Chapter IX: Section 3: This Act shall not take effect until the first day of July, (6)
MAGANESE.—Some attention has lately been given, in France, to a variety of preparations of maganese. Maganese is commonly found associated with iron in minute quantities. It appears to be an invariable constituent of the blood, and in certain diseases, in which the iron, normally contained in that fluid, is deficient, the maganese would seem to be deficient in similar proportion. It is said that the preparations of maganese, given in connection with those of iron, in such diseases, produce effects which cannot be obtained from iron alone. Various formulæ have been offered for its administration. Commonly similar salts of the two articles, as the sulphate, lactate, carbonate, &c., are given together, the manganese being to the iron in the proportion of from 1/2 to 1/3. The subject would seem to deserve further inquiry.
☛OUR EXCHANGES.—Owing to a variety of circumstances, the Journal has not been forwarded with proper regularity to the Editors of the Journals in our own Country, with whom we would desire to exchange. Exchanges and books intended for us should be directed “TO THE EDITOR OF THE NEW YORK JOURNAL OF PHARMACY,” care of GEORGE D. COGGESHALL, 809 Broadway, or of T. B. MERRICK, No. 10 Gold Street. _Foreign Exchanges_ may be sent through the house of H. BAILLIERE, London, or J. B. BAILLERE, Paris.
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NEW YORK
JOURNAL OF PHARMACY.
JULY, 1852.
NOTES IN PHARMACY, No. 3.
EXTR. LIQ. CUBEBÆ.—The formula for this preparation, made officinal in the lately revised U. S. Pharmacopœia, appearing to me to afford rather an ethereal oil, than what may be properly called a fluid extract, I am induced to make known the process which I have been accustomed to adopt, during some years, to obtain what I conceive to be a true extract, containing, in an agreeably administrable form, all and the whole of the properties belonging to the berry, and which has given much satisfaction in practice, particularly to patients, some of whom who have had extensive experience in the use of anti-gonnorrhæl compounds, I have heard state that it is the only thing of the kind they had ever taken which was not disagreeable to the stomach. I take of
Pulv. Cubeb. crud. ℔i Ether. Sulph. Sp. Vin Rect. Aquæ Puræ āā q. s.
The coarsely powdered cubebs, being lightly packed in a displacement funnel, I pour upon it as much of a mixture of equal parts of ether and spirit of wine, as it will imbibe, and, having covered closely the top of the apparatus with moistened bladder, and corked the lower aperture, allow it to stand for twenty-four hours. I then uncork it, and after it has ceased {194} dropping, displace the remainder with Sp. Vin. Rect. until the original quantity (generally a pint,) be obtained; this I set aside in an open and shallow vessel to _evaporate spontaneously_, until all the ether, and most of the spirit has passed off, reducing the quantity to about one half. I then obtain, by displacement with diluted alcohol, another pint of the liquid, exposing it in the same manner, until three-fourths of the quantity is evaporated spontaneously as before; again another pint is obtained by displacement with water, (this will be a proof spirit tincture,) which is added to the former, and allowed to lose by the same means, about one-fourth, or sufficient to leave a resulting quantity of one and a half pints, which will contain about eight ounces of alcohol. The displacement with water is continued to exhaustion, when enough fluid will be obtained to raise the quantity, when added to that already prepared, to two and a half pints, which is transferred to a proper bottle, and there is dissolved in it sixteen ounces of white sugar, yielding, in toto, three pints of fluid extract, equal to one pound of the berries, one fʒi of which represents ℈j of the dry powder. The dregs, when dried, are destitute of sensible properties, appearing to be merely ligneous remains, and the loss in weight, when time is had, may be easily calculated and compared with the recorded analyses. The extract has the appearance of a somewhat thick, brownish colored liquid, possessing the peculiar taste and smell of the cubebs in a remarkable degree, remaining homogeneous for some time after agitation, and showing after settling a large proportion of the oleaginous constituents of the berry. Having aimed more at efficiency than beauty in this preparation, I claim for it the former rather than the latter, and if it should not invite the eye, it will be found very agreeable to the palate. Fluid extract of valerian may be prepared by the same process, and, indeed, all those of a volatile nature, whose active principles are soluble in any of the above menstrua.
UNG. AQUÆ ROSÆ.—The great trouble with this preparation is, that the water will separate from it after a time, giving it a {195} lachrymose and unhandsome appearance. This defect is completely remedied by using _only one half the quantity_ of Aq. Rosæ, by which a better consistence and much nicer preparation is obtained, and one more, in accordance with the soubriquet “Cold Cream,” which is given to it by the fair sex, for whose use, as a cosmetic, it is far superior to the _highly scented_, and irritating fancy article of the same name. It is also an admirable unirritating, cooling, dressing for surgical use; but I would remark, _en passant_, that it is a very unfit medium for the composition of ointments, for which purpose it is sometimes prescribed to the annoyance of the apothecary. In such cases the physician should be apprised that the addition of a drop of oil of rose to simple cerate would answer his purpose much better, as the odor only is the quality desired. I think the above note might not be undeserving the attention of the next revisers of the Pharmacopœias.
UNG. PERUVIAN. It is sometimes difficult to make this ointment smooth, as, though readily miscible at first, continued trituration causes the balsam to separate, and like the colored person who “the more he was called, the more he would not come,” the more it is rubbed, the more it separates. This hostility to union is readily overcome by the addition of ten drops or so of alcohol for each drachm of the balsam. It is perhaps unnecessary to state that this difficulty will not be had when the balsam is adulterated with alcohol—a good practical test of the purity of the article.
