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Organic Chemistry 8th Edition Robert M. Giuliano
Francis A. Carey Digital Instant Download
Author(s): Robert M. Giuliano Francis A. Carey
ISBN(s): 9780077401764, 0073402613
Edition: 8th
File Details: PDF, 151.95 MB
Year: 2011
Language: english
 Chemistry creates its own object. This creative ability, similar to eighth edition
an art, is the main feature that distinguishes chemistry from the
natural and humanitarian sciences.

Organic Chemistry
Marcellin Berthelot (1827–1907)
eighth edition
hT
This
h quote from the French chemist Berthelot is illustrated by our cover, which

Organic Chemistry
eddepicts
e a single-stranded DNA-carbon nanotube hybrid. This material was
yssynthesized
y by Robert R. Johnson, A. T. Charlie Johnson, and Michael L. Klein at
htthe
h University of Pennsylvania. The combination of an inorganic nanomaterial
ussuch
u as a carbon nanotube with a biomolecule, while unheard of in nature,
poopens
p the possibility of creating new materials with novel properties for
paapplications
p in biology and chemistry.

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car02613_fm_i-xxxi.indd Page i 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Eighth Edition

Organic Chemistry
Francis A. Carey
University of Virginia

Robert M. Giuliano
Villanova University
car02613_fm_i-xxxi.indd Page ii 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

ORGANIC CHEMISTRY, EIGHTH EDITION

Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
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Carey, Francis A., 1937-

Organic chemistry / Francis A. Carey.—8th ed. / Robert M. Giuliano.
p. cm.
Includes index.
ISBN 978-0-07-340261-1—ISBN 0-07-340261-3 (hard copy : alk. paper)
1. Chemistry, Organic—Textbooks. I. Giuliano, Robert M., 1954- II. Title.
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car02613_fm_i-xxxi.indd Page iii 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

To our wives, Margot

Giuliano and Jill Carey,

and our children

Michael, Ellen, and

Christopher Giuliano

and Andrew, Robert,

and William Carey.

Frank Carey

Bob Giuliano
car02613_fm_i-xxxi.indd Page iv 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Welcome

It is a pleasure for me to welcome Robert Giuliano as coauthor of Organic Chemistry. Bob

is Professor of Chemistry at Villanova University where he has served as departmental
chair and regularly teaches introductory and graduate-level courses in organic chemistry.
Professor Giuliano’s research in carbohydrate synthesis has been recognized with his cur-
rent appointments as a Regional Editor of the Journal of Carbohydrate Chemistry and as a
member of the Editorial Board for Current Topics in Medicinal Chemistry.
I first met Bob shortly before he began graduate work in our department at the
University of Virginia in the 1970s and was immediately impressed with his intelligence
and sense of purpose. These same personal qualities characterized his efforts in shaping
the present edition. More than that, his background in bioorganic topics provided a fresh
and informed perspective on some of the most active areas of modern organic chemistry.
Although no later edition can be as satisfying to an author as the first, this eighth
edition of Organic Chemistry is special because it signals the resumption of a professional
collaboration begun decades ago.

Francis A. Carey

iv
car02613_fm_i-xxxi.indd Page v 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

About the Authors

Francis A. Carey is a native of Philadelphia, educated at Drexel University (B.S. in chem-

istry), and at Penn State (Ph.D.). 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.

Robert M. Giuliano was born in Altoona, Pennsylvania and attended Penn State (B.S. in
chemistry) and the University of Virginia (Ph.D., under the direction of Francis Carey). Fol-
lowing postdoctoral studies with Bert Fraser-Reid at the University of Maryland, he joined
the chemistry department faculty of Villanova University in 1982, where he is currently
Professor. His research interests are in synthetic organic and carbohydrate chemistry, and
in functionalized carbon nanomaterials.
Bob and his wife Margot, an elementary and preschool teacher he met while attending
UVa, are the parents of Michael, Ellen, and Christopher.

v
car02613_fm_i-xxxi.indd Page vi 11/23/09 11:47:52 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Brief Contents

List of Important Features xvii

Preface xxii
Acknowledgments xxx

1 Structure Determines Properties 2

2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons 56
3 Alkanes and Cycloalkanes: Conformations and cis-trans Stereoisomers 100
4 Alcohols and Alkyl Halides 137
5 Structure and Preparation of Alkenes: Elimination Reactions 184
6 Addition Reactions of Alkenes 226
7 Stereochemistry 278
8 Nucleophilic Substitution 322
9 Alkynes 359
10 Conjugation in Alkadienes and Allylic Systems 388
11 Arenes and Aromaticity 428
12 Reactions of Arenes: Electrophilic and Nucleophilic Aromatic
Substitution 478
13 Spectroscopy 538
14 Organometallic Compounds 606
15 Alcohols, Diols, and Thiols 646
16 Ethers, Epoxides, and Sulfides 686
17 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 724
18 Carboxylic Acids 776
19 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 812
20 Enols and Enolates 866
21 Amines 930
22 Phenols 988
23 Carbohydrates 1022
24 Lipids 1074
25 Amino Acids, Peptides, and Proteins 1116
26 Nucleosides, Nucleotides, and Nucleic Acids 1174
27 Synthetic Polymers 1216

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

vi
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Contents

List of Important Features xvii 2.5 Introduction to Alkanes: Methane, Ethane,

Preface xxii and Propane 62
Acknowledgments xxx Methane and the Biosphere 63
2.6 sp3 Hybridization and Bonding in Methane 63
2.7 Bonding in Ethane 65

C H A P T E R 1 2.8
2.9
2.10
2.11
Isomeric Alkanes: The Butanes 65
Higher n-Alkanes 66
The C5H12 Isomers 67
IUPAC Nomenclature of Unbranched Alkanes 69
Structure Determines Properties 2
What’s in a Name? Organic Nomenclature 70
1.1 Atoms, Electrons, and Orbitals 3 2.12 Applying the IUPAC Rules: The Names of the
1.2 Ionic Bonds 6 C6H14 Isomers 71
1.3 Covalent Bonds, Lewis Structures, and the Octet 2.13 Alkyl Groups 72
Rule 8 2.14 IUPAC Names of Highly Branched Alkanes 74
1.4 Double Bonds and Triple Bonds 10 2.15 Cycloalkane Nomenclature 75
1.5 Polar Covalent Bonds, Electronegativity, and Bond 2.16 Sources of Alkanes and Cycloalkanes 76
Dipoles 11
2.17 Physical Properties of Alkanes and Cycloalkanes 78
Electrostatic Potential Maps 13 2.18 Chemical Properties: Combustion of Alkanes 80
1.6 Formal Charge 13 Thermochemistry 82
1.7 Structural Formulas of Organic Molecules 16
2.19 Oxidation-Reduction in Organic Chemistry 83
1.8 Resonance 19
2.20 sp2 Hybridization and Bonding in Ethylene 85
1.9 Writing Organic Structures 23
2.21 sp Hybridization and Bonding in Acetylene 87
1.10 The Shapes of Some Simple Molecules 26
2.22 Bonding in Water and Ammonia: Hybridization
Molecular Modeling 26 of Oxygen and Nitrogen 89
1.11 Molecular Dipole Moments 28 2.23 Which Theory of Chemical Bonding Is Best? 90
1.12 Curved Arrows and Chemical Reactions 29 2.24 Summary 91
1.13 Acids and Bases: The Arrhenius View 32 Problems 95
1.14 Acids and Bases: The Brønsted-Lowry View 33 Descriptive Passage and Interpretive Problems 2:
1.15 What Happened to pKb? 37 Some Biochemical Reactions of Alkanes 99
1.16 How Structure Affects Acid Strength 38
1.17 Acid-Base Equilibria 42
1.18
1.19
Lewis Acids and Lewis Bases 45
Summary 46
Problems 49
Descriptive Passage and Interpretive Problems 1:
C H A P T E R 3
Amide Lewis Structures 55
Alkanes and Cycloalkanes: Conformations
and cis-trans Stereoisomers 100

2
3.1 Conformational Analysis of Ethane 102
3.2 Conformational Analysis of Butane 105
C H A P T E R Molecular Mechanics Applied to Alkanes
and Cycloalkanes 107
Alkanes and Cycloalkanes: Introduction 3.3 Conformations of Higher Alkanes 108
3.4 The Shapes of Cycloalkanes: Planar or Nonplanar? 108
to Hydrocarbons 56 3.5 Small Rings: Cyclopropane and Cyclobutane 109
2.1 Classes of Hydrocarbons 57 3.6 Cyclopentane 110
2.2 Electron Waves and Chemical Bonds 58 3.7 Conformations of Cyclohexane 111
2.3 Bonding in H2: The Valence Bond Model 59 3.8 Axial and Equatorial Bonds in Cyclohexane 112
2.4 Bonding in H2: The Molecular Orbital Model 60 3.9 Conformational Inversion in Cyclohexane 114

vii
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viii Contents

3.10 Conformational Analysis of Monosubstituted 4.20 Summary 174

Cyclohexanes 115 Problems 177
Enthalpy, Free Energy, and Equilibrium Descriptive Passage and Interpretive Problems 4:
Constant 118 More About Potential Energy Diagrams 182

5
3.11 Disubstituted Cyclohexanes: cis-trans
Stereoisomers 119
3.12 Conformational Analysis of Disubstituted C H A P T E R
Cyclohexanes 120
3.13 Medium and Large Rings 124
Structure and Preparation of Alkenes:
3.14 Polycyclic Ring Systems 124
3.15 Heterocyclic Compounds 127 Elimination Reactions 184
3.16 Summary 128 5.1 Alkene Nomenclature 185
Problems 131 5.2 Structure and Bonding in Alkenes 187
Descriptive Passage and Interpretive Problems 3: Ethylene 188
Cyclic Forms of Carbohydrates 136
5.3 Isomerism in Alkenes 189
5.4 Naming Stereoisomeric Alkenes by the E-Z Notational
System 190

4
5.5 Physical Properties of Alkenes 192
5.6 Relative Stabilities of Alkenes 194
C H A P T E R 5.7 Cycloalkenes 197
5.8 Preparation of Alkenes: Elimination Reactions 198
Alcohols and Alkyl Halides 137 5.9 Dehydration of Alcohols 199
5.10 Regioselectivity in Alcohol Dehydration: The Zaitsev
4.1 Functional Groups 138 Rule 200
4.2 IUPAC Nomenclature of Alkyl Halides 140 5.11 Stereoselectivity in Alcohol Dehydration 202
4.3 IUPAC Nomenclature of Alcohols 141 5.12 The E1 and E2 Mechanisms of Alcohol Dehydration 202
4.4 Classes of Alcohols and Alkyl Halides 141 Mechanism 5.1 The E1 Mechanism for Acid-Catalyzed
4.5 Bonding in Alcohols and Alkyl Halides 142 Dehydration of tert-Butyl Alcohol 203
4.6 Physical Properties of Alcohols and Alkyl Halides: 5.13 Rearrangements in Alcohol Dehydration 204
Intermolecular Forces 143 Mechanism 5.2 Carbocation Rearrangement in
4.7 Preparation of Alkyl Halides from Alcohols Dehydration of 3,3-Dimethyl-2-butanol 205
and Hydrogen Halides 147 Mechanism 5.3 Hydride Shift in Dehydration of
4.8 Mechanism of the Reaction of Alcohols with Hydrogen 1-Butanol 207
Halides: Hammond’s Postulate 148 5.14 Dehydrohalogenation of Alkyl Halides 208
Mechanism 4.1 Formation of tert-Butyl Chloride from 5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl
tert-Butyl Alcohol and Hydrogen Chloride 149 Halides 210
4.9 Potential Energy Diagrams for Multistep Reactions: The Mechanism 5.4 E2 Elimination of an Alkyl Halide 211
SN1 Mechanism 153
5.16 Anti Elimination in E2 Reactions: Stereoelectronic
4.10 Structure, Bonding, and Stability of Effects 212
Carbocations 154
5.17 Isotope Effects and the E2 Mechanism 213
4.11 Effect of Alcohol Structure on Reaction Rate 157
5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl
4.12 Reaction of Methyl Primary Alcohols with Hydrogen Halides 214
Halides: The SN2 Mechanism 158
Mechanism 5.5 The E1 Mechanism for
Mechanism 4.2 Formation of 1-Bromoheptane from Dehydrohalogenation of 2-Bromo-2-methylbutane in
1-Heptanol and Hydrogen Bromide 159 Ethanol 215
4.13 More on Activation Energy 160 5.19 Summary 216
4.14 Other Methods for Converting Alcohols to Alkyl Problems 220
Halides 160
Descriptive Passage and Interpretive Problems 5:
Mechanism 4.3 Conversion of an Alcohol to an Alkyl A Mechanistic Preview of Addition Reactions 224
Chloride with Thionyl Chloride 161
4.15
4.16
4.17
Halogenation of Alkanes 162
Chlorination of Methane 162
Structure and Stability of Free Radicals 163
From Bond Energies to Heats of Reaction 167
C H A P T E R 6
4.18 Mechanism of Methane Chlorination 168 Addition Reactions of Alkenes 226
Mechanism 4.4 Free-Radical Chlorination of 6.1 Hydrogenation of Alkenes 227
Methane 168 6.2 Heats of Hydrogenation 228
4.19 Halogenation of Higher Alkanes 170 Mechanism 6.1 Hydrogenation of Alkenes 229
car02613_fm_i-xxxi.indd Page ix 11/23/09 11:47:53 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Contents ix

6.3 Stereochemistry of Alkene Hydrogenation 230 7.3 Symmetry in Achiral Structures 283
6.4 Electrophilic Addition of Hydrogen Halides to 7.4 Optical Activity 284
Alkenes 232 7.5 Absolute and Relative Configuration 286
6.5 Regioselectivity of Hydrogen Halide Addition: 7.6 The Cahn-Ingold-Prelog R-S Notational
Markovnikov’s Rule 233 System 288
Mechanism 6.2 Electrophilic Addition of a Hydrogen 7.7 Fischer Projections 290
Halide to an Alkene 233 7.8 Properties of Enantiomers 292
6.6 Mechanistic Basis for Markovnikov’s Rule 235 7.9 Chirality Axis 293
Rules, Laws, Theories, and the Scientific Chiral Drugs 294
Method 237 7.10 Reactions That Create a Chirality Center 296
6.7 Carbocation Rearrangements in Hydrogen Halide 7.11 Chiral Molecules with Two Chirality
Addition to Alkenes 237 Centers 299
6.8 Addition of Sulfuric Acid to Alkenes 239 7.12 Achiral Molecules with Two Chirality Centers 301
6.9 Acid-Catalyzed Hydration of Alkenes 240 7.13 Molecules with Multiple Chirality Centers 303
Mechanism 6.3 Acid-Catalyzed Hydration of Chirality of Disubstituted Cyclohexanes 304
2-Methylpropene 241
7.14 Reactions That Produce Diastereomers 305
6.10 Thermodynamics of Addition-Elimination Equilibria 242
7.15 Resolution of Enantiomers 307
6.11 Hydroboration-Oxidation of Alkenes 245
7.16 Stereoregular Polymers 309
6.12 Stereochemistry of Hydroboration-Oxidation 247
7.17 Chirality Centers Other Than Carbon 310
6.13 Mechanism of Hydroboration-Oxidation 247
7.18 Summary 311
Mechanism 6.4 Hydroboration of
Problems 314
1-Methylcyclopentene 248
Descriptive Passage and Interpretive Problems 7:
Mechanism 6.5 Oxidation of an Organoborane 249
Prochirality 320
6.14 Addition of Halogens to Alkenes 250
6.15 Stereochemistry of Halogen Addition 250
6.16 Mechanism of Halogen Addition to Alkenes:
Halonium Ions 251

6.17
Mechanism 6.6 Electrophilic Addition of Bromine to
Ethylene 252
Mechanism 6.7 Formation of Bromohydrin 253
Conversion of Alkenes to Vicinal Halohydrins 253
C H A P T E R 8
6.18 Free-Radical Addition of Hydrogen Bromide to Nucleophilic Substitution 322
Alkenes 254 8.1 Functional Group Transformation by Nucleophilic
Mechanism 6.8 Free-Radical Addition of Hydrogen Substitution 323
Bromide to 1-Butene 256 8.2 Relative Reactivity of Halide Leaving Groups 326
6.19 Epoxidation of Alkenes 257 8.3 The SN2 Mechanism of Nucleophilic
Mechanism 6.9 Epoxidation of an Alkene 259 Substitution 327
6.20 Ozonolysis of Alkenes 259 Mechanism 8.1 The SN2 Mechanism of Nucleophilic
6.21 Reactions of Alkenes with Alkenes: Polymerization 261 Substitution 327
Mechanism 6.10 Acid-Catalyzed Dimerization of 8.4 Steric Effects in SN2 Reaction Rates 330
2-Methylpropene 262 8.5 Nucleophiles and Nucleophilicity 332
Ethylene and Propene: The Most Important 8.6 The SN1 Mechanism of Nucleophilic
Industrial Organic Chemicals 263 Substitution 334
Mechanism 6.11 Free-Radical Polymerization of Enzyme-Catalyzed Nucleophilic Substitutions of
Ethylene 264 Alkyl Halides 335
6.22 Summary 266 Mechanism 8.2 The SN1 Mechanism of Nucleophilic
Problems 269 Substitution 336
Descriptive Passage and Interpretive Problems 6: 8.7 Carbocation Stability and SN1 Reaction Rates 337
Oxymercuration 275 8.8 Stereochemistry of SN1 Reactions 338
8.9 Carbocation Rearrangements in SN1 Reactions 339
8.10 Effect of Solvent on the Rate of Nucleophilic

C H A P T E R 7 8.11
Substitution 340
Mechanism 8.3 Carbocation Rearrangement in the
SN1 Hydrolysis of 2-Bromo-3-methylbutane 340
Substitution and Elimination as Competing
Stereochemistry 278 Reactions 344
7.1 Molecular Chirality: Enantiomers 279 8.12 Nucleophilic Substitution and Elimination of Alkyl
7.2 The Chirality Center 281 Sulfonates 347
car02613_fm_i-xxxi.indd Page x 11/23/09 11:47:53 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

x Contents

8.13 Summary 350 10.10 Bonding in Conjugated Dienes 402

Problems 351 10.11 Bonding in Allenes 404
Descriptive Passage and Interpretive Problems 8: 10.12 Preparation of Dienes 405
Nucleophilic Substitution 356 Diene Polymers 406
10.13 Addition of Hydrogen Halides to Conjugated
Dienes 407

9
Mechanism 10.3 Addition of Hydrogen Chloride
to 1,3 Cyclopentadiene 408
C H A P T E R 10.14 Halogen Addition to Dienes 409
10.15 The Diels-Alder Reaction 410
Alkynes 359 10.16 The  Molecular Orbitals of Ethylene and
1,3-Butadiene 415
9.1 Sources of Alkynes 360
10.17 A  Molecular Orbital Analysis of the Diels-Alder
9.2 Nomenclature 362 Reaction 417
9.3 Physical Properties of Alkynes 362 Mechanism 10.4 Orbital Interaction in the Diels–Alder
9.4 Structure and Bonding in Alkynes: Reaction 417
sp Hybridization 362 10.18 Summary 418
9.5 Acidity of Acetylene and Terminal Alkynes 365 Problems 421
9.6 Preparation of Alkynes by Alkyation of Acetylene Descriptive Passage and Interpretive Problems 10:
and Terminal Alkynes 367 Intramolecular and Retro Diels–Alder Reactions 425
9.7 Preparation of Alkynes by Elimination Reactions 368
9.8 Reactions of Alkynes 370
9.9
9.10
9.11
Hydrogenation of Alkynes 370
Metal-Ammonia Reduction of Alkynes 372
Addition of Hydrogen Halides to Alkynes 373
Mechanism 9.1 Sodium–Ammonia Reduction of an
C H A P T E R 11
Alkyne 373
Arenes and Aromaticity 428
9.12 Hydration of Alkynes 375 11.1 Benzene 429
Mechanism 9.2 Conversion of an Enol to a 11.2 The Structure of Benzene 430
Ketone 376 11.3 The Stability of Benzene 432
9.13 Addition of Halogens to Alkynes 377 11.4 An Orbital Hybridization View of Bonding in
Some Things Can Be Made from Acetylene . . . Benzene 433
But Aren’t 378 11.5 The  Molecular Orbitals of Benzene 434
9.14 Ozonolysis of Alkynes 378 11.6 Substituted Derivatives of Benzene and Their
9.15 Summary 379 Nomenclature 435
Problems 382 11.7 Polycyclic Aromatic Hydrocarbons 438
Descriptive Passage and Interpretive Problems 9: 11.8 Physical Properties of Arenes 439
Thinking Mechanistically About Alkynes 386 Carbon Clusters, Fullerenes, and Nanotubes 440
11.9 Reactions of Arenes: A Preview 440
11.10 The Birch Reduction 442

10
11.11 Free-Radical Halogenation of Alkylbenzenes 442
Mechanism 11.1 The Birch Reduction 443
C H A P T E R 11.12 Oxidation of Alkylbenzenes 446
11.13 SN1 Reactions of Benzylic Halides 448
Conjugation in Alkadienes 11.14 SN2 Reactions of Benzylic Halides 449
11.15 Preparation of Alkenylbenzenes 450
and Allylic Systems 388 11.16 Addition Reactions of Alkenylbenzenes 451
10.1 The Allyl Group 389 11.17 Polymerization of Styrene 453
10.2 Allylic Carbocations 390 Mechanism 11.2 Free-Radical Polymerization of
10.3 SN1 Reactions of Allylic Halides 392 Styrene 453
Mechanism 10.1 Hydrolysis of an Allylic Halide 393 11.18 Cyclobutadiene and Cyclooctatetraene 454
10.4 SN2 Reactions of Allylic Halides 394 11.19 Hückel’s Rule 456
10.5 Allylic Free Radicals 395 11.20 Annulenes 458
10.6 Allylic Halogenation 396 11.21 Aromatic Ions 460
Mechanism 10.2 Allylic Chlorination of Propene 397 11.22 Heterocyclic Aromatic Compounds 463
10.7 Allylic Anions 399 11.23 Heterocyclic Aromatic Compounds and Hückel’s
10.8 Classes of Dienes 400 Rule 465
10.9 Relative Stabilities of Dienes 401 11.24 Summary 467
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13
Problems 470
Descriptive Passage and Interpretive Problems 11:
The Hammett Equation 474 C H A P T E R

