Organic chemistry 7e by paula yurkanis bruice 1

To the Student
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 back cover 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, as can the Appendices, which consolidate useful categories of information. 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,
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
making 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 medical school sometimes wonder
why medical schools pay so much attention to this topic. The importance of organic chemistry is not
in the subject matter alone, however. Mastering organic chemistry requires a thorough understanding
of certain fundamental principles and the ability to use those fundamentals to analyze, classify, and
predict. The study of medicine makes similar demands: a physician uses an understanding of certain
fundamental principles to analyze, classify, and diagnose.
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

Medical Applications

Biological Applications

Fosamax Prevents Bones from Being Nibbled
Away (2.8)
Aspirin Must Be in its Basic Form to be
Physiologically Active (2.10)
Blood: A Buffered Solution (2.11)
Drugs Bind to Their Receptors (3.9)
Cholesterol and Heart Disease (3.15)
How High Cholesterol is Clinically Treated (3.15)
The Enantiomers of Thalidomide (6.17)
Synthetic Alkynes Are Used to Treat Parkinson’s 
Disease (7.0)
Synthetic Alkynes Are Used for Birth Control (7.1)
S-Adenosylimethionine: A Natural Antidepressant (9.9)
The Inability to Perform an SN2 Reaction Causes a
Severe Clinical Disorder (11.3)
Treating Alcoholism with Antabuse (11.5)
Methanol Poisoning (11.5)
Anesthetics (11.6)
Benzo[a]pyrene and Cancer (11.8)
Chimney Sweeps and Cancer (11.8)
Lead Compounds for the Development
of Drugs (11.9)
Alkylating Agents as Cancer Drugs (11.11)
Is Chocolate a Health Food? (13.11)

Artificial Blood (13.12)
Nature’s Sleeping Pill (16.1)
Aspirin, NSAIDs, and Cox-2 Inhibitors (16.11)
The Discovery of Penicillin (16.15)
Penicillin and Drug Resistance (16.15)
Penicillins in Clinical Use (16.15)
Dissolving Sutures (16.21)
Serendipity in Drug Development (17.10)
Cancer Chemotherapy (17.18)
Breast Cancer and Aromatase Inhibitors (18.12)
Discovery of the First Antibiotic (19.22)
Drug Safety (19.22)
Nitrosamines and Cancer (19.23)
Thyroxine (19.5)
Searching for Drugs: An Antihistamine, a
Nonsedating Antihistamine, and a
Drug for Ulcers (20.7)
Porphyrin, Bilirubin, and Jaundice (20.7)
Measuring the Blood Glucose Levels in
Diabetes (21.8)
Lactose Intolerance (21.15)
Galactosemia (21.15)
Why the Dentist is Right (21.16)
Bacterial Resistance (21.17)
Heparin–A Natural Anticoagulant (21.17)
Vitamin C (21.17)
Amino Acids and Disease (22.2)
A Peptide Antibiotic (22.2)
Diabetes (22.8)
Diseases Caused by a Misfolded Protein (22.15)

How Tamiflu Works (23.10)
Niacin Deficiency (24.1)
Assessing the Damage After a Heart Attack (24.5)
The First Antibiotics (24.7)
Cancer Drugs and Side Effects (24.7)
Anticoagulants (24.8)
Phenylketonuria (PKU): An Inborn Error of
Metabolism (25.9)
Alcaptonuria (25.9)
Basal Metabolic Rate (25.11)
How Statins Lower Cholesterol Levels (25.17)
Sickle Cell Anemia (26.9)
Antibiotics That Act by Inhibiting Translation (26.9)
Three Different Antibiotics Act by a Common
Mechanism (26.10)
Influenza Pandemics (26.11)
The X Prize (26.12)
Nanocontainers (27.5)
Melamine Poisoning (27.8)
Health Concerns: Bisphenol A and Phthalates (27.8)
The Sunshine Vitamin (29.6)

Poisonous Amines (2.3)
Cell Membranes (3.9)
Pheromones (5.0)
Trans Fats (6.12)
How a Banana Slug Knows What to Eat (7.2)
Electron Delocalization Affects the ThreeDimensional Shape of Proteins (8.5)
DDT: A Synthetic Organohalide That Kills
Disease-Spreading Insects (9.0)

Naturally Occurring Organohalides That Defend
Against Predators (10.0)
Biological Dehydrations (11.4)
Alkaloids (11.9)
Whales and Echolocation (16.13)
Snake Venom (16.13)
Phosphoglycerides Are Components of
Membranes (16.13)
A Semisynthetic Penicillin (16.15)
Dalmatians: Do Not Fool with Mother
Nature (16.16)
Preserving Biological Specimens (17.11)
A Biological Friedel-Crafts Alkylation (19.8)
Controlling Fleas (21.16)
Primary Structure and Taxonomic Relationship
(22.12)
Competitive Inhibitors (24.7)
There Are More Than Four Bases in DNA (26.7)

Chemical Applications
Natural Organic Compounds versus Synthetic Organic
Compounds (1.0)
Diamond, Graphite, Graphene, and Fullerenes:
Substances Containing Only Carbon Atoms (1.8)
Water—A Unique Compound (1.12)
Acid Rain (2.2)
Bad Smelling Compounds (3.7)
Von Baeyer, Barbituric Acid, and Blue Jeans (3.11)
Starch and Cellulose—Axial and Equatorial (3.13)
Cis-Trans Interconversion in Vision (4.1)

The Difference Between ∆G‡ and Ea (5.9)
Borane and Diborane (6.8)
Cyclic Alkenes (6.15)
Chiral Catalysts (6.16)
Chiral Drugs (4.15)
Sodium Amide and Sodium in Ammonia (7.10)
Green Chemistry: Aiming for Sustainability (7.12)
Buckyballs (8.9)
Organic Compounds That Conduct Electricity (8.13)
Why Are Living Organisms Composed of Carbon
Instead of Silicon? (9.2)
Solvation Effects (9.7)
Eradicating Termites (9.7)
The Lucas Test (11.1)
Crown Ethers: Another Example of Molecular
Recognition (11.7)
Crown Ethers Can be Used to Catalyze SN2
Reactions (11.7)
Mustard–A Chemical Warfare Agent (11.11)
Cyclopropane (13.9)
What Makes Blueberries Blue and Strawberries
Red? (14.21)
Omega Fatty Acids (16.4)
Waxes Are Esters That Have High-Molecular
Weights (16.9)
Synthetic Polymers (16.21)
Nerve Impulses, Paralysis, and Insecticides (16.23)
Enzyme-Catalyzed Carbonyl Additions (17.14)
Carbohydrates (17.12)
b-Carotene (17.16)

