GB853012A - 1:6-dimethyl aromatic steroids and the preparation thereof - Google Patents

Abstract

The invention comprises steroids of the formulae: <FORM:0853012/IV(b)/1> (wherein X is = O, a H b OH or a Hb (Oacyl) and R is hydrogen or acyl containing up to 4 carbon atoms); the preparation of the tetraens (II) by reacting a steroid of the formula : <FORM:0853012/IV(b)/2> with toluene-p-sulphonic acid, sulphuric acid, hydrobromic acid or zinc chloride in an acyl chloride of at most 4 carbon atoms or an acid anhydride of at most 8 carbon atoms, followed by hydrolysis as required; and the preparation of the triens (III) by catalytic hydrogenation of the tetraens e.g. with palladium on charcoal or calcium or barium carbonate in a solvent such as a lower fatty acid ester, dioxan, tetrahydrofuran or, preferably, an aliphatic alcohol of at most 4 carbon atoms. Products containing a 17-keto group may be converted into the corresponding 17b -hydroxy compounds by treatment with sodium borohydride in methanol. The preparation of the 3:17-diacetoxy- and the 3-acetoxy-17-one-compounds and, their hydrolysis to the corresponding free hydroxy compounds of both the tetraens and the triens is described in examples, the hydrolysis being performed either before or after the reduction. 17b -Acetoxy-6-methylandrosta-1 : 4 : 6-trien-3-one is prepared by heating 17b -acetoxy-6-methylandrosta-4 : 6-dien-3-one with 2 : 3-dichloro-5 : 6-dicyano-p-benzoqiunone in dioxan. Specifications 843,355 and 852,847 are referred to.