,

. Jour. Pharm

One of the wholesale firms of this city lately received from a New York importer a sample of what was represented to be cubebs. They are about one-third the size of true cubebs, with a stipe about onethird longer than their diameter, are of a dark purple color, quite shrunken appearance, and of a cubeb odor, but much weaker taste.

On examination with the microscope they are seen to contain numerous oil cells in the mesocarp, but the layer of stone cells which forms the endocarp in the true cubebs can not be discerned.

They contain a very rudimentary seed. In my opinion they are cubebs which have been picked while quite immature, the present high price of cubebs, probably, having tempted the growers to put them upon the market in this condition.

ON THE COMPOSITION OF HYDRANGIN.

By HERMANN J. M. SCHROETER, PH. G.

A contribution from the Chemical Laboratory of the Philadelphia College of Pharmacy. Read at the Pharmaceutical Meeting, February 19th.

A proximate analysis of Hydrangea arborescens, and a description of the active principle, hydrangin, was published in the AMER. JOUR. OF PHARMACY, March, 1887, by C. S. Bondurant. He showed the principle which he had discovered to be a glucoside, and gave a process for preparing it, but was unable to pursue his investigations. The object of this paper is to continue this work and determine the ultimate composition of this interesting compound.

Five kilos of the finely powdered drug were percolated to exhaustion with 96 per cent. methyl alcohol. The alcohol was recovered by distillation in vacuo, and the dark-brown extract further reduced by placing over sulphuric acid. Various experiments were made on the best method for extracting the principle. A portion of the extract was treated with petroleum ether to remove fat, etc, but it was found that this solvent dissolved an appreciable quantity of the principle, therefore this treatment was omitted with the bulk of the extract. The residue was then treated with successive portions of a one per cent. aqueous solution of sulphuric acid. This solution was col

ored reddish, and to remove coloring matter was treated with chloroform, which solvent also extracted some of the principle. The acid solution was next treated with ether, and upon evaporation the slightly reddish colored hydrangin was deposited. To further purify, it was dissolved in absolute alcohol and treated with animal charcoal. This colorless solution was then evaporated under reduced pressure, and upon recrystallization from the same solvent, the principle was deposited in well-defined stellate clusters of pure white crystals. The drug used was apparently of poor quality, the yield being only 0·08 p. c.; it was stated by Mr. Bondurant to probably contain about 0.8 to 1 per cent. of the glucoside.

Some of the crystals were pulverized and dried over sulphuric acid. On heating to 110°C, no loss occurred, showing absence of water of crystallization. Tests for nitrogen gave negative results. Four combustions with cupric oxide gave following results.

Experiments on the physical and chemical properties of hydrangin compared well with those stated by Mr. Bondurant, with but few exceptions. Its melting point was found to be 228°C., instead of 235°C., and the solidifying point at 217°C. Mention was also made that hydrangin dissolves in concentrated sulphuric acid without color. On dissolving a portion in concentrated H2SO,, a distinct violet red fluorescence was observed, although not quite as strong at that produced by an alkali, which is intense opal blue. On addition of 5 volumes of water to the solution in H2 SO,, the fluorescence was destroyed; the addition of ammonia to the same solution destroyed the color also, but on neutralizing the solution, the characteristic opal blue fluorescence reappeared. The substance was also found to be soluble in 80 per cent. acetic acid with slight fluorescence, which became more decided on dilution with 5 to 10 volumes of water.

The decomposition product of hydrangin, obtained by boiling with a dilute acid, was found to be soluble in chloroform, which deposited it as a brownish resin-like body.

. Jour.

, 1

BROMATES OF THE CINCHONA ALKALOIDS.

BY CLAUDE GRANT JOHNSON, PH. G.

From an Inaugural Essay.

Bromates have of late been receiving some attention as therapeutic agents, although they have not yet come into any general notice. Almost all of the inorganic compounds of bromic acid have been made, but none of its alkaloidal salts seem to have been produced until quite recently. It is claimed for the bromates of the metals that they give all of the effects of the corresponding bromides with the advantage of being more gratefully received by the system, which is able to endure them for a longer time without the unpleasant after effects usually following upon an extended treatment. They have been used in chorea, epilepsy, alcoholism and other diseases with good results. "They are for the most part crystallizable, but many of them decompose when their solutions are heated. When heated to redness, they either give off oxygen, leaving bromides, or give off bromine, and part of their oxygen, leaving oxides."—(Watts).

Barium bromate is important as being the salt from which most of the others are prepared. It is best made by adding to a boiling solution of potassium bromate, sufficient anhydrous acetate of barium to saturate it, and allowing to cool slowly. Barium bromate crystallizes out, while potassium acetate remains in solution.

