Vollhardt organic chemistry 7th edition solutions pdf free download

Vollhardt organic chemistry 7th edition solutions pdf free download

vollhardt organic chemistry 7th edition solutions pdf free download

Organic Chemistry Structure and Function 7th Edition [K. Peter C. Vollhardt, Neil E. Schore] on Study Guide/Solutions Manual for Organic Chemistry. organic chemistry i 6th edition 7th edition solutions manual on Organic Chemistry Structure and. Function Solutions chemistry wade 8th edition chemistry structure and function vollhardt solutions Download organic chemistry. 10th edition. Clutch helps you with the textbook Organic Chemistry: Structure and Function by Vollhardt 7th. Check out our videos for help! vollhardt organic chemistry 7th edition solutions pdf free download

Organic Chemistry, Seventh Edition

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Author: Francis A. Carey


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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

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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

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Francis A. Carey University of Virginia

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

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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. 1 2 3 4 5 6 7 8 9 0 DOW/DOW 0 9 8 7 6 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 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) 1. Chemistry, Organic. I. Title. QD251.3.C37 2008 547—dc22 2006031901

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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.

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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 1 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.

*For more about carbon nanotubes, see pages 432–433. †

For more about ferrocene, see page 600.

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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.

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Brief Contents List of Important Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxxi

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Structure Determines Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 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

Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-1 Credits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C-1 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-1

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Contents List of Important Features xix Preface xxv Acknowledgments xxxi I N T R O D U C T I O N

2

The Origins of Organic Chemistry 2 Berzelius, Wöhler, and Vitalism 2 The Structural Theory 4 Electronic Theories of Structure and Reactivity 4 The Influence of Organic Chemistry 5 Computers and Organic Chemistry 5 Challenges and Opportunities 5 Where Did the Carbon Come From? 7

C H A P T E R

1

Structure Determines Properties 1.1 1.2 1.3 1.4 1.5

8

Atoms, Electrons, and Orbitals 9 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

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

2

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

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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

3

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

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

4

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

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CONTENTS C H A P T E R

5

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

6

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 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

7

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

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CONTENTS Chiral Drugs 291 7.9 7.10 7.11 7.12

Reactions That Create a Chirality Center 292 Chiral Molecules with Two Chirality Centers 295 Achiral Molecules with Two Chirality Centers 297 Molecules with Multiple Chirality Centers 299 Chirality of Disubstituted Cyclohexanes 300

7.13 7.14 7.15 7.16 7.17

Reactions That Produce Diastereomers 301 Resolution of Enantiomers 303 Stereoregular Polymers 305 Chirality Centers Other Than Carbon 306 Summary 307 Problems 310 Descriptive Passage and Interpretive Problems 7: Prochirality 316

C H A P T E R

8

Nucleophilic Substitution 8.1 8.2 8.3 8.4 8.5 8.6

318

Functional Group Transformation by Nucleophilic Substitution 319 Relative Reactivity of Halide Leaving Groups 322 The SN2 Mechanism of Nucleophilic Substitution 323 Steric Effects and SN2 Reaction Rates 326 Nucleophiles and Nucleophilicity 328 The SN1 Mechanism of Nucleophilic Substitution 330 Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides 331

8.7 8.8 8.9 8.10 8.11 8.12 8.13 8.14

Carbocation Stability and SN1 Reaction Rates 331 Stereochemistry of SN1 Reactions 334 Carbocation Rearrangements in SN1 Reactions 335 Effect of Solvent on the Rate of Nucleophilic Substitution 337 Substitution and Elimination as Competing Reactions 339 Nucleophilic Substitution of Alkyl Sulfonates 342 Looking Back: Reactions of Alcohols with Hydrogen Halides 344 Summary 346 Problems 347 Descriptive Passage and Interpretive Problems 8: Nucleophilic Substitution 352

C H A P T E R

9

Alkynes 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 9.13

354

Sources of Alkynes 355 Nomenclature 357 Physical Properties of Alkynes 357 Structure and Bonding in Alkynes: sp Hybridization 357 Acidity of Acetylene and Terminal Alkynes 360 Preparation of Alkynes by Alkyation of Acetylene and Terminal Alkynes 361 Preparation of Alkynes by Elimination Reactions 363 Reactions of Alkynes 364 Hydrogenation of Alkynes 365 Metal–Ammonia Reduction of Alkynes 367 Addition of Hydrogen Halides to Alkynes 368 Hydration of Alkynes 370 Addition of Halogens to Alkynes 371 Some Things That Can Be Made from Acetylene . . . But Aren’t 372

9.14 9.15

Ozonolysis of Alkynes 372 Summary 373 Problems 376 Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes 380

C H A P T E R 10

Conjugation in Alkadienes and Allylic Systems 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8

The Allyl Group 383 Allylic Carbocations 384 SN1 Reactions of Allylic Halides 385 SN2 Reactions of Allylic Halides 388 Allylic Free Radicals 389 Allylic Halogenation 390 Allylic Anions 393 Classes of Dienes 394

382

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CONTENTS 10.9 10.10 10.11 10.12 10.13 10.14 10.15

Relative Stabilities of Dienes 395 Bonding in Conjugated Dienes 396 Bonding in Allenes 398 Preparation of Dienes 399 Addition of Hydrogen Halides to Conjugated Dienes 400 Halogen Addition to Dienes 403 The Diels–Alder Reaction 403 Diene Polymers 404

10.16 10.17 10.18

The  Molecular Orbitals of Ethylene and 1,3-Butadiene 407 A  Molecular Orbital Analysis of the Diels–Alder Reaction 408 Summary 410 Problems 413 Descriptive Passage and Interpretive Problems 10: Intramolecular and Retro Diels–Alder Reactions 417

C H A P T E R 11

Arenes and Aromaticity 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9

420

Benzene 421 Kekulé and the Structure of Benzene 422 A Resonance Picture of Bonding in Benzene 424 The Stability of Benzene 424 An Orbital Hybridization View of Bonding in Benzene 426 The  Molecular Orbitals of Benzene 427 Substituted Derivatives of Benzene and Their Nomenclature 428 Polycyclic Aromatic Hydrocarbons 430 Physical Properties of Arenes 431 Carbon Clusters, Fullerenes, and Nanotubes 432

11.10 11.11 11.12 11.13 11.14 11.15 11.16 11.17 11.18 11.19 11.20 11.21 11.22 11.23 11.24 11.25

Reactions of Arenes: A Preview 432 The Birch Reduction 433 Free-Radical Halogenation of Alkylbenzenes 436 Oxidation of Alkylbenzenes 438 SN1 Reactions of Benzylic Halides 440 SN2 Reactions of Benzylic Halides 441 Preparation of Alkenylbenzenes 442 Addition Reactions of Alkenylbenzenes 443 Polymerization of Styrene 445 Cyclobutadiene and Cyclooctatetraene 446 Hückel’s Rule 448 Annulenes 450 Aromatic Ions 452 Heterocyclic Aromatic Compounds 455 Heterocyclic Aromatic Compounds and Hückel’s Rule 457 Summary 459 Problems 462 Descriptive Passage and Interpretive Problems 11: The Hammett Equation 466

C H A P T E R 12

Reactions of Arenes: Electrophilic Aromatic Substitution 12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 12.10 12.11 12.12 12.13 12.14 12.15 12.16 12.17 12.18 12.19



470

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CONTENTS C H A P T E R 13

Spectroscopy 13.1 13.2 13.3 13.4 13.5

516

Principles of Molecular Spectroscopy: Electromagnetic Radiation 518 Principles of Molecular Spectroscopy: Quantized Energy States 519 Introduction to 1H NMR Spectroscopy 519 Nuclear Shielding and 1H Chemical Shifts 521 Effects of Molecular Structure on 1H Chemical Shifts 524 Ring Currents: Aromatic and Antiaromatic 529

13.6 13.7 13.8 13.9 13.10 13.11 13.12

Interpreting 1H NMR Spectra 530 Spin–Spin Splitting in 1H NMR Spectroscopy 532 Splitting Patterns: The Ethyl Group 534 Splitting Patterns: The Isopropyl Group 536 Splitting Patterns: Pairs of Doublets 536 Complex Splitting Patterns 538 1 H NMR Spectra of Alcohols 539 Magnetic Resonance Imaging (MRI) 540

13.13 13.14 13.15 13.16 13.17 13.18 13.19 13.20

NMR and Conformations 540 C NMR Spectroscopy 541 C Chemical Shifts 543 13 C NMR and Peak Intensities 545 13 C—1H Coupling 546 Using DEPT to Count Hydrogens Attached to 2D NMR: COSY and HETCOR 547 Introduction to Infrared Spectroscopy 550 13 13

13

C 546

Spectra by the Thousands 551 13.21 13.22 13.23 13.24 13.25

Infrared Spectra 552 Characteristic Absorption Frequencies 554 Ultraviolet-Visible (UV-VIS) Spectroscopy 557 Mass Spectrometry 559 Molecular Formula as a Clue to Structure 563 Gas Chromatography, GC/MS, and MS/MS 564