Spectroscopy 538
C H A P T E R 12 13.1

13.2
Principles of Molecular Spectroscopy: Electromagnetic
Radiation 539
Principles of Molecular Spectroscopy: Quantized
Reactions of Arenes: Electrophilic and Energy States 541
Nucleophilic Aromatic Substitution 478 13.3 Introduction to 1H NMR Spectroscopy 541
13.4 Nuclear Shielding and 1H Chemical Shifts 543
12.1 Representative Electrophilic Aromatic Substitution 13.5 Effects of Molecular Structure on 1H Chemical
Reactions of Benzene 479 Shifts 546
12.2 Mechanistic Principles of Electrophilic Aromatic
Ring Currents—Aromatic and Antiaromatic 551
Substitution 480
13.6 Interpreting 1H NMR Spectra 552
12.3 Nitration of Benzene 482
13.7 Spin-Spin Splitting in 1H NMR Spectroscopy 555
Mechanism 12.1 Nitration of Benzene 483
13.8 Splitting Patterns: The Ethyl Group 557
12.4 Sulfonation of Benzene 484
13.9 Splitting Patterns: The Isopropyl Group 559
12.5 Halogenation of Benzene 484
13.10 Splitting Patterns: Pairs of Doublets 559
Mechanism 12.2 Sulfonation of Benzene 485
13.11 Complex Splitting Patterns 561
Biosynthetic Halogenation 486 1
13.12 H NMR Spectra of Alcohols 563
Mechanism 12.3 Bromination of Benzene 486
Magnetic Resonance Imaging (MRI) 564
12.6 Friedel-Crafts Alkylation of Benzene 488
13.13 NMR and Conformations 564
Mechanism 12.4 Friedel–Crafts Alkylation 489 13
13.14 C NMR Spectroscopy 565
12.7 Friedel-Crafts Acylation of Benzene 490 13
13.15 C Chemical Shifts 567
Mechanism 12.5 Friedel–Crafts Acylation 491 13
13.16 C NMR and Peak Intensities 569
12.8 Synthesis of Alkylbenzenes by Acylation-Reduction 492 13
13.17 C–1H Coupling 570
12.9 Rate and Regioselectivity in Electrophilic Aromatic
Substitution 494 13.18 Using DEPT to Count Hydrogens Attached to 13C 570
12.10 Rate and Regioselectivity in the Nitration of 13.19 2D NMR: COSY and HETCOR 572
Toluene 495 13.20 Introduction to Infrared Spectroscopy 574
12.11 Rate and Regioselectivity in the Nitration of Spectra by the Thousands 575
(Trifluoromethyl) Benzene 497 13.21 Infrared Spectra 576
12.12 Substituent Effects in Electrophilic Aromatic 13.22 Characteristic Absorption Frequencies 578
Substitution: Activating Substituents 499 13.23 Ultraviolet-Visible (UV-VIS) Spectroscopy 582
12.13 Substituent Effects in Electrophilic Aromatic Substitution: 13.24 Mass Spectrometry 584
Strongly Deactivating Substituents 503 13.25 Molecular Formula as a Clue to Structure 589
12.14 Substituent Effects in Electrophilic Aromatic 13.26 Summary 590
Substitution: Halogens 506 Problems 593
12.15 Multiple Substituent Effects 507 Descriptive Passage and Interpretive Problems 13:
12.16 Regioselective Synthesis of Disubstituted Aromatic Calculating Aromatic 13C Chemical Shifts 603
Compounds 510
12.17 Substitution in Naphthalene 512
12.18 Substitution in Heterocyclic Aromatic

12.19
12.20
Compounds 513
Nucleophilic Aromatic Substitution 514
Nucleophilic Substitution in Nitro-Substituted Aryl
Halides 515
C H A P T E R 14
12.21 The Addition-Elimination Mechanism of Nucleophilic
Organometallic Compounds 606
Aromatic Substitution 516 14.1 Organometallic Nomenclature 607
Mechanism 12.6 Nucleophilic Aromatic Substitution 14.2 Carbon-Metal Bonds in Organometallic
in p-Fluoronitrobenzene by the Addition-Elimination Compounds 608
Mechanism 518 14.3 Preparation of Organolithium Compounds 609
12.22 Related Nucleophilic Aromatic Substitutions 520 14.4 Preparation of Organomagnesium Compounds:
12.23 Summary 521 Grignard Reagents 610
Problems 525 14.5 Organolithium and Organomagnesium Compounds as
Descriptive Passage and Interpretive Problems 12: Brønsted Bases 612
Benzyne 534 14.6 Synthesis of Alcohols Using Grignard Reagents 614
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14.7 Synthesis of Alcohols Using Organolithium Mechanism 15.5 Oxidation of Ethanol by NAD+ 669
Reagents 616 15.12 Thiols 670
14.8 Synthesis of Acetylenic Alcohols 616 15.13 Spectroscopic Analysis of Alcohols and Thiols 674
14.9 Retrosynthetic Analysis 617 15.14 Summary 675
14.10 Alkane Synthesis Using Organocopper Reagents 620 Problems 679
Mechanism 14.1 Formation of a Lithium Diaklycuprate Descriptive Passage and Interpretive Problems 15:
(Gilman Reagent) 621 The Pinacol Rearrangement 684
14.11 An Organozinc Reagent for Cyclopropane

16
Synthesis 622
14.12 Carbenes and Carbenoids 623
Mechanism 14.2 Similarities Between the Mechanisms C H A P T E R
of Reaction of an Alkene with Iodomethylzinc Iodide
and a Peroxy Acid 624
Ethers, Epoxides, and Sulfides 686
14.13 Transition-Metal Organometallic Compounds 625
An Organometallic That Occurs Naturally: 16.1 Nomenclature of Ethers, Epoxides, and Sulfides 687
Coenzyme B12 627 16.2 Structure and Bonding in Ethers and Epoxides 688
14.14 Homogeneous Catalytic Hydrogenation 628 16.3 Physical Properties of Ethers 689
Mechanism 14.3 Homogeneous Hydrogenation of 16.4 Crown Ethers 690
Propene in the Presence of Wilkinson’s Catalyst 629 16.5 Preparation of Ethers 692
14.15 Olefin Metathesis 631 Polyether Antibiotics 693
Mechanism 14.4 Olefin Cross-Metathesis 632 16.6 The Williamson Ether Synthesis 694
14.16 Ziegler-Natta Catalysis of Alkene Polymerization 634 16.7 Reactions of Ethers: A Review and a Preview 695
Mechanism 14.5 Polymerization of Ethylene in the 16.8 Acid-Catalyzed Cleavage of Ethers 696
Presence of a Ziegler-Natta Catalyst 635 Mechanism 16.1 Cleavage of Ethers by Hydrogen
14.17 Summary 636 Halides 697
Problems 639 16.9 Preparation of Epoxides: A Review and a Preview 698
Descriptive Passage and Interpretive Problems 14: 16.10 Conversion of Vicinal Halohydrins to Epoxides 699
The Heck Reaction 643 16.11 Reactions of Epoxides: A Review and a Preview 700
16.12 Nucleophilic Ring Opening of Epoxides 701
Mechanism 16.2 Nucleophilic Ring Opening of an

C H A P T E R 15 16.13
Epoxide 703
Acid-Catalyzed Ring Opening of Epoxides 703
Mechanism 16.3 Acid-Catalyzed Ring Opening of
Ethylene Oxide 704
Alcohols, Diols, and Thiols 646 16.14 Epoxides in Biological Processes 706
15.1 Sources of Alcohols 647 16.15 Preparation of Sulfides 706
15.2 Preparation of Alcohols by Reduction of Aldehydes 16.16 Oxidation of Sulfides: Sulfoxides and Sulfones 707
and Ketones 648 16.17 Alkylation of Sulfides: Sulfonium Salts 708
Mechanism 15.1 Sodium Borohydride Reduction of an Mechanism 16.4 Nucleophilic Substitution of
Aldehyde or Ketone 653 Adenosine Triphosphate (ATP) by Methionine 709
15.3 Preparation of Alcohols by Reduction of Carboxylic 16.18 Spectroscopic Analysis of Ethers, Epoxides,
Acids 654 and Sulfides 709
15.4 Preparation of Alcohols from Epoxides 654 16.19 Summary 711
15.5 Preparation of Diols 656 Problems 715
15.6 Reactions of Alcohols: A Review and a Preview 658 Descriptive Passage and Interpretive Problems 16:
15.7 Conversion of Alcohols to Ethers 658 Epoxide Rearrangements and the NIH Shift 721
15.8 Esterification 660

17
Mechanism 15.2 Acid-Catalyzed Formation of Dietyl
Ether from Ethyl Alcohol 660
15.9 Oxidation of Alcohols 663 C H A P T E R
Mechanism 15.3 Chromic Acid Oxidation of
2-Propanol 665 Aldehydes and Ketones: Nucleophilic
15.10 Biological Oxidation of Alcohols 666
Mechanism 15.4 Dimethyl Sulfoxide Oxidation of an
Addition to the Carbonyl Group 724
Alcohol 666 17.1 Nomenclature 725
Economic and Environmental Factors in Organic 17.2 Structure and Bonding: The Carbonyl Group 728
Synthesis 667 17.3 Physical Properties 730
15.11 Oxidative Cleavage of Vicinal Diols 669 17.4 Sources of Aldehydes and Ketones 730
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17.5 Reactions of Aldehydes and Ketones: A Review 18.15 Intramolecular Ester Formation: Lactones 798
and a Preview 734 18.16 Decarboxylation of Malonic Acid and Related
17.6 Principles of Nucleophilic Addition: Hydration of Compounds 799
Aldehydes and Ketones 735 18.17 Spectroscopic Properties of Carboxylic Acids 802
Mechanism 17.1 Hydration of an Aldehyde or Ketone 18.18 Summary 803
in Basic Solution 738 Problems 805
17.7 Cyanohydrin Formation 739 Descriptive Passage and Interpretive Problems 18:
Mechanism 17.2 Hydration of an Aldehyde or Ketone Lactonization Methods 809
in Acid Solution 739
Mechanism 17.3 Cyanohydrin Formation 740
17.8 Acetal Formation 742

17.9
17.10
Mechanism 17.4 Acetal Formation from Benzaldehyde
and Ethanol 743
Acetals as Protecting Groups 745
Reaction with Primary Amines: Imines 746
C H A P T E R 19
Mechanism 17.5 Imine Formation from Benzaldehyde
Carboxylic Acid Derivatives: Nucleophilic
and Methylamine 747 Acyl Substitution 812
Imines in Biological Chemistry 749 19.1 Nomenclature of Carboxylic Acid Derivatives 814
17.11 Reaction with Secondary Amines: Enamines 751 19.2 Structure and Reactivity of Carboxylic Acid
Mechanism 17.6 Enamine Formation from Derivatives 815
Cyclopentanone and Pyrrolidine 752 19.3 General Mechanism for Nucleophilic Acyl
17.12 The Wittig Reaction 752 Substitution 818
Mechanism 17.7 The Witting Reaction 754 19.4 Nucleophilic Acyl Substitution in Acyl Chlorides 820
17.13 Planning an Alkene Synthesis via the Wittig Mechanism 19.1 Acid-Catalyzed Hydrolysis of an Acyl
Reaction 755 Chloride via a Tetrahedral Intermediate 822
17.14 Stereoselective Addition to Carbonyl Groups 757 19.5 Nucleophilic Acyl Substitution in Acid Anhydrides 823
17.15 Oxidation of Aldehydes 758 Mechanism 19.2 Nucleophilic Acyl Substitution in an
17.16 Spectroscopic Analysis of Aldehydes and Ketones 759 Anhydride 824
17.17 Summary 761 19.6 Sources of Esters 825
Problems 764 19.7 Physical Properties of Esters 827
Descriptive Passage and Interpretive Problems 17: 19.8 Reactions of Esters: A Preview 827
The Baeyer-Villiger Oxidation 772 19.9 Acid-Catalyzed Ester Hydrolysis 829
Mechanism 19.3 Acid-Catalyzed Ester Hydrolysis 830
19.10 Ester Hydrolysis in Base: Saponification 832

C H A P T E R 18 19.11
19.12
Mechanism 19.4 Ester Hydrolysis in Basic
Solution 834
Reaction of Esters with Ammonia and Amines 835
Reaction of Esters with Grignard Reagents: Synthesis
Carboxylic Acids 776 of Tertiary Alcohols 836
18.1 Carboxylic Acid Nomenclature 777 Mechanism 19.5 Reaction of an Ester with a Grignard
18.2 Structure and Bonding 779 Reagent 837
18.3 Physical Properties 780 19.13 Reaction of Esters with Lithium Aluminum
18.4 Acidity of Carboxylic Acids 780 Hydride 838
18.5 Substituents and Acid Strength 783 19.14 Amides 839
18.6 Ionization of Substituted Benzoic Acids 785 19.15 Hydrolysis of Amides 843
18.7 Salts of Carboxylic Acids 786 Mechanism 19.6 Amide Hydrolysis in Acid
18.8 Dicarboxylic Acids 788 Solution 844
18.9 Carbonic Acid 789 Mechanism 19.7 Amide Hydrolysis in Basic
18.10 Sources of Carboxylic Acids 790 Solution 846
18.11 Synthesis of Carboxylic Acids by the Carboxylation 19.16 Lactams 847
of Grignard Reagents 792 -Lactam Antibiotics 847
18.12 Synthesis of Carboxylic Acids by the Preparation 19.17 Preparation of Nitriles 848
and Hydrolysis of Nitriles 793 19.18 Hydrolysis of Nitriles 849
18.13 Reactions of Carboxylic Acids: A Review 19.19 Addition of Grignard Reagents to Nitriles 850
and a Preview 794 Mechanism 19.8 Nitrile Hydrolysis in Basic
18.14 Mechanism of Acid-Catalyzed Esterification 794 Solution 851
Mechanism 18.1 Acid-Catalyzed Esterification of 19.20 Spectroscopic Analysis of Carboxylic Acid
Benzoic Acid with Methanol 796 Derivatives 852
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19.21 Summary 853 20.21 Summary 913

Problems 856 Problems 917
Descriptive Passage and Interpretive Problems 20: Descriptive Passage and Interpretive Problems 20:
Thioesters 863 The Enolate Chemistry of Dianions 926

C H A P T E R 20 C H A P T E R 21
Amines 930
Enols and Enolates 866 21.1 Amine Nomenclature 931
21.2 Structure and Bonding 933
20.1 Aldehyde, Ketone, and Ester Enolates 867
21.3 Physical Properties 935
20.2 Enolate Regiochemistry 872
21.4 Basicity of Amines 936
20.3 The Aldol Condensation 873
Amines as Natural Products 941
Mechanism 20.1 Aldol Addition of Butanal 874
Mechanism 20.2 Dehydration in a Base-Catalyzed 21.5 Tetraalkylammonium Salts as Phase-Transfer
Aldol Condensation 876 Catalysts 942
20.4 Mixed Aldol Condensations 878 21.6 Reactions That Lead to Amines: A Review and a
Preview 943
Chalcones: From the Mulberry Tree to Cancer
21.7 Preparation of Amines by Alkylation of Ammonia 945
Chemotherapy 880
21.8 The Gabriel Synthesis of Primary Alkylamines 946
20.5 The Claisen Condensation 882
21.9 Preparation of Amines by Reduction 947
Mechanism 20.3 The Claisen Condensation of Ethyl
Mechanism 21.1 Lithium Aluminum Hydride Reduction
Acetate 883
of an Amide 950
20.6 Intramolecular Claisen Condensation: The
21.10 Reductive Amination 951
Dieckmann Cyclization 884
21.11 Reactions of Amines: A Review and a Preview 952
20.7 Mixed Claisen Condensations 885
21.12 Reaction of Amines with Alkyl Halides 954
20.8 Acylation of Ketones with Esters 886
21.13 The Hofmann Elimination 954
20.9 Alkylation of Enolates 887
21.14 Electrophilic Aromatic Substitution in Arylamines 956
20.10 The Acetoacetic Ester Synthesis 889
21.15 Nitrosation of Alkylamines 958
20.11 The Malonic Ester Synthesis 891
21.16 Nitrosation of Arylamines 960
20.12 Alkyation of Chiral Enolates 893
Mechanism 21.2 Reactions of an Alkyl Diazonium
20.13 Enolization and Enol Content 895
Ion 960
Mechanism 20.4 Base-Catalyzed Enolization
21.17 Synthetic Transformations of Aryl Diazonium Salts 961
of an Aldehyde or Ketone in Aqueous
Solution 899 21.18 Azo Coupling 965
Mechanism 20.5 Acid-Catalyzed Enolization From Dyes to Sulfa Drugs 966
of an Aldehyde or Ketone in Aqueous 21.19 Spectroscopic Analysis of Amines 967
Solution 899 21.20 Summary 970
20.14  Halogenation of Aldehydes and Ketones 900 Problems 976
Mechanism 20.6 Acid-Catalyzed Bromination of Descriptive Passage and Interpretive Problems 21:
Acetone 901 Synthetic Applications of Enamines 984
Mechanism 20.7 Cleavage of a Tribromomethyl

22
Ketone 903
20.15  Halogenation of Carboxylic Acids: The
Hell-Volhard-Zelinsky Reaction 904 C H A P T E R
The Haloform Reaction and the Biosynthesis of
Trihalomethanes 904 Phenols 988
20.16 Some Chemical and Stereochemical Consequences
of Enolization 906 22.1 Nomenclature 989
20.17 Effects of Conjugation in ,-Unsaturated Aldehydes 22.2 Structure and Bonding 990
and Ketones 907 22.3 Physical Properties 991
20.18 Conjugate Addition to ,-Unsaturated Carbonyl 22.4 Acidity of Phenols 992
Compounds 908 22.5 Substituent Effects on the Acidity of Phenols 993
20.19 Addition of Carbanions to ,-Unsaturated Ketones: 22.6 Sources of Phenols 995
The Michael Reaction 910 22.7 Naturally Occurring Phenols 996
20.20 Conjugate Addition of Organocopper Reagents to 22.8 Reactions of Phenols: Electrophilic Aromatic
,-Unsaturated Carbonyl Compounds 912 Substitution 997
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24
22.9 Acylation of Phenols 999
22.10 Carboxylation of Phenols: Aspirin and the
Kolbe-Schmitt Reaction 1001 C H A P T E R
22.11 Preparation of Aryl Ethers 1002
James Bond, Oxidative Stress, and Antioxidant Lipids 1074
Phenols 1004
24.1 Acetyl Coenzyme A 1075
22.12 Cleavage of Aryl Ethers by Hydrogen Halides 1006
24.2 Fats, Oils, and Fatty Acids 1077
22.13 Claisen Rearrangement of Allyl Aryl Ethers 1007
24.3 Fatty Acid Biosynthesis 1080
22.14 Oxidation of Phenols: Quinones 1008
24.4 Phospholipids 1082
22.15 Spectroscopic Analysis of Phenols 1009
Mechanism 24.1 Biosynthesis of a Butanoyl Group
22.16 Summary 1011
from Acetyl and Malonyl Building Blocks 1082
Problems 1013
24.5 Waxes 1085
Descriptive Passage and Interpretive Problems 22:
24.6 Prostaglandins 1086
Directed Metalation of Aryl Ethers 1019
Nonsteroidal Anti-Inflammatory Drugs (NSAIDS)
and COX-2 Inhibitors 1088

C H A P T E R 23 24.7
24.8
Terpenes: The Isoprene Rule 1090
Isopentenyl Pyrophosphate: The Biological Isoprene
Unit 1093
Carbohydrates 1022 24.9 Carbon-Carbon Bond Formation in Terpene
Biosynthesis 1093
23.1 Classification of Carbohydrates 1023 24.10 The Pathway from Acetate to Isopentenyl
23.2 Fischer Projections and D,L Notation 1024 Diphosphate 1096
23.3 The Aldotetroses 1025 24.11 Steroids: Cholesterol 1098
23.4 Aldopentoses and Aldohexoses 1026 Mechanism 24.2 Biosynthesis of Cholesterol from
23.5 A Mnemonic for Carbohydrate Configurations 1028 Squalene 1100
23.6 Cyclic Forms of Carbohydrates: Furanose Forms 1029 24.12 Vitamin D 1101
23.7 Cyclic forms of Carbohydrates: Pyranose Forms 1032 Good Cholesterol? Bad Cholesterol? What’s
23.8 Mutarotation 1035 the Difference? 1102
Mechanism 23.1 Acid-Catalyzed Mutarotation of 24.13 Bile Acids 1103
D -Glucopyranose 1037 24.14 Corticosteroids 1103
23.9 Carbohydrate Conformation: The Anomeric Effect 1038 24.15 Sex Hormones 1103
23.10 Ketoses 1039 24.16 Carotenoids 1104
23.11 Deoxy Sugars 1040 Crocuses Make Saffron from Carotenes 1105
23.12 Amino Sugars 1041 24.17 Summary 1106
23.13 Branched-Chain Carbohydrates 1042 Problems 1108
23.14 Glycosides: The Fischer Glycosidation 1043 Descriptive Passage and Interpretive Problems 24:
Mechanism 23.2 Preparation of Methyl Polyketides 1112
D -Glucopyranisides by Fischer Glycosidation 1044
23.15 Disaccharides 1046
23.16

23.17
Polysaccharides 1048
How Sweet It Is! 1049
Reactions of Carbohydrates 1050
C H A P T E R 25
23.18 Reduction of Monosaccharides 1050 Amino Acids, Peptides, and Proteins 1116
23.19 Oxidation of Monosaccharides 1051
25.1 Classification of Amino Acids 1118
23.20 Periodic Acid Oxidation 1053
25.2 Stereochemistry of Amino Acids 1123
23.21 Cyanohydrin Formation and Chain Extension 1054
25.3 Acid-Base Behavior of Amino Acids 1124
23.22 Epimerization, Isomerization, and Retro-Aldol
Cleavage 1055 Electrophoresis 1127
23.23 Acylation and Alkylation of Carbohydrate Hydroxyl 25.4 Synthesis of Amino Acids 1128
Groups 1056 25.5 Reactions of Amino Acids 1130
23.24 Glycosides: Synthesis of Oliosaccharides 1058 25.6 Some Biochemical Reactions of Amino Acids 1130
Mechanism 23.3 Silver-Assisted Glycosidation 1060 Mechanism 25.1 Pyridoxal 5-Phosphate-Mediated
23.25 Glycobiology 1062 Decarboxylation of an -Amino Acid 1131
23.26 Summary 1064 Mechanism 25.2 Transamination: Biosynthesis of
Problems 1067 L-Alanaine from L-Glutamic Acid and Pyruvic Acid 1135

Descriptive Passage and Interpretive Problems 23: 25.7 Peptides 1137

Emil Fischer and the Structure of (ⴙ)-Glucose 1072 25.8 Introduction to Peptide Structure Determination 1140
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25.9 Amino Acid Analysis 1140 26.11 Ribonucleic Acids 1193

25.10 Partial Hydrolysis of Peptides 1141 26.12 Protein Biosynthesis 1196
25.11 End Group Analysis 1141 26.13 AIDS 1197
25.12 Insulin 1143 26.14 DNA Sequencing 1198
25.13 The Edman Degradation and Automated Sequencing 26.15 The Human Genome Project 1200
of Peptides 1144 26.16 DNA Profiling and the Polymerase Chain
Mechanism 25.3 The Edman Degradation 1145 Reaction 1201
Peptide Mapping and MALDI Mass 26.17 Recombinant DNA Technology 1204
Spectrometry 1146 26.18 Summary 1205
25.14 The Strategy of Peptide Synthesis 1147 Problems 1208
25.15 Amino Group Protection 1148 Descriptive Passage and Interpretive Problems 26:
25.16 Carboxyl Group Protection 1151 Oligonucleotide Synthesis 1210
25.17 Peptide Bond Formation 1151

27
Mechanism 25.4 Amide Bond Formation Between
a Carboxylic Acid and Amine Using N,N-
Dicyclohexylcarboiimide 1152 C H A P T E R
25.18 Solid-Phase Peptide Synthesis: The Merrifield
Method 1153 Synthetic Polymers 1216
25.19 Secondary Structures of Polypeptides and
Proteins 1155 27.1 Some Background 1217
25.20 Tertiary Structure of Peptides and Proteins 1159 27.2 Polymer Nomenclature 1218
Mechanism 25.5 Carboxypeptidase-Catalyzed 27.3 Classification of Polymers: Reaction Type 1219
Hydrolysis 1162 27.4 Classification of Polymers: Chain Growth
25.21 Coenzymes 1163 and Step Growth 1220
Oh NO! It’s Inorganic! 1164 27.5 Classification of Polymers: Structure 1221
27.6 Classification of Polymers: Properties 1223
25.22 Protein Quaternary Structure: Hemoglobin 1164
27.7 Addition Polymers: A Review and a Preview 1225
25.23 G-Coupled Protein Receptors 1165
27.8 Chain Branching in Free-Radical Polymerization 1227
25.24 Summary 1166
Mechanism 27.1 Branching in Polyethylene Caused by
Problems 1168
Intramolecular Hydrogen Transfer 1228
Descriptive Passage and Interpretive Problems 25:
Mechanism 27.2 Branching in Polyethylene Caused by
Amino Acids in Enatioselective Synthesis 1171
Intermolecular Hydrogen Transfer 1229
27.9 Anionic Polymerization: Living Polymers 1230

