Substituent Effects in Radical Chemistry

Front Matter....Pages i-xiv
A Theoretical Approach to Substituent Effects in Radical Chemistry....Pages 1-48
Sigma and PI Effects in Radicals....Pages 49-68
The Contrasting Strain Energies of Small Ring Carbon and Silicon Rings. The Relationship with free Radical Energies....Pages 69-81
Allylic and Allenic Capto-Dative Stabilization in Nitrogen Centered free Radicals....Pages 83-86
Conformational Preferences in ß-Substituted Ethyl Radicals: A Quantitative Analysis of Hyperconjugation, Homoconjugation, d-Orbital and Steric Effects.....Pages 87-90
Substituent Effects on the Thermochemistry and Electrochemistry of Free Radicals....Pages 91-105
Some Applications of ESR Spectroscopy to the Study of Substituent Effects....Pages 107-122
Substituent Effects on Absolute Rate Constants and Arrhenius Parameters for the Addition of tert-Butyl Radicals to Alkenes....Pages 123-142
Allylic Radicals—An ESR Spectroscopical Study....Pages 143-166
ESR-Spectroscopical Investigation of Capto-Dative Substituent Effects in Benzyl Radicals....Pages 167-170
Determination of Thermodynamic Stabilisation in Amino-Substituted Alkyl Radicals....Pages 171-188
Phosphinylhydrazyls $${{R}_{2}}N\dot{N}P\left( 0 \right){{L}_{2}}.$$ Influence of the Phosphinyl Group on the 3-Electron NN π Bond....Pages 189-190
Substituent Effects on the Dimerization of Vinyl Nitroxides and on the Dissociation of Their Tricyclic Dimers....Pages 191-194
Substituent Effects on the CC-Bond Strength.....Pages 195-198
The Different Recombinations of Diphenyl Methyl Radicals Ph 2 C . -R, R = tBu, CN, COOR’, COR’....Pages 199-218
Some Chemistry of Radical Ions....Pages 219-222
Substituent Effects on the Methylenecyclopropane Rearrangement. A Probe for Free Radical Effects.....Pages 223-244
2-Oxomorpholin-3-YL Radicals....Pages 245-262
Azoalkane Decompositions as Measures of Radical Substituent Effects....Pages 263-270
Orbital Effects in Carbohydrate Radicals....Pages 271-281
ESR-Spectroscopical Investigation of Carbohydrate Radicals in Solution. Radical Stabilization by β -C-O Bonds....Pages 283-296
Studies on the Captodative Effect. Entropy/Enthalpy Compensation as Solvent Effect in Radical Forming Reactions. A Relative Radical Stabilisation Scale....Pages 297-300
σ· Revisited....Pages 301-324
Captodative Effect on the Relative Rates of H-Abstraction by Tert-Butoxy Radicals....Pages 325-328
Substituent Effects in Gas-Phase Thermal Hydroxylation and Hydrogenolysis....Pages 329-330
Heterocyclic Substituents in S RN 1 Reactions....Pages 331-334
Substituent Effects on the Oxidation of Toluenes by Molecular Oxygen: The Surprising Reactivity of p. Methoxytoluene....Pages 335-338
Free Radical Additions of Dichloromethane to δ-Alkenyl T-Butyl Peroxides.....Pages 339-342
The Non-Chain Radicaloid Mechanism of Some Nucleophilic Substitution Reactions....Pages 343-346
Captodative Substituent Effects in Cycloaddition Reactions....Pages 347-360
Captodative Substitution Effect in [2+2] Cycloadditions Between Allenes and Olefins....Pages 361-370
Captodative Alkenes as Dipolarophiles—Kinetic Studies....Pages 371-374
Captodative Alkenes in Concerted 1, 3-Dipolar Cycloadditions....Pages 375-378
Photo-Diels-Alder Addition of two Captodative Alkenes to 1-Acetonaphthone....Pages 379-381
Free Radical Cyclization of Unsaturated Carbonic Acid Derivatives....Pages 383-385
Synthetic Applications of the Polar Effects of the Substituents in Free-Radical Reactions....Pages 387-390
Selectivity in Homolytic Aromatic Substitutions. Alkylations of Pyridines....Pages 391-433
The Invention of High Yielding Radical Chain Reactions....Pages 435-442
Epilogue....Pages 443-461
Back Matter....Pages 463-466
....Pages 467-482