microwaves in organic synthesis 2002 loupy

Microwaves in Organic Synthesis Edited by A Loupy Microwaves in Organic Synthesis Edited by Andr Loupy Copyright # 2002 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-527-30514-9 Related Titles from WILEY-VCH R van Eldik, F.-G Klårner (eds.) High Pressure Chemistry Synthetic, Mechanistic, and Supercritical Applications 474 pages 2002 Hardcover ISBN 3-527-30404-5 F Zaragoza Dærwald (ed.) Organic Synthesis on Solid Phase Supports, Linkers, Reactions 2nd Edition ca 850 pages 2002 Hardcover ISBN 3-527-30603-X P Wasserscheid, T Welton (eds.) Ionic Liquids in Synthesis ca 350 pages 2002 Hardcover ISBN 3-527-30515-7 K Tanaka (ed.) Solvent-free Organic Synthesis ca 300 pages 2003 Hardvover ISBN 3-527-30612-9 Microwaves in Organic Synthesis Edited by Andr Loupy Dr Andr Loupy Laboratoire des Ractions Slectives sur Supports Universit Paris-Sud bat 410 91405 Orsay cedex France & This book was carefully produced Never- theless, authors, editors and publisher not warrant the information contained therein to be free of errors Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate Library of Congress Card No.: applied for A catalogue record for this book is available from the British Library Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the internet at http://dnb.ddb.de  Wiley-VCH Verlag GmbH & Co KGaA, Weinheim, 2002 All rights reserved (including those of translation into other languages) No part of this book may be reproduced in any form ± nor transmitted or translated into a machine language without written permission from the publishers Registered names, trademarks, etc used in this book, even when not specifically marked as such, are not to be considered unprotected by law Printed in the Federal Republic of Germany Printed on acid-free paper Composition ProSatz Unger, Weinheim Printing Strauss Offsetdruck GmbH, Mærlenbach Bookbinding Litges & Dopf Buchbinderei GmbH, Heppenheim ISBN 3-527-30514-9 V Contents Preface XVIII List of Authors XXI 1.1 1.1.1 1.1.1.1 1.1.1.2 1.1.1.3 1.1.2 1.1.2.1 1.1.2.2 1.1.3 1.1.4 1.1.5 1.2 1.2.1 1.2.1.1 1.2.1.2 1.2.1.3 1.2.1.4 1.2.1.5 1.2.2 Wave±Material Interactions, Microwave Technology and Equipment Didier Stuerga and Michel Delmotte Fundamentals of Microwave±Matter Interactions Introduction History The Electromagnetic Spectrum Energetics The Complex Dielectric Permittivity Polarization and Storage of Electromagnetic Energy The physical origin of polarization Orienting effect of a static electric field Thermal Conversion of Electromagnetic Energy Physical origin of dielectric loss Relaxation times Consequences of the thermal changes of the dielectric permittivity 11 Conduction losses 13 Magnetic losses 13 Parameters of the thermal conversion 14 Thermodynamic and other Effects of Electric Fields 15 The Athermal and Specific Effects of Electric Fields 17 Conclusions 18 Overview of Microwave Reactor Design and Laboratory and Industrial Equipment 18 Microwave Ovens and Reactors ± Background 19 Applicators, Waveguides, and Cavities 19 Single-mode or Multimode? 20 Limits of Domestic Ovens 21 Temperature-measurement Limits 21 The Design Principles of Microwave Applicators 21 Commercial Laboratory Microwave Reactors 22 Microwaves in Organic Synthesis Edited by Andr Loupy Copyright # 2002 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-527-30514-9 VI Contents 1.2.2.1 1.2.2.2 1.2.2.3 1.2.2.4 1.2.2.5 1.2.3 1.2.3.1 1.2.3.2 1.2.3.3 1.2.4 1.2.4.1 1.2.4.2 The Prolabo Products 22 The CEM Products 23 The Milestone Products 24 The Personal Chemistry Products 25 Plazmatronika Products 26 Experimental Microwave Reactors 26 The RAMO System 26 The Supercritical Microwave Reactor 27 The Coconut Reactor 28 Industrial Equipment ± Batch or Continuous Flow? The Pulsar System 29 The Thermostar System 30 References 32 Microwave-assisted Organic Chemistry in Pressurized Reactors Christopher R Strauss Introduction 35 Rationale for Pressurized Microwave Reactors 36 The Continuous Microwave Reactor (CMR) 37 The Microwave Batch Reactor (MBR) 38 Transfer of Microwave Energy 39 Contrasts between Synthesis and Digestion 40 Advantages of the MBR and CMR 40 Applications of the MBR and CMR 41 Reactions with Sterically Constrained Molecules 42 Preparation of Thermally Labile Products 43 Depolymerization of Cellulose 43 Hofmann Elimination 43 Alkyl 2-(hydroxymethyl)acrylates 44 New Reactions that Require High Temperature 44 Etherification 44 Uncatalyzed Hydrogen-transfer Reduction 46 Reactions Known to Require High Temperatures 46 Willgerodt Reactions 46 Jacobs±Gould Reactions under Solvent-free Conditions 47 Viscous Reaction Mixtures 47 Reaction Vessels 48 Reactions with a Distillation Step 48 Miscellaneous Reactions 49 Kinetic Products 49 Gaseous Reactants and Media 50 High-temperature Water as a Medium or Solvent for Microwave-assisted Organic Synthesis 51 Biomimetic Reactions 51 Indoles 52 2.1 2.2 2.2.1 2.2.2 2.2.3 2.4 2.5 2.6 2.6.1 2.6.2 2.6.2.1 2.6.2.2 2.6.2.3 2.6.3 2.6.3.1 2.6.3.2 2.6.4 2.6.4.1 2.6.4.2 2.6.5 2.6.6 2.6.7 2.6.8 2.6.9 2.6.10 2.7 2.7.1 2.7.2 28 35 Contents 2.7.3 2.7.4 2.7.5 2.8 2.9 2.10 2.11 3.1 3.2 3.3 3.4 3.4.1 3.4.2 3.4.3 3.4.4 3.5 3.6 3.7 3.7.1 3.7.1.1 3.7.1.2 3.7.1.3 Reactions in Aqueous Acid and Base 53 Avoiding Salt Formation 53 Resin-based Adsorption Processes 54 Metal-catalyzed Processes 54 Pressurized Microwave Systems Developed by Others for Organic and Organometallic Chemistry 55 Technical Considerations and Safety 56 Conclusion 57 Acknowledgments 58 References and Footnotes 58 Nonthermal Effects of Microwaves in Organic Synthesis 61 Laurence Perreux and Andr Loupy Origin of Microwave Effects 62 Specific Microwave Effects 63 Effects of the Medium 65 Effects of Reaction Mechanisms 69 Isopolar Transition-state Reactions 70 Bimolecular Reactions between Neutral Reactants Leading to Charged Products 72 Anionic Bimolecular Reactions Involving Neutral Electrophiles Unimolecular Reactions 74 Effect of