[(E)-(4-nitrophenyl)methylideneamino] 2,2-dimethylpropanoate | 149540-92-1

• 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: [(E)-(4-nitrophenyl)methylideneamino] 2,2-dimethylpropanoate
• CAS: 149540-92-1
• 化学式: C₁₂H₁₄N₂O₄
• 分子量: 250.254
• InChiKey: XVCOGYGMXVKOQI-MDWZMJQESA-N

物化性质

• 沸点：
  361.6±44.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  84.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(E)-(4-nitrophenyl)methylideneamino] 2,2-dimethylpropanoate 在 二异丙胺 作用下， 以 乙腈 为溶剂， 生成 对硝基苯甲腈
  参考文献：
  名称：

  通过MeCN中的R 2 NH消除（E）-2,4,6-三硝基苯甲醛O-新戊酰肟中的腈。β-芳基对腈形成过渡态的影响

  摘要：

  从动力学上研究了由R 2 NH促进的MeCN中（E）-2,4,6-（NO 2）3 C 6 H 2 CH = NOC（O）（CH 3）3形成腈的消除。反应是二阶反应，表现出相当大的Hammettρ和Brönstedβ值。i -Pr 2促进从（E）-2,4,6-三硝基苯甲醛O-新戊酰肟消除的k 2值 对于不同的β-芳基取代基，MeCN中的NH落在Hammett图上的一条直线上，这些取代基已通过E2机理反应。该结果表明，通过引入2,4,6-三硝基取代基不会改变反应机理，并且（E）-苯甲醛O-吡咯烷酮系列的消除反应是通过常见的E2机理进行的。

  DOI：

  10.1134/s0023158411030165
• 作为产物：
  描述：

  4-nitrobenzaldehyde oxime 、 三甲基乙酰氯 在 sodium hydroxide 作用下， 反应 1.0h， 生成 [(E)-(4-nitrophenyl)methylideneamino] 2,2-dimethylpropanoate
  参考文献：
  名称：

  Elimination reactions of (E)-O-pivaloylbenzaldoximes

  摘要：

  Elimination reactions of (E)-O-pivaloylbenzaldoximes promoted by Et3N-MeCN, t-BuOK-t-BuOH, and t-BuOK-DMSO have been studied kinetically. The reactions produce benzonitrile quantitatively. The reactions are second-order and exhibit substantial values of rho,beta, and k(H)/k(D) and an E2 mechanism is evident. The rate of elimination from (E)-O-pivaloylbenzaldoxime increased with base-solvent system variation and gave relative rates of 1, 14.8, and 4.31 X 10(4) for Et3N-MeCN, t-BuOK-t-BuOH, t-BuOK-DMSO, respectively. The k(H)/k(D) value increased, but the Hammett rho value increased and then decreased, with this change in the base-solvent system. These results are compared with the predictions of the More O'Ferrall-Jencks reaction coordinate diagram to assess its scope and limitations in the interpretation of the elimination reactions.

  DOI：

  10.1021/jo00067a022

文献信息

• Elimination Reactions of (<i>E</i>)- and (<i>Z</i>)-Benzaldehyde <i>O</i>-Pivaloyloximes. Transition-State Differences for the Syn and Anti Eliminations Forming Nitriles
  作者：Bong Rae Cho、Nam Soon Cho、Sang Kook Lee

  DOI：10.1021/jo9618637

  日期：1997.4.1

  value of 2.4 +/- 0.1, k(H)/k(D) = 2.7 +/- 0.3, DeltaH() = 12.5 +/- 0.2 kcal/mol, and DeltaS() = -31.0 +/- 0.6 eu have been determined. The corresponding values for 2 are rho = 1.4 +/- 0.1, k(H)/k(D) = 7.8 +/- 0.3, DeltaH() = 8.8 +/- 0.1 kcal/mol, and DeltaS() = -23.6 +/- 0.4 eu, respectively. The results indicate that the nitrile-forming anti eliminations from 2 proceed via a more symmetrical transition

  动力学研究了（E）-和（Z）-苯甲醛O-吡咯烷酮肟1和2与DBU在MeCN中的消除反应。该反应是二阶反应，并显示出Hammett rho和k（H）/ k（D）值的实质值，并且E2机理很明显。从2消除的速率比从1消除的速率快约20 000倍。对于1与DBU在MeCN中的反应，哈米特rho值为2.4 +/- 0.1，k（H）/ k（D）= 2.7 + +/- 0.3，已确定DeltaH（）= 12.5 +/- 0.2 kcal / mol，和DeltaS（）= -31.0 +/- 0.6 eu。2的对应值是rho = 1.4 +/- 0.1，k（H）/ k（D）= 7.8 +/- 0.3，DeltaH（）= 8.8 +/- 0.1 kcal / mol和DeltaS（）= -23.6分别为+/- 0.4 eu。结果表明，2中形成腈的反消除反应是通过更对称的过渡态和较小程度的质子转移进行的，
• Elimination of nitrile from (E)-2,4,6-trinitrobenzaldehyde O-pivaloyloxime promoted by R2NH in MeCN. Effect of β-aryl group on the nitrile-forming transition-state
  作者：S.-Yong Pyun

  DOI：10.1134/s0023158411030165

  日期：2011.5

  Nitrile-forming eliminations from (E)-2,4,6-(NO2)3C6H2CH=NOC(O)(CH3)3 promoted by R2NH in MeCN have been studied kinetically. The reactions are second-order and exhibit substantial Hammett ρ and Brönsted β values. The k 2 value for elimination from (E)-2,4,6-trinitrobenzaldehyde O-pivaloyloxime promoted by i-Pr2NH in MeCN falls on a single line in the Hammett plot for different β-aryl substituents

  从动力学上研究了由R 2 NH促进的MeCN中（E）-2,4,6-（NO 2）3 C 6 H 2 CH = NOC（O）（CH 3）3形成腈的消除。反应是二阶反应，表现出相当大的Hammettρ和Brönstedβ值。i -Pr 2促进从（E）-2,4,6-三硝基苯甲醛O-新戊酰肟消除的k 2值 对于不同的β-芳基取代基，MeCN中的NH落在Hammett图上的一条直线上，这些取代基已通过E2机理反应。该结果表明，通过引入2,4,6-三硝基取代基不会改变反应机理，并且（E）-苯甲醛O-吡咯烷酮系列的消除反应是通过常见的E2机理进行的。
• Elimination reactions of (E)-O-pivaloylbenzaldoximes
  作者：Bong Rae Cho、Wan Jin Jang、Jong Tae Je、Richard A. Bartsch

  DOI：10.1021/jo00067a022

  日期：1993.7

  Elimination reactions of (E)-O-pivaloylbenzaldoximes promoted by Et3N-MeCN, t-BuOK-t-BuOH, and t-BuOK-DMSO have been studied kinetically. The reactions produce benzonitrile quantitatively. The reactions are second-order and exhibit substantial values of rho,beta, and k(H)/k(D) and an E2 mechanism is evident. The rate of elimination from (E)-O-pivaloylbenzaldoxime increased with base-solvent system variation and gave relative rates of 1, 14.8, and 4.31 X 10(4) for Et3N-MeCN, t-BuOK-t-BuOH, t-BuOK-DMSO, respectively. The k(H)/k(D) value increased, but the Hammett rho value increased and then decreased, with this change in the base-solvent system. These results are compared with the predictions of the More O'Ferrall-Jencks reaction coordinate diagram to assess its scope and limitations in the interpretation of the elimination reactions.