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 Organic Chemistry, Sixth Edition © 2012, 2009 Brooks/Cole, Cengage Learning
William H. Brown, Christopher
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 Organic Chemistry
SIXT H EDIT ION

William H. Brown
Beloit College

Christopher S. Foote
University of California, Los Angeles

Brent L. Iverson
University of Texas, Austin

Eric V. Anslyn
University of Texas, Austin

Chapter 29 was originally contributed by

Bruce M. Novak
North Carolina State University

Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States

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 Dedication
This Sixth Edition is dedicated to the memory of our dear friend and
colleague, Christopher Foote. Chris’ insights, encouragement, and
dedication to this project can never be replaced. His kind and nurturing
spirit lives on in all who are lucky enough to have known him.

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About the Authors

WILLIAM H. BROWN is an Emeritus Professor of Chemistry at Beloit College,

where he has twice been named Teacher of the Year. His teaching responsibilities
included organic chemistry, advanced organic chemistry, and special topics in phar-
macology and drug synthesis. He received his Ph.D. from Columbia University under
the direction of Gilbert Stork and did postdoctoral work at California Institute of
Technology and the University of Arizona.

CHRISTOPHER S. FOOTE received his B.S. from Yale University and his Ph.D.
from Harvard University. His scholarly credits include Sloan Fellow; Guggenheim
Fellow; ACS Baekland Award; ACS Cope Scholar; Southern California Section ACS
Tolman Medal; President, American Society for Photobiology; and Senior Editor,
Accounts of Chemical Research. He was a Professor of Chemistry at UCLA.

BRENT L. IVERSON received his B.S. from Stanford University and his Ph.D.
from the California Institute of Technology. He is a University Distinguished Teaching
Professor at The University of Texas, Austin as well as a respected researcher. Brent’s
research spans the interface of organic chemistry and molecular biology. His group
has developed several patented technologies, including an effective treatment for
anthrax.

ERIC V. ANSLYN is a University Distinguished Teaching Professor at The Uni-

versity of Texas at Austin. He earned his bachelor’s degree from California State
University, Northridge, his Ph.D. from the California Institute of Technology and did
postdoctoral work at Columbia University under the direction of Ronald Breslow.
Eric has won numerous teaching awards and his research focuses on the physical and
bioorganic chemistry of synthetic and natural receptors and catalysts.

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 Copyright 2010 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
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Contents in Brief

1. Covalent Bonding and Shapes of Molecules

2. Alkanes and Cycloalkanes
3. Stereoisomerism and Chirality
4. Acids and Bases
5. Alkenes: Bonding, Nomenclature, and Properties
6. Reactions of Alkenes
7. Alkynes
8. Haloalkanes, Halogenation, and Radical Reactions
9. Nucleophilic Substitution and b-Elimination
10. Alcohols
11. Ethers, Epoxides, and Sulfides
12. Infrared Spectroscopy
13. Nuclear Magnetic Resonance Spectroscopy
14. Mass Spectrometry
15. An Introduction to Organometallic Compounds
16. Aldehydes and Ketones
17. Carboxylic Acids
18. Functional Derivatives of Carboxylic Acids
19. Enolate Anions and Enamines
20. Dienes, Conjugated Systems, and Pericyclic Reactions
21. Benzene and the Concept of Aromaticity
22. Reactions of Benzene and Its Derivatives
23. Amines
24. Catalytic Carbon-Carbon Bond Formation
25. Carbohydrates
26. Lipids
27. Amino Acids and Proteins
28. Nucleic Acids
29. Organic Polymer Chemistry

Appendices:
1. Thermodynamics and the Equilibrium Constant
2. Major Classes of Organic Acids
3. Bond Dissociation Enthalpies
4. Characteristic 1H-NMR Chemical Shifts
5. Characteristic 13C-NMR Chemical Shifts
6. Characteristic Infrared Absorption Frequencies
7. Electrostatic Potential Maps
8. Summary of Stereochemical Terms
9. Summary of the Rules of Nomenclature
10. Common Mistakes in Arrow Pushing
11. Organic Chemistry Road Maps
Glossary
Index

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Contents

Chapter 1 Covalent Bonding and Shapes of Molecules 1

1.1 Electronic Structure of Atoms 1
1.2 Lewis Model of Bonding 6
HOW TO Draw Lewis Structures from Condensed Structural Formulas 15

1.3 Functional Groups 16

1.4 Bond Angles and Shapes of Molecules 21
1.5 Polar and Nonpolar Molecules 24
CHEMICAL CONNECTIONS Fullerene—A New Form of Carbon 25

1.6 Quantum or Wave Mechanics 26

1.7 A Combined Valence Bond and Molecular Orbital Theory Approach to
Covalent Bonding 30
CONNECTIONS TO BIOLOGICAL CHEMISTRY Phosphoesters 37

1.8 Resonance 42
HOW TO Draw Curved Arrows and Push Electrons in Creating Contributing Structures 43

1.9 Molecular Orbitals for Delocalized Systems 48

1.10 Bond Lengths and Bond Strengths in Alkanes, Alkenes, and Alkynes 51
Summary 52 • Problems 54

Chapter 2 Alkanes and Cycloalkanes 63

2.1 The Structure of Alkanes 63
2.2 Constitutional Isomerism in Alkanes 65
2.3 Nomenclature of Alkanes and the IUPAC System 67
2.4 Cycloalkanes 72
2.5 Conformations of Alkanes and Cycloalkanes 75
HOW TO Draw Alternative Chair Conformations of Cyclohexanes 86

2.6 Cis,Trans Isomerism in Cycloalkanes and Bicycloalkanes 88

HOW TO Convert Planar Cyclohexanes to Chair Cyclohexanes 90

CHEMICAL CONNECTIONS The Poisonous Puffer Fish 95

2.7 Physical Properties of Alkanes and Cycloalkanes 96

2.8 Reactions of Alkanes 99
2.9 Sources and Importance of Alkanes 101

vi

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 CHEMICAL CONNECTIONS Octane Rating: What Those Numbers at the
Pump Mean 103

Summary 104 • Problems 106

Chapter 3 Stereoisomerism and Chirality 114

3.1 Chirality—The Handedness of Molecules 114
3.2 Stereoisomerism 116
HOW TO Draw Chiral Molecules 117

3.3 Naming Chiral Centers—The R,S System 120

HOW TO Assign R or S Configuration to a Chiral Center 122

3.4 Acyclic Molecules with Two or More Stereocenters 123

3.5 Cyclic Molecules with Two or More Stereocenters 129
3.6 Tying All the Terminology Together 132
3.7 Optical Activity—How Chirality Is Detected in the Laboratory 134
3.8 The Significance of Chirality in the Biological World 137
CONNECTIONS TO BIOLOGICAL CHEMISTRY Chiral Drugs 139

CONNECTIONS TO BIOLOGICAL CHEMISTRY Amino Acids 140

3.9 Separation of Enantiomers—Resolution 140

Summary 144 • Problems 146

Chapter 4 Acids and Bases 153

4.1 Arrhenius Acids and Bases 153
4.2 Brønsted-Lowry Acids and Bases 154
4.3 Acid Dissociation Constants, pKa, and the Relative Strengths of Acids
and Bases 160

4.4 The Position of Equilibrium in Acid-Base Reactions 162

HOW TO Calculate Equilibrium Constants for Acid-Base Reactions 163

CONNECTIONS TO BIOLOGICAL CHEMISTRY The Ionization of Functional Groups

at Physiological pH 164

4.5 Thermochemistry and Mechanisms of Acid-Base Reactions 165

4.6 Molecular Structure and Acidity 169
4.7 Lewis Acids and Bases 174
Summary 177 • Problems 179

Chapter 5 Alkenes: Bonding, Nomenclature, and

Properties 186
5.1 Structure of Alkenes 187
HOW TO Calculate the Index of Hydrogen Deficiency 188

5.2 Nomenclature of Alkenes 190

5.3 Physical Properties of Alkenes 196
CHEMICAL CONNECTIONS The Case of the Iowa and New York Strains of the European
Corn Borer 196

Contents vii

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 5.4 Naturally Occurring Alkenes—Terpene Hydrocarbons 197
CONNECTIONS TO BIOLOGICAL CHEMISTRY The Importance of Cis Double Bonds
in Fats Versus Oils 199

Summary 200 • Problems 201

Chapter 6 Reactions of Alkenes 206

6.1 Reactions of Alkenes—An Overview 206
6.2 Organic Reactions Involving Reactive Intermediates 207
6.3 Electrophilic Additions 217
6.4 Hydroboration-Oxidation 236
6.5 Oxidation 240
HOW TO Write a Balanced Half-Reaction 242

6.6 Reduction 244

CONNECTIONS TO BIOLOGICAL CHEMISTRY Trans Fatty Acids: What They Are
and How To Avoid Them 247

6.7 Molecules Containing Chiral Centers as Reactants

or Products 248
Summary 253 • Problems 257

Chapter 7 Alkynes 266

7.1 Structure of Alkynes 266
7.2 Nomenclature of Alkynes 267
7.3 Physical Properties of Alkynes 269
7.4 Acidity of 1-Alkynes 269
7.5 Preparation of Alkynes 270
7.6 Electrophilic Addition to Alkynes 273
7.7 Hydration of Alkynes to Aldehydes and Ketones 275
7.8 Reduction of Alkynes 280
7.9 Organic Synthesis 282
Summary 285 • Problems 289