PHARMACEUTICAL ETHICS.—Morality being at present in the ascendant, as it should always be, it may not be inappropriate, though more important than practical, to “make a note” of some fashionable practices prevalent amongst the more ostentatious pharmaceutists of the day, savoring much more strongly of “Quackery,” to use a vulgar phrase, than Art Unions, &c. are pronounced by legal wisdom to do of the “Lottery.” I allude, for example, to the system of _getting up_, under some mystified appellation, certain preparations, as “Brown’s Elixir,” “White’s Essence,” or “Black’s Compound,”—something or {196} other, which are merely the ordinary preparations of the shop, or could easily be prepared if they were worth the trouble, but under _assumed names_, are heralded forth at the _ne plus ultra_ of pharmaceutical perfectibility. I do not envy a reputation so acquired, nor do I wish to speak of it in that spirit, but to point out its inconsistency with correct principles, and designate it as unworthy of honorable ambition. Such preparations generally “hail” from some obscure place or person, but are occasionally dabbled with by others who should give themselves to better things. It is self evident, from the nature of his calling, that the exclusive duty of the apothecary _per se_, is to make, as faithfully or skilfully as he may, the various preparations of the Pharmacopœia, as therein set down, when he is called upon to do so, and to compound accurately the prescriptions of the physician. If, by long experience or increased skill, he may have been led to any real discovery or improvement, the minutiæ of which he does not choose to divulge, (the reverse of which would be the more generous,) its nature should be stated, when relating to a preparation, in terms distinct enough at least, to convey an idea of its real composition and medical properties: thus tinctures should not be misnamed Essences or Extracts; Fluid Extracts, or Concentrated Infusions, Elixirs; Syrups, Panaceas, &c. thus avoiding the inconsistency of condemning, if not morally, at least _constitutionally_, the more open mountebank who plunders your pockets, while the beam is in your own eye. It is also perhaps worthy of remark that the necessity does not appear any longer to exist of retaining those prescriptively excellent preparations made by some, no doubt, very respectable apothecary in London, claiming, with a dozen others, to be the sole possessor of the original receipt. They are imported at a very high price, and as the composition of most, perhaps all, is, or can be known, might be made by any apothecary here as well as in London. Some of them might be deserving of adoption into the Pharmacopœia, as have been Dover’s Powder, Daffy’s Elixir, &c. already. It is said by connoisseurs in wines, that madeira is very much improved by {197} crossing the line; but I am not aware that pharmaceutical preparations are at all benefitted by crossing the ocean. Their _genuineness_, too, has become a by-word. By the way, I was gravely informed by a certain importer, the other day, of whom I enquired concerning one of these _genuine_ articles, that it was obtained directly from the inventor. I was at a loss to imagine the “modus transitûs,” nor had I the hardihood to enquire, the good man having been gathered to his fathers scores of years ago.
Various are the unworthy practices, one or two of which are thus curtly alluded to, deserving of a more studied notice and severe censure, than I am able or willing to give them. Such matters, though not exactly “putting money in the purse,” should be attended to. The purging of our profession—for it is one—of them, would be a highly meritorious service.
CHLORIC ETHER.
BY J. F. HOLTON, PROFESSOR OF BOTANY IN THE NEW YORK COLLEGE OF PHARMACY.
In the early part of this century, some chemists in Holland found a peculiar oily fluid of very fragrant smell, resulted from the action of chlorine on Olefiant gas. It is generally known as the Dutch liquid; it has been called also chloric ether and bichloric ether. Its composition is C‗{4} H‗{2} O‗{2}.
In 1831, Mr. Samuel Guthrie of Sackets Harbor, in this State, distilled alcohol from the so called chloride of lime, and obtained a product so closely resembling the Dutch liquid that he though it identical. From some relations to formic acid, it was afterwards called Chloroform, and chloroformid. Its composition is C‗{4} HO‗{3}. In 1847, anaésthetic properties brought {198} chloroform prominently before the public. We find an article by Prof. B. Silliman, Jr., in the American Journal of Science, new series, vol., 5, p. 240, in which it is stated that “the terms chloric ether, bichloric ether, perchloride of formyle, Dutch oil and oil of Dutch chemists, are all synonyms of chloroform.”
In a recent visit of the writer at New Haven he saw a prescription of “chloric ether.” Being reminded of the singular error in the Journal printed there, he inquired into the nature of the article dispensed. It proved to be a solution of chloroform in alcohol, and on his return to this city he found the same practice here to a small extent. The proportions in the article bearing this name vary greatly; often it seems that the mere contents of the wash-bottle are in this way disposed of, containing of course a large proportion of water. Mr. Currie, one of our most careful and consciencious chemists, usually prepares it so as to contain 10 per cent. in bulk of chloroform. A more convenient formula would be, chloroform 1 part, alcohol 10 parts. Some such article under the name of Tinctura Chloroformi ought to have place in our pharmacopœia.
But to our confusion the term chloric ether is applied to yet another, and entirely a different body, formed by the distillation of alcohol and hydrochloric acid, the composition of which is C‗{4} H‗{5} O. This is also called hydrochloric ether and muriatic ether.
But to neither of these four substances does the name chloric ether properly belong. Were there such a thing, it would be obtained from the action of chloric acid on alcohol, a reaction which is prevented by the decomposition of the chloric acid by the alcohol, to which it gives part of its oxygen, forming acetic acid.
This subject is not of so much importance intrinsically as it is by way of illustrating the extreme importance of rigid adhesion to systematic nomenclature as the only means of saving us from dangerous errors and inextricable confusion.
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ON THE PREPARATION OF PURE MAGNESIA.
