GB1051693A - - Google Patents

Abstract

1,051,693. 19-Alkylene-steroids. SYNTEX CORPORATION. June 21, 1963 [July 9, 1962], No. 24767/63. Heading C2U. Novel steroids of the formulae (wherein R<SP>1</SP> is hydrogen, hydroxyl or hydrocarbon carboxylic acyloxy of less than 12 carbon atoms which is optionally substituted; T is hydrogen, α-hydroxy, α-acyloxy, α-methyl or #-methyl; or T and R<SP>1</SP> together are 16α, 17α- di(C 1-8 alkyl)-methylenedioxy; R<SP>2</SP> is hydrogen; or T and R<SP>2</SP> together are as T and R<SP>1</SP> together; R<SP>3</SP> is hydrogen or acyl as above defined; Y is keto or #-hydroxyl; and X is hydrogen or C 1-8 alkyl) are prepared by treating 3,20-cycloethylenedioxy - #<SP>5</SP> - pregnen - 19 - al (which may also contain the groups R<SP>1</SP> and T) with a triphenylphosphonium alkyl bromide in the presence of butyl lithium in an anhydrous inert solvent to give the corresponding 19-methylene compound, i.e. containing the group -CH= CH-X in the 10-position, hydrolysing this to the corresponding 19-methylene-#<SP>4</SP>-pregnene- 3,20-dione, and then, if desired, converting a 17α-hydroxy compound to the 21-iodo derivative with iodine and calcium oxide, reacting the 21-iodo compound with a potassium acylate in. e.g., acetone, to give the 21-acyloxy compound, incubating this with adrenal glands to give the corresponding 11#-ol and oxidizing this to the 11-one. 16α, 17α-Ketonides may be hydrolysed with strong acid to the corresponding diols, which may be esterified to 16-acylates. 21-Acylates may be hydrolysed and the 21-ols reacylated. 17α-ols may also be acylated.. Examples are given. 3,20 - Bis cycloethylenedioxy - #<SP>5</SP> - pregnen - 17α - ol - 19 - al and the corresponding 16α- and 16#-methyl compounds are prepared by hydrolysis of the corresponding 17-acetates.