Product Details
- Pub. Date: October 2008
- Publisher: Taylor & Francis, Inc.
- Format: Hardcover, 672pp
- ISBN-13: 9780849390685
- ISBN: 0849390680
- Edition Number: 2
- Edition Description: REV
Discription:
Much new data concerning the behavior of organic ion-radicals has developed in the past few years. 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. 
Preface .......................................................................................................................................... xiii
Author .............................................................................................................................................xv
Chapter 1
Nature of Organic Ion-Radicals and Their Ground-State Electronic Structure
1.1 Introduction ...............................................................................................................................1
1.2 Unusual Features .......................................................................................................................2
1.2.1 Substituent Effects .........................................................................................................2
1.2.2 Connections between Ion-Radical Reactivity and Electronic Structure of
Ion-Radical Products .....................................................................................................7
1.2.3 Bridge-Effect Peculiarities .......................................................................................... 10
1.3 Acid–Base Properties of Organic Ion-Radicals ...................................................................... 16
1.3.1 Anion-Radicals ............................................................................................................ 16
1.3.1.1 Anion-Radical Basicity ................................................................................. 16
1.3.1.2 Pathways of Hydrogen Detachment from Anion-Radicals ...........................20
1.3.2 Cation-Radicals ...........................................................................................................22
1.3.2.1 Cation-Radical Acidity .................................................................................22
1.3.2.2 Cation-Radical Basicity ................................................................................29
1.3.2.3 Cation-Radicals as Acceptors or Donors of Hydrogen Atoms .....................30
1.4 Metallocomplex Ion-Radicals .................................................................................................30
1.4.1 Metallocomplex Anion-Radicals .................................................................................30
1.4.2 Metallocomplex Cation-Radicals ................................................................................ 33
1.4.3 Bridge Effect in Metallocomplex Ion-Radicals ...........................................................36
1.4.4 Charge-Transfer Coordination to Metallocomplex Ion-Radicals ................................38
1.5 Organic Ion-Radicals with Several Unpaired Electrons or Charges ......................................39
1.6 Polymeric Ion-Radicals ...........................................................................................................48
1.7 Inorganic Ion-Radicals in Reactions with Organic Substrates ............................................... 53
1.7.1 Superoxide Ion .............................................................................................................54
1.7.1.1 Reactions of Superoxide Ion with Organic H Acids ..................................... 55
1.7.1.2 Reactions of Superoxide Ion with Organic Electrophiles .............................56
1.7.1.3 Reactions of Superoxide Ion with Biological Objects .................................. 57
1.7.1.4 Superoxide Ion–Ozone Anion-Radical Relation .......................................... 57
1.7.2 Atomic Oxygen Anion-Radical ...................................................................................58
1.7.3 Molecular Oxygen Cation-Radical ..............................................................................58
1.7.4 Carbon Dioxide Anion-Radical ...................................................................................59
1.7.5 Carbonate Radical .......................................................................................................60
1.7.6 Sulfur Dioxide Anion-Radical .................................................................................... 61
1.7.7 Sulfi te Radical ............................................................................................................. 61
1.7.8 Sulfate Radical ............................................................................................................ 62
1.7.9 Hydroxide Anion .........................................................................................................65
1.7.10 Nitrosonium and Nitronium Ions ................................................................................66
1.7.11 Tris(aryl)amine and Thianthrene Cation-Radicals......................................................67
1.7.12 Trialkyloxonium Hexachloroantimonates ...................................................................69
1.7.13 Transition Metal Ions ...................................................................................................69
1.8 Conclusion ...............................................................................................................................73
References ....................................................................................................................................... 74
viii Contents
Chapter 2
Formation of Organic Ion-Radicals
2.1 Introduction .............................................................................................................................85
2.2 Chemical Methods of Organic Ion-Radical Preparation ........................................................86
2.2.1 Anion-Radicals ............................................................................................................86
2.2.2 Cation-Radicals ...........................................................................................................89
2.2.3 Carbenoid Ion-Radicals ...............................................................................................92
2.3 Equilibria in Liquid-Phase Electron-Transfer Reactions ........................................................93
2.4 Electrochemical Methods versus Chemical Methods .............................................................95
2.4.1 Charge-Transfer Phenomena .......................................................................................96
2.4.2 Template Effects ........................................................................................................ 100
2.4.3 Adsorption Phenomena ............................................................................................. 103
2.4.4 Stereochemical Phenomena ....................................................................................... 106
2.4.5 Concentration Effects on the Fate of Ion-Radicals at Electrodes
and in Solutions ......................................................................................................... 110
2.4.6 Aggregation of Ion-Radical Salts .............................................................................. 111
