2nd Edition
Ion-Radical Organic Chemistry Principles and Applications, Second Edition
By Zory Vlad Todres
Copyright 2009
492 Pages
365 B/W Illustrations
by
CRC Press
496 Pages
by
CRC Press
Also available as eBook on:
Consolidating knowledge from a number of disciplines, Ion-Radical Organic Chemistry: Principles and Applications, Second Edition presents the recent changes that have occurred in the field since the publication of the first edition in 2003.
This volume examines the formation, transformation, and application of ion-radicals in typical conditions of organic synthesis. Avoiding complex mathematics, the author explains the principles of ion-radical organic chemistry and presents an overview of organic ion-radical reactions. He reviews methods of determining ion-radical mechanisms and controlling ion-radical reactions. Wherever applicable, the text addresses issues relating to ecology and biomedical concerns as well as inorganic participants of the ion-radical organic reactions.
After reviewing the nature of organic ion-radicals and their ground-state electronic structure, the book discusses their formation, the relationship between electronic structure and reactivity, mechanism and regulation of reactions, stereochemical aspects, synthetic opportunities, and practical applications. Additional topics include electronic and opto-electronic devices, organic magnets and conductors, lubricants, other materials, and reactions of industrial or biomedical importance.
The book concludes by providing an outlook on possible future development in this field. Researchers and practitioners engaged in active work on synthetic or mechanistic organic chemistry and its practical applications will find this text to be invaluable in both its scope and its depth.
Nature of Organic Ion-Radicals and Their Ground-State Electronic Structure
Introduction
Unusual Features
Substituent Effects
Connections between Ion-Radical Reactivity and Electronic Structure of Ion-Radical Products
Bridge-Effect Peculiarities
Acid–Base Properties of Organic Ion-Radicals
Anion-Radicals
Anion-Radical Basicity
Pathways of Hydrogen Detachment from Anion-Radicals
Cation-Radicals
Cation-Radical Acidity
Cation-Radical Basicity
Cation-Radicals as Acceptors or Donors of Hydrogen Atoms
Metallocomplex Ion-Radicals
Metallocomplex Anion-Radicals
Metallocomplex Cation-Radicals
Bridge Effect in Metallocomplex Ion-Radicals
Charge-Transfer Coordination to Metallocomplex Ion-Radicals
Organic Ion-Radicals with Several Unpaired Electrons or Charges
Polymeric Ion-Radicals
Inorganic Ion-Radicals in Reactions with Organic Substrates
Superoxide Ion
Reactions of Superoxide Ion with Organic H Acids
Reactions of Superoxide Ion with Organic Electrophiles
Superoxide Ion in Reactions with Biological Objects
Superoxide Ion–Ozone Anion-Radical Relation
Atomic Oxygen Anion-Radical
Molecular Oxygen Cation-Radical
Carbon Dioxide Anion-Radical
Carbonate Radical
Sulfur Dioxide Anion-Radical
Sulfite Radical
Sulfate Radical
Hydroxide Anion
Nitrosonium and Nitronium Ions
Tris(aryl)amine and Thianthrene Cation-Radicals
Trialkyloxonium Hexachloroantimonates
Transition Metal Ions
Conclusion
References
Formation of Organic Ion-Radicals
Introduction
Chemical Methods of Organic Ion-Radical Preparation
Anion-Radicals
Cation-Radicals
Carbenoid Ion-Radicals
Equilibria in Liquid-Phase Electron-Transfer Reactions
Electrochemical Methods versus Chemical Methods
Charge-Transfer Phenomena
Template Effects
Adsorption Phenomena
Stereochemical Phenomena
Concentration Effects on the Fate of Ion-Radicals at Electrodes and in Solutions
