The reaction of some substituted 2α,3α-epoxy-5α-hydroxyandrostanes with hydrogen bromide in acetic acid

Abstract

Whereas the reaction of 2α,3α-epoxy-5α-hydroxyandrostanes with hydrogen bromide in acetic acid readily gives 4-methyloestratrienes, the presence of an additional 4β-acetoxy, 6α- or 6β-hydroxy group in the substrate leads to the formation of non-aromatic products. The 6α-alcohol gave 3α-acetoxy-2β-bromo-5β-androstane-6,17-dione, the structure of which was confirmed by X-ray crystallography, whilst the 6β-alcohol gave this ketone and 3α,6β-diacetoxy-2α,5α-epoxyandrostan17-one.