1-(2-叠氮苯基)-3,5-二甲基吡唑 | 78564-50-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 1-(2-叠氮苯基)-3,5-二甲基吡唑
• 英文名称: 1-(2′-azidophenyl)-3,5-dimethylpyrazole
• 英文别名: 1-(2'-azidophenyl)-3,5-dimethypyrazole；1-(2-azidophenyl)-3,5-dimethylpyrazole；1-(2-Azidophenyl)-3,5-dimethyl-1H-pyrazole
• CAS: 78564-50-8
• 化学式: C₁₁H₁₁N₅
• 分子量: 213.242
• InChiKey: JOFVMQNMOWGHJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  32.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(2-叠氮苯基)-3,5-二甲基吡唑 以 环己烷 为溶剂， 反应 0.5h， 以53%的产率得到1,3-二甲基-5H-吡唑并[1,2-a]苯并三唑-4-内盐
  参考文献：
  名称：

  DIMETHYLBENZOPYRAZOLOTRIAZOLE vs METHYLPYRAZOLOQUINOXALINE FROM 3,5-DIMETHYL-1-(2-NITRENOPHENYL)PYRAZOLE

  摘要：

  研究了 3,5-二甲基-1-(2-硝基苯基)吡唑的单重态和三重态的化学性质。研究发现，分子内电子传递在决定单重态容易反应生成(VII)矢尔和三重态 "懒惰 "方面起着关键作用。

  DOI：

  10.1246/cl.1981.331
• 作为产物：
  描述：

  3,5-二甲基-1-(2-亚硝基苯基)吡唑 在 sodium azide 作用下， 以 溶剂黄146 为溶剂， 反应 14.0h， 以73%的产率得到1-(2-叠氮苯基)-3,5-二甲基吡唑
  参考文献：
  名称：

  Albini, Angelo; Bettinetti, Gianfranco; Minoli, Giovanna, Journal of the Chemical Society. Perkin transactions I, 1983, p. 581 - 585

  摘要：

  DOI：

文献信息

• Cobalt and Nickel Complexes Bearing Pyrazolyliminophosphorane Ligands: Synthesis, Characterisation and Catalytic Ethylene Oligomerisation Behaviour
  作者：Cheng Zhang、Wen‐Hua Sun、Zhong‐Xia Wang

  DOI：10.1002/ejic.200600651

  日期：2006.12

  were further characterised by single-crystal X-ray diffraction techniques. Complexes 5-13 are active catalysts for ethylene oligomerisation upon activation with alkylaluminium derivatives (Et2AlCl, MAO or MMAO). These complexes exhibit good to high catalytic activities (up to 3.54 x 10(6) g mol(-1) h atm for the nickel complexes and 5.48 x 10(5) g mol(-1) h atm for the cobalt complexes). The effects of

  分别用 Ph2PR (R = Ph, Me) 和 (Ph2P)(2)CH2 处理 1-(2'-叠氮苯基)-3,5-二甲基吡唑 (1)，得到吡唑基氨基膦 2、3 和 4。 2 或 3 与 [NiCl2(dme)] 或 NiBr2 产生 N,N-螯合镍配合物 5-8，以及 CoCl2 配合物 9 和 10。4 分别与 [NiCl2(dme)]、NiBr2 和 CoCl2 反应，提供 N,N,P-螯合物 11-13。化合物2-4通过H-1、C-13、P-31核磁共振和红外光谱和元素分析表征，而配合物5-13通过红外光谱和元素分析表征。通过单晶 X 射线衍射技术进一步表征了配合物 5、9 和 12 的结构。配合物 5-13 是用烷基铝衍生物（Et2AlCl、MAO 或 MMAO）活化后用于乙烯低聚的活性催化剂。这些配合物表现出良好的高催化活性（镍配合物高达 3.54 x 10(6) g mol(-1)
• 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；
• Heteropentalenes. The thermal addition of 1,3-dimethylpyrazolo-[1,2-a]benzotriazole to dimethyl acetylenedicarboxylate
  作者：Angelo Albini、Gianfranco Bettinetti、Giovanna Minoli

  DOI：10.1039/p19830002491

  日期：——

  compound (3) reacts with dimethyl acetylenedicarboxylate with addition onto the azomethinimine moiety to give dimethyl 2a,4-dimethyl-4a,8b,8c-triazapentaleno[1,6-ab]indene-1,2-dicarboxylate (7)via a zwitterionic intermediate which can be trapped by protic solvents, e.g. methanol or water to give dimethyl 2-[o-(3,5-dimethylpyrazol-1-yl)anilino]-3-methoxymaleate (8) or tetramethyl 3,3′-bis-[o-(3,5-dimeth

  标题化合物（3）与乙炔二羧酸二甲酯反应，并加到偶氮甲亚胺部分上，得到经由（7）的2a，4-二甲基-4a，8b，8c-三氮杂戊烯二烯[1，6- ab ]茚-1,2-二羧酸二甲酯（7）。一种两性离子中间体，可被质子溶剂（例如甲醇或水）捕获，得到2- [ o-（3,5-二甲基吡唑-1-基）苯胺基] -3-甲氧基马来酸二甲酯（8）或四甲基3,3'-双-[邻-（3,5-二甲基吡唑-1-基）苯胺基] -2,2'-氧二马来酸酯（9）。环加合物（7）自发逆向加成至甲基3-甲基吡唑并[1,2- a]苯并三唑-1,2-二羧酸酯（12）和自由基裂解，出乎意料地得到4,5-二氢-2-甲基-4-氧杂吡唑并-[2,3 - a ]喹喔啉-3-羧酸甲酯（17）主要产品，以及少量的两种苯并三唑基戊烯酮（14）和（15）。
• 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.