Have you ever wished you could speed up your organic syntheses without losing control of the reaction? Flash Chemistry is a new concept which offers an integrated scheme for fast, controlled organic synthesis. It brings together the generation of highly reactive species and their reactions in microsystems to enable highly controlled organic syntheses on a preparative scale in timescales of a few seconds or less.Flash Chemistry - Fast Chemical Reactions in Microsystems is the first dedicated book to describe this exciting new technique, and is an essential introduction for anyone working in organic synthesis, process chemistry, chemical engineering and physical organic chemistry concerned with fundamental aspects of chemical reactions and synthesis and the production of organic compounds.

Professor Jun-ichi Yoshida, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Japan

Preface	p. xi
Introduction	p. 1
Flask Chemistry	p. 2
Flash Chemistry	p. 3
Flask Chemistry or Flash Chemistry	p. 4
References	p. 5
The Background to Flash Chemistry	p. 7
How do Chemical Reactions Take Place?	p. 7
Macroscopic View of Chemical Reactions	p. 8
Thermodynamic Equilibrium and Kinetics	p. 8
Kinetics	p. 10
Transition State Theory	p. 12
Femtosecond Chemistry and Reaction Dynamics	p. 12
Reactions for Dynamics and Reactions for Synthesis	p. 13
Bimolecular Reactions in the Gas Phase	p. 15
Bimolecular Reactions in the Solution Phase	p. 16
Fast Chemical Synthesis Inspired by Reaction Dynamics	p. 17
References	p. 18
What is Flash Chemistry?	p. 19
Why is Flash Chemistry Needed?	p. 23
Chemical Reaction, an Extremely Fast Process at Molecular Level	p. 23
Rapid Construction of Chemical Libraries	p. 24
Rapid Synthesis of Radioactive Positron Emission Tomography Probes	p. 27
On-demand Rapid Synthesis in Industry	p. 30
Conclusions	p. 31
References	p. 31
Methods of Activating Molecules	p. 33
Thermal Activation of Organic Molecules	p. 33
High Temperature Reactions	p. 33
Flash Vacuum Pyrolysis	p. 35
Microwave Reactions	p. 36
Photochemical Activation	p. 38
Electrochemical Activation	p. 39
Chemical Activation	p. 41
Accumulation of Reactive Species	p. 43
The Cation-pool Method	p. 44
Continuous Generation of Reactive Species in a Flow System	p. 57
Interconversion Between Reactive Species	p. 59
Conclusions	p. 62
References	p. 63
Control of Extremely Fast Reactions	p. 69
Mixing	p. 69
How Does Mixing Take Place?	p. 70
Molecular Diffusion and Brownian Motion	p. 72
Disguised Chemical Selectivity	p. 73
Lowering the Reaction Temperature	p. 76
The High Dilution Method	p. 77
Micromixing	p. 78
Friedel-Crafts Alkylation Using an N-acyliminium Ion Pool	p. 78
Micromixing as a Powerful Tool for Flash Chemistry	p. 85
Disguised Chemical Selectivity in Competitive Parallel Reactions	p. 85
Temperature Control	p. 87
Exothermicity of Fast Reactions	p. 87
Hammond's Postulate	p. 89
The Friedel-Crafts Reaction	p. 90
Solvent	p. 92
Heat Transfer	p. 93
Precise Temperature Control in Microflow Systems	p. 95
Residence Time Control	p. 97
The Discovery of Benzyne. The Concept of Reactive Intermediates	p. 99
o-Bromophenyllithium	p. 99
Conclusions	p. 102
References	p. 102
Microfluidic Devices and Microflow Systems	p. 105
Brief History	p. 105
Microflow Systems for Chemical Analysis	p. 106
Microflow Systems for Chemical Synthesis	p. 107
Characteristic Features of Microflow Systems	p. 108
Microstructured Fluidic Devices	p. 110
Microchip Reactors	p. 110
Microtube Reactors	p. 112
Micromixer	p. 113
Passive Micromixers	p. 114
Microheat Exchanger	p. 125