Potassium bromate was prepared by adding bromine to a solution. of potassium hydrate, forming the bromide and bromate of potassium, the bromate crystallizing from the solution because of its inferior solubility ("KBr is soluble in 16 parts of water, KBrO, in 16-2 parts."-Walker). The bromide remaining in solution was procured as bromate by adding the requisite quantity (calculated from the molecular weights) of potassium hydrate, and passing a stream of chlorine gas through the solution until saturated, when the bromate separated in small, irregular shaped crystals, the reaction being as follows:

KBr+6 KOH+3 Cl2=KBrO3+6 KCl+3 H2O.

The product was purified by recrystallization. The shape of the crystals depends upon the way in which they are made, from hot solution they separate as needles, but by slow cooling are obtained as four and six-sided plates, colorless and anhydrous.

Quinine bromate has been successfully used in some forms of neuralgia," especially those in which evidence existed of malarious or

. Jour. Pharm

March,

rheumatic influence," the large proportion of easily dissociated oxygen present being supposed to add to its physiological activity. These salts were all prepared by double decomposition between barium bromate and the corresponding sulphates, and a sample of each is presented. On platinum or porcelain, heated to redness, they are decomposed with explosive violence, leaving a very slight charred residue. Barium bromate was dissolved in boiling water, a calculated amount of sulphate of quinine added, and the mixture filtered. The filtrate was of a violet blue color, a circumstance I am unable to explain, the suggestion being offered that it may be due to a compound allied to thalleioquin. Almost immediately, the solution being concentrated, crytals began to separate in small clusters. These were redissolved in a large quantity of water, and set aside for a few days, when the product was procured in the form of handsome stellate clusters of long, white acicular crystals. These were dried upon filtering paper. Exposed to the air for nearly a month, they did not effloresce nor undergo any noticeable change. The solubility in water is very slight, as is indicated by the rapidity with which crystals form. The taste is bitter, and the reaction slightly acid. Dropped upon a heated porcelain lid, the crystals decompose immediately with a slight explosion. Upon concentrating the mother liquor the blue color was much deepened, and the second crop of crystals had a violet tinge, which can be removed by solution and crystallization. A repetition of the process in somewhat more dilute solution gave the same results, except that the solution was but very slightly colored at first, but the crystals were no better, and upon concentration the color was again produced.

Cinchonidine bromate was next prepared, the same process being used. This also gave a blue colored solution, but the salt was found to be much more soluble than the preceding, requiring a very concentrated solution before crystals would form. The first that were procured were tested for quinine, but none was found. The easy solubility of the salt, together with the color complication, made the procuring of white crystals a matter of considerable difficulty. By renewed trials with fresh materials, and recrystallizing the products repeatedly, a fairly good specimen was secured. The best plan would probably be to evaporate a moderately dilute solution spontaneously in a cool place or in vacuo. In heating the solution to concentrate it, care must be taken to see that the process be not carried too far, as decomposition is likely to take place and the salt to be spoiled, even if

it does not go off in a sudden explosion. These crystals are not as handsome as those of the quinine bromate; they are white and in clusters, but are much smaller than the others, and the separate crystals are flatter and broader.

Cinchonine bromate.-In preparing this salt the color of the filtrate was observed to be yellow, and remained so, becoming very little deeper, even after much concentration. The salt, while not as difficultly soluble as the quinine, is more so than the cinchonidine salt, but the product has a slight yellow color. The bunches are smaller and differ in shape from the quinine salt, but are larger than the cinchonidine. They give the usual tests for bromates, are bitter, and neutral to test paper.

Quinidine Bromate.-The color of the solution was a delicate shade of pink, but as soon as heat was applied, it began to change and became blue, the color rapidly deepening into almost a black. In a second attempt, the barium solution being saturated, the pink color was again obtained. No heat was applied but after two days the solution was found to have changed to the same blue color. This salt was also very hard to crystallize, on account of its easy solubility, and the difficulty caused by the change in color, but a product was finally obtained that is colorless. The crystals are very much like the others, being needle shaped, and forming in clusters, explosive on hot porcelain, and of a neutral reaction.

If these salts should come into use as remedies, they could be easily prepared by the above process. It is possible that the differences in solubility shown by the bromates could be made useful as a means of distinguishing the alkaloids of cinchona from each other. Lack of time prevented me from looking into this feature of the subject, but it is worthy of further investigation.

FRAUDULENT “HEAVY CALCINED MAGNESIA." TO THE EDITOR OF THE AMERICAN JOURNAL OF PHARMACY:

Some time ago we were offered by an importing house in a neighboring city what appeared to be a very handsome article of "Heavy Calcined Magnesia," it being represented as such by the seller, with the statement that it was of English manufacture. We analyzed the sample, and thinking an error had been made by the vendors, pro