GB1239479A - - Google Patents

Abstract

1,239,479. 1α,2α - Methylene - steroids. SCHERING A.G. 19 -July, 1968 [19 July, 1967], No. 34548/68. Heading C2U. Novel racemic and optically active steroids of the. formula (wherein R is H or a hydrocarbon group and R<SP>1</SP> is H or acyl) are prepared by -introducing a double bond into the 4,5-position of corresponding ring A-saturated steroids. The introduction is effected by. known methods, e.g. a 3-ketosteroid is converted to a 3-enol ester and this is brominated then dehydrobrominated. Resulting 17-ols may be acylated and 17-acylates hydrolysed. 17# - Acetoxy - 18 - methyl - 1α,2α - methylene- 5α-estran-3-one is prepared by reducing 17#- hydroxy - 18 - methyl - 4 - estren - 3 - one to give 17# - hydroxy - 18 - methyl - 5α - estran - 3- one (and the corresponding 3#,17#-diol, which, alone or in admixture with the 3-one, can be oxidized to the 3,17-dione, this converted to 3,3- dimethoxy - 18 - methyl - 5α - estran - 17 - one and this reduced and hydrolysed to give more of the required 17#-ol-3-one), this is converted to the 17-acetoxy compound, this is brominated and dehydrobrominated to give 17#-acetoxy-18- methyl-5α-estr-1-en-3-one and this is converted to the required product. All the foregoing compounds are racemates. The d-enantiomers are prepared similarly; hydrolysis of the final product gives 17# - hydroxy - 18 - methyl - 1α,2α- methylene-5α-estran-3-one and this on esterification gives the 17-propionyloxy compound. The novel anabolic steroids may be made up into pharmaceutical compositions with suitable carriers.