the Position of the Transition State Along the Reaction Coordinates 74 Effect on Selectivity 75 Some Illustrative Examples 76 Bimolecular Reactions between Neutral Reactants 76 Nucleophilic Additions to Carbonyl Compounds 76 Amines 76 Imine or enamine synthesis 76 Hydrazone synthesis 77 Amidation of carboxylic acids 78 Synthesis of 2-oxazolines 79 Synthesis of aminotoluenesulfonamides 80 Leuckart reductive amination of carbonyl compounds 81 Synthesis of 1,4-dithiocarbonyl piperazines 81 Alcohols 82 Solvent-free esterification of fusel oil 82 Synthesis of alkyl p-toluenesulfinates 82 Synthesis of aminocoumarins by the Pechmann reaction 83 Synthesis of cyclic acetals 83 Michael Additions 84 SN2 Reactions 84 Reaction of pyrazole with phenethyl bromide 84 Ring opening of an epoxide by amines 85 73 VII VIII Contents 3.7.2 3.7.2.1 3.7.2.2 3.7.2.3 3.7.2.4 3.7.3 3.7.3.1 3.7.3.2 3.7.3.3 3.7.3.4 3.7.3.5 3.8 3.8.1 3.8.2 3.8.3 3.8.4 3.8.5 3.8.6 3.9 3.10 4.1 4.2 4.3 N-alkylation of 2-halopyridines 85 Nucleophilic aromatic substitutions 86 Synthesis of phosphonium salts 86 Bimolecular Reactions with One Charged Reactant 87 Anionic SN2 Reactions Involving Charge-localized Anions 88 Selective dealkylation of aromatic alkoxylated compounds 88 Alkylation of dianhydrohexitols under phase-transfer catalysis (PTC) conditions 89 The Krapcho reaction 90 Anionic b-elimination 91 Anionic SN2 Reactions Involving Charge-delocalized Anions 92 Alkylation of potassium benzoate 92 Pyrazole alkylation in basic media 93 Selective alkylation of b-naphthol in basic media 93 Nucleophilic Additions to Carbonyl Compounds 94 Saponification of hindered aromatic esters 94 PTC transesterification in basic medium 94 Ester aminolysis in basic medium 95 Reactions Involving Positively Charged Reactants 97 Friedel±Crafts acylation of aromatic ethers 97 Formylation using Vilsmeier reagent 98 SN2 reactions with tetralkylammonium salts 99 Unimolecular Reactions 99 Imidization Reaction of a Polyamic Acid 99 Cyclization of Monotrifluoroacetylated o-Arylenediamines 100 Intramolecular Nucleophilic Aromatic Substitution 101 Intramolecular Michael Additions 102 Deprotection of Allyl Esters 103 Illustrative Examples of the Effects of Selectivity 103 Benzylation of 2-Pyridone 104 Addition of Vinylpyrazoles to Imine Systems 104 Stereo Control of b-Lactam Formation 105 Cycloaddition to C70 Fullerene 106 Selective Alkylation of 1,2,4-Triazole 106 Rearrangement of Ammonium Ylides 108 Concerning the Absence of Microwave Effects 108 Conclusions 109 References 110 Organic Synthesis using Microwaves in Homogeneous Media 115 Richard N Gedye Introduction 115 Reactions at Elevated Pressures 116 Reactions at Atmospheric Pressure 121 Contents 4.4 4.4.1 4.4.2 4.4.3 4.4.4 4.4.5 4.4.6 4.4.7 4.5 4.6 4.7 5.1 5.2 5.2.1 5.2.1.1 5.2.1.2 5.2.2 5.2.2.1 5.2.2.2 5.2.2.3 5.2.2.4 5.2.2.5 5.2.2.6 5.2.2.7 5.2.2.8 5.2.3 5.2.4 5.2.4.1 5.2.4.2 5.2.5 5.2.5.1 Effect of Microwaves on the Rates of Homogeneous Reactions in Open Vessels 123 Diels±Alder reactions 123 Reactions of Biologically Important Molecules 124 Other Reactions in Polar Solvents 125 Reactions in Nonpolar Solvents 129 Reactions in Homogeneous Media Showing no MW Rate Enhancement 131 Reactions in Homogeneous Media Showing MW Rate Enhancement 133 Possible Explanations of MW Acceleration 135 Selectivity in MW-assisted Reactions 135 Comparison of Homogeneous and Heterogeneous Conditions 140 Advantages and Limitations of MW Heating in Organic Synthesis 142 References 143 Microwave and Phase-transfer Catalysis 147 Andr Loupy, Alain Petit, and Dariusz Bogdal Phase-transfer Catalysis 147 Synthetic Applications of Phase-transfer Processes 150 O-Alkylations 150 Ester Synthesis 150 Alkyl acetates 150 Long-chain esters 151 Aromatic esters 152 Ether Synthesis 153 Aliphatic ethers 153 Furan diethers 153 Diethers from dianhydrohexitols 154 Phenolic ethers 155 Phenolic polyethers 158 N-Alkylations 159 Saccharin 159 Benzoxazinones and Benzothiazinones 159 Barbitone 160 Amides and Lactams 160 Aromatic Amines 161 Phenylpyrrolidino[60]fullerene 161 Five-membered Nitrogen Heterocycles 162 Pyrimidine and Purine Derivatives 162 C-Alkylations of Active Methylenes 163 Alkylations with Dihalogenoalkanes 164 O-Alkylations 164 S-Alkylations 165 Nucleophilic Additions to Carbonyl Compounds 166 Aldol Condensation 166 IX X Contents 5.2.5.2 5.2.5.3 5.2.6 5.2.6.1 5.2.6.2 5.2.6.3 5.2.7 5.2.7.1 5.2.7.2 5.2.7.3 5.2.7.4 5.2.7.5 5.2.7.6 5.2.7.7 5.2.7.8 5.2.7.9 5.2.7.10 5.2.7.11 5.2.7.12 5.2.7.13 5.3 Ester Saponification 167 Base-catalyzed Transesterifications 168 Deprotonations 169 Base-catalyzed Isomerization of Allylic Aromatic Compounds 169 Carbene Generation (a-Elimination) 169 b-Elimination 169 Miscellaneous Reactions 170 Aromatic Nucleophilic Substitution (SNAr) 170 Dealkoxycarbonylations of Activated Esters (Krapcho Reaction) 171 1,3-Dipolar Cycloaddition of Diphenylnitrilimine 172 Synthesis of b-Lactams 172 Selective Dealkylations of Aromatic Ethers 173 Synthesis of Dibenzyl Diselenides 174 Selective Hydrolysis of Nitriles to Amides 174 Synthesis of Diaryl-a-tetralones 175 Intramolecular Cyclization 175 Heck Cross-coupling Reaction 176 Oxidation Reactions 176 S-Alkylation of n-Octyl Bromide 177 Reductive Decyanation of Alkyldiphenylmethanes 177 Conclusion 177 References 178 Organic Synthesis Using Microwaves and Supported Reagents 181 Rajender S Varma 6.1 Introduction 181 6.2 Microwave-accelerated Solvent-free Organic Reactions 182 6.2.1 Protection±Deprotection Reactions 183 6.2.1.1 Formation of Acetals and Dioxolanes 183 6.2.1.2 N-Alkylation Reactions 184 6.2.1.3 Deacylation reactions 184 6.2.1.4 Cleavage of Aldehyde Diacetates 185 6.2.1.5 Debenzylation of Carboxylic Esters 185 6.2.1.6 Selective Cleavage of the N-tert-butoxycarbonyl Group 186 6.2.1.7 Desilylation Reactions 186 6.2.1.8 Dethioacetalization Reaction 186 6.2.1.9 Deoximation Reactions 186 6.2.1.10 Cleavage of Semicarbazones and Phenylhydrazones 188 6.2.1.11 