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Microwaves in Organic Synthesis, 2 Volume Set, 3rd Edition

Antonio de la Hoz (Editor), Andre Loupy (Editor)
ISBN: 978-3-527-33116-1
1303 pages
January 2013
Microwaves in Organic Synthesis, 2 Volume Set, 3rd Edition (3527331166) cover image
The third edition of the bestselling two-volume reference covers everything you need to know about microwave technology for synthesis
- from the best equipment to nonthermal effects, from solid-support reactions to catalysis. Completely revised and updated with half of the authors completely new to the project, this comprehensive work is clearly divided into two parts on the fundamentals of microwave irradiation, and application of microwaves and synergies with other enabling techniques. Also new to this edition are chapters on on-line monitoring, flow chemistry, combination with ultrasounds and natural products, including multicomponent reactions.

An indispensable source for organic, catalytic, physical, and medicinal chemists.
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Contents to Volume 1

Preface XIX

List of Contributors XXI

Part I Fundamental Aspects of Microwave Irradiation in Organic Chemistry 1

1 Microwave–Materials Interactions and Dielectric Properties: from Molecules and Macromolecules to Solids and Colloidal Suspensions 3
Didier Stuerga

1.1 Fundamentals of Microwave–Matter Interactions 3

1.1.1 Introduction 4

1.1.2 The Complex Dielectric Permittivity 11

1.2 Dielectric Properties and Molecular Behavior 30

1.2.1 Dielectric Properties Within a Complex Plane 30

1.2.2 Dielectric Properties of Condensed Phases 33

1.2.3 Dielectric Properties of Macromolecules and Polymers 40

1.2.4 Dielectric Properties of Solids and Adsorbed Phases 43

1.2.5 Dielectric Properties of Interfaces and Colloidal Suspensions 45

1.3 Conclusion 50

References 51

2 Development and Design of Reactors in Microwave-Assisted Chemistry 57
Bernd Ondruschka, Werner Bonrath, and Didier Stuerga

