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

    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
    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-Radical Basicity 
    Pathways of Hydrogen Detachment from Anion-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
    Formation of Organic Ion-Radicals
    Chemical Methods of Organic Ion-Radical Preparation
    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 
    Electronic Structure–Reactivity Relationship in Ion-Radical Organic Chemistry 
    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 
    Discerning Mechanism of Ion-Radical Organic Reactions
    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 
    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
    Regulating Ion-Radical Organic Reactions
    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 
    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 
    Stereochemical Aspects of Ion-Radical Organic Reactions 
    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 
    Synthetic Opportunities of Ion-Radical Organic Chemistry
    Reductive and Oxidative Reactions
    Transformation of Ethylenic Ion-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 
    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 
    Ion-Radical Organic Chemistry in Its Practical Applicability
    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
    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 
    General Outlook 
    Importance of Ion-Radical Organic Chemistry 
    Scientometric Notes 


    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)