Ha K H, Igarashi O
Institute of Environmental Science for Human Life, Ochanomizu University, Tokyo, Japan.
J Nutr Sci Vitaminol (Tokyo). 1990 Aug;36(4):411-21. doi: 10.3177/jnsv.36.4-supplementi_411.
The oxidation products of both types of mixtures of alpha-tocopherol (alpha-Toc) and gamma-tocopherol (gamma-Toc) or alpha-Toc and delta-tocopherol (delta-Toc) during autoxidation of methyl linoleate were isolated and identified. The structures of the oxidation products were characterized by UV, IR, 1H and 13CNMR, and mass spectrometry. The 5-[2-(alpha-tocopherol-5'-yl)ethyl]-alpha-tocopherylquinone, 5-[2-(alpha-tocopherol-5'-yl)ethyl]-8a-hydroxy-alpha-tocopherone, O-[8-(5-ethoxymethyl-7-methyltocol)methyl]-alpha-tocopherol were obtained from both types of the mixtures as the oxidation products derived from alpha-Toc. gamma-Toc diphenyl ether dimer (gamma-TED) and gamma-Toc biphenyl dimer (gamma-TBD) were identified from the mixture of alpha-Toc and gamma-Toc, and delta-Toc diphenyl ether dimer (delta-TED) from the mixture of alpha-Toc and delta-Toc. However, no oxidation product composed of both alpha-Toc and gamma-Toc or delta-Toc was detected in oxidation products of both types of the mixtures. These results support the facts that, at first, oxidation of alpha-Toc proceeds during autoxidation of lipids and then gamma-Toc or delta-Toc decomposes after approximate consumption of alpha-Toc.
分离并鉴定了亚油酸甲酯自氧化过程中α-生育酚（α-Toc）与γ-生育酚（γ-Toc）或α-生育酚与δ-生育酚（δ-Toc）两种混合物的氧化产物。通过紫外光谱、红外光谱、¹H和¹³C核磁共振光谱以及质谱对氧化产物的结构进行了表征。从这两种混合物中均获得了5-[2-(α-生育酚-5'-基)乙基]-α-生育酚醌、5-[2-(α-生育酚-5'-基)乙基]-8a-羟基-α-生育酮、O-[8-(5-乙氧基甲基-7-甲基生育三烯酚)甲基]-α-生育酚，作为源自α-Toc的氧化产物。从α-Toc与γ-Toc的混合物中鉴定出γ-生育酚二苯醚二聚体（γ-TED）和γ-生育酚联苯二聚体（γ-TBD），从α-Toc与δ-Toc的混合物中鉴定出δ-生育酚二苯醚二聚体（δ-TED）。然而，在这两种混合物的氧化产物中均未检测到由α-Toc与γ-Toc或δ-Toc组成的氧化产物。这些结果支持了以下事实：首先，在脂质自氧化过程中α-Toc发生氧化，然后在α-Toc大致消耗后γ-Toc或δ-Toc分解。
