Get a Better Grade in Chemistry! Log in now to the leading online learning system for chemistry Score better on exams, get homework help, and more! • Master chemistry and improve your grade using OWL’s step-by-step tutorials, and homework questions that provide instant answer-speciic feedback Available 24/7 • Learn at your own pace with OWL, a study smart system that ensures you’ve mastered each concept before you move on • Access the Cengage Youbook, an e-version of your textbook enhanced with videos and animations, highlighting, the ability to add notes, and more To get started, use the access code that may have been packaged with your text or purchase access online Check with your instructor to verify that OWL is required for your course before purchasing www.cengage.com/OWL Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Get a Better Grade in Chemistry! Log in now to the leading online learning system for chemistry Score better on exams, get homework help, and more! • Master chemistry and improve your grade using OWL’s step-by-step tutorials, and homework questions that provide instant answer-speciic feedback Available 24/7 • Learn at your own pace with OWL, a study smart system that ensures you’ve mastered each concept before you move on • Access the Cengage Youbook, an e-version of your textbook enhanced with videos and animations, highlighting, the ability to add notes, and more To get started, use the access code that may have been packaged with your text or purchase access online Check with your instructor to verify that OWL is required for your course before purchasing www.cengage.com/OWL Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Get a Better Grade in Chemistry! Log in now to the leading online learning system for chemistry Score better on exams, get homework help, and more! • Master chemistry and improve your grade using OWL’s step-by-step tutorials, and homework questions that provide instant answer-speciic feedback Available 24/7 • Learn at your own pace with OWL, a study smart system that ensures you’ve mastered each concept before you move on • Access the Cengage Youbook, an e-version of your textbook enhanced with videos and animations, highlighting, the ability to add notes, and more To get started, use the access code that may have been packaged with your text or purchase access online Check with your instructor to verify that OWL is required for your course before purchasing www.cengage.com/OWL Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Organic Chemistry SIXT H EDIT ION William H Brown Beloit College Christopher S Foote University of California, Los Angeles Brent L Iverson University of Texas, Austin Eric V Anslyn University of Texas, Austin Chapter 29 was originally contributed by Bruce M Novak North Carolina State University Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Organic Chemistry, Sixth Edition William H Brown, Christopher S Foote, Brent L Iverson, Eric V Anslyn Executive Editor: Lisa Lockwood Senior Developmental Editor: Sandra Kiselica Assistant Editor: Elizabeth Woods Editorial Assistant: Laura Bowen © 2012, 2009 Brooks/Cole, Cengage Learning ALL RIGHTS RESERVED No part of this work covered by the copyright herein may be reproduced, transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the publisher Senior Media Editor: Lisa Weber Media Editor: Stephanie Van Camp Senior Marketing Manager: Barb Bartoszek Marketing Assistant: Julie Stefani Marketing Communications Manager: Linda Yip Content Project Manager: Teresa L Trego For product information and technology assistance, contact us at Cengage Learning Customer & Sales Support, 1-800-354-9706 For permission to use material from this text or product, submit all requests online at www.cengage.com/permissions Further permissions questions can be e-mailed to permissionrequest@cengage.com Library of Congress Control Number: 2010939137 Design Director: Rob Hugel Art Director: John Walker ISBN-13: 978-0-8400-5498-2 ISBN-10: 0-8400-5498-X Print Buyer: Judy Inouye Rights Acquisitions Specialist: Tom McDonough Production Service: PreMediaGlobal Text Designer: Ellen Pettengell Photo Researcher: Bill Smith Group Copy Editor: PreMediaGlobal OWL producers: Stephen Battisti, Cindy Stein, David Hart (Center for Educational Software Development, University of Massachusetts, Amherst) Illustrator: Greg Gambino, PreMediaGlobal Cover