GB468123A - Process for the manufacture of tertiary alcohols of the cyclopentano polyhydro phenanthrene series - Google Patents

Abstract

Tertiary alcohols of the cyclopentanopoly-hydrophenanthrene series are prepared by the interaction of acetylene or a substituted acetylene on saturated or unsaturated compounds of the cyclopentanopolyhydrophenanthrene series which contain a keto group in their cyclopentano nucleus. The reaction is conducted in the presence of alkali metals or alkali metal compounds such as alkali amides or alcoholates. Compounds mentioned which may be submitted to the process of the present invention are the follicle hormones, oestrone, equiline and equilenine, and the male sex hormones androsterone and dehydroandrosterone. In the case of oestrone the reaction product has the constitution <FORM:0468123/IV/1> The ethinyl compounds formed may be hydrogenated either to fully saturated compounds or to compounds of an intermediate degree of saturation. When substituted acetylenes are used, tertiary alcohols with a correspondingly longer side chain are obtained. In examples: (1) An ether solution of follicle hormoneacetate is reacted with sodamide and acetylene passed in until no further absorption takes place. The reaction product on decomposition with water yields ethinyl dihydro-follicle hormone acetate, which can be hydrogenated in the presence of a platinum catalyst to ethyl dihydrofollicle hormone acetate; (2) Androsterone is treated according to the process of example (1) to yield on hydrogenation ethyl androstandiol. Samples have been furnished under Sect. 2 (5) of ethinyl androstendiol monoacetate made (1) by passing acetylene into a benzene solution of dehydroandrosterone acetate in the presence of sodamide for about 42 hours. The reaction product is decomposed with water and the crude product purified by its silver salt, (2) by passing acetylene into a benzene solution of androstenolone acetate in the presence of sodamide. The reaction product is decomposed with weak acid, and the unchanged androstenolone acetate recovered by transformation into its semicarbazide, to give as a residue the required product.