fourth editio ORGANIC CHEMISTRY Francis a, care University of virginia ston Burr Ridge, IA Madison. WI New York San Francisco St louis ta Caracas Lisbon London madrid Mexico City Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
fourth edition ORGANIC CHEMISTRY Francis A. Carey University of Virginia Boston Burr Ridge, IL Dubuque, IA Madison, WI New York San Francisco St. Louis Bangkok Bogotá Caracas Lisbon London Madrid Mexico City Milan New Delhi Seoul Singapore Sydney Taipei Toronto
McGraw-Hill Higher education A Division of The MdGranp-Hill Compani ORGANIC CHEMISTRY FOURTH EDITION Copyright o 2000, 1996, 1992, 1987 by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval ystem, without the prior written permission of the publisher. This book is printed on acid-free paper. 123457890 VNH/VNH9098765432109 ISBN007-290501-8 resident and editorial director: Kevin t. Kane her: James M. Smith ponsoring editor: Kent A. Peterson Developmental editor: Terrance Stanton Editorial assistant: Jennifer Bensin Senior marketing manager: Martin J. Lange Senior marketing assistant: Tami petsche Senior project manager: Peggy J. Sell Senior production supervisor: Sandra Hahn Designet Photo research coordinator: John C. Leland or supplement coordinator: David A. Welsh ompositor: GTS Graphics, Inc. Typeface: 10/12 Times Roman Printer: Von Hoffmann Press, Ine Cover/interio Jamie o'Neal Photo research: Mary Reeg Photo Research The credits section for this book begins on page C-I and is considered an extension of the copyright page Library of Congress Cataloging-in-Publication Data arey, Francis A. Organic chemistry /Francis A Carey.-4th ed. Includes index ISBN007-290501-8-ISBN0407-117499-0(ISE) 1. Chemistry, Organic. I. Title QD251.2C3642000 547-dc21 99-045791 INTERNATIONAL EDITION SBN 0-07-117499-0 opyright o 2000. Exclusive rights by The McGraw-Hill Companies, Inc for manufacture and export This book cannot be re-exported from the country to which it is consigned by McGraw-Hill. The International Edition is not available in North America. w. mhhe. com Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
ORGANIC CHEMISTRY, FOURTH EDITION Copyright © 2000, 1996, 1992, 1987 by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval system, 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 9 ISBN 0-07-290501-8 Vice president and editorial director: Kevin T. Kane Publisher: James M. Smith Sponsoring editor: Kent A. Peterson Developmental editor: Terrance Stanton Editorial assistant: Jennifer Bensink Senior marketing manager: Martin J. Lange Senior marketing assistant: Tami Petsche Senior project manager: Peggy J. Selle Senior production supervisor: Sandra Hahn Designer: K. Wayne Harms Photo research coordinator: John C. Leland Senior supplement coordinator: David A. Welsh Compositor: GTS Graphics, Inc. Typeface: 10/12 Times Roman Printer: Von Hoffmann Press, Inc. Cover/interior designer: Jamie O’Neal Photo research: Mary Reeg Photo Research The 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 Data Carey, 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.C364 2000 547—dc21 99-045791 CIP INTERNATIONAL EDITION ISBN 0-07-117499-0 Copyright © 2000. Exclusive rights by The McGraw-Hill Companies, Inc. for manufacture and export. This book cannot be re-exported from the country to which it is consigned by McGraw-Hill. The International Edition is not available in North America. www. mhhe.com McGraw-Hill Higher Education A Division of The McGraw-Hill Companies
ABOUT THE AUTHOR Francis A. Carey is a native of Pennsylvania, educated Examination in Chemistry. Not only does he get to par- in the public schools of Philadelphia, at Drexel Univer- ticipate in writing the Chemistry Gre, but the annual sity(BS. in chemistry, 1959), and at Penn State(Ph. D. working meetings provide a stimulating environment for 1963). Following postdoctoral work at Harvard and mil- sharing ideas about what should (and should not) be itary service, he joined the chemistry faculty of the Uni- taught in college chemistry courses versity of Virginia in 1966 Professor Careys main interest shifted from With his students, Professor Carey has published research to undergraduate education in the early 1980s over 40 research papers in synthetic and mechanistic He regularly teaches both general chemistry and organic organic chemistry. He is coauthor(with Richard J. Sund hemistry to classes of over 300 students. He enthusi- berg) of Advanced Organic Chemistry, a two-volume astically embraces applications of electronic media to treatment designed for graduate students and advanced chemistry teaching and sees multimedia presentations as undergraduates, and(with Robert C. Atkins) of Organic the wave of the present Chemistry: A Brief Course, an introductory text for the Frank and his wife jill. who is a teacher/director one-semester organic course. of a preschool and a church organist, are the parents of Since 1993, Professor Carey has been a member three grown sons and the grandparents of Riyad and of the Committee of examiners of the graduate record Ava Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
ABOUT THE AUTHOR Francis A. Carey is a native of Pennsylvania, educated in the public schools of Philadelphia, at Drexel University (B.S. in chemistry, 1959), and at Penn State (Ph.D. 1963). Following postdoctoral work at Harvard and military service, he joined the chemistry faculty of the University of Virginia in 1966. With his students, Professor Carey has published over 40 research papers in synthetic and mechanistic organic chemistry. He is coauthor (with Richard J. Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates, and (with Robert C. Atkins) of Organic Chemistry: A Brief Course, an introductory text for the one-semester organic course. Since 1993, Professor Carey has been a member of the Committee of Examiners of the Graduate Record Examination in Chemistry. Not only does he get to participate in writing the Chemistry GRE, but the annual working meetings provide a stimulating environment for sharing ideas about what should (and should not) be taught in college chemistry courses. Professor Carey’s main interest shifted from research to undergraduate education in the early 1980s. He regularly teaches both general chemistry and organic chemistry to classes of over 300 students. He enthusiastically embraces applications of electronic media to chemistry teaching and sees multimedia presentations as the wave of the present. Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of three grown sons and the grandparents of Riyad and Ava
