Researches on morphine. Pt. 2 / by S.B. Schryver and Frederic H. Lees.

  • Samuel Barnett Schryver
Date:
[1901]
Catalogue details

Licence: In copyright

Credit: Researches on morphine. Pt. 2 / by S.B. Schryver and Frederic H. Lees. Source: Wellcome Collection.

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    hydrogen bromide, and after a time a gelatinous hydrobromide separated from the solution. The whole was boiled for an hour, cooled, mixed with an equal bulk of alcohol in order to decompose any excess of phosphorus bromide, thrown into water, rendered alkaline with sodium carbonate, and extracted six times with a chloroform-ether mixture. The chloroform-ether solution of the base, after washing four times with water, was dried over calcium chloride and the chloroform- ether distilled off, when a light yellow oil remained which almost immediately began to crystallise, and soon set to a hard, crystalline cake. This was ground up and recrystallised from ethyl alcohol, in which it is readily soluble while hot, but only sparingly so in the cold ; it separates in the form of beautiful, highly refractive, pearly scales, melting at 162° to a faintly reddish-coloured liquid. On analysis, the following results were obtained : 0-1382 gave 0-3059 C02 and 0-0712 H20. C = 60-4; H = 5-7. 0-3408 „ 0-1758 AgBr. Br = 21*9. ' C18H20O2NBr requires C = 59’7 ; H = 5'5; Br = 22T per cent. A determination of the specific rotation in ethyl alcohol gave the following result : aD= + 1°4'; 1=1 dcm. ; c = 1 -887 ; [ a ]J” = +56-5°. The yield of bromocodeide, prepared as above, is almost quan¬ titative. iso Codeine, C17H1802N(0CH3).—This was obtained from bromo¬ codeide by the action of water, as follows. Bromocodeide (20 grams) was suspended in water (200 c.c.) contained in a reflux apparatus, and to the warmed mixture glacial acetic acid was added, drop by drop, until the suspended base just dissolved. The clear solution so obtained was boiled for 3 hours, cooled, made alkaline with sodium carbonate, and the base which separated taken up by ether. The ethereal solu¬ tion was washed with a little water, dried, and concentrated, when on standing a short time a crystalline base melting at 140—144° separated out. This was collected and recrystallised twice from pure dry ether by extraction in a Soxhlet apparatus. The base separates from boiling ether in beautiful, long, prismatic needles, which are quite free from bromine and melt at 144°. It is very easily soluble in cold methyl or ethyl alcohol, and can be readily recrystallised by dissolving in a small amount of the former solvent and distilling with repeated additions of dry ether. A specimen of the base recrystallised from ether was analysed, with the following results : 0-1775 gave 0-4737 C02 and 0-1152 H20. C = 72*7; H = 72. Ci8H2]03N requires C = 72‘3; H = 7'0 percent.