2,2'-bis(pyrazol-1-yl)azobenzene | 1738-59-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: 2,2'-bis(pyrazol-1-yl)azobenzene
• 英文别名: o,o'-Di-(pyrazol-1-yl)-azobenzol；2,2'-Bis-pyrazolyl-(1)-azobenzol；2,2'-Dipyrazol-1-ylazobenzol；bis-(2-pyrazol-1-yl-phenyl)-diazene；Bis(2-pyrazol-1-ylphenyl)diazene
• CAS: 1738-59-6
• 化学式: C₁₈H₁₄N₆
• 分子量: 314.349
• InChiKey: ZFMKUPLNQLKBOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-(2-azidophenyl)pyrazole 在 二正丙胺 作用下， 以 乙腈 、 苯 为溶剂， 反应 4.67h， 生成 2,2'-bis(pyrazol-1-yl)azobenzene
  参考文献：
  名称：

  Chemistry of nitrenes generated by the photocleavage of both azides and a five-membered heterocycle

  摘要：

  Pyrazolo[1,2-a]benzotriazole and some of its derivatives (2a-c) are photochemically cleaved to form 2-(1-pyrazolyl)phenylnitrenes, which are also obtained through a more conventional path by photodecomposition of the pyrazolylphenyl azides (1a-c). Product studies and laser flash photolysis analysis of nitrenes from both sources show that there is competition between fast intramolecular reclosure to heterocycles 2 and rearrangement to dehydroazepines. The latter species are trapped by nucleophiles, or otherwise slowly rearrange back to the nitrenes (conformational factors affect these processes). The (quite unreactive) triplet nitrenes are identified spectroscopically and possibly are in equilibrium with the previous transients.

  DOI：

  10.1021/ja00018a032

文献信息

• Role of Conformation and Electronic Structure in the Chemistry of Ground and Excited State <i>o-</i>Pyrazolylphenylnitrenes
  作者：Claudio Carra、Thomas Bally、Angelo Albini

  DOI：10.1021/ja043988w

  日期：2005.4.1

  dehydroazepines (via benzoazirines) is calculated to be competitive in both nitrenes, but in the dimethyl derivative, 2b, attack onto the N lone pair (which is made more nucleophilic by the methyl groups) is favored. The higher barriers (by 4-8 kcal/mol) in singlet 2a cause 60-70% of this nitrene to decay by intersystem crossing to the triplet. Thus, the seemingly straightforward formation of benzo-fused

  单线态 2a 中较高的势垒（4-8 kcal/mol）导致 60-70% 的氮烯通过系统间穿过三线态而衰变。因此，通过单线态苯基硝烯对吡唑啉 N 孤对的分子内攻击看似直接形成苯并稠合杂环只能在有利的情况下克服扩环和分子间反应。相对持久的三线态氮烯以基质为特征，光环化产物的产率（主要是 2a 的吡唑并[1,5-a]苯并咪唑 (7) 和 5,6-二氢吡唑并[1,5-a] 喹喔啉 (8) 2b) 显示取决于起始叠氮化物和氮烯的优选构象。通过单线态苯基硝基对吡唑啉N孤对的分子内攻击，看似直接形成苯并稠合杂环只能在有利条件下克服扩环和分子间反应。相对持久的三线态氮烯以基质为特征，光环化产物的产率（主要是来自 2a 的吡唑并[1,5-a]苯并咪唑 (7) 和来自 5,6-二氢吡唑并[1,5-a] 喹喔啉 (8) 2b) 显示取决于起始叠氮化物和氮烯的优选构象。通过单线态苯基硝基对吡唑啉N孤对的分子内攻