N,N′-bis(2,6-dimethylphenyl)pyridine-2,6-diamine | 1127647-92-0

• 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,N′-bis(2,6-dimethylphenyl)pyridine-2,6-diamine
• 英文别名: N,N'-bis-(2,6-dimethylphenyl)pyridine-2,6-diamine；N,N'-bis(2,6-dimethylphenyl)pyridine-2,6-diamine；2,6-bis[(2,6-dimethylphenyl)amino]pyridine；2,6-bis-(2,6-dimethylphenylamino)pyridine；2,6-bis(2,6-dimethylphenylamino)pyridine；2-N,6-N-bis(2,6-dimethylphenyl)pyridine-2,6-diamine
• CAS: 1127647-92-0
• 化学式: C₂₁H₂₃N₃
• 分子量: 317.434
• InChiKey: ZIOMLFACXHJJCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  37
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N′-bis(2,6-dimethylphenyl)pyridine-2,6-diamine 在 三乙胺 作用下， 以 间二甲苯 、 甲苯 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  脒-酰胺吡啶配体的中性和阳离子烷基和酰胺基 3 族金属配合物：合成、结构和聚合催化活性

  摘要：

  脒-氨基吡啶前配体 (NR1NNR1CMeNR2)H [R1 = R2 = Me (1a), R1 = H, R2 = Me (1b), R1 = Me, R2 = iPr (1c)] 和前体之间的烷烃和胺消除反应已经研究了 [Ln(CH2SiMe3)3(thf)2]（Ln = Sc 和 Y）和 [Ln{N(SiHMe2)2}3(thf)x]（Ln = Sc、Y 和 La）。大体积的 1c 和 [Ln(CH2SiMe3)3(thf)2]（Ln = Sc 和 Y）选择性地提供了二烷基配合物 2c-Sc 和 2c-Y。钇和镧二酰氨基配合物 3a-Y、3b-Y、3c-Y 和 3c-La 的合成和高产率分离；然而，制备钪类似物的类似氨解反应没有成功。详细的 29Si NMR 光谱研究与 X 射线晶体学相结合，揭示了 β-Si-H...Ln 在二酰胺络合物中的相互作用。阳离子单酰胺络合物 4a-Y 由

  DOI：

  10.1002/ejic.201402362
• 作为产物：
  描述：

  2,6-二溴吡啶 、 2,6-二甲基苯胺 反应 9.0h， 以88%的产率得到N,N′-bis(2,6-dimethylphenyl)pyridine-2,6-diamine
  参考文献：
  名称：

  Thermal Amination of 2,6-Dihalopyridines by Sterically Demanding Amines

  摘要：

  当过渡金属催化的转化失败时，热诱导下可以实现活化溴吡啶和氯吡啶的胺化反应。辅助碱2,2,6,6-四甲基哌啶被证明是实现高度立体位阻和酸易变胺转化的关键。

  DOI：

  10.1055/s-0028-1083268

文献信息

• Thermal Amination of 2,6-Dihalopyridines by Sterically Demanding Amines
  作者：Siegfried Waldvogel、Andreas Faust、Oliver Wolff

  DOI：10.1055/s-0028-1083268

  日期：2009.1

  When transition-metal-catalyzed transformations fail, the amination reaction of activated bromo- and chloropyridines can be achieved thermally. The auxiliary base 2,2,6,6-tetramethylpiperidine turned out to be the key for the conversion of highly sterically demanding and acid labile amines.

  当过渡金属催化的转化失败时，热诱导下可以实现活化溴吡啶和氯吡啶的胺化反应。辅助碱2,2,6,6-四甲基哌啶被证明是实现高度立体位阻和酸易变胺转化的关键。
• Scandium and yttrium complexes of an hybrid phenoxy-amidopyridinate ligand. Use in ROP of racemic lactide
  作者：Jad El Haj Hassan、Vasily Radkov、Vincent Dorcet、Jean-François Carpentier、Evgueni Kirillov

  DOI：10.1016/j.jorganchem.2016.09.014

  日期：2016.11

  characterized by NMR spectroscopy and microanalysis. Upon crystallization, 1-Sc disproportionates to form the bis(ligand) complex 2-Sc which was isolated and characterized by X-ray crystallography. Complexes 1-Sc and 1-Y were used as initiators in the ring-opening polymerization (ROP) of racemic lactide, alone or in combination with iPrOH, to give atactic PLAs with controlled molecular weights.

