1-bromo-3-methyl-9H-carbazole | 387819-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-bromo-3-methyl-9H-carbazole
• 英文别名: 2-bromo-4-methylcarbazole
• CAS: 387819-80-9
• 化学式: C₁₃H₁₀BrN
• 分子量: 260.133
• InChiKey: GXEBCOGXCYLAGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  15.8
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-bromo-3-methyl-9H-carbazole 、 4-（甲磺酰基）苯硼酸 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 16.0h， 以22%的产率得到3-methyl-1-(4-methylsulfonylphenyl)-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-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

文献信息

• Synthesis of Carbazoles from <i>N</i>-(<i>N</i>,<i>N</i>-Diarylamino)phthalimides with Aluminum Chloride via Diarylnitrenium Ions
  作者：Yasuo Kikugawa、Yutaka Aoki、Takeshi Sakamoto

  DOI：10.1021/jo016124r

  日期：2001.12.1

  Generation of diarylnitrenium ions from N-(N,N-diarylamino)phthalimides by treatment with AlCl3 in benzene or in 1,2-dichloroethane leads to formation of carbazoles by intramolecular C-C bond formation. The reaction proceeds in synthetically useful yields.
• 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).
• 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.