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

  • Samuel Barnett Schryver
Date:
[1901]
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Licence: In copyright

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

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    alcohol, which is only expelled after prolonged heating at 120°, as well as by the fact that the free base is readily soluble in cold water. The method of separation of isomorphine from /5-isomorphine is described in detail in the experimental part of this paper, and the further investi¬ gation of these bases is reserved by one of us (F. H. L.). It was pointed out in our previous communication that isomorphine differs markedly from morphine in its physiological behaviour, and in view of this fact it appeared of interest to determine as fully as pos¬ sible the chemical relationship between these two isomerides. For this purpose, a long series of investigations was instituted. On treatment with acetic anhydride, womorphine yields a diacetyl derivative, Cl7Hl70N(0*C0*CH3)2, which was isolated in the form of a crystalline methiodide. Phosphorus tribromide, as also hydrobromic acid, reacts with iso¬ morphine and regenerates bromomorphide. This reaction with phos¬ phorus tribromide is in marked contrast to that with phosphorus trichloride. Although isomorphine was treated with the latter reagent several times, and under varying conditions, in no case could any chloromorphide be obtained. The only product that could be isolated was a syrupy base, which readily oxidised on exposure to air. It was pointed out in the previous paper that chloromorphide is strongly laevorotatory. The investigation of the action of water on chloromor¬ phide, which is described in detail below, has revealed the fact that different products are obtained from chloromorphide and bromomor¬ phide, and we have reason to believe that the two substances are not chemically analogous, that is, they are not respectively the chloro- and bromo-derivatives of the same base. Bromomorphide is possibly bromoisomorphide, since both morphine and isomorphine, on treatment with phosphorus tribromide, yield the same bromo-derivative. Further experiments described in this paper relate to the exhaustive methylation of isomorphine. It was shown in our last paper (loc. cit., p. 1039) that isomorphine methiodide, on treatment successively with molecular quantities of silver sulphate and barium hydroxide, yields a product to which a phenol-betaine constitution, O N(CH3)2 > was provisionally assigned. Further experiments have demonstrated the correctness of this assumption, for on treatment with methyl iodide, the methiodide of an iso codeine was obtained: c16h15o2< o N(CH3)2 ch3i ^16^-15^2^ och3 N(CH3) According to this equation, the phenolic hydroxyl group of the molecule should become methylated by the action of methyl iodide. That this reaction does in reality take place as shown is evident from