PREFACE .A new Something Extra,"Naturally Occurring Organohalides,"in Chap- ter 12 New coverage of epoxide cleavage by nucleophiles in section 13-10 .A new Section 13-11."Crown Ethers and Ionophores" .New coverage of hydrates of a-keto acids in Section 14-5 A new Something Extra,"Barbiturates,"in Chapter 17 .Threonine catabolism deleted from section 20-4 New coverage of Kiliani-Fischer carbohydrate chain extension and Wohl degradation in Section 21-6 .A new Section 23-7,"Prostaglandins and Other Eicosanoids A new Something Extra."Statin Drugs."in Chapter 23 .A new electronic Chapter 26."Orbitals and Organic Chemistry:Pericyclic Reactions' A new electronic Chapter 27,"Synthetic Polymers" I believe that there is more than enough standard organic chemistry in this book,and that the coverage of biological chemistry far surpasses that found in any other text.My hope is that all the students we teach,including those who worry about medical school,will come to agree that there is also logic and beauty here. Features Reaction Mechanisms The inno vertical pre entation of reaction mechanisms that has be with B om 14 Appli Mecha in this while the ta ep With this fo tep a ring at each s iandtetSeFige149otheiagto ton in a action without hav mp back d fo rth bet nica a biological example. example and Figure 22.8 fo Visualization of Biological Reactions t impor a goals of this book is to demystify biological stu ents how th ms o mhg as tho thi s en ore g reaction large biomole I use an ve n ocusing atte See Figur arge m Other Features ."Why do we have to learn this?"I've been asked this question by students so many times that I thought I should answer it in writing.Thus,every chapter begins with a short introduction called"Why This Chapter?"that provides an up-front answer to the question,explaining why the material about to be covered is important and how the organic chemistry in each chapter relates to biological chemistry
PrefaCe xxi • A new Something Extra, “Naturally Occurring Organohalides,” in Chapter 12 • New coverage of epoxide cleavage by nucleophiles in Section 13-10 • A new Section 13-11, “Crown Ethers and Ionophores” • New coverage of hydrates of a-keto acids in Section 14-5 • A new Something Extra, “Barbiturates,” in Chapter 17 • Threonine catabolism deleted from Section 20-4 • New coverage of Kiliani–Fischer carbohydrate chain extension and Wohl degradation in Section 21-6 • A new Section 23-7, “Prostaglandins and Other Eicosanoids” • A new Something Extra, “Statin Drugs,” in Chapter 23 • A new electronic Chapter 26, “Orbitals and Organic Chemistry: Pericyclic Reactions” • A new electronic Chapter 27, “Synthetic Polymers” I believe that there is more than enough standard organic chemistry in this book, and that the coverage of biological chemistry far surpasses that found in any other text. My hope is that all the students we teach, including those who worry about medical school, will come to agree that there is also logic and beauty here. c features reaction Mechanisms The innovative vertical presentation of reaction mechanisms that has become a hallmark of all my texts is retained in Organic Chemistry with Biological Applications, third edition. Mechanisms in this format have the reaction steps printed vertically, while the changes taking place in each step are explained next to the reaction arrows. With this format, students can see what is occurring at each step in a reaction without having to jump back and forth between structures and text. See Figure 14.4 for a chemical example and Figure 22.8 for a biological example. Visualization of Biological reactions One of the most important goals of this book is to demystify biological chemistry—to show students how the mechanisms of biological reactions are the same as those of laboratory organic reactions. Toward this end, and to let students visualize more easily the changes that occur during reactions of large biomolecules, I use an innovative method for focusing attention on the reacting parts in large molecules by “ghosting” the nonreacting parts. See Figure 13.4 for an example. other features • “Why do we have to learn this?” I’ve been asked this question by students so many times that I thought I should answer it in writing. Thus, every chapter begins with a short introduction called “Why This Chapter?” that provides an up-front answer to the question, explaining why the material about to be covered is important and how the organic chemistry in each chapter relates to biological chemistry. 42912_00_FM_i-xxiv.indd 21 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