Dethiocarbonylation 189 6.2.1.12 Cleavage of Methoxyphenyl Methyl (MPM) and Tetrahydropyranyl (THP) Ethers 190 6.2.2 Condensation Reactions 191 6.2.2.1 Wittig Olefination Reactions 191 6.2.2.2 Knoevenagel Condensation Reactions ± Synthesis of Coumarins 191 6.2.2.3 Synthesis of Imines, Enamines, Nitroalkenes and N-Sulfonylimines 192 References 109 R Haberkorn, M E Mechel-Beyerle, Biophys J 1979, 26, 489±498 110 N J Turro, G C Weed, J Am Chem Soc 1983, 105, 1861±1868 111 A L Buchachenko, E L Frankevich, Chemical Generation and Reception of Radio and Microwaves,VCH, New York, 1994 112 U E Steiner, T Ulrich, Chem Rev 1989, 89, 51±147 113 M R Wasielewski, C H Bock, M K Bowman, J R Norris, Nature 1983, 303, 520±522 114 J R Norris, M K Bowman, D E Budil, J Tang, C A Wraight, G L Closs, Proc Natl Acad Sci USA ± Biophysics 1982, 79, 5532±5536 115 M Okazaki,Y Konishi, K Toriyama, Chem Lett 1994, 737±740 116 M Mukai,Y Fujiwara,Y Tanimoto, Y Konishi, M Okazaki, Z Phys Chem 1993, 180, 223±233 117 K M Salikhov,Y N Molin, R Z Sagdeev, A L Buchachenko, Spin Polarization and Magnetic Field Effects in Radical Reactions, Elsevier, Amsterdam, 1984 118 G Maret, J Kiepenheuer, N Boccara (eds.) Biophysical Effects of Steady Fields, in: Springer Proc Phys.,Vol 11, Springer, Berlin, 1986 119 C R Timmel, U Till, B Brocklehurst, K A McLauchlan, P J Hore, Mol Phys 1998, 95, 71±89 120 U Till, C R Timmel, B Brocklehurst, P J Hore, Chem Phys Lett 1998, 298, 7±14 121 B Brocklehurst, J Chem Soc Faraday Trans 1976, 72, 1869±1884 122 B Brocklehurst, K A McLauchlan, Int J Radiat Biol 1996, 69, 3±24 123 J R Woodward, R J Jackson, C R Timmel, K A McLauchlan, P J Hore, Chem Phys Lett 1997, 272, 376±382 124 D V Stass, J R Woodward, C R Timmel, P J Hore, K A McLauchlan, Chem Phys Lett 2000, 329, 15±22 125 C R Timmel, J R Woodward, P J Hore, K A McLauchlan, D V Stass, Meas Sci Technol 2001, 12, 635±643 126 J R Woodward, C R Timmel, K A McLauchlan, P J Hore, Phys Rev Lett 2001, 87, 077602 127 R J Jackson, K A McLauchlan, J R Woodward, Chem Phys Lett 1995, 236, 395±401 128 J M Canfield, R L Belford, P G Debrunner, K J Schulten, Chem Phys 1994, 182, 1±18 129 J M Canfield, R L Belford, P G Debrunner, K J Schulten, Chem Phys 1995, 195, 59±69 130 J M Canfield, R L Belford, P G Debrunner, Mol Phys 1996, 89, 889±930 131 C R Timmel, P J Hore, Chem Phys Lett 1996, 257, 401±408 132 C Eichwald, J Walleczek, J Chem Phys 1997, 107, 4943±4950 133 T Ritz, S Adem, K Schulten, Biophys J 2000, 78, 707±718 134 A J Hoff, B Cornelissen, Mol Phys 1982, 45, 413±425 135 J P Scott, D F Ollis, Environ Prog 1995, 14, 88±103 136 G Windgasse, L Dauerman, J Microwave Power Electromagn Energy 1992, 27, 23±32 137 L Campanella, R Cresti, M P Sammartino, G Visco, Microwaves Assisted Photodegradation of Pollutant, SPIE Conf Environmental Monitoring and Remediation Technologies, Boston, 1998, pp 105±113 138 J C Matthews, M G Ury, C H Wood, M Greenblatt, US Pat Appl (1985) US 4532427 139 R A Holroyd, B H J Bielski, US Pat Appl (1980) US 4199419 140 A B Buninger, W P Lapatovich, F L Palmer, J M Browne, N H Chen, Eur Pat Appl (1999) EP 0962959 141 J L Moruzzi, PCT Int Appl (2001) WO 0109924 142 M Lipski, J Slawinski, D Zych, J Fluoresc 1999, 9, 133±138 143 W F Downey Jr, US Pat Appl (1995) US 5439595 144 R M G Boucher, US Pat Appl (1975) US 3926556 145 R A R Little, D Briggs, Eur Pat Appl (1997) EP0772226 146 J Lucas, J L Moruzzi, PCT Int Appl (2000) WO 0032244 147 V A Danilychev, US Pat Appl (1997) US 5666640 485 486 14 Microwave Photochemistry 148 V A Danilychev, US Pat Appl (1999) US 5931557 149 J D Michael, US Pat Appl (2001) US 6171452 150 J D Michael, US Pat Appl (2000) US 6162406 487 Index a acetalization 268, 355 acetanilide 160 acetonitrile 383, 397, 475 acidic cation-exchange resin 371 N-acrylated heterocycles 408 activated aromatic substrates 86 activated charcoal 220 activated manganese dioxide±silica 196 activation barriers 305 activation energy 64 activation energy barrier 357 active metal salts 347 active sites 364 acylation of aromatic compounds 235, 239 acylative cleavage of ethers 240 N-acylimidates 283 acylium ion 97 addition of CCl3X to styrene 141 addition of 2-aminothiophenol 137 addition of vinylpyrazoles to imine systems 104 addition to a carbonyl group 72 adsorbed tritium method 439 agrochemical research laboratories 430 Alder reaction 225 Alder±Bong reaction 119 aldimines 163 aldol condensation 166 aliphatic ethers 153 aliquat 151 aliquat 336 150 alkyl 232 alkyl acetates 150 alkyl glycosides 274 alkyl halides 155 alkyl 2-(hydroxymethyl)acrylates 44 N-alkyl imides 412 N-alkylation 158, 177, 184, 288, 356 alkylation of dianhydrohexitols 89 C-alkylation of b-naphthol 94 alkylation of potassium benzoate 92 N-alkylation of 2-halopyridines 85 O-alkylation 150, 159, 164 f C-alkylation of active methylenes 163 alkylation with dihalogenoalkanes 164 O-alkylcarbamates 228 N-alkylimidazolium cations 212 alkynes 333 allylic alkylations 398 allylic aromatic compounds 169 allylic substitution 380 a-Al2O3 367 alumina 20, 69, 84, 151, 164, 184, 190, 346 alumina doped NaBH4 447 alumina-supported nickel catalyst 348 alumina-supported potassium permanganate 200 aluminosilicate support 197 amberlite 354 Amberlyst-15 352, 363 ambident 2-naphthoxide anion 93 amidation of carboxylic acids 78 amide 160, 387 f., 388 amines 448 ortho-aminochalcones 102 aminocoumarins 231 aminolysis 413 2-amino-substituted isoflav-3-enes 204 aminothiophenes 260 ammonium acetate 193 ammonium formate 201, 255, 353 ammonium persulfate on silica 188 amorphous carbon 219, 246 amorphous graphite 219 anilines 356, 388 anionic activation 171, 280 anionic bimolecular reactions 73 anionic b-elimination 91 annelated pyridines 277 anthracene 310, 477 MW apparatus 244 Microwaves in Organic Synthesis Edited by Andr Loupy Copyright # 2002 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-527-30514-9 488 Index apparent activation energy 100 applicator 19 aqueous hydrotope solution 