Mass spectrometry characterization of the 5alpha-, 7alpha-, and 7beta-hydroxy derivatives of beta-sitosterol, campesterol, stigmasterol, and brassicasterol.
The 5alpha-hydroperoxides of beta-sitosterol, campesterol, stigmasterol, and brassicasterol were obtained by photooxidation of the respective sterols in pyridine in the presence of hematoporphyrine as sensitizer. The reduction of the hydroperoxides gives the corresponding 5alpha-hydroxy derivatives. The 7alpha- and 7beta-hydroperoxides of the sterols were obtained by allowing an aliquot of the 5alpha-hydroperoxides to isomerize to 7alpha-hydroperoxides, which in turn epimerize to 7beta-hydroperoxides. The reduction gave the corresponding 7alpha- and 7beta-hydroxy derivatives. The 5alpha-, 7alpha-, and 7beta-hydroxy derivatives of beta-sitosterol, campesterol, stigmasterol, and brassicasterol were identified by comparing thin-layer chromatography mobilities, specific color reactions, and mass spectral data with those of the corresponding hydroxy derivatives of cholesterol, which were synthesized in the same manner. The phytosterols had the same behavior to photooxidation as cholesterol and, moreover, the different phytosterols photooxidized at about the same rate. The mass spectra of the trimethylsilyl ethers of the hydroxy derivatives of the phytosterols investigated and of the corresponding hydroxy derivatives of cholesterol have the same fragmentation patterns and similar relative ion abundances.
Bortolomeazzi
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Food Science Department, Udine University, Italy. Renzo.Bortolomeazzi@DSA.uniud.it
De Zan
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Pizzale
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Conte
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D002775:Cholestadienols / Q000737:chemistry*; D002784:Cholesterol / Q000031:analogs & derivatives* / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D006900:Hydroxylation; D013058:Mass Spectrometry; D010545:Peroxides / Q000032:analysis*; D010840:Phytosterols; D012855:Sitosterols / Q000737:chemistry*; D013265:Stigmasterol / Q000737:chemistry*
D002775:Cholestadienols; D010545:Peroxides; D010840:Phytosterols; D012855:Sitosterols; C003532:brassicasterol; C021273:campesterol; C025473:gamma-sitosterol; D002784:Cholesterol; D013265:Stigmasterol