(4-乙酰氧基-2,3,6-三甲基-苯基)乙酸酯 | 7479-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 中文名称: (4-乙酰氧基-2,3,6-三甲基-苯基)乙酸酯
• 英文名称: 2,3,5-trimethyl-1,4-hydroquinone diacetate
• 英文别名: 2,3,5-trimethylhydroquinone diacetate；trimethyl hydroquinonediacetate；Trimethyl-hydrochinon-diacetat；(4-Acetyloxy-2,3,5-trimethylphenyl) acetate
• CAS: 7479-28-9
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: JXLWCZWBHZGUEE-UHFFFAOYSA-N

物化性质

• 熔点：
  110 °C
• 沸点：
  308.7±30.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4-乙酰氧基-2,3,6-三甲基-苯基)乙酸酯 在 盐酸 、 sulfurcarbonic acid 作用下， 生成 1,4-diacetoxy-2-chloromethyl-3,5,6-trimethyl-benzene
  参考文献：
  名称：

  The Structure of the Chloromethylation Product of Trimethylhydroquinone Diacetate¹

  摘要：

  DOI：

  10.1021/ja01255a015
• 作为产物：
  描述：

  三甲基氢醌 在 乙酸酐 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 (4-乙酰氧基-2,3,6-三甲基-苯基)乙酸酯
  参考文献：
  名称：

  Spiro derivatives as lipoxygenase inhibitors

  摘要：

  本发明涉及某些新颖的螺环取代杂环环衍生物。这些化合物可能在制造用于治疗通过脂氧合酶介导的疾病的药物组合物方面有用。它们也可能在制造用于治疗脂氧合酶介导的疾病的药物配方方面有用。

  公开号：

  US20060128790A1

文献信息

• Substrate substitution effects in the Fries rearrangement of aryl esters over zeolite catalysts
  作者：Ronghe Lin、Sharon Mitchell、Thomas Netscher、Jonathan Medlock、René T. Stemmler、Werner Bonrath、Ulla Létinois、Javier Pérez-Ramírez

  DOI：10.1039/d0cy00590h

  日期：——

  zeolites exhibiting the best performance. Extension of the substrate scope by substituting methyl groups in multiple positions identifies a framework-dependent effect on the rearrangement chemistry and highlights the potential for the transformation of dimethylphenyl acetates. Kinetic studies show that the major competitive path of cleavage of the ester C–O bond usually occurs in parallel to the Fries rearrangement

  为了避免使用传统上使用的腐蚀性和有毒的路易斯和布朗斯台德酸，通过固体酸上的弗里斯重排将芳基酯催化转化为羟基苯乙酮是很有意义的。已知微孔沸石催化简单的底物如乙酸苯酯的反应，但是其在取代衍生物上的应用受到了有限的关注。为了改善结构与活性之间的关系，在这里我们检查了各种参数的影响，包括溶剂极性，水含量，酸性和骨架类型对p的Fries重排反应方案的影响。-乙酸甲苯酯比普通的固体酸。结果证实了提供高浓度可及的布朗斯台德酸位点的重要性，β沸石表现出最佳性能。通过在多个位置上取代甲基来扩大底物范围，可确定对重排化学的构架依赖性，并突出了乙酸二甲基苯酯转化的潜力。动力学研究表明，酯C–O键断裂的主要竞争途径通常与弗里斯重排平行发生。顺序酰化所得苯酚的可能性取决于底物和反应条件。
• [EN] PROCESS FOR THE MANUFACTURE OF TRIMETHYLHYDROQUINE DIALKANOATES<br/>[FR] PROCEDE DE FABRICATION DE TRIMETHYLHYDROQUINE-DIALCANOATES
  申请人：DSM IP ASSETS BV

  公开号：WO2005058792A1

  公开（公告）日：2005-06-30

  The present invention is directed to a process for the manufacture of a 2,3,5-trimethyl­hydroquinone dialkanoate comprising reacting ketoisophorone with an acylating agent in the presence of an indium salt as the catalyst. Preferred are indium(III) salts such as indium trichloride or indium tris (trifluoromethanesulfonate). Further aspects of the present invention are a process for the manufacture of 2,3,5-tri­methylhydroquinone using 2,3,5-trimethylhydroquinone dialkanoate as the starting mate­rial, especially a process for the manufacture of 2,3,5-trimethylhydroquinone by trans­esterification of 2,3,5-trimethylhydroquinone dialkanoate, as well as a process for the manufacture of a-tocopherol and its alkanoates, especially of (all-rac)-a-tocopherol and its acetate, comprising the reaction of ketoisophorone to 2,3,5-trimethylhydroquinone dialka­noate according to the present invention. Furthermore, the present invention also deals with a process for the manufacture of formulations of a-tocopherol and its alkanoates, es­pecially of formulations of (all-rac)-a-tocopherol and its acetate, comprising the reaction of ketoisophorone to 2,3,5-trimethylhydroquinone dialkanoate according to the present invention.

