N-isopropyl-N-phenyl-2,2′-bipyridin-6-amine | 1273567-08-0

• 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-isopropyl-N-phenyl-2,2′-bipyridin-6-amine
• 英文别名: N-isopropyl-N-phenyl-2,2'-bipyridin-6-amine；N-phenyl-N-propan-2-yl-6-pyridin-2-ylpyridin-2-amine
• CAS: 1273567-08-0
• 化学式: C₁₉H₁₉N₃
• 分子量: 289.38
• InChiKey: JLNUIBRDPPPGJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 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-isopropyl-N-phenyl-2,2′-bipyridin-6-amine 在 copper(l) iodide 、 四丁基氯化铵 、 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 、 溶剂黄146 、 乙腈 为溶剂， 反应 291.0h， 生成
  参考文献：
  名称：

  Reaction of N-Isopropyl-N-phenyl-2,2′-bipyridin-6-amine with K₂PtCl₄: Selective C–H Bond Activation, C–N Bond Cleavage, and Selective Acylation

  摘要：

  The selective C H bond activation of N-isopropyl-N-phenyl-2,2'-bipyridin-6-amine promoted by Pt(II) was complicated by the low selectivity of sp(2) C-H bond activation in acetonitrile and low yield of sp(3) C-H activation in acetic acid. The use of a base was found to effectively suppress the competing sp(3) C-H bond activation in acetonitrile, improving the selectivity of sp(2) C-H bond activation from 70% to 99%. In the reaction in acetic acid, the low yield was due to the competing C-N bond cleavage. The use of a base reduced the C-N bond cleavage, but not completely. The reaction of N-tert-butyl-N-phenyl-2,2'-bipyridin-6-amine with K2PtCl4 in acetic acid produced the cyclometalated complex with complete C-N bond cleavage and its acylated derivative. These results indicated that the C-N bond cleavage might proceed via heterolytic C-N bond dissociation. The acylation following the C-N cleavage in the reaction in acetic acid is regioselective. Further experiments showed that the reaction of N-phenyl-2,2'-bipyridin-6-amine with K2PtCl4 in acetic acid produced the cyclometalated complex, while the reaction in a mixture of acetic anhydride and acetic acid produced the acylated cyclometalated complex. An X-ray crystal structure study revealed strong intramolecular H bonding in the acylated complexes. The regioselectivity was explained in terms of H bonding and the electron distribution predicted by the DFT calculations.

  DOI：

  10.1021/om400540y
• 作为产物：
  描述：

  N-异丙基苯胺 、 N-乙基苯胺 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55%的产率得到N-isopropyl-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

• 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。
• Reaction of <i>N</i>-Isopropyl-<i>N</i>-phenyl-2,2′-bipyridin-6-amine with K₂PtCl₄: Selective C–H Bond Activation, C–N Bond Cleavage, and Selective Acylation
  作者：Jeffrey Carroll、Joshua P. Gagnier、Alexander W. Garner、Justin G. Moots、Robert D. Pike、Yumin Li、Shouquan Huo

  DOI：10.1021/om400540y

  日期：2013.9.9

  The selective C H bond activation of N-isopropyl-N-phenyl-2,2'-bipyridin-6-amine promoted by Pt(II) was complicated by the low selectivity of sp(2) C-H bond activation in acetonitrile and low yield of sp(3) C-H activation in acetic acid. The use of a base was found to effectively suppress the competing sp(3) C-H bond activation in acetonitrile, improving the selectivity of sp(2) C-H bond activation from 70% to 99%. In the reaction in acetic acid, the low yield was due to the competing C-N bond cleavage. The use of a base reduced the C-N bond cleavage, but not completely. The reaction of N-tert-butyl-N-phenyl-2,2'-bipyridin-6-amine with K2PtCl4 in acetic acid produced the cyclometalated complex with complete C-N bond cleavage and its acylated derivative. These results indicated that the C-N bond cleavage might proceed via heterolytic C-N bond dissociation. The acylation following the C-N cleavage in the reaction in acetic acid is regioselective. Further experiments showed that the reaction of N-phenyl-2,2'-bipyridin-6-amine with K2PtCl4 in acetic acid produced the cyclometalated complex, while the reaction in a mixture of acetic anhydride and acetic acid produced the acylated cyclometalated complex. An X-ray crystal structure study revealed strong intramolecular H bonding in the acylated complexes. The regioselectivity was explained in terms of H bonding and the electron distribution predicted by the DFT calculations.