《有机化学》课程教学资源（参考书籍）Organic Chemistry, 3rd Ed, Janice Gorzynski Smith 2011, University of Hawai’i at Ma-noa.pdf_P21-P25

xxi Sample Problem 15.4 Draw the products formed when A is treated with NBS + hν. NBS CH2 A hν Solution Hydrogen abstraction at the allylic C forms a resonance-stabilized radical (with two different resonance structures) that reacts with Br2 to form two constitutional isomers as products. two resonance structures two constitutional isomers Br2 H Br A CH2 CH2 CH2 Br2 CH2 CH2Br + HBr Br Problem 15.20 Draw all constitutional isomers formed when each alkene is treated with NBS + hν. a. CH3CH CHCH3 b. CH3 CH3 c. CH2 C(CH2CH3)2 HOW TO Name an Ester (RCO2R') Using the IUPAC System Example Give a systematic name for each ester: a. C CH3 OCH2CH3 O b. C O C O CH3 CH3 CH3 Step [1] Name the R' group bonded to the oxygen atom as an alkyl group. • The name of the alkyl group, ending in the suffi x -yl, becomes the fi rst part of the ester name. C OCH2CH3 O ethyl group CH3 C tert-butyl group O C O CH3 CH3 CH3 Step [2] Name the acyl group (RCO – ) by changing the -ic acid ending of the parent carboxylic acid to the suffi x -ate. • The name of the acyl group becomes the second part of the name. C OCH2CH3 O CH3 derived from acetic acid acetate Answer: ethyl acetate derived from cyclohexanecarboxylic acid cyclohexanecarboxylate Answer: tert-butyl cyclohexanecarboxylate C O C O CH3 CH3 CH3 KEY CONCEPTS Alkenes General Facts About Alkenes • Alkenes contain a carbon–carbon double bond consisting of a stronger σ bond and a weaker π bond. Each carbon is sp2 hybridized and trigonal planar (10.1). • Alkenes are named using the suffi x -ene (10.3). • Alkenes with different groups on each end of the double bond exist as a pair of diastereomers, identifi ed by the prefi xes E and Z (10.3B). • Alkenes have weak intermolecular forces, giving them low mp’s and bp’s, and making them water insoluble. A cis alkene is more polar than a trans alkene, giving it a slightly higher boiling point (10.4). • Because a π bond is electron rich and much weaker than a σ bond, alkenes undergo addition reactions with electrophiles (10.8). Stereochemistry of Alkene Addition Reactions (10.8) A reagent XY adds to a double bond in one of three different ways: • Syn addition—X and Y add from the same side. C H BH2 C H BH2 C C • Syn addition occurs in hydroboration. • Anti addition—X and Y add from opposite sides. X2 or X2, H2O C C X(OH) X C C • Anti addition occurs in halogenation and halohydrin formation. • Both syn and anti addition occur when carbocations are intermediates. and or H2O, H+ H X C C C H X(OH) C X(OH) H C C • Syn and anti addition occur in hydrohalogenation and hydration. Addition Reactions of Alkenes [1] Hydrohalogenation—Addition of HX (X = Cl, Br, I) (10.9–10.11) R CH CH2 X H alkyl halide RCH CH2 + H X • The mechanism has two steps. • Carbocations are formed as intermediates. • Carbocation rearrangements are possible. • Markovnikov’s rule is followed. H bonds to the less substituted C to form the more stable carbocation. • Syn and anti addition occur. [2] Hydration and related reactions (Addition of H2O or ROH) (10.12) R RCH CH2 + H OH R CH CH2 OH H alcohol RCH CH2 + H OR CH CH2 OR H ether H2SO4 H2SO4 For both reactions: • The mechanism has three steps. • Carbocations are formed as intermediates. • Carbocation rearrangements are possible. • Markovnikov’s rule is followed. H bonds to the less substituted C to form the more stable carbocation. • Syn and anti addition occur. Problem Solving Sample Problems Sample Problems show students how to solve organic chemistry problems in a logical, stepwise manner. More than 800 follow-up problems are located throughout the chapters to test whether students understand concepts covered in the Sample Problems. How To’s How To’s provide students with detailed instructions on how to work through key processes. Applications and Summaries Key Concept Summaries Succinct summary tables reinforcing important principles and concepts are provided at the end of each chapter. Margin Notes Margin notes are placed carefully throughout the chapters, providing interesting information relating to topics covered in the text. Some margin notes are illustrated with photos to make the chemistry more relevant. Canola, soybeans, and fl axseed are excellent dietary sources of linolenic acid, an essential fatty acid. Oils derived from omega-3 fatty acids (Problem 10.12) are currently thought to be especially benefi cial for individuals at risk of developing coronary artery disease. smi75625_fm_00i-xxxiv.indd xxi 11/17/09 11:21:44 AM

