GB841411A - New 19-nor-steroid compounds and process for the preparation thereof - Google Patents

Abstract

The invention comprises compounds of the formulae <FORM:0841411/IV(b)/1> (wherein R is an alkenyl or alkynyl group containing 2 to 6 carbon atoms and R1 is hydrogen or a carboxylic acyl group of at most 10 carbon atoms) and their preparation by reaction of the corresponding 17-keto-steroids with an appropriate organometallic compound derived from the hydrocarbon RH, including Grignard reagents and alkali metal or alkaline earth metal compounds of alkynes formed in situ from the alkyne and an alkali metal or an amide or alcoholate thereof. The esters are prepared by esterification of the free hydroxy compounds, suitable esterifying acids being acetic, propionic, butyric, valeric, caproic, isocaproic, succinic, tartaric, cyclopentyl-acetic, b -cyclopentyl-propionic, cyclohexyl-acetic, gammacyclohexyl-butyric, phenylacetic, b -phenylpropionic and benzoic acids, glycine and phenylalanine. The 17-alkenyl compounds may also be prepared by partial reduction of the 17-alkynyl compounds, preferably with hydrogen and a catalyst such as nickel or palladium on barium or calcium sulphate. Examples are given, the groups R being variously ethynyl, hex-5-ynyl, vinyl, pent-4-eryl, allyl, methylethynyl, propargyl and but-3-enyl. D 4 - and D 5(10) - 17b - hydroxy - oestrene an D 3 : 5 - 17b - hydroxy - oestradiene are all prepared by reduction of oestradiol-3-alkyl-ethers with an alkali metal in the presence of liquid ammonia or an aliphatic primary amine and are all converted to the corresponding 17-oxo compounds by oxidation with chromium trioxide. 17b - hydroxy - oestrane is prepared by catalytic reduction of D 4-17b -hydroxy-oestrane and is similarly converted to 17-oxo-oestrane.