1-(2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptyl)-3-(2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecyl)imidazolium nonaflate | 1357370-16-1

• 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-(2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptyl)-3-(2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecyl)imidazolium nonaflate
• CAS: 1357370-16-1
• 化学式: C₄F₉O₃S*C₁₅H₇F₂₂N₂O₅
• 分子量: 1012.29
• InChiKey: HXLVKANMCKBJEK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  61.0
• 可旋转键数：
  18.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  112.16
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  1-(2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptyl)-3-(2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecyl)imidazolium nonaflate 、 silver(l) oxide 以 乙腈 为溶剂， 以77%的产率得到bis[1-(2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptyl)-3-(2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecyl)-1,3-dihydro-2H-imidazol-2-ylidene]silver(I) bis[(nonafluorobutanesulfonyl)oxy]argenate
  参考文献：
  名称：

  Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls?

  摘要：

  A series of fluorous silver complexes bearing two fluorous NHC ligands was synthesized from bis(polyfluoroallcylated) or bis(polyfluoropolyoxaalkylated) imidazolium salts and silver oxide in acetonitrile. The starting salts were prepared either under conventional conditions in two steps via polyfluoroalkylated imidazoles or preferably directly from imidazole and the respective polyfluoroalkyl triflates or polyfluoropolyoxaalkyl nonaflates bearing a nonfluorinated ethylene or methylene spacer. Surprisingly, striking differences in fluorophilicity were observed for both starting imidazolium salts and target Ag-NHC complexes depending on the type of polyfluorinated chains. While the complexes bearing a polyfluoroalkyl ponytail displayed moderate fluorophilicities f(i), in the range of 0.9-1.8, the presence of fluorinated polyether chains resulted in much higher fluorophilicity reaching for unbranched polyethers values as high as 3.2 with excellent solubility in perfluorinated solvents. For the explanation, DFT calculations on the model imidazolium salts showed that, in contrast to polyfluoroalkyl ponytails pointing out of the imidazolium rings, dominant conformation of the polyfluoropolyether chain is able to shield fluorophobic counteranions against the perfluorinated environment, minimizing thus fluorophobic interactions. We also employed DFT calculations for the confirmation of the higher flexibility of perfluoropolyether chains compared with perfluoroalkyl chains, scanning the energy content of two model compounds, perfluorohexane and perfluoro-3-oxahexane, on their C3-C4 or O-C3 torsion angle.

  DOI：

  10.1021/om201062c
• 作为产物：
  描述：

  2,2-二氟-2-[1,1,2,2-四氟-2-[1,1,2,2-四氟-2-(三氟甲氧基)乙氧基]乙氧基]-乙醇 在 sodium hydride 作用下， 以 乙腈 为溶剂， 反应 10.0h， 生成 1-(2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptyl)-3-(2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecyl)imidazolium nonaflate
  参考文献：
  名称：

  Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls?

  摘要：

  A series of fluorous silver complexes bearing two fluorous NHC ligands was synthesized from bis(polyfluoroallcylated) or bis(polyfluoropolyoxaalkylated) imidazolium salts and silver oxide in acetonitrile. The starting salts were prepared either under conventional conditions in two steps via polyfluoroalkylated imidazoles or preferably directly from imidazole and the respective polyfluoroalkyl triflates or polyfluoropolyoxaalkyl nonaflates bearing a nonfluorinated ethylene or methylene spacer. Surprisingly, striking differences in fluorophilicity were observed for both starting imidazolium salts and target Ag-NHC complexes depending on the type of polyfluorinated chains. While the complexes bearing a polyfluoroalkyl ponytail displayed moderate fluorophilicities f(i), in the range of 0.9-1.8, the presence of fluorinated polyether chains resulted in much higher fluorophilicity reaching for unbranched polyethers values as high as 3.2 with excellent solubility in perfluorinated solvents. For the explanation, DFT calculations on the model imidazolium salts showed that, in contrast to polyfluoroalkyl ponytails pointing out of the imidazolium rings, dominant conformation of the polyfluoropolyether chain is able to shield fluorophobic counteranions against the perfluorinated environment, minimizing thus fluorophobic interactions. We also employed DFT calculations for the confirmation of the higher flexibility of perfluoropolyether chains compared with perfluoroalkyl chains, scanning the energy content of two model compounds, perfluorohexane and perfluoro-3-oxahexane, on their C3-C4 or O-C3 torsion angle.

  DOI：

  10.1021/om201062c