丁一酮,二(戊甲基苯基)- | 112752-37-1

• 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
• 中文名称: 丁一酮,二(戊甲基苯基)-
• 英文名称: bis(pentamethylphenyl)ketene
• 英文别名: Bis(pentamethylphenyl)ethen-1-one
• CAS: 112752-37-1
• 化学式: C₂₄H₃₀O
• 分子量: 334.502
• InChiKey: IUMXTZIOVZJNLN-UHFFFAOYSA-N

物化性质

• 熔点：
  156 °C(Solv: acetonitrile (75-05-8))
• 沸点：
  437.1±40.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  丁一酮,二(戊甲基苯基)- 在 溴 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 4.0h， 生成 (Bis-pentamethylphenyl-vinylidene)-methyl-amine
  参考文献：
  名称：

  Hegarty, Anthony F.; Kelly, John G.; Relihan, Colette M., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1997, # 6, p. 1175 - 1181

  摘要：

  DOI：
• 作为产物：
  描述：

  五甲基苯 在 吡啶 、 氯化亚砜 、 硫酸 作用下， 以 溶剂黄146 、 甲苯 为溶剂， 反应 1.5h， 生成 丁一酮,二(戊甲基苯基)-
  参考文献：
  名称：

  Relatively stable N-benzhydryl- and N-benzyldiarylketene imines and their conversion to cyanodiarylmethanes via an isolable radical

  摘要：

  An efficient synthetic route to the sterically hindered ketene imines N-benzyl- and N-benzylhydrylbis(pentamethylphenyl)ketene imines 8 from dipentamethylphenyl ketene 6 is described. The thermal stability of these ketene imines is in marked contrast to the diphenylketene imine analogues which rearrange rapidly to C-tri-substituted nitriles. On heating 8b is converted to the relatively stable free radical 13 which can be reduced to the nitrile 10 in a variety of solvents. These radicals are proposed intermediates in the ketene imine-nitrile rearrangement, and the mechanism of this reaction is considered in in terms of these results.

  DOI：

  10.1021/jo00027a062

文献信息

• The first acid and ester enols: 2,2-bis(pentamethylphenyl)ethene-1,1-diol and 1-t-butoxy-2,2-bis(pentamethylphenyl)ethenol, and their oxidation to stable free radicals
  作者：Patrick O'Neill、Anthony F. Hegarty

  DOI：10.1039/c39870000744

  日期：——

  Desilylation of the ketene acetals (5) and (9) provides the ene-1,1-diols (6) and (10) which undergo relatively slow ketonisation and are oxidized to stable free radicals in basic solution.

  乙烯酮缩醛（5）和（9）的脱甲硅烷基化提供烯-1,1-二醇（6）和（10），其经历相对缓慢的酮化并在碱性溶液中被氧化成稳定的自由基。
• Relatively stable N-benzhydryl- and N-benzyldiarylketene imines and their conversion to cyanodiarylmethanes via an isolable radical
  作者：Leo F. Clarke、Anthony F. Hegarty、Pat O'Neill

  DOI：10.1021/jo00027a062

  日期：1992.1

  An efficient synthetic route to the sterically hindered ketene imines N-benzyl- and N-benzylhydrylbis(pentamethylphenyl)ketene imines 8 from dipentamethylphenyl ketene 6 is described. The thermal stability of these ketene imines is in marked contrast to the diphenylketene imine analogues which rearrange rapidly to C-tri-substituted nitriles. On heating 8b is converted to the relatively stable free radical 13 which can be reduced to the nitrile 10 in a variety of solvents. These radicals are proposed intermediates in the ketene imine-nitrile rearrangement, and the mechanism of this reaction is considered in in terms of these results.
• 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.
• Regiospecificity in the alkylation of ester enolates: synthesis of sterically hindered diarylketene acetals
  作者：P. O'Neill、A. F. Hegarty

  DOI：10.1021/jo00386a046

  日期：1987.5
• Eventova, Irina; Nadler, Ella B.; Rochlin, Elimelech, Journal of the American Chemical Society, 1993, vol. 115, # 4, p. 1290 - 1302
  作者：Eventova, Irina、Nadler, Ella B.、Rochlin, Elimelech、Frey, Joseph、Rappoport, Zvi

  DOI：——

  日期：——