Supplements for the Instructor and Student The following items may accompany this text. Please consult your McGraw-Hill representative for policies, prices, and availability as some restrictions may apply. McGraw-Hill Connect™ Chemistry is a web-based assignment and assessment platform that gives students the means to better connect with their course work, their instructors, and the important concepts that they will need to know for success now and in the future. With Connect Chemistry, instructors can deliver assignments, quizzes, and tests online. A majority of questions from the text are presented in an auto-gradable format and tied to the text’s learning objectives. Instructors can edit existing questions and author entirely new problems. Track individual student performance—by question, assignment, or in relation to the class overall—with detailed grade reports. Integrate grade reports easily with Learning Management Systems (LMS) such as WebCT and Blackboard. By choosing Connect Chemistry, instructors are providing their students with a powerful tool for improving academic performance and truly mastering course material. Connect Chemistry allows students to practice important skills at their own pace and on their own schedule. Importantly, students’ assessment results and instructors’ feedback are all saved online—so students can continually review their progress and plot their course to success. Like Connect Chemistry, Connect Chemistry Plus provides students with online assignments and assessments, plus 24/7 online access to an eBook—an online edition of the text—to aid them in successfully completing their work, wherever and whenever they choose. McGraw-Hill Presentation Center allows instructors to build instructional materials wherever, whenever, and however you want! Presentation Center is an online digital library containing assets such as photos, artwork, PowerPoints, and other media types that can be used to create customized lectures, visually enhanced tests and quizzes, compelling course websites, or attractive printed support materials. The McGraw-Hill Presentation Center library includes thousands of assets from many McGraw-Hill titles. This ever-growing resource gives instructors the power to utilize assets specifi c to an adopted textbook as well as content from all other books in the library. The Presentation Center can be accessed from the instructor side of your textbook’s ARIS website, and the Presentation Center’s dynamic search engine allows you to explore by discipline, course, textbook chapter, asset type, or keyword. Simply browse, select, and download the fi les you need to build engaging course materials. All assets are copyright McGraw-Hill Higher Education, but can be used by instructors for classroom purposes. Brownstone’s Diploma testing software serves up over 1,200 test questions to accompany Organic Chemistry. Diploma’s software allows you to quickly create a customized test using McGraw-Hill’s supplied questions, or by authoring your own questions. Diploma is a downloadable application that allows you to create your tests without an Internet connection—just download the software and question fi les directly to your computer. Student Study Guide/Solutions Manual Written by Janice Gorzynski Smith and Erin Smith Berk, the Student Study Guide/Solutions Manual provides step-by-step solutions to all in-chapter and end-of-chapter problems. Each chapter begins with an overview of key concepts and includes key rules and summary tables. xxii Preface smi75625_fm_00i-xxxiv.indd xxii 11/17/09 11:21:46 AM

Acknowledgments When I st hav I hav ne- itude of the ky to t over the last 30 nd I he task.or any idea of just how many peopleI would rely upon to that the wider chemistry community can benefit from this experience by the way I have presented the material in this ed team or pi ionals at McGraw-Hi text This third edition has evolyed hased on the helpful feed hack of many ple who reviewed the second edition.class uscript pages of the last two editions of Organic Chemistry tested the book,and attended focus groups or symposiums nto stunning texts mi Hodge (Senior Sponsorng E tor many individu collectively provided construc tive improvements to of th the project HetAbouahnah Sa Sheikh Ahmed West and em ncy.I couldn't ask Jung-Mo Ahn,Universiry of Texas.Dallas Thomas Albright,Universiry of Houston assumed the role of Publisher for my project.Senior Market has nsin,Whitewater