SPIROXENONE

1358664 2,2-Dimethyl-6,7-difluoromethylene- 20-spiroxane compounds MERCK & CO Inc 24 July 1972 [28 July 1971] 34514/72 Heading C2U Novel steroids of the formula where R1 and R11 are each H or CH 3 , and R is -CH 2 - or -CO- and the corresponding 3#-ols and their C 1-6 alkanoates are prepared from the corresponding 3-ones lacking the 2,2- dimethyl and 6,7α-difluoromethylene substitution by inserting the 2,2-dimethyl substitution by reaction with CH 3 I and potassium tert.- butoxide at - 50‹ C. to - 80‹ C., oxidizing to the corresponding #4,6-steroid, e.g. by treatment with chloranil, and reacting this with an alkali metal chlorodifluoroacetate to insert the difluoromethylene substituent followed, when a 3,21- dione is desired, by oxidizing with t.-butyl chromate and, when 3-ols or their acylates are desired, by reduction and acylation. The novel steroids are androgen antagonists, and they may be made up into pharmaceutical compositions with suitable carriers.