GB1111448A - 13-alkyl-gonenes and gonadienes - Google Patents

Abstract

Novel steroids of the structure <FORM:1111448/C2/1> (wherein R1 is alkyl; X is a hydrolysable protected 3-keto group accompanied by an ethylenic bond to the 5-position with or without a similar bond to the 3-position; and Y is CHOH, CHO acyl, CO or ketalized CO, or C.R(OH) in which R is a C1- 6 aliphatic hydrocarbon group trans to R1 which may be substituted by halogen, OH, alkoxy or unsubstituted or substituted amino; and each of the hydrogen atoms H is trans to R1) are prepared (1) for 3-etherified hydroxy-D 2,5(10)-dienes, by Birch reduction of the corresponding D 1,3,5(10)-trienes; (2) for 17-R-substituted compounds, by reaction of the corresponding 17-ones with an organo-metallic derivative of R; (3) for 17-R-substituted compounds wherein R is alkyl, by hydrogenation of the compounds wherein R is alkenyl or alkynyl; (4) for 17-acylates, by acylation of the 17-ols; and (5) for 17-ones, by oxidation of the 17-ols. Preferred products are 8-isogonenes i.e. compounds of \sH9a ,8a ,14a ,13b -configuration, and their racemates. The compounds of the invention may also be prepared from the corresponding D 4- or D 5(10)-3-ones e.g. by enol-alkylation to give a D 3,5- or D 3,5(10)-3-alkoxy-compound. Interconversions in ring A may also be effected, e.g. 3-methoxy-D 2,5(10) to 3,3-ethylenedioxy-D 5(10). Examples of the Group X are alkoxy with or without further substituents, alkylthio, disubstituted amino, alkylenedioxy, alkylenedithio, alkylene thiooxy, and acyloxy. (\sB) - 17a - Ethyl - 3 - methoxy - 13b - methyl- 8 - isogona - 1,3,5(10) - trien - 17b - ol is prepared by hydrogenation of the 17a -ethynyl compound, prepared in turn from the 17-one.