Felix A. Carroll - Perspectives on Structure and Mechanism in Organic Chemistry

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Library of Congress Cataloging-in-Publication Data:

Carroll, Felix A.

Perspectives on structure and mechanism in organic chemistry / Felix A. Carroll.

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-27610-5 (cloth)

Preface

This book is the result of my experience teaching physical organic chemistry at Davidson College. During this time I felt a need for a text that not only presents concepts that are central to the understanding and practice of physical organic chemistry but that also teaches students to think about organic chemistry in new ways, particularly in terms of complementary conceptual models. Because of this approach, the first edition of Perspectives on Structure and Mechanism in Organic Chemistry attracted attention beyond the chemistry community and was even quoted in a philosophy dissertation.

Soon after the first edition appeared, I received a telephone call from a student of the philosophy of science, who asked how I came to write a book with this emphasis. I did not have a ready answer, but as we talked I realized that this was primarily due to the influences of George Hammond and Jacob Bronowski. I was a graduate student with George Hammond. Although I cannot recall ever discussing conceptual models with him, his views were nonetheless imprinted on mebut in such a subtle way that I did not fully recognize it at the time. Jacob Bronowskis impact was more distinct because it resulted from a single eventthe film Knowledge or Certainty in a series titled The Ascent of Man. That film offers a powerful commentary on both the limits of human knowledge and the nature of science as a tribute to what we can know although we are fallible.a Perhaps a hybridization of their influences led me to emphasize that familiar conceptual models are only beginning points for describing structures and reactions and that using complementary models can provide a deeper understanding of organic chemistry than can using any one model alone.

As with the first edition, the first five chapters of this book consider structure and bonding of stable molecules and reactive intermediates. There is a chapter on methods organic chemists use to study reaction mechanisms, and then acid-base reactions, substitution reactions, addition reactions, elimination reactions, pericyclic reactions, and photochemical reactions are considered in subsequent chapters. In each case I have updated the content to reflect developments since publication of the first edition.

It is essential for an advanced text to provide complete references. The literature citations in this edition range from 1851 to 2009. They direct interested readers to further information about all of the topics and also acknowledge the researchers whose efforts produced the information sum marized here. A teaching text must also provide a set of problems of varying difficulty. The nearly 400 problems in this edition do more than just allow students to test their understanding of the facts and concepts presented in a chapter. They also encourage readers to actively engage the chemical litera ture and to develop and defend their own ideas. Some problems represent straightforward applications of the information in the text, but other pro blems can best be answered by consulting the literature for background information before attempting a solution. Still other problems are open-ended, with no one correct answer. I have prepared a solutions manual giving answers for problems in the first two categories as well as comments about the open-ended problems.

In Knowledge or Certainty, Bronowski shows many portraits of the same human face and observes that we are aware that these pictures do not so much fix the face as explore it... and that each line that is added strengthens the picture but never makes it final.2b So it is with this book. It is not a photograph but is, instead, a portrait of physical organic chemistry. As with the human face, it is not possible to fix a continually changing sciencewe can only explore it. I hope that the lines added in this edition will better enable readers to develop a deeper and more complete understanding of physical organic chemistry.

FELIX A. CARROLL

Davidson College

1 Weisberg, M. When Less is More: Tradeoffs and Idealization in Model Building; Ph.D. Dissertation, Stanford University, 2003. See also Weisberg, M. Philos. Sci.2004,71, 1071.

2 The quotations are from the book with the same title as the film series: Bronowski, J. The Ascent of Man; Little, Brown and Company, Boston, 1973; (a) p. 374; (b) p. 353.

Acknowledgments

I am grateful to the following colleagues for giving their time to read and to offer comments on portions of this edition.

Igor V. Alabugin, Florida State University

John E. Baldwin, Syracuse University

Christopher M. Hadad, Ohio State University

Richard P. Johnson, University of New Hampshire

Jeffrey I. Seeman, University of Richmond

Benjamin T. King, University of Nevada, Reno

Nancy S. Mills, Trinity University

Sason S. Shaik, Hebrew University, Jerusalem

Richard G. Weiss, Georgetown University

Frank H. Quina, University of Sao Paulo

I am also grateful to readers of the first edition who pointed out errors and made suggestions. In particular, I acknowledge Professor Robert G. Bergman of the University of California, Berkeley and his students for their helpful comments.