2 - oximino - 17ª - hydroxy - 17ª ≠ - methyl - 3 - ketostatines steroids of androstane series and a process for their production

摘要

Novel steroids of the formulae FORM:1065237/C2/1 FORM:1065237/C2/2 FORM:1065237/C2/3 (wherein R1 is hydrogen, halogen, or hydroxy, but is not halogen or hydroxy in compounds I; R2 is hydrogen or methyl; R3 is hydrogen or alkyl; R4 is hydrogen, keto or b -hydroxy; R5 is hydrogen, alkyl, alkenyl, o -haloalkynyl or alkynyl; R6 is hydrogen, alkanoyl, aralkanoyl cycloalkylalkanoyl or chlorophenoxyalkanoyl; R7 is hydrogen, halogen or alkyl, but is not halogen in compounds I and II; and X is hydrogen or halogen) are prepared by reacting the corresponding 2-hydroxymethylene steroids with nitrous acid. Steroids of the formula FORM:1065237/C2/4 are prepared from the corresponding 2-unsubstituted steroids and alkyl formates. Free hydroxy groups may be formylated in this process. 7a ,17a - Dimethyl - 17b - hydroxy - 19 - norandrostan-3-one is prepared by reacting 17b -hydroxy - 17a - methyl - 19 - norandrosta - 4,6-dien-3-one with methyl magnesium bromide to give 7a ,17a - dimethyl - and 7b ,17a - dimethyl-17b - hydroxy - 19 - nor - androst - 4 - en - 3 - ones and reducing the 7a -compound. The corresponding 17a -ethyl compounds are prepared similarly. 17b - Hydroxy - androstan - 3 - one 17b - (3-phenyl-propionate) is prepared by reduction of the D 4-compound. 4,17 - Dihydroxy - 17a - methyl - androst - 4-en - 3 - one is prepared by stirring 4b ,5-epoxy - 17b - hydroxy - 17a - methylandrostan-3-one (prepared from the androst-4-ene compound and H2O2) with glacial acetic acid and sulphuric acid. The corresponding 4-chloro compound is prepared from the 4,5-epoxide and glacial acetic saturated with hydrogen chloride.