ESSENCE OF PINE APPLE.

The above essence is, as already known, butyric ether, more or less diluted with alcohol; to obtain which pure, on the large scale and economically, the following process is recommended:—

Dissolve 6

s. of sugar and half an ounce of tartaric acid, in 26

s. of boiling water. Let the solution stand for several days; then add 8 ounces of putrid cheese broken up with 3

s. {115} of skimmed and curdled sour milk, and 3

s. of levigated chalk. The mixture should be kept and stirred daily in a warm place, at the temperature of about 92° Fahr., as long as gas is evolved, which is generally the case for five or six weeks.

The liquid thus obtained, is mixed with an equal volume of cold water, and 8

s. of crystallized carbonate of soda, previously dissolved in water, added. It is then filtered from the precipitated carbonate of lime; the filtrate is to be evaporated down to 10

s., when 51⁄2 lbs. of sulphuric acid, previously diluted with an equal weight of water, are to be carefully added. The butyric acid, which separates on the surface of the liquid as a dark-colored oil, is to be removed, and the rest of the liquid distilled; the distillate is now neutralized with carbonate of soda, and the butyric acid separated as before, with sulphuric acid.

The whole of the crude acid is to be rectified with the addition of an ounce of sulphuric acid to every pound. The distillate is then saturated with fused chloride of calcium, and re-distilled. The product will be about 28 ounces of pure butyric acid. To prepare the butyric acid, or essence of pine apple, from this acid, proceed as follows:—Mix, by weight, three parts of butyric acid with six parts of alcohol, and two parts of sulphuric acid in a retort, and submit the whole, with a sufficient heat, to a gentle distillation, until the fluid which passes over ceases to emit a fruity odor. By treating the distillate with chloride of calcium, and by its re-distillation, the pure ether may be obtained.

The boiling point of butyric ether is 238° Fahr. Its specific gravity, 0,904, and its formula C12 H12 O4, or C4 H5 O + C8 H7 O3.

Bensch’s process, above described, for the production of butyric acid, affords a remarkable exemplification of the extraordinary transformations that organic bodies undergo in contact with ferment, or by catalytic action. When cane sugar is treated with tartaric acid, especially under the influence of heat, it is converted into grape sugar. This grape sugar, in the {116} presence of decomposing nitrogenous substances, such as cheese, is transformed in the first instance into lactic acid, which combines with the lime of the chalk. The acid of the lactate of lime, thus produced, is by the further influence of the ferment changed into butyric acid. Hence, butyrate of lime is the final result of the catalytic action in the process we here have recommended.

ON A REMARKABLE SPECIMEN OF DECOMPOSED CHLOROFORM. BY JONATHAN PEREIRA, M.D., F.R.S., Physician to the London Hospital.

In July of the present year I received from Mr. Grattan, apothecary of Belfast, a specimen of chloroform, accompanied with a note, from which the following is an extract:—

“Some weeks prior to October 25, 1851, I received from my friend Dr. M’Killen a small bottle of chloroform which he had had of me two or three months previously, and which he stated was subject to very singular changes of color, despite the stopper never having been removed.

At the time he handed it to me the fluid exhibited a delicate pink tint, as though colored with cochineal, and was put aside in a glass case in my shop, of which I kept the key myself. The case was exposed to the diffused light of a large shop window but not to the direct rays of the sun.

Conceiving that the chloroform had by some unobserved means or other become accidentally colored, I took very little interest in the matter, and was not surprised to find it fade gradually, and in a short time become perfectly colorless—and I made a note to that effect upon the 25th of October, {117} concluding that there must have been some error of observation on the part of Dr. M’Killen.

On the 16th of November, however, it again began to change, and the enclosed notes were made, from time to time, as I happened to have opportunity of noticing it.

I tried it under different conditions of light and temperature, without their exerting apparent influence upon it, and being unable to form the slightest conjecture as to the cause or nature of the molecular disturbance which produces these chromatic changes, have taken the liberty of forwarding it to you, should you consider it worthy of attention.

It is at present colorless, and the stopper fast in; and I would only suggest that, before removing the stopper, it might be well to observe for yourself whether changes similar to those I have noticed may not occur again.

