Thermal decomposition of individual positional isomers of methyl linoleate hydroperoxide: Evidence of carbon‐oxygen bond scission

Abstract

Abstract The methyl ester of individual positional isomers of linoleate hydroperoxide were prepared by an enzymic oxidation of linoleate. On injection onto a gas chromatographic column they were thermally decomposed and the resulting volatile components analyzed. The major (67–80% yield on a molar basis) cleavage products were found to be hexanal, methyl octanoate, 2,4‐decadienal isomers, and methyl 9‐oxononanoate. Both the 9 and 13 isomers of linoleate hydroperoxide gave rise to these same four compounds, an observation suggesting carbon‐oxygen scission in their decomposition. This was confirmed by using very pure individual isomers obtained by high performance liquid chromatography. The involvement of an isomerization reaction of the hydroperoxides is discussed.