GB911740A - Enolethers of 2- or 6-substituted í~-3-ketones of the androstane series - Google Patents

Abstract

The invention comprises steroids of the general formula <FORM:0911740/IV (b)/1> wherein R represents an aliphatic or cycloaliphatic group, W represents a keto or b -hydroxy group or a group of the formula <FORM:0911740/IV (b)/2> in which R2 represents an alkyl group containing 1 to 3 carbon atoms, X represents hydrogen or a methyl group and Y represents hydrogen, chlorine or fluorine or a methyl group, X being hydrogen when Y is other than hydrogen and Y being hydrogen when X is methyl, and 17b -carboxylic esters thereof, and the preparation thereof by reacting lower alkyl orthoformates and the required D 4-3-ketones to form the desired 3-lower alkyl enol ethers, and by treating the corresponding 3-methyl or ethyl enol ethers with cycloaliphatic or high alkyl alcohols to form the 3-cycloaliphatic or high aliphatic enol ethers of the above general formula. The enol ethers of 6-halo-testosterone and 6-halo-17a -methyl-testosterone may also be prepared from the corresponding enol ethers of 6-halo-androstenedione by treating the dione with a reducing agent such as lithium borohydride to form the enol ether of 6-halo-testosterone and by treating the dione with methyl magnesium bromide to form the enol ether of 6-chloro-17a -methyl-testosterone. Pharmaceutical compositions having myogenic and anabolic activity contain as the active ingredient steroids of the above general formula. The composition may have a solid or liquid carrier such as sesame, olive or other vegetable oil, ethanol, or glycol. 6a -Chloro-androstenedione is prepared by treating the ethyl enol ether of androstenedione with N-chloro-succinimide to form a mixture of 6a - and 6b -chloro-androstenediones, and treating the mixture with dry hydrogen chloride. 6-Chloro-testosterone and -17a -methyl-testosterone are prepared by treating the enol ethyl ethers of testosterone and 17a -methyl-testosterone respectively with N-chloro-succinimide to form in each case a mixture of the 6a - and 6b -chloro isomers. 3-Ethers of 3-hydroxy-androstanes are prepared by catalytically hydrogenating the 3-enol-ethers of the above general formula.