PREFACE TO THE FOURTH EDITION xxix quizzing engines support an unparalleled range of questions from both the book and a supplementary problem set,focusing on the students'ability to understand and draw molecules.Answer-specific feedback and hints coach students through solving prob- lems.Integration of ebook and multimedia content completes this learning system. The guiding principle at the heart of this system is that,given enough time and effort, every student should be able to earn an"A"on every assignment.Assignments are scored automatically.SmartWork includes equally sophisticated and flexible tools for managing class data and determining how assignments are scored. Assigning,editing,and administering homework within SmartWork is easy. WYSIWYG(What You See Is What You Get)authoring tools allow instructors to modify existing problems or develop new content. Organic Reaction Animations.Since its second year,this book has been graced by its association with the Organic Reaction Animations software created by Steven Fleming,Paul Savage,and Greg Hart.There are now over 50 different reactions in this splendid collection,which are fully integrated into the text,with icons identi- fying each reaction and its place in the book.All versions of ORA 2.3 also include tutorials on the reactions themselves.ORA problems are found at the end of most chapters in the fourth edition. Acknowledgments from Mait Jones Books don't get written by setting an author on his or her way and then waiting for the manuscript to appear.There is a great deal more work to be done than that.In general,it is an editor's job to make it possible for the author to do the best of which he is capable.Don Fusting,Joe Wisnovsky,Vanessa Drake-Johnson,and for this fourth edition,Erik Fahlgren at W.W.Norton were exemplary in their execution of that role.My special thanks go to Erik for keeping the big picture in mind,and for keeping two authors more or less on track.Jeannette Stiefel was copyeditor for the first three editions;Philippa Solomon and Connie Parks copyedited this edi- tion.Kate Barry and Christopher Granville were early project editors at Norton. Carla Talmadge succeeded them for the fourth edition,and was exceptionally help- ful and creative in her dealings with too many author-produced problems. This book also profited vastly from the comments and advice of an army of reviewers,and I am very much in their debt.Their names and affiliations follow this preface.Two special reviewers,Henry L.Gingrich of Princeton and Ronald M. Magid of the University of Tennessee,read the work line by line,word by word, comma by missing comma.Their comments,pungent at times but helpful always, were all too accurate in uncovering both the gross errors and lurking oversimplifi- cations in the early versions of this work. Finally,MJ gives special thanks to Steven Fleming for joining up and adding so much more than his chemical expertise to this project.It has been a great pleasure to work with him! Cape North,June 2009 Acknowledgments from Steven Fleming I am honored to be involved with the Jones text.I thank Mait for letting me join forces to produce the fourth edition.My involvement wouldn't have happened with- out the indefatigable Erik Fahlgren.It has been a pleasure to work with Mait,Erik, and the W.W.Norton team.My interest in understanding and teaching"why"things
quizzing engines support an unparalleled range of questions from both the book and a supplementary problem set, focusing on the students’ability to understand and draw molecules. Answer-specific feedback and hints coach students through solving problems. Integration of ebook and multimedia content completes this learning system. The guiding principle at the heart of this system is that, given enough time and effort, every student should be able to earn an “A” on every assignment. Assignments are scored automatically. SmartWork includes equally sophisticated and flexible tools for managing class data and determining how assignments are scored. Assigning, editing, and administering homework within SmartWork is easy. WYSIWYG (What You See Is What You Get) authoring tools allow instructors to modify existing problems or develop new content. • Organic Reaction Animations. Since its second year, this book has been graced by its association with the Organic Reaction Animations software created by Steven Fleming, Paul Savage, and Greg Hart. There are now over 50 different reactions in this