2.1 Introduction 57

2.2 Basic Concepts for Reactions and Reactors in Organic Synthesis 58

2.3 Methods for Enhancing the Rates of Organic Reactions 59

2.4 Microwave-Assisted Organic Syntheses 61

2.4.1 Microwave Ovens and Reactors – Background 63

2.4.2 Scale-Up of Microwave Cavities 66

2.4.3 Efficiency of Energy and Power 67

2.4.4 Field Homogeneity and Penetration Depth 68

2.4.5 Continuous Tube Reactors 69

2.4.6 MAOS – an Interdisciplinary Field 69

2.5 Commercial Microwave Reactors 70

2.5.1 Market Overview 70

2.5.2 Enterprises’ Products 71

2.5.3 SAIREM’s Products 74

2.6 Selected Equipment and Applications 79

2.6.1 Heterogeneous Catalysis 82

2.6.2 Hyphenated Techniques in Combination with Microwaves 83

2.6.3 Combination of Microwave Irradiation with a Pressure Setup 85

2.6.4 Synthesis of Laurydone 92

2.6.5 Industrial Equipment: Batch or Continuous Flow? 93

2.7 Qualification and Validation of Reactors and Results 96

2.8 Conclusion and the Future 97

References 98

3 Key Ingredients for Mastery of Chemical Microwave Processes 105
Didier Stuerga and Pierre Pribetich

3.1 The Systemic Approach 105

3.2 Thermal Dependence of Dielectric Loss 108

3.2.1 Thermal Dependence of Dielectric Properties 109

3.2.2 Microwave Bistability 110

3.3 Electric Field Effects 111

3.3.1 Penetration and Skin Depths 111

3.3.2 Dimensional Resonances 113

3.4 Loop Modes or Strange Solutions of Maxwell’s Equations 114

3.5 Hydrodynamic Aspects 116

3.6 Thermodynamic and Other Effects of Electric Fields 117

3.7 Athermal and Specific Effects of Electric Field 118

3.8 The Thermal Path Effect: Anisothermal Conditions 120

3.9 Hot Spots and Heterogeneous Kinetics 122

3.10 Conclusion 123

References 124

4 Nonthermal Effects of Microwaves in Organic Synthesis 127
Laurence Perreux, Andr´e Loupy, and Alain Petit

4.1 Introduction 127

4.2 Origin of Microwave Effects 128

4.3 Specific Nonthermal Microwave Effects 130

4.4 Effects of the Medium 134

4.4.1 Polar Solvents 134

4.4.2 Nonpolar Solvents 136

4.4.3 Solvent-Free Reactions 138

4.5 Effects Depending on Reaction Mechanisms 140

4.5.1 Isopolar Transition-State Reactions 141

4.5.2 Bimolecular Reactions Between Neutral Reactants Leading to Charged Products 144

4.5.3 Anionic Bimolecular Reactions Involving Neutral Electrophiles 145

4.5.4 Unimolecular Reactions 146

4.6 Effects Depending on the Position of the Transition State Along the Reaction coordinate 146

4.7 Effects on Selectivity 147

4.8 Some Illustrative Examples 150

4.8.1 Bimolecular Reactions Between Neutral Reactants 151

4.8.2 Bimolecular Reactions with One Charged Reactant 175

4.8.3 Unimolecular Reactions 188

4.8.4 Some Illustrative Examples of the Effects on Selectivity 194

4.9 Concerning the Absence of Microwave Effects 198

4.10 Conclusion: Suitable Conditions for Observation of Specific MW Effects 199

References 200

5 Selectivity Modifications Under Microwave Irradiation 209
A´ngel D´ýaz-Ortiz, Antonio de la Hoz, Jose´ Ramo´n Carrillo, and Mar´ýa

Antonia Herrero

5.1 Introduction 209

5.2 Selective Heating 210

5.2.1 Solvents 210

5.2.2 Catalysts 211

5.2.3 Reagents; Molecular Radiators 214

5.2.4 Susceptors 215

5.3 Modification of Chemoselectivity and Regioselectivity 218

5.3.1 Protection and Deprotection of Alcohols 218

5.3.2 Synthesis and Reactivity of Heterocyclic Compounds 221

5.4 Modification of Stereo- and Enantioselectivity 234

5.5 Conclusion 240

Acknowledgments 240

References 240

6 Elucidation of Microwave Effects: Methods, Theories, and Predictive Models 245
Antonio de la Hoz, A´ ngel D´ýaz-Ortiz, Mar´ýa Victoria Go´mez, Pilar Prieto, and Ana S´anchez Migall´on

