Nucleophilic Substitution in the Allyl System of Codeine and Pseudocodeine in their Reactions with Lithium Methyl- and Aryl-cyanocuprates. Crystal and Molecular Structure of #form_14# and #form_15#

It has been shown that nucleophilic substitution in 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 8β-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan is accompanied by allylic rearrangement with both a change in and retention of the orientation of the substituting group. X-Ray diffraction studies of 8α-phenyl-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 6β-phenyl-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 6β-phenyl-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan have been carried out.