Synthesizing Organic Compounds (17.17)
Semisynthetic Drugs (17.17)
Enzyme-Catalyzed Cis-Trans
Interconversion (17.18)
The Synthesis of Aspirin (18.7)

Measuring Toxicity (19.0)
Incipient Primary Carbocations (19.8)
Synthetic Polymers (16.21)
Olestra: Nonfat with Flavor (21.11)
Hair: Straight or Curly? (22.8)
Right-Handed and Left-Handed Helices (22.14)
b-Peptides: An Attempt to Improve
on Nature (22.14)
Too Much Broccoli (24.8)
Why Did Nature Choose Phosphates? (25.1)
Protein Prenylation (25.17)
Natural Products That Modify DNA (26.6)
Resisting Herbicides (26.14)
Designing a Polymer (27.8)
Luminescence (29.6)
A Biological Reaction That Involves an
Electrocyclic Reaction Followed by a
Sigmatropic Rearrangement (29.6)

General Applications
Derivation of the Henderson-Hasselbalch
Equation (2.10)
How is the Octane Number of Gasoline
Determined? (3.2)

A Few Words About Curved Arrows (5.6)
Calculating Kinetic Parameters (End of Ch 05)
Which are More Harmful, Natural Pesticides or
Synthetic Pesticides? (6.18)
Why Are Drugs so Expensive? (7.0)
Kekule’s Dream (8.1)
Environmental Adaptation (9.7)
The Nobel Prize (10.8)
Grain Alcohol and Wood Alcohol (11.1)
Blood Alcohol Content (11.5)
Natural Gas and Petroleum (13.1)
Fossil Fuels: A Problematic Energy Source (13.1)
Why Radicals No Longer Have to Be Called Free
Radicals (13.2)
Decaffinated Coffee and the Cancer Scare (13.11)
Food Preservatives (13.11)
Mass Spectrometry in Forensics (14.8)
The Originator of Hooke’s Law (14.13)
Ultraviolet Light and Sunscreens (14.18)
Nikola Tesla (15.1)
Structural Databases (15.24)
Soaps and Micelles (16.13)
What Drug-Enforcement Dogs Are Really
Detecting (16.20)
Butanedione: An Unpleasant Compound (17.1)
The Toxicity of Benzene (19.1)
Glucose/Dextrose (21.9)
Acceptable Daily Intake (21.19)
Proteins and Nutrition (22.1)
Water Softeners: Examples of Cation-Exchange

Chromatography (22.3)
Vitamin B1 (24.0)
Curing A Hangover with Vitamin B1 (24.3)
Differences in Metabolism (25.0)
The Structure of DNA: Watson, Crick, Franklin, and
Wilkins (26.1)
DNA Fingerprinting (26.13)
Teflon: An Accidental Discovery (27.2)
Recycling Symbols (27.2)


Organic Chemistry


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Organic Chemistry
SEVENTH EDITION

Paula Yurkanis Bruice
UNIVERSITY OF CALIFORNIA
S A N TA B A R B A R A

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Credits and acknowledgments borrowed from other sources and reproduced, with permission, in
this textbook appear on p. P-1.
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Library of Congress Cataloging-in-Publication Data available upon request from Publisher.

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www.pearsonhighered.com

ISBN 10: 0-321-80322-1
ISBN 13: 978-0-321-80322-1


To Meghan, Kenton, and Alec
with love and immense respect
and to Tom, my best friend


Brief Table of Contents
Preface

vi

xx

CHAPTER 1

Remembering General Chemistry: Electronic Structure and Bonding

CHAPTER 2

Acids and Bases: Central to Understanding Organic Chemistry 53

TUTORIAL

Acids and Bases

CHAPTER 3

An Introduction to Organic Compounds: Nomenclature, Physical
Properties, and Representation of Structure 90

TUTORIAL

Using Molecular Models

CHAPTER 4

Isomers: The Arrangement of Atoms in Space

TUTORIAL

Interconverting Structural Representations 187

CHAPTER 5

Alkenes: Structure, Nomenclature, and an Introduction to Reactivity •
Thermodynamics and Kinetics 190

TUTORIAL

An Exercise in Drawing Curved Arrows: Pushing Electrons

CHAPTER 6

The Reactions of Alkenes: The Stereochemistry of Addition Reactions

CHAPTER 7

The Reactions of Alkynes • An Introduction to Multistep Synthesis

CHAPTER 8

Delocalized Electrons and Their Effect on Stability, pKa, and the Products
of a Reaction 330

TUTORIAL

Drawing Resonance Contributors

CHAPTER 9

Substitution Reactions of Alkyl Halides

CHAPTER 10

Elimination Reactions of Alkyl Halides •
Competition Between Substitution and Elimination

2

82

146
147

225

392
402

444

CHAPTER 11

Reactions of Alcohols, Ethers, Epoxides, Amines, and Thiols

CHAPTER 12

Organometallic Compounds

CHAPTER 13

Radicals • Reactions of Alkanes

TUTORIAL

Drawing Curved Arrows in Radical Systems 590

CHAPTER 14

Mass Spectrometry, Infrared Spectroscopy, and Ultraviolet/ Visible
Spectroscopy 595

CHAPTER 15

NMR Spectroscopy

649

481

535
556

236

299


vii

CHAPTER 16

Reactions of Carboxylic Acids and Carboxylic Derivatives

CHAPTER 17

Reactions of Aldehydes and Ketones • More Reactions of Carboxylic Acid
Derivatives • Reactions of a,b- Unsaturated Carbonyl Compounds 789

