Yamauchi R, Yamamoto N, Kato K
Department of Food Science, Faculty of Agriculture, Gifu University, Japan.
Lipids. 1995 May;30(5):395-404. doi: 10.1007/BF02536297.
alpha-Tocopherol was reacted with methyl 13(S)-hydroperoxy-9(Z), 11(E)-octadecadienoate in the presence of an iron-chelate, Fe(III)-acetylacetonate, at 37 degrees C in benzene. The reaction was carried out either aerobically or anaerobically. The main products of alpha-tocopherol under air were isolated and identified as two stereoisomers of 4a,5-epoxy-8a-hydroperoxy-alpha-tocopherone, four stereoisomers of methyl 9-(8a-dioxy-alpha-tocopherone)-12, 13-epoxy-10(E)-octadecenoate, four stereoisomers of methyl 11-(8a-dioxy-alpha-tocopherone)-12,13-epoxy-9(Z)-octadecenoa te, two stereoisomers of methyl 13(S)-(8a-dioxy-alpha- tocopherone)-9(Z),11(E)-octadecadienoate, and alpha-tocopherol dimer. Besides the 8a-(lipid-peroxy)-alpha-tocopherones, two stereoisomers of methyl 11-(alpha-tocopheroxy)-12(S),13(S)-epoxy- 9(E)-octadecenoate, two stereoisomers of methyl 9-(alpha-tocopheroxy)-12(S), 13(S)-epoxy-10(E)-octadecenoate, and two isomers of methyl (alpha-tocopheroxy)-octadecadienoate were obtained under nitrogen atmosphere. The results indicate that the peroxyl radicals from lipid hydroperoxides prefer to react with the 8a-carbon radical of alpha-tocopherol and the carbon-centered radicals react with the phenoxyl radical of alpha-tocopherol.
在37℃下，α-生育酚与13(S)-氢过氧-9(Z),11(E)-十八碳二烯酸甲酯在铁螯合物乙酰丙酮铁(III)存在下于苯中反应。反应在有氧或无氧条件下进行。在空气中，α-生育酚的主要产物被分离并鉴定为4a,5-环氧-8a-氢过氧-α-生育醌的两种立体异构体、9-(8a-二氧代-α-生育醌)-12,13-环氧-10(E)-十八碳烯酸甲酯的四种立体异构体、11-(8a-二氧代-α-生育醌)-12,13-环氧-9(Z)-十八碳烯酸甲酯的四种立体异构体、13(S)-(8a-二氧代-α-生育醌)-9(Z),11(E)-十八碳二烯酸甲酯的两种立体异构体以及α-生育酚二聚体。除了8a-(脂质过氧)-α-生育醌外，在氮气氛围下还得到了11-(α-生育酚氧基)-12(S),13(S)-环氧-9(E)-十八碳烯酸甲酯的两种立体异构体、9-(α-生育酚氧基)-12(S),13(S)-环氧-10(E)-十八碳烯酸甲酯的两种立体异构体以及(α-生育酚氧基)-十八碳二烯酸甲酯的两种异构体。结果表明，脂质氢过氧化物产生的过氧自由基更倾向于与α-生育酚的8a-碳自由基反应，而碳中心自由基则与α-生育酚的苯氧自由基反应。