BRIEF CONTENT S 1 CHEMICAL BONDING 2 ALKANES 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES 739 4 ALCOHOLS AND ALKYL HALIDES 5 STRUCTURE AND PREPARATION OF ALKENES: ELIMINATION REACTIONS 167 6 REACTIONS OF ALKENES: ADDITION REACTIONS 7 STEREOCHEMISTRY 8 NUCLEOPHILIC SUBSTITUTION 9 ALKYNES 0 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS 11 ARENES AND AROMATICITY 398 12 REACTIONS OF ARENES: ELECTROPHILIC AROMATIC SUBSTITUTION 13 SPECTROSCOPY 14 ORGANOMETALLIC COMPOUNDS 15 ALCOHOLS DIOLS AND THIOLS 16 ETHERS EPOXIDES AND SULFIDES 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 654 18 ENOLS AND ENOLATES 19 CARBOXYLIC ACIDS 20 CARBOXYLIC ACID DERIVATIVES: NUCLEOPHILIC ACYL SUBSTITUTION 21 ESTER ENOLATES 22 AMINES 23 ARYL HALIDES 24 PHENOLS 25 CARBOHYDRATE 27 AMINO ACIDS. PEPTIDES AND PROTEINS. NUCLEIC ACIDS APPENDIX 1 PHYSICAL PROPERTIES A-1 APPENDIX 2 ANSWERS TO IN-TEXT PROBLEMS A-9 APPENDIX 3 LEARNING CHEMISTRY WITH MOLECULAR MODELS. Using Spartan Build and Spartan View GLOSSARY G-1 CREDITS C-1 INDEX -1 Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
ix BRIEF CONTENTS Preface xxv Introduction 1 1 CHEMICAL BONDING 7 2 ALKANES 53 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES 89 4 ALCOHOLS AND ALKYL HALIDES 126 5 STRUCTURE AND PREPARATION OF ALKENES: ELIMINATION REACTIONS 167 6 REACTIONS OF ALKENES: ADDITION REACTIONS 208 7 STEREOCHEMISTRY 259 8 NUCLEOPHILIC SUBSTITUTION 302 9 ALKYNES 339 10 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS 365 11 ARENES AND AROMATICITY 398 12 REACTIONS OF ARENES: ELECTROPHILIC AROMATIC SUBSTITUTION 443 13 SPECTROSCOPY 487 14 ORGANOMETALLIC COMPOUNDS 546 15 ALCOHOLS, DIOLS, AND THIOLS 579 16 ETHERS, EPOXIDES, AND SULFIDES 619 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP 654 18 ENOLS AND ENOLATES 701 19 CARBOXYLIC ACIDS 736 20 CARBOXYLIC ACID DERIVATIVES: NUCLEOPHILIC ACYL SUBSTITUTION 774 21 ESTER ENOLATES 831 22 AMINES 858 23 ARYL HALIDES 917 24 PHENOLS 939 25 CARBOHYDRATES 972 26 LIPIDS 1015 27 AMINO ACIDS, PEPTIDES, AND PROTEINS. NUCLEIC ACIDS 1051 APPENDIX 1 PHYSICAL PROPERTIES A-1 APPENDIX 2 ANSWERS TO IN-TEXT PROBLEMS A-9 APPENDIX 3 LEARNING CHEMISTRY WITH MOLECULAR MODELS: Using SpartanBuild and SpartanView A-64 GLOSSARY G-1 CREDITS C-1 INDEX I-1
PREFACE PHILOSOPHY to grasp the material most readily. Students retain the material best, however, if they understand how organic From its first edition through this, its fourth, Organic reactions take place. Thus, reaction mechanisms are Chemistry has been designed to meet the needs of the stressed early and often, but within a functional group framework. a closer examination of the chapter titles chemistry course. It has evolved as those needs have reveals the close link between a functional group class changed, but its philosophy remains the same. The over arching theme is that organic chemistry is not only an ( Chapter 20, Carboxylic Acid Derivatives)and a reaction interesting subject, but also a logical one. It is logical ype(Nucleophilic Acyl Substitution), for example. It is very satisfying to see students who entered the course because its topics can be connected in a steady pro- believing they needed to memorize everything progress ssion from simple to complex. Our approach has been to reveal the logic of organic chemistry by being to the point of thinking and reasoning mechanistically elective in the topics we cover, as well as thorough and Some of the important stages in this approach are patient in developing them. eaching at all levels is un especially in applying powerful tools that exploit the graphics capability of personal computers. Organic halides. Not only is this a useful functional-group chemistry has always been the most graphical of the transformation, but its first step proceeds by the chemical sciences and is well positioned to benefit sig simplest mechanism of all--proton transfer. The nificantly from these tools. Consistent with our philoso- overall mechanism provides for an early rein- phy, this edition uses computer graphics to enhance the forcement of acid-base chemistry and an early core material. to make it more visual. and more under- introduction to carbocations and nucleophilic sub- standable, but in a way that increases neither the amount station of material nor its level Chapter 5 continues the chemistry of alcohols and alkyl halides by showing how they can be used to ORGANIZATION prepare alkenes by elimination reactions. Here, the students see a second example of the formation of The central message of chemistry is that the properties carbocation intermediates from alcohols, but in of a substance come from its structure. what is less this case, the carbocation travels a different path obvIous. bu very powerful, is the corollary. Someone way to a different destination with training in chemistry can look at the structure of a substance and tell you a lot about its properties. Organic The alkenes prepared in Chapter 5 are studied chemistry has always been, and continues to be, the again in Chapter 6, this time with an eye toward branch of chemistry that best connects structure with their own chemical reactivity. What the students properties. This text has a strong bias toward structure, learned about carbocations in Chapters 4 and 5 and this edition benefits from the availability of versa- serves them well in understanding the mechanisms tile new tools to help us understand that structure of the reactions of alkenes in Chapter 6 The text is organized to flow logically and step by Likewise, the mechanism of nucleophilic addition step from structure to properties and back again. As the the carbonyl group of aldehydes and ketones list of chapter titles reveals, the organization is accord scribed in Chapter 17 sets the stage for aldol con- ing to functional groups--structural units within a mol- densation in Chapter 18, esterification of carboxylic ecule most responsible for a particular property- acids in Chapter 19, nucleophilic acyl substitution in because that is the approach that permits most students Chapter 20, and ester condensation in Chapter 21 Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