Chapter 8 Haloalkanes, Halogenation, and

Radical Reactions 296
8.1 Structure 296
8.2 Nomenclature 297
8.3 Physical Properties of Haloalkanes 298
8.4 Preparation of Haloalkanes by Halogenation of Alkanes 302
8.5 Mechanism of Halogenation of Alkanes 305
CHEMICAL CONNECTIONS Freons 309

8.6 Allylic Halogenation 313

8.7 Radical Autoxidation 317

viii Contents

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 CONNECTIONS TO BIOLOGICAL CHEMISTRY Antioxidants 318

8.8 Radical Addition of HBr to Alkenes 320

Summary 323 • Problems 326

Chapter 9 Nucleophilic Substitution and b-Elimination 331

9.1 Nucleophilic Substitution in Haloalkanes 332
9.2 Mechanisms of Nucleophilic Aliphatic Substitution 334
9.3 Experimental Evidence for SN1 and SN2 Mechanisms 338
9.4 Analysis of Several Nucleophilic Substitution Reactions 353
9.5 b-Elimination 356
9.6 Mechanisms of b-Elimination 357
9.7 Experimental Evidence for E1 and E2 Mechanisms 360
9.8 Substitution Versus Elimination 366
9.9 Analysis of Several Competitions Between Substitutions and
Eliminations 370

9.10 Neighboring Group Participation 372

CONNECTIONS TO BIOLOGICAL CHEMISTRY Mustard Gases and the Treatment
of Neoplastic Diseases 375

Summary 376 • Problems 380

Chapter 10 Alcohols 390

10.1 Structure and Nomenclature of Alcohols 391
10.2 Physical Properties of Alcohols 393
CONNECTIONS TO BIOLOGICAL CHEMISTRY The Importance of Hydrogen Bonding
in Drug-Receptor Interactions 395

10.3 Acidity and Basicity of Alcohols 397

10.4 Reaction of Alcohols with Active Metals 398
10.5 Conversion of Alcohols to Haloalkanes and Sulfonates 399
10.6 Acid-Catalyzed Dehydration of Alcohols 405
10.7 The Pinacol Rearrangement 410
10.8 Oxidation of Alcohols 412
CHEMICAL CONNECTIONS Blood Alcohol Screening 416

CONNECTIONS TO BIOLOGICAL CHEMISTRY The Oxidation of Alcohols by NAD1 418

10.9 Thiols 420

Summary 424 • Problems 428

Chapter 11 Ethers, Epoxides, and Sulfides 436

11.1 Structure of Ethers 436
11.2 Nomenclature of Ethers 437
11.3 Physical Properties of Ethers 438
11.4 Preparation of Ethers 439
Contents ix

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 11.5 Reactions of Ethers 443
11.6 Silyl Ethers as Protecting Groups 445
11.7 Epoxides: Structure and Nomenclature 447
11.8 Synthesis of Epoxides 448
11.9 Reactions of Epoxides 452
11.10 Ethylene Oxide and Epichlorohydrin: Building Blocks in Organic Synthesis 455
11.11 Crown Ethers 458
11.12 Sulfides 459
Summary 460 • Problems 465

Chapter 12 Infrared Spectroscopy 474

12.1 Electromagnetic Radiation 474
12.2 Molecular Spectroscopy 475
12.3 Infrared Spectroscopy 476
12.4 Interpreting Infrared Spectra 481
12.5 Solving Infrared Spectral Problems 490
Summary 490 • Problems 492

Chapter 13 Nuclear Magnetic Resonance

Spectroscopy 495
13.1 Nuclear Spin States 495
13.2 Orientation of Nuclear Spins in an Applied Magnetic Field 496
13.3 Nuclear Magnetic “Resonance” 498
13.4 An NMR Spectrometer 500
13.5 Equivalent Hydrogens 501
13.6 Signal Areas 503
13.7 Chemical Shift 504
13.8 Signal Splitting and the (n 1 1) Rule 508
13.9 The Origins of Signal Splitting 510
13.10 Stereochemistry and Topicity 517
CHEMICAL CONNECTIONS Magnetic Resonance Imaging 520
13
13.11 C-NMR 521
13.12 Interpretation of NMR Spectra 523
HOW TO Solve NMR Spectral Problems 526

Summary 528 • Problems 531

Chapter 14 Mass Spectrometry 539

14.1 A Mass Spectrometer 539
14.2 Features of a Mass Spectrum 542
14.3 Interpreting Mass Spectra 546

x Contents

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 CONNECTIONS TO BIOLOGICAL CHEMISTRY Mass Spectrometry of Biological
Macromolecules 553

14.4 Mass Spectrometry in the Organic Synthesis Laboratory and

Other Applications 554
Summary 555 • Problems 556

Chapter 15 An Introduction to Organometallic

Compounds 561
15.1 Organomagnesium and Organolithium Compounds 561
15.2 Lithium Diorganocopper (Gilman) Reagents 566
15.3 Carbenes and Carbenoids 569
Summary 573 • Problems 575

Chapter 16 Aldehydes and Ketones 581

16.1 Structure and Bonding 581
16.2 Nomenclature 582
16.3 Physical Properties 585
16.4 Reactions 586
16.5 Addition of Carbon Nucleophiles 588
16.6 The Wittig Reaction 594
16.7 Addition of Oxygen Nucleophiles 598
16.8 Addition of Nitrogen Nucleophiles 606
CONNECTIONS TO BIOLOGICAL CHEMISTRY Pyridoxine (Vitamin B6): A Carrier
of Amino Groups 610

16.9 Keto-Enol Tautomerism 612

16.10 Oxidation 616
16.11 Reduction 617
CONNECTIONS TO BIOLOGICAL CHEMISTRY NADH: The Biological Equivalent
of a Hydride Reducing Agent 621

16.12 Reactions at an a-Carbon 624

Summary 627 • Problems 633

Chapter 17 Carboxylic Acids 649

17.1 Structure 649
17.2 Nomenclature 650
17.3 Physical Properties 653
CHEMICAL CONNECTIONS From Willow Bark to Aspirin and Beyond 654

17.4 Acidity 655

17.5 Preparation of Carboxylic Acids 659
17.6 Reduction 659
CHEMICAL CONNECTIONS Industrial Synthesis of Acetic Acid—Transition Metal
Catalysis 660

Contents xi

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 17.7 Esterification 661
CHEMICAL CONNECTIONS The Pyrethrins: Natural Ester-containing Insecticides of
Plant Origin 663

17.8 Conversion to Acid Chlorides 664

CHEMICAL CONNECTIONS Esters as Flavoring Agents 664

17.9 Decarboxylation 665

CONNECTIONS TO BIOLOGICAL CHEMISTRY Ketone Bodies and Diabetes Mellitus 667

Summary 668 • Problems 671

Chapter 18 Functional Derivatives of Carboxylic Acids 680

18.1 Structure and Nomenclature 681
CHEMICAL CONNECTIONS From Cocaine to Procaine and Beyond 683

CHEMICAL CONNECTIONS From Moldy Clover to a Blood Thinner 684

CHEMICAL CONNECTIONS The Penicillins and Cephalosporins: b-Lactam Antibiotics 686

18.2 Acidity of Amides, Imides, and Sulfonamides 687

CONNECTIONS TO BIOLOGICAL CHEMISTRY The Unique Structure of Amide
Bonds 688

18.3 Characteristic Reactions 689

18.4 Reaction with Water: Hydrolysis 694
HOW TO Write Mechanisms for Interconversions of Carboxylic Acid Derivatives 696

CHEMICAL CONNECTIONS Mechanistic Alternatives For Ester Hydrolysis: SN2 and

SN1 Possibilities 702

18.5 Reaction with Alcohols 708

18.6 Reactions with Ammonia and Amines 710
18.7 Reaction of Acid Chlorides with Salts of Carboxylic Acids 712
18.8 Interconversion of Functional Derivatives 712
18.9 Reactions with Organometallic Compounds 713
18.10 Reduction 716
Summary 721 • Problems 727

Chapter 19 Enolate Anions and Enamines 742

19.1 Formation and Reactions of Enolate Anions: An Overview 742
19.2 Aldol Reaction 744
19.3 Claisen and Dieckmann Condensations 751
19.4 Claisen and Aldol Condensations in the Biological World 757
CHEMICAL CONNECTIONS Drugs That Lower Plasma Levels of Cholesterol 758

19.5 Enamines 760

19.6 Acetoacetic Ester Synthesis 763
19.7 Malonic Ester Synthesis 768

xii Contents

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 CHEMICAL CONNECTIONS Ibuprofen: The Evolution of an Industrial Synthesis 770

19.8 Conjugate Addition to a,b-Unsaturated Carbonyl

Compounds 771

19.9 Crossed Enolate Reactions Using LDA 780

Summary 784 • Problems 790

Chapter 20 Dienes, Conjugated Systems, and Pericyclic

Reactions 810
20.1 Stability of Conjugated Dienes 810
20.2 Electrophilic Addition to Conjugated Dienes 814
20.3 UV-Visible Spectroscopy 820
20.4 Pericyclic Reaction Theory 824
CHEMICAL CONNECTIONS Curry and Cancer 825

