Fundamentals and Applications of Organic Electrochemistry: Synthesis, Materials, Devices

Fundamentals and Applications of Organic Electrochemistry: Synthesis, Materials, Devices
Contents
About the Authors
Preface
Introduction
1. Fundamental Principles of Organic Electrochemistry: Fundamental Aspects of Electrochemistry Dealing with Organic Molecules
1.1 FORMATION OF ELECTRICAL DOUBLE LAYER
1.2 ELECTRODE POTENTIALS (REDOX POTENTIALS)
1.3 ACTIVATION ENERGY AND OVERPOTENTIAL
1.4 CURRENTS CONTROLLED BY ELECTRON TRANSFER AND MASS TRANSPORT
References
2. Method for Study of Organic Electrochemistry: Electrochemical Measurements of Organic Molecules
2.1 WORKING ELECTRODES
2.2 REFERENCE ELECTRODES
2.3 AUXILIARY ELECTRODES
2.4 SOLVENTS AND SUPPORTING ELECTROLYTES
2.5 CELLS AND POWER SOURCES
2.6 STEADY-STATE AND NON-STEADY-STATES POLARIZATION CURVES
2.7 POTENTIALS IN ELECTROCHEMICAL MEASUREMENTS
2.8 UTILIZATION OF VOLTAMMETRY FOR THE STUDY OF ORGANIC ELECTROSYNTHESIS
2.8.1 Voltammetric Analysis for Selective Electrosynthesis
2.8.2 Clarification of the Reaction Mechanism
2.8.3 Voltammetry for Selection of Mediator
2.8.4 Voltammetry for Selection of Electrode Material
References
3. Methods for Organic Electrosynthesis
3.1 SELECTION OF ELECTROLYTIC CELLS
3.2 CONSTANT CURRENT ELECTROLYSIS AND CONSTANT POTENTIAL ELECTROLYSIS
3.3 DIRECT ELECTROLYSIS AND INDIRECT ELECTROLYSIS
3.4 ELECTRODE MATERIALS AND REFERENCE ELECTRODES
3.5 ELECTROLYTIC SOLVENTS AND SUPPORTING ELECTROLYTES
3.6 STIRRING
3.7 TRACKING OF REACTANT AND PRODUCT
3.8 WORK-UP, ISOLATION AND DETERMINATION OF PRODUCTS
3.9 CURRENT EFFICIENCY AND EFFECT OF THE POWER UNIT
References
4. Organic Electrode Reactions
4.1 GENERAL CHARACTERISTICS OF ELECTRODE REACTIONS
4.2 MECHANISM OF ORGANIC ELECTRODE REACTIONS
4.3 CHARACTERISTICS OF ORGANIC ELECTROLYTIC REACTIONS
4.3.1 Umpolung
4.3.2 Selectivity
4.3.2.1 Chemoselectivity
4.3.2.2 Reaction Pathway Selectivity
4.3.2.3 Regioselectivity
4.3.2.4 Stereoselectivity
4.3.2.5 Selectivity Depending on Electrode Materials
4.4 MOLECULAR ORBITALS AND ELECTRONS RELATED TO ELECTRON TRANSFER
4.5 ELECTROAUXILIARIES
4.5.1 Electroauxiliaries Based on Molecular Orbital Interactions
4.5.2 Electroauxiliaries Based on Readily Electron-Transferable Functional Groups
4.5.3 Electroauxiliaries Based on Intermolecular Coordination Effects
4.5.4 Electroauxiliaries Based on Intramolecular Coordination Effects
4.6 REACTION PATTERN OF ORGANIC ELECTRODE REACTIONS
4.6.1 Transformation Type of Functional Group
4.6.2 Addition Type
4.6.3 Insertion Type
4.6.4 Substitution Type
4.6.5 Substitutive Exchange Type
4.6.6 Elimination Type
4.6.7 Dimerization Type
4.6.8 Crossed Dimerization
