1-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazole | 1173110-41-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazole
• CAS: 1173110-41-2
• 化学式: C₁₂H₅F₁₇N₂O₂
• 分子量: 532.157
• InChiKey: NGUNFIULSHVJTK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.76
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  36.28
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazole 、 以49%的产率得到3-(2,2-difluoro-2-(1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy)ethoxy)ethyl)-1-(2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propyl)-1H-imidazol-3-ium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate
  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：

  1H,1H-2,5-双(三氟甲基)-3,6-二氧代全氟壬醇 在 sodium hydride 作用下， 以 乙腈 为溶剂， 反应 10.0h， 生成 1-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazole
  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

文献信息

• HFPO Trimer-Based Alkyl Triflate, a Novel Building Block for Fluorous Chemistry. Preparation, Reactions and 19F gCOSY Analysis
  作者：Ondřej Kysilka、Markéta Rybáčková、Martin Skalický、Magdalena Kvíčalová、Josef Cvačka、Jaroslav Kvíčala

  DOI：10.1135/cccc20081799

  日期：——

  Triflate 4, CF₃(CF₂)₂O-CF(CF₃)CF₂O-CF(CF₃)CH₂-OTf (R_FOCH₂OTf), of the HFPO trimer-based alcohol 3 (R_FOCH₂OH) is a novel highly fluorinated building block for fluorous chemistry. In analogy to similar polyfluorinated triflates with methylene spacer, its reactivity is limited to strong and soft nucleophiles. Whereas reactions with cyanide anion, phenolate anion, enolate of diethyl malonate or lithium salt of benzaldehyde bis(phenylsulfanyl)acetal were unsuccessful, the corresponding imidazole 5, iodide 6 or azide 7 were prepared in good yields. Reaction of imidazole 5 with (perfluorohexyl)methyl triflate (9) afforded highly fluorinated non-crystalline imidazolium salt 8, TfO^-R_FOCH₂-(C₃H₃N₂)⁺-CH₂C₆F₁₃-n, which could be employed as fluorous ionic liquid or intermediate for fluorous carbenes. Complete assignment of complex ¹⁹F NMR spectra of all compounds employed was accomplished using ¹⁹F gCOSY NMR method.

  三氟甲基磺酸盐 4，CF₃(CF₂)₂O-CF(CF₃)CF₂O-CF(CF₃)CH₂-OTf（RFOCH₂OTf），基于HFPO三聚体醇 3（RFOCH₂OH）是一种新颖的高度氟化的用于氟化学的构建模块。类似于具有亚甲基间隔的类似多氟代磺酸盐，其反应性仅限于强碱和软碱。虽然与氰根离子、酚酚离子、二乙酯丙二酸烯醇酸根离子或苯甲醛双(苯基硫基)乙醛酸锂盐的反应失败，但相应的咪唑 5，碘化物 6 或叠氮化物 7 得到了良好的产率。咪唑 5 与（全氟己基）甲基磺酸盐 9 反应，得到高度氟化的非晶态咪唑盐 8，TfO⁻RFOCH₂-(C₃H₃N₂)⁺-CH₂C₆F₁₃-n，可用作氟化离子液体或氟化碳中间体。所有使用化合物的复杂 19F NMR 谱图通过 19F gCOSY NMR 方法得以完整分配。
• Fluorous imidazolium room-temperature ionic liquids based on HFPO trimer
  作者：Ondřej Kysilka、Markéta Rybáčková、Martin Skalický、Magdalena Kvíčalová、Josef Cvačka、Jaroslav Kvíčala

  DOI：10.1016/j.jfluchem.2009.04.006

  日期：2009.7

  Imidazole substituted with a polyfluoropolyether chain based on HFPO trimer combined with various polyfluoroalkyl triflates produced novel highly fluorous ionic liquids. Their metathesis with four different anions generated a final set of 20 fluorous ionic liquids of waxy or viscous liquid character, which are all soluble in perfluorinated solvents. Two model reactions using selected ionic liquid, the opening of a THF ring with benzoyl chloride under Friedel-Crafts conditions and substitution of benzyl chloride with sodium azide, led to decomposition of the ionic liquid. However, Diels-Alder reaction of 2,3-dimethylbuta-1,3-diene with dimethyl acetylenedicarboxylate in a fluorous ionic liquid resulted in a reasonable enhancing of the reaction rate with smooth recycle of the fluorous solvent. The fluorophilicity of these fluorous ionic liquids ranges from more than 10 for water, toluene or dichloromethane to less than 0.2 for acetonitrile or methanol. (C) 2009 Elsevier B.V. All rights reserved.