Ionic liquids have distinctive properties that have made them the subject of vigorous research in recent decades. They have primarily been seen as potential green alternatives to volatile organic solvents, and therefore as a vital tool in the development of sustainable industry. In fact, however, ionic liquids can also serve as catalysts, catalyst immobilizers, and initiators, with the result that they have been applied in over 100 known types of chemical reactions.
Ionic Liquid Catalyzed Reactions: Green Concepts and Sustainable Applications offers a detailed overview of these reactions and the catalytic mechanism of ionic liquids. It surveys cutting-edge research into ionic liquid catalysis and the concepts, perspectives, and skills needed for scientists to incorporate it into a range of experimental fields. It is a must-own for anyone looking to understand the range and variety of uses for ionic liquid catalysis.
Ionic Liquid Catalyzed Reactions readers will also find: - Case studies throughout showing ionic liquid catalysis applications - Information for scientists working in organic chemistry, electrochemistry, biotechnology, and many more - Detailed coverage of reactions including CO2 conversion, biomass transformation, organic synthesis, and many others
Ionic Liquid Catalyzed Reactions is ideal for catalytic chemists, organic chemists, environmental chemists, electrochemists, and anyone else working with chemical catalysis in need of new experimental methods.
Table of Contents
Preface xi
Acknowledgments xv
1 Background and Overview 1
1.1 Introduction 1
1.2 Ionic Liquids 2
1.2.1 Acidic ILs 2
1.2.2 Basic ILs 6
1.2.3 Neutral ILs with HB Donor/Acceptor 12
1.2.4 Chiral ILs 14
1.3 Structure of This Book 15
References 17
2 Ionic Liquid-Catalyzed Transformation of Carbon Dioxide to Chemicals
Under Metal-free Conditions 23
2.1 Synthesis of Organic Carbonates 25
2.1.1 Synthesis of Symmetrically Linear Carbonates 25
2.1.2 Synthesis of Asymmetrically Linear Carbonates 28
2.1.3 Synthesis of Cyclic Carbonates 30
2.1.3.1 Cyclization of Epoxides with CO2 31
2.1.3.2 Cyclization of Propargylic Alcohols with CO2 46
2.2 Synthesis of N-containing Heterocycles 49
2.2.1 Synthesis of Quinazoline-2,4(1H, 3H)-Diones 50
2.2.2 Synthesis of 2-Oxazolidinones 52
2.2.3 Synthesis of Benzimidazolones 60
2.3 Reductive Transformation of CO2 60
2.3.1 Formylation of Amines with CO2 and Hydrosilanes 60
2.3.2 Reductive Cyclization of X (NH, S)-o-substituted
Anilines with CO2 and Hydrosilanes 67
2.4 Synthesis of Other Compounds 67
2.5 Remarks and Perspectives 70
References 71
3 Ionic Liquid-Mediated Reductive Transformation of Carbon Dioxide
with Hydrogen 79
3.1 Direct Hydrogenation of CO2 80
3.1.1 CO2 Hydrogenation to CO 80
3.1.2 CO2 Hydrogenation to Formic Acid 81
3.1.3 CO2 Hydrogenation to CH4 85
3.1.4 CO2 Hydrogenation to C2+ Hydrocarbons 86
3.2 N-formylation or N-methylation Reaction of Amines with CO2/H2 89
3.3 Hydroformylation of Olefin with CO2/H2 94
3.4 Hydromethylamination of Olefin with CO2/H2 and Amines 97
