About the Authors ............................................. xii
Chapter 1 Fundamentals of Aqueous Microwave Chemistry .......... 1
Vivek Polshettiwar and Rajender S. Varma
1.1 Introduction ............................................... 1
1.2 Green Chemistry Approach ................................... 2
1.3 Water as Green Solvent ..................................... 3
1.4 Why Microwaves? ............................................ 4
1.4.1 Thermal Effect ...................................... 4
1.4.2 Non-thermal Effect .................................. 5
1.4.3 Selectivity towards Water ........................... 6
1.4.4 Selectivity towards Catalyst ........................ 7
1.4.5 Catalyst as Susceptors .............................. 7
1.4.6 Stability of Catalyst ............................... 7
1.5 Conclusion ................................................. 7
References ................................................. 8
Chapter 2 Metal-catalyzed Reactions in Water under MW
Irradiation .................................................... 10
Victorio Cadierno, Pascale Crochet and Sergio E. García-
Garrido
2.1 Introduction .............................................. 10
2.2 Addition Reactions ........................................ 11
2.3 Isomerization Reactions ................................... 17
2.4 Substitution Reactions .................................... 19
2.5 Cyclization Reactions ..................................... 28
2.6 Reduction and Oxidation Reactions ......................... 38
2.7 Miscellaneous Reactions ................................... 44
2.8 Representative Experimental Examples ...................... 45
2.8.1 Addition Reactions ................................. 45
2.8.2 Isomerization Reactions ............................ 46
2.8.3 Substitution Reactions ............................. 46
2.8.4 Cyclization Reactions .............................. 47
2.8.5 Reduction and Oxidation Reactions .................. 48
2.8.6 Miscellaneous Reactions ............................ 48
2.9 Conclusions ............................................... 49
Acknowledgements .......................................... 49
References ................................................ 49
Chapter 3 Microwave-assisted Coupling Reactions in Aqueous
Media .......................................................... 55
Aziz Fihri and Christophe Len
3.1 Introduction .............................................. 55
3.2 Suzuki-Miyaura Reaction ................................... 56
3.3 Heck Reaction ............................................. 71
3.4 Sonogashira Reactions ..................................... 75
3.5 Stille Reactions .......................................... 78
3.6 Hiyama Reactions .......................................... 78
3.7 Cyanation Reactions ....................................... 79
3.8 Carbonylation Reactions ................................... 80
3.9 Representative Experimental Syntheses ..................... 83
3.9.1 Synthesis of 4,5-Dimethoxy-2-vinyl-2'-
pivaloylamino-biphenyl ............................. 83
3.9.2 Synthesis of 4-Phenyltoluene ....................... 83
3.9.3 Synthesis of m-Carboxycinnamic Acid in
Homogeneous Heck Reactions in D20 .................. 84
3.9.4 Synthesis of Ethyl 3-(6-Methoxy-2-naphthyl)
propanoate ......................................... 84
3.9.5 Synthesis of 5-Chloro-2-phenylethynyl-pyridine ..... 84
3.9.6 Synthesis of 4-Methoxybenzonitrile ................. 85
3.9.7 Aminocarbonylation and Hydroxycarbonylation ........ 85
3.10 Conclusion ................................................ 86
References ................................................ 86
Chapter 4 Microwave-assisted Synthesis of Bio-active
Heterocycles in Aqueous Media .................................. 91
Vivek Polshettiwar and Rajender S. Varma
4.1 Introduction .............................................. 91
4.2 MW-assisted Nitrogen-containing Heterocycle Synthesis in
Water ..................................................... 92
4.3 MW-assisted Synthesis of Oxygen- and Sulfur-containing
Heterocycles in Water .................................... 106
4.4 MW-assisted Miscellaneous Reactions in Water ............. 112
4.5 Representative Experimental Procedures ................... 118
4.5.1 Synthesis of Dihydropyrimidinones ................. 118
4.5.2 Synthesis of 2-Aminochromene Derivatives .......... 118
4.5.3 Synthesis of Dioxane-functionalized Molecules ..... 118
4.5.4 Synthesis of Sulfonyl-benzothiazole-based
Bio-active Compounds .............................. 119
4.5.5 Synthesis of a Series of new β-Aminoketones ....... 119
4.6 Conclusions .............................................. 119
References ............................................... 119
Chapter 5 Microwave-assisted Enzymatic Reactions in Aqueous
Media ......................................................... 123
Hua Zhao
5.1 Introduction ............................................. 123
