Welcome to the fascinating world of organic chemistry. You are about to embark on an exciting journey. This book has been written with students like you in mind—those who are encountering the subject for the first time. The book’s central goal is to make this journey through organic chemistry both stimulating and enjoyable by helping you understand central principles and asking you to apply them as you progress through the pages. You will be reminded about these principles at frequent intervals in references back to sections you have already mastered.
You should start by familiarizing yourself with the book. Inside the front and back covers is information you may want to refer to often during the course. The list of Some Important Things to Remember and the Reaction Summary at each chapter’s end provide helpful checklists of the concepts you should understand after studying the chapter. The Glossary at the end of the book can also be a useful study aid. The molecular models and electrostatic potential maps that you will find throughout the book are provided to give you an appreciation of what molecules look like in three dimensions and to show how charge is distributed within a molecule. Think of the margin notes as the author’s opportunity to inject personal reminders of ideas and facts that are important to remember. Be sure to read them.
Work all the problems within each chapter. These are drill problems that you will find at the end of each section that allow you to check whether you have mastered the skills and concepts the particular section is teaching before you go on to the next section. Some of these problems are solved for you in the text. Short answers to some of the others—those marked with a diamond—are provided at the end of the book. Do not overlook the “Problem-Solving Strategies” that are also sprinkled throughout the text; they provide practical suggestions on the best way to approach important types of problems.
In addition to the within-chapter problems, work as many end-of-chapter problems as you can. The more problems you work, the more comfortable you will be with the subject matter and the better prepared you will be for the material in subsequent chapters. Do not let any problem frustrate you. If you cannot figure out the answer in a reasonable amount of time, turn to the Study Guide and Solutions Manual to learn how you should have approached the problem. Later on, go back and try to work the problem on your own again. Be sure to visit www.MasteringChemistry.com, where you can explore study tools, including Exercise Sets, an Interactive Molecular Gallery, and Biographical Sketches of historically important chemists, and where you can access content on many important topics. The most important advice to remember (and follow) in studying organic chemistry is DO NOT FALL BEHIND! The individual steps to learning organic chemistry are quite simple; each by itself is relatively easy to master. But they are numerous, and the subject can quickly become overwhelming if you do not keep up.
Before many of the theories and mechanisms were figured out, organic chemistry was a discipline that could be mastered only through memorization. Fortunately, that is no longer true. You will find many unifying ideas that allow you to use what you have learned in one situation to predict what will happen in other situations. So, as you read the book and study your notes, always make sure that you understand why each chemical event or behavior happens. For example, when the reasons behind reactivity are understood, most reactions can be predicted. Approaching the course with the misconception that to succeed you must memorize hundreds of unrelated reactions could be your downfall. There is simply too much material to memorize. Understanding and reasoning, not memorization, provide the necessary foundation on which to lay subsequent learning. Nevertheless, from time to time some memorization will be required: some fundamental rules will have to be memorized, and you will need to learn the common names of a number of organic compounds. But that should not be a problem; after all, your friends have common names that you have been able to learn and remember.
Students who study organic chemistry to gain entrance into professional schools sometimes wonder why these schools pay so much attention to this topic. The importance of organic chemistry is not in the subject matter alone. Mastering organic chemistry requires a thorough understanding of certain fundamental principles and the ability to use those fundamentals to analyze, classify, and predict. Many professions make similar demands.
Good luck in your study. I hope you will enjoy studying organic chemistry and learn to appreciate the logic of this fascinating discipline. If you have any comments about the book or any suggestions for improving it, I would love to hear from you. Remember, positive comments are the most fun, but negative comments are the most useful.
Paula Yurkanis Bruice pybruice@chem.ucsb.edu
Common Functional Groups
Alkane
Alkene
Sulfide
Disulfide
Sulfonium ion
Approximate pKa Values
protonated carbonyl groups
protonated alcohols
protonated water + OH + ROH H + HOH H
carboxylic acids
protonated aniline
protonated amines
Common Symbols and Abbreviations
adenosyl specific rotation observed rotation adenosine triphosphate
B0 applied magnetic field
Debye; a measure of dipole moment
partial or chemical shift
G‡ ΔG°
heat free energy of activation
Ea energy of activation
ethyl diethyl ether Et Et2O
FAD H2CrO4 chromic acid
flavin adenine dinucleotide
infrared hypochlorous acid HOCl IR
k rate constant
Ka acid dissociation constant
Keq equilibrium constant
LiAlH4 lithium aluminum hydride mass spectroscopy MS m dipole moment
pyridoxal phosphate PLP pH
S°
DMF
DMSO
Gibbs standard free energy change change in enthalpy change in entropy
dimethylformamide
dimethyl sulfoxide
E entgegen (opposite sides in E,Z nomenclature)
NaBH4 sodium borohydride isoelectric point pI
pKa measure of the strength of an acid (= − log Ka)
parts per million (of the applied field)
Bu butyl tetrahydrofuran or tetrahydrofolate tetramethylsilane, (CH3)4Si
NAD+ nicotinamide adenine dinucleotide
NaOCl sodium hypochlorite nanometers nm nuclear magnetic resonance
THF TMS
TPP
UV/Vis X
alkyl group; group derived from a hydrocarbon R R,S configuration about an asymmetric center
thiamine pyrophosphate
ultraviolet/visible halogen atom
Z zusammen (same side in E,Z nomenclature)
measure of the acidity of a solution (= − log [H+]) NMR ppm
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Essential Organic Chemistry
THIRD EDITION
gl O bal EDITION
UNIVERSITY OF CALIFORNIA
SANTA BARBARA
Paula Yurkanis Bruice
Editor-in-Chief: Jeanne Zalesky
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The rights of Paula Yurkanis Bruice to be identified as the author of this work have been asserted by her in accordance with the Copyright, Designs and Patents Act 1988.
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ISBN 10: 1-292-08903-2
ISBN 13: 978-1-292-08903-4
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
10 9 8 7 6 5 4 3 2 1
14 13 12 11 10
Typeset in Times LT Std 10.5/12 by Lumina Datamatics, Inc.
Printed and bound in Malaysia.
Brief Table of Contents
Preface 19
About the Author 23
C H ap TER 1 Remembering General Chemistry: Electronic Structure and Bonding 29
C H ap TER 2 Acids and Bases: Central to Understanding Organic Chemistry 68
TUTORI al Acids and Bases 93
C H ap TER 3 An Introduction to Organic Compounds 101
C H ap TER 4 Isomers: The Arrangement of Atoms in Space 144
C H ap TER 5 Alkenes 176
TUTORI al An Exercise in Drawing Curved Arrows: Pushing Electrons 202
C H ap TER 6 The Reactions of Alkenes and Alkynes 210
C H ap TER 7 Delocalized Electrons and Their Effect on Stability, pK a, and the Products of a Reaction • Aromaticity and the Reactions of Benzene 242
TUTORI al Drawing Resonance Contributors 283
C H ap TER 8 Substitution and Elimination Reactions of Alkyl Halides 291
C H ap TER 9 Reactions of Alcohols, Ethers, Epoxides, Amines, and Thiols 331
C H ap TER 10 Determining the Structure of Organic Compounds 367
C H ap TER 11 Reactions of Carboxylic Acids and Carboxylic Acid Derivatives 421
C H ap TER 12 Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid Derivatives 459
C H ap TER 13 Reactions at the a-Carbon of Carbonyl Compounds 489
C H ap TER 14 Radicals 513
C H ap TER 15 Synthetic Polymers 527
C H ap TER 16 The Organic Chemistry of Carbohydrates 553
C H ap TER 17 The Organic Chemistry of Amino Acids, Peptides, and Proteins 577
C H ap TER 18 How Enzymes Catalyze Reactions • The Organic Chemistry of the Vitamins available on-line
C H ap TER 19 The Organic Chemistry of the Metabolic Pathways 609
C H ap TER 20 The Organic Chemistry of Lipids 634
C H ap T ER 21 The Chemistry of the Nucleic Acids 650
a pp ENDICE s I Physical Properties of Organic Compounds available on-line
a pp ENDICE s I I Spectroscopy Tables available on-line
Answers to Selected Problems A-1
Glossary G-1
Photo Credits P-1
Index I-1
New chapter on Acid/ Base Chemistry reinforces fundamental concepts and foundational skills needed for future topics in organic chemistry.