PREFACE Worked Examples in each chapter are titled to give students a frame of reference.Each Worked Example includes a Strategy and worked-out Solution.followed by problems for students to try on their own. .a something extra is provided in each chapter following the final text epts to students'lives.New topics in this edition include Organic Foods:Risk versus Benefit(Chapter 1).Alkaloids: From Cocaine to Dental Anesthetics (Chapter 2).Naturally Occurring Organohalides(Chapter 12).Barbiturates(Chapter 17).and Statin Drugs (Chapter 23). .Visualizing Chemistry problems at the end of each chapter offe a to s nt focus on th山rhpdn邮 he Sur The Summary of Reactions at the end of specific chapters brings together the key reactions from those chapters into a single complete list An overview entitled"A Preview of Carbonyl Chemistry"following Chap- ter 13 highlights the idea that studying organic chemistry involves both summarizing past ideas and looking ahead to new ones. ognizing that thes Alternate Edition Hybrid version with access(24 months)to OWLv2 with MindTap Reader ISBN:978-1-285-86784-7 A briefer,paperbound version of Organic Chemistry with Biological Applica- tions,third edition,does not contain the end-of-chapter problems,which can be assigned in OWL,the online homework and learning system for this book Access to OWLv2 and MindTap Reader eBook is included with the Hybrid version.MindTap Reader is the full version of the text,with all end-of-chapter questions and problem sets. Supporting Materials for Students and Instructors Please visi t www.cengage.com/chemistry/mcmurry/ocba3e for information about student and instructor resources for this text Acknowledgments I thank all the peope who helped to shape this book and its message. A ndra Julie Schuster arketing Trego.content production manager:Lisa Web er,media editor Elizabeth Woods.content coordinator:Karolina Kiwak. duct assistant:maria ep art director:and Matt Rosenquist at Graphic World.Special thanks to Jordan Fantini of Denison University,who did an outstanding job in proofing all of the chapters in this text
• Worked Examples in each chapter are titled to give students a frame of reference. Each Worked Example includes a Strategy and worked-out Solution, followed by Problems for students to try on their own. • A Something Extra is provided in each chapter following the final text section to relate real-world concepts to students’ lives. New topics in this edition include Organic Foods: Risk versus Benefit (Chapter 1), Alkaloids: From Cocaine to Dental Anesthetics (Chapter 2), Naturally Occurring Organohalides (Chapter 12), Barbiturates (Chapter 17), and Statin Drugs (Chapter 23). • Visualizing Chemistry problems at the end of each chapter offer students an opportunity to see chemistry in a different way by visualizing whole molecules rather than simply interpreting structural formulas. • The Summary and Key Word list at the end of each chapter helps students focus on the key concepts in that chapter. • The Summary of Reactions at the end of specific chapters brings together the key reactions from those chapters into a single complete list. • An overview entitled “A Preview of Carbonyl Chemistry” following Chapter 13 highlights the idea that studying organic chemistry involves both summarizing past ideas and looking ahead to new ones. • Current IUPAC nomenclature rules are used in this text. Recognizing that these rules have not been universally adopted in the United States, the small differences between new and old rules are also discussed. c alternate edition Hybrid version with access (24 months) to oWlv2 with Mindtap reader isBn: 978-1-285-86784-7 A briefer, paperbound version of Organic Chemistry with Biological Applications, third edition, does not contain the end-of-chapter problems, which can be assigned in OWL, the online homework and learning system for this book. Access to OWLv2 and MindTap Reader eBook is included with the Hybrid version. MindTap