Novel analgesics and molecular rearrangements in the morphine–thebaine group. Part XIV. Substitution in the aromatic nucleus in derivatives of 6,14-endo-ethenotetrahydrothebaine

Abstract

The tetrahydrothebaine ester (1; R = H) has been acetylated with acetic acid and trifluoroacetic anhydride. The product (1; R = Ac) has been reduced to the secondary alcohol and converted by the Schmidt reaction into the acetyl derivative of the amine (1; R = NH₂), which is the product of reduction of the 1-nitro-compound obtainable by nitration of the ester (1; R = H). Chlorination of the tetrahydrothebaine alcohol (2; R = Me) affords the 1-chloro-compound, which has been demethylated to the related phenol. By the Mannich reaction the phenol (2; R = H) has been converted into 2-amino-compounds.