4-hydroxy-2,3,5-trimethylphenyl acetate | 68491-55-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-hydroxy-2,3,5-trimethylphenyl acetate
• 英文别名: TMHQ-4-MA；4-acetoxy-2,3,6-trimethylphenol；trimethylhydroquinone-1-monoacetate；(4-hydroxy-2,3,5-trimethylphenyl) acetate
• CAS: 68491-55-4
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: BMHNIBQPXLPWMA-UHFFFAOYSA-N

物化性质

• 沸点：
  297.2±28.0 °C(Predicted)
• 密度：
  1.114±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-hydroxy-2,3,5-trimethylphenyl acetate 、 乙酸酐 在 Clariant CZB₃₀ (H+) 作用下， 以 甲苯 为溶剂， 反应 6.0h， 生成 (4-乙酰氧基-2,3,6-三甲基-苯基)乙酸酯
  参考文献：
  名称：

  芳基酯在沸石催化剂上的弗里斯重排中的基质取代效应

  摘要：

  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。

  DOI：

  10.1039/d0cy00590h
• 作为产物：
  描述：

  6-Acetoxy-2,5,6-trimethyl-2,4-cyclohexadien-1-on 在 1,3,5-三甲氧基苯 、 三氟化硼-二甲醚络合物 作用下， 以 乙醚 为溶剂， 生成 4-hydroxy-2,3,5-trimethylphenyl acetate
  参考文献：
  名称：

  Budzikiewicz,H.; Gunawan,J., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1974, vol. 29, p. 780 - 791

  摘要：

  DOI：

文献信息

• Choice of Manganese(III) Complexes for the Synthesis of 4,4′-Biphenyldiols and 4,4′-Diphenoquiones
  作者：Hiroshi Nishino、Nobuyuki Itoh、Makiko Nagashima、Kazu Kurosawa

  DOI：10.1246/bcsj.65.620

  日期：1992.2

  6-Disubstituted phenols are oxidized with tris(2,4-pentanedionato)manganese(III), [Mn(acac)3], in glacial acetic acid to give the corresponding 4,4′-biphenyldiols in high yields, whereas similar reactions using manganese(III) acetate, [Mn(OAc)3], insted of [Mn(acac)3] quantitatively yield the corresponding 4,4′-diphenoquinones. Cross-coupling reactions of 2,6-di-t-butylphenol and other substituted phenols afford

  2,6-二取代酚在冰醋酸中被三（2,4-戊二酮）锰（III）[Mn(acac)3]氧化，以高产率得到相应的4,4'-联苯二醇，而类似的使用乙酸锰 (III)，[Mn(OAc)3]，插入 [Mn(acac)3] 的反应定量地产生相应的 4,4'-二苯醌。2,6-二叔丁基苯酚和其他取代苯酚的交叉偶联反应得到相应的交叉偶联 4,4'-联苯二醇和 4,4'-二苯醌以及衍生自起始苯酚本身的氧化产物。讨论了 [Mn(acac)3] 和 [Mn(OAc)3] 在无处不在的苯酚偶联反应中的有利用途。
• Synthesis and Antimicrobial Activity of Nitrobenzyl-oxy-phenol Derivatives
  作者：Malik Suliman Mohamed、Toshihide Maki、Mohammad Monir Shah、Yoshio Ichinose

  DOI：10.1248/bpb.b16-00608

  日期：——

  Two hydroquinone derivatives were prepared and their antimicrobial activity evaluated. Their minimum inhibitory concentrations (MICs) were determined using a broth dilution method. Gentamycin and ciprofloxacin were used as reference antibiotics. The antimicrobial activity of 4-(benzyloxy)phenol (monobenzone) was also evaluated based on its structural similarity to the new compounds; activity was comparable to that of 3,5-dimethyl-4-((4-nitrobenzyl)oxy)phenol (4a). 2,3,5-Trimethyl-4-((4-nitrobenzyl)oxy)phenol (4b) exhibited the best antibacterial activity against both clinical isolates and type strain of Moraxella catarrhalis (M. catarrhalis), with a MIC value of 11 µM, comparable to ciprofloxacin 9 µM.

