Advanced Organic Chemistry March 4

8/13/2019 Advanced Organic Chemistry March 4

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Advanced Organic Chemistry

Reactions, Mechanisms, and Structure

FOURTH EDITION

Jerry March

Professor of Chemistry

Adelphi University


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This text is printed on acid- free paper.

Copyright 1992 by John Wiley & Sons, Inc.

All rights reserved. Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval

system, or ransmitted in any form or by any means, electronic,

mechanical, photocopying, ecording, scanning or otherwise, except as

permitted under Sections 107 and 108 of he 1976 United States

Copyright Act, without either the prior written permission of he

Publisher, or authorization through payment of the appropriate per-copy

fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers,MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the

Publisher for permission should be addressed to the Permissions

Department, John Wiley & Sons, Inc., 605 Third Avenue, New York,

NY 10158-0012. (212) 850-6011, fax (212) 850-6008, E- mail:

[email protected].

Printed in the United States of America

Library of Congress Cataloging -in-Publication Data

March, Jerry, 1929-

Advanced organic chemistry : reactions, mechanisms, and structure/

Jerry March.4th ed.

p. cm.

"A Wiley- lnterscience publication."Includes bibliographical references and indexes.

ISBN 0-471-60180-2

ISBN 0-471-58148-8 (paperback version)

1. Chemistry. Organic I. Title.


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QD251.2.M37 1992

547dc20 92-728

CIP20 19 18 17 16 15 14 13 12


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This book is dedicated to the nearly 20,000 scientists whose names are listed in theAuthor Index, and to my wife, Beverly, and our children, Gale, David, and June


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PREFACE

Knowledge of organic chemistry continues to move ahead on many fronts. New

journals continue to appear and older ones increase in frequency of publication and/or

in number of papers published. This fourth edition of Advanced Organic Chemistry

has been thoroughly revised to reflect this growth. Every topic retained from the third

edition has been brought up to date. Changes, ranging from minor to extensive, have

been made on virtually every page of the third edition. More than 5000 references

have been added. However, no changes were made in the organization: The structure

of the fourth edition is essentially the same as that of the second and the third. Like the

first three editions, the fourth is intended to be a textbook for a course in advancedorganic chemistry taken by students who have had the standard undergraduate organic

and physical chemistry courses.

I have attempted to give equal weight to the three fundamental aspects of the study of

organic chemistry: reactions, mechanisms, and structure. A student who has completed

a course based on this book should be able to approach the literature directly, with a

sound knowledge of modern basic organic chemistry. I have treated lightly or not at all

the major special areas of organic chemistry: terpenes, carbohydrates, proteins,

polymerization and electrochemical reactions, steroids, etc. It is my opinion that these

topics are best approached after the first year of graduate study, when the

fundamentals have been mastered, either in advanced courses, or directly, byconsulting the many excellent books and review articles available on these subjects.

The organization is based on reaction types, so the student can be shown that despite

the large number of organic reactions, a relatively few principles suffice to explain

nearly all of them. Accordingly, the reactions-mechanisms section of this book (Part 2)

is divided into 10 chapters, each concerned with a different type of reaction. In the first

part of each chapter the appropriate basic mechanisms are discussed along withconsiderations of reactivity and orientation, while the second part consists of

numbered sections devoted to individual reactions, where the scope and the

mechanism of each reaction are discussed. I have used numbered sections for the

reactions, because I have found that students learn better when they are presented with

clear outlines (for a further discussion of the arrangement of Part 2, see pp. 287-288).Since the methods for the preparation of individual classes of compounds (e.g.,

ketones, nitriles, etc.) are not treated all in one place, an index has been provided

(Appendix B) by use of which all methods for the preparation of a given type of

compound will be found. For each reaction, a list of Organic Syntheses references isgiven. Thus for most reactions the student can consult actual examples in OrganicSyntheses.

The structure of organic compounds is discussed in the first five chapters of Part 1.

This section provides a necessary background for understanding mechanisms and is

also important in its own right. The discussion begins with chemical bonding and

includes a chapter on stereochemistry. There follow two chapters on reaction


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mechanisms in general, one for ordinary reactions and the other for photochemical

reactions. Part 1 concludes with two more chapters that give further background to the

study of mechanisms. In addition to reactions, mechanis ms, and structure, the student

should have some familiarity with the literature of organic chemistry. A chapterdevoted to this topic has been placed in Appendix A, though many teachers may wish

to cover this material at the beginning of the course.

In the third edition I included the new IUPAC names for organic transformations.

Since then the rules have been broadened to cover additional cases; hence more such

names are given in this edition. Furthermore, IUPAC has now published a new system

for designating reaction mechanisms (see p. 290), and I now include some of the

simpler of these new designations.