26
Mechanism 27.3 Anionic Polymerization of Styrene 1230
27.10 Cationic Polymerization 1232
C H A P T E R 27.11 Polyamides 1233
Mechanism 27.4 Cationic Polymerization of
Nucleosides, Nucleotides, 2-Methylpropene 1233
27.12 Polyesters 1234
and Nucleic Acids 1174 27.13 Polycarbonates 1236
26.1 Pyrimidines and Purines 1175 27.14 Polyurethanes 1236
26.2 Nucleosides 1178 27.15 Copolymers 1237
26.3 Nucleotides 1180 Conducting Polymers 1239
26.4 Bioenergetics 1182 27.16 Summary 1241
26.5 ATP and Bioenergetics 1182 Problems 1243
26.6 Phosphodiesters, Oligonucleotides, Descriptive Passage and Interpretive Problems 27:
and Polynucleotides 1184 Chemical Modification of Polymers 1245
26.7 Nucleic Acids 1185
26.8 Secondary Structure of DNA: The Double Helix 1186 Glossary G-1
“It has not escaped our notice . . . ” 1188
Credits C-1
26.9 Tertiary Structure of DNA: Supercoils 1190
26.10 Replication of DNA 1191 Index I-1
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List of Important Features

Mechanisms 14.2 Similarities Between the Mechanisms of Reaction of

an Alkene with Iodomethylzinc Iodide and a Peroxy
4.1 Formation of tert-Butyl Chloride from tert-Butyl Alcohol Acid 624
and Hydrogen Chloride 149 14.3 Homogeneous Hydrogenation of Propene in the
4.2 Formation of 1-Bromoheptane from 1-Heptanol and Presence of Wilkinson’s Catalyst 629
Hydrogen Bromide 159 14.4 Olefin Cross-Metathesis 632
4.3 Conversion of an Alcohol to an Alkyl Chloride with 14.5 Polymerization of Ethylene in the Presence of a
Thionyl Chloride 161 Ziegler–Natta Catalyst 635
4.4 Free-Radical Chlorination of Methane 168 15.1 Sodium Borohydride Reduction of an Aldehyde or
5.1 The E1 Mechanism for Acid-Catalyzed Dehydration of Ketone 653
tert-Butyl Alcohol 203 15.2 Acid-Catalyzed Formation of Diethyl Ether from Ethyl
5.2 Carbocation Rearrangement in Dehydration of Alcohol 660
3,3-Dimethyl-2-butanol 205 15.3 Chromic Acid Oxidation of 2-Propanol 665
5.3 Hydride Shift in Dehydration of 1-Butanol 207 15.4 The Swern Oxidation 666
5.4 E2 Elimination of an Alkyl Halide 211 15.5 Oxidation of Ethanol by NAD 669
5.5 The E1 Mechanism for Dehydrohalogenation of 16.1 Cleavage of Ethers by Hydrogen Halides 697
2-Bromo-2-methylbutane in Ethanol 215 16.2 Nucleophilic Ring Opening of an Epoxide 703
6.1 Hydrogenation of Alkenes 229 16.3 Acid-Catalyzed Ring Opening of Ethylene Oxide 704
6.2 Electrophilic Addition of a Hydrogen Halide to an 16.4 Nucleophilic Substitution of Adenosine Triphosphate
Alkene 233 (ATP) by Methionine 709
6.3 Acid-Catalyzed Hydration of 2-Methylpropene 241 17.1 Hydration of an Aldehyde or Ketone in Basic
6.4 Hydroboration of 1-Methylcyclopentene 248 Solution 738
6.5 Oxidation of an Organoborane 249 17.2 Hydration of an Aldehyde or Ketone in Acid
6.6 Electrophilic Addition of Bromine to Ethylene 252 Solution 739
6.7 Formation of a Bromohydrin 253 17.3 Cyanohydrin Formation 740
6.8 Free-Radical Addition of Hydrogen Bromide to 17.4 Acetal Formation from Benzaldehyde and
1-Butene 256 Ethanol 743
6.9 Epoxidation of an Alkene 259 17.5 Imine Formation from Benzaldehyde and
6.10 Acid-Catalyzed Dimerization of 2-Methylpropene 262 Methylamine 747
6.11 Free-Radical Polymerization of Ethylene 265 17.6 Enamine Formation from Cyclopentanone and
8.1 The SN2 Mechanism of Nucleophilic Substitution 327 Pyrrolidine 752
8.2 The SN1 Mechanism of Nucleophilic Substitution 336 17.7 The Wittig Reaction 754
8.3 Carbocation Rearrangement in the SN1 Hydrolysis of 18.1 Acid-Catalyst Esterification of Benzoic Acid with
2-Bromo-3-methylbutane 340 Methanol 796
9.1 Sodium–Ammonia Reduction of an Alkyne 373 19.1 Acid-Catalyzed Hydrolysis of an Acyl Chloride via a
9.2 Conversion of an Enol to a Ketone 376 Tetrahedral Intermediate 822
10.1 Hydrolysis of an Allylic Halide 393 19.2 Nucleophilic Acyl Substitution in an
10.2 Allylic Chlorination of Propene 397 Anhydride 823
10.3 Addition of Hydrogen Chloride to 19.3 Acid-Catalyzed Ester Hydrolysis 830
1,3-Cyclopentadiene 408 19.4 Ester Hydrolysis in Basic Solution 834
10.4 Orbital Interactions in the Diels–Alder Reaction 417 19.5 Reaction of an Ester with a Grignard Reagent 837
11.1 The Birch Reduction 443 19.6 Amide Hydrolysis in Acid Solution 844
11.2 Free-Radical Polymerization of Styrene 453 19.7 Amide Hydrolysis in Basic Solution 846
12.1 Nitration of Benzene 483 19.8 Nitrile Hydrolysis in Basic Solution 851
12.2 Sulfonation of Benzene 485 20.1 Aldol Addition of Butanal 874
12.3 Bromination of Benzene 486 20.2 Dehydration in a Base-Catalyzed Aldol
12.4 Friedel–Crafts Alkylation 489 Condensation 878
12.5 Friedel–Crafts Acylation 491 20.3 The Claisen Condensation of Ethyl Acetate 883
14.1 Formation of a Lithium Dialkylcuprate (Gilman 20.4 Base-Catalyzed Enolization of an Aldehyde or Ketone in
Reagent) 621 Aqueous Solution 899

xvii
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xviii List of Important Features

20.5 Acid-Catalyzed Enolization of an Aldehyde or Ketone in 4.3 Some Bond Dissociation Enthalpies 165
Aqueous Solution 899 4.4 Conversions of Alcohols and Alkanes to Alkyl
20.6 Acid-Catalyzed Bromination of Acetone 901 Halides 176
20.7 Cleavage of a Tribromomethyl Ketone 903 5.1 Cahn–Ingold–Prelog Priority Rules 192
21.1 Lithium Aluminum Hydride Reduction of an 5.2 Preparation of Alkenes by Elimination Reactions of
Amide 950 Alcohols and Alkyl Halides 218
21.2 Reactions of an Alkyl Diazonium Ion 960 6.1 Heats of Hydrogenation of Some Alkenes 230
23.1 Acid-Catalyzed Mutarotation of D -Glucopyranose 1037 6.2 Relative Rates of Acid-Catalyzed Hydration of Some
23.2 Preparation of Methyl D -Glucopyranosides by Fisher Representative Alkenes 241
Glycosidation 1044 6.3 Relative Rates of Reaction of Some Representative
23.3 Silver-Assisted Glycosidation 1059 Alkenes with Bromine 252
24.1 Biosynthesis of a Butanoyl Group from Acetyl and 6.4 Relative Rates of Epoxidation of Some Representative
Malonyl Building Blocks 1082 Alkenes with Peroxyacetic Acid 259
24.2 Biosynthesis of Cholesterol from Squalene 1100 6.5 Some Compounds with Carbon–Carbon Double Bonds
25.1 Pyridoxal 5-Phosphate-Mediated Decarboxylation of Used to Prepare Polymers 265
an -Amino Acid 1131 6.6 Addition Reactions of Alkenes 267
25.2 Transamination: Biosynthesis of L-Alanine from 7.1 Absolute Configuration According to the
L-Glutamic Acid and Pyruvic Acid 1135 Cahn–Ingold–Prelog Notational System 288
25.3 The Edman Degradation 1145 7.2 Classification of Isomers 312
25.4 Amide Bond Formation Between a Carboxylic Acid and 8.1 Representative Functional Group Transformations
an Amine Using N,N-Dicyclohexylcarbodiimide 1152 by Nucleophilic Substitution Reactions of Alkyl
25.5 Carboxypeptidase-Catalyzed Hydrolysis 1162 Halides 324
27.1 Branching in Polyethylene Caused by Intramolecular 8.2 Reactivity of Some Alkyl Bromides Toward Substitution
Hydrogen Transfer 1228 by the SN2 Mechanism 330
27.2 Branching in Polyethylene Caused by Intermolecular 8.3 Effect of Chain Branching on Reactivity of Primary
Hydrogen Transfer 1229 Alkyl Bromides Toward Substitution Under SN2
27.3 Anionic Polymerization of Styrene 1230 Conditions 332
27.4 Cationic Polymerization of 2-Methylpropene 1233 8.4 Nucleophilicity of Some Common Nucleophiles 333
8.5 Reactivity of Some Alkyl Bromides Toward Substitution
by the SN1 Mechanism 337
8.6 Properties of Some Solvents Used in Nucleophilic
Tables Substitution 341
1.1 Electron Configurations of the First Twelve Elements of 8.7 Relative Rate of SN2 Displacement of 1-Bromobutane by
the Periodic Table 5 Azide in Various Solvents 342
1.2 Lewis Formulas of Methane, Ammonia, Water, and 8.8 Relative Rate of SN1 Solvolysis of tert -Butyl Chloride as
Hydrogen Fluoride 9 a Function of Solvent Polarity 343
1.3 Selected Values from the Pauling Electronegativity 8.9 Approximate Relative Leaving-Group Abilities 348
Scale 12 8.10 Comparison of SN1 and SN2 Mechanisms of
1.4 Selected Bond Dipole Moments 12 Nucleophilic Substitution in Alkyl Halides 351
1.5 A Systematic Approach to Writing Lewis Structures 16 9.1 Structural Features of Ethane, Ethylene, and
1.6 Introduction to the Rules of Resonance 21 Acetylene 364
1.7 VSEPR and Molecular Geometry 27 9.2 Preparation of Alkynes 380
1.8 Acidity Constants (pKa ) of Acids 35 9.3 Conversion of Alkynes to Alkenes and Alkanes 381
2.1 The Number of Constitutionally Isomeric Alkanes of 9.4 Electrophilic Addition to Alkynes 382
Particular Molecular Formulas 67 11.1 Names of Some Frequently Encountered Derivatives of
2.2 IUPAC Names of Unbranched Alkanes 69 Benzene 436
2.3 Heats of Combustion (H ) of Representative 11.2 Reactions Involving Alkyl and Alkenyl Side Chains in
Alkanes 81 Arenes and Arene Derivatives 469
2.4 Oxidation Number of Carbon in One-Carbon 11.3 Substituent Constants ( ) 475
Compounds 84 12.1 Representative Electrophilic Aromatic Substitution
2.5 Summary of IUPAC Nomenclature of Alkanes and Reactions of Benzene 480
Cycloalkanes 93 12.2 Classification of Substituents in Electrophilic Aromatic
2.6 Summary of IUPAC Nomenclature of Alkyl Groups 94 Substitution Reactions 501
3.1 Heats of Combustion (H ) of Cycloalkanes 109 12.3 Representative Electrophilic Aromatic Substitution
3.2 Heats of Combustion of Isomeric Reactions 522
Dimethylcyclohexanes 121 12.4 Limitations on Friedel–Crafts Reactions 523
4.1 Functional Groups in Some Important Classes of 13.1 Approximate Chemical Shifts of Representative
Organic Compounds 139 Protons 547
4.2 Boiling Point of Some Alkyl Halides and Alcohols 145 13.2 Splitting Patterns of Common Multiplets 559
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List of Important Features xix

13.3 Chemical Shifts of Representative Carbons 567 20.1 pKa Values of Some Aldehydes, Ketones, and Esters 868
13.4 Infrared Absorption Frequencies of Some Common 20.2 Enolization Equilibria of Some Carbonyl
Structural Units 579 Compounds 896
13.5 Absorption Maxima of Some Representative Alkenes 20.3 Carbonyl Condensations 914
and Polyenes 583 20.4 Alkylation and Other Reactions That Involve Enol or
13.6 Incremental 13C Chemical Shift Effects of Enolate Intermediates 915
Substituents ( ), ppm 603 21.1 Basicity of Amines As Measured by the pKa of Their
13.7 Calculated and Observed 13C Chemical Shifts for the Conjugate Acids 937
Ring Carbons in o- and m-Nitrotoluene 604 21.2 Effect of para Substituents on the Basicity of
14.1 Approximate Acidities of Some Hydrocarbons and Aniline 938
Reference Materials 613 21.3 Methods for Carbon–Nitrogen Bond Formation
14.2 Reactions of Grignard Reagents with Aldehydes and Discussed in Earlier Chapters 944
Ketones 615 21.4 Reactions of Amines Discussed in Previous
14.3 Preparation of Organometallic Reagents Used in Chapters 953
Synthesis 637 21.5 Preparation of Amines 971
14.4 Carbon–Carbon Bond-Forming Reactions of 21.6 Reactions of Amines Discussed in This Chapter 972
Organometallic Reagents 637 21.7 Synthetically Useful Transformations Involving Aryl
15.1 Summary of Reactions Discussed in Earlier Chapters Diazonium lons 974
That Yield Alcohols 650 22.1 Comparison of Physical Properties of an Arene, a
15.2 Summary of Reactions of Alcohols Discussed in Earlier Phenol, and an Aryl Halide 992
Chapters 659 22.2 Acidities of Some Phenols 994
15.3 Preparation of Alcohols by Reduction of Carbonyl 22.3 Industrial Syntheses of Phenol 995
Functional Groups 676 22.4 Electrophilic Aromatic Substitution Reactions of
15.4 Summary of Reactions of Alcohols Presented in Phenols 998
This Chapter 677 23.1 Some Classes of Monosaccharides 1024
15.5 Oxidation of Alcohols 678 23.2 Summary of Reactions of Carbohydrates 1065
16.1 Physical Properties of Diethyl Ether, Pentane, and 24.1 Some Representative Fatty Acids 1079
1-Butanol 689 24.2 Classification of Terpenes 1090
16.2 Preparation of Ethers 713 25.1 The Standard Amino Acids 1120
16.3 Preparation of Epoxides 713 25.2 Acid–Base Properties of Amino Acids with Neutral
17.1 Summary of Reactions Discussed in Earlier Chapters Side Chains 1126
That Yield Aldehydes and Ketones 732 25.3 Acid–Base Properties of Amino Acids with lonizable
17.2 Summary of Reactions of Aldehydes and Ketones Side Chains 1126
Discussed in Earlier Chapters 734 25.4 Covalent and Noncovalent Interactions Between Amino
17.3 Equilibrium Constants (Khydr) and Relative Rates of Acid Side Chains in Proteins 1160
Hydration of Some Aldehydes and Ketones 735 26.1 Pyrimidines and Purines That Occur in DNA
17.4 Reaction of Aldehydes and Ketones with Derivatives and/or RNA 1177
of Ammonia 748 26.2 The Major Pyrimidine and Purine Nucleosides in
17.5 Nucleophilic Addition to Aldehydes and RNA and DNA 1179
Ketones 762 26.3 G  for the Hydrolysis of Bioenergetically Important
18.1 Systematic and Common Names of Some Phosphates 1184
Carboxylic Acids 778 26.4 The Genetic Code (Messenger RNA Codons) 1194
18.2 Effect of Substituents on Acidity of Carboxylic 26.5 Distribution of DNAs with Increasing Number of
Acids 784 PCR Cycles 1203
18.3 Acidity of Some Substituted Benzoic Acids 786 27.1 Recycling of Plastics 1224
18.4 Summary of Reactions Discussed in Earlier Chapters 27.2 Summary of Alkene Polymerizations Discussed in
That Yield Carboxylic Acids 791 Earlier Chapters 1226
18.5 Summary of Reactions of Carboxylic Acids Discussed
in Earlier Chapters 795
19.1 Conversion of Acyl Chlorides to Other Carboxylic
Acid Derivatives 820 Boxed Essays
19.2 Conversion of Acid Anhydrides to Other Carboxylic Chapter 1
Acid Derivatives 824 Electrostatic Potential Maps 13
19.3 Preparation of Esters 826 Molecular Modeling 26
19.4 Conversion of Esters to Other Carboxylic Acid
Derivatives 828 Chapter 2
19.5 Reactions of Esters with Grignard Reagents Methane and the Biosphere 63
and with Lithium Aluminum Hydride 828 What’s in a Name? Organic Nomenclature 70
19.6 Preparation of Nitriles 849 Thermochemistry 82
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xx List of Important Features

Chapter 3 Chapter 22
Molecular Mechanics Applied to Alkanes and Cycloalkanes 107 James Bond, Oxidative Stress, and Antioxidant
Enthalpy, Free Energy, and Equilibrium Constant 118 Phenols 1004

Chapter 4 Chapter 23
From Bond Enthalpies to Heats of Reaction 167 How Sweet it is! 1048

Chapter 5 Chapter 24
Ethylene 188 Nonsteroidal Antiinflammatory Drugs (NSAIDs) and
COX-2 Inhibitors 1088
Chapter 6
Good Cholesterol? Bad Cholesterol? What’s the
Rules, Laws, Theories, and the Scientific Method 237 Difference? 1102
Ethylene and Propene: The Most Important Industrial Crocuses Make Saffron from Carotenes 1105
Organic Chemicals 263
Chapter 25
Chapter 7
Electrophoresis 1128
Chiral Drugs 293 Peptide Mapping and MALDI Mass Spectrometry 1146
Chirality of Disubstituted Cyclohexanes 304 Oh NO! It’s Inorganic! 1164
Chapter 8 Chapter 26
Enzyme-Catalyzed Nucleophilic Substitutions of “It Has Not Escaped Our Notice . . .” 1188
Alkyl Halides 335
Chapter 27
Chapter 9
Conducting Polymers 1239
Some Things That Can Be Made from Acetylene . . . But
Aren’t 378

Chapter 10
Diene Polymers 406 Descriptive Passage and Interpretive
Chapter 11
Problems
Carbon Clusters, Fullerenes, and Nanotubes 440 Chapter 1
Amide Lewis Structures 55
Chapter 12
Biosynthetic Halogenation 486 Chapter 2
Some Biochemical Reactions of Alkanes 99
Chapter 13
Ring Currents: Aromatic and Antiaromatic 551 Chapter 3
Magnetic Resonance Imaging (MRI) 564 Cyclic Forms of Carbohydrates 136
Spectra by the Thousands 575 Chapter 4
Chapter 14 More About Potential Energy Diagrams 182
An Organometallic Compound That Occurs Naturally: Chapter 5
Coenzyme B12 627
A Mechanistic Preview of Addition Reactions 224
Chapter 15
Chapter 6
Economic and Environmental Factors in Organic Synthesis 667
Oxymercuration 274
Chapter 16
Chapter 7
Polyether Antibiotics 693
Prochirality 320
Chapter 17
Chapter 8
Imines in Biological Chemistry 749
Nucleophilic Substitution 356
Chapter 19
Chapter 9
-Lactam Antibiotics 847
Thinking Mechanistically About Alkynes 386
Chapter 20
Chapter 10
Chalcones: From the Mulberry Tree to Cancer Chemotherapy 880 Intramolecular and Retro Diels–Alder Reactions 425
The Haloform Reaction and the Biosynthesis of
Trihalomethanes 904 Chapter 11
The Hammett Equation 474
Chapter 21
Amines as Natural Products 941 Chapter 12
From Dyes to Sulfa Drugs 966 Benzyne 535
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List of Important Features xxi

Chapter 13 Chapter 21
Calculating Aromatic 13C Chemical Shifts 603 Synthetic Applications of Enamines 984
Chapter 14 Chapter 22
The Heck Reaction 643 Directed Metalation of Aryl Ethers 1019
Chapter 15 Chapter 23
The Pinacol Rearrangement 684 Emil Fischer and the Structure of ()-Glucose 1071
Chapter 16 Chapter 24
Epoxide Rearrangements and the NIH Shift 721 Polyketides 1112
Chapter 17 Chapter 25
The Baeyer-Villager Oxidation 772 Amino Acids in Enantioselective Synthesis 1171
Chapter 18 Chapter 26
Lactonization Methods 809 Oligonucleotide Synthesis 1210
Chapter 19 Chapter 27
Thioesters 863 Chemical Modification of Polymers 1245
Chapter 20
The Enolate Chemistry of Dianions 926
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xxii Preface

Preface

What Sets This Book Apart?

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 seven 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.

A Functional Group Organization

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.
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 func-
tional group reappears as a characteristic reaction of a different functional group.
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A Mechanistic Emphasis and Its Presentation
The text emphasizes mechanisms and encourages students to see similarities in mecha-
nisms among different functional groups. Mechanisms are developed from observations;
thus, reactions are normally presented first, fol-
Mechanism 4.3
lowed by their mechanism.
Conversion of an Alcohol to an Alkyl Chloride with Thionyl Chloride
In order to maintain consistency with
THE OVERALL REACTION:
what our students have already learned, this text
RCH OH ⫹ SOCl ⫹
2 2 ±± ±£ RCH Cl ⫹ SO ⫹
2 2 ⫹ presents multistep mechanisms in the same way
N N ⫺
H
Cl as most general chemistry textbooks; that is, as
Alcohol Thionyl Pyridine Alkyl chloride Sulfur Pyridinium a series of elementary steps. Additionally, we
chloride dioxide chloride
Step 1: The hydroxyl group oxygen attacks sulfur and displaces chloride to give a protonated chlorosulfite ester:
provide a brief comment about how each step
RCH 2 Cl Cl
contributes to the overall mechanism.
–

O Sœ O Sœ O ⫹ Cl
⫺
Section 1.12 “Curved Arrows and Chemi-
–

H Cl RCH –O
2 ⫹ cal Reactions” introduces the student to the
–

Alcohol Thionyl chloride

H
Protonated alkyl Chloride ion
notational system employed in all of the mecha-
chlorosulfite nistic discussions in the text.
Step 2: Pyridine acts as a base to remove a proton and give a neutral alkyl chlorosulfite:
Numerous reaction mechanisms are
Cl Cl
accompanied by potential energy diagrams.
–
–

Sœ O Sœ O ⫹ ⫹
N
Section 4.9 “Potential Energy Diagrams for
–
–

RCH –O 2 ⫹ RCH – O
2
–

H
N H
Multistep Reactions: The SN1 Mechanism”
Pyridine Alkyl chlorosulfite Pyridinium shows how the potential energy diagrams for
ion

Step 3: Nucleophilic attack of chloride ion breaks the COO bond to form the alkyl chloride:
three elementary steps are combined to give the
Cl
diagram for the overall reaction.
⫺
–

Cl ⫺
Sœ O RCH2Cl ⫹ SO2 ⫹ Cl
–

RCH2–O
Alkyl chlorosulfite Alkyl chloride Sulfur Chloride ion
dioxide

xxii
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Preface xxiii

Enhanced Graphics
The teaching of organic chemistry has espe- Mechanism 5.4
cially benefited as powerful modeling andd E2 Elimination of an Alkyl Halide
graphics software have become routinely avail-
O—H bond is forming
able. Computer-generated molecular models
C—H bond is breaking
and electrostatic potential maps were integratedd C C ␲ bond is forming
into the third edition of this text and theirr Hydroxide ion Transition state
C—X bond is breaking
number has increased in succeeding editions.

