M cGraw-Hill offers various tools and technology to support the seventh edition of Organic Chemistry You can order supplemental study materials by contacting your bookstore or the McGraw-Hill Customer Service Department at 1-800-338-3987 Solutions Manual CPS eInstruction ISBN-13: 978-0-07-304788-1 • ISBN-10: 0-07-304788-0 The Classroom Performance System’s Written by Robert C Atkins (James Madison University) and Francis A Carey, the Solutions Manual provides step-by-step solutions to guide students through the reasoning behind solving each problem in the text There is also a self-test at the end of each chapter designed to assess the student’s mastery of the material (CPS) eInstruction brings interactivity into the classroom or lecture hall It is a wireless response system that gives the instructor and students immediate feedback from the entire class The wireless response pads are essentially remotes that are easy to use and engage students CPS allows instructors to motivate student preparation, promote interactivity and active learning, and receive immediate feedback to assess student understanding Questions covering the content of the Organic Chemistry text and formatted in the CPS eInstruction software are available on the Organic Chemistry ARIS™ site McGraw-Hill Higher Education Apago PDF Enhancer car47872_fm_i-xxxii 11/24/06 23:09 Page i CONFIRMING PAGES S e v e n t h E d i t i o n Francis A Carey University of Virginia Apago PDF Enhancer Boston Burr Ridge, IL Dubuque, IA New York San Francisco St Louis Bangkok Bogotá Caracas Kuala Lumpur Lisbon London Madrid Mexico City Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei Toronto car47872_fm_i-xxxii 11/15/06 18:32 Page ii CONFIRMING PAGES ORGANIC CHEMISTRY, SEVENTH EDITION Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the Americas, New York, NY 10020 Copyright © 2008 by The McGraw-Hill Companies, Inc All rights reserved No part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior written consent of The McGraw-Hill Companies, Inc., including, but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning Some ancillaries, including electronic and print components, may not be available to customers outside the United States E This book is printed on recycled, acid-free paper containing 10% postconsumer waste DOW/DOW ISBN 978–0–07–304787–4 MHID 0–07–304787–2 Publisher: Thomas D Timp Senior Sponsoring Editor: Tamara Good-Hodge Developmental Editor: Jodi Rhomberg Senior Marketing Manager: Todd Turner Senior Project Manager: Gloria G Schiesl Senior Production Supervisor: Kara Kudronowicz Lead Media Project Manager: Judi David Executive Producer: Linda Meehan Avenarius Senior Designer: David W Hash Cover/Interior designer: Elise Lansdon (USE) Cover Image: Nanotube supplied by Dr Dirk Guldi of the University of Erlangen (Germany) and Dr Maurizio Prato of the University of Trieste (Italy) Senior Photo Research Coordinator: John C Leland Photo Research: Mary Reeg Supplement Producer: Tracy L Konrardy Compositor: Techbooks Typeface: 10.5/12 Times Printer: R R Donnelley Willard, OH Apago PDF Enhancer 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., 1937Organic chemistry / Francis A Carey.—7th ed p cm Includes index ISBN 978-0-07-304787-4—ISBN 0-07-304787-2 (hard copy : alk paper) Chemistry, Organic I Title QD251.3.C37 2008 547—dc22 2006031901 www.mhhe.com car47872_fm_i-xxxii 11/24/06 23:10 Page iii CONFIRMING PAGES This edition is dedicated to my colleague and friend Bob Atkins, who is not only the lead author of our Solutions Manual but who also has contributed generously of his time, knowledge, and common sense throughout the seven editions of this text Apago PDF Enhancer car47872_fm_i-xxxii 11/22/06 17:19 Page iv CONFIRMING PAGES About the Cover Chemists are increasingly concerned with preparing compounds designed to have particular properties The compound featured on the cover is the creation of Dr Dirk Guldi of the University of Erlangen (Germany) and Dr Maurizio Prato of the University of Trieste (Italy) The cylindrical object is a form of carbon known as a nanotube.* About percent of the carbons of this nanotube are linked to molecules of the organometallic “sandwich” compound ferrocene.