GB1010052A - 13-alkyl steroids related to oestradiol - Google Patents

Abstract

The invention comprises compounds of the formula <FORM:1010052/C2/1> (wherein R is hydrogen, a substituted or unsubstituted alkyl group or an acyl group, R1 is an alkyl group of at least 2 carbon atoms, X is a hydroxymethylene or acyloxymethylene group and the substituents at the junctions in ring C are in the trans-anti-trans configuration) and their preparation (1) by reducing compounds of the formula <FORM:1010052/C2/2> (wherein R is hydrogen or a substituted or unsubstituted alkyl group, R1 is as defined above, and X is carbonyl or hydroxymethylene, ring C contains a D 8(9) or a D 9(11) double bond, the C : D ring junction is in the trans-configuration and the 8-hydrogen atom when present is anti to the 14-hydrogen atom) with an alkali metal in liquid ammonia to give products wherein R is hydrogen or substituted or unsubstituted alkyl and X is hydroxymethylene; or (2) by catalytic hydrogenation of the corresponding D 9(11)-steroids, followed, when required, by reduction of the 17-keto group to the 17b -hydroxy group, and, if required, acylation to a 17b -acyloxy compound. The above structures include all states of resolution except the resolved 13a -enantiomers. Examples are given, in one of which a 3,17-diacetate is prepared by actylation of a 3,17-diol. (\sB) - 8 - Dehydro - 18 - nor - 13b - n - propyloestradiol 3-methyl ether is prepared by condensing 2 - n - propylcyclopentane - 1,3 - dione with 6 - m - methoxyphenyl - hex - 1 - en - 3 - one to give 2 - n - propyl - 2 - (61 - m - methoxyphenyl-31 - oxohexyl) - cyclopentane - 1,3 - dione, heating this with p-toluenesulphonic acid to give (\sB)-8, 14 - bisdehydro - 18 - nor - 13 - n - propyloestrone methyl ether, catalytically hydrogenating this to give (\sB) - 8 - dehydro - 18 - nor - 13b - n - propyloestrone methyl ether are reducing this with sodium borohydride. Similarly are prepared (\sB) - 8,14 - bisdehydro - 13 - n - butyl - 18 - noroestrone methyl ether and (\sB) - 13b - n - butyl-8-dehydro-18-nor-oestron methyl ether. Specifications 1,010,053, 1,010,054 and 1,010,055 also are referred to. Reference has been directed by the Comptroller to Specification 979,891.