Hydroxy‐Morphinane. Mitteilung. Über ein Photooxydationsprodukt von (+)‐3‐Methoxy‐N‐methyl‐morphinan

Abstract

AbstractPhotooxydation of (+)‐3‐methoxy‐N‐methyl‐morphinan hydrobromide (I, HBr, Romilar Roche) yields (−)‐3‐methoxy‐10‐oxo‐N‐methyl‐morphinan (II). The structure of the compound has been established. The introduction of a carbonyl group in position 10 is easily achieved in good yield also by oxydation with chromic acid. Whereas reduction of the 10‐oxo‐compound with lithium aluminium hydride leaves the tetracyclic ring structure of the morphinan compound unchanged, reduction according to Clemmensen causes scission of the ring, leading to a tricyclic octahydro‐phenanthrene with angular basic side chain, the structure of which has been established by synthesis. Pharmacological tests revealed that the introduction of a carbonyl or hydroxy group in position 10 of the dextro series of morphinans causes a marked decrease in the antitussive activity. The corresponding derivatives of the Zaevo series have almost entirely lost their analgesic activity.