Synthesis and gas chromatographic-mass spectrometric analysis of reduced compounds derived from 6 alpha- and 6 beta-hydroxy-11-deoxycorticosterone.
A series of thirty two 6-hydroxylated steroids were synthesized by selective reduction of the 4-5 double bond, the 3-oxo group, and/or the 20-oxo group of 6 alpha- and 6 beta-hydroxyDOC. The different reactions leading to the production of specific isomers are discussed. The gas chromatographic and spectrometric characteristics of the methoxime-trimethylsilyl (MO-TMS) or trimethylsilyl (TMS) derivatives of the isomers obtained are given. The gas chromatographic separation of the syn- and anti-isomers of the methoxime in position 3 was found to be characteristic of the configuration of the hydroxyl in position 6. The difference between methylene unit values of syn- and anti- isomers is much larger for the 6 alpha-series than for the 6 beta-series. The mass spectral analysis showed that many ions are specific of the MO-TMS derivatives of steroids with 3,6-dihydroxy-4-ene or 3-oxo-6-hydroxy-4-ene structure. In the case of steroids with a saturated ring A no significant ions characteristic of the presence of a 6-trimethylsilyloxy substituent were found. This work provides previously unavailable reference data on 6-hydroxylated steroids which should facilitate the study of corticosteroid metabolism.
Bournot
P
P
Laboratoire de Biochimie des Interactions Cellulaires, Faculté de Sciences, Université de Dijon, France.
Ramirez
L C
LC
Pitoizet
N
N
Maume
B F
BF
Padieu
P
P
D055598:Chemical Phenomena; D002621:Chemistry; D003900:Desoxycorticosterone / Q000031:analogs & derivatives* / Q000032:analysis / Q000138:chemical synthesis; D008401:Gas Chromatography-Mass Spectrometry; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013256:Steroids / Q000138:chemical synthesis*
D013256:Steroids; C060842:6-hydroxy-11-deoxycorticosterone; D003900:Desoxycorticosterone