2-(3-羟基-3-甲基十九烷基)-3,5,6-三甲基环己-2,5-二烯-1,4-二酮 | 113561-37-8

• 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
• 中文名称: 2-(3-羟基-3-甲基十九烷基)-3,5,6-三甲基环己-2,5-二烯-1,4-二酮
• 英文名称: α-Tocopherolchinon
• 英文别名: 2-(3-Hydroxy-3-methylnonadecyl)-3,5,6-trimethyl-2,5-cyclohexadiene-1,4-dione；2-(3-hydroxy-3-methylnonadecyl)-3,5,6-trimethylcyclohexa-2,5-diene-1,4-dione
• CAS: 113561-37-8
• 化学式: C₂₉H₅₀O₃
• 分子量: 446.714
• InChiKey: MMRJMBZSARWOAY-UHFFFAOYSA-N

物化性质

• 沸点：
  546.5±29.0 °C(Predicted)
• 密度：
  0.949±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  32
• 可旋转键数：
  18
• 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：

  三甲基溴硅烷 、 2-(3-羟基-3-甲基十九烷基)-3,5,6-三甲基环己-2,5-二烯-1,4-二酮 以 正己烷 为溶剂， 反应 2.0h， 以95%的产率得到[5-(Bromomethyl)-2-hexadecyl-2,7,8-trimethyl-3,4-dihydrochromen-6-yl]oxy-trimethylsilane
  参考文献：
  名称：

  Novel tocopherol compounds - X. A facile synthesis of O-trimethylsilyl-5a-halo-α-tocopherols

  摘要：

  A simple and efficient procedure for the synthesis of O-trimethylsilyl-5a-bromo-alpha-tocopherol (6) and O-trimethylsilyl-5a-chloro-alpha-tocopherol (7) starting from para-tocopherolquinone (5) has been developed. The products are formed by acid-catalyzed cyclization of para-tocopherolquinone via an ortho-quinone methide intermediate. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01342-7
• 作为产物：
  描述：

  α-tocopherol 在 air 、 氧化亚氮 作用下， 以 环己烷 为溶剂， 反应 0.08h， 生成 2-(3-羟基-3-甲基十九烷基)-3,5,6-三甲基环己-2,5-二烯-1,4-二酮 、 4-Acetyl-4-hydroxy-5-(3-hydroxy-3-methyl-nonadecyl)-2,3-dimethyl-5-nitroso-cyclopent-2-enone
  参考文献：
  名称：

  在有氧条件下与一氧化氮反应的α-生育酚亚硝化-氧化环收缩

  摘要：

  在空气饱和的环己烷中将α-生育酚（1）暴露于一氧化氮（NO）会导致生成复杂的产物混合物，其中一种极性相对较大的产物已被分离出来，并被鉴定为新颖的2,3-二甲基-4 -乙酰基-4-羟基-5-亚硝基-2-环戊烯酮衍生物5。

  DOI：

  10.1016/0040-4039(95)01846-a

文献信息

• Development and Validation of Oxygen Radical Absorbance Capacity Assay for Lipophilic Antioxidants Using Randomly Methylated β-Cyclodextrin as the Solubility Enhancer
  作者：Dejian Huang、Boxin Ou、Maureen Hampsch-Woodill、Judith A. Flanagan、Elizabeth K. Deemer

