19-oxygenated pregnane compounds and process for their production

摘要

Novel steroids of the formulae (wherein R is hydrogen, hydroxyl or hydrocarbon carboxylic acyloxy of less than 12 carbon atoms which is optionally substituted; T is hydrogen, a -hydroxyl, a -hyrocarbon carboxylic acyloxy of less than 12 carbon atoms which is optionally substituted, a -methyl or b -methyl with the proviso that when R is hydrogen T is not hydroxy or acyloxy; or T and R together are di-(C1- 8 alkyl)-methylenedioxy; R1 and R2 are hydrogen or a hydrocarbon carboxylic acyl group of less than 12 carbon atoms which is optionally substituted; and X is C1- 8 alkyl) are prepared by treating a steroid of the formula (wherein T1 is hydrogen, a -methyl or b -methyl, or T1 and R together are di-(C1- 8 alkyl)-methyllenedioxy; and Ac is an acyl group) with ethyleneglycol in presence of p-toluenesulphonic acid, oxidizing the produced 20-ketal with chromium trioxide in a basic medium, hydrolysing in a basic medium the obtained 20-cycloethylenedioxy - D 5 - pregnen - 3b - ol - 19 - al acylate, reacting with dihydropyran in presence of p-toluenesulphonic acid under anhydrous conditions the obtained free 3b -ol, treating the produced 3-tetrahydropyranyl ether with an alkyl magnesium halide, oxidizing the 19hydroxyl group of the formed 3-ether of 20cycloethylenedioxy - 19 - alkyl - D 5 - pregnene3b ,19-diol with chromium trioxide in a neutral or basic medium, hydrolysing the ether and ketal groups in the 19-alkyl compounds with an acid, optionally hydrolysing any 16a ,17a ketonide group with a strong acid to form the 16a ,17a -diol, and if desired esterifying the free hydroxyl groups in any of the 19-alkyl compounds containing them. In the reaction with an alkyl magnesium halide any existing acyloxy groups are hydrolysed. Examples are given.