N,N-dimethyl-N'-<(4-nitrophenyl)methylene>-1,4-benzenediamine | 54050-72-5

• 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,N-dimethyl-N'-<(4-nitrophenyl)methylene>-1,4-benzenediamine
• 英文别名: N,N-dimethyl-4-[(1E)-(4-nitrobenzylidene)amine]aniline；4-dimethylamino-N-(4-nitrobenzylidene)aniline；p-Dimethylamino-(p-nitrobenzyliden)-anilin；p-Nitrobenzyliden-p-dimethylaminoanilin
• CAS: 54050-72-5
• 化学式: C₁₅H₁₅N₃O₂
• 分子量: 269.303
• InChiKey: OYAKOCHANTYBKA-LFIBNONCSA-N

物化性质

• 熔点：
  220 °C(Solv: xylene (1330-20-7))
• 沸点：
  451.8±30.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.41
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  58.74
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  N,N-dimethyl-p-nitrosoaniline 在 盐酸 、 tin 、 溶剂黄146 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 3.0h， 生成 N,N-dimethyl-N'-<(4-nitrophenyl)methylene>-1,4-benzenediamine
  参考文献：
  名称：

  在分子结构中具有二甲氨基电子给体和硝基电子受体基团的染料的溶剂变色行为

  摘要：

  制备并表征了六种在分子结构中具有N，N-二甲基氨基苯基和4-硝基苯基或2,4-二硝基苯基的染料。这些化合物具有连接电子给体和电子受体基团的不同共轭桥（CC，CN和NN）。所有化合物均为溶剂变色，发生反向溶剂变色。在染料的每个光谱中观察到的溶剂化变色带是由于分子内电荷转移性质的ππ**跃迁引起的，该跃迁是由电子给体N，N产生的。分子中电子受体基团的-二甲基氨基苯基基团，通过应用密度泛函理论优化的化合物结构得到增强，这些化合物表现出较高的平面性。考虑两个共振结构解释了反向溶剂变色。在较少极性溶剂中，该苯并合物形式更好地稳定并且表征显示正溶剂溶变色的区域，而在极性溶剂化物变色的区域中，偶极形式在更多极性溶剂中被更好地稳定。使用Catalán多参数方法研究了溶剂酸度，碱性，偶极性和极化性对化合物所表现出的溶剂致变色作用的影响。这些化合物是研究极化率和（在较小程度上）介质的偶极性的良好候选者，

  DOI：

  10.1002/poc.3402

文献信息

• New Kinetic Evidence for Inversional Mechanism in Thermal Geometrical Isomerization about Carbon–Nitrogen Double Bond
  作者：Tsutomu Asano、Toshio Okada

  DOI：10.1246/cl.1987.691

  日期：1987.4.5

  Kinetic pressure and solvent effects were studied for geometrical isomerization about carbon-nitrogen double bond in N,N-dimethyl-N′-[(4-nitrophenyl)methylene]-1,4-benzenediamine and 4-[[4-(dimethylamino)phenyl]imino]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one. In both of the compounds, the effects clearly demonstrate that the polarity of the reactant decreases slightly during activation, and the

  研究了N,N-二甲基-N'-[(4-硝基苯基)亚甲基]-1,4-苯二胺和4-[[4-(二甲氨基)苯基]亚氨基]-2,4-二氢-5-甲基-2-苯基-3H-吡唑-3-one。在这两种化合物中，效果清楚地表明，在活化过程中反应物的极性略有下降，结果很难与先前提出的旋转机制相一致。
• Boedeker, J.; Radeglia, R., Journal fur praktische Chemie (Leipzig 1954), 1981, vol. 323, # 2, p. 349 - 352
  作者：Boedeker, J.、Radeglia, R.

  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.
• 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