NEW 15ALPHA, 16ALPHA-METHYLENE-STEROIDS

摘要

1383334 15α,16α-Methylene-steroids SCHERING AG 21 Feb 1972 [24 Feb 1971] 7943/72 Heading C2U Novel steroids of the formula (wherein R 1 is H or a C 1-4 aliphatic hydrocarbon group and R 2 is H or acyl), are prepared by (a) hydrolysing a novel 3#-acyloxy-15α,16α,methylene-#5-androsten-17-one (prepared by oxidative degradation of a 3#-acyloxy-15α,16α-methylene- #5-pregnene-17α,20#-diol), to the 3#ol oxidizing this by the Oppenauer method to the novel 15α,16α - methylene - #4 - androstene - 3,17- dione, reducing this with a complex metal hydride to the corresponding 3#,17#-diol and oxidizing this to the required 3-one (wherein R 1 and R 2 are each H), which may subsequently be esterified; or (b) converting the starting material for process (a) to a 17α-hydrocarbyl- 15α,16α - methylene - #5 - androstene - 3#,17#- diol by reaction with a suitable hydrocarbonmetal compound, if desired hydrogenating any 17α-alkynyl group to a 17α-alkenyl or 17α-alkyl group, and then oxidizing to give the required product (wherein R 2 is H and R 1 is an aliphatic hydrocarbon group), which may subsequently be esterified. 3# - Acyloxy - 15α,16α - methylene - #5- pregnene-17α,20#-diols (e.g. the 3#-acetoxy compound), are prepared by the action of methylene iodide and a Zn-Cu couple on the corresponding 3# - acyloxy - #5,15 - pregnadiene- 17α,20#-diols, prepared in turn by reduction of the corresponding 20-ones. The novel steroids of the above formula are stated to display a high androgenic activity combined with a favourably differentiated anabolic activity, and they may be made up into pharmaceutical compositions with suitable carriers.