262 aqueous media 182 aromatic amines 161 aromatic decarboxylation 449 aromatic dehalogenation 446 aromatic esters 152 aromatic ethers 155 aromatic nucleophilic substitution 170 Arrhenius law 63 aryl iodides 396 aryl phosphonates 396 N-arylated heterocycles 400 aryldiazepinone synthesis 67 arylimidazole synthesis 269 asymmetric catalysis 396 asymmetric Diels±Alder reactions 315 1,2 asymmetric induction 84 asynchronous mechanism 71 athermal effects 17 aza Diels-Alder additions 49 azadiene 312 azadienes 222 azaheterocycles 162 azeotropic removal 192 azetidinones 337 azides 333 aziridation of olefins 400 aziridination of olefins 255 aziridine synthesis 255, 268 aziridines 269, 319, 400 azolic fungicides 107 azomethine imines 333 azomethine ylides 317 b barbitone 160 base-catalyzed isomerization 169 base-catalyzed transesterification 168 basic alumina 86 basic clays 355 basic zeolites 349, 362 batch 359 batch reactor 28, 369 Baylis-Hillman 50 Baylis±Hillman adducts 329 Baylis-Hillman reaction 44 Beckmann rearrangement 188, 194 f bentonite 319 benzimidazole 122, 269 benzodiazepine 260 benzoic acid 388 benzotrifluoride 419 benzoxazinones and benzothiazinones 159 benzoxazoles 195 benzoylation of benzene 238 benzyl halides 152 benzylation of 2-pyridone 104 betonite 421 Biginelli condensation 208, 421, 426 Biginelli cyclocondensation 264 Biginelli dihydropyrimidine synthesis 65, 422 Biginelli synthesis of dihydropyrimidines 128 bimolecular reactions between neutral reactants 72, 76 bimolecular reactions with one charged reactant 87 bioactivity 405 biological properties 405 biomimetic reactions 51 biradicals 476 bismuth trichloride 189 Boc-protected allylamine 383 f borohydride reductions 447 bromoacetals 169 Brownian motion 3, building blocks 406 bulk temperature 4, 183, 357 c C70 321 C±C bond formation 209 Cannizzaro reaction 203 capacitive coupling 465 carbamates 414 carbene generation (a-elimination) 169 carbohydrate glycosylations 274 carbohydrates 94 carbon lattice 234 carbon monoxide 387 carbon±carbon coupling reactions 380 carbonylative coupling 380, 387 carboxylic acids 387, 395 carboxylic amides 395 carboxylic amines 395 catalyst 149 catalyst activation and reactivation 350 catalyst active sites 357 catalytic activity 347 catalytic conversion of methane 374 catalytic cycle 346 catalytic effect 242 catalytic effect of graphite 237 catalytic gas-phase reactions 357 catalytic hydrogenation 361 catalytic sites 359 cation 168 Index cellulose membranes 414 CEM Corp 427 CEM products 23 chalcone 175 charge-delocalized anions 92 charge-localized anions 88 chelation-controlled Heck reactions 382 chemical equilibrium 15, 406 chemoselectivity 295, 381 chloroquinoline ring 101 chromatography 405 chromium trioxide±wet alumina 196 cineole derivatives 166, 278 cineole ketone 83 ortho-Claisen rearrangement 119, 261 Claisen rearrangements 412 Claisen±Schmidt condensation 53 classical heating 15 claycop±hydrogen peroxide 198 clayfen 189, 197, 209 clays 69 cleavage of aldehyde diacetates 185 cleavage of benzoic acid 413 cleavage of methoxyphenyl methyl ethers 190 cleavage of semicarbazones and phenylhydrazones 188 closed system 36 closed Teflon vessels 115 coconut reactor 28 combinatorial chemistry 41, 143, 405, 442 combinatorial library 263 combinatorial synthesis 208 combined MW/UV irradiation 479 comparison of homogeneous and heterogeneous conditions 140 complex dielectric permittivity concerning the absence of microwave effects 108 condensation reactions 191 condensed phases 11 conduction losses 13 continuous flow 24, 28 continuous microwave reactor 37 continuous process 27 continuous-flow process 247 continuous-flow reactor 352, 371 convection 364 conventional heating 62 Cope rearrangement 70 copper sulfate or oxone±alumina 198 cosmetic compounds 156 cosmetic products 278 coumarin synthesis 67 coumarins 229, 261, 272 coupling of aryl halides 55 coupling reactions 54 cracking 361 creatinine 265, 282 cross-coupling 380, 389 cross-coupling reactions 389 crossed-aldol condensations 125 cross-linked polymer 417 cross-linking of polymers 143 18-crown-6 275 crown ethers 147 cyanation of aryl bromides 395 cyanuric acid 233 cyclic b-ketoesters 90, 171 cyclization of monotrifluoroacetylated o-arylenediamines 100 cycloaddition 71, 76, 295, 302, 316, 335 cycloaddition reactions 295 cycloaddition to C70 fullerene 106 cyclocondensation 101 1,2-cyclohexanedione 384 cyclopentadiene 224 d Danishefsky's diene 139 deacylation reactions 184 dealkoxycarbonylations of activated esters (Krapcho Reaction) 90, 171 Dean±Stark apparatus 192 debenzylation of carboxylic esters 185 Debye decarboxylation 52, 322 decomplexation of metal complexes 231 deethylation 173 dehydration of aldoxime 208 demethylation 88, 173 deoximation 188 deoximation reactions 186 depolymerization of cellulose 43 deprotection 186 deprotection of N-Cbz and N-Bn derivatives 266 deprotection of allyl esters 102 deprotonations 169 desilylation reactions 186 dethioacetalization reaction 186 dethiocarbonylation 189 detritiation reactions 453 deuterated ionic liquid 445 deuteration 442 deuteration and tritiation reactions 210 deuterium labeled compounds 436 deuterium labeling 267 489 490 Index diacylhydrazines 415 N,N-dialkylimidazolium cations 444 1,3-dialkylimidazoliums 287 dianhydrohexitols 154, 281 diaroyl furoxans 327 diastereoisomeric excess 84 diastereoisomers 324 diazepines 130 diazoketones 337 1,3-dicarbonyl compounds 411, 421 dielectric constant 57 dielectric heating dielectric loss 7, 10 dielectric permittivity 4, f., 11 dielectric relaxation 65 Diels-Alder additions 49 Diels±Alder cycloadditions 70 Diels±Alder reaction 67, 105, 123, 136, 221, 299, 386 digestion 40 3,5-dihydroimidazol-4-one derivatives 277 dihydropyridine 277, 428 dihydropyridine library 429 dihydropyrimidines 421 dimethyl acetylenedicarboxylate 308, 312 dimethyl malonate 397 dimethyl sulfoxide (DMSO) 181, 447 dimethylformamide (DMF) 168, 181 dioxolane 273 