CHAPTER 18

Reactions at the a-Carbon of Carbonyl Compounds

CHAPTER 19

Reactions of Benzene and Substituted Benzenes

TUTORIAL

Synthesis and Retrosynthetic Analysis 974

CHAPTER 20

More About Amines • Reactions of Heterocyclic Compounds

CHAPTER 21

The Organic Chemistry of Carbohydrates

CHAPTER 22

The Organic Chemistry of Amino Acids, Peptides, and Proteins

CHAPTER 23

Catalysis in Organic Reaction and in Enzymatic Reactions

CHAPTER 24

The Organic Chemistry of the Coenzymes, Compounds Derived from
Vitamins 1132

CHAPTER 25

The Organic Chemistry of the Metabolic Pathways •
Terpene Biosynthesis 1170

CHAPTER 26

The Chemistry of the Nucleic Acids

CHAPTER 27

Synthetic Polymers

1236

CHAPTER 28

Pericyclic Reactions

1266

APPENDICES I

pKa Values

II Kinetics

720

853

907

989

1017
1053

1099

1207

A-1

A-3

III Summary of Methods Used to Synthesize a Particular

Functional Group

A-8

IV Summary of Methods Employed to Form Carbon-Carbon Bonds

Answers to Selected Problems
Glossary

G-1

Photo Credits
Index

I-1

P-1

Available in the Study Area in
MasteringChemistry

A-11


Contents

New material on how to draw
Lewis structures and how to
predict bond angles and the
orbitals used in bonding.

PART 1

AN INTRODUCTION TO THE STUDY
OF ORGANIC CHEMISTRY 1

1

Remembering General Chemistry:
Electronic Structure and Bonding 2

1.1
1.2
1.3
1.4

The Structure of an Atom 4
How the Electrons in an Atom Are Distributed 5
Ionic and Covalent Bonds 7
How the Structure of a Compound Is Represented
P R O B L E M - S O LV I N G S T R AT E G Y

1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14

Atomic Orbitals 21
An Introduction to Molecular Orbital Theory 23
How Single Bonds Are Formed in Organic Compounds 28

How a Double Bond Is Formed: The Bonds in Ethene 31
How a Triple Bond Is Formed: The Bonds in Ethyne 34
The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion
The Bonds in Ammonia and in the Ammonium Ion 37
The Bonds in Water 38
The Bond in a Hydrogen Halide 40
Hybridization and Molecular Geometry 42
P R O B L E M - S O LV I N G S T R AT E G Y

1.15

New chapter on Acid/
Base Chemistry reinforces
fundamental concepts.

The Dipole Moments of Molecules

• Acids and Bases: Factors Influencing
Acid Strength
• Acids and Bases: pH Influence on Acid
and Base Structure

viii

■

PROBLEMS

49

2.1
2.2

An Introduction to Acids and Bases
pKa and pH 55
Organic Acids and Bases

2.4
2.5
2.6
2.7

2.11
2.12

56

60

How to Predict the Outcome of an Acid–Base Reaction
How to Determine the Position of Equilibrium 61
How the Structure of an Acid Affects its pKa Value 63
How Substituents Affect the Strength of an Acid 66
P R O B L E M - S O LV I N G S T R AT E G Y

2.8
2.9
2.10

53

57
61

67

An Introduction to Delocalized Electrons 68
A Summary of the Factors that Determine Acid Strength 70
How pH Affects the Structure of an Organic Compound 72
P R O B L E M - S O LV I N G S T R AT E G Y

• Acids and Bases: Equilibrium Basics

48

Acids and Bases:
Central to Understanding Organic Chemistry 53

P R O B L E M - S O LV I N G S T R AT E G Y

Enhanced by

47

2

P R O B L E M - S O LV I N G S T R AT E G Y

New tutorial on Acid/
Base Chemistry provides

students with opportunities
to self assess and develop
foundational skills needed
for future topics in organic
chemistry.

47

SOME IMPORTANT THINGS TO REMEMBER

2.3

Buffer Solutions 76
Lewis Acids and Bases

72

77

SOME IMPORTANT THINGS TO REMEMBER 78

TUTORIAL

ACIDS AND BASES

36

42

Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles

P R O B L E M - S O LV I N G S T R AT E G Y

1.16

14

17

82

■

PROBLEMS

79

43


ix

3
3.1
3.2
3.3

An Introduction to Organic Compounds:
Nomenclature, Physical Properties, and
Representation of Structure 90
How Alkyl Substituents Are Named 94

The Nomenclature of Alkanes 97
The Nomenclature of Cycloalkanes • Skeletal Structures
P R O B L E M - S O LV I N G S T R AT E G Y

3.4
3.5
3.6
3.7
3.8
3.9

3.14
3.15

133

SOME IMPORTANT THINGS TO REMEMBER

TUTORIAL

4
4.1
4.2
4.3
4.4
4.5
4.6
4.7

4.8

4.9
4.10
4.11
4.12

USING MOLECULAR MODELS

PROBLEMS

140

Enhanced by

146

• Using Molecular Models: Basics of
Model Building

Cis–Trans Isomers Result From Restricted Rotation 148
A Chiral Object Has a Nonsuperimposable Mirror Image 151
An Asymmetric Center Is a Cause of Chirality in a Molecule 152
Isomers with One Asymmetric Center 153
Asymmetric Centers and Stereocenters 154
How to Draw Enantiomers 154
Naming Enantiomers by the R,S System 155
P R O B L E M - S O LV I N G S T R AT E G Y

15 8

P R O B L E M - S O LV I N G S T R AT E G Y

15 8

Chiral Compounds Are Optically Active 160
How Specific Rotation Is Measured 161
Enantiomeric Excess 163
Compounds with More than One Asymmetric Center
Stereoisomers of Cyclic Compounds 167

• Using Molecular Models: Interpret Cyclic
Models

Two new tutorials reinforce
student understanding and
visualization of structure.

164

16 8

169

17 1

Enhanced by

How to Name Isomers with More than One Asymmetric Center

173

• Interconverting Structural
Representations: Interpreting Fischer
Projections

17 5

How Enantiomers Can Be Separated 178
Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers
SOME IMPORTANT THINGS TO REMEMBER

TUTORIAL

• Using Molecular Models: Interpret Chiral
Models

The coverage of stereoisomers
now precedes the coverage of
the reactions of alkenes.

