Microreactors in Organic Chemistry and Catalysis -- Contents -- Preface to the First Edition -- Preface to the Second Edition -- List of Contributors -- 1 Properties and Use of Microreactors -- 1.1 Introduction -- 1.1.1 A Brief History of Microreactors -- 1.1.2 Advantages of Microreactors -- 1.2 Physical Characteristics of Microreactors -- 1.2.1 Geometries -- 1.2.2 Constructional Materials and Their Properties -- 1.3 Fluid Flow and Delivery Regimes -- 1.3.1 Fluid Flow -- 1.3.2 Fluid Delivery -- 1.3.3 Mixing Mechanisms -- 1.4 Multifunctional Integration -- 1.5 Uses of Microreactors -- 1.5.1 Overview -- 1.5.1.1 Fast and Exothermic Reactions -- 1.5.2 Precision Particle Manufacture -- 1.5.3 Wider Industrial Context -- 1.5.3.1 Sustainability Agenda -- 1.5.3.2 Point-of-Demand Synthesis -- References -- 2 Fabrication of Microreactors Made from Metals and Ceramic -- 2.1 Manufacturing Techniques for Metals -- 2.2 Etching -- 2.3 Machining -- 2.4 Generative Method: Selective Laser Melting -- 2.5 Metal Forming Techniques -- 2.6 Assembling and Bonding of Metal Microstructures -- 2.7 Ceramic Devices -- 2.8 Joining and Sealing -- References -- 3 Microreactors Made of Glass and Silicon -- 3.1 How Microreactors Are Constructed -- 3.1.1 Glass As Material -- 3.1.2 Silicon As Material -- 3.2 The Structuring of Glass and Silicon -- 3.2.1 Structuring by Means of Masked Etching As in Microsystems Technology -- 3.2.2 Etching Technologies -- 3.2.2.1 Anisotropic (Crystallographic) Wet Chemical Etching of Silicon (KOH) -- 3.3 Isotropic Wet Chemical Etching of Silicon -- 3.3.1 3.3.1.1 Isotropic Wet Chemical Etching of Silicon -- 3.3.1.2 Isotropic Wet Chemical Etching of Silicon Glass -- 3.3.2 Other Processes -- 3.3.2.1 Photostructuring of Special Glass -- 3.3.3 Drilling, Diamond Lapping, Ultrasonic Lapping -- 3.3.4 Micro Powder Blasting -- 3.3.5 Summary.

3.4 Other Processes -- 3.4.1 Sensor Integration -- 3.5 Thin Films -- 3.6 Bonding Methods -- 3.6.1 Anodic Bonding of Glass and Silicon -- 3.6.2 Glass Fusion Bonding -- 3.6.3 Silicon Direct Bonding (Silicon Fusion Bonding) -- 3.6.4 Establishing Fluid Contact -- 3.7 Other Materials -- References -- 4 Automation in Microreactor Systems -- 4.1 Introduction -- 4.2 Automation System -- 4.3 Automated Optimization with HPLC Sampling -- 4.4 Automated Multi-Trajectory Optimization -- 4.5 Kinetic Model Discrimination and Parameter Fitting -- 4.6 Conclusions and Outlook -- References -- 5 Homogeneous Reactions -- 5.1 Acid-Promoted Reactions -- 5.2 Base-Promoted Reactions -- 5.3 Radical Reactions -- 5.4 Condensation Reactions -- 5.5 Metal-Catalyzed Reactions -- 5.6 High Temperature Reactions -- 5.7 Oxidation Reactions -- 5.8 Reaction with Organometallic Reagents -- References -- 6 Homogeneous Reactions II: Photochemistry and Electrochemistry and Radiopharmaceutical Synthesis -- 6.1 Photochemistry in Flow Reactors -- 6.2 Electrochemistry in Microreactors -- 6.3 Radiopharmaceutical Synthesis in Microreactors -- 6.3.1 Fluorinations in Microreactors -- 6.3.2 Synthesis of 11C-Labeled PET Radiopharmaceuticals in Microreactors -- 6.4 Conclusion and Outlook -- References -- 7 Heterogeneous Reactions -- 7.1 Arrangement of Reactors in Flow Synthesis -- 7.2 Immobilization of the Reagent/Catalyst -- 7.2.1 A Packed-Bed Reactor -- 7.2.2 Monolith Reactors -- 7.2.3 Miscellaneous -- 7.3 Flow Reactions with an Immobilized Stoichiometric Reagent -- 7.4 Flow Synthesis with Immobilized Catalysts: Solid Acid Catalysts -- 7.5 Flow Reaction with an Immobilized Catalyst: Transition Metal Catalysts Dispersed on Polymer -- 7.5.1 Catalytic Hydrogenation -- 7.5.2 Catalytic Cross-Coupling Reactions and Carbonylation Reactions -- 7.5.3 Miscellaneous.

