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ORGANIC CHEMISTRY (hóa học hữu cơ _FOURTH EDITION_Maitland Jones, Jr. Steven A. Fleming
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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. 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.
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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
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
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
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
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
4 Stereochemistry 147
4.1 Preview 148
4.2 Chirality 149
4.3 The (R/S) Convention 152
4.4 Properties of Enantiomers: Physical Differences 155
4.5 The Physical Basis of Optical Activity 157
4.6 Properties of Enantiomers: Chemical Differences 159
4.7 Interconversion of Enantiomers by Rotation about a Single Bond:
gauche-Butane 163
4.8 Diastereomers and Molecules Containing More than One Stereogenic
Atom 164
4.9 Physical Properties of Diastereomers: Resolution, a Method of Separating
Enantiomers from Each Other 169
4.10 Determination of Absolute Configuration (R or S) 172
4.11 Stereochemical Analysis of Ring Compounds (a Beginning) 173
4.12 Summary of Isomerism 176
4.13 Special Topic: Chirality without “Four Different Groups Attached to One
Carbon” 177
4.14 Special Topic: Stereochemistry in the Real World: Thalidomide, the
Consequences of Being Wrong-Handed 180
4.15 Summary 181
4.16 Additional Problems 182
5 Rings 185
5.1 Preview 186
5.2 Rings and Strain 187
5.3 Quantitative Evaluation of Strain Energy 193
5.4 Stereochemistry of Cyclohexane: Conformational Analysis 197
5.5 Monosubstituted Cyclohexanes 199
5.6 Disubstituted Ring Compounds 204
5.7 Bicyclic Compounds 211
5.8 Special Topic: Polycyclic Systems 216
5.9 Special Topic: Adamantanes in Materials and Biology 217
5.10 Summary 219
5.11 Additional Problems 220
CONTENTS ix
6 Alkyl Halides, Alcohols, Amines, Ethers,
and Their Sulfur-Containing Relatives 223
6.1 Preview 224
6.2 Alkyl Halides: Nomenclature and Structure 225
6.3 Alkyl Halides as Sources of Organometallic Reagents:
A Synthesis of Hydrocarbons 227
6.4 Alcohols 230
6.5 Solvents in Organic Chemistry 238
6.6 Diols (Glycols) 240
6.7 Amines 240
6.8 Ethers 249
6.9 Special Topic: Thiols (Mercaptans) and Thioethers (Sulfides) 251
6.10 Special Topic: Crown Ethers 254
6.11 Special Topic: Complex Nitrogen-Containing
Biomolecules—Alkaloids 255
6.12 Summary 256
6.13 Additional Problems 258
7 Substitution and Elimination Reactions:
The SN2, SN1, E1, and E2 Reactions 261
7.1 Preview 262
7.2 Review of Lewis Acids and Bases 263
7.3 Reactions of Alkyl Halides: The Substitution Reaction 267
7.4 Substitution, Nucleophilic, Bimolecular: The SN2 Reaction 268
7.5 The SN2 Reaction in Biochemistry 288
7.6 Substitution, Nucleophilic, Unimolecular: The SN1 Reaction 289
7.7 Summary and Overview of the SN2 and SN1 Reactions 296
7.8 The Unimolecular Elimination Reaction: E1 298
7.9 The Bimolecular Elimination Reaction: E2 301
7.10 What Can We Do with These Reactions?
How to Do Organic Synthesis 312
7.11 Summary 320
7.12 Additional Problems 323
8 Equilibria 331
8.1 Preview 332
8.2 Equilibrium 334
x CONTENTS
8.3 Entropy in Organic Reactions 337
8.4 Rates of Chemical Reactions 339
8.5 Rate Constant 341
8.6 Energy Barriers in Chemical Reactions:
The Transition State and Activation Energy 342
8.7 Reaction Mechanism 349
8.8 The Hammond Postulate: Thermodynamics versus Kinetics 351
8.9 Special Topic: Enzymes and Reaction Rates 357
8.10 Summary 358
8.11 Additional Problems 360
9 Additions to Alkenes 1 363
9.1 Preview 364
9.2 Mechanism of the Addition of Hydrogen Halides to Alkenes 365
9.3 Effects of Resonance on Regiochemistry 366
9.4 Brief Review of Resonance 372
9.5 Resonance and the Stability of Carbocations 374