Photochemical Microflow Reactor	p. 126
Electrochemical Microflow Reactor	p. 128
Catalyst-containing Microflow Reactor	p. 129
Microflow Reactors for High-pressure and High-temperature Conditions	p. 131
Conclusions	p. 133
References	p. 133
Applications of Flash Chemistry in Organic Synthesis	p. 137
Highly Exothermic Reactions that are Difficult to Control in Macrobatch Reactors	p. 138
Fluorination	p. 138
Chlorination and Bromination	p. 139
Nitration	p. 142
1,4-Addition Reactions of Amines	p. 143
Halogen-magnesium Exchange Reactions	p. 143
Oxidation of an Alkene with H[subscript 2]O[subscript 2]/HCO[subscript 2]H	p. 145
Reactions in which a Reactive Intermediate Easily Decomposes in Macrobatch Reactors	p. 147
Swern-Moffatt Oxidation	p. 147
Organolithium Reactions	p. 150
Reactions with Products which Easily Decompose in Macrobatch Reactors	p. 153
Dehydration of an Allylic Alcohol to Give a Diene as an Unstable Product	p. 153
Reactions in which Undesired By-products are Produced in the Subsequent Reactions in Macrobatch Reactors	p. 154
Friedel-Crafts Reactions	p. 154
Iodination of Aromatic Compounds	p. 157
Reaction of Phenylmagnesium Bromide with Boronic Acid Trimethyl Ester	p. 158
[4 + 2] Cycloaddition Reaction of N-acyliminium Ion with Olefin	p. 160
Biphasic Azo-coupling Reactions	p. 162
Reactions that can be Accelerated Using Microflow Systems	p. 163
Acceleration of Reactions at High Temperatures	p. 163
Acceleration of Radical Reactions Using Quickly Decomposing Radical Initiators	p. 165
Acceleration by Controlled Mass Transfer	p. 166
Acceleration by Microwaves	p. 167
Acceleration by High-pressure and High-temperature Conditions	p. 167
Conclusions	p. 169
References	p. 169
Polymer Synthesis Based on Flash Chemistry	p. 173
Polymerization	p. 173
Chain-growth Polymerization and Step-growth Polymerization	p. 174
Molecular Weight and Molecular-weight Distribution	p. 176
Cationic Polymerization	p. 176
Conventional Cationic Polymerization	p. 176
Living Cationic Polymerization	p. 178
Ideal Living Cationic Polymerization	p. 180
Fast Initiation and Mixing	p. 181
Cation-pool Initiated Polymerization of Vinyl Ethers Using a Microflow System	p. 182
Livingness of the Microflow System-controlled Cationic Polymerization	p. 184
Comparison Between Conventional Living Cationic Polymerization and Microflow System-controlled Cationic Polymerization	p. 185
Microflow System-controlled Cationic Polymerization Initiated by CF[subscript 3]SO[subscript 3]H	p. 187
Free-radical Polymerization	p. 189
Conventional Free-radical Polymerization	p. 189
Living-radical Polymerization	p. 190
Emulsion and Suspension Polymerization	p. 191
Radical Polymerization in Microflow Systems	p. 192
Simulation of Free-radical Polymerization in Microflow Systems	p. 196
Conclusions	p. 197
References	p. 197
Industrial Applications of Flash Chemistry	p. 199
Synthesis of Diarylethene as a Photochromic Compound (Micrometer-size Single-channel Reactor)	p. 201
Synthesis of a Pharmaceutically Interesting Spiro Lactone Fragment of Neuropeptide Y (Millimeter-size Single-channel Reactor)	p. 206
Grignard Exchange Process (Internal Numbering-up)	p. 208
Radical Polymerization Process (Numbering-up)	p. 212
Other Examples of Industrial Applications of Flash Chemistry	p. 218
Flash Chemistry as a Powerful Means of Sustainable Chemical Synthesis	p. 219
Conclusions	p. 220
References	p. 221
Outlook for Flash Chemistry	p. 223
Index	p. 225
Table of Contents provided by Ingram. All Rights Reserved.

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