Mark E.Arant,University of Louisiana,Monr Thurston E.Banks,Tennessee Technological University sen(Designer)and Carrie Burger (Photo Researcher)who are ky University responsible for the visually pleasing appearance of this edi- Thanks due Pr essor Spen Knapp and David Berkowitz.University of Nebraska.Lincon in the third edition m Jo Murd oeticgd Steve Bertman,We humo ous insights on my project Silas Cg.Blan Organic C with David I Boatright Uni suppl sity of West Gee hanks go to Kathleen Halligan of York College of Penns nia who authored the instructor's test bank,and Layne Morsch L ot The Unr ersity of Illinois,Springfield who prepared the es Callam.The Ohie Suzanne Carpenter,Armstrong Arlantic State University Ma Steven Castle,Brigh m Young University Kuz of the University of Texas-San Antonio.and Margare tie.The Ur Ruth Leslie of Kent State Uni ersity for their careful acc llen cS.Ch hecking of Bank and Pov Point Lecture Outlines to Sergio Cortes,University of Texas.Dallas diate family has ed the day-to-day James Ricky Cox,Murn State University demands of living with a busy author.Thanks go to my hus and Dan and my children Er Jenna,Ma tthew and Zachary rsiry.Fullerton all of wh Amy m deveau university of new eneland m keep me gro 1g山 Brahmadeo Dewprashad,Borough of Manhattan Community of the Student Study Guide Solutions Manual.continued this mportant task this year in the midst of planning a wedding ela S Do completing a resi ncy in emergency medicine,and settling nto a Nicholas Drapela.Ores on state University e a the Norma Kay Dunlap,Middle Tennessee State University profoundly affected this work are the thousands of studentsI hasn Erden,San Francisco State University

xxiii Acknowledgments When I started working on the fi rst edition of Organic Chemistry in the fall of 1999, I had no sense of the magnitude of the task, or any idea of just how many people I would rely upon to complete it. Fortunately, I have had the steadfast support of a dedicated team of publishing professionals at McGraw-Hill. I am especially thankful for the opportunity to work with three terrifi c women who have transformed the ideas and manuscript pages of the last two editions of Organic Chemistry into stunning texts—Tami Hodge (Senior Sponsoring Editor), Donna Nemmers (Senior Developmental Editor), and Jayne Klein (Senior Project Manager). All aspects of this project— from devising the overall plan for the third edition to obtaining valuable reviews to setting a workable production schedule— have been carried out with skill and effi ciency. I couldn’t ask for a better team of individuals with which to work. Thanks also go out to Ryan Blankenship, who has recently assumed the role of Publisher for my project. Senior Marketing Manager Todd Turner has provided me with many valuable insights that result from his many contacts with current and potential users. I also appreciate the work of Laurie Janssen (Designer) and Carrie Burger (Photo Researcher) who are responsible for the visually pleasing appearance of this edition. Thanks are again due to Professor Spencer Knapp and his crew at Rutgers University, who prepared the many new spectra that appear in the third edition, and to freelance Developmental Editor John Murdzek for his meticulous editing and humorous insights on my project. Organic Chemistry is complemented with useful supplements prepared by qualifi ed and dedicated individuals. Special thanks go to Kathleen Halligan of York College of Pennsylvania who authored the instructor’s test bank, and Layne Morsch of The University of Illinois, Springfi eld who prepared the PowerPoint lecture outlines. I am also grateful for the keen eyes of Matthew Dintzner of DePaul University, Michael Kurz of the University of Texas–San Antonio, and Margaret Ruth Leslie of Kent State University for their careful accuracy checking of the Test Bank and PowerPoint Lecture Outlines to accompany this text. My immediate family has experienced the day-to-day demands of living with a busy author. Thanks go to my husband Dan and my children Erin, Jenna, Matthew, and Zachary, all of whom keep me grounded during the time-consuming process of writing and publishing a textbook. Erin, co-author of the Student Study Guide/Solutions Manual, continued this important task this year in the midst of planning a wedding, completing a residency in emergency medicine, and settling into a new home and profession. Among the many others that go unnamed but who have profoundly affected this work are the thousands of