5.2 Microwave-assisted Enzymatic Reactions in Water
(or Aqueous Buffer) ...................................... 125
5.2.1 Effect of Microwave Irradiation on Enzyme
Activity in Aqueous Solutions ..................... 125
5.2.2 Microwave-assisted Enzymatic Protein Digestion .... 130
5.3 Microwave-assisted Enzymatic Reactions in Aqueous
Solutions of Organic Solvents ............................ 132
5.4 Microwave-assisted Enzymatic Reactions in Ionic Liquids .. 133
5.5 Non-thermal Effect of Microwave Irradiation on Enzymes ... 136
5.6 Prospects of Microwave Irradiation in Aqueous Phase
Biocatalysis ............................................. 137
5.7 Experimental ............................................. 137
5.7.1 Enzymatic Hydrolysis of Starch in Water under
Microwave Irradiation ............................. 137
5.7.2 Enzymatic Transglycosylation of Lactose in
Hexanol-Water (70:30, v/v) under Microwave
Irradiation ....................................... 138
5.7.3 Enzymatic Digestion of Proteins (Cytochrome
c, Myoglobin, Lysozyme, and Ubiquitin) ............ 138
Acknowledgements ......................................... 138
References ............................................... 138
Chapter 6 Microwave-assisted Synthesis of Polymers in
Aqueous Media ................................................. 145
Catherine Marestin and Régis Mercier
6.1 Introduction ............................................. 145
6.2 Radical Polymerization in Aqueous Medium ................. 146
6.2.1 Free-Radical Polymerization ....................... 146
6.2.2 Radical Polymerization in Dispersed Media ......... 151
6.2.3 Controlled/Living Radical Polymerization in
Dispersed Media ................................... 155
6.3 Step-growth Polymerization in Aqueous Media .............. 157
6.3.1 Synthesis of Poly(ether)s ......................... 157
6.3.2 Synthesis of Poly(amide)s and Poly(imide)s ........ 158
6.3.3 Synthesis of Polytriazoles ........................ 160
6.3.4 C-C Coupling Polymerizations ...................... 160
6.4 Miscellaneous Polymer Synthesis in Aqueous Media ......... 162
6.4.1 Cationic Polymerization ........................... 162
6.4.2 Polymer Modifications ............................. 162
6.4.3 Solid-phase Peptide Synthesis in Water ............ 169
6.5 Experimental ............................................. 170
6.5.1 PMMA Grafting onto a Polysaccharide ............... 170
6.5.2 PMMA Synthesis in Emulsion Polymerization ......... 170
6.5.3 Synthesis of PMMA Nanoparticles ................... 171
6.5.4 Synthesis of Polyacrylamide-Calcium Phosphate
Nanocomposites .................................... 171
6.5.5 Nitroxide-assisted Synthesis of Styrene in
Miniemulsion ...................................... 171
6.5.6 Synthesis of Poly(ether)s ......................... 171
6.5.7 Synthesis of Poly(imide)s ......................... 171
6.5.8 Polymerization by C-C Coupling .................... 172
6.5.9 Cationic Polymerization ........................... 172
6.5.10 Polymer Modification by Click Chemistry ........... 172
References ............................................... 172
Chapter 7 Microwave-assisted Synthesis of Nanomaterials in
Aqueous Media ................................................. 176
Babita Baruwati, Vivek Polshettiwar and Rajender S. Varma
7.1 Introduction ............................................. 176
7.2 Synthesis of Metal Nanoparticles using Water under
Microwave Irradiation .................................... 178
7.2.1 Gold (Au) Nanoparticles ........................... 178
7.2.2 Silver (Ag) Nanoparticles ......................... 182
7.2.3 Palladium (Pd) and Platinum (Pt) Nanoparticles .... 185
7.3 Synthesis of Metal Oxide Nanoparticles in Aqueous
Medium under MW Irradiation Conditions ................... 186
7.3.1 Synthesis of Titania (TiO2) Nanoparticles ......... 187
7.3.2 Synthesis of ZnO Nanoparticles .................... 189
7.3.3 Synthesis of Ferrite Nanoparticles ................ 191
7.3.4 Synthesis of Quantum Dots in Aqueous Medium
under Microwave Conditions ........................ 194
7.4 Nanoparticles as Catalysts ............................... 195
7.5 Ruthenium Hydroxide Nano-catalyst for Microwave-
assisted Hydration of Nitriles in Water .................. 202
7.6 Glutathione-based Nano-organocatalyst for Microwave-
assisted Synthesis of Heterocycles in Water .............. 203
7.7 Representative Experimental Procedures ................... 205
7.7.1 Synthesis of Gold Nanoparticles ................... 205
7.7.2 Synthesis of Silver Nanoparticles ................. 206
7.7.3 Synthesis of Different ТiO2 Nanoparticles ......... 207
7.7.4 Synthesis of ZnO Nanostructures ................... 207
7.7.5 Selected Methods for Production of Ferrite
Nanoparticles ..................................... 208
7.8 Conclusion ............................................... 209
References ............................................... 209
Subject-Index ................................................. 217
|