7.6 Flow Reaction with an Immobilized Catalyst: Metal Catalysts Coordinated by a Polymer-Supported Ligand -- 7.6.1 Flow Reactions Using Immobilized Ligands with a Transition Metal Catalyst -- 7.7 Organocatalysis in Flow Reactions -- 7.8 Flow Biotransformation Reactions Catalyzed by Immobilized Enzymes -- 7.9 Multistep Synthesis -- 7.10 Conclusion -- References -- 8 Liquid-Liquid Biphasic Reactions -- 8.1 Introduction -- 8.2 Background -- 8.3 Kinetics of Biphasic Systems -- 8.4 Biphasic Flow in Microchannels -- 8.5 Surface and Liquid-Liquid Interaction -- 8.6 Liquid-Liquid Microsystems in Organic Synthesis -- 8.7 Micromixer -- 8.8 Conclusions and Outlook -- References -- 9 Gas-Liquid Reactions -- 9.1 Introduction -- 9.2 Contacting Principles and Microreactors -- 9.2.1 Contacting with Continuous Phases -- 9.2.1.1 Falling Film Microreactor -- 9.2.1.2 Continuous Contactor with Partly Overlapping Channels -- 9.2.1.3 Mesh Microcontactor -- 9.2.1.4 Annular-Flow Microreactors -- 9.2.2 Contacting with Disperse Phases -- 9.2.2.1 Taylor-Flow Microreactors -- 9.2.2.2 Micromixer-Capillary/Tube Reactors -- 9.2.2.3 Micro-packed Bed Reactors -- 9.2.2.4 Membrane Microreactors -- 9.2.2.5 Tube in Tube Microreactor -- 9.2.3 Scaling Up of Microreactor Devices -- 9.3 Gas-Liquid Reactions -- 9.3.1 Direct Fluorination of Aromatics -- 9.3.1.1 Direct Fluorination of Aromatics -- 9.3.1.2 Direct Fluorination of Aliphatics and Non-C-Moieties -- 9.3.1.3 Direct Fluorination of Heterocyclic Aromatics -- 9.3.2 Oxidations of Alcohols, Diols, and Ketones with Fluorine -- 9.3.3 Photochlorination of Aromatic Isocyanates -- 9.3.4 Photoradical Chlorination of Cycloalkenes -- 9.3.5 Mono-Chlorination of Acetic Acid -- 9.3.6 Sulfonation of Toluene -- 9.3.7 Photooxidation Reactions -- 9.3.8 Reactive Carbon Dioxide Absorption -- 9.4 Gas-Liquid-Solid Reactions -- 9.4.1 Hydrogenations.