† On irradiation with visible light, ferrocene transfers an electron to the nanotube, generating a charge-separated species Thus, nanotubes that bear appropriate attached groups hold promise as materials suitable for devices, such as solar cells, that are capable of converting sunlight to electricity Apago PDF Enhancer *For more about carbon nanotubes, see pages 432–433 † For more about ferrocene, see page 600 iv car47872_fm_i-xxxii 11/15/06 18:32 Page v CONFIRMING PAGES About the Author Francis A Carey, a native of Philadelphia, was educated at Drexel University (B.S in chemistry, 1959) and Penn State (Ph.D., 1963) Following postdoctoral work at Harvard and military service, he served on the faculty of the University of Virginia from 1966 until retiring as Professor Emeritus in 2000 In addition to this text, Professor Carey is coauthor (with Robert C Atkins) of Organic Chemistry: A Brief Course and (with Richard J Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and advanced undergraduates Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava Apago PDF Enhancer v car47872_fm_i-xxxii 11/15/06 18:32 Page vi CONFIRMING PAGES Brief Contents List of Important Features xix Preface xxv Acknowledgments xxxi 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Introduction Structure Determines Properties Alkanes and Cycloalkanes: Introduction to Hydrocarbons 58 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 102 Alcohols and Alkyl Halides 138 Structure and Preparation of Alkenes: Elimination Reactions 182 Addition Reactions of Alkenes 224 Stereochemistry 276 Nucleophilic Substitution 318 Alkynes 354 Conjugation in Alkadienes and Allylic Systems 382 Arenes and Aromaticity 420 Reactions of Arenes: Electrophilic Aromatic Substitution 470 Spectroscopy 516 Organometallic Compounds 578 Alcohols, Diols, and Thiols 620 Ethers, Epoxides, and Sulfides 662 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 700 Enols and Enolates 752 Carboxylic Acids 790 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 825 Ester Enolates 880 Amines 908 Aryl Halides 964 Phenols 990 Carbohydrates 1022 Lipids 1064 Amino Acids, Peptides, and Proteins 1106 Nucleosides, Nucleotides, and Nucleic Acids 1162 Synthetic Polymers 1200 Apago PDF Enhancer Glossary G-1 Credits C-1 Index I-1 vi car47872_fm_i-xxxii 11/15/06 18:32 Page vii CONFIRMING PAGES Contents List of Important Features xix Preface xxv Acknowledgments xxxi I N T R O D U C T I O N The Origins of Organic Chemistry Berzelius, Wöhler, and Vitalism The Structural Theory Electronic Theories of Structure and Reactivity The Influence of Organic Chemistry Computers and Organic Chemistry Challenges and Opportunities Where Did the Carbon Come From? C H A P T E R Structure Determines Properties 1.1 1.2 1.3 1.4 1.5 Atoms, Electrons, and Orbitals Ionic Bonds 12 Covalent Bonds, Lewis Structures, and the Octet Rule 14 Double Bonds and Triple Bonds 16 Polar Covalent Bonds and Electronegativity 16 Electrostatic Potential Maps 19 1.6 1.7 1.8 1.9 Apago PDF Enhancer Structural Formulas of Organic Molecules 19 Formal Charge 22 Resonance 24 The Shapes of Some Simple Molecules 29 Molecular Modeling 30 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 Molecular Dipole Moments 32 Curved Arrows and Chemical Reactions 33 Acids and Bases: The Arrhenius View 35 Acids and Bases: The Brønsted–Lowry View 36 What Happened to pKb? 40 How Structure Affects Acid Strength 41 Acid–Base Equilibria 45 Lewis Acids and Lewis Bases 48 Summary 49 Problems 52 Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures 57 C H A P T E R Alkanes and Cycloalkanes: Introduction to Hydrocarbons 2.1 2.2 2.3 2.4 2.5 58 Classes of Hydrocarbons 59 Electron Waves and Chemical Bonds 60 Bonding in H2: The Valence Bond Model 61 Bonding in H2: The Molecular Orbital Model 63 Introduction to Alkanes: Methane, Ethane, and Propane 64 Methane and the Biosphere 65 2.6 2.7 2.8 2.9 2.10 2.11 sp3 Hybridization and Bonding in Methane 66 Bonding in Ethane 68 Isomeric Alkanes: The Butanes 68 Higher n-Alkanes 68 The C5H12 Isomers 69 IUPAC Nomenclature of Unbranched Alkanes 71 What’s In a Name? Organic Nomenclature 72 vii car47872_fm_i-xxxii 11/15/06 18:32 Page viii viii CONFIRMING PAGES CONTENTS 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 Applying the IUPAC Rules: The Names of the C6H14 Isomers 73 Alkyl Groups 74 IUPAC Names of Highly Branched Alkanes 76 Cycloalkane Nomenclature 77 Sources of Alkanes and Cycloalkanes 78 Physical Properties of Alkanes and Cycloalkanes 80 Chemical Properties: Combustion of Alkanes 82 Oxidation–Reduction in Organic Chemistry 85 Thermochemistry 86 2.20 2.21 2.22 2.23 sp2 Hybridization and Bonding in Ethylene 89 sp Hybridization and Bonding in Acetylene 91 Which Theory of Chemical Bonding Is Best? 92 Summary 93 Problems 97 Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes 100 C H A P T E R Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 3.1 3.2 102 Conformational Analysis of Ethane 104 Conformational Analysis of Butane 107 Molecular Mechanics Applied to Alkanes and Cycloalkanes 109 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 Conformations of Higher Alkanes 110 The Shapes of Cycloalkanes: Planar or Nonplanar? 