1-methyl-5-(4-methylbenzyl)-4-nitro-1H-pyrazole

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 1-methyl-5-(4-methylbenzyl)-4-nitro-1H-pyrazole
• 英文别名: 1-methyl-5-[(4-methylphenyl)methyl]-4-nitro-1H-pyrazole；1-Methyl-5-[(4-methylphenyl)methyl]-4-nitropyrazole；1-methyl-5-[(4-methylphenyl)methyl]-4-nitropyrazole
• 化学式: C₁₂H₁₃N₃O₂
• 分子量: 231.254
• InChiKey: VEGBZMFXSQBVIS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  63.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙酸对甲基苄酯 、 1-甲基-4-硝基吡唑 在 palladium diacetate 、 caesium carbonate 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 16.0h， 以74%的产率得到1-methyl-5-(4-methylbenzyl)-4-nitro-1H-pyrazole
  参考文献：
  名称：

  Palladium Catalyzed Arylation and Benzylation of Nitroarenes Using Aryl Sulfonates and Benzyl Acetates

  摘要：

  Pd-catalyzed arylation or benzylation of nitroazoles using aryl sulfonates or benzyl acetates is described. Electronically varied aryl tosylates and mesylates, as well as benzyl acetates, afford the arylated and benzylated products. Arylation of nitrobenzene is also reported. The relative rate for the arylation of halides is greater than that of tosylates using the reported reaction parameters. These studies enhance the scope of electrophiles for nitroarene arylations and benzylations, which was hitherto limited to the use of halide electrophiles.

  DOI：

  10.1021/acs.joc.7b00550

文献信息

• Catalytic C–H Allylation and Benzylation of Pyrazoles
  作者：Seri Bae、Ha-Lim Jang、Haeun Jung、Jung Min Joo

  DOI：10.1021/jo5025317

  日期：2015.1.2

  general approach for the synthesis of allylated and benzylated pyrazoles. An electron-withdrawing substituent, such as nitro, chloro, and ester groups, at C4 renders the Lewis basic nitrogen atom to be less basic and the C–H bond more acidic than the ones of the parent ring, enabling Pd-catalyzed C–H allylation and benzylation reactions of pyrazoles. The new method expanding the scope of the C–H functionalization

  我们描述了合成烯丙基化和苄基化吡唑的一般方法。C4上的吸电子取代基（例如硝基，氯和酯基）使路易斯碱性氮原子的碱性更低，而C–H键比母环的酸性更高，从而使Pd催化的C–吡唑的烯丙基化和苄基化反应。新方法将吡唑的CH–H官能化范围扩大到芳基化反应以外，从而使人们能够快速获得复杂的吡唑化合物。
• Palladium Catalyzed Arylation and Benzylation of Nitroarenes Using Aryl Sulfonates and Benzyl Acetates
  作者：Zubaoyi Yi、Yodit Aschenaki、Ryan Daley、Stephen Davick、Abigail Schnaith、Rylee Wander、Dipannita Kalyani

  DOI：10.1021/acs.joc.7b00550

  日期：2017.7.7

  Pd-catalyzed arylation or benzylation of nitroazoles using aryl sulfonates or benzyl acetates is described. Electronically varied aryl tosylates and mesylates, as well as benzyl acetates, afford the arylated and benzylated products. Arylation of nitrobenzene is also reported. The relative rate for the arylation of halides is greater than that of tosylates using the reported reaction parameters. These studies enhance the scope of electrophiles for nitroarene arylations and benzylations, which was hitherto limited to the use of halide electrophiles.