3-(4-chlorobenzyl)-1-phenyl-5-pyrazolone | 221641-13-0

• 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: 3-(4-chlorobenzyl)-1-phenyl-5-pyrazolone
• 英文别名: 5-(4-Chlorobenzyl)-2-phenyl-2,4-dihydro-3H-pyrazol-3-one；5-[(4-chlorophenyl)methyl]-2-phenyl-4H-pyrazol-3-one
• CAS: 221641-13-0
• 化学式: C₁₆H₁₃ClN₂O
• 分子量: 284.745
• InChiKey: RCKLKJQLSOCTMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(4-chlorobenzyl)-1-phenyl-5-pyrazolone 在 sodium azide 、 三氯氧磷 作用下， 以 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 77.5h， 生成 3-(4-chlorobenzyl)-4-cyano-1-phenylpyrazole
  参考文献：
  名称：

  A Pyrazole to Furan Rearrangement. Thermolysis of 5-Azido-4-formylpyrazoles

  摘要：

  5-Azido-3-benzyl-4-formyl-1-phenylpyrazoles 1a-c extrude dinitrogen upon heating in toluene to give the corresponding nitrenes, which immediately rearrange via a new ring-opening ring-closure reaction to produce an equimolar mixture of 4-cyano-2-phenyl-3-phenylazofurans 2a-c and 3-benzyl-4-cyano-1-phenylpyrazoles 3a-c. The formation of the 4-cyano-2-phenyl-3-phenylazofurans 2a-c is the first example in the pyrazole series of a nitrene rearrangement, in which the parent heterocyclic system of the product differs from that of the starting material. The isolation of equimolar amounts of the two products points to the fact that their formation occurs by two mechanistically interconnected pathways, between which the exchange of a redox equivalent takes place. Evidence for the existence of two mechanistically interlinked pathways is presented, and the insight into the stoechiometry of the reaction is taken advantage of to optimize the reaction with respect to either of the two products 2 or 3. Thus, it is demonstrated how one can bias the two pathways using external reagents, thereby changing the product distribution ratio 2:3 from 1:1 in the unbiased case, to 1:4 in one direction, and to better than 20:1 in the other direction.

  DOI：

  10.1021/jo9822075
• 作为产物：
  描述：

  对氯苯乙酰氯 在 吡啶 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 10.5h， 生成 3-(4-chlorobenzyl)-1-phenyl-5-pyrazolone
  参考文献：
  名称：

  A Pyrazole to Furan Rearrangement. Thermolysis of 5-Azido-4-formylpyrazoles

  摘要：

  5-Azido-3-benzyl-4-formyl-1-phenylpyrazoles 1a-c extrude dinitrogen upon heating in toluene to give the corresponding nitrenes, which immediately rearrange via a new ring-opening ring-closure reaction to produce an equimolar mixture of 4-cyano-2-phenyl-3-phenylazofurans 2a-c and 3-benzyl-4-cyano-1-phenylpyrazoles 3a-c. The formation of the 4-cyano-2-phenyl-3-phenylazofurans 2a-c is the first example in the pyrazole series of a nitrene rearrangement, in which the parent heterocyclic system of the product differs from that of the starting material. The isolation of equimolar amounts of the two products points to the fact that their formation occurs by two mechanistically interconnected pathways, between which the exchange of a redox equivalent takes place. Evidence for the existence of two mechanistically interlinked pathways is presented, and the insight into the stoechiometry of the reaction is taken advantage of to optimize the reaction with respect to either of the two products 2 or 3. Thus, it is demonstrated how one can bias the two pathways using external reagents, thereby changing the product distribution ratio 2:3 from 1:1 in the unbiased case, to 1:4 in one direction, and to better than 20:1 in the other direction.

  DOI：

  10.1021/jo9822075

文献信息

• A Pyrazole to Furan Rearrangement. Thermolysis of 5-Azido-4-formylpyrazoles
  作者：Niels Svenstrup、Klaus B. Simonsen、Niels Thorup、Jørgen Brodersen、Wim Dehaen、Jan Becher

  DOI：10.1021/jo9822075

  日期：1999.4.1

  5-Azido-3-benzyl-4-formyl-1-phenylpyrazoles 1a-c extrude dinitrogen upon heating in toluene to give the corresponding nitrenes, which immediately rearrange via a new ring-opening ring-closure reaction to produce an equimolar mixture of 4-cyano-2-phenyl-3-phenylazofurans 2a-c and 3-benzyl-4-cyano-1-phenylpyrazoles 3a-c. The formation of the 4-cyano-2-phenyl-3-phenylazofurans 2a-c is the first example in the pyrazole series of a nitrene rearrangement, in which the parent heterocyclic system of the product differs from that of the starting material. The isolation of equimolar amounts of the two products points to the fact that their formation occurs by two mechanistically interconnected pathways, between which the exchange of a redox equivalent takes place. Evidence for the existence of two mechanistically interlinked pathways is presented, and the insight into the stoechiometry of the reaction is taken advantage of to optimize the reaction with respect to either of the two products 2 or 3. Thus, it is demonstrated how one can bias the two pathways using external reagents, thereby changing the product distribution ratio 2:3 from 1:1 in the unbiased case, to 1:4 in one direction, and to better than 20:1 in the other direction.