| 摘要 |
1,255,186. 22,25-Epoxy-steroids. SCHERING A.G. 30 Dec., 1968 [30 Dec., 1967], No. 61561/68. Heading C2U. Novel steroids of the partial formula in which R 1 is H, OH or O acyl and R 5 is H or OH, the 21-CH 3 group and the 22 C-O-bond each having the α F - or # F -configuration, are prepared from steroids of the partial formula in which Z is H or tetrahydropyranyl or, if the C-O-bond in the product is to have mainly the #F-configuration, is preferably N0 2 , and C 23 ¸¸¸C 24 represents a single or triple carboncarbon bond, and if it is a single bond the keto group may be present in the enol form, byreaction with hydrogen in the presence of a metal catalyst, and a neutral or acidic solvent if the 22-keto group is an enol form, or an acidic solvent if the 22-keto group is present as such. In the products a free OH group may be esterified or an acyloxy group saponified. Diastereoisomeric products may be separated chromatographically. 20 -(4<SP>1</SP> - Hydroxy - 4<SP>1</SP>-methylpent - 1<SP>1</SP>- yn 1<SP>1</SP> - yl)- 5-pregnene-3#,20-diol is prepared from pregnenolone and 4-methylpentyn-2-ol under Grignard conditions; and is converted to 20-,(1<SP>1</SP>-oxo.4<SP>1</SP>- hydroxy - 4<SP>1</SP> - methylpent - 1<SP>1</SP> - yl) - 5 - pregnene-3#,20-diol by the action of mercuric acetate and BF 3 ; and to 20-(4<SP>1</SP>-hydroxy-1<SP>1</SP>. acetoxy. - 4<SP>1</SP> - methyl - 1<SP>1</SP> - penten - 1<SP>1</SP> - yl) - 5 - pregnene-3#,20-diol by the action of mercuric acetate and acetic acid. (22R) - 14,22 - dihydrory - 25 - (tetrahydropyranyloxy)- 2#,3#- diacetoxy - 5a - cholest - 7 - en - 23 - yn - 6 - one is prepared by SeO 2 oxidation of the corresponding 14-unsubstituted compound, and is subsequently oxidized to the corresponding 22-one which on hydrogenation gives 14,25- dihydroxy - 2#,3# - diacetoxy - 5α - cholest - 7 - ene- 6,22-dione; also the 14-unsubstituted compound is directly oxidized to 25-(tetrahydropyranyloxy) - 2#,3# - diacetoxy - 5α - cholest- 7 - en - 23 - yne - 6,22 - dione, and the corresponding 25-ol is converted via the corresponding 25-nitryloxy compound to 14-hydroxy-25- nitryloxy - 2#,3# - diacetoxy - 5α - cholest - 7 - ene- 23-yne-6,22-dione. |
