Chemistry in Alternative Reaction Media

by Adams, Dave J.; Dyson, Paul J.; Tavener, Stewart J.

• ISBN13: 9780471498490
• ISBN10: 0471498491
• Edition: 1st
• Format: Paperback
• Copyright: 2003-11-21
• Publisher: WILEY

Summary

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.

Author Biography

Dave J. Adams is the author of Chemistry In Alternative Reaction Media, published by Wiley.

Paul J. Dyson is the author of Chemistry In Alternative Reaction Media, published by Wiley.

Stewart J. Tavener is the author of Chemistry In Alternative Reaction Media, published by Wiley.

Table of Contents

Preface	p. xi
Abbreviations and Acronyms	p. xv
Chemistry in Alternative Reaction Media	p. 1
Economic and Political Considerations	p. 2
Why Do Things Dissolve?	p. 6
Solvent Properties and Solvent Classification	p. 8
Density	p. 8
Mass Transport	p. 9
Boiling Point, Melting Point and Volatility	p. 10
Solvents as Heat-Transfer Media	p. 11
Cohesive Pressure, Internal Pressure, and Solubility Parameter	p. 11
Solvent Polarity	p. 13
Dipole Moment and Dispersive Forces	p. 14
Dielectric Constant	p. 14
Electron Pair Donor and Acceptor Numbers	p. 16
Empirical Polarity Scales	p. 17
E[superscript N subscript T] and E[subscript T](30) Parameters	p. 18
Kamlet--Taft Parameters	p. 21
Hydrogen Bond Donor (HBD) and Hydrogen Bond Acceptor (HBA) Solvents	p. 23
The Effect of Solvent Polarity on Chemical Systems	p. 24
The Effect of Solvent Polarity on Chemical Reactions	p. 24
The Effect of Solvent Polarity on Equilibria	p. 26
What is Required from Alternative Solvent Strategies?	p. 28
References	p. 30
Multiphasic Solvent Systems	p. 33
An Introduction to Multiphasic Chemistry	p. 33
The Traditional Biphasic Approach	p. 34
Temperature Dependent Solvent Systems	p. 34
Single- to Two-Phase Systems	p. 35
Multiphasic Systems	p. 35
Solvent Combinations	p. 36
Water	p. 37
Fluorous Solvents	p. 38
Ionic Liquids	p. 38
Supercritical Fluids and Other Solvent Combinations	p. 38
Benefits and Problems Associated with Multiphasic Systems	p. 39
Partially Miscible Liquids	p. 40
Kinetics of Homogeneous Reactions	p. 43
Rate is Independent of Stoichiometry	p. 44
Rate is Determined by the Probability of Reactants Meeting	p. 45
Rate is Measured by the Concentration of the Reagents	p. 45
Catalysed Systems	p. 47
Kinetics of Biphasic Reactions	p. 47
The Concentration of Reactants in Each Phase is Affected by Diffusion	p. 47
The Concentration of the Reactants and Products in the Reacting Phase is Determined by Their Partition Coefficients	p. 49
The Partition Coefficients of the Reactants and Products May Alter the Position of the Equilibrium	p. 50
Effect of Diffusion on Rate	p. 53
Determining the Rate of a Reaction in a Biphasic System	p. 54
Conclusions	p. 55
References	p. 55
Reactions in Fluorous Media	p. 57
Introduction	p. 57
Properties of Perfluorinated Solvents	p. 58
Designing Molecules for Fluorous Compatibility	p. 60
Probing the Effect of Perfluoroalkylation on Ligand Properties	p. 64
Partition Coefficients	p. 66
Liquid--Liquid Extractions	p. 67
Solid Separations	p. 68
Conclusions	p. 71
References	p. 71
Ionic Liquids	p. 75
Introduction	p. 75
The Cations and Anions	p. 77
Synthesis of Ionic Liquids	p. 77
Physical Properties of Ionic Liquids	p. 80
Benefits and Problems Associated with Using Ionic Liquids in Synthesis	p. 88
Catalyst Design	p. 90
Conclusions	p. 92
References	p. 92
Reactions in Water	p. 95
The Structure and Properties of Water	p. 95
The Structure of Water	p. 95
Near-Critical Water	p. 99
The Hydrophobic Effect	p. 99
