This is a special edition of an established title widely used by colleges and GLOBAL GLOBAL universities throughout the world. Pearson published this exclusive edition for the benefit of students outside the United States and Canada. If you EDITION EDITION purchased this book within the United States or Canada, you should be aware EG DL that it has been imported without the approval of the Publisher or Author. ITO IOBA Organic NL Chemistry Wade and Simek’s Organic Chemistry is a foundational text for chemistry and biochemistry majors, O aimed at helping students master the compounds, names, reactions, and mechanisms that make up r the mammoth discipline that is organic chemistry. This modern, eminently readable text teaches g not only the basic principles of organic chemistry but also the many extensions and applications of a these principles. Rather than suggesting rote memorization, it makes a student’s learning process n TENTH GLOBAL EDITION i easier by stacking concepts logically while providing essential problem-solving skills along the way. c Leroy G. Wade C Key Features Jan William Simek h • New! Margin boxes on notable chemists offer a glimpse into the lives of extraordinary e people who contributed greatly to scientific progress. m • New! Focus Features highlight key aspects of complex topics and reactions to help students i understand them better. s t • Starburst Reaction Summaries, present towards the end of “reaction-based” chapters, aid r y students in categorizing these reactions and recognizing their similarities and differences. • Visual Guides to Organic Reactions place the reactions covered in each chapter within the overall context of reactions covered in the course to enable learning. • Key Mechanism Boxes highlight the fundamental mechanistic principles that form the basis G of complex reactions and that recur throughout the course. L O B AT Available separately for purchase is Mastering Chemistry for Organic Chemistry, the teaching and LE N learning platform that empowers instructors to personalize learning for every student. When ET D H combined with Pearson’s trusted educational content, this optional suite helps deliver the desired IT I O learning outcomes. The new edition of Mastering comes with Dynamic Study Modules, Key N Mechanism and Mechanism Overview Videos (paired videos explaining a mechanism and then representing it), and Mechanism Practice Problems (completion-based learning practice). SW i m a ed ke CVR_WADE4255_10_GE_CVR_Ashford.indd All Pages 15/07/2022 14:25 O R G A N I C C H E M I S T R Y T E N T H G L O B A L E D I T I O N LEROY G. WADE, JR. WHITMAN COLLEGE CONTRIBUTING AUTHOR: JAN WILLIAM SIMEK CALIFORNIA POLYTECHNIC STATE UNIVERSITY A01_WADE4255_10_GE_FM.indd 1 18/07/22 4:07 PM Product Management: Gargi Banerjee and Neelakantan K.K. Content Strategy: Shabnam Dohutia, Amrita Naskar, and Afshaan Khan Product Marketing: Wendy Gordon, Ashish Jain, and Ellen Harris Supplements: Bedasree Das Digital Studio: Vikram Medepalli and Jayaprakash Kothandapani Rights and Permissions: Anjali Singh and Nilofar Jahan Cover Photo Credit: Danny Ye/Shutterstock Please contact https://support.pearson.com/getsupport/s/contactsupport with any queries on this content. Pearson Education Limited KAO Two KAO Park Harlow CM17 9SR United Kingdom and Associated Companies throughout the world Visit us on the World Wide Web at: www.pearsonglobaleditions.com © Pearson Education Limited 2023 The rights of Leroy G. Wade, Jr. and Jan William Simek to be identified as the authors of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988. Authorized adaptation from the United States edition, entitled Organic Chemistry, 9th edition, ISBN 9780321971371, by Leroy G. Wade, Jr. and Jan William Simek, published by Pearson Education © 2017. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without either the prior written permission of the publisher or a license permitting restricted copying in the United Kingdom issued by the Copyright Licensing Agency Ltd, Saffron House, 6–10 Kirby Street, London EC 1N 8TS. All trademarks used herein are the property of their respective owners. The use of any trademark in this text does not vest in the author or publisher any trademark ownership rights in such trademarks, nor does the use of such trademarks imply any affiliation with or endorsement of this book by such owners. Acknowledgements of third party content appear on page 1399, which constitutes an extension of this copyright page. PEARSON, ALWAYS LEARNING, and Mastering CHEMISTRY are exclusive trademarks in the U.S. and/or other countries owned by Pearson Education, Inc. or its affiliates. Unless otherwise indicated herein, any third-party trademarks that may appear in this work are the property of their respective owners and any references to third-party trademarks, logos or other trade dress are for demonstrative or descriptive purposes only. Such references are not intended to imply any sponsorship, endorsement, authorization, or promotion of Pearson’s products by the owners of such marks, or any relationship between the owner and Pearson Education, Inc. or its affiliates, authors, licensees or distributors. This eBook may be available as a standalone product or integrated with other Pearson digital products like MyLab and Mastering. This eBook may or may not include all assets that were part of the print version. The publisher reserves the right to remove any material in this eBook at any time. Print ISBN 10: 1-292-42425-7 Print ISBN 13: 978-1-292-42425-5 eBook ISBN 13: 978-1-292-42429-3 British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library eBook formatted by B2R Technologies Pvt. Ltd. To my students and colleagues at Whitman College About the Authors L. G. “Skip” Wade decided to become a chemistry major during his sophomore year at Rice University, while taking organic chemistry from Professor Ronald M. Magid. After receiving his B.A. from Rice in 1969, Wade went on to Harvard University, where he did research with Professor James D. White. While at Harvard, he served as the Head Teaching Fellow for the organic laboratories and was strongly influenced by the teaching methods of two master educators, Professors Leonard K. Nash and Frank H. Westheimer. After completing his Ph.D. at Harvard in 1974, Dr. Wade joined the chemistry faculty at Colorado State University. Over the course of fifteen years at Colorado State, Dr. Wade taught organic chemistry to thousands of students working toward careers in all areas of biology, chemistry, h uman medicine, veterinary medicine, and environmental studies. He also authored research papers in organic synthesis and in chemical education, as well as eleven books reviewing current research in organic synthesis. In 1989, Dr. Wade joined the chemistry faculty at Whitman College, where he con- tinued to teach organic chemistry and pursue research interests in o rganic synthesis and forensic chemistry. Dr. Wade received the A. E. Lange Award for Distinguished Science Teaching at Whitman in 1993. Dr. Wade’s interest in forensic science has led him to testify as an expert witness in court cases involving drugs and firearms, and he has worked as a police firearms instructor, drug consultant, and boating safety officer. He also enjoys repairing and restoring old violins and bows, which he has done professionally for many years. Jan Simek was born to humble, coal-mining parents who taught him to appreciate the importance of carbon at a very early age. At age 14, he was inspired to pursue a career teaching chemistry