A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A？ form) in non-aqueous media. The anion loading of the AER (OH？ form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A？ form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.
References
[1]
Sowmiah, S.; Srinivasadesikan, V.; Tseng, M.-C.; Chu, Y.-H. On the chemical stabilities of ionic liquids. Molecules 2009, 14, 3780–3813, doi:10.3390/molecules14093780. 19783957
[2]
MacFarlane, D.R.; Pringle, J.M.; Howlett, P.C.; Forsyth, M. Ionic liquids and reactions at the electrochemical interface. Phys. Chem. Chem. Phys. 2010, 12, 1659–1669, doi:10.1039/b923053j. 20145830
[3]
Dupont, J.; Scholten, J.D. On the structural and surface properties of transition-metal nanopartícules in ionic liquids. Chem. Soc. Rev. 2010, 39, 1780–1804, doi:10.1039/b822551f. 20419219
[4]
Hallett, J.P.; Welton, T. Room-temperature ionic liquids: Solvents for synthesis and catalysis. 2. Chem. Rev. 2011, 111, 3508–3576, doi:10.1021/cr1003248.
[5]
le Bideau, J.; Viau, L.; Vioux, A. Ionogels, ionic liquid based hybrid materials. Chem. Soc. Rev. 2011, 40, 907–925, doi:10.1039/c0cs00059k. 21180731
[6]
Plechkova, N.V.; Seddon, K.R. Applications of ionic liquids in the chemical industry. Chem. Soc. Rev. 2008, 37, 123–150, doi:10.1039/b006677j. 18197338
[7]
Stoimenovski, J.; MacFarlane, D.R.; Bica, K.; Rogers, R.D. Crystalline vs. ionic liquid salt forms of active pharmaceutical ingredients: A position paper. Pharm. Res. 2010, 27, 521–526, doi:10.1007/s11095-009-0030-0.
[8]
Deetlefs, M.; Seddon, K.R. Assessing the greenness of some typical laboratory ionic liquid preparations. Green Chem. 2010, 12, 17–30, doi:10.1039/b915049h.
Petkovic, M.; Seddon, K.R.; Rebelo, L.P.N.; Pereira, C.S. Ionic liquids: A pathway to environmental acceptability. Chem. Soc. Rev. 2011, 40, 1383–1403, doi:10.1039/c004968a. 21116514
[11]
Sun, N.; Rodríguez, H.; Rahmana, M.; Rogers, R.D. Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Chem. Commun. 2011, 47, 1405–1421, doi:10.1039/c0cc03990j.
Clare, B.; Sirwardana, A.; MacFarlane, D.R. Synthesis and purification of ionic liquids. Top. Curr. Chem. 2009, 290, 1–40.
[14]
Olivier-Bourbigou, H.; Magna, L.; Morvan, D. Ionic liquids and catalysis: Recent progress from knowledge to applications. Appl. Catal. A 2010, 373, 1–56, doi:10.1016/j.apcata.2009.10.008.
[15]
Smiglak, M.; Hines, C.C.; Rogers, R.D. New hydrogen carbonate precursors for efficient and byproduct-free syntheses of ionic liquids based on 1,2,3-trimethylimidazolium and N,N-dimethylpyrrolidinium cores. Green Chem. 2010, 12, 491–501, doi:10.1039/b920003g.
[16]
Nockemann, P.; Thijs, B.; Driesen, K.; Janssen, C.R.; van Hecke, K.; van Meervelt, L.; Kossmann, S.; Kirchner, B.; Binnemans, K. Choline saccharinate and choline acesulfamate: Ionic liquids with low toxicities. J. Phys. Chem. B 2007, 111, 5254–5263, doi:10.1021/jp068446a. 17444674
[17]
Alcalde, E.; Dinarès, I.; Fayet, J.-P.; Vertut, M.-C.; Elguero, J. Synthesis of highly dipolar betaines: Pyridinium azolates. J. Chem. Soc. Chem. Commun. 1986, 734–735.
[18]
Alcalde, E.; Alemany, M.; Pérez-García, L.; Rodríguez, M.L. Non-classical [14]metaheterophanes containing betaine units. Synthesis, NMR spectroscopy, and X-ray crystallography. J. Chem. Soc. Chem. Commun. 1995, 1239–1240.