2.4.6.1 Direct Infl uence on Electron-Transfer Equilibrium .................................... 112
2.4.6.2 Electron-Transfer Reactions with Participation of Ion-Radical
Aggregates................................................................................................... 113
2.4.6.3 Kinetic and Mechanistic Differences between Electrode and
Chemical (Homogeneous) Ion-Radical Dimerization ................................ 114
2.5 Formation of Organic Ion-Radicals in Living Organisms .................................................... 115
2.6 Isotope-Containing Organic Compounds as Ion-Radical Precursors .................................. 117
2.6.1 Kinetic Isotope Effects in Electron-Transfer Reactions ............................................ 118
2.6.2 Behavior of Isotope Mixtures in Electron-Transfer Reactions ..................................120
2.7 Organic Ion-Radicals in Solid Phases ...................................................................................126
2.7.1 Organic Ion-Radicals in Frozen Solutions ................................................................126
2.7.2 Organic Ion-Radical as Constituents of Solid Salts .................................................. 130
2.8 Formation and Behavior of Ion-Radicals within Confi nes ................................................... 130
2.8.1 Micellar Media .......................................................................................................... 130
2.8.2 Porous Media ............................................................................................................. 131
2.8.3 Capsule Media ........................................................................................................... 133
2.9 Conclusion ............................................................................................................................. 135
References ..................................................................................................................................... 136
Chapter 3
Electronic Structure–Reactivity Relationship in Ion-Radical
Organic Chemistry ................................................................................................... 143
3.1 Introduction ........................................................................................................................... 143
3.2 Principle of “Detained” Electron That Controls Ion-Radical Reactivity ............................. 144
3.2.1 Frontier-Orbital Control ............................................................................................ 144
3.2.2 Steric Control over Spin Delocalization .................................................................... 153
3.2.3 Unpaired Electron Localization in the Field of Two or More Atoms ....................... 155
3.2.4 Spin–Charge Separation (Distonic Stabilization of Ion-Radicals) ........................... 161
3.2.4.1 Distonic Stabilization of Anion-Radicals ................................................... 163
3.2.4.2 Distonic Stabilization of Cation-Radicals................................................... 165
3.2.5 Ion-Pair Formation .................................................................................................... 168
3.2.5.1 Detention of Unpaired Electron in a Framework of One Specifi c
Molecular Fragment .................................................................................... 169
3.2.5.2 Formation of Closed Contour for Unpaired Electron Delocalization ......... 170
Contents ix
3.3 Principle of “Released” Electron That Controls Ion-Radical Reactivity .............................. 178
3.3.1 Effects of Spread Conjugation in Ion-Radicals Derived from Molecules
with Large Contours of Delocalization ..................................................................... 180
3.3.2 Spin Delocalization in Ion-Radicals Derived from Molecules of Increased
Dimensionality .......................................................................................................... 183
3.4 Biomedical Aspects of Ion-Radical Organic Chemistry ...................................................... 186
3.4.1 Cation-Radical Damage in Deoxyribonucleic Acid .................................................. 186
3.4.1.1 Ionization Potentials of Carcinogens .......................................................... 187
3.4.1.2 Localization of Charges and Spins in Cation-Radicals of Carcinogens ..... 187
3.4.2 On Geometrical and Spatial Factors Governing the Behavior of
Ion-Radicals in Biological Systems ........................................................................... 189
3.4.3 Ion-Radical Repair of Damaged Deoxyribonucleic Acid.......................................... 191
3.4.4 Cation-Radical Intermediates in Metabolism of Furan Xenobiotics ........................ 194
3.4.5 Behavior of Anion-Radicals in Living Organisms .................................................... 194
3.5 Conclusion ............................................................................................................................. 196
References ..................................................................................................................................... 197
Chapter 4
Discerning Mechanism of Ion-Radical Organic Reactions
4.1 Introduction ...........................................................................................................................205
4.2 Why Do Reactions Choose Ion-Radical Mechanism? ..........................................................205
4.3 Chemical Approaches to Identifi cation of Ion-Radical Organic Reactions ..........................209
4.3.1 Identifi cation According to Structure of Final Products ...........................................209
4.3.2 Identifi cation According to Correlation within Reaction Series ............................... 213
4.3.3 Identifi cation According to Disturbance of “Leaving-Group Strength”
Correlation ................................................................................................................. 215
4.3.4 Kinetic Approaches to Identifi cation of Ion-Radical Reactions ................................ 216
4.3.4.1 Kinetic Isotope Effect ................................................................................. 216
4.3.4.2 Other Kinetic Approaches .......................................................................... 217
4.3.5 Positional Reactivity and Distribution of Spin Density in
Substrate Ion-Radicals ............................................................................................... 219
4.3.6 Identifi cation by Methods of Chemical Probes .........................................................223
4.3.6.1 Initiation of Polymerization of Vinyl Additives ..........................................223
4.3.6.2 Method of Inhibitors ...................................................................................224
4.3.6.3 Method of Radical and Spin Traps .............................................................227
4.4 Physical Approaches to Identifi cation of Ion-Radical Reactions .......................................... 232
4.4.1 Radiospectroscopy..................................................................................................... 232
4.4.1.1 Electron Spin Resonance Methods ............................................................. 232
