Cyclic fatty esters: hydroperoxides from autoxidation of methyl 9-(6-propyl-3-cyclohexenyl)-(Z)8-nonenoate

Abstract

Autoxidation of the cyclic fatty acid ester, methyl 9-(6-propyl-3-cyclohexenyl)-(Z)8-nonenoate (I) was investigated to characterize the hydroperoxide isomers formed and to provide basic information on their chemistry, detection and effect on the quality of polyunsaturated cooking oils. Oxidation at 60 C with 1% hydroperoxide initiator produced a monohydroperoxide fraction containing five positional isomers (7-, 11-, 12-, 13- and 14-OOH), resolved by high performance liquid chromatography, as their allylic hydroxy esters. Their structures were established by 1H- and 13C-NMR spectroscopy and by capillary gas chromatography-mass spectrometry (GC-MS) as trimethylsilyl ether derivatives. Two additional isomers (8- and 9-OOH) were detected by GC-MS in only trace (less than 1%) quantities. Capillary GC resolved some geometric and stereoisomers, as well as positional isomers. Compared to photosensitized oxidation, two additional positional isomers (11- and 14-OOH) were produced by autoxidation. More stereoisomers were formed, and oxidation of the ring double bond was favored 8:1 over that of the side chain. This selectivity may be attributed to greater steric hindrance for oxygen attack at the side-chain double bond. A free radical mechanism is proposed to explain the greater isomeric complexity of the hydroperoxide products compared to photosensitized oxidation.