Aggregation of Ion-Radical Salts
Direct Influence on Electron-Transfer Equilibrium
Electron-Transfer Reactions with Participation of Ion-Radical Aggregates
Kinetic and Mechanistic Differences between Electrode and Chemical (Homogeneous) Ion-Radical Dimerization
Formation of Organic Ion-Radicals in Living Organisms
Isotope-Containing Organic Compounds as Ion-Radical Precursors
Kinetic Isotope Effects in Electron-Transfer Reactions
Behavior of Isotope Mixtures in Electron-Transfer Reactions
Organic Ion-Radicals in Solid Phases
Organic Ion-Radicals in Frozen Solutions
Organic Ion-Radical as Constituents of Solid Salts
Formation and Behavior of Ion-Radicals within Confines
Micellar Media
Porous Media
Capsule Media
Conclusion
References
Electronic Structure–Reactivity Relationship in Ion-Radical Organic Chemistry
Introduction
Principle of “Detained” Electron That Controls Ion-Radical Reactivity
Frontier-Orbital Control
Steric Control over Spin Delocalization
Unpaired Electron Localization in the Field of Two or More Atoms
Spin–Charge Separation (Distonic Stabilization of Ion-Radicals)
Distonic Stabilization of Anion-Radicals
Distonic Stabilization of Cation-Radicals
Ion-Pair Formation
Detention of Unpaired Electron in a Framework of One Specific Molecular Fragment
Formation of Closed Contour for Unpaired Electron Delocalization
Principle of “Released” Electron that Controls Ion-Radical Reactivity
Effects of Spread Conjugation in Ion-Radicals Derived from Molecules with Large Contours of Delocalization
Spin Delocalization in Ion-Radicals Derived from Molecules of Increased Dimensionality
Biomedical Aspects of Ion-Radical Organic Chemistry
Cation-Radical Damage in Deoxyribonucleic Acid
Ionization Potentials of Carcinogens
Localization of Charges and Spins in Cation-Radicals of Carcinogens
On Geometrical and Spatial Factors Governing the Behavior of Ion-Radicals in Biological Systems
Ion-Radical Repair of Damaged Deoxyribonucleic Acid
Cation-Radical Intermediates in Metabolism of Furan Xenobiotics
Behavior of Anion-Radicals in Living Organisms
Conclusion
References
Discerning Mechanism of Ion-Radical Organic Reactions
Introduction
Why Do Reactions Choose Ion-Radical Mechanism?
Chemical Approaches to Identification of Ion-Radical Organic Reactions
Identification According to Structure of Final Products
Identification According to Correlation within Reaction Series
Identification According to Disturbance of “Leaving-Group Strength” Correlation
Kinetic Approaches to Identification of Ion-Radical Reactions
Kinetic Isotope Effect
Other Kinetic Approaches
Positional Reactivity and Distribution of Spin Density in Substrate Ion-Radicals
Identification by Methods of Chemical Probes
Initiation of Polymerization of Vinyl Additives
Method of Inhibitors
Method of Radical and Spin Traps
Physical Approaches to Identification of Ion-Radical Reactions
Radiospectroscopy
Electron Spin Resonance Methods
Nuclear Magnetic Resonance Methods
Optical Spectroscopy Methods
Electron Spectroscopy
Vibration Spectroscopy
Other Physical Methods
Magnetic Susceptibility
Mass Spectrometry
Electrochemical Modeling of Ion-Radical Reactions
X-Ray Diffraction
Examples of Complex Approaches to Discernment of Ion-Radical Mechanism of Organic Reactions
Oxidative Polymerization of Anilines
Reactions of Hydroperoxides with Phosphites and Sulfides
Ter Meer Reaction
Aromatic Nitration
System of HNO3 and H2SO4 with Catalytic Amounts of HNO2
System of HNO3 and (CH3CO)2O
System of NaNO2 and CF3SO3H
Systems of Metal Nitrites with Oxidizers
Systems of Metal Nitrates with Oxidizers