BY HENRY WURTZ, M. A.
The preparation of few substances presents such difficulties as that of _Pure Magnesia_.
It seems, however, at first glance, that the cheapness and general purity of the sulphate which occurs in commerce, would render this an easy task. Unfortunately, however, no simple process has yet been proposed for obtaining pure magnesia from the sulphate. The usual course is to precipitate from the boiling solution with carbonate of soda, and to expel the carbonic acid from the magnesia alba thus obtained, by ignition. On trying this process, however, it was found that the carbonate of magnesia thus precipitated could not be freed from soda by washing. After an enormous quantity of hot distilled water had passed through it on the filter, the slight residue left by evaporation of the washings, still gave the soda tinge to flame.
It is true that the trace of the soda compound thus retained might probably be washed out of the magnesia after its ignition, but the difficulty and tedium of the operation of washing the very voluminous precipitate, together with the expense attendant upon the necessity of using _pure_ carbonate of soda, to avoid the presence of silica, phosphoric acid, and other impurities, which, if present, would inevitably contaminate the magnesia, induced me to reject this method. In fact this method, which was formerly almost used universally by analysts for the _determination_ of magnesia is now rejected by them, except in some unavoidable cases.[16]
[16] _H. Ross’s Handbuch_, last edition, 2, 33.
The substitution of carbonate of ammonia for carbonate of soda is inadmissible with any regard to economy, on account of the existence of the soluble double sulphates of ammonia and magnesia. A trial was made to decompose sulphate of magnesia by mixing its anhydrous powder with a large quantity of carbonate of ammonia, and igniting, but the only trace of {200} decomposition which appeared was a slight alkaline re-action of the aqueous solution of the mass.
I must here mention an impurity which I have met with in commercial sulphate of magnesia, and this is a double sulphate of magnesia and potash, which occurs in small crystals, apparently rhombohedrons, among the rectangular prisms of the Epsom salt. It may probably be separable by recrystallization, though this, with sulphate of magnesia, is rather a difficult affair.
The method which I adopted for preparing pure magnesia was the ignition of the nitrate prepared from the commercial _magnesia alba_. The impurities in the commercial carbonate which I made use of were sulphate and chloride, a surprisingly large quantity of silica, a trace of phosphoric acid easily detectable by molybdate of ammonia, oxide of iron, alumina, lime, alkalies and some organic matter. A small excess of this impure article was added to commercial nitric acid and the whole boiled; the silica, oxide of iron, alumina and phosphoric acid were thus separated by the excess of magnesia and the filtered solution contained no trace of either of them; the solution was slightly colored by organic matter.
Either of two methods may now be adopted for separating the _lime_.
One is to add a late excess of ammonia, then a little oxalic acid, and filter. To this method, besides the expense of so large a quantity of _pure_ ammonia the necessity of the subsequent decomposition and expulsion by heat of the very large quantity of nitrate of ammonia formed is a serious objection.
Unsuccessful attempts were made to separate the lime by adding oxalic acid immediately to the neutral solution of nitrate of magnesia. It was found upon experiment that oxalate of lime is somewhat soluble in a solution of nitrate of magnesia.
The other method, which is preferable, consists in adding to the solution a little sulphate of magnesia, and then a quantity of alcohol, but not enough of the latter to produce any immediate precipitation. If a precipitate is formed immediately, {201} water is added, for, singularly enough, it was found that the liquid filtered from this first precipitate still contained lime. In the course of time the sulphate of lime separates in the form of small crystals.
The filtered liquid is now evaporated in porcelain dishes, and the residue transferred to porcelain crucibles, or still better, to platinum dishes, and the nitric acid expelled by a gentle heat. By a slight modification I have succeeded in shortening this operation very much, that is by adding, from time to time, powdered carbonate of ammonia to the mass, and stirring with a glass rod, or a platinum spatula. When no more red gases are evolved the heat is raised to redness for a few minutes. The mass thus obtained requires washing with pure water to separate alkaline salts and some sulphate of magnesia which it still contains.
Magnesia thus prepared was found, by a most rigid qualitative analysis, to be perfectly pure. I am aware, however, that the process is a troublesome one, and it is very much to be desired that some one would present us with a simple and direct process of obtaining pure magnesia from the sulphate.
ON TINCTURE OF IPECACUANHA.
BY G. F. LEROY, OF BRUSSELS.
Officinal preparations during reposition or preservation, when placed in situations proper to preserve them from all changes, yet undergo such important modifications, that the pharmaceutist is frequently obliged to reject them as worthless. We are accustomed to consider alcoholic tinctures, by reason of the vehicle used in their preparation, as amongst the most stable of officinal preparations; and therefore very few {202} pharmacologists have observed the changes they undergo. Amongst those whose attention has been drawn to the subject, I may particularly cite: 1st, Baumé, who has remarked that tincture of saffron deposits a substance analagous to amber.—(_Elements of Pharmacy_, 2d _ed._ 1789.)
2nd. Guibourt, who presented to the Academy of Medicine at Paris, some observations on the changes in its composition which tincture of iodine undergoes according to the time when it was prepared, (year 1846.)
3rd. Bastick, with the desire of ascertaining the nature of the changes to which alcoholic preparations are subject, placed various tinctures, during several months, in situations similar to those of a pharmacy, that is to say, exposed to a temperature varying from 60° to 80° Fahrenheit, in bottles half filled, and to which air was, from time to time, admitted.
