2,2-bis(2,4,6-trimethylphenyl)acetic acid | 5740-42-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2,2-bis(2,4,6-trimethylphenyl)acetic acid
• 英文别名: 2,2-dimesitylacetic acid；dimesitylacetic acid；Dimesityl-essigsaeure；Benzeneacetic acid, 2,4,6-trimethyl-alpha-(2,4,6-trimethylphenyl)-
• CAS: 5740-42-1
• 化学式: C₂₀H₂₄O₂
• 分子量: 296.409
• InChiKey: VKIULHPHCQRBSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-bis(2,4,6-trimethylphenyl)acetic acid 在 吡啶 、 氯化亚砜 、 苯 作用下， 生成 dimesityl-acetic acid methyl ester
  参考文献：
  名称：

  Vinyl Alcohols. XV.¹ Trisubstituted Vinyl Alcohols

  摘要：

  DOI：

  10.1021/ja01219a010
• 作为产物：
  描述：

  2′,4′,6′-三甲基苯乙酮 在 氢氧化钾 、 selenium(IV) oxide 、 硫酸 、 水 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 56.75h， 生成 2,2-bis(2,4,6-trimethylphenyl)acetic 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

文献信息

• A comprehensive picture of the one-electron oxidation chemistry of enols, enolates and α-carbonyl radicals: oxidation potentials and characterization of radical intermediates
  作者：Michael Schmittel、Mukul Lal、Rupali Lal、Maik Röck、Anja Langels、Zvi Rappoport、Ahmad Basheer、Jens Schlirf、Hans-Jörg Deiseroth、Ulrich Flörke、Georg Gescheidt

  DOI：10.1016/j.tet.2009.10.039

  日期：2009.12

  stable simple enols of amides. The results allow to clarify the primary reaction pathway of enol radical cations as a rapid deprotonation and—if warranted by the redox potential and the strength of the oxidant—a follow-up oxidation of the resultant α-carbonyl radical to the α-carbonyl cation. Moreover, the experimental oxidation potentials were linearly correlated with AM1 computed ionization potentials

  介绍了40种烯醇，烯醇化物和一些选定的α-羰基自由基的氧化电位，并通过适用的各种技术对其进行了表征（X射线，EPR，ENDOR，一般三重，磁化率测量，UV-vis，快速扫描循环伏安法，同位素效应）。模型化合物包括与多个取代基（烷基，烯基，炔基，芳基，杂芳基，炔丙基醇）连接的稳定的简单烯醇和酰胺的稳定的简单烯醇的代表。结果可以阐明烯醇自由基阳离子作为快速去质子化的主要反应途径，并且（如果需要氧化还原电势和氧化剂的强度的话）可以将所得的α-羰基自由基后续氧化为α-羰基阳离子。而且，校正溶剂化后，将实验氧化电位与AM1计算的电离电位线性相关。该相关性使得能够可靠地预测包括α-羰基的自由基的氧化电位。在计算了相关自由基的氧化还原电势后，评估了烯醇盐与黄素之间单电子转移的可能性以及抗坏血酸的各种自由基参与氧化过程的可能性。
• Stable simple enols. 3. Static and dynamic NMR behavior of crowded triarylethenols and related compounds. Three-ring flip as the threshold mechanism for enantiomerization of crowded triarylvinyl propellers
  作者：Silvio E. Biali、Zvi Rappoport

  DOI：10.1021/ja00315a003

  日期：1984.2

  Analyse de la stereochimie statique et dynamique des agitateurs moleculaires du type Ar 3 Ar 2 C=C(X)Ar 1 , et comparaison avec les molecules Ar 1 Ar 2 Ar 3 Z ou Ar 1 Ar 2 Ar 3 ZX (avec Z=C, B ou N); rotations autour des liaisons C(sp 2 )-C(Ar) et de la double liaison, addition-rotation-elimination, cetonisation-enolisation, ionisation-recombinaison avec ou sans un rearrangement du β-aryl sur la double

