The nitration of thebaine with tetranitromethane

Abstract

Thebaine (1) reacts in methanol with tetranitromethane to give, as the major product, 14β-nitrocodeinone dimethyl acetal (2a), which has been converted into, inter alia, 14β-nitrocodeinone (3a), 14β-aminocodeinone dimethyl acetal (2b), 14β-aminocodeinone (3b), and 14β-aminocodeine. The nitration of thebaine with tetranitromethane in benzene in the presence of oxygen takes a different course. The major product has been identified as the cyclic peroxide 8α,10α-epidioxy-8,14-dihydro-14β-nitrothebaine (5) by a series of degradations leading to new 10α-hydroxy- and 10-oxo-thebaine derivatives.