On examining them, some time afterwards, he found that most of them had undergone active fermentation in a greater or less degree, and that the alcohol had gradually become converted into acetic acid. The tinctures had generally lost their color and taste, and contained _a precipitate which was partially re-soluble_ in a proportion of alcohol corresponding to that which had been decomposed.—(_Pharmaceutical Journal and Transactions_, 1848.)
The tinctures prepared with weak alcohol are the most subject to this species of change.
4th. Tincture of kino changes so with time, that it passes from the liquid to the gelatinized state. This change even affords an excellent test when it is suspected that catechu may have been substituted for kino in this preparation.—(_Dorvault, Officine_, 1850, 3d. ed.)
In general, pharmacologists consider that tinctures only deteriorate by the evaporation of the alcohol used in their preparation, and that this evaporation has the effect of concentrating them too much, and of giving rise to the precipitation of a part of the principles which were held in solution.
I do not entirely concur in this opinion; on the contrary, I {203} believe that, in many cases, the precipitates which are formed in the tinctures, do not arise from the evaporation of a part of the vehicle, but from a modification which takes place in a part of the principles held in solution, and which, becoming less soluble, or even insoluble, are precipitated.
Amongst these precipitates I shall place that which is almost uniformly found in tincture of ipecacuanha.
Druggists generally are aware that this tincture, shortly after its preparation, throws down a deposite of a yellowish white color, very light, and increasing daily; that when separated by filtration a new deposit immediately commences, and recourse must again be had to filtering.
It is only after three or four filterings, at intervals of five or six weeks, that the formation of this deposit can be arrested. In the course of July of this year, I prepared from the _Belgian Pharmacopœia_, some tincture of ipecacuanha, to be used in the preparation of some syrup of the same.
Desiring to follow the different phases which it presents, and to study, as far as possible, the nature of the precipitate formed in it, (for as yet I believe that no research has been directed to this subject.) I took advantage of the opportunity which this preparation afforded me.
About six weeks after its preparation, this tincture contained a deposit which was yellowish white, tolerably abundant, very light, and rising on being shaken.
I again suffered the precipitate to form, and after some days, I decanted the clear liquor, and threw the deposit on a filter. I afterwards mixed the decanted liquors and that which was filtered, in a bottle.
The precipitate remaining on the filter, I repeatedly washed. I put it to dry spontaneously, but perceiving, after twenty-four hours, that it was becoming the prey of a number of little cryptogami, formed in the same manner as in animal gelatine which dries slowly in the air, I hastened the desication by carrying the filter into a medium of from 30° to 35° centigrade. {204}
This deposit, during the process of drying, loses its hydrogen, changes color, becoming reddish brown, and is slightly translucid, when very dry it is friable.
The quantity obtained in this first filtering, weighed 5 grains of the Netherland weights, or 0,3250 milligrammes; from an ounce or 32 grammes of roots, employed towards the end of October, I again saved the deposit which was formed: it weighed 1 grain, Netherland, or 0,065 milligrammes.
At present, at the end of November, a third deposition is taking place, and will be collected to be added to the others.
During the whole time the tincture had no effect either upon blue or red litmus paper.
_Physical properties._ The precipitate is solid, friable, of a reddish color, slightly translucent, without taste.
_Chemical properties._ Ether, alcohol, water, cold or boiling, have no action upon it; dilute hydrochloric, sulphuric and nitric acids, have no action when cold. Concentrated nitric acid, when cold, produces no effect upon it, but if heated to ebullition it attacks it actively, becoming of a brownish red color. Put in a glass tube closed by one only of its extremities, the other being furnished with two pieces of litmus paper, the one becomes blue, the other red. If the tube is placed in the flame of a spirit lamp, in a few instants the matter swells and the reddened paper becomes again blue.
Placed on a slip of platina, and exposed to the flame of a spirit lamp, it swells, giving out a strong odor of burnt animal matter; it burns without flame and leaves a white ash. This ash treated by reagents, has the characteristics of lime.
As may be seen by this short exposition, the deposit is by no means a product resulting from the evaporation of a part of the alcohol, which holds in solution the principles that are deposited, but a particular organic matter united to lime, which is formed at the expense of the azotized principle contained in the roots of the ipecac. What is the azotised principle which concurs in the formation of this substance? Certainly it is not one {205} of those which are commonly met with in vegetables, otherwise the phenomenon which is observed in the tincture of ipecac would be observed in the tinctures made with the other roots. Is it the emetine which is decomposed? If that be the case, the tincture of ipecac would be considered rightly an uncertain preparation.
From the character assigned by M. Willigh to his ipecacuan acid, as well as to the tribasic salt of lead, (Journal de Chimie et de Pharmacie, Octobre, 1851,) it will be readily understood, how I at first thought, without, however, having made any serious researches, that it might be this acid united with the lime, to which the precipitate was owing. But the analysis made by that chemist, which denotes the absence of nitrogen in its composition, does not permit us to entertain this idea.
As will readily be perceived, my researches are far from complete, as I had not a sufficient quantity of the precipitate at my disposition. But while waiting to complete them, I did not wish to delay acquainting the learned world with a fact which appears to me extraordinary and until now unique, and at the same time to call to it the attention of those better situated than myself to pursue such researches.—_Presse Medicale Belge._
ON THE MODE OF ASCERTAINING THE PURITY OF ESSENTIAL OIL OF BITTER ALMONDS.
Mr. Redwood laid before the meeting some samples of _oil of bitter almonds_, prepared by different makers, together with the results of experiments he had made with the view of ascertaining whether or not they had been subjected to adulteration.
He stated, that his attention had been directed to the subject by more than one of the dealers in this article, in consequence of its having been represented that some of the samples had {206} been adulterated with alcohol, an inference which had been drawn from the fact that the suspected samples had a much lower specific gravity than others met with in commerce.
