The Fruit of Illicium Anisatum, Loureiro.
By CARL E. SCHLEGEL, PH.G.
From an Inaugural Essay.
The glossy brown-yellow seeds were removed, and the capsules reduced to a No. 80 powder. This powder, dried at 100°C., until it ceased to lose weight, was found to contain 10.36 per cent. of moisture and volatile oil. On incinerating this dried powder there remained 3.5 per cent. of ash, the acid solution of which showed that there were present the bases: K, Na, Fe and Al; also hydrochloric, sulphuric and phosphoric acids.
A proximate analysis of the drug gave the following results:
Portion soluble in petroleum spirit.—Twenty gm. of powder were exhausted with petroleum spirit by repeated maceration and decantation, and the petroleum spirit distilled off until 200 Ccm. remained. A portion of it was allowed to evaporate spontaneously, the residue amounting to 5.875 per cent. of the whole, which residue had the appearance of a thick oily dark-green liquid, of a strong distinct anise odor. On adding strong sulphuric acid to a solution of a portion of it in chloroform, it turned yellow, then brown, and rapidly deep red. These characteristic colorations, combined with its odor, proved it to contain oil of star anise.
To another portion of the liquid, 95 per cent. alcohol was added, which completely dissolved it. On adding to this alcoholic solution a solution of sodic hydrate, applying moderate heat, and shaking it, it failed to saponify, proving the absence of fixed oil,
The liquid was found to contain 4.675 per cent. of volatile oil. On heating in a water-bath at 100°C. a portion of the liquid, for eight hours, this volatile oil was all driven off, and then remained 1.2 per cent. of green wax, fusing at 51°C.
Portion soluble in stronger ether.—The residue from the petroleum spirit extraction, dried and freed from all traces of petroleum spirit, was exhausted with stronger ether by maceration and decantation, and the liquid then subjected to distillation until 200 Ccm. remained in the retort. This was allowed to evaporate spontaneously, and there remained a solid residue of 1.2 per cent. Of this residue 30 per cent. was soluble in water, and 70 per cent. soluble in absolute alcohol. The aqueous solution gave with ferric chloride an inky greenish black color; with gelatin no precipitate; with lead acetate a grayish precipitate; and with ammonic hydrate a green color, immediately changing to reddish-brown. From these reactions it may be inferred that the aqueous solution probably contained gallic acid. The portion soluble in absolute alcohol was found to be a resinous substance, partially soluble in aqueous solution of caustic potassa.
Portion soluble in absolute alcohol.—The residue from the ether extract, dried, was exhausted with absolute alcohol, and from the tincture the alcohol was distilled off, until 200 Ccm. remained. This was allowed to evaporate spontaneously and left a residue amounting to 3.75 per cent. This residue was completely soluble in distilled water. The aqueous solution of this residue was then made acid in reaction, and successively shaken up with petroleum, benzol, ether and chloroform, but gave no noteworthy results.
After having removed from this aqueous solution all traces of the other solvents, it was made alkaline. Upon shaking this solution with petroleum, decanting the petroleum, and evaporating spontaneously, there remained a crystalline principle of very strong musk odor, but which corresponded neither to the reactions of an alkaloid, nor those of a glucoside. Subsequent shakings with benzol, ether and chloroform, showed nothing of value.
Portion soluble in distilled water.—The residue from the alcohol extraction dried, was exhausted with distilled water by maceration and on evaporation, and drying a portion of this liquid in a water-bath, the residue amounted to 0.94 per cent. A portion of the aqueous extract was acidified and successively agitated with petroleum, benzol, ether and chloroform; but on evaporating these several shakings no crystalline residue was observed. This same portion was then carefully heated to expel all traces of the other solvents, and was then made alkaline. Here likewise, no results were obtained by agitating with the same solvents.
To 20 Ccm of the aqueous extract, 35 Ccm. of alcohol (95 per cent.) were added, and allowed to stand in a cool place for twenty-four hours. It was found that all the gum had been precipitated, which precipitate was then removed to a filter, and washed with alcohol of 66 per cent, carefully dried to a constant weight, the gum was found to amount to two per cent. of the whole. It was completely soluble in water, and formed a mucilage therewith.
The acrid taste of the aqueous extract, and its frothing, when shaken up, indicated the possible presence of saponin, hence the necessary tests were made as follows: To a portion of the aqueous extract, baryta-water was added, and this allowed to stand in a cool place for forty-eight hours. This caused quite a large precipitate, which was removed to a filter, and repeatedly washed with saturated baryta-water. The precipitate was then removed from the filter, mixed with a little distilled water, and carbonic acid gas passed into it. This broke tip the compound, which had been formed with the baryta, and the principle remained in solution. The filtrate was shaken up with chloroform, which took up the principle from its watery solution, and on evaporating left it in an amorphous condition. In contact with a few drops of concentrated sulphuric acid, after some time it gradually assumed a reddish color. A portion of the principle in solution was boiled with a little acid, and then treated with freshly prepared Fehling's solution; the blue color immediately changed to green, and a brownish-red precipitate, consisting of Cuprous oxide resulted. A portion of the solution formed an insoluble compound with basic acetate of lead. All these reactions go to show that the principle in question was the glucoside saponin.