Systems with Tetranitromethane as Nitrating Agent
Systems with Participation of Nitrogen Dioxide
Nitration and Hydroxylation by Peroxynitrite
Gas-Phase Nitration
Meerwein and Sandmeyer Reactions
Conclusion
References
Regulating Ion-Radical Organic Reactions
Introduction
Physical Effects
Effect of Light
Effect of Electric Field
Effect of Magnetic Field
Effect of Microwave Field
Effect of Acoustic Field
Effect of Mechanical Action
Mechanochromism
Mechanopolymerization and Mechanolysis
Effect of Chemical Additives
Solvent Effects
Static Effects
General Solvation
Selective Solvation and Solute-Solvent Binding
Dynamic Effects
Solvent Reorganization
Solvent Polarity and Polarization
Solvent Internal Pressure
Solvent Conformational Transition
Solvent Temperature
Liquid Crystals and Ionic Liquids as Solvents
Salt Effects
Salt Effect on Spin Density Distribution
Salt-Cage Effect Interplay
Salt Effect on Course of Ion-Radical Reactions
Conclusion
References
Stereochemical Aspects of Ion-Radical Organic Reactions
Introduction
Problem of Steric Restrictions
Reflection of the Ion-Radical Step in Reaction Steric Results
Conformational Transition of Ion-Radicals
Space Structure and Skeletal Isomerization of Ion-Radicals
Conclusion
References
Synthetic Opportunities of Ion-Radical Organic Chemistry
Introduction
Reductive and Oxidative Reactions
Transformation of Ethylenic Ion-Radicals
Anion-Radicals
Cation-Radicals
Reduction of Ketones into Alcohols
Preparation of Dihydroaromatics
Synthetic Suitability of (Dialkylamino)benzene Cation-Radicals
Ion-Radical Polymerization
Anion-Radical Polymerization
Cation-Radical Polymerization
Formation of Linear Main Chains
Formation of Cyclic and Branched Chains
Ring Closure
Cation-Radical Ring Closure
H-Acid Catalysis
Cation-Radical Mechanism
Anion-Radical Ring Closure
Ring Closure Involving Cation- and Anion-Radicals in Linked
Molecular Systems
Ring Opening
Fragmentation
Selective Oxidation
Selective Oxidation of Alkylbenzenes
Selective Oxidation of Dimethylimidazole
Cation-Radical Route to Group Deprotection
Removal of Butoxycarbonyl Protective Group
Removal of Methoxybenzyl Protective Group
Removal of Trimethylsilyl Protective Group
Scission of Carbon–Carbon Bonds
Synthon-Influential Bond Scission
Bond Formation
Opportunities Associated with SRN1 Reactions
Substrate Structure
Nature of Introducing Groups
Reaction Medium
Dark SRN1 Reactions
Conclusion
References
Ion-Radical Organic Chemistry in Its Practical Applicability
Introduction
Organic Ion-Radicals in Microelectronics
Ion-radical Approach to Molecular Switches and Modulators
Cation-Radicals of Triarylamines in Optical-Recording Media
Ladder Polymerization of Fluoranthene-Based Cation-Radicals as Route to Electrochromic Materials
Organic Metals
Semiconductors
Organic Magnets
Lubrication in Terms of Ion-Radical Organic Chemistry
Ion-Radical Organic Chemistry in Its Contributions to Wood Delignification and
Fossil-Fuel Desulfurization
Paper Fabrication
Manufacture of Commercial Products from Delignification Wastes
Desulfurization of Fossil Fuels
Conclusion
References
General Outlook
Importance of Ion-Radical Organic Chemistry
Scientometric Notes
Prospects
References
Index
Introduction
Unusual Features
Substituent Effects
Connections between Ion-Radical Reactivity and Electronic Structure of Ion-Radical Products
Bridge-Effect Peculiarities
Acid–Base Properties of Organic Ion-Radicals
Anion-Radicals
Anion-Radical Basicity
Pathways of Hydrogen Detachment from Anion-Radicals
Cation-Radicals
Cation-Radical Acidity
Cation-Radical Basicity