In treating a subject as broad as the basic structures, reactions, and mechanisms of

organic chemistry, it is obviously not possible to cover each topic in great depth. Nor

would this be desirable even if possible. Nevertheless, students will often wish to

pursue individual topics further. An effort has therefore been made to guide the reader

to pertinent review articles and books published since about 1965. In this respect, this

book is intended to be a guide to the secondary literature (since about 1965) of the

areas it covers. Furthermore, in a graduate course, students should be encouraged to

consult primary sources. To this end, more than 15,000 references to original papers

have been included.

Although basically designed for a one- year course on the graduate level, this book can

also be used in advanced undergraduate courses as long as they are preceded byoneyear courses in organic and physical chemistry. It can also be adapted, by the

omission of a large part of its contents, to a one-semester course. Indeed, even for a

one-year course, more is included than can be conveniently covered. Many individual

sections can be easily omitted without disturbing continuity.

The reader will observe that this text contains much material that is included in

firstyear organic and physical chemistry courses, though in most cases it goes moredeeply into each subject and, of course, provides references, which firstyear texts do

not. It has been my experience that students who have completed the first-year courses

often have a hazy recollection of the material and greatly profit from a re-presentation

of the material if it is organized in a different way. It is hoped that the organization of

the material on reactions and mechanisms will greatly aid the memory and theunderstanding. In any given course the teacher may want to omit some chapters

because the students already have an adequate knowledge of the material, or because

there are other graduate courses that cover the areas more thoroughly. Chapters 1, 4,

and 7 especially may fall into one of these categories.

Although this is a textbook, it has been designed to have reference value also. Students

preparing for qualifying examinations and practicing organic chemists will find that

Part 2 contains a survey of what is known about the mechanism and scope of about

580 reactions, arranged in an orderly manner based on reaction type and on which

bonds are broken and formed. Also valuable for reference purposes are the previously


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mentioned lists of reactions classified by type of compound prepared (Appendix B)

and of all of the Organic Syntheses references to each reaction.

Anyone who writes a book such as this is faced with the question of which units touse, in cases where international rules mandate one system, but published papers use

another. Two instances are the units for energies and for bond distances. For energies,

IUPAC mandates joules, and many journals do use this unit exclusively. However,

organic chemists who publish in United States journals overwhelmingly use calories

and this situation shows no signs of changing in the near future. Since previous

editions of this book have been used extensively both in this country and abroad, I

have now adopted the practice of giving virtually all energy values in both calories and

joules. The question of units for bond distances is easier to answer. Although IUPAC

does not recommend Angstrom units, nearly all bond distances published in theliterature anywhere in the world, whether in organic or in crystallographic journals, are

in these units, though a few papers do use picometers. Therefore, I continue to use

only Angstrom units.


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CONTENTS

Bibliographical Note xv

Part 1 1

Chapter 1

Localized Chemical Bonding 3

Chapter 2

Delocalized Chemical Bonding 26Aromaticity 40

Hyperconjugation 68

Tautomerism 69

Chapter 3

Bonding Weaker than Covalent 75

Hydrogen Bonding 75

Addition Compounds 79

Chapter 4

Stereochemistry 94

Optical Activity and Chirality 94

Cis-trans Isomerism 127

Conformational Analysis 138

Strain 150

Chapter 5

Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 165

Carbocations 165

Carbanions 175

Free Radicals 186

Carbenes 195

Nitrenes 202

Chapter 6

Mechanisms and Methods of Determining Them 205

Chapter 7

Photochemistry 231


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Chapter 8

Acids and Bases 248

Chapter 9

Effects of Structure on Reactivity 273

Part 2 287

Chapter 10

Aliphatic Nucleophilic Substitution 293

Mechanisms 293Reactivity 339

Reactions 369

Chapter 11

Aromatic Electrophilic Substitution 501

Mechanisms 501

Orientation and Reactivity 507

Reactions 521

Chapter 12

Aliphatic Electrophilic Substitution 569

Mechanisms 569

Reactivity 578

Reactions 580

Chapter 13Aromatic Nucleophilic Substitution 641

Mechanisms 641

Reactivity 649

Reactions 653

Chapter 14

Free-Radical Substitution 677

Mechanisms 677Reactivity 683

Reactions 689

Chapter 15

Addition to Carbon-Carbon Multiple Bonds 734


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Mechanisms 734

Orientation and Reactivity 747

Reactions 758

Chapter 16

Addition to Carbon-Hetero Multiple Bonds 879

Mechanisms and Reactivity 879

Reactions 882

Chapter 17

Eliminations 982Mechanisms and Orientation 982

Reactivity 1003

Mechanisms and Orientation in Pyrolytic Eliminations 1006

Reactions 1010

Chapter 18

Rearrangements 1051

Mechanisms 1052Reactions 1068

Chapter 19

Oxidations and Reductions 1158

Mechanisms 1158

Reactions 1161

Appendix A

The Literature of Organic Chemistry 1239

Primary Sources 1239

Secondary Sources 1244

Literature Searching 1258

Appendix B

Classification of Reactions by Type of Compound Synthesized 1269

Indexes 1301

Author Index 1301

Subject Index 1433


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Documents

Advanced Organic Chemistry March 4