Chemical reactions and processes under flow conditions

Pharmaceutical and fine chemical products are typically synthesised batchwise which is an anomaly since batch processes have a series of practical and economical disadvantages. On the contrary, flow continuous processes present a series of advantages leading to new ways to synthesise chemical products. Flow processes - * enable control reaction parameters more precisely (temperature, residence time, amount of reagents and solvent etc.), leading to better reproducibility, safer and more reliable processes * can be performed more advantageously using immobilized reagents or catalysts * improve the selectivity and productivity of the process and possibly even the stability of the catalyst * offer opportunities for heat exchange and energy conservation as well as an easy separation and recycling of the reactants and products by adequate process design * achieve multistep syntheses by assembling a line of reactors with minimum or no purification in between two reaction steps * can be assured by facile automation * scale-up can be easily conducted by number-up With all the new research activity in manufacturing chemical products, this comprehensive book is very timely, as it summarises the latest trends in organic synthesis. It gives an insight into flow continuous processes, outlining the basic concepts and explaining the terminology of, and systems approach to, process design dealing with both homogeneous and heterogeneous catalysis and mini- or micro-reactors. The book contains case studies, extensive bibliographies and reference lists in each chapter to enable the reader to grasp the contents and to go on to more detailed texts on specific subjects if desired. The book is written by both organic chemists and engineers giving a multidisciplinary vision of the new tools and methodologies in this field. It is essential reading for organic chemists (in industry or academia) working alongside chemical engineers or who want to undertake chemical engineering projects. It will also be of interest for chemical engineers to see how basic engineering concepts are applied in modern organic chemistry.

Author Notes

Santiago V Luis is Professor of organic chemistry at the University Jaume I, Castellon, Spain. Eduardo Garcia-Verdugo is a Research Associate in the Inorganic and Organic Chemistry Department at the University Jaume I, Castellon, Spain. He obtained his Ph.D. degree in organic chemistry and materials science from the University Jaume I, Castellon, Spain. In 2000, Dr Garcia-Verdugo received a post-doctoral Marie Curie Fellowship from the EU commission whilst working at the Clean Technology Group at Nottingham University. In 2004, he was elected for the prestigious Ram¾n y Cajal research program from the Spanish Ministry of Education and Science (MEC). He is also co-author of 41 publications in peer-reviewed, high impact, international chemistry journals and has given 20 communications and 7 lectures in international conferences and Symposia.

Alexei A. Lapkin and Pawel K. PlucinskiEduardo García-Verdugo and Santiago V. LuisMaria J. Sabater Fernando Rey and Jesús LázaroPaola Laurino and Arjan Odedra and Xiao Yin Mak Tomas Gustafsson and Karolin Geyer and Peter H. SeebergerTânia Quintats and David J. Cole-Hamilton