13.26

Summary 566 Problems 569 Descriptive Passage and Interpretive Problems 13: Calculating Aromatic

13

C Chemical Shifts 575

C H A P T E R 14

Organometallic Compounds 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10 14.11 14.12 14.13 14.14

Organometallic Nomenclature 580 Carbon–Metal Bonds in Organometallic Compounds 580 Preparation of Organolithium Compounds 581 Preparation of Organomagnesium Compounds: Grignard Reagents 583 Organolithium and Organomagnesium Compounds as Brønsted Bases 584 Synthesis of Alcohols Using Grignard Reagents 586 Synthesis of Alcohols Using Organolithium Reagents 588 Synthesis of Acetylenic Alcohols 588 Retrosynthetic Analysis 589 Preparation of Tertiary Alcohols from Esters and Grignard Reagents 592 Alkane Synthesis Using Organocopper Reagents 593 An Organozinc Reagent for Cyclopropane Synthesis 595 Carbenes and Carbenoids 596 Transition-Metal Organometallic Compounds 599

14.15 14.16 14.17 14.18

Homogeneous Catalytic Hydrogenation 602 Olefin Metathesis 605 Ziegler–Natta Catalysis of Alkene Polymerization 607 Summary 610 Problems 613 Descriptive Passage and Interpretive Problems 14: Oxymercuration 617

578

An Organometallic Compound That Occurs Naturally: Coenzyme B12 601

C H A P T E R 15

Alcohols, Diols, and Thiols 15.1 15.2 15.3

Sources of Alcohols 621 Preparation of Alcohols by Reduction of Aldehydes and Ketones 622 Preparation of Alcohols by Reduction of Carboxylic Acids and Esters 628

620

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CONTENTS 15.4 15.5 15.6 15.7 15.8 15.9 15.10 15.11

Preparation of Alcohols from Epoxides 629 Preparation of Diols 630 Reactions of Alcohols: A Review and a Preview 632 Conversion of Alcohols to Ethers 632 Esterification 635 Esters of Inorganic Acids 637 Oxidation of Alcohols 638 Biological Oxidation of Alcohols 640 Economic and Environmental Factors in Organic Synthesis 641

15.12 15.13 15.14 15.15

Oxidative Cleavage of Vicinal Diols 643 Thiols 644 Spectroscopic Analysis of Alcohols and Thiols 647 Summary 648 Problems 652 Descriptive Passage and Interpretive Problems 15: The Pinacol Rearrangement 658

C H A P T E R 16

Ethers, Epoxides, and Sulfides 16.1 16.2 16.3 16.4 16.5

662

Nomenclature of Ethers, Epoxides, and Sulfides 663 Structure and Bonding in Ethers and Epoxides 664 Physical Properties of Ethers 665 Crown Ethers 667 Preparation of Ethers 668 Polyether Antibiotics 669

16.6 16.7 16.8 16.9 16.10 16.11 16.12 16.13 16.14 16.15 16.16 16.17 16.18 16.19

The Williamson Ether Synthesis 670 Reactions of Ethers: A Review and a Preview 671 Acid-Catalyzed Cleavage of Ethers 672 Preparation of Epoxides: A Review and a Preview 674 Conversion of Vicinal Halohydrins to Epoxides 675 Reactions of Epoxides: A Review and a Preview 676 Nucleophilic Ring Opening of Epoxides 677 Acid-Catalyzed Ring Opening of Epoxides 679 Epoxides in Biological Processes 682 Preparation of Sulfides 682 Oxidation of Sulfides: Sulfoxides and Sulfones 683 Alkylation of Sulfides: Sulfonium Salts 684 Spectroscopic Analysis of Ethers, Epoxides, and Sulfides 685 Summary 688 Problems 692 Descriptive Passage and Interpretive Problems 16: Epoxide Rearrangements and the NIH Shift 697

C H A P T E R 17

Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 17.9 17.10

Nomenclature 701 Structure and Bonding: The Carbonyl Group 704 Physical Properties 706 Sources of Aldehydes and Ketones 707 Reactions of Aldehydes and Ketones: A Review and a Preview 710 Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones 711 Cyanohydrin Formation 715 Acetal Formation 718 Acetals as Protecting Groups 721 Reaction with Primary Amines: Imines 722 Imines in Biological Chemistry 725

17.11 17.12 17.13 17.14 17.15 17.16 17.17 17.18

Reaction with Secondary Amines: Enamines 727 The Wittig Reaction 728 Planning an Alkene Synthesis via the Wittig Reaction 730 Stereoselective Addition to Carbonyl Groups 732 Oxidation of Aldehydes 733 Baeyer–Villiger Oxidation of Ketones 734 Spectroscopic Analysis of Aldehydes and Ketones 736 Summary 738 Problems 742 Descriptive Passage and Interpretive Problems 17: Alcohols, Aldehydes, and Carbohydrates 749

700

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CONTENTS C H A P T E R 18

Enols and Enolates 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 18.9 18.10

752

The  Hydrogen and Its pKa 753 The Aldol Condensation 757 Mixed Aldol Condensations 761 Alkylation of Enolate Ions 763 Enolization and Enol Content 764 Stabilized Enols 766  Halogenation of Aldehydes and Ketones 768 Mechanism of  Halogenation of Aldehydes and Ketones 768 The Haloform Reaction 770 Some Chemical and Stereochemical Consequences of Enolization 772 The Haloform Reaction and the Biosynthesis of Trihalomethanes 773

18.11 18.12 18.13 18.14 18.15

Effects of Conjugation in ,-Unsaturated Aldehydes and Ketones 774 Conjugate Addition to ,-Unsaturated Carbonyl Compounds 775 Addition of Carbanions to ,-Unsaturated Ketones: The Michael Reaction 778 Conjugate Addition of Organocopper Reagents to ,-Unsaturated Carbonyl Compounds 778 Summary 779 Problems 782 Descriptive Passage and Interpretive Problems 18: Enolate Regiochemistry and Stereochemistry 787

C H A P T E R 19

Carboxylic Acids 19.1 19.2 19.3 19.4 19.5 19.6 19.7 19.8 19.9 19.10 19.11 19.12 19.13 19.14 19.15 19.16 19.17 19.18 19.19

790

Carboxylic Acid Nomenclature 791 Structure and Bonding 793 Physical Properties 794 Acidity of Carboxylic Acids 794 Salts of Carboxylic Acids 797 Substituents and Acid Strength 799 Ionization of Substituted Benzoic Acids 801 Dicarboxylic Acids 802 Carbonic Acid 802 Sources of Carboxylic Acids 803 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents 806 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles 806 Reactions of Carboxylic Acids: A Review and a Preview 807 Mechanism of Acid-Catalyzed Esterification 808 Intramolecular Ester Formation: Lactones 811  Halogenation of Carboxylic Acids: The Hell–Volhard–Zelinsky Reaction 813 Decarboxylation of Malonic Acid and Related Compounds 815 Spectroscopic Analysis of Carboxylic Acids 817 Summary 818 Problems 821 Descriptive Passage and Interpretive Problems 19: Lactonization Methods 825

C H A P T E R 20

Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 20.1 20.2 20.3 20.4 20.5 20.6 20.7 20.8 20.9 20.10 20.11 20.12 20.13 20.14

Nomenclature of Carboxylic Acid Derivatives 830 Structure and Reactivity of Carboxylic Acid Derivatives 831 General Mechanism for Nucleophilic Acyl Substitution 834 Nucleophilic Acyl Substitution in Acyl Chlorides 836 Nucleophilic Acyl Substitution in Acid Anhydrides 839 Sources of Esters 842 Physical Properties of Esters 842 Reactions of Esters: A Review and a Preview 844 Acid-Catalyzed Ester Hydrolysis 844 Ester Hydrolysis in Base: Saponification 848 Reaction of Esters with Ammonia and Amines 851 Amides 852 Hydrolysis of Amides 857 Lactams 861 -Lactam Antibiotics 861

20.15 20.16

Preparation of Nitriles 862 Hydrolysis of Nitriles 863

825

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CONTENTS 20.17 20.18 20.19

Addition of Grignard Reagents to Nitriles 864 Spectroscopic Analysis of Carboxylic Acid Derivatives 866 Summary 867 Problems 870 Descriptive Passage and Interpretive Problems 20: Thioesters 876

C H A P T E R 21

Ester Enolates 21.1 21.2 21.3 21.4 21.5 21.6 21.7 21.8 21.9 21.10 21.11

880

Ester  Hydrogens and Their pKa’s 881 The Claisen Condensation 883 Intramolecular Claisen Condensation: The Dieckmann Cyclization 886 Mixed Claisen Condensations 886 Acylation of Ketones with Esters 887 Ketone Synthesis via -Keto Esters 888 The Acetoacetic Ester Synthesis 889 The Malonic Ester Synthesis 892 Michael Additions of Stabilized Anions 894 Reactions of LDA-Generated Ester Enolates 895 Summary 897 Problems 899 Descriptive Passage and Interpretive Problems 21: The Enolate Chemistry of Dianions 903

