GB967606A - Improvements in or relating to steroids - Google Patents

Abstract

The invention comprises a steroid compound having the formula: <FORM:0967606/C1/1> or <FORM:0967606/C1/2> where R and R1 are alkyl groups having 1-8 carbon atoms and a process of preparing a 6a , 16a -dialkyl -17- hydroxyprogesterone which comprises (a) reducing a 5a , 6a -oxido - 16a - alkyl pregnan-3b , 17a -diol -20- one with an alkali metal borohydride to provide a mixture of 20a and 20b epimers of 5a , 6a -oxido -16a - alkyl-pregnan-3b , 17a , 20-triol, (b) alkylating the 20b -epimer of (a) with an alkyl or dialkyl metal halide to provide a 6b , 16a -dialkyl-pregnan-3b , 5a , 17a , 20b -tetrol, microbiologically oxidising the product of (b) to provide the corresponding 3-keto compound, and (d) dehydrating and epimerising the product of (c) to provide a 6a , 16a -dialkyl -17a - hydroxyprogesterone. The alkylation may be effected with methyl magnesium bromide and the microbiological oxidation with Flavobacterium dehydrogenans var. hydrolyticum. The 5a , 6a -oxido -16a - alkyl-pregnan-3b , 17a -diol -20- one starting compound may be obtained by (a) alkylating a 5a , 6a -oxido -16- pregnen -3b - ol -20- one 3-acylate with an alkali metal halide, (b) acylating the product of (a), (c) epoxidising the acylated product with a peracid to provide a 5a , 6a ; 17a , 20-dioxido compound and (d) hydrolysing said dioxido compound under alkaline conditions to provide 5a , 6a -oxido -16a - alkylpregnan-3b , 17a -diol -20- one. Alternatively the starting compound may be obtained by (a) alkylating a 5, 6-pregnadien-3b -ol-20-one 3-acylate with an alkyl metal halide, (b) acylating the product of (a), (c) epoxidising the acylated product with a peracid to provide, a mixture of isomeric forms of a 5, 6; 17, 20-dioxido compound, (d) hydrolysing said dioxido compound under alkaline conditions to provide an isomeric mixture of 5, 6-oxido -16a - alkylpregnan-3b , 17a -diol -20- one, (e) acylating the product of (d) to provide the 3-acylate (f) hydrolysing the product of (e) under acid conditions to provide the trans diaxial 5, 6-diol, and (g) reclosing the trans diol system by treatment with an alkyl sulphonyl chloride followed by heating under alkaline conditions to provide 5a , 6a -oxido -16a - alkylpregnan-3b , 17a -diol-20-one. Specifications 938,445 and 967,005 are referred to.