Green Chemical Synthesis with Microwaves and Ultrasound

A guide to the efficient and sustainable synthesis of organic compounds

Chemical processes and the synthesis of compounds are essential aspects of numerous industries, and particularly central to the creation of drug-like structures. Their often significant environmental biproducts, however, have driven substantial innovations in the areas of green and organic synthesis, which have the potential to drive efficient, solvent-free synthesis and create more sustainable chemical processes. The use of microwaves and ultrasounds in chemical synthesis has proven an especially fruitful area of research, with the potential to produce a more sustainable industrial future. Green Chemical Synthesis with Microwaves and Ultrasound provides a comprehensive overview of recent advances in microwave- and ultrasound-driven synthesis and their cutting-edge applications.

Green Chemical Synthesis with Microwaves and Ultrasound readers will also find:

• Introduction to the key equipment and tools of green chemical synthesis
• Detailed discussion of methods including ultrasound irradiation, metal-catalyzed reactions, enzymatic reactions, and many more
• An authorial team with immense experience in environmentally friendly organic chemical production

Green Chemical Synthesis with Microwaves and Ultrasound is ideal for chemists, organic chemists, chemical engineers, biochemists, and any researchers or industry professionals working on the synthesis of chemicals and/or organic compounds.

About the Editors xiii

Preface xv

1 Ultrasound Irradiation: Fundamental Theory, Electromagnetic Spectrum, Important Properties, and Physical Principles 1
Sumit Kumar, Amrutlal Prajapat, Sumit K. Panja, and Madhulata Shukla

1.1 Introduction 1

1.2 Cavitation History 3

1.2.1 Basics of Cavitation 3

1.2.2 Types of Cavitation 5

1.3 Application of Ultrasound Irradiation 7

1.3.1 Sonoluminescence and Sonophotocatalysis 9

1.3.2 Industrial Cleaning 10

1.3.3 Material Processing 11

1.3.4 Chemical and Biological Reactions 12

1.4 Conclusion 14

Acknowledgments 15

References 15

2 Fundamental Theory of Electromagnetic Spectrum, Dielectric and Magnetic Properties, Molecular Rotation, and the Green Chemistry of Microwave Heating Equipment 21
Raghvendra K. Mishra, Akshita Yadav, Vinayak Mishra, Satya N. Mishra, Deepa S. Singh, and Dakeshwar Kumar Verma

2.1 Introduction 21

2.1.1 Historical Background 25

2.1.2 Green Chemistry Principles for Sustainable System 28

2.2 Fundamental Concepts of the Electromagnetic Spectrum Theory 35

2.3 Electrical, Dielectric, and Magnetic Properties in Microwave Irradiation 38

2.4 Microwave Irradiation Molecular Rotation 41

2.5 Fundamentals of Electromagnetic Theory in Microwave Irradiation 42

2.5.1 Electromagnetic Radiations and Microwave 43

2.5.2 Heating Mechanism of Microwave: Conventional Versus Microwave Heating 44

2.6 Physical Principles of Microwave Heating and Equipment 46

2.7 Green Chemistry Through Microwave Heating: Applications and Benefits 53

2.8 Conclusion 57

References 57

3 Conventional Versus Green Chemical Transformation: MCRs, Solid Phase Reaction, Green Solvents, Microwave, and Ultrasound Irradiation 69
Shailendra Yadav, Dheeraj S. Chauhan, and Mumtaz A. Quraishi

3.1 Introduction 69

3.2 A Brief Overview of Green Chemistry 69

3.2.1 Definition and Historical Background 69

3.2.2 Significance 70

3.3 Multicomponent Reactions 71

3.4 Solid Phase Reactions 73

3.5 Microwave Induced Synthesis 74

3.6 Ultrasound Induced Synthesis 75

3.7 Green Chemicals and Solvents 77

3.8 Conclusions and Outlook 78

References 79

4 Metal-Catalyzed Reactions Under Microwave and Ultrasound Irradiation 83
Suresh Maddila, Immandhi S.S. Anantha, Pamerla Mulralidhar, Nagaraju Kerru, and Sudhakar Chintakula