diphenylnitrilimine 172, 331 1,3-dipolar cycloaddition 70, 71, 172, 289, 299, 317 dipolar polarization 62, 69 dipolar transition states 74 dipolar TS 86 dipolarophiles 172 1,3-dipole 317 dipole moment dipole orientation dipole rotation 39 dipole±dipole interactions 62 diradical intermediates 335 Discover 244, 441 Discover I 429 dissipation 14 dissipation factor 39 dissolution of solid samples 40 distribution of dipoles dithiolanes 274 DMF 259, 383, 388, 395 DMSO 387 domestic ovens 18 doped catalysts 357 dry media 35, 56 drying and calcination 347 dry-media reactions 422 dummy load 470 e eco-friendly green procedures 182 effect of selectivity 75 effects of reaction mechanisms 69 effects of the medium 65 electrodeless 464 electrodeless discharge lamp (EDL) 464 electrodeless mercury lamp 464 electromagnetic energy electromagnetic spectrum electron-deficient dienophiles 312 electrophilic aromatic substitution 99 electrostatic interactions 70 eletrodeless MW±UV lamp 479 b-elimination 73, 165, 169, 280 enamines 76 enantiomeric excess 396, 398 enantiomeric purity 399 enantioselectivity 211 endo and exo isomers 307 endo/exo selectivity 303 ene reactions 115, 131, 225 energy 14 energy of activation 17 energy transfer 67 enthalpy of activation 17 entropy 303 entropy of activation 17 environment 35 environmentally benign 57 enzymatic catalysis 279 enzyme-catalyzed reactions 211 epichlorohydrin 50, 157 epoxidation 177, 362 epoxide 157 epoxide ring-opening 164 equipment 424 Eshweiler-Clarke reaction 448 ester aminolysis 95 ester saponification 167 ester synthesis 150 esterification 42, 56, 65, 141, 351 esterification of acetic acid 131 esterification of benzoic acid 131 esterification of carboxylic acids 115 esterification of stearic acid by n-butanol 234 esters 387 ether synthesis 153 etherification 44 Index Ethos SYNTH 425, 441 ethylene glycol 388 eugenol±isoeugenol isomerization 195 exo/endo 307 explosions 35 f fatty compounds 168 fatty oxirane 276 fatty sulfides 200 Ferrier rearrangement 196 ferrocene 337 fiber optic thermometer 370 f fiber-optic probes 425 field distribution 424 Fischer indole synthesis 52 five-membered heterocycles 317 five-membered nitrogen heterocycles 162 flash heating 254 flash thermolysis 299, 311 flavones 204 fluidization technique 373 fluidized bed 369 fluorinated dipolarophiles 323 fluorocarbon solvents 419 fluoroptic probe 397 fluorous chemistry 393 fluorous phase 406 fluorous Stille reactions 394 fluorous-phase synthesis 419 Fmoc-protected amino acids 407 focused microwave 23 focused waves 126 formate 445 formation of acetals and dioxolanes 183 formylation using Vilsmeier reagent 98 fractal dimension 220 free energy change 17 free or conduction electrons frequency Friedel±Crafts acylation 235, 355 Friedel±Crafts acylation of aromatic ethers 97 frontier orbital interactions 302 C70 fullerene 76, 246 fullerene derivatives 309 fullerenes 309 fulleropyrrolidines 319 fulvenes 316 functionalized tartramides 79 furan 304 furan diethers 153 furanic diethers 281 furfuryl alcohol 164 g Gabriel amine synthesis 160 Gabriel synthesis 191 gamma radiation 325 gaseous reactants and media 50 gas-phase reactions 219, 351 Gedye 37, 56, 61 generators 27 germanium tetrahalides 232 Giguere 37 glass transition temperature 134 glyoxal monohydrazones 276 grafted ionic liquid phase 289 graphite 177, 299, 311 f., 315, 352 graphite as a sensitizer 220 graphite as sensitizer and catalyst 234 graphite-supported catalysts 227 graphitization of carbon 246 green chemistry 61, 240, 298, 445 Grignard reagent 329 ground state 70 h halogenated acetals 91, 280 halogenated heterocycles 411 halogermanes 232 Hammond postulate 74 Hantzsch procedure 205 Hantzsch pyridine synthesis 421 Hantzsch-1,4-dihydropyridine synthesis 262 hard ions 74 hardness 321 harsh conditions 81 heat transfer 368 heat-transfer mechanisms 471 Heck arylation 353 Heck coupling 380 Heck coupling reactions 354 Heck cross-coupling reaction 176 Heck reaction 54 Heck vinylation 254 Henry reaction 193 hetero Diels±Alder reactions 312 heterobicycles 265 heterobicyclic lactams 275 heterocycles 122, 395 heterocyclic chemistry 204, 253 heterocyclic ketene aminals 282 hetero-Diels±Alder reaction 222, 299 heterodienes 312 heterodienophiles 315 heterogeneous catalyst 54, 346 heterogeneous media 69 high pressures 22 491 492 Index high-boiling solvents 36 higher hydrocarbons 358 high-pressure conditions 315, 380 high-temperature water 51 HIV protease inhibitor 139, 390, 392, 395 Hofmann elimination 43 homogeneous and heterogeneous catalysis 141 homogeneous catalysis 379 homogeneous electromagnetic field 126 homogeneous media 115 hot spots 63, 227, 359, 362, 364 Hughes±Ingold model 70 hydrazines 194 hydrazone synthesis 77 hydrazones 193 hydrazonyl chlorides 331 hydroacylation of 1-alkenes with aldehyde 110 hydrogen cyanide 360 hydrogen isotope exchange 442 hydrogen peroxide 176 f., 356 hydrogenation 353, 438, 445 hydrogenation reactions using formates 211 hydrogen±deuterium exchange 443 hydrogenolysis 353, 361 hydrogen-transfer reduction 46 hydrolysis of amides 42, 115 hydrolysis of sucrose 354, 363, 371 hydrosilylation 399 hydrostannylation 393 a-hydroxy b-lactams 337 o-hydroxychalcones 204 a-hydroxyketones 198 Hyflo Super Cell 211, 279 i imidazole 272, 355, 422, 444 imidazoline 319 imidazolones 318 imidization 64 imidization reaction 64 imidization reactions of a polyamic acid 99 imine 76 a-iminoacids 449 impregnated reagents 69 impregnation 347 incident power 20 increased selectivity 75 indole 52, 272, 443, 449 indolizines 319 industrial applications 373, 480 industrial equipment 18 industrial scale 27 infrared 21 infrared sensor 118 inner electrons inorganic chemistry 295 intercalated compounds 220 intercalating guest 234 intercalation 246 interfacial reactions 69, 148 internal arylation 383 internal pressure 36 intramolecular addition 74 intramolecular cyclization 175, 226 intramolecular Diels±Alder reaction 304 intramolecular hetero-Diels±Alder