Potential energy
Also seeing increasing use are graphically cor-
rect representations of orbitals and the role off Alkene
Water
orbital interactions in chemical reactivity. The Halide ion

E2 mechanism of elimination, which involves Alkyl halide

a single elementary step, is supplemented by Reaction coordinate

showing the orbital interactions that occur dur-

ing that step.
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Generous and Effective Use of Tables

The relative reactivity of different compounds is relevant to both
the theory and practice of organic chemistry. While it is helpful—
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 several tables of quantitative relative rate data of which
the following is but one example.
Annotated summary tables have been a staple of Organic *
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.
Chemistry since the first edition. Some tables review reactions
from earlier chapters, others the reactions or concepts of a cur-
rent chapter. Still others walk the reader step-by-step through skilll bbuilders
ild and d concepts
unique to organic chemistry. Well received by students and faculty alike, these summary
tables remain one of the text’s strengths.
Problem 8.16
A standard method for the synthesis of ethers is an SN2 reaction between an alkoxide

Problems and an alkyl halide.

R O ⫺
⫹ R⬘ X R O R⬘ ⫹ X ⫺

Show possible combinations of alkoxide and alkyl halide for the preparation of the
Problem-solving strategies and skills are emphasized through- following ethers. Which of these ethers can be prepared effectively by this method?
out. Understanding is progressively reinforced by problems (a) CH3CH2CHOCH(CH3)2 (b) CH3CH2CH2OCH(CH3)2

that appear within topic sections. For many problems, sam- CH3
Sample Solution
ple solutions are given, including examples of handwritten
solutions from the author.
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xxiv Preface

Pedagogy
◾ A list of tables, mechanisms, boxes and Descriptive Passages and Interpretive
Questions is included in the front matter (page xvii) as a quick reference to
these important learning tools in each chapter.
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◾ Each chapter opens with a

two-page spread of “coming Like all soccer balls
made since the 1980s,

attractions” that lists section

27
the official ball for the
2006 World Cup
was constructed of

headings, reaction mechanisms Synthetic Polymers polymeric materials. Four

layers of polyurethane,
with a total thickness of

and Descriptive Passages and 1.1 mm, make up the

outer covering.
Polyurethanes are

Interpretive Problems along Chapter Outline

normally prepared
from a diol and a
diisocyanate, such as
H3C

with their corresponding page 27.1

27.2
Some Background 1217
Polymer Nomenclature 1218
toluene diisocyanate. OCN NCO

A POLYMER IS A substance composed of macromolecules, molecules that contain

na
27.3 Classification of Polymers: Reaction Type 1219

numbers. 27.4
27.5
Classification of Polymers: Chain Growth and Step Growth 1220
Classification of Polymers: Structure 1221
very large number of atoms and have a high molecular weight. Starch, cellulose, silk, and
DNA are examples of naturally occurring polymers. Synthetic polymers include nylon,
polyethylene, and Bakelite, among countless others. Polymers need not be homogeneous,
on,
us,
27.6 Classification of Polymers: Properties 1223 and most are not. Even one as simple as polyethylene is a mixture of macromolecules les
27.7 Addition Polymers: A Review and a Preview 1225 with different chain lengths and different degrees of branching.
27.8 Chain Branching in Free-Radical Polymerization 1227 This chapter is about synthetic polymers, many of which have been introduced in
27.9 Anionic Polymerization: Living Polymers 1230 earlier chapters where we emphasized the connection between the reactions used to pre-
pare polymers and the core reactions of organic chemistry. In this chapter, we will add
27.10 Cationic Polymerization 1232
new polymers and methods to those already introduced and expand our understanding of
27.11 Polyamides 1233 their synthesis, structure, and properties. As we do so, keep in mind that the reactions
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27.12 Polyesters 1234 used to prepare polymers/Users/elhi3/Documents/Smart
are the same fundamental reactions that occur withConnection/InDesign/41332
simple
27.13 Polycarbonates 1236 organic compounds.
27.14 Polyurethanes 1236
27.15 Copolymers 1237
◾ Conducting Polymers 1239 27.1 Some Background
27.16 Summary 1241 The earliest applications of polymer chemistry involved chemical modification Vulcanization was summarized in the
Problems 1243 designed to improve the physical properties of naturally occurring polymers. In essay Diene Polymers in Chapter 10,
1839, Charles Goodyear transformed natural rubber, which is brittle when cold and p. 000.
Descriptive Passage and Interpretive Problems 27:
Chemical Modification of Polymers 1245 tacky when warm, to a substance that maintains its elasticity over a wider tem-
perature range by heating it with sulfur (vulcanization). The first synthetic fibers—
Mechanisms called rayons—were made by chemical modification of cellulose near the end of
the nineteenth century.
27.1 Branching in Polyethylene Caused by Intramolecular Hydrogen Transfer 1228 Leo Baekeland patented the first totally synthetic polymer, which he called Bakelite,
27.2 Branching in Polyethylene Caused by Intermolecular Hydrogen Transfer 1229 in 1910 (Figure 27.1). Bakelite is a versatile, durable material prepared from low-cost
materials (phenol and formaldehyde) and was the most successful synthetic material of
27.3 Anionic Polymerization of Styrene 1230
its kind for many years.
27.4 Cationic Polymerization of 2-Methylpropene 1233 These early successes notwithstanding, knowledge about polymer structure was
meager. Most chemists believed that rubber, proteins, and the like were colloidal disper-
sions of small molecules. During the 1920s Hermann Staudinger, beginning at the Swiss
Figure 27.1
Federal Institute of Technology and continuing at the University of Freiburg, argued
that polymers were high-molecular-weight compounds held together by normal covalent At one time, it almost always went
bonds. Staudinger’s views received convincing support in a 1929 paper by Wallace without saying that anything plastic was
made of Bakelite. Many Bakelite items
H. Carothers of Du Pont who reached similar conclusions. are now sought after as collectibles.
Staudinger’s studies of polymer structure and Carothers’ achievements in polymer
synthesis accelerated the development of polymer chemistry, especially its shift from

1216 1217

14.17 SUMMARY
◾ Summary tables allow the student easy access Section 14.1 Organometallic compounds contain a carbon–metal bond. They are named as alkyl
to a wealth of information in an easy-to-use (or aryl) derivatives of metals.

CH3CH2CH2CH2Li C6H5MgBr
format while reviewing information from previous Butyllithium Phenylmagnesium bromide
chapters.
Section 14.2 Carbon is more electronegative than metals and carbon–metal bonds are polarized
◾ End-of-Chapter Summaries highlight and so that carbon bears a partial to complete negative charge and the metal bears a
partial to complete positive charge.
consolidate all of the important concepts and H H
reactions within a chapter. ␦⫺
C Li␦⫹ HC
⫺
C Na⫹
H
Methyllithium has a polar Sodium acetylide has an
covalent carbon–lithium ionic bond between carbon
bond. and sodium.

Section 14.3 See Table 14.3

Section 14.4 See Table 14.3
Section 14.5 Organolithium compounds and Grignard reagents are strong bases and react
instantly with compounds that have OOH groups.

R M⫹ H O R⬘ R H ⫹ M ⫹ ⫺O R⬘

These organometallic compounds cannot therefore be formed or used in solvents

such as water and ethanol. The most commonly employed solvents are diethyl
ether and tetrahydrofuran.
Section 14.6 See Tables 14.2 and 14.4
Section 14.7 See Table 14.4
Section 14.8 See Table 14.4
Section 14.9 When planning the synthesis of a compound using an organometallic reagent,
or indeed any synthesis, the best approach is to reason backward from the
product. This method is called retrosynthetic analysis. Retrosynthetic analysis
of 1-methylcyclohexanol suggests it can be prepared by the reaction of
methylmagnesium bromide and cyclohexanone.

CH3
O ⫹ CH3MgBr
OH
1-Methylcyclohexanol Cyclohexanone Methylmagnesium
bromide
car02613_fm_i-xxxi.indd Page xxv 11/23/09 5:50:58 PM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Preface xxv

Audience car02613_ch08_322-358.indd Page 323 11/5/09 11:37:03 AM user-s131

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 This electrostatic
potential map is of
have remained grounded in some fundamental the transition state
for the reaction of
notions. These include important issues con- hydroxide ion with
chloromethane. The
cerning the intended audience. Is the topic tetrahedral arrangement
appropriate for them with respect to their of bonds inverts like
an umbrella in a storm
interests, aspirations, and experience? Just as during the reaction.

important is the need to present an accurate

picture of the present state of organic chem-
istry. 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 has been designed with the audience in mind.
The electrostatic potential maps combined with a graphic of a familiar object help con-
nect the map to the chapter’s content. Chapter 8, for example, opens by illustrating
the umbrella-in-a-windstorm analogy used by virtually everyone who has ever taught
nucleophilic substitution.

Descriptive Passage and Interpretive Problems

Many organic chemistry students later take standardized pre-professional examinations
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composed of problems derived from a descriptive passage, this text includes comparable
passages and problems to familiarize students with this testing style.
Thus, every chapter concludes Descriptive Passage and Interpretive Problems 15
with a self-contained Descriptive The Pinacol Rearrangement
We would expect a vicinal diolcar02613_ch15_646-685.indd Page 685 11/10/09 11:20:38 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332
Passage and Interpretive Problems such as 2,3-dimethyl-2,3-butanediol
double dehydration on treatment with an acid catalyst.
to give a conjugated diene by

unit that complements the chapter’s H3C

CH3 CH3
C C CH3
acid catalyst
H3C
C C
CH2
⫹ 2H2O

content while emulating the “MCAT OH OH

2,3-Dimethyl-2,3-butanediol 2,3-Dimethyl-1,3-butadiene
H2C
Water
CH3 Problems 685

style.” These 27 passages—listed tions a different reaction occurs.

15.43 Which word or phrase best describes the stereochemistry
Although 2,3-dimethyl-1,3-butadiene can be prepared byofjust
the such a process,
product
diol shown?
formedunder
in thecertain
pinacolcondi-
rearrangem
ment of the
rearrangement
15.47 The group that is anti to oxygen migrates in the pinacol
rearrangement of the diol shown. What is the product?

on page xx—are accompanied by OH OH

H2SO4
CH3 O
CH3

OH
H3C C C CH3 H3C C HC3C CH3 ⫹3 H O4
H22SO

more than 100 total multiple-choice H3C CH3 CH3 HO OH

CH
O CH3
CH
H3
OH

CH3
problems. 2,3-Dimethyl-2,3-butanediol
(Common name: pinacol)
3,3-Dimethyl-2-butanone
(CommonA. name:
Water
Achiral
pinacolone)
B. A single enantiomer of a chiral molecule O
The passages focus on a wide This reaction is called the pinacol rearrangement after C.

the OH groups of the vicinal diol.

the Chiral,
common name of
but racemic
D. Two diastereomers
the diol reactant.
The mechanism for conversion of pinacol to pinacolone begins with protonation of one of
CH3
O

CCH3

range of topics—from structure, H 3C CH3

CH3 ⫹
H
15.44–15.45 Consider the two diols (1

⫹
H3ketones
C CH
(3 3and 4).
(1 and 2)
H
2) and thee two

CH3 ⫹
CH3 CH3
H O O A. B.

synthesis, mechanism, and natural H 3C

O O
H
H3C
CH3CH2C
O
OH OH
O
⫹ 2H
CCH CH3 CHH3C
OH OH
CCH2CH3 15.48 Rather than following a mechanism in which a group
H migrates in the same step as water departs, the pinacol
products to using the Internet to Pinacol
H H
H3C
H
1
CH3 H3C CH2CH3
2
rearrangement of the vicinal diol shown proceeds by way
of the more stable of two possible carbocations. A single

calculate 13C chemical shifts. They This is followed by loss of water and migration of a methyl group, usuallyVicinal
which the group anti to the departing water migrates.
in a single
diols step in

O CH2CH3 O CH2CH3
ketone is formed in 73% yield. What is the structure of
this ketone?
OH OH
CH3 CH3 H
provide instructors with numerous H3C
H 3C
CH3
H3C
⫹
CH3C
CH3
CH3
⫹2 CCH CH3
O
CH3CH2C CCH3
CH3
H3C C C C6H5

O H O H3C C6H5
opportunities to customize their H
O
H
⫹ H CH3
3 H
Ketones
4
2-Methyl-1,1-diphenyl-1,2-propanediol

own organic chemistry course while A key to understanding this migration is to recall that
ization of a lone pair of an attached oxygen.
carbocations
A mixture are 4stabilized
of 3 and is formedbybydelocal-
pinacol rearr
rearrangement
rangement
of either 1 or 2. Given that an ethyl migrates in preference
H3C
O

C
O

C
C6H5
C6H5
CH3 toHmethyl in
CHpinacol rearrangements, predict the major H3C C C6H5 H3C C
giving students practice in combin- H 3C
⫹
CH3
3C
ketone formed
3
by rearrangement
⫹
of each diol.
CH3
C6H5 CH3
H O 15.44 HDiolO1 gives
CHpredominantly A. B.
ing new information with what they CH3
A. Ketone 3
B.Major contributor
Ketone 4
3

15.49 Like the pinacol rearrangement in the preceding problem,

have already learned. Thus, the rearrangement follows the usual generalization that a less stable carbocation is converted
to a more stable one. Deprotonation of oxygen 15.45 2 gives
Diolthe
completes predominantly
mechanism.
this one also begins with the formation of the more stable
of two possible carbocations from a vicinal diol. A 99%
yield of a single ketone was isolated. What is this ketone?
A. Ketone 3
H
HC CH3 HB. Ketone 4 H C CH3 OH
3 ⫹ 3
O ⫹ O isHthe⫹product of the following C6H5
CH3 15.46 What CH reaction?
3
H H O⫹ CH3 O
H O CH3
OH C6H5 OH

Pinacolone H2SO4
The term “pinacol rearrangement” is applied in a general way to any
HO rearrangement that C6H5
transforms a vicinal diol to a ketone. O
O O O
C6H5
C6H5 C6H5
A. C.
A. C.
C6H5
O O
O
O
C6H5 C6H5 C6H5
B. D.
B. D.
car02613_fm_i-xxxi.indd Page xxvi 11/23/09 11:48:01 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

xxvi Preface
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What’s New
Reorganization and Consolidation Reactions of Arenes:
By reorganizing certain related topics, the number
of chapters in Organic Chemistry has been reduced
12 Electrophilic and Nucleophilic
Aromatic Substitution
from 29 in the 7th edition to 27 in the 8th. Thus,
nucleophilic aromatic substitution has now joined Chapter Outline
12.1 Representative Electrophilic Aromatic 12.13 Substituent Effects in Electrophilic Aromatic
electrophilic aromatic substitution in: Chapter 12 12.2
Substitution Reactions of Benzene 479
Mechanistic Principles of Electrophilic
Substitution: Strongly Deactivating Substituents 503
12.14 Substituent Effects in Electrophilic Aromatic

Reactions of Arenes: Electrophilic and Nucleophilic Aromatic Substitution 480

12.3 Nitration of Benzene 482
Substitution: Halogens 506
12.15 Multiple Substituent Effects 507
12.4 Sulfonation of Benzene 484 12.16 Regioselective Synthesis of Disubstituted Aromatic
Aromatic Substitution while Chapter 20 Enols and 12.5 Halogenation of Benzene 484
◾ Biosynthetic Halogenation 486
Compounds 510
12.17 Substitution in Naphthalene 512

Enolates combines the treatment of ester enolates 12.6 Friedel–Crafts Alkylation

12.7 Friedel–Crafts
of Benzene 488
car02613_ch20_866-929.indd Page 866
fts Acylation of Benzene 490
12.18 Substitution in Heterocyclic Aromatic
11/12/09 10:13:48 AM elhi3
Compounds 513
/Users/elhi3/Documents/Smart Connection/InDesign/41332

12.19 Nucleophilic Aromatic Substitution 514

with that of aldehyde and ketone enols and enolates. 12.8 Synthesis of Alkylbenzenes by
Acylation–Reduction
Reduction 492 12.20 Nucleophilic Substitution in Nitro-Substituted
Aryl Halides 515
12.9 Rate and Regioselectivity in Electrophilic
Each of the two new chapters offers the Aromatic Substitution
ubstitution 494
12.10 Rate and Regioselectivity in the Nitration
12.21 The Addition–Elimination Mechanism of Nucleophilic
Aromatic Substitution 516

advantage of a timely treatment of core material of Toluene 495

12.11 Rate and Regioselectivity in the Nitration of
12.22 Related Nucleophilic Aromatic Substitutions 520
12.23 Summary 521

20
(Trifluoromethyl)benzene
ethyl)benzene 497 Problems 525
along with efficiency in its delivery. Nucleophilic 12.12 Substituentt Effects in Electrophilic
Aromatic Substitution:
ubstitution: Activating
Descriptive Passage and Interpretive
Problems 12: Benzyne 534

aromatic substitution, for example, becomes a “first- Substituents

ts 499
Enols and Enolates
Mechanisms
semester” or “second-quarter” topic along with both 12.1 Nitration off Benzene 483 12.5 Friedel–Crafts Acylation 491

nucleophilic aliphatic and electrophilic aromatic 12.2

12.3
Sulfonation
n of Benzene 485
Brominationn of Benzene 486
12.6 Nucleophilic Aromatic Substitution in
p-Fluoronitrobenzene
Fluoronitrobenzene by the Addition–Elimination
Addition Elimination
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12.4 Friedel–Crafts
fts Alkylation 489 Mechanism 518 /Users/elhi3/Documents/Smart Connection/InDesign/41332
substitution. Chapter Outline
20.1 Aldehyde, Ketone, and Ester Enolates 867 ◾ The Haloform Reaction and the Biosynthesis
20.2 Enolate Regiochemistry 872 of Trihalomethanes 904
20.3 The Aldol Condensation 873 20.15 ␣ Halogenation of Carboxylic Acids: The Hell–
20.4 Mixed Aldol Condensations 878 Volhard–Zelinsky Reaction 904
◾ Chalcones: From the Mulberry Tree 20.16 Some Chemical and Stereochemical Consequences
to Cancer Chemotherapy 880 of Enolization 906
20.5 The Claisen Condensation 882 20.17 Effects of Conjugation in ␣,␤-Unsaturated Aldehydes
and Ketones 907
478 20.6 Intramolecular Claisen Condensation: The
Dieckmann Cyclization 884 20.18 Conjugate Addition to ␣,␤-Unsaturated Carbonyl
Compounds 908
20.7 Mixed Claisen Condensations 885
20.19 Addition of Carbanions to ␣,␤-Unsaturated Ketones:
20.8 Acylation of Ketones with Esters 886
The Michael Reaction 910
20.9 Alkylation of Enolates 887
20.20 Conjugate Addition of Organocopper Reagents to
20.10 The Acetoacetic Ester Synthesis 889 ␣,␤-Unsaturated Carbonyl Compounds 912
20.11 The Malonic Ester Synthesis 891 20.21 Summary 913
20.12 Alkylation of Chiral Enolates 893 Problems 917
20.13 Enolization and Enol Content 895

Updated Carbohydrates Chapter

Descriptive Passage and Interpretive Problems 20:
20.14 ␣ Halogenation of Aldehydes and Ketones 900 The Enolate Chemistry of Dianions 926

Mechanisms
20.1 Aldol Addition of Butanal 874 20.5 Acid-Catalyzed Enolization of an Aldehyde or Ketone
Chapter 23: “Carbohydrates” has been significantly 20.2 Dehydration in a Base-Catalyzed Aldol
Condensation 876 20.6
in Aqueous Solution 899
Acid-Catalyzed Bromination of Acetone 901

updated. The mechanism for the Fischer glycosidation 20.3

20.4
The Claisen Condensation of Ethyl Acetate 883
Base-Catalyzed Enolization of an Aldehyde or Ketone
20.7 Cleavage of a Tribromomethyl Ketone 903

in Aqueous Solution 899

has been revised to be more consistent with current
understanding of this fundamental reaction. New sections
have been added on the synthesis of oligosacccharides
and Glycobiology.
866

Updated Spectroscopy Chapter

Chapter 13: “Spectroscopy” now includes several new spectroscopy problems that
include NMR spectra. These problems encompass a range of topics from analysis of
splitting patterns in proton spectra of
alcohols and alkyl halides, to DEPT 1856.7 1760.6
1751.0
spectra, to the effect of chirality center 1840.3

on adjacent methylene groups. O

1981.7
1965.2
Ha 1972.1
S 1955.6
Hc
Hb
Phenyl vinyl sulfoxide

6.6 6.4 6.2 6.0 5.8

Chemical shift (δ, ppm)
Figure 13.47
Vinyl proton region of the 300-MHz 1H NMR spectrum of phenyl vinyl sulfoxide.
car02613_fm_i-xxxi.indd Page xxvii 11/23/09 11:48:03 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Preface xxvii

New Problems
Over one hundred seventy new problems have been added, many of which involve the
synthesis of pharmaceuticals and natural products.

Bioorganic Emphasis
There is an increased emphasis on bioorganic chemistry, with new coverage of
glycobiology, liposomes, G-coupled protein receptors, recombinant DNA technology,
and other topics.

New Boxed Essays

Chapter 12: “Biosynthetic Halogenation” Chalcones: From the Mulberry Tree to Cancer Chemotherapy
describes the enzymatic halogenation
E
xcluding certain types of skin cancer, breast cancer is risk for developing it because of changes in the production of
that occurs in the biosynthesis of the the most common cancer among women. The chance of the hormone estrogen. One approach to the treatment of breast
developing invasive breast cancer during a woman’s lifetime cancer is through the use of drugs such as tamoxifen that restrict
antibiotic pyrrolnitrin. A mechanism is approximately 1 in 8, and postmenopausal women are at greater tumor growth by binding to an estrogen receptor in tumor cells.

showing the electrophilic chlorinating OCH2CH2N(CH3)2

species is included as well as a new car02613_ch20_866-929.indd Page 881 11/12/09 10:14:06 AM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

problem that is based on an electrophilic

halogenation with a reagent that has an CH3CH2

oxygen-halogen bond. Tamoxifen

Chapter 20: “Chalcones: From the

Mulberry Tree to Cancer Chemotherapy” focuses An alternative strategy is to reduce the body’s production of
estrogen by inhibiting the pathway for its biosynthesis. Aromatase
of anticancer drugs. For example, the enzyme aromatase catalyzes
the conversion of androstenedione to estrone. By blocking the
on aromatase inhibitors in the treatment of breast inhibitors, which block the final step in the biosynthetic pathway
to the estrogens estrone and estradiol, constitute one such class
action of this enzyme, estrone production is inhibited, but the
production of other necessary steroids is not affected.
cancer, and illustrates the use of a mixed aldol
O O
condensation in the synthesis of a naturally H 3C H3C

occurring chalcone. H 3C
aromatase

Chapter 22: “James Bond, Oxidation Stress, and O

Androstenedione
HO
Estrone (an estrogen)
Antioxidant Phenols” shows how phenolic compounds
The potential of aromatase inhibitors in the treatment tree, Broussonetia papyrifera. One of these compounds is a chalcone
such as vitamin E can protect cell membranes of breast cancer has spurred efforts to find more potent drugs. called morachalcone A. Chalcone and its derivatives are present in
Bioassays of over 4000 plants led to the discovery of potent many plants, have a long history in folk medicine, and continue to
against damage caused by reactive oxygen species by aromatase inhibitors from organic extracts of the paper mulberry be widely used as alternatives to conventional therapies.

terminating a free-radical chain reaction. O OH O OH

Chapter 27: “Conducting Polymers” describes organic

HO OH
light emitting diodes (OLEDs) which are conducting Chalcone Morachalcone A

polymers that can be used in the production of In one synthesis of morachalcone A, an aldol condensation compound shown. The remaining steps involved adding the five-
displays used in cellular telephone and flat panel between an aldehyde and a ketone was used to prepare the carbon side chain and removing the three groups shown in red.

televisions. OH O OCH2OCH3

(CH3)3SiCH2CH2O OCH2OCH3

Problem 20.12
Two carbonyl compounds react in ethanol in the presence of KOH to yield the morachalcone precursor just shown. Write
structural formulas for these two compounds.

