Preface make iteasier for students to identify difficutograsp material by referring them to the section of t ding then with en f-chapte totetandreitntorce ered in each chapter.These include prose descriptions of mechanisms as well as im- bee tep sy proidudenqilufmtnaion heir a thorough"Summary of Stereochemical Terms"(Appendix ).Stereochemical terms are subtle and ifficult to master,so chapters,as we orovides a practical listing of the nomenclature rules described throughout the text.In esponse to student requests,this appendix provides a single location for the rules stu- dents need when naming complex molecules that contain multiple functional groups. UNIQUE ORGANIZATIONAL ELEMENTS o Together.Chapter 1(comprehensive description of electronic theory)and Chapter 4(detailed description of acids and bases in organic chemistry)provide a fundamental grasp ofm cular structure and propertie pects of the mechani ving students the basis to Whdertanda ons tha qupping stu erficial memorization cal of the in sed use of NMR spectre ss the for medical diag Chapter 13,"Nuclear Magnetic Resonance Spectroscopy,"is detailed and up to date The practical and theoretical aspects concerning NM es a stronge Carbonyl chemistry (Chap aced earlier than in most texts so that professors ave tme to tea Is mat nts i abon cemistry is fundamental to the chemistry of livin svstems and connections between carbonyl chemistry and the chemistry of carbohydrates is high- ighted earlier in the book.This latter change mirrors the increasing importance of car ohydrate chemistry on the MCAT ●Chapter24,"Catal ytic Carbor -Carbon Bond Formation,"combines content from previ ters and cha chaes stude intent is to expose students enge of m de WHAT'S NEW In this edition.we made maior chan to rovide a better theoretical understanding o Two new primer sections were added to better as opposed to simply memorize,reaction mechanisms.The first,"Primer I:Reaction Mechanisms,"added prior to Chapter 6,introduces the concept of fundamental mechanis ments and explal s how to predict which me element f consi differences between different reactions,and perhaps more important,leads students to an intuitive understanding of how molecules react. xxvi Unless oth se noted all art on this pageCengage Learning 2013
Unless otherwise noted all art on this page © Cengage Learning 2013 Preface xxvi make it easier for students to identify difficult-to-grasp material by referring them to the section of the text for a full explanation and then providing them with end-of-chapter problems that test and reinforce their comprehension. As a companion to the summary outlines, end-of-chapter summaries of key reactions systematically list the reactions covered in each chapter. These include prose descriptions of mechanisms as well as important information such as observed stereochemistry or regiochemistry. Students will find these reaction summaries particularly efficient when preparing for exam questions requiring application of reactions in the context of new molecules or even multistep syntheses. The appendix reference material has been enhanced with two unique items to provide students with a quickly accessible source of important information. The first is a thorough “Summary of Stereochemical Terms” (Appendix 8). Stereochemical terms are subtle and difficult to master, so having them compiled in one location allows students to compare and contrast any new terms with those learned in earlier chapters, as well as prepare for exams. In addition, Appendix 9, “Summary of the Rules of Nomenclature,” provides a practical listing of the nomenclature rules described throughout the text. In response to student requests, this appendix provides a single location for the rules students need when naming complex molecules that contain multiple functional groups. unIQuE orgAnIzATIonAL ELEMEnTS ● Together, Chapter 1 (comprehensive description of electronic theory) and Chapter 4 (detailed description of acids and bases in organic chemistry) provide a fundamental grasp of molecular structure and properties, giving students the basis to understand all aspects of the mechanistic discussions that follow. Equipping students with the proper tools from the beginning will give them a predictive command of reactivity and foster chemical intuition, while discouraging superficial memorization. ● Because of the increased use of NMR spectroscopy in chemical and biochemical research, as well as the growing dependence on MRI for medical diagnosis, Chapter 13, “Nuclear Magnetic Resonance Spectroscopy,” is detailed and up to date. The practical and theoretical aspects concerning NMR spectra and signal splitting