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Hydrocarbon Thermal Isomerizations summarizes rearrangements which are induced by heating neutral hydrocarbons under non-catalytic conditions in the vapor phase or in non-polar solution. This subject has attracted the interest of mechanistic organic chemists and theorists in the last quarter century because it is one of the few fields workable by state of the art techniques of both camps. This work collects together most of the crucial rate and stereochemical data in a single volume, along with a critical analysis of each of these reactions.Unlike reviews or other books in this area that focus on reaction types, e.g.. electrocyclic reactions, or Claisen rearrangements, this volume is organized like the Chemical Abstracts Formula Index, but with an important exception: all of the relevant derivatives of each parent compound are discussed with the parent and not in their logical formula index positions. As it is not always obvious what is a parent material and what is a derivative, detailed cross-references are included throughout. An important aspect of this edition is the inclusion of calculational results that provide insight, often more than was anticipated, into these relatively simple reactions ·Energetics of thermal isomerization reactions·Stereochemistry of thermal isomerization reactions·Organization to facilitate and integrate global analyses·Comparison of experimental and theoretical results
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Preface to the Second Edition It is rare to be able to visit an old book on fundamental chemical processes and to be able to modify and amplify the conclusions with the insight from recent experimental and theoretical results. It was a privilege to follow this pursuit even though it was embarrassing at times when typographical errors, incorrect citations of fact, and fundamental mistakes in the previous version became obvious. Hopefully more errors were corrected than were introduced in the wealth of new information. An important aspect of this edition is the inclusion of calculational results that provide insight, often more than was anticipated, into these relatively simple reactions. I thank particularly Ernest Davidson, Ken Houk, and Wes Borden for their willingness to collaborate and for their many contributions to this science. Thanks are also due to John Baldwin for employing new experimental techniques to provide important details on a number of the pathways for some of the simplest hydrocarbons. Acknowledgement is also due to the graduate students and post docs who continued to pursue some of this work in my laboratory, namely Jangir Emrani, Jose´ Jimenez, Mike Squicciarrini, Andrea Gortva, Jeff Scheibel, Chris Hawkins, Charles Benner, Jahagir Emrani, Jurjus Jurayj, Kyle Gee, Ken Tupper, Thomas Kreek, Leif Olson, Nancy Brichford, Nathan Harris, Jo Ann Currey, and Ilya Kuchuk. Gitendra Paul, a long time post doc pursued a number of problems in the area. Also, visitors Chris Samuel, Adrian Brook, and Richard Holder were especially helpful. To these and others who worked on different problems I thank you for your interest and your contributions both experimentally and intellectually. You enriched my understanding of chemistry. I hope that the undergrads who participated in this and other research projects, namely Bob Gajewski, Ruth Kinder, John Gajewski and Paiboon Ngernmeesri learned as much as I did in the course of their efforts. Thanks are also due to the U.S. Department of Energy for their support during the writing of this edition. Finally, I thank Jack Crandall and Mike Montgomery for their insights, criticisms, and friendship over the years. Joseph J. Gajewski
1 Introduction
CONTENTS 1 Introduction 2 Activation in Unimolecular Reactions 3 Transition State Theory 4 Non-interacting Biradical Hypothesis 5 Woodward –Hoffmann Rules 6 Energetics and Stereochemistry of Concerted Reactions 7 Calc