C H A P T E R 22

Amines 22.1 22.2 22.3 22.4

908

Amine Nomenclature 909 Structure and Bonding 911 Physical Properties 913 Basicity of Amines 914 Amines as Natural Products 919

22.5 22.6 22.7 22.8 22.9 22.10 22.11 22.12 22.13 22.14 22.15 22.16 22.17 22.18

Tetraalkylammonium Salts as 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 by Reduction 926 Reductive Amination 928 Reactions of Amines: A Review and a Preview 929 Reaction of Amines with Alkyl Halides 931 The Hofmann Elimination 931 Electrophilic Aromatic Substitution in Arylamines 932 Nitrosation of Alkylamines 935 Nitrosation of Arylamines 937 Synthetic Transformations of Aryl Diazonium Salts 938 Azo Coupling 942 From Dyes to Sulfa Drugs 943

22.19 22.20

Spectroscopic Analysis of Amines 944 Summary 947 Problems 953 Descriptive Passage and Interpretive Problems 22: Synthetic Applications of Enamines 960

C H A P T E R 23

Aryl Halides 23.1 23.2 23.3 23.4 23.5 23.6 23.7 23.8 23.9 23.10 23.11

Bonding in Aryl Halides 965 Sources of Aryl Halides 966 Physical Properties of Aryl Halides 966 Reactions of Aryl Halides: A Review and a Preview 966 Nucleophilic Substitution in Nitro-Substituted Aryl Halides 968 The Addition–Elimination Mechanism of Nucleophilic Aromatic Substitution 971 Related Nucleophilic Aromatic Substitution Reactions 973 The Elimination–Addition Mechanism of Nucleophilic Aromatic Substitution: Benzyne 974 Diels–Alder Reactions of Benzyne 978 m-Benzyne and p-Benzyne 979 Summary 980 Problems 982 Descriptive Passage and Interpretive Problems 23: The Heck Reaction 986

964

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CONTENTS C H A P T E R 24

Phenols 24.1 24.2 24.3 24.4 24.5 24.6 24.7 24.8 24.9 24.10 24.11

990

Nomenclature 991 Structure and Bonding 992 Physical Properties 993 Acidity of Phenols 994 Substituent Effects on the Acidity of Phenols 995 Sources of Phenols 996 Naturally Occurring Phenols 998 Reactions of Phenols: Electrophilic Aromatic Substitution 999 Acylation of Phenols 1001 Carboxylation of Phenols: Aspirin and the Kolbe–Schmitt Reaction 1002 Preparation of Aryl Ethers 1004 Agent Orange and Dioxin 1005

24.12 24.13 24.14 24.15 24.16

Cleavage of Aryl Ethers by Hydrogen Halides 1006 Claisen Rearrangement of Allyl Aryl Ethers 1006 Oxidation of Phenols: Quinones 1007 Spectroscopic Analysis of Phenols 1009 Summary 1010 Problems 1013 Descriptive Passage and Interpretive Problems 24: Directed Metalation of Aryl Ethers 1018

C H A P T E R 25

Carbohydrates 25.1 25.2 25.3 25.4 25.5 25.6 25.7 25.8 25.9 25.10 25.11 25.12 25.13 25.14 25.15

1022

Classification of Carbohydrates 1023 Fischer Projections and D–L Notation 1024 The Aldotetroses 1025 Aldopentoses and Aldohexoses 1026 A Mnemonic for Carbohydrate Configurations 1028 Cyclic Forms of Carbohydrates: Furanose Forms 1029 Cyclic Forms of Carbohydrates: Pyranose Forms 1032 Mutarotation and the Anomeric Effect 1035 Ketoses 1037 Deoxy Sugars 1038 Amino Sugars 1039 Branched-Chain Carbohydrates 1040 Glycosides 1040 Disaccharides 1042 Polysaccharides 1044 How Sweet It Is! 1045

25.16 25.17 25.18 25.19 25.20 25.21 25.22 25.23

Reactions of Carbohydrates 1047 Reduction of Monosaccharides 1047 Oxidation of Monosaccharides 1047 Cyanohydrin Formation and Chain Extension 1049 Epimerization, Isomerization, and Retro-Aldol Cleavage 1050 Acylation and Alkylation of Hydroxyl Groups 1052 Periodic Acid Oxidation 1053 Summary 1054 Problems 1057 Descriptive Passage and Interpretive Problems 25: Emil Fischer and the Structure of (+)-Glucose 1061

C H A P T E R 26

Lipids 26.1 26.2 26.3 26.4 26.5 26.6

Acetyl Coenzyme A 1066 Fats, Oils, and Fatty Acids 1067 Fatty Acid Biosynthesis 1070 Phospholipids 1073 Waxes 1075 Prostaglandins 1076 Nonsteroidal Antiinflammatory Drugs (NSAIDs) and COX-2 Inhibitors 1078

26.7 26.8 26.9 26.10 26.11 26.12

Terpenes: The Isoprene Rule 1079 Isopentenyl Diphosphate: The Biological Isoprene Unit 1082 Carbon–Carbon Bond Formation in Terpene Biosynthesis 1082 The Pathway from Acetate to Isopentenyl Diphosphate 1086 Steroids: Cholesterol 1087 Vitamin D 1090

1064

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CONTENTS Good Cholesterol? Bad Cholesterol? What’s the Difference? 1091 26.13 26.14 26.15 26.16

Bile Acids 1092 Corticosteroids 1092 Sex Hormones 1093 Carotenoids 1093 Anabolic Steroids 1094 Crocuses Make Saffron from Carotenes 1095

26.17

Summary 1096 Problems 1098 Descriptive Passage and Interpretive Problems 26: Polyketides 1101

C H A P T E R 27

Amino Acids, Peptides, and Proteins 27.1 27.2 27.3 27.4

1106

Classification of Amino Acids 1108 Stereochemistry of Amino Acids 1113 Acid–Base Behavior of Amino Acids 1114 Synthesis of Amino Acids 1117 Electrophoresis 1117

27.5 27.6 27.7 27.8 27.9 27.10 27.11 27.12 27.13

Reactions of Amino Acids 1119 Some Biochemical Reactions of Amino Acids 1120 Peptides 1127 Introduction to Peptide Structure Determination 1130 Amino Acid Analysis 1130 Partial Hydrolysis of Peptides 1131 End Group Analysis 1132 Insulin 1133 The Edman Degradation and Automated Sequencing of Peptides 1134 Peptide Mapping and MALDI Mass Spectrometry 1136

27.14 27.15 27.16 27.17 27.18 27.19 27.20 27.21

The Strategy of Peptide Synthesis 1137 Amino Group Protection 1138 Carboxyl Group Protection 1140 Peptide Bond Formation 1141 Solid-Phase Peptide Synthesis: The Merrifield Method 1143 Secondary Structures of Peptides and Proteins 1145 Tertiary Structure of Polypeptides and Proteins 1148 Coenzymes 1152 Oh NO! It’s Inorganic! 1153

27.22 27.23

Protein Quaternary Structure: Hemoglobin 1153 Summary 1154 Problems 1156 Descriptive Passage and Interpretive Problems 27: Amino Acids in Enantioselective Synthesis 1159

C H A P T E R 28

Nucleosides, Nucleotides, and Nucleic Acids 28.1 28.2 28.3 28.4 28.5 28.6 28.7 28.8

Pyrimidines and Purines 1163 Nucleosides 1166 Nucleotides 1167 Bioenergetics 1170 ATP and Bioenergetics 1170 Phosphodiesters, Oligonucleotides, and Polynucleotides 1172 Nucleic Acids 1173 Secondary Structure of DNA: The Double Helix 1174 “It Has Not Escaped Our Notice . . .” 1175

28.9 28.10 28.11 28.12

Tertiary Structure of DNA: Supercoils 1177 Replication of DNA 1178 Ribonucleic Acids 1180 Protein Biosynthesis 1183 RNA World 1184

28.13 28.14 28.15 28.16 28.17

AIDS 1184 DNA Sequencing 1185 The Human Genome Project 1187 DNA Profiling and the Polymerase Chain Reaction 1188 Summary 1191 Problems 1194 Descriptive Passage and Interpretive Problems 28: Oligonucleotide Synthesis 1195

1162

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CONTENTS C H A P T E R 29

Synthetic Polymers 29.1 29.2 29.3 29.4 29.5 29.6 29.7 29.8 29.9 29.10 29.11 29.12 29.13 29.14 29.15 29.16

