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.
• Solvent-controlled switch of selectivity between sp²and sp³C–H bond activation by platinum(<scp>ii</scp>)
  作者：Alexander W. Garner、Caleb F. Harris、Dileep A. K. Vezzu、Robert D. Pike、Shouquan Huo

  DOI：10.1039/c0cc04581k

  日期：——

  By merely changing the solvent, two different cyclometalated platinum complexes resulted from either sp2 or sp3 C–H bond activation can be prepared selectively. For example, the reaction of L1 with K2PtCl4 in MeCN gave exclusively kinetic product 1a, while the reaction in AcOH was thermodynamically controlled and produced predominantly 1b.

  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。