methyl 3,4,5-triphenyl-4H-pyrazole-4-carboxylate | 53870-17-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: methyl 3,4,5-triphenyl-4H-pyrazole-4-carboxylate
• 英文别名: Methyl-3,4,5-triphenyl-4H-pyrazol-4-carboxylat；3,4,5-triphenyl-4H-pyrazole-4-carboxylic acid methyl ester；3,4,5-Triphenyl-4H-pyrazol-4-carbonsaeure-methylester；Methyl 3,4,5-triphenyl-4H-pyrazole-4-carboxylate；methyl 3,4,5-triphenylpyrazole-4-carboxylate
• CAS: 53870-17-0
• 化学式: C₂₃H₁₈N₂O₂
• 分子量: 354.408
• InChiKey: IHZWDIZHTRZXFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  51
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3,4,5-triphenyl-4H-pyrazole-4-carboxylate 以 苯 为溶剂， 反应 2.0h， 以61%的产率得到1-methyl-3,4,5-triphenyl-1H-pyrazole
  参考文献：
  名称：

  Thermal and acid-catalyzed transformations of 3H-pyrazoles obtained from diphenyldiazomethane and methyl phenylpropiolate

  摘要：

  Reaction of diphenyldiazomethane with methyl phenylpropiolate in diethyl ether alongside the expected methyl triphenyl-3H-pyrazole-4- and -5-carboxylates (I and II) (38 and 24%) gave rise also to 8% of methyl 3,5-diphenyl- 1-(1-ethoxyethyl)-1H-pyrazole-4-carboxylate. The main thermolysis product obtained from 4-methoxycarbonyl derivative I was methyl 1,3,5-triphenyl-1H-pyrazole-4-carboxylate, whereas from regioisomer II formed predominantly methyl 4,4,5-triphenyl-4H-pyrazole-3-carboxylate and 1-methoxycarbonyl-2,3,3-triphenylcyclopropene that was a minor product of 3H-pyrazole I thermolysis. Addition of concn. H2SO4 to the solutions of methyl triphenyl-3H-pyrazole-4- and -5-carboxylates in AcOH resulted in fast regioselective isomerization of the 3H-pyrazole derivatives into the corresponding 4H-pyrazoles.

  DOI：

  10.1134/s1070428007020145
• 作为产物：
  描述：

  3.3.5-Triphenyl-pyrazolenin-carbonsaeure-(4)-methylester 生成 methyl 3,4,5-triphenyl-4H-pyrazole-4-carboxylate
  参考文献：
  名称：

  在含C 4和C 5的吸电子取代基的3,3-二苯基-3 H-吡唑系列中，热和酸催化的范Alphen–Hüttel重排的区域选择性的相似性和差异

  摘要：

  在5位上带有吸电子取代基的3,3-Diphenyl-3 H-吡唑类化合物也经历了VanAlphen-Hüttel重排，在非质子溶剂（苯，甲苯）中加热时，一个苯基迁移至C 4如在催化量的浓硫酸存在下于20℃保持在乙酸中。在相似条件下，C 4上具有强吸电子基团（磺基或氰基）的3,3-二苯基-3 H-吡唑通过一个苯基向N 2的迁移异构化为1 H-吡唑。如果在4-位存在一个适度的吸电子取代基（烷氧基羰基或乙酰基），则酸催化的苯基迁移主要针对C 4原子，而热迁移则针对N 2。有人提出了观察到的热和酸催化的范·阿尔芬-赫特尔重排的区域选择性相似和不同的可能原因。

  DOI：

  10.1134/s1070428018070138

文献信息

• van Alphen, Recueil des Travaux Chimiques des Pays-Bas, 1943, vol. 62, p. 491,492, 495
  作者：van Alphen

  DOI：——

  日期：——
• Thermal and acid-catalyzed transformations of 3H-pyrazoles obtained from diphenyldiazomethane and methyl phenylpropiolate
  作者：A. A. Fedorov、Sh. E. Duisenbaev、V. V. Razin、M. A. Kuznetsov、E. Linden

  DOI：10.1134/s1070428007020145

  日期：2007.2

  Reaction of diphenyldiazomethane with methyl phenylpropiolate in diethyl ether alongside the expected methyl triphenyl-3H-pyrazole-4- and -5-carboxylates (I and II) (38 and 24%) gave rise also to 8% of methyl 3,5-diphenyl- 1-(1-ethoxyethyl)-1H-pyrazole-4-carboxylate. The main thermolysis product obtained from 4-methoxycarbonyl derivative I was methyl 1,3,5-triphenyl-1H-pyrazole-4-carboxylate, whereas from regioisomer II formed predominantly methyl 4,4,5-triphenyl-4H-pyrazole-3-carboxylate and 1-methoxycarbonyl-2,3,3-triphenylcyclopropene that was a minor product of 3H-pyrazole I thermolysis. Addition of concn. H2SO4 to the solutions of methyl triphenyl-3H-pyrazole-4- and -5-carboxylates in AcOH resulted in fast regioselective isomerization of the 3H-pyrazole derivatives into the corresponding 4H-pyrazoles.
• Similarity and Differences in the Regioselectivities of Thermal and Acid-Catalyzed van Alphen–Hüttel Rearrangements in the Series of 3,3-Diphenyl-3H-pyrazoles Containing Electron-Withdrawing Substituents on C4 and C5
  作者：V. A. Vasin、V. V. Razin、E. V. Bezrukova

  DOI：10.1134/s1070428018070138

  日期：2018.7

  Alphen–Hüttel rearrangement with migration of one phenyl group to C4 on heating in an aprotic solvent (benzene, toluene), as well as on keeping at 20°C in acetic acid in the presence of a catalytic amount of concentrated sulfuric acid. Under similar conditions, 3,3-diphenyl-3H-pyrazoles with a strong electronwithdrawing group (sulfo or cyano) on C4 isomerize to 1H-pyrazoles via migration of one phenyl group to

  在5位上带有吸电子取代基的3,3-Diphenyl-3 H-吡唑类化合物也经历了VanAlphen-Hüttel重排，在非质子溶剂（苯，甲苯）中加热时，一个苯基迁移至C 4如在催化量的浓硫酸存在下于20℃保持在乙酸中。在相似条件下，C 4上具有强吸电子基团（磺基或氰基）的3,3-二苯基-3 H-吡唑通过一个苯基向N 2的迁移异构化为1 H-吡唑。如果在4-位存在一个适度的吸电子取代基（烷氧基羰基或乙酰基），则酸催化的苯基迁移主要针对C 4原子，而热迁移则针对N 2。有人提出了观察到的热和酸催化的范·阿尔芬-赫特尔重排的区域选择性相似和不同的可能原因。