Reaction products of α-tocopherol with a free radical initiator, 2,2′-azobis(2,4-dimethylvaleronitrile)

α-Tocopherol wss reacted with an alkylperoxyl radical at 37°C in ethanol. 2,2′-Azobis(2,4-dimethylvaleronitrile) was used to generate the alkylperoxyl radicals. The reaction products of α-tocopherol were isolated by reverse-phase and normal-phase high performance liquid chromatography, and their structures were characterized by infrared, ultraviolet,¹H and¹³C nuclear magnetic resonances and mass spectrometry. They were 8aS-hydroperoxy-α-tocopherone, 8aR-hydroperoxy-α-tocopherone, a mixure of 7,8-epoxy-8aS-ethoxy-α-tocopherone, and 7,8-epoxy-8aR-ethoxy-α-tocopherone, 8aS-(1R-cyano-1,3-dimethyl)butylperoxy-α-tocopherone, 8aS-(1S-cyano-1,3-dimethyl)butylperoxy-α-tocopherone, a mixture of 8aR-(1S-cyano-1,3-dimethyl)butylperoxy-α-tocopherone and 8aR-(1S-cyano-1,3-dimethyl)butylperoxy-α-tocopherone, 4aR,5S-epoxy-8aS-ethoxy-α-tocopherone, 4aS,5R-epoxy-8aS-ethoxy-α-tocopherone and 4aR,5S-epoxy-8aR-ethoxy-α-tocopherone.