N-[1-(4-methyl-phenyl)-methylidene]-N-[4-nitrophenyl]amine | 33442-37-4

• 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-[1-(4-methyl-phenyl)-methylidene]-N-[4-nitrophenyl]amine
• 英文别名: N-(4-nitrobenzylidene)-4-methylaniline；(E)-N-(4-nitrophenyl)-1-(p-tolyl)methanimine；(E)-4-methyl-N-(4-nitrobenzylidene)aniline；4-nitro-4'-methylbenzylidene amiline；N-((E)-4-nitro-benzylidene)-p-toluidine；N-((E)-4-Nitro-benzyliden)-p-toluidin；4-Nitro-benzaldehyd-(E)-p-tolylimin
• CAS: 33442-37-4
• 化学式: C₁₄H₁₂N₂O₂
• 分子量: 240.261
• InChiKey: GSOZSSDYIVFJRF-XNTDXEJSSA-N

物化性质

• 熔点：
  122-123 °C
• 沸点：
  407.8±38.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 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：
  0.07
• 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：

  N-[1-(4-methyl-phenyl)-methylidene]-N-[4-nitrophenyl]amine 在 yttrium(III) trifluoromethanesulfonate 作用下， 以 氘代乙腈 为溶剂， 反应 4.0h， 生成 N-[[(2S,3S,4S)-4-anilino-6-methyl-2-(4-nitrophenyl)-1,2,3,4-tetrahydroquinolin-3-yl]methyl]acetamide
  参考文献：
  名称：

  Three component coupling reactions of N-acetyl-2-azetine- rapid stereoselective entry to 2,3,4-trisubstituted tetrahydroquinolines

  摘要：

  N-乙酰基-2-氮杂环丁烷与芳香胺衍生的亚胺在路易斯酸催化下进行[4 + 2]-环加成，得到外-内非对映异构氮杂环丁烷环加合物的1:1混合物，该混合物进一步与芳香胺反应，得到2,3 ,4-三取代的四氢喹啉，收率良好至优异，主要为一种非对映异构体。

  DOI：

  10.1039/b110242g
• 作为产物：
  描述：

  [1-(4-Nitro-phenyl)-meth-(Z)-ylidene]-p-tolyl-amine 以 苯 为溶剂， 生成 N-[1-(4-methyl-phenyl)-methylidene]-N-[4-nitrophenyl]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

• Synthesis and molecular docking studies of imines as α-glucosidase and α-amylase inhibitors
  作者：Analy Aispuro-Pérez、Juan López-Ávalos、Fernando García-Páez、Julio Montes-Avila、Lorenzo A. Picos-Corrales、Adrián Ochoa-Terán、Pedro Bastidas、Sarita Montaño、Loranda Calderón-Zamora、Ulises Osuna-Martínez、Juan I. Sarmiento-Sánchez

  DOI：10.1016/j.bioorg.2019.103491

  日期：2020.1

  (E)-1-phenyl-N-(pyridin-2-yl)methanimine (3c) displayed similar activity that acarbose against α-glucosidase. The molecular docking studies in α-glucosidase and α-amylase reveal that aryl imines mainly establish an H-bond with the R2-subtituent and hydrophobic interactions with the R1-subtituent. The docking analysis reveals these synthetic aryl imines 3d-i interact in same active site than acarbose drug in

  在具有重要生物活性的许多化合物中发现亚胺功能。因此，开发新的亚胺合成方法很重要。在这项工作中，提出了在氧化铝-硫酸催化的微波辐射下芳基亚胺的简单，环保和直接的合成途径。另外，进行了体外酶抑制，抗氧化活性和分子对接研究。分离出芳基亚胺，产率为37-94％。评价所有合成的芳基亚胺在体外对α-葡糖苷酶和α-淀粉酶的抑制潜力，结果表明大多数化合物对两种酶均表现出抑制活性。（E）-1-（4-硝基苯基）-N-（吡啶-2-基）甲亚胺（3d）为1。抗α-淀粉酶的活性比阿卡波糖高15倍，而（E）-1-苯基-N-（吡啶-2-基）甲亚胺（3c）的活性类似于阿卡波糖对α-葡糖苷酶的活性。对α-葡萄糖苷酶和α-淀粉酶的分子对接研究表明，芳基亚胺主要与R2取代基建立H键，并与R1取代基发生疏水相互作用。对接分析显示，在两种酶中，这些合成的芳基亚胺3d-i在与阿卡波糖药物相同的活性位点相互作用。
• Origin of the Relative Stereoselectivity of the β-Lactam Formation in the Staudinger Reaction
  作者：Lei Jiao、Yong Liang、Jiaxi Xu

  DOI：10.1021/ja056711k

  日期：2006.5.1

  stereoselectivity of the beta-lactam formation is one of the critical issues in the Staudinger reaction. Although many attempts have been made to explain and to predict the stereochemical outcomes, the origin of the stereoselectivity remains obscure. We are proposing a model that explains the relative stereoselectivity based on a kinetic analysis of the cis/trans ratios of reaction products. The results were

  β-内酰胺形成的相对（顺式、反式）立体选择性是施陶丁格反应中的关键问题之一。尽管已经进行了许多尝试来解释和预测立体化学结果，但立体选择性的起源仍然模糊不清。我们提出了一个模型，该模型基于对反应产物的顺式/反式比率的动力学分析来解释相对立体选择性。结果来自详细的哈米特分析。环亚胺被用来研究烯酮取代基的电子效应，发现立体选择性不能简单地归因于扭矩电子模型。基于我们的结果，相对立体选择性的起源可以描述如下：(1) 立体选择性是两性中间体中亚胺部分的直接闭环和异构化之间竞争的结果；(2) 闭环步骤很可能是烯醇化物与亚胺部分的分子内亲核加成，这显然受烯酮和亚胺取代基的电子效应影响；(3) 给电子烯酮取代基和吸电子亚胺取代基加速直接闭环，导致优先形成顺-β-内酰胺，而吸电子烯酮取代基和吸电子亚胺取代基减慢直接闭环，导致偏好形成反式β-内酰胺；
• 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。
• Rate acceleration of organic reaction by immediate solvent evaporation
  作者：Akihiro Orita、Genta Uehara、Kai Miwa、Junzo Otera

  DOI：10.1039/b609567d

  日期：——

  Several types of organic reactions were accelerated by immediate evaporation of solvents because of remarkable enhancement of molecule-to-molecule contacts between reactants.

  由于显着提高了反应物之间的分子与分子之间的接触，可通过立即蒸发溶剂来加速几种类型的有机反应。