2-(N'-methyl-N'-phenylamino)-N-methylbenzimidazole | 31413-78-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-(N'-methyl-N'-phenylamino)-N-methylbenzimidazole
• 英文别名: N,1-dimethyl-N-phenyl-1H-benzoimidazol-2-amine；N,1-dimethyl-N-phenyl-1H-benzo[d]imidazol-2-amine；2-(N-Methylanilino)-1-methyl-benzimidazol；1-Methyl-2-(N-methylanilino)-benzimidazol；methyl-(1-methyl-1H-benzoimidazol-2-yl)-phenyl-amine；N,1-dimethyl-N-phenylbenzimidazol-2-amine
• CAS: 31413-78-2
• 化学式: C₁₅H₁₅N₃
• 分子量: 237.304
• InChiKey: IUJZWXXZAHRQKB-UHFFFAOYSA-N

物化性质

• 熔点：
  123-125 °C
• 沸点：
  391.0±25.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  21.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-甲基苯并咪唑 、 N-甲基苯胺 在 氧气 、 copper diacetate 、 sodium acetate 、 三苯基膦 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 20.0h， 以51%的产率得到2-(N'-methyl-N'-phenylamino)-N-methylbenzimidazole
  参考文献：
  名称：

  Copper-catalyzed oxidative C‒H, N‒H coupling of azoles and thiophenes

  摘要：

  C-H, N-H coupling of azole and thiophene derivatives takes place in the presence of a catalytic amount of Cu(OAc)(2) and an additive. The reaction of azoles smoothly occurs with several amines and amides catalyzed by 20 mol % of Cu(OAc)(2)-2PPh(3) and 4 equiv of NaOAc under O-2 or in the presence of Ag2CO3 under N-2. The coupling reaction leads to a facile synthesis of a N-substituted analogue of 2,5-diarylthiazole, which shows photoluminescent properties with extended pi-conjugation. Spectroscopic characteristics of the obtained thiazole derivatives are discussed by measurements of UV-vis absorption and photoluminescent spectra. Under the reaction conditions using Ag2CO3 as an additive and Cu(OAc)2-2PPh3 as a catalyst, thiophene derivatives also react with 2-pyrrolidone to undergo C-H, N-H amidation. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.001

文献信息

• Metal-Free Synthesis of Heteroaryl Amines or Their Hydrochlorides via an External-Base-Free and Solvent-Free C–N Coupling Protocol
  作者：Guang-Gao Fan、Bo-Wen Jiang、Wei Sang、Hua Cheng、Rui Zhang、Bao-Yi Yu、Ye Yuan、Cheng Chen、Francis Verpoort

  DOI：10.1021/acs.joc.1c01467

  日期：2021.11.5

  Herein, a metal-free and solvent-free protocol was developed for the C–N coupling of heteroaryl halides and amines, which afforded numerous heteroaryl amines or their hydrochlorides without any external base. Further investigations elucidated that the basicity of amines and specific interactions derived from the X-ray crystallography analysis of 3j′·HCl played pivotal roles in the reactions. Moreover

  在此，开发了一种无金属和无溶剂的方案，用于杂芳基卤化物和胺的 C-N 偶联，在没有任何外部碱的情况下提供了许多杂芳基胺或其盐酸盐。进一步的研究表明，胺的碱性和源自3j'·HCl的 X 射线晶体学分析的特定相互作用在反应中起关键作用。此外，该协议可扩展到克级并适用于药物分子，这证明了其进一步应用的实用价值。
• Scope and Mechanism of Palladium-Catalyzed Amination of Five-Membered Heterocyclic Halides
  作者：Mark W. Hooper、Masaru Utsunomiya、John F. Hartwig

  DOI：10.1021/jo0266339

  日期：2003.4.1

  Detailed studies have been conducted to determine the activity of palladium catalysts for the amination of five-membered heterocyclic halides and to determine the factors that control the scope of this reaction. Palladium-catalyzed aminations of the electron-rich furanyl, thiophenyl, and indolyl halides and of the related 2-halogenated thiazoles, benzimidazole, and benzoxazole have been shown to occur

  已经进行了详细的研究，以确定钯催化剂对五元杂环卤化物胺化的活性，并确定控制该反应范围的因素。富电子的呋喃基，噻吩基和吲哚基卤化物以及相关的2-卤代噻唑，苯并咪唑和苯并恶唑的钯催化胺化反应均与一部分胺一起发生。测试了钯前体和P（t）Bu（3）的各种组合作为3-溴噻吩与N-甲基苯胺反应的催化剂，最快的反应是Pd（I）二聚体[PdBr（P（t）Bu） （3））]（2）。噻唑，苯并咪唑和苯并恶唑的最快胺化反应发生在三氟乙酸钯和P（t）Bu（3）的组合催化下。
• Direct Amination of Azoles via Catalytic C−H, N−H Coupling
  作者：Daiki Monguchi、Taiki Fujiwara、Hirotoshi Furukawa、Atsunori Mori

  DOI：10.1021/ol900298e

  日期：2009.4.2

  C-H, N-H Coupling of azoles takes place with several amines in the presence of a copper catalyst to undergo amination at the 2-position. The reaction of benzothiazole with N-methylaniline in the presence of sodium acetate and 20 mol % Cu(OAc)(2) in xylene under an oxygen atmosphere afforded the aminated product in 81% yield.
• Cu(acac)2 catalyzed oxidative C–H bond amination of azoles with amines under base-free conditions
  作者：Yogesh S. Wagh、Bhalchandra M. Bhanage

  DOI：10.1016/j.tetlet.2012.09.064

  日期：2012.11

  This work reports a simple and efficient methodology for oxidative C-H bond amination of azoles with aromatic/aliphatic amines using copper-bis-acetylacetonate complex catalyst. The catalyst works very well in the absence of external acid or base and requires only molecular oxygen as an oxidant. The methodology is applicable for the oxidative C-H bond amination of various azoles with different types of aromatic/aliphatic amines for the synthesis of various aminoheterocycles with good to excellent yields. (C) 2012 Elsevier Ltd. All rights reserved.