Reader is the full version of the text, with all end-of-chapter questions and problem sets. c supporting Materials for students and instructors Please visit www.cengage.com/chemistry/mcmurry/ocba3e for information about student and instructor resources for this text. c acknowledgments I thank all the people who helped to shape this book and its message. At Cengage Learning they include Maureen Rosener, product manager; Sandra Kiselica, content developer; Julie Schuster, marketing manager; Teresa Trego, content production manager; Lisa Weber, media editor; Elizabeth Woods, content coordinator; Karolina Kiwak, product assistant; Maria Epes, art director; and Matt Rosenquist at Graphic World. Special thanks to Jordan Fantini of Denison University, who did an outstanding job in proofing all of the chapters in this text. xxii PrefaCe 42912_00_FM_i-xxiv.indd 22 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
PREFACE Iam grateful to the following colleagues who reviewed the manuscript for REVIEWERS OF THE THIRD EDITION Peter Bell,Tarleton State University Andrew Frazer.University of Central Florida Lee Friedman.University of Maryland-College Park Tom Gardner,Gustavus Adolphus College Bobbie Grey,Riverside City College Susan Klein,Manchester College William Lavel Camden County College Jason Locklin.University of Georgia 8 ath Coll Linfeng Xie University of Wisconsin-Oshkosh REVIEWERS OF PREVIOUS EDITIONS Peter Alaimo,Seattle University Rizalia Klausmever,Baylor Manfred Reinecke,Texas Christian Helen E.Blackwell,University of University Wisconsin Bette Kreuz.University of Michigan- Frank Rossi,State University of New Dearborn 10r Thomas Lectka,Johns Hopkins Miriam Rossi, Vassar College ihade,Carl Paul Sampson,Kent State University S.C Paul Martind Flathead Valley K.Barbara Schowen,University of gene Maslak ersity of Ariz nelhack,Princeton ohn Hoberg.University of Texas A&M University Kevin Minbiole,James Madison rsity of Eric Kantor ski Californig Unive Alabama-Huntsville Polytechnic State University Andrew Morehead,East Carolina Kevin Kittredge,Siena College University
PrefaCe xxiii Peter Bell, Tarleton State University Andrew Frazer, University of Central Florida Lee Friedman, University of Maryland–College Park Tom Gardner, Gustavus Adolphus College Bobbie Grey, Riverside City College Susan Klein, Manchester College William Lavell, Camden County College Jason Locklin, University of Georgia Barbara Mayer, California State University–Fresno James Miranda, Sacramento State University Gabriela Smeureanu, Hunter College Catherine Welder, Dartmouth College Linfeng Xie, University of Wisconsin–Oshkosh Peter Alaimo, Seattle University Helen E. Blackwell, University of Wisconsin Sheila Browne, Mount Holyoke College Joseph Chihade, Carleton College Robert S. Coleman, Ohio State University Gordon Gribble, Dartmouth College John Grunwell, Miami University John Hoberg, University of Wyoming Eric Kantorowski, California Polytechnic State University Kevin Kittredge, Siena College Rizalia Klausmeyer, Baylor University Bette Kreuz, University of Michigan– Dearborn Thomas Lectka, Johns Hopkins University Paul Martino, Flathead Valley Community College Eugene Mash, University of Arizona Pshemak Maslak, Pennsylvania State University Kevin Minbiole, James Madison University Andrew Morehead, East Carolina University Manfred Reinecke, Texas Christian University Frank Rossi, State University of New York–Cortland Miriam Rossi, Vassar College Paul Sampson, Kent State University K. Barbara Schowen, University of Kansas Martin Semmelhack, Princeton University Megan Tichy, Texas A&M University Bernhard Vogler, University of Alabama–Huntsville r e V i e W e r s o f t H e t H i r D e D i t i o n r e V i e W e r s o f P r e V i o U s e D i t i o n s I am grateful to the following colleagues who reviewed the manuscript for this book. 42912_00_FM_i-xxiv.indd 23 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
All author royalties from this book are being donated to the Cystic Fibrosis Foundation
All author royalties from this book are being donated to the Cystic Fibrosis Foundation. 42912_00_FM_i-xxiv.indd 24 1/16/14 3:00 PM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it
