Patent GB-1457439-A (GB)
Title: 11-oxygenated pregneno-17,16a-d-1,3,-oxathiolans
IPC: C07J71/00
Filed: 1973-12-19
Abstract: 1457439 11 - Oxygenated pregneno[17,- 16α-d] - 1<SP>1</SP>, 3<SP>1</SP> - oxathiolans SCHERING AG 19 Dec 1973 [22 Dec 1972] 58773/73 Heading C2U Novel steroids of the formula wherein R<SP>1</SP> and R<SP>2</SP> are each H, an optionally substituted aliphatic hydrocarbon group, an optionally substituted cycloaliphatic group which may be interrupted by a hetero atom, an optionally substituted aryl group or an optionally substituted heteroaryl group, or R<SP>1</SP> and R<SP>2</SP> together are -(CH 2n - (where n is 2-6) which may be interrupted by a hetero atom; R<SP>3</SP> is H, F or alkyl; X is H, F or Cl; Y is O or H(#-OR<SP>4</SP>) in which R<SP>4</SP> is H or acyl; and C<SP>1</SP> = C<SP>2</SP> is a single or double carbon-carbon bond are prepared by condensation of steroids of the formula with aldehydes or ketones R<SP>1</SP>R<SP>2</SP>CO in the presence of an acidic catalyst. In the products an 11-OH group may be acylated, or oxidized to an 11-oxo group, an 11-acyloxy group may be hydrolysed, a 9α-halogen atom may be introduced, e.g. via a #<SP>9(11)</SP>-steroid and possibly a 9#,11#-epoxide, and a #<SP>1</SP>-double bond may be introduced. 16# - Hydroxy - 11# - acetoxy - 17α - mercapto- #<SP>1,4</SP> - pregnadiene - 3,20 - dione is prepared from 11#,21 - diacetoxy - #<SP>1,4,16</SP> - pregnatriene- 3,20 - dione via 11# - acetoxy - #<SP>1,4,16</SP> - pregnatriene - 3,20 - dione, 17 - bromo - 16# - hydroxy- 11# - acetoxy - #<SP>1,4</SP> - pregnadiene - 3,20 - diene, and 11# - acetoxy - 16#,17 - epoxy - 17α - pregna- 1,4 - diene - 3,20 - dione. 9α - Fluoro - 11#,16#- dihydroxy - 17α - mercapto - #<SP>4</SP> - pregnene- 3,20 - dione is prepared from 9α - fluoro- 11#,17 - dihydroxy - 21 - acetoxy - #<SP>4</SP> - pregnene - 3,20 - dione via 9α - fluoro - 11#,17- dinitryloxy - 21 - acetoxy - #<SP>4</SP> - pregnene - 3,20- dione, 9α - fluoro - 11# - nitryloxy - 21 - acetoxy- #<SP>4,16</SP> - pregnadiene - 3,20 - dione, 9α - fluoro- 11#,20α - dihydroxy - #<SP>4,16</SP> - pregnadien - 3 - one, 9α - fluoro - 11# - hydroxy - #<SP>4,16</SP> - pregnadiene- 3,20 - dione, 9α - fluoro - 17 - bromo - 11#,16#- dihydroxy - #<SP>4</SP> - pregnene - 3,20 - dione, and 9α - fluoro - 11# - hydroxy - 16#,17 - epoxy - 17α- pregn - 4 - ene - 3,20 - dione. 6α - Fluoro - 11#,16# - dihydroxy - 17α- mercapto - #<SP>1,4</SP> - pregnadiene - 3,20 - dione is prepared from 6α - fluoro - 11# - hydroxy- #<SP>4,16</SP> - pregnadiene - 3,20 - dione via 6α - fluoro- 11# - hydroxy - #<SP>1,4,16</SP> - pregnatriene - 3,20 - dione, 6α - fluoro - 17 - bromo - 11#,16# - dihydroxy- #<SP>1,4</SP> - pregnadiene - 3,20 - dione and 6α - fluoro- 11# - hydroxy - 16#,17 - epoxy - 17α - pregna- 1,4 - diene - 3,20 - dione. 11#,16# - Dihydroxy- 17α - mercapto - 6α - methyl - #<SP>1,4</SP> - pregnadiene- 3,20 - dione is prepared from 11# - hydroxy- 6α - methyl - #<SP>4,16</SP> - pregnadiene - 3,20 - dione via 11# - hydroxy - 6α - methyl - #<SP>1,4,16</SP> - pregnatriene - 3,20 - dione, 17 - bromo - 11#,16#- dihydroxy - 6α - methyl - #<SP>1,4</SP> - pregnadiene- 3,20 - dione and 16#,17 - epoxy - 6α - methyl- 17α - pregna - 1,4 - diene - 3,20 - dione. The novel steroids are anti-inflammatory agents and may be made up into pharmaceutical compositions with suitable carriers.