Ionic Liquid Catalyzed Reactions: Green Concepts and Sustainable Applications [Hardback]

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 LiquidCatalyzed 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 CO 2 31

2.1.3.2 Cyclization of Propargylic Alcohols with CO 2 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 CO 2 60

2.3.1 Formylation of Amines with CO 2 and Hydrosilanes 60

2.3.2 Reductive Cyclization of X (NH, S)-o-substituted Anilines with CO 2
and Hydrosilanes 67

2.4 Synthesis of Other Compounds 67

2.5 Remarks and Perspectives 70

References 71

3 Ionic LiquidMediated Reductive Transformation of Carbon Dioxide with
Hydrogen 79

3.1 Direct Hydrogenation of CO 2 80

3.1.1 CO 2 Hydrogenation to CO 80

3.1.2 CO 2 Hydrogenation to Formic Acid 81

3.1.3 CO 2 Hydrogenation to CH 4 85

3.1.4 CO 2 Hydrogenation to C 2+ Hydrocarbons 86

3.2 N-formylation or N-methylation Reaction of Amines with CO 2 /H 2 89

3.3 Hydroformylation of Olefin with CO 2 /H 2 94

3.4 Hydromethylamination of Olefin with CO 2 /H 2 and Amines 97

3.5 Carbonylation of Alcohol/Ethers with CO 2 /H 2 99

3.6 Remarks and Perspectives 102

References 102

4 Electroreduction of Carbon Dioxide in Ionic LiquidBased Electrolytes 105

4.1 Fundamentals of CO 2 Electroreduction 107

4.1.1 Basic Principles of CO 2 Electroreduction 107

4.1.2 Reaction Pathways of CO 2 Electroreduction 108

4.2 IL-based Electrolytes for CO 2 Electroreduction 109

4.2.1 CO 2 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 CO 2 to Various Chemicals in IL-based Electrolytes
121

4.3.1 Electroreduction of CO 2 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 CO 2 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 CO 2 to CH 3 OH 134

4.3.4 Electroreduction of CO 2 to CH 4 136

4.3.5 Electroreduction of CO 2 to C 2+ Compounds 137

4.4 Electrotransformation of CO 2 into Value-added Chemicals 140

4.4.1 Electrosynthesis of Carboxylic Acids 141

4.4.2 Electrosynthesis of Organic Carbonates with CO 2 144

4.4.3 Electrosynthesis of Organic Carbamates from CO 2 and Amines 145

4.4.4 Electrosynthesis of Methylanilines from CO 2 146

4.5 Remarks and Perspectives 147

References 150

5 Ionic LiquidCatalyzed Chemical Transformation of Lignocellulose 157

5.1 Ionic LiquidCatalyzed 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 Liquidcatalyzed Transformation of Hemicellulose and Xylose to
Furfural 170

5.3 Ionic LiquidCatalyzed 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 LiquidCatalyzed 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 BaeyerVilliger 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 LiquidCatalyzed WaterInvolved 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 Liquidcatalyzed 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 LiquidCatalyzed Other Organic Reactions 269

8.1 Alkylation Reaction 269

8.1.1 Alkylation of Olefins 269

8.1.2 FriedelCrafts Alkylation 271

8.2 Michael Addition Reaction 274

8.2.1 AzaMichael Reaction 274

8.2.2 Synthesis of Chiral Chemicals 277

8.3 DielsAlder Reactions 281

8.4 Markovnikov Addition 284

8.5 Knoevenagel Condensation 290

8.6 Aldol Condensation Reaction 295

8.7 Ring-Closing CO/CO and CO/OH 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 LiquidCatalyzed 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

9.1.2.1 Alcoholysis 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 357

Zhimin Liu, PhD, is Professor at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS), China. She has spent most of her career conducting research at ICCAS. She is the recipient of numerous scientific awards. She is an Editor-in-Chief of Current Opinion in Green and Sustainable Chemistry.

Yanfei Zhao, PhD, is Associate Professor at ICCAS, China. Her current research interest concentrates on the ionic liquid-promoted transformation of renewable carbon resources.