N-methyl-N-[(Z)-pentan-2-ylideneamino]aniline | 133165-88-5

• 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: N-methyl-N-[(Z)-pentan-2-ylideneamino]aniline
• CAS: 133165-88-5
• 化学式: C₁₂H₁₈N₂
• 分子量: 190.288
• InChiKey: MDILTYBFOOKMJR-QBFSEMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-N-[(Z)-pentan-2-ylideneamino]aniline 在 环丁砜 、 甲烷磺酸 、 phosphorus pentoxide 作用下， 生成 3-ethyl-1,2-dimethylindole 、 N-methyl-2-propylindole
  参考文献：
  名称：

  Mechanistic studies of the Fischer indole reaction

  摘要：

  Kinetic and solvent isotope effects were measured for the Fischer indole reactions of four hydrazones. Under neat acid conditions (5 % P2O5/ MeSO3H) the KIE's ranged from 3.2 to 5.8, while the solvent isotope effects (k(H)/k(D)) ranged from 0.4 to 0.7. Under dilute acid conditions in sulfolane solvent, both isotope effects were near unity. The large kinetic isotope effect and large inverse solvent isotope effect, along with the observation that isotopic exchange occurs in the aromatic ring of the hydrazones, suggest that a preequilibrium protonation of the aromatic ring occurs followed by the rate-determining ene-hydrazine formation under the neat acid conditions. In contrast, under the dilute acid conditions, the lack of isotope effects and the lack of ring isotope exchange indicate that no ring protonation is occurring, that ene-hydrazine formation is no longer rate-determining, and that the rate-limiting step is now most likely the [3,3] rearrangement.

  DOI：

  10.1021/jo00053a041

文献信息

• Mechanistic studies of the Fischer indole reaction
  作者：David L. Hughes、Dalian Zhao

  DOI：10.1021/jo00053a041

  日期：1993.1

  Kinetic and solvent isotope effects were measured for the Fischer indole reactions of four hydrazones. Under neat acid conditions (5 % P2O5/ MeSO3H) the KIE's ranged from 3.2 to 5.8, while the solvent isotope effects (k(H)/k(D)) ranged from 0.4 to 0.7. Under dilute acid conditions in sulfolane solvent, both isotope effects were near unity. The large kinetic isotope effect and large inverse solvent isotope effect, along with the observation that isotopic exchange occurs in the aromatic ring of the hydrazones, suggest that a preequilibrium protonation of the aromatic ring occurs followed by the rate-determining ene-hydrazine formation under the neat acid conditions. In contrast, under the dilute acid conditions, the lack of isotope effects and the lack of ring isotope exchange indicate that no ring protonation is occurring, that ene-hydrazine formation is no longer rate-determining, and that the rate-limiting step is now most likely the [3,3] rearrangement.