4a,5-epoxy-8a-hydroperoxy-α-tocopherone | 186429-17-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4a,5-epoxy-8a-hydroperoxy-α-tocopherone
• 英文别名: 4a,5-epoxy-8a-hydroperoxytocopherone；(6R)-4a-hydroperoxy-1a,3,4,6-tetramethyl-6-[(4R,8R)-4,8,12-trimethyltridecyl]-7,8-dihydrooxireno[2,3-e]chromen-2-one
• CAS: 186429-17-4
• 化学式: C₂₉H₅₀O₅
• 分子量: 478.713
• InChiKey: FTDAVYLKBDZWCU-XCXCCZTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  68.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4a,5-epoxy-8a-hydroperoxy-α-tocopherone 生成 2,3-epoxy-α-tocopherylquinone
  参考文献：
  名称：

  LIEBLER, DANIEL C.;BAKER, PETER F.;KAYSEN, KATHRYN L., J. AMER. CHEM. SOC., 112,(1990) N, C. 6995-7000

  摘要：

  DOI：
• 作为产物：
  描述：

  DL-α-生育酚 生成 4a,5-epoxy-8a-hydroperoxy-α-tocopherone
  参考文献：
  名称：

  LIEBLER, DANIEL C.;BAKER, PETER F.;KAYSEN, KATHRYN L., J. AMER. CHEM. SOC., 112,(1990) N, C. 6995-7000

  摘要：

  DOI：

文献信息

• Oxidation of vitamin E: evidence for competing autoxidation and peroxyl radical trapping reactions of the tocopheroxyl radical
  作者：Daniel C. Liebler、Peter F. Baker、Kathryn L. Kaysen

  DOI：10.1021/ja00175a037

  日期：1990.9

  Peroxyl radicals generated by thermolysis of azobis(2,4-dimethylvaleronitrile) (AMVN) in oxygenated acetonitrile reacted with d-α-tocopherol (vitamin E, 1) to produce 8a-[(2,4-dimethyl-1-nitrilopent-2-yl)dioxy]tocopherone (3a), 4a,5-epoxy-8a-hydroperoxytocopherone (4a), and 7,8-epoxy-8a-hydroperoxytocopherone (5a). When formed in acetonitrile/water (6:4, v/v), 4a and 5a hydrolyzed quantitatively to

  由偶氮双（2,4-二甲基戊腈）（AMVN）在含氧乙腈中热解产生的过氧自由基与 d-α-生育酚（维生素 E，1）反应生成 8a-[(2,4-二甲基-1-nitrilopent-2) -基)二氧基]生育酚(3a)、4a,5-环氧-8a-氢过氧生育酚(4a)和7,8-环氧-8a-氢过氧生育酚(5a)。当在乙腈/水 (6:4, v/v) 中形成时，4a 和 5a 分别定量水解为 2,3-环氧-α-生育酚醌 (6) 和 5,6-环氧-α-生育酚醌 (7)，而 3a 有限水解为 α-生育酚醌 (8)
• UVB Induced Photooxidation of Vitamin E
  作者：Kimberly A. Kramer、Daniel C. Liebler

  DOI：10.1021/tx960163u

  日期：1997.2.1

  alpha-tocopherol dihydroxy dimer and several 8a-(hydroperoxy)epoxytocopherones were identified by HPLC and HPLC-MS. The dimer appears to result from recombination of photoinduced tocopheroxyl radicals. Products associated with peroxyl radical scavenging (quinones, epoxyquinones, 8a-(hydroperoxy)epoxytocopherones) and with UVB dependent production of tocopheroxyl radicals (dihydroxy dimer) also were found when

  α-生育酚（α-TH，维生素E）的光化学作用可能有助于抑制UVB（290-320 nm）的光致癌作用。通过监测UVB照射的脂质体和溶液中α-TH的命运，研究了α-TH的光化学反应。向大豆磷脂酰胆碱（SPC）和油酰磷脂酰胆碱（DOPC）脂质体中补充α-TH（1.0 mol％α-TH/磷脂），并以6.0 J m-2s-1的剂量率用UVB照射长达90分钟。α-TH在UVB照射的脂质体中迅速耗尽。通过监测脂质过氧化作用评估的氧化损伤在SPC脂质体中得到抑制，直到α-TH耗尽至初始水平的20％。乙腈/ H2O（4：1 v / v）溶液中的UVB照射也迅速耗尽了α-TH。在SPC脂质体中，观察到先前鉴定为α-TH清除过氧自由基的标记产物的产品，包括α-生育酚醌，5,6-环氧-α-生育酚醌和2,3-环氧-α-生育酚醌。这些产物也形成于对脂质过氧自由基形成具有抗性的DOPC脂质体中。另外，通过HPLC和H
• Free-Radical Scavenging Reactions of .alpha.-Tocopherol during the Autoxidation of Methyl Linoleate in Bulk Phase
  作者：Ryo Yamauchi、Koji Kato、Yoshimitsu Ueno

  DOI：10.1021/jf00054a008

  日期：1995.6

  Methyl linoleate containing alpha-tacopherol was autoxidized at 37 and 60 degrees C in bulk phase. The reaction products of alpha-tocopherol at 37 degrees C were 4a,5-epoxy-8a-hydroperoxy-alpha-tocopherones (1), a mixture of methyl 9-(8a-dioxy-alpha-tocopherone)-10(E),12(Z)-octadecadienoates and methyl 13-(8a-dioxy-alpha-tocopherone)-9(Z),1 1(E)-octadecadienoates (2), a mixture of methyl 9-(alpha-tocopheroxy)-10(E),12(Z)-octadecadienoates and methyl 13-(alpha-tocopheroxy)-9(Z),1 1(E)-octadecadienoates (3), alpha-tocopherol spirodiene dimer (4), and alpha-tocopherol trimer (5). Compound 3 was the major product at 60 degrees C, and the E,E-isomers of 3 were produced in addition to the E,Z-isomers. When methyl Linoleate containing a low concentration of a-tocopherol was autoxidized at 37 degrees C, alpha-tocopherol suppressed the formation of methyl linoleate hydroperoxides, and the main products of a-tocopherol were 1 and 2. In contrast, alpha-tocopherol at a high concentration induced the accumulation of methyl linoleate hydroperoxides, and the reaction products were 1-5. The autoxidation at 60 degrees C proceeded rapidly, and the main product of alpha-tocopherol was 1. In addition, the accumulation of 3 was observed under air-insufficient conditions. The results indicate that the alpha-tocopheroxyl radical produced can react with both alkyl and alkylperoxyl radicals of unsaturated lipids during the autoxidation. Competing with these trapping reactions, 1 appears to be formed primarily by autoxidation reactions of alpha-tocopherol.