Synthetic steroids. Part VII. The preparation of 3β,14β-dihydroxy-androst-5-en-17-one

Abstract

3β,14β-Dihydroxyandrost-5-en-17-one has been prepared from 3β-acetoxy-5α,6β-dichloroandrost-14-en-17-one by epoxidation at Δ¹⁴ and subsequent rearrangement of the resulting oxide to give the 14β-hydroxy-Δ¹⁵-17-ketone. Removal of the 5α,6β-chlorine atoms from this ketone followed by reduction at Δ¹⁵ gave the required product. The direct oxidation of 3β-acetoxy-5α,6β-dichloroandrostan-17-one with chromic anhydride in acetic acid to give the corresponding 14α-hydroxy-derivative has been investigated. It has been found that for a successful oxidation to take place it is necessary to have hydrobromic acid present in the reaction mixture. Oxidation by chromyl acetate, however, offers an improved route to the 14α-hydroxy-steroid.