splendid collection, which are fully integrated into the text, with icons identifying each reaction and its place in the book. All versions of ORA 2.3 also include tutorials on the reactions themselves. ORA problems are found at the end of most chapters in the fourth edition. Acknowledgments from Mait Jones Books don’t get written by setting an author on his or her way and then waiting for the manuscript to appear. There is a great deal more work to be done than that. In general, it is an editor’s job to make it possible for the author to do the best of which he is capable. Don Fusting, Joe Wisnovsky, Vanessa Drake-Johnson, and for this fourth edition, Erik Fahlgren at W. W. Norton were exemplary in their execution of that role. My special thanks go to Erik for keeping the big picture in mind, and for keeping two authors more or less on track. Jeannette Stiefel was copyeditor for the first three editions; Philippa Solomon and Connie Parks copyedited this edition. Kate Barry and Christopher Granville were early project editors at Norton. Carla Talmadge succeeded them for the fourth edition, and was exceptionally helpful and creative in her dealings with too many author-produced problems. This book also profited vastly from the comments and advice of an army of reviewers, and I am very much in their debt.Their names and affiliations follow this preface. Two special reviewers, Henry L. Gingrich of Princeton and Ronald M. Magid of the University of Tennessee, read the work line by line, word by word, comma by missing comma. Their comments, pungent at times but helpful always, were all too accurate in uncovering both the gross errors and lurking oversimplifications in the early versions of this work. Finally, MJ gives special thanks to Steven Fleming for joining up and adding so much more than his chemical expertise to this project. It has been a great pleasure to work with him! Cape North, June 2009 Acknowledgments from Steven Fleming I am honored to be involved with the Jones text. I thank Mait for letting me join forces to produce the fourth edition. My involvement wouldn’t have happened without the indefatigable Erik Fahlgren. It has been a pleasure to work with Mait, Erik, and the W.W. Norton team. My interest in understanding and teaching “why”things PREFACE TO THE FOURTH EDITION xxix
XXX PREFACE TO THE FOURTH EDITION happen led me to this text.I can't remember when I developed such an interest in cause and effect,but it must have been my genetics or environment.My brother, Ron Fleming,is also an organic chemist and he has been my chemistry hero.I have appreciated the opportunities to discuss this topic with him for the past 40 years.It has also been my good fortune to have Paul Savage as a close colleague.He has taught me much.There are over 100 students(mostly undergraduates)who have attended my weekly group meetings since 1986.I have enjoyed having them along for the ride,and it has been a joy to work with them and learn from them.I look forward to the next 100 unsuspecting souls and the topics we will learn together in the next 23 years.This is"for my children"Melissa,Nathan,Amy,and Erin. Philadelphia,June 2009 Despite all the efforts of editors and reviewers,errors will persist.These are our fault only.When you find them,let us know. Fourth Edition Reviewers Margaret Asirvatham,University of Bonnie Dixon,University of Maryland Colorado,Boulder Tom Eberlein,Penn State,Harrisburg France-Isabelle Auzanneau,University of Amy Gottfried,University of Michigan Guelph Eric J.Kantorowski,California K.Darrell Berlin,Oklahoma State Polytechnic State University University Rizalia Klausmeyer,Baylor University Brian M.Bocknack,University of Texas, Masato Koreeda,University of Michigan Austin Brian Kyte,Saint Michael's College Peter Buist,Carleton University Tim Minger,Mesa Community College Arthur Cammers,University of Kentucky Susan J.Morante,Mount Royal College Paul Carlier,Virginia Tech Jonathan Parquette,Ohio State Dana Chatellier,University of Delaware University Tim Clark,Western Washington Chris Pigge,University of lowa University John Pollard,University of Arizona Barry A.Codens,Northwestern T.Andrew Taton,University of University Minnesota Gregory Dake,University of British Alexander Wurthmann,University of Columbia Vermont Previous Editions'Reviewers Mark Arant,University of Louisiana at Peter Buist,Carleton University Monroe Jeffrey Charonnat,California State Arthur Ashe,University of Michigan University,Northridge William F.Bailey,University of Marc d'Arlacao,Tufts University Connecticut Donald B.Denney,Rutgers University John Barbaro,University of Georgia Robert Flowers,Lehigh University Ronald J.Baumgarten,University of David C.Forbes,University of South Illinois at Chicago Alabama Michael Biewer,University of Texas at B.Lawrence Fox,University of Dayton Dallas John C.Gilbert,University of Texas at David Birney,Texas Tech University Austin John I.Brauman,Stanford University Henry L.Gingrich,Princeton University
