Nucleophilic aromatic substitution in carbo- and heteroaromatic systems is a subject of considerable interest to chemists. This book uniquely addresses the systematic analysis of a vast range of nucleophilic substitutions of aromatic hydrogen. - Nucleophilic displacement of hydrogen (the S N/H reactions) in pi-deficient aromatics, such as nitroarenes, arene-metal complexes, and the like - Nucleophilic displacement of hydrogen in heterocyclic substrates such as pyridines, their aza and benzo analogs, pyrylium and thiapyrylium cations, and other heterocycles - Mechanisms for the S N/H reactions (S N/H(AE), vicarious nucleophilic substitutions, and radical S N/H substitutions

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 series Topics in Heterocyclic Chemistry presents critical reviews on present and future trends in the research of heterocyclic compounds. Overall the scope is to cover topics dealing with all areas within heterocyclic chemistry, both experimental and theoretical, of interest to the general heterocyclic chemistry community. The series consists of topic related volumes edited by renowned editors with contributions of experts in the field.

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.

Introduction what is organic chemistry all about?; Structural organic chemistry the shapes of molecules functional groups; Organic nomenclature; Alkanes; Stereoisomerism of organic molecules; Bonding in organic molecules atomic-orbital models; More on nomenclature compounds other than hydrocarbons; Nucleophilic substitution and elimination reactions; Separation and purification identification of organic compounds by spectroscopic techniques; Alkenes and alkynes. Ionic and radical addition reactions; Alkenes and alkynes; Oxidation and reduction reactions; Acidity or alkynes.