Designer: RHDG | Riezebos Holzbaur Brooks/Cole 20 Davis Drive Belmont, CA 94002-3098 USA Cengage Learning is a leading provider of customized learning solutions with office locations around the globe, including Singapore, the United Kingdom, Australia, Mexico, Brazil, and Japan Locate your local office at www.cengage.com/global Cengage Learning products are represented in Canada by Nelson Education, Ltd To learn more about Brooks/Cole, visit www.cengage.com/brookscole Purchase any of our products at your local college store or at our preferred online store www.cengagebrain.com Cover Image: © Corbis Images/Tobias Bernhard Compositor: PreMediaGlobal Printed in the United States of America 14 13 12 11 10 Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Organic Chemistry, Sixth Edition William H Brown, Christopher S Foote, Brent L Iverson, Eric V Anslyn Executive Editor: Lisa Lockwood Senior Developmental Editor: Sandra Kiselica Assistant Editor: Elizabeth Woods Editorial Assistant: Laura Bowen © 2012, 2009 Brooks/Cole, Cengage Learning ALL RIGHTS RESERVED No part of this work covered by the copyright herein may be reproduced, transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the publisher Senior Media Editor: Lisa Weber Media Editor: Stephanie Van Camp Senior Marketing Manager: Barb Bartoszek Marketing Assistant: Julie Stefani Marketing Communications Manager: Linda Yip Content Project Manager: Teresa L Trego For product information and technology assistance, contact us at Cengage Learning Customer & Sales Support, 1-800-354-9706 For permission to use material from this text or product, submit all requests online at www.cengage.com/permissions Further permissions questions can be e-mailed to permissionrequest@cengage.com Library of Congress Control Number: 2010939137 Design Director: Rob Hugel Art Director: John Walker ISBN-13: 978-0-8400-5498-2 ISBN-10: 0-8400-5498-X Print Buyer: Judy Inouye Rights Acquisitions Specialist: Tom McDonough Production Service: PreMediaGlobal Text Designer: Ellen Pettengell Photo Researcher: Bill Smith Group Copy Editor: PreMediaGlobal OWL producers: Stephen Battisti, Cindy Stein, David Hart (Center for Educational Software Development, University of Massachusetts, Amherst) Illustrator: Greg Gambino, PreMediaGlobal Cover Designer: RHDG | Riezebos Holzbaur Brooks/Cole 20 Davis Drive Belmont, CA 94002-3098 USA Cengage Learning is a leading provider of customized learning solutions with office locations around the globe, including Singapore, the United Kingdom, Australia, Mexico, Brazil, and Japan Locate your local office at www.cengage.com/global Cengage Learning products are represented in Canada by Nelson Education, Ltd To learn more about Brooks/Cole, visit www.cengage.com/brookscole Purchase any of our products at your local college store or at our preferred online store www.cengagebrain.com Cover Image: © Corbis Images/Tobias Bernhard Compositor: PreMediaGlobal Printed in the United States of America 14 13 12 11 10 Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Dedication This Sixth Edition is dedicated to the memory of our dear friend and colleague, Christopher Foote Chris’ insights, encouragement, and dedication to this project can never be replaced His kind and nurturing spirit lives on in all who are lucky enough to have known him Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it About the Authors WILLIAM H BROWN is an Emeritus Professor of Chemistry at Beloit College, where he has twice been named Teacher of the Year His teaching responsibilities included organic chemistry, advanced organic chemistry, and special topics in pharmacology and drug synthesis He received his Ph.D from Columbia University under the direction of Gilbert Stork and did postdoctoral work at California Institute of Technology and the University of Arizona CHRISTOPHER S FOOTE received his B.S from Yale University and his Ph.D from Harvard University His scholarly credits include Sloan Fellow; Guggenheim Fellow; ACS Baekland Award; ACS Cope Scholar; Southern California Section ACS Tolman Medal; President, American Society for Photobiology; and Senior Editor, Accounts of Chemical Research He was a Professor of Chemistry at UCLA BRENT L IVERSON received his B.S from Stanford University and his Ph.D from the California Institute of Technology He is a University Distinguished Teaching Professor at The University