The foregoing changes of color were not influenced by any change of temperature between 27° and 86° Fahr., nor by exposure to, nor seclusion from light. The stopper being fast, atmospheric pressure cannot have been connected therewith. Whether it may have been influenced by electrical changes, am not prepared to say.” {118}

The specimen of chloroform sent me by Mr. Grattan was, in July, quite colorless, and on the sides of the bottle a few minute crystals were observed. The stopper of the bottle was, however, so firmly fixed in that I could not remove it, and I, therefore, placed the bottle on the mantel-shelf in my library exposed to diffused light, for the purpose of observing the changes which its contents would undergo.

In the course of a few weeks it began to acquire a pinkish or amethystine tint, as described by Mr. Grattan. This slightly augmented in intensity for a few days, and then became somewhat paler. But for several weeks, during which it remained in the same situation, it never became colorless, though the intensity of the color was frequently changing.

The color of the liquid was precisely that of a weak solution of permanganate of potash.

Some weeks ago I placed the bottle in a dark cupboard, and at the expiration of about three weeks found that the liquid had become quite colorless. As the stopper was still immovable, I was obliged to cut off the neck of the bottle to get at the contents. I found that the chloroform had undergone decomposition, and had acquired a powerful and irritating odor, somewhat allied to, but distinct from, that of hypochlorous acid. The vapor yielded white fumes when a rod moistened with solution of ammonia was brought in contact with it, blue litmus paper was reddened but not bleached by it. A few drops of the liquid were placed on a watch glass and volatilized by a spirit lamp; they left scarcely any appreciable residue.

The crystals which lined the bottle were then examined. They were few in number, and not larger than pins’ points. They were white, and when examined by the microscope, were found to be six-sided pyramids, like the crystals of sulphate of potash. Some of them were heated to dull redness in a test tube, without undergoing any appreciable change. When heated on the point of a moistened thread in the outer cone of the flame of a candle, they communicated a violet-white tinge to the flame, char­ac­ter­is­tic of a potash-salt. They readily {119} dissolved in water, and the solution did not yield any precipitate on the addition of a solution of nitrate of baryta, showing that the salt was not a sulphate. The solution was boiled with nitric acid, and then treated with a solution of nitrate of baryta, but no precipitate was observed. Nitrate of silver produced in the aqueous solution of the crystals a white precipitate, soluble in ammonia, but insoluble in nitric acid.

Whether these crystals were in any way connected with the change of color which this sample of chloroform underwent, I am unable to determine; but I suspect not. I am anxious, however, to draw the attention of others to the subject, in the hope that larger specimens of the salt may be obtained for examination. For at present the circumstances under which chloroform frequently undergoes decomposition are very obscure. Except in this instance, I have never met with, nor heard of, any sample of chloroform which underwent these remarkable changes of color.

The chloroform was transferred into another bottle, on the sides of which a few minute crystals are now formed. But since the removal of the stopper the pink color has not re-appeared.

I have written to Mr. Grattan to obtain, if possible, further information respecting this specimen of chloroform. But he tells me he has not any more of the sample, and has no means of ascertaining by whom it was made, as about the time it was purchased of him he had in his shop parcels from London, Edinburgh and Dublin, as well as a small quantity prepared in Belfast, and he is quite unprepared to say from which of them it was taken.

I suspect that the pink color of the chloroform must have been due to the presence of manganese. If so, was this metal derived from the chloride of lime used in the manufacture of chloroform? Mr. Squire informs me that he has occasionally found the solution of chlorinated soda to become of a pinkish hue after being prepared a few days (not immediately), and that he has attributed it to some manganese carried over with the {120} chlorine gas, as he does not remember having observed this change when the gas had been passed through water before entering the solution of carbonate of soda.

If this suspicion should prove well founded, it is obvious that the purity of the chloride of lime employed in the preparation of chloroform deserves the attention of the manufacturer.

