Verfahren zur Herstellung von 17ª‡-Oxy-6ª‡-methyl-16-methylenpregn-4-en-3, 20-dion bzw. von dessen Acylderivaten

The invention comprises: (a) 17a -hydroxy-6a -methyl-16-methylenepregn-4-ene-3 : 20-dione; (b) acyl derivatives of compound (a), of the general formula: wherein R represents an acyl group of up to 10 carbon atoms; (c) 6a : 16-dimethyl-16a : 17a -epoxypregn-4-ene-3 : 20-dione; (d) the preparation of compound (a) by oxidizing 3b -hydroxy-6 : 16-dimethylpregna-5 : 16-dien-20-by the Oppenauer procedure to give 6a : 16-dimethylpregna-4 : 16-diene-3 : 20-dione, reacting this with alkaline hydrogen peroxide to give compound (c), and treating this with a hydrogen halide and then with Raney nickel in an organic solvent; and (e) the preparation of compounds (b) by acylation of the product of (d). Compound (a) can also be obtained by treating compound (c) with sulphuric acid in dioxan. Compounds (b) are useful as progestational agents (see Group VI). The reaction with H2O2 is preferably effected in a water-miscible organic solvent at temperatures between 0 DEG and 100 DEG C. The treatment with hydrogen halide is advantageously performed with hydrogen bromide in an aliphatic acid and an inert organic solvent or with aqueous hydrogen iodide in a water-miscible organic solvent, and the treatment with Raney nickel is preferably performed in ethanol. Examples are given, the values of R illustrated being acetyl and caproyl. Specification 850,423 is referred to.ALSO:Pharmaceutical compositions comprise compounds of the formula: (wherein R is an acyl group of up to 10 carbon atoms) and a solid or liquid carrier. They may take the form of tablets, powders, capsules, pills, solutions, emulsions, suspersions, syrups or elixirs. An example describes tablets containing the acetyl derivative of 17 a -hydroxy-6a -methyl-16-methylenepregn-4-ene-3 : 20-dione. Specification 850,423 is referred to.