for Organic Chemistry
MasteringChemistry tutorials guide you through topics in chemistry with selfpaced tutorials that provide individualized coaching. These assignable, in-depth tutorials are designed to coach you with hints and feedback specific to your individual needs. For additional practice on Acids and Bases, go to MasteringChemistry where the following tutorials are available:
• Acids and Bases: Base Strength and the Effect of pH on Structure
• Acids and Bases: Factors that Influence Acid Strength
• Acids and Bases: Predicting the Position of Equilibrium
• Acids and Bases: Definitions
1
Remembering General Chemistry: electronic Structure and Bonding 29
Natural Orga N ic cO mp O u N ds Versus s y N thetic
Orga N ic cO mp O u N ds 30
1.1 The Structure of an Atom 31
1.2 How the Electrons in an Atom Are Distributed 32
1.3 Ionic and Covalent Bonds 34
1.4 How the Structure of a Compound Is Represented 40 pr OB lem - s O lV i N g strategy 42
1.5 Atomic Orbitals 45
1.6 How Atoms Form Covalent Bonds 46
1.7 How Single Bonds Are Formed in Organic Compounds 47 1.8 How a Double Bond Is Formed: The Bonds in Ethene 50 d iam ON d, g raphite, g raphe N e, a N d Fullere N es: s u B sta N ces that cON tai N O N ly c ar BON at O ms 52
1.9 How a Triple Bond Is Formed: The Bonds in Ethyne 52
1.10 The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion 54
1.11 The Bonds in Ammonia and in the Ammonium Ion 56
1.12 The Bonds in Water 57
Water— a cO mp O u N d c e N tral t O l i F e 58
1.13 The Bond in a Hydrogen Halide 58
1.14 Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles 60 pr OB lem - s O lV i N g strategy 62
1.15 The Dipole Moments of Molecules 63
SOME IMPORTANT THINGS TO REMEMBER 64 ■ PROBLEMS 65 2
Acids and Bases: Central to understanding organic Chemistry 68
2.1 An Introduction to Acids and Bases 68
2.2 pK a and pH 70 a cid r ai N 72
2.3 Organic Acids and Bases 72
pO is ONO us a mi N es 73
pr OB lem - s O lV i N g strategy 75
2.4 How to Predict the Outcome of an Acid–Base Reaction 76
2.5 How to Determine the Position of Equilibrium 76
2.6 How the Structure of an Acid Affects Its pK a Value 77
2.7 How Substituents Affect the Strength of an Acid 81
pr OB lem - s O lV i N g strategy 82
2.8 An Introduction to Delocalized Electrons 83 F O
2.9 A Summary of the Factors that Determine Acid Strength 85 2.10 How pH Affects the Structure of an Organic Compound 86 pr OB lem - s O lV i N g strategy 87 a spiri N m ust Be i N i ts Basic F O rm t O Be p hysi O l O gically a cti V e 88
2.11
Buffer Solutions 89
Bl OO d: a Bu FF ered sO luti ON 89
SOME IMPORTANT THINGS TO REMEMBER 90 ■ PROBLEMS 91
TUTORIAL
A C id S A nd B AS e S 93
An introduction to organic Compounds 101
3.1 How Alkyl Substituents Are Named 104
Bad- s melli N g cO mp O u N ds 105
3.2 The Nomenclature of Alkanes 108
hOW i s the Octa N e Num B er OF g as O li N e d etermi N ed? 110
3.3 The Nomenclature of Cycloalkanes • Skeletal Structures 111
pr OB lem - s O lV i N g strategy 112
3.4 The Nomenclature of Alkyl Halides 114
pr OB lem - s O lV i N g strategy 114
3.5 The Classification of Alkyl Halides, Alcohols, and Amines 115
Nitr O sami N es a N d c a N cer 115
3.6 The Structures of Alkyl Halides, Alcohols, Ethers, and Amines 116
3.7 Noncovalent Interactions 118
pr OB lem - s O lV i N g strategy 121 d rugs Bi N d t O t heir r ecept O rs 122
3.8 Factors that Affect the Solubility of Organic Compounds 122
c ell m em B ra N es 125
3.9 Rotation Occurs About Carbon—Carbon Single Bonds 125
3.10 Some Cycloalkanes have Angle Strain 128
V ON Baeyer, Bar B ituric a cid, a N d Blue Jea N s 129
3.11 Conformers of Cyclohexane 129
3.12 Conformers of Monosubstituted Cyclohexanes 132
s tarch a N d c ellul O se— a xial a N d e quat O rial 133
3.13 Conformers of Disubstituted Cyclohexanes 134
pr OB lem - s O lV i N g strategy 134
3.14 Fused Cyclohexane Rings 137
c h O lester O l a N d h eart d isease 138
hOW h igh c h O lester O l i s t reated c li N ically 138
SOME IMPORTANT THINGS TO REMEMBER 139 ■ PROBLEMS 139
4 isomers: The Arrangement of Atoms in Space 144
4.1 Cis–Trans Isomers Result from Restricted Rotation 145
c is– t ra N s iN terc ONV ersi ON i N Visi ON 148
4.2 Designating Geometric Isomers Using the E,Z System 148
pr OB lem - s O lV i N g strategy 151
4.3 A Chiral Object Has a Nonsuperimposable Mirror Image 151
4.4 An Asymmetric Center Is a Cause of Chirality in a Molecule 152
4.5 Isomers with One Asymmetric Center 153
4.6 How to Draw Enantiomers 154
4.7 Naming Enantiomers by the R,S System 154
pr OB lem - s O lV i N g strategy 156
pr OB lem - s O lV i N g strategy 157
4.8 Chiral Compounds Are Optically Active 158
4.9 How Specific Rotation Is Measured 160
4.10 Isomers with More than One Asymmetric Center 162
4.11 Stereoisomers of Cyclic Compounds 163
pr OB lem - s O lV i N g strategy 164
4.12 Meso Compounds Have Asymmetric Centers but Are Optically Inactive 165
pr OB lem - s O lV i N g strategy 167
New Feature—Tutorials help students develop and practice important problem solving skills.
New coverage of stereoisomers now precedes the coverage of the reactions of alkenes.
for Organic Chemistry
MasteringChemistry tutorials guide you through the toughest topics in chemistry with self-paced tutorials that provide individualized coaching. These assignable, in-depth tutorials are designed to coach you with hints and feedback specific to your individual misconceptions. For additional practice on Drawing Curved Arrows: Pushing Electrons, go to MasteringChemistry where the following tutorials are available:
• An Exercise in Drawing Curved Arrows: Pushing Electrons
• An Exercise in Drawing Curved Arrows: Predicting Electron Movement
• An Exercise in Drawing Curved Arrows: Interpreting Electron Movement
4.13 Receptors 168
t he eN a N ti O mers OF t halid O mide 170
4.14 How Enantiomers Can Be Separated 170
c hiral d rugs 171
SOME IMPORTANT THINGS TO REMEMBER 171 ■ PROBLEMS 172
5
Alkenes 176
p her O m ON es 177
5.1 The Nomenclature of Alkenes 177
5.2 How an Organic Compound Reacts Depends on its Functional Group 180
5.3 How Alkenes React • Curved Arrows Show the Flow of Electrons 181
a Fe W W O rds aBO ut c ur V ed a rr OW s 183
5.4 Thermodynamics: How Much Product Is Formed? 185
5.5 Increasing the Amount of Product Formed in a Reaction 187
5.6 Using ΔH° Values to Determine the Relative Stabilities of Alkenes 188
pr OB lem - s O lV i N g strategy 189
t ra N s Fats 192
5.7 Kinetics: How Fast Is the Product Formed? 192
5.8 The Rate of a Chemical Reaction 194
5.9 The Reaction Coordinate Diagram for the Reaction of 2-Butene with HBr 194
5.10 Catalysis 196
5.11 Catalysis by Enzymes 197
SOME IMPORTANT THINGS TO REMEMBER 199 ■ PROBLEMS 200
TUTORIAL
6
An e xe RC i S e in dRA win G Cu R ved A RR ow S : Pu S hin G e le CTR on S 202
The Reactions of Alkenes and Alkynes 210
g ree N c hemistry: a imi N g FO r s ustai N a B ility 211
6.1 The Addition of a Hydrogen Halide to an Alkene 211
6.2 Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon 212
6.3 Electrophilic Addition Reactions Are Regioselective 215
Which a re mO re h arm F ul, Natural p esticides O r s y N thetic p esticides? 217
pr OB lem - s O lV i N g strategy 217
6.4 A Carbocation will Rearrange if It Can Form a More Stable Carbocation 219
6.5 The Addition of Water to an Alkene 221
6.6 The Stereochemistry of Alkene Reactions 222
pr OB lem - s O lV i N g strategy 224
6.7 The Stereochemistry of Enzyme-Catalyzed Reactions 225
6.8 Enantiomers Can Be Distinguished by Biological Molecules 226
6.9 An Introduction to Alkynes 227
s y N thetic a lky N es a re u sed t O t reat parki N s ON ’s d isease 228 Why a re d rugs sO e xpe N si V e? 229
6.10 The Nomenclature of Alkynes 229
s y N
6.11 The Structure of Alkynes 231
6.12 The Physical Properties of Unsaturated Hydrocarbons 231
6.13 The Addition of a Hydrogen Halide to an Alkyne 232
6.14 The Addition of Water to an Alkyne 233
6.15 The Addition of Hydrogen to an Alkyne 235
SOME IMPORTANT THINGS TO REMEMBER 236 ■ SUMMARY OF REACTIONS 237 ■ PROBLEMS 238
delocalized electrons and Their effect on Stability, pKa, and the Products of a Reaction • Aromaticity and the Reactions of Benzene 242
7.3 Resonance Contributors and the Resonance Hybrid 246
7.4 How to Draw Resonance Contributors 247
e lectr ON d el O calizati ON aFF ects the t hree- d ime N si ON al s hape OF
p r O tei N s 250
7.5 The Predicted Stabilities of Resonance Contributors 250
7.6 Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound 252
7.7 Delocalized Electrons Increase Stability 253
pr OB lem - s O lV i N g strategy 255
pr OB lem - s O lV i N g strategy 256
7.8 Delocalized Electrons Affect pK a Values 256
pr OB lem - s O lV i N g strategy 259
7.9 Electronic Effects 259
7.10 Delocalized Electrons Can Affect the Product of a Reaction 262
7.11 Reactions of Dienes 263
7.12 The Diels–Alder Reaction Is a 1,4-Addition Reaction 266
7.13 Benzene Is an Aromatic Compound 268
7.14 The Two Criteria for Aromaticity 269
7.15 Applying the Criteria for Aromaticity 270 Bucky B alls 271
7.16 How Benzene Reacts 272
7.17 The Mechanism for Electrophilic Aromatic Substitution Reactions 273 t hyr O xi N e 275
7.18 Organizing What We Know About the Reactions of Organic Compounds 276
SOME IMPORTANT THINGS TO REMEMBER 277 ■ SUMMARY OF REACTIONS 277 ■ PROBLEMS 278
TUTORIAL
Substitution and elimination Reactions of Alkyl halides 291
ddt: a s y N thetic Orga NO halide t hat k ills d isease- s preadi N g iN sects 292
8.1 The Mechanism for an SN2 Reaction 293
8.2 Factors That Affect SN2 Reactions 297
Why a re l i V i N g Orga N isms cO mp O sed OF c ar BON iN stead OF
8.3 The Mechanism for an SN1 Reaction 301
8.4 Factors That Affect SN1 Reactions 304
8.5 Comparing SN2 and SN1 Reactions 305 pr OB lem - s O lV i N g strategy 305 Naturally Occurri N g Orga NO halides t
8.6 Intermolecular versus Intramolecular Reactions 307
pr OB lem - s O lV i N g strategy 309
8.7 Elimination Reactions of Alkyl Halides 309
8.8 The Products of an Elimination Reaction 311
8.9 Relative Reactivities of Alkyl Halides Reactions 315
t he N OB el p rize 316
8.10 Does a Tertiary Alkyl Halide Undergo SN2/E2 Reactions or SN1/E1 Reactions? 316
8.11 Competition between Substitution and Elimination 317
for Organic Chemistry
MasteringChemistry tutorials guide you through the toughest topics in chemistry with self-paced tutorials that provide individualized coaching. These assignable, in-depth tutorials are designed to coach you with hints and feedback specific to your individual misconceptions. For additional practice on Drawing Resonance Contributors, go to MasteringChemistry where the following tutorials are available:
• Drawing Resonance Contributors I
• Drawing Resonance Contributors II
• Drawing Resonance Contributors of Substituted Benzenes
New Feature—
Organizing What We Know About Organic Chemistry lets students see how families of organic compounds react in similar ways.