[19]
Alcalde, E.; Alemany, M.; Gisbert, M. A direct synthetic approach to novel quadrupolar [14] azolophanes. Tetrahedron 1996, 52, 15171–15188, doi:10.1016/S0040-4020(96)00925-8.
Alcalde, E.; Mesquida, N.; Vilaseca, M.; Alvarez-Rúa, C.; García-Granda, S. Imidazolium-based dicationic cyclophanes. Solid-state aggregates with unconventional (C-H)+···Cl？ hydrogen bonding revealed by X-ray diffraction. Supramol. Chem. 2007, 19, 501–509, doi:10.1080/10610270601132624.
[22]
Dinarès, I.; de Miguel, C.G.; Mesquida, N.; Alcalde, E. Bis(imidazolium)-calix[4]arene receptors for anion binding. J. Org. Chem. 2009, 74, 482–485, doi:10.1021/jo8023285. 19053578
[23]
Ogihara, W.; Yoshizawa, M.; Ohno, H. Novel ionic liquids composed of only azole ions. Chem. Lett. 2004, 33, 1022–1023, doi:10.1246/cl.2004.1022.
[24]
Fukumoto, K.; Yoshizawa, M.; Ohno, H. Room temperature ionic liquids from 20 natural amino acids. J. Am. Chem. Soc. 2005, 127, 2398–2399, doi:10.1021/ja043451i. 15724987
[25]
Fukaya, Y.; Iizuka, Y.; Sekikawa, K.; Ohno, H. Bio ionic liquids: Room temperature ionic liquids composed wholly of biomaterials. Green Chem. 2007, 9, 1155–1157, doi:10.1039/b706571j.
[26]
Ou, G.; Zhu, M.; Shea, J.; Yuan, Y. Ionic liquid buffers: A new class of chemicals with potential for controlling pH in non-aqueous media. Chem. Commun. 2006, 4626–4628.
[27]
Lall, S.I.; Mancheno, D.; Castro, S.; Behaj, V.; Cohen, J.I.; Engel, R. Polycations. Part X. LIPs, a new category of room temperature ionic liquid based on polyammonium salts. Chem. Commun. 2000, 2413–2414.
[28]
Golding, J.; Forsyth, S.; MacFarlane, D.R.; Forsyth, M.; Deacon, G.B. Methanesulfonate and p-toluenesulfonate salts of the N-methyl-N-alkylpyrrolidinium and quaternary ammonium cations: Novel low cost ionic liquids. Green Chem. 2002, 4, 223–229, doi:10.1039/b201063a.
[29]
Machado, M.Y.; Dorta, R. Synthesis and characterization of chiral imidazolium salts. Synthesis 2005, 2473–2475.
[30]
Nobuoka, K.; Kitaoka, S.; Kunimitsu, K.; Iio, M.; Harran, T.; Wakisaka, A.; Ishikawa, Y. Camphor ionic liquid: Correlation between stereoselectivity and cation-anion interaction. J. Org. Chem. 2005, 70, 10106–10108, doi:10.1021/jo051669x. 16292848
[31]
Ruiz-Toral, A.; de los Ríos, A.P.; Hernández, F.J.; Janssen, M.H.A.; Schoevaart, R.; van Rantwijk, F.; Sheldon, R.A. Cross-linked Candida antarctica lipase B is active in denaturing ionic liquids. Enzyme Microb. Technol. 2007, 40, 1095–1099, doi:10.1016/j.enzmictec.2006.08.027.
[32]
Dinarès, I.; de Miguel, C.G.; Ibá？ez, A.; Mesquida, N.; Alcalde, E. Imidazolium ionic liquids: A simple anion exchange protocol. Green Chem. 2009, 11, 1507–1510, doi:10.1039/b915743n.
[33]
Alcalde, E.; Dinarès, I.; Ibá？ez, A.; Mesquida, N. A general halide-to-anion switch for imidazolium-based ionic liquids and oligocationic systems using anion exchange resins (A？ form). Chem. Commun. 2011, 47, 3266–3268, doi:10.1039/c0cc05350c.
[34]
Viau, L.; Tourné-Péteilh, C.; Devoisselle, J.-M.; Vioux, A. Ionogels as drug delivery system: One-step sol-gel synthesis using imidazolium ibuprofenate ionic liquid. Chem. Commun. 2010, 46, 228–230, doi:10.1039/b913879j.