20.5 The Diels-Alder Reaction 827

20.6 Sigmatropic Shifts 836
Summary 841 • Problems 845

Chapter 21 Benzene and the Concept of Aromaticity 853

21.1 The Structure of Benzene 854
21.2 The Concept of Aromaticity 858
21.3 Nomenclature 867
CHEMICAL CONNECTIONS Carcinogenic Polynuclear Aromatic Hydrocarbons
and Smoking 870

21.4 Phenols 870

CHEMICAL CONNECTIONS Capsaicin, for Those Who Like It Hot 872

21.5 Reactions at a Benzylic Position 879

Summary 883 • Problems 888

Chapter 22 Reactions of Benzene and Its Derivatives 906

22.1 Electrophilic Aromatic Substitution 907
22.2 Disubstitution and Polysubstitution 917
22.3 Nucleophilic Aromatic Substitution 924
Summary 928 • Problems 932

Chapter 23 Amines 947

23.1 Structure and Classification 947
23.2 Nomenclature 948
23.3 Chirality of Amines and Quaternary Ammonium Ions 951
23.4 Physical Properties 952
CHEMICAL CONNECTIONS The Poison Dart Frogs of South America 953

23.5 Basicity 954

Contents xiii

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 CONNECTIONS TO BIOLOGICAL CHEMISTRY The Planarity of !NH2 Groups
on Aromatic Rings 958

23.6 Reactions with Acids 961

23.7 Preparation 964
23.8 Reaction with Nitrous Acid 966
23.9 Hofmann Elimination 974
23.10 Cope Elimination 976
Summary 977 • Problems 983

Chapter 24 Catalytic Carbon-Carbon Bond Formation 1000

24.1 Carbon-Carbon Bond-Forming Reactions from
Earlier Chapters 1001

24.2 Organometallic Compounds and Catalysis 1002

24.3 The Heck Reaction 1002
24.4 Catalytic Allylic Alkylation 1008
24.5 Palladium-Catalyzed Cross-Coupling Reactions 1012
24.6 Alkene Metathesis 1017
Summary 1019 • Problems 1023

Chapter 25 Carbohydrates 1037

25.1 Monosaccharides 1038
25.2 The Cyclic Structure of Monosaccharides 1042
CHEMICAL CONNECTIONS L-Ascorbic Acid (Vitamin C) 1044

25.3 Reactions of Monosaccharides 1046

CHEMICAL CONNECTIONS Testing for Glucose 1051

25.4 Disaccharides and Oligosaccharides 1052

CHEMICAL CONNECTIONS A, B, AB, and O Blood Group Substances 1055

25.5 Polysaccharides 1055

CHEMICAL CONNECTIONS High-Fructose Corn Syrup 1057

25.6 Glucosaminoglycans 1058

Summary 1059 • Problems 1063

Chapter 26 Lipids 1071

26.1 Triglycerides 1071
26.2 Soaps and Detergents 1074
CONNECTIONS TO BIOLOGICAL CHEMISTRY FAD/FADH2: Agents for Electron
Transfer in Biological Oxidation-Reductions: Fatty Acid Oxidation 1077

26.3 Prostaglandins 1078

26.4 Steroids 1081

xiv Contents

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26.5 Phospholipids 1085
CHEMICAL CONNECTIONS Snake Venom Phospholipases 1087

26.6 Fat-Soluble Vitamins 1088

CHEMICAL CONNECTIONS Vitamin K, Blood Clotting, and Basicity 1090

Summary 1091 • Problems 1093

Chapter 27 Amino Acids and Proteins 1098

27.1 Amino Acids 1098
27.2 Acid-Base Properties of Amino Acids 1101
27.3 Polypeptides and Proteins 1106
27.4 Primary Structure of Polypeptides and Proteins 1107
27.5 Synthesis of Polypeptides 1113
27.6 Three-Dimensional Shapes of Polypeptides and Proteins 1117
CHEMICAL CONNECTIONS Spider Silk 1123

Summary 1124 • Problems 1128

Chapter 28 Nucleic Acids 1134

28.1 Nucleosides and Nucleotides 1135
28.2 The Structure of DNA 1137
CHEMICAL CONNECTIONS The Search for Antiviral Drugs 1140

28.3 Ribonucleic Acids 1143

CHEMICAL CONNECTIONS The Fountain of Youth 1144

28.4 The Genetic Code 1146

28.5 Sequencing Nucleic Acids 1148
CHEMICAL CONNECTIONS DNA Fingerprinting 1152

Summary 1153 • Problems 1155

Chapter 29 Organic Polymer Chemistry 1158

29.1 The Architecture of Polymers 1159
29.2 Polymer Notation and Nomenclature 1159
29.3 Molecular Weights of Polymers 1160
29.4 Polymer Morphology—Crystalline Versus Amorphous Materials 1161
29.5 Step-Growth Polymerizations 1162
CHEMICAL CONNECTIONS Stitches That Dissolve 1168

29.6 Chain-Growth Polymerizations 1169

CHEMICAL CONNECTIONS Organic Polymers That Conduct Electricity 1172

CHEMICAL CONNECTIONS The Chemistry of Superglue 1179

CHEMICAL CONNECTIONS Recycling of Plastics 1184

Summary 1186 • Problems 1189

Contents xv

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 Appendices:
1. Thermodynamics and the Equilibrium Constant A-1
2. Major Classes of Organic Acids A-2
3. Bond Dissociation Enthalpies A-3
4. Characteristic 1H-NMR Chemical Shifts A-4
5. Characteristic 13C-NMR Chemical Shifts A-5
6. Characteristic Infrared Absorption Frequencies A-6
7. Electrostatic Potential Maps A-7
8. Summary of Stereochemical Terms A-8
9. Summary of the Rules of Nomenclature A-12
10. Common Mistakes in Arrow Pushing A-20
11. Organic Chemistry Road Maps A-25
Glossary G-1
Index I-1

xvi Contents

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List of Mechanisms

Chapter 6 Reactions of Alkenes

Electrophilic Addition of HBr to 2-Butene (Section 6.3A)
Acid-Catalyzed Hydration of Propene (Section 6.3B)
Carbocation Rearrangement in the Addition of HCl to an Alkene (Section 6.3C)
Addition of Bromine with Anti Stereoselectivity (Section 6.3D)
Halohydrin Formation and Its Anti Stereoselectivity (Section 6.3E)
Oxymercuration-Reduction of an Alkene (Section 6.3F)
Hydroboration (Section 6.4)
Oxidation of a Trialkylborane by Alkaline Hydrogen Peroxide (Section 6.4)
Formation of an Ozonide (Section 6.5B)

Chapter 7 Alkynes
Addition of HBr to an Alkyne (Section 7.6B)
HgSO4/H2SO4 Catalyzed Hydration of an Alkyne (Section 7.7B)
Reduction of an Alkyne by Sodium in Liquid Ammonia (Section 7.8C)

Chapter 8 Haloalkanes, Halogenation, and Radical Reactions

Radical Chlorination of Ethane (Section 8.5B)
Allylic Bromination of Propene Using NBS (Section 8.6A)
Radical-Initiated Non-Markovnikov Addition of HBr to Alkenes (Section 8.8)

Chapter 9 Nucleophilic Substitution and b-Elimination

An SN2 Reaction (Section 9.2A)
An SN1 Reaction (Section 9.2B)
Rearrangement During Solvolysis of 2-Chloro-3-phenylbutane (Section 9.3F)
E1 Reaction of 2-Bromo-2-methylpropane (Section 9.6A)
E2 Reaction of 2-Bromopropane (Section 9.6B)
E2 Reaction of meso-1,2-Dibromo-1,2-diphenylethane (Section 9.7C)
E2 Reaction of the Enantiomers of 1,2-Dibromo-1,2-diphenylethane (Section 9.7C)
E2 Reaction of cis-1-Chloro-2-isopropylcyclohexane (Section 9.7C)
Hydrolysis of a Sulfur Mustard—Participation by a Neighboring Group (Section 9.10)

Chapter 10 Alcohols
Reaction of a 3° Alcohol with HBr—An SN1 Reaction (Section 10.5A)
Reaction of a 1° Alcohol with HBr—An SN2 Reaction (Section 10.5A)
Rearrangement upon Treatment of Neopentyl Alcohol with HCl (Section 10.5A)

xvii

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 Reaction of a Primary Alcohol with PBr3 (Section 10.5B)
Acid-Catalyzed Dehydration of 2-Butanol—An E1 Reaction (Section 10.6)
Acid-Catalyzed Dehydration of an Unbranched Primary Alcohol (Section 10.6)
The Pinacol Rearrangement of 2,3-Dimethyl-2,3-butanediol (Pinacol) (Section 10.7)
Chromic Acid Oxidation of an Alcohol (Section 10.8A)
Oxidation of a Glycol by Periodic Acid (Section 10.8C)
Oxidation of an Alcohol by NAD+ (Section 10.8C)

Chapter 11 Ethers, Epoxides, and Sulfides

Acid-Catalysed Intermolecular Dehydration of a Primary Alcohol (Section 11.4B)

Acid-Catalyzed Addition of an Alcohol to an Alkene (Section 11.4C)

Acid-Catalyzed Cleavage of a Dialkyl Ether (Section 11.5A)
Epoxidation of an Alkene by RCO3H (Section 11.8C)
Acid-Catalyzed Hydrolysis of an Epoxide (Section 11.9A)
Nucleophilic Opening of an Epoxide Ring (Section 11.9B)