reaction 312 intramolecular Michael addition 102, 204 intramolecular nucleophilic aromatic substitution 101 iodine 190, 199 iodobenzene diacetate (IBD)-impregnated alumina 199 ionic and radical pathways 108 ionic conduction 39, 472 ionic conductivity 13 ionic equilibrium 16 ionic liquid 182, 212, 253, 416, 436, 444 ionization 74, 466 ion-pair exchange 148 f ion-radicals 481 IR pyrometer 470 IR thermometer 370 isatin 331 isatin derivatives 322 isocyanates 282 isocyanides 207 isomerization 139 isomerization and rearrangement reactions 194 isomerization of carvone 131 isophorone 164, 175 isopolar transition-state reactions 70 isosorbide 154 isotopes 435 isotopic incorporation 451 j Jacobs±Gould reactions 47 jasminaldehyde 166 k K 10 356 K 10 clay 185 ketene acetals 169 ketene±imine reaction pathway 336 Index ketodecarboxylation of carboxylic diacids 235, 241 b-ketoester 128, 129, 411 KF±alumina 319 kinetic products 49 KMnO4±Al2O3 200 Knoevenagel condensation 67, 191, 282 Knoevenagel reaction 127, 166, 410 Krapcho reaction 90 KSF 356 l labeled compounds 435, 455 f labeling with 18F 307 b-lactam chemistry 255 b-lactam derivatives 335 lactam synthesis 269, 275 b-lactams 66, 160, 353, 450 lactone 183 lactone preparation 276 Langevin function Langevin theory Lawesson's reagent 206, 422 Lawesson-type thionating reagent 415 layer structure 220 leaving groups 151 Leuckart reductive amination 81 Lewis acid 186, 194 liquid±liquid PTC 147 f liquid-phase reactions 351 liquids 470 localized hot-spots 124 localized superheating in the solid phase 365 long chain alkyl bromides 156 long-chain esters 151 loose ion pairs 73 f loss tangent 414 m magnetic losses 13 magnetic susceptibility magnetite (Fe3O4) 236, 242 magnetron 19 Marshall linker 414 MARS-S multimode reactor 427 Maxwell equations medicinal chemistry 395, 406 Meerwein-Ponndorf-Verley reduction 46 Merrifield 407 Merrifield resin 193 MES company 29 f metal inclusions of graphite 220 metal-catalyzed processes 54 metal-catalyzed reactions 380 methods for incorporating tritium 436 methylation reactions 448 N-methylformamide (NMF) 391 N-methylmorpholine (NMM) 326, 332 Michael additions 49, 84 Michael condensation 175 Michael reaction 160 microscopic high temperatures 65 microwave absorption 63 microwave batch reactor 38 microwave catalysis 345 microwave cavity 13 microwave discharge 466 microwave flash heating 379, 408 microwave heating 15 f microwave heterogeneous catalysis 345 microwave homogeneous catalysis 345 microwave instrumentation 424 microwave organic reaction enhancement (MORE) 297 microwave photochemical reactor 467 microwave photochemistry 463 microwave plasma 350 microwave reactor design 18 microwave-accelerated solvent-free organic reactions 182 microwave-assisted combinatorial chemistry 430 microwave-assisted digestion 40 microwave-assisted library synthesis 428 microwave-enhanced tritiation reactions 442 microwave-generated plasma 350 microwave±matter interactions microwave±ultrasound reactor 56 Milestone 425 Milestone ETHOS 1600 series 128 Milestone products 24 mineral oxides 63, 182 mineral supports 149 mineralization 471 modification of zeolites 349 modified commercial microwave ovens 296 modified domestic oven 56 modified MW 469 modified zeolites 362 molecular collisions 11 molecular sieves 351, 400 molybdenum hexacarbonyl complex 387 molybdenum-catalyzed asymmetric reaction 398 monoalkylation 163 monobenzylated isosorbide 90 monobenzyloxy isosorbide 165 monomodal cavity 441 493 494 Index monomode cavity 245 monomode instrument 412 monomode reactor 167, 416 montmorillonite 76, 84, 349, 352 montmorillonite K 10 100, 103, 183, 188, 202, 422 montmorillonite KSF 87 MORE 256 MORE chemistry 35 multi-component reactions 207, 409 multimodal mode 441 multimode 20 multimode cavities 19, 424 multiple component condensation 207 multiPREP rotors 425 multistep synthesis of polyheterocyclic systems 258 mutarotation of glucose 138 mutual orientation 64 MW±UV combined reactor 470 MW±UV-assisted reaction 475 n Nafion 445 NaY zeolite 349 near-synchronous mechanism 72 neutral alumina 184 nickel catalysts 359 Niementowski reaction 77 nitration of styrenes 209 nitrile imines 331 nitrile oxides 326 nitriles 395 nitroalkanes 193 nitrones 71, 323 NMM 335 nonpolar 470 nonpolar molecules 63 nonpolar solvents 10, 67, 368 nonthermal effects 17, 61 Norrish type II reaction 474 nucleation 474 nucleation regulator 63 nucleophilic additions 73 nucleophilic additions to carbonyl compounds 76, 94, 166 nucleophilic aromatic substitution 86, 456 nucleophilic substitution 412, 420 o oligomerization of methane 359 oligomers 359 one-pot conditions 225 one-pot procedure 299 on±off cycles 369 optical fiber thermometer 21, 245 organoboron compounds 389 organometallic chemistry 379 organometallic compounds 120 organometallic reactions 209 organotin reactants 389 orientation polarization orienting effect 6, 17 orienting effect of electric field orienting effects origin of microwave effects 62 orthoesters 269 oscillating magnetic field effect 477 1,3,4-oxadiazole synthesis 264 oxadiazoles 324, 328, 415 oxathiolanes 274 oxazolidine 319 oxazolidones 395 oxazoline 397, 458 oxidation of alkyl benzenes 115 oxidation of arenes and enamines 200 oxidation of benzene 356 oxidation of enamines 200 oxidation of propan-2-ol 227 oxidation of sulfides 199 oxidation of toluene 361 oxidation reactions 176, 196 oxidation using KMnO4±Al2O3 278 oxidative cleavage 186 oxidative coupling of methane 358, 374 oximes 195 p palladium 54, 176, 379, 409 palladium catalyst 353 f., 388 palladium complexes 209 palladium-catalyzed reactions 334 palladium-catalyzed Stille couplings 419 palladium(0)-catalyzed transformations 380 palladium-doped alumina 210 parallel synthesis 406, 420 partial oxidation of methane 360 Pechmann reaction 83, 229 PEG 391, 400 PEG-bound aryl iodides 418 PEG-400 174, 177 penetration depth 27 peptide bond 407 pericyclic reactions 296 perimidine derivatives 