Yamauchi R, Miyake N, Kato K, Ueno Y
Department of Food Science, Faculty of Agriculture, Gifu University, Japan.
Lipids. 1993 Mar;28(3):201-6. doi: 10.1007/BF02536640.
alpha-Tocopherol was reacted with alkyl and alkylperoxyl radicals at 37 degrees C in bulk phase. The lipid-free radicals were generated by the reaction of methyl linoleate with the free radical initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (AMVN) under air-insufficient conditions. The products were isolated by high-performance liquid chromatography. Their structures were identified as 2-(alpha-tocopheroxy)-2,4- dimethylvaleronitrile (1), a mixture of methyl 9-(8a-peroxy-alpha-tocppherone)-10(E),12(Z)-octadecadienoate and methyl 13-(8a-peroxy-alpha-tocopherone)-9(Z),11(E)-octadecadienoate (2), methyl 9-(alpha-tocopheroxy)-10(E),12(Z)-octadecadienoate (3a), methyl 13-(alpha-tocopheroxy)-9(Z),12(E)-octadecadienoate (3b), alpha-tocopherol spirodiene dimer (4) and alpha-tocopherol trimer (5). When methyl linoleate containing alpha-tocopherol was oxidized with AMVN under air-sufficient conditions, the main products were 8a-alkylperoxy-alpha-tocopherones (2). In addition to these compounds, 6-O-alkyl-alpha-tocopherols (1, 3a and 3b) were formed when the reaction was carried out under air-insufficient conditions. The results indicate that alpha-tocopherol can react with both alkyl and alkylperoxyl radicals during the autoxidation of polyunsaturated lipids.
在37℃下，α-生育酚在本体相中与烷基和烷基过氧自由基发生反应。无脂质自由基通过亚油酸甲酯与自由基引发剂2,2'-偶氮二(2,4-二甲基戊腈)(AMVN)在空气不足的条件下反应生成。产物通过高效液相色谱法分离。它们的结构被鉴定为2-(α-生育酚氧基)-2,4-二甲基戊腈(1)、9-(8a-过氧-α-生育酚酮)-10(E),12(Z)-十八碳二烯酸甲酯和13-(8a-过氧-α-生育酚酮)-9(Z),11(E)-十八碳二烯酸甲酯的混合物(2)、9-(α-生育酚氧基)-10(E),12(Z)-十八碳二烯酸甲酯(3a)、13-(α-生育酚氧基)-9(Z),12(E)-十八碳二烯酸甲酯(3b)、α-生育酚螺二烯二聚体(4)和α-生育酚三聚体(5)。当含α-生育酚的亚油酸甲酯在空气充足的条件下用AMVN氧化时，主要产物是8a-烷基过氧-α-生育酚酮(2)。除了这些化合物外，当反应在空气不足的条件下进行时，还会形成6-O-烷基-α-生育酚(1、3a和3b)。结果表明，在多不饱和脂质的自动氧化过程中，α-生育酚能与烷基和烷基过氧自由基发生反应。
