Chemistry in alternative reaction media

At a time when environmental concerns are increasing, it's important that chemical processes are as environmentally friendly as possible. This book outlines various methods for producing inorganic and organic solvents without the use of traditional solvents that can have detrimental effects on the environment. This is the first book to give extensive and exclusive coverage to the topic Includes important environmental issues

This book will appeal to anyone with an interest in organic synthesis; reaction chemistry; catalysis; and process development, and to undergraduate and graduate students of organic chemistry; catalysis; green chemistry; clean technology and environmental chemistry courses.

Preface	p. xi
Abbreviations and Acronyms	p. xv
1 Chemistry in Alternative Reaction Media	p. 1
1.1 Economic and Political Considerations	p. 2
1.2 Why Do Things Dissolve?	p. 6
1.3 Solvent Properties and Solvent Classification	p. 8
1.3.1 Density	p. 8
1.3.2 Mass Transport	p. 9
1.3.3 Boiling Point, Melting Point and Volatility	p. 10
1.3.4 Solvents as Heat-Transfer Media	p. 11
1.3.5 Cohesive Pressure, Internal Pressure, and Solubility Parameter	p. 11
1.4 Solvent Polarity	p. 13
1.4.1 Dipole Moment and Dispersive Forces	p. 14
1.4.2 Dielectric Constant	p. 14
1.4.3 Electron Pair Donor and Acceptor Numbers	p. 16
1.4.4 Empirical Polarity Scales	p. 17
1.4.5 E[superscript N subscript T] and E[subscript T](30) Parameters	p. 18
1.4.6 Kamlet--Taft Parameters	p. 21
1.4.7 Hydrogen Bond Donor (HBD) and Hydrogen Bond Acceptor (HBA) Solvents	p. 23
1.5 The Effect of Solvent Polarity on Chemical Systems	p. 24
1.5.1 The Effect of Solvent Polarity on Chemical Reactions	p. 24
1.5.2 The Effect of Solvent Polarity on Equilibria	p. 26
1.6 What is Required from Alternative Solvent Strategies?	p. 28
References	p. 30
2 Multiphasic Solvent Systems	p. 33
2.1 An Introduction to Multiphasic Chemistry	p. 33
2.1.1 The Traditional Biphasic Approach	p. 34
2.1.2 Temperature Dependent Solvent Systems	p. 34
2.1.3 Single- to Two-Phase Systems	p. 35
2.1.4 Multiphasic Systems	p. 35
2.2 Solvent Combinations	p. 36
2.2.1 Water	p. 37
2.2.2 Fluorous Solvents	p. 38
2.2.3 Ionic Liquids	p. 38
2.2.4 Supercritical Fluids and Other Solvent Combinations	p. 38
2.3 Benefits and Problems Associated with Multiphasic Systems	p. 39
2.3.1 Partially Miscible Liquids	p. 40
2.4 Kinetics of Homogeneous Reactions	p. 43
2.4.1 Rate is Independent of Stoichiometry	p. 44
2.4.2 Rate is Determined by the Probability of Reactants Meeting	p. 45
2.4.3 Rate is Measured by the Concentration of the Reagents	p. 45
2.4.4 Catalysed Systems	p. 47
2.5 Kinetics of Biphasic Reactions	p. 47
2.5.1 The Concentration of Reactants in Each Phase is Affected by Diffusion	p. 47
2.5.2 The Concentration of the Reactants and Products in the Reacting Phase is Determined by Their Partition Coefficients	p. 49
2.5.3 The Partition Coefficients of the Reactants and Products May Alter the Position of the Equilibrium	p. 50
2.5.4 Effect of Diffusion on Rate	p. 53
2.5.5 Determining the Rate of a Reaction in a Biphasic System	p. 54
2.6 Conclusions	p. 55
References	p. 55
3 Reactions in Fluorous Media	p. 57
3.1 Introduction	p. 57
3.2 Properties of Perfluorinated Solvents	p. 58
3.3 Designing Molecules for Fluorous Compatibility	p. 60
3.4 Probing the Effect of Perfluoroalkylation on Ligand Properties	p. 64
3.5 Partition Coefficients	p. 66
3.6 Liquid--Liquid Extractions	p. 67
3.7 Solid Separations	p. 68
3.8 Conclusions	p. 71
References	p. 71
4 Ionic Liquids	p. 75
4.1 Introduction	p. 75
4.1.1 The Cations and Anions	p. 77
4.1.2 Synthesis of Ionic Liquids	p. 77
4.2 Physical Properties of Ionic Liquids	p. 80
4.3 Benefits and Problems Associated with Using Ionic Liquids in Synthesis	p. 88
4.4 Catalyst Design	p. 90
4.5 Conclusions	p. 92
References	p. 92
5 Reactions in Water	p. 95
5.1 The Structure and Properties of Water	p. 95
5.1.1 The Structure of Water	p. 95
5.1.2 Near-Critical Water	p. 99