Chapter 14 Mass Spectrometry

McLafferty Rearrangement of a Ketone (Section 14.3E)
McLafferty Rearrangement of a Carboxylic Acid (Section 14.3F)

Chapter 15 An Introduction to Organometallic Compounds

Formation of Dichlorocarbene and Its Reaction with Cyclohexene (Section 15.3B)

The Simmons-Smith Reaction with an Alkene (Section 15.3C)

Chapter 16 Aldehydes and Ketones

Grignard Reagent Reacting with Formaldehyde (Section 16.5A)
Organolithium Reagent Reacting with a Ketone (Section 16.5B)
Alkyne Anion Reacting with a Ketone (Section 16.5C)
Formation of a Cyanohydrin (Section 16.5D)
The Wittig Reaction (Section 16.6)
Base-Catalyzed Formation of a Hemiacetal (Section 16.7B)
Acid-Catalyzed Formation of a Hemiacetal (Section 16.7B)
Acid-Catalyzed Formation of an Acetal (Section 16.7B)
Formation of an Imine from an Aldehyde or Ketone (Section 16.8A)
Base-Catalyzed Equilibration of Keto and Enol Tautomers (Section 16.9)
Acid-Catalyzed Equilibration of Keto and Enol Tautomers (Section 16.9A)
Sodium Borohydride Reduction of an Aldehyde or Ketone (Section 16.11A)
Wolff-Kishner Reduction (Section 16.11E)
Acid-Catalyzed a-Halogenation of a Ketone (Section 16.12C)
Base-Promoted a-Halogenation of a Ketone (Section 16.12C)

xviii List of Mechanisms

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Chapter 17 Carboxylic Acids
Formation of a Methyl Ester Using Diazomethane (Section 17.7B)
Decarboxylation of a b-Ketocarboxylic Acid (Section 17.9A)
Decarboxylation of a b-Dicarboxylic Acid (Section 17.9B)

Chapter 18 Functional Derivatives of Carboxylic Acids

Fischer Esterification (Section 18.3E)
Hydrolysis of an Acid Chloride (Section 18.4A)
Hydrolysis of an Ester in Aqueous Base (Saponification) (Section 18.4C)
Hydrolysis of an Amide in Aqueous Acid (Section 18.4D)
Hydrolysis of an Amide in Aqueous Base (Section 18.4D)
Hydrolysis of a Cyano Group to an Amide in Aqueous Base (Section 18.4E)
Reaction of an Acid Chloride and Ammonia (Section 18.6A)
Reaction of an Ester with a Grignard Reagent (Section 18.9A)
Reduction of an Ester by Lithium Aluminum Hydride (Section 18.10A)
Reduction of an Amide by Lithium Aluminum Hydride (Section 18.10B)

Chapter 19 Enolate Anions and Enamines

Base-Catalyzed Aldol Reaction (Section 19.2A)
Acid-Catalyzed Aldol Reaction (Section 19.2A)
Acid-Catalyzed Dehydration of an Aldol Product (Section 19.2A)
Claisen Condensation (Section 19.3A)
Alkylation of an Enamine (Section 19.5A)
Michael Reaction—Conjugate Addition of Enolate Anions (Section 19.8A)

Chapter 20 Dienes, Conjugated Systems, and

Pericylic Reactions
1,2- and 1,4-Addition to a Conjugated Diene (Section 20.2A)
The Claisen Rearrangement (Section 20.6A)
The Cope Rearrangement (Section 20.6B)

Chapter 21 Benzene and the Concept of Aromaticity

Kolbe Carboxylation of Phenol (Section 21.4E)

Chapter 22 Reactions of Benzene and its Derivatives

Electrophilic Aromatic Substitution—Chlorination (Section 22.1A)
Formation of the Nitronium Ion (Section 22.1B)
Friedel-Crafts Alkylation (Section 22.1C)
Friedel-Crafts Acylation—Generation of an Acylium Ion (Section 22.1C)
Nucleophilic Aromatic Substitution via a Benzyne Intermediate (Section 22.3A)

Nucleophilic Aromatic Substitution by Addition-Elimination (Section 22.3B)

List of Mechanisms xix

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 Chapter 23 Amines
Formation of the Nitrosyl Cation (Section 23.8)
Reaction of a 2° Amine with the Nitrosyl Cation to Give an N-Nitrosamine
(Section 23.8C)

Reaction of a 1° Amine with Nitrous Acid (Section 23.8D)

The Tiffeneau-Demjanov Reaction (Section 23.8D)
The Hofmann Elimination (Section 23.9)
The Cope Elimination (Section 23.10)

Chapter 24 Catalytic Carbon-Carbon Bond Formation

The Heck Reaction (Section 24.3B)
The Catalytic Cycle for Allylic Alkylation (Section 24.4A)
The Catalytic Cycle of Cross-Coupling (Section 24.4A)

Chapter 26 Lipids
Oxidation of a Fatty Acid !CH2!CH2! to !CH"CH! by FAD (Section 26.2C)

Chapter 27 Amino Acids and Proteins

Cleavage of a Peptide Bond at Methionine by Cyanogen Bromide (Section 27.4B)

Edman Degradation—Cleavage of an N-Terminal Amino Acid (Section 27.4B)

Chapter 29 Organic Polymer Chemistry

Radical Polymerization of a Substituted Ethylene (Section 29.6A)
Ziegler-Natta Catalysis of Ethylene Polymerization (Section 29.6B)
Homogeneous Catalysis for Ziegler-Natta Coordination Polymerization (Section 29.6B)
Initiation of Anionic Polymerization of Alkenes (Section 29.6D)
Initiation of Anionic Polymerization of Butadiene (Section 29.6D)
Initiation of Cationic Polymerization of an Alkene by HF ? BF3 (Section 29.6D)
Initiation of Cationic Polymerization of an Alkene by a Lewis Acid (Section 29.6D)

xx List of Mechanisms

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Preface

Introduction
This Sixth Edition of Organic Chemistry significantly extends the transformation
started in the Fifth Edition. Students taking an organic chemistry course have two
objectives; the first is to learn organic chemistry, and the second is to establish the
intellectual foundation for other molecular science courses. Most often, these other
courses involve biochemistry or specialized topics such as materials science. This
textbook addresses these two objectives head-on by first presenting mechanistic and
synthetic organic chemistry geared toward giving students a fundamental under-
standing of organic molecules and reactions, as well as their mechanisms and uses
in organic synthesis. The text then builds upon the fundamentals by providing
an emphasis on bridging concepts that will prepare students for subsequent
science courses. Several unique elements including comprehensive end of chapter
summaries, a new paradigm for learning mechanisms and a new learning tool we
call Organic Chemistry Road Maps have been included to increase the efficiency of
student studying and learning.

Making Connections
All the important reaction mechanistic and synthetic details are still found throughout
the text, but we have increased the important connections between different reaction
mechanisms. The intent is to make the study of organic chemistry a process involving
the learning and application of fundamental principles and not an exercise in
memorization. Throughout this edition, the uniting concept of nucleophiles reacting
with electrophiles is highlighted. Especially helpful is the use of electrostatic potential
surface models of reacting molecules. These maps emphasize, in an easily interpreted,
color-coded fashion, how the majority of reactions involve areas of higher electron
density on one reactant (a nucleophile) interacting with areas of lower electron
density on the other reactant (an electrophile).

A Fresh Look at Mechanisms

Starting in Chapter 6, this edition introduces a revolutionary new paradigm for learn-
ing organic chemistry mechanisms. Students are introduced to a small set of individual
mechanism elements in Chapter 6. The mechanism elements are explained in detail,
including when they are appropriate to use. Reaction mechanisms throughout the
book are then described as combinations of these individual mechanism elements,
which are written in stepwise fashion. This new approach not only simplifies the learning
of mechanisms for students, it makes it easier for them to recognize similarities
and differences among related reactions. Most important, it makes the prediction
of reaction mechanisms simpler, analogous to a multiple choice situation in which
the correct mechanism element is chosen from a small menu of choices. Also, to
give students more confidence with writing mechanisms, Appendix 10 on Common
Mistakes in Arrow Pushing has been added. In addition, many mechanisms (particularly
in Chapter 18) have been broken down into more descriptive steps to make it easier
for students to understand the concepts involved.

xxi

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 A Fresh Look at Orbitals
An organic chemist’s theoretical framework for understanding electron density
within molecules is based on atomic and molecular orbitals. Paradoxically, organic
chemistry texts generally provide only passing coverage of orbitals, never revealing
their true shapes or full significance. The Sixth Edition is the first organic text to
paint a detailed picture of the orbital nature of electron density in Chapter 1 by
focusing on the interplay between the two complementary approaches to orbital
descriptions, valence bond theory and molecular orbital theory. Chapter 1 provides
a comprehensive description of how electronic theory is used by organic chemists
to understand structure, bonding, and reactivity. Significantly, students are given
easy-to-use guidelines that detail when and how to use electronic theory, even in
complex situations, such as molecules described by multiple resonance contributing
structures. The inclusion of calculated orbital diagrams side-by-side with the familiar
orbital cartoons gives students a greater appreciation for orbital sizes and shapes that
are reinforced throughout the book. The intent is to provide students with a strong
theoretical foundation that will give them unprecedented insight and intuition into
molecular structure and reactivity.

