Microwaves in organic synthesis . v. 1

목차 (Table of Contents)

• 자료제공 :
• 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