2-(Pentafluoroethyl)-exo-5-(2,2,2-trifluoroethoxy)bicyclo<2.2.1>hept-2-ene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(Pentafluoroethyl)-exo-5-(2,2,2-trifluoroethoxy)bicyclo<2.2.1>hept-2-ene
• 英文别名: (1S,4S,5R)-2-(1,1,2,2,2-pentafluoroethyl)-5-(2,2,2-trifluoroethoxy)bicyclo[2.2.1]hept-2-ene
• 化学式: C₁₁H₁₀F₈O
• 分子量: 310.187
• InChiKey: AAEAZLULPODOQC-VMHSAVOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  三环[2.2.1.0(2,6)]庚烷-3-酮 在 2,6-二甲基吡啶 、 potassium hydride 作用下， 以 乙醚 为溶剂， 反应 5.25h， 生成 2-(Pentafluoroethyl)-exo-5-(2,2,2-trifluoroethoxy)bicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  Synthesis and Solvolysis of 7-(Perfluoroalkyl)-7-bicyclo[2.2.1]heptyl Derivatives

  摘要：

  Several alpha-(trifluoromethyl)- and alpha-(pentafluoroethyl)carbinols were synthesized by the addition of perfluoroalkylating agents (TMSCF(3), TMSC(2)F(5), and/or C2F5Li) to polycyclic ketones. An improved procedure for the preparation of alpha-(perfluoroalkyl)trimethylsilyl ethers from (perfluoroalkyl)trimethylsilanes and ketones was developed to facilitate the synthesis of the compounds of interest. All of the alcohols featured the bicyclo[2.2.1]heptyl skeleton or some analog of this structure containing double bonds or cyclopropyl groups. Sulfonate esters of the carbinols were prepared, and these sulfonates were solvolyzed in different solvents to examine the competition between destabilization of the carbocationic intermediates by perfluoroalkyl groups and stabilization by neighboring-group participation. The extent of the destabilization of the cations was gauged by the difference in rates of solvolysis of the alpha-hydrogen and alpha-(perfluoroalkyl) derivatives. The k(alpha-H)/k(alpha-RF) ratios ranged from 8 to similar to 10(4), and the extent of anchimeric assistance that occurred in each system influenced the difference in rates. The pentafluoroethyl group exerted a slightly smaller rate-retarding effect when compared to the trifluoromethyl group (k(alpha-C2F5)/k(alpha-CF3) = 1.1-8.0). The products of the solvolysis reactions revealed a general trend of destabilization of both localized and delocalized cations by perfluoroalkyl groups.

  DOI：

  10.1021/jo00105a037

文献信息

• Synthesis and Solvolysis of 7-(Perfluoroalkyl)-7-bicyclo[2.2.1]heptyl Derivatives
  作者：Derek W. Nelson、Neil J. O'Reilly、Jon Speier、Paul G. Gassman

  DOI：10.1021/jo00105a037

  日期：1994.12

  Several alpha-(trifluoromethyl)- and alpha-(pentafluoroethyl)carbinols were synthesized by the addition of perfluoroalkylating agents (TMSCF(3), TMSC(2)F(5), and/or C2F5Li) to polycyclic ketones. An improved procedure for the preparation of alpha-(perfluoroalkyl)trimethylsilyl ethers from (perfluoroalkyl)trimethylsilanes and ketones was developed to facilitate the synthesis of the compounds of interest. All of the alcohols featured the bicyclo[2.2.1]heptyl skeleton or some analog of this structure containing double bonds or cyclopropyl groups. Sulfonate esters of the carbinols were prepared, and these sulfonates were solvolyzed in different solvents to examine the competition between destabilization of the carbocationic intermediates by perfluoroalkyl groups and stabilization by neighboring-group participation. The extent of the destabilization of the cations was gauged by the difference in rates of solvolysis of the alpha-hydrogen and alpha-(perfluoroalkyl) derivatives. The k(alpha-H)/k(alpha-RF) ratios ranged from 8 to similar to 10(4), and the extent of anchimeric assistance that occurred in each system influenced the difference in rates. The pentafluoroethyl group exerted a slightly smaller rate-retarding effect when compared to the trifluoromethyl group (k(alpha-C2F5)/k(alpha-CF3) = 1.1-8.0). The products of the solvolysis reactions revealed a general trend of destabilization of both localized and delocalized cations by perfluoroalkyl groups.