6.1 Introduction 245

6.2 Thermal Effects 246

6.2.1 Elimination of Wall Effects Caused by Inverted Temperature Gradients 246

6.2.2 Overheating 247

6.2.3 ‘‘Hot Spots’’: Inhomogeneities 249

6.3 Non-Thermal Effects 256

6.3.1 Reactions and Theories 257

6.3.2 Methods to Elucidate the Occurrence of Non-Thermal Microwave Effects 271

6.4 Conclusion 291

Acknowledgments 291

References 291

7 Microwave Susceptors 297
Thierry Besson and C. Oliver Kappe

7.1 Introduction 297

7.2 Graphite as a Sensitizer 299

7.2.1 Diels–Alder Reactions 299

7.2.2 Ene Reactions 304

7.2.3 Oxidation of Propan-2-ol 305

7.2.4 Thermolysis of Esters 306

7.2.5 Thermal Reactions in Heterocyclic Syntheses 307

7.2.6 Decomplexation of Metal Complexes 313

7.2.7 Redistribution Reactions Between Tetraalkyl- or Tetraarylgermanes and Germanium Tetrahalides 314

7.2.8 Pyrolysis of Urea 315

7.2.9 Esterification of Stearic Acid by n-Butanol 316

7.3 Graphite as Sensitizer and Catalyst 316

7.3.1 Analysis of Two Synthetic Commercial Graphites 317

7.3.2 Acylation of Aromatic Compounds 318

7.3.3 Acylative Cleavage of Ethers 322

7.3.4 Ketodecarboxylation of Carboxylic Diacids 323

7.4 The Use of Silicon Carbide Susceptors in Microwave Chemistry 326

7.4.1 Silicon Carbide as Passive Heating Element 326

7.4.2 Silicon Carbide Reaction Vessels 332

7.4.3 Microtiter Plates Made from Silicon Carbide 337

Acknowledgments 340

References 340

8 Tools for Monitoring Reactions Performed Using Microwave Heating 347
Nicholas E. Leadbeater, Jason R. Schmink, and Trevor A. Hamlin