Structure and Bonding CONTENTS Atomic Structure The Nudeus Atomic Structure:Orbitals Atomic Structure:Electro Confieurations neory 17 and the A model of the enzyme HMG-CoA reductase. 18 which catalyzes a crucial step in the 19 of cholesterol. 110 WHY THIS Sulfur CHAPTER? n this call atoms and ly to be fa stry next to you bu ss a good to make sure you understand it before going on. 12 A scientific afer and m taking nedicines tic dis life spans, es.The revolution is based in understanding the st and function of the a 21.000 genes in the human bod dv.and it relies on chemical understanding of biological orocesses at the molecular level that has made the revolution nossible and that continues to drive it anvone who wants to understand or be a part of the remarkable advances now occurring in medicine and the biological sciences must first understand organic chemistrv. As an example of how organic and biological chemistry together are affecting modern medicine,look at coronary heart disease-the buildup of cholesterol-containing plaques on the walls of arteries,leading to restricted blood flow and eventual heart attack.Coronary heart disease is the leading r both mon and women oider than age 20.and t's estmated -third of women and one-half of men will develop the disease ndheart dis their lives. on ease is directly CO on t only about 25% four blo stero m dietary fats and made Unlessothenvse notedall content on this page isCenoage Leaming
1 1 C O N T E N T S 1-1 Atomic Structure: The Nucleus 1-2 Atomic Structure: Orbitals 1-3 Atomic Structure: Electron Configurations 1-4 Development of Chemical Bonding Theory 1-5 Describing Chemical Bonds: Valence Bond Theory 1-6 sp3 Hybrid Orbitals and the Structure of Methane 1-7 sp3 Hybrid Orbitals and the Structure of Ethane 1-8 sp2 Hybrid Orbitals and the Structure of Ethylene 1-9 sp Hybrid Orbitals and the Structure of Acetylene 1-10 Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur 1-11 Describing Chemical Bonds: Molecular Orbital Theory 1-12 Drawing Chemical Structures Something extra Organic Foods: Risk versus Benefit Structure and Bonding Why thiS ChaPter? We’ll ease into the study of organic chemistry by first reviewing some ideas about atoms, bonds, and molecular geometry that you may recall from your general chemistry course. Much of the material in this chapter and the next is likely to be familiar to you, but it’s nevertheless a good idea to make sure you understand it before going on. A scientific revolution is now taking place—a revolution that will give us safer and more effective medicines, cure our genetic diseases, increase our life spans, and improve the quality of our lives. The revolution is based in understanding the structure, regulation, and function of the approximately 21,000 genes in the human body, and it relies on organic chemistry as the enabling science. It is our fundamental chemical understanding of biological processes at the molecular level that has made the revolution possible and that continues to drive it. Anyone who wants to understand or be a part of the remarkable advances now occurring in medicine and the biological sciences must first understand organic chemistry. As an example of how organic and biological chemistry together are affecting modern medicine, look at coronary heart disease—the buildup of cholesterol-containing plaques on the walls of arteries, leading to restricted blood flow and eventual heart attack. Coronary heart disease is the leading cause of death for both men and women older than age 20, and it’s estimated that up to one-third of women and one-half of men will develop the disease at some point in their lives. The onset of coronary heart disease is directly correlated with blood cholesterol levels, and the first step in disease prevention is to lower those levels. It turns out that only about 25% of our blood cholesterol comes from what we eat; the remaining 75% (about 1000 mg each day) is made, or biosynthesized, by our bodies from dietary fats and carbohydrates. Thus, any effective plan for A model of the enzyme HMG-CoA reductase, which catalyzes a crucial step in the body’s synthesis of cholesterol. Unless otherwise noted, all content on this page is © Cengage Learning. 42912_01_Ch01_0001-0027h.indd 1 1/10/14 11:40 AM Copyright 2015 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it