Photolysis of unsaturated fatty acid hydroperoxides. 4. Fatty acid products from the aerobic decomposition of methyl 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoate dissolved in cyclohexane

In the presence of oxygen, UV-irradiation of a solution of methyl 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoate (13-HPOD) in cyclohexane leads to a broad pattern of reaction products of which a trihydroxyene, seven epoxyhydroxides, four hydroxydienes, four epoxyhydroperoxides, six oxodienes and an epoxycyclohexylene were identified as the main components. Two oxodienes having a (Z)-double bond adjacent to the carbonyl group and the epoxycyclohexylene are reported for the first time. In contrast to results published recently for the UV-degradation of the 13-HPOD in methanol, the decomposition of the 13-HPOD in cyclohexane results in the formation of the 9-HPOD by a rearrangement of the hydroperoxy group. Consequently the reaction products are formed as mixtures of positional isomers. The reaction pathways leading to the identified compounds are discussed.