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Synlett 2009(13): 2101-2104  
DOI: 10.1055/s-0029-1217530
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Facile One-Pot Synthesis of 1-Alkyl-3-polyfluoroalkyl Imidazolium Ionic Liquids

Dong Sub Kima, Debby Nataliaa, Dihn Quan Nguyenb, Dong Jin Suha, Honggon Kima, Hoon Sik Kim*b, Hyunjoo Lee*a
a Division of Energy and Environment, Korea Institute of Science & Technology, Hawolgok-dong, Sungbuk-gu, Seoul 136-791, Korea
Fax: +82(2)9585807; e-Mail: hjlee@kist.re.kr;
b Department of Chemistry, Kyung Hee University, 1 Hoegi-dong, Dondaemoon-gu, Seoul 130-701, Korea
Fax: +82(2)9654408; e-Mail: khs2004@khu.ac.kr;
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Publication History

Received 25 March 2009
Publication Date:
01 July 2009 (online)

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Abstract

Imidazolium-based ionic liquids bearing a polyfluorinated alkyl group on the cation were efficiently synthesized in excellent yields and selectivities from the one-pot reaction of a fluoroolefin with [1-alkyl-3H-imidazolium]X, where X = Cl, NO3, CF3CO2, BF4 or (CF3SO2)2N, formed in situ from the interaction of an alkylimidazole with an acid, HX.

