PREGNAN-21-OIC ACID DERIVATIVES AND THE USE AND MANUFACTURE OF PREGNAN-21-OIC ACID DERIVATIVES

摘要

1497265 Pregnan-21-oic acid derivatives SCHERING AG 23 Dec 1974 [21 Dec 1973 27 Aug 1974 16 Sept 1974] 55527/74 Heading C2U [Also in Division A5] Steroids of the formula wherein X is H, F or CH 3 ; Y is H, F or Cl; Z is methylene, carbonyl or #-hydroxy- or #- acyloxymethylene, or, when Y is Cl, may also be #-fluoro- or -chloro-methylene, or, when Y is F, may also be #-fluoromethylene; V is methylene, ethylidene (the 16-methyl group having - or #-configuration) or vinylidene; R 1 is H or acyl; R 2 is H, the cation of a base, or an esterifying group derived from an alcohol; and #SP1/SP is optional are prepared (1) by oxidation of corresponding 2l-ols or their hydrates or hemiacetals with MnO 2 or O 2 in an alcohol containing CN- and buffered to pH 4-7 to give an ester corresponding to the alcohol used; or (2) by oxidation of corresponding 20-ols using MnO 2 or PbO 2 in an inert solvent; or (3) for the 9-Cl compounds, by addition of HOCl, Cl 2 or F and Cl to a corresponding #SP9(11)/SP- steroid; or (4) for the 9-halo compounds, by reaction of the corresponding 9#,11#-epoxides with HF or HCl. Resulting 11#-ols may be oxidized to 11-ones and a #SP1/SP-double bond may be inserted into 1,2-saturated products. The steroids are novel, except for 17-hydroxy-3,20- dioxo-#SP4/SP-pregnan-21-oic acid and its methyl ester. Steroids of the formula are prepared by oxidation of the corresponding 21-hydroxy-steroids, using copper (II) acetate and atmospheric oxygen in a C 1-4 alkanol at room temperature for 20-120 minutes. Steroids of the formula are prepared by oxidation of the corresponding 21-hydroxy-20-oxo-steroids using copper (II) acetate in an alcohol at room temperature for several days. The steroids of the first general formula above are anti-inflammatory agents and may be made up into pharmaceutical compositions (see Heading A5B).