Flow Chemistry

Broader theoretical insight on organic reactions in driving them automatically opens the window towards new technologies particularly to flow chemistry. This emerging concept promotes the transformation of present day's organic processes into a more rapid continuous set of synthesis operations, more compatible with the envisioned sustainable world. Our book provides a comprehensive discussion on the theoretical foundation of flow chemistry.

Preface5 About the editors13 Abbreviations17 Part I Introduction and outlook19 1 Introduction and outlook21 Part II Theoretical foundations25 2 Fundamentals of Flow Chemistry27 2.1 Fundamentals of chemical reactions27 2.1.1 Thermodynamic requirements for reaction27 2.1.2 Kinetic requirements for a reaction28 2.1.3 Reaction order and kinetics30 2.1.4 Diffusion control31 2.1.5 Kinetic versus thermodynamic control31 2.1.6 Competing reactions33 2.1.7 Initiation and termination of chemical reactions33 2.1.8 Exotherm and endoterm reactions34 2.1.9 How to accelerate an organic chemical reaction. Shifting the equilibrium towards product formation34 2.2 Batch versus flow reactions38 2.2.1 Performing chemical reactions in batch and flow41 2.2.2 Multistep reactions in batch and flow44 2.2.3 The dimensions of batch (flask) and flow (micro) reactors44 2.2.4 Mixing in batch versus microreactors45 2.2.5 Mass transfer in batch and flow46 2.2.6 Temperature control in batch and flow47 2.2.7 Heterogeneous catalytic reactions in batch and flow50 2.3 Introduction to the basics of microfluidics52 2.3.1 Electroosmotic (electrokinetic) flow (EOF)52 2.3.2 Hydrodynamic (pressure-driven) pumping54 2.3.3 Segmented flow55 2.3.4 Centrifugal pumping56 2.3.5 Laminar and turbulent flow regimes, the Reynolds number56 2.3.6 Axial dispersion versus radial dispersion (Bodenstein and Peclet Numbers)59 2.3.7 Mixing versus reaction rate–Damköhler Number59 2.3.8 Heat transfer in flow60 2.3.9 Flow rates in microreactors61 2.4 Microreactors in general62 2.4.1 General properties of flow reactors62 2.4.2 Major flow reactor configurations65 2.5 Essentials of reaction planning and realization in continuous flow67 2.5.1 Classification of chemical reactions based on reaction kinetics67 2.5.2 Flash chemistry68 2.5.3 High-resolution reaction time control69 2.5.4 Novel process windows70 2.5.5 Process intensification73 3 Principles of controlling reactions in flow chemistry77 3.1 Introduction77 3.2 Reactions in a flow microreactor77 3.2.1 Reaction time in a batch reactor77 3.2.2 Residence time control in a flow reactor78 3.2.3 Why micro?80 3.3 High-resolution reaction time control of reactions in flow86 3.3.1 The principle86 3.3.2 Example 1: Phenyllthiums bearing alkoxycarbonyl groups88 3.3.3 Temperature–residence time map90 3.3.4 Example 2: Control of isomerization. Aryllithiums bearing a nitro group94 3.4 Space integration of reactions95 3.4.1 The concept95 3.4.2 Example 3: Synthesis of disubstituted benzenes from dibromobenzene96 3.4.3 Example 4: Synthesis of TAC-10197 3.4.4 Linear integration and convergent integration98 3.4.5 Example 5: Synthesis of unsymmetrically-substituted photochromic diarylethenes. Convergent integration99 3.4.6 Example 6: Integration of lithiation and cross-coupling100 3.4.7 Example 7: Anionic polymerization of styrene and synthesis of block copolymers with a silicon core103 3.4.8 Example 8: Anionic block copolymerization of styrene and methyl methacrylate106 3.5 Summary107 4 Technology overview/Overview of the devices113 4.1 General aspects113 4.2 Pumps for liquid handling114 4.2.1 Syringe pump114 4.2.2 Piston pump115 4.2.3 Other pumps116 4.3 Mass-flow controllers117 4.4 Heating/cooling of the reaction zone117 4.5 Back-pressure regulators118 4.6 Mixers119 4.6.1 Modular mixers120 4.6.2 In-line mixers121 4.7 Reactors123 4.7.1 Coil reactors124 4.7.2 Chip reactors126 4.7.3 Packed-bed or fixed-bed reactors127 4.8 Miscellaneous techniques130 4.8.1 Tube-in-tube reactor130 4.8.2 Segmented flow biphasic reactions131 4.8.3 Falling film reactors134 4.8.4 Flow microwave reactors135 4.8.5 UV reactors136 4.8.6 Working with supercritical CO2137 4.9 Assembling and using a flow reactor138 4.10 Commercially available systems for the laboratory use141 5 From batch to continuous chemical synthesis – a toolbox approach159 5.1 Chemical process development and scale-up challenges159 5.1.1 Batch synthesis: Current profile of the pharmaceutical and fine-chemical industry159 5.1.2 Flow chemistry and microreactor technology: a viable alternative?160 5.1.3 Modularized process intensification – use the right tool