N-methyl-N-phenyl-2,2'-bipyridin-6-amine | 1273567-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-methyl-N-phenyl-2,2'-bipyridin-6-amine
• 英文别名: N-methyl-N-phenyl-6-pyridin-2-ylpyridin-2-amine
• CAS: 1273567-06-8
• 化学式: C₁₇H₁₅N₃
• 分子量: 261.326
• InChiKey: WNZFJMURVRRZMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  29
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-methyl-N-phenyl-2,2'-bipyridin-6-amine 以 溶剂黄146 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Solvent-controlled switch of selectivity between sp²and sp³C–H bond activation by platinum(ii)

  摘要：

  通过仅仅改变溶剂，可以选择性地得到两种不同的环金属化铂配合物，这两种配合物分别源自sp2或sp3 C–H键的活化。例如，在MeCN中用K2PtCl4与L1反应仅生成动力学产物1a，而在醋酸中反应则是热力学控制，主要生成1b。

  DOI：

  10.1039/c0cc04581k
• 作为产物：
  描述：

  6-溴-2,2'-联吡啶 、 N-甲基苯胺 在 1,1'-双(二苯基膦)二茂铁 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以79%的产率得到N-methyl-N-phenyl-2,2'-bipyridin-6-amine
  参考文献：
  名称：

  Solvent-controlled switch of selectivity between sp²and sp³C–H bond activation by platinum(ii)

  摘要：

  通过仅仅改变溶剂，可以选择性地得到两种不同的环金属化铂配合物，这两种配合物分别源自sp2或sp3 C–H键的活化。例如，在MeCN中用K2PtCl4与L1反应仅生成动力学产物1a，而在醋酸中反应则是热力学控制，主要生成1b。

  DOI：

  10.1039/c0cc04581k

文献信息

• Computational and Experimental Study on Selective sp²/sp³ or Vinylic/Aryl Carbon–Hydrogen Bond Activation by Platinum(II): Geometries and Relative Stability of Isomeric Cycloplatinated Compounds
  作者：Yumin Li、Jeffrey Carroll、Bradley Simpkins、Deepak Ravindranathan、Christopher M. Boyd、Shouquan Huo

  DOI：10.1021/acs.organomet.5b00326

  日期：2015.7.13

  Cyclometalating ligands 6-(1-phenylethyl)-2,2'-bipyridine (L4), 6-(1-phenylvinyl)-2,2'-bipyridine (LS), and 6-(prop-1-en-2-yl)-2,2'-bipyridine (L6) were synthesized by the Negishi coupling of 6-bromo-2,2'-bipyridine with the corresponding organo-zinc reagents. The reaction of L4 with K2PtCl4 produced only the cycloplatinated compound 4a via sp(2) C-H bond activation. The reactions of L5 and L6 produced exclusively the cycloplatinated compounds 5b and 6a, respectively, via vinylic C-H bond activation. DFT calculations were performed on 12 possible cycloplatination products from the reaction of N-alkyl-N-phenyl-'2,2'-bipyridin-6-amine (alkyl = methyl (L1), ethyl (L2), and isopropyl (L3)) and L4 L6. The results show that compounds 1b-3b resulting from the sp(3) C-H bond activation of L1-L3 are thermodynamic products, and their relative stability is attributed to the planar geometry that allows for a better conjugation. Similar reasoning also applies to the stability of products from vinylic C-H bond activation of L5 and L6. The relative stability of isomeric cycloplatinated compounds 4a and 4b may be due to the different strengths of C-Pt bonds. The steric interaction is the major cause of severe distortion from a planar coordination geometry in the cycloplatinated compounds, which leads to instability of the corresponding cyclometalated products and a higher kinetic barrier for C-H bond activation.