4-methyl-N-(2-pyridin-2-ylpropan-2-yl)aniline | 882994-35-6

• 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: 4-methyl-N-(2-pyridin-2-ylpropan-2-yl)aniline
• CAS: 882994-35-6
• 化学式: C₁₅H₁₈N₂
• 分子量: 226.321
• InChiKey: DZVGSYKTVOVXKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  24.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  carbonylbis(acetonitrile)(η5-cyclopentadienyl)ruthenium(II) hexafluorophosphate 、 4-methyl-N-(2-pyridin-2-ylpropan-2-yl)aniline 以 二氯甲烷 为溶剂， 以71%的产率得到[Ru(η5-C5H5)(NC5H4C(Me)2NHC6H4-4-Me)(CO)]PF6
  参考文献：
  名称：

  Diastereospecific and Diastereoselective Syntheses of Ruthenium(II) Complexes Using N,N‘ Bidentate Ligands Aryl-pyridin-2-ylmethyl-amine ArNH-CH₂-2-C₅H₄N and Their Oxidation to Imine Ligands

  摘要：

  Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)(2)-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)(2)](2+), [Ru(eta(5)-C5H5)L](+) (L = CH3CN, CO), or [RU(eta(6)-arene)Cl](2+) (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)(2)(1b)](PF6)(2), 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)(2), 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta(6)-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.

  DOI：

  10.1021/ic051590a
• 作为产物：
  描述：

  4-甲苯硼酸 、 2-(吡啶-2-基)-2-丙胺 在 吡啶 、 copper(II) acetate monohydrate 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以62%的产率得到4-methyl-N-(2-pyridin-2-ylpropan-2-yl)aniline
  参考文献：
  名称：

  醋酸铜（II）催化螯合芳香仲胺脱氢反应中醋酸盐的双重作用：铜催化氧化反应的动力学案例研究

  摘要：

  醋酸铜 (II) 是铜 (II) 介导的氧化还原反应中铜源的常见经验选择。醋酸盐反离子的影响似乎很关键，但尚未得到充分研究。在此，我们报告乙酸铜（II）催化螯合芳香仲胺的有氧脱氢。该反应中乙酸盐和螯合胺的化学选择性为机理研究提供了独特的机会。通过使用电子顺磁共振光谱、UV/Vis 吸收光谱和测压法监测这种均相反应的进程。对胺底物、铜 (II) 和醋酸盐反离子的动力学依赖性，以及动力学同位素和取代基效应实验的结果，表明醋酸盐既可以作为双核催化中心的桥接配体来介导双电子转移步骤，又可以作为限制周转的 C-H 键断裂步骤中的碱基。在包含 1,8-二氮杂双环 [5.4.0] undec-7-ene (DBU) 作为替代碱后，DBU 和乙酸盐以互补的方式起作用，以实现螯合仲胺底物的快速催化脱氢反应。最后，醋酸铜（II）（促进双电子转移）和高氯酸铜（II）（促进单电子转移）之间的对比反应性强调了抗衡离

  DOI：

  10.1002/ejic.201600540

文献信息

• Dual Role of Acetate in Copper(II) Acetate Catalyzed Dehydrogenation of Chelating Aromatic Secondary Amines: A Kinetic Case Study of Copper‐Catalyzed Oxidation Reactions
  作者：Kesavapillai Sreenath、Zhao Yuan、Miguel Macias‐Contreras、Vasanth Ramachandran、Ronald J. Clark、Lei Zhu

  DOI：10.1002/ejic.201600540

  日期：2016.8

  dehydrogenation of chelating aromatic secondary amines. The chemoselectivity of acetate and chelating amines in this reaction provides a unique opportunity for a mechanistic study. The progression of this homogeneous reaction is monitored by using electron paramagnetic resonance spectroscopy, UV/Vis absorption spectroscopy, and manometry. The kinetic dependence on the amine substrate, copper(II), and

  醋酸铜 (II) 是铜 (II) 介导的氧化还原反应中铜源的常见经验选择。醋酸盐反离子的影响似乎很关键，但尚未得到充分研究。在此，我们报告乙酸铜（II）催化螯合芳香仲胺的有氧脱氢。该反应中乙酸盐和螯合胺的化学选择性为机理研究提供了独特的机会。通过使用电子顺磁共振光谱、UV/Vis 吸收光谱和测压法监测这种均相反应的进程。对胺底物、铜 (II) 和醋酸盐反离子的动力学依赖性，以及动力学同位素和取代基效应实验的结果，表明醋酸盐既可以作为双核催化中心的桥接配体来介导双电子转移步骤，又可以作为限制周转的 C-H 键断裂步骤中的碱基。在包含 1,8-二氮杂双环 [5.4.0] undec-7-ene (DBU) 作为替代碱后，DBU 和乙酸盐以互补的方式起作用，以实现螯合仲胺底物的快速催化脱氢反应。最后，醋酸铜（II）（促进双电子转移）和高氯酸铜（II）（促进单电子转移）之间的对比反应性强调了抗衡离
• Diastereospecific and Diastereoselective Syntheses of Ruthenium(II) Complexes Using N,N‘ Bidentate Ligands Aryl-pyridin-2-ylmethyl-amine ArNH-CH₂-2-C₅H₄N and Their Oxidation to Imine Ligands
  作者：Javier Gómez、Gabriel García-Herbosa、José V. Cuevas、Ana Arnáiz、Arancha Carbayo、Asunción Muñoz、Larry Falvello、Phillip E. Fanwick

  DOI：10.1021/ic051590a

  日期：2006.3.1

  Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)(2)-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)(2)](2+), [Ru(eta(5)-C5H5)L](+) (L = CH3CN, CO), or [RU(eta(6)-arene)Cl](2+) (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)(2)(1b)](PF6)(2), 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)(2), 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta(6)-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.