4.6.9 Cyclization Type
4.6.10 Polymorphism Formation Type
4.6.11 Polymerization Type
4.6.12 Cleavage Type
4.6.13 Metalation Type
4.6.14 Asymmetric Synthesis Type
4.7 ELECTROCHEMICALLY GENERATED REACTIVE SPECIES
4.7.1 Carbon Species
4.7.1.1 Anodically Generated Carbon Species
4.7.1.2 Cathodically Generated Carbon Species
4.7.2 Heteroatom Species
4.7.2.1 Nitrogen Species
4.7.2.2 Oxygen Species
4.7.2.3 Calcogeno (Sulfur, Selenium, Tellurium) Species
4.7.2.4 Halogen Species
4.7.2.5 14-Family and 15-Family Element Species
References
5. Organic Electrosynthesis
5.1 ELECTROCATALYSIS
5.1.1 Classification and Kinds of Mediators
5.1.2 Organic Electrolytic Reactions Using Mediators
5.1.2.1 Electrosynthesis Using Multivalent Metal Ion Mediators
5.1.2.2 Electrosynthesis Using Halogen Mediators
5.1.2.3 Electrosynthesis Using Triarylamine Mediators
5.1.2.4 Electrosynthesis Using Multi-Mediatory Systems
5.1.2.5 Electrosynthesis Using Hypervalent Compounds as Mediators
5.1.2.6 Electrosynthesis Using Transition Metal Complex Mediators
5.1.2.7 Electrosynthesis Using Mediator Immobilzed on Solid
5.2 ELECTROGENERATED ACIDS AND BASES
5.2.1 Electrogenerated Bases
5.2.2 Electrogenerated Acids
5.3 ELECTROCHEMICAL ASYMMETRIC SYNTHESIS
5.4 MODIFIED ELECTRODES
5.4.1 Electrodes Modified with Adsorbants
5.4.2 Foreign Metal Adatom Modified Electrodes
5.4.3 Chemically Modified Electrodes
5.4.4 Polymer-Modified (Coated) Electrodes
5.5 PAIRED ELECTROSYNTHESIS
5.6 REACTIVE ELECTRODES
5.7 ELECTROCHEMICAL FLUORINATION
5.7.1 Electrochemical Fluorination of Aromatic Rings
5.7.2 Electrochemical Fluorination of Olefins
5.7.3 Benzylic Electrochemical Fluorination
5.7.4 Electrochemical Fluorination of Sulfides
5.7.5 Electrochemical Fluorination of Heterocyclic Compounds
5.7.6 Electrochemical Fluorination of Heterocyclic Compounds with PhS Group as Electroauxiliary
5.7.7 Electrochemical Fluorination Using Inorganic Fluoride Salts
5.8 ELECTROCHEMICAL POLYMERIZATION
5.8.1 Electro-oxidative Polymerization of Aromatic Monomers
5.8.2 Electrochemical Polymerization
5.8.3 Conditions for Electrochemical Polymerization
5.8.4 Electrochemical Doping
5.8.5 Electro-reductive Polymerization of Aromatic Monomers
5.8.6 Applications of Conducting Polymers
5.8.7 Electrochemical Synthesis of Polysilanes
5.8.8 Chain Polymerization Initiated with Electrogenerated Reactive Species
References
6. New Methodology of Organic Electrochemical Synthesis
6.1 SPE ELECTROLYSIS AND ITS APPLICATIONS
6.1.1 Principle of SPE Electrolysis
6.1.2 SPE Electrolysis with Cogeneration (Chemicals Production Using Fuel Cell Reactions)
6.2 ELECTROLYTIC SYSTEMS USING SOLID BASES AND ACIDS
6.3 SOLID-SUPPORTED MEDIATORS
