Iron‐Catalyzed Reaction of γ‐Tocopherol with Methyl Linoleate Hydroperoxides in Solutions

γ‐Tocopherol is one of the main constituents in vegetable oils and acts as an antioxidant by trapping lipid‐peroxyl radicals. This study reports reaction products of γ‐tocopherol with lipid‐peroxyl radicals formed by iron‐catalyzed decomposition of methyl linoleate hydroperoxides (MeLOOH) in toluene and methanol solutions. The products in toluene solution were tocored, methyl (8a‐dioxy‐γ‐tocopherone)‐epoxyoctadecenoates (γT‐OO‐epoxyMeL), methyl (8a‐dioxy‐γ‐tocopherone)‐octadecadienoates (γT‐OO‐MeL), γ‐tocopherol biphenyl dimer (γTBD), γ‐tocopherol diphenylether dimer (γTED), and adducts of γ‐tocopherol dimers with the MeLOOH‐derived peroxyl radicals (γTED‐OO‐epoxyMeL, γTBD‐OO‐MeL, and γTED‐OO‐MeL). The iron‐catalyzed reaction in toluene proceeded slowly, whereas the reaction in methanol was relatively fast. The reaction products in methanol were γT‐OO‐epoxyMeL and γTED‐OO‐epoxyMeL together with tocored, γTBD, and γTED. The results indicate that the iron‐catalyzed decomposition of MeLOOH in toluene produces both epoxyperoxyl and peroxyl radicals and that the decomposition in methanol yields only the epoxyperoxyl radicals. These peroxyl radicals could react with the 8a‐carbon‐centered radical of γ‐tocopherol or its dimers.