Acetomorphine and Acetocodeine

Abstract

The introduction of an acetyl group into the aromatic ring of morphine and codeine by the action of sulfoacetic acid, H0S02CH2C00H (1), was first described in a patent of Knoll and Co. (2). Later, Knorr (3) prepared various derivatives of acetocodeine, degraded it to aceto-0-methyhnorphimethine, and ultimately to acetomethylmorphol. More recently, Small and Mallonee (4) proved by way of the Beckmann rearrangement of aceto-6-acetylcodeine oxime, that the acetyl ("aceto") group occupies the 1 -position. It is convenient to retain the term "aceto" for this group to distinguish it from O-acetyl groups. SUMMARY Acetylation of dihydromorphine and dihydrocodeine with sulfoacetic acid is described. The same nuclear acetylated compounds are obtained by hydrogenation of 1-acetomorphine and 1-acetocodeine derivatives. In the acetocodeine series, stepwise reduction of the nuclear acetyl group to the 1-hydroxyethyl and ethyl group can be accomplished.1-Acetocodeine can be degraded to 1-aceto-a-methylmorphimethine, and this in turn converted to l-aceto-/3-methylmorphimethine, thus establishing the heretofore doubtful nature of the latter.Bethbsda 14, Md.

L-Selectride as a General Reagent for the O-Demethylation and N-Decarbomethoxylation of Opium Alkaloids and Derivatives1

“…Dihydromorphine (17). , Dihydrocodeinone ( 16 ) (540 mg, 1.8 mmol) was treated with 3 equiv of L-Selectride at room temperature for 0.5 h, followed by reflux for 3 h. After aqueous workup, crystallization from water gave 17 ·H 2 O (230 mg, 42%).…”