Organic Chemistry FOURTH EDITION Maitland Jones,Jr. NEW YORK UNIVERSITY Steven A.Fleming TEMPLE UNIVERSITY G W.W.Norton Company New York London
Organic Chemistry FOURTH EDITION Maitland Jones, Jr. NEW YORK UNIVERSITY Steven A. Fleming TEMPLE UNIVERSITY W. W. N o r t o n & C o m p a n y N e w Yo r k • L o n d o n
Drawing structures and reactions is critical to understanding them.The front and back covers show chair cyclohexanes,which are introduced in Chapter 5 and appear over and over again in the natural world. These structures were hand-drawn and have ever-so-small imperfections.Evaluate these chairs,and after you finish Chapter 5,we suggest you take a very close look to see how you might improve them. W.W.Norton&Company has been independent since its founding in 1923,when William Warder Norton and Mary D.Herter Norton first published lectures delivered at the People's Institute,the adult education division of New York City's Cooper Union.The Nortons soon expanded their program beyond the Institute, publishing books by celebrated academics from America and abroad.By mid-century,the two major pillars of Norton's publishing program-trade books and college texts-were firmly established.In the 1950s,the Norton family transferred control of the company to its employees,and today-with a staff of four hundred and a comparable number of trade,college,and professional titles published each year-W.W.Norton Company stands as the largest and oldest publishing house owned wholly by its employees. Copyright 2010,2005,2000,1997 by W.W.Norton Company,Inc. All rights reserved Printed in the United States of America Editor:Erik Fahlgren Project editor:Carla L Talmadge Marketing manager:Kelsey Volker Editorial assistant:Mary Lynch Production manager:Chris Granville Managing editor,College:Marian Johnson Ancillaries editor:Matthew A.Freeman Media editor:Rob Bellinger Developmental editor:Irene Nunes Design director:Rubina Yeh Photo editor:Junenoire Mitchell Cover design:John Hamilton Composition:Prepare,Inc. Illustration studio:Penumbra Design,Inc. Manufacturing:Transcontinental Interglobe Library of Congress Cataloging-in-Publication Data Jones,Maitland,1937- Organic chemistry/Maitland Jones,J-4th ed./Steven A.Fleming. p.cm. Includes bibliographical references and index. ISBN978-0-393-93149-5(hardcover) 1.Chemistry,Organic-Textbooks.I.Fleming.Steven A.II.Title. QD253.2.J662010 547-dc22 2009033807 W.W.Norton Company,Inc.,500 Fifth Avenue,New York,N.Y.10110 www.wwnorton.com W.W.Norton Company Ltd.,Castle House,75/76 Wells Street,London W1T 3QT 1234567890
Drawing structures and reactions is critical to understanding them. The front and back covers show chair cyclohexanes, which are introduced in Chapter 5 and appear over and over again in the natural world. These structures were hand-drawn and have ever-so-small imperfections. Evaluate these chairs, and after you finish Chapter 5, we suggest you take a very close look to see how you might improve them. W.W. Norton & Company has been independent since its founding in 1923, when William Warder Norton and Mary D. Herter Norton first published lectures delivered at the People’s Institute, the adult education division of New York City’s Cooper Union. The Nortons soon expanded their program beyond the Institute, publishing books by celebrated academics from America and abroad. By mid-century, the two major pillars of Norton’s publishing program—trade books and college texts—were firmly established. In the 1950s, the Norton family transferred control of the company to its employees, and today—with a staff of four hundred and a comparable number of trade, college, and professional titles published each year—W.W. Norton & Company stands as the largest and oldest publishing house owned wholly by its employees. Copyright © 2010, 2005, 2000, 1997 by W. W. Norton & Company, Inc. All