PREFACE xxv PHILOSOPHY From its first edition through this, its fourth, Organic Chemistry has been designed to meet the needs of the “mainstream,” two-semester, undergraduate organic chemistry course. It has evolved as those needs have changed, but its philosophy remains the same. The overarching theme is that organic chemistry is not only an interesting subject, but also a logical one. It is logical because its topics can be connected in a steady progression from simple to complex. Our approach has been to reveal the logic of organic chemistry by being selective in the topics we cover, as well as thorough and patient in developing them. Teaching at all levels is undergoing rapid change, especially in applying powerful tools that exploit the graphics capability of personal computers. Organic chemistry has always been the most graphical of the chemical sciences and is well positioned to benefit significantly from these tools. Consistent with our philosophy, this edition uses computer graphics to enhance the core material, to make it more visual, and more understandable, but in a way that increases neither the amount of material nor its level. ORGANIZATION The central message of chemistry is that the properties of a substance come from its structure. What is less obvious, but very powerful, is the corollary. Someone with training in chemistry can look at the structure of a substance and tell you a lot about its properties. Organic chemistry has always been, and continues to be, the branch of chemistry that best connects structure with properties. This text has a strong bias toward structure, and this edition benefits from the availability of versatile new tools to help us understand that structure. The text is organized to flow logically and step by step from structure to properties and back again. As the list of chapter titles reveals, the organization is according to functional groups—structural units within a molecule most responsible for a particular property— because that is the approach that permits most students to grasp the material most readily. Students retain the material best, however, if they understand how organic reactions take place. Thus, reaction mechanisms are stressed early and often, but within a functional group framework. A closer examination of the chapter titles reveals the close link between a functional group class (Chapter 20, Carboxylic Acid Derivatives) and a reaction type (Nucleophilic Acyl Substitution), for example. It is very satisfying to see students who entered the course believing they needed to memorize everything progress to the point of thinking and reasoning mechanistically. Some of the important stages in this approach are as follows: • The first mechanism the students encounter (Chapter 4) describes the conversion of alcohols to alkyl halides. Not only is this a useful functional-group transformation, but its first step proceeds by the simplest mechanism of all—proton transfer. The overall mechanism provides for an early reinforcement of acid-base chemistry and an early introduction to carbocations and nucleophilic substitution. • Chapter 5 continues the chemistry of alcohols and alkyl halides by showing how they can be used to prepare alkenes by elimination reactions. Here, the students see a second example of the formation of carbocation intermediates from alcohols, but in this case, the carbocation travels a different pathway to a different destination. • The alkenes prepared in Chapter 5 are studied again in Chapter 6, this time with an eye toward their own chemical reactivity. What the students learned about carbocations in Chapters 4 and 5 serves them well in understanding the mechanisms of the reactions of alkenes in Chapter 6. • Likewise, the mechanism of nucleophilic addition to the carbonyl group of aldehydes and ketones described in Chapter 17 sets the stage for aldol condensation in Chapter 18, esterification of carboxylic acids in Chapter 19, nucleophilic acyl substitution in Chapter 20, and ester condensation in Chapter 21
PREFACE THE SPARTAN INTEGRATION vide must be woven into. not added to. the books The third edition of this text broke new ground with its emphasis on molecular modeling, including the addition The level of the coverage had to remain the same. of more than 100 exercises of the model-building type Spartan is versatile. We used the same software This. the fourth edition. moves to the next level of mod package to develop this edition that is used in eling. Gwendolyn and Alan Shusterman's 1997 Journal research laboratories worldwide. It was essential of Chemical Education article "Teaching Chemistry with that we limit ourselves to only those features that Electron Density Models"described how models show- clarified a particular point. Organic chemistry is ing the results of molecular orbital calculations, espe challenging enough. We didnt need to make it ally electrostatic potential maps, could be used effec- difficult. If we were to err. it would there. tively in introductory courses. The software used to fore be better to err on the side of caution create the Shustermans'models was Spartan, a product of wavefunction. Inc. a third consideration surfaced soon after the work In a nutshell, the beauty of electrostatic potential maps is their ability to display the charge distribution in Student access to Spartan would be essential. a molecule. At the most fundamental level. the forces ing could help students connect with molec- that govern structure and properties in organic chemistry ular modeling better than owning the same soft are the attractions between opposite charges and the ware used to produce the text or, even better, soft repulsions between like charges. We were therefore opti ware that allowed them not only to view models mistic that electrostatic potential maps held great from the text but also to make their own. promise for helping students make the connection between structure, especially electronic structure, and All of this led to a fruitful and stimulating collab- properties. Even at an early stage we realized that tw oration with Dr. Warren Hehre. a leading theoretical main considerations had to guide our efforts chemist and the founder, president, and CEO of Wave- function, Inc. Warren was enthusiastic about the project An integrated approach was required. To be effec- and agreed to actively participate in it. He and Alan tive, Spartan models and the information they pro- Shusterman produced a CD tailored specifically to NEW IN THIS EDITION ALL-NEW ILLUSTRATIONS All figures were redrawn specific applications of either the Spartanview or to convey visual concepts clearly and forcefully In ad- Spartan Build program, found on the accompanying dition, the author created a number of new image les CD-ROM. Appendix 3 provides a complete guide to using the Spartan molecular modeling application. the Learning By Modeling CD-ROM Now students can view electrostatic potential maps to see the charge distribution of a molecule in vivid ALL-NEW SPECTRA Chapter 13, Spectroscopy, was color. These striking images afford the instructor a heavily revised, with rewritten sections on NMR and powerful means to lead students to a better under with all the NMR spectra generated on a high-fie standing of organic molecules Instrument FULL SPARTAN IMAGE INTEGRATION The Spartan- maries are recast into a more open, easier-to-read generated images are impressive in their own right, format, inspired by the popularity of the accompany- but for teaching purposes they are most effective when they are closely aligned with the text content. g summary tables Because the author personally generated the images NEW DESIGN This edition sports a new look, with an as he wrote this edition, the molecular models are emphasis on neatness, clarity, and color carefully lly integrated with text, and the educational value used to heighten interest and to create visual cues for is maximized. Additionally, icons direct students to important information. Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