8.12 Solvent Effects 320
sO lVati ON eFF ects 320
8.13 Substitution Reactions in Synthesis 324
SOME IMPORTANT THINGS TO REMEMBER 325 ■ SUMMARY OF REACTIONS 326 ■ PROBLEMS 327
9
Reactions of Alcohols, ethers, epoxides, Amines, and Thiols 331
9.1 The Nomenclature of Alcohols 331
g rai N a lc O h O l a N d W OO d a lc O h O l 333
9.2 Activating an Alcohol for Nucleophilic Substitution by Protonation 334
9.3 Activating an OH Group for Nucleophilic Substitution in a Cell 336
t he iN a B ility t O p er FO rm a N s N 2 r eacti ON c auses a s e V ere
c li N ical d is O rder 338
9.4 Elimination Reactions of Alcohols: Dehydration 338
9.5 Oxidation of Alcohols 341
Bl OO d a lc O h O l cON te N t 343
t reati N g a lc O h O lism W ith aN ta B use 343
m etha NO l pO is ON i N g 344
9.6 Nomenclature of Ethers 344
9.7 Nucleophilic Substitution Reactions of Ethers 345
aN esthetics 347
9.8 Nucleophilic Substitution Reactions of Epoxides 347
9.9 Using Carbocation Stability to Determine the Carcinogenicity of an Arene Oxide 351
Be N z O [ a ]pyre N e a N d c a N cer 353 c him N ey sW eeps a N d c a N cer 354
9.10 Amines Do Not Undergo Substitution or Elimination Reactions 354 a lkal O ids 355 l ead cO mp O u N ds FO r the d e V el O pme N t OF d rugs 356
9.11 Thiols, Sulfides, and Sulfonium Salts 356
m ustard g as— a c hemical War F are a ge N t 357 a lkylati N g a ge N ts as c a N cer d rugs 358
9.12 Methylating Agents Used by Chemists versus Those Used by Cells 358 e radicati N g t ermites 359
S - a de NO sylmethi ON i N e: a Natural aN tidepressa N t 360
9.13 Organizing What We Know about the Reactions of Organic Compounds 360
SOME IMPORTANT THINGS TO REMEMBER 361 ■ SUMMARY OF REACTIONS 361 ■ PROBLEMS 363
10 determining the Structure of organic Compounds 367
10.1 Mass Spectrometry 368
10.2 The Mass Spectrum • Fragmentation 369
10.3 Using The m/z Value of The Molecular Ion to Calculate the Molecular Formula 371 pr OB lem - s O lV i N g strategy 372
10.4 Isotopes in Mass Spectrometry 373
10.5 High-Resolution Mass Spectrometry Can Reveal Molecular Formulas 374
10.6 Fragmentation Patterns 375
10.7 Gas Chromatography–Mass Spectrometry 376 m ass s pectr O metry i N F O re N sics 376
10.8 Spectroscopy and the Electromagnetic Spectrum 376
10.13 The Position and Shape of an Absorption Band Is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding 380 pr OB lem - s O lV i N g strategy 382
10.14 The Absence of Absorption Bands 385
10.15 How to Interpret an Infrared Spectrum 386
10.16 Ultraviolet and Visible Spectroscopy 387
u ltraV i O let l ight a N d s u N scree N s 388
10.17 The Effect of Conjugation on max 389
10.18 The Visible Spectrum and Color 390
What m akes Blue B erries Blue a N d s tra WB erries r ed? 391
10.19 Some Uses of UV/VIS Spectroscopy 391
10.20 An Introduction to NMR Spectroscopy 392
Nik O la t esla (1856–1943) 393
10.21 Shielding Causes Different Hydrogens to Show Signals at Different Frequencies 394
10.22 The Number of Signals in an 1H NMR Spectrum 395
10.23 The Chemical Shift Tells How Far the Signal Is from the Reference Signal 396
10.24 The Relative Positions of 1H NMR Signals 397
10.25 The Characteristic Values of Chemical Shifts 397
10.26 The Integration of NMR Signals Reveals the Relative Number of Protons Causing Each Signal 399
10.27 The Splitting of Signals Is Described by the N + 1 Rule 401
10.28 More Examples of 1H NMR Spectra 404
pr OB lem - s O lV i N g strategy 406
10.29 13C NMR Spectroscopy 407
pr OB lem - s O lV i N g strategy 410 N mr u sed i N m edici N e is c alled m ag N etic r es ON a N ce i
SOME IMPORTANT THINGS TO REMEMBER 412 ■ PROBLEMS 413
11
Reactions of Carboxylic Acids and Carboxylic Acid
derivatives 421
11.1 The Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives 423
11.2
Nature’s s leepi N g p ill 425
The Structures of Carboxylic Acids and Carboxylic Acid Derivatives 426
11.3 The Physical Properties of Carbonyl Compounds 427
11.4 How Carboxylic Acids and Carboxylic Acid Derivatives React 427
pr OB lem - s O lV i N g strategy 429
11.5 The Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives 430
11.6 The Reactions of Acyl Chlorides 431
11.7 The Reactions of Esters 432
11.8 Acid-Catalyzed Ester Hydrolysis and Transesterification 434
11.9 Hydroxide-Ion-Promoted Ester Hydrolysis 437
a spiri N , N said s, a N d c O x -2 iN hi B it O rs 438
11.10 Reactions of Carboxylic Acids 440
11.11 Reactions of Amides 441
d almatia N s: dO N O t F OO l W ith mO ther Nature 442
11.12 Acid-Catalyzed Amide Hydrolysis and Alcoholysis 442
t he d isc OV ery OF p e N icilli N 444
p e N icilli N a N d d rug r esista N ce 444
p e N icilli N s i N c li N ical u se 445
a s emisy N thetic p e N icilli N 445
11.13 Nitriles 446
11.14 Acid Anhydrides 447
What d rug- eNFO rceme N t dO gs a re r eally d etecti N g 449
11.15 How Chemists Activate Carboxylic Acids 449
11.16 How Cells Activate Carboxylic Acids 450
Ner V e i mpulses, paralysis, a N d iN secticides 453
SOME IMPORTANT THINGS TO REMEMBER 454
■ PROBLEMS 456
■ SUMMARY OF REACTIONS 454
12
Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid derivatives 459
12.1 The Nomenclature of Aldehydes and Ketones 460
Buta N edi ON e: aN uN pleasa N t cO mp O u N d 461
12.2 The Relative Reactivities of Carbonyl Compounds 462
12.3 How Aldehydes and Ketones React 463
12.4 Organometallic Compounds 463
12.5 The Reactions of Carbonyl Compounds with Grignard Reagents 465
s y N thesizi N g Orga N ic cO mp O u N ds 467
s emisy N thetic d rugs 468
pr OB lem - s O lV i N g strategy 469
12.6 The Reactions of Aldehydes and Ketones with Cyanide Ion 469
12.7 The Reactions of Carbonyl Compounds with Hydride Ion 470
12.8 The Reactions of Aldehydes and Ketones with Amines 473
s ere N dipity i N d rug d e V el O pme N t 476
12.9 The Reactions of Aldehydes and Ketones with Alcohols 477 c ar BO hydrates F O rm h emiacetals a N d a cetals 479
12.10 Nucleophilic Addition to a,-Unsaturated Aldehydes and Ketones 479
12.11 Nucleophilic Addition to a,-Unsaturated Carboxylic Acid Derivatives 481
eN zyme- c atalyzed c is– t ra N s iN terc ONV ersi ON 481
12.12 Conjugate Addition Reactions in Biological Systems 482 c a N cer c hem O therapy 482
SOME IMPORTANT THINGS TO REMEMBER 483 ■ SUMMARY OF REACTIONS 483
■ PROBLEMS 485
13
Reactions at the a-Carbon of Carbonyl Compounds 489
13.1 The Acidity of an a-Hydrogen 490 pr OB lem - s O lV i N g strategy 492
13.2 Keto–Enol Tautomers 492
13.3 Keto–Enol Interconversion 493
13.4 Alkylation of Enolate Ions 495
t he s y N thesis OF a spiri N 496
13.5 An Aldol Addition Forms -Hydroxyaldehydes or -Hydroxyketones 496
13.6 The Dehydration of Aldol Addition Products forms a,-Unsaturated Aldehydes and Ketones 498
13.7 A Crossed Aldol Addition 499
Breast c a N cer a N d a r O matase iN hi B it O rs 500
13.8 A Claisen Condensation Forms a -Keto Ester 500
13.9 CO2 Can Be Removed from a Carboxylic Acid with a Carbonyl Group at the 3-Position 503
13.10 Reactions at the a-Carbon in Cells 504
13.11 Organizing What We Know about the Reactions of Organic Compounds 508
SOME IMPORTANT THINGS TO REMEMBER 508 ■ SUMMARY OF REACTIONS 509
■ PROBLEMS 510
14 Radicals 513
14.1 Alkanes are Unreactive Compounds 513
Natural g as a N d p etr O leum 514
F O ssil Fuels: a p r OB lematic eN ergy sO urce 514
14.2 The Chlorination and Bromination of Alkanes 515
Why r adicals N O lON ger h aV e t O Be c alled Free r adicals 516
14.3 Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron 516
14.4 The Distribution of Products Depends on Radical Stability 517
pr OB lem - s O lV i N g strategy 518
14.5 The Stereochemistry of Radical Substitution Reactions 519
14.6 Formation of Explosive Peroxides 520
14.7 Radical Reactions Occur in Biological Systems 521
d eca FF ei N ated cOFF ee a N d the c a N cer s care 522
F OO d p reser Vati V es 523
i s c h O c O late a h ealth F OO d? 523
14.8 Radicals and Stratospheric Ozone 524
a rti F icial Bl OO d 525
SOME IMPORTANT THINGS TO REMEMBER 525 ■ SUMMARY OF REACTIONS 525 ■ PROBLEMS 526
15 Synthetic Polymers 527
15.1 There Are Two Major Classes of Synthetic Polymers 528
15.2 Chain-Growth Polymers 529
t e F l ON : aN a ccide N tal d isc OV ery 532
r ecycli N g s ym BO ls 533
15.3 Stereochemistry of Polymerization • Ziegler–Natta Catalysts 538
15.4 Organic Compounds That Conduct Electricity 539
15.5 Polymerization of Dienes • Natural and Synthetic Rubber 540
15.6 Copolymers 542
Na NO c ON tai N ers 542
15.7 Step-Growth Polymers 543
15.8 Classes of Step-Growth Polymers 543
h ealth cON cer N s: Bisphe NO l a a N d p hthalates 547
d esig N i N g a pO lymer 547
15.9 Recycling Polymers 549
15.10 Biodegradable Polymers 549
SOME IMPORTANT THINGS TO REMEMBER 550 ■ PROBLEMS 551
16
The organic Chemistry of Carbohydrates 553
16.1 Classification of Carbohydrates 554
16.2 The d and l Notations 555
16.3 The Configurations of Aldoses 556
16.4 The Configurations of Ketoses 557
16.5 The Reactions of Monosaccharides in Basic Solutions 558
m easuri N g the Bl OO d g luc O se l e V els i N d ia B etes 559
16.6 Monosaccharides Form Cyclic Hemiacetals 560
Vitami N c 562
16.7 Glucose Is the Most Stable Aldohexose 563
16.8 Formation of Glycosides 564
16.9 Disaccharides 566
l act O se iN t O lera N ce 567
16.10 Polysaccharides 568
Why the d e N tist i s r ight 569
h epari N a Natural aN tic O agula N t 569
cON tr O lli N g Fleas 571
16.11 Carbohydrates on Cell Surfaces 571
16.12 Artificial Sweeteners 572
a ccepta B le d aily iN take 574
SOME IMPORTANT THINGS TO REMEMBER 574 ■ SUMMARY OF REACTIONS 575
■ PROBLEMS 575
17
The organic Chemistry of Amino Acids, Peptides, and Proteins 577
17.1 The Nomenclature of Amino Acids 578
p r O tei N s a N d Nutriti ON 581
17.2 The Configuration of Amino Acids 582
a mi NO a cids a N d d isease 582
17.3 The Acid–Base Properties of Amino Acids 583
17.4 The Isoelectric Point 584
17.5 Separating Amino Acids 585
