1-(Diazonioiminomethyl)-4-methoxybenzene | 132645-95-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(Diazonioiminomethyl)-4-methoxybenzene
• 英文别名: 1-(diazonioiminomethyl)-4-methoxybenzene
• CAS: 132645-95-5
• 化学式: C₈H₈N₃O
• 分子量: 162.171
• InChiKey: LFTXEGSJCIYACK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  49.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(Diazonioiminomethyl)-4-methoxybenzene 在 高氯酸 、 水 作用下， 以 乙腈 为溶剂， 生成 diazido(4-methoxyphenyl)methane
  参考文献：
  名称：

  Richard, John P.; Amyes, Tina L.; Jagannadham, Vandanapu, Journal of the American Chemical Society, 1995, vol. 117, # 19, p. 5198 - 5205

  摘要：

  DOI：
• 作为产物：
  描述：

  diazido(4-methoxyphenyl)methane 在 sodium perchlorate 、 水 作用下， 以 various solvent(s) 为溶剂， 生成 1-(Diazonioiminomethyl)-4-methoxybenzene
  参考文献：
  名称：

  Amyes, Tina L.; Richard, John P., Journal of the American Chemical Society, 1991, vol. 113, # 5, p. 1867 - 1869

  摘要：

  DOI：

文献信息

• The effects of .alpha.-substituents on the kinetic and thermodynamic stability of 4-methoxybenzyl carbocations: carbocation lifetimes that are independent of their thermodynamic stability
  作者：Tina L. Amyes、Ishmael W. Stevens、John P. Richard

  DOI：10.1021/jo00074a036

  日期：1993.10

  The following new rate constants for reaction of alpha-substituted 4-methoxybenzyl carbocations, 4-MeOC6H4CR1(R2)+, With a solvent of 50:50 (v/v) trifluoroethanol/water at 25-degrees-C and ionic strength 0.50 (NaClO4) are reported: 4-MeOC6H4CH(OMe)+, k(S) = 2.2 X 10(7) s-1; 4-MeOC6H4CH(N3)+, k(S) = 3.3 X 10(5) s-1; 4-MeOC6H4C(CH3)2+, k(S) = 1.3 x 10(7) s-1; 4-MeOC6H4CH(CO2Et)+, k(S) = 1.4 X 10(7) s-1; 4-MeOC6H4CCH3(CF3)+, k(S) = 2.5 x 10(7) s-1. The values of k(S) for reaction of 4-MeOC6H4CR1(R2)+ with 50:50 (v/v) trifluoroethanol/water are nearly independent of very large changes in the thermodynamic stability of these carbocations caused by the addition of a wide range of electron-withdrawing or electron-donating groups at the alpha-position. In the most extreme case, the change from an alpha-methoxy to two alpha-(trifluoromethyl) substituents leads to a 23 kcal/mol thermodynamic destabilization of 4-MeOCrH4CR1(R2)+ relative to the neutral azide ion adducts but a 5-fold decrease in its reactivity toward solvent. The data show that the effects of alpha-substituents on the kinetic stability of 4-MeOC6H4CR1(R2)+ are complex and do not parallel the thermodynamic stability of these carbocations. The results are explained by consideration of the polar and resonance effects of the alpha-substituents on both the thermodynamic driving force and the intrinsic barrier for capture of the carbocations by solvent. These reactions are a new example of the consequences of the ''principle of nonperfect synchronization''.41