The paper mulberry tree Broussonetia papyrifera is a source of a

compound that holds promise as an anticancer drug.
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xxviii Preface

New Sections
Every section was reviewed thoroughly and numerous changes were made on a
continuing basis to ensure accuracy, relevance, and readability. Thus, many sections
from previous editions, although substantially reworked, are not considered “new.” The
following lists those sections that are.
◾ Section 2.22: “Bonding in Water and Ammonia: Hybridization of Oxygen and
Nitrogen”
◾ Section 4.13: “More on Activation Energy”
◾ Section 7.9: “The Chirality Axis”
◾ Section 20.12: “Alkylation of Chiral Enolates”
◾ Section 23.24: “Glycosides: Synthesis of Oligasaccharides”
◾ Section 23.25: “Glycobiology”
◾ Section 25.23: “G-Coupled Protein Receptors”
◾ Section 26.17: “Recombinant DNA Technology”

New Descriptive Passages

◾ Chapter 17 The Baeyer-Villiger Oxidation
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◾ Chapter 20 Benzyne

New Mechanisms Mechanism 23.1

Acid-Catalyzed Mutarotation of D -Glucopyranose
◾ 4.3 Conversion of an Alcohol to an Alkyl THE OVERALL REACTION:
Chloride with Thionyl Chloride HOCH2 HOCH2
◾ 15.4 Oxidation of an Alcohol with Dimethyl
O O
HO HO
HO H HO OH
Sulfoxide —Oxalyl Chloride (Swern HO
OH
HO
H
Oxidation) ␣-D-Glucopyranose ␤-D-Glucopyranose

◾ 19.1 Acid-Catalyzed Hydrolysis of an Acyl Step 1: Protonation of the oxygen of the pyranose ring by the acid catalyst. In aqueous solution, the acid catalyst is
the hydronium ion.
Chloride via a Tetrahedral Intermediate
◾ 19.5 Reaction of an Ester with a Grignard HO
HOCH2
O
H
HO
HOCH2
O⫹
⫹ O H H ⫹ O H
Reagent HO
HO
H
H
⫹ HO
HO
H
H
◾ 21.1 Lithium Aluminum Hydride Reduction
OH OH
␣-D-Glucopyranose Hydronium ion Conjugate acid of Water
of an Amide ␣-D-glucopyranose

◾ 23.1 Acid-Catalyzed Mutarotation of Step 2: The pyranose ring opens by cleaving the bond between the anomeric carbon and the positively charged
oxygen. This ring opening is facilitated by electron release from the OH group at the anomeric carbon and
d-Glucopyranose gives the conjugate acid of the open-chain form of d-glucose.

◾ 23.2 Preparation of Methyl HO

HOCH2
O⫹ HO
HOCH2
O
H H
d-Glucopyranosides by Fischer Glycosidation HO H HO
CHœOH
⫹

HO HO
◾ 23.3 Silver-Assisted Glycosidation OH
Conjugate acid of Conjugate acid of open-chain
␣-D-glucopyranose form of D-glucose

Step 3: The species formed in the preceding step cyclizes to give the conjugate acid of ␤-d-glucopyranose. This
cyclization is analogous to the acid-catalyzed nucleophilic additions to aldehydes and ketones in Chapter 17.

HOCH2 HOCH2
HO O HO O⫹
H H
HO ⫹ HO OH
CHœOH
HO HO
H
Conjugate acid of open-chain Conjugate acid of
form of D-glucose ␤-D-glucopyranose

Step 4: The product of step 3 transfers a proton to water to regenerate the acid catalyst and yield the neutral form of
the product.

HOCH2 HOCH2 H
HO O
⫹ HO O ⫹
H ⫹ O H ⫹ O H
HO OH HO OH
HO H HO H
H H
Conjugate acid of Water ␤-D-Glucopyranose Hydronium ion
␤-D-glucopyranose
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Preface xxix

Supplementary Materials Nothing could be easier!

Accessed from the instructor side of your textbook’s website,
For the Instructor and Student: Presentation Center’s dynamic search engine allows you to
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The Presentation Center library includes thousands of assets
from many McGraw-Hill titles. This ever-growing resource Schaum’s Outline of Organic Chemistry
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Acknowledgments

It has been nearly five years since I received an email from New mass spectra were recorded and formatted by Anthony
Thomas Timp of McGraw-Hill inviting me to contribute Lagalante, who is also a faculty member in our department.
ideas for a new edition of the Carey textbook. Having been New NMR and IR spectra were recorded and formatted by
a Carey student in graduate school, I was thrilled to have Walter Boyko, our NMR Laboratory Director. Other members
the opportunity to work with Frank again. Textbook writ- of the Villanova community are also to be thanked for their
ing was completely new to my experience, but I have been support. I wish to mention particularly the staff of Villanova
fortunate to have the support of many talented individuals. I Graphics Services, and the staff of the Villanova Mailroom.
have worked most closely with Jodi Rhomberg, Developmen- The other new member of the Carey team is Professor
tal Editor II, who made my entry into this project as smooth Neil Allison, University of Arkansas, who is the author of
as possible and was extremely patient in dealing with a new the Student Solutions Manual. I wish to thank Neil and
author. The other individuals from McGraw-Hill that I wish his predecessor, Professor Robert Atkins, James Madison
to thank are Tami Hodge, Senior Sponsoring Editor, Ryan University, for their work on this excellent resource.
Blankenship, Publisher, Thomas Timp, Marketing Director, I remain indebted to my teachers and mentors in organic
Tammy Ben, Editorial Assistant, Todd Turner, Chemistry chemistry, to whom I am deeply grateful, especially Frank
Marketing Manager, and finally, Larissa Youshock, the Sales Carey, Bert Fraser-Reid, and the senior faculty in organic
Representative for the region that includes Villanova. Revis- chemistry at Villanova who guided my development as a
ing a textbook has turned out to be a much larger undertaking teacher and researcher. Hopefully, they would recognize
than I had imagined. The encouragement that I have received the results of that guidance at many places in this edition.
from these individuals has helped sustain my efforts through- Frank’s skill in solving problems in textbook writing was
out the entire process. just as invaluable as his direction of my research when I
I have benefitted from the support of the faculty, staff, and was a student in his laboratory. Finally, I wish to thank my
students of the Chemistry Department of Villanova University, family, especially my wife Margot, and children Michael,
in particular, my organic chemist colleagues, Joseph Bausch, Ellen, and Christopher. The end-of-chapter problem on native
Eduard Casillas, and Brian Ohta. The calculation of the electro- chemical ligation in chapter 25 is based on a discussion I had
static potential map of digitoxigenin that is part of the opener with Michael, who is a doctoral student in chemistry at the
for chapter 24 was carried out by Brian Ohta. The synthesis of University of Wisconsin–Madison. I also wish to thank my
the aromatase inhibitor that is included in the new boxed essay parents, William and Edith, and my brother, William Jr., all
on chalcones in chapter 20 is from research carried out by Ed of whom were with me at the time I began working on this
Casillas and his students. Joe Bausch was the accuracy checker project. I am grateful to all of you.
for this edition, and contributed many ideas during the revision.
Robert Giuliano

Reviewers
Hundreds of teachers of organic chemistry have reviewed David Berkowitz, University of Nebraska, Lincoln
Organic Chemistry in its various editions. Those listed below Chad Booth, Texas State University
are the most recent. Ned Bowden, University of Iowa
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xxx
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Acknowledgments xxxi

Peter de Lijser, California State University-Fullerton David R. Mootoo, Hunter College/City University of New York
Andrew P. Dicks, University of Toronto Harry Morrison, Purdue University
Matthew R. Dintzner, DePaul University Richard W. Morrison, University of Georgia
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Norma Dunlap, Middle Tennessee State University Felix N. Ngassa, Grand Valley State University
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Lee Friedman, University of Maryland, College Park Jon R. Parquette, Ohio State University
Charles M. Garner, Baylor University Michael W. Rathke, Michigan State University
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Kenn Harding, Texas A & M University Raymond Sadeghi, University of Texas, San Francisco
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Paul Higgs, University of Tennessee at Martin Joe C. Saunders, Concord University
Edwin Hillinski, Florida State University James Schreck, University of Northern Colorado
Michael T. Huggins, University of West Florida Alexander J. Seed, Kent State University
Colleen S. Kaczmarek, Connecticut College Grigoriy Sereda, University of South Dakota
Bob Kane, Baylor University Irina P. Smoliakova, University of North Dakota
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Steven Kass, University of Minnesota David Spurgeon, University of Arizona
Robert Kerber, Stony Brook University Chad Stearman, Missouri State University
Rebecca M. Kissling, Binghamton University Daniela Tapu, Kennesaw State University
Spencer Knapp, Rutgers University Kevin Walker, Michigan State University
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Michael Kurz, University of Texas, San Antonio James K. Whitesell, University of California, San Diego
Kenneth Laali, Kent State University Ron Wikholm, University of Connecticut
Chunmei Li, Stephen F. Austin State University Jane E. Wissinger, University of Minnesota
Todd Lowary, The University of Alberta Laurie A. Witucki, Grand Valley State University
Cecilia H. Marzabadi, Seton Hall University Evelyn A. Wolfe, St. Francis College
Jeremy E. B. McCallum, Loyola Marymount University Catherine Woytowicz, The George Washington University
Kevin P. C. Minbiole, James Madison University David G. J. Young, East Tennessee State University
Neil Miranda, University of Illinois at Chicago Viktor V. Zhdankin, University of Minnesota Duluth
Miguel O. Mitchell, Salisbury University
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car02613_fm_i-xxxiii.indd Page 1 11/25/09 7:38:52 PM elhi3 /Users/elhi3/Documents/Smart Connection/InDesign/41332

Organic Chemistry
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1 Structure Determines
Properties

Chapter Outline
Ch O li
1.1 Atoms, Electrons, and Orbitals 3
1.2 Ionic Bonds 6
1.3 Covalent Bonds, Lewis Structures, and the Octet Rule 8
1.4 Double Bonds and Triple Bonds 10
1.5 Polar Covalent Bonds, Electronegativity, and Bond Dipoles 11
◾ Electrostatic Potential Maps 13
1.6 Formal Charge 13
1.7 Structural Formulas of Organic Molecules 16
1.8 Resonance 19
1.9 Writing Organic Structures 23
1.10 The Shapes of Some Simple Molecules 26
◾ Molecular Modeling 26
1.11 Molecular Dipole Moments 28
1.12 Curved Arrows and Chemical Reactions 29
1.13 Acids and Bases: The Arrhenius View 32
1.14 Acids and Bases: The Brønsted–Lowry View 33
1.15 What Happened to pKb? 37
1.16 How Structure Affects Acid Strength 38
1.17 Acid–Base Equilibria 42
1.18 Lewis Acids and Lewis Bases 45
1.19 Summary 46
Problems 49
Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures 55

2
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Although function
dictates form in the
things we build,
structure determines
properties in
molecules.

STRUCTURE* is the key to everything in chemistry. The properties of a substance

nce
depend on the atoms it contains and the way these atoms are connected. What is less ess
obvious, but very powerful, is the idea that someone who is trained in chemistry can
his
look at the structural formula of a substance and tell you a lot about its properties. This
chapter begins your training toward understanding the relationship between structure and
properties in organic compounds. It reviews some fundamental principles of the Lewis wis
approach to molecular structure and bonding. By applying these principles, you will learn
to recognize structural patterns that are more stable than others and develop skills in
communicating structural information that will be used throughout your study of organic
chemistry. A key relationship between structure and properties will be introduced by
examining the fundamentals of acid–base chemistry from a structural perspective.

1.1 Atoms, Electrons, and Orbitals

Before discussing structure and bonding in molecules, let’s first review some fundamen-
tals of atomic structure. Each element is characterized by a unique atomic number Z,
which is equal to the number of protons in its nucleus. A neutral atom has equal numbers
of protons, which are positively charged, and electrons, which are negatively charged.
Electrons were believed to be particles from the time of their discovery in 1897
until 1924, when the French physicist Louis de Broglie suggested that they have wave-
like properties as well. Two years later Erwin Schrödinger took the next step and calcu-
lated the energy of an electron in a hydrogen atom by using equations that treated the
electron as if it were a wave. Instead of a single energy, Schrödinger obtained a series of
them, each of which corresponded to a different mathematical description of the electron
wave. These mathematical descriptions are called wave functions and are symbolized
by the Greek letter ␺ (psi).
According to the Heisenberg uncertainty principle, we can’t tell exactly where
an electron is, but we can tell where it is most likely to be. The probability of finding
an electron at a particular spot relative to an atom’s nucleus is given by the square of
the wave function (␺2) at that point. Figure 1.1 illustrates the probability of finding an
electron at various points in the lowest energy (most stable) state of a hydrogen atom.
The darker the color in a region, the higher the probability. The probability of finding an
electron at a particular point is greatest near the nucleus and decreases with increasing
distance from the nucleus but never becomes zero. We commonly describe Figure 1.1 as
an “electron cloud” to call attention to the spread-out nature of the electron probability.

*A glossary of the terms shown in boldface may be found immediately before the index at the back of the book.

3
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4 Chapter 1 Structure Determines Properties

z Be careful, though. The “electron cloud” of a hydrogen atom, although drawn as a col-
lection of many dots, represents only one electron.
Wave functions are also called orbitals. For convenience, chemists use the term
“orbital” in several different ways. A drawing such as Figure 1.1 is often said to repre-
x sent an orbital. We will see other kinds of drawings in this chapter, and use the word
“orbital” to describe them too.
y
Orbitals are described by specifying their size, shape, and directional properties.
Spherically symmetrical ones such as shown in Figure 1.1 are called s orbitals. The letter s
Figure 1.1 is preceded by the principal quantum number n (n  1, 2, 3, etc.), which specifies
the shell and is related to the energy of the orbital. An electron in a 1s orbital is likely
Probability distribution (2) for an
electron in a 1s orbital.
to be found closer to the nucleus, is lower in energy, and is more strongly held than an
electron in a 2s orbital.
Instead of probability distributions, it is more common to represent orbitals by their
boundary surfaces, as shown in Figure 1.2 for the 1s and 2s orbitals. The boundary
surface encloses the region where the probability of finding an electron is high—on the
order of 90–95%. Like the probability distribution plot from which it is derived, a picture
of a boundary surface is usually described as a drawing of an orbital.
A hydrogen atom (Z  1) has one electron; a helium atom (Z  2) has two. The
single electron of hydrogen occupies a 1s orbital, as do the two electrons of helium. We
write their electron configurations as:
Hydrogen: 1s1 Helium: 1s2
In addition to being negatively charged, electrons possess the property of spin. The
spin quantum number of an electron can have a value of either 2 or 2 . According
1 1

to the Pauli exclusion principle, two electrons may occupy the same orbital only when
they have opposite, or “paired,” spins. For this reason, no orbital can contain more than
two electrons. Because two electrons fill the 1s orbital, the third electron in lithium
(Z  3) must occupy an orbital of higher energy. After 1s, the next higher energy orbital
is 2s. The third electron in lithium therefore occupies the 2s orbital, and the electron
configuration of lithium is
Lithium: 1s22s1
A complete periodic table of the The period (or row) of the periodic table in which an element appears corresponds to
elements is presented on the inside the principal quantum number of the highest numbered occupied orbital (n  1 in the
back cover. case of hydrogen and helium). Hydrogen and helium are first-row elements; lithium
(n  2) is a second-row element.
With beryllium (Z  4), the 2s level becomes filled and, beginning with boron
(Z  5), the next orbitals to be occupied are 2px , 2py , and 2pz. These three orbitals (Fig-
Other methods are also used to ure 1.3) are of equal energy and are characterized by boundary surfaces that are usually
contrast the regions of an orbital where
the signs of the wave function are
described as “dumbell-shaped.” The axes of the three 2p orbitals are at right angles to
different. Some mark one lobe of a one another. Each orbital consists of two “lobes,” represented in Figure 1.3 by regions
p orbital  and the other . Others of different colors. Regions of a single orbital, in this case, each 2p orbital, may be
shade one lobe and leave the other separated by nodal surfaces where the wave function changes sign and the probability
blank. When this level of detail isn’t of finding an electron is zero.
necessary, no differentiation is made
between the two lobes.

Figure 1.2 z z

Boundary surfaces of a 1s orbital and

a 2s orbital. The boundary surfaces
enclose the volume where there is
a 90–95% probability of finding an x x
electron.

y
y

1s 2s
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1.1 Atoms, Electrons, and Orbitals 5

z z z

x x x

y y y
2 px 2 py 2 pz

Figure 1.3
Boundary surfaces of the 2p orbitals. The wave function changes sign at the nucleus. The two halves
of each orbital are indicated by different colors. The yz -plane is a nodal surface for the 2px orbital. The
probability of finding a 2px electron in the yz -plane is zero. Analogously, the xz -plane is a nodal surface for
the 2py orbital, and the xy -plane is a nodal surface for the 2pz orbital.

The electron configurations of the first 12 elements, hydrogen through magnesium,

are given in Table 1.1. In filling the 2p orbitals, notice that each is singly occupied
before any one is doubly occupied. This general principle for orbitals of equal energy
is known as Hund’s rule. Of particular importance in Table 1.1 are hydrogen, carbon,
nitrogen, and oxygen. Countless organic compounds contain nitrogen, oxygen, or both in
addition to carbon, the essential element of organic chemistry. Most of them also contain
hydrogen.
It is often convenient to speak of the valence electrons of an atom. These are the
outermost electrons, the ones most likely to be involved in chemical bonding and
reactions. For second-row elements these are the 2s and 2p electrons. Because four
orbitals (2s, 2px, 2py , 2pz) are involved, the maximum number of electrons in the valence
shell of any second-row element is 8. Neon, with all its 2s and 2p orbitals doubly
occupied, has eight valence electrons and completes the second row of the periodic table.
For main-group elements, the number of valence electrons is equal to its group number
in the periodic table.

TABLE 1.1 Electron Configurations of the First Twelve Elements

of the Periodic Table
Number of electrons in indicated orbital

Atomic
Element number Z 1s 2s 2px 2py 2pz 3s

Hydrogen 1 1

Helium 2 2

Lithium 3 2 1

Beryllium 4 2 2

Boron 5 2 2 1

Carbon 6 2 2 1 1

Nitrogen 7 2 2 1 1 1

Oxygen 8 2 2 2 1 1

Fluorine 9 2 2 2 2 1

Neon 10 2 2 2 2 2

Sodium 11 2 2 2 2 2 1

Magnesium 12 2 2 2 2 2 2
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6 Chapter 1 Structure Determines Properties

Detailed solutions to all of the Problem 1.1

problems are found in the Solutions
Manual along with a brief discussion How many electrons does carbon have? How many are valence electrons? What third-
and advice on how to do problems of row element has the same number of valence electrons as carbon?
the same type.

Once the 2s and 2p orbitals are filled, the next level is the 3s, followed by the 3px,
3py, and 3pz orbitals. Electrons in these orbitals are farther from the nucleus than those
in the 2s and 2p orbitals and are of higher energy.

In-chapter problems that contain Problem 1.2

multiple parts are accompanied by a
sample solution to part (a).
Referring to the periodic table as needed, write electron configurations for all the
elements in the third period.
Sample Solution The third period begins with sodium and ends with argon. The atomic
number Z of sodium is 11, and so a sodium atom has 11 electrons. The maximum number
of electrons in the 1s, 2s, and 2p orbitals is ten, and so the eleventh electron of sodium
occupies a 3s orbital. The electron configuration of sodium is 1s22s22px22py22pz23s1.

Neon, in the second period, and argon, in the third, have eight electrons in their valence
shell; they are said to have a complete octet of electrons. Helium, neon, and argon belong to
the class of elements known as noble gases or rare gases. The noble gases are characterized
by an extremely stable “closed-shell” electron configuration and are very unreactive.
Structure determines properties and the properties of atoms depend on atomic
structure. All of an element’s protons are in its nucleus, but the element’s electrons are
distributed among orbitals of various energy and distance from the nucleus. More than
anything else, we look at its electron configuration when we wish to understand how an
element behaves. The next section illustrates this with a brief review of ionic bonding.

1.2 Ionic Bonds

Atoms combine with one another to give compounds having properties different from
the atoms they contain. The attractive force between atoms in a compound is a chemical
bond. One type of chemical bond, called an ionic bond, is the force of attraction between
oppositely charged species (ions) (Figure 1.4). Positively charged ions are referred to as
cations; negatively charged ions are anions.
Whether an element is the source of the cation or anion in an ionic bond depends on
several factors, for which the periodic table can serve as a guide. In forming ionic com-
pounds, elements at the left of the periodic table typically lose electrons, giving a cation that
has the same electron configuration as the preceding noble gas. Loss of an electron from
sodium, for example, yields Na, which has the same electron configuration as neon.

Figure 1.4
An ionic bond is the force of attraction
between oppositely charged ions. Each
Na ion in the crystal lattice of solid
NaCl is involved in ionic bonding to each
of six surrounding Cl ions and vice
versa. The smaller balls are Na and the
larger balls are Cl.
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1.2 Ionic Bonds 7

Na(g) ±£ Na(g)  e
Sodium atom Sodium ion Electron
1s22s22p63s1 1s22s22p6
[The symbol (g) indicates that the species is present in the gas phase.]

Problem 1.3
Species that have the same number of electrons are described as isoelectronic. What
2 ion is isoelectronic with Na? What 2 ion?

A large amount of energy, called the ionization energy, must be transferred to any The SI (Système International d’Unites )
atom to dislodge an electron. The ionization energy of sodium, for example, is 496 kJ/mol unit of energy is the joule (J). An older
(119 kcal/mol). Processes that absorb energy are said to be endothermic. Compared unit is the calorie (cal). Many chemists
with other elements, sodium and its relatives in group 1A have relatively low ionization still express energy changes in units of
energies. In general, ionization energy increases across a row in the periodic table. kilocalories per mole (1 kcal/mol 
4.184 kJ/mol).
Elements at the right of the periodic table tend to gain electrons to reach the
electron configuration of the next higher noble gas. Adding an electron to chlorine, for
example, gives the anion Cl, which has the same closed-shell electron configuration as
the noble gas argon.

Cl(g)  e ±£ Cl(g)
Chlorine atom Electron Chloride ion
1s22s22p63s23p5 1s22s22p63s23p6

Problem 1.4
What 2 ion is isoelectronic with Cl?

