α-tocopherol quinone | 758720-42-2

• 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: α-tocopherol quinone
• 英文别名: 2-[(7R,11R)-3-hydroxy-3,7,11,15-tetramethylhexadecyl]-3,5,6-trimethylcyclohexa-2,5-diene-1,4-dione
• CAS: 758720-42-2
• 化学式: C₂₉H₅₀O₃
• 分子量: 446.714
• InChiKey: LTVDFSLWFKLJDQ-ZNRVYKQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  α-tocopherol quinone 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 生成 (4R,8R)-4,8,12-trimethyltridecyl acetate
  参考文献：
  名称：

  Mayer,H. et al., Helvetica Chimica Acta, 1963, vol. 46, p. 963 - 982

  摘要：

  DOI：
• 作为产物：
  描述：

  天然维生素E 以 various solvent(s) 为溶剂， 240.0 ℃ 、700.0 Pa 条件下， 反应 1.5h， 生成 α-tocopherol quinone
  参考文献：
  名称：

  Identification of α-Tocopherol Oxidation Products in Triolein at Elevated Temperatures

  摘要：

  The effect of high-temperature treatment on the stability of alpha -tocopherol (1) in triolein tvas assessed under a reduced-pressure atmosphere (4-40 mbar) simulating the deodorization step of the refining of vegetable oils. A marked degradation of 1 was observed, which increased with increasing temperature (180-260 degreesC) and heating time (20-80 min). The degradation of 1 in triolein at 240 degreesC was inhibited by the:addition of the synthetic antioxidant TBHQ or when heating was performed under nitrogen atmosphere, indicating oxidative degradation. The oxidation products were isolated and identified as alpha -tocopherolquinone (2), 4a,5-epoxy-alpha -tocopherolquinone (3), and 7,8-epoxy-alpha -tocopherolquinone (4).

  DOI：

  10.1021/jf001142f

文献信息

• "Vitamin CE," a Novel Prodrug Form of Vitamin E.
  作者：Thomas ROSENAU、Wolf Dieter HABICHER

  DOI：10.1248/cpb.45.1080

  日期：——

  Reaction of 5a-bromo-α-tocopherol with ascorbic acid produces 5a-tocopheryl ascorbate which is designated "vitamin CE." This novel tocopherol derivative represents an interesting prodrug form of α-tocopherol (vitamin E) that is stable under acidic conditions, but regenerates finely dispersed vitamin E in basic media. The reaction mechanism of the base-induced decomposition of vitamin CE involves elimination of ascorbate and production of an ortho-quinone methide intermediate that oxidizes ascorbate, and is reduced to vitamin E. Kinetic experiments showed the reaction to proceed in the pH range of 8 to 11 under physiological conditions. Tissue culture measurements demonstrated that vitamin E generated from the novel derivative is absorbed at much higher rates than conventional preparations and can even be absorbed under simulated conditions of malabsorption where there is no uptake of conventional vitamin E medications.

  5a-bromo-α-tocopherol 与抗坏血酸反应生成 5a-tocopheryl ascorbate，并命名为 "维生素 CE"。这种新型生育酚衍生物是 α-生育酚（维生素 E）的一种有趣的原药形式，它在酸性条件下稳定，但在碱性介质中可再生出精细分散的维生素 E。碱诱导维生素 CE 分解的反应机理包括消除抗坏血酸，生成氧化抗坏血酸的原醌甲酰胺中间体，然后还原成维生素 E。动力学实验表明，在生理条件下，该反应的 pH 值范围为 8 到 11。组织培养测量结果表明，由这种新型衍生物生成的维生素 E 的吸收率远高于传统制剂，甚至可以在模拟吸收不良的条件下被吸收，而在这种条件下，传统维生素 E 药物不会被吸收。
• Copper(II)-Catalyzed Oxidation of d-.ALPHA.-Tocopherol by Oxygen in Aqueous Solution.
  作者：Yoshiko NAGATA、Chie MIYAMOTO、Yoshikazu MATSUSHIMA、Shigenobu MATSUMOTO

  DOI：10.1248/cpb.48.71

  日期：——

  solutions using 13 solubilizing agents and the products of oxidation by oxygen in the presence and the absence of Cu(II) were analyzed by HPLC. In the presence of Cu(II), the oxidation was accelerated and 5-formyl-7,8-dimethyltocol and alpha-tocoquinone were the major oxidation products. Their yields greatly increased in the presence of Cu(II). The yields and the rates of formation of the products were