xxvi PREFACE THE SPARTAN INTEGRATION The third edition of this text broke new ground with its emphasis on molecular modeling, including the addition of more than 100 exercises of the model-building type. This, the fourth edition, moves to the next level of modeling. Gwendolyn and Alan Shusterman’s 1997 Journal of Chemical Education article “Teaching Chemistry with Electron Density Models” described how models showing the results of molecular orbital calculations, especially electrostatic potential maps, could be used effectively in introductory courses. The software used to create the Shustermans’ models was Spartan, a product of Wavefunction, Inc. In a nutshell, the beauty of electrostatic potential maps is their ability to display the charge distribution in a molecule. At the most fundamental level, the forces that govern structure and properties in organic chemistry are the attractions between opposite charges and the repulsions between like charges. We were therefore optimistic that electrostatic potential maps held great promise for helping students make the connection between structure, especially electronic structure, and properties. Even at an early stage we realized that two main considerations had to guide our efforts. • An integrated approach was required. To be effective, Spartan models and the information they provide must be woven into, not added to, the book’s core. • The level of the coverage had to remain the same. Spartan is versatile. We used the same software package to develop this edition that is used in research laboratories worldwide. It was essential that we limit ourselves to only those features that clarified a particular point. Organic chemistry is challenging enough. We didn’t need to make it more difficult. If we were to err, it would therefore be better to err on the side of caution. A third consideration surfaced soon after the work began. • Student access to Spartan would be essential. Nothing could help students connect with molecular modeling better than owning the same software used to produce the text or, even better, software that allowed them not only to view models from the text, but also to make their own. All of this led to a fruitful and stimulating collaboration with Dr. Warren Hehre, a leading theoretical chemist and the founder, president, and CEO of Wavefunction, Inc. Warren was enthusiastic about the project and agreed to actively participate in it. He and Alan Shusterman produced a CD tailored specifically to NEW IN THIS EDITION ALL-NEW ILLUSTRATIONS All figures were redrawn to convey visual concepts clearly and forcefully. In addition, the author created a number of new images using the Spartan molecular modeling application. Now students can view electrostatic potential maps to see the charge distribution of a molecule in vivid color. These striking images afford the instructor a powerful means to lead students to a better understanding of organic molecules. FULL SPARTAN IMAGE INTEGRATION The Spartangenerated images are impressive in their own right, but for teaching purposes they are most effective when they are closely aligned with the text content. Because the author personally generated the images as he wrote this edition, the molecular models are fully integrated with text, and the educational value is maximized. Additionally, icons direct students to specific applications of either the SpartanView or SpartanBuild program, found on the accompanying CD-ROM. Appendix 3 provides a complete guide to the Learning By Modeling CD-ROM. ALL-NEW SPECTRA Chapter 13, Spectroscopy, was heavily revised, with rewritten sections on NMR and with all the NMR spectra generated on a high-field instrument. IMPROVED SUMMARIES The end-of-chapter summaries are recast into a more open, easier-to-read format, inspired by the popularity of the accompanying summary tables. NEW DESIGN This edition sports a new look, with an emphasis on neatness, clarity, and color carefully used to heighten interest and to create visual cues for important information
PREFACE accompany our text. We call it Learning By Modelin Two new boxed essays, "How Sweet It Is! "in It and Organic Chemistry truly complement each other. hapter 25, and"Good Cholesterol? Bad Choles Many of the problems in Organic Chemistry have been terol? What's the Difference? "in Chapter 26 written expressly for the model-building software Spar cover topics of current interest from an organic tan Build that forms one part of Learning By Modeling chemists perspective Another tool, Spartan View, lets students inspect more than 250 already constructed models and animations The already-numerous examples of enzyme catalyzed organic reactions were supplemented by ranging in size from hydrogen to carboxypeptidase adding biological Baeyer-Villiger oxidations and We were careful to incorporate Spartan so it would fumaric acid dehydrogenation be a true amplifier of the textbook, not just as a stand alone tool that students might or might not use, depend- Chapters 25-27 have benefited substantially from ng on the involvement of their instructor. Thus, the the Spartan connection. We replaced many of the artist- content of the CD provides visual, three-dimensional rendered structural drawings of complex biomolecules reinforcement of the concepts covered on the printe from earlier editions with accurate models generated page. The Spartan View icon O invites students to view from imported crystallographic data. These include a molecule or animation as they are reading the text. maltose, cellobiose, and cellulose in Chapter 25 Opportunities to use Spartan Build are similarly correlated to the text with an icon 2 directing students triacylglycerols in Chapter 26 to further explore a concept or solve a modeling-based alanylglycine, leucine enkephalin, a pleated B- problem with the software sheet, an a-helix, carboxypeptidase, myoglobin, In addition to its role as the electronic backbone DNA, and phenylalanine tRNA in Chapter 27 of the CD component and the integrated learnin All of these are included on Learning By Model- approach, the Spartan software makes a visible impact ing, where you can view them as wire, ball-and-spoke on the printed pages of this edition. I used Spartan or tube, or space-filling models while rotating them in three my own computer to create many of the figures, pro- dimensions viding students with numerous visual explorations of the Both the text and Learning by modeling include oncepts of charge distribution