patterns are highlighted, and a complete description of FT-NMR provides a stronger technical connection to MRI. ● Carbonyl chemistry (Chapters 16–19) is placed earlier than in most texts so that professors have time to teach this material to the majority of students in an organic chemistry class, who are geared toward a life science degree and/or career in the health professions. Carbonyl chemistry is fundamental to the chemistry of living systems, and connections between carbonyl chemistry and the chemistry of carbohydrates is highlighted earlier in the book. This latter change mirrors the increasing importance of carbohydrate chemistry on the MCAT. ● Chapter 24, “Catalytic Carbon-Carbon Bond Formation,” combines content from previous chapters and challenges students to devise syntheses. The intent is to expose students to the excitement and challenge of modern synthetic chemistry. WHAT’S nEW In this edition, we made major changes to provide a better theoretical understanding of organic chemistry as well as to provide better tools to prepare for exams. ● Two new primer sections were added to better prepare students to understand, as opposed to simply memorize, reaction mechanisms. The first, “Primer I: Reaction Mechanisms,” added prior to Chapter 6, introduces the concept of fundamental mechanistic elements and explains how to predict which mechanistic element is appropriate for a given step in the reaction mechanism being considered. This revolutionary approach promotes student understanding of the similarities and differences between different reactions, and perhaps more important, leads students to an intuitive understanding of how molecules react. Copyright 2013 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
."Primer II,Carboxylic Acid Derivative Reaction Mechanisms"was added just Preface prior to Chapter 18,the chapter describing the reactions of carboxylic acid deriva- c的choper tor duseocan0 have numerous steps w ces among mechanistic element approach in front of this chapter,students are given the ap- propriate foundation to develop an intuitive understanding of carboxylic acid de- rivative mechanisms .Acknowledging that a significant number of students take organic chemistry d exan MCAT,this new edition nving multinle choice auestions in almost euer chanter A nificant portion of the organic chemistry section of the MCAT involves passages about intentionally new ma- terial that is related to concepts with which students should be familiar,followed by a seiesofnmipechoicequestionsntendeint stu ents reading compreh the material pre etednhechaptesbutasOpoideshdenseWhRee prehension and analytical skills they need to do well in the organic chemistry passages sections of the mCaT exam. o Organic chemistry reaction roadmaps were completely redrawn and highly refined in this edition.This innovation in organic chemistry learning gives students a visual representation of the iegentamlpomomnnhetcmehotkweaeaded.indiading Swern, ons SPECIAL FEATURES for lea od in "prin throughout the hook New The new mechanis for laar is reviewed and applied to the mechanisms for carboxylic acid derivatives in a sec- ond all-new "Primer II,Carboxylic Acid Derivative Reaction Mechanisms"just prior to Chapter 18. New Several more modern synthetic methods were added,such as the Swern, Dess-Martin,and Pinnick oxidations. .New MCAT Practice:Passage and Questions are incorporated into almost ev- ese new passages an of the d questions not only introduce interesting ap- mater I pre apters but hey ne Updated Organic Chemistry Reaction Roa maps were completely redra wn t chemistrY roadmaps are presented in nd in the designed appendix 11 tear-out o Updated accurate orbital diagra ms were added throughout the text to pro vide students with a more realistic understanding of electronic theory as applied to organic chemistry. Updated Chemical Connections These essays illustrate applications of organic chemistry to everyday settings.Topics range from Chiral Drugs to Drugs That Lower ound or K cover Unless otherwise noted all art on this page Cengage Leaming 2013 xxvii
