xxxii Preface ACKNOWLEDGMENTS apter p ity while ad Dennison niversity.who arof alenc ollho checked vern ofo foraccPavid Y M.D.orhisthe for errors.and The following reviewers have played an enormously important role in the development of this book. Eighth Edition Contributors Benjamin W.Gung.Miami Unive Donna K.Howell,Park Universiry Eighth Edition Accuracy Reviewers Tim Humphry.Gonz David Boyajian,Palomar College Gayane Godjoian,Los Angeles Mission College Delbert Howard Miles.Universirof Central Florid Laura B.Sessions,Valencia College Richard J.Mullins,Xavier University Eighth Edition Reviewers Thomas Bertolini,University of Southern Califomia i证 Adam Braunschweig.Universiry of Miami Michael Pollastri.Northeaster Universiry Santos vir Steve Samuel.SUNY Old Westbury lacob d schroeder clemson universitv Susan Schelble,Metropolitan State Universiry Edward B.Skibo,Arizona State University Seventh Edition Reviewers ason P.Anderson,Monroe Communiry College rtheastern University Seventh Edition Accuracy Reviewers ordan fantini deni Daniel Blanchard,Kutztown Universiry Malcolm D.E.Forbes,University of North Carolina Ned Bowden,Universiry of lowa Stephen Miller.University of Florida Many people made this book possible,but at the top of the list is my editor,Jeanne Zalesky.who has been involved and supportive at every stage of its creation and whose many talents guided the dce.Ierml teful to have had the opportyo o how today' made the book actually happen.And I want to thank the other talented and dedicated people at Pearson whose contributions made this book a reality: the many wond To make this textbook as user friendly as possible,I would appreciate any comments that will help me achieve this goal in future editions.If you find sections that could be clarified or expanded Paula Yurkanis Bruice University of California.Santa Barbara pybruice @chem.ucsb.edu
xxxii Preface Eighth Edition Contributors Richard Morrison, University of Georgia Jordan Fantini, Denison University Eighth Edition Accuracy Reviewers David Boyajian, Palomar College Gayane Godjoian, Los Angeles Mission College Laura B. Sessions, Valencia College Eighth Edition Reviewers Ardeshir Azadnia, Michigan State University Christopher Beaudry, Oregon State University Thomas Bertolini, University of Southern California Adam Braunschweig, University of Miami Alexei Demchenko, University of Missouri–St. Louis Christina DeMeo, Southern Illinois University Steve Samuel, SUNY Old Westbury Susan Schelble, Metropolitan State University Seventh Edition Reviewers Jason P. Anderson, Monroe Community College Gabriele Backes, Portland Community College Michael A. G. Berg, Virginia Tech Thomas Bertolini, University of Southern California Daniel Blanchard, Kutztown University Ned Bowden, University of Iowa Nancy Christensen, Waubonsee Community College Veronica Curtin-Palmer, Northeastern University Benjamin W. Gung, Miami University—Oxford Ohio Matthew E. Hart, Grand Valley State University Donna K. Howell, Park University Tim Humphry, Gonzaga University Frederick A. Luzzio, University of Louisville Robert C. Mebane, University of Tennessee—Chattanooga Delbert Howard Miles, University of Central Florida Richard J. Mullins, Xavier University Feliz Ngasse, Grand Valley State University Anne B. Padias, University of Arizona Matt A. Peterson, Brigham Young University Christine Ann Prius, Arizona State University Michael Pollastri, Northeastern University Michael Rathke, Michigan State University Harold R. Rodgers, California State University Fullerton Webster Santos, Virginia Tech Jacob D. Schroeder, Clemson University Edward B. Skibo, Arizona State University David Spivak, Louisiana State University Zhaohui Sunny Zhou, Northeastern University Seventh Edition Accuracy Reviewers Jordan Fantini, Denison University Malcolm D.E. Forbes, University of North Carolina Stephen Miller, University of Florida Christopher Roy, Duke University Chad Snyder, Western Kentucky University The following reviewers have played an enormously important role in the development of this book. ACKNOWLEDGMENTS It gives me great pleasure to acknowledge the dedicated efforts of many good friends who made this book a reality. In particular, a loud thanks goes to Richard Morrison of the University of Georgia, who read every page, made critically important suggestions, checked every answer in the Solutions Manual, and created many new end-of-chapter problems—and to Jordan Fantini of Dennison University, who created the interactive digital modules designed to engage students in the fundamental principles of reactivity while advancing their visualization skills. I am also deeply grateful to Laura Sessions of Valencia College who checked every inch