Principles of IONIC ORGANIC REACTIONS The Late ELLIOT R. ALEXANDER Assistant Professor of Chemistry in the University of Illinois NEW YORK JOHN WILEY SONS, INC. LONDON TOPPAN COMPANY, LTD., TOKYO, JAPAN Authorized reprint of the edition published by John Wiley Sons, Inc., New York and London. Copyright 1950 by John Wiley Sons, Inc. All f Rights Reserved. No part of this book may be reproduced in any form without the written permission of John Wiley Sons, Inc. Printed in Japan by TOPPAN PRINTING COMPANY, LTD. PREFACE It is becoming increasingly apparent that it is possible to break down a very large number of organic reactions into different sequences of a few basic transformations, the nature of which does not change regardless of the process being carried out. Such a sequence is commonly called a reaction mechanism. To many organic chemists, however, a reaction m hanism is more often regarded merely as a pleasant form of retro spection not useful for stimulating research or for implementing the chemical intuition for which all synthetic chemists strive. To a certain extent this attitude is understandable. For many years organic chemists have been trained to think in terms of the reactions of functional groups, and it is often very difficult to see the thread of conti nuity connecting a number of transformations in which the similarities are only those of electronic distribution or behavior. Even the way organic formulas are written obscures the electrons in a molecule and minimizes their importance in understanding chemical reactions. Fre quently, since it is not always clear that the individual steps of a mech anism are of a general naturu, the mechanisms themselves are more difficult to remember than the starting materials and tlfie end-products. Nomenclature has also proved to be a stumbling block to the assimilation of organic chemical theory. It is always exasperating to find unfamiliar terms used to describe phenomena which may be well known in other situations. Finally, to the despair of organic chemists, the physical rather than the chemical aspects of organic theory have been stressed. Occasionally rather unimportant organic reactions have been studied and discussed in great detail because they could be treated experimen tally in a precise quantitative fashion, while other more important reac tions, for which there is only qualitative information, have been omitted from discussion. Obviously such information does not belong in books dealing with the physical nature of organic chemistry, but it is of con siderable importance to us for whom these reactions are the tools of our profession. Accordingly, in writing this book for advanced undergraduates and first-year graduate students, the objective has been twofold. First an attempt has been made to present from the point of view of an organic chemist the mechanisms which seem to be most reasonable for a number vi PREFACE of organic reactions together with the pertinent data which support them. It is well known that while our interpretation of data may change in the light of later experimental work, the facts themselves do not change. Second, I have attempted to present the material in a sequence that will stress the similarities rather than the differences between seemingly diverse organic reactions. In the first six chapters are dis cussed the fundamental intermediates and types of reactions from which most ionic transformations can be constructed. The remaining chapters of the book are concerned with a more detailed discussion of individual organic reactions. Such a book as this could not have been written without the aid of a great many people, most of whom cannot be properly credited in these pages. This I regret because my debt to them is very real...