Unless otherwise noted all art on this page © Cengage Learning 2013 Preface xxvii ● “Primer II, Carboxylic Acid Derivative Reaction Mechanisms” was added just prior to Chapter 18, the chapter describing the reactions of carboxylic acid derivatives. This is a critical chapter for students because the reaction mechanisms of carboxylic acids have numerous steps with only subtle differences among them. Students who approach mechanisms by trying to memorize them generally do very poorly with this material. On the other hand, by reintroducing the unifying mechanistic element approach in front of this chapter, students are given the appropriate foundation to develop an intuitive understanding of carboxylic acid derivative mechanisms. ● Acknowledging that a significant number of students take organic chemistry courses as preparation for standardized exams such as the MCAT, this new edition is the first and only text on the market to contain MCAT-style passages and accompanying multiple-choice questions in almost every chapter. A significant portion of the organic chemistry section of the MCAT involves passages about intentionally new material that is related to concepts with which students should be familiar, followed by a series of multiple-choice questions intended to test students’ reading comprehension and analytical skills. These new passages not only introduce interesting applications of the material presented in the chapters but also provide students with the reading comprehension and analytical skills they need to do well in the organic chemistry passages sections of the MCAT exam. ● Organic chemistry reaction roadmaps were completely redrawn and highly refined in this edition. This innovation in organic chemistry learning gives students a visual representation of the different reactions and shows how these roadmaps can be used in specific sequences for the multistep synthesis of complex molecules. ● The description of several more modern synthetic methods were added, including the Swern, Dess-Martin, and Pinnick oxidations. SPECIAL FEATurES ● New A revolutionary new paradigm for learning organic chemistry mechanisms is introduced in “Primer I: Reaction Mechanisms” just prior to Chapter 6 and then used throughout the book. ● New The new mechanism paradigm for learning organic chemistry mechanisms is reviewed and applied to the mechanisms for carboxylic acid derivatives in a second all-new “Primer II, Carboxylic Acid Derivative Reaction Mechanisms” just prior to Chapter 18. ● New Several more modern synthetic methods were added, such as the Swern, Dess-Martin, and Pinnick oxidations. ● New MCAT Practice: Passage and Questions are incorporated into almost every chapter. These new passages and questions not only introduce interesting applications of the material presented in the chapters but also provide students with the reading comprehension and analytical skills they need to do well in the organic chemistry passages sections of the MCAT exam. ● Updated Organic Chemistry Reaction Roadmaps were completely redrawn to make them even more useful as an innovation in learning organic chemistry. Organic chemistry roadmaps are presented in end-of-chapter problems and in the newly designed Appendix 11 tear-out. ● Updated Accurate Orbital Diagrams were added throughout the text to provide students with a more realistic understanding of electronic theory as applied to organic chemistry. ● Updated Chemical Connections These essays illustrate applications of organic chemistry to everyday settings. Topics range from Chiral Drugs to Drugs That Lower Plasma Levels of Cholesterol and The Chemistry of Superglue. A complete list can be found on the inside back cover. Copyright 2013 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 .Updated Connections to Biological Chemistry Application of organic chem- text in the Conne ons to Biologica n end- ac in biological oxidation-reduction reactions. n How To features of ke new to this edition o Updated in-Chapter Examples There are an abundance of in-chapter examples each with a detailed solution,so that students can immediately see how the con- cpstiphapter Problem degnd toentth le is a comparab opport Updated End-of-Chapter Summaries highlight,in outline Iof the m well as to the roblems de cha ed End-of-Chapter Sun aries of Key R eacti s list the d End-o -Chapter Proble ms Th e p s a prob. plied,real-world problem.There are numerous multistep synthesis problems,man and Keacti Updated Glossary of Key Terms Throughout the book,definitions for new n addit on,all definitions ossary at the e he text and keyed re tn dated P ecise s are students with a resource they can refer to often as they 。Updated A Uniq appe all the rules e text governing complex molecules arrow pushing is emphasized and students are encourag ed to avoid common mistakes Updated Full-color At p st distinctive feat s of thi text is its visual impact.The text'sexoe ram includes a large number of molecular models generated with a three-dimer ●Updated Electrost tatic Potential Maps are provided at appropriate places throughout th xt to illustrate the important concepts of resonance,electrophilicity, SUPPORTING MATERIALS Please visit www.cengage.com/chemistry/brown/organic7e for information about student and instructor resources for this text. ▣
