Analysis of autoxidized fats by gas chromatography‐mass spectrometry: III. Methyl linolenate

The gas chromatography‐mass spectrometry (GC‐MS) method developed in the preceding papers was extended to the analysis of autoxidation products of methyl linolenate. Four isomeric hydroxy allylic trienes with a conjugated diene system were identified after reduction of the linolenate hydroperoxides. All eight geometrictrans,cis‐ andtrans, trans‐conjugated diene isomers of these hydroxy allylic compounds were identified and partially separated by GC of the trimethylsilyl (TMS) ether derivatives. The proportion found of 9‐ and 16‐hydroperoxides was significantly higher (75–81%) than the 12‐ and 13‐hydroperoxides (18–25%). The tendency of the 12‐ and 13‐hydroperoxides to form cyclic peroxides, cyclic peroxidehydroperoxides, and prostaglandin‐like endoperoxides was supported by indirect evidence for the presence of 9,10,12‐ and 13,15,16‐trihydroxyoctadecanoate in hydrogenated derivatives of the highly oxygenated products. The quantitative GC‐MS method was used to determine the relative contribution of linolenate, linoleate, and oleate in mixtures to the formation of hydroperoxides.