Novel process windows : innovative gates to intensified and sustainable chemical processes /: innovative gates to intensified and sustainable chemical processes. (2014)

• Record Type: Book
• Further Information: Note: Volker Hessel, Dana Kralisch, and Norbert Kockmann.
• Authors: Hessel, Volker; Kralisch, Dana; Kockmann, Norbert
• Contents: Motivation –Who should read the book!? XVII Acknowledgments XIX Abbreviations XXI Nomenclature XXIII 1 FromGreen Chemistry to Green Engineering – Fostered by Novel ProcessWindows Explored in Micro-Process Engineering/Flow Chemistry 1 1.1 Prelude – Potential for Green Chemistry and Engineering 1 1.2 Green Chemistry 2 1.2.1 12 Principles in Green Chemistry 2 1.3 Green Engineering 3 1.3.1 10 Key Research Areas in Green Engineering 3 1.3.2 12 Principles in Chemical Product Design 4 1.4 Micro- and Milli-Process Technologies 6 1.4.1 Microreactors 6 1.4.2 Microstructured Reactors 6 1.5 Flow Chemistry 9 1.5.1 10 Key Research Areas in Flow Chemistry 9 1.6 Two Missing Links – Cross-Related 9 References 12 2 Novel ProcessWindows 15 2.1 Transport Intensification –The Potential of Reaction Engineering 15 2.2 Chemical Reactivity in Match or Mismatch to Intensified Engineering 17 2.3 Chemical Intensification through Harsh Conditions – Novel Process Windows 18 2.4 Flash Chemistry 19 2.5 Process-Design Intensification 21 References 23 3 Chemical Intensification – Fundamentals 25 3.1 Length Scale 25 3.2 Time Scale 26 3.3 Length and Time Scale of Chemical Reactions 28 3.3.1 Solution of Kinetic Equations 29 3.3.2 Reaction Time and Reaction Classification 31 3.3.3 Example for Reaction Time and Residence Time 32 3.4 Temperature Intensification 33 3.4.1 Harsh Process Conditions 33 3.4.2 New TemperatureWindows 33 3.4.3 Reaction Rate – Arrhenius Equation 35 3.5 Pressure Intensification 36 3.5.1 Reaction Rate – Activation Volumes 36 3.5.2 Equilibrium 37 3.5.3 Electron Kinetic Energy 38 3.5.4 Material Properties 38 3.5.5 Mixture Properties 40 3.5.6 Illustration of Pressure Effect on Selected Chemical Reactions 41 References 42 4 Making Use of the “Forbidden” – Ex-Regime/High Safety Processing 45 4.1 Hazardous Reactants and Intermediates 45 4.1.1 Tetrazole Formation 45 4.1.2 Strecker Synthesis 47 4.1.3 Phosgene Chemistry 47 4.1.4 Diazomethane Synthesis 48 4.1.5 Ozonolysis 50 4.1.6 Organic Peroxide Formation 51 4.2 Ex-Regime andThermal Runaway Processing 52 4.2.1 Oxidation 52 4.2.2 Hydrogen Peroxide Synthesis 52 4.2.3 Direct Fluorination 53 4.2.4 Ionic Liquid Synthesis 53 4.2.5 Moffatt–Swern Oxidation 54 4.2.6 Reaction Between Cyclohexanecarboxylic Acid and Oleum 55 4.2.7 Nitration of Toluene 55 4.2.8 Aromatic Amidoxime Formation 56 4.2.9 Decarboxylative Trichloromethylation of Aromatic Aldehydes 56 4.2.10 Dihydroxylation Reactions with Nanobrush-Immobilized OsO4 58 References 58 5 Exploring New Paths – New Chemical Transformations 61 5.1 Direct Syntheses via One Step 61 5.1.1 Fluorination with Elemental Fluorine 61 5.1.2 Hydrogen Peroxide Synthesis out of the Elements 62 5.1.3 Direct Aryllithiums Route 62 5.1.4 C–O Bond Formation by a Direct α-C–H Bond Activation 63 5.1.5 Direct Adipic Acid Route from Cyclohexene 65 5.1.6 New Biocatalytic Pathways without Protecting Groups – Inter-Glycosidic Condensation 68 5.2 Direct Syntheses via Multicomponent Reactions 69 5.2.1 “Odor-Sealed” Isocyanide Formation 69 5.3 Multistep One-Flow Syntheses 70 5.4 Multistep Syntheses in One Microreactor/Chip 73 5.4.1 Multistep Synthesis of [18F]-Radiolabeled Molecular Imaging Probe 73 5.4.2 Combining Asymmetric Organocatalysis and Analysis on a Single Microchip 75 5.4.3 Two-Step Strecker Reaction 75 5.5 Multistep Syntheses in Coupled Microreactors/Chips 76 5.5.1 Chlorohydrination of Allyl Chloride 76 5.5.2 Lithiation/Borylation/Suzuki–Miyaura Cross-Coupling 77 5.5.3 Suzuki–Miyaura Cross-Coupling-Phenols-Aryl Triflates-Biaryls 77 5.5.4 Ring-Closing Metathesis and Heck Reaction 77 5.5.5 Imidazo[1, 