ethyl 5-methyl-1-p-tolyl-1H-pyrazole-3-carboxylate | 840-34-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: ethyl 5-methyl-1-p-tolyl-1H-pyrazole-3-carboxylate
• 英文别名: 5-Methyl-1-p-tolyl-pyrazol-3-carbonsaeure-aethylester；ethyl 1-(4-methylphenyl)-5-methyl-pyrazole-3-carboxylate；5-methyl-1-p-tolyl-1H-pyrazole-3-carboxylic acid ethyl ester；5-Methyl-1-p-tolyl-1h-pyrazole-3-carboxylic acid ethyl ester；ethyl 5-methyl-1-(4-methylphenyl)pyrazole-3-carboxylate
• CAS: 840-34-6
• 化学式: C₁₄H₁₆N₂O₂
• 分子量: 244.293
• InChiKey: GUVWBEXEDKHUSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  44.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 5-methyl-1-p-tolyl-1H-pyrazole-3-carboxylate 在 dipotassium peroxodisulfate 、 palladium diacetate 作用下， 以 三氟乙酸 、 三氟乙酸酐 为溶剂， 反应 12.0h， 以73%的产率得到ethyl 1-(2-hydroxy-4-methylphenyl)-5-methyl-1H-pyrazole-3-carboxylate
  参考文献：
  名称：

  Palladium-Catalyzed Chelation-Assisted Regioselective Oxidative Dehydrogenative Homocoupling/Ortho-Hydroxylation in N-Phenylpyrazoles

  摘要：

  A palladium-catalyzed pyrazole-directed regioselective oxidative C(sp2)-H functionalization of the N-phenyl ring in N-phenylpyrazoles to afford either a biaryl bis-pyrazole (via dehydrogenative homocoupling) or N-(o-hydroxyphenyl)pyrazole (via C-H oxygenation) or their mixture is described. The substitutions on the N-phenyl ring and the pyrazole ring and the dilution of the reaction medium with respect to the TFA/TFAA mixture (substrate concentration) have a remarkable influence on the outcome of the reaction. It was discovered that if the reactions were performed under highly dilute conditions (ca. 10 times) then N-(o-hydroxyphenyl)pyrazoles were the major or the sole products.

  DOI：

  10.1021/acs.joc.5b00733
• 作为产物：
  描述：

  乙酰丙酮酸乙酯 、 对甲基苯肼 以 乙醇 为溶剂， 反应 1.0h， 以50%的产率得到ethyl 5-methyl-1-p-tolyl-1H-pyrazole-3-carboxylate
  参考文献：
  名称：

  通过吡唑N-杂环卡宾的重排官能化的4-氨基喹啉

  摘要：

  消旋甜菜碱类物质中的1-苯基吡唑-3-羧酸盐的热脱羧反应生成吡唑-N-杂环卡宾，其立即重排成多个取代的4-氨基喹啉（参见方案）。这些物质对于杂环和药理活性化合物的合成是令人感兴趣的。

  DOI：

  10.1002/anie.200905436

文献信息

• Palladium-Catalyzed Chelation-Assisted Regioselective Oxidative Dehydrogenative Homocoupling/<i>Ortho</i>-Hydroxylation in <i>N</i>-Phenylpyrazoles
  作者：Harikrishna Batchu、Soumya Bhattacharyya、Ruchir Kant、Sanjay Batra

  DOI：10.1021/acs.joc.5b00733

  日期：2015.8.7

  A palladium-catalyzed pyrazole-directed regioselective oxidative C(sp2)-H functionalization of the N-phenyl ring in N-phenylpyrazoles to afford either a biaryl bis-pyrazole (via dehydrogenative homocoupling) or N-(o-hydroxyphenyl)pyrazole (via C-H oxygenation) or their mixture is described. The substitutions on the N-phenyl ring and the pyrazole ring and the dilution of the reaction medium with respect to the TFA/TFAA mixture (substrate concentration) have a remarkable influence on the outcome of the reaction. It was discovered that if the reactions were performed under highly dilute conditions (ca. 10 times) then N-(o-hydroxyphenyl)pyrazoles were the major or the sole products.
• Functionalized 4-Aminoquinolines by Rearrangement of Pyrazole N-Heterocyclic Carbenes
  作者：Andreas Schmidt、Niels Münster、Andrij Dreger

  DOI：10.1002/anie.200905436

  日期：2010.4.1

  Thermal decarboxylation of 1‐phenylpyrazolium‐3‐carboxylates from the mesomeric betaine class of substances leads to pyrazole‐N‐heterocyclic carbenes, which immediately rearrange to multiply substituted 4‐aminoquinolines (see scheme). These species are of interest for the synthesis of heterocycles and pharmacologically active compounds.

  消旋甜菜碱类物质中的1-苯基吡唑-3-羧酸盐的热脱羧反应生成吡唑-N-杂环卡宾，其立即重排成多个取代的4-氨基喹啉（参见方案）。这些物质对于杂环和药理活性化合物的合成是令人感兴趣的。