8.1 Introduction 347

8.2 Watching Microwave-Heated Reactions in Real Time 348

8.2.1 Use of a Digital Camera Interfaced with a Scientific Microwave Unit 348

8.2.2 Use of Thermal Imaging Equipment 350

8.3 Monitoring Microwave-Heated Reactions Using InSitu Spectroscopic Tools 353

8.3.1 Introduction 353

8.3.2 Raman Spectroscopy 354

8.3.3 Infrared Spectroscopy 367

8.3.4 UV–Visible Spectroscopy 370

8.3.5 Neutron and X-Ray Scattering 372

8.4 Conclusion 374

References 374

9 Microwave Frequency Effects in Organic Synthesis 377
Satoshi Horikoshi and Nick Serpone

9.1 Introduction 377

9.2 Historical Review of Microwave Frequency Effects in Chemical Reactions 380

9.3 Microwave Chemical Reaction Apparatus Operating at Various Frequencies 381

9.3.1 Basic Configuration of Single-Mode Resonance Microwave Irradiation Apparatus 381

9.3.2 Types of Microwave Generator 382

9.3.3 Commercial Microwave Organic Synthesis Apparatus Operating at Various Frequencies 384

9.4 Frequency Effects and Heating Efficiency in Various Solutions 386

9.4.1 Microwave Frequency Effect in Water as a Green Solvent 386

9.4.2 Features of Microwave Frequency Effects of Various Aqueous Electrolyte Solutions 390

9.4.3 Frequency Effect in the Heating of Some Common Solvents 394

9.4.4 Rates of Temperature Increase for Common Organic Solvents and for Water 395

9.4.5 Dielectric Parameters of Common Organic Solvents and Water at Different Frequencies 399

9.4.6 Rate of Temperature Increase of Common Solvents with a Single-Mode Resonance Microwave Applicator 402

9.5 Examples of Chemical Reactions Impacted by Microwave Frequency Effects 404

9.5.1 Microwave Frequency Effect in a Diels–Alder Reaction Taken as a Model Organic Synthesis 404

9.5.2 Microwave Frequency Effect in the Synthesis of the Ionic Liquid [BMIM]BF4 406

9.5.3 Microwave Frequency Effect in Catalyzed Reactions 412

9.5.4 Synthesis of Gemini Surfactants under 915MHz Microwave Irradiation 420

9.6 Conclusion 421

Acknowledgments 421

References 422

Part II Applications of Microwave Irradiation 425

10 Organic Synthesis Using Microwaves and Supported Reagents 427
Rajender S. Varma and R.B. Nasir Baig

10.1 Introduction 427

10.2 Microwave-Accelerated Solvent-Free Organic Reactions 428

10.3 Protection–Deprotection Reactions 429

10.3.1 Formation of Acetals and Dioxolanes 429

10.3.2 N-Alkylation Reactions 430

10.3.3 Deacylation Reactions 431

10.3.4 Cleavage of Aldehyde Diacetates 431

10.3.5 Cleavage of Carboxylic Esters on a Solid Support 432

10.3.6 Selective Cleavage of the N-tert-Butoxycarbonyl Group 433

10.3.7 Desilylation Reactions 433

10.3.8 Dethioacetalization Reaction 434

10.3.9 Deoximation Reactions 435

10.3.10 Cleavage of Semicarbazones and Phenylhydrazones 436

10.3.11 Dethiocarbonylation 437

10.3.12 Cleavage of Methoxyphenyl Methyl and Tetrahydropyranyl Ethers 437

10.4 Condensation Reactions 438

10.4.1 Wittig Olefination Reactions 438

10.4.2 Knoevenagel Condensation Reactions – Synthesis of Coumarins 439

10.4.3 Synthesis of Imines, Enamines, Nitroalkenes, and N-Sulfonylimines 439

10.4.4 MW-Assisted Michael Addition Reactions 443

10.4.5 MW-Assisted Solid Mineral-Promoted Miscellaneous Condensation Reaction 444

10.5 Isomerization and Rearrangement Reactions 445

10.5.1 Eugenol–Isoeugenol Isomerization 446

10.5.2 Pinacol–Pinacolone Rearrangement 446

10.5.3 Beckmann Rearrangement 447

10.5.4 Claisen Rearrangement 447

10.6 Diels–Alder Cycloaddition of a Triazole Ring 448

10.7 Addition Reactions 448

10.8 Oxidation Reactions – Oxidation of Alcohols and Sulfides 448

10.8.1 Activated Manganese Dioxide–Silica 449

10.8.2 Chromium Trioxide–Wet Alumina 449

10.8.3 Selective Solvent-Free Oxidation with Clayfen 450

10.8.4 Oxidations with Claycop–Hydrogen Peroxide 451

10.8.5 Other Metallic Oxidants: Copper Sulfate–or Oxone–Alumina 451

10.8.6 Nonmetallic Oxidants: Iodobenzene Diacetate Impregnated on Alumina 452

10.8.7 Oxidation of Thiols to Disulfides 452

10.8.8 Oxidation of Sulfides to Sulfoxides and Sulfones: Sodium Periodate–Silica 453

10.8.9 Oxidation of Sulfides to Sulfoxides: Iodobenzene Diacetate–Alumina 453

10.8.10 Oxidation of Arenes and Enamines: Potassium Permanganate–Alumina 454

10.8.11 Oxidation Using [Hydroxyl(tosyloxy)iodo]benzene 454

10.8.12 Other Oxidation Reactions 455

10.9 Reduction Reactions 455

10.9.1 Reduction of Carbonyl Compounds with Aluminum Alkoxides 455

