Progress In Physical Organic Chemistry, Vol. 8

Progress in Physical Organic Chemistry, Volume 8 Editors Andrew Streitwieser, Jr. Robert W. Taft JOHN WILEY & SONS Progress in PHYSICAL ORGANIC CHEMISTRY VOLUME 8 \\ Progress in PHYSICAL ORGANIC CHEMISTRY 1 VOLUME 8 // Editors ANDREW STREITWIESER, JR., Department of Chemistry University of California, Berkeley, California ROBERT W. TAFT, Department of Chemistry University of California, Iruine, California 1971 WILEY-INTERSCIENCE a division of John Wiley & Sons, Znc. - New York . London - Sydney * Toronto Copyright 0 1971, by John Wiley & Sons, Inc. All rights reserved. No part of this book may be reproduced by any means, nor transmitted, nor translated into a machine language without the written permission of the publisher. Library of Congress Catalog Card Number: 63-19364 ISBN 0 471 83354 1 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 Introduction to the Series Physical organic chemistry is a relatively modern field with deep roots in chemistry. The subject is concerned with investigations of organic chemistry by quantitative and mathematical methods. The wedding of physical and organic chemistry has provided a remarkable source of inspiration for both of these classical areas of chemical endeavor. Further, the potential for new developments resulting from this union appears to be still greater. A closening of ties with all aspects of molecular structure and spectroscopy is clearly anticipated. The field provides the proving ground for the development of basic tools for investigations in the areas of molecular biology and biophysics. The subject has an inherent association with phenomena in the condensed phase and thereby with the theories of this state of matter. The chief directions of the field are: (a) the effects of structure and environment on reaction rates and equilibria; (b) mechanism of reactions; and (c) applications of statistical and quantum mechanics to organic compounds and reactions. Taken broadly, of course, much of chemistry lies within these confines. The dominant theme that characterizes this field is the emphasis on interpretation and understanding which permits the effective practice of organic chemistry. The field gains its momentum from the application of basic theories and methods of physical chemistry to the broad areas of knowledge of organic reactions and organic structural theory. The nearly inexhaustible diversity of organic structures permits detailed and systematic investigations which have no peer. The reactions of complex natural products have contributed to the development of theories of physical organic chemistry, and in turn, these theories have ultimately provided great aid in the elucidation of structures of natural products. Fundamental advances are offered by the knowledge of energy states and their electronic distributions in organic compounds and the relationship of these to reaction mechanisms. The development, for example, of even an empirical and approximate general scheme for the estimation of activation energies would indeed be most notable. The complexity of even the simplest organic compounds in terms of