美国经典的有机化学教材（organic chemistry）.pdf

f o u r t h e d i t i o nORGANIC CHEMISTRYFrancis A.CareyUniversity of VirginiaBostonBurr Ridge,ILDubuque,IAMadison,WINew YorkSan FranciscoSt.LouisBangkokBogotCaracasLisbonLondonMadridMexico CityMilanNew DelhiSeoulSingaporeSydneyTaipeiTorontoBackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsiteORGANIC CHEMISTRY,FOURTH EDITIONCopyright 2000,1996,1992,1987 by The McGraw-Hill Companies,Inc.All rights reserved.Printed in theUnited States of America.Except as permitted under the United States Copyright Act of 1976,no part of thispublication may be reproduced or distributed in any form or by any means,or stored in a data base or retrievalsystem,without the prior written permission of the publisher.This book is printed on acid-free paper.1 2 3 4 5 7 8 9 0 VNH/VNH 9 0 9 8 7 6 5 4 3 2 1 0 9ISBN 0-07-290501-8Vice president and editorial director:Kevin T.KanePublisher:James M.SmithSponsoring editor:Kent A.PetersonDevelopmental editor:Terrance StantonEditorial assistant:Jennifer BensinkSenior marketing manager:Martin J.LangeSenior marketing assistant:Tami PetscheSenior project manager:Peggy J.SelleSenior production supervisor:Sandra HahnDesigner:K.Wayne HarmsPhoto research coordinator:John C.LelandSenior supplement coordinator:David A.WelshCompositor:GTS Graphics,Inc.Typeface:10/12 Times RomanPrinter:Von Hoffmann Press,Inc.Cover/interior designer:Jamie ONealPhoto research:Mary Reeg Photo ResearchThe credits section for this book begins on page C-1 and is considered an extension of the copyright page.Library of Congress Cataloging-in-Publication DataCarey,Francis A.Organic chemistry/Francis A.Carey.4th ed.p.cm.Includes index.ISBN 0-07-290501-8 ISBN 0-07-117499-0(ISE)1.Chemistry,Organic.I.Title.QD251.2.C3642000547dc2199-045791CIPINTERNATIONAL EDITIONISBN 0-07-117499-0Copyright 2000.Exclusive rights by The McGraw-Hill Companies,Inc.for manufacture and export.Thisbook cannot be re-exported from the country to which it is consigned by McGraw-Hill.The InternationalEdition is not available in North AMcGraw-Hill Higher EducationA Division of The McGraw-Hill CompaniesBackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsiteA B O U T T H E A U T H O RFrancis A.Carey is a native of Pennsylvania,educatedin the public schools of Philadelphia,at Drexel Univer-sity(B.S.in chemistry,1959),and at Penn State(Ph.D.1963).Following postdoctoral work at Harvard and mil-itary service,he joined the chemistry faculty of the Uni-versity of Virginia in 1966.With his students,Professor Carey has publishedover 40 research papers in synthetic and mechanisticorganic chemistry.He is coauthor(with Richard J.Sund-berg)of Advanced Organic Chemistry,a two-volumetreatment designed for graduate students and advancedundergraduates,and(with Robert C.Atkins)of OrganicChemistry:A Brief Course,an introductory text for theone-semester organic course.Since 1993,Professor Carey has been a memberof the Committee of Examiners of the Graduate RecordExamination in Chemistry.Not only does he get to par-ticipate in writing the Chemistry GRE,but the annualworking meetings provide a stimulating environment forsharing ideas about what should(and should not)betaught in college chemistry courses.Professor Careys main interest shifted fromresearch to undergraduate education in the early 1980s.He regularly teaches both general chemistry and organicchemistry to classes of over 300 students.He enthusi-astically embraces applications of electronic media tochemistry teaching and sees multimedia presentations asthe wave of the present.Frank and his wife Jill,who is a teacher/directorof a preschool and a church organist,are the parents ofthree grown sons and the grandparents of Riyad andAva.BackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsiteixB R I E F C O N T E N T SPrefacexxvIntroduction11CHEMICAL BONDING72ALKANES533CONFORMATIONS OF ALKANES AND CYCLOALKANES894ALCOHOLS AND ALKYL HALIDES1265STRUCTURE AND PREPARATION OF ALKENES:ELIMINATION REACTIONS1676REACTIONS OF ALKENES:ADDITION REACTIONS2087STEREOCHEMISTRY2598NUCLEOPHILIC SUBSTITUTION3029ALKYNES33910CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS36511ARENES AND AROMATICITY39812REACTIONS OF ARENES:ELECTROPHILIC AROMATIC SUBSTITUTION44313SPECTROSCOPY48714ORGANOMETALLIC COMPOUNDS54615ALCOHOLS,DIOLS,AND THIOLS57916ETHERS,EPOXIDES,AND SULFIDES61917ALDEHYDES AND KETONES:NUCLEOPHILIC ADDITION TO THECARBONYL GROUP65418ENOLS AND ENOLATES70119CARBOXYLIC ACIDS73620CARBOXYLIC ACID DERIVATIVES:NUCLEOPHILIC ACYL SUBSTITUTION77421ESTER ENOLATES83122AMINES85823ARYL HALIDES91724PHENOLS93925CARBOHYDRATES97226LIPIDS101527AMINO ACIDS,PEPTIDES,AND PROTEINS.NUCLEIC ACIDS1051APPENDIX 1PHYSICAL PROPERTIESA-1APPENDIX 2ANSWERS TO IN-TEXT PROBLEMSA-9APPENDIX 3LEARNING CHEMISTRY WITH MOLECULAR MODELS:Using SpartanBuild and SpartanViewA-64GLOSSARYG-1CREDITSC-1INDEXI-1BackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsiteP R E F A C ExxvPHILOSOPHYFrom its first edition through this,its fourth,OrganicChemistry