313 personal chemistry products 25 PersonalChemistry 427 pesticides 479 Index petrochemistry 357 pharmaceutical 430 pharmaceutical industry 436 phase transfer agent 96 phase transfer catalysis 69, 147, 436 phase transfer catalyst 152, 391 phase-transfer conditions 384 phenacylations of 1,2,4-triazole 107 phenethylation of pyrazole 84 phenol 481 phenolic acetates 184 phenolic ethers 155 phenolic polyethers 158 phenylethanol 400 N-phenylmaleimide 308 phenylpyrrolidino[60]fullerene 161 phosphine alkylation 72 phosphine ligands 391 phosphonium salts 191 phosphorus ylides 191 photocatalytic activity 475 photocatalytic oxidation 475 photochemical reactions 463 photochemistry photodegradation of pollutants 479 photolithography 480 photolysis of organic compounds 468 phthalimide 397 phthalimide synthesis 283 pinacol±pinacolone rearrangement 195 Planck's law 63 plasma discharge 463 Plazmatronika products 26 polar mechanisms 70, 440 polar molecules 10, 63 polar solvents 115, 470 polar transition state 192, 481 polarization f pollutants 479 polyethers 154 polyheterocyclic compounds 133 polymer-bound 406 polymer-bound ester 413 polymerization 136 polymer-supported building blocks 264 polymer-supported Burgess reagent 264, 415 polymer-supported reagents 415 polystyrene resins 408 polystyrene Wang resin 407 porous silica gel 349 position of the transition state 74 positron emission tomography 454 possible explanations of MW acceleration 135 potassium carbonate 152, 160, 162 potassium fluoride 206 potassium hydroxide 155, 160, 162 pre-exponential factor 64 preparation of Benzo[b]furans 281 preparation of heterogeneous catalysts 347 pressure control 23 pressure increases 121 pressure-controlling device 56 pressure-release Savillex 118 pressurized reactors 35 product distribution 368 Prolabo products 22 Prolabo Synthewave S402 441 protected carbohydrates 168 protection group 456 protection of amines 266 protection±deprotection reactions 183 protection±deprotection strategy 458 PTC 331 pulsar system 29 purine derivatives 162 pyrazine 270, 310 pyrazole 257, 284, 314 pyrazole alkylation in basic media 93 pyrazole derivatives 314 2-pyrazoline 333 pyridazinones 276 pyridine 270, 285, 314, 442, 456 pyridone 285 pyrimidine 162, 270, 283 pyrimidone 314 pyrolysis of urea 56, 233 pyrolytic sublimation 231 IR pyrometer 245 a-pyrones 316 pyrroles 272 q quantum mechanics quaternary onium salts 147 quinazolines 133 quinolines 271 quinolinyl ethers 157 quinolone antibacterials 47 quinoxalines 271 r racemization of amino acids 124 racemization of L-proline 125 radar applications radical pairs 476 radical-mediated cyclizations 419 radical-pair chemistry 477 radical-recombination 476 495 496 Index radioactive waste 453 radiochemical syntheses 441 radiochemistry 295, 435 radioisotopes 435 radiopharmaceuticals 120, 435 radiopharmaceuticals labeled 56 RAMO system 26 Raney nickel 188 rare earth basic oxides 359 rate enhancement 35, 118 rates of homogeneous reactions 123 rationalization of microwave effects 109 reaction mechanisms 67 reaction medium 65 reaction of pyrazole with phenethyl bromide 84 reaction under pressure 296 reaction vessels 48 SN2 reactions 84 reactions at atmospheric pressure 121 reactions at elevated pressures 116 reactions in aqueous acid and base 53 reactions in nonpolar solvents 129 reactions involving positively charged reactants 97 reactions of biologically important molecules 124 reactions of methane 358 reactions under reflux 296 reactions with a distillation step 48 SN2 reactions with tetraalkylammonium salts 99 reactons on graphite 219 reagents 406 rearrangement of ammonium ylides 108 rearrangement of geraniol 126 recoil labeling 439 recombination reaction 476 recyclability 182 reduction reactions 201 reductive amination of carbonyls 202 reductive decyanation of alkyldiphenylmethanes 177 regeneration of carbonyl compounds 186 regeneration of zeolites 350 regioselective esterification of glycopyranosides 279 regioselectivity 75, 85, 104, 295, 381, 383 relaxation frequency 12 relaxation time f reproducibility 117, 197 resin cleavage 413 resin-based adsorption processes 54 resin-bound nitroalkenes 410 resonant cavities 19 retardation of nucleation 63 retention mechanism of reactants on graphite 246 retro-Diels±Alder reaction 221, 299, 309, 311 retro-ene reaction 228 reversibility 295 rhodium dimer 123 ring opening of an epoxide by amines 85 ring-expansion 195 ring-opening 157 Robinson annulation 175 room temperature ionic liquids 287, 418 rotating reactor 245 rotational states 11 ruthenium catalysis 400 s saccharin 159 safety 35, 116 safety considerations 471 safety measures 244 salicylaldehydes 281 saponification 75 saponification of hindered aromatic esters 94 scaling-up 36, 373 Schiff base 418 selective alkylation of b-naphthol 93 selective alkylation of 1,2,4-triazole 106 selective cleavage of the N-tert-butoxycarbonyl group 186 selective dealkylation of aromatic alkoxylated compounds 88 selective dealkylations of aromatic ethers 173 selective deprotection 190 selective heating 41, 347, 364 selective heating of active sites 351 selective heating of the catalyst 141 selective hydrolysis of nitriles to amides 174 selectivity 61, 135, 301, 361, 381 selectivity effects 103 selenium 174 semiconductor devices 480 sensitizer 220 sequential MW irradiation 224 silica 69, 346, 352 silica gel 82, 102, 159, 193 silyl protecting groups 186 single-mode 20 single-mode cavities 20 single-mode continuous-flow reactors 371 singlet excited state 476 singlet state 476 slow-reacting system 92 Index small-molecule libraries 207 SmithSynthesizer 25, 427, 441 sodium borohydride±alumina 201 sodium cyanoborohydride 202 sodium periodate 188 sodium periodate±silica 199 soft ions 74 solid mineral supports 69 solid phase 54 solid supports 30, 390 solid±liquid PTC 147 f solid-phase organic synthesis 406 f., 415 solid-phase Ugi reactions 410 solid-state deuteration 202 soluble polymer-supported synthesis 417 