N-(4-fluorophenyl)-1-(4-nitrophenyl)methanimine | 799291-50-2

• 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-(4-fluorophenyl)-1-(4-nitrophenyl)methanimine
• CAS: 799291-50-2
• 化学式: C₁₃H₉FN₂O₂
• 分子量: 244.225
• InChiKey: UEWFWADWOAOYFA-OQLLNIDSSA-N

物化性质

• 熔点：
  112-113 °C
• 沸点：
  393.9±27.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

反应信息

• 作为反应物：
  描述：

  Ethyl 2-(1,3-dithian-2-ylidene)but-3-ynoate 、 N-(4-fluorophenyl)-1-(4-nitrophenyl)methanimine 在 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以61%的产率得到ethyl 2-(1,3-dithian-2-ylidene)-2-(6-fluoro-2-(4-nitrophenyl)quinolin-4-yl)acetate
  参考文献：
  名称：

  Ethynyl Ketene-S,S-acetals:  The Highly Reactive Electron-Rich Dienophiles and Applications in the Synthesis of 4-Functionalized Quinolines via a One-Pot Three-Component Reaction

  摘要：

  An efficient synthetic method for 4-functionalized quinoline derivatives, 4-((1,3-dithian-2-ylidene)methyl)quinolines, has been developed. Mediated by trifluoromethanesulfonic acid, ethynyl ketene-S,S-acetals can react in a one-pot procedure with various arylamines and aldehydes under mild conditions to give the corresponding quinoline derivatives in good to high yields via a consecutive arylimine formation, regiospecific aza-Diels-Alder (Povarov) reaction, and reductive amination.

  DOI：

  10.1021/jo070069q
• 作为产物：
  描述：

  (4-Fluoro-phenyl)-[1-(4-nitro-phenyl)-meth-(Z)-ylidene]-amine 以 苯 为溶剂， 生成 N-(4-fluorophenyl)-1-(4-nitrophenyl)methanimine
  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

• [EN] NEW METHOD FOR PREPARING EZETIMIBE<br/>[FR] NOUVEAU PROCÉDÉ DE PRÉPARATION D'ÉZÉTIMIBE
  申请人：MOEHS IBERICA SL

  公开号：WO2012004382A1

  公开（公告）日：2012-01-12

  The present invention relates to a new method for preparing ezetimibe comprising a step of cyclizing the compound (4S)-phenyl-3-[(5S)-(4-fluorophenyl)-(2R)-[(1S)-(4-fluorophenylamino)-1-(4-nitrophenyl)methyl]-5-hydroxypentanoyl]oxazolidin-2-one or the derivatives thereof in which the hydroxyl group is protected. The invention also relates to new intermediates used in this method.

  本发明涉及一种制备依折麦布的新方法，包括环化化合物(4S)-苯基-3-[(5S)-(4-氟苯基)-(2R)-[(1S)-(4-氟苯基氨基)-1-(4-硝基苯基)甲基]-5-羟基戊酰基]噁唑烷-2-酮或其中羟基团被保护的衍生物的步骤。本发明还涉及在此方法中使用的新中间体。
• 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。
• Infrared Irradiation: Effective Promoter in the Formation of<i>N</i>‐Benzylideneanilines in the Absence of Solvent
  作者：Miguel Á. Vázquez、Miguel Landa、Leonor Reyes、René Miranda、Joaquín Tamariz、Francisco Delgado

  DOI：10.1081/scc-200026190

  日期：2004.1

  series of Schiff bases in the condensation reaction between benzaldehydes and anilines, in the absence of solvent. Benzaldehydes and anilines, containing either electron‐withdrawing or electron‐releasing groups, were assessed to identify any substituent effect on the formation of the Schiff bases. This methodology is characterized by ease of set‐up and work‐up, and the reaction yields were comparable with

  摘要 在无溶剂条件下，苯甲醛与苯胺的缩合反应中，红外辐射促进了一系列席夫碱的形成。对含有吸电子或放电子基团的苯甲醛和苯胺进行评估，以确定对席夫碱形成的任何取代基影响。该方法的特点是易于设置和处理，反应产率与之前报道的方法中获得的产率相当。此外，这种新程序对环境无害，因为在转化过程中没有使用溶剂。
• NEW METHOD FOR PREPARING EZETIMIBE
  申请人：Moehs Ibérica, S.L.

  公开号：EP2590940B1

  公开（公告）日：2014-08-27