16,17-SECO-A-NOR STEROIDS

1346403 16,17-Seco-A-nor-steroids SYNTEX CORP 16 June 1972 [1 July 1971] 28323/72 Heading C2C Novel compounds of the formula (wherein R is C 1-4 alkyl, carboxyl, C 2-5 alkylcarbonyl or acetyl, or hydroxymethyl optionally substituted by one or two C 1-4 alkyl groups or by one C 1-4 alkyl group and a phenyl group and optionally etherified or acylated; R1 is C 1-4 alkyl; and R11 is H or CH 3 ) are prepared as illustrated in the following reaction scheme wherein R3 is = O or α-H(#-OH); R4 is H or C 1-4 alkyl; R2, R5 and R7 are C 1-4 alkyl; and R6 is C 1-4 alkyl or phenyl. The starting materials are fused with an excess of an alkali metal hydroxide to yield compounds (II), these are esterified and then enol-etherified and then the COOR4 group is converted to other required values of R and the enol ether group removed. Thus, (III)#(IV) involves reduction with a double metal hydride; (IV)#(XII) is an oxidation; (XII)#(XIII) (R7=CH 3 ) is a reduction involving for example conversion to a thioacetal and desulphurization or reduction by the Wolff-Kishner or Clemmenson methods; (VI)# (XIII) is a similar reduction; (III)#(VI) is effected using an alkali magnesium halide, (VII) (R6=C 1-4 alkyl) also being produced; (VI)# (VII) (R6 = phenyl) is achieved with phenyl lithium; and (VI)-(IX) is a reduction using a double metal hydride. The 2-keto function may alternatively be protected as an ethylene ketal. Products containing OH groups can be esterified or acylated. The compounds of the invention are stated to possess anti-androgenic activity and they may be made up into pharmaceutical compositions with suitable carriers.