  DOI：10.1021/jf0113732

  日期：2002.3.1

  We recently reported the improved oxygen radical absorbance capacity (ORAC) assay using fluorescein (FL) as the fluorescent probe. The current ORAC(FL) assay is limited in hydrophilic antioxidant due to the aqueous environment of the assay. Lipophilic antioxidants mainly include the vitamin E family and carotenoids, which play a critical role in biological defense systems. In this paper, we expanded the current ORAC(FL) assay to lipophilic antioxidants. Randomly methylated beta-cyclodextrin (RMCD) was introduced as the water solubility enhancer for lipophilic antioxidants. Seven percent RMCD (w/v) in a 50% acetone-H2O mixture was found to sufficiently solubilize vitamin E compounds and other lipophilic phenolic antioxidants in 75 mM phosphate buffer (pH 7.4). This newly developed ORAC assay (abbbreviated ORAC(FL-LIPO)) was validated through linearity, precision, accuracy, and ruggedness. The validation results demonstrate that the ORAC(FL-LIPO) assay is reliable and robust. For the first time, by using 6-hydroxy-2,5,7,8-tetramethyl-2-carboxylic acid as a standard (1.0), the ORAC values of alpha-tocopherol, (+)-gamma-tocopherol, (+)-delta-tocopherol, alpha-tocopherol acetate, tocotrienols, 2,6-di-tert-butyl-4-methylphenol, and gamma-oryzanol were determined to be 0.5 +/- 0.02, 0.74 +/- 0.03, 1.36 +/- 0.14, 0.00, 0.91 +/- 0.04, 0.16 +/- 0.01, and 3.00 +/- 0.26, respectively. The structural information of oxidized alpha-tocopherol obtained by liquid chromatography/mass spectrometry reveals that the mechanism for the reaction between the vitamin E and the peroxyl radical follows the hydrogen atom transfer mechanism, which is in agreement with the notion that vitamin E is the chain-breaking antioxidant.
• Dye-sensitized photooxidation of vitamin E revisited. New 7-oxaspiro[4.5]dec-1-ene-3,6-dione products by oxygenation and ring-contraction of .alpha.-tocopherol
  作者：Marco D'Ischia、Claudio Costantini、Giuseppe Prota

  DOI：10.1021/ja00022a023

  日期：1991.10

  The dye-sensitized photooxidation of alpha-tocopherol, the major component of the biological antioxidant vitamin E, was reinvestigated under biomimetic conditions. When methylene blue was used as the sensitizer and ethanol-phosphate buffer (pH 6.8; 7:3, v/v) as the solvent, the reaction led to the formation, besides alpha-tocopherol qunione (3) and its epoxide (4), of three hitherto unknown photooxygenation products accounting overall for about 15% of the consumed substrate. These were identified as two diastereoisomers corresponding to the gross structure of 1,2,8-trimethyl-4-methylene-8-phytyl-7-oxaspiro[4.5]dec-1-ene-3,6-dione (8) and one diastereomer of the hydrated derivative 4-hydroxy-1,2,4,8-tetramethyl-8-phytyl-7-oxaspiro[4.5]dec-1-ene-3,6-dione (9). Formation of the 7-oxaspiro[4.5]dec-1-ene-3,6-dione system was envisaged as resulting from a ring-contracting rearrangement of an epoxyquinone hemiketal intermediate (10) or a related species arising from singlet oxygenation of alpha-tocopherol.
• Novel tocopherol compounds - X. A facile synthesis of O-trimethylsilyl-5a-halo-α-tocopherols
  作者：T. Rosenau、W.D. Habicher

  DOI：10.1016/s0040-4039(97)01342-7

  日期：1997.8

  A simple and efficient procedure for the synthesis of O-trimethylsilyl-5a-bromo-alpha-tocopherol (6) and O-trimethylsilyl-5a-chloro-alpha-tocopherol (7) starting from para-tocopherolquinone (5) has been developed. The products are formed by acid-catalyzed cyclization of para-tocopherolquinone via an ortho-quinone methide intermediate. (C) 1997 Elsevier Science Ltd.
• Nitrosation-oxidative ring contraction of α-tocopherol by reaction with nitric oxide under aerobic conditions
  作者：Marco d'Ischia

  DOI：10.1016/0040-4039(95)01846-a

  日期：1995.11

  Exposure of α-tocopherol (1) to nitric oxide (NO) in air-saturatcd cyclohexane leads to a complex mixture of products, one of which, relatively more polar, has been isolated and identified as the novel 2,3-dimethyl-4-acetyl-4-hydroxy-5-nitroso-2-cyclopentenone derivative 5.

  在空气饱和的环己烷中将α-生育酚（1）暴露于一氧化氮（NO）会导致生成复杂的产物混合物，其中一种极性相对较大的产物已被分离出来，并被鉴定为新颖的2,3-二甲基-4 -乙酰基-4-羟基-5-亚硝基-2-环戊烯酮衍生物5。