Mastering Skills
Mastering organic chemistry requires the development of certain intellectual skills.
To this end, eleven How To boxes highlight “survival skills” for organic chemistry
students. Topics include, How To Draw Alternative Chair Conformations of Cyclohexanes
(Section 2.5), How To Draw Curved Arrows and Push Electrons (Section 1.8), and How
to Write Mechanisms for Interconversions of Carboxylic Acid Derivatives (Section 18.4).

Helping Students Prepare More Efficiently

A key feature of the Sixth Edition is the end-of-chapter summaries, which are mini study
guides designed to help students prepare for class exams and later for standardized tests
such as the MCAT. When preparing for exams, students will benefit from the bulleted
lists of important concepts with highlighted keywords. These mini study guides make it
easier for students to identify hard-to-grasp material by referring them to the sections of
the text for a full explanation and then providing them with end-of-chapter problems
that test and reinforce their comprehension.
As a companion to the summary outlines, newly expanded end-of-chapter
summaries of reactions systematically list the reactions covered in each chapter.
These include prose descriptions of mechanisms as well as important information
such as observed stereochemistry or regiochemistry. Students will find these
reaction summaries particularly efficient when preparing for exam questions
requiring application of reactions in the context of new molecules or even multi-
step syntheses.
The appendix reference material has been enhanced with two unique items
to provide students with a quickly accessible source of important information. The
first is a thorough list of stereochemical definitions (Appendix 8). Stereochemical
terms are subtle and difficult to master, so having them compiled in one location
allows students to compare and contrast any new terms with those learned in earlier
chapters, as well as prepare for exams. In addition, Appendix 9, Summary of the Rules
of Nomenclature provides a practical listing of the nomenclature rules described
throughout the text. In response to student requests, this appendix provides a single
location for the rules students need when naming complex molecules that contain
multiple functional groups.

xxii Preface

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Organic Chemistry Applied to the Synthesis
of Important Molecules
Organic chemistry enables the synthesis of thousands of useful molecules. Synthetic
applications of the reactions covered in this text are emphasized throughout, partly
through the many new challenging Synthesis problems, the goal of which is to
demonstrate to students how synthetic organic chemistry is used in pharmaceutical
research and in the production of useful pharmaceuticals. The text provides
applications of the reactions to the synthesis of important molecules such as Valium,
fluoxetine (Prozac), meperidine (Demerol), albuterol (Proventil), tamoxifene, and
sildefanil (Viagra). Multi-Step Synthesis problems challenge students to develop their
own multi-step synthetic plan for converting a relatively simple starting material
into a more complex target molecule. Multi-step synthesis is supported by an
expanded description of retrosynthetic analysis in multiple chapters, including tips
on recognizing when to use certain reactions, such as those involving enolates in the
construction of complex structures.

Road Maps for Organic Chemistry, an Innovative

and Powerful Way to Visualize Organic Reactions
In this Sixth Edition, we introduce an innovation in organic chemistry learning that
we refer to as the Organic Chemistry Road Map. It is a graphical representation of
the different organic reactions taught in the context of the important functional
groups. The functional groups of an organic chemistry road map are analogous to
cities on a real road map, and the reactions are like the roads between those cities.
Arrows are used to represent routes that are known between functional groups,
and the reagents required to bring about each reaction are written next to the
corresponding arrow. Multi-step synthesis questions are often the most challenging
for organic chemistry students even though synthesis is at the core of organic
chemistry as a discipline. The power of an Organic Chemistry Road Map is that it
helps students visualize the reactions needed to interconvert key functional groups
in multi-step synthesis problems. The construction and use of Organic Chemistry
Road Maps are introduced in the end-of-chapter problems beginning in Chapter 6
and is presented in complete form in a new Appendix 11.

Organic Chemistry Applied to Biology

The application of organic chemistry principles to important biological molecules
is integrated where appropriate to establish a bridge with biochemistry courses. In
particular, Connections to Biological Chemistry gives special attention to those aspects of
organic chemistry that are essential to an understanding of the chemistry of living
systems. For example, the organic chemistry of amino acids is highlighted beginning in
Section 3.9, along with the importance of alkene geometry to both membrane fluidity
and nutrition (Section 5.4). How hydrogen bonding is involved with drug-receptor
interactions (Section 10.2) is discussed. Importantly, these Connections to Biological
Chemistry features have been added throughout the book, not just at the end, in
recognition of the fact that not all instructors make it through the biological chemistry
chapters at the end of the text. Relevance to practical application is also emphasized
in an expanded array of essays titled Chemical Connections. Topics include: medicines
like penicillins and cephalosporins (Section 18.1), food supplements like antioxidants
(Section 8.7) and materials science concepts such as spider silk (Section 27.6). These
sections provide a bridge between the theory of Organic Chemistry and well-known,
current, practical applications. A list of the Chemical Connections as well as Connections to
Biological Chemistry essays can be found on the inside back cover of this text.

Preface xxiii

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 Unique Organizational Elements
❱ Together, Chapter 1 (comprehensive description of electronic theory) and Chapter 3
(detailed description of acids and bases in organic chemistry) provide a fundamental
grasp of molecular structure and properties, giving students the basis to understand all
aspects of the mechanistic discussions that follow. Equipping students with the proper
tools from the beginning gives them a predictive command of reactivity and foster
chemical intuition, while discouraging superficial memorization.
❱ Because of the increased use of NMR spectroscopy in chemical and biochemical
research, as well as the growing dependence on MRI for medical diagnosis, Chapter 13,
Nuclear Magnetic Resonance Spectroscopy, is detailed and up-to-date. The practical
and theoretical aspects concerning NMR spectra and signal splitting patterns are
highlighted and a complete description of FT-NMR provides a stronger technical
connection to MRI.
❱ Carbonyl chemistry (Chapters 16–19) is placed earlier than most texts so professors
have the time to teach this material to the majority of students in an organic chemistry
class, who are geared toward a life-science degree and/or career in the health
professions. Carbonyl chemistry is fundamental to the chemistry of living systems
and connections between carbonyl chemistry and the chemistry of carbohydrates is
highlighted earlier in the book. This latter change mirrors the increasing importance
of carbohydrate chemistry on the MCAT.
❱ Chapter 24, Carbon–Carbon Bonding Forming Reactions, combines knowledge
from previous chapters and challenges students to devise syntheses. The intent to is
expose students to the excitement and challenge of modern synthetic chemistry.

New to the Sixth Edition

In this edition, we introduce revolutionary new approaches to teaching organic
chemistry that are designed to promote an unprecedented level of student learning
and comprehension.

❱ Chapter 1 was extensively rewritten. The two different approaches to electronic

theory and bonding are described in a comprehensive fashion. Importantly,
students are shown how to use these theories, even in complex situations, such as
those involving resonance contributing structures.
❱ Calculated orbitals were added throughout the text to provide students with
important insights concerning electron density location extending far beyond that
obtained using only the cursory description and cartoon depiction of orbitals.
❱ Energy diagrams are introduced in the acid-base chapter (Chapter 4) to give
students an appreciation for the energetic aspects of chemistry in the context of
the mechanistically most straightforward reaction they will encounter, namely
proton transfer. Placing energy diagrams in Chapter 4 also introduces important
thermodynamic and kinetic concepts early in the course to help lay the foundation
before discussing specific functional group reactions.
❱ Chapter 6 has new material on the correct use of arrows to indicate electron
movement and simplifies the learning of mechanisms. We introduce a small
number of mechanism elements and then explain how these can be assembled
in predicable ways to construct in systematic fashion the vast majority of organic
reaction mechanisms. This paradigm-shifting approach to teaching mechanism gives
students the tools they need to understand and predict mechanisms eliminating the
need for superficial memorization.
❱ Organic Chemistry Road Maps are introduced in Chapter 6. This innovation in
organic chemistry learning gives students a visual representation of the different
reactions and shows how these road maps can be used in specific sequences for the
multi-step synthesis of complex molecules.

xxiv Preface

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❱ Chapter 9 was extensively rewritten to provide a clear description of the interplay
of parameters that determine mechanism among substitution and elimination
reactions. Students are shown how to analyze structures of the nucleophile and
electrophile and the reaction conditions that enable the accurate prediction of
reaction outcome.
❱ In Chapter 16, there is an increased emphasis on mechanism as the new format
was used for all mechanisms, and several new mechanism boxes were added.
❱ In Chapter 18, Section 18.3 on Characteristic Reactions was expanded to make it
easier to understand and an entirely new section was added in order to underscore
the key concept of microscopic reversibility.
❱ Chapter 20 was reorganized and renamed to reflect an expanded description
of pericyclic reaction theory with application to the Diels-Alder reaction and
sigmatropic shifts. The advanced concept of frontier molecular orbital (FMO)
interactions is now introduced and used to explain the various reactions in the
chapter.
❱ Chapter 24 has been expanded to include the Stille and Sonagashira couplings.
❱ OWL (Online Web Learning) for Organic Chemistry This fully integrated online
system features more than 6,000 practice and homework problems. OWL for Organic
Chemistry provides students with instant analysis and feedback to homework
problems, modeling questions, end-of-chapter questions, molecular-structure
building exercises, and animations created specifically for Organic Chemistry, Sixth
Edition.