Postscript.—Subsequently to the reading of this paper before the Phar­ma­ceu­ti­cal Society, I have received from Mr. William Huskisson, jun., a specimen of pink chloroform, which, he informs me, owes its remarkable color to the presence of manganese, derived from peroxide of manganese employed in the purification of chloroform, as recommended by Dr. Gregory, (see Phar­ma­ceu­ti­cal Journal, vol. ix., p. 580.)

Mr. W. Huskisson, jun., tells me, that he has observed in his specimen neither the alterations of color nor the crystals met with in the specimen sent me by Mr. Grattan.

The chairman stated, that he had never, in the various specimens of chloroform, of which his firm had always a large quantity in stock, observed the pink color described by Dr. Pereira, nor had he ever seen any crystals deposited in the bottles, but he would have a more minute examination made with the view of ascertaining whether such existed. When the chloroform was first drawn over, and before it was purified, it frequently possessed more or less of a brown color, but this was quite distinct from the character described in the paper which had just been read.

Mr. D. Hanbury observed, that the use of manganese had been suggested in the process for purifying chloroform, and its presence might in this way be accounted for.

Mr. Barnes thought it desirable that the decomposed chloroform should be examined for formic acid. Although constantly subject to decomposition, no satisfactory explanation of the nature of the change had yet been afforded.

{121}

REPORT PRESENTED TO THE ACADEMY OF MEDICINE OF PARIS, ON THE SUBSTITUTION OF AN AR­TI­FIC­IAL IO­DU­RET­TED OIL FOR COD LIV­ER OIL. By a Commission composed of Messrs. Gibert, Ricord, Soubeiren and Guibourt.

On the 20th of August, 1850, the Academy appointed a commission, composed as above, to whom was submitted a memoir, by M. Personne, entitled, “Researches on the Cod-liver and Skate Oils; and on the preparation of an ioduretted oil, by which they may be replaced as Medicinal Agents.” A note was also submitted to us on the same subject, from M. Deschamps, and another from M. Marchall, the latter of which claimed for the author priority in the employment of ioduretted oil of almonds, as a substitute for cod-liver oil.

We proceed now to report the results of our examinations of these communications, and of the investigations to which the enquiry has led.

Cod-liver oil has long been the object of a considerable commerce arising principally from the decided superiority which it possesses over other animal oils, for the preparation of chamois leather; but it has only been within about twenty years that it has been used in medicine. It was first employed as a remedy for rheumatic pains, then for bronchial affections, and subsequently as a remedy for scrofula and consumption. It now constitutes one of the medicinal agents most extensively used, and one of those, on the action of which medical men place the greatest reliance, as a remedy capable either of curing very formidable diseases, or of retarding their fatal termination.

The most important memoir which has been published on cod-liver oil is that of Dr. Jongh, in which three kinds of oil are described as met with in commerce, which are called the black, the brown, and the white cod-liver oil. These oils are represented to consist, principally, of oleic and margaric acids, and glycerine, and, as accessory bodies, of butyric acid, acetic {122} acid; some principles appertaining to the bile, a non-azotised yellow or brown coloring matter, called gaduine, iodine, phosphorus, and some inorganic salts. In France, Messrs. Girardin and Preisser have been engaged in comparing the effects of the oil obtained from the cod with that obtained from the ray; and they advocate the superiority of the latter for medicinal use. But this superiority seems to depend, in part, on the circumstance, that the oil obtained from the livers of the ray, being carefully prepared by the pharmaciens, and being transparent, and of a light yellow color, proves less offensive to the patients than the cod-liver oil of commerce, which is generally thick, of a dark color, and has a disagreeable flavor. This, however, is scarcely admitted at the present time. Moreover, it appears from recent observations, that the above characters cannot be much depended upon for distinguishing the two kinds of oil, in consequence of their being so variable.

According to Messrs. Girardin and Preisser, these two oils contain iodine in the state of iodide of potassium, and in quantity much less than had been indicated by Dr. Jongh. The latter author gives, as follows, the quantity of iodine in 1,000 parts of oil:—

Black cod-liver oil0,295 parts of iodine.
Brown cod-liver oil0,406 parts of iodine.
White cod-liver oil0,374 parts of iodine.

