GB1143437A - 6,13- and 7,13-dialkyl steroids - Google Patents

Abstract

1,143,437. 6,13- and 7,13-Dialkyl-steroids. H. SMITH. 2 June, 1966 [3 March, 1965; 21 Oct., 1965], Nos. 24556/66 and 44629/65. Divided out of 1,103,205. Addition to 1,041,279. Heading C2U. Novel steroids of the formulµ (wherein R<SP>1</SP> is C 2-4 alkyl; R<SP>3</SP> is H or a C 1-6 aliphatic hydrocarbon group which may be substituted and is trans to R<SP>1</SP>; R<SP>4</SP> is OH or Oacyl, or R<SP>3</SP> + R<SP>4</SP> is oxo which may be ketalized; one of R is H and the other is C 1-6 alkyl; in Formula (I) there is a #<SP>4</SP> or #<SP>5(10)</SP> double bond; in Formula (II) X is a hydrolysable protected oxo group and there is a double bond terminating at the 5-position with or without a second double bond terminating at the 3-position, or X is OH or Oacyl with a #<SP>4</SP> or #<SP>5(10)</SP> double bond; and the hydrogen atoms and R<SP>1</SP> at the ring C junctions are in the trans-anti-trans configuration) are prepared by Birch reduction of #<SP>1</SP>'<SP>3</SP>'<SP>5(10)</SP>-3-ol ethers to give #<SP>2</SP>'<SP>5(10)</SP>-3-ol ethers which may then be hydrolysed to #<SP>4</SP>- or #<SP>5(10)</SP>- 3-ones and these reduced to the corresponding 3-ols which may be acylated. Groups in the 17-position may be introduced or interconverted by standard procedures, with or without 3-ketoprotection. 3-Ols may be oxidized and other standard procedures used to interconvert groups in the 3-position. 6- or 7-Alkyl groups may be introduced into #<SP>4</SP>-3-ones by known methods. 6 - Dibromomethylene - 13# - ethylgon - 4 - ene - 3,17-dione is prepared from 3-ethoxy-13#-ethylgona - 3,5 - dien - 17 - one (prepared by enol acylation of the #<SP>4</SP>-3-one) and CBr 4 . 13# - Ethyl - 17# - acetoxygona - 4,6 - dien-3-one is prepared by acetylating 13#-ethyl-17#- hydroxygon - 4 - en - 3 - one to give 3,17#- diacetoxy - 13# - ethylgona - 3,5 - diene and reacting this with N-bromosuccinimide and then calcium carbonate and dimethyl formamide. 3,17# - Diacetoxy - 13#,17α - diethylgona - 3,5 - diene and 17# - acetoxy - 13#,17α - diethylgona- 4,6-dien- 3-one are prepared similarly. Steroids of the Formula (I), and those of the Formula (II) which contain a 3#-hydroxy or - acyloxy group, these steroids being in resolved 13#-form or as racemates with their 13α- enantiomers, may be made up into pharmaceutical compositions with suitable carriers. They have steroid hormone properties, particularly anti-estrogenic, progestogenic and anabolic properties.