by his high school c hemistry teacher, Joe Plaskas. Under the guidance of Professor Kurt Kaufman at Kalamazoo College, Dr. Simek began lab work in synthesis of natural prod- ucts that turned into research in hop extracts for the Kalamazoo Spice Extrac- tion Company. After receiving a master’s degree from Stanford University, Dr. Simek worked in the pharmaceutical industry, synthesizing compounds designed to control diabetes and atherosclerosis, and assisted in the isola- tion of anti-cancer antibiotics from natural sources. Returning to Stanford University, Dr. Simek completed his Ph.D. with the legendary Professor Carl Djerassi, who developed the first synthesis of steroidal oral contraceptives. Dr. Simek’s 35-year teaching career was spent primarily at California Polytechnic State University, San Luis Obispo, where he received the uni- versity’s Distinguished Teaching Award. Other teaching experiences include Albion College, the University of Colorado at Boulder, Kalamazoo College, and the University of California at Berkeley. In addition to his pharmaceuti- cal research, he has industrial experience investigating dyes, surfactants, and liquid crystals, and he continues to consult for the biotechnology industry. Although his outside interests include free climbing in Yosemite, perform- ing in a reggae band, and parasailing over the Pacific, as close as he gets to any of those is tending his backyard garden with his wife Judy. A01_WADE4255_10_GE_FM.indd 3 18/07/22 4:07 PM Brief Contents Preface 25 1 Structure and Bonding 37 2 Acids and Bases; Functional Groups 93 3 Structure and Stereochemistry of Alkanes 146 4 The Study of Chemical Reactions 197 5 Stereochemistry 244 6 Alkyl Halides; Nucleophilic Substitution 292 7 Structure and Synthesis of Alkenes; Elimination 342 8 Reactions of Alkenes 406 9 Alkynes 476 10 Structure and Synthesis of Alcohols 510 11 Reactions of Alcohols 557 12 Infrared Spectroscopy and Mass Spectrometry 609 13 Nuclear Magnetic Resonance Spectroscopy 661 14 Ethers, Epoxides, and Thioethers 726 15 Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy 770 16 Aromatic Compounds 820 17 Reactions of Aromatic Compounds 865 18 Ketones and Aldehydes 932 19 Amines 998 20 Carboxylic Acids 1059 21 Carboxylic Acid Derivatives 1101 22 Condensations and Alpha Substitutions of Carbonyl Compounds 1171 23 Carbohydrates and Nucleic Acids 1232 24 Amino Acids, Peptides, and Proteins 1283 25 Lipids 1326 26 Synthetic Polymers 1347 Appendices 1369 Answers to Selected Problems 1393 Photo Credits 1399 Index 1400 4 A01_WADE4255_10_GE_FM.indd 4 18/07/22 4:07 PM Contents About the Authors 3 Preface 25 1 STRUCTURE AND BONDING 37 1-1 The Origins of Organic Chemistry 37 1-2 Principles of Atomic Structure 39 1-3 Bond Formation: The Octet Rule 43 1-4 Lewis Structures 44 1-5 Multiple Bonding 45 S ummary: Common Bonding Patterns (Uncharged) 45 1-6 Electronegativity and Bond Polarity 46 S S OH 1-7 Formal Charges 47 O C N N Summary: Common Bonding Patterns in Organic Compounds and Ions 49 luciferin OH 1-8 Ionic Structures 49 luciferin Lspuecciifeesr. iLnu ics itfheeri nli grehat-cetms wittiitnhg a ctmomosppohuenrdic fooxuyngde inn, munadneyr fithreefl cyo n(Ltraoml opfy raind aeen)z yme, 1-9 Resonance 50 to emit the yellow light that fireflies use to attract mates and prey. PROBLEM-SOLVING STRATEGY: Drawing and Evaluating Resonance Forms 54 1-10 Structural Formulas 58 1-11 Molecular Formulas and Empirical Formulas 62 1-12 Wave Properties of Electrons in Orbitals 63 1-13 Molecular Orbitals 65 1-14 Pi Bonding 68 1-15 Hybridization and Molecular Shapes 69 1-16 Drawing Three-Dimensional Molecules 72 1-17 General Rules of Hybridization and Geometry 73 Summary: Hybridization and Geometry 74 1-18 Bond Rotation 79 1-19 Isomerism 81 Essential Terms 