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.

The past twenty years has seen an explosion of interest in free radicals, as their pivotal role in both chemistry and biology has come to light. This introductory textbook aims to capture this excitement for advanced level undergraduates, with particular emphasis on the importance of radical reactions in organic synthesis. The book provides a gentle, stepwise introduction to the subject, taking the student from the basic principles of radical reactions through to their applications in industry and their role in biological and environmental processes, allowing the relevance of the subject to be grasped more easily. Suitable for advanced level undergraduates and postgraduates in chemistry and biochemistry, the book will also be invaluable for research level scientists requiring an update in the area.

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.

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.