N-(Diphenylmethylen)-o-chloranilin | 53847-32-8

• 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-(Diphenylmethylen)-o-chloranilin
• 英文别名: N-(2-Chlorophenyl)-1,1-diphenylmethanimine
• CAS: 53847-32-8
• 化学式: C₁₉H₁₄ClN
• 分子量: 291.78
• InChiKey: WLFKBUHYQMCHSI-UHFFFAOYSA-N

物化性质

• 沸点：
  407.0±37.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(Diphenylmethylen)-o-chloranilin 在 potassium tert-butylate 、 乙二醇 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以96%的产率得到6-苯基菲啶
  参考文献：
  名称：

  Intramolecular Direct C–H Bond Arylation from Aryl Chlorides: A Transition-Metal-Free Approach for Facile Access of Phenanthridines

  摘要：

  A C-H arylation with aryl chloride Is made viable through a transition-metal-free approach. In the presence of a simple diol associating with KOt-Bu, various phenanthridine derivatives can be conveniently accessed. In particular, only 10 mol % of simple and inexpensive ethylene glycol is required for this protocol. These results represent the first general examples of aryl chloride/C-H coupling under transition-metal-free conditions.

  DOI：

  10.1021/ol302489n
• 作为产物：
  描述：

  苯 在 aluminum (III) chloride 、 AlCl₄^(1-)*CCl₃⁽¹⁺⁾ 作用下， 以 四氯化碳 为溶剂， 反应 1.0h， 生成 N-(Diphenylmethylen)-o-chloranilin
  参考文献：
  名称：

  从苯方便地一锅合成二苯甲酮席夫碱

  摘要：

  基于苯与CCl4·AlCl3配合物的反应，开发了一种简单，高效的一锅法从苯，CCl4和芳族胺合成二苯甲酮席夫碱。该方法选择性地且高收率地提供了Ph2CCl2及其随后与芳族胺，二苯甲酮席夫碱的反应产物。

  DOI：

  10.1016/j.mencom.2020.03.037

文献信息

• Facile Synthesis of Triarylmethanimine Promoted by a Lewis Acid - Base Pair: Theoretical and Experimental Studies
  作者：Yan Liu、Qiwu Yang、Dongling Hao、Wenqin Zhang

  DOI：10.1071/ch12090

  日期：——

  An efficient method for triarylmethanimine synthesis promoted by a Lewis acid–base pair (AlCl3–Et3N) was designed using mechanistic analysis with the aid of density functional theory. A series of triarylmethanimines were successfully prepared under mild conditions in good to excellent yields with a simple work-up procedure. The promoter, the Lewis acid–base pair (AlCl3–Et3N), is inexpensive, efficient, and shows good functional group tolerance. The experimental results show that the electronic effect played a significant role, i.e. the reactions proceeded smoothly when electron-sufficient arylamines and electron-deficient ketones were used as substrates.

  在密度泛函理论的帮助下，利用机理分析设计了一种由路易斯酸碱对（AlCl3-Et3N）促进的三芳基甲亚胺的高效合成方法。通过简单的操作步骤，在温和的条件下成功地制备了一系列三芳基甲亚胺，产率从良好到极佳。路易斯酸碱对（AlCl3-Et3N）是一种廉价、高效且具有良好官能团耐受性的促进剂。实验结果表明，电子效应发挥了重要作用，即当使用电子充足的芳胺和电子不足的酮作为底物时，反应进展顺利。
• Reductive Cross-Coupling of Aldehydes and Imines Mediated by Visible Light Photoredox Catalysis
  作者：Rui Wang、Mengyue Ma、Xu Gong、Xinyuan Fan、Patrick J. Walsh

  DOI：10.1021/acs.orglett.8b03394

  日期：2019.1.4

  As a result, chemoselective cross-electrophile couplings between aldehydes and ketimines are achieved via umpolung reactivity of ketimines to furnish amino alcohols (44 examples with good to excellent yields). To illustrate the utility of the amino alcohol products, 1,2-dihydroindol-3-one-based fluorophores are easily synthesized using the coupling products. Finally, a plausible reaction pathway is

