Patent GB-1504410-A (GB)
Title: 11beta-fluoroandrostenes
IPC: A61K31/568
Filed: 1975-03-03
Abstract: 1504410 11#-Fluoro-androstenes SCHERING AG 3 March 1975 [1 March 1974] 8742/75 Heading C2U Novel steroids of the formula wherein C<SP>6</SP>#C<SP>7</SP> is a single or double bond between the 6 and 7 positions; X is CO, or C(α-R<SP>7</SP>)(#-OR<SP>6</SP>) in which R<SP>5</SP> is H, acyl, alkyl, cycloalkyl or an oxygen-containing heterocycle, R<SP>6</SP> is H or acyl and R<SP>7</SP> is an optionally substituted aliphatic hydrocarbon group; R<SP>1</SP> and R<SP>2</SP> are each H or together they represent a methylene group or a #<SP>1</SP>-double bond; R<SP>3</SP> is H or Cl; and R<SP>4</SP> is H, Cl or F (α- or #-configuration when #<SP>6</SP> is absent) are prepared by dehalogenation of corresponding 9α-halo steroids followed, if desired, by introduction of Cl into the 4-position and/or Cl or F into the 6-position, and/or a #<SP>1</SP> and/or #<SP>6</SP> double bond and/or a 1α,2α-methylene group and/or reduction of a 17-keto group (with protection of 3-keto if necessary) with or without concomitant introduction of a 17α-hydrocarbon group, and/or hydrogenation of an unsaturated group in the 17α-position and/or acylation or etherification of a 17#-OH group and/or hydrolysis of an esterified or etherified 17#-OH group. Dehalogenation is generally effected with a tri-hydrocarbyltin hydride.  17# - Acetoxy - 9 - bromo - 11# - fluoro - #<SP>4</SP>- androsten - 3 - one is prepared from 17#- acetoxy - #<SP>4,9(11)</SP> - androstadien - 3 - one. 9 - Bromo - 11# - fluoro - #<SP>4</SP> - androstene - 3,17- dione, 17# - acetoxy - 9 - chloro - 11# - fluoro - #<SP>4</SP>- androsten - 3 - one and 9 - chloro - 11# - fluoro- #<SP>4</SP> - androstene - 3,17 - dione are prepared similarly. 17# - Acetoxy - 9 - bromo - 11#- fluoro - #<SP>4,6</SP> - androstadien - 3 - one is prepared from the #<SP>4</SP>-compound and 17#-acetoxy-9-bromo- 11# - fluoro - #<SP>1,4,6</SP> - androstatrien - 3 - one from the #<SP>4,6</SP> compound.  17# - Acetoxy - 6α,7α - epoxy - 11# -fluoro - #<SP>4</SP>- androsten - 3 - one is prepared from the corresponding #<SP>4,6</SP>-steroid and is subsequently converted to the corresponding 6-chloro-#<SP>4,6</SP>- steroid. 17α - Ethynyl - 6α,7α - epoxy - 11#- fluoro - 17# - hydroxy - #<SP>4</SP> - androsten - 3 - one is prepared and used similarly. 3-Ethoxy-11#- fluoro - #<SP>3,5</SP> - androstadien - 17 - one is prepared from the corresponding #<SP>4</SP>-3-one and is converted into 11#-fluoro-17#-hydroxy-17α-methyl- #<SP>4</SP> - androsten - 3 - one. 17# - Acetoxy - 6#,11#- difluoro - 7α - mesyloxy - #<SP>4</SP> - androsten - 3 - one is prepared from the corresponding 7α-ol (in turn prepared from 17#-acetoxy-6α,7α-epoxy- 11# - fluoro - #<SP>4</SP> - androsten - 3 - one) and is converted into 17#-acetoxy-6,11#-difluoro-#<SP>4,6</SP>- androstadien - 3 - one. 11# - Fluoro - #<SP>4</SP>- androstene - 3#,17# - diol is an unisolated by-product in the reduction of 11#-fluoro-#<SP>4</SP>- androstene - 3,17 - dione to the corresponding 17#-ol. The novel steroids possess anabolic, androgenic and gestagenic activity and they may be made up into pharmaceutical compositions with suitable carriers. They may be used as contraceptives.