Water sOF te N ers: e xamples OF c ati ON - e xcha N ge c hr O mat O graphy 588
17.6 The Synthesis of Amino Acids 589
17.7 The Resolution of Racemic Mixtures of Amino Acids 590
17.8 Peptide Bonds and Disulfide Bonds 591
r u NN er’s h igh 592
d ia B etes 594
h air: s traight O r c urly? 594
17.9 An Introduction to Protein Structure 595
p rimary s tructure a N d tax ONO mic r elati ON ship 595
17.10 How to Determine the Primary Structure of a Polypeptide or a Protein 595
pr OB lem - s O lV i N g strategy 597
17.11 Secondary Structure 600
17.12 Tertiary Structure 602
d iseases c aused B y a m is FO lded p r O tei N 603
17.13 Quaternary Structure 604
17.14 Protein Denaturation 605
SOME IMPORTANT THINGS TO REMEMBER 605 ■ PROBLEMS 606
18
How Enzymes Catalyze Reactions •
The organic Chemistry of the vitamins available on-line
18.1 Enzyme-Catalyzed Reactions 1
18.2 An Enzyme-Catalyzed Reaction That Involves Two Sequential SN2 Reactions 4 hOW tami F lu W O rks 5
18.3 An Enzyme-Catalyzed Reaction That Is Reminiscent of Acid-Catalyzed Amide and Ester Hydrolysis 8
18.4 An Enzyme-Catalyzed Reaction That Is Reminiscent of the Base-Catalyzed Enediol Rearrangement 10
18.5 An Enzyme-Catalyzed Reaction That Is Reminiscent of a Retro-Aldol Addition 12
18.6 Vitamins and Coenzymes 13
Vitami N B 1 15
18.7 Niacin: The Vitamin Needed for Many Redox Reactions 15
Niaci N d e F icie N cy 16
18.8 Riboflavin: Another Vitamin Used in Redox Reactions 20
18.9 Vitamin B1: The Vitamin Needed for Acyl Group Transfer 23
c uri N g a h a N g OV er W ith Vitami N B 1 26
18.10 Vitamin H: The Vitamin Needed for Carboxylation of an a-Carbon 28
pr OB lem - s O lV i N g strategy 30
18.11 Vitamin B6: The Vitamin Needed for Amino Acid Transformations 30
a ssessi N g the d amage aF ter a h eart attack 34
18.12 Vitamin B12: The Vitamin Needed for Certain Isomerizations 35
18.13 Folic Acid: The Vitamin Needed for One-Carbon Transfer 37
t he First aN ti B i O tics 38
cO mpetiti V e iN hi B it O rs 41 c a N cer d rugs a N d s ide eFF ects 41
18.14 Vitamin K: The Vitamin Needed for Carboxylation of Glutamate 41
aN tic O agula N ts 42
tOO m uch Br O cc O li 43
SOME IMPORTANT THINGS TO REMEMBER 43 ■ PROBLEMS 44
19
The organic Chemistry of the Metabolic Pathways 609
d i FF ere N ces i N m eta BO lism 610
19.1 ATP Is Used for Phosphoryl Transfer Reactions 610
Why d id Nature c h OO se p h O sphates? 611
19.2 The “High-Energy” Character of Phosphoanhydride Bonds 611
19.3 The Four Stages of Catabolism 612
19.4 The Catabolism of Fats 613
19.5 The Catabolism of Carbohydrates 616
pr OB lem - s O lV i N g strategy 620
19.6 The Fate of Pyruvate 620
19.7 The Catabolism of Proteins 621
p he N ylket ON uria ( pku ): aN iNBO r N e rr O r OF m eta BO lism 623
19.8 The Citric Acid Cycle 623
19.9 Oxidative Phosphorylation 626
Basal m eta BO lic r ate 627
19.10 Anabolism 627
19.11 Gluconeogenesis 628
19.12 Regulating Metabolic Pathways 629
19.13 Amino Acid Biosynthesis 630
SOME IMPORTANT THINGS TO REMEMBER 631 ■ PROBLEMS 632
20
The organic Chemistry of lipids 634
20.1 Fatty Acids Are Long-Chain Carboxylic Acids 635
Omega Fatty a cids 636
Waxes a re e sters t hat h aV e h igh mO lecular Weights 636
20.2 Fats and Oils Are Triglycerides 637
Whales a N d e ch O l O cati ON 638
20.3 Soaps and Detergents 638
20.4 Phosphoglycerides and Sphingolipids 640
sN ake Ve NO m 641
m ultiple s cler O sis a N d the m yeli N s heath 642
20.6 Terpenes Contain Carbon Atoms in Multiples of Five 642
20.7 How Terpenes are Biosynthesized 644
pr OB lem - s O lV i N g strategy 645
20.8 How Nature Synthesizes Cholesterol 646
20.9 Synthetic Steroids 647
SOME IMPORTANT THINGS TO REMEMBER 648 ■ PROBLEMS 648
21 The Chemistry of the nucleic Acids 650
21.1 Nucleosides and Nucleotides 650
t he s tructure OF d N a : Wats ON , c rick, Fra N kli N , a N d Wilki N s 653
21.2 Nucleic Acids Are Composed of Nucleotide Subunits 653
21.3 The Secondary Structure of DNA—The Double Helix 654
21.4 Why DNA Does Not Have a 2-OH Group 656
21.5 The Biosynthesis of DNA Is Called Replication 657
21.6 DNA and Heredity 658
Natural p r O ducts t hat mO di F y d N a 658
21.7 The Biosynthesis of RNA Is Called Transcription 659
21.8 The RNAs Used for Protein Biosynthesis 660
21.9 The Biosynthesis of Proteins Is Called Translation 662
s ickle c ell aN emia 664
aN ti B i O tics t hat a ct B y iN hi B iti N g t ra N slati ON 664
21.10 Why DNA Contains Thymine Instead of Uracil 665 aN ti B i O tics a ct B y a cO mm ON m echa N ism 666
21.11 Antiviral Drugs 666
iNF lue N za pa N demics 667
21.12 How the Base Sequence of DNA Is Determined 667
21.13 Genetic Engineering 669
r esisti
669
reat the eBO la Virus 670
SOME IMPORTANT THINGS TO REMEMBER 670 ■ PROBLEMS 671
Appendix I Physical Properties of Organic Compounds available on-line
Appendix II Spectroscopy Tables available on-line
Answers to Selected Problems A-1
Glossary G-1
Photo Credits P-1
Index I-1
Preface
In deciding what constitutes “essential” organic chemistry, I asked myself the following question: What do students need to know if they are not planning to be synthetic organic chemists? In other words, what do they need to know for their careers in medicine, dentistry, applied health professions, nutrition, or engineering?
Based on the answers to that question, I made content and organizational choices with the following goals in mind:
■ Students should understand how and why organic compounds react the way they do.
■ Students should understand that the reactions they learn in the first part of the course are the same as the reactions that occur in biological systems (that is, that occur in cells).
■ Students should appreciate the fun and challenge of designing simple syntheses. (This is also a good way to check if they truly understand reactivity.)
■ Students should understand how organic chemistry is integral to biology, to medicine, and to their daily lives.
■ In order to achieve the above goals, students need to work as many problems as possible.
To counter the impression that the study of organic chemistry consists primarily of memorizing a diverse collection of molecules and reactions, this book is organized around shared features and unifying concepts, emphasizing principles that can be applied again and again. I want students to learn how to apply what they have learned to new settings, reasoning their way to a solution rather than memorizing a multitude of facts.
A new feature, “Organizing What We Know about the Reactions of Organic Compounds,” lets students see where they have been and where they are going as they proceed through the course, encouraging them to keep in mind the fundamental reason behind the reactions of all organic compounds: electrophiles react with nucleophiles
When students see the first reaction of an organic compound (other than an acid–base reaction), they are told that all organic compounds can be divided into families and all members of a family react in the same way. To make things even easier, each family can be put into one of four groups and all the families in a group react in similar ways.
The book then proceeds with each of the four groups (Group I: compounds with carbon–carbon double and triple bonds; Group II: benzene; Group III: compounds with an electronegative group attached to an sp3 carbon; and Group IV: carbonyl compounds). When the chemistry of all the members of a particular group has been covered, students see a summary of the characteristic reactions of that group (see pages 276, 360, 508) that they can compare with the summary of the characteristic reactions of the group(s) studied previously.
The margin notes throughout the book encapsulate key points that students should remember. (For example, “when an acid is added to a reaction, it protonates the most basic atom in the reactant”; “with bases of the same type, the weaker the base, the better it is as a leaving group”; and stable bases are weak bases”.) To simplify mechanistic understanding, common features are pointed out in margin notes (see pages 435, 443, 474, 478).
There are about 140 application boxes sprinkled throughout the book. These are designed to show the students the relevance of organic chemistry to medicine (dissolving sutures, mad cow disease, artificial blood, cholesterol and heart disease), to agriculture (acid rain, resisting herbicides, pesticides: natural and synthetic), to nutrition (trans fats, basal metabolic rate, lactose intolerance, omega fatty acids), and to our shared life on this planet (fossil fuels, biodegradable polymers, whales and echolocation).
Success in organic chemistry requires students to work as many problems as possible. Therefore, the book is structured to encourage problem solving. The answers (and explanations, when needed) to all the problems are in the accompanying Study Guide and Solutions Manual, which I authored to ensure consistency in language with the text.
New Tutorials following relevant chapters give students extra practice so that they can better master important topics: Acids and Bases, Drawing Curved Arrows: Pushing Electrons, and Drawing Resonance Contributors.
The problems within each chapter are primarily drill problems. They appear at the end of each section, so they allow students to test themselves on the material they have just read to see if they are ready to move on to the next section. Selected problems in each chapter are accompanied by worked-out solutions to provide insight into problem-solving techniques. Short answers are provided at the back of the book for problems marked with a diamond to give students immediate feedback concerning their mastery of a skill or concept.
The many Problem-Solving Strategies in the book teach students how to approach various kinds of problems. Each Problem-Solving Strategy is followed by an exercise to give the student an opportunity to use the strategy just learned.
