α-tocopheramine | 3398-70-7

• 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: α-tocopheramine
• 英文别名: (2R)-3,4-Dihydro-2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltridecyl]-2H-1-benzopyran-6-amine；(2R)-2,5,7,8-tetramethyl-2-[(4R,8R)-4,8,12-trimethyltridecyl]-3,4-dihydrochromen-6-amine
• CAS: 3398-70-7
• 化学式: C₂₉H₅₁NO
• 分子量: 429.73
• InChiKey: VHDHAAWAAIWBBG-IEOSBIPESA-N

物化性质

• 沸点：
  533.6±50.0 °C(Predicted)
• 密度：
  0.920±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  31
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-tocopheramine 在 1,1-二苯-2-苦基肼 作用下， 以 乙醇 为溶剂， 生成 D-α-托可醌
  参考文献：
  名称：

  Tocotrienamines and tocopheramines: Reactions with radicals and metal ions

  摘要：

  The antioxidant activity of vitamin E (VE) homologs alpha, gamma and delta-tocotrienamines (4b-6b), never studied before, and alpha, gamma and delta-tocopheramines (4a-7a) was investigated by means of different total antioxidant capacity (TAC) tests. In all the test model systems, compounds 4a-7a and 4b-6b showed similar or higher TAC values than the parental vitamin E forms and their physiological metabolites. alpha-Homologs of VE amines showed markedly higher activity than the VE congeners in the TEAC test, which is tailored for liposoluble antioxidants, while gamma-homologs of the amine analogs showed higher activity in the FRAP tests. Kinetics analysis of the reaction with DPPH center dot showed higher second order rate k for 4a than for alpha-tocopherol (1a). alpha-Tocopherolquinone 1f was the common main oxidation product for both 1a and alpha-tocopheramine (4a) exposed to ferric ions or DPPH center dot, and the implied oxidative deamination of 4a was accompanied by a nitration reaction of phenolic substrates that were added to the reaction medium. Possible mechanisms of these reactions were studied. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.08.050
• 作为产物：
  描述：

  (R)‑2‑[(4R,8R)‑4,8,12‑trimethyltridecyl]‑2,5,7,8‑tetramethyl‑6‑nitro‑chroman 在 5% Pd/C 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 10.0h， 以95.1%的产率得到α-tocopheramine
  参考文献：
  名称：

  A novel synthesis of tocopheryl amines and amides

  摘要：

  We report the synthesis of tocopheryl amines and amides from commercially available tocopherols. This synthesis improves the yield and diastereomeric purity of these biologically important compounds. The tocopheryl amines were prepared from the corresponding alpha- and delta-tocopherols using two distinct synthetic routes. The introduction of the C(6)-amino group can be achieved by aryl nitration/reduction or by Pd-catalyzed Substitution of an aryl triflate, depending on the structure of the starting material. We also prepared the succinamide and maleamide derivatives of each amine. Tocopheryl amides are more potent pro-apoptotic anti-cancer agents than the corresponding alpha-tocopheryl esters. These compounds act selectively within the mitochondria of cancer cells. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.10.056
• 作为试剂：
  描述：

  D-gamma-生育酚 在 α-tocopheramine 、 silver(l) oxide 作用下， 以 正己烷 为溶剂， 生成 5-nitro-γ-tocopherol
  参考文献：
  名称：

  Tocotrienamines and tocopheramines: Reactions with radicals and metal ions

  摘要：

  The antioxidant activity of vitamin E (VE) homologs alpha, gamma and delta-tocotrienamines (4b-6b), never studied before, and alpha, gamma and delta-tocopheramines (4a-7a) was investigated by means of different total antioxidant capacity (TAC) tests. In all the test model systems, compounds 4a-7a and 4b-6b showed similar or higher TAC values than the parental vitamin E forms and their physiological metabolites. alpha-Homologs of VE amines showed markedly higher activity than the VE congeners in the TEAC test, which is tailored for liposoluble antioxidants, while gamma-homologs of the amine analogs showed higher activity in the FRAP tests. Kinetics analysis of the reaction with DPPH center dot showed higher second order rate k for 4a than for alpha-tocopherol (1a). alpha-Tocopherolquinone 1f was the common main oxidation product for both 1a and alpha-tocopheramine (4a) exposed to ferric ions or DPPH center dot, and the implied oxidative deamination of 4a was accompanied by a nitration reaction of phenolic substrates that were added to the reaction medium. Possible mechanisms of these reactions were studied. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.08.050

文献信息

• Vitamin E conjugates
  申请人：Lal Manjari

  公开号：US06858227B1

  公开（公告）日：2005-02-22

  Vitamin E conjugates, methods for their preparation, and compositions that include the conjugates. The vitamin E conjugates include a tocopherol moiety covalently coupled through a linker moiety to either a pyroglutamate moiety, a pyrrolidinone moiety, or a gentisic acid moiety.