of Texas, Austin as well as a respected researcher Brent’s research spans the interface of organic chemistry and molecular biology His group has developed several patented technologies, including an effective treatment for anthrax ERIC V ANSLYN is a University Distinguished Teaching Professor at The University of Texas at Austin He earned his bachelor’s degree from California State University, Northridge, his Ph.D from the California Institute of Technology and did postdoctoral work at Columbia University under the direction of Ronald Breslow Eric has won numerous teaching awards and his research focuses on the physical and bioorganic chemistry of synthetic and natural receptors and catalysts Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Contents in Brief 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Covalent Bonding and Shapes of Molecules Alkanes and Cycloalkanes Stereoisomerism and Chirality Acids and Bases Alkenes: Bonding, Nomenclature, and Properties Reactions of Alkenes Alkynes Haloalkanes, Halogenation, and Radical Reactions Nucleophilic Substitution and b-Elimination Alcohols Ethers, Epoxides, and Sulides Infrared Spectroscopy Nuclear Magnetic Resonance Spectroscopy Mass Spectrometry An Introduction to Organometallic Compounds Aldehydes and Ketones Carboxylic Acids Functional Derivatives of Carboxylic Acids Enolate Anions and Enamines Dienes, Conjugated Systems, and Pericyclic Reactions Benzene and the Concept of Aromaticity Reactions of Benzene and Its Derivatives Amines Catalytic Carbon-Carbon Bond Formation Carbohydrates Lipids Amino Acids and Proteins Nucleic Acids Organic Polymer Chemistry Appendices: 10 11 Thermodynamics and the Equilibrium Constant Major Classes of Organic Acids Bond Dissociation Enthalpies Characteristic 1H-NMR Chemical Shifts Characteristic 13C-NMR Chemical Shifts Characteristic Infrared Absorption Frequencies Electrostatic Potential Maps Summary of Stereochemical Terms Summary of the Rules of Nomenclature Common Mistakes in Arrow Pushing Organic Chemistry Road Maps Glossary Index v Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 Acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride, the same reagent used to convert an alcohol to a chloroalkane (Section 10.5C) O O OH Butanoic acid Cl SO2 HCl SOCl2 Thionyl chloride Butanoyl chloride The mechanism for the reaction of thionyl chloride with a carboxylic acid to form an acid chloride is similar to that presented in Section 10.5C for the conversion of an alcohol to a chloroalkane, and involves initial chlorosulite formation, followed by nucleophilic attack of chloride ion on the carbonyl carbon to give a tetrahedral carbonyl addition intermediate, which decomposes to give the acid chloride, SO2, and chloride ion Example 17.5 Complete the equation for each reaction O O OH SOCl2 (a) OH SOCl2 (b) Solution Following are the products of each reaction O O Cl SO2 HCl (a) Cl SO2 HCl (b) Problem 17.5 Complete the equation for each reaction COOH OH SOCl2 (a) SOCl2 (b) OCH3 17.9 Decarboxylation A b-Ketoacids Decarboxylation is the loss of CO2 from the carboxyl group of a molecule Almost any carboxylic acid, heated to a very high temperature, undergoes thermal decarboxylation Decarboxylation Loss of CO2 from a carboxyl group O RCOH decarboxylation heat RH CO2 Most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation Exceptions are carboxylic acids that have a carbonyl group b to the carboxyl group This type of carboxylic acid undergoes decarboxylation quite readily on mild heating For example, warming 3-oxobutanoic acid brings about its decarboxylation to give acetone and carbon dioxide O O O OH 3-Oxobutanoic acid (Acetoacetic acid) warm CO2 Acetone 17.9 Decarboxylation Copyright 2010 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 665 ... Organic Chemistry, Sixth Edition William H Brown, Christopher S Foote, Brent L Iverson, Eric V Anslyn Executive Editor: Lisa Lockwood Senior Developmental Editor: Sandra Kiselica Assistant Editor:... Organic Chemistry, Sixth Edition William H Brown, Christopher S Foote, Brent L Iverson, Eric V Anslyn Executive Editor: Lisa Lockwood Senior Developmental Editor: Sandra Kiselica Assistant Editor:... Professor of Chemistry at Beloit College, where he has twice been named Teacher of the Year His teaching responsibilities included organic chemistry, advanced organic chemistry, and special topics