Microreactors in Organic Synthesis and Catalysis

Transcription

1 Microreactors in Organic Synthesis and Catalysis Edited by Thomas Wirth WILEY- VCH WILEY-VCH Verlag GmbH & Co. KGaA

2 I» Contents Preface XI List of Contributors XIII 1 Fabrication of Microreactors Made from Metals and Ceramics 1 JuergenJ. Brandner 1.1 Manufacturing Techniques for Metals Etching Machining Generative Method: Selective Laser Melting (SLM) Metal-Forming Techniques Assembling and Bonding of Metal Microstructures Ceramic Devices Joining and Sealing 14 References 15 2 Fabrication and Assembling of Microreactors Made from Class and Silicon 19 Thomas Frank 2.1 How Microreactors are Constructed Glass as Material Silicon as Material The Structuring of Glass and Silicon Structuring by Means of Masked Etching in Microsystems Technology Etching Technologies Anisotropie (Crystallographic) Wet Chemical Etching of Silicon (KOH) Isotropie Wet Chemical Etching of Silicon Anisotropie Dry Etching of Silicon Isotropie Wet Chemical Etching of Silicon Glass Photostructuring of Special Glass 32 Microreactors in Organic Synthesis and Catalysis. Edited by Thomas Wirth Copyright 2008 WILEY-VCH Verlag GmbH & Co. KGaA. All rights reserved. ISBN:

3 Contents 2.7 Chip Removing Processing Drilling, Diamond Lapping, Ultrasonic Lapping Micropowder Blasting Summary Bonding Methods Anodic Bonding of Glass and Silicon Silicon Direct Bonding (Silicon Fusion Bonding) Glass Fusion Bonding Establishing Fluid Contact Other Materials 41 References 41 3 Properties and Use of Microreactors 43 David Barrow 3.1 Introduction Physical Characteristics of Microreactors Geometries Constructional Materials and Their Properties Fluid Flow and Delivery Regimes Fluid Flow Fluid Delivery Mixing Mechanisms Multifunctional Integration Uses of Microreactors Overview Unstable Intermediates Fast and Exothermic Reactions Precision Particle Manufacture Wider Industrial Context Sustainability Agenda Point-of-Demand Synthesis 53 References 54 4 Organic Chemistry in Microreactors Homogeneous Reactions 59 Takahide Fukuyama, Md Taifur Rahman, llhyong Ryu Acid-Promoted Reactions Base-Promoted Reactions Condensation Reactions Metal-Catalyzed Reactions Photochemical Reactions Electrochemical Reactions Miscellaneous Swern Oxidation Grignard Exchange Reaction Lithium-Halogen Exchange Reaction 81

4 Phenyl Boronic Acid Synthesis 81 References Heterogeneous Reactions 84 lan R. Baxendale, John J. Hayward, Steve Lanners, Steven V. Ley, Christopher D. Smith Introduction Concepts in Flow Mode Synthesis Methods of Conducring Flow Chemistry On-Bead Synthesis Solution-Phase Synthesis Library Synthesis in Flow Heterocycle Synthesis Introduction to Monoliths Transition Metal Chemistry Under Flow Conditions Reduction Oxidation Cross-Coupling Reactions Olefin Metathesis Enantioselective Reactions Hydrolytic Kinetic Resolution Organometallic Additions Enantioselective Diels-Alder Reactions Ene Reactions Cyclopropanation Asymmetrie Conjugate Addition ß-Lactam Synthesis Asymmetrie Chlorination Multistep Synthesis Conclusions and Outlook 117 References Liquid-Liquid Biphasic Reactions 122 Batoul Ahmed-Omer, Thomas Wirth Introduction Background Kinetics of Biphasic Systems Biphasic Flow in Microchannels Surface-Liquid and Liquid-Liquid Interactions Liquid-Liquid Microsystems in Organic Synthesis Conclusions and Outlook 137 References Gas-Liquid Reactions 139 Volker Hessel, Patrick Lob, Holger Löwe Introduction Contacting Principles and Microreactors Contacting with Continuous Phases 139