of the book for accuracy; David Yerzley, M.D., for his assistance with the section on MRI; Warren Hehre of Wavefunction, Inc., and Alan Shusterman of Reed College for their advice on the electrostatic potential maps; and to my student, Jeremy Davis, who created the dog cartoons that appear on page 144. I also thank my many students, who pointed out sections that needed clarification, searched for errors, and whose questions guided the creation of new problems. Many people made this book possible, but at the top of the list is my editor, Jeanne Zalesky, who has been involved and supportive at every stage of its creation and whose many talents guided the book to make it as good as it could be. I am also extremely grateful to have had the opportunity to work with Matt Walker, the development editor. His insights into how today’s students learn and his creative art development skills have had a huge effect on this edition. I am also grateful to Elisa Mandelbaum, the project editor, whose attention to detail and creation of manageable deadlines made the book actually happen. And I want to thank the other talented and dedicated people at Pearson whose contributions made this book a reality: I particularly want to thank the many wonderful and talented students I have had over the years, who inspired me, challenged me, and who taught me how to be a teacher. And I want to thank my children, from whom I may have learned the most. To make this textbook as user friendly as possible, I would appreciate any comments that will help me achieve this goal in future editions. If you find sections that could be clarified or expanded, or examples that could be added, please let me know. Finally, this edition has been painstakingly combed for typographical errors. Any that remain are my responsibility. If you find any, please send me a quick email so they can be corrected in future printings of this edition. Paula Yurkanis Bruice University of California, Santa Barbara pybruice@chem.ucsb.edu
About the Author Paula Bruice with Zeus,Bacchus,andAbigai Paula Yurkanis Bruice was raised primarily in Massachusetts.After graduating from the Girls Latin School in Boston,she earned an A.B.from Mount Holyoke Colles and a PhD.in chemistry from the University of Virginia.She then received an NIH postdoctoral fellowship for study in the parment of Biochemistry at the University ofrgnl hnd a posidoctor ain the p a Barbara since aula has beensiy of Califomes SB Alumni A sociation Teaching Awar and biographies and enjoying her pets(three dogs,two cats.and two parrots). xxxiii
xxxiii About the Author Paula Yurkanis Bruice was raised primarily in Massachusetts. After graduating from the Girls’ Latin School in Boston, she earned an A.B. from Mount Holyoke College and a Ph.D. in chemistry from the University of Virginia. She then received an NIH postdoctoral fellowship for study in the Department of Biochemistry at the University of Virginia Medical School and held a postdoctoral appointment in the Department of Pharmacology at the Yale School of Medicine. Paula has been a member of the faculty at the University of California, Santa Barbara since 1972, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, two Mortar Board Professor of the Year Awards, and the UCSB Alumni Association Teaching Award. Her research interests center on the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading mysteries and biographies and enjoying her pets (three dogs, two cats, and two parrots). Paula Bruice with Zeus, Bacchus, and Abigail
Organic Chemistry
Organic Chemistry
PART An Introduction to the ONE Study of Organic Chemistry Chapter 1 Remembering General Chemistry:Electronic Structure and Bonding Chapter 1 reviews the topics description of the structure of molecules.Molecular orbital theory is introduced. Chapter 2 Acids and Bases:Central to Understanding Organic Chemistry Chapter 2 discusses acid-base chemistry,a topic that is central to understanding many organic reactions.You will see how the structure of a molecule affects its acidity and how the acidity of a solution affects molecular structure. Chapter 3 An Introduction to Organic Compounds: Nomenclature,Physical Properties,and Representation of Structure To discuss organic compounds,you must know how to name them and be able to visualize their structures when you read or hear their names.In Chapter 3,you will learn how to name five differ Chapter3 also compares and contrasts the structures and physical properties of these compounds which makes learning about them a little easier than if the structure and physical properties of each