students I have been lucky to teach over the last 30 years. I have learned so much from my daily interactions with them, and I hope that the wider chemistry community can benefi t from this experience by the way I have presented the material in this text. This third edition has evolved based on the helpful feedback of many people who reviewed the second edition, classtested the book, and attended focus groups or symposiums. These many individuals have collectively provided constructive improvements to the project. Heba Abourahma, Indiana University of Pennsylvania Madeline Adamczeski, San José City College Sheikh Ahmed, West Virginia University Jung-Mo Ahn, University of Texas, Dallas Thomas Albright, University of Houston Scott E. Allen, University of Tampa Steven W. Anderson, University of Wisconsin, Whitewater Mark E. Arant, University of Louisiana, Monroe Thurston E. Banks, Tennessee Technological University Debra L. Bautista, Eastern Kentucky University David Bergbreiter, Texas A&M University John M. Berger, Montclair State University David Berkowitz, University of Nebraska, Lincoln Steve Bertman, Western Michigan University Silas C. Blackstock, The University of Alabama James R. Blanton, The Citadel David L. Boatright, University of West Georgia Chad Booth, Texas State University, San Marcos Ned Bowden, University of Iowa Kathleen Brunke, Christopher Newport University Christopher S. Callam, The Ohio State University Suzanne Carpenter, Armstrong Atlantic State University Steven Castle, Brigham Young University Hamish S. Christie, The University of Arizona Allen Clauss, University of Wisconsin, Madison Barry A. Coddens, Northwestern University Sergio Cortes, University of Texas, Dallas James Ricky Cox, Murray State University Jason P. Cross, Temple University Peter de Lijser, California State University, Fullerton Amy M. Deveau, University of New England Brahmadeo Dewprashad, Borough of Manhattan Community College Matthew Dintzner, DePaul University Pamela S. Doyle, Essex County College Nicholas Drapela, Oregon State University Norma Kay Dunlap, Middle Tennessee State University Ihasn Erden, San Francisco State University smi75625_fm_00i-xxxiv.indd xxiii 11/19/09 9:27:28 AM

John Michael Ferguson, University of Central Oklahoma David Flanigan, Hillsborough Community College David C. Forbes, University of South Alabama John W. Francis, Columbus State Community College Lee Friedman, University of Maryland, College Park Anne Gaquere, University of West Georgia Bob Gawley, University of Arkansas Jose L. Gonzalez–Roman, Georgia Perimeter College, Decatur Anne Elizabeth V. Gorden, Auburn University Steven M. Graham, Saint John’s University Dennis J. Gravert, Saint Mary’s University of Minnesota Ray A. Gross, Jr., Prince George’s Community College Stephen M. Gross, Creighton University Greg Hale, University of Texas, Arlington Kathleen M. Halligan, York College of Pennsylvania Scott Handy, Middle Tennessee State University Kenn Harding, Texas A&M University Jill Harp, Winston Salem State University Paul Higgs, Barry University Ed Hilinski, Florida State University Nadene Houser–Archield, Prince George’s Community College Michael T. Huggins, University of West Florida Thomas G. Jackson, University of South Alabama Peter A. Jacobi, Dartmouth College Tamera S. Jahnke, Missouri State University David Andrew Jeffrey, Georgia State University Hima S. Joshi, California Polytechnic State University, San Luis Obispo Eric Kantorowski, California Polytechnic State University, San Luis Obispo Steven Kass, University of Minnesota Mushtaq Khan, Union County College Rebecca Kissling, SUNY, Binghampton Vera Kolb, University of Wisconsin, Parkside Grant Krow, Temple University Michael Kurz, University of Texas, San Antonio Michael Langohr, Tarrant County College District Michael S. Leonard, Washington & Jefferson College Chunmei Li, Stephen F. Austin State University Harriet A. Lindsay, Eastern Michigan University Robert D. Long, Eastern New Mexico University Douglas A. Loy, The University of Arizona Mitch Malachowski, University of San Diego Ned H. Martin, University of North Carolina, Wilmington Michael M. McCormick, Boise State University Owen McDougal, Boise State University Matt McIntosh, University of Arkansas Keith T. Mead, Mississippi State University Thomas Minehan, California State University, Northridge James A. Miranda, California State University, Sacramento Miguel O. Mitchell, Salisbury University Thomas W. Nalli, Winona State University xxiv Acknowledgments Donna