10.9.2 Reduction of Carbonyl Compounds to Alcohols: Sodium Borohydride–Alumina 456

10.9.3 Reductive Amination of Carbonyl Compounds 457

10.9.4 Solid-State Cannizzaro Reaction 458

10.9.5 Reduction of Aromatic Nitro Compounds to Amines with Alumina-Supported Hydrazine 458

10.10 Synthesis of Heterocyclic Compounds 459

10.10.1 Flavones 459

10.10.2 Synthesis of Isobenzofuran-1(3H)-ones 460

10.10.3 Substituted Thiazoles, Benzothiazepines, and Thiiranes 461

10.10.4 Synthesis of 1,3,4-Thiadiazoles 462

10.10.5 Synthesis of 2-Aroylbenzofurans 463

10.10.6 Synthesis of Quinolones and Other Nitrogen Heterocycles 463

10.10.7 Synthesis of 1,3,4-Oxadiazoles 466

10.10.8 Solvent-Free Assembly of Pyrido-Fused Ring Systems 466

10.10.9 Synthesis of Uracils 467

10.10.10 MW-Assisted Synthesis of Benzoxazinones 467

10.10.11 Multicomponent Reactions 468

10.11 Miscellaneous Reactions 471

10.11.1 Conversion of Arylaldehydes to Nitriles 471

10.11.2 Nitration of Styrenes – Preparation of β-Nitrostyrenes 471

10.11.3 Bromination of Alkanones Using Microwaves 472

10.11.4 MW-Assisted Elimination Reactions 472

10.11.5 Synthesis of N-Arylsulfonylimines 473

10.11.6 Synthesis of β-Amino Alcohols 473

10.11.7 N-Formylation of Amines 473

10.11.8 Organometallic Reactions (Carbon–Carbon Bond-Forming Reactions) 474

10.11.9 Synthesis of Radiolabeled Compounds – Exchange Reactions 475

10.11.10 Enzyme-Catalyzed Reactions 476

10.11.11 Solvent-Free Synthesis of Ionic Liquids 476

10.12 Conclusion 478

References 479

11 Gaseous Reactants in Microwave-Assisted Synthesis 487
Achim Stolle, Peter Scholz, and Bernd Ondruschka

11.1 Introduction 487

11.2 Liquid-Phase Synthesis 488

11.2.1 Application of Hydrogen as a Reducing Agent 489

11.2.2 Application of Oxygen for Synthesis 493

11.2.3 Reactions with Carbon Monoxide 494

11.2.4 Reactions Employing Carbon Dioxide 498

11.2.5 Hydroformylation Reactions 500

11.2.6 Reactions with Ethylene and Propyne 503

11.2.7 Reactions with Ammonia and Hydrogen Sulfide 505

11.3 Wet Air Oxidation 508

11.4 Gas-Phase Synthesis 508

11.4.1 Oxidative Coupling of Methane 509

11.4.2 Reforming 512

11.4.3 Oxidative Dehydrogenation of Hydrocarbons 514

11.4.4 Other Reactions 515

11.5 Waste Gas Treatment 516

11.5.1 Combustion Engines 516

11.5.2 Total Oxidation of Volatile Organic Compounds 516

11.5.3 Catalytic NOx and SO2 Reductions 517

11.5.4 Other Reactions 519

11.6 Conclusion and Outlook 519

References 520

12 Microwaves and Electrochemistry 525
Sara E.C. Dale, Richard G. Compton, and Frank Marken

12.1 Introduction to Microwave Assisted Electrode Processes 525

12.2 Macroelectrode Processes in the Presence of Microwaves 527

12.3 Microelectrode Processes in the Presence of Microwaves 530

12.4 Junction-Electrode Processes in the Presence of Microwaves 533

12.5 Electrochemical Flow Reactor Processes in the Presence of Microwaves 533

12.6 Future Trends 536

References 537

13 The Combined Use of Microwaves and Ultrasound: Methods and Practice 541
Giancarlo Cravotto and Pedro Cintas

13.1 Introduction 541

13.2 The Search for the Best Coupling 542

13.2.1 Dielectric Heating and Sound: a Bird’s-Eye View 542

13.2.2 First Insights and Technical Implementation 544

13.3 Microwave- and Ultrasound-Enhanced Synthesis and Catalysis 549

13.4 Formation of Advanced Materials 558

13.5 Conclusion and Future Trends 560

References 560

14 Microwaves in Photochemistry and Photocatalysis 563
Vladim´ýr C´ýrkva

14.1 Introduction 563

14.2 UV/Vis Discharges in Electrodeless Lamps 564

14.2.1 Theory of Plasma-Chemical Microwave Discharges 565

14.2.2 Construction of MW-Powered EDLs 566

14.2.3 Preparation of the Thin Titania Films on EDLs 568

14.2.4 Spectral Characteristics of the EDLs 571

14.2.5 Performance of the EDLs 572

14.3 Microwave Photochemical and Photocatalytic Reactors 579

14.3.1 Performance in Batch Photoreactors 579

14.3.2 Performance in Flow-Through Photoreactors 585

14.4 Interactions of UV/Vis and Microwave Radiation with Matter 589

14.5 Microwave Photochemistry and Photocatalysis 591

14.6 Applications 591

14.6.1 Analytical Applications 591

14.6.2 Environmental Applications 591

14.6.3 Other Applications 597

14.7 Future Trends 598

Acknowledgments 598

References 598

Contents to Volume 2

Preface XV

List of Contributors XVII

15 Microwave-Heated Transition Metal-Catalyzed Coupling Reactions 607
Francesco Russo, Luke R. Odell, Kristofer Olofsson, Peter Nilsson, and Mats Larhed