Meso Compounds Have Asymmetric Centers but Are Optically Inactive

P R O B L E M - S O LV I N G S T R AT E G Y

4.15
4.16

■

Isomers: The Arrangement of Atoms in Space 147

P R O B L E M - S O LV I N G S T R AT E G Y

4.14

139

ELECTROPHILIC ADDITION REACTIONS,
STEREOCHEMISTRY, AND ELECTRON
DELOCALIZATION 145

P R O B L E M - S O LV I N G S T R AT E G Y

4.13

130

133

Conformers of Disubstituted Cyclohexanes
Fused Cyclohexane Rings 137

PART 2

121

126

Conformers of Cyclohexane 127
Conformers of Monosubstituted Cyclohexanes
P R O B L E M - S O LV I N G S T R AT E G Y

113

117

Rotation Occurs About Carbon–Carbon Single Bonds
Some Cycloalkanes Have Angle Strain 125
P R O B L E M - S O LV I N G S T R AT E G Y

3.12
3.13

101

10 3

The Nomenclature of Alkyl Halides 104
The Nomenclature of Ethers 105
The Nomenclature of Alcohols 106
The Nomenclature of Amines 109
The Structures of Alkyl Halides, Alcohols, Ethers, and Amines 112
The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines
P R O B L E M - S O LV I N G S T R AT E G Y

3.10
3.11

Increased content on
noncovalent interactions
in chemical and biological

systems.

181

■

180

PROBLEMS

INTERCONVERTING STRUCTURAL REPRESENTATIONS

181

187

• Interconverting Structural
Representations: Fischer Projections
with Multiple Stereocenters
• Interconverting Structural
Representations: Interpreting Newman
Projections


x
Introduces a new feature,
"Organizing What We Know,"
which highlights how all organic
compounds can be divided into
families and all members of a

family react in the same way.
Furthermore, each family can be
put into one of four groups and
all the families in a group react in
similar ways.

5

Alkenes: Structure, Nomenclature, and an Introduction
to Reactivity • Thermodynamics and Kinetics 190

5.1
5.2
5.3
5.4

Molecular Formulas and the Degree of Unsaturation
The Nomenclature of Alkenes 192
The Structure of Alkenes 195
Naming Alkenes Using the E,Z System 196

5.5
5.6
5.7
5.8
5.9
5.10
New tutorial gives students
practice drawing curved
arrows.

Enhanced by

• An Exercise in Drawing Curved Arrows:

5.11
5.12

Predicting Electron Movement

• An Exercise in Drawing Curved Arrows:
Interpreting Electron Movement

Alkoxymercuration was removed
since it is now rarely used
because of toxicity concerns.
Ozonolysis has been added as has
using 9-BBN for hydroboration
and MCPBA for epoxidation.

19 9

P R O B L E M - S O LV I N G S T R AT E G Y

200

How an Organic Compound Reacts Depends on its Functional Group 200
How Alkenes React • Curved Arrows Show the Flow of Electrons 201
Thermodynamics and Kinetics 205
The Rate of a Chemical Reaction 212

The Difference Between the Rate of a Reaction and the Rate Constant for a Reaction 213
A Reaction Coordinate Diagram Describes the Energy Changes that Take Place during
a Reaction 216
Catalysis 218
Catalysis by Enzymes 219
SOME IMPORTANT THINGS TO REMEMBER

TUTORIAL

Basics of Pushing Electrons

• An Exercise in Drawing Curved Arrows:

P R O B L E M - S O LV I N G S T R AT E G Y

6
6.1
6.2
6.3
6.4

Discussion of reactivity
has been reorganized and
clarified. The mechanism for
keto-enol interconversion has
been added.

250

260

The Addition of a Peroxyacid to an Alkene 260
The Addition of Ozone to an Alkene: Ozonolysis 262
264

The Addition of Hydrogen to an Alkene

266

269

The Relative Stabilities of Alkenes 269
Regioselective, Stereoselective, and Stereospecific Reactions 271
The Stereochemistry of Electrophilic Addition Reactions of Alkenes
P R O B L E M - S O LV I N G S T R AT E G Y

6.16
6.17
6.18

221

245

The Addition of Water to an Alkene 246
The Addition of an Alcohol to an Alkene 248
A Carbocation Will Rearrange if it Can Form a More Stable Carbocation
The Addition of Borane to an Alkene: Hydroboration–Oxidation 252
The Addition of a Halogen to an Alkene 256

P R O B L E M - S O LV I N G S T R AT E G Y

6.13
6.14
6.15

PROBLEMS

The Addition of a Hydrogen Halide to an Alkene 237
Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively
Charged Carbon 238
What Does the Structure of the Transition State Look Like? 240
Electrophilic Addition Reactions Are Regioselective 242

P R O B L E M - S O LV I N G S T R AT E G Y

6.12

■

The Reactions of Alkenes •
The Stereochemistry of Addition Reactions 236

P R O B L E M - S O LV I N G S T R AT E G Y

6.10
6.11

220

AN EXERCISE IN DRAWING CURVED ARROWS:
PUSHING ELECTRONS 225

P R O B L E M - S O LV I N G S T R AT E G Y

6.5
6.6
6.7
6.8
6.9

191

The Stereochemistry of Enzyme-Catalyzed Reactions 284
Enantiomers Can Be Distinguished by Biological Molecules
Reactions and Synthesis 288
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

291

272

282

■

286

290

PROBLEMS

292

7

The Reactions of Alkynes
An Introduction to Multistep Synthesis

7.1
7.2
7.3
7.4

The Nomenclature of Alkynes 301
How to Name a Compound That Has More than One Functional Group
The Physical Properties of Unsaturated Hydrocarbons 305
The Structure of Alkynes 305

299
303


xi
7.5
7.6
7.7
7.8
7.9

7.10

Alkynes Are Less Reactive than Alkenes 306
The Addition of Hydrogen Halides and the Addition of Halogens to an Alkyne
The Addition of Water to an Alkyne 311
The Addition of Borane to an Alkyne: Hydroboration–Oxidation 313
The Addition of Hydrogen to an Alkyne 314
A Hydrogen Bonded to an sp Carbon Is “Acidic” 316
P R O B L E M - S O LV I N G S T R AT E G Y

