Reactions of derivatives of steroidal 3,4,5- and 3,5,6-triols with hydrobromic acid

Abstract

3β,17β-Diacetoxy-4α,5α-dihydroxy-, 3β,17β-diacetoxy-4β,5α-dihydroxy-, and 4β,17β-diacetoxy-3β,5α-dihydroxy-androstane gave 17β-acetoxy-4-methylostra-1,3,5(10)-triene and testosterone acetate on treatment with hydrobromic acid in glacial acetic acid. 3β-Acetoxy-4α,5α-dihydroxyandrostane-6,17-dione gave a 1-methyl aromatic steroid and androst-4-ene-3,6,17-trione, whilst 3β,17β-diacetoxy-4α,5α-dihydroxyandrostan-11-one gave a low yield of the 1-methyl aromatic steroid together with 17β-acetoxyandrost-4-ene-3,11-dione. Whereas 3β,6β-diacetoxy-5α-hydroxy-steroids gave 4-methyloestratrienes, 3β,6α,17β-triacetoxy-5α-hydroxyandrostane gave 3β,17β-diacetoxyandrostan-6-one, and a 6α-methanesulphonate gave an A-homo-B-nor-steroid.