J. Nelson, University of Oklahoma Dallas New, University of Central Oklahoma Jacqueline A. Nikles, University of Alabama, Birmingham William J. Nixon, Jr., St. Petersburg College David Allan Owen, Murray State University Anne B. Padias, The University of Arizona Daniel Palleros, University of California, Santa Cruz James W. Pavlik, Worcester Polytechnic Institute Otto Phanstiel, University of Central Florida Charles U. Pittman, Jr., Mississippi State University John R. Pollard, The University of Arizona Daniel P. Predecki, Shippensburg University Michael B. Ramey, Appalachian State University Michael Rathke, Michigan State University Partha S. Ray, University of West Georgia J. Ty Redd, Southern Utah University J. Michael Robinson, The University of Texas, Permian Basin Tomislav Rovis, Colorado State University Lev Ryzhkov, Towson University Raymond Sadeghi, University of Texas, San Antonio Robert Sammelson, Ball State University Jason M. Serin, Glendale Community College Heather Sklenicka, Rochester Community and Technical College Irina P. Smoliakova, University of North Dakota David Spurgeon, The University of Arizona Laurie S. Starkey, California State Polytechnic University, Pomona Chad Stearman, Missouri State University Jonathan M. Stoddard, California State University, Fullerton Robert Stolow, Tufts University Todd Swanson, Gustavus Adolphus College Richard Tarkka, University of Central Arkansas Eric S. Tillman, Bucknell University Eric L. Trump, Emporia State University Ken Walsh, University of Southern Indiana Don Warner, Boise State University Arlon A. Widder, Georgia Perimeter College Milton J. Wieder, Metropolitan State College, Denver Viktor Zhdankin, University of Minnesota, Duluth Although every effort has been made to make this text and its accompanying Student Study Guide/Solutions Manual as error-free as possible, some errors undoubtedly remain and for them, I am solely responsible. Please feel free to email me about any inaccuracies, so that subsequent editions may be further improved. With much aloha, Janice Gorzynski Smith jgsmith@hawaii.edu smi75625_fm_00i-xxxiv.indd xxiv 11/17/09 11:21:46 AM

xxv List of How To’s How To boxes provide detailed instructions for key procedures that students need to master. Below is a list of each How To and where it is presented in the text. Chapter 1 Structure and Bonding How To Draw a Lewis Structure 13 Chapter 2 Acids and Bases How To Determine the Relative Acidity of Protons 69 Chapter 4 Alkanes How To Name an Alkane Using the IUPAC System 121 How To Name a Cycloalkane Using the IUPAC System 125 How To Draw a Newman Projection 132 How To Draw the Chair Form of Cyclohexane 139 How To Draw the Two Conformations for a Substituted Cyclohexane 142 How To Draw Two Conformations for a Disubstituted Cyclohexane 145 Chapter 5 Stereochemistry How To Assign R or S to a Stereogenic Center 172 How To Find and Draw All Possible Stereoisomers for a Compound with Two Stereogenic Centers 176 Chapter 7 Alkyl Halides and Nucleophilic Substitution How To Name an Alkyl Halide Using the IUPAC System 230 Chapter 9 Alcohols, Ethers, and Epoxides How To Name an Alcohol Using the IUPAC System 315 Chapter 10 Alkenes How To Name an Alkene 362 How To Assign the Prefi xes E and Z to an Alkene 364 Chapter 11 Alkynes How To Develop a Retrosynthetic Analysis 418 Chapter 13 Mass Spectrometry and Infrared Spectroscopy How To Use MS and IR for Structure Determination 486 Chapter 14 Nuclear Magnetic Resonance Spectroscopy How To Determine the Number of Protons Giving Rise to an NMR Signal 508 How To Use 1 H NMR Data to Determine a Structure 520 Chapter 16 Conjugation, Resonance, and Dienes How To Draw the Product of a Diels–Alder Reaction 590 Chapter 17 Benzene and Aromatic Compounds How To Use the Inscribed Polygon Method to Determine the Relative Energies of MOs for Cyclic, Completely Conjugated Compounds 629 Chapter 18 Electrophilic Aromatic Substitution How To Determine the Directing Effects of a Particular Substituent 661 Chapter 21 Aldehydes and Ketones—Nucleophilic Addition How To Determine the Starting Materials for a Wittig Reaction Using Retrosynthetic Analysis 795 Chapter 22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution How To Name an Ester (RCO2R') Using the IUPAC System 831 How To Name a 2° or 3° Amide 831 Chapter 24 Carbonyl Condensation Reactions How To Synthesize a Compound Using the Aldol Reaction 921 How To Synthesize a Compound Using the Robinson Annulation 939 smi75625_fm_00i-xxxiv.indd xxv 11/17/09 11:21:47 AM