2,4,6-trimethylphenylglyoxal hydrate | 860571-42-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4,6-trimethylphenylglyoxal hydrate
• 英文别名: 2,2-dihydroxy-1-mesityl-ethanone；2,2-Dihydroxy-1-mesityl-aethanon；2,2-Dihydroxy-1-mesitylethanone；2,2-dihydroxy-1-(2,4,6-trimethylphenyl)ethanone
• CAS: 860571-42-2
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: CRBLCVRWBUAGPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 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：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,4,6-trimethylphenylglyoxal hydrate 在 氢氧化钾 作用下， 反应 1.0h， 以64%的产率得到2,4,6-trimethylmandelic acid
  参考文献：
  名称：

  Hydration of bis(pentamethylphenyl)- and bismesityl-ketenes leading to ene-1,1-diols (enols of carboxylic acids)

  摘要：

  The reaction of the sterically hindered diarylketenes (Ar = Me5C6 or 2,4,6-Me3C2H2) with water is pH independent over the range 1-9 and is not subject to strong buffer catalysis. The primary products formed are the corresponding ene-1,1-diols which result from addition across the C=O (rather than the C=C) of the ketene. These `enols of carboxylic acids' are relatively long lived owing to slow protonation of the beta-carbon (because of steric hindrance caused by the o-Me groups) and evidence for their structures in solution is presented. On attempted isolation of the ene-l,l -diols facile oxidation to a stable free radical, as well as ketonisation to the corresponding acids, occurs. Evidence is presented in terms of the large negative entropy of activation (ca. 200 J K-1 mol-1), solvent isotope effects and the absence of significant general-base catalysis, that (despite the sterically hindered nature of these ketenes) the characteristics of their hydration are typical of other ketenes and that this most likely involves an initial concerted reaction with a water oligomer. Updated ab initio calculations are also presented, which are consistent with this view.

  DOI：

  10.1039/p29920000927
• 作为产物：
  描述：

  2′,4′,6′-三甲基苯乙酮 在 selenium(IV) oxide 、 水 作用下， 以 1,4-二氧六环 为溶剂， 生成 2,4,6-trimethylphenylglyoxal hydrate
  参考文献：
  名称：

  TOX/Cu(II)催化下的高效和对映选择性分子内坎尼扎罗反应

  摘要：

  基于新开发的拥挤 TOX 配体和活性乙二醛从乙二醛一水合物中逐渐释放的方案，芳基和烷基乙二醛与醇的不对称分子内 Cannizzaro 反应以前所未有的高水平对映选择性实现。初步结果表明，除了半缩醛中间体的动态动力学拆分之外，醇对映选择性加成到乙二醛的机制对立体选择性贡献最大。

  DOI：

  10.1021/ja409859x

文献信息

• The Highly Activated Carbonyl Group: Mesitylglyoxal
  作者：Arzy R. Gray、Reynold C. Fuson

  DOI：10.1021/ja01318a065

  日期：1934.3
• A Highly Efficient and Enantioselective Intramolecular Cannizzaro Reaction under TOX/Cu(II) Catalysis
  作者：Pan Wang、Wen-Jie Tao、Xiu-Li Sun、Saihu Liao、Yong Tang

  DOI：10.1021/ja409859x

  日期：2013.11.13

  An asymmetric intramolecular Cannizzaro reaction of aryl and alkyl glyoxals with alcohols has been realized with an unprecedented high level of enantioselectivity, on the basis of a newly developed congested TOX ligand and a gradual liberation protocol of active glyoxals from glyoxal monohydrates. Preliminary results suggested a mechanism of enantioselective addition of alcohols to glyoxals contributing

  基于新开发的拥挤 TOX 配体和活性乙二醛从乙二醛一水合物中逐渐释放的方案，芳基和烷基乙二醛与醇的不对称分子内 Cannizzaro 反应以前所未有的高水平对映选择性实现。初步结果表明，除了半缩醛中间体的动态动力学拆分之外，醇对映选择性加成到乙二醛的机制对立体选择性贡献最大。
• Hydration of bis(pentamethylphenyl)- and bismesityl-ketenes leading to ene-1,1-diols (enols of carboxylic acids)
  作者：Barbara M. Allen、Anthony F. Hegarty、Pat O'Neill、Minh Tho Nguyen

  DOI：10.1039/p29920000927

  日期：——

  The reaction of the sterically hindered diarylketenes (Ar = Me5C6 or 2,4,6-Me3C2H2) with water is pH independent over the range 1-9 and is not subject to strong buffer catalysis. The primary products formed are the corresponding ene-1,1-diols which result from addition across the C=O (rather than the C=C) of the ketene. These `enols of carboxylic acids' are relatively long lived owing to slow protonation of the beta-carbon (because of steric hindrance caused by the o-Me groups) and evidence for their structures in solution is presented. On attempted isolation of the ene-l,l -diols facile oxidation to a stable free radical, as well as ketonisation to the corresponding acids, occurs. Evidence is presented in terms of the large negative entropy of activation (ca. 200 J K-1 mol-1), solvent isotope effects and the absence of significant general-base catalysis, that (despite the sterically hindered nature of these ketenes) the characteristics of their hydration are typical of other ketenes and that this most likely involves an initial concerted reaction with a water oligomer. Updated ab initio calculations are also presented, which are consistent with this view.