Unless otherwise noted all art on this page © Cengage Learning 2013 Preface xxviii ● Updated Connections to Biological Chemistry Application of organic chemistry to biology is emphasized throughout the text in the Connections to Biological Chemistry essays and in end-of-chapter problems. See the inside back cover for a complete list. New essays include pyridoxine (vitamin B6) and electron transfer agents in biological oxidation-reduction reactions. ● Updated Fifteen How To features of key tools and topics are included. These describe “survival skills” for the organic chemistry student. Five How To boxes are new to this edition. ● Updated In-Chapter Examples There are an abundance of in-chapter examples, each with a detailed solution, so that students can immediately see how the concepts just discussed relate to specific questions and their answers. Following each inchapter example is a comparable in-chapter problem designed to give students the opportunity to solve a related problem on their own. ● Updated End-of-Chapter Summaries highlight, in outline form, all of the important ideas of the chapter. Each concept is keyed to the section in the chapter that provides a full explanation, as well as to the problems that reinforce understanding. ● Updated End-of-Chapter Summaries of Key Reactions list the reactions described in the chapter, complete with a prose description of the mechanism and important considerations such as stereochemistry and regiochemistry. ● Updated End-of-Chapter Problems There are plentiful end-of-chapter problems, with the majority categorized by topic. A red problem number indicates an applied, real-world problem. There are numerous multistep synthesis problems, many dealing with the synthesis of important pharmaceuticals, and Reactions in Context problems dealing with functional group transformations of more complex molecules. ● Updated Glossary of Key Terms Throughout the book, definitions for new terms are placed in the margin for easy reference. In addition, all definitions are collected in a handy glossary at the end of the text and keyed to the section where the term is introduced. ● Updated Precise Stereochemical Definitions are compiled in a unique appendix. A comprehensive listing of stereochemical terms in a single collection provides students with a resource they can refer to often as they encounter new terms. ● Updated A Unique Nomenclature Appendix This appendix provides a comprehensive listing of all the rules introduced in the text governing nomenclature of complex molecules. ● Updated A Unique Arrow Pushing Appendix In this appendix, the correct use of arrow pushing is emphasized and students are encouraged to avoid common mistakes. ● Updated Full-Color Art Program One of the most distinctive features of this text is its visual impact. The text’s extensive full-color art program includes a large number of molecular models generated with a three-dimensional look, as well as applied photos. In addition, special colors are used to highlight parts of molecules and to follow the course of reactions. ● Updated Electrostatic Potential Maps are provided at appropriate places throughout the text to illustrate the important concepts of resonance, electrophilicity, and nucleophilicity. SuPPorTIng MATErIALS Please visit www.cengage.com/chemistry/brown/organic7e for information about student and instructor resources for this text. Copyright 2013 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
Acknowledgments the many. Chri ext as acquisitions editor has masterfully guided the revision of the beeaocKotpportn5deeopmea nd so ap ostant as we worked to meet those deadlines.Others at the Cen- gage Learning organization have helped to shape our words into this text,includ- ing leresa r e 0.u an Ea of Denison for this book with an eve for accuracy. he page pro We are also indebted to the many reviewers of our manuscript who helped shape Seventh Edition Philip Albiniak Ball State University Andrew Fraze University of Central Florida Katie Hailer MontanaTech Eric Helms State University of New York College at Geneseo Patrick Jokie The Cllege of New Jersey Steven Kass University of Minnesota Susan Klein Manchester College Thuy Le The College of New Jersey Deborah Lieberman University of Cincinnati Barbara Mayer California State University,Fresno Donna nelson University of Oklahoma Hasan palandoken California Polytechnic State University Lucas Tucker Siena College Sixth Edition 2 University of Houston Indiana University Valerie ashby University of North Carolina B.Mikael Bergdahl San Diego State University Robert Boikess Rutgers University Jean Chmielewski Purdue University Elizabeth Harbron The College of William and Mary Unless otherwise noted all art on this page Cengage Leaming 2013 xxix
