D-HOMO-20-KETO-PREGNANES

摘要

1494097 D - homo - 20 - keto - pregnanes SCHERING AG 25 Nov 1974 [30 Nov 1973 19 April 1974] 51006/74 Heading C2U Novel D-homo-steroids of the formula wherein R 1 is O, H(#-OR 5 ) or H(α-OR 5 ) in which R 5 is H or C 1-5 acyl, R 2 is H or CH 3 ; R 3 is O, H 2 , H(α-OH) or H(#-OH); R 4 is H, OH or O acyl; R 6 is H or CH 3 ; and R 7 is H, -COCH 3 , OH or C 1-5 acyloxy, and the wavy lines indicate α- or #-configuration, are prepared by catalytic hydrogenation of corresponding D-homo-steroids of the formula wherein there is a #4- or #5-double bond and/or a #16- or #17-double bond, followed, when desired, by inversion of a 3- and/or an 11- and/or a 16-OH group, oxidation of a 3- and/or 11-OH group, reduction of a keto group, hydrolysis of an acyloxy group and/or esterification of an OH group. 3α-Acetoxy-D-homo-5#-pregnane- 11,20-dione and the corresponding 3α-ol, and the preparation of the first of these from the corresponding #17(17a)-compound, are however not claimed. D - homo - pregna - 4,17(17a) - diene - 3,20- dione is prepared by Oppenauer oxidation of 3# - hydroxy - D - homo - pregna - 5,17(17a)- dien - 20 - one. 21 - Acetoxy - 11# - hydroxy- D - homo - #4 - pregnene - 3,20 - dione is prepared by microbiological hydroxylation, using Curvularia lunata, of 21-acetoxy-D-homo-#4- pregnene - 3,20 - dione to give 11#,21 - dihydroxy - D - homo - #4 - pregnene - 3,20 - dione followed by re-acetylation of this. D-homo- #4 - pregnen - 3,11,20 - trione is prepared by microbiological hydroxylation, using Aspergillus ochraceus, of D-homo-progesterone to give 11α- hydroxy - D - homo - #4 - pregnene - 3,20 - dione, or, using Curvularia lunata, to give the corresponding 11#-ol, followed by oxidation of either of these. 3# - Acetoxy - 17α - methyl - D - homo- #5 - pregnen - 20 - one is prepared from 3#- acetoxy - D - homo - pregna - 5,17(17a) - dien- 20 - one. 3# - Hydroxy - D - homo - 17a α- pregn - 5 - en - 20 - one. is prepared by hydrolysis of the corresponding 3#-acetoxy compound, in turn prepared, together with 3#-acetoxy-D- homo - #5 - pregnen- 20 - one, by catalytic hydrogenation of 3#-acetoxy-D-homo-pregna- 5,17(17a) - dien - 20 - one. 16 - Acetyl - 3#- hydroxy - D - homo - pregna - 5,16 - dien - 20- one is prepared from 3#,20-diacetoxy-D-homopregna-5,16,17a(20)-triene. 3α - Hydroxy - D - homo - 5# - pregnane- 11,20-dione is prepared by hydrolysis of the corresponding 3α-acetoxy compound. The steroids of the Formula (I), including the 2 compounds not claimed per se, are anaesthetic agents, and they may be made up into pharmaceutical compositions with suitable carriers.