is 
proved by their structure, development and proliferation. 
The presence of water and oxygen of the atmosphere are conditions, 
however, which are invariably necessary for the septic process, and on 
the exclusion of these several antiseptic proceedings are based. 
Little as the above remarks may seem to bear on the direct solution 
of our query, they will probably explain, to some extent, the action of 
the so-called antiseptics hereinafter mentioned. 
Antiseptics may be termed all such substances which, by their 
chemical or organic action, exercise a destructive influence on the low- 
est type of organic existence. That this is a peculiar and chemically 
not well explained process or function would result from the fact that 
such bodies acting destructively on animal and vegetable tissue and 
existence, are not always found to behave in this manner towards the 
minute spores and growths of microscopic organisms, while again 
valuable and powerful antiseptics have but a relatively unimportant 
elfect, if any whatever, on the higher developed animal or vegetable 
existence. 
Formic acid, the subject of consideration in this query, is repre- 
sented by the symbols HCH02, and occurs variously in nature, in 
ants (therefore its name) and some plants, but is best and most easily 
obtained by decomposing oxalic acid in presence of glycerin and water. 
It is a colorless liquid of 1’235 sp. gr., and produces violent irritation, 
and even vesication, if applied to the skin. Diluted with water, it 
proves less caustic. Internally, it acts as a gastro-intestinal irritant. 
Its principal therapeutical application is as a local irritant and rubefa- 
cient, but it is not employed internally for any corrective or curative 
purpose. It is not apparent what has caused its repute as an antisep- 
tic in the above sense of the word, for neither its chemical composi- 
tion and properties, nor its therapeutic action, would speak for this. 
As, however, the origin of many of our remedies and antiseptics has 
been obscure and purely empirical, their value as such can only be 
ascertained by a series of experiments, with a view of demonstrating 
this point comparatively with other agents of this class. These expe- 8 
rimer)ts, in order to be reliable, will have to be conducted simultane- 
ously, and under the same influences; for it is a fact to be well borne 
in mind, that these ferments exciting causes of organic changes are in 
their development and action subject to the influence of temperature, 
atmosphere and climate. While in cool and dry climates of moun- 
tain regions, as on our western high plateaus, organic decomposi- 
tion takes place very gradually, and is altogether impossible in 
the eternal ice of the Arctic, or at the boiling temperature, it 
goes on with astounding rapidity in the tropics, and their humid 
atmospheres. 
Owing to the difference of the processes of fermentation and 
putrefaction, and the different exciting causes thereof, antiseptics 
thus of service in the former would not necessarily be of use in the 
latter. 
The spores composing the fungi of yeast, variously termed toruhe 
cerevisue, saccharomyces cerevisue, or mycodenne, cryptococci, hor- 
miscii, etc., seem the true exciting causes of fermentation, and may 
require different antiseptics than those of other septic processes. 
To test these points, as well as to ascertain the comparative value of 
formic acid to arrest the action of these fungi, I diluted an aqueous 
extract of malt, containing glucose, dextrin and diastase, thus composed 
of all elements necessary for fermentation, largely with water, and 
exposed it in open vessels at a temperature of between 80° and 90°F., 
with the following results: 
One part extract of malt with four parts of water : 
Antiseptic. Time fermented in. 
None, . . . . .48 hours 
Glycerin, 20 drops, . . 7H hours 
Formic acid, 4 drops, . . .96 hours 
Boracic acid, 2 grains, . . . 108 hours 
Benzoic acid, 2 grains, . . .6 days 
Carbolic acid, 4 drops, . .10 days 
Thymol, 2 grains, . . . .2 weeks 
Salicylic acid, 2 grains, . . .18 days 
It will readily be seen from the above that whatever the anti- 
fermentive powers of formic acid are they are so feeble as to deserve 
no consideration as such. I would point to the fact that, recent 
writings to the contrary, which claim that pure salicylic acid, devoid 
of phenic acid, possessed no antiseptic properties, it is shown in 9 
this table, which presents the average of a series of 
that it proved itself superior to any and all, even to carbolic acid,, 
to the presence of which, as a contamination, its antiseptic properties 
were attributed. 
As putrid decomposition of organic bodies is due to different 
causes, largely of foreign influence, the antiseptics, to prevent this, 
should probably differ in their action on the factors exciting such 
decomposition. 
It is claimed for this septic process, and well illustrated by micro- 
scopic observations, that it is originated and effected through micro- 
coci in the atmosphere invading the substances and thus bringing 
about in an inexplicable manner their oxidation and decomposition.. 
These bacteria;, vibriones, zoogloes, monades, mycrocymas, and what- 
ever else they may be called, present the most primitive form of 
organic life, and it is the destructive effect on them by antiseptics 
which preserves organic bodies from chemical change and loss of char- 
acter and form. 
To examine an agent as to its utility as an antiputrid can only 
be accomplished by actual experiment, and for this purpose I have 
in this case selected as base that highly organized and susceptible sub- 
stance, approaching protoplasm in its arrangement and character, the 
white of egg. 
One part of white of egg was diluted with one part of water, and 
to it was added with results as below stated : 
Antiseptic. Time of Decomposition. 
4 drops of formic acid, . . .3d day 
20 drops of glycerin, . . . 4th day 
None, ..... 5th day 
2 grains boracic acid, . . . 9th day 
2 grains benzoic acid, . . 16th day 
2 grains salicylic acid, . . . 24th day 
4 drops carbolic acid, . . . 26th day 
2 grains thymol, .... 30tli day 
These experiments were conducted simultaneously, at the same 
temperature, and are again the average of a number of them. They 
clearly demonstrate that formic acid has not alone no antiputrid 
action, but it seems really to invite the averages of bacteria; and 
vibriones, thus causing a more rapid decomposition. The same may be 
said of glycerin, although it has antifermentive powers, which, in the 10 
quantities as used in the former experiments, were, however, of but 
little avail. 