  制备了新的多齿杂酚-氨基吡啶配体N Me2 NN Me2 C i Pr2 O} H 2（1-H 2），并将其与三烷基前体M（CH 2 SiMe 3）3（THF ）进行σ-键复分解反应。）2（M = Sc，Y）。这些反应干净地提供了相应的烷基络合物N Me2 NN Me2 C iPr2 O} M（CH 2 SiMe 3）（THF）（M = Sc（1-Sc），Y（1-Y）），通过NMR光谱和显微分析对其进行表征。结晶后，1-Sc歧化形成双（配体）复合物2-Sc，将其分离并通过X射线晶体学表征。配合物1-Sc和1-Y单独或与i PrOH一起用作外消旋丙交酯的开环聚合（ROP）的引发剂，可得到分子量受控的无规立构PLA。
• Tandem C(sp²)–OMe Activation/C(sp²)–C(sp²) Coupling in Early Transition-Metal Complexes: Aromatic C–O Activation beyond Late Transition Metals
  作者：Vasily Radkov、Thierry Roisnel、Alexander Trifonov、Jean-François Carpentier、Evgueni Kirillov

  DOI：10.1021/jacs.6b01877

  日期：2016.4.6

  of a unique, highly selective intramolecular C(sp(2))-OMe cleavage/C(sp(2))-C(sp(2)) coupling tandem reaction in group 3 metal (Y and Sc) complexes of amidine-amidopyridinate ligands. The latter process represents a rare stoichiometric model of the nonredox cleavage of inert C(sp(2))-O bonds relevant to cross-coupling reactions of aromatic ethers catalyzed by late transition metals.

  我们报告了组合结构、动力学和计算研究，揭示了独特的、高选择性的分子内 C(sp(2))-OMe 裂解/C(sp(2))-C(sp(2)) 耦合串联反应的机制在脒-脒基吡啶配体的第 3 族金属（Y 和 Sc）配合物中。后一个过程代表了惰性 C(sp(2))-O 键的非氧化还原裂解的罕见化学计量模型，与晚期过渡金属催化的芳香醚的交叉偶联反应相关。
• Alkylyttrium Complexes of Amidine–Amidopyridinate Ligands. Intramolecular C(sp³)–H Activation and Reactivity Studies
  作者：Vasily Rad’kov、Vincent Dorcet、Jean-François Carpentier、Alexander Trifonov、Evgeny Kirillov

  DOI：10.1021/om400027d

  日期：2013.3.11

  The new multidentate amidine-aminopyridine proligand (NNNCNMe2)-N-Me2-C-Me2-N-Me}H (1) was used in sigma-bond metathesis reactions with the trialkyl precursors Y(CH2-SiMe3)(3)(THF)(2) and Y(CH2C6H4-o-NMe2)(3). These reactions generate the dialkyl complexes (NNNCNMe2)-N-Me2-C-Me2-N-Me}Y-(CH2SiMe3)(2)(THF) (2a) and (NNNCNMe2)-N-Me2-C-Me2-N-Me}Y- (CH2C6H4-o-NMe2)(2) (2b), respectively, which were characterized by NMR spectroscopy and microanalysis (for 2b). Complex 2a is unstable at -30 degrees C in toluene and selectively undergoes intramolecular C(sp(3))-H activation to give (NNNCNMe)-N-Me2-C-Me2-N-Me-CH2}Y(CH2SiMe3)(THF) (2a'), authenticatecl by X-ray crystallography, NMR spectroscopy, and elemental analysis. The reactivity of 2a' toward a number of Lewis and Bronsted acids and bases as well as oxidants and reductants was explored. In the course of these studies, the new complexes (NNNCNCH2B)-N-Me2-C-Me2-N-Me-C-Me(C6F5)(3)}Y(CH2SiMe3)-(THF) (3), [(NNNCNCH2)-N-Me2-C-Me2-N-Me-C-Me2}Y(CH2SiMe3)(THF)(x)](+)[BPh4](-) (4), (NNNCNCH2)-N-Me2-C-Me2-N-Me-C-Me2}Y(iPrNC(PPh2)NiPr) (5), [(NNNCNMe2)-N-Me2-C-Me2-N-Me)Y(mu 2BH3)(mu(2)-NH)}](2) (6), and [(NNNCNCH2)-N-Me2-C-Me2-N-Me-C-Me2(mu-O))Y(CH2SiMe3)](2) (7) were isolated and characterized by NMR spectroscopy and X-ray crystallography and microanalysis (for 6 and 7). Complex 6 was found to be active in the ROP of rac-lactide, affording slightly heterotactic-enriched PLAs.
• A practical synthesis of substituted 2,6-diaminopyridines via microwave-assisted copper-catalyzed amination of halopyridines
  作者：Matthias Mastalir、Egon E. Rosenberg、Karl Kirchner

  DOI：10.1016/j.tet.2015.08.042

  日期：2015.10

  selective substitution of one or two halogens by aryl or alkylamines was achieved within 2–6 h with temperatures between 80 and 225 °C affording 2,6-diaminopyridines in good to excellent isolated yields. The reaction allows easy variation between educts and different N-substitutions. The target compounds are valuable precursors for the synthesis of bis-phosphorylated 2,6-diaminopyridines which are

  据报道，利用一系列的2，6-二卤代和2-氨基-6-卤代吡啶前体，进行了微波辅助的铜催化的胺化反应。使用该方法，被芳基或烷基胺一个或两个卤素选择性取代物2-6小时内用80和225之间的温度下℃下，得到良好的2,6-二氨基吡啶，以优异的分离产率来实现的。该反应允许离析物和不同之间容易变化Ñ -substitutions。目标化合物可用于被用作过渡金属络合物PNP钳配体的双-磷酸化2,6-二氨基吡啶合成有价值的前体。