He had been furnished with five samples from different makers, the specific gravities of which were as follows:―
1. 1052.4 2. 1055.2 3. 1067. 4. 1081. 5. 1082.2
The merchants having no better mode of testing the quality of this oil than by its flavor, its specific gravity, and other physical characters, it was important to ascertain what reliance could be placed on this class of observations. It was well known that spirit was sometimes mixed with it, the effect of which would be to reduce its specific gravity, and this addition, to the extent to which it would be likely to be made, would not impair the flavor of the oil, or alter its sensible characters in any other way than is above stated. The light oils were, therefore, very naturally suspected to have been reduced with alcohol.
The experiments he had made in reference to this subject had fully satisfied him that the specific gravity of essential oil of bitter almonds, within certain limits, could not be relied on as affording evidence of purity or adulteration. The specimens on the table, to which he had already referred, although differing in specific gravity to the extent of nearly thirty grains in the thousand grain-measures, he believed to be all free from adulteration.
Before describing the tests which he had found to afford the most satisfactory indications, he described the proximate constituents of the crude oil, which vary considerably in proportion in different samples, and hence the differences in density and in some of the properties of the oil.
According to Liebig and Gregory, crude oil of bitter almonds consists of _hyduret of benzoyle_, _hydrocyanic acid_, _benzoic acid_, and _benzoine_, and these probably are not its only constituents. Of these the two first may be said to be essential constituents, and the others accidental, being the result of changes which {207} the hyduret of benzoyle, or true oil of bitter almonds, undergoes.
The _hyduret of benzoyle_ has the ordinary characters of an essential oil. When pure it is a colorless, transparent liquid, the specific gravity of which is 1043. It possesses the peculiar almond flavor, and is not poisonous. This, which is the true oil of bitter almonds, ought to constitute about eighty-five or ninety per cent. of the crude oil. When oil of vitriol is added to pure hyduret of benzoyle the mixture acquires a dark reddish brown color, but no other visible change takes place.
If the hyduret of benzoyle be exposed to the air it speedily becomes oxidized, and by the substitution of an atom of oxygen for one of hydrogen it is converted into benzoic acid. The _benzoic acid_ present in oil of bitter almonds is the result of this transformation, and sometimes it occurs to such an extent that it is deposited from the oil in crystals. Benzoic acid is not colored by the action of oil of vitriol.
_Benzoine_ is also a product of a remarkable change which hyduret of benzoyle, when mixed with hydrocyanic acid, is liable to undergo. Like benzoic acid, it is a solid crystalline body, but unlike benzoic acid, when mixed with oil of vitriol, it forms a violet colored compound.
The characters and properties of _hydrocyanic acid_ are too well known to require notice. It is this constituent, which is sometimes present to the extent of eight or ten per cent., that gives to oil of bitter almonds its poisonous properties.
In examining oil of bitter almonds, with the view of determining whether it be pure or not, it is necessary to consider the influence on the action of the reagents employed, of variations in the number and proportions of the several constituents present. This is especially the case with reference to the use of oil of vitriol as a test.
On adding _oil of vitriol_ to the samples of oil under notice, it was found that it formed with all of them a clear but very dark colored mature, from which no separation took place. The color of the mixture thus produced, however, differed to a {208} greater or less extent in each case. The lightest of the oils produced a reddish-brown color, similar to that afforded by pure hyduret of benzoyle, while the heaviest oil formed a bright red mixture, having a shade of violet, and those of intermediate density gave intermediate shades of color.
These results, viewed in connection with the differences of density in the different specimens, were at first thought to indicate that the light specimens had some admixture foreign to the oil, but on examining the action of the test on pure hyduret of benzoyle and the other legitimate constituents of the crude oil, it was evident that such an inference could not be justly drawn, and, indeed, suspicion now seemed rather to attach to the heavy oil. Subsequent experiments, however, showed that the light oil distils at a lower temperature than the heavy, and that if the heaviest specimens were distilled with water, the first portions that passed over produced precisely the same reaction as the light specimens above referred to, while the last portions that passed over, and especially the oil obtained from the water by distilling it, after saturating it with common salt, produced with oil of vitriol a splendid crimson color, the purity and intensity of which could hardly be surpassed.
It thus became pretty evident that the differences in the reaction of oil of vitriol with the different specimens of oil under notice, arose from variations in the circumstances under which the oils were distilled, and it seemed probable that the heavy oil had been obtained by distilling the almond cake with water, to which a large quantity of salt had been added, so as to raise the point of ebullition, while the light oil either was the product of a process in which less salt had been added to the water, or consisted of the first portions distilled.
In order to obtain more satisfactory evidence of the absence of spirit, or other foreign substance, from these samples of oil, _nitric acid_ was used as a test. If oil of bitter almonds be mixed with about twice its volume of nitric acid, of specific gravity 1.420, no immediate action occurs. The greater part of the oil floats over the surface of the acid, and, if the former be free {209} from adulteration, no change of color takes place within several hours in either; but after the lapse of three or four days crystals of benzoic acid will begin to be formed from the oxidation of the hyduret of benzoyle by the nitric acid, and these will increase in quantity until the whole becomes a solid mass of crystals, which will gradually assume a bright emerald green color. This reaction is very characteristic. If spirit be present in the oil to the extent of eight or ten per cent., the acid, after a few minutes, will begin to react upon this, and a violent effervescence will shortly ensue, accompanied by the disengagement of nitrous vapors.