The end-of-chapter problems vary in difficulty. They begin with drill problems that integrate material from the entire chapter, requiring students to think in terms of all the material in the chapter rather than focusing on individual sections. The problems become more challenging as the student proceeds. The net result for the student is a progressive building of both problem-solving ability and confidence. (I have chosen not to label problems as particularly challenging so as not to intimidate the students before they try to solve the problem.)
Many of the end-of-chapter problems can also be found in MasteringChemistry. Students can master concepts through traditional homework assignments in Mastering that provide hints and answer-specific feedback. Students learn chemistry by practicing chemistry.
Additionally, tutorials in MasteringChemistry, featuring specific wrong-answer feedback, hints, and a wide variety of educationally effective content, guide your students through the course. The hallmark Hints and Feedback offer scaffolded instruction similar to what students would experience in an office hour, allowing them to learn from their mistakes without being given the answer. Organic Chemistry Tutorials in MasteringChemistry pinpoint errors by assessing the logic and accuracy of the student’s answers. Individual evaluators written and linked to each problem by organic chemists look at the validity of the student’s entry and generate error-specific feedback based on information received from a JChem database.
The book contains two new chapters: “Radicals” and “Synthetic Polymers.” There is no longer a chapter on the “Organic Chemistry of Drugs.” Much of the material that was in that chapter is now in application boxes, so students have the opportunity to learn about that material who may have not had that opportunity if that last chapter were not covered in their course.
Similarly, some of the information on the chemistry of living systems has been integrated into earlier chapters. As examples, noncovalent interactions in biological systems has been added to Chapter 3, the discussion of catalysis in Chapter 5 now includes a discussion of enzymatic catalysis, and acetal formation by glucose has been added to Chapter 12.
The six chapters (Chapters 16–21) that focus primarily on the organic chemistry of living systems have been rewritten to emphasize the connection between the organic reactions that occur in the laboratory and those that occur in cells. Each organic reaction that occurs in a cell is explicitly compared to the organic reaction with which the student is already familiar. Chapter 18 can be found on the Instructor Resource Center.
The chapter on spectroscopy is modular, so it can be covered at any time during the course—at the very beginning, at the very end, somewhere in between, or not covered at all. When I wrote that chapter, I did not want students to be overwhelmed by a topic they may never revisit in their lives, but I did want them to enjoy being able to interpret relatively simple spectra. In addition to the spectroscopy problems in the text, there are over forty new spectroscopy problems in the Study Guide and Solutions Manual with workedout answers. The answers come after the problems, so students have the opportunity to try to solve them on their own first.
New modern design, streamlined narrative, and bulleted summaries at the end of each chapter allow students to navigate through the content and study more efficiently with the next.
ACK nowled GM en TS
It gives me great pleasure to acknowledge the dedicated efforts of Jordan Fantini and Malcolm Forbes, who checked every inch of the book for accuracy; David Yerzley, M.D., for his assistance with the section on MRI; Warren Hehre of Wavefunction, Inc., and Alan Shusterman of Reed College for their advice on the electrostatic potential maps that appear in the book; and Jeremy Davis, who created the art that appears on page 147. I am also very grateful to my students, who pointed out sections that needed clarification, worked the problems and suggested new ones, and searched for errors.
The following reviewers have played an enormously important role in the development of this book.
Third Edition Reviewers
Marisa Blauvelt, Springfield College
Dana Chatellier, University of Delaware
Karen Hammond, Boise State University
Bryan Schmidt, Minot State University
Wade McGregor, Arizona State University, Tempe
William Wheeler, Ivey Tech Community College
Julia Kubanek, Georgia Institute of Technology
Colleen Munro-Leighton, Truman State University
Rick Mullins, Xavier University
Erik Berda, University of New Hampshire
Michael Justik, Pennsylvania State University, Erie
Hilkka Kenttamaa, Purdue University
Kristina Mack, Grand Valley State University
Jason Serin, Glendale Community College
Anthony St. John, Western Washington University
Third Edition Accuracy Reviewers
Jordan Fantini, Denison University
Malcolm D.E. Forbes, University of North Carolina
Second Edition Reviewers
Deborah Booth, University of Southern Mississippi
Paul Buonora, California State University–Long Beach
Tom Chang, Utah State University
Dana Chatellier, University of Delaware
Amy Deveau, University of New England
J. Brent Friesen, Dominican University
Anne Gorden, Auburn University
Christine Hermann, University of Radford
Scott Lewis, James Madison University
Cynthia McGowan, Merrimack College
Keith Mead, Mississippi State University
Amy Pollock, Michigan State University
Second Edition Accuracy Reviewer
Malcolm Forbes, University of North Carolina
I am deeply grateful to my editor, Jeanne Zalesky, whose talents guided this book and caused it to be as good as it could be, and to Coleen Morrison, whose gentle prodding and attention to detail made the book actually happen. I also want to thank the other talented and dedicated people at Pearson whose contributions made this book a reality. And thank you to Lauren Layn, the creative brains behind the technology that accompanies the book.
I particularly want to thank the many wonderful and talented students I have had over the years, who taught me how to be a teacher. And I want to thank my children, from whom I may have learned the most.
To make this textbook as user friendly as possible, I would appreciate any comments that will help me achieve this goal in future editions. If you find sections that could be clarified or expanded, or examples that could be added, please let me know. Finally, this edition has been painstakingly combed for typographical errors. Any that remain are my responsibility; if you find any, please send me a quick e-mail so that they can be corrected in future printings of this edition.
Paula Yurkanis Bruice University of California, Santa Barbara pybruice@chem.ucsb.edu
Pearson wishes to thank and acknowledge the following reviewers for their work on the Global Edition:
Dharam Vir Singh Jain, Department of Chemistry, Punjab University
Rajarshi Banerjee, PhD Scholar, Delhi
About the Author
Paula Yurkanis Bruice was raised primarily in Massachusetts. After graduating from the Girls’ Latin School in Boston, she earned an A.B. from Mount Holyoke College and a Ph.D. in chemistry from the University of Virginia. She then received an NIH postdoctoral fellowship for study in the Department of Biochemistry at the University of Virginia Medical School and held a postdoctoral appointment in the Department of Pharmacology at the Yale School of Medicine.
Paula has been a member of the faculty at the University of California, Santa Barbara since 1972, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, two Mortar Board Professor of the Year Awards, and the UCSB Alumni Association Teaching Award. Her research interests center on the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading suspense novels, any biographies, and enjoying her pets (three dogs, two cats, and two parrots).
Paula Bruice with Zeus, Bacchus, and Abigail
Essential Skills for Organic Chemistry
New features and major revisions to this third edition focus on developing students’ problem solving and analytical reasoning skills. Organized around mechanistic similarities, Bruice encourages students to be mindful of the fundamental reasoning behind the reactions of all organic compounds: electrophiles react with nucleophiles.
New Tutorials Skill Builders following select chapters deepen student understanding of key topics while developing their problem solving skills. Tutorials include acid-base chemistry, building molecular models, and drawing curved arrows and are paired with assignable MasteringChemistry® tutorials with wrong answer-specific feedback and coaching.
New Applications Boxes Throughout!
Numerous new interest boxes throughout each chapter connect chemistry to students lives and often provide any needed additional explanation on the organic chemistry occurring. New applications include: Using Genetic Engineering to Treat Ebola, Diseases Caused by a Misfolded Protein, The Inability to Perform an S 2 Reaction Causes a Severe Clinical Disorder,
Student Tutorials
MasteringChemistry® provides instant feedback specific to the structure or mechanism each student has drawn. Rather than simply providing feedback of the “right/wrong/try again” variety, Mastering recognizes the individual student error by applying evaluators to each problem that analyze chemical accuracy, employing data gathered from all student entries in Mastering, and providing wrong answer-specific feedback that helps students overcome misconceptions. An updated, mobile compatible drawing tool (java-free), provides wrong-answer feedback and guidance on every mechanism problem.
Mastering Chemistry®
MasteringChemistry® from Pearson is the leading online teaching and learning system designed to improve results by engaging students before, during, and after class with powerful content. Ensure that students arrive ready to learn by assigning educationally effective content before class, and encourage critical thinking and retention with in-class resources such as Learning Catalytics. Students can further master concepts after class through traditional homework assignments that provide hints and answer-specific feedback. The Mastering gradebook records scores for all automatically graded assignments while diagnostic tools give instructors access to rich data to assess student understanding and misconceptions.
Mastering brings learning full circle by continuously adapting to each student and making learning more personal than ever—before, during, and after class.
Before Class
Reading Quizzes
Mobile-friendly Reading Quizzes give instructors the opportunity to assign reading and test students on their comprehension of chapter content. Wrong answerspecific feedback directs students to the explanation within the eBook while hints support student problemsolving skills.
During Class
Learning CatalyticsTM
Learning Catalytics is a “bring your own device” student engagement, assessment, and classroom intelligence system. With Learning Catalytics you can:
• Assess students in real time, using open-ended tasks to probe student understanding.
• Understand immediately where students are and adjust your lecture accordingly.
• Improve your students’ criticalthinking skills.
• Access rich analytics to understand student performance.
• Add your own questions to make Learning Catalytics fit your course exactly.
• Manage student interactions with intelligent grouping and timing.
After Class
Students learn chemistry by practicing chemistry.
Tutorials, featuring wrong answer-specific feedback, hints, and a wide variety of educationally effective content, guide your students through the toughest topics in chemistry. The hallmark Hints and Feedback offer instruction similar to what students would experience in an office hour, allowing them to learn from their mistakes without being given the answer.
Name of Supplement
Digital and Print Resources
Essential Organic Chemistry provides an integrated teaching and learning package of support material for both students and professors.
Available Online
MasteringChemistry® www.mastering chemistry.com ✔
Pearson eText
Instructor or Student Resource Description
Students & Instructors
ISBN: 0133866890 within Mastering Chemistry® ✔ Student
MasteringChemistry® from Pearson is the leading online teaching and learning system designed to improve results by engaging students before, during, and after class with powerful content.
Essential Organic Chemistry features a Pearson eText within MasteringChemistry®. The Pearson eText offers students the power to create notes, highlight text in different colors, create bookmarks, zoom, and view single or multiple pages.
TestGen Test Bank ✔ Instructor Prepared by Ethan Tsai, this resource includes more than 1200 questions in multiple-choice, matching, true/false, and short answer format. Available for download on the Pearson catalog page for Essential Organic Chemistry at www.pearsonglobaleditions.com
Instructor Resource Materials ✔ Instructor Includes all the art, photos, and tables from the book in JPEG format for use in classroom projection or when creating study materials and tests. Available for download on the Pearson catalog page for Essential Organic Chemistry at www.pearsonglobaleditions.com
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newspapers could have the benefit of such a basis, the suggestion fretted him. His speech at the annual banquet of the New England Society, which created such a tremendous sensation, was an impromptu effort from beginning to end. It was the creature of the occasion. Fortunately, a reporter of the New York Tribune was present, and he has preserved for us something of the flavor and finish of the words which the young Southerner uttered on his first introduction to a Northern audience. The tremendous impression that he made, however, has never been recorded. There was a faint echo of it in the newspapers, a buzz and a stir in the hotel lobbies, but all that was said was inadequate to explain why these sons of New England, accustomed as they were to eloquence of the rarer kind, as the volumes of their proceedings show, rose to their feet and shouted themselves hoarse over the simple and impromptu effort of this young Georgian.
