trans-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid | 26350-60-7

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: trans-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid
• 英文别名: thomasidioic acid；rac.-Thomasidiosaeure；(1S,2R)-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid
• CAS: 26350-60-7；52802-10-5
• 化学式: C₂₂H₂₂O₁₀
• 分子量: 446.411
• InChiKey: MQRBOKLXGOXXGG-RDJZCZTQSA-N

物化性质

• 沸点：
  673.1±55.0 °C(Predicted)
• 密度：
  1.444±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  152
• 氢给体数：
  4
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  trans-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid 在 盐酸 作用下， 生成
  参考文献：
  名称：

  胸苷酸的合成

  摘要：

  通过将芥子酸（6）氧化苯酚偶联至双内酯（7），然后进行酸催化的重排，通过两个步骤合成了托马斯二酸（2）。脱苄基化和碱水解后，通过苄基化然后通过LAH还原从硫代二酸二甲酯（9）衍生而来的二醇二苄基醚（15）被选择性氧化，生成胸苷酸（1）。

  DOI：

  10.1016/0040-4020(73)80192-9
• 作为产物：
  描述：

  3,5-二甲氧基-4-羟基肉桂酸 在 air 作用下， 以 水 为溶剂， 生成 trans-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid
  参考文献：
  名称：

  Thomasidioic acid and 6-hydroxy-5,7-dimethoxy-2-naphthoic acid: Are they really natural products?

  摘要：

  It has been shown that air oxidation of alkaline aqueous solutions of sinapic acid produces both thomasidioic acid (1), and 6-hydroxy-5,7-dimethoxy-2-naphthoic acid (2) in high yield, with the relative amounts dependent on the basicity of the solution. It has also been shown that naphthoic acid 2 is a secondary oxidation product of thomasidioic acid, a reaction that also produces 2,6-dimethoxy-p-benzoquione (3). The question of whether compounds 1, 2 and 3 are really natural products, as previously reported, is discussed. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01775-9

文献信息

• Asymmetric Biomimetic Oxidations of Phenols: The Mechanism of the Diastereo- and Enantioselective Synthesis of Thomasidioic Acid
  作者：Luca Zoia、Maurizio Bruschi、Marco Orlandi、Eeva-Liisa Tolppa、Bruno Rindone

  DOI：10.3390/molecules13010129

  日期：——

  Enantiopure chiral amidic derivatives of sinapic acid were oxidised withhydrogen peroxide using horseradish peroxidase (HRP) as the catalyst to give thearyltetraline dilignol thomasidioic acid. Trans-diastereoselectivity and enantioselectivity inthe formation of thomasidioic acid was observed. Computational methods show that theenantioselectivity is controlled by the β-β oxidative coupling step, while thediastereoselectivity is controlled by the stability of the reactive conformation of theintermediate quinomethide.

  纯对映体的手性酰胺类芥子酸衍生物在辣根过氧化物酶（HRP）催化下，通过过氧化氢氧化生成芳基四氢化茚二联木脂酸托马斯二酸。在托马斯二酸的形成过程中观察到了反式非对映选择性和对映选择性。计算方法表明，对映选择性由β-β氧化偶联步骤控制，而非对映选择性则由中间体醌甲烷的反应构象的稳定性控制。
• Determination of free diferulic, disinapic and dicoumaric acids in plants and foods
  作者：Jiří Grúz、Jiří Pospíšil、Hana Kozubíková、Tomáš Pospíšil、Karel Doležal、Mirko Bunzel、Miroslav Strnad

  DOI：10.1016/j.foodchem.2014.08.131

  日期：2015.3

  Hydroxycinnamates are common phenolic compounds of plants and plant foods, often found in substantial quantities. Due to their high in vitro antioxidant activity they can easily be oxidized under oxidative conditions. In this study, we found that in vitro oxidation of coumaric, ferulic and sinapic acids resulted mainly in dimeric compounds. We hypothesized that these dimers are present in plants and plant foods not only in their bound form but also as free acids that can be extracted from non-hydrolyzed samples. By applying sensitive UHPLC-MSIMS method, we were able to identify and quantify four free hydroxycinnamic acid dimers for the first time, namely 8-8'-disinapic, 8-5'-diferulic, 8-O-4'-diferulic and 8-3'-dicoumaric acids, in wheat sprouts, Chinese cabbage, millet sprouts, light beer and parsley. Concentrations of dicinnamates in plant tissues ranged from 0.05 to 2.8 mu g g(-1) DW and the monomer:dimer ratio ranged from 2 to 850. (C) 2014 Elsevier Ltd. All rights reserved.
• Lignans of Ulmus thomasii heartwood—II
  作者：Frances D. Hostettler、Margaret K. Seikel

  DOI：10.1016/s0040-4020(01)82782-4

  日期：1969.1
• Sinapate Dehydrodimers and Sinapate−Ferulate Heterodimers in Cereal Dietary Fiber
  作者：Mirko Bunzel、John Ralph、Hoon Kim、Fachuang Lu、Sally A. Ralph、Jane M. Marita、Ronald D. Hatfield、Hans Steinhart

  DOI：10.1021/jf020910v

  日期：2003.2.1

  Two 8-8-coupled sinapic acid dehydrodimers and at least three sinapate-ferulate heterodimers have been identified as saponification products from different insoluble and soluble cereal grain dietary fibers. The two 8-8-disinapates were authenticated by comparison of their GC retention times and mass spectra with authentic dehydrodimers synthesized from methyl or ethyl sinapate using two different single-electron metal oxidant systems. The highest amounts (481 mug/g) were found in wild rice insoluble dietary fiber. Model reactions showed that it is unlikely that the dehydrodisinapates detected are artifacts formed from free sinapic acid during the saponification procedure. The dehydrodisinapates presumably derive from radical coupling of sinapate-polymer esters in the cell wall; the radical coupling origin is further confirmed by finding 8-8 and 8-5 (and possibly 8-O-4) sinapate-ferulate cross-products. Sinapates therefore appear to have an analogous role to ferulates in cross-linking polysaccharides in cereal grains and presumably grass cell walls in general.
• Evaluation of Alkaline Conversion of Sinapic Acid to Thomasidioic Acid
  作者：Maria I. Rubino、Susan D. Arntfield、James L. Charlton

  DOI：10.1021/jf950431e

  日期：1996.1.1

  Conditions which promote the alkaline conversion of sinapic acid (SA), the main phenolic acid in canola, to the lignan thomasidioic acid (TA) were investigated as the presence of TA could affect nutritional and functional properties of canola products. Reaction rates were studied using ultraviolet spectroscopy under oxygen, nitrogen, and air and in the presence of antioxidants. High-pressure liquid chromatography was used to quantify the conversion of SA to TA. This reaction appears to involve an oxidative coupling of SA molecules which can be controlled by purging with nitrogen. By including ascorbic acid, the reaction was slowed but not completely controlled, and the presence of sodium bisulfite accelerated the reaction. In the presence of air, there was complete conversion of SA to TA at pH 8.5 and 30% conversion at pH 7.