Bis[2-(3,5-dimethylpyrazol-1-yl)phenyl]diazene | 78564-52-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: Bis[2-(3,5-dimethylpyrazol-1-yl)phenyl]diazene
• CAS: 78564-52-0
• 化学式: C₂₂H₂₂N₆
• 分子量: 370.457
• InChiKey: UQIPTJPZOVZBSB-UHFFFAOYSA-N

物化性质

• 熔点：
  181-182.5 °C(Solv: cyclohexane (110-82-7))
• 沸点：
  558.7±50.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  28
• 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-叠氮苯基)-3,5-二甲基吡唑 以 乙醇 为溶剂， 反应 0.13h， 生成 2-(3,5-二甲基-吡唑-1-基)-苯胺 、 1,3-二甲基-5H-吡唑并[1,2-a]苯并三唑-4-内盐 、 Bis[2-(3,5-dimethylpyrazol-1-yl)phenyl]diazene
  参考文献：
  名称：

  Photodecomposition of Some Para-Substituted 2-Pyrazolylphenyl Azides. Substituents Affect the Phenylnitrene S−T Gap More Than the Barrier to Ring Expansion

  摘要：

  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.

  DOI：

  10.1021/ja982585r

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
• Reactivity of Singlet and Triplet Arylnitrenes:  Temperature-Dependent Photodecomposition of 1-(2-Azidophenyl)-3,5-dimethylpyrazole
  作者：Angelo Albini、Gianfranco Bettinetti、Giovanna Minoli

  DOI：10.1021/ja970588i

  日期：1997.8.1

  gives 1,3-dimethylpyrazolobenzotriazole (6, by electrophilic cyclization of singlet nitrene 14) or, in the presence of diethylamine, aminoazepine 8 (by addition of the nucleophile and rearrangement). At lower temperatures, the yield of these products decreases and the azo derivative 9 (from the dimerization of triplet nitrene 34) as well as products from intramolecular radical cyclization (again via

  在 >200 K 时，1-(2-叠氮苯基)-3,5-二甲基吡唑 (5) 的光解得到 1,3-二甲基吡唑并苯并三唑 (6，通过单线态氮烯 14 的亲电环化) 或在二乙胺存在下，氨基氮杂 8 (通过添加亲核试剂和重排）。在较低温度下，这些产物的产率降低，并且获得偶氮衍生物 9（来自三线态氮烯 34 的二聚）以及分子内自由基环化（再次通过 34）的产物，成为 <100 K 时唯一的产物。通过分析产物分布的温度依赖性（ΔΔH⧧ = -10 kJ mol-1 和ΔΔS⧧ = 34 J mol-1 K-1 在乙醇中）确定了 14 和 34 反应的微分热力学参数。胺的添加可能需要预先扩环以得到脱氢氮杂卓12；
• Albini, Angelo; Bettinetti, Gianfranco; Minoli, Giovanna, Heterocycles, 1995, vol. 40, # 2, p. 597 - 606
  作者：Albini, Angelo、Bettinetti, Gianfranco、Minoli, Giovanna

  DOI：——

  日期：——
• 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.