Special Features
❱ New A revolutionary new paradigm for learning organic chemistry mechanisms is
introduced in Chapter 6 and then used throughout the book.
❱ New Organic Chemistry Road Maps are introduced as an innovation in organic
chemistry learning. Organic chemistry road maps are presented in end-of-chapter
problems and a new Appendix 11.
❱ New Accurate Orbital Diagrams have been added throughout the text to provide
students with a more realistic understanding of electronic theory as applied to
organic chemistry.
❱ New Two new appendices Appendix 10 on Common Mistakes in Arrow Pushing
and Appendix 11 on Organic Chemistry Road Maps.
❱ Updated Chemical Connections These essays illustrate applications of organic
chemistry to everyday settings. Topics range from Chiral Drugs to Drugs That Lower
Plasma Levels of Cholesterol and The Chemistry of Superglue. A complete list can
be found on the inside of the back cover.
❱ Updated Connections to Biological Chemistry Application of organic chemistry
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Preface xxv

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them. In order both to ascertain such suspicion, and
discover so dangerous a person, all the Nuns were
ordered into one room, and there made to strip
themselves stark naked; when the Abbess, with her
spectacles on her nose (whence the Tale has received
its name) inspected them all, one after another,
carefully. To relate how the young Man,
notwithstanding the ingenious precautions he had
taken, came to be found out, and how the Abbess’s
spectacles were thrown from her nose and broken, is
foreign to our subject: let it here suffice to say that the
young Man was really found out; and that the Nuns,
except those who had been concerned with him, who
were previously locked up in a safe place,—that the
Nuns, I say, laid hold of him, led him into a wood that
stood close to their Convent, and there tied him to a
tree, naked as he was, in order to make him atone for
his audaciousness by a smart flagellation. Having
forgotten to supply themselves with the necessary
instruments of correction, they ran back to the Convent
to fetch them, and whether from the mislaying of a key,
or some other accident, were detained a little time. In
the mean time a Miller, riding upon his Ass, went
through the wood; and seeing the young Man in the
abovementioned plight, stopped, and asked him the
reason of it: to which the latter made answer, that it
was those wicked Nuns who had put him in that
situation, because he would not gratify their wanton
requests; that he had rather die than be guilty of such
thing. The Miller then cast upon him a look of the
utmost contempt ... but it will be better to refer the
Reader to the abovementioned Author himself, for the
inimitable Dialogue that passed between the young
Man and the Miller: here it will be enough to say, that
this latter proposed to the other to put himself in his
place, and warranted him he would behave in quite a
different manner, and much more to the satisfaction of
the Nuns than he had done. The young Man had no
need of much encouragement to accept the proposal:
after the Miller had released him, and stripped himself,
he tied him fast to the same tree, and had just time
enough to steal away, and hide himself behind some
neighbouring bush, when the Nuns rushed again out of
the same door at which they had got in, armed with all
the disciplines and besoms they had been able to find
in the Convent. They immediately marched up to the
person who was tied to the tree, and without minding
the broad shoulders and brawny limbs which were now
offered to their view, began to use their disciplines with
great agility. In vain did the Miller expostulate with
them on their using him so ill: in vain did he
remonstrate that he was not the Man whom they took
him to be; that he was not that beardless stripling, that
milk-sop simpleton, with whom they had formerly had
to do, that woman-hater who had given them so just a
cause of dissatisfaction; that they ought to try him
before they entertained so bad an opinion of him:—in
vain did he even at last, in the extremity of pain, apply
to the utmost powers of his native language, to convey
to them the clearest ideas he could, both to those
wishes he supposed in them, and of his great abilities
to gratify them: the more loudly and clearly he spoke,
the more unmercifully they laid on, and only left him
when they had worn out their disciplines.
Cervantes likewise, whose authority is equal to that
of any Author, and who has moreover thrown a great
light upon the subject of flagellations, has introduced a
fact which greatly serves to confirm the observations
we are discussing here. I mean to speak of what
happened in that memorable night in which the Senora
Rodriguez paid a visit to the valorous Don Quixote, in
his bed. That Gentlewoman having, in the course of
the conversation she had with the Knight, dropped
several reflections of a very bad kind on the Duchess
and the fair Altisidora, who were at that very instant
listening at the door, these two Ladies, though justly
and greatly offended at the liberty that was thus taken
with their character, recurred to no expedient of a
coarse and rough kind to avenge the insult; but they
immediately applied to the summary, yet smart,—
genteel, yet effectual, mode of correction here alluded
to, namely, a flagellation. And here the Author we
mention has taken an opportunity of giving a singular
instance of the readiness of wit of the fair Sex, and of
the quickness with which they usually extricate
themselves out of the seemingly most perplexing
difficulties. The Duchess and Altisidora were entirely
destitute of the necessary instruments to inflict the
chastisement they had resolved upon; but they had the
great presence of mind to think of using their slippers
for that purpose: they presently pulled them off their
feet; bounced the door open; ran to the Senora
Rodriguez; in the twinkling of an eye made her ready
for flagellation, and immediately began to exert their
new weapons with great dexterity. Thence, still in the
dark, they passed to the astonished Knight, who lay
snug in his bed, and who, by his listening to the stories
of the Senora, and also by his questions, had
encouraged her to proceed in her reflections (a thing
which he might full as well have avoided doing) and
bestowed upon him a few of those favours they had so
plentifully heaped upon the above Gentlewoman.
At this place might also be mentioned, as being
extremely well in point to the subject we are treating,
the kind of satisfaction required by Dulcinea, from
Sancho, and that which the Lady introduced by Butler,
prescribed to the renowned Hudibras, while he was in
the stocks; though, I confess, it might be said that the
corrections here alluded to, were only advised, not
inflicted, by the above Ladies. But it will suffice to
mention, as a conclusion of these quotations from
great Authors, the manner in which Lazarillo de
Tormes, the notorious Spanish Cheat, was served by
his four Wives. Having found out the place of his
abode, they immediately agreed among themselves to
serve him with the elegant kind of chastisement here
mentioned; and having all together surprized him one
morning, while he was asleep, they tied him fast to his
bed, and served upon him one of the most dreadful
flagellations that ever were inflicted, since the use of
them has been contrived, as we are told in the History
of the Life of the said Lazarillo; a Book which is still in
repute in Spain, it being written with humour, and
containing true pictures of the manners of that Country,
and being even, as some say, founded on real facts.
Nor are true and well-authenticated instances
wanting, to confirm the same observations. None,
however, can be mentioned, that sets in a stronger
light the love of justice inherent in the female Sex, and
their constant attention to make choice of expedients
of an elegant kind to express their resentment, than
the custom that prevails in France and Italy, and
perhaps in other Countries, according to which, Ladies
use to flagellate their acquaintances, while they are yet
in bed, on the morning of the day of the festival of the
Innocents; whence this flagellatory custom is called
“giving the Innocents” (dar gli Innocenti): the word
Innocent, we may observe, has, in both the Italian and
French languages, besides the English signification of
it, that of fool, or simpleton; hence the words, the Day
of the Innocents, seem also to signify in those two
languages, the Fools day, or the day of the Unwary.
Nay, so well established is the custom we mention,
that Women, in those parts, look upon that day, as a
day of general justice and retribution, or an Assize or
Sessions day, to which they refer taking satisfaction for
the slight offences they may receive in the course of
the year, especially from their male friends. They even
will sometimes, when the latter hesitate too much in
granting their requests, or misbehave in any manner,
hint to them the fatal consequences that may ensue
from such a conduct, and plainly intimate to them, that
a certain day in the year is to come on which every
thing is to be atoned for.
When this important day is arrived, those Ladies
who have agreed to join together in the same party, or
(to continue the comparison drawn from the law that
has been above employed) who have agreed to go
together upon the circuit, repair early in the morning to
the appointed place of rendezvous, for instance the
apartment of one of them, sufficiently provided with
disciplines from their respective kitchens; and after
laying the plan of their operations, they sally out, to
take a round to the apartments of their different
acquaintances.
The prudent and cautious, on such an important day,
take great care to secure well the bolts and locks of
their doors; or rather, fearing that sleep should
overcome them, and knowing how fatal neglect might
prove, they take that precaution on the evening before,
when going to bed, and as an additional security, they
heap all the chairs and tables against the door. Others,
who are of a bold and daring spirit, on the contrary
affect on that day, to leave the doors of their rooms
wide open, and stay in bed, resolved to wait the event,
and undauntedly to face the storm. However, as such
an affectation of bravery seems to indicate that some
present trick, or at least some future retaliation of
some kind or other is intended, the Ladies commonly
keep clear from a place they judge so ominous; unless
there happens to be one among them of an
uncommonly courageous turn of mind, who places
herself in the van, encourages the whole party; and
they all together rush into the room and fall upon the
adventurous Hero, who is then made to pay dearly for
his temerity. When this does not happen to be the
case, and at the same time they find the doors of all
those persons whom they had expressly marked out
for chastisement, to be proof against either a coup-de-
main or a regular siege, as they must not part without
some effectual business has been transacted, the
cloud commonly breaks upon some unfortunate
Simpleton, who has left his door open for no other
reason than because he had forgot what day of the
month it was; they lay fast hold of him, and seldom
leave him before their disciplines are worn out to the
stumps. The story is soon circulated in whispers in the
neighbourhood; and if any person who has not yet
heard of it, observes that the Gentleman appears that
day uncommonly grave and sulky, his wonder
presently ceases, when he is told that, on the morning,
they have given him the Innocents.
The custom we mention, seems to be of pretty
ancient date; it is alluded to in that old Book formerly
quoted, The Tales of the Queen of Navarre. A Man, an
Upholsterer by trade, as it is said in one of these Tales
(for Men will sometimes avail themselves of the
practice in question when it may serve their turn) a
Man was in love with his servant Maid; and as he did
not know how to find an opportunity to escape the
vigilance of his Wife, and be alone with her, he
pretended, in a conversation he brought about on the
subject, on the eve of Innocent’s day, to find much fault
with the Maid; complained that she was a lazy Wench,
and so on; and added, that, in order to teach her
better, he proposed, on the next morning, to give her
the Innocents. The Wife greatly applauded his
resolution: at break at day, he accordingly rose from
his bed, took up a discipline of such a monstrous size,
that his Wife’s heart aked to think what correction the
Maid was about to undergo, and ran up stairs with a
disposition of seemingly very great severity: however, I
am happy to inform the Reader, that, after he had
bounced the door open, and at first frighted the Maid
very much, every thing was concluded in an amicable
manner.
If from Ladies of a middling station in life, and in the
class of Upholsterers, we turn our eyes towards Ladies
of rank, and Court Ladies, we shall meet with
instances no less instructive and interesting.
We may, in the first place, mention the case of the
Poet Clopinel, which has been alluded to in a former
Chapter. This Poet, who was also called John of
Mehun (a small Town on the river Loire) lived about the
year 1300, under the reign of Philip the Fair, King of
France, at whose Court he was well received. He
wrote several Books, and among others translated into
French the Letters of Abelard to Heloisa: but that of his
works which gave him most reputation, was his
conclusion of the celebrated Roman de la Rose; a
Poem of much the same turn with Ovid’s Art of Love,
which had been begun by William de Lorris, and met
with prodigious success in those times, and was
afterwards imitated by Chaucer. However, Clopinel
gave great offence to the whole Sex, by four lines he
had inserted in that Poem, the meaning of which is as
follows:—“All of you are, will be, or were, either in
deed, or intention, wh-res; and whoever would well
search into your conduct, wh-res would find you all to
be.”
Toutes êtes, serez, ou futes
De fait ou de volonté, putes;
Et qui bien vous chercheroit
Toutes putes vous trouveroit.
The meaning of these verses, if we take from them
the coarseness of the expressions, which did not
perhaps sound so harsh in those times as they would
in our days, did not at bottom differ from the well-
known line of Pope,
“—Every Woman is at heart a Rake.”