other structures of biological interest including BIOLOGICAL APPLICATIONS AND THEIR electrostatic potential maps of the 20 common INTEGRATION amino acids showing just how different the vari- Comprehensive coverage of the important classes of bio- ous side chains are( Chapter 27) molecules(carbohydrates, lipids, amino acids, peptides proteins, and nucleic acids) appears in Chapters 25-27. SPECTROSCOPY But biological applications are such an important part of organ hemistry that they deserve more attention Because it offers an integrated treatment of nuclear mag- throughout the course. We were especially alert to oppor- netic resonance(NMR), infrared (IR), and ultraviolet tunities to introduce more biologically oriented material visible (Uv-vIS) spectroscopy, and mass spectrometry to complement that which had already grown signifi- (MS), Chapter 13 is the longest in the text. It is also the cantly since the first edition. Some specific examples chapter that received the most attention in this edition All of the sections dealing with NMR were extensively The new boxed essay"Methane and the Bio- rewritten, all of the NMR spectra were newly recorded sphere"in Chapter 2 combines elements of on a high-field instrument, and all of the text figures organic chemistry, biology, and environmental sci- were produced directly from the electronic data files ence to tell the story of where methane comes Likewise, the IR and UV-VIs sections of Chapter from and where it goes 13 were revised and all of the IR spectra were recorded A new boxed essay,"An Enzyme-Catalyzed especially for this text. Nucleophilic Substitution of an Alkyl Halide, in After being first presented in Chapter 13, spec Chapter 8 makes a direct and simple connection troscopy is then integrated into the topics that follow it between SN2 reactions and biochemistry. The functional-group chapters, 15, 16, 17, Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
PREFACE xxvii accompany our text. We call it Learning By Modeling. It and Organic Chemistry truly complement each other. Many of the problems in Organic Chemistry have been written expressly for the model-building software SpartanBuild that forms one part of Learning By Modeling. Another tool, SpartanView, lets students inspect more than 250 already constructed models and animations, ranging in size from hydrogen to carboxypeptidase. We were careful to incorporate Spartan so it would be a true amplifier of the textbook, not just as a standalone tool that students might or might not use, depending on the involvement of their instructor. Thus, the content of the CD provides visual, three-dimensional reinforcement of the concepts covered on the printed page. The SpartanView icon invites students to view a molecule or animation as they are reading the text. Opportunities to use SpartanBuild are similarly correlated to the text with an icon directing students to further explore a concept or solve a modeling-based problem with the software. In addition to its role as the electronic backbone of the CD component and the integrated learning approach, the Spartan software makes a visible impact on the printed pages of this edition. I used Spartan on my own computer to create many of the figures, providing students with numerous visual explorations of the concepts of charge distribution. BIOLOGICAL APPLICATIONS AND THEIR INTEGRATION Comprehensive coverage of the important classes of biomolecules (carbohydrates, lipids, amino acids, peptides, proteins, and nucleic acids) appears in Chapters 25–27. But biological applications are such an important part of organic chemistry that they deserve more attention throughout the course. We were especially alert to opportunities to introduce more biologically oriented material to complement that which had already grown signifi- cantly since the first edition. Some specific examples: • The new boxed essay “Methane and the Biosphere” in Chapter 2 combines elements of organic chemistry, biology, and environmental science to tell the story of where methane comes from and where it goes. • A new boxed essay, “An Enzyme-Catalyzed Nucleophilic Substitution of an Alkyl Halide,” in Chapter 8 makes a direct and simple connection between SN2 reactions and biochemistry. • Two new boxed essays, “How Sweet It Is!” in Chapter 25, and “Good Cholesterol? Bad Cholesterol? What’s the Difference?” in Chapter 26, cover topics of current interest from an organic chemist’s perspective. • The already-numerous examples of enzymecatalyzed organic reactions were supplemented by adding biological Baeyer-Villiger oxidations and fumaric acid dehydrogenation. Chapters 25–27 have benefited substantially from the Spartan connection. We replaced many of the artistrendered structural drawings of complex biomolecules from earlier editions with accurate models generated from imported crystallographic data. These include: • maltose, cellobiose, and cellulose in Chapter 25 • triacylglycerols in Chapter 26 • alanylglycine, leucine enkephalin, a pleated - sheet, an -helix, carboxypeptidase, myoglobin, DNA, and phenylalanine tRNA in Chapter 27 All of these are included on Learning By Modeling, where you can view them as wire, ball-and-spoke, tube, or space-filling models while rotating them in three dimensions. Both the text and Learning By Modeling include other structures of biological interest including: • a space-filling model of a micelle (Chapter 19) • electrostatic potential maps of the 20 common amino acids showing just how different the various side chains are (Chapter 27) SPECTROSCOPY Because it offers an integrated treatment of nuclear magnetic resonance (NMR), infrared (IR), and ultravioletvisible (UV-VIS) spectroscopy, and mass spectrometry (MS), Chapter 13 is the longest in the text. It is also the chapter that received the most attention in this edition. All of the sections dealing with NMR were extensively rewritten, all of the NMR spectra were newly recorded on a high-field instrument, and all of the text figures were produced directly from the electronic data files. Likewise, the IR and UV-VIS sections of Chapter 13 were revised and all of the IR spectra were recorded especially for this text. After being first presented in Chapter 13, spectroscopy is then integrated into the topics that follow it. The functional-group chapters, 15, 16, 17, 19, 20, 22,
