March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure 8th Edition

Book Preface

This eighth edition of March’s Advanced Organic Chemistry has been thoroughly updated to include new advances in areas of organic chemistry published between 2011 and 2017. Every topic retained from the seventh edition has been brought up to date if there was activity in that area during that six-year period. Changes also include a significant rewrite of most of the book. More than 5800 new references have been added for work published since 2011. As with the seventh edition, many older references were deleted to make room for new ones. In cases where a series of papers by the same principal author were cited, most but the most recent were deleted. Be aware that the older citations can usually be found by referring to the more recent publications. It is noted that more than 250 000 articles for the years 2011–2017, from 31 journals, were scanned for this edition. Of this huge number of articles, just over 8000 were examined in detail for inclusion in this work, with 5853 finally chosen. With such numbers, it is inevitable that some work was not included, and it was impossible to include representative research in many areas. For example, over 2000 of the 8000 articles examined were relevant to the transition metal-catalyzed reactions covered in reactions 13-3 to 13-13. It was simply impossible to keep a representative number of articles for this subject area. There were other areas of research that were also too extensive for complete inclusion of all references.

Many of the reaction drawings considered to be redundant or not very useful were deleted when compiling the eighth edition. A few new sections of text were added to better reflect some areas of research. Several of the older sections were moved to new chapters, especially the ones that deal with hydrogenation of alkenes and alkynes; as these are clearly reductions they were moved to Chapter 19. Some sections were combined with others and the original section deleted. These actions required renumbering the sections for the eighth edition. A correlation table of the sections in the seventh edition and their placement in the eighth edition is provided below. However, the fundamental structure of the eighth edition is essentially the same as that of all previous editions.

The goal, as in previous editions, is to give equal weight to three fundamental aspects of the study of organic chemistry: reactions, mechanisms, and structure. References are provided, and every effort has been given to provide a snapshot of current research.

Specific but specialized areas of organic chemistry—terpenes, carbohydrates, proteins, many organometallic reagents, combinatorial chemistry, polymerization and electrochemical reactions, steroids, etc.—have been incorporated into a great many pertinent sections rather than segregated into their own sections.

This book is largely directed at graduate students in their first year of study and to undergraduates advanced in their studies, but previous editions have, for many years, been used as an off-the-shelf reference book. This practice should continue with the eighth edition. It is hoped that this book will lead a student to consult the many excellent books and review articles cited for various topics in order to understand the subject in more detail. Indeed, most of these topics are so vast they cannot be explained completely in this book.

The structure of organic compounds is discussed in Chapters 1–5 (found in Part I); these chapters provide the background that is necessary for understanding mechanisms, but are important in their own right. The discussion begins with chemical bonding (Chapter 1) and
ends with a chapter on stereochemistry (Chapter 4). Chapter 5 discusses the structure of intermediates. Chapters 6 and 7 then address reaction mechanisms in general, Chapter 6 for ordinary reactions and Chapter 7 for photochemical reactions. Other methods related to reactions are included in Chapter 7, including microwave chemistry, the use of ultrasound, mechanochemistry, and the relatively new area of reactions done under flow conditions. Part I concludes with Chapters 8 and 9, which give further background to the study of mechanisms and reaction conditions.

The Introduction to Part II briefly describes how the second part of the book is organized. The organization is based on reaction types, and a relatively few principles suffice to explain nearly all the types, despite the large number of organic reactions. Accordingly, the reactions and mechanisms section of this book (Part II) is divided into ten chapters, each being concerned with a different type of reaction. In the first part of each chapter the appropriate basic mechanisms are discussed, along with considerations of reactivity and orientation. The second part of each chapter is devoted to individual reaction types, where the scope and the mechanism of each reaction are discussed. Numbered sections are used for the reactions and theses are set in boldface when given as cross-references. Since the methods for the preparation of individual classes of compounds (e.g., ketones, nitriles, etc.) are not treated all in one place, an updated and revised index has been provided (Appendix B) by use of which the synthesis of a given type of compound may be found.