Yet we do not hear that this Poet suffered any

flagellation on that account, from the Court Ladies, or
any other Ladies; whether it was that he prudently took
care, after writing the above line, to keep for some time
out of the way, or that the Ladies felt no resentment at
the accusation. With respect to Clopinel, however, the
case proved otherwise: and whether his expressions
really had, notwithstanding what has been above
suggested, much the same coarse meaning as now, or
Ladies had, in those days, a nicer sensibility to any
thing that might touch their honour, the Ladies at Court
were much offended at the harsh charge that was thus
brought against the whole Sex without distinction: they
resolved to make the insolent Poet properly feel the
effects of their resentment: and as they were at the
same time firmly determined, especially being Court
Ladies, not to use any expedient but of an elegant and
refined kind, they resolved upon a flagellation. One
day, accordingly, as Clopinel was coming to Court,
entirely ignorant of the fate that awaited him, the
Ladies, who had previously supplied themselves with
proper instruments, laid hold of him, and immediately
proceeded to make him ready for correction. No
possible assistance could rescue Clopinel from having
that chastisement served upon him which he so justly
deserved, except his wit; which happily did not fail him
in so imminent a danger, and suggested to him to ask
leave to speak a few words. The favour was granted
him, with express injunction, however, to make his
story short: when, after acknowledging the justice of
the sentence that had been passed upon him, he
requested it, as an act of mercy, that that Lady who
thought herself most affronted by his lines, should give
the first blow: this request struck the Ladies with so
much surprise (owing no doubt to the fear every one of
them immediately conceived, of giving an advantage
against herself for which she might afterwards repent)
that, to use the expression of the Author of Moreri’s
Dictionary, from which this fact is extracted, the rods
fell from their hands, and Clopinel escaped
unpunished.
Court Ladies of more modern times, have given
similar instances of refinement and elegance in their
method of revenging the affronts they had received.
On this occasion the Reader may be reminded of the
case of the Marchioness of Tresnel, which has been
related at length in a former place. Another instance of
the justice of Ladies, still more interesting by far,
occurred at the Court of Russia about the year 1740.
The object of the Ladies resentment, was a Fop of
quality, lately returned from his Travels; nor will the
Reader question the propriety of the flagellation that
was served upon him, when he shall be informed that
this presumptuous Spark had been guilty of no less an
offence than having publicly boasted of having
received favours which had never been shewn him.
The fact is related in a Book intitled, Letters from
Russia, which was published by a Lady whose
husband resided at that Court in a public capacity,
between the years 1730 and 1740: the book is written
in a pleasing style, and contains a deal of interesting
information concerning the Russian Court at that time.
The Author, it is said, lived a few years ago at Windsor:
her Letters from Russia were addressed to a female
friend in England.
In the eleventh letter, the following account is
contained. ‘I long to tell you a story; but your prudery (I
beg pardon, your prudence) frightens me: however, I
cannot resist; so pop your fan before your face, for I
am going to begin. We have here a young fellow of
fashion, who has made the tour of France, &c. &c. At
his return he fell in company with three or four pretty
Women at a friend’s house, where he sung, danced,
laughed, was very free with the Ladies, and behaved
quite a-la-mode de Paris. As he had given the gazing
audience a specimen of his airs, so he did not fail
afterwards to brag of the fondness of the Ladies for
him, and of the proofs they had given him of it. This he
repeated in all companies, till it reached the ears of the
husbands, who looked glum in silence; and at last, in
plain terms, expressed the cause of their ill-humour.’
To abridge the account, it will suffice to say that the
Ladies resolved to punish the vain-boasting fop as he
deserved: a letter was written to him by one of them,
appointing a place where she was to meet him: “he
flew on the wings of love to the rendezvous,”
perfumed, we are to suppose, and in his smartest
dress. Though he expected to meet only one of the
Ladies, he found them all four waiting for him; and
instead of that delightful afternoon he had prepared
himself to spend, he was entertained with a most
serious flagellation. ‘Some say (continues the Author
who relates this fact) that the Ladies actually whipped
him; others, they ordered their maids to do it: that the
punishment was inflicted with so much rigour as to
oblige him to keep his bed some time, is certain; but
whether the Ladies were executioners or spectators
only, is a doubt.’
For my own part, I shall be bolder than the fair
Author who gives this account; and I will take upon
myself to decide that the Ladies were spectators only.
Had this young fellow of fashion we are speaking of,
committed an offence of no very grievous kind; had he,
for instance, been guilty of some word, or even action,
moderately indecent in the presence of the Ladies, or
affronted them by some ill-timed jokes, or had he, like
Clopinel, indulged himself in a bon-mot, or even a
whole song, against the honour of the Sex, then we
might suppose the Ladies arms, to have possessed
sufficient vigour to have served him with a correction
proportioned to the degree of his guilt. Not that I
consider, however, as some Readers will perhaps do,
the falsehood of the facts he had boasted of, as being
any aggravation of his offence: very far from it: it is
when such facts are true, that the boasting of them is
really a fault of a black nature: it is such, in my humble
opinion, that no possible flagellation can atone for it;
the ungrateful Tell-tale ought to be stitched in a bag,
and thrown into the river. However, as the vain
speeches of the young fellow were in themselves
highly wicked, we are to suppose that the Ladies
trusted the care of chastising him to more robustious
hands than their own; and we must side with that part
of the Public, who thought that they ordered their
Maids to perform for them; that is to say, a set of Maid
slaves selected among the stoutest of those who
composed their housholds, Maids imported from the
banks of the Palus-meotis, or the Black Sea, and who
thought it a glorious opportunity for shewing their
mistresses their zeal in serving them. This supposition
agrees extremely well with the ensuing part of the
account, viz. that this vain-boasting Coxcomb was
obliged to keep his bed some time: who knows?
perhaps five or six weeks.
The only personal share, we are to think, the Ladies
took in the affair, was, when the execution was
concluded, to admonish the culprit as to his future
conduct. Milton makes the observation, which is
quoted by the Author of the Spectator, that the Devil
seemed once to be sensible of shame; it was when he
received a censure (unexpected for him, we may
suppose) from a young Angel of remarkable beauty. In
like manner, what must have been the shame of that
young Coxcomb, who perhaps had never blushed in
his life, when he heard himself addressed by the
Ladies who had caused him to be served with so just a
chastisement! what must have been his remorse for
his naughty behaviour! his grief in considering, that,
had he perhaps waited patiently a little time longer,
they would have willingly honoured him with their most
valuable favours! The Lady who possessed the easiest
and most elegant delivery, advanced towards him a
few steps; and, accompanying her short speech with
the action of an arm of an exquisite form and hand as
white as snow, and with a frown on her face, which,
without lessening its beauty, gave a true expression of
her just resentment, she made him sensible, in few
words, of the greatness of his fault, and the justice of
the chastisement that had been administered to him:
then turning towards the Calmouk and Tartarian Maids
who had so well executed her former orders, she
directed them to shew him the way to the street door.
To these instances of the justice of Ladies, we may
add those of the corrections they have bestowed upon
their husbands; as they have an undoubted right. A
very remarkable case of that sort is alluded to, in the I.
Canto P. II. of Hudibras.
Did not a certain Lady whip
Of late her husband’s own Lordship?
And, though a Grandee of the House,
Clawed him with fundamental blows.
Tied him stark-naked to a bed-post,
And firked his hide, as if sh’ had rid post;
And after, in the Sessions Court,
Where whipping’s judged, had honour for’t.
The noble person here mentioned, was Lord
Munson: similar acts of authority on their husbands,
were performed, about the same time, by Sir William
Waller’s Lady, Mrs. May, and Sir Henry Mildmay’s
Lady. From these instances we find, that, amidst the
general wreck of the Monarchical, Aristocratical, and
Clerical, powers in the Nation, and while the King,
Lords, and High Clergy, had their prerogatives wrested
from them and annihilated, Wives knew how to assert
their jurisdiction over their Husbands, and preserve
their just authority. The subject however is too deep to
be discussed at large here: I intend to offer more facts
to the Public in a separate Work, which will be a
compleat Treatise, and a kind of Matrimonial Code in
which the true principles shall be laid concerning the
rights of Wives, and the submission of Husbands[112].
Those Authors who have treated of the manner in
which Men ought to behave in their intercourse with
the fair Sex, have been so sensible that the latter must
unavoidably, at one time or other, have occasion to
bestow lectures and corrections on their Suitors or
Lovers (and also their Husbands) that they have made
it a point to these, to bear those momentary
mortifications with patience and humility, and not to
think that such submission reflects any dishonour upon
them. This is the precept expressly given by Ovid, in
his Art of Love;—‘Do not think it in any degree
shameful for you, to submit to the harsh words, and
the blows, of the young Woman you court.’
Nec maledicta puta, nec verbera ferre puellæ
Turpe——