Some Background 1201 Polymer Nomenclature 1202 Classification of Polymers: Reaction Type 1203 Classification of Polymers: Chain Growth and Step Growth 1204 Classification of Polymers: Structure 1205 Classification of Polymers: Properties 1207 Addition Polymers: A Review and a Preview 1209 Chain Branching in Free-Radical Polymerization 1211 Anionic Polymerization: Living Polymers 1214 Cationic Polymerization 1216 Polyamides 1217 Polyesters 1218 Polycarbonates 1219 Polyurethanes 1220 Copolymers 1221 Summary 1223 Problems 1225 Descriptive Passage and Interpretive Problems 29: Chemical Modification of Polymers 1227

Glossary G-1 Credits C-1 Index I-1

1200

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List of Important Features Mechanisms 4.1

Formation of tert-Butyl Chloride from tert-Butyl Alcohol and Hydrogen Chloride 150

10.4 Orbital Interactions in the Diels–Alder Reaction 409 11.1 The Birch Reduction 435 11.2 Free-Radical Polymerization of Styrene 445

4.2

Formation of 1-Bromoheptane from 1-Heptanol and Hydrogen Bromide 160

12.1 Nitration of Benzene 475

4.3

Free-Radical Chlorination of Methane 167

12.3 Bromination of Benzene 478

5.1

The E1 Mechanism for Acid-Catalyzed Dehydration of tert-Butyl Alcohol 200

12.4 Friedel–Crafts Alkylation 479

5.2

Carbocation Rearrangement in Dehydration of 3,3-Dimethyl-2-butanol 202

5.3

Hydride Shift in Dehydration of 1-Butanol 205

5.4

E2 Elimination of an Alkyl Halide 209

5.5

The E1 Mechanism for Dehydrohalogenation of 2-Bromo-2-methylbutane in Ethanol 212

6.1

Hydrogenation of Alkenes 227

14.3 Formation of Dibromocarbene from Tribromomethane 597

6.2

Electrophilic Addition of a Hydrogen Halide to an Alkene 231

14.4 Homogeneous Hydrogenation of Propene in the Presence of Wilkinson’s Catalyst 603

6.3

Free-Radical Addition of Hydrogen Bromide to 1-Butene 238

14.5 Olefin Cross-Metathesis 606

6.4

Addition of Sulfuric Acid to Propene 240

6.5

Acid-Catalyzed Hydration of 2-Methylpropene 242

6.6

Hydroboration of 1-Methylcyclopentene 249

6.7

Oxidation of an Organoborane 250

6.8

Electrophilic Addition of Bromine to Ethylene 253

6.9

Formation of a Bromohydrin 254

6.10 Epoxidation of an Alkene 257 6.11 Acid-Catalyzed Dimerization of 2-Methylpropene 262 6.12 Free-Radical Polymerization of Ethylene 263

12.2 Sulfonation of Benzene 477

12.5 Friedel–Crafts Acylation 482 14.1 Formation of a Lithium Dialkylcuprate (Gilman Reagent) 594 14.2 Similarities Between the Mechanisms of Reaction of an Alkene with Iodomethylzinc Iodide and a Peroxy Acid 597

14.6 Polymerization of Ethylene in the Presence of a Ziegler–Natta Catalyst 609 15.1 Sodium Borohydride Reduction of an Aldehyde or Ketone 627 15.2 Acid-Catalyzed Formation of Diethyl Ether from Ethyl Alcohol 634 15.3 Chromic Acid Oxidation of 2-Propanol 640 15.4 Oxidation of Ethanol by NAD 642 16.1 Cleavage of Ethers by Hydrogen Halides 673 16.2 Nucleophilic Ring Opening of an Epoxide 679 16.3 Acid-Catalyzed Ring Opening of Ethylene Oxide 680

8.1

The SN2 Mechanism of Nucleophilic Substitution 323

8.2

The SN1 Mechanism of Nucleophilic Substitution 332

8.3

Carbocation Rearrangement in the SN1 Hydrolysis of 2-Bromo-3-methylbutane 336

9.1

Sodium–Ammonia Reduction of an Alkyne 367

17.2 Hydration of an Aldehyde or Ketone in Acid Solution 715

9.2

Conversion of an Enol to a Ketone 370

17.3 Cyanohydrin Formation 716

10.1 Hydrolysis of an Allylic Halide 387

16.4 Nucleophilic Substitution of Adenosine Triphosphate (ATP) by Methionine 685 17.1 Hydration of an Aldehyde or Ketone in Basic Solution 714

10.2 Allylic Chlorination of Propene 391

17.4 Acetal Formation from Benzaldehyde and Ethanol 719

10.3 Addition of Hydrogen Chloride to 1,3-Cyclopentadiene 401

17.5 Imine Formation from Benzaldehyde and Methylamine 723 xix

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17.6 Enamine Formation from Cyclopentanone and Pyrrolidine 728 17.7 The Wittig Reaction 730 17.8 Baeyer–Villiger Oxidation of a Ketone 735 18.1 Aldol Addition of Butanal 758 18.2 Dehydration in a Base-Catalyzed Aldol Condensation 760

27.5 Carboxypeptidase-Catalyzed Hydrolysis 1151 29.1 Branching in Polyethylene Caused by Intramolecular Hydrogen Transfer 1212 29.2 Branching in Polyethylene Caused by Intermolecular Hydrogen Transfer 1213 29.3 Anionic Polymerization of Styrene 1214 29.4 Cationic Polymerization of 2-Methylpropene 1217

18.3 Base-Catalyzed Enolization of an Aldehyde or Ketone in Aqueous Solution 764 18.4 Acid-Catalyzed Enolization of an Aldehyde or Ketone in Aqueous Solution 765

Tables 1.1

Electron Configurations of the First Twelve Elements of the Periodic Table 11

1.2

Lewis Formulas of Methane, Ammonia, Water, and Hydrogen Fluoride 15

18.8 1,2- Versus 1,4-Addition to ,-Unsaturated Aldehydes and Ketones 777

1.3

Selected Values from the Pauling Electronegativity Scale 18

19.1 Acid-Catalyzed Esterification of Benzoic Acid with Methanol 809

1.4

Selected Bond Dipole Moments 18

1.5

A Systematic Approach to Writing Lewis Structures 20

1.6

Introduction to the Rules of Resonance 27

1.7

VSEPR and Molecular Geometry 31

1.8

Acidity Constants (pKa) of Acids 38

2.1

The Number of Constitutionally Isomeric Alkanes of Particular Molecular Formulas 70

2.2

IUPAC Names of Unbranched Alkanes 71

2.3

Heats of Combustion (H ) of Representative Alkanes 83

2.4

Oxidation Number of Carbon in One-Carbon Compounds 85

22.1 Reactions of an Alkyl Diazonium Ion 937

2.5

23.1 Nucleophilic Aromatic Substitution in pFluoronitrobenzene by the Addition–Elimination Mechanism 971

Oxidation Numbers in Compounds with More Than One Carbon 88

2.6

Summary of IUPAC Nomenclature of Alkanes and Cycloalkanes 95

23.2 Nucleophilic Aromatic Substitution in Chlorobenzene by the Elimination–Addition (Benzyne) Mechanism 976

2.7

Summary of IUPAC Nomenclature of Alkyl Groups 96

3.1

Heats of Combustion (H ) of Cycloalkanes 111

26.1 Biosynthesis of a Butanoyl Group from Acetyl and Malonyl Building Blocks 1072

3.2

Heats of Combustion of Isomeric Dimethylcyclohexanes 122

26.2 Biosynthesis of Cholesterol from Squalene 1089

4.1

27.1 Pyridoxal 5-Phosphate-Mediated Decarboxylation of an -Amino Acid 1121

Functional Groups in Some Important Classes of Organic Compounds 140

4.2

27.2 Transamination: Biosynthesis of L-Alanine from L-Glutamic Acid and Pyruvic Acid 1125

Boiling Point of Some Alkyl Halides and Alcohols 146

4.3

Bond Dissociation Enthalpies of Some Representative Compounds 165

4.4

Conversions of Alcohols and Alkanes to Alkyl Halides 174

5.1

Cahn–Ingold–Prelog Priority Rules 190

18.5 Acid-Catalyzed Bromination of Acetone 769 18.6  Bromination of Acetone in Basic Solution 770 18.7 Haloform Reaction of Acetone 772

20.1 Hydrolysis of an Acyl Chloride 838 20.2 Acid Catalysis in Formation of a Tetrahedral Intermediate 841 20.3 Acid-Catalyzed Ester Hydrolysis 846 20.4 Ester Hydrolysis in Basic Solution 851 20.5 Amide Formation by the Reaction of a Secondary Amine with an Ethyl Ester 853 20.6 Amide Hydrolysis in Acid Solution 858 20.7 Amide Hydrolysis in Basic Solution 860 20.8 Nitrile Hydrolysis in Basic Solution 865 21.1 The Claisen Condensation of Ethyl Acetate 884

