A-NOR-STEROIDS

1,269,224. A-Norsteroids. E. R. SQUIBB & SONS Inc. 24 March, 1969, No. 15325/69. Heading C2C. The invention comprises A-norsteroids of Formulµ I and II wherein R is α- or #-OH, α- or #-acyloxy or α-C 1-6 alkoxy; R1 is α- or #-OH and R2 is H or R1 and R2 together are OXO; R3 is #-OH and R4 is H or R3 and R4 together are OXO; Y is carbonyl or #-hydroxymethylene with the proviso that Y has the latter value when R3 is #-OH; P and Q are each H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-7 carboxyalkyl (or a salt or ester thereof monocyclic cycloalkyl, monocyclic aryl, monocyclic aryl-C 1-6 alkyl, monocyclic heterocyclic or monocyclic heterocyclic-C 1-6 alkyl (except that Q is not H), or P, Q and the intervening carbon atom together form cycloalkylidene or monocyclic heterocyclic ylidene. Preparation.-The 2,11,20-trioxo compounds of Formula I are prepared from compounds of Formula B (wherein X is Cl or Br) by reaction with alkali metal alkoxide/alkanol to give a 12α-alkoxy trione (D), or with alkali metal hydroxide/ dioxane to give the 12α-hydroxy trione (C) which may then be epimerized with alkali metal hydroxide/alkanol to the 12#-hydroxy trione (E). Reduction of C, D and E with LiAlH 4 yields respectively the 2#,11α,12α,20#-tetrol (F), the 12α-alkoxy-2#,11α,20#-triol (M) and the 2#,11#,12#,20#-tetrol (L). Acetalization or ketalization of compounds F and L yields the 2#,20#-dihydroxy compounds of Formula II which may then be oxidized to the 2,20-diones. Preparation of other compounds within the scope of Formulµ I and II is not disclosed. Compounds of Formula B are prepared by oxidation of the corresponding 11#-ols.