The Salt Effect	p. 100
The Benefits and Problems Associated with Using Water in Chemical Synthesis	p. 101
Organometallic Reactions in Water	p. 103
Aqueous Biphasic Catalysis	p. 104
Ligands for Aqueous--Organic Biphasic Catalysis	p. 104
Phase Transfer Catalysis	p. 109
The Transfer of Nucleophiles into Organic Solvents	p. 112
Mechanisms of Nucleophilic Substitutions Under Phase Transfer Conditions	p. 112
The Rates of Phase Transfer Reactions	p. 114
Using Inorganic Reagents in Organic Reactions	p. 119
Organometallic Catalysis under Phase Transfer Conditions	p. 122
Triphase Catalysis	p. 123
Mixing Efficiency in Solid--Liquid Reactions	p. 126
Conclusions	p. 126
References	p. 126
Supercritical Fluids	p. 131
Introduction	p. 131
Physical Properties	p. 132
Local Density Augmentation	p. 135
Supercritical Fluids as Replacement Solvents	p. 136
Reactor Design	p. 138
Spectroscopic Analysis of Supercritical Media	p. 141
Vibrational Spectroscopy	p. 141
NMR Spectroscopy	p. 142
Reactions in Supercritical Media	p. 143
Conclusions	p. 145
References	p. 146
Diels--Alder Reactions in Alternative Media	p. 149
Diels--Alder Reactions in Water	p. 150
Diels--Alder Reactions in Perfluorinated Solvents	p. 153
Diels--Alder Reactions in Ionic Liquids	p. 153
Diels--Alder Reactions in Supercritical Carbon Dioxide	p. 155
Conclusions	p. 156
References	p. 156
Hydrogenation and Hydroformylation Reactions in Alternative Solvents	p. 159
Introduction	p. 159
Hydrogenation of Simple Alkenes and Arenes	p. 161
Hydrogenation in Water	p. 163
Hydrogenation in Ionic Liquids	p. 166
Hydrogenation in Fluorous Solvents	p. 169
Hydrogenation in Supercritical Fluids	p. 170
Hydroformylation Reactions in Alternative Media	p. 171
Hydroformylation in Water	p. 171
Hydroformylation in Ionic Liquids	p. 172
Hydroformylation in Fluorous Solvents	p. 174
Hydroformylation in Supercritical Fluids	p. 178
Conclusions	p. 179
References	p. 179
From Alkanes to CO[subscript 2]: Oxidation in Alternative Reaction Media	p. 181
Oxidation of Alkanes	p. 183
Oxidation of Alkenes	p. 184
Oxidation of Alcohols	p. 188
Oxidation of Aldehydes and Ketones	p. 190
Destructive Oxidation	p. 191
Conclusions	p. 192
References	p. 193
Carbon--Carbon Bond Formation, Metathesis and Polymerization	p. 195
Carbon--Carbon Coupling Reactions	p. 195
Heck Coupling Reactions	p. 196
Suzuki Coupling Reactions	p. 199
Reactions Involving the Formation of C=C Double Bonds	p. 201
Metathesis Reactions	p. 202
Ring Opening Metathesis Polymerization	p. 202
Ring Closing Metathesis	p. 204
Polymerization Reactions in Alternative Reaction Media	p. 205
Polymerization Reactions in Water	p. 206
Polymerization Reactions in Supercritical Carbon Dioxide	p. 208
Polymerization in Fluorous Solvents	p. 214
Conclusions	p. 215
References	p. 215
Alternative Reaction Media in Industrial Processes	p. 217
Obstacles and Opportunities for Alternative Media	p. 217
Reactor Considerations for Alternative Media	p. 219
Batch Reactors	p. 219
Flow Reactors	p. 220
New Technology Suitable for Multiphasic Reactions	p. 222
Industrial Applications of Alternative Solvent Systems	p. 223
The Development of the First Aqueous--Organic Biphasic Hydroformylation Plant	p. 224
Other Examples of Processes Using Water as a Solvent	p. 227
Scale-Up of PTC Systems	p. 227
Thomas Swan Supercritical Fluid Plant	p. 229
Other Applications of Supercritical Carbon Dioxide	p. 230
Outlook for Fluorous Solvents and Ionic Liquids	p. 232
Conclusions	p. 233
References	p. 234
Index	p. 237
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