5a-bromo-α-tocopherol | 187806-29-7

• 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: 5a-bromo-α-tocopherol
• 英文别名: 5-(Bromomethyl)-2,7,8-trimethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol
• CAS: 187806-29-7
• 化学式: C₂₉H₄₉BrO₂
• 分子量: 509.611
• InChiKey: HDXQHUAYLMPECY-UHFFFAOYSA-N

物化性质

• 沸点：
  558.2±50.0 °C(Predicted)
• 密度：
  1.070±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.9
• 重原子数：
  32
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5a-bromo-α-tocopherol 在 sodium hydroxide 、 sodium azide 、 硫酸 、 sodium dodecyl-sulfate 作用下， 以 甲醇 、 phosphate buffer 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 4.0h， 生成 1,3',4',8,9,10-hexahydro-2',5,6,7',8,8'-hexamethyl-2',8-bis(4,8,12-trimethyltridecyl)-spiro-dipyran>-3(2H),5'-<5H-1>benzopyran-6'(2'H)-one
  参考文献：
  名称：

  5a-α-生育酚叠氮化物的合成及其对1-(5a-α-生育酚)-1,2,3-三唑的[2+3]-环加成反应

  摘要：

  具有 1 位取代基的 1,2,3-三唑类化合物源自 α-生育酚（维生素 E），通过 5a-叠氮基-α-生育酚乙酸酯与炔烃的 1,3-偶极环加成反应合成，并经过全面分析表征. 提供了化合物的 NMR 光谱和具有截短的类异戊二烯侧链的衍生物的晶体结构。生育酚部分在碱性介质中很容易裂解，这是在显示 pH 依赖性药物释放的递送系统中使用的先决条件。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  DOI：

  10.1002/ejoc.200500898
• 作为产物：
  描述：

  DL-α-生育酚 在 溴 作用下， 以 正己烷 为溶剂， 反应 2.0h， 以99%的产率得到5a-bromo-α-tocopherol
  参考文献：
  名称：

  新型生育酚化合物I.α-生育酚的溴化反应机理及合成应用

  摘要：

  与较早的报道相反，α-生育酚的溴化过程显示为两步过程，其中包括邻醌甲基化物的发生，而不是自由基链反应。邻苯二甲酮甲基化物中间体也可通过α-生育酚与氧化银的氧化反应制得，并可在富电子二烯亲和体存在下，通过杂Diels-Alder反应捕获，以高收率形成新型重铬烷。

  DOI：

  10.1016/0040-4020(95)00421-4

文献信息

• Treatment of mitochondrial diseases
  申请人：Walkinshaw Gail

  公开号：US20050065099A1

  公开（公告）日：2005-03-24

  The invention relates the method of treatment or amelioration of mitochondrial disorders such as Alzheimer's disease, Parkinson's disease, Friedreich's ataxia (FRDA), cerebellar ataxias, Leber's hereditary optic neuropathy (LHON), mitochondrial myopathy, encephalopathy, lactacidosis, stroke (MELAS), Myoclonic Epilepsy with Ragged Red Fibers (MERFF), amyotrophic lateral sclerosis (ALS), motor neuron diseases, Huntington's disease, macular degeneration, and epilepsy, with chroman derivatives of Formula I or Formula II as described herein.

  这项发明涉及治疗或改善线粒体疾病，如阿尔茨海默病、帕金森病、弗里德雷希共济失调症（FRDA）、小脑共济失调、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）、带有红色纤维的肌阵挛性癫痫（MERFF）、肌萎缩侧索硬化症（ALS）、运动神经元疾病、亨廷顿病、黄斑变性和癫痫等疾病的治疗方法，所述方法使用本文描述的Formula I或Formula II的类胡萝卜素衍生物。
• Novel Tocopherol Compounds VII. γ-Tocopherol-5-carboxylic Acid - a Novel Route to γ-Tocopherol
  作者：Thomas Rosenau、Wolf Habicher

  DOI：10.1055/s-1997-730

  日期：1997.2

  A novel route for the synthesis of γ-tocopherol starting from the readily available vitamin E (α-tocopherol) has been found. The key step is the photochemical decarboxylation of γ-tocopherol -5-carboxylic acid.