  本发明涉及一种制备2,3,5-三甲基羟基喹啉二烷酸酯的方法，包括在铟盐存在的情况下，将酮异佛酮与酰化剂反应。首选铟（III）盐，如三氯化铟或三(三氟甲磺酸盐)铟。本发明的进一步方面包括使用2,3,5-三甲基羟基喹啉二烷酸酯作为起始材料制备2,3,5-三甲基羟基喹啉的方法，特别是通过2,3,5-三甲基羟基喹啉二烷酸酯的酯交换制备2,3,5-三甲基羟基喹啉的方法，以及通过本发明的方法将酮异佛酮与2,3,5-三甲基羟基喹啉二烷酸酯反应制备α-生育酚及其烷酸酯，特别是(all-rac)-α-生育酚及其乙酸酯的方法。此外，本发明还涉及制备α-生育酚及其烷酸酯的配方，特别是(all-rac)-α-生育酚及其乙酸酯的配方的方法，包括根据本发明的方法将酮异佛酮与2,3,5-三甲基羟基喹啉二烷酸酯反应。
• Efficient Access to (All-<i>rac</i>)-α-Tocopherol Acetate by a Crombie Chromene Synthesis
  作者：Vincent Gembus、Nathalie Sala-Jung、Daniel Uguen

  DOI：10.1246/bcsj.82.843

  日期：2009.7.15

  In contrast to reports in the literature, the pyridine-catalysed condensation of phenolic compounds and conjugated aldehydes to chromenes was found to be applicable to trimethylhydroquinone 2a with the result of complementary convergent approaches to the title acetate using citral 3a and dihydromyrcene 9 as precursors of the phytyl residue.

  与文献中的报告相比，发现吡啶催化的酚类化合物与共轭醛类的缩合反应可以适用于三甲基氢醌2a，从而得到了利用香草醛3a和二氢美克烯9作为植基残基前体的互补聚合途径生成的目标醋酸酯。
• Process for preparing trimethylhydroquinone diacetate and trimethylhydroquinone
  申请人：Degussa AG

  公开号：US06350897B2

  公开（公告）日：2002-02-26

  A process for preparing trimethylhydroquinone diacetate, with subsequent hydrolysis to give trimethylhydroquinone, the process including reacting 2,2,6-trimethylcyclohexane-1,4-dione under oxidative conditions, in the presence of a sulfonating agent and a strong acid, and in the presence of an acylating agent.

  一种制备三乙酰基三甲基对苯二酚，并随后水解得到三甲基对苯二酚的过程，包括在氧化条件下，在磺化剂和强酸的存在下，以及在酰化剂的存在下，反应2,2,6-三甲基环己烷-1,4-二酮。
• [EN] MANUFACTURE OF TOCOPHERYL ACETATE<br/>[FR] FABRICATION D'ACETATE DE TOCOPHERYLE
  申请人：DSM IP ASSETS BV

  公开号：WO2004046126A1

  公开（公告）日：2004-06-03

  A process for the manufacture of 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate, and optionally therefrom tocopheryl acetate, comprises either C-alkylating 2,3,6-trimethylhydroquinone-l-acetate with isophytol or phytol in the presence of a sulphur(VI) containing catalyst of the formulaR1SO2OH, wherein Rl signifies hydroxy, halogen, lower alkyl, halogenated lower alkyl or aryl, in an aprotic organic solvent, or O-alkylating 2,3,6-trimethylhydroquinone-l-acetate with a phytyl halide in a polar aprotic organic solvent in the presence of a base, and subjecting the so-obtained 4-O-phytyl-2,3,6-trimethylhydroquinone-l-acetate to a rearrangement reaction, and in each case optionally submitting the so-obtained 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate to a ring closure reaction to produce tocopheryl acetate. The invention also includes the novel compound 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate and certain stereoisomers thereof, and also the further novel compound 4-hydroxy-2,3,6-trimethyl-5-[3-(4,8,12-trimethyltridecyl)-but-3enyl]phenyl acetate which itself is one of several isomers of 3-phytyl-2,5,6- trimethylhydroquinone-l-acetate formed by isomerization under the influence of heating, e.g. during its distillation as part of the isolation and purification procedure following its manufacture as indicated above. (All-rac)-α -tocopherol, which may be derived from its acetate, is known to be the most active industrially important member of the vitamin E group.

  一种制备3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯的工艺，以及可选择性地由此制备生育酚乙酸酯，包括将2,3,6-三甲基对羟基苯甲酸-1-乙酸酯在含有符合R1SO2OH式的硫(VI)催化剂的无极性有机溶剂中与异生育醇或生育醇进行C-烷基化，其中R1表示羟基、卤素、低烷基、卤代低烷基或芳基，或者在极性无极性有机溶剂中，在碱的存在下，将2,3,6-三甲基对羟基苯甲酸-1-乙酸酯与生育醇卤化物进行O-烷基化，并将所得的4-O-生育醇-2,3,6-三甲基对羟基苯甲酸-1-乙酸酯进行重排反应，然后可选择性地将所得的3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯进行环闭合反应以产生生育酚乙酸酯。该发明还包括新型化合物3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯及其某些立体异构体，以及进一步的新型化合物4-羟基-2,3,6-三甲基-5-[3-(4,8,12-三甲基十三烷基)-丁-3-烯基]苯乙酸酯，它本身是在受热影响下异构化形成的3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯的若干异构体之一，例如在其作为随后其制备过程中的分离和纯化过程的一部分的蒸馏过程中。从其乙酸酯中提取的(全反)-α-生育醇被认为是维生素E类中最活跃的工业重要成员。