happen led me to this text. I can’t remember when I developed such an interest in cause and effect, but it must have been my genetics or environment. My brother, Ron Fleming, is also an organic chemist and he has been my chemistry hero. I have appreciated the opportunities to discuss this topic with him for the past 40 years. It has also been my good fortune to have Paul Savage as a close colleague. He has taught me much. There are over 100 students (mostly undergraduates) who have attended my weekly group meetings since 1986. I have enjoyed having them along for the ride, and it has been a joy to work with them and learn from them. I look forward to the next 100 unsuspecting souls and the topics we will learn together in the next 23 years. This is “for my children” Melissa, Nathan, Amy, and Erin. Philadelphia, June 2009 Despite all the efforts of editors and reviewers, errors will persist. These are our fault only. When you find them, let us know. Fourth Edition Reviewers xxx PREFACE TO THE FOURTH EDITION Margaret Asirvatham, University of Colorado, Boulder France-Isabelle Auzanneau, University of Guelph K. Darrell Berlin, Oklahoma State University Brian M. Bocknack, University of Texas, Austin Peter Buist, Carleton University Arthur Cammers, University of Kentucky Paul Carlier, Virginia Tech Dana Chatellier, University of Delaware Tim Clark, Western Washington University Barry A. Codens, Northwestern University Gregory Dake, University of British Columbia Bonnie Dixon, University of Maryland Tom Eberlein, Penn State, Harrisburg Amy Gottfried, University of Michigan Eric J. Kantorowski, California Polytechnic State University Rizalia Klausmeyer, Baylor University Masato Koreeda, University of Michigan Brian Kyte, Saint Michael’s College Tim Minger, Mesa Community College Susan J. Morante, Mount Royal College Jonathan Parquette, Ohio State University Chris Pigge, University of Iowa John Pollard, University of Arizona T. Andrew Taton, University of Minnesota Alexander Wurthmann, University of Vermont Previous Editions’ Reviewers Mark Arant, University of Louisiana at Monroe Arthur Ashe, University of Michigan William F. Bailey, University of Connecticut John Barbaro, University of Georgia Ronald J. Baumgarten, University of Illinois at Chicago Michael Biewer, University of Texas at Dallas David Birney, Texas Tech University John I. Brauman, Stanford University Peter Buist, Carleton University Jeffrey Charonnat, California State University, Northridge Marc d’Arlacao, Tufts University Donald B. Denney, Rutgers University Robert Flowers, Lehigh University David C. Forbes, University of South Alabama B. Lawrence Fox, University of Dayton John C. Gilbert, University of Texas at Austin Henry L. Gingrich, Princeton University
PREFACE TO THE FOURTH EDITION xxxi David Goldsmith,Emory University Roger K.Murray,Jr.,University of Nancy S.Goroff,State University of Delaware New York,Stony Brook Thomas W.Nalli,State University of David N.Harpp,McGill University New York at Purchase Richard K.Hill,University of Georgia R.M.Paton,University of Edinburgh Ian Hunt,University of Calgary Patrick Perlmutter,Monash University A.William Johnson,University of Matthew S.Platz,Ohio State University Massachusetts Lawrence M.Principe,Johns Hopkins Guilford Jones II,Boston University University Richard Keil,University of Washington Kathleen S.Richardson,Capital S.Bruce King,Wake Forest University University Grant Krow,Temple University Christian Rojas,Barnard College Joseph B.Lambert,Northwestern Alan M.Rosan,Drew University University Charles B.Rose,University of Philip Le Quesne,Northeastern Nevada-Reno University Carl H.Schiesser,Deakin University Steven V.Ley,Imperial College of Martin A.Schwartz,Florida State Science,Technology and Medicine University Robert Loeschen,California State John F.Sebastian,Miami University University,Long Beach Jonathan L.Sessler,University of Texas Carl Lovely,University of