N-(2,6-dimethylphenyl)pyridin-2-amine | 376353-22-9

• 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-(2,6-dimethylphenyl)pyridin-2-amine
• 英文别名: N-(2,6-Dimethylphenyl)-2-pyridinamine
• CAS: 376353-22-9
• 化学式: C₁₃H₁₄N₂
• 分子量: 198.268
• InChiKey: JFOFKAMVQRNPPL-UHFFFAOYSA-N

物化性质

• 沸点：
  314.0±27.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 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：

  N-(2,6-dimethylphenyl)pyridin-2-amine 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  Pentamethylcyclopentadienyltitanium aryl(pyridyl)amide complexes: Synthesis, characterization and catalytic performance for olefin polymerization

  摘要：

  A series of new half-sandwich pentamethylcyclopentadienyl titanium (IV) aryl(pyridyl) amide complexes, Cp*TiCl2[N(Ar)(2-Py)] [Ar = 2,6-(Pr2Ph)-Pr-i (1), 2,6-Et2Ph (2), 2,6-Me2Ph (3), 4-MePh (4)], have been synthesized from the reactions of Cp*TiCl3 with the lithium salts of the corresponding aryl(pyridyl) amido ligands in toluene. A byproduct with two aryl(pyridyl) amido ligands, Cp*TiCl[N(4-MePh)(2-Py)]2 (5) was also obtained from the synthetic reaction of complex 4 in a small amount. The new titanium complexes 1-4 were characterized by H-1 and C-13 NMR and elemental analyses. The molecular structures of complexes 1, 2, 4 and 5 were determined by single-crystal X-ray diffraction analysis. X-ray crystallographic analysis on complexes 1, 2, 4 demonstrates that these complexes possess a relatively crowded heptacoordinating environment surrounding the central titanium atom. Upon activation with (AlBu3)-Bu-i and Ph3CB(C6F5)(4), complexes 1-4 exhibited moderate to high catalytic activity for ethylene and propylene polymerization, producing high molecular weight linear polyethylene and atactic polypropylene. It was found that complex 1 shows the highest catalytic activity for ethylene polymerization while complex 4 shows the highest catalytic activity for propylene polymerization among these complexes under similar conditions. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.12.029
• 作为产物：
  描述：

  2-氨基吡啶 、 1,3-二甲基-2-碘苯 在 copper(l) iodide 、 potassium tert-butylate 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以97%的产率得到N-(2,6-dimethylphenyl)pyridin-2-amine
  参考文献：
  名称：

  CuI / 2-氨基吡啶-1-氧化物催化脂肪族胺与芳基氯化物的胺化反应。

  摘要：

  发现一类2-氨基吡啶1-氧化物是用于铜反应性较低的（杂）芳基氯化物的铜催化胺化的有效配体。在CuI / 2-氨基吡啶1-氧化物的催化剂下，各种官能化的（杂）芳基氯化物与各种脂族胺反应，以良好或优异的收率提供所需的产物。此外，该催化剂体系对于环状仲胺和N-甲基苄基胺与（杂）芳基氯化物的偶联作用良好。

  DOI：

  10.1021/acs.orglett.0c02672

文献信息

• Amination with PdNHC Complexes: Rate and Computational Studies Involving Substituted Aniline Substrates
  作者：Ka Hou Hoi、Selçuk Çalimsiz、Robert D. J. Froese、Alan C. Hopkinson、Michael G. Organ

  DOI：10.1002/chem.201102428

  日期：2012.1.2

  chloride to be electron poor, although oxidative addition is not rate limiting. Anilines couple best when they are electron rich, which would seem to discount deprotonation of the intermediate metal ammonium complex as being rate limiting in favour of reductive elimination. In previous studies with secondary amines using PEPPSI complexes, deprotonation was proposed to be the slow step in the cycle. These

  使用N杂环卡宾基Pd络合物Pd-PEPPSI-IPr和Pd-PEPPSI-IPent（PEPPSI =吡啶，增强的前催化剂，制备，稳定和引发; IPr =二异丙基苯基咪唑鎓衍生物;已经研究了IPent ＝二异戊基苯基咪唑鎓衍生物）。速率研究表明对芳基氯的依赖是电子贫乏的，尽管氧化加成没有速率限制。当苯胺富含电子时，苯胺的耦合效果最佳，这似乎降低了中间金属铵络合物的去质子化，因为它限制了速率，有利于还原性消除。在先前使用PEPPSI配合物对仲胺进行的研究中，提出去质子化是该循环中的缓慢步骤。这些与机理有关的实验发现通过计算得到了证实。Pd-PEPPSI-IPr和受阻更严重的Pd-PEPPSI-IPent催化剂用于将失活的芳基氯化物与电子贫乏的苯胺偶联。尽管IPr催化剂反应缓慢，但IPent催化剂的性能非常好，再次显示了这种广泛使用的催化剂的高反应活性。
• Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald–Hartwig Amination in Air
  作者：Xiao-Bing Lan、Yinwu Li、Yan-Fang Li、Dong-Sheng Shen、Zhuofeng Ke、Feng-Shou Liu

  DOI：10.1021/acs.joc.6b02867

  日期：2017.3.17

  well-defined palladium complexes were found to be excellent precatalysts for Buchwald–Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence

  为了实现与柔性空间体积策略温和的反应条件下有效的钯催化的交叉耦合反应，一系列的Pd-PEPPSI的（PEPPSI：吡啶增强预催化剂制备，稳定化，和起始）络合物C1 - C6被合成和表征，其中不对称的柔性空间本体被引入到萘基骨架的N-芳基上。这些良好定义的钯络合物是在空气中用胺进行布赫瓦尔德-哈特维格胺化芳基氯化物的极好预催化剂。评估了Pd-PEPPSI配合物的电子效应和辅助吡啶配体的效应，其中配合物C3表现出最高的效率。结果表明，在钯含量为0.5-0.1 mol％的情况下，以优异的产率获得了交叉偶联产物。各种芳基氯化物和杂芳基氯化物以及各种胺均相容。芳基氯的氧化加成被证明是催化循环中决定速率的步骤。可以通过将供电子基团引入Pd-PEPPSI配合物中来增强催化活性。这种类型的Pd-PEPPSI预催化剂显示出迄今为止最具挑战性的C–N交叉偶联反应的效率，该反应不需要无水和惰性气氛保护，表明灵活
• Streamlined Synthesis of the Bippyphos Family of Ligands and Cross-Coupling Applications
  作者：Gregory J. Withbroe、Robert A. Singer、Janice E. Sieser

  DOI：10.1021/op7002858

  日期：2008.5.1

  the efficient preparation of Bippyphos, 1. The key precursor to Bippyphos, 5, was prepared via a one-pot bromination of diketone 2 followed by alkylation with pyrazole and condensation with phenylhydrazine. Lithiation of 5 and trapping with di-tert-butylchlorophosphine afforded Bippyphos, 1. Using this approach we have prepared several derivatives of Bippyphos to probe the structure and activity relationships

  我们描述了Bippyphos，1的有效制备方法。Bippyphos的关键前体5是通过二锅2的一锅溴化反应，然后用吡唑烷基化并与苯肼缩合制备的。5的锂化并用二叔丁基氯膦捕获，得到Bippyphos，1。使用这种方法，我们已经制备了Bippyphos的几种衍生物，以探测该膦配体家族的结构和活性之间的关系。我们还证明了这些配体在钯催化的胺化反应和其他交叉偶联反应中的效用。
• Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands
  作者：W. Ryan Osterloh、Gabriel Galindo、Michelle J. Yates、Eric Van Caemelbecke、Karl M. Kadish

  DOI：10.1021/acs.inorgchem.9b02838

  日期：2020.1.6

  6-F5ap, 2,4,6-F3ap, 2-Fap, ap, 2-Meap, 2,6-Me2ap, or 2,4,6-Me3ap, where ap is the anilinopyridinate anion, have been characterized as to their structural and physicochemical properties in H2O and DMSO. Five of the newly synthesized complexes were structurally characterized, and the Ru-Cl bond lengths range from 2.477 to 2.544 Å while the Ru-Ru bond lengths range from 2.2838 to 2.2935 Å. The UV-vis spectra

  Ru2（O2CCH3）3（L）Cl类型的一系列水溶性Ru25 +络合物，其中L = 2,3,4,5,6-F5ap，2,4,6-F3ap，2-Fap，ap，2 -Meap，2,6-Me2ap或2,4,6-Me3ap（其中ap是苯胺吡啶酸根阴离子）的特征在于它们在H2O和DMSO中的结构和物理化学性质。对五个新合成的配合物进行了结构表征，Ru-Cl键长范围为2.477至2.544Å，而Ru-Ru键长范围为2.2838至2.2935Å。每种化合物的UV-vis光谱均以H2O和DMSO中的三个吸收带为特征，其吸收强度和位置随桥连配体类型和溶剂的不同而变化。所检查的七个Ru25 +络合物在水中以1：1电解质的形式存在，并且在两种研究的溶剂中，每种都经历了可逆的单电子还原，这归因于Ru25 + / Ru24 +。在DMSO中，在负电位更高的情况下，每种化合物也观察到第二次不可逆的还原，归因于Ru24 +
• Carbene adduct of cyclopalladated ferrocenylimine-assisted synthesis of aminopyridine derivatives by the amination of chloropyridines with primary and secondary amines
  作者：Bing Mu、Jingya Li、Yangjie Wu

  DOI：10.1002/aoc.3026

  日期：2013.9

  on Buchwald–Hartwig aminations. Using 1 mol% N‐heterocyclic carbene adduct of cyclopalladated ferrocenylimine in the presence of 1.5 equiv. tBuOK as base in dioxane at 110°C offered moderate to excellent yields in the reaction of chloropyridines with primary and secondary amines, including sterically hindered amines and alkyl amines.

  基于布赫瓦尔德-哈特维格胺的胺化反应，提出了一种高效，简单的合成氨基吡啶衍生物的方法。在1.5当量的情况下，使用1 mol％的N-杂环卡宾环合钯的二茂铁亚胺加成物。吨丁醇钾作为在110℃下基在二恶烷中的氯吡啶与伯和仲胺反应提供中度至良好的产率，包括空间位阻胺和烷基胺。