4.1 Ultrasonic Irradiation 83

4.1.1 Iron-Based Catalysts 86

4.1.2 Copper-Based Catalysts 89

4.1.2.1 Dihydropyrimidinones by Cu-Based Catalysts 91

4.1.2.2 Dihydroquinazolinones by Cu-Based Catalysts 92

4.1.3 Misalliances Metal-Based Catalysts 94

4.2 Microwave-Assisted Reactions 97

4.2.1 Solid Acid and Base Catalysts 98

4.2.1.1 Condensation Reactions 98

4.2.1.2 Cyclization Reactions 100

4.2.1.3 Multi-component Reactions 104

4.2.1.4 Friedel–Crafts Reactions 106

4.2.1.5 Reaction Involving Catalysts of Biological Origin 107

4.2.1.6 Reduction 109

4.2.1.7 Oxidation 110

4.2.1.8 Coupling Reactions 113

4.2.1.9 Micelliances Reactions 121

4.2.1.10 Click Chemistry 125

4.3 Conclusion 127

Acknowledgments 128

References 128

5 Microwave- and Ultrasonic-Assisted Coupling Reactions 133
Sandeep Yadav, Anirudh P.S. Raman, Kashmiri Lal, Pallavi Jain, and Prashant Singh

5.1 Introduction 133

5.2 Microwave 134

5.2.1 Microwave-Assisted Coupling Reactions 135

5.2.2 Ultrasound-Assisted Coupling Reactions 142

5.3 Conclusion 150

References 151

6 Synthesis of Heterocyclic Compounds Under Microwave Irradiation Using Name Reactions 157
Sheryn Wong and Anton V. Dolzhenko

6.1 Introduction 157

6.2 Classical Methods for Heterocyclic Synthesis Under Microwave Irradiation 158

6.2.1 Piloty–Robinson Pyrrole Synthesis 158

6.2.2 Clauson–Kaas Pyrrole Synthesis 158

6.2.3 Paal–Knorr Pyrrole Synthesis 159

6.2.4 Paal–Knorr Furan Synthesis 160

6.2.5 Paal–Knorr Thiophene Synthesis 160

6.2.6 Gewald Reaction 161

6.2.7 Fischer Indole Synthesis 162

6.2.8 Bischler–Möhlau Indole Synthesis 162

6.2.9 Hemetsberger–Knittel Indole Synthesis 163

6.2.10 Leimgruber–Batcho Indole Synthesis 163

6.2.11 Cadogan–Sundberg Indole Synthesis 163

6.2.12 Pechmann Pyrazole Synthesis 164

6.2.13 Debus–Radziszewski Reaction 164

6.2.14 van Leusen Imidazole Synthesis 166

6.2.15 van Leusen Oxazole Synthesis 166

6.2.16 Robinson–Gabriel Reaction 167

6.2.17 Hantzsch Thiazole Synthesis 167

6.2.18 Einhorn–Brunner Reaction 168

6.2.19 Pellizzari Reaction 169

6.2.20 Huisgen Reaction 169

6.2.21 Finnegan Tetrazole Synthesis 171

6.2.22 Four-component Ugi-azide Reaction 172

6.2.23 Kröhnke Pyridine Synthesis 172

6.2.24 Bohlmann–Rahtz Pyridine Synthesis 173

6.2.25 Boger Reaction 174

6.2.26 Skraup Reaction 174

6.2.27 Gould–Jacobs Reaction 175

6.2.28 Friedländer Quinoline Synthesis 176

6.2.29 Povarov Reaction 176

6.3 Conclusion 177

Acknowledgments 177

References 177

7 Microwave- and Ultrasound-Assisted Enzymatic Reactions 185
Nafseen Ahmed, Chandan K. Mandal, Varun Rai, Abbul Bashar Khan, and Kamalakanta Behera