PREFACE and 24, all contain spectroscopy sections as well as I liked, for example, writing the new boxed essay examples and problems based on display spectra. Laws, Theories, and the Scientific Method"and placing it in Chapter 6. The scientific method is one thing that NTEGRATION OF TOPICS who takes a college-level chemistry should be familiar with. but most arent. It normall Too often, in too many courses(and not just in organic appears in Chapter I of general chemistry texts, before the chemistry), too many interesting topics never get cov students have enough factual knowledge to really under- ered because they are relegated to the end of the text as stand it, and it's rarely mentioned again. By the time our special topic chapters"that, unfortunately, fall by the organic chemistry students get to"Laws, Theories, and the wayside as the end of the term approaches. We have Scientific Method, however, we have told them about the from the beginning and with each succeeding edition experimental observations that led to Markovnikov's law, looked for opportunities to integrate the most important ng has prog of these"special topics into the core material. I am a broadly accepted theory based on carbocation stability pleased with the results. Typically, this integration is It makes a nice story. Lets use it accomplished by breaking a topic into its component elements and linking each of those elements to one or FEWER TOPICS EQUALS MORE HELP more conceptually related core topics There is, for example, no end-of-text chapter enti- By being selective in the topics we cover, we can tled"Heterocyclic Compounds. Rather, heteroatoms include more material designed to help the student learn. are defined in Chapter 1 and nonaromatic heterocyclic Solved sample problems: In addition to a generous number of end-of-chapter problems, the text electrophilic and nucleophilic aromatic substitution reac includes more than 450 problems within the chap- tions described in Chapters 12 and 23, respectively. Het- rs themselves. Of these in-chapter problems rocyclic compounds appear in numerous ways througl approximately one-third are multipart exercises out the text and the biological role of two classes of that contain a detailed solution to part (a) outlin- them-the purines and pyrimidines--features promi ing the reasoning behind the answer. nently in the discussion of nucleic acids in Chapter 27 Summary tables: Annotated summary tables have he economic impact of synthetic polymers is too been a staple of Organic Chemistry ever since the great to send them to the end of the book as a separate first edition and have increased in number to more chapter or to group them with biopolymers. We regard than 50. Well received by students and faculty polymers as a natural part of organic chemistry and pay alike, they remain one of the texts strengths attention to them throughout the text. The prepara End-of-chapter summaries: Our with the vinyl polymers is described in Chapter 6, poly summary tables prompted us to recast the narra- geochemistry in Chapter 7, diene polymers in tive part of the end-of-chapter summaries into a 10, Ziegler-Natta catalysis in Chapter 14, and conder more open, easier-to-read format sation polymers in Chapter 20 SUPPLEMENTS INTEGRATING THE CHEMISTRY CURRICULUM For the student Study Guide and Solutions Manual by Francis A I always thought that the general chemistry course Carey and Robert C. Atkins. This valuable supplement would be improved if more organic chemists taught it, provides solutions to all problems in the text. More than and have done just that myself for the past nine years imply providing answers, most solutions guide the stu I now see that just as general chemistry can benefit from dent with the reasoning behind each problem. In addi the perspective that an organic chemist brings to it, so tion, each chapter of the Study Guide and Solutions can the teaching and learning of organic chemistry be Manual concludes with a Self- Test designed to assess improved by making the transition from general chem- the students mastery of the material istry to organic smoother. Usually this is more a matter of style and terminology than content-an incremental Online Learning Center atherthanaradicalchangeIstartedmakingsuchAtwww.mhhe.com/carey,thiscomprehensiveexclusive changes in the third edition and continue here Web site provides a wealth of electronic resources for Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
xxviii PREFACE and 24, all contain spectroscopy sections as well as examples and problems based on display spectra. INTEGRATION OF TOPICS Too often, in too many courses (and not just in organic chemistry), too many interesting topics never get covered because they are relegated to the end of the text as “special topic chapters” that, unfortunately, fall by the wayside as the end of the term approaches. We have, from the beginning and with each succeeding edition, looked for opportunities to integrate the most important of these “special” topics into the core material. I am pleased with the results. Typically, this integration is accomplished by breaking a topic into its component elements and linking each of those elements to one or more conceptually related core topics. There is, for example, no end-of-text chapter entitled “Heterocyclic Compounds.” Rather, heteroatoms are defined in Chapter 1 and nonaromatic heterocyclic compounds introduced in Chapter 3; heterocyclic aromatic compounds are included in Chapter 11, and their electrophilic and nucleophilic aromatic substitution reactions described in Chapters 12 and 23, respectively. Heterocyclic compounds appear in numerous ways throughout the text and the biological role of two classes of them—the purines and pyrimidines—features prominently in the discussion of nucleic acids in Chapter 27. The economic impact of synthetic polymers is too great to send them to the end of the book as a separate chapter or to group them with biopolymers. We regard polymers as a natural part of organic chemistry and pay attention to them throughout the text. The preparation of vinyl polymers is described in Chapter 6, polymer stereochemistry in Chapter 7, diene polymers in Chapter 10, Ziegler–Natta catalysis in Chapter 14, and condensation polymers in Chapter 20. INTEGRATING THE CHEMISTRY CURRICULUM I always thought that the general chemistry course would be improved if more organic chemists taught it, and have done just that myself for the past nine years. I now see that just as general chemistry can benefit from the perspective that an organic chemist brings to it, so can the teaching and learning of organic chemistry be improved by making the transition from general chemistry to organic smoother. Usually this is more a matter of style and terminology than content—an incremental rather than a radical change. I started making such changes in the third edition and continue here. I liked, for example, writing the new boxed essay “Laws, Theories, and the Scientific Method” and placing it in Chapter 6. The scientific method is one thing that everyone who takes a college-level chemistry course should be familiar with, but most aren’t. It normally appears in Chapter 1 of general chemistry texts, before the students have enough factual knowledge to