Half A Century Of Free Radical Chemistry

This book describes the experience over 25 years of the senior author with the chemistry of organic free radicals. It begins with a mechanistic study of industrial importance on the pyrolysis of chlorinated alkanes. It continues with a theory on the biosynthesis of phenolate derived alkaloids involving phenolate radical coupling. There follows 20 years of practical work to prove the theory correct, especially in the case of morphine alkaloids. The book then describes the work on nitrile photolysis (Barton reaction) which involved the invention of new radical chemistry leading to a simple synthesis of the important hormone, aldosterone. There follows a description of the invention of an important new method for the deoxygenation of biologically important molecules, especially sugars and nucleosides, using radical chemistry applied to thiocarbonyl derivatives. Some years later, in a logical extension to carboxylic acids, another new reaction was invented which provides carbon, nitrogen, oxygen and other radicals under mild conditions. A final chapter summarizes recent applications of thiocarbonyl group derived radical reactions by other authors.

This series is designed to provide a vehicle in which investigators, who have demonstrated a high degree of competence in some aspect of free radical chemistry, can present a particular area of interest. The series encompasses a wide variety of topics which are of current interest.

Frontiers of Free Radical Chemistry covers the proceedings of the 1979 symposium on Frontiers of Free Radical Chemistry, held in Louisiana State University Chemistry Department, supported by the Exxon Education Foundation. The contributors discuss the mechanisms of hydrocarbon cracking; oxidation processes; inhibition; and the theory of organic radical reactions, halogenations, and organic peroxide chemistry. This book is organized into three parts encompassing 15 chapters. Part I deals with the understanding of molecular and free radical mechanisms in predicting thermochemical data for radicals and molecules. This part also describes the relationship between distortions of organic molecules and the reactions of pericyclic, ionic, and radical molecules. Part II presents quantitative evaluations of gas phase reactions or carbynes and hydrocarbon pyrolysis and cracking. Discussions on the reactions of free atoms and radicals in the chemistry of the stratosphere and natural troposphere, with an emphasis on the ozone layer and its potential depletion by artificial pollutants, are included in this part. Part III explores the pertinent free radical reactions related to fuel research. Petroleum chemists, researchers, and engineers will find this book invaluable.

This volume is the autobiography of Cheves Walling, famous American organic chemist and previously Professor of Chemistry at Columbia University and the University of Utah. Noted for his discoveries in the field of free radical chemistry, Walling bridged the university-industrial gap. Many of his discoveries played an important role in the development of polymer chemistry. Walling was, for many years, Editor-in-Chief of the Journal of the American Chemical Society. Many photographs depict both the professional as well as the personal side of this renowned chemist.

Covers the most advanced computational and experimental methods for studying carbon-centered radical intermediates With its focus on the chemistry of carbon-centered radicals and radical cations, this book helps readers fully exploit the synthetic utility of these intermediates in order to prepare fine chemicals and pharmaceutical products. Moreover, it helps readers better understand their role in complex atmospheric reactions and biological systems. Thoroughly up to date, the book highlights the most advanced computational and experimental methods available for studying and using these critically important intermediates. Carbon-Centered Free Radicals and Radical Cations begins with a short history of the field of free radical chemistry, and then covers: A discussion of the relevant theory Mechanistic chemistry, with an emphasis on synthetic utility Molecular structure and mechanism, focusing on computational methods Spectroscopic investigations of radical structure and kinetics, including demonstrations of spin chemistry techniques such as CIDNP and magnetic field effects Free radical chemistry in macromolecules Each chapter, written by one or more leading experts, explains difficult concepts clearly and concisely, with references to facilitate further investigation of individual topics. The authors were selected in order to provide insight into a broad range of topics, including small molecule synthesis, polymer degradation, computational chemistry as well as highly detailed experimental work in the solid, liquid, and gaseous states. This volume is essential for students or researchers interested in building their understanding of the role of carbon-centered radical intermediates in complex systems and how they may be used to develop a broad range of useful products.