5.1.3 The Hydrophobic Effect	p. 99
5.1.4 The Salt Effect	p. 100
5.2 The Benefits and Problems Associated with Using Water in Chemical Synthesis	p. 101
5.3 Organometallic Reactions in Water	p. 103
5.4 Aqueous Biphasic Catalysis	p. 104
5.4.1 Ligands for Aqueous--Organic Biphasic Catalysis	p. 104
5.5 Phase Transfer Catalysis	p. 109
5.5.1 The Transfer of Nucleophiles into Organic Solvents	p. 112
5.5.2 Mechanisms of Nucleophilic Substitutions Under Phase Transfer Conditions	p. 112
5.5.3 The Rates of Phase Transfer Reactions	p. 114
5.5.4 Using Inorganic Reagents in Organic Reactions	p. 119
5.6 Organometallic Catalysis under Phase Transfer Conditions	p. 122
5.7 Triphase Catalysis	p. 123
5.7.1 Mixing Efficiency in Solid--Liquid Reactions	p. 126
5.8 Conclusions	p. 126
References	p. 126
6 Supercritical Fluids	p. 131
6.1 Introduction	p. 131
6.2 Physical Properties	p. 132
6.3 Local Density Augmentation	p. 135
6.4 Supercritical Fluids as Replacement Solvents	p. 136
6.5 Reactor Design	p. 138
6.6 Spectroscopic Analysis of Supercritical Media	p. 141
6.6.1 Vibrational Spectroscopy	p. 141
6.6.2 NMR Spectroscopy	p. 142
6.7 Reactions in Supercritical Media	p. 143
6.8 Conclusions	p. 145
References	p. 146
7 Diels--Alder Reactions in Alternative Media	p. 149
7.1 Diels--Alder Reactions in Water	p. 150
7.2 Diels--Alder Reactions in Perfluorinated Solvents	p. 153
7.3 Diels--Alder Reactions in Ionic Liquids	p. 153
7.4 Diels--Alder Reactions in Supercritical Carbon Dioxide	p. 155
7.5 Conclusions	p. 156
References	p. 156
8 Hydrogenation and Hydroformylation Reactions in Alternative Solvents	p. 159
8.1 Introduction	p. 159
8.2 Hydrogenation of Simple Alkenes and Arenes	p. 161
8.2.1 Hydrogenation in Water	p. 163
8.2.2 Hydrogenation in Ionic Liquids	p. 166
8.2.3 Hydrogenation in Fluorous Solvents	p. 169
8.2.4 Hydrogenation in Supercritical Fluids	p. 170
8.3 Hydroformylation Reactions in Alternative Media	p. 171
8.3.1 Hydroformylation in Water	p. 171
8.3.2 Hydroformylation in Ionic Liquids	p. 172
8.3.3 Hydroformylation in Fluorous Solvents	p. 174
8.3.4 Hydroformylation in Supercritical Fluids	p. 178
8.4 Conclusions	p. 179
References	p. 179
9 From Alkanes to CO[subscript 2]: Oxidation in Alternative Reaction Media	p. 181
9.1 Oxidation of Alkanes	p. 183
9.2 Oxidation of Alkenes	p. 184
9.3 Oxidation of Alcohols	p. 188
9.4 Oxidation of Aldehydes and Ketones	p. 190
9.5 Destructive Oxidation	p. 191
9.6 Conclusions	p. 192
References	p. 193
10 Carbon--Carbon Bond Formation, Metathesis and Polymerization	p. 195
10.1 Carbon--Carbon Coupling Reactions	p. 195
10.1.1 Heck Coupling Reactions	p. 196
10.1.2 Suzuki Coupling Reactions	p. 199
10.1.3 Reactions Involving the Formation of C=C Double Bonds	p. 201
10.2 Metathesis Reactions	p. 202
10.2.1 Ring Opening Metathesis Polymerization	p. 202
10.2.2 Ring Closing Metathesis	p. 204
10.3 Polymerization Reactions in Alternative Reaction Media	p. 205
10.3.1 Polymerization Reactions in Water	p. 206
10.3.2 Polymerization Reactions in Supercritical Carbon Dioxide	p. 208
10.3.3 Polymerization in Fluorous Solvents	p. 214
10.4 Conclusions	p. 215
References	p. 215
11 Alternative Reaction Media in Industrial Processes	p. 217
11.1 Obstacles and Opportunities for Alternative Media	p. 217
11.2 Reactor Considerations for Alternative Media	p. 219
11.2.1 Batch Reactors	p. 219
11.2.2 Flow Reactors	p. 220
11.2.3 New Technology Suitable for Multiphasic Reactions	p. 222
11.3 Industrial Applications of Alternative Solvent Systems	p. 223
11.3.1 The Development of the First Aqueous--Organic Biphasic Hydroformylation Plant	p. 224
11.3.2 Other Examples of Processes Using Water as a Solvent	p. 227
11.3.3 Scale-Up of PTC Systems	p. 227
11.3.4 Thomas Swan Supercritical Fluid Plant	p. 229
11.3.5 Other Applications of Supercritical Carbon Dioxide	p. 230
11.4 Outlook for Fluorous Solvents and Ionic Liquids	p. 232
11.5 Conclusions	p. 233
References	p. 234
Index	p. 237

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