1-(3-benzoyl-1H-pyrazol-5-yl)ethan-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(3-benzoyl-1H-pyrazol-5-yl)ethan-1-one
• 英文别名: 1-(5-benzoyl-1(2)H-pyrazol-3-yl)-ethanone；1-(5-Benzoyl-1(2)H-pyrazol-3-yl)-aethanon；NoName_1062；1-(5-benzoyl-1H-pyrazol-3-yl)ethanone
• 化学式: C₁₂H₁₀N₂O₂
• 分子量: 214.224
• InChiKey: HSLXHRLWFVEJDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-二氮杂-1-苯乙酮 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 苯 为溶剂， 反应 10.0h， 生成 1-(3-benzoyl-1H-pyrazol-5-yl)ethan-1-one
  参考文献：
  名称：

  Synthesis and Relative Stability of 3,5-Diacyl-4,5-dihydro-1H-pyrazoles Prepared by Dipolar Cycloaddition of Enones and α-Diazoketones

  摘要：

  An unusual reaction process that produced unexpected heterocyclic systems by a fragmentation-recombination mechanism is described. Thus treatment of the triketone, 3-acetyl-2,6-heptanedione, 1, with methanesulfonyl azide gave, in addition to the expected alpha-diazo ketone 3a, the dihydropyrazole 3c and its oxidation product, the pyrazole 3d. We propose that the initially formed alpha-diazo ketone 3a fragments into the simple alpha-diazomethyl ketone and methyl vinyl ketone which then undergo an intermolecular [2,3]-dipolar cycloaddition. Analogous treatment of the trifluoromethyl trione 2 again afforded a pyrazole 4c. Further experiments were carried out to lend evidence to our mechanistic hypothesis. Thus alpha-diazoacetophenone 5 and MVK underwent a [2,3]-dipolar cycloaddition under mild conditions to give the two regioisomeric dihydropyrazoles 6a and 6b. Interestingly these were formed in a 2:1 ratio, which suggested that 6a was more stable than 6b. The structures of 6a and 6b were optimized by using the B3LYP density functional method and the 6-31G* basis set and isomer 6a was predicted to be 1.5 kcal/mol more stable than isomer 6b. This energy difference could be rationalized by the greater capacity of the acetyl group than the benzoyl group to conjugate with the hydrazone. This difference in conjugation is reflected by key bond length differences. Thus we have discovered a novel fragmentation-cycloaddition process. We have also presented evidence for the mechanism of the formation of the dihydropyrazoles and carried out calculations to support these findings.

  DOI：

  10.1021/jo048741w

文献信息

• Metal-free C–C, C–O, C–S and C–N bond formation enabled by SBA-15 supported TFMSA
  作者：Xiangyan Yi、Jiajun Feng、Fei Huang、Jonathan Bayldon Baell

  DOI：10.1039/c9cc08389h

  日期：——

  The intermolecular C–C, C–O, C–S and C–N bonds construction between diazo compounds and acyclic, cyclic 1,3-dicarbonyl compounds, thiophenol, alkynes were developed by using a TFMSA@SBA-15, providing a metal-free and eco-friendly platform.

  通过使用TFMSA@SBA-15，发展了二氮化合物与无环、环状1,3-二羰基化合物、硫酚、炔烃之间的分子间C–C、C–O、C–S和C–N键的构建，提供了一个无金属、环保的平台。
• Kotschetkow et al., Zhurnal Obshchei Khimii, 1959, vol. 29, p. 2964,2968; engl. Ausg. S. 2927, 2930
  作者：Kotschetkow et al.

  DOI：——

  日期：——
• Synthesis and Relative Stability of 3,5-Diacyl-4,5-dihydro-1<i>H</i>-pyrazoles Prepared by Dipolar Cycloaddition of Enones and α-Diazoketones
  作者：Michael E. Jung、Sun-Joon Min、K. N. Houk、Daniel Ess

  DOI：10.1021/jo048741w

  日期：2004.12.1

  An unusual reaction process that produced unexpected heterocyclic systems by a fragmentation-recombination mechanism is described. Thus treatment of the triketone, 3-acetyl-2,6-heptanedione, 1, with methanesulfonyl azide gave, in addition to the expected alpha-diazo ketone 3a, the dihydropyrazole 3c and its oxidation product, the pyrazole 3d. We propose that the initially formed alpha-diazo ketone 3a fragments into the simple alpha-diazomethyl ketone and methyl vinyl ketone which then undergo an intermolecular [2,3]-dipolar cycloaddition. Analogous treatment of the trifluoromethyl trione 2 again afforded a pyrazole 4c. Further experiments were carried out to lend evidence to our mechanistic hypothesis. Thus alpha-diazoacetophenone 5 and MVK underwent a [2,3]-dipolar cycloaddition under mild conditions to give the two regioisomeric dihydropyrazoles 6a and 6b. Interestingly these were formed in a 2:1 ratio, which suggested that 6a was more stable than 6b. The structures of 6a and 6b were optimized by using the B3LYP density functional method and the 6-31G* basis set and isomer 6a was predicted to be 1.5 kcal/mol more stable than isomer 6b. This energy difference could be rationalized by the greater capacity of the acetyl group than the benzoyl group to conjugate with the hydrazone. This difference in conjugation is reflected by key bond length differences. Thus we have discovered a novel fragmentation-cycloaddition process. We have also presented evidence for the mechanism of the formation of the dihydropyrazoles and carried out calculations to support these findings.