110 Small Rings: Cyclopropane and Cyclobutane 111 Cyclopentane 112 Conformations of Cyclohexane 112 Axial and Equatorial Bonds in Cyclohexane 113 Conformational Inversion (Ring Flipping) in Cyclohexane 115 Conformational Analysis of Monosubstituted Cyclohexanes 116 Disubstituted Cycloalkanes: cis–trans Stereoisomers 119 Enthalpy, Free Energy, and Equilibrium Constant 120 3.12 3.13 3.14 3.15 3.16 Apago PDF Enhancer Conformational Analysis of Disubstituted Cyclohexanes 121 Medium and Large Rings 125 Polycyclic Ring Systems 125 Heterocyclic Compounds 128 Summary 129 Problems 132 Descriptive Passage and Interpretive Problems 3: Cyclic Forms of Carbohydrates 137 C H A P T E R Alcohols and Alkyl Halides 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 Functional Groups 139 IUPAC Nomenclature of Alkyl Halides 141 IUPAC Nomenclature of Alcohols 142 Classes of Alcohols and Alkyl Halides 142 Bonding in Alcohols and Alkyl Halides 143 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces 144 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides 148 Mechanism of the Reaction of Alcohols with Hydrogen Halides 149 Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism 154 Structure, Bonding, and Stability of Carbocations 155 Effect of Alcohol Structure on Reaction Rate 158 Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The SN2 Mechanism 159 Other Methods for Converting Alcohols to Alkyl Halides 160 Halogenation of Alkanes 161 Chlorination of Methane 162 Structure and Stability of Free Radicals 162 Mechanism of Methane Chlorination 167 Halogenation of Higher Alkanes 168 From Bond Enthalpies to Heats of Reaction 169 4.19 Summary 173 Problems 176 Descriptive Passage and Interpretive Problems 4: More About Potential Energy Diagrams 180 138 car47872_fm_i-xxxii 11/15/06 18:32 Page ix CONFIRMING PAGES CONTENTS C H A P T E R Structure and Preparation of Alkenes: Elimination Reactions 5.1 5.2 182 Alkene Nomenclature 183 Structure and Bonding in Alkenes 185 Ethylene 186 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5.17 5.18 5.19 Isomerism in Alkenes 187 Naming Stereoisomeric Alkenes by the E–Z Notational System 188 Physical Properties of Alkenes 189 Relative Stabilities of Alkenes 191 Cycloalkenes 195 Preparation of Alkenes: Elimination Reactions 196 Dehydration of Alcohols 197 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule 198 Stereoselectivity in Alcohol Dehydration 199 The E1 and E2 Mechanisms of Alcohol Dehydration 200 Rearrangements in Alcohol Dehydration 202 Dehydrohalogenation of Alkyl Halides 205 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides 207 Anti Elimination in E2 Reactions: Stereoelectronic Effects 209 Isotope Effects and the E2 Mechanism 210 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides 211 Summary 213 Problems 217 Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions 222 C H A P T E R Addition Reactions of Alkenes 6.1 6.2 6.3 6.4 6.5 6.6 224 Hydrogenation of Alkenes 225 Heats of Hydrogenation 226 Stereochemistry of Alkene Hydrogenation 229 Electrophilic Addition of Hydrogen Halides to Alkenes 229 Regioselectivity of Hydrogen Halide Addition: Markovnikov’s Rule 231 Mechanistic Basis for Markovnikov’s Rule 233 Apago PDF Enhancer Rules, Laws, Theories, and the Scientific Method 235 6.7 6.8 6.9 6.10 6.11 6.12 6.13 6.14 6.15 6.16 6.17 6.18 6.19 6.20 6.21 6.22 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes 235 Free-Radical Addition of Hydrogen Bromide to Alkenes 236 Addition of Sulfuric Acid to Alkenes 239 Acid-Catalyzed Hydration of Alkenes 241 Thermodynamics of Addition–Elimination Equilibria 243 Hydroboration–Oxidation of Alkenes 246 Stereochemistry of Hydroboration–Oxidation 248 Mechanism of Hydroboration–Oxidation 248 Addition of Halogens to Alkenes 251 Stereochemistry of Halogen Addition 251 Mechanism of Halogen Addition to Alkenes: Halonium Ions 252 Conversion of Alkenes to Vicinal Halohydrins 254 Epoxidation of Alkenes 255 Ozonolysis of Alkenes 257 Introduction to Organic Chemical Synthesis 259 Reactions of Alkenes with Alkenes: Polymerization 260 Ethylene and Propene: The Most Important Industrial Organic Chemicals 265 6.23 Summary 266 Problems 269 Descriptive Passage and Interpretive Problems 6: Some Unusual Electrophilic Additions 274 C H A P T E R Stereochemistry 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 Molecular Chirality: Enantiomers 277 The Chirality Center 279 Symmetry in Achiral Structures 281 Optical Activity 282 Absolute and Relative Configuration 284 The Cahn–Ingold–Prelog R–S Notational System 285 Fischer Projections 288 Properties of Enantiomers 290 276 ix ... undergraduates Frank and his wife Jill, who is a teacher/director of a preschool and a church organist, are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava Apago PDF Enhancer... Phase-Transfer Catalysts 921 Reactions That Lead to Amines: A Review and a Preview 922 Preparation of Amines by Alkylation of Ammonia 923 The Gabriel Synthesis of Primary Alkylamines 924 Preparation of Amines... Biochemical Reactions of Alkanes 100 C H A P T E R Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 3.1 3.2 102 Conformational Analysis of Ethane 104 Conformational Analysis of Butane