7.1 Introduction 185

7.2 Influence Microwave Radiation on the Stability and Activity of Enzymes 186

7.3 Principle of Ultrasonic-Assisted Enzymolysis 190

7.4 Applications of Ultrasonic-Assisted Enzymolysis 192

7.4.1 Proteins and Other Plant Components Can Be Transformed and Extracted 192

7.4.2 Modification of Protein Functionality 193

7.4.3 Enhancement of Biological Activity 194

7.4.4 Ultrasonic-Assisted Acceleration of Hydrolysis Time 195

7.5 Enzymatic Reactions Supported by Ultrasound 196

7.5.1 Lipase 196

7.5.2 Protease 196

7.5.3 Polysaccharide Enzymes 198

7.6 Biodiesel Production via Ultrasound-Supported Transesterification 198

7.6.1 Homogenous Acid-Catalyzed Ultrasound-Assisted Transesterification 199

7.6.2 Transesterification with Ultrasound Assistance and Homogenous Base Catalysis 199

7.6.3 Heterogeneous Acid-Catalyzed Ultrasound-Assisted Transesterification 201

7.6.4 Heterogeneous Base-Catalyzed Ultrasound-Assisted Transesterification 205

7.6.5 Enzyme-Catalyzed Ultrasound-Assisted Transesterification 207

7.7 Conclusions 207

Acknowledgments 209

References 209

8 Microwave- and Ultrasound-Assisted Synthesis of Polymers 219
Anupama Singh, Sushil K. Sharma, and Shobhana Sharma

8.1 Introduction 219

8.2 Microwave-Assisted Synthesis of Polymers 220

8.3 Ultrasound-Assisted Synthesis of Polymers 223

8.4 Conclusion 228

References 229

9 Synthesis of Nanomaterials Under Microwave and Ultrasound Irradiation 235
Ahmed A. Mohamed

9.1 Introduction 235

9.2 Synthesis of Metal Nanoparticles 236

9.3 Synthesis of Carbon Dots 239

9.4 Synthesis of Metal Oxides 240

9.5 Synthesis of Silicon Dioxide 243

9.6 Conclusion 243

References 244

10 Microwave- and Ultrasound-Assisted Synthesis of Metal-Organic Frameworks (MOF) and Covalent Organic Frameworks (COF) 249
Sanjit Gaikwad and Sangil Han

10.1 Introduction 249

10.2 Principles 250

10.2.1 Principles of Microwave Heating 250

10.2.2 Principle of Ultrasound-Assisted Techniques 250

10.2.3 Advantages and Disadvantages of Microwave- and Ultrasound-Assisted Techniques 252

10.3 MOF Synthesis by Microwave and Ultrasound Method 252

10.3.1 Microwave-Assisted Synthesis of MOF 253

10.3.2 Ultrasound-Assisted Synthesis of MOFs 256

10.4 Factors That Affect MOF Synthesis 257

10.4.1 Solvent 257

10.4.2 Temperature and pH 258

10.5 Application of MOF 260

10.6 COF Synthesis by Microwave and Ultrasound Method 262

10.6.1 Ultrasound-Assisted Synthesis of COFs 262

10.6.2 Microwave-Assisted Synthesis of COF 262

10.6.3 Structure of COF (2D and 3D) 263

10.7 Factors Affecting the COF Synthesis 266

10.8 Applications of COFs 267

10.9 Future Predictions 269

10.10 Summary 269

Acknowledgments 269

References 270

11 Solid Phase Synthesis Catalyzed by Microwave and Ultrasound Irradiation 283
R.M. Abdel Hameed, Amal Amr, Amina Emad, Fatma Yasser, Haneen Abdullah, Mariam Nabil, Nada Hazem, Sara Saad, and Yousef Mohamed

11.1 Introduction 283

11.2 Wastewater Treatment 284

11.3 Biodiesel Production 289

11.4 Oxygen Reduction Reaction 297

11.5 Alcoholic Fuel Cells 306

11.6 Conclusion and Future Plans 313

References 313

12 Comparative Studies on Thermal, Microwave-Assisted, and Ultrasound-Promoted Preparations 337
Tri P. Adhi, Aqsha Aqsha, and Antonius Indarto

