6-diazo-2,4-cyclohexadien-1-imine | 106627-10-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6-diazo-2,4-cyclohexadien-1-imine
• 英文别名: 6-Diazocyclohexa-2,4-dien-1-imine；6-diazocyclohexa-2,4-dien-1-imine
• CAS: 106627-10-5
• 化学式: C₆H₅N₃
• 分子量: 119.126
• InChiKey: AFCCKCQYXXLOAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-diazo-2,4-cyclohexadien-1-imine 在 sodium hydroxide 、 sodium perchlorate 作用下， 生成 T406石油添加剂
  参考文献：
  名称：

  Photochemistry of 1H-Benzotriazole in Aqueous Solution:  A Photolatent Base

  摘要：

  Flash photolysis of 1H-benzobiazole (1) has shown that N-N bond fission occurs within a few picoseconds of excitation (248 nm) giving 6-diazo-2,4-cyclohexadien-1-imine (2), lambda(max) = 430 nm. Fluorescence and intersystem crossing do not compete measurably, and photodenitrogenation is a minor side reaction (<1%). The rate constant for recyclization in the ground state, 2 --> 1, is on the order of 2 x 10(9) s(-1) in aprotic solvents, and 3.2 x 10(7) s(-1) in aqueous solution. DFT calculations gave Delta(2-->1)G(double dagger) = 3.7 and Delta(2-->1)G(0) = -28.0 kcal mol(-1) for the activation and reaction free energies, respectively. Imine 2 is a moderately strong base, pK(a) = 12.7, that is protonated by water yielding 2-aminophenyl diazonium ion (2(+)), lambda(max) = 405 nm. The rate constant for cyclization of the cation, 2(+) --> 1 + H+, is k = 3 s(-1). The reversible photoreaction of 1 may be used to induce an upward pH jump in unbuffered water, or as a kinetic pH-indicator for the range of 6-12 in buffered solutions. An erroneous Value for the acidity constant of protonated 1 is corrected to pK(a)(1(+)) = 0.42 +/- 0.02 (I = 1.0 M). Several derivatives of 1 were also investigated.

  DOI：

  10.1021/ja994464c
• 作为产物：
  描述：

  T406石油添加剂 以 乙醚 、 乙醇 、 2-甲基丁烷 为溶剂， 生成 6-diazo-2,4-cyclohexadien-1-imine
  参考文献：
  名称：

  苯并三唑在酒精玻璃中在77 K下的光解

  摘要：

  DOI：

  10.1021/j100291a023

文献信息

• Kiszka, Mariusz; Dunkin, Ian R.; Gebicki, Jerzy, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 12, p. 2420 - 2426
  作者：Kiszka, Mariusz、Dunkin, Ian R.、Gebicki, Jerzy、Wang, Hong、Wirz, Jakob

  DOI：——

  日期：——
• Photolysis of benzotriazole in alcoholic glass at 77 K
  作者：Haruo. Shizuka、Hiroshi. Hiratsuka、Mamoru. Jinguji、Hiroyuki. Hiraoka

  DOI：10.1021/j100291a023

  日期：1987.3
• Photochemistry of 1<i>H</i>-Benzotriazole in Aqueous Solution:  A Photolatent Base
  作者：Hong Wang、Clemens Burda、Gaby Persy、Jakob Wirz

  DOI：10.1021/ja994464c

  日期：2000.6.1

  Flash photolysis of 1H-benzobiazole (1) has shown that N-N bond fission occurs within a few picoseconds of excitation (248 nm) giving 6-diazo-2,4-cyclohexadien-1-imine (2), lambda(max) = 430 nm. Fluorescence and intersystem crossing do not compete measurably, and photodenitrogenation is a minor side reaction (<1%). The rate constant for recyclization in the ground state, 2 --> 1, is on the order of 2 x 10(9) s(-1) in aprotic solvents, and 3.2 x 10(7) s(-1) in aqueous solution. DFT calculations gave Delta(2-->1)G(double dagger) = 3.7 and Delta(2-->1)G(0) = -28.0 kcal mol(-1) for the activation and reaction free energies, respectively. Imine 2 is a moderately strong base, pK(a) = 12.7, that is protonated by water yielding 2-aminophenyl diazonium ion (2(+)), lambda(max) = 405 nm. The rate constant for cyclization of the cation, 2(+) --> 1 + H+, is k = 3 s(-1). The reversible photoreaction of 1 may be used to induce an upward pH jump in unbuffered water, or as a kinetic pH-indicator for the range of 6-12 in buffered solutions. An erroneous Value for the acidity constant of protonated 1 is corrected to pK(a)(1(+)) = 0.42 +/- 0.02 (I = 1.0 M). Several derivatives of 1 were also investigated.