84 Study Problems 88 2 ACIDS AND BASES; FUNCTIONAL GROUPS 93 2-1 Polarity of Bonds and Molecules 94 2-2 Intermolecular Forces 98 2-3 Polarity Effects on Solubilities 103 2-4 Arrhenius Acids and Bases 107 2-5 Brønsted–Lowry Acids and Bases 108 2-6 Strengths of Acids and Bases 109 2-7 Equilibrium Positions of Acid–Base Reactions 112 PROBLEM-SOLVING STRATEGY: Predicting Acid–Base Equilibrium Positions 114 2-8 Solvent Effects on Acidity and Basicity 115 Summary: Acidity and Basicity Limitations in Common Solvents 117 5 A01_WADE4255_10_GE_FM.indd 5 18/07/22 4:07 PM 6 Contents 2-9 Effects of Size and Electronegativity on Acidity 117 2-10 Inductive Effects on Acidity 119 2-11 Hybridization Effects on Acidity 120 2-12 Resonance Effects on Acidity and Basicity 122 2-13 Lewis Acids and Bases 125 2-14 The Curved-Arrow Formalism 127 2-15 Hydrocarbons 129 2-16 Functional Groups with Oxygen 132 2-17 Functional Groups with Nitrogen 135 Essential Terms 137 Study Problems 140 3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 146 3-1 Classification of Hydrocarbons (Review) 147 3-2 Molecular Formulas of Alkanes 147 3-3 Nomenclature of Alkanes 149 Summary: Rules for Naming Alkanes 154 3-4 Physical Properties of Alkanes 157 3-5 Uses and Sources of Alkanes 158 3-6 Reactions of Alkanes 161 3-7 Structure and Conformations of Alkanes 162 3-8 Conformations of Butane 166 3-9 Conformations of Higher Alkanes 169 3-10 Cycloalkanes 170 3-11 Cis-trans Isomerism in Cycloalkanes 172 3-12 Stabilities of Cycloalkanes; Ring Strain 173 3-13 Cyclohexane Conformations 177 PROBLEM-SOLVING STRATEGY: Drawing Chair Conformations 179 3-14 Conformations of Monosubstituted Cyclohexanes 181 3-15 Conformations of Disubstituted Cyclohexanes 184 PROBLEM-SOLVING STRATEGY: Recognizing Cis and Trans Isomers 184 3-16 Bicyclic Molecules 188 Essential Terms 190 Study Problems 194 4 THE STUDY OF CHEMICAL REACTIONS 197 4-1 Introduction 197 4-2 Chlorination of Methane 198 4-3 The Free-Radical Chain Reaction 199 4-4 Equilibrium Constants and Free Energy 203 4-5 Enthalpy and Entropy 205 4-6 Bond-Dissociation Enthalpies 207 4-7 Enthalpy Changes in Chlorination 208 4-8 Kinetics and the Rate Equation 211 A01_WADE4255_10_GE_FM.indd 6 18/07/22 4:07 PM Contents 7 4-9 Activation Energy and the Temperature Dependence of Rates 213 4-10 Transition States 214 4-11 Rates of Multistep Reactions 216 4-12 Temperature Dependence of Halogenation 217 4-13 Selectivity in Halogenation 218 4-14 Hammond’s Postulate 225 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 226 4-15 Radical Inhibitors 229 4-16 Reactive Intermediates 230 Summary: Reactive Intermediates 237 Essential Terms 237 Study Problems 240 5 STEREOCHEMISTRY 244 5-1 Introduction 244 5-2 Chirality 245 5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms 251 5-4 Optical Activity 256 5-5 Biological Discrimination of Enantiomers 261 5-6 Racemic Mixtures 262 5-7 Enantiomeric Excess and Optical Purity 263 5-8 Chirality of Conformationally Mobile Systems 265 5-9 Chiral Compounds Without Asymmetric Atoms 267 5-10 Fischer Projections 269 Summary: Fischer Projections and Their Use 274 5-11 Diastereomers 274 Summary: Types of Isomers 276 5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons 277 5-13 Meso Compounds 277 5-14 Absolute and Relative Configuration 280 5-15 Physical Properties of Diastereomers 282 5-16 Resolution of Enantiomers 283 Essential Terms 286 Study Problems 289 6 ALKYL HALIDES; NUCLEOPHILIC SUBSTITUTION 292 6-1 Introduction 292 6-2 Nomenclature of Alkyl Halides 293 6-3 Common Uses of Alkyl Halides 295 6-4 Structure of Alkyl Halides 297 6-5 Physical Properties of Alkyl Halides 298 6-6 Preparation of Alkyl Halides 300 Summary: Methods for Preparing Alkyl Halides 304 6-7 Reactions of Alkyl Halides: Substitution and Elimination 