12.1 Introduction 337

12.1.1 Background on Preparative Techniques in Chemistry 337

12.1.2 Overview of Thermal, Microwave-Assisted, and Ultrasound-Promoted Preparations 338

12.1.3 Significance of Comparative Studies in Enhancing Synthetic Methodologies 341

12.1.3.1 Optimization of Conditions 341

12.1.3.2 Efficiency Improvement 342

12.1.3.3 Methodological Advances 343

12.1.3.4 Sustainability and Green Chemistry 343

12.2 Fundamentals of Thermal, Microwave-Assisted, and Ultrasound-Assisted Reactions 345

12.2.1 Explanation of Thermal Reactions and Their Advantages and Limitations 345

12.2.2 Introduction to Microwave-Assisted Reactions and How They Differ from Traditional Method 346

12.2.3 Understanding the Principles and Mechanisms of Ultrasound-Promoted Reactions 347

12.3 Case Studies in Organic Synthesis 349

12.3.1 Examining Examples of Organic Reactions Performed Under Thermal Conditions 349

12.3.1.1 Esterification Reaction Under Thermal Conditions 349

12.3.1.2 Dehydration of Alcohols 349

12.3.1.3 Oxidation of Aldehydes to Carboxylic Acids Using Water 350

12.3.2 Case Studies Showcasing the Application of Microwave-Assisted Reactions 350

12.3.2.1 Microwave-Assisted C—C Bond Formation 351

12.3.2.2 Microwave-Assisted Cyclization 352

12.3.2.3 Microwave-Assisted Dehydrogenation Reactions 353

12.3.2.4 Microwave-Assisted Organic Synthesis 353

12.3.3 Highlighting Successful Instances of Ultrasound-Promoted Organic Synthesis 353

12.3.3.1 Ultrasound-Promoted in Organic Synthesis 354

12.3.3.2 Ultrasound-Promoted Oxidations 354

12.3.3.3 Ultrasound-Promoted Esterification 354

12.3.3.4 Ultrasound-Promoted Cyclization 354

12.4 Scope and Limitations 355

12.4.1 Discussing the Applicability of Each Method to Different Reaction Types 355

12.4.2 Identifying the Limitations and Challenges Faced by Each Technique 357

12.4.3 Opportunities for Combining Approaches to Overcome Specific Limitations 358

12.5 Future Directions and Emerging Trends 359

12.5.1 Overview of Recent Advancements and Ongoing Research in Thermal, Microwave, and Ultrasound-Assisted Preparations 359

12.5.1.1 Food Processing Technologies 360

12.5.1.2 Chemical Routes to Materials: Thermal Oxidation of Graphite for Graphene Preparation 360

12.5.1.3 Environmental and Sustainable Applications: Waste to Energy 361

12.5.2 Recent Findings in Microwave-Assisted Preparation 361

12.5.2.1 Catalyst 361

12.5.2.2 Nanotechnology 362

12.5.3 Food Processing Technologies 362

12.5.4 Ultrasound-Assisted Preparations 363

12.5.4.1 Biomedical 363

12.5.4.2 Artificial Intelligence (AI) 363

12.6 Identification of Potential Areas for Further Exploration and Improvement 363

12.6.1 Reaction Mechanisms and Kinetics 363

12.6.2 Synergistic Effects 364

12.6.3 Green Chemistry and Sustainability 366

12.6.4 Scale-Up and Industrial Application 366

12.6.5 Catalysis and Selectivity 367

12.6.6 In Situ Monitoring and Control 367

12.6.7 Mechanistic Studies 368

12.6.8 Temperature and Energy Management 368

12.6.9 Materials Processing 369

12.6.10 Biomedical Applications 370

12.7 The Role of Artificial Intelligence and Computational Approaches in Optimizing Preparative Techniques 370

References 372

Index 381

Dakeshwar Kumar Verma, PhD, is Assistant Professor of Chemistry at the Govt. Digvijay Autonomous Postgraduate College, Rajnandgaon, Chhattisgarh, India.

Chandrabhan Verma, PhD, is a Researcher in the Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates.

Paz Otero Fuertes, PhD, is a Senior Researcher in the Nutrition and Bromatology Group, Faculty of Food Science and Technology, University of Vigo, Spain.