(4-Bromo-phenyl)-[1-(4-nitro-phenyl)-meth-(E)-ylidene]-amine | 799291-51-3

• 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: (4-Bromo-phenyl)-[1-(4-nitro-phenyl)-meth-(E)-ylidene]-amine
• 英文别名: (E)-N-(4-bromophenyl)-1-(4-nitrophenyl)methanimine
• CAS: 799291-51-3
• 化学式: C₁₃H₉BrN₂O₂
• 分子量: 305.131
• InChiKey: XFWKPZJJOUWIBB-OQLLNIDSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 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：
  0.0
• 拓扑面积：
  55.5
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2H-naphtho[2,3-d][1,3]oxazine-2,4(1H)-dione 、 (4-Bromo-phenyl)-[1-(4-nitro-phenyl)-meth-(E)-ylidene]-amine 在 溶剂黄146 作用下， 反应 1.0h， 以74%的产率得到3-(4-Bromophenyl)-2-(4-nitrophenyl)-1,2-dihydrobenzo[g]quinazolin-4-one
  参考文献：
  名称：

  One-Pot Synthesis of 2,3-Dihydro-2,3-disubstituted Benzo[g]-quinazolin-4(1H)-ones

  摘要：

  Condensation of 2H-naphth[2,3-d][3,1]oxazin-2,4 (1H)-dione (1) with schiff bases (2) in acetic acid resulted in the formation of 2,3-dihydro-2,3-diarylbenzo[g]quinazolin-4(1H)-ones (3). Reaction of 1 with ketoanils generated in situ results in 2,3-dihydro-2,2-substituted-3-phenylbenzo[g]quinazolin-4(1H)-ones (6) and the spiroalkanes (5). Dehydrogenation of 3 gave 2,3-diaryl benzo[g]quinazolin-4(3H)-ones (7).

  DOI：

  10.1080/00397919208021645
• 作为产物：
  描述：

  (4-Bromo-phenyl)-[1-(4-nitro-phenyl)-meth-(Z)-ylidene]-amine 以 苯 为溶剂， 生成 (4-Bromo-phenyl)-[1-(4-nitro-phenyl)-meth-(E)-ylidene]-amine
  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

• Modeling Substituent-Dependence of the Twist and Shielding in a Series of 4-Substituted N-(4-Nitrobenzylidene)anilines
  作者：Vladimír Proks、Miroslav Holík

  DOI：10.1135/cccc20041566

  日期：——

  A series of 15 4-substituted N-(4-nitrobenzylidene)anilines was synthesized and studied by ¹H NMR spectroscopy. Their ab initio calculated geometries and the shielding as expressed by aromatic ring currents were used in correlation analysis. The geometries were fully optimized using density functional theory B3LYP/6-311G** approaches. For the determination of the ring current contribution to the shielding of azomethine hydrogens H_α was used direct ab initio calculation of the chemical shielding in a model system. Experimental chemical shift values free of these contributions were successfully correlated with increments a_p of chemical shift for monosubstituted benzenes. In the same manner, the contribution of the anisotropy of C=N double bond to H_m hydrogen were calculated and values of the H_m chemical shift free of this contribution were successfully correlated with increments of chemical shift a_m.

  一系列15个4-取代N-(4-硝基苯甲基亚胺)苯胺经过合成并通过1H核磁共振光谱进行研究。它们的从头算几何结构以及由芳香环电流表示的屏蔽效应被用于相关性分析。几何结构完全优化使用密度泛函理论B3LYP/6-311G**方法。为了确定环电流对偶氮甲基氢Hα屏蔽的贡献，使用了在模型体系中直接从头算化学屏蔽的计算。实验化学位移值中不包含这些贡献的部分成功地与对单取代苯乙烯的化学位移增量ap相关联。以相同的方式，计算了C=N双键对Hm氢的各向异性贡献，并且不包含这种贡献的Hm化学位移值成功地与化学位移增量am相关联。
• A novel <scp>water‐dispersible</scp> and magnetically recyclable nickel nanoparticles for the one‐pot <scp>reduction‐Schiff</scp> base condensation of nitroarenes in pure water
  作者：Pouya Ghamari Kargar、Asiye Ravanjamjah、Ghodsieh Bagherzade