CH3CH2NH2 CH3CH2Br CH3OCH3 CH3CH2Cl CH3CH2OH An Introduction to the Study of Organic Chemistry The first three chapters of this textbook cover a variety of topics with which you need to be familiar to start your study of the reactions and synthesis of organic compounds. Chapter 1 Remembering General Chemistry: Electronic Structure and Bonding Chapter 1 reviews the topics from general chemistry that are important to your study of organic chemistry. The chapter starts with a description of the structure of atoms and then proceeds to a description of the structure of molecules. Molecular orbital theory is introduced. Chapter 2 Acids and Bases: Central to Understanding Organic Chemistry Chapter 2 discusses acid–base chemistry, a topic that is central to understanding many organic reactions. You will see how the structure of a molecule affects its acidity and how the acidity of a solution affects molecular structure. Chapter 3 An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure To discuss organic compounds, you must know how to name them and be able to visualize their structures when you read or hear their names. In Chapter 3, you will learn how to name five different families of organic compounds. This will give you a good understanding of the basic rules for naming compounds. Because the compounds examined in the chapter are the reactants or the products of many of the reactions presented in the first third of the book, you will have numerous opportunities to review the nomenclature of these compounds as you proceed through these chapters. Chapter 3 also compares and contrasts the structures and physical properties of these compounds, which makes learning about them a little easier than if the structure and physical properties of each family were presented separately. Because organic chemistry is a study of compounds that contain carbon, the last part of Chapter 3 discusses the spatial arrangement of the atoms in both chains and rings of carbon atoms. PART ONE
Remembering General Chemistry: Electronic Structure and Bonding staylive.early humansut have been ableodistin betweedferentnds of in their world."You can live on roots and berries,"they might have said,"but you can't eat dirt.You bu NOTETOTHE STUDENT can stay warm by buing ree branches.but you cn rocks ned the nat and in 1807.Jons Jakob ounds derived from living organisms were believed to contain an immeasurable vital force-the essence of life. These he called"organic."Compounds derived from minerals-those lacking the vital force-were inorganic in 1828 Wohler produced urea a compound excreted by mammals by heating ammonium cyanate.an inorganic mineral. NH.OCN heat amn NH, For the first time,an"organic compound had obtained from something other than a liv 0oampocl6asornatbbadonearbon on carbon. Why is an entire branch of chemistry devoted to the study of carbon-containing compounds? npounds that make 2
2 1 Remembering General Chemistry: Electronic Structure and Bonding To stay alive, early humans must have been able to distinguish between different kinds of materials in their world. “You can live on roots and berries,” they might have said, “but you can’t eat dirt. You can stay warm by burning tree branches, but you can’t burn rocks.” By the early eighteenth century, scientists thought they had grasped the nature of that difference, and in 1807, Jöns Jakob Berzelius gave names to the two kinds of materials. Compounds derived from living organisms were believed to contain an immeasurable vital force—the essence of life. These he called “organic.” Compounds derived from minerals—those lacking the vital force—were “inorganic.” Because chemists could not create life in the laboratory, they assumed they could not create compounds that have a vital force. You can imagine their surprise when, in 1828, Friedrich Wöhler produced urea—a compound excreted by mammals—by heating ammonium cyanate, an inorganic mineral. C NH2 O heat NH4 OCN ammonium cyanate inorganic mineral H2N urea ”organic“ compound + − For the first time, an “organic” compound had been obtained from something other than a living organism and, therefore, did not contain a vital force. Thus, chemists needed a new definition for “organic compounds.” Organic compounds are now defined as compounds that are based on carbon. Why is an entire branch of chemistry devoted to the study of carbon-containing compounds? We study organic chemistry because just about all of the compounds that make life possible and that make us who we are—proteins, enzymes, vitamins, lipids, carbohydrates, DNA, RNA—are organic compounds. Thus, the chemical reactions that take place in living systems, including our NOTE TO THE STUDENT • Biographies of the scientists mentioned in this text book can be found on the book’s Website. Organic compounds are compounds that are based on carbon