GB1040031A - 19-alkyl-steroids and process for their production - Google Patents

Abstract

The invention comprises compounds of the formula <FORM:1040031/C2/1 wherein R is hydrogen or a hydrocarbon carboxylic acyl group of less than 12 carbon atoms which may be substituted; R1 is hydrogen, lower alkyl, lower alkenyl or lower alkynyl; Z is a double bond or a saturated link between C-1 and C-2; and X is lower alkyl; the word " lower " referring to groups containing at most 8 carbon atoms) and their preparation by Oppenauer oxidation of the corresponding D 5-3b -ols. This process cannot be effected on free 17-secondary alcohols, which are prepared by hydrolysis of the 17-acylates. The 17-ols may be re-esterified. D 1,4-compounds are prepared by chemical or microbiological dehydrogenation of the corresponding D 4-compounds. 17a -alkenyl compounds may also be prepared by hydrogenation of 17a -alkynyl compounds. Examples are given, and the conversion of the products into 6-substituted derivatives, by conversion to D 5-3-ethylene-ketals and then 5a ,6a -epoxy-3-ethyleneketals and reaction of these (a) with methyl magnesium halides followed by acid treatment of the 6b -methyl-5a -hydroxy-3-ethylene-dioxy compounds to give the 6a -methyl-D 4-3-ketones; or (b) with anhydrous hydrogen chloride to give the 6a -chloro-D 4-3-ketones; or (c) with anhydrous hydrogen fluoride, followed by treatment with hydrogen chloride, to give the 6a -fluoro-D 4-3-ketones. 19 - Alkyl - 17b - acyloxy - D 5 - androsten - 3b - ols used as starting materials are prepared from the corresponding 19-alkyl-D 5-androsten-3b -ol-17-ones by conversion to 3-tetrahydropyranyl ethers, reduction to 17b -ols, acylation to 17b -acylates, and hydrolysis of the 3-ether group.