3 17

7.11

Synthesis Using Acetylide Ions

7.12

An Introduction to Multistep Synthesis 319

318

SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

8
8.1
8.2
8.3
8.4

8.5
8.6

325

342

347

Aromatic Heterocyclic Compounds 347
Antiaromaticity 349
A Molecular Orbital Description of Aromaticity and Antiaromaticity 350
More Examples that Show How Delocalized Electrons Increase Stability 351
A Molecular Orbital Description of Stability 356
How Delocalized Electrons Affect pKa Values 360
362

Delocalized Electrons Can Affect the Product of a Reaction 364
Reactions of Dienes 365
Thermodynamic versus Kinetic Control 369
The Diels–Alder Reaction Is a 1,4-Addition Reaction 374
Retrosynthetic Analysis of the Diels–Alder Reaction 380
Organizing What We Know About the Reactions of Organic Compounds
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

TUTORIAL

PART 3

9
9.1
9.2
9.3
9.4
9.5

326

Benzene Is an Aromatic Compound 343
The Two Criteria for Aromaticity 343
Applying the Criteria for Aromaticity 344

P R O B L E M - S O LV I N G S T R AT E G Y

8.16
8.17
8.18
8.19
8.20
8.21

325

PROBLEMS

Discussion of aromaticity
has been added to allow
this concept to be carried
throughout the text starting

at an earlier point.

Delocalized Electrons Explain Benzene’s Structure 331
The Bonding in Benzene 333
Resonance Contributors and the Resonance Hybrid 334
How to Draw Resonance Contributors 335
The Predicted Stabilities of Resonance Contributors 338
Delocalization Energy Is the Additional Stability Delocalized Electrons Give
to a Compound 341

P R O B L E M - S O LV I N G S T R AT E G Y

8.10
8.11
8.12
8.13
8.14
8.15

■

DESIGNING A
SYNTHESIS I

Delocalized Electrons and Their Effect on Stability,
pKa, and the Products of a Reaction 330

P R O B L E M - S O LV I N G S T R AT E G Y

8.7

8.8
8.9

308

383

■

New tutorial gives students
practice drawing resonance
contributors.

382

PROBLEMS

384

DRAWING RESONANCE CONTRIBUTORS

Enhanced by

392

• Drawing Resonance Contributors:
Moving p Electrons

SUBSTITUTION AND ELIMINATION
REACTIONS 401

The Mechanism for an SN2 Reaction 404
Factors that Affect SN2 Reactions 409
The Mechanism for an SN1 Reaction 417
Factors that Affect SN1 Reactions 420
Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides
423

• Drawing Resonance Contributors:
Predicting Contributor Structure
• Drawing Resonance Contributors:
Substituted Benzene Compounds

Rewritten to incorporate the
new finding that secondary
alkyl halides do not undergo
SN1 reactions.

Substitution Reactions of Alkyl Halides 402

P R O B L E M - S O LV I N G S T R AT E G Y

381

421


xii
9.6

Competition Between SN2 and SN1 Reactions
P R O B L E M - S O LV I N G S T R AT E G Y

9.7
9.8

The Role of the Solvent in SN1 and SN2 Reactions 428
Intermolecular versus Intramolecular Reactions 433
P R O B L E M - S O LV I N G S T R AT E G Y

9.9
Rewritten to incorporate the
new finding that secondary
alkyl halides do not undergo
E1 reactions.

SUMMARY OF REACTIONS

439

■

436

438

PROBLEMS

439

Reactions of Alkyl Halides •
10 Elimination
Competition Between Substitution and Elimination
The E2 Reaction 445
An E2 Reaction Is Regioselective
The E1 Reaction 452
P R O B L E M - S O LV I N G S T R AT E G Y

10.4
10.5
10.6

444

446
455

Benzylic and Allylic Halides 455
Competition Between E2 and E1 Reactions 456
E2 and E1 Reactions Are Stereoselective 457
P R O B L E M - S O LV I N G S T R AT E G Y

10.7
10.8
10.9
10.10

460

Elimination from Substituted Cyclohexanes 462

A Kinetic Isotope Effect Can Help Determine a Mechanism
Competition Between Substitution and Elimination 466
Substitution and Elimination Reactions in Synthesis 471

465

10.11 Approaching the Problem 474
SOME IMPORTANT THINGS TO REMEMBER 476
SUMMARY OF REACTIONS 477 ■ PROBLEMS

D E S IGNING A
S Y N THES IS II

477

of Alcohols, Ethers, Epoxides,
11 Reactions
Amines, and Thiols 481
11.1
11.2
11.3
11.4

Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides
Other Methods Used to Convert Alcohols into Alkyl Halides 487
Converting an Alcohol Into a Sulfonate Ester 488
Elimination Reactions of Alcohols: Dehydration 492
P R O B L E M - S O LV I N G S T R AT E G Y

Discussion of palladiumcatalyzed coupling reactions

and their mechanisms has
been expanded. Solved
problems and problemsolving strategies were added
to facilitate understanding.

435

Methylating Agents Used by Chemists versus Those Used by Cells
SOME IMPORTANT THINGS TO REMEMBER

10.1
10.2
10.3

Hypochlorous acid
introduced as an alternative
to toxic-chromuiumcontaining compounds.

424

426

11.5
11.6
11.7
11.8
11.9
11.10
11.11
11.12

495

Oxidation of Alcohols 499
Nucleophilic Substitution Reactions of Ethers 502
Nucleophilic Substitution Reactions of Epoxides 505
Arene Oxides 512
Amines Do Not Undergo Substitution or Elimination Reactions 516
Quaternary Ammonium Hydroxides Undergo Elimination Reactions 519
Thiols, Sulfides, and Sulfonium Salts 521
Organizing What We Know About the Reactions of Organic Compounds 524
SOME IMPORTANT THINGS TO REMEMBER 525
SUMMARY OF REACTIONS 526 ■ PROBLEMS 528

12 Organometallic Compounds
12.1
12.2
12.3
12.4

535

Organolithium and Organomagnesium Compounds
Transmetallation 538
Organocuprates 538
Palladium-Catalyzed Coupling Reactions 541

536

P R O B L E M - S O LV I N G S T R AT E G Y 5 4 6

12.5

482

Alkene Metathesis 548
SOME IMPORTANT THINGS TO REMEMBER 551
SUMMARY OF REACTIONS 552 ■ PROBLEMS

553


xiii

13 Radicals • Reactions of Alkanes
13.1
13.2
13.3
13.4
13.5

Alkanes Are Unreactive Compounds 556
The Chlorination and Bromination of Alkanes 558
Radical Stability Depends On the Number of Alkyl Groups Attached to the Carbon with
the Unpaired Electron 560
The Distribution of Products Depends On Probability and Reactivity 561
The Reactivity–Selectivity Principle 564
P R O B L E M - S O LV I N G S T R AT E G Y

13.6

13.7
13.8
13.9

Now includes the mechanism
for the oxidation of fats and
oils by oxygen.