Mr. Grady attended the New England banquet for the purpose of making a mere formal response to the toast of “The South,” but, as he said afterwards, there was something in the scene that was inspiring. Near him sat General Tecumseh Sherman, who marched through Georgia with fire and sword, and all around him were the fat and jocund sons of New England who had prospered by the results of the war while his own people had had the direst poverty for their portion. “When I found myself on my feet,” he said, describing the scene on his return, “every nerve in my body was strung as tight as a fiddle-string, and all tingling. I knew then that I had a message for that assemblage, and as soon as I opened my mouth it came rushing out.”
That speech, as we all know, was an achievement in its way It stirred the whole country from one end to the other, and made Mr. Grady famous. Invitations to speak poured in upon him from all quarters, and he at last decided to deliver an address at Dallas, Texas. His friends advised him to prepare the speech in advance, especially as many of the newspapers of the country would be glad to have proofs of it to be used when it was delivered. He saw how essential this would be, but the preparation of a speech in cold blood (as he phrased it) was irksome to him, and failed to meet the
approval of his methods, which were as responsive to the occasion as the report of the thunder-clap is to the lightning’s flash. He knew that he could depend on these methods in all emergencies and under all circumstances, and he felt that only by depending on them could he do himself justice before an audience. The one characteristic of all his speeches, as natural to his mind as it was surprising to the minds of others, was the ease and felicity with which he seized on suggestions born of the moment and growing out of his immediate surroundings. It might be some incident occurring to the audience, some failure in the programme, some remark of the speaker introducing him, or some unlooked-for event; but, whatever it was, he seized it and compelled it to do duty in pointing a beautiful moral, or he made it the basis of that swift and genial humor that was a feature not only of his speeches, but of his daily life.
He was prevailed on, however, to prepare his Dallas speech in advance. It was put in type in the Constitution office, carefully revised, and proof slips sent out to a number of newspapers. Mr. Grady’s journey from Atlanta to Dallas, which was undertaken in a special car, was in the nature of an ovation. He was met at every station by large crowds, and his appearance created an enthusiasm that is indescribable. No such tribute as this has ever before been paid, under any circumstances, to any private American citizen, and it is to be doubted whether even any public official, no matter how exalted his station, has ever been greeted with such hearty and spontaneous enthusiasm. His reception in Dallas was the culmination of the series of ovations through which he had passed. Some sort of programme had been arranged by a committee, but the crowds trampled on this, and the affair took the shape of an American hullaballoo, so to speak, and, as such, it was greatly enjoyed by Mr. Grady.
Meanwhile, the programme that had been arranged for the speech-making was fully carried out. The young editor completely captured the vast crowd that had assembled to hear him. This information had been promptly carried to the Constitution office by private telegrams, and everything was made ready for giving the
speech to the public the next morning; but during the afternoon this telegram came:
“Suppress speech: It has been entirely changed Notify other papers ”
At the last moment, his mind full of the suggestions of his surroundings, he felt that the prepared speech could not be depended on, and he threw it away. It was a great relief to him, he told me afterward, to be able to do this. Whatever in the prepared speech seemed to be timely he used, but he departed entirely from the line of it at every point, and the address that the Texans heard was mainly an impromptu one. It created immense enthusiasm, and confirmed the promise of the speech before the New England Society.
The speech before the University of Virginia was also prepared beforehand, but Mr. Grady made a plaything of the preparation before his audience. “I was never so thoroughly convinced of Mr. Grady’s power,” said the Hon. Guyton McLendon, of Thomasville, to the writer, “as when I heard him deliver this speech.” Mr. McLendon had accompanied him on his journey to Charlottesville. “We spent a day in Washington,” said Mr. McLendon, recalling the incidents of the trip. “The rest of the party rode around the capital looking at the sights, but Mr. Grady, myself, and one or two others remained in the car. While we were waiting there, Mr. Grady read me the printed slips of his speech, and I remember that it made a great impression on me. I thought it was good enough for any occasion, but Mr. Grady seemed to have his doubts about it. He examined it critically two or three times, and made some alterations. Finally he laid it away. When he did come to deliver the speech, I was perhaps the most astonished person you ever saw. I expected to hear again the speech that had been read to me in the Pullman coach, but I heard a vastly different and a vastly better one. He used the old speech only where it was most timely and most convenient. The incident of delivering the prize to a young student who had won it on a literary exercise of some sort, started Mr. Grady off in a new vein and on a new line, and after that he used the printed speech merely to fill out
with here and there. It was wonderful how he could break away from it and come back to it, fitting the old with the new in a beautiful and harmonious mosaic. If anybody had told me that the human mind was capable of such a performance as this on the wing and in the air, so to speak, I shouldn’t have believed it. To me it was a wonderful manifestation of genius, and I knew then, for the first time, that there was no limit to Mr. Grady’s power and versatility as a speaker.”
In his speeches in the country towns of Georgia and before the farmers, Mr. Grady made no pretense of preparation. His private secretary, Mr. James R. Holliday, caught and wrote out the pregnant paragraphs that go to make up his Elberton speech, which was the skeleton and outline on which he based his speeches to the farmers. Each speech, as might be supposed, was a beautiful variation of this rural theme to which he was wedded, but the essential part of the Elberton speech was the bone and marrow of all. I think there is no passage in our modern literature equal in its effectiveness and pathos to his picture of a Southern farmer’s home. It was a matter on which his mind dwelt. There was that in his nature to which both sun and soil appealed. The rain falling on a fallow field, the sun shining on the bristling and waving corn, and the gentle winds of heaven blowing over all—he was never tired of talking of these, and his talk always took the shape of a series of picturesque descriptions. He appreciated their spiritual essence as well as their material meaning, and he surrendered himself entirely to all the wholesome suggestions that spring from the contemplation of rural scenes.
I suppose it is true that all men—except those who are brought in daily contact with the practical and prosy side of it—have a longing for a country life. Mr. Grady’s longing in that direction took the shape of a passion that was none the less serious and earnest because he knew it was altogether romantic. In the Spring of 1889, the matter engaged his attention to such an extent, that he commissioned a compositor in the Constitution office to purchase a suburban farm. He planned it all out beforehand, and knew just where the profits were to come in. His descriptions of his imaginary farm were inimitable, and the details, as he gave them out, were marked by the
rare humor with which he treated the most serious matters. There was to be an old-fashioned spring in a clump of large oak-trees on the place, meadows of orchard grass and clover, through which mildeyed Jerseys were to wander at will, and in front of the house there was to be a barley patch gloriously green, and a colt frolicking and capering in it. The farm was of course a dream, but it was a very beautiful one while it lasted, and he dwelt on it with an earnestness that was quite engaging to those who enjoyed his companionship. The farm was a dream, but he no doubt got more enjoyment and profit out of it than a great many prosy people get out of the farms that are real. Insubstantial as it was, Mr. Grady’s farm served to relieve the tension of a mind that was always busy with the larger affairs of this busy and stirring age, and many a time when he grew tired of the incessant demands made on his time and patience he would close the door of his room with a bang and instruct the officeboy to tell all callers that he had “gone to his farm.” The fat cows that grazed there lowed their welcome, the chickens cackled to see him come, and the colt capered nimbly in the green expanse of barley— children of his dreams all, but all grateful and restful to a busy mind.
II.
In this hurriedly written sketch, which is thrown together to meet the modern exigencies of publishing, the round, and full, and complete biography cannot be looked for. There is no time here for the selection and arrangement in an orderly way of the details of this busy and brilliant life. Under the circumstances, even the hand of affection can only touch it here and there so swiftly and so lightly that the random result must be inartistic and unsatisfactory. It was at such moments as these—moments of hurry and high-pressure—that Mr. Grady was at his best. His hand was never surer,—the machinery of his mind was never more responsive to the tremendous demands he made on it,—than when the huge press of the Constitution was waiting his orders; when the forms were waiting to be closed, when the compositors were fretting and fuming for copy, and when, perhaps, an express train was waiting ten minutes over its time to carry the Constitution to its subscribers. All his faculties were trained to meet emergencies; and he was never happier than when meeting them, whether in a political campaign, in conventions, in local issues, or in the newspaper business as correspondent or managing editor. Pressed by the emergency of his death, which to me was paralyzing, and by the necessity of haste, which, at this juncture, is confusing, these reminiscences have taken on a disjointed shape sadly at variance with the demands of literary art. Let me, therefore, somewhere in the middle, begin at the beginning.
Henry Woodfin Grady was born in Athens, Georgia, on the 24th of April, 1850. As a little boy he was the leader of all the little boys of his acquaintance—full of that moral audacity that takes the lead in all innocent and healthy sports. An old gentleman, whose name I have forgotten, came into the Constitution editorial rooms shortly after Mr. Grady delivered the New England banquet speech, to say that he knew Henry when a boy. I listened with interest, but the memory of what he said is vague. I remember that his reminiscences had a touch of enthusiasm, going to show that the little boy was attractive
enough to make a deep impression on his elders. He had, even when a child, all those qualities that draw attention and win approval. It is easy to believe that he was a somewhat boisterous boy. Even after he had a family of his own, and when he was supposed (as the phrase is) to have settled down, he still remained a boy to all intents and purposes. His vitality was inexhaustible, and his flow of animal spirits unceasing. In all athletic sports and out-door exercises he excelled while at school and college, and it is probable that his record as a boxer, wrestler, sprinter, and an all-around athlete is more voluminous than his record for scholarship. To the very last, his enthusiasm for these sports was, to his intimate friends, one of the most interesting characteristics of this many-sided man.
