6-bromo-N-tert-butyl-N-phenylpyridin-2-amine | 1451255-08-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6-bromo-N-tert-butyl-N-phenylpyridin-2-amine
• CAS: 1451255-08-5
• 化学式: C₁₅H₁₇BrN₂
• 分子量: 305.217
• InChiKey: RIEBLEPOCPKOOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  16.13
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  6-bromo-N-tert-butyl-N-phenylpyridin-2-amine 在 copper(l) iodide 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 66.0h， 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：

  2,6-二溴吡啶 、 N-叔丁基苯胺 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 26.0h， 以31%的产率得到6-bromo-N-tert-butyl-N-phenylpyridin-2-amine
  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