  维生素E共轭物，其制备方法以及包括这些共轭物的组合物。维生素E共轭物包括一个生育酚基团，通过连接基团共价偶联到吡咯谷氨酸基团、吡咯烷酮基团或间苯二羧酸基团。
• Efficient Synthesis of Vitamin E Amines
  作者：Francesco Mazzini、Thomas Netscher、Piero Salvadori

  DOI：10.1002/ejoc.200900088

  日期：2009.5

  A short and efficient synthesis of all VE amines (-, -, -, -tocopheramines and -tocotrienamines) in enantiopure form is described. These amino analogues of natural vitamin E compounds (-, -, -, -tocopherols and -tocotrienols) can be prepared by Pd-catalyzed N-arylation reactions on the corresponding triflates, synthesized under controlled conditions from the phenols. The benzophenone imine or benzylamine

  描述了对映体纯形式的所有 VE 胺（-、-、-、-生育酚胺和 -生育三烯胺）的简短有效合成。这些天然维生素 E 化合物的氨基类似物（-、-、-、-生育酚和 -生育三烯酚）可以通过 Pd 催化的相应三氟甲磺酸酯的 N-芳基化反应制备，在受控条件下由酚类合成。二苯甲酮亚胺或苄胺中间体在脱保护后以高产率和纯度提供 VE 胺。制备的化合物是 VE 酰胺的关键前体，在寻找具有抗肿瘤活性的新疗法方面具有重要意义。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• 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
• Synthesis and analytical characterization of monomeric N-oxidized derivatives of α-tocopheramine
  作者：Anjan Patel、Andreas Hofinger、Thomas Rosenau

  DOI：10.1007/s00706-021-02805-8

  日期：2021.8

  oxidation of α-tocopheramine in aqueous media, including the hydroxylamine, nitroso, and nitro derivative, in this way providing standards for the identification of the so far elusive byproducts. Synthesis and stability of the derivatives are discussed. Graphic abstract

  α-生育酚已显示出作为合成和天然聚合物稳定剂的巨大希望，但也在各种生物医学场景中进行了研究。由于 α-生育酚胺的氧化产物尚未得到正确鉴定，且仍缺乏分析数据，因此许多研究受到阻碍。在本研究中，我们合成并完全分析表征了所有在水性介质中氧化 α-生育酚时可以形成的 N-氧化产物，包括羟胺、亚硝基和硝基衍生物，以此方式为鉴定这些产物提供了标准。难以捉摸的副产品。讨论了衍生物的合成和稳定性。 图形摘要
• Synthesis and analytical characterization of N-methylated derivatives of α-tocopheramine and their oxidation products
  作者：Anjan Patel、Thomas Rosenau

  DOI：10.1007/s00706-022-02970-4

  日期：2022.10

  N-Methylated derivatives of α-tocopheramine, which have preliminarily been shown to have good performance as stabilizers of cellulose solutions in ionic liquids for production of cellulosic manmade fibers, have not been accessible in sufficient amounts by green syntheses. In this study, the N-methyl-, N,N-dimethyl-, and N,N,N-trimethylammonium derivatives of α-tocopheramine were synthesized and fully

  α-生育酚胺的N-甲基化衍生物已初步显示在离子液体中作为纤维素溶液的稳定剂具有良好的性能，用于生产纤维素人造纤维，但尚未通过绿色合成获得足够量。本研究合成了α-生育酚胺的N-甲基-、N-、N-二甲基-和N-、N-、N-三甲基铵衍生物，并对其进行了全面的分析表征。该程序使用碳酸二甲酯作为溶剂和甲基化剂以及氧化铝作为可重复使用的催化剂。小心确保程序符合绿色化学原则并且易于升级。 图形概要