  DOI：10.1002/jccs.202100172

  日期：2021.10

  electron microscopy (FESEM) analyses. From the satisfactory results obtained from the reduction of nitrogen, this catalytic system is used for a one-pot protocol containing a reduction-Schiff base concentration of diverse nitroarenes. It was corroborated with the heterogeneous catalytic experiments on the one-pot tandem synthesis of imines from nitroarenes and aldehydes. Finally, the novel Ni-Fe3O4@Pectin~PPA ~ Piconal

  在这项工作中，首先合成了一种称为 Ni-Fe 3 O 4 @Pectin~PPA~Piconal的多相纳米催化剂，并将其作为含有镍官能团的双功能催化剂进行研究。另一方面，这种 Ni-Fe 3 O 4 @Pectin~PPA ~ Piconal 催化剂在水性溶剂中在环境温度下对与硼氢化钠的硝基芳烃还原反应显示出非常有效的性能，其中 NaBH 4被认为是还原剂。这是一种新型磁性催化剂，已通过多种方法批准，包括傅里叶变换红外光谱 (FT-IR)、X 射线粉末衍射 (XRD)、动态光散射 (DLS)、透射电子显微镜 (TEM)、振动样品磁力计 (VSM)、电感耦合等离子体 (ICP)、能量色散 X 射线光谱 (EDX) 和场发射扫描电子显微镜 (FESEM) 分析。根据从氮还原中获得的令人满意的结果，该催化系统用于包含多种硝基芳烃的还原希夫碱浓度的一锅法。硝基芳烃和醛类一锅串联合成亚胺的多相催化实验证实了这一点。最后，新型Ni-Fe
• Cation Radical Imino Diels-AlderReaction: A New Approach for the Synthesis of Tetrahydroquinolines
  作者：Zhong-Li Liu、Xiaodong Jia、Hechun Lin、Congde Huo、Wei Zhang、Jianming Lü、Li Yang、Guangyu Zhao

  DOI：10.1055/s-2003-40989

  日期：——

  Cycloaddition of N-arylimines with α-methylstyrenesor 2,3-dihydrofuran was efficiently catalyzed by tris(4-bromophenyl)aminiumhexachloroantimonate (Ar3N + ˙SbCl6 - ) producing tetrahydroquinolinederivatives in excellent yields. The reaction was controlled sensitivelyby the oxidation potentials of the imine and the dienophile.

  在三(4-溴苯基)六氯锑酸铵（Ar3N + ËSbCl6 - ）的高效催化下，N-芳基亚胺与δ-甲基苯乙烯或 2,3-二氢呋喃发生了环加成反应，生成的四氢喹啉二衍生物收率极高。反应受亚胺和亲二烯烃氧化电位的控制。
• One-Pot Synthesis of 2,3-Dihydro-2,3-disubstituted Benzo[g]-quinazolin-4(1H)-ones
  作者：P. Rajender Kumar、M. Satyanarayana Reddy

  DOI：10.1080/00397919208021645

  日期：1992.9

  Condensation of 2H-naphth[2,3-d][3,1]oxazin-2,4 (1H)-dione (1) with schiff bases (2) in acetic acid resulted in the formation of 2,3-dihydro-2,3-diarylbenzo[g]quinazolin-4(1H)-ones (3). Reaction of 1 with ketoanils generated in situ results in 2,3-dihydro-2,2-substituted-3-phenylbenzo[g]quinazolin-4(1H)-ones (6) and the spiroalkanes (5). Dehydrogenation of 3 gave 2,3-diaryl benzo[g]quinazolin-4(3H)-ones (7).
• 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.