Unless otherwise noted all art on this page © Cengage Learning 2013 xxix This book is the product of collaboration of many individuals—some obvious, others not so obvious. It is with gratitude that we herein acknowledge the contributions of the many. Chris Simpson as acquisitions editor has masterfully guided the revision of the text. Sandi Kiselica has been a rock of support as developmental editor. We so appreciate her ability to set challenging but manageable schedules for us and then her constant encouragement as we worked to meet those deadlines. Others at the Cengage Learning organization have helped to shape our words into this text, including Teresa Trego, content project manager; Maria Epes, art director; and Lisa Weber, media editor. Erin Donahue of PreMediaGlobal served as our production editor. Also, many thanks to Jordan Fantini of Denison University, who read all of the page proofs for this book with an eye for accuracy. We are also indebted to the many reviewers of our manuscript who helped shape its contents. With their guidance, we have revised this text to better meet the needs of our and their students. Seventh Edition Philip Albiniak Ball State University Andrew Frazer University of Central Florida Katie Hailer Montana Tech Eric Helms State University of New York College at Geneseo Patrick Jokiel The College of New Jersey Steven Kass University of Minnesota Susan Klein Manchester College Thuy Le The College of New Jersey Deborah Lieberman University of Cincinnati Barbara Mayer California State University, Fresno Donna Nelson University of Oklahoma Hasan Palandoken California Polytechnic State University Lucas Tucker Siena College Sixth Edition Thomas Albright University of Houston Zachary D. Aron Indiana University Valerie Ashby University of North Carolina B. Mikael Bergdahl San Diego State University Robert Boikess Rutgers University Jean Chmielewski Purdue University Elizabeth Harbron The College of William and Mary Acknowledgments Copyright 2013 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
Acknowledgments Arif Karim University of California,Los Angeles Susan King University of California,Irvine Mark Linton Purdue University Allan Pinhas University of Cincinnati Owen Priest Northwestem University Jonathan Stoddard California state University.Fullerton Fifth Edition Jon Antilla University of Southern Florida Christopher Bielawski University of Texas Alan Campion University of Texas David Cartrette South Dakota State University H.J.Peter de Lijser Califomia State University,Fullerton Malcolm Forbes University of North carolina John Grutzne Purdue University Robert C.Kerber SUNY,Stony Brook Spencer Knapp Rutgers University University of North Carolina University of Cincinnati James Mack University of Cincinnati Felix Ngassa Grand Valley State University Milton Orchin University of Cincinnati Allan Pinhas University of Cincinna Suzanne Ruder Virginia Commonwealth University Laurie Starkey Califoria State Polytechnic University Pomona Oian Wang University of South Carolina Alexander Wei Purdue University Laurie Witucki Grand Valley State University Lei Zhu Florida State University XXX nless otherwise noted all art on this pageCengage Learning 2013
Unless otherwise noted all art on this page © Cengage Learning 2013 Acknowledgments xxx Arif Karim University of California, Los Angeles Susan King University of California, Irvine Mark Lipton Purdue University Allan Pinhas University of Cincinnati Owen Priest Northwestern University Jonathan Stoddard California State University, Fullerton Fifth Edition Jon Antilla University of Southern Florida Christopher Bielawski University of Texas Alan Campion University of Texas David Cartrette South Dakota State University H. J. Peter de Lijser California State University, Fullerton Malcolm Forbes University of North Carolina John Grutzner Purdue University Robert C. Kerber SUNY, Stony Brook Spencer Knapp Rutgers University Paul Kropp University of North Carolina Deborah Lieberman University of Cincinnati James Mack University of Cincinnati Felix Ngassa Grand Valley State University Milton Orchin University of Cincinnati Allan Pinhas University of Cincinnati Suzanne Ruder Virginia Commonwealth University Laurie Starkey California State Polytechnic University, Pomona Qian Wang University of South Carolina Alexander Wei Purdue University Laurie Witucki Grand Valley State University Lei Zhu Florida State University Copyright 2013 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