One of his characteristics as a boy, and it was a characteristic that clung to him through all his life, was his love and sympathy for the poor and lowly, for the destitute and the forlorn. This was one of the problems of life that he could never understand,—why, in the economy of Providence, some human beings should be rich and happy, and others poor and friendless. When a very little child he began to try to solve the problem in his own way. It was a small way, indeed, but if all who are fortunately situated should make the same effort charity would cause the whole world to smile, and Heaven could not possibly withhold the rich promise of its blessings. From his earliest childhood, Mr. Grady had a fondness for the negro race. He was fond of the negroes because they were dependent, his heart went out to them because he understood and appreciated their position. When he was two years old, he had a little negro boy named Isaac to wait on him. He always called this negro “Brother Isaac,” and he would cry bitterly, if any one told him that Isaac was not his brother. As he grew older his interest in the negroes and his fondness for them increased. Until he was eight or nine years old he always called his mother “Dear mother,” and when the weather was very cold, he had a habit of waking in the night and saying: “Dear mother, do you think the servants have enough cover? It’s so cold, and I want them to be warm.” His first thought was always for the destitute and the lowly—for those who were dependent on him or on others. At home he always shared his lunch with the negro children, and after the slaves were freed, and were in such a destitute
condition, scarcely a week passed that some forlorn-looking negro boy did not bring his mother a note something like this: “D M : Please give this child something to eat. He looks so hungry. H. W. G.” It need not be said that no one bearing credentials signed by this thoughtful and unselfish boy was ever turned away hungry from the Grady door. It may be said, too, that his love and sympathy for the negroes was fully appreciated by that race. His mother says that she never had a servant during all his life that was not devoted to him, and never knew one to be angry or impatient with him. He could never bear to see any one angry or unhappy about him. As a child he sought to heal the wounds of the sorrowing, and to the last, though he was worried by the vast responsibilities he had taken on his shoulders and disturbed by the thoughtless demands made on his time and patience, he suffered more from the sorrows of others than from any troubles of his own. When he went to school, he carried the same qualities of sympathy and unselfishness that had made him charming as a child. If, among his school-mates, there was to be found a poor or a delicate child, he took that child under his especial care, and no one was allowed to trouble it in any way.
Shortly after he graduated at the State University, an event occurred that probably decided Mr. Grady’s future career. In an accidental way he went on one of the annual excursions of the Georgia Press Association as the correspondent of the Constitution. His letters describing the incidents of the trip were written over the signature of “King Hans.”
They were full of that racy humor that has since become identified with a large part of Mr Grady’s journalistic work. They had a flavor of audacity about them, and that sparkling suggestiveness that goes first by one name and then another, but is chiefly known as individuality. The letters created a sensation among the editors. There was not much that was original or interesting in Georgia journalism in that day and time. The State was in the hands of the carpet-baggers, and the newspapers reflected in a very large degree the gloom and the hopelessness of that direful period. The editors abused the Republicans in their editorial columns day after day, and
made no effort to enlarge their news service, or to increase the scope of their duties or their influence. Journalism in Georgia, in short, was in a rut, and there it was content to jog.
Though the “King Hans” letters were the production of a boy, their humor, their aptness, their illuminating power (so to say), their light touch, and their suggestiveness, showed that a new star had arisen. They created a lively diversion among the gloomy-minded editors for a while, and then the procession moved sadly forward in the old ruts. But the brief, fleeting, and humorous experience that Mr. Grady had as the casual correspondent of the Constitution decided him. Perhaps this was his bent after all, and that what might be called a happy accident was merely a fortunate incident that fate had arranged, for to this beautiful and buoyant nature fate seemed to be always kind. Into his short life it crowded its best and dearest gifts. All manner of happiness was his—the happiness of loving and of being beloved—the happiness of doing good in directions that only the Recording Angel could follow—and before he died Fame came and laid a wreath of flowers at his feet. Fate or circumstance carried him into journalism. His “King Hans” letters had attracted attention to him, and it seemed natural that he should follow this humorous experiment into a more serious field.
He went to Rome not long afterwards, and became editor of the Rome Courier. The Courier was the oldest paper in the city, and therefore the most substantial. It was, in fact, a fine piece of property. But the town was a growing town, and the Courier had rivals, the Rome Daily, if my memory serves me, and the Rome Commercial. Just how long Mr. Grady edited the Courier, I have no record of; but one fine morning, he thought he discovered a “ring” of some sort in the village. I do not know whether it was a political or a financial ring. We have had so many of these rings in one shape or another that I will not trust my memory to describe it; but it was a ring, and probably one of the first that dared to engage in business. Mr. Grady wrote a fine editorial denouncing it, but when the article was submitted to the proprietor, he made some objection. He probably thought that some of his patrons would take offense at the strong language Mr. Grady had used. After some conversation on the
subject, the proprietor of the Courier flatly objected to the appearance of the editorial in his paper. Mr. Grady was about eighteen years old then, with views and a little money of his own. In the course of a few hours he had bought out the two opposing papers, consolidated them, and his editorial attack on the ring appeared the next morning in the Rome Daily Commercial. It happened on the same morning that the two papers, the Courier and the Daily Commercial, both appeared with the name of Henry W. Grady as editor. The ring, or whatever it was, was smashed. Nobody heard anything more of it, and the Commercial was greeted by its esteemed contemporaries as a most welcome addition to Georgia journalism. It was bright and lively, and gave Rome a new vision of herself.
It was left to the Commercial to discover that Rome was a city set on the hills, and that she ought to have an advertising torch in her hands. The Commercial, however, was only an experiment. It was run, as Mr. Grady told me long afterwards, as an amateur casual. He had money to spend on it, and he gave it a long string to go on. Occasionally he would fill it up with his bright fancies, and then he would neglect it for days at a time, and it would then be edited by the foreman. It was about this time that I met Mr. Grady. We had had some correspondence. He was appreciative, and whatever struck his fancy he had a quick response for. Some foolish paragraph of mine had appealed to his sense of humor, and he pursued the matter with a sympathetic letter that made a lasting impression. The result of that letter was that I went to Rome, pulled him from his flying ponies, and had a most enjoyable visit. From Rome we went to Lookout Mountain, and it is needless to say that he was the life of the party. He was its body, its spirit, and its essence. We found, in our journey, a dissipated person who could play on the zither. Just how important that person became, those who remember Mr. Grady’s pranks can imagine. The man with the zither took the shape of a minstrel, and in that guise he went with us, always prepared to make music, which he had often to do in response to Mr. Grady’s demands.
Rome, however, soon ceased to be large enough for the young editor. Atlanta seemed to offer the widest field, and he came here,
and entered into partnership with Colonel Robert A. Alston and Alex St. Clair-Abrams. It was a queer partnership, but there was much that was congenial about it. Colonel Alston was a typical South Carolinian, and Abrams was a Creole. It would be difficult to get together three more impulsive and enterprising partners. Little attention was paid to the business office. The principal idea was to print the best newspaper in the South, and for a time this scheme was carried out in a magnificent way that could not last. Mr. Grady never bothered himself about the finances, and the other editors were not familiar with the details of business. The paper they published attracted more attention from newspaper men than it did from the public, and it was finally compelled to suspend. Its good will —and it had more good will than capital—was sold to the Constitution, which had been managed in a more conservative style. It is an interesting fact, however, that Mr. Grady’s experiments in the Herald, which were failures, were successful when tried on the Constitution, whose staff he joined when Captain Evan P. Howell secured a controlling interest. And yet Mr. Grady’s development as a newspaper man was not as rapid as might be supposed. He was employed by the Constitution as a reporter, and his work was intermittent.
One fact was fully developed by Mr. Grady’s early work on the Constitution,—namely, that he was not fitted for the routine work of a reporter. One day he would fill several columns of the paper with his bright things, and then for several days he would stand around in the sunshine talking to his friends, and entertaining them with his racy sayings. I have seen it stated in various shapes in books and magazines that the art of conversation is dead. If it was dead before Mr. Grady was born, it was left to him to resurrect it. Charming as his pen was, it could bear no reasonable comparison with his tongue. I am not alluding here to his eloquence, but to his ordinary conversation. When he had the incentive of sympathetic friends and surroundings, he was the most fascinating talker I have ever heard. General Toombs had large gifts in that direction, but he bore no comparison in any respect to Mr Grady, whose mind was responsive to all suggestions and to all subjects. The men who have made large reputations as talkers have had the habit of selecting their own
subjects and treating them dogmatically We read of Coleridge buttonholing an acquaintance and talking him to death on the street, and of Carlyle compelling himself to be heard by sheer vociferousness. Mr. Grady could have made the monologue as interesting as he did his orations, but this was not his way. What he did was to take up whatever commonplace subject was suggested, and so charge it with his nimble wit and brilliant imagination as to give it a new importance.
It was natural, under the circumstances, that his home in Atlanta should be the center of the social life of the city. He kept open house, and, aided by his lovely wife and two beautiful children, dispensed the most charming hospitality. There was nothing more delightful than his home-life. Whatever air or attitude he had to assume in business, at home he was a rollicking and romping boy. He put aside all dignity there, and his most distinguished guest was never distinguished enough to put on the airs of formality that are commonly supposed to be a part of social life. His home was a typical one,—the center of his affections and the fountain of all his joys—and he managed to make all his friends feel what a sacred place it was. It was the headquarters of all that is best and brightest in the social and intellectual life of Atlanta, and many of the most distinguished men of the country have enjoyed the dispensation of his hospitality, which was simple and homelike, having about it something of the flavor and ripeness of the old Southern life.
In writing of the life and career of a man as busy in so many directions as Mr. Grady, one finds it difficult to pursue the ordinary methods of biographical writing. One finds it necessary, in order to give a clear idea of his methods, which were his own in all respects, to be continually harking back to some earlier period of his career. I have alluded to his distaste for the routine of reportorial work. The daily grind—the treadmill of trivial affairs—was not attractive to him; but when there was a sensation in the air—when something of unusual importance was happening or about to happen—he was in his element. His energy at such times was phenomenal. He had the faculty of grasping all the details of an event, and the imagination to group them properly so as to give them their full force and effect.
The result of this is shown very clearly in his telegrams to the New York Herald and the Constitution from Florida during the disputed count going on there in 1876 and the early part of 1877. Mr. Tilden selected Senator Joseph E. Brown, among other prominent Democrats, to proceed to Florida, and look after the Democratic case there. Mr. Grady went as the special correspondent of the New York Herald and the Atlanta Constitution, and though he had for his competitors some of the most famous special writers of the country, he easily led them all in the brilliancy of his style, in the character of his work, and in his knack of grouping together gossip and fact. He was always proud of his work there; he was on his mettle, as the saying is, and I think there is no question that, from a journalist’s point of view, his letters and telegrams, covering the history of what is known politically as the Florida fraud, have no equal in the newspaper literature of the day. There is no phase of that important case that his reports do not cover, and they represent a vast amount of rapid and accurate work—work in which the individuality of the man is as prominent as his accuracy and impartiality. One of the results of Mr. Grady’s visit to Florida, and his association with the prominent politicians gathered there, was to develop a confidence in his own powers and resources that was exceedingly valuable to him when he came afterwards to the management of the leading daily paper in the South. He discovered that the men who had been successful in business and in politics had no advantage over him in any of the mental qualities and attributes that appertain to success, and this discovery gave purpose and determination to his ambition.
Another fruitful fact in his career, which he used to dwell on with great pleasure, was his association while in Florida with Senator Brown—an association that amounted to intimacy. Mr. Grady always had a very great admiration for Senator Brown, but in Florida he had the opportunity of working side by side with the Senator and of studying the methods by which he managed men and brought them within the circle of his powerful influence. Mr. Grady often said that it was one of the most instructive lessons of his life to observe the influence which Senator Brown, feeble as he was in body, exerted on men who were almost total strangers. The contest between the politicians for the electoral vote of Florida was in the nature of a still
hunt, where prudence, judgment, skill, and large knowledge of human nature were absolutely essential. In such a contest as this, Senator Brown was absolutely master of the situation, and Mr. Grady took great delight in studying his methods, and in describing them afterwards.
