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.
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.
Li
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Department of Chemistry, Hebei University, China.
Li
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D002783:Cholestenones / Q000737:chemistry; D002784:Cholesterol / Q000737:chemistry*; D002855:Chromatography, Thin Layer; D004126:Dimethylformamide; D008752:Methylene Chloride; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011282:Pregnenediones / Q000737:chemistry*; D011284:Pregnenolone / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry*
D002783:Cholestenones; D011282:Pregnenediones; D011726:Pyridinium Compounds; C111515:pregn-4-en-3,6,20-trione; C061685:pyridinium dichromate; D008752:Methylene Chloride; D011284:Pregnenolone; D004126:Dimethylformamide; D002784:Cholesterol; C111514:cholest-4-en-3,6-dione; C111019:pyridinium chlorochromate