3.5 Carbonylation of Alcohol/Ethers with CO2/H2 99
3.6 Remarks and Perspectives 102
References 102
4 Electroreduction of Carbon Dioxide in Ionic Liquid-Based
Electrolytes 105
4.1 Fundamentals of CO2 Electroreduction 107
4.1.1 Basic Principles of CO2 Electroreduction 107
4.1.2 Reaction Pathways of CO2 Electroreduction 108
4.2 IL-based Electrolytes for CO2 Electroreduction 109
4.2.1 CO2 Activation by IL-based Electrolytes 110
4.2.2 Influence of Chemical Structures of IL-based Electrolytes 111
4.2.2.1 Influence of Cation Structures 111
4.2.2.2 Influence of Anion Structures 113
4.2.2.3 Structural Influence of ILs for Homogeneous Electrocatalysts 115
4.2.3 Influence of Composition of the IL-based Electrolytes 117
4.3 Electroreduction of CO2 to Various Chemicals in
IL-based Electrolytes 121
4.3.1 Electroreduction of CO2 to HCOOH 122
4.3.1.1 Ag-based Catalysts 122
4.3.1.2 Bi-based Catalysts 124
4.3.1.3 In-based Catalysts 124
4.3.1.4 Pt-based Catalysts 124
4.3.1.5 Sn-based Catalysts 124
4.3.1.6 Cu-based Catalysts 124
4.3.1.7 Mo-based Catalysts 125
4.3.1.8 Pb-based Catalysts 125
4.3.2 Electroreduction of CO2 to CO 126
4.3.2.1 Molecular Electrocatalysts 126
4.3.2.2 Single Atomic Catalysts 130
4.3.2.3 Metal Catalysts 131
4.3.2.4 Transition Metal Dichalcogenide Catalysts 133
4.3.2.5 Metal-free Catalysts 134
4.3.3 Electroreduction of CO2 to CH3OH 134
4.3.4 Electroreduction of CO2 to CH4 136
4.3.5 Electroreduction of CO2 to C2+ Compounds 137
4.4 Electrotransformation of CO2 into Value-added Chemicals 140
4.4.1 Electrosynthesis of Carboxylic Acids 141
4.4.2 Electrosynthesis of Organic Carbonates with CO2 144
4.4.3 Electrosynthesis of Organic Carbamates from CO2 and Amines 145
4.4.4 Electrosynthesis of Methylanilines from CO2 146
4.5 Remarks and Perspectives 147
References 150
5 Ionic Liquid-Catalyzed Chemical Transformation of Lignocellulose 157
5.1 Ionic Liquid-Catalyzed Transformation of Cellulose and
Its Derivatives 159
5.1.1 Hydrolysis of Cellulose to Reducing Sugars 159
5.1.2 Dehydration of Cellulose and Glucose to 5-Hydroxymethylfurfural 160
5.1.3 Dehydration of Cellulose and Glucose to Levulinic Acid 164
5.1.4 Oxidation of Cellulose to Formic Acid 167
5.1.5 Transesterification of Cellulose to Cellulose Esters 168
5.1.6 Pyrolysis of Cellulose to 5-Methylfurfural 169
5.2 Ionic Liquid-catalyzed Transformation of Hemicellulose and
Xylose to Furfural 170
5.3 Ionic Liquid-Catalyzed Transformation of Lignin and Its Platforms 172
5.3.1 Direct Depolymerization of Lignin 173
5.3.2 Oxidative Depolymerization of Lignin and Its Derivatives 176
5.3.2.1 Oxidative Depolymerization of Lignin to Vanillin 176
5.3.2.2 Oxidative Depolymerization of Lignin and Derivatives to Aromatic
Carboxylic Acids 178
5.3.2.3 Oxidative Cleavage of Lignin Aromatic Unit to Diethyl Maleate 182
5.4 Remarks and Perspectives 184
References 185
6 Ionic Liquid-Catalyzed Oxidation Reactions 189
6.1 Oxidation of Alcohols/Aldehydes 190
6.1.1 Oxidation of Primary Alcohols to Esters 190
6.1.2 Oxidation of Alcohols to Aldehydes or Ketones 193