By using strong nitric acid, of specific gravity not less than 1.5, the presence of a very minute quantity of spirit may be detected. The pure oil, when mixed with an equal volume of this strong acid, forms a clear and uniform mixture, from which nothing separates, and which undergoes but a very slight change of color and no other visible alteration. The presence of two or three per cent. of spirit, however, is sufficient to cause a violent reaction and the disengagement of nitrous vapors.
After trying several other reagents, the foregoing were those which were found to afford the most satisfactory results, and appeared to be conclusive with regard to those adulterations, likely to be practised.—_Pharmaceutical Journal, London._
ON HOFFMAN’S ANODYNE LIQUOR.
BY WILLIAM PROCTER, JR.
Perhaps in no preparation in general use does the practice of manufacturers, and the requirements of pharmacopœial authorities, more widely differ than in the compound spirit of {210} ether, universally known as Hoffman’s Anodyne Liquor. According to the United States and London Pharmacopœias it consists of three fluid drachms of heavy oil of wine (Oleum Ethereum, U. S. P.) dissolved in a mixture of eight fluid ounces of ether and sixteen fluid ounces of alcohol. The Edinburgh Pharmacopœia has only the simple spirit of ether, without the oil of wine, whilst the Dublin Pharmacopœia of 1850 under the name of Spiritus Æthereus Oleosus, gives the following formula, which includes the preparation of the oil of wine and its subsequent solution, to make the anodyne:—Mix a pint of alcohol and a pint and a half of oil of vitriol in a glass matrass, adapt a Liebig’s condenser, and by heat distil until a black froth rises. Separate the lighter etherial liquid in the receiver, expose it for 24 hours in a capsule, wash the residual oil with water, and dissolve it in a mixture of five fluid ounces of ether, and ten fluid ounces of alcohol. In France, Hoffman’s anodyne consists of equal parts of ether and alcohol, without oil of wine.
Owing to the careless or intentionally mystified manner of expressing himself, it is impossible now to ascertain whether the original preparation of Hoffman (published in 1732) was constant in its strength, as now recommended by the Pharmacopœia. Beaumé, (as quoted in Macquer’s Chem. Dict., London, 1771,) says, in speaking of the rectification of sulphuric ether, “By distilling the liquor in the first receiver, together with a very small quantity of oil of tartar, by a very gentle heat of a lamp furnace, about two pounds and four ounces of pure ether may be obtained; and afterwards, when a new receiver is adapted, and a stronger heat applied, from eight to ten ounces of aromatic liquor, which makes a good _anodyne mineral liquor of Hoffman_, will be distilled.”
The third edition of Lewis’ Dispensatory, published at Dublin, 1768, has the following formula for this preparation, which appears to be what the apothecaries of that day employed:―
“_Hoffman’s Mineral Anodyne Liquor._”
Into half a pound of concentrated oil of vitriol, placed in a {211} large glass retort, pour by little and little, through a long stemmed funnel, one pint and a half of highly rectified spirit of wine. Stop the mouth of the retort, digest for some days, and then distil with a very gentle heat. At first a fragrant spirit of wine will arise; and after it a more fragrant volatile spirit, to be caught in a fresh receiver. The receiver being again changed, a sulphurous, volatile, acid phlegm comes over, and at length a _sweet oil of vitriol_, which should be immediately separated, lest it be absorbed by the phlegm. Mix the first and second spirits together, and in [every] two ounces of this mixture dissolve twelve drops of the sweet oil. If the liquor has any sulphurous smell, re-distil it from a little salt of tartar.
“Whether this is the exact preparation, so much recommended and so often prescribed by Hoffman as an anodyne and anti-spasmodic, we cannot determine. We learn from his own writings that his anodyne liquor was composed of the dulcified spirit of vitriol, [crude ether] and the aromatic oil which rises after it; but not in what proportions he mixed them together. The College of Wirtemburg seems to think that all the oil was mixed with all the spirit obtained in one operation without regard to the precise quantities.”
The product of this recipe must have been analogous to the present officinal spirit, the formula for which is evidently modeled after it. The great excess of alcohol distills over first, until the boiling point rises to the ether producing temperature, when ether is obtained, and finally the sulphurous oily product. The recipe gives no direction to isolate the oil of wine before measuring it, which is perhaps less necessary, as the ethereal part of the distillate is removed previously to the production of the oil which is found in the receiver in globules, and not in solution.
The process now adopted by the manufacturers in this city, avoids the isolation of the oil of wine, and from the nature of the conditions the product is liable to vary in the proportions of its ingredients, not only in different laboratories, but at different operations in the same laboratory. In the preparation of ether it is usual in this city to push the process as far as {212} possible, as long as the residue is not so concentrated as to eliminate much permanent gas. In the rectification of this first crude product, the distillate is reserved as rectified ether as long as its specific gravity marks 54° Beaumé, or there about. By continuing the process the product is found to consist of ether, alcohol and water, impregnated with oil of wine. Every one who has made ether, knows how very liable the product is to vary with an ill regulated heat; on the one hand unaltered alcohol will pass over, if the temperature is too low, whilst too great a heat, especially towards the last of the process, will favor the formation of oil of wine and sulphurous acid. This last distillate, therefore, will vary in composition, and it is from this that Hoffman’s anodyne is made in some of the best of our laboratories. _There is no known practicable method of ascertaining the per centage of heavy oil of wine in this liquid._ The means used by the manufacturer are founded on the sensible properties of an arbitrary standard specimen of Hoffman’s anodyne previously made, and on the degree of opalesence or milkiness it produces when added to a certain measure of water.—This milkiness is occasioned by the oil of wine present; but experience has shown that the degree of milkiness is not strictly in proportion to the quantity of oil present, the relative proportion of ether and alcohol, and perhaps water present in the anodyne liquid has a marked influence on the phenomenon; if too much alcohol, the milkiness is not produced, or but partially; if too much ether, oily globules separate and float with but moderate opalescence. In converting this second etherial distillate into commercial Hoffman’s anodyne, the operator has to make several essays, sometimes adding water, sometimes alcohol or ether, until the taste, the smell, and the opalescence agree, as nearly as can be approached, with his standard specimen. In the process of rectification it is probable that at least a part of the heavy oil of wine is decomposed, with the production of the light oil or etherole, and that the commercial Hoffman’s anodyne differs in this respect, as well as in containing a much smaller proportion of oil of wine, from that of the Pharmacopœia. {213}
To get a better idea of the preparation in use here, authentic specimens were obtained from four of our largest manufacturing chemists, and compared with compound spirit of ether made for the occasion strictly according to the United States Pharmacopœia. Their density was carefully taken with the 1000 grs. bottle.