16 Microwaves in Heterocyclic Chemistry 673
Jean Pierre Bazureau, Ludovic Paquin, Daniel Carri´e, Jean Martial L’Helgoual’ch, Sol´ene Guih´eneuf, Karime Wacothon Coulibaly, Guillaume Burgy, Sarah Komaty, and Emmanuelle Limanton

17 Microwave-Assisted Cycloaddition Reactions 737
Khalid Bougrin and Rachid Benhida

18 Microwave-Assisted Heterogeneously Catalyzed Processes 811
Rafael Luque, Alina Mariana Balu, and Duncan J. Macquarrie

19 Microwaves in the Synthesis of Natural Products 843
Erik V. Van der Eycken, Jitender B. Bariwal, and Jalpa J. Bariwal

20 Microwave-Enhanced Synthesis of Peptides, Proteins, and Peptidomimetics 897
Jonathan M. Collins

21 A Journey into Recent Microwave-Assisted Carbohydrate Chemistry 961
Antonino Corsaro, Venerando Pistar ` a, Maria Assunta Chiacchio, and Giovanni Romeo

22 Polymer Chemistry Under Microwave Irradiation 1013
Dariusz Bogdal and Urszula Pisarek

23 Application of Microwave Irradiation in Carbon Nanostructures 1059
Fernando Langa and Pilar de la Cruz

24 Microwave-Assisted Multicomponent Reactions in the Synthesis of Heterocycles 1099
Art Kruithof, Eelco Ruijter, and Romano V.A. Orru

25 Microwave-Assisted Continuous Flow Organic Synthesis (MACOS) 1173
Jesus Alc´azar and Juan de M. Mu˜noz

Index 1205

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André Loupy received his PhD in 1975 from Paris-South University under the direction of Dr. Jacqueline Seyden-Penne in the Centre National de la Recherche Scientifi que (CNRS) in Thiais. He joined the Laboratory of Selective Reactions in Centre of Orsay from Paris-South University
(director : Pr. Georges Bram). He became the first class director of research at CNRS, where he led this lab until the end of 2005 when he retired. He was co-author of roughly 300 publications and 10 chapters in several books. Together with Pr. Georges Bram, Dr. Loupy was
concerned with microwave activation since 1987, especially when coupled with safe and economical solvent-free conditions ('green chemistry') and the non-alimentary valorization of products from agriculture. His most recent research was focused on medium effects in organic synthesis including solvent and salt effects, solvent-free conditions with a special interest in supported reactions and phase transfer catalysis and activation by microwaves.

Antonio de la Hoz is Professor in Organic Chemistry in the University of Castilla-La Mancha. He obtained his PhD from the Universidad Complutense in Madrid in 1986 under the supervision of Prof. José Elguero and Carmen Pardo. After postdoctoral research in 1987 with
Prof. Mikael Begtrup at the Danmarks Tekniske Høskole, Denmark, he joined the Faculty of Chemistry of the Universidad de Castilla-La Mancha in Ciudad Real in 1988 as an Assistant Professor. In 1993 he worked under the supervision Prof. André Loupy in the Université de
Paris-Sud in Microwave Assisted Organic Chemistry. Prof. de la Hoz has authored over 170 scientific publications - 100 of them related to Microwaves in Organic Synthesis. Dr. de la Hoz is a founding member of the Spanish Green Chemistry Network. His current research
interests focus on Green methodologies, microwave activation, mechanochemistry, flow methodologies and solvent-free reactions, and the applications of heterocyclic compounds in material and supramolecular chemistry.
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