  使用13种增溶剂将α-生育酚（α-Toc）溶解在水溶液中，并通过HPLC分析在存在和不存在Cu（II）的情况下氧的氧化产物。在Cu（II）的存在下，氧化被加速，并且5-甲酰基-7,8-二甲基生育酚和α-生育酚是主要的氧化产物。在Cu（II）的存在下，它们的产率大大提高。产物的产率和形成速率取决于增溶剂的性质和其他条件以及Cu（II）或其他金属离子的存在。建议增溶剂结构的轻微变化会影响反应过程。
• Identification of α-Tocopherol and Its Oxidation Products by Ultra-Performance Liquid Chromatography Coupled with Quadrupole Time-of-Flight Mass Spectrometry
  作者：Chuanhui Tang、Guanjun Tao、Yue Wang、Yuanfa Liu、Jinwei Li

  DOI：10.1021/acs.jafc.9b06544

  日期：2020.1.15

  This study aimed to determine α-tocopherol (α-T) and its thermal oxidation products simultaneously. A novel method based on an ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was developed. This approach was achieved by means of a BEH C18 analytical column under gradient elution conditions with eluents of acetonitrile/isopropanol (1:9

  本研究旨在同时测定α-生育酚（α-T）及其热氧化产物。开发了一种基于超高效液相色谱结合四极杆飞行时间质谱（UPLC-Q-TOF-MS）的新方法。通过BEH C18分析柱在梯度洗脱条件下使用乙腈/异丙醇（1：9，v / v）和乙腈/水（4：6，v / v）的洗脱液实现该方法。通过从Q-TOF-MS检测器获得的确切分子量和碎片离子来阐明化合物。鉴定了两种氧化产物，即α-生育酚醌和5-甲酰基-γ-生育酚，并确定了一种新的化合物。这种方法提供了一种简单，精确和可靠的方法来确定α-T的氧化产物，
• Synthesis and analytical characterization of all N–N-coupled, dimeric oxidation products of α-tocopheramine: hydrazo-, azo-, and azoxy-tocopherol
  作者：Anjan Patel、Thomas Rosenau

  DOI：10.1007/s00706-021-02833-4

  日期：2021.10

  Tocopherols are a mixture of antioxidants which are commonly referred to as vitamin E. Tocopheramines differ from tocopherols by an amino function in lieu of the phenolic OH group. They are potent antioxidants which are used in biomedical scenarios as well as stabilizers for polymers against aging. While in aqueous media α-tocopheramine is mainly oxidized to α-tocopherylquinone and N-oxidized by-products

  生育酚是通常称为维生素 E 的抗氧化剂的混合物。生育酚与生育酚的不同之处在于取代酚羟基的氨基官能团。它们是有效的抗氧化剂，用于生物医学场景以及聚合物抗老化的稳定剂。虽然在水性介质中 α-生育酚主要被氧化为 α-生育酚醌和 N-氧化的副产物，但在非极性介质或聚合物基质中的氧化主要导致迄今为止未知结构的二聚化合物。在本研究中，我们首次合成了 α-生育酚胺的全系列 N,N-二聚产物，包括偶氮、偶氮和偶氮衍生物，并提供了全面的分析数据以及访问这些化合物的通用方案在简单的合成中。 图形摘要
• Redox-active therapeutics for treatment of mitochondrial diseases and other conditions and modulation of energy biomarkers
  申请人：Miller Guy M.

  公开号：US11021424B2

  公开（公告）日：2021-06-01

  Methods of treating or suppressing mitochondrial diseases, such as Friedreich's ataxia (FRDA), Leber's Hereditary Optic Neuropathy (LHON), mitochondrial myopathy, encephalopathy, lactacidosis, stroke (MELAS), or Kearns-Sayre Syndrome (KSS) are disclosed, as well as compounds useful in the methods of the invention, such as alpha-tocopherol quinone. Methods and compounds useful in treating other disorders are also disclosed. Energy biomarkers useful in assessing the metabolic state of a subject and the efficacy of treatment are also disclosed. Methods of modulating, normalizing, or enhancing energy biomarkers, as well as compounds useful for such methods, are also disclosed.

  本发明公开了治疗或抑制线粒体疾病的方法，如弗里德雷希共济失调（FRDA）、勒伯遗传性视神经病变（LHON）、线粒体肌病、脑病、乳酸中毒、中风（MELAS）或卡恩斯-赛尔综合征（KSS），以及用于本发明方法的化合物，如α-生育酚醌。本发明还公开了用于治疗其他疾病的方法和化合物。本发明还公开了用于评估受试者代谢状态和治疗效果的能量生物标志物。还公开了调节、正常化或增强能量生物标志物的方法，以及用于此类方法的化合物。