Benzenamine, N,N-dimethyl-4-[[(3-methylphenyl)imino]methyl]-, (Z)- | 58200-51-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Benzenamine, N,N-dimethyl-4-[[(3-methylphenyl)imino]methyl]-, (Z)-
• 英文别名: N,N-dimethyl-4-[(3-methylphenyl)iminomethyl]aniline；3-methyl-4'-(N,N-dimethylamino)benzylideneaniline；N-(4-dimethylamino-benzylidene)-m-toluidine；N-(4-Dimethylamino-benzyliden)-m-toluidin；4-Dimethylamino-benzaldehyd-m-tolylimin
• CAS: 58200-51-4；149742-40-5
• 化学式: C₁₆H₁₈N₂
• 分子量: 238.332
• InChiKey: OGQXRISMZHIJLV-SFQUDFHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Benzenamine, N,N-dimethyl-4-[[(3-methylphenyl)imino]methyl]-, (Z)- 、 四氯苯醌 在 氧气 作用下， 以 乙酸乙酯 为溶剂， 反应 48.0h， 以46%的产率得到2,5-dichloro-3,6-di-m-toluidino-[1,4]benzoquinone
  参考文献：
  名称：

  Reaction of Amidine Phenylogous withp-Benzoquinones

  摘要：

  N-(4-二甲氨基亚苄基)苯胺和 N1-(4-二甲氨基苯基)-N1,N2-二苯基甲脒与四氯、四溴和四氟对苯醌通过电荷转移络合物的形成发生反应，生成 2-单芳基氨基-3,5,6-三卤对苯醌和 2,5-双(芳基氨基)-3,6-二卤对苯醌。对生成产物的反应过程进行了解释。

  DOI：

  10.1246/bcsj.64.1966
• 作为产物：
  描述：

  以 苯 为溶剂， 生成 Benzenamine, N,N-dimethyl-4-[[(3-methylphenyl)imino]methyl]-, (Z)-
  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

• KERZHNER, B. K.;KOFANOV, V. I.;VRUBEL, T. L., J. LIQUID CHROMATOGR., 11,(1988) N5, C. 3091-3102
  作者：KERZHNER, B. K.、KOFANOV, V. I.、VRUBEL, T. L.

  DOI：——

  日期：——
• Mechanism of thermal Z/E isomerization of substituted N-benzylideneanilines. Nature of the activated complex with an sp-hybridized nitrogen atom
  作者：Tsutomu Asano、Hiroyuki Furuta、Hans Joerg Hofmann、Renzo Cimiraglia、Yuho Tsuno、Mizue Fujio

  DOI：10.1021/jo00068a042

  日期：1993.7

  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.
• Reaction of Amidine Phenylogous with<i>p</i>-Benzoquinones
  作者：Ahmed M. Nour El-Din、Aboul-Fetouh E. Mourad、Alaa A. Hassan、Mohsen A. Gomaa

  DOI：10.1246/bcsj.64.1966

  日期：1991.6

  N-(4-Dimethylaminobenzylidene)anilines and N1-(4-dimethylaminophenyl)-N1,N2-diphenylformamidine reacted with tetrachloro-, tetrabromo,- and tetrafluoro-p-benzoquinones via charge-transfer complexes formation giving 2-monoarylamino-3,5,6-trihalo-p-benzoquinones and 2,5-bis(arylamino)-3,6-dihalo-p-benzoquinones. The course of the reaction leading to the formation of the products has been interpreted.

  N-(4-二甲氨基亚苄基)苯胺和 N1-(4-二甲氨基苯基)-N1,N2-二苯基甲脒与四氯、四溴和四氟对苯醌通过电荷转移络合物的形成发生反应，生成 2-单芳基氨基-3,5,6-三卤对苯醌和 2,5-双(芳基氨基)-3,6-二卤对苯醌。对生成产物的反应过程进行了解释。