9.6 Inductive Effects on Addition Reactions 378
9.7 HX Addition Reactions: Hydration 380
9.8 Dimerization and Polymerization of Alkenes 384
9.9 Rearrangements during HX Addition to Alkenes 386
9.10 Hydroboration 390
9.11 Hydroboration in Synthesis: Alcohol Formation 398
9.12 Special Topic: Rearrangements in Biological Processes 401
9.13 Summary 402
9.14 Additional Problems 404
10 Additions to Alkenes 2 and Additions to Alkynes 409
10.1 Preview 410
10.2 Addition of H2 and X2 Reagents 410
10.3 Hydration through Mercury Compounds: Oxymercuration 421
10.4 Other Addition Reactions Involving Three-Membered Rings: Oxiranes
and Cyclopropanes 423
10.5 Dipolar Addition Reactions: Ozonolysis and the Synthesis
of Carbonyl (R2C O) Compounds 436
10.6 Addition Reactions of Alkynes: HX Addition 444
10.7 Addition of X2 Reagents to Alkynes 447
P
CONTENTS xi
10.8 Hydration of Alkynes 448
10.9 Hydroboration of Alkynes 450
10.10 Hydrogenation of Alkynes: Alkene Synthesis
through syn Hydrogenation 452
10.11 Reduction by Sodium in Ammonia: Alkene Synthesis
through anti Hydrogenation 452
10.12 Special Topic: Three-Membered Rings in Biochemistry 455
10.13 Summary 456
10.14 Additional Problems 460
11 Radical Reactions 467
11.1 Preview 468
11.2 Formation and Simple Reactions of Radicals 469
11.3 Structure and Stability of Radicals 477
11.4 Radical Addition to Alkenes 481
11.5 Other Radical Addition Reactions 487
11.6 Radical-Initiated Addition of HBr to Alkynes 489
11.7 Photohalogenation 490
11.8 Allylic Halogenation: Synthetically Useful Reactions 497
11.9 Special Topic: Rearrangements (and Nonrearrangements)
of Radicals 501
11.10 Special Topic: Radicals in Our Bodies; Do Free Radicals Age Us? 504
11.11 Summary 505
11.12 Additional Problems 507
12 Dienes and the Allyl System: 2pOrbitals in Conjugation 511
12.1 Preview 512
12.2 Allenes 513
12.3 Related Systems: Ketenes and Cumulenes 515
12.4 Allenes as Intermediates in the Isomerization of Alkynes 516
12.5 Conjugated Dienes 519
12.6 The Physical Consequences of Conjugation 521
12.7 Molecular Orbitals and Ultraviolet Spectroscopy 525
12.8 Polyenes and Vision 533
12.9 The Chemical Consequences of Conjugation:
Addition Reactions of Conjugated Dienes 534
12.10 Thermodynamic and Kinetic Control of Addition Reactions 537
xii CONTENTS
12.11 The Allyl System: Three Overlapping 2p Orbitals 541
12.12 The Diels–Alder Reaction of Conjugated Dienes 544
12.13 Special Topic: Biosynthesis of Terpenes 554
12.14 Special Topic: Steroid Biosynthesis 559
12.15 Summary 563
12.16 Additional Problems 564
13 Conjugation and Aromaticity 571
13.1 Preview 572
13.2 The Structure of Benzene 573
13.3 A Resonance Picture of Benzene 575
13.4 The Molecular Orbital Picture of Benzene 578
13.5 Quantitative Evaluations of Resonance Stabilization in Benzene 580
13.6 A Generalization of Aromaticity: Hückel’s 4n + 2 Rule 582
13.7 Substituted Benzenes 595
13.8 Physical Properties of Substituted Benzenes 598
13.9 Heterobenzenes and Other Heterocyclic Aromatic Compounds 598
13.10 Polynuclear Aromatic Compounds 602
13.11 Introduction to the Chemistry of Benzene 606
13.12 The Benzyl Group and Its Reactivity 610
13.13 Special Topic: The Bio-Downside, the Mechanism of Carcinogenesis
by Polycyclic Aromatic Compounds 614
13.14 Summary 617
13.15 Additional Problems 619
14 Substitution Reactions of Aromatic Compounds 623
14.1 Preview 624
14.2 Hydrogenation of Aromatic Compounds 626
14.3 Diels–Alder Reactions 628
14.4 Substitution Reactions of Aromatic Compounds 631
14.5 Carbon–Carbon Bond Formation: Friedel–Crafts Alkylation 639
14.6 Friedel–Crafts Acylation 643
14.7 Synthetic Reactions We Can Do So Far 646
14.8 Electrophilic Aromatic Substitution of Heteroaromatic Compounds 652
14.9 Disubstituted Benzenes: Ortho, Meta, and Para Substitution 655
14.10 Inductive Effects in Aromatic Substitution 666
CONTENTS xiii