New cyclopentanophenanthrene derivatives and processes for the production thereof

摘要

The invention comprises 19-norandrostanes of the formula FORM:0890989/IV (b)/1 in which R is hydrogen or hydrocarbon carboxylic acyl group of up to 12 carbon atoms, R2 is hydrogen, vinyl, ethinyl or lower alkyl of up to 6 carbon atoms, R1 is the same as R when R2 is hydrogen or hydrogen when R2 is other than hydrogen together with a process for their preparation by reacting the corresponding 19-nortestosterone compound with an alkali metal in liquid ammonia and reducing the corresponding 19-norandrostan-17b -ol-3-one thus obtained with an alkali metal double hydride, preferably sodium borohydride. The products so obtained may be subsequently acylated to the 3-mono or 3,17-di-esters. Typical carboxylic acyl groups specified are acetyl, propionyl, benzoyl, caproyl, udecenoyl, and cyclopentylpropionyl. In examples (1) 17a -ethinyl-19-nortestosterone in dioxane-ether is added to lithium in liquid ammonia, ammonium chloride added and 17a -ethinyl-19-norandrostan-17b -ol-3-one extracted with methylene chloride and reduced in dioxane with sodium borohydride to 17a -ethinyl-19-norandrostane-3b ,17b -diol; similarly 19-norandrostane-3b ,17b -diol, its 17a -vinyl, 17a -ethyl and 17a -methyl derivatives are prepared from the corresponding 19-nortestosterones; (2) 17a -ethyl-19-norandrostane-3b ,17b -diol is treated with acetic anhydride and pyridine in the cold giving the 3-acetate; the 3-propionate, butyrate, hemisuccinate, caproate, trimethylacetate, cyclopentylpropionate, benzoate, phenoxypropionate and b -chloro-propionate esters and also the same 3-esters of the 17a -vinyl-, ethinyl- and methyl-19-nor-androstane-3b ,17b -diols and 3,17-diesters of 19-norandrostane-3b ,17b -diol are similarly prepared. Specification 890,988 and U.S.A. Specification 2,756,244 are referred to.