specific gravity at 60° F. A, Wetherill & Brothers, .8925 B, Smith, Pemberton & Co. .8723 C, Rosengarten & Dennis, .8495 D, Powers & Weightman, .8394 E, U. S. Pharmacopœia .8151
Equal measures of each specimen and distilled water were mixed together; they all produced opaque milky liquids; globules of oil of wine soon separated from the mixture with E, and floated on the surface, while the liquid gradually lost its opacity as more of the oil arose. The mixture with D became less opaque by standing, a small portion of oil rising to the surface. The mixture with A, B and C retained their opacity without apparent separation of oil of wine, A being the most so.
A was the mildest and least repulsive to the taste, because least ethereal. C was the next least ethereal, but had pungency not arising from ether. B was more ethereal than the preceding, notwithstanding its greater specific gravity. D was yet more charged with ether. E presented sensible properties differing from all the others, being more etherial and aromatic, but without a peculiar taste noticeable in the other specimens, more especially in C.
When 2 1/2 fluid drachms of each specimen was shaken in graduated tubes with 60 grains of carbonate of potassa, they were de-hydrated somewhat in the ratio of their specific gravities. A and B dissolved the salt readily by a few minutes’ agitation, and the separated aqueous alkaline solution equalled a third of the bulk of the mixture. In C and D only about half of the salt was dissolved, whilst in E the salt was merely rendered pasty.
To get an idea of the proportion of ether present in these {214} specimens, a solution of dry chloride of calcium in an equal weight of water, was made. Five parts of this solution was mixed with three parts of each of specimens of Hoffman’s anodyne, in tall tubular vials, corked, well agitated and allowed to stand for twelve hours. In A, B and C, no separation of ether occurred, but in each of them a few globules arose to the surface, consisting chiefly of light oil of wine. In D a stratum of ether holding oil of wine in solution, equal to one seventh of the bulk of the spirit used, or nearly half a part. Whilst in E the super-stratum of ether equalled one-third of the spirit used, and had a light yellow color, due to the oil of wine.
These data will give an approximative idea of their compositions; it would appear that A was chiefly alcohol and water, with but little ether; that B contained almost as much water as A, but less alcohol and more ether; that C contained much less water than A or B, but less ether and more alcohol than B, and more ether and less alcohol than A; that D contained rather more water than C, but more ether and less alcohol than either of the preceding; and lastly that E contains more ether, and less alcohol and water than either of the others.
In regard to the proportion of ethereal oil, the experiments give no positive clue. It would appear that B and D contained the most among the commercial specimens, and that D approaches nearest the composition of the officinal spirit, yet all of them when compared with the officinal are deficient in this ingredient.
It must be apparent from these results, that the opacity of a mixture of Hoffman’s anodyne and water, is no index of the proportion of oil of wine the former contains, that property being dependent apparently on the state of combination in which the oil exists, nor would we pronounce on the medicinal value of the specimens, a task belonging to the physician. Whatever curative reputation the compound spirit of ether may have earned, certainly belongs to the commercial spirit, and not to that of the Pharmacopœia, which is not to be had in the shops.
The exact nature of the liquid left after the rectification of {215} ether is an inquiry well worthy of further investigation. The alcohol of commerce is not a homogenous substance. Besides water, it contains odoriferous oily matter, produced in the original fermentation, and which is not wholly removed in the rectification of whiskey. This matter, modified by the action of sulphuric acid and heat, with the volatile substances generated during the ether process, are contained in it. It may also be that the ether in this residue is more intimately combined with water than in a mere mixture of water, alcohol, and ether of the same strength, as suggested to me by Mr. Pemberton.
The question very naturally arises, why do not the manufacturers prepare the officinal Hoffman’s anodyne, or why do they not furnish the ethereal oil of the Pharmacopœia, that the apothecary may make it himself by simple mixing? There are several reasons. 1st, the apothecary, the physician, and to a large extent the consumer, have become accustomed to the present commercial preparation, and the majority, both of apothecaries and physicians, would reject the true officinal spirit, if presented to them, as not correctly made; 2d, druggists, as a general rule, would refuse to pay the greatly increased price, absolutely required to remunerate the manufacturer, for the greater consumption of time and materials, and increased skill and risk in manipulation. Having, on several occasions, prepared the officinal oil of wine and Hoffman’s anodyne, I can corroborate the statements of Mr. Kent, at p. 255, relative to the small yield, and consequent costliness of officinal heavy oil of wine. The so-called oil of wine, which is imported into this city from England, and which is sometimes employed for making the officinal spirit, is an ethereal solution of etherole, one specimen yielding only seven per cent. of it. And 3d, in the preparation of ether, the residue left in the still after the rectification of the ether above 54° Beaumé, must either be thrown away, or converted to the only use to which it can be applied with advantage, viz., Hoffman’s anodyne. It is for this reason that the price of the commercial “anodyne” is so low, being about fifteen cents per pound. {216}
It may become a question in the next revision of the Pharmacopœia, whether it would not be better to reconstruct the formula for compound spirit of ether, somewhat on the plan of the manufacturers, or that quoted at page 213, from Lewis’s Dispensatory, so as to render it more practicable and likely to be followed. Of course it should be done with due consideration of the difficulties involved in the production of a spirit of uniform strength.—_American Journal of Pharmacy._
ON GUTTA TABAN.
