The ozonation of cholesterol: separation and identification of 2,4-dinitrophenylhydrazine derivatization products of 3 beta-hydroxy-5-oxo-5,6-secocholestan-6-al.
The ozonation products of cholesterol, which are of interest as possible biomarkers of O3 exposure, were studied by derivatization with 2,4-dinitrophenylhydrazine (DNPH). The DNPH derivatization of 3 beta-hydroxy-5-oxo-5,6-secocholestan-6-al (2) produces the expected trans (3b) and cis (3c) derivatives of 3 beta-hydroxy-5-oxo-5,6-secocholestan-6-al, and the unexpected DNPH derivative of 3,5-dihydroxy-B-norcholestane-6-carboxaldehyde (3a). The structures of 3a, 3b, and 3c were identified with 1H nuclear magnetic resonance (NMR), 13C NMR, DEPT, COSY, and H-C correlation two-dimensional NMR techniques, and by comparison with the spectra of known compounds. A possible mechanism involving an enamine functionality is proposed for the formation of 3a. The ratio of 3a/(3b + 3c) depends on the concentration of acid used and the reaction time.
Wang
K
K
Biodynamics Institute, Louisiana State University, Baton Rouge 70803-1800.
Bermúdez
E
E
Pryor
W A
WA
D002778:Cholestanones / Q000737:chemistry*; D002784:Cholesterol / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010126:Ozone / Q000737:chemistry*; D010659:Phenylhydrazines / Q000737:chemistry*; D012632:Secosteroids / Q000737:chemistry*
D002778:Cholestanones; D010659:Phenylhydrazines; D012632:Secosteroids; C004787:2,4-dinitrophenylhydrazine; D010126:Ozone; C082684:3-hydroxy-5-oxo-5,6-secocholestan-6-al; D002784:Cholesterol