Cation-Radicals as Acceptors or Donors of Hydrogen Atoms
Metallocomplex Ion-Radicals
Metallocomplex Anion-Radicals
Metallocomplex Cation-Radicals
Bridge Effect in Metallocomplex Ion-Radicals
Charge-Transfer Coordination to Metallocomplex Ion-Radicals
Organic Ion-Radicals with Several Unpaired Electrons or Charges
Polymeric Ion-Radicals
Inorganic Ion-Radicals in Reactions with Organic Substrates
Superoxide Ion
Reactions of Superoxide Ion with Organic H Acids
Reactions of Superoxide Ion with Organic Electrophiles
Superoxide Ion in Reactions with Biological Objects
Superoxide Ion–Ozone Anion-Radical Relation
Atomic Oxygen Anion-Radical
Molecular Oxygen Cation-Radical
Carbon Dioxide Anion-Radical
Carbonate Radical
Sulfur Dioxide Anion-Radical
Sulfite Radical
Sulfate Radical
Hydroxide Anion
Nitrosonium and Nitronium Ions
Tris(aryl)amine and Thianthrene Cation-Radicals
Trialkyloxonium Hexachloroantimonates
Transition Metal Ions
Conclusion
References
Formation of Organic Ion-Radicals
Introduction
Chemical Methods of Organic Ion-Radical Preparation
Anion-Radicals
Cation-Radicals
Carbenoid Ion-Radicals
Equilibria in Liquid-Phase Electron-Transfer Reactions
Electrochemical Methods versus Chemical Methods
Charge-Transfer Phenomena
Template Effects
Adsorption Phenomena
Stereochemical Phenomena
Concentration Effects on the Fate of Ion-Radicals at Electrodes and in Solutions
Aggregation of Ion-Radical Salts
Direct Influence on Electron-Transfer Equilibrium
Electron-Transfer Reactions with Participation of Ion-Radical Aggregates
Kinetic and Mechanistic Differences between Electrode and Chemical (Homogeneous) Ion-Radical Dimerization
Formation of Organic Ion-Radicals in Living Organisms
Isotope-Containing Organic Compounds as Ion-Radical Precursors
Kinetic Isotope Effects in Electron-Transfer Reactions
Behavior of Isotope Mixtures in Electron-Transfer Reactions
Organic Ion-Radicals in Solid Phases
Organic Ion-Radicals in Frozen Solutions
Organic Ion-Radical as Constituents of Solid Salts
Formation and Behavior of Ion-Radicals within Confines
Micellar Media
Porous Media
Capsule Media
Conclusion
References
Electronic Structure–Reactivity Relationship in Ion-Radical Organic Chemistry
Introduction
Principle of “Detained” Electron That Controls Ion-Radical Reactivity
Frontier-Orbital Control
Steric Control over Spin Delocalization
Unpaired Electron Localization in the Field of Two or More Atoms
Spin–Charge Separation (Distonic Stabilization of Ion-Radicals)
Distonic Stabilization of Anion-Radicals
Distonic Stabilization of Cation-Radicals
Ion-Pair Formation
Detention of Unpaired Electron in a Framework of One Specific Molecular Fragment
Formation of Closed Contour for Unpaired Electron Delocalization
Principle of “Released” Electron that Controls Ion-Radical Reactivity
Effects of Spread Conjugation in Ion-Radicals Derived from Molecules with Large Contours of Delocalization
Spin Delocalization in Ion-Radicals Derived from Molecules of Increased Dimensionality
Biomedical Aspects of Ion-Radical Organic Chemistry
Cation-Radical Damage in Deoxyribonucleic Acid
Ionization Potentials of Carcinogens
Localization of Charges and Spins in Cation-Radicals of Carcinogens
On Geometrical and Spatial Factors Governing the Behavior of Ion-Radicals in Biological Systems
Ion-Radical Repair of Damaged Deoxyribonucleic Acid
Cation-Radical Intermediates in Metabolism of Furan Xenobiotics
Behavior of Anion-Radicals in Living Organisms
Conclusion
References
Discerning Mechanism of Ion-Radical Organic Reactions
Introduction
Why Do Reactions Choose Ion-Radical Mechanism?