really understand it, and it’s rarely mentioned again. By the time our organic chemistry students get to “Laws, Theories, and the Scientific Method,” however, we have told them about the experimental observations that led to Markovnikov’s law, and how our understanding has progressed to the level of a broadly accepted theory based on carbocation stability. It makes a nice story. Let’s use it. FEWER TOPICS EQUALS MORE HELP By being selective in the topics we cover, we can include more material designed to help the student learn. Solved sample problems: In addition to a generous number of end-of-chapter problems, the text includes more than 450 problems within the chapters themselves. Of these in-chapter problems approximately one-third are multipart exercises that contain a detailed solution to part (a) outlining the reasoning behind the answer. Summary tables: Annotated summary tables have been a staple of Organic Chemistry ever since the first edition and have increased in number to more than 50. Well received by students and faculty alike, they remain one of the text’s strengths. End-of-chapter summaries: Our experience with the summary tables prompted us to recast the narrative part of the end-of-chapter summaries into a more open, easier-to-read format. SUPPLEMENTS For the Student Study Guide and Solutions Manual by Francis A. Carey and Robert C. Atkins. This valuable supplement provides solutions to all problems in the text. More than simply providing answers, most solutions guide the student with the reasoning behind each problem. In addition, each chapter of the Study Guide and Solutions Manual concludes with a Self-Test designed to assess the student’s mastery of the material. Online Learning Center At www.mhhe.com/carey, this comprehensive, exclusive Web site provides a wealth of electronic resources for
PREFACE instructors and students alike Content includes tutorials, For the instructor problem-solving strategies, and assessment exercises for Overhead Transparencies. These full-color transparen every chapter in the text cies of illustrations from the text include reproductions Learning By Modeling CD-ROM spectr In collaboration with Wavefunction, we have created a generated molecular models, and step-by-step reaction cross-function CD-Rom that contains an electronic Test Bank. This collection of 1000 multiple model-building kit and a rich collection of animations choice questions, prepared by Professor Bruce Osterby Ind molecular models that reveal the interplay between of the University of Wisconsin-LaCrosse, is available to electronic structure and reactivity in organic chemistry. Packaged free with the text, Learning By Model- adopters in print, Macintosh, or Windows format. Visual Resource Library. This invaluable lecture ing has two components: Spartan Build, a user-friendly aid provides the instructor with all the images from the electronic toolbox that lets you build, examine, and eval uate literally thousands of molecular models; and Spar- textbook on a CD-RoM. The Power Point format tan View, an application with which you can view and enables easy customization and formatting of the images into the lecture examine more than 250 molecular models and anima tions discussed in the text. In the textbook, icons point The Online Learning Center, described in the pre the way to where you can use these state-of-the-art mol- vIous section, has special features for instructors, includ- ecular modeling applications to expand your under ing quiz capabilities standing and sharpen your conceptual skills. This edi- Please contact your McGraw-Hill representative tion of the text contains numerous problems that take for additional information concerning these supple advantage of these applications. Appendix 3 provides aments complete guide to using the CD Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
PREFACE xxix instructors and students alike. Content includes tutorials, problem-solving strategies, and assessment exercises for every chapter in the text. Learning By Modeling CD-ROM In collaboration with Wavefunction, we have created a cross-function CD-ROM that contains an electronic model-building kit and a rich collection of animations and molecular models that reveal the interplay between electronic structure and reactivity in organic chemistry. Packaged free with the text, Learning By Modeling has two components: SpartanBuild, a user-friendly electronic toolbox that lets you build, examine, and evaluate literally thousands of molecular models; and SpartanView, an application with which you can view and examine more than 250 molecular models and animations discussed in the text. In the textbook, icons point the way to where you can use these state-of-the-art molecular modeling applications to expand your understanding and sharpen your conceptual skills. This edition of the text contains numerous problems that take advantage of these applications. Appendix 3 provides a complete guide to using the CD. For the Instructor Overhead Transparencies. These full-color transparencies of illustrations from the text include reproductions of spectra, orbital diagrams, key tables, computergenerated molecular models, and step-by-step reaction mechanisms. Test Bank. This collection of 1000 multiplechoice questions, prepared by Professor Bruce Osterby of the University of Wisconsin–LaCrosse, is available to adopters in print, Macintosh, or Windows format. Visual Resource Library. This invaluable lecture aid provides the instructor with all the images from the textbook on a CD-ROM. The PowerPoint format enables easy customization and formatting of the images into the lecture. The Online Learning Center, described in the previous section, has special features for instructors, including quiz capabilities. Please contact your McGraw-Hill representative for additional information concerning these supplements
