An Introduction To Free Radical Chemistry

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.

Free radicals constitute the most frequently used class of reaction intermediates in organic chemistry. This study describes the structure and reactivity of free radicals, and explores their role in both natural phenomena and in the design of new reaction pathways.

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 free-radical chemistry of DNA had been discussed in some detail in 1987 in my book The Chemical Basis of Radiation Biology. Obviously, the more recent developments and the concomitant higher level of understanding of mechanistic details are missing. Moreover, in the living cell, free-radical DNA damage is not only induced by ionizing radiation, but free-radical-induced DNA damage is a much more general phenomenon. It was, therefore, felt that it is now timely to review our present knowledge of free-radical-induced DNA damage induced by all conceivable free-radical-generating sources. Originally, it had been thought to include also a very important aspect, the repair of DNA damage by the cell’s various repair enzymes. Kevin Prise (Cancer Campaign, Gray Laboratory, L- don) was so kind to agree to write this part. However, an adequate description of this strongly expanding area would have exceeded the allocated space by much, and this section had to be omitted. The directors of the Max-Planck-Institut für Strahlenchemie (now MPI für Bioanorganische Chemie), Karl Wieghardt and Wolfgang Lubitz, kindly allowed me to continue to use its facilities after my retirement in 2001. Notably, our - brarian, Mrs. Jutta Theurich, and her right-hand help, Mrs. Rosemarie Schr- er, were most helpful in getting hold of the literature. I thank them very much. Without their constant help, this would have been very difficult indeed.

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.

"Authoritative and clearly written."—Applied Optics The direct observation of short-lived free radicals and the consequent study of their structure and reactions have led to important developments in almost every branch of chemistry as well as in other areas. This volume by a Nobel laureate offers an excellent introduction to the essentials of molecular spectroscopy. The introductory chapter discusses experimental methods and illustrates the observed spectra of various molecules and free radicals. Subsequent chapters explore rotational, vibrational, and electronic energy levels of diatomic molecules and ions; radiative transitions; linear and nonlinear polyatomic radicals and ions; continuous and diffuse spectra; predissociation and pre-ionization; and recombination. The well-illustrated text features more than 100 figures and spectra. A distilled version of the author's monumental three-volume study, Molecular Spectra and Molecular Structure, it constitutes a superb resource for anyone wishing a concise but complete treatment of the fundamentals of molecular spectroscopy.