Key words

ionic liquids - imidazolium - fluorine - fluoroolefin - hydroamination

    References and Notes

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11

Representative example of the synthesis of 1-butyl-3-(1,1,1,2,3,3-hexafluoropropyl)imidazolium trifluoroacetate (3a). In a 100 mL high-pressure glass reactor, 1-butylimidazole (7.6 mmol) was reacted with TFA (7.6 mmol) in THF (35 mL) at 0 ˚C for 1 h. To this solution was added hexafluoropropylene (HFP; 15.2 mmol) and the reaction was continued for 5 h at an ambient temperature. Evaporation of all the volatiles under a reduced pressure produced 1-butyl-3-(1,1,1,2,3,3-hexafluoropropyl)imid-azolium trifluoroacetate, as a viscous liquid in >99% yield. ¹H NMR (300 MHz, CD3CN): δ = 9.87 (s, 1 H), 7.94 (s, 1 H), 7.71 (s, 1 H), 6.6-6.38 (m, 1 H), 4.33-4.28 (t, J = 7.5 Hz, 2 H), 1.87-1.81 (m, 2 H), 1.46-1.30 (m, 2 H), 1.00-0.96 (t, J = 7.2 Hz, 3 H). ¹9F NMR (300 MHz, D2O): δ = 1.38-1.27 (m, 3 F), 0.53-0.34 (m, 3 F), -11.44 to -12.31 (m, 1 F), -18.40 to -19.29 (m, 1 F), -134.70 to -134.94 (m, 1 F). Anal. Calcd for C12H13F9N2O2: C, 37.12; H, 3.38; N, 7.22. Found: C, 37.32; H, 3.56; N, 7.41.
3-Butyl-1-(1,1,2,3,3,3-hexafluoropropyl)imidazolium chloride (3b). ¹H NMR (300 MHz, D2O): δ = 8.01 (s, 1 H), 7.84 (s, 1 H), 6.30-6.02 (m, 1 H), 4.33-4.37 (t, J = 7.2 Hz, 2 H), 1.87-1.97 (m, 2 H), 1.29-1.41 (m, 2 H), 0.91-0.96 (t, J = 7.5 Hz, 3 H). ¹9F NMR (300 MHz, D2O): δ = 1.41-1.29 (m, 3 F), -11.45 to -12.33 (m, 1 F), -18.34 to -19.27 (m, 1 F), -134.69 to -134.91 (m, 1 F). Anal. Calcd for C10H13ClF6N2: C, 38.66; H, 4.22; N, 9.02. Found: C, 39.12; H, 4.43; N, 8.89.
3-Butyl-1-(1,1,2,3,3,3-hexafluoropropyl)imidazolium nitrate (3c). ¹H NMR (300 MHz, D2O): δ = 9.73 (s, 1 H), 8.02 (s, 1 H), 7.85 (s, 1 H), 7.32-6.05 (m, 1 H), 4.38-4.33 (t, J = 7.2 Hz, 2 H), 1.92-1.87 (m, 2 H), 1.39-1.29 (m, 2 H), 0.97-0.92 (t, J = 7.4 Hz, 3 H). ¹9F NMR (300 MHz, D2O):
δ = 1.40-1.28 (m, 3 F), -7.19 to -12.35 (m, 1 F), -18.32 to -19.28 (m, 1 F), -134.69 to -134.96 (m, 1 F). Anal. Calcd for C10H13F6N3O3: C, 35.62; H, 3.89; N, 12.46. Found: C, 35.43; H, 4.05; N, 12.72.
3-Butyl-1-(1,1,2,3,3,3-hexafluoropropyl)imidazolium tetrafluoroborate (3d). ¹H NMR (300 MHz, CD3CN): δ = 9.17 (s, 1 H), 7.84 (s, 1 H), 7.72 (s, 1 H), 6.05-5.83 (m, 1 H), 4.31-4.26 (t, J = 7.4 Hz, 3 H), 1.97-1.88 (m, 2 H), 1.43-1.35 (m, 2 H), 0.99-0.95 (t, J = 7.3 Hz, 3 H). ¹9F NMR (300 MHz, D2O): δ = 3.82-3.71 (m, 3 F), -10.38 to -11.24 (m, 1 F),
-15.98 to -16.90 (m, 1 F), -72.48 to -72.54 (d, J = 16.2 Hz, 1 F), -132.36 to -132.59 (m, 1 F). Anal. Calcd for C10H13BF10N2: C, 33.18; H, 3.62; N, 7.74. Found: C, 33.48; H, 3.88; N, 7.90.
1-(1,1,2,3,3,3-Hexafluoropropyl)-3-methylimidazolium nitrate (3e). ¹H NMR (300 MHz, D2O): δ = 7.99 (s, 1 H), 7.96 (s, 1 H), 6.27-6.06 (m, 1 H), 4.04 (s, 3 H). ¹9F NMR (300 MHz, D2O): δ = 1.43-1.35 (m, 3 F), -11.42 to -12.33 (m, 1 F), -18.43 to -19.36 (m, 1 F), -134.69 to -134.96 (m, 1 F). Anal. Calcd for C7H7F6N3O3: C, 28.49; H, 2.39; N, 14.24. Found: C, 28.77; H, 2.46; N, 14.04.
1-(1,1,2,3,3,3-Hexafluoropropyl)-3-methylimidazolium trifluoroacetate (3f). ¹H NMR (300 MHz, D2O): δ = 9.63 (s, 1 H), 7.99 (s, 1 H), 7.76 (s, 1 H), 6.28-6.04 (m, 1 H), 4.02 (s, 3 H). ¹9F NMR (300 MHz, D2O): δ = 1.43-1.38 (m, 3 F), 0.43 (s, 3 F), -11.38 to -12.26 (m, 1 F), -18.43 to -19.36 (m, 1 F), -134.69 to -134.96 (m, 1 F). Anal. Calcd for C9H7F9N2O2: C, 31.23; H, 2.04; N, 8.09. Found: C, 30.96; H, 2.07; N, 8.00.
1-(1,1,2,3,3,3-Hexafluoropropyl)-3-(methoxyl-carbonyl-ethyl)imidazolium trifluoroacetate (3g). ¹H NMR (400 MHz, D2O): δ = 9.72 (s, 1 H), 7.93 (s, 1 H), 7.80 (s, 1 H), 6.16-6.02 (m, 1 H), 4.57-4.54 (t, J = 6.1 Hz, 2 H), 3.65 (s, 3 H), 3.03-3.00 (t, J = 6.2 Hz, 2 H). ¹9F NMR (300 MHz, D2O): δ = 1.39-1.26 (m, 3 F), 0.52 (s, 3 F), -11.40 to -12.26 (m, 1 F), -18.41 to -19.30 (m, 1 F), -134.73 to -135.00 (m, 1 F). Anal. Calcd for C12H11F9N2O4: C, 34.46; H, 2.65; N, 6.70. Found: C, 34.64; H, 2.71; N, 6.88.
3-Butyl-1-(1,1,2,3,3,3-hexafluoropropyl)imidazolium bis(trifluoromethanesulfonyl)imide (3h). ¹H NMR (300 MHz, CD3CN): δ = 9.08 (s, 1 H), 7.79 (s, 1 H), 7.69 (s, 1 H), 5.96-5.75 (m, 1 H), 4.27-4.22 (t, J = 7.5 Hz, 2 H), 1.91-1.80 (m, 2 H), 1.44-1.32 (m, 2 H), 0.99-0.94 (t, J = 7.2 Hz, 3 H). ¹9F NMR (300 MHz, D2O): δ = 3.85-3.72 (m, 3 F), -1.34 (s, 6 F), -10.10 to -10.96 (m, 1 F), -15.87 to -16.75 (m, 1 F),
-132.11 to -132.31 (m, 1 F). Anal. Calcd for C12H13F12N3O4S2: C, 25.95; H, 2.36; N, 7.57. Found: C, 25.81; H, 2.26; N, 7.69.
3-Butyl-1-(1,1,2,2-tetrafluoroethyl)imidazolium trifluoroacetate (4i). ¹H NMR (400 MHz, D2O): δ = 9.56 (s, 1 H), 7.87 (s, 1 H), 7.72 (s, 1 H), 6.77-6.51 (t, J = 51.9 Hz, 1 H), 4.28-4.22 (m, 2 H), 1.85-1.78 (m, 2 H), 1.30-1.20 (m, 2 H), 0.88-0.81 (t, J = 7.4 Hz, 3 H). ¹9F NMR (300 MHz, D2O): δ = 0.49 (s, 3 F), -22.91 (s, 2 F), -60.50 to -60.68 (d, J = 55.2 Hz, 1 F). Anal. Calcd for C11H13F7N2O2: C, 39.06; H, 3.87; N, 8.28. Found: C, 38.80; H, 3.61; N, 8.47.