ON THE JUICE OF TARAXACUM.*

BY L. E. SAYRE, PH. G., UNIVERSITY OF KANSAS.

In a communication from the chairman of the Scientific Section, it was suggested that I take up the investigation of taraxacum root, as suggested by Queries 11 and 12.

In response to the request I consented to do as much work in the investigation as my time would allow, but as the meeting of the Association takes place much earlier this year than usual, little time is allowed for the experiments necessary.

Some years ago this subject received considerable attention, and from the pens of very able men. We find communications upon it especially in the Pharmaceutical Fournal and Transactions. But it would seem from a review of this literature that high authorities differ, and entirely satisfactory results were not arrived at. Moreover, we find by consulting the various authorities--Universal Pharmacopeia, United States Dispensatory, and the pharmaceutical literature of some years ago—that very different seasons of the year are recommended as the best time for collecting the root. One recommends the beginning of spring, even before blooming; another, July, August and September, as the proper period for collecting; another, that it should be gathered between September and February. It would therefore seem to be an unsettled question, and worthy of being brought forward anew, so that it might receive further consideration.

The time at my disposal has been insufficient to examine the root for such constituents as taraxacin and inulin, but if I be allowed to continue the subject for next year, I shall be glad to make an estimation of these constituents, as found in the root in the different months of the year.

But one lot of the root, that collected in May, could be examined at all and reported upon in time for the present meeting.

The present experiments include the estimates of moisture in the fresh root, moisture in the dry root, etc.

Examination of taraxacum root collected May 10th, 1892.

*Answer to Query 11. Composition of the Juice of Taxaracum Root. It is desirable to determine at intervals during the year, beginning as early and continuing as late as possible: 1st, the percentage of juice obtained by expression; 2d, its specific gravity; 3d, its total solids; 4th, ash; 5th, sugar; 6th, inulin and other amyloid bodies; and 7th, its bitter principle. And to

Query 12. It is claimed that it is becoming yearly more and more difficult to obtain a taraxacum root collected at the proper season and of proper quality, and that a valuable drug is in danger of being discredited and discarded from this cause. Has the proper season for gathering been fully and satisfactorily settled, and how can the quality of the drug be most easily determined?

The juice after expression had a decided bitter taste.

LAWRENCE, KANSAS, May 15, 1892.

MR. MAISCH: I wish to call attention to a figure in the author' stable where it is stated, that drying at 100° 10 per cent. is lost; but the original loss amounting to over 79 per cent., left only 20 per cent. of air-dry material, and this would have still contained 50 per cent. of moisture, in case the figure 10 applies to the weight of the original fresh root. It is known that the spring root yields less dry material than the fall root.

APPLICATION OF VOLUMETRIC ANALYSIS TO OIL OF WINTERGREEN.* BY BENJ. H. EWING, PH.G., EWINGVILLE, OHIO.

The composition of oil of wintergreen and its well-known commercial substitute, oil of sweet birch, has been the subject of repeated investigation, the tendency of which has been to prove the constituents of the two oils to be identical, or the existence of a slight difference in favor of the birch product, as being a more nearly pure representative of absolute natural methyl salicylate; yet, to the author's knowledge, no easy method has been proposed for the use of the pharmacist in estimating the salicylic value of the article before making a purchase in the market.

Being composed of a definite chemical compound, the deportment of which with alkalies is well-defined, there remains no reason why volumetric analysis should not be applied to this purpose.

With a view of proving the feasibility of such a method, in January of the present year the writer obtained two genuine specimens (one oil of gaultheria, the other oil of sweet birch) through the kindness of Mr. C. M. Driggs, of White Haven, Pa., who has furnished other investigators with authentic specimens of these oils. These, with a specimen of the commercial oil obtained from a prominent dealer, were first subjected to a gravimetric assay according to the following process:

A small, convenient quantity (1.5 to 2 gm.) was weighed in a tared flask of 50 c.c. capacity, a slight known excess of a strong solution of soda added, the flask securely corked, and the contents rotated over a moderate heat until the disappearance of the precipitate formed by the soda solution. After cooling, the cork was removed, and the liquid again subjected to heat for five minutes, this time at the boiling point, after which it was

* Under supervision of Wm. Simonson, Ph.G., Chemical Laboratory, Cincinnati College of Pharmacy.

transferred to a separatory funnel, where it was treated with a slight excess of hydrochloric acid, and the precipitated salicylic acid taken up by shaking the resulting mixture with two volumes of ether. After subsidence, the aqueous stratum was drawn off into a second separator and shaken with two volumes of ether; again drawn off into a third separator, after subsiding, and shaken with one volume of ether; when, upon resting, the aqueous solution was finally drawn off, found to be free from salicylic acid, and rejected.

The ethereal solutions in the separators were then washed in succession, four times, each time with two volumes of distilled water, to free them froin sodium chloride. That in the first separator was transferred to a tared platinum dish, as was that in the second, after passing through the first, and that in the third, after passing through the second and thence also through the first. The ethereal liquids were carefully evaporated, and the residue dried over sulphuric acid to a constant weight.

