GB1004667A - Improvements in or relating to steroids and the manufacture thereof - Google Patents

Abstract

The invention comprises a compound having the formula <FORM:1004667/C2/1> wherein R is hydrogen or the acyl radical of a hydrocarbon carboxylic acid containing 1-12 carbon atoms, the corresponding D 1,D 4,6, D 1,4 and D 1,4,6 compounds, a compound having the formula <FORM:1004667/C2/2> wherein Ac is the acyl radical of a hydrocarbon carboxylic acid containing 1-12 carbon atoms and Hal represents iodine chlorine or bromine, a compound of the formula <FORM:1004667/C2/3> wherein R is hydrogen or the acyl radical of a hydrocarbon carboxylic acid containing 1-12 carbon atoms and processes for the preparation thereof wherein 3b ,17a -dihydroxy-5-pregnen-20-one 3,17-diacylates is treated with carbon mon-oxide and hydrogen to obtain the corresponding 6-hydroxymethyl compound, treating the latter with a halogenating agent to produce the corresponding 6-halomethyl compound e.g. 6a -iodomethyl - 3b ,17a - dihydroxy - 5a - pregnan-20-one reacting the latter with silver fluoride to obtain a mixture of a 6-fluoromethyl- and a 6-methylene - 3b ,17a - dihydroxy - 5a - pregnan-20-one 3,17-diacylate, hydrolysing the mixture to obtain the corresponding 3-hydroxy compounds, and hydrolysing the latter e.g. with chromic acid to obtain a mixture of 6a -fluoromethyl -17a - hydroxy -5a - pregnane -3,20 -dione 17 - acylate and 6 - methylene - 17a - hydroxy-5a - pregnane - 3,20 - dione 17 - acylate which may be separated by chromatography. Dehydrogenation may be effected (1) (a) with selenium dioxide, (b) with dibenzoyloxy selenium dioxide, (c) by 2,4-dihalogenating agents followed by lithium chloride, (d) with a microorganism from the genus Fusarium to obtain the corresponding D 1,4 compounds; (2) by 2-halogenating agents followed by lithium chloride to obtain the corresponding D 1 compounds; (3) (a) by 2,4-dihalogenation followed by sodium iodide, or (b) with a microorganism of the genus Nocardia to obtain the corresponding D 4 compounds; (4) by treating the D 4 compounds with chloranil to obtain the D 4,6 compounds; (5) by treating the D 4,6 compound with a microorganism of the genus Septoxmyxa to obtain the corresponding D 1,4,6 compounds. Pharmaceutical compositions having progestational activity and useful also as anti-estrogens and anti-gonadotropins and containing the above compounds are administered orally in pills, tablets, capsules, syrups or elixirs, and in liquid form e.g. solution or suspensions as injectable products. Specifications 829,903 and 1,004,668 are referred to.