Energy is released when a chlorine atom captures an electron. Energy-releasing

reactions are described as exothermic, and the energy change for an exothermic process
has a negative sign. The energy change for addition of an electron to an atom is referred
to as its electron affinity and is −349 kJ/mol (−83.4 kcal/mol) for chlorine.

Problem 1.5
Which of the following ions possess a noble gas electron configuration? Which ions are
isoelectronic?
(a) K (c) H (e) F
(b) He (d) O (f) Ca2
Sample Solution (a) Potassium has atomic number 19, and so a potassium atom
has 19 electrons. The ion K, therefore, has 18 electrons, the same as the noble gas
argon. The electron configurations of both K and Ar are 1s22s22p63s23p6. K and Ar
are isoelectronic.

Transfer of an electron from a sodium atom to a chlorine atom yields a sodium

cation and a chloride anion, both of which have a noble gas electron configuration:

Na(g)  Cl(g) ±£ NaCl(g)

Sodium atom Chlorine atom Sodium chloride

Were we to simply add the ionization energy of sodium (496 kJ/mol) and the electron
affinity of chlorine (349 kJ/mol), we would conclude that the overall process is endothermic
by 147 kJ/mol. The energy liberated by adding an electron to chlorine is insufficient to
override the energy required to remove an electron from sodium. This analysis, however,
fails to consider the force of attraction between the oppositely charged ions Na and Cl,
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8 Chapter 1 Structure Determines Properties

which exceeds 500 kJ/mol and is more than sufficient to make the overall process exo-
thermic. Attractive forces between oppositely charged particles are termed electrostatic, or
Ionic bonding was proposed by the coulombic, attractions and are what we mean by an ionic bond between two atoms.
German physicist Walther Kossel in
1916, in order to explain the ability of
substances such as molten sodium Problem 1.6
chloride to conduct an electric current. What is the electron configuration of C? Of C? Does either one of these ions have a
He was the son of Albrecht Kossel,
noble gas (closed-shell) electron configuration?
winner of the 1910 Nobel Prize in
physiology or medicine for early studies
in nucleic acids.
Ionic bonds are very common in inorganic compounds, but rare in organic ones.
The ionization energy of carbon is too large and the electron affinity too small for car-
bon to realistically form a C4 or C4 ion. What kinds of bonds, then, link carbon to
other elements in millions of organic compounds? Instead of losing or gaining electrons,
carbon shares electrons with other elements (including other carbon atoms) to give what
are called covalent bonds.

1.3 Covalent Bonds, Lewis Structures, and the Octet Rule

The covalent, or shared electron pair, model of chemical bonding was first suggested
Gilbert Newton Lewis (born Weymouth, by G. N. Lewis of the University of California in 1916. Lewis proposed that a sharing
Massachusetts, 1875; died Berkeley, of two electrons by two hydrogen atoms permits each one to have a stable closed-shell
California, 1946) has been called the electron configuration analogous to helium.
greatest American chemist.

H H HH
Two hydrogen atoms, Hydrogen molecule:
each with a single covalent bonding by way of
electron a shared electron pair

Structural formulas of this type in which electrons are represented as dots are called
Lewis structures. It is customary to represent a shared electron-pair bond by a dash
(O). Thus, H:H becomes HOH.
The amount of energy required to dissociate a hydrogen molecule H2 to two separate
hydrogen atoms is its bond dissociation enthalpy. For H2 it is quite large, amounting to
435 kJ/mol (104 kcal/mol). The main contributor to the strength of the covalent bond in
H2 is the increased binding force exerted on its two electrons. Each electron in H2 “feels” the
attractive force of two nuclei, rather than one as it would in an isolated hydrogen atom.
Only the electrons in an atom’s valence shell are involved in covalent bonding.
Fluorine, for example, has nine electrons, but only seven are in its valence shell. Pairing
a valence electron of one fluorine atom with one of a second fluorine gives a fluorine
molecule (F2) in which each fluorine has eight valence electrons and an electron configu-
ration equivalent to that of the noble gas neon. Shared electrons count toward satisfying
the octet of both atoms.

F F F F

Two fluorine atoms, each Fluorine molecule:

with seven electrons in covalent bonding by way of
its valence shell a shared electron pair

The six valence electrons of each fluorine that are not involved in bonding comprise
Unshared pairs are also called lone three unshared pairs.
pairs.
The Lewis model limits second-row elements (Li, Be, B, C, N, O, F, Ne) to a total
of eight electrons (shared plus unshared) in their valence shells. Hydrogen is limited
to two. Most of the elements that we’ll encounter in this text obey the octet rule: In
forming compounds they gain, lose, or share electrons to achieve a stable electron
configuration characterized by eight valence electrons. When the octet rule is satisfied
for carbon, nitrogen, oxygen, and fluorine, each has an electron configuration analogous
to the noble gas neon. The Lewis structures of methane (CH4), ammonia (NH3), water
(H2O), and hydrogen fluoride (HF) given in Table 1.2 illustrate the octet rule.
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1.3 Covalent Bonds, Lewis Structures, and the Octet Rule 9

With four valence electrons, carbon normally forms four covalent bonds as shown
in Table 1.2 for CH4. In addition to COH bonds, most organic compounds contain
covalent COC bonds. Ethane (C2H6) is an example.

H H
P P H H
Combine two R R to write a HH A A
carbons and HTTCT TCTTH Lewis structure H C C H or HOCOCOH
six hydrogens P P for ethane HH A A
R R H H
H H

Problem 1.7
Write Lewis structures, including unshared pairs, for each of the following. Carbon has
four bonds in each compound.
(a) Propane (C3H8) (c) Methyl fluoride (CH3F)
(b) Methanol (CH4O) (d) Ethyl fluoride (C2H5F)
Sample Solution (a) The Lewis structure of propane is analogous to that of ethane
but the chain is three carbons long instead of two.
H H H
Combine three P
R P
R P
R
carbons and HT TCT TCT TCT TH
eight hydrogens P
R P
R P
R
H H H

H H H
to write a HHH A A A
Lewis structure HCCCH or HOCOCOCOH
for propane HHH A A A
H H H

The ten covalent bonds in the Lewis structure shown account for 20 valence electrons,
which is the same as that calculated from the molecular formula (C3H8). The eight
hydrogens of C3H8 contribute 1 electron each and the three carbons 4 each, for a
total of 20 (8 from the hydrogens and 12 from the carbons). Therefore, all the valence
electrons are in covalent bonds; propane has no unshared pairs.
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10 Chapter 1 Structure Determines Properties

1.4 Double Bonds and Triple Bonds

Lewis’s concept of shared electron pair bonds allows for four-electron double bonds
and six-electron triple bonds. Ethylene (C2H4) has 12 valence electrons, which can be
distributed as follows:
H H
P P
Combine two carbons R R HH
and four hydrogens TCT TCT to write C C
P P HH
R R
H H

The structural formula produced has a single bond between the carbons and seven electrons
around each. By pairing the unshared electron of one carbon with its counterpart of the other
carbon, a double bond results and the octet rule is satisfied for both carbons.

H H H H
HH

±
±
C C to give C C or CœC

±
HH H H H H

Share these two electrons

between both carbons

Likewise, the ten valence electrons of acetylene (C2H2) can be arranged in a struc-
tural formula that satisfies the octet rule when six of them are shared in a triple bond
between the carbons.
H C C H or HOC COH
Carbon dioxide (CO2) has two carbon–oxygen double bonds, thus satisfying the
octet rule for both carbon and oxygen.

O C O or OœCœO

Problem 1.8
All of the hydrogens are bonded to carbon in both of the following. Write a Lewis
structure that satisfies the octet rule for each.
(a) Formaldehyde (CH2O) (b) Hydrogen cyanide (HCN)
Sample Solution (a) Formaldehyde has 12 valence electrons; 4 from carbon,
2 from two hydrogens, and 6 from oxygen. Connect carbon to oxygen and both
hydrogens by covalent bonds.

H
P
R H
Combine C O to give CO
P H
R
H
Pair the unpaired electron on carbon with the unpaired electron on oxygen to give a
carbon–oxygen double bond. The resulting structural formula satisfies the octet rule.
H
H H
CO to give C O or C O
H H
H

Share these two electrons

between carbon and oxygen
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1.5 Polar Covalent Bonds, Electronegativity, and Bond Dipoles 11

1.5 Polar Covalent Bonds, Electronegativity,

and Bond Dipoles
Electrons in covalent bonds are not necessarily shared equally by the two atoms that they con-
nect. If one atom has a greater tendency to attract electrons toward itself than the other, the
electron distribution is polarized, and the bond is described as polar covalent. The tendency of
an atom to attract the electrons in a covalent bond toward itself defines its electronegativity.
An electronegative element attracts electrons; an electropositive one donates them.
Hydrogen fluoride, for example, has a polar covalent bond. Fluorine is more elec-
tronegative than hydrogen and pulls the electrons in the HOF bond toward itself, giving
fluorine a partial negative charge and hydrogen a partial positive charge. Two ways of
representing the polarization in HF are:

H±F  H±F
(The symbols  and  (The symbol represents
indicate partial positive the direction of polarization
and partial negative of electrons in the H±F bond)
charge, respectively)

A third way of illustrating the electron polarization in HF is graphically, by way of an

electrostatic potential map, which uses the colors of the rainbow to show the charge distri-
bution. Blue through red tracks regions of greater positive charge to greater negative charge.
(For more details, see the boxed essay Electrostatic Potential Maps in this section.)

Positively charged Negatively charged

region of molecule region of molecule

Contrast the electrostatic potential map of HF with those of H2 and F2.

H—H + H—F – F—F

The covalent bond in H2 joins two hydrogen atoms. Because the bonded atoms are identi-
cal, so are their electronegativities. There is no polarization of the electron distribution,
the HOH bond is nonpolar, and a neutral yellow-green color dominates the electrostatic
potential map. Likewise, the FOF bond in F2 is nonpolar and its electrostatic potential Linus Pauling (1901–1994) was born
map resembles that of H2. The covalent bond in HF, on the other hand, unites two atoms in Portland, Oregon, and was educated
at Oregon State University and at the
of different electronegativity, and the electron distribution is very polarized. Blue is the
California Institute of Technology,
dominant color near the positively polarized hydrogen, and red the dominant color near where he earned a Ph.D. in chemistry
the negatively polarized fluorine. in 1925. In addition to research in
The most commonly used electronegativity scale was devised by Linus Pauling. bonding theory, Pauling studied the
Table 1.3 keys Pauling’s electronegativity values to the periodic table. structure of proteins and was awarded
the Nobel Prize in Chemistry for that
Electronegativity increases from left to right across a row in the periodic table. Of
work in 1954. Pauling won a second
the second-row elements, the most electronegative is fluorine, the least electronegative Nobel Prize (the Peace Prize) in 1962
is lithium. Electronegativity decreases going down a column. Of the halogens, fluorine for his efforts to limit the testing of
is the most electronegative, then chlorine, then bromine, then iodine. Indeed, fluorine is nuclear weapons. He was one of only
the most electronegative of all the elements; oxygen is second. four scientists to have won two Nobel
Prizes. The first double winner was a
In general, the greater the electronegativity difference between two elements, the
woman. Can you name her?
more polar the bond between them.
car02613_ch01_002-055.indd Page 12 10/26/09 9:30:47 AM user-s131

12 Chapter 1 Structure Determines Properties

Problem 1.9
In which of the compounds CH4, NH3, H2O, SiH4, or H2S is  for hydrogen the
greatest? In which one does hydrogen bear a partial negative charge?

Table 1.4 compares the polarity of various bond types according to their bond
dipole moments. A dipole exists whenever opposite charges are separated from each
other, and a dipole moment μ is the product of the amount of the charge e multiplied
by the distance d between the centers of charge.
ed
Because the charge on an electron is 4.80  1010 electrostatic units (esu) and the dis-
tances within a molecule typically fall in the 108 cm range, molecular dipole moments
are on the order of 1018 esucm. To simplify the reporting of dipole moments, this value
The debye unit is named in honor of of 1018 esucm is defined as a debye, D. Thus the experimentally determined dipole
Peter Debye, a Dutch scientist who moment of hydrogen fluoride, 1.7  1018 esu·cm is stated as 1.7 D.
did important work in many areas of The bond dipoles in Table 1.4 depend on the difference in electronegativity of the
chemistry and physics and was
awarded the Nobel Prize in Chemistry
bonded atoms and on the bond distance. The polarity of a COH bond is relatively low;
in 1936. substantially less than a COO bond, for example. Don’t lose sight of an even more
important difference between a COH bond and a COO bond, and that is the direction