ACKNOWLEDGMENTS ou may have noticed that this preface is almost entirely Steven Bachrach, Trinity University rand"my. That is because Jared A. Butcher, Jr, Ohio University Organic Chemistry is, and always has been, a team Barry Carpenter, Cornell University effort From the first edition to this one, the editorial and Pasquale R. Di Raddo, Ferris State University production staffs at WCB/McGraw-Hill have been com- Jill Discordia, Le Moyne College mitted to creating an accurate, interesting, student- William A. Donaldson, Marquette University oriented text. Special thanks go to Kent Peterson, Terry Mark Forman, St Josephs University Stanton, and Peggy Selle for their professionalism, skill, Warren Giering, Boston University and cooperative spirit. Linda Davoli not only copy Benjamin Gross, University of Tennessee-Chattanooga edited the manuscript but offered valuable advice about R J. Hargrove, Mercer University style and presentation. GTS Graphics had the critical job E. Alexander Hill, University of Wisconsin-Milwaukee of converting the copy-edited manuscript to a real book. Shawn Hitchcock, Illinois State University Our contact there was Heather Stratton; her enthusiasm L A. Hull, Union College for the project provided us an unusual amount of free- Colleen Kelley, Northern Arizona University dom to fine-tune the text Brenda Kesler, San Jose State University I have already mentioned the vital role played by C. A Kingsbury, University of Nebraska-Lincoln Warren Hehre and Alan Shusterman in integrating Spar- Francis M. Klein, Creighton University tan into this edition. I am grateful for their generosity in Paul M. Lahti, University of Massachusetts-Amherst giving their time, knowledge, and support to this proj Rita s. Majerle, South Dakota State University ect. I also thank Dr. Michal Sabat of the University of Michael Millam, Phoenix College Virginia for his assistance in my own modeling efforts. Tyra Montgomery, University of Houston-Downtown All of the NMR and IR spectra in this edition were Richard Narske, Augustana University recorded at the Department of Chemistry of James Michael A Nichols, John Carroll University Madison University by two undergraduate students, Jef Bruce E Norcross, SUNY-Binghamton frey Cross and Karin Hamburger, under the guidance of Charles A. Panetta, University of Mississippi Thomas Gallaher. We are indebted to them for their Michael J. Panigot, Arkansas State University lp. Joe Pavelites, William Woods College . gain, as in the three previous editions, Dr. Robert Ty Redd, Southern Utah University C. Atkins has been indispensable. Bob is the driving Charles Rose, University of Nevada force behind the Study Guide and Solutions Manual that Suzanne Ruder, Virginia Commonwealth University accompanies this text. He is much more than that, Christine M. Russell, College of DuPage though He reads and critiques every page of the man- Dennis A. Sardella, Boston College uscript and every page of two rounds of proofs. I trust Janice G. Smith, Mt. Holyoke College his judgment completely when he suggests how to sim- Tami I Spector, University of San Francisco plify a point or make it clearer. Most of all, he is a great Ken Turnbull, Wright State University friend This text has benefited from the comments offered Curt Wentrup, University of Queensland Clifford M. Utermoehlen USAF Academ by a large number of teachers of organic chemistry who S D. Worley, Auburn University reviewed it at various stages of its development. I appre ciate their help. They include Reviewers for the third Edition Edward Alexander, San Diego Mesa College Reviewers for the fourth edition Ronald Baumgarten, University of Illinois-Chicago Jennifer Adamski, Old Dominion University Barry Carpenter, Cornell University Jeffrey B. Arterburn, New Mexico State University John Cochran, Colgate University Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
ACKNOWLEDGMENTS xxxi You may have noticed that this preface is almost entirely “we” and “our,” not “I” and “my.” That is because Organic Chemistry is, and always has been, a team effort. From the first edition to this one, the editorial and production staffs at WCB/McGraw-Hill have been committed to creating an accurate, interesting, studentoriented text. Special thanks go to Kent Peterson, Terry Stanton, and Peggy Selle for their professionalism, skill, and cooperative spirit. Linda Davoli not only copy edited the manuscript but offered valuable advice about style and presentation. GTS Graphics had the critical job of converting the copy-edited manuscript to a real book. Our contact there was Heather Stratton; her enthusiasm for the project provided us an unusual amount of freedom to fine-tune the text. I have already mentioned the vital role played by Warren Hehre and Alan Shusterman in integrating Spartan into this edition. I am grateful for their generosity in giving their time, knowledge, and support to this project. I also thank Dr. Michal Sabat of the University of Virginia for his assistance in my own modeling efforts. All of the NMR and IR spectra in this edition were recorded at the Department of Chemistry of James Madison University by two undergraduate students, Jeffrey Cross and Karin Hamburger, under the guidance of Thomas Gallaher. We are indebted to them for their help. Again, as in the three previous editions, Dr. Robert C. Atkins has been indispensable. Bob is the driving force behind the Study Guide and Solutions Manual that accompanies this text. He is much more than that, though. He reads and critiques every page of the manuscript and every page of two rounds of proofs. I trust his judgment completely when he suggests how to simplify a point or make it clearer. Most of all, he is a great friend. This text has benefited from the comments offered by a large number of teachers of organic chemistry who reviewed it at various stages of its development. I appreciate their help. They include Reviewers for the Fourth Edition Jennifer Adamski, Old Dominion University Jeffrey B. Arterburn, New Mexico State University Steven Bachrach, Trinity University Jared A. Butcher, Jr., Ohio University Barry Carpenter, Cornell University Pasquale R. Di Raddo, Ferris State University Jill Discordia, Le Moyne College William A. Donaldson, Marquette University Mark Forman, St. Joseph’s University Warren Giering, Boston University Benjamin Gross, University of Tennessee–Chattanooga R. J. Hargrove, Mercer University E. Alexander Hill, University of Wisconsin–Milwaukee Shawn Hitchcock, Illinois State University L. A. Hull, Union College Colleen Kelley, Northern Arizona University Brenda Kesler, San Jose State University C. A. Kingsbury, University of Nebraska–Lincoln Francis M. Klein, Creighton University Paul M. Lahti, University of Massachusetts–Amherst Rita S. Majerle, South Dakota State University Michael Millam, Phoenix College Tyra Montgomery, University of Houston–Downtown Richard Narske, Augustana University Michael A. Nichols, John Carroll University Bruce E. Norcross, SUNY–Binghamton Charles A. Panetta, University of Mississippi Michael J. Panigot, Arkansas State University Joe Pavelites, William Woods College Ty Redd, Southern Utah University Charles Rose, University of Nevada Suzanne Ruder, Virginia Commonwealth University Christine M. Russell, College of DuPage Dennis A. Sardella, Boston College Janice G. Smith, Mt. Holyoke College Tami I. Spector, University of San Francisco Ken Turnbull, Wright State University Clifford M. Utermoehlen, USAF Academy Curt Wentrup, University of Queensland S. D. Worley, Auburn University Reviewers for the Third Edition Edward Alexander, San Diego Mesa College Ronald Baumgarten, University of Illinois–Chicago Barry Carpenter, Cornell University John Cochran, Colgate University
