Phenyl-2-azaallenium-ion | 82880-17-9

• 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: Phenyl-2-azaallenium-ion
• 英文别名: N-Methylidene(phenyl)methaniminium；benzylidene(methylidene)azanium
• CAS: 82880-17-9
• 化学式: C₈H₈N
• 分子量: 118.158
• InChiKey: JXWUSCZKOXGWML-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Phenyl-2-azaallenium-ion 在 水 作用下， 以 乙腈 为溶剂， 生成 Benzalaminomethanol
  参考文献：
  名称：

  [3 + 2] Cycloadditions and Protonation by Alcohols of Photochemically Generated Nitrile Ylides from 2H-Azirines. Formation and Reactivities of Azaallenium Cations

  摘要：

  On photolysis of 2H-phenylazirines id acetonitrile or alcohol solution with 248 nm laser light, phenylnitrile ylides are formed by heterolytic cleavage of the C-C bond of the azirines. The absorption spectra of the ylides are characterized by two strong bands, at ca. 240 and 280 nm, and a weak band, at 380 nm. Electron-deficient olefins react with the nitrile ylides by 1,3-dipolar cycloaddition to yield 5-membered N-heterocycles (rate constants between 4 x 10(5) and 7 x 10(9) M-1 s(-1), the Hammett-p value for the para-substituent on the phenyl ring is -0.9). In alcohols as solvents, the nitrile ylides are protonated to yield azaallenium cations, whose spectroscopic properties and reactivities with nucleophiles are described. The protonation rates of the ylides in alcohols increase with the acidity of the alcohol. On the basis of the large kinetic isotope effect for protonation of ylide by alcohol (k(H)/k(D) = 5.5), the transition state for the ylide protonation is concluded to be linear.

  DOI：

  10.1021/ja971648n
• 作为产物：
  描述：

  phenyl nitrile ylide 在 水 作用下， 以 乙腈 为溶剂， 生成 Phenyl-2-azaallenium-ion
  参考文献：
  名称：

  [3 + 2] Cycloadditions and Protonation by Alcohols of Photochemically Generated Nitrile Ylides from 2H-Azirines. Formation and Reactivities of Azaallenium Cations

  摘要：

  On photolysis of 2H-phenylazirines id acetonitrile or alcohol solution with 248 nm laser light, phenylnitrile ylides are formed by heterolytic cleavage of the C-C bond of the azirines. The absorption spectra of the ylides are characterized by two strong bands, at ca. 240 and 280 nm, and a weak band, at 380 nm. Electron-deficient olefins react with the nitrile ylides by 1,3-dipolar cycloaddition to yield 5-membered N-heterocycles (rate constants between 4 x 10(5) and 7 x 10(9) M-1 s(-1), the Hammett-p value for the para-substituent on the phenyl ring is -0.9). In alcohols as solvents, the nitrile ylides are protonated to yield azaallenium cations, whose spectroscopic properties and reactivities with nucleophiles are described. The protonation rates of the ylides in alcohols increase with the acidity of the alcohol. On the basis of the large kinetic isotope effect for protonation of ylide by alcohol (k(H)/k(D) = 5.5), the transition state for the ylide protonation is concluded to be linear.

  DOI：

  10.1021/ja971648n

文献信息

• [3 + 2] Cycloadditions and Protonation by Alcohols of Photochemically Generated Nitrile Ylides from 2<i>H</i>-Azirines. Formation and Reactivities of Azaallenium Cations
  作者：Evelyn Albrecht、Jochen Mattay、Steen Steenken

  DOI：10.1021/ja971648n

  日期：1997.12.1

  On photolysis of 2H-phenylazirines id acetonitrile or alcohol solution with 248 nm laser light, phenylnitrile ylides are formed by heterolytic cleavage of the C-C bond of the azirines. The absorption spectra of the ylides are characterized by two strong bands, at ca. 240 and 280 nm, and a weak band, at 380 nm. Electron-deficient olefins react with the nitrile ylides by 1,3-dipolar cycloaddition to yield 5-membered N-heterocycles (rate constants between 4 x 10(5) and 7 x 10(9) M-1 s(-1), the Hammett-p value for the para-substituent on the phenyl ring is -0.9). In alcohols as solvents, the nitrile ylides are protonated to yield azaallenium cations, whose spectroscopic properties and reactivities with nucleophiles are described. The protonation rates of the ylides in alcohols increase with the acidity of the alcohol. On the basis of the large kinetic isotope effect for protonation of ylide by alcohol (k(H)/k(D) = 5.5), the transition state for the ylide protonation is concluded to be linear.