Chapter 1 Engineering Factors for Efficient Flow Processes in Chemical Industries	p. 1
1.1 Introduction	p. 1
1.2 Heterogeneous Catalytic Flow Processes in the Petrochemical Industry: A Brief Overview	p. 5
1.2.1 Gas-solid and Liquid-solid Catalytic and Non-catalytic Continuous Processes	p. 5
1.2.2 Two-phase Gas-liquid Continuous Industrial Reactors	p. 6
1.2.3 Three-phase Catalytic Reactors	p. 9
1.3 Scale-up of Conventional Continuous Reactors	p. 16
1.4 Process Intensification: An Overview	p. 18
1.4.1 Process-intensifying Equipment	p. 19
1.4.2 Process-intensifying Methods	p. 21
1.4.3 Multifunctional Reactors	p. 21
1.4.4 Membrane Reactors	p. 23
1.4.5 Spinning Disk Reactor	p. 23
1.5 Engineering of Multifunctional, Micro- and Compact Reactors	p. 24
1.5.1 p. 24
1.5.2 Principles of Multiphase Contacting in Micro-and Compact Reactors	p. 26
1.5.3 Heterogeneous Catalyst Design for Micro- and Compact Reactors	p. 28
1.5.4 Fabrication of Micro- and Compact Reactors	p. 30
1.6 Scale-up of Micro- and Compact Reactors	p. 32
1.6.1 Blockage of Microreactors	p. 33
1.6.2 Flow Distribution in Multiple Parallel Channels	p. 34
1.7 Concluding Remarks	p. 35
1.8 Symbols/Nomenclature	p. 36
References	p. 37
Chapter 2 Flow Processes Using Polymer-supported Reagents, Scavengers and Catalysts	p. 44
2.1 Introduction	p. 44
2.2 Flow Processes with Use of Bead-type Resins	p. 50
2.2.1 Use of Gel-type Beads	p. 50
2.2.2 Use of Macroporous Beads	p. 55
2.3 Flow Processes with Use of Polymeric Monoliths	p. 58
2.3.1 General Remarks	p. 58
2.3.2 Monolithic Reagents and Scavengers	p. 59
2.3.3 Monolithic Non-chiral Catalysts	p. 62
2.3.4 Monolithic Chiral Catalysts	p. 64
2.4 Functionalised Polymers and Potential for Industrial Applications under Flow Conditions	p. 70
2.4.1 Scaling-up with Polymer-supported Systems	p. 70
2.4.2 Use of Ion Exchange Resins as Catalysts for Flow Processes	p. 70
Ongoing Developments and Future Prospective	p. 72
2.5.1 Multistage Flow Synthesis with Use of Coupled Columns Packed with Different Functionalised Polymers	p. 72
2.5.2 Flow Processes Involving Functionalised Polymers and Microwave Irradiation	p. 74
2.5.3 Flow Processes Involving Functionalised Polymers and Supercritical Fluids	p. 76
2.5.4 Polymer-supported Biocatalysts under Flow Conditions	p. 77
2.5.5 Miscellaneous Approaches	p. 77
References	p. 79
Chapter 3 Zeolites and Related Materials for Developing Continuous Flow Systems	p. 86
3.1 Introduction	p. 86
3.2 Zeolites and Zeotypes: Outstanding Inorganic Materials for Heterogeneous Processes in Chemistry	p. 87
3.3 Current Industrial Applications of Zeolites and Related Materials	p. 90
3.3.1 Zeolites in Refining and Petrochemical Processes	p. 90
3.3.2 Current Applications in the Fine Chemicals Industry	p. 103
3.4 From Laboratory-scale to Production: Petrochemicals and Fine Chemicals	p. 111
3.5 Future and Industrial Perspectives	p. 113
References	p. 113
Chapter 4 Microfluidic Devices for Organic Processes	p. 118
4.1 Microreactors and Microfluidic Devices: Concepts and Definitions	p. 118
4.2 Main Advantages of Microfluidic Devices	p. 119
4.3 Scale-up of Microflow Reactions	p. 120
4.4 Liquid-Liquid Reactions	p. 122
4.4.1 Photochemical Reactions	p. 122
4.4.2 Heterocycle Synthesis	p. 124
4.4.3 Synthesis of Bio-oligomers	p. 126
4.4.4 Multistep Reactions	p. 127
4.4.5 Free Radical Reactions	p. 129
4.4.6 Reactions Involving Hazardous Materials and Unstable Intermediates	p. 130
4.4.7 Biphasic Liquid-Liquid Reactions	p. 134
4.5 Liquid-Gas Reactions	p. 136
4.5.1 Oxidation with Ozone	p. 136
4.5.2 Singlet Oxygen Oxidation	p. 136
4.5.3 Fluorination	p. 137
4.5.4 Chlorination	p. 138
4.5.5 Cross-coupling Reactions	p. 138
4.6 Liquid-Gas-Solid Reactions	p. 140
4.6.1 Hydrogenation	p. 140
4.6.2 Reductive Amination	p. 141
4.6.3 Aminocarbonylation	p. 141
4.6.4 Alcohol Oxidation	p. 143
4.7 Solid Supports and Monolith-bound Reagents in Continuous Flow	p. 144
4.7.1 Solid-supported Reagents	p. 144
4.7.2 Solid-supported Catalysts	p. 150
4.8 Industrial Uses and Perspectives	p. 153
References	p. 157
Chapter 5 Flow Processes in Non-Conventional Media	p. 163
5.1 The Need for Alternative Solvents in Flow Catalysis	p. 163
5.1.1 Homogeneous vs. Heterogeneous Catalysis	p. 163
5.2 Continuous Flow Processing using Homogeneous Catalysis	p. 165
5.3 The Use of Solvents	p. 167
5.3.1 Traditional Solvents vs. Non-conventional Solvents	p. 168
5.4 Ionic Liquids	p. 168
5.4.1 The concept of Ionic Liquids	p. 168
5.4.2 Continuous Flow Catalysis using Ionic Liquids	p. 170
5.5 Supercritical Fluids	p. 179
5.5.1 Supercritical Fluids for Product Separation in Homogeneous Catalysis	p. 181
5.5.2 Recycling CO 2	p. 188
5.6 Final Remarks	p. 190
References	p. 191
Subject Index	p. 196

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