  在光氧化还原催化条件下，酮亚胺的常规亲电反应性被颠倒以产生亲核物质。结果，醛和酮亚胺之间的化学选择性的交叉亲电子偶联是通过酮亚胺与氨基醇的upolung反应来实现的（44个实例，收率高到极好）。为了说明氨基醇产物的效用，使用偶联产物容易地合成基于1，2-二氢吲哚-3-酮的荧光团。最后，讨论了可能的反应途径。
• Homolytic Aromatic Substitution by Iminyl Radicals. Photolysis of Aromatic Ketone<i>O</i>-Acyloximes in Aromatic Solvents
  作者：Hirochika Sakuragi、Shun-ichi Ishikawa、Toshihiro Nishimura、Masayuki Yoshida、Naoki Inamoto、Katsumi Tokumaru

  DOI：10.1246/bcsj.49.1949

  日期：1976.7

  effected aromatic substitution on the solvent molecules by diphenylmethaniminyl radicals to give N-diphenylmethylenearylamines only when benzoxyl or p-chlorobenzoxyl radicals were generated concurrently. A mechanism involving a participation of the sufficiently long-lived acyloxyl radicals is proposed for the iminylation reaction on the basis of the reactivity patterns in this substitution reaction

  在苯、甲苯、氯苯或邻二甲苯中照射二苯甲酮 O-乙酰肟、O-苯基乙酰肟、O-苯甲酰肟和 O-（对氯苯甲酰基）肟，通过二苯基甲胺基自由基对溶剂分子进行芳香取代，得到 N-二苯基亚甲基芳胺仅当同时产生苯甲氧基或对氯苯甲氧基自由基时。基于该取代反应中的反应模式，提出了一种涉及足够长寿命的酰氧基自由基参与的机理用于亚胺化反应。邻苯基二苯甲酮 O-苯甲酰肟在苯中也被光解得到 9-苯基菲啶，这是 2-联苯基苯基甲氨基亚胺基自由基的分子内环化产物。
• Arylamine synthesis
  申请人：Massachusetts Institute of Technology

  公开号：US06323366B1

  公开（公告）日：2001-11-27

  The present invention provides a method for the preparation of a wide range of primary arylamines. The arylamines are prepared in two efficient, straightforward transformations: 1) an activated aryl group and an imine group are combined, in the presence of a transition metal catalyst, under conditions wherein the transition metal catalyst catalyzes the formation of a carbon-nitrogen bond between the activated carbon of the arene and the imine nitrogen; and 2) the resulting N-aryl imine is transformed, via any of a number of standard protocols, to the primary arylamine. The method of the invention may also be exploited in the preparation of vinylamines.

  本发明提供了一种制备广泛范围的主要芳胺的方法。这些芳胺是通过两种高效、直接的转化制备的：1）在过渡金属催化剂的存在下，将活化的芳基和亚胺基结合在一起，在过渡金属催化剂催化的条件下，在芳烃的活化碳和亚胺氮之间催化形成碳-氮键；2）通过任何一种标准方案将产生的N-芳基亚胺转化为主要芳胺。该发明的方法还可用于制备乙烯胺。
• Palladium-Catalyzed Intramolecular C–H Activation/C–C Bond Formation: A Straightforward Synthesis of Phenanthridines
  作者：Jinsong Peng、Tonghui Chen、Chunxia Chen、Bin Li

  DOI：10.1021/jo2017108

  日期：2011.11.18

  The palladium-catalyzed intramolecular C-H activation/C-C cross-coupling has been developed for a straightforward and efficient synthesis of phenanthridines. With Pd(OAc)(2) (4 mol %) as the catalyst, PCy3 (8 mol %) as the ligand, and Cs2CO3 as the base, this protocol was applied to synthesize a small library of phenanthridine derivatives in good yields in THF.