Busy as Mr. Grady was in Florida with the politicians and with his newspaper correspondence, he nevertheless found time to make an exhaustive study of the material resources of the State, and the result of this appeared in the columns of the Constitution at a later date in the shape of a series of letters that attracted unusual attention throughout the country. This subject, the material resources of the South, and the development of the section, was always a favorite one with Mr. Grady. He touched it freely from every side and point of view, and made a feature of it in his newspaper work. To his mind there was something more practical in this direction than in the heat and fury of partisan politics. Whatever would aid the South in a material way, develop her resources and add to her capital, population, and industries, found in him not only a ready, but an enthusiastic and a tireless champion. He took great interest in politics, too, and often made his genius for the management of men and issues felt in the affairs of the State; but the routine of politics— the discussion that goes on, like Tennyson’s brook, forever and forever—were of far less importance in his mind than the practical development of the South. This seemed to be the burthen of his speeches, as it was of all his later writings. He never tired of this subject, and he discussed it with a brilliancy, a fervor, a versatility, and a fluency marvelous enough to have made the reputation of half a dozen men. Out of his contemplation of it grew the lofty and patriotic purpose which drew attention to his wonderful eloquence, and made him famous throughout the country—the purpose to draw the two sections together in closer bonds of union, fraternity, harmony, and good-will. The real strength and symmetry of his career can only be properly appreciated by those who take into consideration the unselfishness with which he devoted himself to this patriotic purpose. Instinctively the country seemed to understand something of this, and it was this instinctive understanding that caused him to be regarded with affectionate interest and
appreciation from one end of the country to the other by people of all parties, classes, and interests. It was this instinctive understanding that made him at the close of his brief career one of the most conspicuous Americans of modern times, and threw the whole country into mourning at his death.
When in 1880 Mr. Grady bought a fourth interest in the Constitution, he gave up, for the most part, all outside newspaper work, and proceeded to devote his time and attention to his duties as managing editor, for which he was peculiarly well fitted. His methods were entirely his own. He borrowed from no one. Every movement he made in the field of journalism was stamped with the seal of his genius. He followed no precedent. He provided for every emergency as it arose, and some of his strokes of enterprise were as bold as they were startling. He had a rapid faculty of organization. This was shown on one occasion when he determined to print official reports of the returns of the congressional election in the seventh Georgia district. Great interest was felt in the result all over the State. An independent candidate was running against the Democratic nominee, and the campaign was one of the liveliest ever had in Georgia. Yet it is a district that lies in the mountains and winds around and over them. Ordinarily, it was sometimes a fortnight and frequently a month before the waiting newspapers and the public knew the official returns. Mr. Grady arranged for couriers with relays of horses at all the remote precincts, and the majority of them are remote from the lines of communication, and his orders to these were to spare neither horse-flesh nor money in getting the returns to the telegraph stations. At important points, he had placed members of the Constitution’s editorial and reportorial staff, who were to give the night couriers the assistance and directions which their interest and training would suggest. It was a tough piece of work, but all the details and plans had been so perfectly arranged that there was no miscarriage anywhere. One of the couriers rode forty miles over the mountains, fording rushing streams and galloping wildly over the rough roads. It was a rough job, but he had been selected by Mr. Grady especially for this piece of work; he was a tough man and he had tough horses under him, and he reached the telegraph station on time. This sort of thing was going on all over the district, and the next morning the whole State had the official returns. Other feats of
modern newspaper enterprise have been more costly and as successful, but there is none that I can recall to mind showing a more comprehensive grasp of the situation or betraying a more daring spirit. It was a feat that appealed to the imagination, and therefore on the Napoleonic order.
And yet it is a singular fact that all his early journalistic ventures were in the nature of failures. The Rome Commercial, which he edited before he had attained his majority, was a bright paper, but not financially successful. Mr. Grady did some remarkably bold and brilliant work on the Atlanta Daily Herald, but it was expensive work, too, and the Herald died for lack of funds. Mr. Marion J. Verdery, in his admirable memorial of Mr. Grady, prepared for the Southern Society of New York (which I have taken the liberty of embodying in this volume) alludes to these failures of Mr. Grady, and a great many of his admirers have been mystified by them. I think the explanation is very simple. Mr. Grady was a new and a surprising element in the field of journalism, and his methods were beyond the comprehension of those who had grown gray watching the dull and commonplace politicians wielding their heavy pens as editors, and getting the news accidentally, if at all. There are a great many people in this world of ours—let us say the average people, in order to be mathematically exact—who have to be educated up to an appreciation of what is bright and beautiful, or bold and interesting. Some of Mr. Grady’s methods were new even in American journalism, and it is no wonder that his dashing experiments with the Daily Herald were failures, or that commonplace people regarded them as crude and reckless manifestations of a purpose and a desire to create a sensation. Moreover, it should be borne in mind that when the Daily Herald was running its special locomotives up and down the railroads of the State, the field of journalism in Atlanta was exceedingly narrow and provincial. The town had been rescued from the village shape, but neither its population nor its progress warranted the experiments on the Herald. They were mistakes of time and place, but they were not mistakes of conception and execution. They helped to educate and enlighten the public, and to give that dull, clumsy, and slow-moving body a taste of the spirit and purpose of modern journalism. The public liked the taste that it got, and smacked its lips over it and
remembered it, and was always ready after that to respond promptly to the efforts of Mr. Grady to give it the work of his head and hands.
Bright and buoyant as he was, his early failures in journalism dazed and mortified him, but they did not leave him depressed. If he had his hours of depression and gloom he reserved them for himself. Even when all his resources had been exhausted, he was the same genial, witty, and appreciative companion, the center of attraction wherever he went. The year 1876 was the turning-point in his career in more ways than one. In the fall of that year, Captain Evan P. Howell bought a controlling interest in the Constitution. The day after the purchase was made, Captain Howell met Mr. Grady, who was on his way to the passenger station.
“I was just hunting for you,” said Captain Howell. “I want to have a talk with you.”
“Well, you’ll have to talk mighty fast,” said Mr. Grady. “Atlanta’s either too big for me, or I am too big for Atlanta.”
It turned out that the young editor, discomfited in Atlanta, but not discouraged, was on his way to Augusta to take charge of the Constitutionalist of that city. Captain Howell offered him a position at once, which was promptly accepted. There was no higgling or bargaining; the two men were intimate friends; there was something congenial in their humor, in their temperaments, and in a certain fine audacity in political affairs that made the two men invincible in Georgia politics from the day they began working together. Before the train that was to bear Mr. Grady to Augusta had steamed out of the station, he was on his way to the Constitution office to enter on his duties, and then and there practically began between the two men a partnership as intimate in its relations of both friendship and business as it was important on its bearings on the wonderful success of the Constitution and on the local history and politics of Georgia. It was an ideal partnership in many respects, and covered almost every movement, with one exception, that the two friends made. That exception was the prohibition campaign in Atlanta, that attracted such widespread attention throughout the country. Mr. Grady represented the prohibitionists and Captain Howell the anti-
prohibitionists, and it was one of the most vigorous and amusing campaigns the town has ever witnessed. Each partner was the chief speaker of the side he represented, and neither lost an opportunity to tell a good-humored joke at the other’s expense. Thus, while the campaign was an earnest one in every respect, and even embittered to some small extent by the thoughtless utterances of those who seem to believe that moral issues can best be settled by a display of fanaticism, the tension was greatly relieved by the wit, the humor, the good nature and the good sense which the two leaders injected into the canvas.
The sentimental side of Mr. Grady’s character was more largely and more practically developed than that of any other person I have ever seen. In the great majority of cases sentiment develops into a sentimentality that is sometimes maudlin, sometimes officious, and frequently offensive. In most people it develops as the weakest and least attractive side of their character. It was the stronghold of Mr. Grady’s nature. It enveloped his whole career, to use Matthew Arnold’s phrase, in sweetness and light, and made his life a real dispensation in behalf of the lives of others. Wherever he found suffering and sorrow, no matter how humble—wherever he found misery, no matter how coarse and degraded, he struck hands with them then and there, and wrapped them about and strengthened them with his abundant sympathy. Until he could give them relief in some shape, he became their partner, and a very active and energetic partner he was. I have often thought that his words of courage and cheer, always given with a light and humorous touch to hide his own feelings, was worth more than the rich man’s grudging gift. It was this side of Mr. Grady’s nature that caused him to turn with such readiness to the festivities of Christmas. He was a great admirer of Charles Dickens, especially of that writer’s Christmas literature. It was an ideal season with Mr. Grady, and it presented itself to his mind less as a holiday time than as an opportunity to make others happy—the rich as well as the poor. He had a theory that the rich who have become poor by accident or misfortune suffer the stings of poverty more keenly than the poor who have always been poor, for the reason that they are not qualified to fight against conditions that are at once strange and crushing. Several
Christmases ago, I had the pleasure of witnessing a little episode in which he illustrated his theory to his own satisfaction as well as to mine.
On that particular Christmas eve, there was living in Atlanta an old gentleman who had at one time been one of the leading citizens of the town. He had in fact been a powerful influence in the politics of the State, but the war swept away his possessions, and along with them all the conditions and surroundings that had enabled him to maintain himself comfortably. His misfortunes came on him when he was too old to begin the struggle with life anew with any reasonable hope of success. He gave way to a disposition that had been only convivial in his better days when he had hope and pride to sustain him, and he sank lower until he had nearly reached the gutter.
I joined Mr. Grady as he left the office, and we walked slowly down the street enjoying the kaleidoscopic view of the ever-shifting, ever hurrying crowd as it swept along the pavements. In all that restless and hastening throng there seemed to be but one man bent on no message of enjoyment or pleasure, and he was old and seedylooking. He was gazing about him in an absent-minded way The weather was not cold, but a disagreeable drizzle was falling.
“Yonder is the Judge,” said Mr Grady, pointing to the seedylooking old man. “Let’s go and see what he is going to have for Christmas.”
I found out long afterwards that the old man had long been a pensioner on Mr. Grady’s bounty, but there was nothing to suggest this in the way in which the young editor approached the Judge. His manner was the very perfection of cordiality and consideration, though there was just a touch of gentle humor in his bright eyes.
“It isn’t too early to wish you a merry Christmas, I hope,” said Mr. Grady, shaking hands with the old man.
“No, no,” replied the Judge, straightening himself up with dignity; “not at all. The same to you, my boy.”
“Well,” remarked Mr. Grady lightly, “you ought to be fixing up for it. I’m not as old as you are, and I’ve got lots of stirring around and