As the results of the above and other original experiments, along 
with research in the literature of this subject, I would respectfully 
report to the Pennsylvania Pharmaceutical Association that formic 
acid is not possessed of properties entitling it to the asserted claims as 
an antiseptic, that it is only a feeble antifermentive and of no value 
whatever as an antiputrid agent. CASCARA SAGRADA. 
L. Wolff, M.D. 
Read at the Meeting of the Pennsylvania Pharmaceutical Association, 
June 15, 1881. 
Query No. 7.—What are the true therapeutic properties of Rhamnus 
purshiana so-called Cascara sagrada? It is recommended by some as an 
active cathartic, whilst others assert that it is a very mild laxative, and in 
order to increase its activity a certain amount of mandrake is added. 
Since the above query was accepted there have appeared at various 
times a number of essays in some of our journals, which tended to clear 
up many doubts on this subject. 
Before entering on the direct answer to the above query I would 
submit a few remarks condensed from a recent article in “ New 
Remedies ”: 
Rhamnus purshiana, D. C.—Rhamnus aliifolius, Pursh-Frangula 
purshiana, Cooper, the Cascara sagrada, or sacred bark, also Chittem 
bark of the Mexican settlers of California, is a small shrub of the 
natural order of Rhamnacese, indigenous to the western slope of the 
Rocky Mountains, ranging between the southern California and the 
British possessions. The bark is the principal part used in medicine, 
and has long been known as a mild cathartic to the Mexicans, the 
native inhabitants of California. It comes in curved pieces or quills, 
of divers lengths, from one-sixth to one-eighth inch in thickness. 
Externally, it is nearly smooth, gray,’ sometimes with whitish patches. 12 
The middle layer is brown- to reddish-brown, and the inner is light 
yellowish to light brown. It presents a smooth fracture, is colored 
red by potassa, is without odor, and imparts a bitter-sweetish, slightly 
astringent taste. 
The excellent analysis of Dr. A. B. Prescott (“ A. J. Ph.”) reveals: 
1st. A brown resin, sparingly soluble in water, readily soluble in 
stronger and dilute alcohol, of strong bitter taste, colored purple-red 
by potassium hydrate; this is mostly contained in the middle and inner 
layers. 
2d. A red resin, nearly tasteless, colored brown by potassium 
hydrate, insoluble in water, soluble in stronger and dilute alcohol; it 
is principally found in the outer layer. 
3d. A light yellow resin or neutral body, tasteless, not colored by 
potassium hydrate. It is soluble in hot, sparingly so in cold alcohol 
of seventy per cent. 
4th. A crystallizable body (possibly a product rather than educt), 
then tannic acid, oxalic acid, malic acid, fat oil, volatile oil, wax and 
starch. 
The resemblance of its composition and structure, as well as its 
proximate principles to that of the bark of Rhamnus frangula, even 
if the continued change of one of these bodies into another by glu- 
■cosic fermentation is conceded, seems to point to the close relation 
of these species, and shows the reason for their similar action. 
As to its therapeutic value, I have found it in a number of cases 
under observation quite similar to that of Rhamnus frangula, although 
the latter appears to be the more active of the two, and apt to occasion 
griping and nausea. 
That its laxative or cathartic effect is due to the resins contained 
therein will appear from the fact that the powder, after being thor- 
oughly exhausted by stronger alcohol, I have found to be utterly 
inert. 
Its physiological action is that of a stimulant to the mucous secre- 
tions of the intestines and colon. It imparts to the stomach and bow- 
els, when taken, a sensation of warmth. 
By its tonic effect on the muscular fibres of the intestines, and espe- 
cially on those of the colon, it relieves habitual constipation when due 
to a lack of peristaltic motion and atony of those fibres. Through its 
stimulant effect on the mucous surfaces of the intestines it acts also as 
a mild cholagogue. It increases slightly the secretion of urine, pro- 13 
duces in from four to six hours, without exciting the vascular tissue 
or nerve centres, a number of copious stools, improving the appetite 
thereby, without manifesting an instant effect on the stomach or intes- 
tines, or causing exhaustion. It seems well intended as an evacuant 
for subjects of sluggish portal circulation, and especially for the suffer- 
ers of hemorrhoidal troubles. 
While I have not been able to ascertain a probable change in the 
bark, as is well known to occur in the bark of Rhamnus frangula, for 
a year or two after being gathered, the inference by its close resem- 
blance to the latter would be in favor thereof, and thus probably the 
reports of the difference in the action of this drug, as enumerated in 
this query, may be accounted for. 
The dose in which it is employed as a laxative is a half fluidrachm 
of the alcoholic fluid extract; as a cathartic, from one to two flui- 
drachms. In comparison to this, I quote that the laxative dose of an 
alcoholic fluid extract of the one-year-old bark of Rhamnus frangula 
ought not to exceed twenty drops. A teaspoonful of such a prepa- 
ration will produce in some persons most violent and hydragogue 
catharsis. 
In answer to that part of the query, if an addition of mandrake 
would be necessary to increase its activity, I would state that such 
addition seems for that purpose unnecessary, although it may be 
useful in hepatic torpor, where a special impression on the biliary 
secretion seems desirable, and thus its cholagogue action is to be 
increased. 
I would close this answer by stating that, in my experience, and 
according to the observation of myself and a number of physicians 
who kindly furnished me with their data for this report, the bark 
of Rhamnus purshiana, popularly known as Cascara sagrada, is in 
smaller doses a useful mild laxative of some cholagogue action, and 
in larger doses decidedly cathartic; that also an admixture of man- 
drake or other substances to increase its cathartic action seems totally 
superfluous.