  制备了两种氢醌衍生物，并对其抗菌活性进行了评估。采用肉汤稀释法测定了它们的最低抑菌浓度（MIC）。庆大霉素和环丙沙星被用作参考抗生素。根据 4-(苄氧基)苯酚（单苯甲酮）与新化合物的结构相似性，还对其抗菌活性进行了评估；其活性与 3,5-二甲基-4-((4-硝基苄基)氧基)苯酚（4a）相当。2,3,5-三甲基-4-((4-硝基苄基)氧基)苯酚（4b）对临床分离菌株和卡他沙雷氏菌（M. catarrhalis）类型菌株的抗菌活性最佳，其 MIC 值为 11 µM，与环丙沙星 9 µM 相当。
• [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。
• [EN] PROCESS FOR THE MANUFACTURE OF alpha-TOCOPHERYL ACETATE<br/>[FR] PROCESSUS DE FABRICATION D'ACETATE TOCOPHERYLE
  申请人：DSM IP ASSETS BV

  公开号：WO2004063182A1

  公开（公告）日：2004-07-29

  The present invention is concerned with a novel process for the manufacture of α-tocopheryl acetate which comprises reacting 2,3,6-trimethylhydroquinone-1-acetate with a compound selected from the group consisting of phytol (formula IV with R = OH), iso-phytol (formula III with R = OH), and (iso) phytol derivatives represented by the following formulae III and IV with R = C2-to C5-alkonoyloxy, benzoyloxy, mesyloxy, benzenesul-fonyloxy or tosyloxy, (IV) in the presence of a catalyst of the formula Mn+(R1SO3-)n, wherein Mn+ is a silver, copper, gallium, hafnium or rare earth metal cation, n is the valence of the cation Mn+, and R1 is fluorine, C1-8-perfluoroalkyl or perfluoroaryl, and, if required, cyclizing any 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate or a double bond isomer thereof obtained as an intermediate reaction product, to produce α-tocopheryl acetate. In the catalyst Mn+ is preferably Ag+, Cu+, Ga3+, Sc3+, Lu3+, Ho3+, Tm3+, Yb3+ or Hf4+.

  本发明涉及一种用于制备α-生育酚醋酸酯的新型工艺，包括将2,3,6-三甲基对羟基苯甲酸醋酯与从植物醇（式IV，其中R = OH）、异植物醇（式III，其中R = OH）或以下式III和IV（其中R = C2至C5-烷酰氧基，苯甲酰氧基，甲磺氧基，苯基磺酰氧基或对甲苯基磺酰氧基）所表示的（异）植物醇衍生物中选择的一种化合物反应，催化剂为式Mn+（R1SO3-）n，其中Mn+是银、铜、镓、铪或稀土金属阳离子，n是阳离子Mn+的化合价，R1是氟、C1-8全氟烷基或全氟芳基，如有必要，将作为中间反应产物获得的任何3-植醇-2,5,6-三甲基对羟基苯甲酸醋酯或其双键异构体环化，以制备α-生育酚醋酸酯。在催化剂Mn+中，优选Ag+，Cu+，Ga3+，Sc3+，Lu3+，Ho3+，Tm3+，Yb3+或Hf4+。
• Method for producing trimethylhydroquinone
  申请人：Nippon Petrochemicals Company Limited

  公开号：US20010039366A1

  公开（公告）日：2001-11-08

  An inexpensive method for producing trimethylhydroquinone free from the problem of the disposal of waste catalyst, which method comprises the steps of: (1) reacting isophorone in the presence of an acid catalyst and recovering &bgr;-isophorone by distiiulation, (2) oxidizing the &bgr;-isophorone in the presence of amorphous carbon and a base to obtain 4-oxoisophorone, (3) reacting the 4-oxoisophorone with an acid anhydride in a liquid phase or with a carboxylic acid in a vapor phase in the presence of a solid acid catalyst to obtain trimethylhydroquinones, and (4) hydrolyzing the trimethylhydroquinones to obtaining trimethylhydroquinone.

  一种生产无游离催化剂的三甲基对苯二酚廉价方法，该方法包括以下步骤：（1）在酸催化剂的存在下反应异佛冬酮并通过蒸馏回收β-异佛冬酮，（2）在无定形碳和碱的存在下氧化β-异佛冬酮以获得4-氧基异佛冬酮，（3）在固体酸催化剂的存在下，将4-氧基异佛冬酮与液相酸酐或蒸汽相的羧酸反应以获得三甲基对苯二酚，（4）水解三甲基对苯二酚以获得三甲基对苯二酚。