2,2'-bis(3,5-dimethylpyrazolyl)-4,4'-dichloroazobenzene | 134817-11-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2,2'-bis(3,5-dimethylpyrazolyl)-4,4'-dichloroazobenzene
• 英文别名: Bis[4-chloro-2-(3,5-dimethylpyrazol-1-yl)phenyl]diazene
• CAS: 134817-11-1
• 化学式: C₂₂H₂₀Cl₂N₆
• 分子量: 439.347
• InChiKey: FMFJRSMPVYHTHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 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-叠氮-5-氯苯基)-3,5-二甲基吡唑 以 乙腈 为溶剂， 反应 0.67h， 以5%的产率得到2,2'-bis(3,5-dimethylpyrazolyl)-4,4'-dichloroazobenzene
  参考文献：
  名称：

  Albini, Angelo; Bettinetti, Gianfranco; Minoli, Giovanna, Heterocycles, 1995, vol. 40, # 2, p. 597 - 606

  摘要：

  DOI：

文献信息

• Photodecomposition of Some Para-Substituted 2-Pyrazolylphenyl Azides. Substituents Affect the Phenylnitrene S−T Gap More Than the Barrier to Ring Expansion
  作者：Angelo Albini、Gianfranco Bettinetti、Giovanna Minoli

  DOI：10.1021/ja982585r

  日期：1999.4.1

  A series of para-substituted (H, Me, Cl, F, CF3, OMe, NMe2) phenyl azides bearing a dimethylpyrazolyl group in position 2 allowing intramolecular trapping of singlet nitrene have been photolyzed at both 295 and 90 K in ethanol. For three significant models (H, CF3, NMe2), the reaction has been further studied in the presence of diethylamine (DEA) and of oxygen. With all substituents but NMe2, singlet nitrene (trapped intramolecularly to give pyrazolobenzotriazoles) and didehydroazepine (trapped with DEA to give 5H-azepines and then rearranging to 3H-azepines) are in equilibrium. With the NMe2 derivative, the nonelectrophilic singlet is not trapped, while DEA adds to the benzoazirine, the precursor of the didehydroazepine. Thus, electronic effects do not hinder the equilibrium between singlet nitrene and its cyclic isomers, while determining which of the above intermediates decays to a stable end product. The electron-donating group NMe2 has a second important effect, causing a drastic enhancement of the triplet nitrene energy and reduction of the S-T gap, so that triplet nitrene is also in equilibrium with the singlet and the benzoazirine. As for triplet nitrenes,these have been characterized in matrix at 90 K, and the competition between dimerization (to give;azo compounds, as typical of such stabilized species) and hydrogen abstraction from the solvent (involving a sizable barrier) has been studied. The energetic p-dimethylamino triplet undergoes hydrogen abstraction exclusively. When present, oxygen adds efficiently to all of the nitrenes, giving a nitroso oxide, Likewise characterized in the matrix, which then converts to the nitroso and nitro,derivatives in good yields. Photochemical excitation of the triplet in matrix leads to intramolecular hydrogen abstraction.
• Chemistry of nitrenes generated by the photocleavage of both azides and a five-membered heterocycle
  作者：A. Albini、G. Bettinetti、G. Minoli

  DOI：10.1021/ja00018a032

  日期：1991.8

  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.