Products of unsaturated fatty acid oxidation catalyzed by hematin compounds

Summary A study has been made of the initial and secondary products resulting from the hematin catalyzed decomposition of hydroperoxides. The initial product was found to be the alkoxy free‐radical produced by the homolytic cleavage of the O‐OH bond of the hydroperoxide. The system was arranged so that the alkoxy radicals reacted with a hydrogen donor as they were formed to produce the corresponding alcohol. The alcohol was then identified by standard physical and chemical procedures. The secondary products resulting from the hematin catalyzed decomposition of linoleate hydroperoxide in the absence of oxygen were found to be composed principally of oxirane, hydroxyl, and carbonyl compounds. Cleavage of the carbon chain, loss of conjugated double bonnds, and polymerization also took place. Reactions to account for these products were proposed, along with a general mechanism of hematin catalysis.