3,4,5-三甲氧基苯甲酸异丙酯 | 6510-89-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,4,5-三甲氧基苯甲酸异丙酯
• 英文名称: isopropyl 3,4,5-trimethoxybenzoate
• 英文别名: 1-Methylethyl 3,4,5-trimethoxybenzoate；propan-2-yl 3,4,5-trimethoxybenzoate
• CAS: 6510-89-0
• 化学式: C₁₃H₁₈O₅
• mdl: MFCD20927250
• 分子量: 254.283
• InChiKey: WSGQQLRXHFUPKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.461
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2918990090

反应信息

• 作为反应物：
  描述：

  3,4,5-三甲氧基苯甲酸异丙酯 在 sodium tetrahydroborate 、 lithium chloride 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 5.0h， 以83%的产率得到3,4,5-三甲氧基苄醇
  参考文献：
  名称：

  Reductions of Carboxylic Acids and Esters with NaBH₄ in Diglyme at 162°C

  摘要：

  Aromatic esters, including the extremely sterically hindered ester: t-amyl 2-chlorobenzoate, are readily reduced to the corresponding benzyl alcohols in high yield with NaBH4 in refluxing diglyme (162 degreesC). In sharp contrast, aliphatic esters usually gave only low yields of alcohols. Instead, diglyme fragmentation products are formed which undergo transesterification reactions, producing complex product mixtures including products such as RCOOCH2CH2OCH3. The mechanism of this process involves sodium borohydride-induced S(N)2 cleavage of diglyme (hydride attack) at high temperatures. However, when the extremely electron rich, 3,4,5-trimethoxybenzoic acid is treated with NaBH4/diglyme at 162 degreesC (with or without an equivalent of LiCl), no 3,4,5-trimethyoxybenzyl alcohol is formed. The electron rich and hindered ester, t-amyl-3,4,5-trimethoxybenzoate, also does not reduce under these conditions (with or without LiCl). However, both methyl and isopropyl 3,4,5-trimethoxybenzoate esters were converted into 3,4,5-trimethyoxybenzyl alcohol in good yields in NaBH4/diglyme/LiCl at 162 degreesC. These reductions did not occur unless LiCl was present, illustrating the electron releasing effect of the three methoxy functions which reduce the carbonyl group's reactivity.

  DOI：

  10.1081/scc-120018935
• 作为产物：
  描述：

  3,4,5-三甲氧基苯甲醛 、 异丙醇 在 双氧水 、 C₂₈H₁₈CuN₂O₂ 作用下， 以74 %的产率得到3,4,5-三甲氧基苯甲酸异丙酯
  参考文献：
  名称：

  基于苯酚基的 Cu(II) 络合物在醛直接氧化制酯中的应用

  摘要：

  已经描述了一种合成方法，通过使用 Cu(II) 方形平面复合物 {[Cu II L] LH 2 , 9,9'- (ethane-1,2-diylbis(azanediyl)) 将各种醛转化为相应的酯bis(1H-phenalen-1-one} 和 H 2 O 2作为氧化试剂。发现所开发的方法温和、无添加剂，并且对广泛的密集取代醛具有稳健性，可以轻松制备芳族、杂环、多环和共轭酯，包括衍生自 CD 3 OD、甲醇、乙醇、异丙醇和炔丙醇的酯，可分离产率为 70%-94% 且完全转化。

  DOI：

  10.1016/j.tetlet.2023.154608

文献信息

• Vanadium (IV)oxo catalyzed One-Pot transformation of cinnamate to aromatic ester and its mechanistic aspects
  作者：Ghanshyam Mali、Indresh Verma、Himanshu Arora、Amit Rajput、Manoj V. Mane、Akhilesh Kumar、Rohan D. Erande

  DOI：10.1016/j.tetlet.2024.155133

  日期：2024.7

  [(L)VO](ClO) and green oxidant HO in alcohol-reflux condition. The reaction on cinnamate proceeded via CC bond breaking to generate aldehyde intermediate, followed by oxidative esterification to yield two carbon less aromatic esters in 52–95% yields. Further, experimental and DFT studies confirmed the mechanism and in-situ aldehyde formation which consequently supported to the developed protocol.

  金属催化不饱和碳-碳键的氧化裂解是合成有机化学中最有价值的化学转化之一。然而，肉桂酸盐直接转化为苯甲酸盐仍然是该系列中未解决的任务。在此，我们开发了一种前所未有的一锅法策略，在酒精回流条件下使用 V 催化剂 [(L)VO](ClO) 和绿色氧化剂 H2O 将肉桂酸酯直接转化为芳香酯。肉桂酸酯上的反应通过 CC 键断裂生成醛中间体，然后氧化酯化生成两种少碳芳香酯，产率 52-95%。此外，实验和 DFT 研究证实了机制和原位醛形成，从而支持了所开发的方案。
• Pd-Catalyzed Aldehyde to Ester Conversion: A Hydrogen Transfer Approach
  作者：Brittany A. Tschaen、Jason R. Schmink、Gary A. Molander

  DOI：10.1021/ol303298g

  日期：2013.2.1

  Aliphatic and aromatic aldehydes are successfully converted Into their corresponding esters using Pd(OAc)(2) and XPhos. This approach utilizes a hydrogen transfer protocol: concomitant reduction of acetone to isopropanol provides an inexpensive and sustainable approach that mitigates the need for other oxidants.
• N-Heterocyclic Carbene-Mediated Oxidative Electrosynthesis of Esters in a Microflow Cell
  作者：Robert A. Green、Derek Pletcher、Stuart G. Leach、Richard C. D. Brown

  DOI：10.1021/acs.orglett.5b01459

  日期：2015.7.2

  An efficient N-heterocyclic carbene (NHC)-mediated oxidative esterification of aldehydes has been achieved in an undivided microfluidic electrolysis C-ell at ambient temperature. Productivities of up to 4.3 g h(-1) in a single pass are demonstrated, with excellent yields, and conversions for 19 examples presented: Notably, the oxidative acylation, reactions were,shown to proceed with a 1:1 stoichiometry of aldehyde and alcohol (for primary alcohols), with remarkably short residence tithes in the electrolysis cell (<13 s), and without added electrolyte.
• Sarbhai,K.P.; Mathur,K.B.L., Indian Journal of Chemistry, 1966, vol. 4, p. 81 - 85
  作者：Sarbhai,K.P.、Mathur,K.B.L.

  DOI：——

  日期：——