It is important to note that the reaction numbers (e.g., 10-25) for many reactions in the eighth edition are different from those in the sixth and seventh editions. A table is included that precedes this Preface that directly correlates the reaction numbers found in the eighth edition with the reaction numbers that were used in the sixth and seventh editions. Note also that changes in the sixth edition made the reaction numbers from editions 1–5 different in many cases to those in the sixth edition. To see the differences between the fifth and sixth editions, the reader is referred to the sixth edition.

Although IUPAC has published a system for designating reaction mechanisms, the designations for reactions that were featured in editions 1–7 have been removed, in large part because they are not extensively used and in part because many reactions were deemed by this author as difficult to categorize using only one designation. In treating subjects as broad as structure, reactions, and mechanisms of organic chem istry, it is impossible to cover each topic in great depth, though this would not be desirable even if possible. This book is intended to point the reader to the primary literature (the original journal publications). Secondary literatures sources, including reviews, books, and monographs, have also been included.

Appendix A provides a brief introduction to using modern computer-based search engines such as Reaxys® and SciFinder®.

Although basically designed as a reference text for a one-year course at graduate level, this book can also be used in advanced undergraduate courses but is most useful after completion of a one-year course in organic chemistry.

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 easily accessible. The material in the first nine chapters, particularly chapters 1, 2, 4, 6, and 8, may be helpful for reviewing such material when this book is used in connection with a course

This book is probably most valuable as a reasonably up-to-date reference work. Both students preparing for qualifying examinations and practicing organic chemists will find that Part II contains a survey of the mechanism and scope of a large number of reactions, arranged in an orderly manner based on reaction type and on which bonds are broken and formed.

IUPAC mandates joules for units of energy, but many journals do not use this unit exclusively. Indeed, organic chemists who publish in United States’ journals commonly use calories. Virtually all energy values are presented here in both calories and joules. Although IUPAC does not recommend angstrom units (A) for bond distances, preferring ˚ instead picometers (pm), a vast number of bond distances published in the literature are in angstrom units, and this book therefore uses angstrom units.

I would like to acknowledge the contributions of those chemists cited and thanked by Professor March in the first four editions, and those I thanked in the fifth, sixth, and seventh editions. This book would not be possible without their contributions. I thank the many people who have contributed comments or have pointed out errors in editions 5–7 that were invaluable to putting together this edition. I thank Warren Hehre and Sean Ohlinger of Wavefunction, Inc., Irvine, CA (www.wavefun.com) for providing Spartan 10 Macintosh (v. 1.0.1), allowing the incorporation of Spartan models for selected molecules and intermediates. All structures and line drawings in this book were done using ChemDraw® Professional 15.1.0.144 (2348350), graciously provided by PerkinElmer Corporation, Waltham, MA.

Special thanks are due to the Interscience division of John Wiley & Sons and to Stefanie Volk and to Jonathan Rose, and also to Katrina Maceda at Wiley for their fine work as editors in turning the manuscript into the finished book. I also thank Tim Jackson for an excellent job of copy editing the manuscript.

With gratitude, I acknowledge the work of the late Jerry March, upon whose work all the editions I have authored is built, although updates and changes have been made, beginning with the fifth edition, However, Jerry is responsible for the concept and fundamental organization of this book and he carried it through four very successful editions. I used Jerry’s book as a student and it is an honor to continue this tradition.

I encourage those who read and use the eight edition to contact me directly with comments and errors and with publications that might be appropriate for future editions. I hope that this new edition will do justice to the tradition that Professor March began nearly 60 years ago.

My email address is: [email protected] Finally, I want to thank my wife Sarah for her patience and understanding during the preparation of this manuscript. I also thank my son Steven. Without them, this work would not have been possible.

Michael B. Smith
Professor Emeritus
October, 201