Partial Modifications of Hydroxy Groups in 5-Methyl-5β-estr-9-ene Derivatives

Abstract

In compounds of the Westphalen type the substituent in position 6 has been removed: the 6β-hydroxyl in 3β,17β-dibenzoyloxy-5-methyl-5β-estr-9-en-6β-ol (1) by oxidation to ketone 2 and Huang Minlon reduction, the 6β-chlorine atom in 3β-acetoxy-6β-chloro-5-methyl-5β-estr-9-en-17-one (13) by reduction with tributyltin hydride. Androstenedione, testosterone and methyltestosterone analogues 4, 5, and 16, respectively, were prepared from 3β,17β-dihydroxy-5-methyl-5β-estr-9-ene (3) by partial oxidation or partial acylation followed by oxidation. Alternatively, these derivatives were prepared from compound 13 without the need of partial transformations.