4-[(2-methoxyphenyl)amino]benzonitrile | 255835-95-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-[(2-methoxyphenyl)amino]benzonitrile
• 英文别名: 2-methoxy-4'-cyanodiphenylamine；4-(2-methoxyanilino)benzonitrile
• CAS: 255835-95-1
• 化学式: C₁₄H₁₂N₂O
• mdl: MFCD11135513
• 分子量: 224.262
• InChiKey: STSXFKHYPFLJSB-UHFFFAOYSA-N

物化性质

• 熔点：
  108-109 °C
• 沸点：
  383.7±27.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.071
• 拓扑面积：
  45
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-氯苯甲醚 、 对氨基苯腈 在 tris-(dibenzylideneacetone)dipalladium(0) 、 dicyclohexyl(2',4',6'-triisopropyl-[1,1':3',1''-terphenyl]-2-yl)phosphane 、 sodium t-butanolate 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 以89%的产率得到4-[(2-methoxyphenyl)amino]benzonitrile
  参考文献：
  名称：

  钯间-Terarylphosphine催化剂催化的N-芳基化反应的经验和计算洞察力。

  摘要：

  原位生成的Pd-Cy * Phine催化剂已成功应用于伯胺和仲胺的N-芳基化反应，并在多种底物类别中均表现出高性能。Cy * Phine配体的间-叔芳基膦基序诱导的CN交叉偶联所产生的性能与其双芳基膦同类物XPhos仅存在细微的差异。DFT研究表明，Pd-Cy * Phine和Pd-XPhos在催化循环步骤中具有可比的反应能，这与以前的发现是一致的。计算研究还表明，假定的速率确定步骤发生在胺结合之后，这很可能已经废除了具有间-三芳基膦配体结构的预期益处。

  DOI：

  10.1002/cplu.201700042

文献信息

• Sodium-iodide-promoted nickel-catalyzed C–N cross-coupling of aryl chlorides and <i>N</i>-nucleophiles under visible-light irradiation
  作者：Yunhui Feng、Hang Luo、Fangnian Yu、Qian Liao、Luqing Lin

  DOI：10.1039/d2gc04630j

  日期：——

  Herein, we report visible-light-promoted single nickel catalysis to smoothly achieve various C–N couplings of aryl chlorides/bromides and diverse N-nucleophiles with sodium iodide as the activator. Single nickel catalysts play two compatible roles: halogen exchange and C–N coupling, which are critical to successfully obtaining desired coupling products. The catalytic process does not need an exogenous

  在此，我们报告了可见光促进的单镍催化以碘化钠作为活化剂顺利实现芳基氯/溴和多种N-亲核试剂的各种 C-N 偶联。单一镍催化剂扮演着两个兼容的角色：卤素交换和 C-N 偶联，这对于成功获得所需的偶联产物至关重要。催化过程不需要外源光催化剂，并提供了一种可持续且有效的方法来在温和条件下实现 C-N 偶联。结合紫外-可见和核磁共振分析的实验研究表明，Ni II和 Ni III -卤化物络合物与碘化物阴离子的卤素交换是产生偶联产物的重要过程。
• Photoinduced Reduction of Nitroarenes and Tandem C–N Cross-Coupling with Haloarenes
  作者：Haoshi Bao、Leifeng Wang

  DOI：10.1021/acs.orglett.3c03656

  日期：2023.12.15

  photocatalytic C–N cross-coupling of nitroarenes with haloarenes has been developed using simple and cheap Ni(acac)2 as a cocatalyst. The reaction is confirmed as a stepwise process: (1) metal free photoinduced reduction of nitroarenes into aniline derivatives and (2) photo- and Ni-catalyzed C–N cross-coupling of anilines with haloarenes. The reaction conditions are simple and mild, giving high-value diarylamines

  使用简单且廉价的 Ni(acac) 2作为助催化剂，开发了硝基芳烃与卤代芳烃的高效光催化 C-N 交叉偶联。该反应被证实是一个逐步过程：（1）无金属光诱导硝基芳烃还原成苯胺衍生物，（2）苯胺与卤代芳烃的光催化和镍催化C-N交叉偶联。反应条件简单温和，可得到高价值的二芳基胺，具有良好的收率和良好的官能团耐受性。
• Ligands for metals and improved metal-catalyzed processes based thereon
  申请人：Massachusetts Insitute of Technology

  公开号：EP1354887A1

  公开（公告）日：2003-10-22

  One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject processes provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.

  本发明的一个方面涉及过渡金属的新型配体。本发明的第二个方面涉及在过渡金属催化的碳-异原子和碳-碳键形成反应中使用包含这些配体的催化剂。本发明的工艺改进了过渡金属催化反应的许多特性，包括适用底物的范围、反应条件和效率。
• Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates
  作者：John P. Wolfe、Hiroshi Tomori、Joseph P. Sadighi、Jingjun Yin、Stephen L. Buchwald

  DOI：10.1021/jo991699y

  日期：2000.2.1

  Palladium complexes supported by (o-biphenyl)P(t-Bu)(2) (3) or (o-biphenyl)PCy2 (4) are efficient catalysts for the catalytic amination of a wide variety of aryl halides and triflates. Use of ligand 3 allows for the room-temperature catalytic amination of many aryl chloride, bromide, and triflate substrates, while ligand 4 is effective for the amination of functionalized substrates or reactions of acyclic secondary amines. The catalysts perform well for a large number of different substrate combinations at 80-110 degrees C, including chloropyridines and functionalized aryl halides and triflates using 0.5-1.0 mol % Pd; some reactions proceed efficiently at low catalyst levels (0.05 mol % Pd). These ligands are effective for almost all substrate combinations that have been previously reported with various other ligands, and they represent the most generally effective catalyst system reported to date. Ligands 3 and 4 are air-stable, crystalline solids that are commercially available. Their effectiveness is believed to be due to a combination of steric and electronic properties that promote oxidative addition, Pd-N bond formation, and reductive elimination.
• LIGANDS FOR METALS AND METAL-CATALYZED PROCESSES
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP1097158B1

  公开（公告）日：2006-01-25