  分析 de lastereochimie statique et dynamique des agitateurs molculaires du type Ar 3 Ar 2 C=C(X)Ar 1 , et 比较 avec les 分子 Ar 1 Ar 2 Ar 3 Z ou Ar 1 Ar 2 Ar 3 ZX (avec Z=C , B ou N); 旋转自动连接 C(sp 2 )-C(Ar) 和 de la 双重连接，加成-旋转-消除，cetonisation-enolisation，电离-重组 avec ou sans un rerangement du β-aryl sur la double liaison
• Metal‐Free Hydrosilylation of Ketenes with Silicon Electrophiles: Access to Fully Substituted Aldehyde‐Derived Silyl Enol Ethers
  作者：Avijit Roy、Martin Oestreich

  DOI：10.1002/chem.202100877

  日期：2021.6.4

  catalysts is reported. The boron Lewis acid tris(pentafluorophenyl)borane accelerates the slow uncatalyzed reaction of ketenes and hydrosilanes, thereby providing a convenient access to the new class of β,β-di- and β-monoaryl-substituted aldehyde-derived silyl enol ethers. Yields are moderate to high, and Z configuration is preferred. The corresponding silyl bis-enol ethers are also available when using

  报道了由主族催化剂促进的烯酮氢化硅烷化的研究很少。硼路易斯酸三（五氟苯基）硼烷加速了烯酮和氢硅烷的缓慢未催化反应，从而为获得新型 β,β-二-和 β-单芳基取代的醛衍生的甲硅烷基烯醇醚提供了便利。产量中等至高，Z型配置是首选。当使用二氢硅烷时，也可以使用相应的甲硅烷基双烯醇醚。相关的三苯甲基阳离子引发的氢化硅烷化涉及甲硅烷离子的自我再生，效果要差得多。
• Silica sulfuric acid as a highly efficient catalyst for the synthesis of diarylacetic acids
  作者：Desiree L. Moore、Allison E. Denton、Rose M. Kohinke、Brandon R. Craig、William E. Brenzovich

  DOI：10.1080/00397911.2016.1158269

  日期：2016.4.2

  ABSTRACT An efficient heterogeneous method for the synthesis of diarylacetic acids was developed utilizing silica sulfuric acid as a catalyst. The reaction is highly efficient with a small amount of catalyst for the combination of a variety of electron-neutral to electron-rich arenes with glyoxylic acid. The reaction can also be utilized to synthesize unsymmetric derivatives from activated mandelic

  摘要 利用二氧化硅硫酸作为催化剂，开发了一种合成二芳基乙酸的高效多相方法。该反应在少量催化剂的情况下非常有效，用于将各种电子中性至富电子芳烃与乙醛酸结合。该反应还可用于从活化的扁桃酸以良好到极好的收率合成不对称衍生物。图形概要
• Hindered Tetraphenylethylene Helicates: Chiral Fluorophores with Deep‐Blue Emission, Multiple‐Color CPL, and Chiral Recognition Ability
  作者：Ming Hu、Feng‐Ying Ye、Cong Du、Weizhou Wang、Wei Yu、Minghua Liu、Yan‐Song Zheng

  DOI：10.1002/anie.202115216

  日期：2022.2.14

  propeller-like conformation through substitution at the 2,6-positions of the phenyl rings, were prepared by a short synthetic route. These helicates, with their many modification positions, show deep-blue to violet emission, circularly polarized luminescence (CPL) that can be tuned over a wide range, and highly enantioselective chiral recognition.

  通过短合成路线制备了通过在苯环的 2,6 位取代而具有完全固定的螺旋桨状构象的受阻四苯基乙烯 (TPE) 螺旋体。这些螺旋体具有许多修饰位置，显示出深蓝色至紫色发射、可在宽范围内调节的圆偏振发光 (CPL) 以及高度对映选择性的手性识别。