27.3 The Edman Degradation 1135 27.4 Amide Bond Formation Between a Carboxylic Acid and an Amine Using N,N-Dicyclohexylcarbodiimide 1142

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xxi

5.2

Preparation of Alkenes by Elimination Reactions of Alcohols and Alkyl Halides 215

12.3 Representative Electrophilic Aromatic Substitution Reactions 505

6.1

Heats of Hydrogenation of Some Alkenes 228

12.4 Limitations on Friedel–Crafts Reactions 506

6.2

Relative Rates of Acid-Catalyzed Hydration of Some Representative Alkenes 242

13.1 Approximate Chemical Shifts of Representative Protons 526

6.3

Relative Rates of Reaction of Some Representative Alkenes with Bromine 253

13.2 Splitting Patterns of Common Multiplets 536

6.4

Relative Rates of Epoxidation of Some Representative Alkenes with Peroxyacetic Acid 257

13.4 Infrared Absorption Frequencies of Some Common Structural Units 554

6.5

Some Compounds with Carbon–Carbon Double Bonds Used to Prepare Polymers 264

13.5 Absorption Maxima of Some Representative Alkenes and Polyenes 558

6.6

Addition Reactions of Alkenes 266

7.1

Absolute Configuration According to the Cahn–Ingold–Prelog Notational System 286

13.6 Incremental 13C Chemical Shift Effects of Substituents ( ), ppm 575

7.2

Classification of Isomers 308

8.1

Representative Functional Group Transformations by Nucleophilic Substitution Reactions of Alkyl Halides 321

8.2

Reactivity of Some Alkyl Bromides Toward Substitution by the SN2 Mechanism 326

13.3 Chemical Shifts of Representative Carbons 543

13.7 Calculated and Observed 13C Chemical Shifts for the Ring Carbons in o - and m-Nitrotoluene 576 14.1 Approximate Acidities of Some Hydrocarbons and Reference Materials 585 14.2 Reactions of Grignard Reagents with Aldehydes and Ketones 587 14.3 Relative Reactivity Toward Alkenes 598

8.3

Effect of Chain Branching on Reactivity of Primary Alkyl Bromides Toward Substitution Under SN2 Conditions 328

8.4

Nucleophilicity of Some Common Nucleophiles 329

8.5

Reactivity of Some Alkyl Bromides Toward Substitution by the SN1 Mechanism 333

8.6

Relative Rate of SN1 Solvolysis of tert-Butyl Chloride as a Function of Solvent Polarity 337

8.7

Relative Rate of SN2 Displacement of 1-Bromobutane by Azide in Various Solvents 338

8.8

Approximate Relative Leaving-Group Abilities 343

15.4 Summary of Reactions of Alcohols Presented in This Chapter 650

8.9

Comparison of SN1 and SN2 Mechanisms of Nucleophilic Substitution in Alkyl Halides 346

15.5 Oxidation of Alcohols 651

9.1

Structural Features of Ethane, Ethylene, and Acetylene 359

9.2

Preparation of Alkynes 374

16.3 Preparation of Epoxides 690

9.3

Conversion of Alkynes to Alkenes and Alkanes 375

9.4

Electrophilic Addition to Alkynes 376

17.1 Summary of Reactions Discussed in Earlier Chapters That Yield Aldehydes and Ketones 708

14.4 Preparation of Organometallic Reagents Used in Synthesis 610 14.5 Carbon–Carbon Bond-Forming Reactions of Organometallic Reagents 612 15.1 Summary of Reactions Discussed in Earlier Chapters That Yield Alcohols 624 15.2 Summary of Reactions of Alcohols Discussed in Earlier Chapters 633 15.3 Preparation of Alcohols by Reduction of Carbonyl Functional Groups 649

16.1 Physical Properties of Diethyl Ether, Pentane, and 1-Butanol 666 16.2 Preparation of Ethers 689

11.1 Names of Some Frequently Encountered Derivatives of Benzene 428

17.2 Summary of Reactions of Aldehydes and Ketones Discussed in Earlier Chapters 710

11.2 Reactions Involving Alkyl and Alkenyl Side Chains in Arenes and Arene Derivatives 461

17.3 Equilibrium Constants (Khydr) and Relative Rates of Hydration of Some Aldehydes and Ketones 711

11.3 Substituent Constants ( ) 467

17.4 Reaction of Aldehydes and Ketones with Derivatives of Ammonia 724

12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene 472 12.2 Classification of Substituents in Electrophilic Aromatic Substitution Reactions 491

17.5 Nucleophilic Addition to Aldehydes and Ketones 739 18.1 pKa Values of Some Aldehydes and Ketones 754

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LIST OF IMPORTANT FEATURES

18.2 Reactions of Aldehydes and Ketones That Involve Enol or Enolate Ion Intermediates 780

26.1 Some Representative Fatty Acids 1069

19.1 Systematic and Common Names of Some Carboxylic Acids 792

27.1 The Standard Amino Acids 1110

19.2 Effect of Substituents on Acidity of Carboxylic Acids 800

26.2 Classification of Terpenes 1080 27.2 Acid–Base Properties of Amino Acids with Neutral Side Chains 1115

19.3 Acidity of Some Substituted Benzoic Acids 802

27.3 Acid–Base Properties of Amino Acids with lonizable Side Chains 1116

19.4 Summary of Reactions Discussed in Earlier Chapters That Yield Carboxylic Acids 805

27.4 Covalent and Noncovalent Interactions Between Amino Acid Side Chains in Proteins 1149

19.5 Summary of Reactions of Carboxylic Acids Discussed in Earlier Chapters 808

28.1 Pyrimidines and Purines That Occur in DNA and/or RNA 1166

20.1 Conversion of Acyl Chlorides to Other Carboxylic Acid Derivatives 837

28.2 The Major Pyrimidine and Purine Nucleosides in RNA and DNA 1168

20.2 Conversion of Acid Anhydrides to Other Carboxylic Acid Derivatives 840

28.3 The Genetic Code (Messenger RNA Codons) 1181

20.3 Preparation of Esters 843

28.4 Distribution of DNAs with Increasing Number of PCR Cycles 1190

20.4 Reactions of Esters Discussed in Earlier Chapters 844

29.1 Recycling of Plastics 1208

20.5 Conversion of Esters to Other Carboxylic Acid Derivatives 845

29.2 Summary of Alkene Polymerizations Discussed in Earlier Chapters 1210

20.6 Preparation of Nitriles 863 21.1 Preparation of -Keto Esters 898 22.1 Basicity of Amines As Measured by the pKa of Their Conjugate Acids 915 22.2 Effect of para Substituents on the Basicity of Aniline 916 22.3 Methods for Carbon–Nitrogen Bond Formation Discussed in Earlier Chapters 922 22.4 Reactions of Amines Discussed in Previous Chapters 930 22.5 Preparation of Amines 948 22.6 Reactions of Amines Discussed in This Chapter 950 22.7 Synthetically Useful Transformations Involving Aryl Diazonium lons 951 23.1 Carbon–Hydrogen and Carbon–Chlorine Bond Dissociation Enthalpies of Selected Compounds 966

Boxed Essays Introduction Where Did the Carbon Come From? 7

Chapter 1 Electrostatic Potential Maps 19 Molecular Modeling 30

Chapter 2 Methane and the Biosphere 65 What’s in a Name? Organic Nomenclature 72 Thermochemistry 86

Chapter 3

23.2 Summary of Reactions Discussed in Earlier Chapters That Yield Aryl Halides 967

Molecular Mechanics Applied to Alkanes and Cycloalkanes 109 Enthalpy, Free Energy, and Equilibrium Constant 120

23.3 Summary of Reactions of Aryl Halides Discussed in Earlier Chapters 968

Chapter 4

24.1 Comparison of Physical Properties of an Arene, a Phenol, and an Aryl Halide 994 24.2 Acidities of Some Phenols 995 24.3 Industrial Syntheses of Phenol 997 24.4 Electrophilic Aromatic Substitution Reactions of Phenols 999 25.1 Some Classes of Monosaccharides 1024 25.2 Summary of Reactions of Carbohydrates 1056

From Bond Enthalpies to Heats of Reaction 169

Chapter 5 Ethylene 186

Chapter 6 Rules, Laws, Theories, and the Scientific Method 235 Ethylene and Propene: The Most Important Industrial Organic Chemicals 265

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LIST OF IMPORTANT FEATURES

Chapter 7

Chapter 25

Chiral Drugs 291 Chirality of Disubstituted Cyclohexanes 300

How Sweet It Is! 1045

Chapter 8

Nonsteroidal Antiinflammatory Drugs (NSAIDs) and COX-2 Inhibitors 1078 Good Cholesterol? Bad Cholesterol? What’s the Difference? 1091 Anabolic Steroids 1094 Crocuses Make Saffron from Carotenes 1095

Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides 331

Chapter 9 Some Things That Can Be Made from Acetylene . . . But Aren’t 372

xxiii

Chapter 26

Chapter 27 Chapter 10 Diene Polymers 404

Chapter 11

Electrophoresis 1117 Peptide Mapping and MALDI Mass Spectrometry 1136 Oh NO! It’s Inorganic! 1153

Carbon Clusters, Fullerenes, and Nanotubes 432

Chapter 28

Chapter 13

“It Has Not Escaped Our Notice . . .” 1175 RNA World 1184

Ring Currents: Aromatic and Antiaromatic 529 Magnetic Resonance Imaging (MRI) 540 Spectra by the Thousands 551 Gas Chromatography, GC/MS, and MS/MS 564

Chapter 14

Descriptive Passage and Interpretive Problems Chapter 1 Amide Lewis Structures 57

An Organometallic Compound That Occurs Naturally: Coenzyme B12 601

Chapter 2

Chapter 15

Chapter 3

Economic and Environmental Factors in Organic Synthesis 641

Cyclic Forms of Carbohydrates 137

Chapter 16 Polyether Antibiotics 669

Chapter 17

Some Biochemical Reactions of Alkanes 100

Chapter 4 More About Potential Energy Diagrams 180

Chapter 5 A Mechanistic Preview of Addition Reactions 222

Imines in Biological Chemistry 725

Chapter 18 The Haloform Reaction and the Biosynthesis of Trihalomethanes 773

Chapter 20 -Lactam Antibiotics 861

Chapter 22

Chapter 6 Some Unusual Electrophilic Additions 274

Chapter 7 Prochirality 316

Chapter 8 Nucleophilic Substitution 352

Amines as Natural Products 919 From Dyes to Sulfa Drugs 943

Chapter 9

Chapter 24

Chapter 10

Agent Orange and Dioxin 1005

Intramolecular and Retro Diels–Alder Reactions 417

Thinking Mechanistically About Alkynes 380

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LIST OF IMPORTANT FEATURES

Chapter 11

Chapter 21

The Hammett Equation 466

The Enolate Chemistry of Dianions 903

Chapter 12

Chapter 22

Nucleophilic Aromatic Substitution 512

Synthetic Applications of Enamines 960

Chapter 13

Chapter 23

Calculating Aromatic

13

C Chemical Shifts 575

The Heck Reaction 986

Chapter 14

Chapter 24

Oxymercuration 617

Directed Metalation of Aryl Ethers 1018

Chapter 15

Chapter 25

The Pinacol Rearrangement 658

Emil Fischer and the Structure of ()-Glucose 1061

Chapter 16

Chapter 26

Epoxide Rearrangements and the NIH Shift 697

Polyketides 1101

Chapter 17

Chapter 27

Alcohols, Aldehydes, and Carbohydrates 749

Amino Acids in Enantioselective Synthesis 1159

Chapter 18

Chapter 28

Enolate Regiochemistry and Stereochemistry 787

Oligonucleotide Synthesis 1195

Chapter 19

Chapter 29

Lactonization Methods 825

Chemical Modification of Polymers 1227

Chapter 20 Thioesters 876

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Preface What Sets This Book Apart?

A Functional Group 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. The goal of this text, as it has been through six previous editions, is to provide students with the conceptual tools to understand and apply the relationship between the structures of organic compounds and their properties. Both the organization of the text and the presentation of individual topics were designed with this objective in mind.

The text is organized according to functional groups— structural units within a molecule that are most closely identified with characteristic properties. This organization offers two major advantages over alternative organizations based on mechanisms or reaction types.

A Mechanistic Emphasis and Its Presentation The text emphasizes mechanisms and encourages students to see similarities in mechanisms among different functional groups. Mechanisms are developed from observations; thus, reactions are normally presented first, followed by their mechanism. To maintain consistency with what our students have already learned, this text presents multistep mechanisms in the same way as do most general chemistry textbooks—that is, as a series of elementary steps. Additionally, we provide a brief comment about how each step contributes to the overall mechanism. Section 1.11, “Curved Arrows and Chemical Reactions,” introduces students to the notational system employed in all of the mechanistic discussions in the text. Numerous reaction mechanisms are accompanied by potential energy diagrams. Section 4.9, “Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism,” shows how the potential energy diagrams for three elementary steps are combined to give the diagram for the overall reaction.

1. The information content of individual chapters is more manageable when organized according to functional groups. 2. Patterns of reactivity are reinforced when a reaction used to prepare a particular functional group reappears as a characteristic reaction of a different functional group.

MECHANISM 6.5 Acid-Catalyzed Hydration of 2-Methylpropene The overall reaction:



(CH3)2CPCH2

H O

±3£

H2O

2-Methylpropene

Water

(CH3)3COH tert-Butyl alcohol

The mechanism:

STEP 1: Protonation of the carbon–carbon double bond in the direction that leads to more stable carbocation: H3C CPCH2





H BA

H–O

H3C

H3C

slow

COCH3



O

H3C

H

2-Methylpropene

H



Hydronium ion

H

tert-Butyl cation

Water

STEP 2: Water acts as a nucleophile to capture tert-butyl cation: H3C

H



C–CH3

fast



BA

O H

H3C tert-Butyl cation

Water

CH3 H W  H3COCOO W CH3 H tert-Butyloxonium ion

STEP 3: Deprotonation of tert-butyloxonium ion. Water acts as a Brønsted base: CH3 H W  H3COCOO W CH3 H tert-Butyloxonium ion

H

CH3 W H3COCOOH W CH3

Water

tert-Butyl alcohol

H 

fast

BA

O





H

H–O H Hydronium ion

xxv

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PREFACE

Enhanced Graphics The teaching of organic chemistry has especially benefited as powerful modeling and graphics software have become routinely available. For example, computer-generated molecular models and electrostatic potential maps were integrated into the third edition of this text, and their number has increased with each succeeding edition. Also seeing increasing use are graphically correct representations of orbitals and the role of orbital interactions in chemical reactivity. The E2 mechanism of elimination, which involves a single elementary step, is supplemented by showing the orbital interactions that occur during that step.

MECHANISM 5.4 E2 Elimination of an Alkyl Halide

O—H bond is forming C—H bond is breaking Hydroxide ion

C

Transition state

C ␲ bond is forming

C—X bond is breaking Potential energy

xxvi

Alkene Reactants

Water Halide ion

Alkyl halide Products Reaction coordinate

Problems Problem-solving strategies and skills are emphasized throughout. Understanding is progressively reinforced by problems that appear within topic sections. For many problems, sample solutions are given, including an increased number of examples of handwritten solutions from the author. PROBLEM 10.6 Evaluate 2,3,3-trimethyl-1-butene as a candidate for free-radical bromination. How many allylic bromides would you expect to result from its treatment with N-bromosuccinimide?

Generous and Effective Use of Tables The relative reactivity of different compounds is pertinent to both the theory and practice of organic chemistry. While it is helpful—and even important—to know that one compound is more reactive than another, it is even better to know by how much. Our text provides more experimental information of this type than is customary. Chapter 8, “Nucleophilic Substitution,” for example, contains seven tables of quantitative relative rate data, of which the following is but one example.

TABLE 8.2 Reactivity of Some Alkyl Bromides Toward Substitution by the SN2 Mechanism* Alkyl bromide

Structure

Class

Methyl bromide Ethyl bromide Isopropyl bromide tert-Butyl bromide

CH3Br CH3CH2Br (CH3)2CHBr (CH3)3CBr

Unsubstituted Primary Secondary Tertiary

Relative rate† 221,000 1,350 1 Too small to measure

*Substitution of bromide by lithium iodide in acetone. †

Ratio of second-order rate constant k for indicated alkyl bromide to k for isopropyl bromide at 25°C.

Annotated summary tables have been a staple of Organic Chemistry since the first edition. Some tables review reactions from earlier chapters, others review reactions or concepts of a current chapter, and still others walk the reader step-by-step through skill builders and concepts unique to organic chemistry. Well received by students and faculty alike, these summary tables remain one of the text’s strengths.

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PREFACE

xxvii

Pedagogy • A list of mechanisms, tables, boxed essays and Descriptive Passages and Interpretive Problems is included in the front matter (page xix) as a quick reference to these important learning tools in each chapter.