305 A01_WADE4255_10_GE_FM.indd 7 18/07/22 4:07 PM 8 Contents 6-8 Bimolecular Nucleophilic Substitution: The S 2 Reaction 306 N 6-9 Generality of the S 2 Reaction 308 N Summary: S 2 Reactions of Alkyl Halides 309 N 6-10 Factors Affecting S 2 Reactions: Strength of the Nucleophile 310 N Summary: Trends in Nucleophilicity 311 6-11 Reactivity of the Substrate in S 2 Reactions 315 N 6-12 Stereochemistry of the S 2 Reaction 318 N 6-13 Unimolecular Nucleophilic Substitution: The S 1 Reaction 320 N 6-14 Stereochemistry of the S 1 Reaction 326 N 6-15 Rearrangements in S 1 Reactions 328 N 6-16 Comparison of S 1 and S 2 Reactions 331 N N Summary: Nucleophilic Substitutions 332 Summary: Reactions of Alkyl Halides 333 Essential Terms 335 Study Problems 337 7 STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION 342 7-1 Introduction 342 7-2 The Orbital Description of the Alkene Double Bond 343 7-3 Elements of Unsaturation 345 7-4 Nomenclature of Alkenes 347 7-5 Nomenclature of Cis-Trans Isomers 349 Summary: Rules for Naming Alkenes 351 7-6 Commercial Importance of Alkenes 352 7-7 Physical Properties of Alkenes 354 7-8 Stability of Alkenes 356 squalene 7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl Halides 365 7-10 Unimolecular Elimination: The E1 Reaction 366 Summary: Carbocation Reactions 370 7-11 Positional Orientation of Elimination: Zaitsev’s Rule 371 7-12 Bimolecular Elimination: The E2 Reaction 373 7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation 375 7-14 Stereochemistry of the E2 Reaction 376 7-15 E2 Reactions in Cyclohexane Systems 379 7-16 Comparison of E1 and E2 Elimination Mechanisms 381 Summary: Elimination Reactions 382 7-17 Competition Between Substitutions and Eliminations 383 Summary: Substitution and Elimination Reactions of Alkyl Halides 385 PROBLEM-SOLVING STRATEGY: Predicting Substitutions and Eliminations 387 7-18 Alkene Synthesis by Dehydration of Alcohols 388 7-19 Alkene Synthesis by High-Temperature Industrial Methods 391 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 393 Summary: Methods for Synthesis of Alkenes 396 Essential Terms 397 Study Problems 400 A01_WADE4255_10_GE_FM.indd 8 18/07/22 4:07 PM Contents 9 8 REACTIONS OF ALKENES 406 8-1 Reactivity of the Carbon–Carbon Double Bond 406 8-2 Electrophilic Addition to Alkenes 407 8-3 Addition of Hydrogen Halides to Alkenes 409 8-4 Addition of Water: Hydration of Alkenes 417 8-5 Hydration by Oxymercuration–Demercuration 419 8-6 Alkoxymercuration–Demercuration 422 8-7 Hydroboration of Alkenes 423 8-8 Addition of Halogens to Alkenes 430 8-9 Formation of Halohydrins 433 8-10 Catalytic Hydrogenation of Alkenes 436 8-11 Addition of Carbenes to Alkenes 439 8-12 Epoxidation of Alkenes 441 8-13 Acid-Catalyzed Opening of Epoxides 443 8-14 Syn Dihydroxylation of Alkenes 446 8-15 Oxidative Cleavage of Alkenes 448 8-16 Polymerization of Alkenes 451 8-17 Olefin Metathesis 455 PROBLEM-SOLVING STRATEGY: Organic Synthesis 458 Summary: Reactions of Alkenes 460 Summary: Electrophilic Additions to Alkenes 463 Summary: Oxidation and Cyclopropanation Reactions of Alkenes 464 Essential Terms 465 Study Problems 469 9 ALKYNES 476 9-1 Introduction 476 9-2 Nomenclature of Alkynes 477 9-3 Physical Properties of Alkynes 479 9-4 Commercial Importance of Alkynes 479 9-5 Electronic Structure of Alkynes 481 9-6 Acidity of Alkynes; Formation of Acetylide Ions 482 9-7 Synthesis of Alkynes from Acetylides 484 9-8 Synthesis of Alkynes by Elimination Reactions 488 Summary: Syntheses of Alkynes 489 9-9 Addition Reactions of Alkynes 490 9-10 Oxidation of Alkynes 499 PROBLEM-SOLVING STRATEGY: Multistep Synthesis 501 Summary: Reactions of Alkynes 503 Summary: Reactions of Terminal Alkynes 505 Essential Terms 506 Study Problems 507 A01_WADE4255_10_GE_FM.indd 9 18/07/22 4:07 PM