at the right place161 5.2 Reaction categories based on rate164 5.2.1 Type A reactions164 5.2.2 Type B reactions164 5.2.3 Type C reactions165 5.3 Reacting phases165 5.3.1 Single phase systems – mix-then-reside165 5.3.2 Liquid-liquid systems – mix-and-reside versus active mixing166 5.3.3 Gas-liquid systems – use of pressure168 5.3.4 Liquid-solid systems168 5.4 Summary168 Part III Lab and teaching practise173 6 Experimental procedures for conducting organic reactions in continuous flow175 6.1 Flow chemistry calculations175 6.1.1 Reaction and microreactor temperature175 6.1.2 Determination of flow rates175 6.1.3 Example calculation176 6.2 Wittig reaction in a continuous-flowmicroreactor177 6.2.1 Continuous-flow design177 6.2.2 Basic experiment178 6.2.3 Optimization experiment179 6.3 Swern–Moffatt oxidation in a continuous-flow microreactor181 6.3.1 Continuous-flow design181 6.3.2 Basic experiment182 6.3.3 Optimization experiment184 6.3.4 Optimization experiment on a different substrate185 6.4 Synthesis of silver nanoparticles in a continuous-flow microreactor186 6.4.1 Continuous-flow design187 6.4.2 Basic experiment187 6.4.3 Optimization experiment190 6.5 1,2,3-triazole synthesis in continuous flow with copper powder and additives190 6.5.1 Continuous-flow design191 6.5.2 Basic experiment192 6.5.3 Optimization experiment192 6.6 Heterogeneous catalytic deuteration with D2O in continuous flow194 6.6.1 Continuous-flow design194 6.6.2 Basic experiment195 6.6.3 Optimization experiment196 6.7 Aldol reaction in a continuous-flow microreactor196 6.7.1 Continuous-flow design197 6.7.2 Basic aldol experiment197 6.7.3 Aldol reaction optimization198 6.8 Prilezhaev epoxidation in a continuous-flow microreactor199 6.8.1 Continuous-flow design199 6.8.2 Basic epoxidation experiment200 6.9 Peptide catalyzed stereoselective reactions in a continuous-flow reactor202 6.9.1 Continuous-flow design204 6.9.2 Basic aldol experiment204 6.9.3 Reaction optimization205 7 Experimental procedures for conducting organic reactions in continuous flow209 7.1 Pyrrole synthesis by Paal–Knorr cyclocondensation210 7.1.1 Background210 7.1.2 The flow process211 7.1.3 Experimental procedures213 7.2 Diels–Alder Reactions in flow chemistry214 7.2.1 Background214 7.2.2 The flow process214 7.2.3 Experimental procedures217 7.3 Copper-catalyzed azide-alkyne cycloaddition in flow using inductive heating218 7.3.1 Background218 7.3.2 The flow process220 7.3.3 Experimental procedures221 7.4 Nef Oxidation of nitroalkanes with KMnO222 7.4.1 Background222 7.4.2 The flow process222 7.4.3 Experimental procedures224 7.5 Suzuki–Miyaura cross-coupling with palladium-catalysts generated in flow225 7.5.1 Background225 7.5.2 The flow process226 7.5.3 Experimental procedures228 7.6 Oxidative amidation of aromatic aldehydes229 7.6.1 Background229 7.6.2 The flow process230 7.6.3 Experimental procedures231 7.7 Azide synthesis in flow via diazotransfer233 7.7.1 Background233 7.7.2 The flow process234 7.7.3 Experimental procedures235 7.8 Boronic acid/ester synthesis via lithium halogen exchange in a Cryo-Flow Reactor237 7.8.1 Background237 7.8.2 The flow process237 7.8.3 Experimental procedures240 7.9 The Ritter Reaction in Continuous Flow241 7.9.1 Background241 7.9.2 The flow process242 7.9.3 Experimental procedures243 7.10 Vilsmeier–Haack formylation of electron-rich arenes244 7.10.1 Background244 7.10.2 The flow process245 7.10.3 Experimental procedures248 7.11 Appel reaction using monolithic triphenylphosphine in flow248 7.11.1 Background248 7.11.2 The flow process250 7.11.3 Experimental procedures252 7.12 Schenck ene reaction in flow using singlet oxygen253 7.12.1 Background253 7.12.2 The flow process254 7.12.3 Experimental procedure257 7.13 Chemoenzymatic flow synthesis of cyanohydrins259 7.13.1 Background259 7.13.2 The flow process260 7.13.3 Experimental procedures261 7.14 Summary262 8 The Microwave-to-flow paradigm: translating batch microwave chemistry to continuous-flow processes269 8.1 Microwave chemistry269 8.2 Converting microwave to flow chemistry270 8.3 Summary275 9 Incorporation of continuous-flow processing into the undergraduate teaching laboratory: key concepts and two case studies277 9.1 Introduction277 9.2 Equipment278 9.3 Experiments developed for the undergraduate teaching laboratory280 9.4 Development of two new experiments for the undergraduate laboratory280 9.4.1 The Biginelli Reaction282 9.4.2 The Claisen–Schmidt Reaction287 9.5 Summary291 9.6 Acknowledgements291 Answers to the study questions295 Index309

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