Messrs. Girardin and Preisser have found in a litre (thirty-five fluid ounces),

Of ray-liver oil0,180 gramme of iodine.
Of cod-liver oil0,150 gramme of iodine.

According to M. Gobley, a litre of ray-liver oil, prepared by direct action of the fire, contains twenty-five centigrammes of iodide of potassium. M. Goodley was unable to find phosphorus in this oil.

Such were the principal analytical results known when M. Personne presented his memoir to the Academy. The uncertainty which appeared to attach to the subject, and the {123} variations in the statements of chemists, induced him to put to himself the following questions:—

1st. Do the oils of cod and ray-liver contain iodide of potassium or iodine?

2nd. Do the different sorts of these oils contain the same proportion of iodine?

3rd. Do these oils contain phosphorus, to which their effects may be partly attributed?

For detecting the presence of the iodine, M. Personne saponified the oil with an excess of caustic potassa, incinerated the soap, and treated the product of incineration with strong alcohol. The alcohol was evaporated, the residue dissolved in water, and to this, solution of starch and sulphuric acid were added. The quantity of iodine was estimated by the intensity of the color; it is too small to be estimated by the balance.

Mr. Personne examined in this way the dark brown and thick cod-liver oil, such as is employed in the hospitals of Paris; the transparent and nearly colorless oil of English commerce; and the ray-liver oil prepared by the direct action of a moderate heat, and subsequent filtration. The following are the results:—

1st. The brown cod-liver oil of the hospitals of Paris contains more iodine than the fine white oil of English commerce.

2nd. It also contains more iodine than the ray-liver oil, and, moreover, the quantity present is certainly less than a decigramme of iodine in a kilogramme of oil (1 in 10,000.)

3rd. The residue of the liver, left after the preparation of the oil, contains much more iodine than the oil itself.

With regard to the question as to whether the iodine exists in cod-liver oil in the state of iodide of potassium, or directly combined with the oil, M. Personne, while he admits the difficulty of satisfactorily determining the point, inclines to favor the opinion that the iodine is directly combined with the elements of the oil.

[The different methods which have been suggested for the preparation of the ioduretted oil proposed as a substitute for {124} cod-liver oil are described. A discussion follows of the claims of the authors, whose communications were submitted to the commissioners, for having first introduced the artificial ioduretted oil, which discussion is also omitted here as being uninteresting to our readers. The commissioners next proceed to state the result of the evidence obtained, by the medical members of the commission, of the therapeutical action of the artificial ioduretted oil.]

M. Gibert administered the ioduretted oil for periods varying from several weeks to several months, to patients suffering with eruptive complaints and scrofulous tumors; and, in some instances, found the benefit to be greater than from the use of cod-liver oil, under similar circumstances. He states, that he does not think he has tried it in a sufficient number of cases, and for a sufficient length of time, to enable him to state decidedly what its absolute value is as a specific for eruptive and scrofulous complaints; but the results he has obtained are sufficient to prove, that it is easy of ad­min­i­stra­tion and devoid of any injurious quality, and that it possesses a resolutive action, which renders it a valuable remedy for certain chronic eruptions and glandular swellings.

M. Ricord has employed the ioduretted oil for twelve months, in a great number of cases of scrofula, some of which were considered to be of venereal origin. He thus obtained excellent results in the treatment of strumous bubo, tubercular epididymis, and in some cases of scrofulous enlargement of the joints, etc., and other things being equal, curable cases were cured, or relief afforded, much more quickly by the use of the artificial ioduretted oil than by the natural cod-liver oil.

The average dose in which the ioduretted oil was administered was sixty grammes (

ij.), which was sometimes raised to 100 grammes (

iiiss.) The patient generally took it without inconvenience. It was only in a few instances, where the dose had been raised, that vomiting, colic, and diarrhœa were produced. If the precautions which are necessary in the ad­min­i­stra­tion of every remedy be observed, and the degrees of {125} susceptibility of the patients, together with all special conditions, properly studied, it may be affirmed that the ioduretted oil is a medicine of great value and that it presents considerable advantage over the cod-liver oil.—Journal de Pharmacie, in Pharmaceutic Journal.