6.4 BIPHASIC ELECTROLYTIC SYSTEMS
6.4.1 Emulsion Electrolysis
6.4.2 Suspension Electrolysis
6.4.3 Electrolysis Using Phase-Transfer Catalysis
6.4.4 Thermomorphic Biphasic Electrochemical Reaction System
6.5 CATION POOL METHOD
6.6 TEMPLATE-DIRECTED METHODS
6.7 ELECTROLYSIS IN SUPERCRITICAL FLUIDS
6.8 ELECTROLYSIS IN IONIC LIQUIDS
6.8.1 Structures of Ionic Liquids
6.8.2 Hydrophilicity and Hydrophobicity of Ionic Liquids
6.8.3 Polarity of Ionic Liquids
6.8.4 Electrochemical Properties of Ionic Liquids
6.8.5 Voltammetry in Ionic Liquids
6.8.6 Organic Electrochemical Reactions in Ionic Liquids
6.8.6.1 Organic Electrosynthesis
6.8.6.2 Electrochemical Fluorination
6.8.6.3 Electropolymerization
6.8.6.4 Others
6.9 THIN-LAYER ELECTROLYTIC CELLS
6.10 ELECTROCHEMICAL MICROFLOW SYSTEMS
6.11 ELECTROLYSIS UNDER ULTRASONICATION
6.12 ELECTROSYNTHESIS USING SPECIFIC ELECTRODE MATERIALS
6.12.1 Electrochemical Synthesis Using Hydrophobic Electrodes
6.12.1.1 Hydrophobic Composite-Plated Electrodes
6.12.1.2 PTFE-Fibre-Coated Electrodes
6.12.2 Electrolytic Reactions Using Diamond Electrodes
6.12.2.1 Electrochemical Features and Application to Highly Sensitive Electroanalysis
6.12.2.2 Application to Organic Electrosynthesis
6.12.2.3 Application to Inorganic Electrosynthesis
6.13 PHOTOELECTROLYSIS AND PHOTOCATALYSIS
6.13.1 Photoelectrolysis
6.13.2 Photocatalysts
6.14 ELECTROCHEMICAL POLYMER REACTIONS
References
7. Related Fields of Organic Electrochemistry
7.1 APPLICATION IN ORGANIC ELECTRONIC DEVICES
7.1.1 Organic Electroluminescence
7.1.2 Organic Photovoltaic Cells
7.1.3 Dye-sensitized Solar Cells
7.1.4 Organic Transistors
7.1.5 Electrochromic Devices
7.1.6 Conducting Polymer-based Capacitors
7.2 ELECTROCHEMICAL CONVERSION OF BIOMASS TO VALUABLE MATERIALS
7.3 APPLICATION TO C1 CHEMISTRY
7.4 ENVIRONMENTAL CLEANUP
References
8. Examples of Commercialized Organic Electrode Processes
8.1 AVENUE TO INDUSTRIALIZATION
8.2 EXAMPLES
8.2.1 Electrosynthesis of Adiponitrile
8.2.2 Electrosynthesis of Aromatic Aldehydes
8.2.3 Paired Electrosynthesis of Phthalide and t-Butylbenzaldehyde
8.2.4 Electrochemical Perfluorination
8.2.5 Other Examples
8.2.5.1 3,6-Dichloropicolic Acid
8.2.5.2 β-Lactam Derivative
8.2.5.3 Cysteine
8.2.5.4 Tetramethylammonium Hydroxide
8.2.5.5 Other Examples
References
Appendix A: Examples of Organic Electrosynthesis
A.1 ELECTROCHEMICAL FLUORINATION
A.2 ELECTROSYNTHESIS USING A HYDROPHOBIC ELECTRODE
A.3 NATURAL PRODUCT SYNTHESIS USING ANODIC OXIDATION
A.4 KOLBE ELECTROLYSIS
A.5 INDIRECT ELECTROSYNTHESIS USING A MEDIATOR
A.6 ELECTROSYNTHESIS OF CONDUCTING POLYMERS
REFERENCES
Appendix B. Tables of Physical Data
Index
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