C

H

A

P

T

7

E

R

Stereochemistry C H A P T E R 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8

O U T L I N E

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 • Chiral Drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291 Reactions That Create a Chirality Center . . . . . . . . . . . . . . . . . . . . . . . . 292 Chiral Molecules with Two Chirality Centers . . . . . . . . . . . . . . . . . . . . . . 295 Achiral Molecules with Two Chirality Centers . . . . . . . . . . . . . . . . . . . . . 297 Molecules with Multiple Chirality Centers . . . . . . . . . . . . . . . . . . . . . . . 299 • Chirality of Disubstituted Cyclohexanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300 Reactions That Produce Diastereomers . . . . . . . . . . . . . . . . . . . . . . . . . 301 Resolution of Enantiomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303 Stereoregular Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305 Chirality Centers Other Than Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . 306 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 Descriptive Passage and Interpretive Problems 7: Prochirality . . . . . . . . . . . .316

7.9 7.10 7.11 7.12

• Each chapter opens with a list of section headings, boxed essays, reaction mechanisms, and Descriptive Passages and Interpretive Problems along with their corresponding page numbers. • Summary tables allow the student easy access to a wealth of information in an easy-to-use format while reviewing information from previous chapters. 7.13 7.14 7.15 7.16 7.17

Bromochlorofluoromethane molecules come in right- and left-handed versions.

Stereochemistry is chemistry in three dimensions. Its foundations were laid by Jacobus van’t Hoff* and Joseph Achille Le Bel in 1874. Van’t Hoff and Le Bel independently proposed that the four bonds to carbon were directed toward the corners of a tetrahedron. One consequence of a tetrahedral arrangement of bonds to carbon is that two compounds may be different because the arrangement of their atoms in space is different. Isomers that have the same constitution but differ in the spatial arrangement of their atoms are called stereoisomers. We have already had considerable experience with certain types of stereoisomers—those involving cis and trans substitution in alkenes and in cycloalkanes. Our major objectives in this chapter are to develop a feeling for molecules as threedimensional objects and to become familiar with stereochemical principles, terms, and notation. A full understanding of organic and biological chemistry requires an awareness of the spatial requirements for interactions between molecules; this chapter provides the basis for that understanding.

7.1

Molecular Chirality: Enantiomers

Everything has a mirror image, but not all things are superimposable on their mirror images. Mirror-image superimposability characterizes many objects we use every day. Cups and saucers, forks and spoons, chairs and beds are all identical with their mirror images. Many other objects though—and this is the more interesting case—are not. Your left hand and your right hand, for example, are mirror images of each other but can’t be made to coincide point for point, palm to palm, knuckle to knuckle, in three dimensions. In 1894, William Thomson (Lord Kelvin) coined a word for this property. He defined an object as chiral if it is not superimposable on its mirror image. Applying Thomson’s term to chemistry, we say that a molecule is chiral if its two mirror-image forms are not superimposable in three dimensions. The word chiral is derived from the Greek word cheir, meaning “hand,” and it is entirely appropriate to speak of the “handedness” of *Van’t Hoff was the recipient of the first Nobel Prize in chemistry in 1901 for his work in chemical dynamics and osmotic pressure—two topics far removed from stereochemistry.

276

Audience

• End-of-chapter summaries highlight and consolidate all of the important concepts and reactions within a chapter. 12.19 SUMMARY Section 12.1

On reaction with electrophilic reagents, compounds that contain a benzene ring undergo electrophilic aromatic substitution. Table 12.1 in Section 12.1 and Table 12.3 in this summary give examples.

Section 12.2

The mechanism of electrophilic aromatic substitution involves two stages: bonding of the electrophile by the  electrons of the ring (slow, ratedetermining), followed by rapid loss of a proton to restore the aromaticity of the ring. E

H

␦

 Benzene

E

␦

Y

slow 

Electrophilic reagent

H

E  Y

fast

Cyclohexadienyl cation intermediate

 H Product of electrophilic aromatic substitution

Sections 12.3–12.5

See Table 12.3

Sections 12.6–12.7

See Tables 12.3 and 12.4.

Section 12.8

Friedel–Crafts acylation, followed by Clemmensen or Wolff–Kishner reduction is a standard sequence used to introduce a primary alkyl group onto an aromatic ring.

CH2CH3 CH2CH3

CH2CH3 CH2CH3

O X CH3CCl AlCl3

1,2,4-Triethylbenzene

CH2CH3 CH2CH3 H2NNH2, NaOH triethylene glycol, heat

CH3C CH2CH3

Y

Organic Chemistry is designed to meet the needs of the “mainstream” two-semester undergraduate organic chemistry course. From the beginning and with each new edition, we have remained grounded in some fundamental notions. These include important issues about our intended audience. Is the topic appropriate for them with respect to their interests, aspirations, and experience? Just as important is the need to present an accurate picture of the present state of organic chemistry. How do we know what we know? What makes organic chemistry worth knowing? Where are we now? Where are we headed? Even the art that opens each chapter in this edition has been designed with the audience in mind. The electrostatic potential maps that have opened the chapters through several editions have been joined by a graphic of a familiar object that connects the map to the chapter’s content. Chapter 8, for example, opens by illustrating the umbrellain-a-windstorm analogy used by virtually everyone who has ever taught nucleophilic substitution.

O

CH3CH2 CH2CH3

2,4,5-Triethylacetophenone (80%)

CH2CH3 1,2,4,5-Tetraethylbenzene (73%)

This electrostatic potential map is of the transition state for the reaction of hydroxide ion with chloromethane. The tetrahedral arrangement of bonds inverts like an umbrella in a storm during the reaction.

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PREFACE

What’s New? Descriptive Passages and Interpretive Problems New to this edition is an original feature that adds breadth, flexibility, and timeliness to our coverage. Because so many organic chemistry students later take standardized pre-professional examinations composed of problems derived from a descriptive passage, we decided to include comparable passages and problems in our text to familiarize students with this testing style. We soon discovered that descriptive passages accompanied by interpretive problems can serve the even greater purpose of enhancing this text’s content.

274

CHAPTER SIX

Thus, every chapter now concludes with a selfcontained Descriptive Passage and Interpretive Problems unit that complements the chapter’s content while emulating the “MCAT style.” These 29 passages (listed on p. xxiii) are accompanied by a total of 179 multiple-choice problems. The passages focus on a wide range of topics—from structure, synthesis, mechanism, and natural products to using the Internet to calculate 13C chemical shifts. They provide instructors with numerous opportunities to customize their own organic chemistry course while giving students practice in combining new information with what they have already learned.

Addition Reactions of Alkenes

6.64 The sex attractant of the female arctiid moth contains, among other components, a compound of molecular formula C21H40 that yields

O

O

CH3(CH2)10CH

O

CH3(CH2)4CH

and

O

6.65

Which compound has the smallest dipole moment? A. I2 C. IN3 B. HI D. INCO

The effect of substituents on the rate of addition of INCO to alkenes is similar to that of addition of other electrophilic reagents. Which of the following is the correct order of reactivity?

6.66

Fastest rate H CH2CH3

HCCH2CH

on ozonolysis. What is the constitution of this material? A.



I–NœCœO

Iodine azide (IN3)

Iodine isocyanate (INCO)

I

I

C

C

R

R

X

I

Compound A

X

Compound B

• Conversion to vinyl azides by E2

N3

R2C

KOC(CH3)3 DMSO

CR N3

• Reaction of the ONCO group with methanol R2COCHR

I

NCO

C. (CH3)2C

CH3OH

6.67

C(CH3)2

CH3(CH2)5CH

C(CH3)2

H CH2CH3 C

CH2

C

C

CH3CH2

H

CH3(CH2)5CH

CH2

H

I

I

I N3

N3 A.

B.

N3

C.

D.

Which product would you expect to be formed if the regioselectivity of addition of INCO to 1-butene was analogous to HOBr addition? Assume iodine is the electrophilic atom of INCO. NCO CH3CH2CHCH2NCO

CH3CH2CHCH2I

I

B.

A

N3 2-Azido-4,4-dimethyl-1-pentene

B. (CH3)3CCH2CH2CH2OH C. (CH3)3CCHCH2CH3

KOC(CH3)3 DMSO

NHCOCH3

D. (CH3)3CCHCH2CH3 OH

H2SO4 heat

D. 6.70 trans-1-Azido-2-iodocyclopentane did not give a vinyl azide (compound B) on E2 elimination. Instead compound A was formed. Why? 3

IN3

H2SO4 heat

KOC(CH3)3 DMSO

I

C.

Which is the best synthesis of 2-azido-4,4-dimethyl-1-pentene? (CH3)3CCH2CPCH2

A. (CH3)3CCH2CH2CH2Br

CH3CH2CCH3

I

NCO

A. 6.69

CH3CH2CH2CHNCO

KOC(CH3)3 DMSO

IN3

2

1

I

E2

N3

KOC(CH3)3 trans-1-Azido-2-iodocyclopentane DMSO

IN3

KOC(CH3)3 DMSO

IN3

KOC(CH3)3 DMSO

Br

O

C

CH2CH3 C

N3

R2COCHR

I

CH2CH3 C

The product of the reaction of iodine azide with cyclohexene is: I

R2COCHR

and/or

I

Compound A corresponds to attack by the nucleophile X at the more-substituted carbon of the iodonium ion, compound B at the less-substituted carbon. Once formed, the addition products are normally subjected to reactions such as the following prior to further transformations.

