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.

This book provides a comprehensive overview of nucleophilic aromatic substitutions, focusing on the mechanistic and synthetic features that govern these reactions. The first chapter presents a detailed mechanistic analysis of the factors determining the feasibility of SNAr substitutions, providing decisive information to predict regioselectivity of many reactions and to define the conditions for concerted SNAr processes. Reflecting the key role played by these species as intermediates in most SNAr reactions, chapter 2 then discusses the chemistry of anionic sigma-complexes. Chapter 3 describes the concept of superelectrophilicity in SNAr substitutions, as it has recently emerged from the reactivity of strongly electron-deficient aromatic and heteroaromatic structures. The numerous synthetic applications are considered in depth in the chapters 4 and 5 that follow on intermolecular and intramolecular nucleophilic aromatic substitutions. Then, chapter 6 focuses on substitutions proceeding formally through displacement of a hydride ion, a hot topic in the field. The final chapter brings together concise yet comprehensive discussions surrounding SNAr photosubstitutions, radical substitutions, and ANRORC substitutions. Authored by a highly respected chemist who has contributed greatly to the field over the past two decades, this is a valuable information source for all organic chemists working in academia or the pharmaceutical and agrochemical industries.

The only book series to summarize the latest progress on organic reaction mechanisms, Organic Reaction Mechanisms, 1972 surveys the development in understanding of the main classes of organic reaction mechanisms reported in the primary scientific literature in 1972. The 8th annual volume in this highly successful series highlights mechanisms of stereo-specific reactions. Reviews are compiled by a team of experienced editors and authors, allowing advanced undergraduates, graduate students, postdocs, and chemists to rely on the volume's continuing quality of selection and presentation.