And indeed we find that those Lovers who have best

understood their business, have not only constantly
followed the advice of Ovid, and chearfully submitted
to receive such corrections as their Mistresses were
pleased to impose upon them; but when they have
happened to have been involuntarily guilty of offences
of a somewhat grievous kind, they have done more;
they have, of themselves, offered freely to submit to
them. Thus Polyenos, in the Satyr of Petronius, who
had been guilty with Circe of one of those faults which
Ladies so difficultly prevail upon themselves to forgive,
who had in short committed that offence which the
abovementioned Miller boasted he never happened to
be guilty of, wrote afterwards to her,—“If you want to
kill me, I will come to you with an iron weapon; or if you
are satisfied with stripes, I run naked to my Mistress.”
(Polyaenos Circæ salutem.... Sive occidere placet,
cum ferro venio; sive verberibus contenta es, curro
nudus ad dominam. Id tantum memento, non me, sed
instrumenta, peccasse, &c. Cap. 130.)
The illustrious Count of Guiche, as we find in the
Count of Buffi’s Amorous History of Gauls, a Book
which caused the disgrace of its Author, on account of
the liberties he had taken in it with the character of
King Lewis the Fourteenth, and his Mistress, Madame
de la Valiere, the Count of Guiche, I say, one of the
first-rate Beaux of the Court of the King just
mentioned, behaved in the same manner that
Polyenos had done. Having committed a fault with the
well-known Countess of Olonne, of the same kind with
that of Polyenos, he wrote the next day to the
Countess in much the same terms as the latter had
done to Circe. ‘If you want me to die, I will bring you
my sword; if you think I only deserve to be flagellated, I
will come to you in my shirt.’ (Si vous voulez ma mort,
j’irai vous porter mon épée; si vous jugez que je ne
mérite que le fouët, j’irai vous trouver en chemise.)
The celebrated Earl of Essex, in one of the
misunderstandings between him, and Queen
Elizabeth, having given her a more than common
cause of offence, and wishing in a particular manner to
soothe her resentment, wrote to her in much the same
terms as those abovementioned. He gave the Queen,
as we find in Camden, explicit thanks for the
corrections she had inflicted upon him, and kissed (to
use his words, as recited by the above Author) and
‘kissed her Majesty’s Royal Hand, and the rod which
had chastised him.’ Not that I propose, however, by
quoting the above expressions of the Earl, positively to
affirm that they were meant to allude to any express
corrections of the kind mentioned in this Book, which
his Royal Mistress had at any time used to inflict upon
him, or the other persons in her service; but yet, when
we, on the one hand, attend to the invariable
corruption, profligacy, shamelessness, wickedness,
and perverseness of Ministers, ever since the
beginning of the world, and on the other, consider to
what degree those employed by the Princess we
speak of, proved just, and zealous for the public good,
we cannot help thinking that that great and
magnanimous Queen had found out some very
peculiar method of rendering them such[113].
[112] The abovementioned Lord Munson had sat as
one of the Judges at the King’s Trial: he lived at St.
Edmundsbury, when his Wife, with the assistance of
her Maids, served him with a flagellation. An allusion to
the same fact is also made in a song which is to be
found in the Collection of Loyal Songs. The thanks her
Ladyship received from the Sessions Court, were
owing to its being generally suspected the Noble Lord
had altered his political principles; for which his Wife
had chastised him.
It really seems that a kind of flagellating fanaticism
had taken place, in those days, in this Country, similar
in many respects to that which arose in the times of
Cardinal Damian and Dominic the Cuirassed: there
was this difference however, that it had for its object to
flagellate, not one’s-self, but others; which was the
wiser folly of the two. The thanks publicly decreed to
Lady Munson (not to mention several puritanical
publications of those days) are proofs of that
flagellating spirit we mention; as well as the correction
inflicted by Zachary Crofton upon his servant maid
(see p. 238), and the pamphlet he wrote in defence of
it; which was very likely grounded on certain religious
tenets concerning the mortification of the flesh, &c. that
were current in those times.
[113] It came out, in a certain late debate in the
House of Commons (June 1783) that, among the
expences in the office of a prime Minister, about a year
before out of place, there was an article (introduced
among the Stationary ware) of three hundred and forty
pounds for whip-cord, for one year. It is very probably
since the days of Queen Elizabeth, that this kind of
commodity has been made part of the national
expenditure.
 C H A P. XXIII.

Formation of the public Processions of

Flagellants. Different success they meet with,
in different Countries.

THE example which so many illustrious personages

had given of voluntarily submitting to flagellation, and
the pains which Monks had been at, to promote that
method of mortification by their example likewise, as
well as by the stories they related on that subject,
had, as we have seen, induced the generality of
people to adopt the fondest notions of its efficacy.
But about the year 1260, the intoxication became as
it were complete. People, no longer satisfied to
practise mortifications of this kind in private, began to
perform them in sight of the Public, under pretence of
greater humiliation: regular associations and
fraternities were formed for that purpose; and
numerous bodies of half-naked Men began to make
their appearance in the public streets, who after
performing a few religious ceremonies contrived for
the occasion, flagellated themselves with astonishing
fanaticism and cruelty.
The first institution of public Associations and
Solemnities of this kind, must needs have filled with
surprise all moderate persons in those days, and in
fact we see that Historians of different Countries,
who lived in the times when their ceremonies were
first introduced, have taken much notice of them, and
recorded them at length in their Histories or
Chronicles. I will lay extracts from a few of these
different Books, before the Reader; it being the best
manner, I think, of acquainting him with the origin of
these singular flagellating solemnities and
processions, which continue in use in several
Countries.
The first Author from whom we have a
circumstantial account on that subject, is that Monk
of St. Justina, in Padua, whose Chronicle Wechelius
printed afterwards at Basil. He relates how the public
superstitious ceremonies we mention, made their first
appearance in the Country in the neighbourhood of
Bologna, which is the spot where, it seems, they took
their first origin, and whence they were afterwards
communicated to other Countries. The following is
the above Author’s own account.
 “When all Italy was sullied with crimes of every
kind, a certain sudden superstition, hitherto unknown
to the world, first seized the inhabitants of Perusa,
afterwards the Romans, and then almost all the
Nations of Italy. To such a degree were they affected
with the fear of God, that noble as well as ignoble
persons, young and old, even children five years of
age, would go naked about the streets, with only their
private parts covered, and, without any sense of
shame, thus walked in public, two and two, in the
manner of a solemn procession. Every one of them
held in his hand a scourge made of leather-thongs,
and with tears and groans they lashed themselves on
their backs, till the blood ran; all the while weeping
and giving tokens of the same bitter affliction as if
they had really been spectators of the passion of our
Saviour, imploring the forgiveness of God and his
Mother, and praying that He who had been appeased
by the repentance of so many Sinners, would not
disdain theirs.
“And not only in the day time, but likewise during
the nights, hundreds, thousands, and ten thousands
of these Penitents, ran, notwithstanding the rigour of
winter, about the streets, and in churches, with
lighted wax-candles in their hands, and preceded by
Priests who carried crosses and banners along with
them, and with humility prostrated themselves before