A 2H n.m.r. study of the dienol–benzene and related steroid aromatization reactions

Abstract

² H N.m.r. studies have shown that when the dienol–benzene rearrangements of 5α,6β-epoxy-3β-mesyloxyandrostan-17-one, the corresponding 5α,6β-bromohydrin, 4β-acetoxy-3β-mesyloxyandrost-5-en-17-one, 17β-acetoxy-4β,5β-epoxy-3α-mesyloxyandrostane, and 17β-acetoxy-3β,4β-epoxy-5β-hydroxyandrostane are carried out in ²HBr–CH₃CO₂²H, deuterium labels are introduced at predominantly the 6β position and at both 7 positions in the resultant 4-methyloestratriene. However the 4-methylpestratriene arising from a 3-hydroxyandrosta-1,4-diene only bears deuterium labels on the aromatic ring.