1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate | 1207109-39-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate
• CAS: 1207109-39-4
• 化学式: CF₃O₃S*C₁₈H₉F₂₆N₂
• 分子量: 896.312
• InChiKey: QSKJUCGBGPDMOG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.69
• 重原子数：
  54.0
• 可旋转键数：
  13.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  66.01
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate 、 silver(l) oxide 以 乙腈 为溶剂， 以96%的产率得到1-bis(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate
  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：

  1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)imidazole 、 2-(perfluorohexyl)ethyl triflate 以 甲苯 为溶剂， 反应 72.0h， 以86.7%的产率得到1-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate
  参考文献：
  名称：

  双（多氟烷基化）咪唑鎓盐的合成作为氟代NHC配体的关键中间体

  摘要：

  合成了多氟链和非氟间隔基长度不同的1,3-双（聚氟烷基）-和1-甲-3-（聚氟烷基）咪唑鎓盐，作为氟代NHC（N-杂环卡宾）配体。采用了一种新的方法，该方法使用多氟烷基三氟甲磺酸酯代替相应的碘化物，可以精细地调整氟的性质以及咪唑环的电子密度。使用双（多氟烷基化）咪唑鎓盐，合成了PEPPSI™催化剂的氟类似物，并通过X射线衍射确认了其结构。该催化剂以中等收率用于型号的Heck和Suzuki偶合中，但是，其回收并不成功。与相似的基于全氟聚醚的盐相比，发现双（多氟烷基化）咪唑鎓盐的亲氟性低得令人惊讶。

  DOI：

  10.1016/j.jfluchem.2009.07.015