I

C(CH3)2

6.68

Bridged iodonium ion

R2COCHR

C(CH3)2

H

X

Evidence in support of a bridged iodonium ion comes from two main observations: (a) rearrangements characteristic of carbocation intermediates do not occur; and (b) the stereochemistry of addition is anti. The regiochemistry of addition of IN3 and INCO is inconsistent, varying both with respect to the reagent and the structure of the alkene.

R2COCHR

(CH3)2C

CH3CH2

G

I–X

(CH3)2C

CH3CH2

D. (CH3)2C

X

R2COCR2

I–X

R2CœCHR

CH2

H

I–NœNœN

CH2

H

B. CH3(CH2)5CH

Both react with alkenes in a manner similar to Cl2 and Br2. A bridged iodonium ion is formed that then reacts with a nucleophile (N3 or OCN) to give the product of electrophilic addition. R R 

Slowest rate CH3(CH2)5CH

C

H

Some Unusual Electrophilic Additions We have seen reactions in this chapter that convert alkenes to alkyl halides, alcohols, and epoxides; that is, compounds with carbon–halogen or carbon–oxygen bonds. It would be useful if methods were available to convert alkenes to compounds with carbon–nitrogen bonds. Chemists have solved the problem of CON bond formation by developing a number of novel nitrogen-containing reagents that add to alkenes. Examples include iodine azide and iodine isocyanate. 

C CH3CH2

DESCRIPTIVE PASSAGE AND INTERPRETIVE PROBLEMS 6

R2CœCR2

275

Descriptive Passage and Interpretive Problems 6

A certain compound of molecular formula C19H38 was isolated from fish oil and from plankton. On hydrogenation it gave 2,6,10,14-tetramethylpentadecane. Ozonolysis gave (CH3)2CPO and a 16carbon aldehyde. What is the structure of the natural product? What is the structure of the aldehyde? 6.63

not N3

N3 Compound A

Compound B

A. Compound A is more stable than compound B. B. C-3 has twice as many hydrogens as C-1. C. Only C-3 has a hydrogen that can be anti coplanar with respect to iodine. D. The hydrogens at C-3 are less crowded than the hydrogen at C-1.

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PREFACE

Boxed Essays: Revised and New • What’s in a Name? Organic Nomenclature describes the evolution of organic nomenclature and compares the 1979, 1993, and 2004 IUPAC recommendations for naming organic compounds. • -Lactam Antibiotics expands the familiar penicillin story beyond its discovery to include its large-scale development as a lifesaving drug during World War II and its mode of action. • Peptide Mapping and MALDI Mass Spectrometry illustrates the application of a cutting-edge mass spectrometric technique to peptide sequencing.

New Topics • Section 10.4: “SN2 Reactions of Allylic Halides”

Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides

N

ucleophilic substitution is one of a variety of mechanisms by which living systems detoxify halogenated organic compounds introduced into the environment. Enzymes that catalyze these reactions are known as haloalkane dehalogenases. The hydrolysis of 1,2-dichloroethane to 2-chloroethanol, for example, is a biological nucleophilic substitution catalyzed by the dehalogenase shown in Figure 8.4.

ClCH2CH2Cl

• Section 11.15: “SN2 Reactions of Benzylic Halides”

 2H2O

1,2-Dichloroethane

Cl

H Cl

HO CH3

H2O dehalogenase

O Racemic 2-chloropropanoic acid

HO CH3 O (S)-2-Chloropropanoic acid

H OH  HO

dehalogenase enzyme

CH3 O

Water

ClCH2CH2OH  2-Chloroethanol

H3 O



Hydronium ion

O X  Enzyme ±C±O  CH2±Cl W CH2Cl

(S)-Lactic acid

Cl Chloride ion

This haloalkane dehalogenase is believed to act by using one of its side-chain carboxylates to displace chloride by an SN2 mechanism. (Recall the reaction of carboxylate ions with alkyl halides from Table 8.1.) SN2

In this enzymatic resolution (Section 7.14), the dehalogenase enzyme catalyzes the hydrolysis of the R-enantiomer of 2-chloropropanoic acid to (S)-lactic acid. The desired (S)-2chloropropanoic acid is unaffected and recovered in a nearly enantiomerically pure state. Some of the most common biological SN2 reactions involve attack at methyl groups, especially a methyl group of S-adenosylmethionine. Examples of these will be given in Chapter 16.

O X  Enzyme ±C±O±CH2  Cl W CH2Cl The product of nucleophilic substitution then reacts with water, restoring the enzyme to its original state and giving the observed products of the reaction. O X Enzyme ±C±O±CH2  2H2O W CH2Cl

several steps

O X  Enzyme ±C±O  HOCH2  H3O W CH2Cl

• Section 10.7: “Allylic Anions” • Section 11.14: “SN1 Reactions of Benzylic Halides”

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This stage of the reaction proceeds by a mechanism that will be discussed in Chapter 20. Both stages are faster than the reaction of 1,2-dichloroethane with water in the absence of the enzyme. Enzyme-catalyzed hydrolysis of racemic 2-chloropropanoic acid is a key step in the large-scale preparation of (S)-2-chloropropanoic acid used for the preparation of agricultural chemicals.

F I G U R E 8.4 A ribbon diagram of the dehalogenase enzyme that catalyzes the hydrolysis of 1,2-dichloroethane. The progression of amino acids along the chain is indicated by a color change. The nucleophilic carboxylate group is near the center of the diagram.

Major Revisions • Sections 13.20–13.22 are a complete rewrite of infrared (IR) spectroscopy. All of the IR spectra displayed in the text are new and were recorded by Thomas Gallaher of James Madison University using the attenuated total reflectance (ATR) method.

• Section 25.8 “Mutarotation and the Anomeric Effect” revises the previous discussion of mutarotation to include the now-generally accepted molecular orbital explanation for the anomeric effect.

Instructor Resources McGraw-Hill’s ARIS The Assessment, Review, and Instruction System for Organic Chemistry is a complete online tutorial, electronic homework, and course management system. Instructors can create and share course materials and assignments with colleagues with a few clicks of the mouse. All PowerPoint® images, PowerPoint lecture outlines, mechanism animations, assignments, quizzes, and tutorials are directly tied to text-specific materials in Organic Chemistry. Instructors can also edit questions and algorithms, import their own content, and create announcements and due dates for assignments. ARIS has automatic grading and reporting of easy-to-assign algorithmically generated homework, quizzing, and

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testing. All student activity within McGraw-Hill’s ARIS is automatically recorded and available to the instructor through a fully integrated grade book that can be downloaded to Excel®. Contact your local McGraw-Hill Sales representative for more information on getting started with ARIS.

ARIS Presentation Center Build instructional materials where-ever, when-ever, and how-ever you want! ARIS Presentation Center is an online digital library containing assets such as photos, artwork, animations, PowerPoints, and other media types that can be used to create customized lectures, visually enhanced tests and quizzes, compelling course websites, or attractive print support materials. Access to your book, access to all books! The Presentation Center library includes thousands of assets from many McGraw-Hill titles. This evergrowing resource enables instructors to use assets specific to an adopted textbook as well as content from all the other books in the library. Nothing could be easier! Accessed from the instructor side of your textbook’s ARIS website, Presentation Center’s dynamic search engine allows you to explore by discipline, course, textbook chapter, asset type, or keyword. Simply browse, select, and download the files you need to build engaging course materials.

Course Management Software With help from Blackboard or WebCT, you can take complete control over your course content. These course cartridges also feature online testing and powerful student tracking. Contact your McGraw-Hill sales representative for more details.

The Classroom Performance System’s (CPS) eInstruction CPS 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, which are essentially remotes, are easy to use and engage students. CPS helps instructors motivate student preparation, interactivity, and active learning. Instructors receive immediate feedback to gauge which concepts students understand. Questions covering the content of the Organic Chemistry text and formatted in the CPS eInstruction software are available on the Organic Chemistry ARIS site.

Instructor’s Testing and Resource CD-ROM The cross-platform CD-ROM contains the Test Bank. The Test Bank questions are also found in a computerized test bank, which utilizes testing software to quickly create customized exams. This user-friendly program enables instructors to sort questions by format, edit existing questions or add

new ones, and scramble questions for multiple versions of the same test.

Solutions Manual Prepared by Robert Atkins (James Madison University) and Francis Carey, this manual provides complete solutions to all problems in the text. The Solutions Manual also includes self-tests to assess student understanding.

Overhead Transparencies A selection of full-color transparencies of illustrations from the text include reproductions of spectra, orbital diagrams, key tables, computer-generated molecular models, and stepby-step reaction mechanisms.

Student Resources Solutions Manual Written by Robert C. Atkins and Francis A. Carey, the Solutions Manual provides step-by-step solutions that guide the student through the reasoning behind each problem in the text. There is also a self-test at the end of each chapter, which is designed to assess the student’s mastery of the material.

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