2,2,3,3,4,4,5-Heptafluoro-cyclopentanone | 180690-74-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2,3,3,4,4,5-Heptafluoro-cyclopentanone
• 英文别名: 2,2,3,3,4,4,5-Heptafluorocyclopentanone；2,2,3,3,4,4,5-heptafluorocyclopentan-1-one
• CAS: 180690-74-8
• 化学式: C₅HF₇O
• 分子量: 210.051
• InChiKey: OCNKVPIYWRQFQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,2,3,3,4,4,5-Heptafluoro-cyclopentanone 在 N-甲基吡咯烷酮 作用下， 以 四氯化碳 为溶剂， 生成 全氟环戊烯-1-醇
  参考文献：
  名称：

  Perfluorinated Cyclic and Acyclic Keto−Enol Systems:  A Remarkable Contrast

  摘要：

  Recent reports from this laboratory have revealed that highly fluorinated 4- and 5-membered-ring enols are comparable in stability to, or more stable thermodynamically than, the corresponding ketones, even in non-Lewis-basic media. Work on perfluorinated keto-enol systems has now been extended to 2H-perfluorocyclohexanone plus its enol and to a series of acyclic analogues. In carbon tetrachloride, K-E/K = 0.33 (22 degrees C) for the six-ring system, but only enol is detectable in Lewis-basic solvents. This shift is attributable to strong hydrogen-bond formation between the enol and Lewis base. A perfluoroenol has been shown to form significantly stronger hydrogen bonds than the potent hexafluoroisopropyl alcohol. Acyclic systems (e.g., 3H-perfluoro-2-butanone and its enol) contrast sharply with the cyclic, as no enol is detectable at equilibrium even in powerfully Lewis-basic media. Ab initio quantum mechanical calculations indicate that it is principally the enols, not the ketones, that are responsible for the difference between the two types of keto-enol systems, i.e. acyclic perfluoroenols are strongly destabilized relative to cyclic counterparts.

  DOI：

  10.1021/ja963788n
• 作为产物：
  描述：

  1-benzoxyperfluorocyclopentene 在 硫酸 、 水 、 溴 、 三正丁基氢锡 作用下， 以 四氯化碳 、 二氯甲烷 、 氘代苯 为溶剂， 反应 1.5h， 生成 2,2,3,3,4,4,5-Heptafluoro-cyclopentanone
  参考文献：
  名称：

  Highly Fluorinated Cyclopentanones and Their Enols

  摘要：

  2H-Perfluorocyclopentanone (Ik) and its enol (le) have been independently synthesized and equilibrated. In carbon tetrachloride, the enol is the only detectable form at equilibrium. In addition to its high relative stability, this enol displays interesting reactivity, including reversible bromination and hydrolysis reactions. Replacing the vinyl fluorine of le with hydrogen changes the relative enol stability dramatically as the enol is only present to the extent of 13% in carbon tetrachloride under equilibrating conditions. In Lewis basic solvents, however, the enol is the only detectable form because of its strength as a hydrogen bond donor. Quantum mechanical calculations on both systems suggest that ketone destabilization, but not enol stabilization, by fluorination is responsible for the remarkable relative stability of the enols.

  DOI：

  10.1021/jo9602940

文献信息

• Highly Fluorinated Cyclopentanones and Their Enols
  作者：Patrick E. Lindner、David M. Lemal

  DOI：10.1021/jo9602940

  日期：1996.1.1

  2H-Perfluorocyclopentanone (Ik) and its enol (le) have been independently synthesized and equilibrated. In carbon tetrachloride, the enol is the only detectable form at equilibrium. In addition to its high relative stability, this enol displays interesting reactivity, including reversible bromination and hydrolysis reactions. Replacing the vinyl fluorine of le with hydrogen changes the relative enol stability dramatically as the enol is only present to the extent of 13% in carbon tetrachloride under equilibrating conditions. In Lewis basic solvents, however, the enol is the only detectable form because of its strength as a hydrogen bond donor. Quantum mechanical calculations on both systems suggest that ketone destabilization, but not enol stabilization, by fluorination is responsible for the remarkable relative stability of the enols.
• Perfluorinated Cyclic and Acyclic Keto−Enol Systems:  A Remarkable Contrast
  作者：Patrick E. Lindner、David M. Lemal

  DOI：10.1021/ja963788n

  日期：1997.4.1

  Recent reports from this laboratory have revealed that highly fluorinated 4- and 5-membered-ring enols are comparable in stability to, or more stable thermodynamically than, the corresponding ketones, even in non-Lewis-basic media. Work on perfluorinated keto-enol systems has now been extended to 2H-perfluorocyclohexanone plus its enol and to a series of acyclic analogues. In carbon tetrachloride, K-E/K = 0.33 (22 degrees C) for the six-ring system, but only enol is detectable in Lewis-basic solvents. This shift is attributable to strong hydrogen-bond formation between the enol and Lewis base. A perfluoroenol has been shown to form significantly stronger hydrogen bonds than the potent hexafluoroisopropyl alcohol. Acyclic systems (e.g., 3H-perfluoro-2-butanone and its enol) contrast sharply with the cyclic, as no enol is detectable at equilibrium even in powerfully Lewis-basic media. Ab initio quantum mechanical calculations indicate that it is principally the enols, not the ketones, that are responsible for the difference between the two types of keto-enol systems, i.e. acyclic perfluoroenols are strongly destabilized relative to cyclic counterparts.