solution-phase library 322 solvent effects 65 solvent-free 61 solvent-free conditions 35, 297 solvent-free esterification of fusel oil 82 solvent-free synthesis 267 solvolytic processes 45 Sommelet±Hauser sigmatropic rearrangement 108 sonication 169 sonochemistry 65 Sonogashira coupling 380 Sonogashira coupling reaction 210, 388 soybean oil 353 SP 435 Novozym 211, 279 spatial distribution 21 specific absorption 67 specific effects 17, 301 specific microwave effects 63 specific selectivity 298 specific surface 246 Spencer stabilization of the transition state 70 stearic acid 351, 363 stereo control of b-lactam formation 105 stereochemistry 139 stereoselectivity 295, 301 steric constraints 42 sterilization techniques 481 steroid compounds 353 Stevens rearrangement 108 Stille coupling reactions 253 Stille couplings 392 structure of reactive ion pairs 73 structuring effect 10 styrene 399 substituted amides 96 N-substituted imidazoles and imidazolines 276 substituted thiazoles 205 substitution and elimination reactions 136 SN2 substitutions 73 sulfonation of naphthalene 137 sulfonylation of mesitylene 98 N-sulfonylimines 193 supercritical fluids 436 supercritical microwave reactor 27 superheating 364, 397 superheating effect 63, 123, 297 superheating of liquid 364 superheating of polar solvents 474 superheating of the catalyst 351 superheating of the solvent 394 superoxide radicals 480 supported catalysts 346 supported reagents 181, 299 surface area 347 surface reaction 346 Suzuki couplings 389, 417 Suzuki cross-coupling reaction 210 synchronous mechanisms 108 synergic effect 463, 473 synthesis 76 synthesis of a thiazoquinazoline 133 synthesis of alkyl-p-toluenesulfinates 82 synthesis of aminocoumarins 83 synthesis of aminotoluenesulfonamides 80 synthesis of 2-aroylbenzofurans 206 synthesis of 1,5-aryldiazepines-2-ones 129 synthesis of chalcones 125 synthesis of coumarins 191 synthesis of cyclic acetals 83 synthesis of diaryl-a-tetralones 175 synthesis of dibenzyl diselenides 174 synthesis of enamines 192 synthesis of heterocycles 253 synthesis of imines 192 synthesis of b-lactams 172 synthesis of nitroalkenes 192 synthesis of b-nitrostyrenes 209 synthesis of phosphonium salts 86 synthesis of phthalimides 130 synthesis of phthalimidoacetic acid 122 synthesis of quinolones 206 synthesis of radiolabeled compounds 210 synthesis of N-sulfonylimines 192 synthesis of thiazoloquinazoline 258 synthesis of trifluoromethyl aryldiazepines 129 synthesis of 1,4-dithiocarbonyl piperazines 81 synthesis of 2-oxazolines 79 synthetic commercial graphites 235 497 498 Index Synthewave 402 23, 256, 274, 285 Synthewave 1000 23, 151, 244 Synthewave 402 (Prolabo) 470 t tandem Claisen rearrangement±cyclization 261 TantaGel resins 414 technical considerations and safety 56 Teflon 21 Teflon flask 26 temperature gradients 69, 364, 424 temperature homogeneity 69 temperature level 109 temperature measurement 21, 23, 245, 425 temperature-profile 62 TentaGel resin 408 TE033 propagation mode 31 tetraalkylammonium salts 69 tetraarylgermanes tetrahalides 232 tetrabutylammonium bromide (TBAB) 149, 184 tetrahydropyranyl ethers 190 tetrahydroquinolones 102 tetraphenyl porphyrin 267 tetrazines 222 tetrazole 334, 395, 408 thalidomide 284 theoretical calculations 71, 336 thermal conversion 14 thermal conversion of electromagnetic energy thermal cure of epoxy resins 134 thermal effects 474 thermal gradients 47 thermal reactions in heterocyclic syntheses 229 thermal runaway 20, 56, 388 thermally labile products 43 thermodynamic effects 15 thermolysis ammonium 78 thermolysis of esters 227 thermostar system 30 thia-Fries rearrangement 194 thiazoles 395 thienamycin side chain 335 thioacetals 184 thioamides 415 thiocarbonyls 189 thiohydantoin 265 thionation of amides 416 thiophene 311 tight ion pairs 74, 89 TMEDA 446 p-toluenesulfinate esters 82 p-toluenesulfonic acid 101, 132, 183 a-tosyloxyketones 206 transesterification 94, 168, 351, 363, 418 transfer of microwave energy 39 transformation of arylaldehydes to nitriles 208 transglycosylation 211, 280 transition metal catalysis 379 transition states 321 transition-metal catalyzed reactions 429 transmission electron microscopy 235 triazine 314, 411 1,2,4-triazole 285, 333 triazoles 66, 257, 395 triazoline-2-one derivatives 331 tricyclic taxoid skeletons 306 triglycerides 352, 363 triphenylphosphine 416 triplet excited state 476 triplet radical pair 478 tritiated formates 446 tritiation procedures 437 Turbosphere 28 u Ugi-type multicomponent reaction 422 ultrasonic 200 ultrasound 91, 170, 189, 280, 352, 463 ultraviolet discharge in electrodeless lamps 464 ultraviolet radiation 56, 466 unimolecular reactions 74, 99 unnatural D-amino acids 124 unsymmetrical acetylenes 388 v valence electrons valerophenones 474 van der Waals interactions 246 vibrational states 11 vinylation 386 vinyl-b-lactams 337 vinylpyrazoles 308 2-vinylpyridine 399 viscous reaction mixtures 47 volume of the vessel 118 V2O5/SiO2 catalyst 348 w Wang and Merrifield resins 408 Wang resin 407 water 51 waveguides 19 Index wavelength Weflon 427 Wilkinson's catalyst 400, 416, 445 Willgerodt 50 Willgerodt reactions 46 Williamson synthesis 44, 153 Wittig olefination reactions 191 Wolff±Kishner reduction 78, 193 x X-ray diffraction 235 z zeolite 197, 219, 445 zeolite±HY 355 zinc chloride 194 zwitterionic intermediates 335 499 ... 76 Amines 76 Imine or enamine synthesis 76 Hydrazone synthesis 77 Amidation of carboxylic acids 78 Synthesis of 2-oxazolines 79 Synthesis of aminotoluenesulfonamides 80 Leuckart reductive amination... 269 Pyridine, Pyrazine, and Pyridine Derivatives 270 Quinolines and Quinoxalines 271 Pyrroles, Indoles and Related Compounds; Imidazoles 272 Preparations of Coumarins 272 Dioxolane Synthesis. .. microwave-assisted organic Microwaves in Organic Synthesis Edited by Andr Loupy Copyright # 2002 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-527-30514-9 XX Preface synthesis in homogeneous