4.4.1.2 Nuclear Magnetic Resonance Methods ....................................................... 233
4.4.2 Optical Spectroscopy Methods .................................................................................236
4.4.2.1 Electron Spectroscopy ................................................................................236
4.4.2.2 Vibration Spectroscopy ...............................................................................238
4.4.3 Other Physical Methods ............................................................................................238
4.4.3.1 Magnetic Susceptibility...............................................................................238
4.4.3.2 Mass Spectrometry .....................................................................................238
4.4.3.3 Electrochemical Modeling of Ion-Radical Reactions .................................238
4.4.3.4 X-Ray Diffraction ....................................................................................... 239
4.5 Examples of Complex Approaches to Discernment of Ion-Radical
Mechanism of Organic Reactions .........................................................................................240
4.5.1 Oxidative Polymerization of Anilines .......................................................................240
4.5.2 Reactions of Hydroperoxides with Phosphites and Sulfi des ..................................... 241
x Contents
4.5.3 ter Meer Reaction ......................................................................................................243
4.5.4 Aromatic Nitration ....................................................................................................247
4.5.4.1 System of HNO3 and H2SO4 with Catalytic Amounts of HNO2 ................ 251
4.5.4.2 System of HNO3 and (CH3CO)2O ............................................................... 253
4.5.4.3 System of NaNO2 and CF3SO3H ................................................................. 253
4.5.4.4 Systems of Metal Nitrites with Oxidizers ................................................... 255
4.5.4.5 Systems of Metal Nitrates with Oxidizers ..................................................256
4.5.4.6 Systems with Tetranitromethane as Nitrating Agent .................................. 257
4.5.4.7 Systems with Participation of Nitrogen Dioxide .........................................258
4.5.4.8 Nitration and Hydroxylation by Peroxynitrite .............................................259
4.5.4.9 Gas-Phase Nitration ....................................................................................260
4.5.5 Meerwein and Sandmeyer Reactions ........................................................................262
4.6 Conclusion .............................................................................................................................263
References .....................................................................................................................................264
Chapter 5
Regulating Ion-Radical Organic Reactions
5.1 Introduction ........................................................................................................................... 271
5.2 Physical Effects ..................................................................................................................... 271
5.2.1 Effect of Light ........................................................................................................... 271
5.2.2 Effect of Electric Field .............................................................................................. 274
5.2.3 Effect of Magnetic Field ............................................................................................277
5.2.4 Effect of Microwave Field ......................................................................................... 278
5.2.5 Effect of Acoustic Field ............................................................................................. 279
5.2.6 Effect of Mechanical Action ..................................................................................... 281
5.2.6.1 Mechanochromism ......................................................................................282
5.2.6.2 Mechanopolymerization and Mechanolysis ................................................283
5.3 Effect of Chemical Additives ................................................................................................286
5.4 Solvent Effects ......................................................................................................................295
5.4.1 Static Effects ..............................................................................................................295
5.4.1.1 General Solvation ........................................................................................295
5.4.1.2 Selective Solvation and Solute-Solvent Binding .........................................297
5.4.2 Dynamic Effects ........................................................................................................ 301
5.4.2.1 Solvent Reorganization ............................................................................... 301
5.4.2.2 Solvent Polarity and Polarization ................................................................303
5.4.2.3 Solvent Internal Pressure ............................................................................304
5.4.2.4 Solvent Conformational Transition .............................................................305
5.4.2.5 Solvent Temperature ...................................................................................306
5.4.3 Liquid Crystals and Ionic Liquids as Solvents ..........................................................306
5.5 Salt Effects ............................................................................................................................308
5.5.1 Salt Effect on Spin Density Distribution ...................................................................308
5.5.2 Salt-Cage Effect Interplay ......................................................................................... 310
5.5.3 Salt Effect on Course of Ion-Radical Reactions ........................................................ 312
5.6 Conclusion ............................................................................................................................. 316
References ..................................................................................................................................... 317
Chapter 6
Stereochemical Aspects of Ion-Radical Organic Reactions
6.1 Introduction ........................................................................................................................... 323
6.2 Problem of Steric Restrictions .............................................................................................. 323
6.3 Refl ection of the Ion-Radical Step in Reaction Steric Results .............................................. 328
Contents xi
6.4 Conformational Transition of Ion-Radicals .......................................................................... 331
6.5 Space Structure and Skeletal Isomerization of Ion-Radicals ................................................ 341
6.6 Conclusion .............................................................................................................................344
