Acid-catalyzed isomerization of fucosterol and delta5-avenasterol

This work shows that fucosterol, delta5-avenasterol, and similar ethylidene-side chain sterols can undergo acid-catalyzed isomerization to give a mixture of five isomers. Four isomers formed from fucosterol were analyzed, using gas chromatography-mass spectrometry, and were characterized as delta5-avenasterol, two delta5,23-stigmastadienols, and delta5,24(25)-stigmastadienol. When the unsaponifiables fraction from oat oil was subjected to acid hydrolysis, the two delta5,23-stigmastadienol isomers and delta5,24(25)-stigmastadienol were detected while fucosterol coeluted with sitosterol. Interisomerization of ethylidene-side chain sterols represents a limitation to the use of the acid hydrolysis method in the determination of sterols in food and other plant materials rich in these sterols, e.g., oat lipids.