Homolytic Aromatic Substitution

Book excerpt: Homolytic Aromatic Substitution deals with the theoretical aspects of homolytic aromatic substitution reactions. The effect of various kinds of free radicals on the substitution of atoms or groups (usually hydrogen) attached to aromatic nuclei is examined, and the preparative use of homolytic substitution reactions is also considered. This book is comprised of seven chapters and begins with an introduction to the general characteristics of homolysis, along with homolytic and heterolytic aromatic substitution. The discussion then turns to the various theoretical approaches used to rationalize aromatic substitution, particularly those that are germane to a consideration of the problems of orientation and reactivity in homolytic substitution. The following chapters explore homolytic arylation reactions, including those between aryl radicals and aromatic substrates; relative rates of arylation and partial rate factors for phenylation; the reaction mechanism underlying intramolecular arylation; and homolytic alkylation reactions. The final chapter deals with hydroxylation and some other substitution reactions such as benzoyloxylation, acetyloxylation, halogenation, amination and amidation, and mercuration. This monograph will be of interest to organic chemists.