has been designed to meet the needs of the“mainstream,”two-semester,undergraduate organicchemistry course.It has evolved as those needs havechanged,but its philosophy remains the same.The over-arching theme is that organic chemistry is not only aninteresting subject,but also a logical one.It is logicalbecause its topics can be connected in a steady pro-gression from simple to complex.Our approach hasbeen to reveal the logic of organic chemistry by beingselective in the topics we cover,as well as thorough andpatient in developing them.Teaching at all levels is undergoing rapid change,especially in applying powerful tools that exploit thegraphics capability of personal computers.Organicchemistry has always been the most graphical of thechemical sciences and is well positioned to benefit sig-nificantly from these tools.Consistent with our philoso-phy,this edition uses computer graphics to enhance thecore material,to make it more visual,and more under-standable,but in a way that increases neither the amountof material nor its level.ORGANIZATIONThe central message of chemistry is that the propertiesof a substance come from its structure.What is lessobvious,but very powerful,is the corollary.Someonewith training in chemistry can look at the structure of asubstance and tell you a lot about its properties.Organicchemistry has always been,and continues to be,thebranch of chemistry that best connects structure withproperties.This text has a strong bias toward structure,and this edition benefits from the availability of versa-tile new tools to help us understand that structure.The text is organized to flow logically and step bystep from structure to properties and back again.As thelist of chapter titles reveals,the organization is accord-ing to functional groupsstructural units within a mol-ecule most responsible for a particular propertybecause that is the approach that permits most studentsto grasp the material most readily.Students retain thematerial best,however,if they understand how organicreactions take place.Thus,reaction mechanisms arestressed early and often,but within a functional groupframework.A closer examination of the chapter titlesreveals the close link between a functional group class(Chapter 20,Carboxylic Acid Derivatives)and a reactiontype(Nucleophilic Acyl Substitution),for example.It isvery satisfying to see students who entered the coursebelieving they needed to memorize everything progressto the point of thinking and reasoning mechanistically.Some of the important stages in this approach areas follows:The first mechanism the students encounter(Chap-ter 4)describes the conversion of alcohols to alkylhalides.Not only is this a useful functional-grouptransformation,but its first step proceeds by thesimplest mechanism of allproton transfer.Theoverall mechanism provides for an early rein-forcement of acid-base chemistry and an earlyintroduction to carbocations and nucleophilic sub-stitution.Chapter 5 continues the chemistry of alcohols andalkyl halides by showing how they can be used toprepare alkenes by elimination reactions.Here,thestudents see a second example of the formation ofcarbocation intermediates from alcohols,but inthis case,the carbocation travels a different path-way to a different destination.The alkenes prepared in Chapter 5 are studiedagain in Chapter 6,this time with an eye towardtheir own chemical reactivity.What the studentslearned about carbocations in Chapters 4 and 5serves them well in understanding the mechanismsof the reactions of alkenes in Chapter 6.Likewise,the mechanism of nucleophilic addition to the carbonyl group of aldehydes and ketonesdescribed in Chapter 17 sets the stage for aldol con-densation in Chapter 18,esterification of carboxylicacids in Chapter 19,nucleophilic acyl substitution inChapter 20,and ester condensation in Chapter 21.BackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsitexxviPREFACETHE SPARTAN INTEGRATIONThe third edition of this text broke new ground with itsemphasis on molecular modeling,including the additionof more than 100 exercises of the model-building type.This,the fourth edition,moves to the next level of mod-eling.Gwendolyn and Alan Shustermans 1997 Journalof Chemical Education article“Teaching Chemistry withElectron Density Models”described how models show-ing the results of molecular orbital calculations,espe-cially electrostatic potential maps,could be used effec-tively in introductory courses.The software used tocreate the Shustermans models was Spartan,a productof Wavefunction,Inc.In a nutshell,the beauty of electrostatic potentialmaps is their ability to display the charge distribution ina molecule.At the most fundamental level,the forcesthat govern structure and properties in organic chemistryare the attractions between opposite charges and therepulsions between like charges.We were therefore opti-mistic that electrostatic potential maps held greatpromise for helping students make the connectionbetween structure,especially electronic