4,4,4-trifluoro-3-(phenylhydrazono)butanoic acid ethyl ester | 328-64-3

• 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: 4,4,4-trifluoro-3-(phenylhydrazono)butanoic acid ethyl ester
• 英文别名: 4,4,4-trifluoro-3-phenylhydrazono-butyric acid ethyl ester；4,4,4-Trifluor-3-phenylhydrazono-buttersaeure-aethylester；ethyl (3E)-4,4,4-trifluoro-3-(2-phenylhydrazinylidene)butanoate；ethyl (3E)-4,4,4-trifluoro-3-(phenylhydrazinylidene)butanoate
• CAS: 328-64-3
• 化学式: C₁₂H₁₃F₃N₂O₂
• 分子量: 274.243
• InChiKey: VZFNVXSZHLNSCL-LICLKQGHSA-N

物化性质

• 沸点：
  286.5±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  4,4,4-三氟-2-丁炔乙酯 、 苯肼 以 二氯甲烷 为溶剂， 以84.6%的产率得到4,4,4-trifluoro-3-(phenylhydrazono)butanoic acid ethyl ester
  参考文献：
  名称：

  Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles

  摘要：

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.

  DOI：

  10.1021/jo00047a021

文献信息

• Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles
  作者：Bruce C. Hamper、Mitchell L. Kurtzweil、James P. Beck

  DOI：10.1021/jo00047a021

  日期：1992.10

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.