(E)-4-nitro-N-(4-nitrobenzylidene)aniline | 60682-81-7

• 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-nitro-N-(4-nitrobenzylidene)aniline
• 英文别名: 4-nitro-N-(4-nitrobenzylidene)aniline；p-Nitrobenzal-p-nitroanilin
• CAS: 60682-81-7
• 化学式: C₁₃H₉N₃O₄
• 分子量: 271.232
• InChiKey: KRLIGBJKICAQHW-NTEUORMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 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：
  0.0
• 拓扑面积：
  98.64
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (E)-4-nitro-N-(4-nitrobenzylidene)aniline 在 磺酰氯 、 水 、 乙腈 作用下， 生成 4-Nitro-N-(4-nitro-phenyl)-benzamidine
  参考文献：
  名称：

  Dhar, Durga N.; Gupta, Sudha R., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1986, vol. 25, p. 533 - 535

  摘要：

  DOI：
• 作为产物：
  描述：

  (4-Nitro-phenyl)-[1-(4-nitro-phenyl)-meth-(Z)-ylidene]-amine 以 苯 为溶剂， 生成 (E)-4-nitro-N-(4-nitrobenzylidene)aniline
  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。
• Solvent-free synthesis of azomethines, spectral correlations and antimicrobial activities of some E-benzylidene-4-chlorobenzenamines
  作者：R. Suresh、S. P. Sakthinathan、D. Kamalakkannan、K. Ranganathan、K. Sathiyamoorthi、V. Mala、R. Arulkumaran、S. Vijayakumar、R. Sundararajan、G. Vanangamudi、M. Subramanian、G. Thirunarayanan、G. Vanaja、P. Kanagambal

  DOI：10.4314/bcse.v29i2.10

  日期：——

  Some azomethines including substituted benzylidene-4-chlorobenzenamines (E-imines) have been synthesized by fly-ash: PTS catalyzed microwave assisted condensation of 4-chloroaniline and substituted benzaldehydes under solvent-free conditions. The yield of the imines has been found to be more than 85%. The purity of all imines has been checked using their physical constants and UV, IR and NMR spectral data. These spectral data have been correlated with Hammett substituent constants and F and R parameters using single and multi-linear regression analysis. From the results of statistical analysis, the effect of substituents on the above spectral data has been studied. The antimicrobial activities of all imines have been studied using standard methods.

  一些偶氮甲碱，包括取代苄叉-4-氯苯胺（E-亚胺），已在无溶剂条件下通过飞灰：PTS催化的微波辅助缩合4-氯苯胺和取代苯甲醛合成。亚胺的产率已发现超过85%。所有亚胺的纯度已通过其物理常数以及紫外、红外和核磁共振光谱数据进行检查。这些光谱数据已通过单一和多元线性回归分析与Hammett取代常数以及F和R参数相关联。从统计分析的结果中，研究了取代基对上述光谱数据的影响。所有亚胺的抗菌活性已采用标准方法进行研究。
• Copper(<scp>i</scp>) catalyzed diastereoselective multicomponent synthesis of spiroindolo-pyrrolidines/-imidazolidines/-triazolidines from diazoamides via azomethine ylides
  作者：Sengodagounder Muthusamy、Singaravelan Ganesh Kumar

  DOI：10.1039/c5ob02322j

  日期：——

  of regio-, chemo- and diastereoselective studies on three- as well as four-component reactions using diazooxindoles, imines, aldehydes, amines, alkenes, alkynes or diazenes in the presence of copper(I) thiophene-2-carboxylate are performed to furnish spiroindolo-pyrrolidine/-imidazolidine/-triazolidine ring systems in good yields. A mixture of products was obtained when unsymmetrical alkenes were used

  在重氮，噻吩，亚胺，亚胺，烯，炔或二氮烯存在下，在铜（I）噻吩-2-羧酸铜存在下，对三组分和四组分反应进行区域，化学和非对映选择性研究以良好的产率提供螺吡咯并-吡咯烷/-咪唑烷/-三唑烷环系统。当使用不对称烯烃作为亲极性化合物时，获得了产物的混合物。这项研究证明了由铜（I）类胡萝卜素成功生成了分子间的甲亚胺基化物，以及它们随后与各种双极性亲和剂（例如烯烃（CC ），亚胺（CN），二氮杂（N）的1，3-偶极环加成反应）。N）以立体选择的方式。进行了单晶X射线分析，以明确确定螺杂环环系统的结构和立体化学。
• Staudinger reactions of unsymmetrical cyclic ketenes: a synthetically useful approach to spiro β-lactams and derivatives. Reaction mechanism and theoretical studiesElectronic supplementary information (ESI) available: Spectral data for compounds 4b–4m and 5b–5d and Cartesian coordinates and energies (hartrees) of zwitterionic intermediates (IZ1, IZ2, IZ3, and IZ4) and transition structures (TS1, TS2, TS3 and TS4). See http://www.rsc.org/suppdata/p1/b1/b103279h/
  作者：Eduardo Alonso、Carlos del Pozo、Javier González

  DOI：10.1039/b103279h

  日期：2002.2.6

  efficient and operationally simple synthesis of tetrahydrofuran-derived spiro-β-lactams using the ketene–imine cycloaddition route is described. Also the preparation of spiro-N-sulfonyl-β-lactam derivatives, which are analogs of monobactams, is reported. As far as we know, this is the first time that an unsymmetrical cyclic ketene is used in a Staudinger-type reaction. The experimental evidence suggests

  高效且操作简单的合成四氢呋喃衍生的螺β-内酰胺。 烯酮–亚胺描述了环加成路线。还制备螺-N-磺酰基-β-内酰胺衍生物，它们是单bactams，据报道。据我们所知，这是第一次非对称循环烯酮用于施陶丁格型反应。实验证据表明烯酮 源自 酰氯反应中的前体。为了获得对控制反应的立体化学结果的电子效应的深入了解，已进行了从头算的高级从头计算。
• 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：——