  发现了一种从易得的维生素E（α-生育酚）合成γ-生育酚的新路线。关键步骤是γ-生育酚-5-羧酸的光化学脱羧反应。
• A Concise Synthesis of <i>N</i>-(Trideuteromethyl)morpholine-<i>N</i>-oxide Monohydrate
  作者：Thomas Rosenau、Antje Potthast、Paul Kosma

  DOI：10.1055/s-1999-2963

  日期：1999.12

  An efficient synthesis of N-(trideuteromethyl)morpholine-N-oxide monohydrate (3) is described. The procedure applies the tocopheryl protecting group, and makes use of sodium percarbonate as the oxidant and water donor, thus avoiding both the troublesome direct alkylation of morpholine and the unsuitable oxidation by aqueous hydrogen peroxide. Overall yields of purified material range above 90%.

  描述了一种高效合成N-(三氘甲基)morpholine-N-氧化物单水合物（3）的方法。该过程采用了生育酚保护基团，并使用过碳酸钠作为氧化剂和供水体，从而避免了morpholine的直接烷基化带来的麻烦以及水合过氧化氢的不适合氧化。纯化物的总体产率超过90%。
• Novel tocopherol compounds. III. Reaction of 5a-Bromo-?-tocopherol with Nucleophiles
  作者：T. Rosenau、W. D. Habicher

  DOI：10.1002/prac.199633801123

  日期：——

  The synthesis of different classes of 5a-substituted tocopherols is described. These compounds are potent antioxidants and highly interesting as vitamin E carriers. The reaction of the readily available 5a-bromo-alpha-tocopherol with alcohols and phenols is shown to produce 5a-alklxy-alpha-tocopherols (3-5, 8, 9) and 5a-aryloxy-alpha-tocopherols (6, 7), respectively, with high yields. 5a-alpha-Tocopheryl esters (10, 11) are prepared by reaction with metal carboxylates. 5a-Bromo-alpha-tocopherol is used as well to introduce tocopheryl groupsinto tertiary amines by quaternization, that renders these compounds (13, 14) soluble in water and in common organic solvents. 5a-Bromo-alpha-tocopherol also reacts as an alkylating agent with sterically hindered phenols in a Friedel-Crafts reaction. Phenols not highly substituted are exclusively alkylated in the para position at room temperature or below, whereas at higher temperature the para- as well as the ortho-alkylated product is observed.
• NOVEL TOCOPHEROL COMPOUNDS IX. SYNTHESIS OF 5a-FUNCTIONALIZED TOCOPHEROLS WITH ORGANOELEMENT SUBSTITUENTS
  作者：D. Weber、T. Rosenau、W. D. Habicher

  DOI：10.1080/10426509708033704

  日期：1997.11

  ja-Substituted tocopherols bearing silicon, sulfur, or phosphorus moieties at position 5a have been synthesized starting from 5a-bromo-alpha-tocopherol (5). 5a-Trialkylsilyl-alpha-tocopherols (6, 7) were obtained by a sonochemically catalyzed reaction as the key step. Reaction of Sa-bromo-oc-tocopherol with N-substituted thioureas provided satisfying yields of the corresponding 5a-alpha-tocopheryl-thiouronium salts (8-10), whereas the reaction with thiols did not produce the Sa-substituted products, but a complex mixture of products due to the occurrence of uncontrollable redox processes during the reaction. Tocopheryltriphenylphosphunium bromide (11) was obtained by a simple quaternization reaction, and has been further exploited as a useful intermediate in the syntheses of novel vitamin E derivatives (12-18) with the tocopherol unit bring incorporated into a stable furobenzopyran structure.