Chemical Approaches to Identification of Ion-Radical Organic Reactions
Identification According to Structure of Final Products
Identification According to Correlation within Reaction Series
Identification According to Disturbance of “Leaving-Group Strength” Correlation
Kinetic Approaches to Identification of Ion-Radical Reactions
Kinetic Isotope Effect
Other Kinetic Approaches
Positional Reactivity and Distribution of Spin Density in Substrate Ion-Radicals
Identification by Methods of Chemical Probes
Initiation of Polymerization of Vinyl Additives
Method of Inhibitors
Method of Radical and Spin Traps
Physical Approaches to Identification of Ion-Radical Reactions
Radiospectroscopy
Electron Spin Resonance Methods
Nuclear Magnetic Resonance Methods
Optical Spectroscopy Methods
Electron Spectroscopy
Vibration Spectroscopy
Other Physical Methods
Magnetic Susceptibility
Mass Spectrometry
Electrochemical Modeling of Ion-Radical Reactions
X-Ray Diffraction
Examples of Complex Approaches to Discernment of Ion-Radical Mechanism of Organic Reactions
Oxidative Polymerization of Anilines
Reactions of Hydroperoxides with Phosphites and Sulfides
Ter Meer Reaction
Aromatic Nitration
System of HNO3 and H2SO4 with Catalytic Amounts of HNO2
System of HNO3 and (CH3CO)2O
System of NaNO2 and CF3SO3H
Systems of Metal Nitrites with Oxidizers
Systems of Metal Nitrates with Oxidizers
Systems with Tetranitromethane as Nitrating Agent
Systems with Participation of Nitrogen Dioxide
Nitration and Hydroxylation by Peroxynitrite
Gas-Phase Nitration
Meerwein and Sandmeyer Reactions
Conclusion
References
Regulating Ion-Radical Organic Reactions
Introduction
Physical Effects
Effect of Light
Effect of Electric Field
Effect of Magnetic Field
Effect of Microwave Field
Effect of Acoustic Field
Effect of Mechanical Action
Mechanochromism
Mechanopolymerization and Mechanolysis
Effect of Chemical Additives
Solvent Effects
Static Effects
General Solvation
Selective Solvation and Solute-Solvent Binding
Dynamic Effects
Solvent Reorganization
Solvent Polarity and Polarization
Solvent Internal Pressure
Solvent Conformational Transition
Solvent Temperature
Liquid Crystals and Ionic Liquids as Solvents
Salt Effects
Salt Effect on Spin Density Distribution
Salt-Cage Effect Interplay
Salt Effect on Course of Ion-Radical Reactions
Conclusion
References
Stereochemical Aspects of Ion-Radical Organic Reactions
Introduction
Problem of Steric Restrictions
Reflection of the Ion-Radical Step in Reaction Steric Results
Conformational Transition of Ion-Radicals
Space Structure and Skeletal Isomerization of Ion-Radicals
Conclusion
References
Synthetic Opportunities of Ion-Radical Organic Chemistry
Introduction
Reductive and Oxidative Reactions
Transformation of Ethylenic Ion-Radicals
Anion-Radicals
Cation-Radicals
Reduction of Ketones into Alcohols
Preparation of Dihydroaromatics
Synthetic Suitability of (Dialkylamino)benzene Cation-Radicals
Ion-Radical Polymerization
Anion-Radical Polymerization
Cation-Radical Polymerization
Formation of Linear Main Chains
Formation of Cyclic and Branched Chains
Ring Closure
Cation-Radical Ring Closure
H-Acid Catalysis
Cation-Radical Mechanism
Anion-Radical Ring Closure
Ring Closure Involving Cation- and Anion-Radicals in Linked
Molecular Systems
Ring Opening
Fragmentation
Selective Oxidation
Selective Oxidation of Alkylbenzenes
Selective Oxidation of Dimethylimidazole
Cation-Radical Route to Group Deprotection
Removal of Butoxycarbonyl Protective Group
Removal of Methoxybenzyl Protective Group
Removal of Trimethylsilyl Protective Group
Scission of Carbon–Carbon Bonds
Synthon-Influential Bond Scission
Bond Formation
Opportunities Associated with SRN1 Reactions
Substrate Structure
Nature of Introducing Groups
Reaction Medium
Dark SRN1 Reactions
Conclusion
References
Ion-Radical Organic Chemistry in Its Practical Applicability
Introduction
Organic Ion-Radicals in Microelectronics
Ion-radical Approach to Molecular Switches and Modulators
Cation-Radicals of Triarylamines in Optical-Recording Media
Ladder Polymerization of Fluoranthene-Based Cation-Radicals as Route to Electrochromic Materials
Organic Metals
Semiconductors
Organic Magnets
Lubrication in Terms of Ion-Radical Organic Chemistry
Ion-Radical Organic Chemistry in Its Contributions to Wood Delignification and
Fossil-Fuel Desulfurization
Paper Fabrication
Manufacture of Commercial Products from Delignification Wastes
Desulfurization of Fossil Fuels
Conclusion
References
General Outlook
Importance of Ion-Radical Organic Chemistry
Scientometric Notes
Prospects
References
Index
Biography
Zory Vlad Todres
"The author offers broad yet deeply detailed coverage… This book will be a useful resource for specialists already versed in aspects of ion-radical chemistry as well for those seeking a survey of the primary literature as a foundation to begin research in the area… I would recommend it as an addition to the monograph collections of chemical research libraries."
— Journal of the American Chemical Society, 2009, 131 (6)