556

566

Formation of Explosive Peroxides 567
The Addition of Radicals to an Alkene 568
The Stereochemistry of Radical Substitution and Radical Addition Reactions
Radical Substitution of Benzylic and Allylic Hydrogens 573

13.10 More Practice With Multistep Synthesis 576
13.11 Radical Reactions Occur In Biological Systems 578
13.12 Radicals and Stratospheric Ozone 583
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

TUTORIAL

PART 4

14
14.1
14.2

14.3

585

585

PROBLEMS

586

590

Mass Spectrometry 597
The Mass Spectrum • Fragmentation 598
Using the m/z Value of the Molecular Ion to Calculate the Molecular Formula 600
6 01

Isotopes in Mass Spectrometry 602
High-Resolution Mass Spectrometry Can Reveal Molecular Formulas 603
The Fragmentation Patterns of Functional Groups 604
Other Ionization Methods 611
Gas Chromatography–Mass Spectrometry 611
Spectroscopy and the Electromagnetic Spectrum 611
Infrared Spectroscopy 614
Characteristic Infrared Absorption Bands 616
The Intensity of Absorption Bands 617
The Position of Absorption Bands 618
The Position and Shape of an Absorption Band Is Affected By Electron Delocalization,
Electron Donation and Withdrawal, and Hydrogen Bonding 619
622

The Absence of Absorption Bands 626
Some Vibrations Are Infrared Inactive 627
How to Interpret an Infrared Spectrum 629
Ultraviolet and Visible Spectroscopy 631
The Beer–Lambert Law 633
The Effect of Conjugation on lmax 634
The Visible Spectrum and Color 635
Some Uses of UV/ VIS Spectroscopy 637
639

■

PROBLEMS

• Curved Arrows in Radical Systems:
Interpreting Electron Movement

• Curved Arrows in Radical Systems:
Resonance

Mass Spectrometry, Infrared Spectroscopy, and Ultraviolet/
Visible Spectroscopy 595

SOME IMPORTANT THINGS TO REMEMBER

Enhanced by

• Curved Arrows in Radical Systems:
Predicting Electron Movement

IDENTIFICATION OF ORGANIC
COMPOUNDS 594

P R O B L E M - S O LV I N G S T R AT E G Y

14.15
14.16
14.17
14.18
14.19
14.20
14.21
14.22

DESIGNING A
SYNTHESIS III

DRAWING CURVED ARROWS IN RADICAL SYSTEMS

P R O B L E M - S O LV I N G S T R AT E G Y

14.4
14.5
14.6
14.7
14.8
14.9
14.10
14.11

14.12
14.13
14.14

■

571

640

Added the “rule of 13”.


xiv
There are now 50 additional
spectroscopy problems in the
Study Guide and Solutions
Manual.

15 NMR Spectroscopy
15.1
15.2
15.3
15.4

649

An Introduction to NMR Spectroscopy 649
Fourier Transform NMR 652
Shielding Causes Different Hydrogens to Show Signals at Different Frequencies

The Number of Signals in an 1H NMR Spectrum 654
P R O B L E M - S O LV I N G S T R AT E G Y

15.5
15.6
15.7
15.8
15.9
15.10
15.11
15.12
15.13

655

The Chemical Shift Tells How Far the Signal Is from the Reference Signal 656
The Relative Positions of 1H NMR Signals 658
The Characteristic Values of Chemical Shifts 659
Diamagnetic Anisotropy 661
The Integration of NMR Signals Reveals the Relative Number of Protons Causing
Each Signal 663
The Splitting of Signals Is Described by the N + 1 Rule 665
What Causes Splitting? 668
More Examples of 1H NMR Spectra 670
Coupling Constants Identify Coupled Protons 675
P R O B L E M - S O LV I N G S T R AT E G Y

15.14
15.15
15.16

15.17
15.18
15.19
15.20

653

677

Splitting Diagrams Explain the Multiplicity of a Signal 679
Diastereotopic Hydrogens are Not Chemically Equivalent 681
The Time Dependence of NMR Spectroscopy 683
Protons Bonded To Oxygen and Nitrogen 684
The Use of Deuterium in 1H NMR Spectroscopy 686
The Resolution of 1H NMR Spectra 687
13
C NMR Spectroscopy 689
P R O B L E M - S O LV I N G S T R AT E G Y 6 9 2

Acid anhydrides are carboxylic
acid derivatives but they
don’t look like carboxylic
acids. Anhydrides, therefore,
were moved to the end of
the chapter to allow students
to focus on the similarities
between carboxylic acids, acyl
chlorides, esters, and amides.
Acid anhydrides are now
better placed since they come

just before phosphoric acid
anhydrides.