References .....................................................................................................................................345
Chapter 7
Synthetic Opportunities of Ion-Radical Organic Chemistry
7.1 Introduction ...........................................................................................................................349
7.2 Reductive and Oxidative Reactions ......................................................................................349
7.2.1 Transformation of Ethylenic Ion-Radicals ................................................................349
7.2.1.1 Anion-Radicals ...........................................................................................349
7.2.1.2 Cation-Radicals ........................................................................................... 352
7.2.2 Reduction of Ketones into Alcohols .......................................................................... 352
7.2.3 Preparation of Dihydroaromatics .............................................................................. 354
7.2.4 Synthetic Suitability of (Dialkylamino)benzene Cation-Radicals ............................ 357
7.3 Ion-Radical Polymerization .................................................................................................. 358
7.3.1 Anion-Radical Polymerization .................................................................................. 358
7.3.2 Cation-Radical Polymerization ................................................................................. 359
7.3.2.1 Formation of Linear Main Chains .............................................................. 359
7.3.2.2 Formation of Cyclic and Branched Chains .................................................360
7.4 Ring Closure ......................................................................................................................... 362
7.4.1 Cation-Radical Ring Closure .................................................................................... 362
7.4.2 Anion-Radical Ring Closure .....................................................................................369
7.4.3 Ring Closure Involving Cation- and Anion-Radicals in Linked
Molecular Systems .................................................................................................... 377
7.5 Ring Opening ........................................................................................................................ 378
7.6 Fragmentation ....................................................................................................................... 379
7.6.1 Selective Oxidation .................................................................................................... 379
7.6.1.1 Selective Oxidation of Alkylbenzenes ........................................................ 379
7.6.1.2 Selective Oxidation of Dimethylimidazole ................................................. 381
7.6.2 Cation-Radical Route to Group Deprotection ........................................................... 382
7.6.2.1 Removal of Butoxycarbonyl Protective Group ........................................... 382
7.6.2.2 Removal of Methoxybenzyl Protective Group ............................................ 383
7.6.2.3 Removal of Trimethylsilyl Protective Group ..............................................384
7.6.3 Scission of Carbon–Carbon Bonds ...........................................................................384
7.6.4 Synthon-Infl uential Bond Scission ............................................................................387
7.7 Bond Formation ....................................................................................................................388
7.8 Opportunities Associated with SRN1 Reactions ....................................................................392
7.8.1 Substrate Structure .................................................................................................... 393
7.8.2 Nature of Introducing Groups ...................................................................................394
7.8.3 Reaction Medium ......................................................................................................394
7.8.4 Dark SRN1 Reactions ................................................................................................. 395
7.9 Conclusion ............................................................................................................................. 398
References ..................................................................................................................................... 398
Chapter 8
Ion-Radical Organic Chemistry in Its Practical Applicability
8.1 Introduction ...........................................................................................................................403
8.2 Organic Ion-Radicals in Microelectronics ............................................................................403
8.2.1 Ion-radical Approach to Molecular Switches and Modulators..................................403
8.2.2 Cation-Radicals of Triarylamines in Optical-Recording Media ...............................407
xii Contents
8.2.3 Ladder Polymerization of Fluoranthene-Based Cation-Radicals
as Route to Electrochromic Materials .......................................................................408
8.3 Organic Metals ......................................................................................................................409
8.4 Semiconductors ..................................................................................................................... 418
8.5 Organic Magnets ...................................................................................................................420
8.6 Lubrication in Terms of Ion-Radical Organic Chemistry .....................................................424
8.7 Ion-Radical Organic Chemistry in Its Contributions to Wood Delignifi cation and
Fossil-Fuel Desulfurization................................................................................................... 428
8.7.1 Paper Fabrication ....................................................................................................... 428
8.7.2 Manufacture of Commercial Products from Delignifi cation Wastes ........................ 433
8.7.3 Desulfurization of Fossil Fuels ................................................................................. 434
8.8 Conclusion ............................................................................................................................. 435
References ..................................................................................................................................... 435
Chapter 9
General Outlook
9.1 Importance of Ion-Radical Organic Chemistry .................................................................... 441
9.2 Scientometric Notes .............................................................................................................. 441
9.3 Prospects ...............................................................................................................................442
References .....................................................................................................................................443
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