The chemistry of 9α-hydroxysteroids. 1. preparation of 9α,17β-dihydroxy-17α-ethynylandrost-4-en-3-one

Abstract 9α-Hydroxyandrost-4-ene-3, 17-dione 1 , when allowed to react with dipotassium acetylide in tetrahydrofuran, resulted, after chromatographic separation, in 4-methyl-19-norandrosta-4, 9-diene-1, 17-dione 2 , 4ξ-methyl-19-norandrosta-5(10), 9(11)-diene-1, 17-dione 3 . 4-methyl-17α-ethynyl-17β-hydroxy-19-norandrosta-4, 9-dien-1-one 4 , 4ξ-methyl-17α-ethynyl-17ξ-hydroxy-19-norandrosta-5(10), 9(11)-dien-1-one 5 , and 17α-ethynyl-17β-hydroxy-9, 10-secoandrost-4-ene-3, 9-dione 6 . Selective protection of Δ 4 -3-ketone of 9α-hydroxyandrost-4-ene-3, 17-dione 1 as its dienol methyl ether 7 , and subsequent reaction with lithium acetylide-ethylenediamine followed by acidic hydrolysis, afforded 9α, 17β-dihydroxy-17α-ethynylandrost-4-en-3-one 8 .