15.21
15.22
15.23
15.24

Dept 13C NMR Spectra 694
Two-Dimensional NMR Spectroscopy 695
NMR Used in Medicine Is Called Magnetic Resonance Imaging
X-Ray Crystallography 699
SOME IMPORTANT THINGS TO REMEMBER

PART 5

701

CARBONYL COMPOUNDS

■

698

PROBLEMS

701

719

of Carboxylic Acids and
16 Reactions
Carboxylic Derivatives 720
16.1
16.2
16.3
16.4
16.5

The Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives 722
The Structures of Carboxylic Acids and Carboxylic Acid Derivatives 726
The Physical Properties of Carbonyl Compounds 728
Fatty Acids Are Long-Chain Carboxylic Acids 729
How Carboxylic Acids and Carboxylic Acid Derivatives React 731
P R O B L E M - S O LV I N G S T R AT E G Y

16.6
16.7
16.8
16.9
16.10
16.11
16.12
16.13
16.14

P R O B L E M - S O LV I N G S T R AT E G Y

16.15
16.16

16.17
16.18
16.19

733

The Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives 733
The General Mechanism for Nucleophilic Addition–Elimination Reactions 736
The Reactions of Acyl Chlorides 737
The Reactions of Esters 739
Acid-Catalyzed Ester Hydrolysis and Transesterification 741
Hydroxide-Ion-Promoted Ester Hydrolysis 746
How the Mechanism for Nucleophilic Addition–Elimination Was Confirmed 749
Fats and Oils Are Triglycerides 751
Reactions of Carboxylic Acids 755
756

Reactions of Amides 757
Acid–Catalyzed Amide Hydrolysis and Alcoholysis 760
Hydroxide-Ion Promoted Hydrolysis of Amides 762
The Hydrolysis of an Imide: A Way to Synthesize Primary Amines
Nitriles 764

763


xv
16.20
16.21
16.22

16.23

Acid Anhydrides 766
Dicarboxylic Acids 769
How Chemists Activate Carboxylic Acids 771
How Cells Activate Carboxylic Acids 773
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

777

■

776

PROBLEMS

Enhanced discussion of
reduction reactions. Added a
discussion of chemoselective
reactions.

780

of Aldehydes and Ketones •
17 Reactions
More Reactions of Carboxylic Acid Derivatives •

Reactions of A,B-Unsaturated Carbonyl Compounds 789

17.1
17.2
17.3
17.4

The Nomenclature of Aldehydes and Ketones 790
The Relative Reactivities of Carbonyl Compounds 793
How Aldehydes and Ketones React 795
The Reactions of Carbonyl Compounds with Gringard Reagents
P R O B L E M - S O LV I N G S T R AT E G Y

17.5
17.6
17.7
17.8
17.9
17.10
17.11
17.12

The Reactions of Carbonyl Compounds with Acetylide Ions 801
The Reactions of Aldehydes and Ketones with Cyanide Ion 801
The Reactions of Carbonyl Compounds with Hydride Ion 803
More About Reduction Reactions 808
Chemoselective Reactions 810
The Reactions of Aldehydes and Ketones with Amines 811
The Reactions of Aldehydes and Ketones with Water 817
The Reactions of Aldehydes and Ketones with Alcohols 820
P R O B L E M - S O LV I N G S T R AT E G Y

17.13
17.14
17.15
17.16

796

800

822

Protecting Groups 823
The Addition of Sulfur Nucleophiles 825
The Reactions of Aldehydes and Ketones with a Peroxyacid
The Wittig Reaction Forms an Alkene 827

826

DESIGNING A
17.17 Disconnections, Synthons, and Synthetic Equivalents 829
17.18 Nucleophilic Addition to a, b-Unsaturated Aldehydes and Ketones 832 S Y N T H E S I S I V
17.19 Nucleophilic Addition to a, b-Unsaturated Carboxylic Acid Derivatives 837

SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

839

■

PROBLEMS

843

18 Reactions at the A-Carbon of Carbonyl Compounds
18.1

The Acidity of an a-Hydrogen

18.6
18.7

18.12
18.13
18.14
18.15
18.16

856

Keto–Enol Tautomers 857
Keto–Enol Interconversion 858
Halogenation of the a-Carbon of Aldehydes and Ketones 859
Halogenation of the a-Carbon of Carboxylic Acids: The Hell–Volhard–Zelinski
Reaction 861
Forming an Enolate Ion 862
Alkylating the a-Carbon of Carbonyl Compounds 863
P R O B L E M - S O LV I N G S T R AT E G Y

18.8

18.9
18.10
18.11

853

854

P R O B L E M - S O LV I N G S T R AT E G Y

18.2
18.3
18.4
18.5

Streamlined the discussion of
both the reactions of enolate
ions and crossed aldol
additions and condensations.
Added new examples of
retrosynthetic analysis.

838

865

Alkylating and Acylating the a-Carbon Using an Enamine Intermediate 866
Alkylating the b-Carbon: The Michael Reaction 867
An Aldol Addition Forms b-Hydroxyaldehydes or b-Hydroxyketones 869
The Dehydration of Aldol Addition Products Forms a,b-Unsaturated Aldehydes

and Ketones 871
A Crossed Aldol Addition 872
A Claisen Condensation Forms a b-Keto Ester 875
Other Crossed Condensations 878
Intramolecular Condensations and Intramolecular Aldol Additions 879
The Robinson Annulation 881
P R O B L E M - S O LV I N G S T R AT E G Y

882


xvi
18.17 Carboxylic Acids with a Carbonyl Group at the 3-Position Can Be Decarboxylated 883
18.18 The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid 885
18.19 The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone 887
18.20 Making New Carbon–Carbon Bonds 888
18.21 Reactions at the a-Carbon in Living Systems 890
18.22 Organizing What We Know About the Reactions of
Organic Compounds

894

SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

PART 6

D E S IGNING A
S Y N THES IS V

895

■

894

PROBLEMS

898

AROMATIC COMPOUNDS

906

19 Reactions of Benzene and Substituted Benzenes
19.1
19.2
19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11
19.12
19.13
19.14
19.15

19.16

907

The Nomenclature of Monosubstituted Benzenes 909
How Benzene Reacts 910
The General Mechanism for Electrophilic Aromatic Substitution Reactions 912
The Halogenation of Benzene 913
The Nitration of Benzene 916
The Sulfonation of Benzene 917
The Friedel–Crafts Acylation of Benzene 918
The Friedel–Crafts Alkylation of Benzene 920
The Alkylation of Benzene by Acylation–Reduction 922
Using Coupling Reactions to Alkylate Benzene 924
It Is Important to Have More than One Way to Carry Out a Reaction 924
How Some Substituents on a Benzene Ring Can Be Chemically Changed 925
The Nomenclature of Disubstituted and Polysubstituted Benzenes 927
The Effect of Substituents on Reactivity 929
The Effect of Substituents on Orientation 935
The Effect of Substituents on pKa 939
P R O B L E M - S O LV I N G S T R AT E G Y

940

19.17 The Ortho–Para Ratio 941
19.18 Additional Considerations Regarding Substituent Effects 941
19.19
19.20
19.21
19.22

19.23
19.24
New tutorial on synthesis
and retrosynthetic analysis
including two examples of a
multistep synthesis from the
literature.

