SYNTHESIS AND CHARACTERIZATION OF THE 6-ALPHA-HYDROXYLATED AND 6-BETA-HYDROXYLATED DERIVATIVES OF CORTICOSTERONE, 11-DEHYDROCORTICOSTERONE,AND 11-DEOXYCORTISOL

This report describes the synthesis of 6alpha,17,21- and 6beta,17,21-t rihydroxypregn-4-ene-3,20-dione, 6alpha,7,21- and 6beta,11beta,21-trih ydroxypregn-4-ene-3,20-dione, and-for the first time-that of 6alpha,21 - and 6beta,21-dihydroxypregn-4-ene-3,11,20-trione. The former four co mpounds were prepared by 6-hydroxylation of 17,21-trihydroxypregn-4-en e-3,20-dione and 11beta,21-dihydroxypregn-4-ene-3,20-dione, respective ly. This was achieved by autoxidation or by oxidation with 3-chloroper benzoic acid, of the 3-methoxy-pregna-3,5-dienes of the latter two ste roids. The yield of the 6beta-hydroxylated steroids, but not of their corresponding 6alpha-epimers, was higher using autoxidation than the p eracid. The two 6-hydroxylated pregnenetriones were prepared from ,21- diacetoxy-11beta-hydroxypregn-4-ene-3,20-dione and 21-diacetoxy-11beta -hydroxypregn-4-ene-3,20-dione, respectively, by oxidation with pyridi nium chlorochromate. The above-mentioned six steroids were identified and characterized by nuclear magnetic resonance, infrared, ultraviolet , high performance liquid chromatography, gas chromatography, and mass spectrometry.