BY BERTHOLD SEEMANN.
The Taban (_Isonandra Gutta_, Hook.), which was formerly so plentiful [in Singapore], has long since been extinct. A few isolated trees may here and there occur, but they are very scarce, and I have not been able to obtain even the sight of one. Several of the white residents keep in their gardens as a curiosity, a plant or two, but they grow very slowly. It must ever be an object of regret, that on the first introduction of the Taban gum, its proper name was not promulgated. Now everybody in Europe and America speaks of Gutta Percha, when, in fact, all the time they mean the Gutta Taban. The substance termed by the Malays “Gutta Percha” is not the produce of the _Isonandra Gutta_, Hook., but that of a botanically unknown tree, a species of _Ficus_, I am told. The confusion of these two names has become a popular error—an error which science will have to rectify.
The exportation of the indigenous Gutta Taban from Singapore commenced in 1844, but as early as the end of 1847, all, {217} or at least most, of the trees had been exterminated. That at present shipped from the place, is brought in coasting vessels from the different ports of Borneo, Sumatra, the Malayan peninsula, and Jahore Archipelago.[17] The difference existing in its appearance and property is owing to the intermixture of Gutta Percha, Jelotong, Gegrek, Litchu, and other inferior Guttas, made by the natives in order to increase the weight.—Though far from being extinct in the Indian Archipelago, Gutta Taban will every year be more difficult to obtain, as the coast region is said to be pretty well cleared, and a long transport from the interior must, by augmenting the labor, increase the value of the article.
[17]
“The total export of Gutta Taban from Singapore has been:―
In 1844 1 picul In 1845 169 picul In 1846 5,364 picul In 1847 9,296 picul In 1848 to the 1st of July 6,768 picul ──── Total 21,598 piculs.
valued at 274,190 Spanish dollars. About 270,000 trees have probably been felled during the three and a half years that the trade has existed, and the value of each tree has thus on an average, been about a dollar.”—J. R. Logan, “_On the Range of the Gutta Taban Collectors, and present Amount of Import into Singapore_.” Mr. Logan has promised an article on the various substances intermixed with the Taban, a subject of the highest interest; but he has hitherto disappointed his readers.
A few months after the publication of your first account of the plant, in January, 1847, an article on the same subject appeared in the _Journal of the Indian Archipelago_, by one of its most able contributors, Dr. T. Oxley. As that article contains many statements not contained in yours, and as it may possibly have escaped your notice, I shall make a few extracts from it.
“The Gutta Taban tree belongs to the natural order _Sapotaceæ_, but differs so much from all described genera, that I am inclined to consider it a new one. I shall, therefore, endeavor to give its general character, leaving the honor of naming it to a more competent botanist, especially as, from want of {218} complete specimens, I have not quite satisfied myself regarding the stamens and fruit.
“The tree is from sixty to seventy feet high, from two to three feet in diameter. In its general aspect it resembles the Durian (_Durio Zibethinus_, Linn.), so much so as to strike the most superficial observer. The leaves are alternate, obovate-lanceolate, entire, coriaceous, their upper surface is of a pale green, and their under surface covered with a close, short, reddish-brown hair. The flowers are axillary, from one to three in the axils, supported on short curved pedicels, and numerous along the extremities of the branches. The calyx is inferior, persistent coriaceous, divided into six sepals, which are arranged in double series. The corolla is monopetalous, hypogenous, and divided, like the calyx, into six acuminate segments. The stamens, inserted into the throat of the corolla, are in a single series, and variable in number, but to the best of my observation, their normal number is twelve; they are most generally all fertile. The anthers are supported on slender bent filaments, and open by two lateral pores. The ovary is superior, terminated by a long single style, and six-celled; the cells are monospermous. The fruit is unknown to me.
“Only a short time ago the Taban tree was tolerably abundant on the Island of Singapore, but already, (middle of 1847) all the large timber has been felled. Its geographical range, however, appears to be considerable, it being found all up the Malayan peninsula, as far as Penang, where I have ascertained it to be plentiful. Its favorite localities are the alluvial tracts on the foot of hills, where it forms the principal portion of the jungle.
“The quantity of solid gutta obtained from each tree varies from five to twenty catties, so that, taking the average of ten catties, which is a tolerably liberal one, it will require the destruction of ten trees to produce one picul. Now, the quantity exported from Singapore to Europe, from the 1st of January, 1845, to the middle of 1847, amounted to 6,918 piculs, to obtain {219} which, 69,180 trees must have been sacrificed! How much better would it be to adopt the method of tapping the tree practised by the Burmese, in obtaining the caoutchouc, than to continue the present process of extermination.”[18]
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New York Journal of Pharmacy, Volume 1 (of 3), 1852Chapter IX: Section 3: This Act shall not take effect until the first day of July, (6)
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