Chapter 1 Introduction ......................................... 1
1.1 Definition of Ionic Liquids ................................ 1
1.2 Synonyms ................................................... 1
1.3 Attraction of Ionic Liquids ................................ 2
1.4 Cations and Anions ......................................... 3
1.5 Shorthand Notation for Cations and Anions .................. 4
1.6 Apro tic and Pro tic Ionic Liquids ......................... 5
1.7 Binary Mixtures ............................................ 6
1.8 Organic and Inorganic Ionic Liquids ........................ 6
1.9 Deep Eutectic Solvents ..................................... 6
1.10 Task-specific Ionic Liquids ................................ 7
1.11 Chiral Ionic Liquids ....................................... 8
1.12 Generations of Ionic Liquids ............................... 8
References ..................................................... 10
Chapter 2 History ............................................. 12
2.1 Origins ................................................... 12
2.2 Key Dates in the History of Ionic Liquids ................. 13
References ..................................................... 16
Chapter 3 Synthesis of Ionic Liquids .......................... 19
3.1 Introduction .............................................. 19
3.2 Alkylation ................................................ 20
3.3 Anion Exchange ............................................ 20
3.4 Microwave- and Ultrasound-assisted Synthesis .............. 23
3.5 Halide-free Synthesis ..................................... 23
3.6 Synthesis by Protonation .................................. 24
3.7 Synthesis of Haloaluminate Ionic Liquids .................. 25
3.8 Synthesis of Task-specific Ionic Liquids .................. 25
3.9 Chiral Synthesis .......................................... 27
References ..................................................... 29
Chapter 4 Properties of Ionic Liquids ......................... 31
4.1 Introduction .............................................. 31
4.2 Liquid Range and Thermal Stability ........................ 32
4.3 Melting Points ............................................ 32
4.4 Vapour Pressure ........................................... 33
4.5 Heat Capacity and Heat Transfer ........................... 34
4.6 Viscosity ................................................. 34
4.7 Density ................................................... 35
4.8 Solubility and Miscibility ................................ 35
4.9 Water Stability ........................................... 35
4.10 Conductivity .............................................. 36
4.11 Electrochemical Potential Window .......................... 36
4.12 Surface Tension ........................................... 36
4.13 Fluorescence .............................................. 37
4.14 Refractive Indices ........................................ 37
4.15 Impact of Impurities ...................................... 38
References ..................................................... 39
Chapter 5 Ionic Liquids as Designer Solvents .................. 41
5.1 Introduction .............................................. 41
5.2 Solubility and Miscibility ................................ 42
5.3 Polarity and Solvation .................................... 43
5.4 Miscibility with Water .................................... 44
5.5 Miscibility with Organic Compounds ........................ 44
5.6 Solubility of Metal Salts ................................. 46
5.7 Gas Solubility ............................................ 46
5.8 Biphasic Systems .......................................... 48
5.9 Phase Diagrams ............................................ 48
5.10 Partitioning of Solutes between Ionic Liquids and Water ... 52
5.11 Biphasic Systems of Hydrophilic Ionic Liquids and Water ... 53
5.12 Mutually Immiscible Ionic Liquids ......................... 53
5.13 Separations and Extractions ............................... 54
5.14 Extraction of Organic Compounds ........................... 54
5.15 Gas Separations ........................................... 56
5.16 Carbon Dioxide Extractions and Separations ................ 51
5.17 Metal Ion Extractions ..................................... 58
5.18 Extractive Distillations .................................. 60
5.19 Membrane Separations ...................................... 61
References ..................................................... 62
Chapter 6 Green Credentials of Ionic Liquids .................. 65
6.1 Introduction .............................................. 65
6.2 Vapour Pressure ........................................... 68
6.3 Flammability and Combustibility ........................... 70
6.4 Recycling ................................................. 71
6.5 Environmental Exposure and Toxicity ....................... 72
6.5.1 Release into the Environment ....................... 72
6.5.2 Spatiotemporal Range ............................... 73
6.5.3 Biodegradability ................................... 73
6.5.4 Biological Activity ................................ 73
6.5.5 Bioaccumulation .................................... 75
References ..................................................... 77
Chapter 7 Electrochemistry .................................... 79
7.1 Introduction .............................................. 79
7.2 Cyclic Voltammetry ........................................ 80
7.3 Batteries ................................................. 83
7.4 Fuel Cells ................................................ 85
7.5 Dye-sensitized Solar Cells ................................ 86
7.6 Electrodeposition ......................................... 88
7.7 Actuators ................................................. 91
7.8 Supercapacitors ........................................... 92
7.9 Electrosynthesis .......................................... 94
References ..................................................... 95
Chapter 8 Catalysis ........................................... 99
8.1 Introduction .............................................. 99
8.2 Monophasic and Biphasic Catalysis ........................ 100
8.3 Solvents, Catalysts and Ligands .......................... 101
8.4 Catalyst Performance ..................................... 105
8.5 Supported Ionic Liquid Catalysis ......................... 108
8.6 Nanoparticle Catalysts ................................... 110
8.7 Acid-Base Catalysis ...................................... 112
8.8 Transition Metal Catalysis ............................... 113
8.9 Chiral Transition Metal Catalysis ........................ 115
8.10 Task-specific Ionic Liquids in Catalysis ................. 117
