MORPHINE ALKALOIDS .117. INVESTIGATION OF THE AZIDOLYSIS OF TERTIARY ALCOHOLS OF THEBAINE DERIVATIVES WITH BRIDGED RING-C

Replacement of the C-19 tertiary hydroxyl group of some thebaine and o ripavine derivatives with bridged ring C (so called Bentley's compound s) for an azido group has been performed with hydrazoic acid. In case the hydroxyl group was connected to a centre of chirality, substitutio n resulted in the formation of diastereomeric mixture of azides and el imination took place as well, the extent of which was dependent mainly on steric factors. Configuration of the C-19 has been determined by H -1-NMR spectral and calculated proton-proton distances of amines 13a a nd 13b obtained by the reduction of 10c followed by separation.