Ionic liquids : are they worth their salts?
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(46) Contents 1 About Ionic Liquids. ?? ?& ?A ?2 ?1. > % -
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(75) . . . . . . . . . . . . . . . . 1 2 6 9 19 24 33 34 39 52 73 85 89 90 94 103 104. 4 Ionic liquids under scrutiny - Their impact on the hydroaminomethylation reaction 115. 2? 2& 2A 22. -
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(83) Contents. 5 Biocatalysis in a biphasic ionic liquid/water system. 1? 1& 1A 12. -
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(97) . . . . . . . . . . . . . . . . . . . . . . . . . . . 145 146 151 164 165 171 172 175 175 185 191 192. Summary. 202. Samenvatting. 204. Curriculum Vitae. 206. List of publications. 207. Dankwoord. 208. ii.
(98) 1. Chapter 1. About Ionic Liquids. Ionic Liquids receive more and more attention as alternative reaction media due to their properties which clearly discriminate them from water or classical organic solvents. They are tuneable like no other solvent and therefore unique. A short introduction to these unique solvents and their properties is given in this chapter to outline their characteristics and application.. 1.
(99) 1 About Ionic Liquids. 1.1 History of Ionic Liquids.
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(340) 1 About Ionic Liquids. N. N. N. OH. Tf2N. Br. Howarth et al. 1997. Wasserscheid et al. 2001 OH. N. N N. OH O. N. R Br. O. Seddon et al. 1999. Bao et al. 2002. Figure 1.2: First chiral ionic liquids reported.
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(436) 1 About Ionic Liquids.
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(596) 1 About Ionic Liquids. OH. O SO3 N. SO3. Ru / C. N. N. N. H2 O. O. [N1888]. N. Tos. Tos O +. O NH. HO. OH. O. PPh3. B O. chiral ionic liquid. O. O. O. O. X. X. chiral ionic liquid X = Br, Me, NO2 Tos = 4-toluenesulfonyl [N1888] = Trioctylmethylammonium. Scheme 1.1: Applied chiral ILs. Above: Hydrogenation [34] ; below: Baylis-Hillman reactions. [35]. C
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(625) ! . . 1.2 Synthesis of Ionic Liquids. 7
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(661) 1 About Ionic Liquids. Table 1.1: Major steps in ionic liquids history. Year Discovery 1914 First mention of an ionic liquid 1934 First ionic liquid patent 1948 Chloroaluminate ionic liquids were discovered 1972 Hydroformylation of ethene in an ionic liquid 1982 Imidazolium is recognised as a ionic liquid cation 1990/92 First homogeneous reaction in a room temperature ionic liquid 1997/99 Functionlised and chiral ionic liquids are introduced 2007/08 Chirality induced by chiral ionic liquids. Literature [8] [9] [10] [11] [15] [28,29] [28,31] [35–37]. %
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(755) 1 About Ionic Liquids. 9 ?A
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(774) commonly used cations. commonly used anions. C2H5 N. N. C2H5. N. (CF3SO3)2N. CH3 N. C2H5. BF4 PF6. immidazolium. piperidinium. ammonium. CF3SO3 C2H5 N. C2H5. P. Cl S. CH3. C2H5. pyridinium. Br. phosphonium. sulfonium. Figure 1.3: Examples of frequently used cations and anions.
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(847) 1 About Ionic Liquids. Alkylation R1, R2. H2NR. Anion exchange. Quaternisation R2X. R1R2NR. R1R2NR2 X. N NH3, C2H2O2 NH2. N. +Y -X. R1R2NR2 Y. N EtBr. N NaBF4. N. N. HCHO. Br. BF4. Scheme 1.2: Above: General synthesis of an ionic liquid; below: Example of an ionic liquid synthesis [33]. :
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(934) 1 About Ionic Liquids.
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(968) ?& Table 1.2: Comparison of organic solvents and ionic liquids Property Number of solvents Catalytic ability Chirality Vapour pressure Flammability Solvation Polarity Tuneability Cost Recyclability Viscosity / cP Density / g cm3. Organic solvent > 1000 little little significant given weakly Conventional polarity concept limited low priced Green imperative 0.2 - 100 0.6 - 1.7. Ionic Liquid > 1,000,000 common common negligible usually non-flammable strongly Polarity differs ’designer solvents’ all price classes Cost imperative 22 - 40,000 0.8 - 3.3. Melting point. %"
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(1009) 1 About Ionic Liquids. Table 1.3: Melting points of chloride salts Entry 1 2 3. Ionic Liquid EMIM Cl BMIM Cl HMIM Cl. Melting Point 89 41 - 75. Reference [53] [53] [53]. EMIM = 1-ethyl-3-methylimidazolium, BMIM = 1-butyl-3-methylimidazolium, HMIM = 1-hexyl-3-methylimidazolium.
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