rights reserved Printed in the United States of America Editor: Erik Fahlgren Project editor: Carla L. Talmadge Marketing manager: Kelsey Volker Editorial assistant: Mary Lynch Production manager: Chris Granville Managing editor, College: Marian Johnson Ancillaries editor: Matthew A. Freeman Media editor: Rob Bellinger Developmental editor: Irene Nunes Design director: Rubina Yeh Photo editor: Junenoire Mitchell Cover design: John Hamilton Composition: Prepare, Inc. Illustration studio: Penumbra Design, Inc. Manufacturing: Transcontinental Interglobe Library of Congress Cataloging-in-Publication Data Jones, Maitland, 1937– Organic chemistry / Maitland Jones, Jr.—4th ed. / Steven A. Fleming. p. cm. Includes bibliographical references and index. ISBN 978-0-393-93149-5 (hardcover) 1. Chemistry, Organic—Textbooks. I. Fleming, Steven A. II. Title. QD253.2.J66 2010 547—dc22 2009033807 W. W. Norton & Company, Inc., 500 Fifth Avenue, New York, N.Y. 10110 www.wwnorton.com W. W. Norton & Company Ltd., Castle House, 75/76 Wells Street, London W1T 3QT 1234567890
Brief Contents 1 Atoms and Molecules;Orbitals and Bonding 1 2 Alkanes 50 3 Alkenes and Alkynes 97 4 Stereochemistry 147 5 Rings 185 6 Alkyl Halides,Alcohols,Amines,Ethers, and Their Sulfur-Containing Relatives 223 7 Substitution and Elimination Reactions: The SN2,SN1,E1,and E2 Reactions 261 8 Equilibria 331 9 Additions to Alkenes 1 363 10 Additions to Alkenes 2 and Additions to Alkynes 409 11 Radical Reactions 467 12 Dienes and the Allyl System:2 Orbitals in Conjugation 511 13 Conjugation and Aromaticity 571 14 Substitution Reactions of Aromatic Compounds 623 15 Analytical Chemistry:Spectroscopy 694 16 Carbonyl Chemistry 1:Addition Reactions 762 17 Carboxylic Acids 828 18 Derivatives of Carboxylic Acids:Acyl Compounds 876 19 Carbonyl Chemistry 2:Reactions at the a.Position 931 20 Special Topic:Reactions Controlled by Orbital Symmetry 1030 21 Special Topic:Intramolecular Reactions and Neighboring Group Participation 1080 22 Special Topic:Carbohydrates 1124 23 Special Topic:Amino Acids and Polyamino Acids (Peptides and Proteins)1173
1 Atoms and Molecules; Orbitals and Bonding 1 2 Alkanes 50 3 Alkenes and Alkynes 97 4 Stereochemistry 147 5 Rings 185 6 Alkyl Halides, Alcohols, Amines, Ethers, and Their Sulfur-Containing Relatives 223 7 Substitution and Elimination Reactions: The SN2, SN1, E1, and E2 Reactions 261 8 Equilibria 331 9 Additions to Alkenes 1 363 10 Additions to Alkenes 2 and Additions to Alkynes 409 11 Radical Reactions 467 12 Dienes and the Allyl System: 2p Orbitals in Conjugation 511 13 Conjugation and Aromaticity 571 14 Substitution Reactions of Aromatic Compounds 623 15 Analytical Chemistry: Spectroscopy 694 16 Carbonyl Chemistry 1: Addition Reactions 762 17 Carboxylic Acids 828 18 Derivatives of Carboxylic Acids: Acyl Compounds 876 19 Carbonyl Chemistry 2: Reactions at the α Position 931 20 Special Topic: Reactions Controlled by Orbital Symmetry 1030 21 Special Topic: Intramolecular Reactions and Neighboring Group Participation 1080 22 Special Topic: Carbohydrates 1124 23 Special Topic: Amino Acids and Polyamino Acids (Peptides and Proteins) 1173 Brief Contents v
Contents Selected Applications xix Organic Reaction Animations xxi Preface to the Fourth Edition xxiii Introduction xxxiii 1 Atoms and Molecules;Orbitals and Bonding 1 1.1 Preview 2 1.2 Atoms and Atomic Orbitals 4 1.3 Covalent Bonds and Lewis Structures 13 1.4 Resonance Forms 22 1.5 Hydrogen(H2):Molecular Orbitals 30 1.6 Bond Strength 36 1.7 An Introduction to Reactivity:Acids and Bases 41 1.8 Special Topic:Quantum Mechanics and Babies 42 1.9 Summary 43 1.10 Additional Problems 45 2 Alkanes 50 2.1 Preview 51 2.2 Hybrid Orbitals:Making a Model for Methane 52 2.3 The Methyl Group(CH3)and Methyl Compounds(CH3X)60 2.4 The Methyl Cation(CH3),Anion(-:CH3),and Radical(CH3)62 2.5 Ethane(C2H),Ethyl Compounds(C2HsX), and Newman Projections 64 2.6 Structure Drawings 70 2.7 Propane(C3Hs)and Propyl Compounds(C3H-X)71 2.8 Butanes(C H10),Butyl Compounds(CaHoX), and Conformational Analysis 73 2.9 Pentanes(CsH12)and Pentyl Compounds(CsHiX)76 2.10 The Naming Conventions for Alkanes 78 vii
