Jones M., Fleming S.A. Organic Chemistry
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FOURTH EDITION
ORGANIC CHEMISTRY
Maitland Jones, Jr.
Steven A. Fleming
Organic Chemistry
Organic Chemistry
FOURTH EDITION
Maitland Jones, Jr.
NEW YORK UNIVERSITY
Steven A. Fleming
TEMPLE UNIVERSITY
W. W. Norton & Company
New York • London
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.
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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
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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 S
N
2, S
N
1, 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
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 (H
2
): 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 (CH
3
) and Methyl Compounds (CH
3
X) 60
2.4 The Methyl Cation (
+
CH
3
), Anion (
−
:
CH
3
), and Radical (·CH
3
)62
2.5 Ethane (C
2
H
6
), Ethyl Compounds (C
2
H
5
X),
and Newman Projections 64
2.6 Structure Drawings 70
2.7 Propane (C
3
H
8
) and Propyl Compounds (C
3
H
7
X) 71
2.8 Butanes (C
4
H
10
), Butyl Compounds (C
4
H
9
X),
and Conformational Analysis 73
2.9 Pentanes (C
5
H
12
) and Pentyl Compounds (C
5
H
11
X) 76
2.10 The Naming Conventions for Alkanes 78
vii
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
viii CONTENTS