*The direction of the dipole moment is toward the more electronegative atom. In the listed examples hydrogen and
carbon are the positive ends of the dipoles. Carbon is the negative end of the dipole associated with the C—H bond.
Exploring the Variety of Random
Documents with Different Content
General Lee’s rear, and will go by Camden and Lancaster, leaving Lincolnton
on their west flank.
The McLeans are kind people. They ask no rent for their rooms—only $20 a
week for firewood. Twenty dollars! and such dollars—mere waste paper.
Mrs. Munroe took up my photograph book, in which I have a picture of all
the Yankee generals. “I want to see the men who are to be our masters,” said
she. “Not mine” I answered, “thank God, come what may. This was a free
fight. We had as much right to fight to get out as they had to fight to keep us
in. If they try to play the masters, anywhere upon the habitable globe will I
go, never to see a Yankee, and if I die on the way so much the better.” Then I
sat down and wrote to my husband in language much worse than anything I
can put in this book. As I wrote I was blinded by tears of rage. Indeed, I
nearly wept myself away.
February 26th.—Mrs. Munroe offered me religious books, which I declined,
being already provided with the Lamentations of Jeremiah, the Psalms of
David, the denunciations of Hosea, and, above all, the patient wail of Job. Job
is my comforter now. I should be so thankful to know life never would be any
worse with me. My husband is well, and has been ordered to join the great
Retreater. I am bodily comfortable, if somewhat dingily lodged, and I daily
part with my raiment for food. We find no one who will exchange eatables for
Confederate money; so we are devouring our clothes.
Opportunities for social enjoyment are not wanting. Miss Middleton and
Isabella often drink a cup of tea with me. One might search the whole world
and not find two cleverer or more agreeable women. Miss Middleton is brilliant
and accomplished. She must have been a hard student all her life. She knows
everybody worth knowing, and she has been everywhere. Then she is so
high-bred, high-hearted, pure, and true. She is so clean-minded; she could
not harbor a wrong thought. She is utterly unselfish, a devoted daughter and
sister. She is one among the many large-brained women a kind Providence
has thrown in my way, such as Mrs. McCord, daughter of Judge Cheves; Mary
Preston Darby, Mrs. Emory, granddaughter of old Franklin, the American wise
man, and Mrs. Jefferson Davis. How I love to praise my friends!
As a ray of artificial sunshine, Mrs. Munroe sent me an Examiner. Daniel
thinks we are at the last gasp, and now England and France are bound to step
in. England must know if the United States of America are triumphant they
will tackle her next, and France must wonder if she will not have to give up
Mexico. My faith fails me. It is all too late; no help for us now from God or
man.
 Thomas, Daniel says, was now to ravage Georgia, but Sherman, from all
accounts, has done that work once for all. There will be no aftermath. They
say no living thing is found in Sherman’s track, only chimneys, like telegraph
poles, to carry the news of Sherman’s army backward.
In all that tropical down-pour, Mrs. Munroe sent me overshoes and an
umbrella, with the message, “Come over.” I went, for it would be as well to
drown in the streets as to hang myself at home to my own bedpost. At Mrs.
Munroe’s I met a Miss McDaniel. Her father, for seven years, was the
Methodist preacher at our negro church. The negro church is in a grove just
opposite Mulberry house. She says her father has so often described that fine
old establishment and its beautiful lawn, live-oaks, etc. Now, I dare say there
stand at Mulberry only Sherman’s sentinels—stacks of chimneys. We have
made up our minds for the worst. Mulberry house is no doubt razed to the
ground.
Miss McDaniel was inclined to praise us. She said: “As a general rule the
Episcopal minister went to the family mansion, and the Methodist missionary
preached to the negroes and dined with the overseer at his house, but at
Mulberry her father always stayed at the ‘House,’ and the family were so kind
and attentive to him.” It was rather pleasant to hear one’s family so spoken of
among strangers.
So, well equipped to brave the weather, armed cap-a-pie, so to speak, I
continued my prowl farther afield and brought up at the Middletons’. I may
have surprised them, for “at such an inclement season” they hardly expected
a visitor. Never, however, did lonely old woman receive such a warm and
hearty welcome. Now we know the worst. Are we growing hardened? We
avoid all allusion to Columbia; we never speak of home, and we begin to
deride the certain poverty that lies ahead.
How it pours! Could I live many days in solitary confinement? Things are
beginning to be unbearable, but I must sit down and be satisfied. My husband
is safe so far. Let me be thankful it is no worse with me. But there is the
gnawing pain all the same. What is the good of being here at all? Our world
has simply gone to destruction. And across the way the fair Lydia languishes.
She has not even my resources against ennui. She has no Isabella, no Miss
Middleton, two as brilliant women as any in Christendom. Oh, how does she
stand it! I mean to go to church if it rains cats and dogs. My feet are wet two
or three times a day. We never take cold; our hearts are too hot within us for
that.
 A carriage was driven up to the door as I was writing. I began to tie on my
bonnet, and said to myself in the glass, “Oh, you lucky woman!” I was all in a
tremble, so great was my haste to be out of this. Mrs. Glover had the
carriage. She came for me to go and hear Mr. Martin preach. He lifts our
spirits from this dull earth; he takes us up to heaven. That I will not deny. Still
he can not hold my attention; my heart wanders and my mind strays back to
South Carolina. Oh, vandal Sherman! what are you at there, hard-hearted
wretch that you are! A letter from General Chesnut, who writes from camp
near Charlotte under date of February 28th:
“I thank you a thousand, thousand times for your kind letters. They are
now my only earthly comfort, except the hope that all is not yet lost. We have
been driven like a wild herd from our country. And it is not from a want of
spirit in the people or soldiers, nor from want of energy and competency in
our commanders. The restoration of Joe Johnston, it is hoped, will redound to
the advantage of our cause and the reestablishment of our fortunes! I am still
in not very agreeable circumstances. For the last four days completely water-
bound.
“I am informed that a detachment of Yankees were sent from Liberty Hill to
Camden with a view to destroying all the houses, mills, and provisions about
that place. No particulars have reached me. You know I expected the worst
that could be done, and am fully prepared for any report which may be made.
“It would be a happiness beyond expression to see you even for an hour. I
have heard nothing from my poor old father. I fear I shall never see him
again. Such is the fate of war. I do not complain. I have deliberately chosen
my lot, and am prepared for any fate that awaits me. My care is for you, and I
trust still in the good cause of my country and the justice and mercy of Cod.”
It was a lively, rushing, young set that South Carolina put to the fore. They
knew it was a time of imminent danger, and that the fight would be ten to
one. They expected to win by activity, energy, and enthusiasm. Then came
the wet blanket, the croakers; now, these are posing, wrapping Cæsar’s
mantle about their heads to fall with dignity. Those gallant youths who dashed
so gaily to the front lie mostly in bloody graves. Well for them, maybe. There
are worse things than honorable graves. Wearisome thoughts. Late in life we
are to begin anew and have laborious, difficult days ahead.
We have contradictory testimony. Governor Aiken has passed through,
saying Sherman left Columbia as he found it, and was last heard from at
Cheraw. Dr. Chisolm walked home with me. He says that is the last version of
the story. Now my husband wrote that he himself saw the fires which burned
up Columbia. The first night his camp was near enough to the town for that.
They say Sherman has burned Lancaster—that Sherman nightmare, that
ghoul, that hyena! But I do not believe it. He takes his time. There are none
to molest him. He does things leisurely and deliberately. Why stop to do so
needless a thing as burn Lancaster court-house, the jail, and the tavern? As I
remember it, that description covers Lancaster. A raiding party they say did
for Camden.
No train from Charlotte yesterday. Rumor says Sherman is in Charlotte.
February 29th.—Trying to brave it out. They have plenty, yet let our men
freeze and starve in their prisons. Would you be willing to be as wicked as
they are? A thousand times, no! But we must feed our army first—if we can
do so much as that. Our captives need not starve if Lincoln would consent to
exchange prisoners; but men are nothing to the United States—things to
throw away. If they send our men back they strengthen our army, and so
again their policy is to keep everybody and everything here in order to help
starve us out. That, too, is what Sherman’s destruction means—to starve us
out.
Young Brevard asked me to play accompaniments for him. The guitar is my
instrument, or was; so I sang and played, to my own great delight. It was a
distraction. Then I made egg-nog for the soldier boys below and came home.
Have spent a very pleasant evening. Begone, dull care; you and I never
agree.
Ellen and I are shut up here. It is rain, rain, everlasting rain. As our money
is worthless, are we not to starve? Heavens! how grateful I was to-day when
Mrs. McLean sent me a piece of chicken. I think the emptiness of my larder
has leaked out. To-day Mrs. Munroe sent me hot cakes and eggs for my
breakfast.
March 5th.—Is the sea drying up? Is it going up into mist and coming down
on us in a water-spout? The rain, it raineth every day. The weather typifies
our tearful despair, on a large scale. It is also Lent now—a quite convenient
custom, for we, in truth, have nothing to eat. So we fast and pray, and go
dragging to church like drowned rats to be preached at.
My letter from my husband was so—well, what in a woman you would call
heart-broken, that I began to get ready for a run up to Charlotte. My hat was
on my head, my traveling-bag in my hand, and Ellen was saying “Which
umbrella, ma’am?” “Stop, Ellen,” said I, “someone is speaking out there.” A
tap came at the door, and Miss McLean threw the door wide open as she said
in a triumphant voice: “Permit me to announce General Chesnut.” As she went
off she sang out, “Oh, does not a meeting like this make amends?”
We went after luncheon to see Mrs. Munroe. My husband wanted to thank
her for all her kindness to me. I was awfully proud of him. I used to think that
everybody had the air and manners of a gentleman. I know now that these
accomplishments are things to thank God for. Father O’Connell came in, fresh
from Columbia, and with news at last. Sherman’s men had burned the
convent. Mrs. Munroe had pinned her faith to Sherman because he was a
Roman Catholic, but Father O’Connell was there and saw it. The nuns and
girls marched to the old Hampton house (Mrs. Preston’s now), and so saved
it. They walked between files of soldiers. Men were rolling tar barrels and
lighting torches to fling on the house when the nuns came. Columbia is but
dust and ashes, burned to the ground. Men, women, and children have been
left there homeless, houseless, and without one particle of food—reduced to
picking up corn that was left by Sherman’s horses on picket grounds and
parching it to stay their hunger.
How kind my friends were on this, my fête day! Mrs. Rutledge sent me a
plate of biscuit; Mrs. Munroe, nearly enough food supplies for an entire
dinner; Miss McLean a cake for dessert. Ellen cooked and served up the
material happily at hand very nicely, indeed. There never was a more
successful dinner. My heart was too full to eat, but I was quiet and calm; at
least I spared my husband the trial of a broken voice and tears. As he stood
at the window, with his back to the room, he said: “Where are they now—my
old blind father and my sister? Day and night I see her leading him out from
under his own rooftree. That picture pursues me persistently. But come, let us
talk of pleasanter things.” To which I answered, “Where will you find them?”
He took off his heavy cavalry boots and Ellen carried them away to wash
the mud off and dry them. She brought them back just as Miss Middleton
walked in. In his agony, while struggling with those huge boots and trying to
get them on, he spoke to her volubly in French. She turned away from him
instantly, as she saw his shoeless plight, and said to me, “I had not heard of
your happiness. I did not know the General was here.” Not until next day did
we have time to remember and laugh at that outbreak of French. Miss
Middleton answered him in the same language. He told her how charmed he
was with my surroundings, and that he would go away with a much lighter
heart since he had seen the kind people with whom he would leave me.
I asked my husband what that correspondence between Sherman and
Hampton meant—this while I was preparing something for our dinner. His
back was still turned as he gazed out of the window. He spoke in the low and
steady monotone that characterized our conversation the whole day, and yet
there was something in his voice that thrilled me as he said: “The second day
after our march from Columbia we passed the M.’s. He was a bonded man and
not at home. His wife said at first that she could not find forage for our
horses, but afterward she succeeded in procuring some. I noticed a very
handsome girl who stood beside her as she spoke, and I suggested to her
mother the propriety of sending her out of the track of both armies. Things
were no longer as heretofore; there was so much straggling, so many camp
followers, with no discipline, on the outskirts of the army. The girl answered
quickly, ‘I wish to stay with my mother.’ That very night a party of Wheeler’s
men came to our camp, and such a tale they told of what had been done at
the place of horror and destruction, the mother left raving. The outrage had
been committed before her very face, she having been secured first. After this
crime the fiends moved on. There were only seven of them. They had been
gone but a short time when Wheeler’s men went in pursuit at full speed and
overtook them, cut their throats and wrote upon their breasts: ‘These were
the seven!’”
“But the girl?”
“Oh, she was dead!”
“Are his critics as violent as ever against the President?” asked I when
recovered from pity and horror. “Sometimes I think I am the only friend he
has in the world. At these dinners, which they give us everywhere, I spoil the
sport, for I will not sit still and hear Jeff Davis abused for things he is no more
responsible for than any man at that table. Once I lost my temper and told
them it sounded like arrant nonsense to me, and that Jeff Davis was a
gentleman and a patriot, with more brains than the assembled company.”
“You lost your temper truly,” said I. “And I did not know it. I thought I was as
cool as I am now. In Washington when we left, Jeff Davis ranked second to
none, in intellect, and may be first, from the South, and Mrs. Davis was the
friend of Mrs. Emory, Mrs. Joe Johnston, and Mrs. Montgomery Blair, and
others of that circle. Now they rave that he is nobody, and never was.” “And
she?” I asked. “Oh, you would think to hear them that he found her yesterday
in a Mississippi swamp!” “Well, in the French Revolution it was worse. When a
man failed he was guillotined. Mirabeau did not die a day too soon, even
Mirabeau.”
He is gone. With despair in my heart I left that railroad station. Allan Green
walked home with me. I met his wife and his four ragged little boys a day or
so ago. She is the neatest, the primmest, the softest of women. Her voice is
like the gentle cooing of a dove. That lowering black future hangs there all the
same. The end of the war brings no hope of peace or of security to us. Ellen
said I had a little piece of bread and a little molasses in store for my dinner
to-day.
March 6th.—To-day came a godsend. Even a small piece of bread and the
molasses had become things of the past. My larder was empty, when a tall
mulatto woman brought a tray covered by a huge white serviette. Ellen
ushered her in with a flourish, saying, “Mrs. McDaniel’s maid.” The maid set
down the tray upon my bare table, and uncovered it with conscious pride.
There were fowls ready for roasting, sausages, butter, bread, eggs, and
preserves. I was dumb with delight. After silent thanks to heaven my powers
of speech returned, and I exhausted myself in messages of gratitude to Mrs.
McDaniel.
“Missis, you oughtn’t to let her see how glad you was,” said Ellen. “It was a
lettin’ of yo’sef down.”
Mrs. Glover gave me some yarn, and I bought five dozen eggs with it from
a wagon—eggs for Lent. To show that I have faith yet in humanity, I paid in
advance in yarn for something to eat, which they promised to bring to-
morrow. Had they rated their eggs at $100 a dozen in “Confederick” money, I
would have paid it as readily as $10. But I haggle in yarn for the millionth part
of a thread.
Two weeks have passed and the rumors from Columbia are still of the
vaguest. No letter has come from there, no direct message, or messenger.
“My God!” cried Dr. Frank Miles, “but it is strange. Can it be anything so
dreadful they dare not tell us?” Dr. St. Julien Ravenel has grown pale and
haggard with care. His wife and children were left there.
Dr. Brumby has at last been coaxed into selling me enough leather for the
making of a pair of shoes, else I should have had to give up walking. He knew
my father well. He intimated that in some way my father helped him through
college. His own money had not sufficed, and so William C. Preston and my
father advanced funds sufficient to let him be graduated. Then my uncle,
Charles Miller, married his aunt. I listened in rapture, for all this tended to
leniency in the leather business, and I bore off the leather gladly. When asked
for Confederate money in trade I never stop to bargain. I give them $20 or
$50 cheerfully for anything—either sum.
March 8th.—Colonel Childs came with a letter from my husband and a
newspaper containing a full account of Sherman’s cold-blooded brutality in
Columbia. Then we walked three miles to return the call of my benefactress,
Mrs. McDaniel. They were kind and hospitable at her house, but my heart was
like lead; my head ached, and my legs were worse than my head, and then I
had a nervous chill. So I came home, went to bed and stayed there until the
Fants brought me a letter saying my husband would be here to-day. Then I
got up and made ready to give him a cheerful reception. Soon a man called,
Troy by name, the same who kept the little corner shop so near my house in
Columbia, and of whom we bought things so often. We had fraternized. He
now shook hands with me and looked in my face pitifully. We seemed to have
been friends all our lives. He says they stopped the fire at the Methodist
College, perhaps to save old Mr. McCartha’s house. Mr. Sheriff Dent, being
burned out, took refuge in our house. He contrived to find favor in Yankee
eyes. Troy relates that a Yankee officer snatched a watch from Mrs. McCord’s
bosom. The soldiers tore the bundles of clothes that the poor wretches tried
to save from their burning homes, and dashed them back into the flames.
They meant to make a clean sweep. They were howling round the fires like
demons, these Yankees in their joy and triumph at our destruction. Well, we
have given them a big scare and kept them miserable for four years—the little
handful of us.
A woman we met on the street stopped to tell us a painful coincidence. A
general was married but he could not stay at home very long after the
wedding. When his baby was born they telegraphed him, and he sent back a
rejoicing answer with an inquiry, “Is it a boy or a girl?” He was killed before he
got the reply. Was it not sad? His poor young wife says, “He did not live to
hear that his son lived.” The kind woman added, sorrowfully, “Died and did
not know the sect of his child.” “Let us hope it will be a Methodist,” said
Isabella, the irrepressible.
At the venison feast Isabella heard a good word for me and one for General
Chesnut’s air of distinction, a thing people can not give themselves, try as
ever they may. Lord Byron says, Everybody knows a gentleman when he sees
one, and nobody can tell what it is that makes a gentleman. He knows the
thing, but he can’t describe it. Now there are some French words that can not
be translated, and we all know the thing they mean—gracieuse and svelte, for
instance, as applied to a woman. Not that anything was said of me like that—
far from it. I am fair, fat, forty, and jolly, and in my unbroken jollity, as far as
they know, they found my charm. “You see, she doesn’t howl; she doesn’t
cry; she never, never tells anybody about what she was used to at home and
what she has lost.” High praise, and I intend to try and deserve it ever after.
March 10th.—Went to church crying to Ellen, “It is Lent, we must fast and
pray.” When I came home my good fairy, Colonel Childs, had been here
bringing rice and potatoes, and promising flour. He is a trump. He pulled out
his pocket-book and offered to be my banker. He stood there on the street,
Miss Middleton and Isabella witnessing the generous action, and straight out
offered me money. “No, put up that,” said I. “I am not a beggar, and I never
will be; to die is so much easier.”
Alas, after that flourish of trumpets, when he came with a sack of flour, I
accepted it gratefully. I receive things I can not pay for, but money is
different. There I draw a line, imaginary perhaps. Once before the same thing
happened. Our letters of credit came slowly in 1845, when we went
unexpectedly to Europe and our letters were to follow us. I was a poor little,
inoffensive bride, and a British officer, who guessed our embarrassment, for
we did not tell him (he came over with us on the ship), asked my husband to
draw on his banker until the letters of credit should arrive. It was a nice thing
for a stranger to do.
We have never lost what we never had. We have never had any money—
only unlimited credit, for my husband’s richest kind of a father insured us all
manner of credit. It was all a mirage only at last, and it has gone just as we
drew nigh to it.
Colonel Childs says eight of our Senators are for reconstruction, and that a
ray of light has penetrated inward from Lincoln, who told Judge Campbell that
Southern land would not be confiscated.
March 12th.—Better to-day. A long, long weary day in grief has passed
away. I suppose General Chesnut is somewhere—but where? that is the
question. Only once has he visited this sad spot, which holds, he says, all that
he cares for on earth. Unless he comes or writes soon I will cease, or try to
cease, this wearisome looking, looking, looking for him.
March 13th.—My husband at last did come for a visit of two hours. Brought
Lawrence, who had been to Camden, and was there, indeed, during the raid.
My husband has been ordered to Chester, S. C. We are surprised to see by the
papers that we behaved heroically in leaving everything we had to be
destroyed, without one thought of surrender. We had not thought of ourselves
from the heroic point of view. Isaac McLaughlin hid and saved everything we
trusted him with. A grateful negro is Isaac.
March 15th.—Lawrence says Miss Chesnut is very proud of the presence of
mind and cool self-possession she showed in the face of the enemy. She lost,
after all, only two bottles of champagne, two of her brother’s gold-headed
canes, and her brother’s horses, including Claudia, the brood mare, that he
valued beyond price, and her own carriage, and a fly-brush boy called Battis,
whose occupation in life was to stand behind the table with his peacock
feathers and brush the flies away. He was the sole member of his dusky race
at Mulberry who deserted “Ole Marster” to follow the Yankees.
Now for our losses at the Hermitage. Added to the gold-headed canes and
Claudia, we lost every mule and horse, and President Davis’s beautiful Arabian
was captured. John’s were there, too. My light dragoon, Johnny, and heavy
swell, is stripped light enough for the fight now. Jonathan, whom we trusted,
betrayed us; and the plantation and mills, Mulberry house, etc., were saved
by Claiborne, that black rascal, who was suspected by all the world. Claiborne
boldly affirmed that Mr. Chesnut would not be hurt by destroying his place;
the invaders would hurt only the negroes. “Mars Jeems,” said he, “hardly ever
come here and he takes only a little sompen nur to eat when he do come.”
Fever continuing, I sent for St. Julien Ravenel. We had a wrangle over the
slavery question. Then, he fell foul of everybody who had not conducted this
war according to his ideas. Ellen had something nice to offer him (thanks to
the ever-bountiful Childs!), but he was too angry, too anxious, too miserable
to eat. He pitched into Ellen after he had disposed of me. Ellen stood glaring
at him from the fireplace, her blue eye nearly white, her other eye blazing as
a comet. Last Sunday, he gave her some Dover’s powders for me; directions
were written on the paper in which the medicine was wrapped, and he told
her to show these to me, then to put what I should give her into a wine-glass
and let me drink it. Ellen put it all into the wine-glass and let me drink it at
one dose. “It was enough to last you your lifetime,” he said. “It was murder.”
Turning to Ellen: “What did you do with the directions?” “I nuvver see no
d’rections. You nuvver gimme none.” “I told you to show that paper to your
mistress.” “Well, I flung dat ole brown paper in de fire. What you makin’ all dis
fuss for? Soon as I give Missis de physic, she stop frettin’ an’ flingin’ ’bout, she
go to sleep sweet as a suckling baby, an’ she slep two days an’ nights, an’
now she heap better.” And Ellen withdrew from the controversy.
“Well, all is well that ends well, Mrs. Chesnut. You took opium enough to kill
several persons. You were worried out and needed rest. You came near
getting it—thoroughly. You were in no danger from your disease. But your
doctor and your nurse combined were deadly.” Maybe I was saved by the
adulteration, the feebleness, of Confederate medicine.

A letter from my husband, written at Chester Court House on March 15th,

says: “In the morning I send Lieut. Ogden with Lawrence to Lincolnton to
bring you down. I have three vacant rooms; one with bedsteads, chairs,
wash-stands, basins, and pitchers; the two others bare. You can have half of
a kitchen for your cooking. I have also at Dr. Da Vega’s, a room, furnished, to
which you are invited (board, also). You can take your choice. If you can get
your friends in Lincolnton to assume charge of your valuables, only bring such
as you may need here. Perhaps it will be better to bring bed and bedding and
the other indispensables.”
 XX
CHESTER, S. C.
March 21, 1865-May 1, 1865

hester, S. C., March 21, 1865.—Another flitting has occurred.

Captain Ogden came for me; the splendid Childs was true as steel
to the last. Surely he is the kindest of men. Captain Ogden was
slightly incredulous when I depicted the wonders of Colonel
Childs’s generosity. So I skilfully led out the good gentleman for
inspection, and he walked to the train with us. He offered me Confederate
money, silver, and gold; and finally offered to buy our cotton and pay us now
in gold. Of course, I laughed at his overflowing bounty, and accepted nothing;
but I begged him to come down to Chester or Camden and buy our cotton of
General Chesnut there.
On the train after leaving Lincolnton, as Captain Ogden is a refugee, has
had no means of communicating with his home since New Orleans fell, and
was sure to know how refugees contrive to live, I beguiled the time acquiring
information from him. “When people are without a cent, how do they live?” I
asked. “I am about to enter the noble band of homeless, houseless refugees,
and Confederate pay does not buy one’s shoe-strings.” To which he replied,
“Sponge, sponge. Why did you not let Colonel Childs pay your bills?” “I have
no bills,” said I. “We have never made bills anywhere, not even at home,
where they would trust us, and nobody would trust me in Lincolnton.” “Why
did you not borrow his money? General Chesnut could pay him at his leisure?”
“I am by no means sure General Chesnut will ever again have any money,”
said I.
As the train rattled and banged along, and I waved my handkerchief in
farewell to Miss Middleton, Isabella, and other devoted friends, I could only
wonder if fate would ever throw me again with such kind, clever, agreeable,
congenial companions? The McLeans refused to be paid for their rooms. No
plummet can sound the depths of the hospitality and kindness of the North
Carolina people.
Misfortune dogged us from the outset. Everything went wrong with the
train. We broke down within two miles of Charlotte, and had to walk that
distance; which was pretty rough on an invalid barely out of a fever. My spirit
was further broken by losing an invaluable lace veil, which was worn because
I was too poor to buy a cheaper one—that is, if there were any veils at all for
sale in our region.
My husband had ordered me to a house in Charlotte kept by some great
friends of his. They established me in the drawing-room, a really handsome
apartment; they made up a bed there and put in a washstand and plenty of
water, with everything refreshingly clean and nice. But it continued to be a
public drawing-room, open to all, so that I was half dead at night and wanted
to go to bed. The piano was there and the company played it.
The landlady announced, proudly, that for supper there were nine kinds of
custard. Custard sounded nice and light, so I sent for some, but found it
heavy potato pie. I said: “Ellen, this may kill me, though Dover’s powder did
not.” “Don’t you believe dat, Missis; try.” We barricaded ourselves in the
drawing-room that night and left the next day at dawn. Arrived at the station,
we had another disappointment; the train was behind time. There we sat on
our boxes nine long hours; for the cars might come at any moment, and we
dared not move an inch from the spot.
Finally the train rolled in overloaded with paroled prisoners, but heaven
helped us: a kind mail agent invited us, with two other forlorn women, into
his comfortable and clean mail-car. Ogden, true to his theory, did not stay at
the boarding-house as we did. Some Christian acquaintances took him in for
the night. This he explained with a grin.
My husband was at the Chester station with a carriage. We drove at once to
Mrs. Da Vega’s.
March 24th.—I have been ill, but what could you expect? My lines, however,
have again fallen in pleasant places. Mrs. Da Vega is young, handsome, and
agreeable, a kind and perfect hostess; and as to the house, my room is all
that I could ask and leaves nothing to be desired; so very fresh, clean, warm,
and comfortable is it. It is the drawing-room suddenly made into a bedroom
for me. But it is my very own. We are among the civilized of the earth once
more.
March 27th.—I have moved again, and now I am looking from a window
high, with something more to see than the sky. We have the third story of Dr.
Da Vega’s house, which opens on the straight street that leads to the railroad
about a mile off.
 Mrs. Bedon is the loveliest of young widows. Yesterday at church Isaac
Hayne nestled so close to her cap-strings that I had to touch him and say, “Sit
up!” Josiah Bedon was killed in that famous fight of the Charleston Light
Dragoons. The dragoons stood still to be shot down in their tracks, having no
orders to retire. They had been forgotten, doubtless, and they scorned to take
care of themselves.
In this high and airy retreat, as in Richmond, then in Columbia, and then in
Lincolnton, my cry is still: If they would only leave me here in peace and if I
were sure things never could be worse with me. Again am I surrounded by
old friends. People seem to vie with each other to show how good they can be
to me.
To-day Smith opened the trenches and appeared laden with a tray covered
with a snow-white napkin. Here was my first help toward housekeeping again.
Mrs. Pride has sent a boiled ham, a loaf of bread, a huge pancake; another
neighbor coffee already parched and ground; a loaf of sugar already cracked;
candles, pickles, and all the other things one must trust to love for now. Such
money as we have avails us nothing, even if there were anything left in the
shops to buy.
We had a jolly luncheon. James Lowndes called, the best of good company.
He said of Buck, “She is a queen, and ought to reign in a palace. No Prince
Charming yet; no man has yet approached her that I think half good enough
for her.”
Then Mrs. Prioleau Hamilton, née Levy, came with the story of family
progress, not a royal one, from Columbia here: “Before we left home,” said
she, “Major Hamilton spread a map of the United States on the table, and
showed me with his finger where Sherman was likely to go. Womanlike, I
demurred. I But, suppose he does not choose to go that way?’ ‘Pooh, pooh!
what do you know of war?’ So we set out, my husband, myself, and two
children, all in one small buggy. The 14th of February we took up our line of
march, and straight before Sherman’s men for five weeks we fled together. By
incessant hurrying and scurrying from pillar to post, we succeeded in acting
as a sort of avant-courier of the Yankee army. Without rest and with much
haste, we got here last Wednesday, and here we mean to stay and defy
Sherman and his legions. Much the worse for wear were we.”
The first night their beauty sleep was rudely broken into at Alston with a
cry, “Move on, the Yanks are upon us!” So they hurried on, half-awake, to
Winnsboro, but with no better luck. There they had to lighten the ship, leave
trunks, etc., and put on all sail, for this time the Yankees were only five miles
behind. “Whip and spur, ride for your life!” was the cry. “Sherman’s objective
point seemed to be our buggy,” said she; “for you know that when we got to
Lancaster Sherman was expected there, and he keeps his appointments; that
is, he kept that one. Two small children were in our chariot, and I began to
think of the Red Sea expedition. But we lost no time, and soon we were in
Cheraw, clearly out of the track. We thanked God for all his mercies and
hugged to our bosoms fond hopes of a bed and bath so much needed by all,
especially for the children.
“At twelve o’clock General Hardee himself knocked us up with word to
‘March! march!’ for ‘all the blue bonnets are over the border.’ In mad haste we
made for Fayetteville, when they said: ‘God bless your soul! This is the seat of
war now; the battle-ground where Sherman and Johnston are to try
conclusions.’ So we harked back, as the hunters say, and cut across country,
aiming for this place. Clean clothes, my dear? Never a one except as we took
off garment by garment and washed it and dried it by our camp fire, with our
loins girded and in haste.” I was snug and comfortable all that time in
Lincolnton.

