(2'R,8R)-2',5,6,7',8,8'-hexamethyl-2',8-bis-[(4R,8R)-4,8,12-trimethyl-tridecyl]-1,3',4',8,9,10-hexahydro-2'H-spiro[benzo[1,2-b:4,3-b']dipyran-3(2H),5'-[5H-1]benzopyran]-6'-one | 1604-73-5

• 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: (2'R,8R)-2',5,6,7',8,8'-hexamethyl-2',8-bis-[(4R,8R)-4,8,12-trimethyl-tridecyl]-1,3',4',8,9,10-hexahydro-2'H-spiro[benzo[1,2-b:4,3-b']dipyran-3(2H),5'-[5H-1]benzopyran]-6'-one
• 英文别名: spirodiene dimer of α-tocopherol；(2'R,8R)-2',5,6,7',8,8'-hexamethyl-2',8-bis[(4R,8R)-4,8,12-trimethyltridecyl]spiro[1,2,9,10-tetrahydropyrano[3,2-f]chromene-3,5'-3,4-dihydrochromene]-6'-one
• CAS: 1604-73-5
• 化学式: C₅₈H₉₆O₄
• 分子量: 857.398
• InChiKey: LBZILIZDKITSKL-POCRPCFWSA-N

物化性质

• 沸点：
  822.3±65.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  19.4
• 重原子数：
  62
• 可旋转键数：
  24
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2'R,8R)-2',5,6,7',8,8'-hexamethyl-2',8-bis-[(4R,8R)-4,8,12-trimethyl-tridecyl]-1,3',4',8,9,10-hexahydro-2'H-spiro[benzo[1,2-b:4,3-b']dipyran-3(2H),5'-[5H-1]benzopyran]-6'-one 在 2,6-二甲基苯酚 、 偶氮二异丁腈 作用下， 以 正己烷 为溶剂， 反应 1.0h， 以46%的产率得到1,2-bis(5-γ-tocopheryl)ethane
  参考文献：
  名称：

  维生素E化学。α-生育酚的初始氧化中间体的研究：改善以5a- C为中心的“色丁醇甲氧基”自由基的参与

  摘要：

  与维生素E研究初期文献中提出的概念相反，维生素E的单电子氧化不涉及以5a- C为中心的自由基。分析技术的组合方法，特别是电子顺磁共振光谱法（EPR），特殊衍生物的有机合成，同位素标记，动力学研究和计算化学方法，被用于重新评估α的单电子和二电子氧化化学-生育酚（α-toc）。EPR与5a - 13 C标记的化合物结合使用，未提供涉及5a- C中心自由基的迹象。特殊生育酚衍生物的氧化被用来证明5a- C的发生中心的单电子中间体。此外，还表明，通常被诱使以C为中心的生育酚自由基参与的那些维生素E反应实际上是通过杂化即非自由基中间体进行的。结果将有助于消除对维生素E化学的广泛传播的误解，并将对基于生育酚的超分子结构和5a-取代的α-生育酚衍生物的合成具有机械学意义。

  DOI：

  10.1021/jo062553j
• 作为产物：
  描述：

  天然维生素E 以 氘代苯 为溶剂， 反应 10.0h， 生成 (2'R,8R)-2',5,6,7',8,8'-hexamethyl-2',8-bis-[(4R,8R)-4,8,12-trimethyl-tridecyl]-1,3',4',8,9,10-hexahydro-2'H-spiro[benzo[1,2-b:4,3-b']dipyran-3(2H),5'-[5H-1]benzopyran]-6'-one
  参考文献：
  名称：

  维生素E化学。α-生育酚的初始氧化中间体的研究：改善以5a- C为中心的“色丁醇甲氧基”自由基的参与

  摘要：

  与维生素E研究初期文献中提出的概念相反，维生素E的单电子氧化不涉及以5a- C为中心的自由基。分析技术的组合方法，特别是电子顺磁共振光谱法（EPR），特殊衍生物的有机合成，同位素标记，动力学研究和计算化学方法，被用于重新评估α的单电子和二电子氧化化学-生育酚（α-toc）。EPR与5a - 13 C标记的化合物结合使用，未提供涉及5a- C中心自由基的迹象。特殊生育酚衍生物的氧化被用来证明5a- C的发生中心的单电子中间体。此外，还表明，通常被诱使以C为中心的生育酚自由基参与的那些维生素E反应实际上是通过杂化即非自由基中间体进行的。结果将有助于消除对维生素E化学的广泛传播的误解，并将对基于生育酚的超分子结构和5a-取代的α-生育酚衍生物的合成具有机械学意义。