Selected Applications xix Organic Reaction Animations xxi Preface to the Fourth Edition xxiii Introduction xxxiii 1 Atoms and Molecules; Orbitals and Bonding 1 1.1 Preview 2 1.2 Atoms and Atomic Orbitals 4 1.3 Covalent Bonds and Lewis Structures 13 1.4 Resonance Forms 22 1.5 Hydrogen (H2): Molecular Orbitals 30 1.6 Bond Strength 36 1.7 An Introduction to Reactivity: Acids and Bases 41 1.8 Special Topic: Quantum Mechanics and Babies 42 1.9 Summary 43 1.10 Additional Problems 45 2 Alkanes 50 2.1 Preview 51 2.2 Hybrid Orbitals: Making a Model for Methane 52 2.3 The Methyl Group (CH3) and Methyl Compounds (CH3X) 60 2.4 The Methyl Cation (+ CH3), Anion (−:CH3), and Radical (·CH3) 62 2.5 Ethane (C2H6), Ethyl Compounds (C2H5X), and Newman Projections 64 2.6 Structure Drawings 70 2.7 Propane (C3H8) and Propyl Compounds (C3H7X) 71 2.8 Butanes (C4H10), Butyl Compounds (C4H9X), and Conformational Analysis 73 2.9 Pentanes (C5H12) and Pentyl Compounds (C5H11X) 76 2.10 The Naming Conventions for Alkanes 78 vii Contents
vili CONTENTS 2.11 Drawing Isomers 82 2.12 Rings 83 2.13 Physical Properties of Alkanes and Cycloalkanes 86 2.14 Nuclear Magnetic Resonance Spectroscopy 88 2.15 Acids and Bases Revisited:More Chemical Reactions 90 2.16 Special Topic:Alkanes as Biomolecules 92 2.17 Summary 93 2.18 Additional Problems 94 3 Alkenes and Alkynes 97 3.1 Preview 98 3.2 Alkenes:Structure and Bonding 99 3.3 Derivatives and Isomers of Alkenes 107 3.4 Nomenclature 110 3.5 The Cahn-Ingold-Prelog Priority System 112 3.6 Relative Stability of Alkenes:Heats of Formation 115 3.7 Double Bonds in Rings 118 3.8 Physical Properties of Alkenes 123 3.9 Alkynes:Structure and Bonding 123 3.10 Relative Stability of Alkynes:Heats of Formation 126 3.11 Derivatives and Isomers of Alkynes 126 3.12 Triple Bonds in Rings 128 3.13 Physical Properties of Alkynes 129 3.14 Acidity of Alkynes 129 3.15 Molecular Formulas and Degrees of Unsaturation 130 3.16 An Introduction to Addition Reactions of Alkenes and Alkynes 131 3.17 Mechanism of the Addition of Hydrogen Halides to Alkenes 132 3.18 The Regiochemistry of the Addition Reaction 137 3.19 A Catalyzed Addition to Alkenes:Hydration 139 3.20 Synthesis:A Beginning 141 3.21 Special Topic:Alkenes and Biology 142 3.22 Summary 143 3.23 Additional Problems 144
2.11 Drawing Isomers 82 2.12 Rings 83 2.13 Physical Properties of Alkanes and Cycloalkanes 86 2.14 Nuclear Magnetic Resonance Spectroscopy 88 2.15 Acids and Bases Revisited: More Chemical Reactions 90 2.16 Special Topic: Alkanes as Biomolecules 92 2.17 Summary 93 2.18 Additional Problems 94 3 Alkenes and Alkynes 97 3.1 Preview 98 3.2 Alkenes: Structure and Bonding 99 3.3 Derivatives and Isomers of Alkenes 107 3.4 Nomenclature 110 3.5 The Cahn–Ingold–Prelog Priority System 112 3.6 Relative Stability of Alkenes: Heats of Formation 115 3.7 Double Bonds in Rings 118 3.8 Physical Properties of Alkenes 123 3.9 Alkynes: Structure and Bonding 123 3.10 Relative Stability of Alkynes: Heats of Formation 126 3.11 Derivatives and Isomers of Alkynes 126 3.12 Triple Bonds in Rings 128 3.13 Physical Properties of Alkynes 129 3.14 Acidity of Alkynes 129 3.15 Molecular Formulas and Degrees of Unsaturation 130 3.16 An Introduction to Addition Reactions of Alkenes and Alkynes 131 3.17 Mechanism of the Addition of Hydrogen Halides to Alkenes 132 3.18 The Regiochemistry of the Addition Reaction 137 3.19 A Catalyzed Addition to Alkenes: Hydration 139 3.20 Synthesis: A Beginning 141 3.21 Special Topic: Alkenes and Biology 142 3.22 Summary 143 3.23 Additional Problems 144 viii CONTENTS