2-a]pyridine-2-carboxylic Acids in Two Steps 78 5.5.6 Suzuki–Miyaura Cross-Coupling/Hydrogenation 78 5.5.7 Sodium Nitrotetrazolate – Diazonium Ion Formation/Sandmeyer Reaction 79 5.5.8 Murahashi Coupling/Br–Li Exchange 79 5.5.9 5′-Deoxyribonucleoside Glycosylation 80 5.5.10 Two-Carbon Homologation of Esters to α, β-Unsaturated Esters 81 5.5.11 Low-Pressure Carbonylations with Acids as CO Precursors 81 5.5.12 Coupled Microreactor-Purification-Analytics for δ-Opioid Receptor Agonist 82 5.5.13 Synthesis of TAC-101 Analogs 82 5.5.14 Multistep Enzymatic Synthesis to 2-Amino-1, 3, 4-Butanetriol 83 5.5.15 Multistep Enzymatic Synthesis to δ-D-Gluconolactone 83 5.5.16 Diarylethene Synthesis in Two Steps 87 References 87 6 Activate – High-T Processing 91 6.1 Tailored High-T Microreactor Design and Fabrication 93 6.1.1 Glass Capillary Coil in Ceramic Housing 93 6.1.2 Modularly Packaged Silicon Microreactor 93 6.1.3 Modular Thermal Platform for High-Temperature Flow Reactions 93 6.2 Cryogenic to Ambient – Allowing Fast Reactions to be Fast 94 6.2.1 Synthesis of Triflates for the Heck Alkenylation 94 6.2.2 Enantioselective 1, 4-Addition of Enones 96 6.2.3 Swern–Moffatt Oxidation of Benzyl Alcohol 97 6.2.4 Tf2NH-Catalyzed [2+2] Cycloaddition 98 6.3 From Reflux to Superheated – Speeding-Up Reactions 99 6.3.1 Kolbe–Schmitt Reaction 99 6.3.2 C–F Bond Formation 99 6.3.3 NMP Radical Polymerization of Styrene 100 6.3.4 Noncatalytic Claisen Rearrangement 100 6.3.5 Nucleophilic Substitution of Difluoro-benzenes 100 6.3.6 Aminolysis of Epoxides 101 6.3.7 Synthesis of 2, 4, 5-Trisubstituted Imidazoles 102 6.3.8 2-Methylbenzimidazole Formation, 3, 5-Dimethyl-1-Phenylpyrazole Formation, and Diels–Alder Cycloaddition – Benchmarking High-p, t Flow to Microwave 102 6.3.9 Fischer Indole Synthesis of Tetrahydrocarbazole 103 6.3.10 Thermal Hydrolysis of Triglycerides 103 6.3.11 Chlorodehydroxylation to n-Alkyl Chlorides 104 6.3.12 1, 3, 4-Oxadiazoles via N-Acylation of 5-Substituted Tetrazoles 105 6.3.13 Cobalt-Catalyzed Borohydride Reduction of Tetralone 106 6.3.14 Dimethylcarbonate Methylation 107 6.3.15 Selective Aerobic Oxidation of Benzyl Alcohol Using Iron Oxide Nano-/TEMPO Catalyst 108 6.3.16 Rufinamide Synthesis 110 6.3.17 Several High-T, High-p Processes 111 6.3.18 Click Chemistry 111 6.3.19 4-(Pyrazol-1-yl) Carboxanilide Multistep Synthesis 112 6.3.20 4-Hydroxy-2-cyclopentenone Synthesis 113 6.3.21 Hydrothermal Treatment of Glucose 114 6.3.22 Tetrahydroisoquinoline Synthesis 114 6.4 Solvent-ScopeWidening by Virtue of Pressurizing Existing High-T Reactions 116 6.4.1 Nucleophilic Aromatic Substitution of 2-Halopyridines 116 6.4.2 IntramolecularThermal Cyclization and Benzannulation 116 6.4.3 Catalyst-Free Transesterification and Esterification of Aliphatic and Aromatic Acids 117 6.4.4 Aminolysis of Epoxides 117 6.5 New Temperature Field for Product and Material Control 118 6.5.1 Palladium-Catalyzed Aminocarbonylation 118 6.5.2 Aminolysis of Epoxides 119 6.5.3 Flash Flow Pyrolysis 119 6.5.4 Indium Phosphide Nanocrystal 120 6.5.5 Quantum Dot Synthesis 121 6.5.6 High-T Flow Cycloaddition to Fullerene Derivatives 123 6.6 Energy Activation Other than Temperature – Photo, Electrochemical, Plasma 125 6.6.1 Photo-Oxygenation of Dimethylsulfide 125 6.6.2 Microwave Flow Reactor for Stable High-p, T Operation 125 References 125 7 Press – High-p Processing 129 7.1
• Publisher Details: Place of publication not identified : Wiley-VCH
• Publication Date: 2014
• Extent: 1 online resource (344 pages)
• Subjects: 660; Chemical processes
• Languages: English
• ISBNs: 9783527654840
• Access Rights: Legal Deposit; Only available on premises controlled by the deposit library and to one user at any one time; The Legal Deposit Libraries (Non-Print Works) Regulations (UK).
• Access Usage: Restricted: Printing from this resource is governed by The Legal Deposit Libraries (Non-Print Works) Regulations (UK) and UK copyright law currently in force.