9.4.1.1 Cyclohexene Hydrogenation over Pt/Al2O3 -- 9.4.1.2 Hydrogenation of p-Nitrotoluene and Nitrobenzene over Pd/C and Pd/Al2O3 -- 9.4.1.3 Hydrogenation of Azide -- 9.4.1.4 Hydrogenation of Pharmaceutical Intermediates -- 9.4.1.5 Selective Hydrogenation of Acetylene Alcohols -- 9.4.1.6 Hydrogenation of a-Methylstyrene over Pd/C -- 9.4.2 Oxidations -- 9.4.2.1 Oxidation of Alcohols -- 9.4.2.2 Oxidation of Sugars -- 9.5 Homogeneously Catalyzed Gas-Liquid Reactions -- 9.5.1 Asymmetric Hydrogenation of Cinnamic Acid Derivatives -- 9.5.2 Asymmetric Hydrogenation of Methylacetamidocynamate -- 9.6 Other Applications -- 9.6.1 Segmented Gas-Liquid Flow for Particle Synthesis -- 9.6.2 Catalyst Screening -- 9.7 Conclusions and Outlook -- References -- 10 Bioorganic and Biocatalytic Reactions -- 10.1 General Introduction -- 10.2 Bioorganic Syntheses Performed in Microreactors -- 10.2.1 Biomolecular Syntheses in Microreactors: Peptide, Sugar and Oligosaccharide, and Oligonucleotide -- 10.2.1.1 Peptide Synthesis -- 10.2.1.2 Sugar and Oligosaccharide Synthesis -- 10.2.1.3 Oligonucleotide Synthesis -- 10.3 Biocatalysis by Enzymatic Microreactors -- 10.3.1 Classification of Enzymatic Microreactors Based on Application -- 10.3.1.1 Applications of Microreactors for Enzymatic Diagnostics and Genetic Analysis -- 10.3.1.2 Application of Microreactors for Enzyme-Linked Immunoassays -- 10.3.1.3 Applications of Microfluidic Enzymatic Microreactors in Proteomics -- 10.3.2 Enzymatic Microreactors for Biocatalysis -- 10.3.3 Advantages of Microreactors in Biocatalysis -- 10.3.4 Biocatalytic Transformations in Microfluidic Systems -- 10.3.4.1 Solution-phase Enzymatic Reactions -- 10.3.4.2 Microfluidic Reactors with Immobilized Enzymes for Biocatalytic Transformations -- 10.4 Multienzyme Catalysis in Microreactors -- 10.5 Conclusions -- References.

11 Industrial Microreactor Process Development up to Production -- 11.1 Mission Statement from Industry on Impact and Hurdles -- 11.2 Screening Studies in Laboratory -- 11.2.1 Peptide Synthesis -- 11.2.2 Hantzsch Synthesis -- 11.2.3 Knorr Synthesis -- 11.2.4 Enamine Synthesis -- 11.2.5 Aldol Reaction -- 11.2.6 Wittig Reaction -- 11.2.7 Polyethylene Formation -- 11.2.8 Diastereoselective Alkylation -- 11.2.9 Multistep Synthesis of a Radiolabeled Imaging Probe -- 11.3 Process Development at Laboratory Scale -- 11.3.1 Nitration of Substituted Benzene Derivatives -- 11.3.2 Microflow Azide Syntheses -- 11.3.3 Vitamin Precursor Synthesis -- 11.3.4 Ester Hydrolysis to Produce an Alcohol -- 11.3.5 Synthesis of Methylenecyclopentane -- 11.3.6 Condensation of 2-Trimethylsilylethanol -- 11.3.7 Staudinger Hydration -- 11.3.8 (S)-2-Acetyl Tetrahydrofuran Synthesis -- 11.3.9 Synthesis of Intermediate for Quinolone Antibiotic Drug -- 11.3.10 Domino Cycloadditions in Parallel Fashion -- 11.3.11 Phase-Transfer Catalysis-Mediated Knoevenagel Condensation -- 11.3.12 Ciprofloxazin1 Multistep Synthesis -- 11.3.13 Methyl Carbamate Synthesis -- 11.3.14 Newman-Kuart Rearrangement -- 11.3.15 Ring-Expansion Reaction of N-Boc-4-Piperidone -- 11.3.16 Synthesis of Aldehydes -- 11.3.17 Grignard Reactions and Li-Organic Reactions -- 11.3.18 Continuous Synthesis of Disubstituted Triazoles -- 11.3.19 Production of 6-Hydroxybuspirone -- 11.3.20 Swern-Moffatt Oxidation -- 11.4 Pilot Plants and Production -- 11.4.1 Hydrogen Peroxide Synthesis -- 11.4.2 Phenylboronic Acid Synthesis -- 11.4.3 Diverse Case Studies at Lonza -- 11.4.4 Alkylation Reactions Based on Butyllithium -- 11.4.5 Microprocess Technology in Japan -- 11.4.6 Pilot Plant for Methyl Methacrylate Manufacture -- 11.4.7 Grignard Exchange Reaction -- 11.4.8 Halogen-Lithium Exchange Pilot Plant.

11.4.9 Swern-Moffatt Oxidation Pilot Plant.