structure,andproperties.Even at an early stage we realized that twomain considerations had to guide our efforts.An integrated approach was required.To be effec-tive,Spartan models and the information they pro-vide must be woven into,not added to,the bookscore.The level of the coverage had to remain the same.Spartan is versatile.We used the same softwarepackage to develop this edition that is used inresearch laboratories worldwide.It was essentialthat we limit ourselves to only those features thatclarified a particular point.Organic chemistry ischallenging enough.We didnt need to make itmore difficult.If we were to err,it would there-fore be better to err on the side of caution.A third consideration surfaced soon after the workbegan.Student access to Spartan would be essential.Nothing could help students connect with molec-ular modeling better than owning the same soft-ware used to produce the text or,even better,soft-ware that allowed them not only to view modelsfrom the text,but also to make their own.All of this led to a fruitful and stimulating collab-oration with Dr.Warren Hehre,a leading theoreticalchemist and the founder,president,and CEO of Wave-function,Inc.Warren was enthusiastic about the projectand agreed to actively participate in it.He and AlanShusterman produced a CD tailored specifically toNEW IN THIS EDITIONALL-NEW ILLUSTRATIONS All figures were redrawnto convey visual concepts clearly and forcefully.In ad-dition,the author created a number of new imagesusing the Spartan molecular modeling application.Now students can view electrostatic potential mapsto see the charge distribution of a molecule in vividcolor.These striking images afford the instructor apowerful means to lead students to a better under-standing of organic molecules.FULL SPARTAN IMAGE INTEGRATION The Spartan-generated images are impressive in their own right,but for teaching purposes they are most effectivewhen they are closely aligned with the text content.Because the author personally generated the imagesas he wrote this edition,the molecular models arefully integrated with text,and the educational valueis maximized.Additionally,icons direct students tospecific applications of either the SpartanView orSpartanBuild program,found on the accompanyingCD-ROM.Appendix 3 provides a complete guide tothe Learning By Modeling CD-ROM.ALL-NEW SPECTRA Chapter 13,Spectroscopy,washeavily revised,with rewritten sections on NMR andwith all the NMR spectra generated on a high-fieldinstrument.IMPROVED SUMMARIES The end-of-chapter sum-maries are recast into a more open,easier-to-readformat,inspired by the popularity of the accompany-ing summary tables.NEW DESIGN This edition sports a new look,with anemphasis on neatness,clarity,and color carefullyused to heighten interest and to create visual cues forimportant information.BackForwardMain MenuTOCStudy Guide TOCStudent OLCMHHE WebsitePREFACExxviiaccompany our text.We call it Learning By Modeling.It and Organic Chemistry truly complement each other.Many of the problems in Organic Chemistry have beenwritten expressly for the model-building software Spar-tanBuild that forms one part of Learning By Modeling.Another tool,SpartanView,lets students inspect morethan 250 already constructed models and animations,ranging in size from hydrogen to carboxypeptidase.We were careful to incorporate Spartan so it wouldbe a true amplifier of the textbook,not just as a stand-alone tool that students might or might not use,depend-ing on the involvement of their instructor.Thus,thecontent of the CD provides visual,three-dimensionalreinforcement of the concepts covered on the printedpage.The SpartanView icon invites students to viewa molecule or animation as they are reading the text.Opportunities to use SpartanBuild are similarlycorrelated to the text with an icon directing studentsto further explore a concept or solve a modeling-basedproblem with the software.In addition to its role as the electronic backboneof the CD component and the integrated learningapproach,the Spartan software makes a visible impacton the printed pages of this edition.I used Spartan onmy own computer to create many of the figures,pro-viding students with numerous visual explorations of theconcepts of charge distribution.BIOLOGICAL APPLICATIONS AND THEIRINTEGRATIONComprehensive coverage of the important classes of bio-molecules(carbohydrates,lipids,amino acids,peptides,proteins,and nucleic acids)appears in Chapters 2527.But biological applications are such an important part oforganic chemistry that they deserve more attentionthroughout the course.We were especially alert to oppor-tunities to introduce more biologically oriented materialto complement that which had already grown signifi-cantly since the first edition.Some specific examples:The new boxed essay“Methane and the Bio-sphere”in Chapter 2 combines elements oforganic chemistry,biology,and environmental sci-ence to tell the story of where methane comesfrom and where it goes.A new boxed essay,“An En