N-{[4-(dimethylamino)phenyl]-methylene}-4-nitrobenzenamine | 117985-09-8

• 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: N-{[4-(dimethylamino)phenyl]-methylene}-4-nitrobenzenamine
• CAS: 117985-09-8
• 化学式: C₁₅H₁₅N₃O₂
• 分子量: 269.303
• InChiKey: RLDPRVKBHPQKIK-WJDWOHSUSA-N

物化性质

• 沸点：
  451.8±30.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

反应信息

• 作为反应物：
  描述：

  N-{[4-(dimethylamino)phenyl]-methylene}-4-nitrobenzenamine 以 various solvent(s) 为溶剂， -10.0~10.0 ℃ 、100.0 kPa 条件下， 生成 N,N-dimethyl-4-{(E)-[(4-nitrophenyl)imino]methyl}aniline
  参考文献：
  名称：

  溶剂波动对偶氮苯和N-亚苄基苯胺的热Z/EI异构化速率的影响

  摘要：

  在 2-甲基-2,4-戊二醇中研究了压力对取代的 N-亚苄基苯胺和偶氮苯的热 Z/E 异构化的影响。在三乙酸甘油酯中还研究了取代偶氮萘 Z/E 异构化的压力依赖性。根据这篇论文和早期论文的结果，得出了以下结论。1) 可以将缓慢的热反应转变为高粘性液相中的波动控制状态，通过粘性液体和高压的组合实现。2) 速率常数的粘度依赖性可以通过 Sumi 开发的二维反应坐标模型来合理化，但不能通过 Grote-Hynes 的频率相关摩擦理论来合理化。即，能量势垒交叉发生在溶剂分子重新排列以适应过渡态之后。3) 溶剂重排是否涉及具有可观能量增加的化学转化取决于反应的性质和溶剂。

  DOI：

  10.1246/bcsj.69.551
• 作为产物：
  描述：

  4-硝基苯胺 、 对二甲氨基苯甲醛 生成 N-{[4-(dimethylamino)phenyl]-methylene}-4-nitrobenzenamine
  参考文献：
  名称：

  Mechanism of thermal Z/E isomerization of substituted N-benzylideneanilines. Nature of the activated complex with an sp-hybridized nitrogen atom

  摘要：

  In order to study the mechanism of thermal geometrical isomerization involving a sp2-hybridized nitrogen atom, kinetic effects of substituent, solvent, and pressure were studied in substituted N-benzylideneanilines. The effect of the substituent on the aniline moiety was almost independent of the electronic nature of the benzylidene group, and the results could be described satisfactorily by log (k/k(o)) = rho[sigma-degrees + r+(sigma+-sigma-degrees)+ r-(sigma--sigma-degrees)], except for the 4-(dimethylamino) group. The r- values were more than twice as large as r+, suggesting strongly that the aniline ring is in conjugation not with the carbon-nitrogen pi bond but with the nitrogen lone pair in the transition state. The lower activation enthalpies and fairly large negative activation entropies observed in N-(4-X-benzylidene)4-nitroanilines also support this view. When a dimethylamino group exists in the 4-position of the aniline ring, the rate constants observed were larger than that expected from the above equation. This deviation suggests the existence of a reaction route where the two phenyl groups become coplanar in the transition state. Ab initio calculations on selected N-phenylformaldimines and N-benzylideneanilines were performed to characterize the actual relation between both reaction possibilities as alternative and parallel routes, respectively. On the basis of the experimental data, the rate constants for the two inversion isomerizations were estimated by assuming parallel reactions for three cases.

  DOI：

  10.1021/jo00068a042

文献信息

• Effects of Solvent Fluctuations on the Rate of the Thermal<i>Z</i>/<i>E</i>Isomerization of<i>N</i>-Benzylideneanilines in a Highly Viscous Liquid Hydrocarbon
  作者：Tsutomu Asano、Kohei Matsuo、Hitoshi Sumi

  DOI：10.1246/bcsj.70.239

  日期：1997.1

  The effects of the solvent viscosity on the thermal Z/E isomerization of three substituted N-benzylideneanilines were studied in a nonpolar aprotic solvent, 2,4-dicyclohexyl-2-methylpentane. By increasing the pressure to several hundred megapascals, the viscosity of the reaction system was raised high enough to retard the isomerization. The viscosity dependence of the observed rate constant was analyzed

  在非极性非质子溶剂 2,4-二环己基-2-甲基戊烷中研究了溶剂粘度对三种取代 N-亚苄基苯胺的热 Z/E 异构化的影响。通过将压力增加到几百兆帕，反应体系的粘度升高到足以阻止异构化。通过假设基于本作者之一提出的二维反应坐标模型的两步机制来分析观察到的速率常数的粘度依赖性。这种机制的速率常数由 1/(kTST−1 + kf−1) 给出，其中 kTST 代表过渡态理论预期的速率常数，而 kf (>0) 代表在热过程中受溶剂重排控制的部分波动。与理论一致，kf 值与粘度的分数幂成反比。还发现，在相同温度和粘度下，本溶剂中的kf值大于...
• Mechanism of geometrical isomerization about the carbon-nitrogen double bond
  作者：Tsutomu Asano、Toshio Okada、William G. Herkstroeter

  DOI：10.1021/jo00263a022

  日期：1989.1
• Asano, Tsutomu; Furuta, Hiroyuki; Sumi, Hitoshi, Journal of the American Chemical Society, 1994, vol. 116, # 13, p. 5545 - 5550
  作者：Asano, Tsutomu、Furuta, Hiroyuki、Sumi, Hitoshi

  DOI：——

  日期：——