  DOI：

  10.1021/jo062553j

文献信息

• Bromination of α-tocopherol methano-dimer and ethano-dimer
  作者：Thomas Rosenau、Christian Adelwöhrer、Elisabeth Kloser、Kurt Mereiter、Thomas Netscher

  DOI：10.1016/j.tet.2005.11.050

  日期：2006.2

  Bromination of the ethano-dimer of alpha-tocopherol (6) afforded pyrano-spirodimer of alpha-tocopherol (7) quantitatively, while the methano-dimer of alpha-tocopherol (10) produced a mixture of products, including the furano-spirodimer 11, pyrano-spirodimer 7, and 5-bromo-gamma-tocopherol (12), the latter two formed in ail unusual dealkylative fragmentation step. The mechanisms were studied by a combination of trapping reactions as well as kinetic and computational studies. (c) 2005 Elsevier Ltd. All rights reserved.
• Effect of α-tocopherol on the hemin-catalyzed decomposition of 1-palmitoyl-2-linoleoyl-3-sn-phosphatidylcholine 13-hydroperoxide in micelles and liposomes
  作者：Ryo Yamauchi、Siori Watanabe、Ana S Martín、Satoshi Iwamoto

  DOI：10.1016/j.chemphyslip.2014.10.001

  日期：2014.12

  The secondary process of lipid peroxidation produces some toxic aldehydes. Since this process takes place via free radical reaction in lipophilic circumstances, alpha-tocopherol would suppress the formation of such aldehydes by trapping free-radical intermediates. This study reports the effect of alpha-tocopherol on the hemin-catalyzed decomposition of 1-palmitoyl-2-linoleoyl-3-sn-phosphatidylcholine 13-hydroper-oxide (PLPC-OOH) in micelles and liposomes. PLPC-OOH and alpha-tocopherol were reacted with hemin in micelles, and the reaction products were characterized to be 1-palmitoyl-2-(alpha-tocopheroxy-12,13-epoxyoctadecenoyl)-3-sn-phosphatidylcholines (T-epoxyPLPC) and known compounds, 1-palmitoyl-2[(8a-dioxy-alpha-tocopherone)-12,13-epoxyoctadecenoyl]-3-sn-phosphatidylcholines (TOO-epoxyPLPC) and alpha-tocopherol dimer. The hemin-catalyzed decomposition of PLPC-OOH in micelles produced hexanal as one of secondary aldehydic products. alpha-Tocopherol suppressed the formation of hexanal, and alpha-tocopherylquinone, alpha-tocopherol dimer, TOO-epoxyPLPC, and T-epoxyPLPC were detected during the reaction. In liposomes, alpha-tocopherol could partially suppress the formation of hexanal, and the main products were TOO-epoxyPLPC and alpha-tocopherol dimer. The results indicate that alpha-tocopherol may suppress the formation of hexanal by trapping the epoxyperoxyl and epoxyalkyl radicals derived from PLPC-OOH. (C) 2014 Elsevier Ireland Ltd. All rights reserved.
• Yamauchi, Ryo; Matsui, Tomoatsu; Kato, Koji, Agricultural and Biological Chemistry, 1989, vol. 53, # 12, p. 3257 - 3262
  作者：Yamauchi, Ryo、Matsui, Tomoatsu、Kato, Koji、Ueno, Yoshimitsu

  DOI：——

  日期：——
• Stabilization and First Direct Spectroscopic Evidence of the <i>o</i>-Quinone Methide Derived from Vitamin E
  作者：Thomas Rosenau、Antje Potthast、Tom Elder、Paul Kosma

  DOI：10.1021/ol026917f

  日期：2002.11.1

  graphicThe o-quinone methide (2) derived from vitamin E (1) can be stabilized at low temperatures in a complex with the highly polar N-methylmorpholine-N-oxide (5). The lifetime of 2 can thus be prolonged from less than 10 s to several minutes. In the complex formed, 2 adopts a zwitterionic, aromatic structure with the exocyclic methylene group in perpendicular arrangement to the ring plane, stabilized by the negatively charged oxygen in 5.
• YAMAUCHI, RYO;MATSUI, TOMOATSU;KATO, KOJI;UENO, YOSHIMITSU, AGR. AND BIOL. CHEM., 53,(1989) N2, C. 3257-3262
  作者：YAMAUCHI, RYO、MATSUI, TOMOATSU、KATO, KOJI、UENO, YOSHIMITSU

  DOI：——

  日期：——