5 VIII Contents Falling-Film Microreactor Contact with Disperse Phases Gas-Liquid Reactions Direct Fluorination of Aromatics Oxidations of Alcohols, Diols and Ketones with Fluorine Photochlorination of Aromatic Isocyanates Monochlorination of Acetic Acid Sulfonation of Toluene Photooxidation of a-terpinene and Cyclopentadiene Reactive Carbon Dioxide Absorption Gas-Liquid-Solid Reactions Cyclohexene Hydrogenation over Pt/Al Hydrogenation of p-nitrotoluene and Nitrobenzene over Pd/C and Pd/Al Hydrogenation of a-methylstyrene over Pd/C Hydrogen Peroxide Formation from the Elements Homogeneously Catalyzed Gas-Liquid Reactions Asymmetrie Hydrogenation of Cinnamic Acid Derivatives Asymmetrie Hydrogenation of Methylacetamidocinnamate Other Applications Segmented Gas-Liquid flow for Particle Synthesis Conclusions and Outlook 378 References Bioorganic Reactions 183 Kaspar Koch, Floris P.J.T. Rutjes.Jan CM. van Hest, General Introduction Diagnostic Applications Protein and DNA Analysis DNA Amplifkations Enzyme-Linked Immunoassays Other Diagnostic Applications Biocatalysis Enzyme Kinetics in Microreactors Biocatalyzed Synthesis in Microreactors Complex Catalysis in Microbioreactors Conclusions 205 References Industrial Microreactor Process Development up to Production 23 3 Volker Hessel, Patrick Lob, Holger Löwe 5.1 Mission Statement from Industry on Impact and Hurdles Screening Studies in Laboratory Peptide Synthesis Hantzsch Synthesis Knorr Synthesis 236

6 5.2.4 Enamine Synthesis Aldol Reaction Wittig Reaction Polyethylene Formation Diastereoselective Alkylation Multistep Synthesis of a Radiolabeled Imaging Probe Process Development at Laboratory Scale Nitration of Substituted Benzene Derivatives Phenyl Boronic Acid Synthesis Azo Pigment Yellow 12 Manufacrure Desymmetrization of Thioureas Vitamin Precursor Synthesis Ester Hydrolysis to Produce an Alcohol Synthesis of Methylenecyclopentane Condensation of 2-Trimethylsilylethanol (S)-2-Acetyl Tetrahydrofuran Synthesis Synthesis of Intermediate for Quinolone Antibiotic Drug Domino Cycloadditions in Parallel Fashion Ciprofloxazin Multistep Synthesis Methyl Carbamate Synthesis Newman-Kuart Rearrangement Ring-Expansion Reaction of N-Boc-4-Piperidone Grignard and Organolithium Reagents Pilots Plants and Production Hydrogen Peroxide Synthesis Diverse Case Studies at Lonza Polyacrylate Formation Butyl Lithium-Based Alkylation Reactions German Project Cluster Development for OLED Materials Production Development for Liquid/Liquid and Gas/liquid Fine-Chemicals Production Development of Pharmaceutical Intermediäres Production by Ozonolysis and Halogenation Industrial Photochemistry Development of Ionic Liquid Production Japanese Project Cluster Pilot Plant for MMA Manufacrure Grignard Exchange Reaction Halogen-Lithium Exchange Pilot Plant Swem-Moffat Oxidation Pilot Plant Yellow Nano Pigment Plant Polycondensation Friedel-Crafts Alkylation H 2 Q 2 Based Oxidation to 2-Methyl-l,4-Naphthoquinone 260 Contents I IX

7 X I Contents Direct Fluorination of Ethyl 3-Oxobutanoate Propene Oxide Formation Diverse Industrial Pilot-Oriented Involvements Production of Polymer Intermediates Synthesis ofdiazo Pigments Nitroglycerine Production Fine-Chemical Production Process Grignard-Based Enolate Formation Challenges and Concerns 271 References 272 Index 277 S