2-Azido-1-bromo-5-methyl-3-phenylbenzene | 1140969-79-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-Azido-1-bromo-5-methyl-3-phenylbenzene
• CAS: 1140969-79-4
• 化学式: C₁₃H₁₀BrN₃
• 分子量: 288.147
• InChiKey: IAYGUOWIYLCAIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  14.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Azido-1-bromo-5-methyl-3-phenylbenzene 在 dirhodium(II) tetrakis(perfluorobutyrate) 作用下， 以 甲苯 为溶剂， 反应 15.0h， 以85%的产率得到1-bromo-3-methyl-9H-carbazole
  参考文献：
  名称：

  Examination of the Mechanism of Rh₂(II)-Catalyzed Carbazole Formation Using Intramolecular Competition Experiments

  摘要：

  The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed, and correlation of the product ratios with Hammett sigma(+) values produced a plot with two intersecting lines with opposite rho values. These data suggest that electronic donation by the biaryl pi-system accelerates the formation of rhodium nitrenoid and that C-N bond formation occurs through a 4 pi-electron-5-atom electrocyclization.

  DOI：

  10.1021/jo901224k
• 作为产物：
  描述：

  2-bromo-4-methyl-6-phenylaniline 在 溶剂黄146 、 sodium nitrite 、 sodium azide 作用下， 以 水 为溶剂， 反应 1.0h， 以83%的产率得到2-Azido-1-bromo-5-methyl-3-phenylbenzene
  参考文献：
  名称：

  Rh₂(II)-Catalyzed Synthesis of Carbazoles from Biaryl Azides

  摘要：

  An array of carbazoles (23 examples) can be synthesized from substituted biaryl azides at 60 degrees C using substoichiometric quantities of Rh-2(O2CC3F7)(4) or Rh-2(O2CC7H15)(4).

  DOI：

  10.1021/jo9002536

文献信息

• Examination of the Mechanism of Rh₂(II)-Catalyzed Carbazole Formation Using Intramolecular Competition Experiments
  作者：Benjamin J. Stokes、Kathleen J. Richert、Tom G. Driver

  DOI：10.1021/jo901224k

  日期：2009.9.4

  The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed, and correlation of the product ratios with Hammett sigma(+) values produced a plot with two intersecting lines with opposite rho values. These data suggest that electronic donation by the biaryl pi-system accelerates the formation of rhodium nitrenoid and that C-N bond formation occurs through a 4 pi-electron-5-atom electrocyclization.
• Rh₂(II)-Catalyzed Synthesis of Carbazoles from Biaryl Azides
  作者：Benjamin J. Stokes、Brankica Jovanović、Huijun Dong、Kathleen J. Richert、Ryan D. Riell、Tom G. Driver

  DOI：10.1021/jo9002536

  日期：2009.4.17

  An array of carbazoles (23 examples) can be synthesized from substituted biaryl azides at 60 degrees C using substoichiometric quantities of Rh-2(O2CC3F7)(4) or Rh-2(O2CC7H15)(4).