References .................................................... 118
Chapter 9 Inorganic Chemistry ................................ 121
9.1 Introduction ............................................ 121
9.2 Main Group Chemistry .................................... 121
9.3 Transition Metal Chemistry .............................. 124
9.4 Organometallic Compounds ................................ 125
9.5 Nuclear Chemistry ....................................... 130
9.6 Nanoparticles ........................................... 132
9.7 Carbon Nanotubes ........................................ 133
9.8 Metal and Semiconductor Nanoparticles ................... 134
9.9 Alloy Nanoparticles ..................................... 136
9.10 Metal Oxide Nanoparticles ............................... 137
9.11 Other Nanoparticles ..................................... 137
9.12 Microspheres ............................................ 138
9.13 Sol-Gel Synthesis of Porous Materials ................... 140
9.14 Ionothermal Synthesis of Porous Materials ............... 141
References .................................................... 143
Chapter 10 General Organic Reactions .......................... 146
10.1 Introduction ............................................ 146
10.2 Aldol Condensation ...................................... 146
10.3 Alkylation .............................................. 148
10.4 Cracking ................................................ 149
10.5 Cycloaddition ........................................... 151
10.6 Debromination ........................................... 152
10.7 Dimerization and Oligomerization ........................ 152
10.8 Electrophilic Reactions ................................. 155
10.9 Epoxidation ............................................. 155
10.10 Esterification .......................................... 157
10.11 Etherization ............................................ 159
10.12 Halogenation ............................................ 160
10.13 Hydroformylation ........................................ 161
10.14 Hydrogenation ........................................... 162
10.15 Hydrosilylation ......................................... 166
10.16 Nitration of Aromatics .................................. 168
10.17 Nucleophilic Reactions .................................. 169
10.18 Olefin Metathesis ....................................... 171
10.19 Oxidation ............................................... 174
10.20 Peptide Synthesis ....................................... 175
10.21 Photochemical Reactions ................................. 176
10.22 Polymerizations ......................................... 179
References .................................................... 183
Chapter 11 Named Organic Reactions ............................ 188
11.1 Baeyer-Villiger Oxidation ............................... 188
11.2 Baylis-Hillman Reaction ................................. 188
11.3 Beckmann Rearrangement .................................. 190
11.4 Diels-Alder Reaction .................................... 190
11.5 Friedel-Crafts Reactions ................................ 193
11.6 Grignard Reaction ....................................... 197
11.7 Heck Reaction ........................................... 198
11.8 Knoevenagel Condensation and Robinson Annulation ........ 200
11.9 Mannich Reaction ........................................ 202
11.10 Michael Addition ........................................ 203
11.11 Sonogashira Coupling .................................... 205
11.12 Stille Coupling ......................................... 206
11.13 Suzuki Cross-coupling ................................... 207
11.14 Swern Oxidation ......................................... 208
11.15 Ullmann Coupling ........................................ 209
11.16 Wacker Oxidation ........................................ 210
11.17 Wittig Reaction ......................................... 210
References .................................................... 211
Chapter 12 Biotechnology ...................................... 214
12.1 Introduction ............................................ 214
12.2 Carbohydrate Solubility ................................. 214
12.3 Biomass Conversion ...................................... 216
12.4 Enzyme Catalysis ........................................ 218
12.5 Early Studies of Ionic Liquid-Enzyme Systems ............ 220
12.6 Lipases ................................................. 222
12.7 Proteases, Esterases and other Enzymes .................. 223
12.8 Enantioselectivity and Regioselectivity ................. 225
12.9 Biphasic Systems and Separations ........................ 227
References .................................................... 229
Chapter 13 Analysis ........................................... 232
13.1 Introduction ............................................ 232
13.2 Chromatography .......................................... 232
13.3 Capillary Electrophoresis ............................... 234
13.4 Sensors ................................................. 236
13.5 Gas Sensors ............................................. 236
13.6 Ion-selective Electrodes ................................ 239
13.7 Biosensors .............................................. 240
13.8 Spectroscopy ............................................ 241
13.9 Mass Spectrometry ....................................... 242
References .................................................... 244
Chapter 14 Applications ....................................... 246
14.1 Introduction ............................................ 246
14.2 Synthesis of 2,5-Dihydrofuran ........................... 247
14.3 Difasol Process ......................................... 248
14.4 BASIL Process ........................................... 249
14.5 Storage of Hazardous Gases .............................. 250
14.6 Lubrication ............................................. 251
14.7 Compressors ............................................. 252
14.8 Energetic Materials and Propellants ..................... 253
14.9 Optical Immersion Fluids ................................ 255
14.10 Lunar Liquid Mirror Telescope ........................... 256
14.11 Thermometers ............................................ 257
14.12 Antimicrobial Agents .................................... 259
14.13 Active Pharmaceutical Ingredients ....................... 260
14.14 Nucleoside-based Antiviral Drugs ........................ 261
14.15 Embalming and Tissue Preservation Fluids ................ 264
References .................................................... 264
Subject Index ................................................. 266
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