Procédé de préparation de nouveaux cétonides

1280523 Steroid 16,17-acetals and ketals E R SQUIBB & SONS Inc 4 July 1969 [29 July 1968] 33799/69 Heading C2U The invention comprises compounds of Formulµ I, II and III wherein R1 and R2, which are the same, are both H or C 1-11 (hydrocarbon carboxylic acyl) ; R4 is hydroxy or C 1-11 (hydrocarbon carboxylic acyloxy) ; R3 is the same as R4 or is 2-tetrahydropyranyloxy; X is halo; P and Q are each H, C 1-6 alkyl, C 1-6 haloalkyl, optionally salified or esterified carboxy-(C 1-6 alkyl), monocyclic cycloalkyl, monocyclic aryl, monocyclic aryl- (C 1-6 alkyl), monocyclic heterocyclic or monocyclic heterocyolic-(C 1-6 alkyl), except that Q cannot be H; or P, Q and the intervening carbon atom together form cycloalkylidene or monocyclic heterocyclic ylidene; and Z indicates a single or double bond. Compounds I are prepared by reduction of the corresponding 21 - ol - 3 - ones, e.g. with LiAl(OBut) 3 H, optionally followed by diacylation of the resulting 3#,21-diols. Compounds II are likewise prepared by reduction of compounds III optionally followed by acylation. Compounds III wherein R3 is OH are prepared by hydrolysis of the 3-ethylene ketals thereof and may subsequently be 21-acylated. Compounds III wherein R3 is 2-tetrahydropyranyloxy are prepared by basic isomerization of the corresponding 3-oxo-4-enes. Compounds I, II and III are said to be antiinflammatory and may be made up into pharmaceutical compositions for oral, parenteral and topical administration.