6.2 Oxidation of Organic Sulfides and Oxidative Desulfurization 199
6.2.1 Oxidation of Organic Sulfides 199
6.2.2 Oxidative Desulfurization 205
6.2.2.1 Polyoxometalates-based IL Catalysts for Oxidative Desulfurization 206
6.2.2.2 Acidic Ionic Liquids for Oxidative Desulfurization 210
6.3 Oxidative Cyclization of Olefins and Allylic Alcohols 213
6.4 Oxidation of Amines 218
6.5 Baeyer-Villiger Oxidation 221
6.6 Oxidation of Other Compounds 224
6.6.1 Oxidation of Oxime 224
6.6.2 Oxidation of Toluene 224
6.6.3 Oxidation of Organic Halides 225
6.7 Remarks and Perspectives 225
References 226
7 Ionic Liquid-Catalyzed Water-Involved Reactions 229
7.1 Dehydrative Esterification 229
7.1.1 Acidic Ionic Liquids 230
7.1.2 Basic Ionic Liquids 236
7.2 Dehydrative Etherification of Alcohols 237
7.3 Dehydration Alkenylation 243
7.4 Dehydrative Amidation 244
7.5 Ionic Liquid-catalyzed Hydration Reaction 249
7.5.1 Hydration of Alkynes 250
7.5.2 Hydration Reaction of Propargyl Alcohols 250
7.5.3 Hydration Reaction of Nitriles 254
7.5.4 Hydration of Epoxides 257
7.6 Hydrolysis of Esters/Ethers 260
7.6.1 Hydrolysis of Ester 260
7.6.2 Hydrolysis of Cyclic Carbonate 262
7.7 Remarks and Perspectives 264
References 264
8 Ionic Liquid-Catalyzed Other Organic Reactions 269
8.1 Alkylation Reaction 269
8.1.1 Alkylation of Olefins 269
8.1.2 Friedel-Crafts Alkylation 271
8.2 Michael Addition Reaction 274
8.2.1 Aza-Michael Reaction 274
8.2.2 Synthesis of Chiral Chemicals 277
8.3 Diels-Alder Reactions 281
8.4 Markovnikov Addition 284
8.5 Knoevenagel Condensation 290
8.6 Aldol Condensation Reaction 295
8.7 Ring-Closing C─O/C─O and C─O/O─H Bond Metathesis 298
8.7.1 Ring-Closing Metathesis of Aliphatic Diethers 298
8.7.2 Metathesis of Alkyloxy Alcohols 301
8.8 Remarks and Perspectives 303
References 303
9 Ionic Liquid-Catalyzed Recycling of Spent Polymers 309
9.1 Degradation of Polyesters 310
9.1.1 Degradation of PET 310
9.1.1.1 Hydrolysis of PET 311
9.1.1.2 Alcoholysis of PET 312
9.1.1.3 Aminolysis of PET 323
9.1.2 Degradation of PLA 324
9.1.2.2 Hydrolysis of PLA 327
9.1.2.3 Aminolysis of PLA 330
9.1.3 Degradation of PHB 332
9.1.3.1 Methanolysis of PHB 332
9.1.3.2 Decomposition of PHB 333
9.1.4 Degradation of PSS 334
9.1.5 Degradation of PC 336
9.1.5.1 Hydrolysis of PC 337
9.1.5.2 Alcoholysis of PC 338
9.1.5.3 Ammonolysis of PC 340
9.1.6 Methanolysis of PCL 342
9.1.7 General Approaches to Decompose Polyesters to Carboxylic Acids 343
9.2 Degradation of Polyamides 347
9.3 Upcycling of Polyolefins 348
9.4 Co-upcycling of Polyvinyl Chloride and Polyester 350
9.5 Remarks and Perspectives 351
References 351
Index 357Why Do Affirmations Work? 174 The Power of Writing Things Down 175 Daily Affirmations 176 Feel It, See It, Live It 177 Step 6: Have Role Models 178 Step 7: Research Before You Begin 181 Step 8: Create a Strategic Plan 183 Step 9: Create Your Dream Team 184 Step 10: Move Before You’re Ready 187 Step 11: Do Whatever It Takes 189 Step 12: Focus on Your Goals 191 Closing Words 195 Sources and Literature 199 About the Author 201 Index 203
