GB748824A - Cyclopentanophenanthrene derivatives and process for the preparation thereof - Google Patents

Abstract

The invention comprises D 4-19-norandrostenes of the formula <FORM:0748824/IV(a)/1> where X is -C­CH or -CH3, and a process for their preparation by reducing a lower alkyl ether of estrone (of which the alkyl group contains not more than six carbon atoms) with an alkali metal in liquid ammonia, followed by hydrolysis with a mineral acid and oxidation with chromic acid to form D 4-19-norandrostene-3:17-dione, which is then converted to its 3-enol ether or thioenol ether and treated with either a methyl Grignard reagent, or acetylene and an alkali metal alkoxide, followed by acid hydrolysis. In examples: (1) 3 - methoxy estrone in dioxane is treated with lithium or sodium in liquid ammonia, the product refluxed with hydrochloride acid and then oxidized with chromic acid in acetic acid to D 4-19-norandosten-3:17-dione. The 3:17-dione is refluxed with ethyl orthoformate and pyridine hydrochloride to yield D 3:5-19-nor-3-ethoxy-androstadien-17-one, which is treated with ethereal methyl magnesium bromide and then acid to give D 4 - 19 - nor 17a - methyl - androsten - 17b - ol - 3 - one. (2) D 3:5 - 19 - nor - 3 - ethoxy-androstadien-17-one prepared as in (1) is treated with potassium in tertiary amyl alcohol under nitrogen, and then with acetylene to give D 4 - 19 - nor - 17a - ethynyl - androsten - 17b - ol-3-one on acid hydrolysis. Specifications 662,400, 745,636, 748,860 and U.S.A. Specification 2,363,338 are referred to.