To-day Stephen D. Lee’s corps marched through—only to surrender. The

camp songs of these men were a heartbreak; so sad, yet so stirring. They
would have warmed the blood of an Icelander. The leading voice was
powerful, mellow, clear, distinct, pathetic, sweet. So, I sat down, as women
have done before, when they hung up their harps by strange streams, and I
wept the bitterness of such weeping. Music? Away, away! Thou speakest to
me of things which in all my long life I have not found, and I shall not find.
There they go, the gay and gallant few, doomed; the last gathering of the
flower of Southern pride, to be killed, or worse, to a prison. They continue to
prance by, light and jaunty. They march with as airy a tread as if they still
believed the world was all on their side, and that there were no Yankee bullets
for the unwary. What will Joe Johnston do with them now?
The Hood melodrama is over, though the curtain has not fallen on the last
scene. Cassandra croaks and makes many mistakes, but to-day she believes
that Hood stock is going down. When that style of enthusiasm is on the wane,
the rapidity of its extinction is miraculous. It is like the snuffing out of a
candle; “one moment white, then gone forever.” No, that is not right; it is the
snow-flake on the river that is referred to. I am getting things as much mixed
as do the fine ladies of society.
 Lee and Johnston have each fought a drawn battle; only a few more dead
bodies lie stiff and stark on an unknown battle-field. For we do not so much
as know where these drawn battles took place.
Teddy Barnwell, after sharing with me my first luncheon, failed me cruelly.
He was to come for me to go down to the train and see Isabella pass by. One
word with Isabella worth a thousand ordinary ones! So, she has gone by and
I’ve not seen her.
Old Colonel Chesnut refuses to say grace; but as he leaves the table audibly
declares, “I thank God for a good dinner.” When asked why he did this odd
thing he said: “My way is to be sure of a thing before I return thanks for it.”
Mayor Goodwyn thanked Sherman for promised protection to Columbia; soon
after, the burning began.
I received the wife of a post-office robber. The poor thing had done no
wrong, and I felt so sorry for her. Who would be a woman? Who that fool, a
weeping, pining, faithful woman? She hath hard measures still when she
hopes kindest. And all her beauty only makes ingrates!
March 29th.—I was awakened with a bunch of violets from Mrs. Pride.
Violets always remind me of Kate and of the sweet South wind that blew in
the garden of paradise part of my life. Then, it all came back: the dread
unspeakable that lies behind every thought now.
Thursday.—I find I have not spoken of the box-car which held the Preston
party that day on their way to York from Richmond. In the party were Mr. and
Mrs. Lawson Clay, General and Mrs. Preston and their three daughters,
Captain Rodgers, and Mr. Portman, whose father is an English earl, and
connected financially and happily with Portman Square. In my American
ignorance I may not state Mr. Portman’s case plainly. Mr. Portman is, of
course, a younger son. Then there was Cellie and her baby and wet-nurse,
with no end of servants, male and female. In this ark they slept, ate, and
drank, such being the fortune of war. We were there but a short time, but Mr.
Portman, during that brief visit of ours, was said to have eaten three
luncheons, and the number of his drinks, toddies, so called, were counted,
too. Mr. Portman’s contribution to the larder had been three small pigs. They
were, however, run over by the train, and made sausage meat of unduly and
before their time.
General Lee says to the men who shirk duty, “This is the people’s war;
when they tire, I stop.” Wigfall says, “It is all over; the game is up.” He is on
his way to Texas, and when the hanging begins he can step over into Mexico.
 I am plucking up heart, such troops do I see go by every day. They must
turn the tide, and surely they are going for something more than surrender. It
is very late, and the wind flaps my curtain, which seems to moan, “Too late.”
All this will end by making me a nervous lunatic.
Yesterday while I was driving with Mrs. Pride, Colonel McCaw passed us! He
called out, “I do hope you are in comfortable quarters.” “Very comfortable,” I
replied. “Oh, Mrs. Chesnut!” said Mrs. Pride, “how can you say that?”
“Perfectly comfortable, and hope it may never be worse with me,” said I. “I
have a clean little parlor, 16 by 18, with its bare floor well scrubbed, a dinner-
table, six chairs, and—well, that is all; but I have a charming lookout from my
window high. My world is now thus divided into two parts—where Yankees are
and where Yankees are not.”
As I sat disconsolate, looking out, ready for any new tramp of men and
arms, the magnificent figure of General Preston hove in sight. He was
mounted on a mighty steed, worthy of its rider, followed by his trusty squire,
William Walker, who bore before him the General’s portmanteau. When I had
time to realize the situation, I perceived at General Preston’s right hand Mr.
Christopher Hampton and Mr. Portman, who passed by. Soon Mrs. Pride, in
some occult way, divined or heard that they were coming here, and she sent
me at once no end of good things for my tea-table. General Preston entered
very soon after, and with him Clement Clay, of Alabama, the latter in pursuit
of his wife’s trunk. I left it with the Rev. Mr. Martin, and have no doubt it is
perfectly safe, but where? We have written to Mr. Martin to inquire. Then
Wilmot de Saussure appeared. “I am here,” he said, “to consult with General
Chesnut. He and I always think alike.” He added, emphatically: “Slavery is
stronger than ever.” “If you think so,” said I, “you will find that for once you
and General Chesnut do not think alike. He has held that slavery was a thing
of the past, this many a year.”
I said to General Preston: “I pass my days and nights partly at this window.
I am sure our army is silently dispersing. Men are moving the wrong way, all
the time. They slip by with no songs and no shouts now. They have given the
thing up. See for yourself. Look there.” For a while the streets were thronged
with soldiers and then they were empty again. But the marching now is
without tap of drum.
March 31st.—Mr. Prioleau Hamilton told us of a great adventure. Mrs.
Preston was put under his care on the train. He soon found the only other
women along were “strictly unfortunate females,” as Carlyle calls them,
beautiful and aggressive. He had to communicate the unpleasant fact to Mrs.
Preston, on account of their propinquity, and was lost in admiration of her
silent dignity, her quiet self-possession, her calmness, her deafness and
blindness, her thoroughbred ignoring of all that she did not care to see. Some
women, no matter how ladylike, would have made a fuss or would have
fidgeted, but Mrs. Preston dominated the situation and possessed her soul in
innocence and peace.
Met Robert Johnston from Camden. He has been a prisoner, having been
taken at Camden. The Yankees robbed Zack Cantey of his forks and spoons.
When Zack did not seem to like it, they laughed at him. When he said he did
not see any fun in it, they pretended to weep and wiped their eyes with their
coat-tails. All this maddening derision Zack said was as hard to bear as it was
to see them ride off with his horse, Albine. They stole all of Mrs. Zack’s
jewelry and silver. When the Yankee general heard of it he wrote her a very
polite note, saying how sorry he was that she had been annoyed, and
returned a bundle of Zack’s love-letters, written to her before she was
married. Robert Johnston said Miss Chesnut was a brave and determined
spirit. One Yankee officer came in while they were at breakfast and sat down
to warm himself at the fire. “Rebels have no rights,” Miss Chesnut said to him
politely. “I suppose you have come to rob us. Please do so and go. Your
presence agitates my blind old father.” The man jumped up in a rage, and
said, “What do you take me for—a robber?” “No, indeed,” said she, and for
very shame he marched out empty-handed.
April 3d.—Saw General Preston ride off. He came to tell me good-by. I told
him he looked like a Crusader on his great white horse, with William, his
squire, at his heels. Our men are all consummate riders, and have their
servants well mounted behind them, carrying cloaks and traps—how different
from the same men packed like sardines in dirty railroad cars, usually floating
inch deep in liquid tobacco juice.
For the kitchen and Ellen’s comfort I wanted a pine table and a kitchen
chair. A woman sold me one to-day for three thousand Confederate dollars.
Mrs. Hamilton has been disappointed again. Prioleau Hamilton says the
person into whose house they expected to move to-day came to say she
could not take boarders for three reasons: First, “that they had small-pox in
the house.” “And the two others?” “Oh, I did not ask for the two others!”
April 5th.—Miss Middleton’s letter came in answer to mine, telling her how
generous my friends here were to me. “We long,” she says, “for our own small
sufficiency of wood, corn, and vegetables. Here is a struggle unto death,
although the neighbors continue to feed us, as you would say, ‘with a spoon.’
We have fallen upon a new device. We keep a cookery book on the
mantelpiece, and when the dinner is deficient we just read off a pudding or a
crême. It does not entirely satisfy the appetite, this dessert in imagination,
but perhaps it is as good for the digestion.”
As I was ready to go, though still up-stairs, some one came to say General
Hood had called. Mrs. Hamilton cried out, “Send word you are not at home.”
“Never!” said I. “Why make him climb all these stairs when you must go in
five minutes?” “If he had come here dragging Sherman as a captive at his
chariot wheels I might say ‘not at home,’ but not now.” And I ran down and
greeted him on the sidewalk in the face of all, and walked slowly beside him
as he toiled up the weary three stories, limping gallantly. He was so well
dressed and so cordial; not depressed in the slightest. He was so glad to see
me. He calls his report self-defense; says Joe Johnston attacked him and he
was obliged to state things from his point of view. And now follow statements,
where one may read between the lines what one chooses. He had been
offered a command in Western Virginia, but as General Lee was concerned
because he and Joe Johnston were not on cordial terms, and as the fatigue of
the mountain campaign would be too great for him, he would like the chance
of going across the Mississippi. Texas was true to him, and would be his
home, as it had voted him a ranch somewhere out there. They say General
Lee is utterly despondent, and has no plan if Richmond goes, as go it must.
April 7th.—Richmond has fallen and I have no heart to write about it. Grant
broke through our lines and Sherman cut through them. Stoneman is this side
of Danville. They are too many for us. Everything is lost in Richmond, even
our archives. Blue black is our horizon. Hood says we shall all be obliged to go
West—to Texas, I mean, for our own part of the country will be overrun.
Yes, a solitude and a wild waste it may become, but, as to that, we can
rough it in the bush at home.
De Fontaine, in his newspaper, continues the old cry. “Now Richmond is
given up,” he says, “it was too heavy a load to carry, and we are stronger than
ever.” “Stronger than ever?” Nine-tenths of our army are under ground and
where is another army to come from? Will they wait until we grow one?
April 15th.—What a week it has been—madness, sadness, anxiety, turmoil,
ceaseless excitement. The Wigfalls passed through on their way to Texas. We
did not see them. Louly told Hood they were bound for the Rio Grande, and
intended to shake hands with Maximilian, Emperor of Mexico. Yankees were
expected here every minute. Mrs. Davis came. We went down to the cars at
daylight to receive her. She dined with me. Lovely Winnie, the baby, came,
too. Buck and Hood were here, and that queen of women, Mary Darby. Clay
behaved like a trump. He was as devoted to Mrs. Davis in her adversity as if
they had never quarreled in her prosperity. People sent me things for Mrs.
Davis, as they did in Columbia for Mr. Davis. It was a luncheon or breakfast
only she stayed for here. Mrs. Brown prepared a dinner for her at the station.
I went down with her. She left here at five o’clock. My heart was like lead, but
we did not give way. She was as calm and smiling as ever. It was but a brief
glimpse of my dear Mrs. Davis, and under altered skies.
April 17th.—A letter from Mrs. Davis, who writes: “Do come to me, and see
how we get on. I shall have a spare room by the time you arrive, indifferently
furnished, but, oh, so affectionately placed at your service. You will receive
such a loving welcome. One perfect bliss have I. The baby, who grows fat and
is smiling always, is christened, and not old enough to develop the world’s
vices or to be snubbed by it. The name so long delayed is Varina Anne. My
name is a heritage of woe.
“Are you delighted with your husband? I am delighted with him as well as
with my own. It is well to lose an Arabian horse if one elicits such a tender
and at the same time knightly letter as General Chesnut wrote to my poor old
Prometheus. I do not think that for a time he felt the vultures after the
reception of the General’s letter.
“I hear horrid reports about Richmond. It is said that all below Ninth Street
to the Rocketts has been burned by the rabble, who mobbed the town. The
Yankee performances have not been chronicled. May God take our cause into
His own hands.”
April 19th.—Just now, when Mr. Clay dashed up-stairs, pale as a sheet,
saying, “General Lee has capitulated,” I saw it reflected in Mary Darby’s face
before I heard him speak. She staggered to the table, sat down, and wept
aloud. Mr. Clay’s eyes were not dry. Quite beside herself Mary shrieked, “Now
we belong to negroes and Yankees!” Buck said, “I do not believe it.”
How different from ours of them is their estimate of us. How contradictory
is their attitude toward us. To keep the despised and iniquitous South within
their borders, as part of their country, they are willing to enlist millions of men
at home and abroad, and to spend billions, and we know they do not love
fighting per se, nor spending money. They are perfectly willing to have three
killed for our one. We hear they have all grown rich, through “shoddy,”
whatever that is. Genuine Yankees can make a fortune trading jack-knives.
“Somehow it is borne in on me that we will have to pay the piper,” was
remarked to-day. “No; blood can not be squeezed from a turnip. You can not
pour anything out of an empty cup. We have no money even for taxes or to
be confiscated.”
While the Preston girls are here, my dining-room is given up to them, and
we camp on the landing, with our one table and six chairs. Beds are made on
the dining-room floor. Otherwise there is no furniture, except buckets of water
and bath-tubs in their improvised chamber. Night and day this landing and
these steps are crowded with the élite of the Confederacy, going and coming,
and when night comes, or rather, bedtime, more beds are made on the floor
of the landing-place for the war-worn soldiers to rest upon. The whole house
is a bivouac. As Pickens said of South Carolina in 1861, we are “an armed
camp.”
My husband is rarely at home. I sleep with the girls, and my room is given
up to soldiers. General Lee’s few, but undismayed, his remnant of an army, or
the part from the South and West, sad and crestfallen, pass through Chester.
Many discomfited heroes find their way up these stairs. They say Johnston will
not be caught as Lee was. He can retreat; that is his trade. If he would not
fight Sherman in the hill country of Georgia, what will he do but retreat in the
plains of North Carolina with Grant, Sherman, and Thomas all to the fore?
We are to stay here. Running is useless now; so we mean to bide a Yankee
raid, which they say is imminent. Why fly? They are everywhere, these
Yankees, like red ants, like the locusts and frogs which were the plagues of
Egypt.
The plucky way in which our men keep up is beyond praise. There is no
howling, and our poverty is made a matter of laughing. We deride our own
penury. Of the country we try not to speak at all.
April 22d.—This yellow Confederate quire of paper, my journal, blotted by
entries, has been buried three days with the silver sugar-dish, tea-pot, milk-
jug, and a few spoons and forks that follow my fortunes as I wander. With
these valuables was Hood’s silver cup, which was partly crushed when he was
wounded at Chickamauga.
It has been a wild three days, with aides galloping around with messages,
Yankees hanging over us like a sword of Damocles. We have been in queer
straits. We sat up at Mrs. Bedon’s dressed, without once going to bed for
forty-eight hours, and we were aweary.
Colonel Cadwallader Jones came with a despatch, a sealed secret despatch.
It was for General Chesnut. I opened it. Lincoln, old Abe Lincoln, has been
killed, murdered, and Seward wounded! Why? By whom? It is simply
maddening, all this.
I sent off messenger after messenger for General Chesnut. I have not the
faintest idea where he is, but I know this foul murder will bring upon us worse
miseries. Mary Darby says, “But they murdered him themselves. No
Confederates are in Washington.” “But if they see fit to accuse us of
instigating it?” “Who murdered him? Who knows?” “See if they don’t take
vengeance on us, now that we are ruined and can not repel them any longer.”
The death of Lincoln I call a warning to tyrants. He will not be the last
President put to death in the capital, though he is the first.
Buck never submits to be bored. The bores came to tea at Mrs. Bedon’s,
and then sat and talked, so prosy, so wearisome was the discourse, so
endless it seemed, that we envied Buck, who was mooning on the piazza. She
rarely speaks now.
 A NEWSPAPER EXTRA.

HIGHLY IMPORTANT NEWS!

AN ARMISTICE AGREED UPON!!!

Lincoln Assassinated and Seward Mortally

Wounded in Washington!!

Greensboro, April 19, 1865.

General Order No. 14.
It is announced to the Army that a
suspension of arms has been agreed upon
pending negotiations between the two
Governments.
During its continuance the two armies are
to occupy their present position.
By command of General Johnston:
[Signed,] ARCHER ANDERSON,
Lieut. Col. and A. A. G.
Official Copy: Isaac Hayne.

Washington, April 12, 1865.

To Major-General Sherman:
President Lincoln was murdered, about ten
o’clock last night, in his private box at Ford’s
Theatre, in this city, by an assassin, who
shot him in the head with a pistol ball. At the
same hour Mr. Seward’s house was entered
by another assassin, who stabbed the
Secretary in several places. It is thought he
may possibly recover, but his son Fred may
possibly die of the wounds he received.
The assassin of the President leaped from
the private box, brandishing his dagger and
exclaiming: “Sic Semper Tyrannis—Virginia is
revenged!” Mr. Lincoln fell senseless from his
seat, and continued in that condition until 22
minutes past 10 o’clock this morning, at
which time he breathed his last.
Vice President Johnson now becomes
President, and will take the oath of office
and assume the duties to-day.
[Signed,] E. M. STANTON

TO THE CITIZENS OF CHESTER.

Chester, S. C., April 22, 1865.
FLOUR and MEAL given out to the citizens
by order of Major Mitchell, Chief Commissary
of South Carolina, to be returned when
called for, is badly wanted to ration General
Johnston’s army. Please return the same at
once.
E. M. GRAHAM, Agent Subsistence Dep’t.

HEADQUARTERS RESERVE FORCES S. C.

Chesterville, April 20, 1865.
The Brigadier-General Commanding has
been informed that, in view of the approach
of the enemy, a large quantity of supplies of
various kinds were given out by the various
Government officers at this post to the
 citizens of the place. He now calls upon, and
earnestly requests all citizens, who may have
such stores in their possession, to return
them to the several Departments to which
they belong. The stores are much needed at
this time for the use of soldiers, passing
through the place, and for the sick at the
Hospital.
By command of Brig. Gen. Chesnut:
M. R. CLARK, Major and A. A. General.
April 23d.—My silver wedding-day, and I am sure the unhappiest day of my
life. Mr. Portman came with Christopher Hampton. Portman told of Miss Kate
Hampton, who is perhaps the most thoroughly ladylike person in the world.
When he told her that Lee had surrendered she started up from her seat and
said, “That is a lie.” “Well, Miss Hampton, I tell the tale as it was told me. I
can do no more.”
No wonder John Chesnut is bitter. They say Mulberry has been destroyed by
a corps commanded by General Logan. Some one asked coolly, “Will General
Chesnut be shot as a soldier, or hung as a senator?” “I am not of sufficient
consequence,” answered he. “They will stop short of brigadiers. I resigned my
seat in the United States Senate weeks before there was any secession. So I
can not be hung as a senator. But after all it is only a choice between
drumhead court martial, short shrift, and a lingering death at home from
starvation.”
These negroes are unchanged. The shining black mask they wear does not
show a ripple of change; they are sphinxes. Ellen has had my diamonds to
keep for a week or so. When the danger was over she handed them back to
me with as little apparent interest in the matter as if they had been garden
peas.
Mrs. Huger was in church in Richmond when the news of the surrender
came. Worshipers were in the midst of the communion service. Mr. McFarland
was called out to send away the gold from his bank. Mr. Minnegerode’s
English grew confused. Then the President was summoned, and distress of
mind showed itself in every face. The night before one of General Lee’s aides,
Walter Taylor, was married, and was off to the wars immediately after the
ceremony.
 One year ago we left Richmond. The Confederacy has double-quicked down
hill since then. One year since I stood in that beautiful Hollywood by little Joe
Davis’s grave. Now we have burned towns, deserted plantations, sacked
villages. “You seem resolute to look the worst in the face,” said General
Chesnut, wearily. “Yes, poverty, with no future and no hope.” “But no slaves,
thank God!” cried Buck. “We would be the scorn of the world if the world
thought of us at all. You see, we are exiles and paupers.” “Pile on the agony.”
“How does our famous captain, the great Lee, bear the Yankees’ galling
chain?” I asked. “He knows how to possess his soul in patience,” answered my
husband. “If there were no such word as subjugation, no debts, no poverty,
no negro mobs backed by Yankees; if all things were well, you would shiver
and feel benumbed,” he went on, pointing at me in an oratorical attitude.
“Your sentence is pronounced—Camden for life.”
May 1st.—In Chester still. I climb these steep steps alone. They have all
gone, all passed by. Buck went with Mr. C. Hampton to York. Mary, Mrs.
Huger, and Pinckney took flight together. One day just before they began to
dissolve in air, Captain Gay was seated at the table, half-way between me on
the top step and John in the window, with his legs outside. Said some one to-
day, “She showed me her engagement ring, and I put it back on her hand.
She is engaged, but not to me.” “By the heaven that is above us all, I saw you
kiss her hand.” “That I deny.” Captain Gay glared in angry surprise, and
insisted that he had seen it. “Sit down, Gay,” said the cool captain in his most
mournful way. “You see, my father died when I was a baby, and my
grandfather took me in hand. To him I owe this moral maxim. He is ninety
years old, a wise old man. Now, remember my grandfather’s teaching forever-
more—‘A gentleman must not kiss and tell.’”
General Preston came to say good-by. He will take his family abroad at
once. Burnside, in New Orleans, owes him some money and will pay it. “There
will be no more confiscation, my dear madam,” said he; “they must see that
we have been punished enough.” “They do not think so, my dear general.
This very day a party of Federals passed in hot pursuit of our President.”
A terrible fire-eater, one of the few men left in the world who believe we
have a right divine, being white, to hold Africans, who are black, in bonds
forever; he is six feet two; an athlete; a splendid specimen of the animal man;
but he has never been under fire; his place in the service was a bomb-proof
office, so-called. With a face red-hot with rage he denounced Jeff Davis and
Hood. “Come, now,” said Edward, the handsome, “men who could fight and
did not, they are the men who ruined us. We wanted soldiers. If the men who
are cursing Jeff Davis now had fought with Hood, and fought as Hood fought,
we’d be all right now.”
And then he told of my trouble one day while Hood was here. “Just such a
fellow as you came up on this little platform, and before Mrs. Chesnut could
warn him, began to heap insults on Jeff Davis and his satrap, Hood. Mrs.
Chesnut held up her hands. ‘Stop, not another word. You shall not abuse my
friends here! Not Jeff Davis behind his back, not Hood to his face, for he is in
that room and hears you.’” Fancy how dumfounded this creature was.
Mrs. Huger told a story of Joe Johnston in his callow days before he was
famous. After an illness Johnston’s hair all fell out; not a hair was left on his
head, which shone like a fiery cannon-ball. One of the gentlemen from Africa
who waited at table sniggered so at dinner that he was ordered out by the
grave and decorous black butler. General Huger, feeling for the agonies of
young Africa, as he strove to stifle his mirth, suggested that Joe Johnston
should cover his head with his handkerchief. A red silk one was produced, and
turban-shaped, placed on his head. That completely finished the gravity of the
butler, who fled in helplessness. His guffaw on the outside of the door became
plainly audible. General Huger then suggested, as they must have the waiter
back, or the dinner could not go on, that Joe should eat with his hat on,
which he did.
 XXI
CAMDEN, S. C.
May 2, 1865-August 2, 1865

amden, S. C., May 2, 1865.—Since we left Chester nothing but

solitude, nothing but tall blackened chimneys, to show that any
man has ever trod this road before. This is Sherman’s track. It is
hard not to curse him. I wept incessantly at first. The roses of the
gardens are already hiding the ruins. My husband said Nature is a
wonderful renovator. He tried to say something else and then I shut my eyes
and made a vow that if we were a crushed people, crushed by weight, I
would never be a whimpering, pining slave.
We heard loud explosions of gunpowder in the direction of Camden.
Destroyers were at it there. Met William Walker, whom Mr. Preston left in
charge of a car-load of his valuables. General Preston was hardly out of sight
before poor helpless William had to stand by and see the car plundered. “My
dear Missis! they have cleaned me out, nothing left,” moaned William the
faithful. We have nine armed couriers with us. Can they protect us?
Bade adieu to the staff at Chester. No general ever had so remarkable a
staff, so accomplished, so agreeable, so well bred, and, I must say, so
handsome, and can add so brave and efficient.
May 4th.—Home again at Bloomsbury. From Chester to Winnsboro we did
not see one living thing, man, woman, or animal, except poor William
trudging home after his sad disaster. The blooming of the gardens had a
funereal effect. Nature is so luxuriant here, she soon covers the ravages of
savages. No frost has occurred since the seventh of March, which accounts for
the wonderful advance in vegetation. This seems providential to these
starving people. In this climate so much that is edible can be grown in two
months.
At Winnsboro we stayed at Mr. Robertson’s. There we left the wagon train.
Only Mr. Brisbane, one of the general’s couriers, came with us on escort duty.
The Robertsons were very kind and hospitable, brimful of Yankee anecdotes.
To my amazement the young people of Winnsboro had a May-day celebration
amid the smoking ruins. Irrepressible is youth.
 The fidelity of the negroes is the principal topic. There seems to be not a
single case of a negro who betrayed his master, and yet they showed a
natural and exultant joy at being free. After we left Winnsboro negroes were
seen in the fields plowing and hoeing corn, just as in antebellum times. The
fields in that respect looked quite cheerful. We did not pass in the line of
Sherman’s savages, and so saw some houses standing.
Mary Kirkland has had experience with the Yankees. She has been
pronounced the most beautiful woman on this side of the Atlantic, and has
been spoiled accordingly in all society. When the Yankees came, Monroe, their
negro manservant, told her to stand up and hold two of her children in her
arms, with the other two pressed as close against her knees as they could
get. Mammy Selina and Lizzie then stood grimly on each side of their young
missis and her children. For four mortal hours the soldiers surged through the
rooms of the house. Sometimes Mary and her children were roughly jostled
against the wall, but Mammy and Lizzie were stanch supporters. The Yankee
soldiers taunted the negro women for their foolishness in standing by their
cruel slave-owners, and taunted Mary with being glad of the protection of her
poor ill-used slaves. Monroe meanwhile had one leg bandaged and pretended
to be lame, so that he might not be enlisted as a soldier, and kept making
pathetic appeals to Mary.
“Don’t answer them back, Miss Mary,” said he. “Let ’em say what dey want
to; don’t answer ’em back. Don’t give ’em any chance to say you are
impudent to ’em.”
One man said to her: “Why do you shrink from us and avoid us so? We did
not come here to fight for negroes; we hate them. At Port Royal I saw a
beautiful white woman driving in a wagon with a coal-black negro man. If she
had been anything to me I would have shot her through the heart.” “Oh, oh!”
said Lizzie, “that’s the way you talk in here. I’ll remember that when you
begin outside to beg me to run away with you.”
Finally poor Aunt Betsy, Mary’s mother, fainted from pure fright and
exhaustion. Mary put down her baby and sprang to her mother, who was lying
limp in a chair, and fiercely called out, “Leave this room, you wretches! Do you
mean to kill my mother? She is ill; I must put her to bed.” Without a word
they all slunk out ashamed. “If I had only tried that hours ago,” she now said.
Outside they remarked that she was “an insolent rebel huzzy, who thinks
herself too good to speak to a soldier of the United States,” and one of them
said: “Let us go in and break her mouth.” But the better ones held the more
outrageous back. Monroe slipped in again and said: “Missy, for God’s sake,
when dey come in be sociable with ’em. Dey will kill you.”