2nd Edition

Ion-Radical Organic Chemistry
Principles and Applications, Second Edition




ISBN 9780849390685
Published October 20, 2008 by CRC Press
496 Pages 365 B/W Illustrations

USD $290.00

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Book Description

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.

Table of Contents

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)2
System of NaNO2 and CF3SO3
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  

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Reviews

"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)