tert.-Butyl-p-tolylperacetat | 27396-20-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert.-Butyl-p-tolylperacetat
• 英文别名: Tert-butyl 2-(4-methylphenyl)ethaneperoxoate
• CAS: 27396-20-9
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: GXDVFKKXKOTTHV-UHFFFAOYSA-N

物化性质

• 沸点：
  291.2±43.0 °C(Predicted)
• 密度：
  1.036±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert.-Butyl-p-tolylperacetat 在 potassium fluoride 、 苯硫酚 作用下， 以 氘代氯仿 为溶剂， 生成 对二甲苯 、 对甲基苯乙酸
  参考文献：
  名称：

  苯硫酚引起的叔丁基苯基过乙酸酯的热分解：同时发生均解和单电子转移。

  摘要：

  苯硫基叔丁基叔丁基酯在硫酚存在下的热解通过双重机理进行。两键均质表明rho（+）（4）= -1.16，证明为极性跃迁态。单电子转移产生自由基阴离子中间体，该中间体发生碎裂，rho（ET）= 1.01。

  DOI：

  10.1021/jo0106290
• 作为产物：
  描述：

  叔丁基过氧化氢 、 对甲基苯乙酸 在 N,N'-羰基二咪唑 作用下， 生成 tert.-Butyl-p-tolylperacetat
  参考文献：
  名称：

  Secondary α-Deuterium Kinetic Isotope Effects Signifying a Polar Transition State in the Thermolysis of Ring-Substituted tert-Butyl Phenylperacetates

  摘要：

  Several ring-substituted tert-butyl phenylperacetates (YC6H4CH2CO3But) and their deuterated versions (YC6H4CD2CO3But) were prepared (Y: p-OCH3, P-CH3, p-H; and p-NO2). Thermolyses at 80 degrees C in CDCl3 showed excellent first-order kinetics. The rates have been measured as k(YH) x 10(4) and k(YD) x 10(4) s(-1): 11.9 and 9.20 (p-OCH3), 2.64 and 2.22 (p-CH3), 1.06 and 0.93 (p-H), 0.164 and 0.156 (p-NO2). Hammett correlations were derived to yield rho(YH)(+) = -1.17 and rho(YD)(+) = -1.12. However, better Hammett plots were obtained with three points (p-OCH3, p-CH3, and p-H) showing rho(YH)(+) = -1.35 and rho(YD)(+) = -1.28. SDKIE was calculated as 1.293 (p-OCH3), 1.189 (p-CH3), 1.140 (p-H), and 1.051 (p-NO2), showing substantial substituent effects. Values of k(YH)/k(YD) for p-NO2 showed little temperature dependence. Hammett correlations and SDKIE were derived from the same kinetic entity that is the band cleavage.

  DOI：

  10.1021/jo9814492

文献信息

• Thermolysis of <i>tert</i>-Butyl Phenylperacetates:  Delicate Control of the Rates through Contributions from Translational and Rotational Entropy
  作者：Sung Soo Kim、In Sang Baek、Alexey Tuchkin、Kyoung Moon Go

  DOI：10.1021/jo010143j

  日期：2001.6.1

  m-Cl, and p-NO(2). The relative rates (k(Y)/k(H)) exhibit excellent rho(+)/sigma(+) Hammett correlations with rho(+) < 0, indicating a polar TS. Activation parameters (DeltaH()(Y) and DeltaS()(Y)) and their differential terms (DeltaDeltaH()(Y)(-)(H) and DeltaDeltaS()(Y)(-)(H)) were obtained from the Eyring plot. Differential activation terms (DeltaDeltaH()(Y)(-)(H) and DeltaDeltaS()(Y)(-)(H)) disclose

  测量YC（6）H（4）CH（2）CO（3）C（CH（3））（）在CDCl（3）中几个温度下的一阶速率常数（k（Y）） 3）Y为p-OCH（3），p-OPh，p-CH（3），p-Ph，pH，p-Cl，m-Cl和p-NO（2）。相对比率（k（Y）/ k（H））表现出极好的rho（+）/ sigma（+）Hammett相关性，其中rho（+）<0，表明极性TS。获得激活参数（DeltaH（）（Y）和DeltaS（）（Y））及其微分项（DeltaDeltaH（）（Y）（-）（H）和DeltaDeltaS（）（Y）（-）（H））从Eyring剧情。差异激活术语（DeltaDeltaH（）（Y）（-）（H）和DeltaDeltaS（）（Y）（-）（H））揭示了与p-CH（3），p-Ph，pH，p- Cl和m-Cl（等速温度，230 K）。但是，p-OCH（3）和p-OPh显示负偏差，而p-NO（2）出
• Secondary α-Deuterium Kinetic Isotope Effects Signifying a Polar Transition State in the Thermolysis of Ring-Substituted <i>tert</i>-Butyl Phenylperacetates
  作者：Sung Soo Kim、Alexey Tuchkin

  DOI：10.1021/jo9814492

  日期：1999.5.1

  Several ring-substituted tert-butyl phenylperacetates (YC6H4CH2CO3But) and their deuterated versions (YC6H4CD2CO3But) were prepared (Y: p-OCH3, P-CH3, p-H; and p-NO2). Thermolyses at 80 degrees C in CDCl3 showed excellent first-order kinetics. The rates have been measured as k(YH) x 10(4) and k(YD) x 10(4) s(-1): 11.9 and 9.20 (p-OCH3), 2.64 and 2.22 (p-CH3), 1.06 and 0.93 (p-H), 0.164 and 0.156 (p-NO2). Hammett correlations were derived to yield rho(YH)(+) = -1.17 and rho(YD)(+) = -1.12. However, better Hammett plots were obtained with three points (p-OCH3, p-CH3, and p-H) showing rho(YH)(+) = -1.35 and rho(YD)(+) = -1.28. SDKIE was calculated as 1.293 (p-OCH3), 1.189 (p-CH3), 1.140 (p-H), and 1.051 (p-NO2), showing substantial substituent effects. Values of k(YH)/k(YD) for p-NO2 showed little temperature dependence. Hammett correlations and SDKIE were derived from the same kinetic entity that is the band cleavage.
• Induced Thermolysis of <i>tert</i>-Butyl Phenylperacetates by Thiophenol: Simultaneous Occurrence of Homolysis and Single Electron Transfer
  作者：Sung Soo Kim、Alexey Tuchkin、Chun Soo Kim

  DOI：10.1021/jo0106290

  日期：2001.11.1

  Thermolysis of tert-butyl phenylperacetates in the presence of thiophenol takes place via dual mechanism. The two-bond homolysis indicates rho(+)(4)= -1.16, testifying to polar transition states. The single electron transfer yields a radical anion intermediate which undergoes fragmentation with rho(ET) = 1.01.

  苯硫基叔丁基叔丁基酯在硫酚存在下的热解通过双重机理进行。两键均质表明rho（+）（4）= -1.16，证明为极性跃迁态。单电子转移产生自由基阴离子中间体，该中间体发生碎裂，rho（ET）= 1.01。