Search

Details of the synthesis of the 19-methyl, 19-methylene and 19-chloro derivatives of 17α, 21-dihydroxy-pregn-4-ene-3, 20-dione from the 19-hydroxy-Δ5 intermediate 6a are reported. Incubation of the 19-methyl and 19-chloro compounds 13 and 19 with bovine adrenal homogenates produced 19-methyl-11β,17α,21-trihydroxypregn-4-ene-3, 20-dione ( 20a ) and 17α, 21-dihydroxy-11β,19-oxidopregn-4-ene-3, 20-dione ( 22a ) respectively. The incubation of the 19-methylene steroid 11a took an unexpected course and afforded after acetylation a product tentatively formulated as 17α, 21-dihydroxy-19-methyleneoxypregn-4-ene-3, 20-dione 21-acetate ( 23 ).

The conversion of 19-nortestosterone acetate into 19-norandrosta-4,7-diene-3,17-dione (X) is described. The latter compound is transformed directly into equilin by a microbiological dehydrogenation process with Corynebacterium simplex , thus representing the first synthesis of this important female sex hormone. Alternate attempts to synthesise equilin are discussed.