Iodination of thebaine and synthesis of 9-substituted indolinocodeinone derivatives

Abstract

Iodination of thebaine in methanol, with or without silver salt catalysis, gives, in good yield, 7β-iodoneopinone dimethyl acetal, which reacts with a-wide variety of nucleophiles to provide indolinocodeinone derivatives carrying the following 9α-substituents: OH, OMe, ONO, OAc, NC, N₃, NMe₂, CN, and SCN. 9,10-Didehydroindolinocodeinone dimethyl acetal and 9α-chloroindolinocodeinone have also been prepared. Treatment of the iodoacetal or 14-bromocodeinone dimethyl acetal with silver perchlorate in benzene gave an aziridinium salt believed to be an intermediate in the solvolvtic rearrangement reactions of both halogeno-acetals.