MECHANISM OF THE REARRANGEMENT OF LINOLEATE HYDROPEROXIDES

Linoleate hydroperoxides undergo rearrangement leading to their isomerisation in which the OOH group is relocated or the stereochemistry of a double bond changed, or both. The reaction was studied mainly with pure isomers of methyl hydroperoxylinoleates since conditions could be found in which rearrangement occurred with little accompanying decomposition. The rearrangement was found to be non-stereoselective and took place by a free-radical chain mechanism. Using 18O-labelled hydroperoxide on 18O2, it was shown that the oxygen atoms of the OOH group of the hydroperoxides exchanged with surrounding molecular oxygen during the rearrangement. A mechanism for the rearrangement is proposed. © 1979.