[35]
Dupont, J.; Suarez, P.A.Z.; de Souza, R.F.; Burrow, R.A.; Kintzinger, J.-P. C-H—π interactions in 1-n-Butyl-3-methylimidazolium Tetraphenylborate molten salt: Solid and solution structures. Chem.-Eur. J. 2000, 6, 2377–2381, doi:10.1002/1521-3765(20000703)6:13<2377::AID-CHEM2377>3.0.CO;2-L. 10939740
[36]
Yong, L.; Yao, M.-L.; Green, J.F.; Kelly, H.; Kabalka, G.W. Syntheses and characterization of polymer-supported organotrifluoroborates: Applications in radioiodination reactions. Chem. Commun. 2010, 46, 2623–2625, doi:10.1039/b925258d.
[37]
MacFarlane, D.R.; Pringle, J.M.; Johansson, K.M.; Forsyth, S.A.; Forsyth, M. Lewis base ionic liquids. Chem. Commun. 2006, 1905–1917.
[38]
Rodríguez, H.; Gurau, G.; Holbreya, J.D.; Rogers, R.D. Reaction of elemental chalcogens with imidazolium acetates to yield imidazole-2-chalcogenones: Direct evidence for ionic liquids as proto-carbenes. Chem. Commun. 2011, 47, 3222–3224, doi:10.1039/c0cc05223j.
[39]
Lee, K.M.; Lee, C.K.; Lin, I.J.B. First example of interdigitated U-shape benzimidazolium ionic liquid crystals. Chem. Commun. 1997, 899–900.
[40]
Wang, K.F.; Jian, F.F.; Zhuang, R.R.; Xiao, H.L. New ionic liquids of N,N'-dialkylbenzimidazolium salt comprising copper(II) ions. Cryst. Growth Des. 2009, 9, 3934–3940, doi:10.1021/cg900031c.
[41]
Wang, K.F.; Jian, F.F.; Zhuang, R.R. A new ionic liquid comprising lanthanum(III) bulk-modified carbon paste electrode: Preparation, electrochemistry and electrocatalysis. Dalton Trans. 2009, 4532–4537.
[42]
Zhuang, R.R.; Jian, F.F.; Wang, K.F. A new binuclear Cd(II)-containing ionic liquid: Preparation and electrocatalytic activities. J. Organomet. Chem. 2009, 694, 3614–3618, doi:10.1016/j.jorganchem.2009.07.012.
[43]
Arduengo, A.J., III. Looking for stable carbenes: The difficulty in starting anew. Acc. Chem. Res. 1999, 32, 913–921, doi:10.1021/ar980126p.
[44]
Vijayaraghavan, R.; Thompson, B.C.; MacFarlane, D.R.; Kumar, R.; Surianarayanan, M.; Aishwarya, S.; Sehgal, P.K. Biocompatibility of choline salts as crosslinking agents for collagen based biomaterials. Chem. Commun. 2010, 46, 294–296, doi:10.1039/b910601d.
[45]
Hough, W.L.; Smiglak, M.; Rodríguez, H.; Swatloski, R.P.; Spear, S.K.; Daly, D.T.; Pernak, J.; Grisel, J.E.; Carliss, R.D.; Soutullo, M.D.; et al. The third evolution of ionic liquids: Active pharmaceutical ingredients. New J. Chem. 2007, 31, 1429–1436, doi:10.1039/b706677p.
[46]
Clare, B.R.; Bayley, P.M.; Best, A.S.; Forsyth, M.; MacFarlane, D.R. Purification or contamination? The effect of sorbents on ionic liquids. Chem. Commun. 2008, 2689–2691.
[47]
Burrell, A.K.; del Sesto, R.E.; Baker, S.N.; McCleskey, T.M.; Baker, G.A. The large scale synthesis of pure imidazolium and pyrrolidinium ionic liquids. Green Chem. 2007, 9, 449–454, doi:10.1039/b615950h.
[48]
Wang, J.; Cao, W.-F.; Su, J.-H.; Tian, H.; Huang, Y.-H.; Sun, Z.-R. Syntheses and nonlinear absorption of novel unsymmetrical cyanines. Dyes Pigm. 2003, 57, 171–179, doi:10.1016/S0143-7208(03)00034-2.
[49]
Arduengo, A.J., III; Krafczyk, R.; Schmutzler, R. Imidazolylidenes, imidazolinylidenes and imidazolidines. Tetrahedron 1999, 55, 14523–l4534, doi:10.1016/S0040-4020(99)00927-8.