W. Simonson was kind enough to verify each estimation made by this method.

A plan for volumetric estimation was now devised, which, in outline, consists in saponifying a weighed portion of the oil with an excess of normal solution of soda, and neutralizing the excess with normal hydrochloric acid, and in detail as follows:

Weigh 5 gm. of the oil in a tared flask of 100 c.c. capacity, and pour upon it 40 c.c. volumetric solution of soda. Cork the flask securely, and heat the contents at 60° C. until the precipitate formed at first has totally disappeared. Cool, remove the cork, and again apply, and maintain heat at the boiling point for five minutes; again cool, add enough solution of phenolphthalein to impart a red color, and then enough normal hydrochloric acid to render the liquid neutral, as will be sharply indicated by the disappearance of the red color. Subtract the volume of acid required. from 40, and multiply the remainder by .138 (one-thousandth of the molecular weight of salicylic acid), and the resulting product by 20, to get the per cent. of salicylic acid; or multiply the remainder by .152 (onethousandth of the molecular weight of methyl salicylate), and the resulting product by 20, to get the per cent. of methyl salicylate.

This method was applied to each specimen of oil, the following table showing the results compared with those obtained by the gravimetric method:

Three more specimens of the commercial oil, obtained from different

manufacturers of natural salicylic acid, were estimated by the volumetric

method, one of which proved to be absolute methyl salicylate, the other two 99.10 per cent. and 99.50 per cent. respectively.

This method has since proved effectual in one instance in detecting an oil offered for sale by a traveling broker, which contained but 68 per cent. of methyl salicylate.

Cincinnati, O., May 25th, 1892.

MR. LLOYD: I would like to ask whether Professor Simonson's method is not used in this paper?

MR. FENNEL: The paper was printed according to the directions of Mr. Simonson, and he is entitled to the credit. The volumetric method given here is interesting.

MR. CASPARI: Professor Power suggested, I think, to the Revision Committee, a similar method for determining the purity of oil of wintergreen, and an article of his was published a few months ago in some of the journals, where he stated that certain quantities of the oil and warm soda solution would give a perfectly clear solution, indicating an absolutely pure oil of wintergreen. If that is the case, what is the use of determining the acid volumetrically? I think that the Pharmacopoeial Committee should indicate some method for determining the purity of cil of wintergreen without the troublesome gravimetric or volumetric method.

Secretary Fennel read the following paper :

SOLUTION OF BIMECONATE OF MORPHINE.

BY ALICE L. BRAUNWARTH, PH. G., MUSCATINE, IOWA.

Although this preparation of opium has been in great favor for many years, no positive formula for its preparation nor standard for strength exists in any authoritative work. In view of these facts the work was undertaken, and the following data obtained. At the outset it became necessary to decide upon a precise method for the estimation of morphine, the preliminary trials being made upon a commercial specimen of sulphate of morphine:

Water, by drying at 140°-to 160°C.

H.SO,, as barium sulphate.

Morphine, by separation from a strong aqueous solution of ammonia, and purification by amyl alcohol.

Results:

Water-1.0372 lost at 140°–160°C., 0.1145 H2O........

Sulphuric acid-0.6797 produced 0.2110 BaSO4

Sulphuric acid - 0.9607 produced 0.2980 BaSO,
Morphine-0.2644 produced 0.2011 C,,H1NO, dry at 110°C...

Total.

17 19

On applying amyl alcohol to morphine estimations, several practical difficulties were encountered. Very much more of the solvent is needed than would be supposed from the stated solubilities of the alkaloid. Thus Prescott states that solubility is 1-97, but in precipitation it was found to

be soluble in about 3 that quantity, yet readily crystallizing from this solvent, and when equilibrium was established the solubility was found to be 1 in 160-200. Secondly, the high solubility of the solvent in water requiring repeated washings. Thirdly, extreme slowness of evaporation. Conclusion. While amyl alcohol is necessary in rigidly accurate morphine estimations, it is practically useless when a large number of estimations are made, owing to the labor and time attending its use.

Ethyl acetate is free from these objections and yet defective, owing to its deficient solvent power of the alkaloid, requiring 600 parts for 1 of alkaloid.

Under such conditions the ammonia precipitation was resorted to, and the following factors considered :

First. Solubility in water of the alkaloid, and in slightly ammoniated liquid resulting from the precipitation.

Ist. In water.

Morphine 2.00 shaken for 24 hours with 50 c.c. water, filtered in a filtering tube through a small plug of well cleaned asbestos, a weighed portion of the clear filtrate evaporated to dryness in a tared platinum dish, and drying at 100-105 C.

Result, 0.0178 CHNO. Solubility, 1 part morphine in 1806 parts of

water.

2d. a. Morphine 0.3311, dry at 110° C., dissolved in little water with the least possible excess of hydrochloric acid, diluted to 20 c.c., precipitated with 5 c.c. of ammonia water, I per cent., during 24 hours, collected in a small tared filtering tube, washed with 5 c.c. of water in portions of 1 c.c., dried at 100 C. to constant weight. Loss 0.0157, indicating solubility of one part of morphine in 1600 parts of the liquids.

b. Morphine 0.3181. Morphine lost 0.0131, corresponding to a solubility of 1 part in 1530 parts of the fluids. Correction, therefore, 1-1600 in precipitating liquid was adopted.

MECONIC ACID.

While meconic acid is a tribasic acid, and forms with silver and other univalent metal elements, more than one salt, it combines with lead in but one proportion, forming the triplumbic meçonate Pb, 2C,HO,. Whether obtained in neutral or (acetic acid) acidified solution, or from an aqueous solution of free meconic acid, the lead salt was always the same, proven by the estimation of lead in the precipitate as oxide or sulphate. The quantity, however, will vary with the degree of acidity of the solution (acetic) acid being the free acid). The variations were determined as follows, the precipitate being dried at 125° C. (below which temperature the salt cannot be obtained anhydrous):

Ist. Free meconic acid:

0.2740 HC,HO,3H,O gave 0.5370 Pb 2C,HO.. Calculated 0.5460, a recovery of 98.4 per cent.