甾体5-烯-3-酮，是甾体5-烯-3β-醇转化为甾体4-烯-3,6-二酮的中间体，可被重铬酸吡啶鎓和氯铬酸吡啶鎓氧化。

Steroidal 5-en-3-ones, intermediates of the transformation of steroidal 5-en-3 beta-ols to steroidal 4-en-3,6-diones oxidized by pyridinium dichromate and pyridinium chlorochromate.

作者信息

Li S H, Li T S

机构信息

Department of Chemistry, Hebei University, China.

出版信息

Steroids. 1998 Feb;63(2):76-9. doi: 10.1016/s0039-128x(97)83224-2.

DOI:10.1016/s0039-128x(97)83224-2

PMID:9516716

Abstract

Oxidation of cholesterol (1a) or pregnenolone (1b) with pyridinium dichromate (PDC) in dimethylformamide (DMF) or in dichloromethane (DCM) and pyridinium chlorochromate (PCC) in DCM provided cholest-4-en-3,6-dione (2a) or pregn-4-en-3,6,20-trione (2b). TLC monitoration of the reactions implied that cholest-5-en-3-one (3a) or pregn-5-en-3,20-dione (3b) and cholest-4-en-3-one (4a) or pregn-4-en-3,20-dione (4b) might be intermediates. Individual oxidation of 3a or 3b with PDC and PCC could give 2a or 2b, but 4a or 4b remained unchanged. Further investigation indicated that 4a or 4b was an isomerization product of 3a or 3b on silica gel TLC plate rather than really existence in the reaction mixture. These results shown steroidal 5-en-3-ones were intermediates of the transformation of steroidal 5-en-3 beta-ols to steroidal 4-en-3,6-diones oxidized by PDC and PCC.

摘要

在二甲基甲酰胺（DMF）中，用重铬酸吡啶鎓（PDC）氧化胆固醇（1a）或孕烯醇酮（1b），或在二氯甲烷（DCM）中用重铬酸吡啶鎓（PDC）和氯铬酸吡啶鎓（PCC）氧化，可得到胆甾-4-烯-3,6-二酮（2a）或孕-4-烯-3,6,20-三酮（2b）。反应的薄层色谱监测表明，胆甾-5-烯-3-酮（3a）或孕-5-烯-3,20-二酮（3b）以及胆甾-4-烯-3-酮（4a）或孕-4-烯-3,20-二酮（4b）可能是中间体。用PDC和PCC分别氧化3a或3b可得到2a或2b，但4a或4b保持不变。进一步研究表明，4a或4b是3a或3b在硅胶薄层板上的异构化产物，而非反应混合物中实际存在的物质。这些结果表明，甾体5-烯-3-酮是甾体5-烯-3β-醇被PDC和PCC氧化转化为甾体4-烯-3,6-二酮过程中的中间体。