Texas at at Austin Arlington Valerie V.Sheares,Iowa State University Ronald M.Magid,University of Robert S.Sheridan,University of Tennessee-Knoxville Nevada-Reno Eugene A.Mash,Jr.,University of Philip B.Shevlin,Auburn University Arizona Matthew Sigman,University of Utah John McClusky,University of Texas at William Tam,University of Guelph San Antonio Edward Turos,University of South Lydia McKinstry,University of Nevada, Florida Las Vegas Harry H.Wasserman,Yale University Robert J.McMahon,University of David Wiedenfeld,New Mexico Wisconsin-Madison Highlands University Keith Mead,Mississippi State University Craig Wilcox,University of Pittsburgh Andrew F.Montana,California State David R.Williams,Indiana University University,Fullerton Kathleen Morgan,Xavier University of Louisiana
David Goldsmith, Emory University Nancy S. Goroff, State University of New York, Stony Brook David N. Harpp, McGill University Richard K. Hill, University of Georgia Ian Hunt, University of Calgary A. William Johnson, University of Massachusetts Guilford Jones II, Boston University Richard Keil, University of Washington S. Bruce King, Wake Forest University Grant Krow, Temple University Joseph B. Lambert, Northwestern University Philip Le Quesne, Northeastern University Steven V. Ley, Imperial College of Science, Technology and Medicine Robert Loeschen, California State University, Long Beach Carl Lovely, University of Texas at Arlington Ronald M. Magid, University of Tennessee–Knoxville Eugene A. Mash, Jr., University of Arizona John McClusky, University of Texas at San Antonio Lydia McKinstry, University of Nevada, Las Vegas Robert J. McMahon, University of Wisconsin–Madison Keith Mead, Mississippi State University Andrew F. Montana, California State University, Fullerton Kathleen Morgan, Xavier University of Louisiana Roger K. Murray, Jr., University of Delaware Thomas W. Nalli, State University of New York at Purchase R. M. Paton, University of Edinburgh Patrick Perlmutter, Monash University Matthew S. Platz, Ohio State University Lawrence M. Principe, Johns Hopkins University Kathleen S. Richardson, Capital University Christian Rojas, Barnard College Alan M. Rosan, Drew University Charles B. Rose, University of Nevada–Reno Carl H. Schiesser, Deakin University Martin A. Schwartz, Florida State University John F. Sebastian, Miami University Jonathan L. Sessler, University of Texas at Austin Valerie V. Sheares, Iowa State University Robert S. Sheridan, University of Nevada–Reno Philip B. Shevlin, Auburn University Matthew Sigman, University of Utah William Tam, University of Guelph Edward Turos, University of South Florida Harry H. Wasserman, Yale University David Wiedenfeld, New Mexico Highlands University Craig Wilcox, University of Pittsburgh David R. Williams, Indiana University PREFACE TO THE FOURTH EDITION xxxi
Introduction These days,a knowledge of science must be part of the intellectual equipment of any educated person.Of course,that statement may always have been true,but we think there can be no arguing that an ability to confront the problems of concern to scientists is especially important today.Our world is increasingly technological, and many of our problems,and the answers to those problems,have a scientific or technological basis.Anyone who hopes to understand the world we live in,to eval- uate many of the pressing questions of the present and the future-and to vote sen- sibly on them-must be scientifically literate. The study of chemistry is an ideal way to acquire at least part of that literacy. Chemistry is a central science in the sense that it bridges such disparate areas as physics and biology,and connects those long-established sciences to the emerging disciplines of molecular biology and materials science.Similarly,as this book shows, organic chemistry sits at the center of chemistry,where it acts as a kind of intellec- tual glue,providing connections between all areas of chemistry.One does not have to be a chemist,or even a scientist,to profit from the study of organic chemistry. The power of organic chemistry comes from its ability to give insight into so many parts of our lives.How does penicillin work?Why is Teflon nonstick?Why does drinking a cup of coffee help me stay awake?How do plants defend themselves against herbivores?Why is ethyl alcohol a depressant?All these questions have answers based in organic chemistry.And the future will be filled with more organ- ic chemistry-and more questions.What's