4-nitro-N-phenylpyridin-2-amine | 1267963-47-2

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 4-nitro-N-phenylpyridin-2-amine
• CAS: 1267963-47-2
• 化学式: C₁₁H₉N₃O₂
• 分子量: 215.211
• InChiKey: QJVZTWMMWUSPOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  70.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-nitro-N-phenylpyridin-2-amine 、 苯基三氟硼酸钾 在 copper diacetate 、 palladium diacetate 、 对苯醌 作用下， 以 叔丁醇 为溶剂， 反应 4.0h， 以45%的产率得到N-([1,1'-biphenyl]-2-yl)-4-nitropyridin-2-amine
  参考文献：
  名称：

  Palladium(II)-Catalyzed Direct Ortho Arylation of 4-Methyl-N-phenylpyridin-2-amines via C–H Activation/C–C Coupling and Synthetic Applications

  摘要：

  The direct ortho arylation of 4-methyl-N-phenylpyridin-2-amines via palladium(II)-catalyzed C-H activation is described. Treatment of 4-methyl-N-phenylpyridin-2-amine with potassium aryltrifluoroborate using 10 mol % of palladium(II) acetate as the catalyst, 2 equiv of copper(II) acetate as the oxidant, and 1 equiv of p-benzoquinone in tert-butyl alcohol gave ortho-arylated products in modest to excellent yields. This reaction shows good functional group compatibility. A series of H-1 NMR titration experiments and controlled experiments elucidating the reaction mechanism were carried out. The key intermediate, 4-methyl-N-phenylpyridin-2-amine palladacycle, was isolated and characterized by X-ray crystallography. The advanced transformations of ortho-phenylated 4-methyl-N-phenylpyridin-2-amine to N-(4-methylpyridin-2-yl)-9H-carbazole, biphenyl-2-amine, and 3-methyl-6-phenylpyrido[1,2-a]benzimidazole were successfully demonstrated as potential synthetic applications.

  DOI：

  10.1021/om401195w
• 作为产物：
  描述：

  2-溴-4-硝基吡啶 、 苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 potassium tert-butylate 、 双(2-二苯基磷苯基)醚 作用下， 以 甲苯 为溶剂， 以49%的产率得到4-nitro-N-phenylpyridin-2-amine
  参考文献：
  名称：

  Palladium(II)-Catalyzed Direct Ortho Arylation of 4-Methyl-N-phenylpyridin-2-amines via C–H Activation/C–C Coupling and Synthetic Applications

  摘要：

  The direct ortho arylation of 4-methyl-N-phenylpyridin-2-amines via palladium(II)-catalyzed C-H activation is described. Treatment of 4-methyl-N-phenylpyridin-2-amine with potassium aryltrifluoroborate using 10 mol % of palladium(II) acetate as the catalyst, 2 equiv of copper(II) acetate as the oxidant, and 1 equiv of p-benzoquinone in tert-butyl alcohol gave ortho-arylated products in modest to excellent yields. This reaction shows good functional group compatibility. A series of H-1 NMR titration experiments and controlled experiments elucidating the reaction mechanism were carried out. The key intermediate, 4-methyl-N-phenylpyridin-2-amine palladacycle, was isolated and characterized by X-ray crystallography. The advanced transformations of ortho-phenylated 4-methyl-N-phenylpyridin-2-amine to N-(4-methylpyridin-2-yl)-9H-carbazole, biphenyl-2-amine, and 3-methyl-6-phenylpyrido[1,2-a]benzimidazole were successfully demonstrated as potential synthetic applications.

  DOI：

  10.1021/om401195w

文献信息

• Palladium(II)-Catalyzed Direct Ortho Arylation of 4-Methyl-<i>N</i>-phenylpyridin-2-amines via C–H Activation/C–C Coupling and Synthetic Applications
  作者：Jean-Ho Chu、Hao-Ping Huang、Wen-Ting Hsu、Shih-Tien Chen、Ming-Jung Wu

  DOI：10.1021/om401195w

  日期：2014.3.10

  The direct ortho arylation of 4-methyl-N-phenylpyridin-2-amines via palladium(II)-catalyzed C-H activation is described. Treatment of 4-methyl-N-phenylpyridin-2-amine with potassium aryltrifluoroborate using 10 mol % of palladium(II) acetate as the catalyst, 2 equiv of copper(II) acetate as the oxidant, and 1 equiv of p-benzoquinone in tert-butyl alcohol gave ortho-arylated products in modest to excellent yields. This reaction shows good functional group compatibility. A series of H-1 NMR titration experiments and controlled experiments elucidating the reaction mechanism were carried out. The key intermediate, 4-methyl-N-phenylpyridin-2-amine palladacycle, was isolated and characterized by X-ray crystallography. The advanced transformations of ortho-phenylated 4-methyl-N-phenylpyridin-2-amine to N-(4-methylpyridin-2-yl)-9H-carbazole, biphenyl-2-amine, and 3-methyl-6-phenylpyrido[1,2-a]benzimidazole were successfully demonstrated as potential synthetic applications.