| 摘要 |
<p>1,053,045. #<SP>1(10),5</SP>-Pregnane derivatives. SYNTEX CORPORATION. Feb. 19, 1964 [March 14, 1963], No. 6912/64. Heading C2U. Novel steroids of the formulae (wherein X is hydrogen C 1-8 alkyl, C 2-8 alkenyl or C 2-8 alkynyl; R is hydrogen or acyl; R<SP>1</SP> is hydrogen, hydroxy or acyloxy ; X<SP>1</SP> is hydrogen, α- or #-methyl, α-hydroxy or α-acyloxy or R<SP>1</SP> and X<SP>1</SP> together are mono- or di-substituted α α-methylenedioxy, the substituents being one alkyl, aryl or aralkyl radical or two alkyl radicals, each of these radicals containing at most 8 carbon atoms; the acyl radicals being derived from hydrocarbon carboxylic acids of less than 12 carbon atoms which are optionally substituted. Y is hydrogen, #-hydroxy or keto; and R<SP>4</SP> is hydroxy or R<SP>4</SP> and X<SP>1</SP> are as R<SP>1</SP> and X<SP>1</SP> together) are prepared (I) for the 21-unsubstituted steroids, by reducing an appropriate 6 - keto - #<SP>5(10)</SP> - 19 - nor - pregnene in which a 20-keto group is ketalized for protection to a mixture of the 6α- and 6#-ols with simultaneous saponification of any 3- or 17-acyloxy groups and, if desired, introduction of a 6- hydrocarbon group, treating the products with an acid to give a 3.hydroxy.#<SP>1(10),5</SP>-19-norpregnadiene with simultaneous hydrolysis of a 20-ketal group and, if desired, acylating and selectively saponifying; (2) for the steroids possessing a dihydroxyacetone side chain, by a similar series of reactions to those listed under (I) on a similar starting material with a bismethylenedioxy - 17 - side chain which is removed during the acid treatment or subsequently, and if desired, oxidation of an 11#-ol to an 11-ketone; or (3) for the steroids of (2), by introducing a 21-hydroxy group into the products of (1) by standard procedures via the 21-iodo and 21-acetoxy compounds and, if desired, microbiologically hydroxylating at the 11- or 16-position. 3 - Acetoxy - 20 - ethylenedioxy - #<SP>5(10)</SP> - 19- nor - pregnen 6 - one is prepared from 3- acetoxy - 20 - ethylenedioxy - #<SP>5</SP> - pregnen - 19 - ol (prepared by ketalization of the 20-one) by standing with chromium trioxide and pyridine for one week. The corresponding 16α- and 16#- methyl derivatives, the 16α, 17α-isopropylidenedioxy derivative, the 17α-acetoxy derivative and the 17α-acetoxy-16α-methyl derivative are prepared similarly. These products are then converted to the 3#, 6 - diols and their 6-X homologues. 17,20; 20,21 - Bismethylenedioxy - 6- ethynyl - #<SP>5(10)</SP> -19 - nor - pregnene - 3#, 6 - diol is prepared similarly.</p> |