a buckyball or a nanotube,and how might it be important to my life?How might an organic superconductor be constructed? Why is something called the Michael reaction important in a potential cancer ther- apy?Read on,because this book will help you to deal with questions such as these, and many more we can't even think up yet. What Is Organic Chemistry?Organic chemistry is traditionally described as the chemistry of carbon-containing compounds.Until the nineteenth century,it was thought that organic molecules were related in an immutable way to living things, hence the term"organic."The idea that organic compounds could be made only from molecules derived from living things was widespread,and gave rise to the notion of a vital force being present in carbon-containing molecules.In 1828 Friedrich Wohler(1800-1882)synthesized urea,a certified organic substance,from heating ammonium cyanate,a compound considered to be inorganic.Wohler's experiment Wohler's urea is an end product of the metabolism of proteins in mammals,and is a major component of human urine.An adult human excretes about 25 g(6-8 level teaspoons)of urea each day.The formation of urea is our way of getting rid of the detritus of protein breakdown through a series of enzymatic reactions.If you are missing one of the enzymes necessary to produce urea,it's very bad news indeed,as coma and rapid death result. xxxiii
These days, a knowledge of science must be part of the intellectual equipment of any educated person. Of course, that statement may always have been true, but we think there can be no arguing that an ability to confront the problems of concern to scientists is especially important today. Our world is increasingly technological, and many of our problems, and the answers to those problems, have a scientific or technological basis. Anyone who hopes to understand the world we live in, to evaluate many of the pressing questions of the present and the future—and to vote sensibly on them—must be scientifically literate. The study of chemistry is an ideal way to acquire at least part of that literacy. Chemistry is a central science in the sense that it bridges such disparate areas as physics and biology, and connects those long-established sciences to the emerging disciplines of molecular biology and materials science. Similarly, as this book shows, organic chemistry sits at the center of chemistry, where it acts as a kind of intellectual glue, providing connections between all areas of chemistry. One does not have to be a chemist, or even a scientist, to profit from the study of organic chemistry. The power of organic chemistry comes from its ability to give insight into so many parts of our lives. How does penicillin work? Why is Teflon nonstick? Why does drinking a cup of coffee help me stay awake? How do plants defend themselves against herbivores? Why is ethyl alcohol a depressant? All these questions have answers based in organic chemistry. And the future will be filled with more organic chemistry—and more questions.What’s a buckyball or a nanotube, and how might it be important to my life? How might an organic superconductor be constructed? Why is something called the Michael reaction important in a potential cancer therapy? Read on, because this book will help you to deal with questions such as these, and many more we can’t even think up yet. What Is Organic Chemistry? Organic chemistry is traditionally described as the chemistry of carbon-containing compounds. Until the nineteenth century, it was thought that organic molecules were related in an immutable way to living things, hence the term “organic.”The idea that organic compounds could be made only from molecules derived from living things was widespread, and gave rise to the notion of a vital force being present in carbon-containing molecules. In 1828 Friedrich Wöhler (1800–1882) synthesized urea, a certified organic substance, from heating ammonium cyanate, a compound considered to be inorganic.1 Wöhler’s experiment xxxiii Introduction 1 Wöhler’s urea is an end product of the metabolism of proteins in mammals, and is a major component of human urine. An adult human excretes about 25 g (6–8 level teaspoons) of urea each day. The formation of urea is our way of getting rid of the detritus of protein breakdown through a series of enzymatic reactions. If you are missing one of the enzymes necessary to produce urea, it’s very bad news indeed, as coma and rapid death result