Synthesis and characterization of the 6 alpha- and 6 beta-hydroxylated derivatives of corticosterone, 11-dehydrocorticosterone, and 11-deoxycortisol.
This report describes the synthesis of 6 alpha, 17,21- and 6 beta, 17,21-trihydroxypregn-4-ene-3,20-dione, 6 alpha, 7,21- and 6 beta, 11 beta, 21-trihydroxypregn-4-ene-3,20-dione, and--for the first time--that of 6 alpha, 21- and 6 beta, 21-dihydroxypregn-4-ene-3,11,20-trione. The former four compounds were prepared by 6-hydroxylation of 17,21-trihydroxypregn-4-ene-3,20-dione and 11 beta, 21-dihydroxypregn-4-ene-3,20-dione, respectively. This was achieved by autoxidation or by oxidation with 3-chloroperbenzoic acid, of the 3-methoxy-pregna-3,5-dienes of the latter two steroids. The yield of the 6 beta-hydroxylated steroids, but not of their corresponding 6 alpha-epimers, was higher using autoxidation than the peracid. The two 6-hydroxylated pregnenetriones were prepared from 6 alpha, 21-diacetoxy-11 beta-hydroxypregn-4-ene-3,20-dione and 6 beta, 21-diacetoxy-11 beta-hydroxypregn-4-ene-3,20-dione, respectively, by oxidation with pyridinium 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.
Kraan
G P
GP
Department of Pediatrics, University of Groningen, The Netherlands.
van Wee
K T
KT
Wolthers
B G
BG
van der Molen
J C
JC
Nagel
G T
GT
Drayer
N M
NM
van Leusen
D
D
D002723:Chlorobenzoates; D002849:Chromatography, Gas; D002851:Chromatography, High Pressure Liquid; D003345:Corticosterone / Q000031:analogs & derivatives* / Q000737:chemistry; D003350:Cortodoxone / Q000031:analogs & derivatives* / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D006900:Hydroxylation; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010084:Oxidation-Reduction; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
D002723:Chlorobenzoates; C003552:11-dehydrocorticosterone; C000433:3-chloroperbenzoic acid; D003345:Corticosterone; D003350:Cortodoxone