Enhanced by
• Synthesis and Retrosynthetic Analysis:
Functional Groups
• Synthesis and Retrosynthetic Analysis:
Carbon Chain
• Synthesis and Retrosynthetic Analysis:
Retrosynthesis of 2-Pentanone Using
Reactions of Carbonyl Compounds

D E S IGNING A
The Synthesis of Monosubstituted and Disubstituted Benzenes 943
S Y N THES IS V I
The Synthesis of Trisubstituted Benzenes 945
The Synthesis of Substituted Benzenes Using Arenediazonium Salts 947
The Arenediazonium Ion as an Electrophile 950
The Mechanism for the Reaction of Amines with Nitrous Acid 953
Nucleophilic Aromatic Substitution: An Addition–Elimination Reaction 955

19.25 The Synthesis of Cyclic Compounds 957
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS

TUTORIAL

960

■

D E S IGNING A
S Y N TH ES IS V II

959

PROBLEMS

962

SYNTHESIS AND RETROSYNTHETIC ANALYSIS

About Amines •
20 More
Reactions of Heterocyclic Compounds
20.1
20.2
20.3
20.4
20.5
20.6

More About Amine Nomenclature 990
More About the Acid–Base Properties of Amines 991
Amines React as Bases and as Nucleophiles 993

The Synthesis of Amines 994
Aromatic Five-Membered-Ring Heterocycles 994
Aromatic Six-Membered-Ring Heterocycles 999
P R O B L E M - S O LV I N G S T R AT E G Y 9 9 9

989

974


xvii
20.7
20.8

Some Amine Heterocycles Have Important Roles in Nature 1005
Organizing What We Know About the Reactions of Organic Compounds
SOME IMPORTANT THINGS TO REMEMBER
SUMMARY OF REACTIONS 1011

PART 7

1010

PROBLEMS

■

1012

BIOORGANIC COMPOUNDS

1016

21 The Organic Chemistry of Carbohydrates
21.1
21.2
21.3
21.4
21.5
21.6
21.7
21.8
21.9
21.10
21.11
21.12
21.13
21.14
21.15
21.16
21.17
21.18
21.19

SUMMARY OF REACTIONS

1049

■

The reactions of aromatic
heterocycles now follows the
reactions of other aromatic
compounds.

1017

The Classification of Carbohydrates 1018
The D and L Notation 1019
The Configurations of the Aldoses 1020
The Configurations of the Ketoses 1022
The Reactions of Monosaccharides in Basic Solutions 1023
The Oxidation–Reduction Reactions of Monosaccharides 1024
Lengthening the Chain: The Kiliani–Fischer Synthesis 1026
Shortening the Chain: The Wohl Degradation 1026
The Stereochemistry of Glucose: The Fischer Proof 1027
Monosaccharides Form Cyclic Hemiacetals 1030
Glucose Is the Most Stable Aldohexose 1032
Formation of Glycosides 1034
The Anomeric Effect 1036
Reducing and Nonreducing Sugars 1036
Disaccharides 1037
Polysaccharides 1040
Some Naturally Occurring Compounds Derived from Carbohydrates
Carbohydrates on Cell Surfaces 1045
Artificial Sweeteners 1047
SOME IMPORTANT THINGS TO REMEMBER

1010

1043

1048

PROBLEMS

1050

A new discussion on diseases
caused by protein misfolding.

Organic Chemistry of Amino Acids, Peptides,
22 The
and Proteins 1053
22.1
22.2
22.3
22.4
22.5
22.6
22.7
22.8
22.9
22.10
22.11
22.12
22.13

The Nomenclature of Amino Acids 1054
The Configuration of Amino Acids 1058

The Acid–Base Properties of Amino Acids 1060
The Isoelectric Point 1062
Separating Amino Acids 1064
The Synthesis of Amino Acids 1068
The Resolution of Racemic Mixtures of Amino Acids 1070
Peptide Bonds and Disulfide Bonds 1071
Some Interesting Peptides 1075
The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation 1076
Automated Peptide Synthesis 1079
An Introduction to Protein Structure 1081
How to Determine the Primary Structure of a Polypeptide or Protein 1082
P R O B L E M - S O LV I N G S T R AT E G Y

22.14
22.15
22.16
22.17

10 8 4

Secondary Structure 1088
Tertiary Structure 1091
Quaternary Structure 1093
Protein Denaturation 1094
SOME IMPORTANT THINGS TO REMEMBER

1094

■

PROBLEMS

1095


xviii
Revised to emphasize the
connection between the organic
reactions that occur in test tubes
with the organic reactions that
occur in cells.

Added the mechanism for the
conversion of succinate to
fumarate.

New coverage of organic
reactions that occur in
gluconeogenesis and
discussions of thermodynamic
control and the regulation of
metabolic pathways. Revised
to emphasize the connection
between the organic reactions
that occur in test tubes with
those that occur in cells.
New section on terpene
biosynthesis.

in Organic Reactions and in Enzymatic

23 Catalysis
Reactions 1099
23.1
23.2
23.3
23.4
23.5
23.6
23.7
23.8
23.9

Catalysis in Organic Reactions 1101
Acid Catalysis 1101
Base Catalysis 1105
Nucleophilic Catalysis 1106
Metal-Ion Catalysis 1107
Intramolecular Reactions 1109
Intramolecular Catalysis 1111
Catalysis in Biological Reactions 1113
The Mechanisms for Two Enzyme-Catalyzed Reactions that are Reminiscent of Acid-Catalyzed
Amide Hydrolysis 1115
23.10 The Mechanism for an Enzyme-Catalyzed Reaction that Involves Two Sequential
SN2 Reactions 1121
23.11 The Mechanism for an Enzyme-Catalyzed Reaction that Is Reminiscent of the Base-Catalyzed
Enediol Rearrangement 1125
23.12 The Mechanism for an Enzyme-Catalyzed Reaction that Is Reminiscent of an Aldol
Addition 1126
SOME IMPORTANT THINGS TO REMEMBER

1128

■

PROBLEMS

1129

Organic Chemistry of the Coenzymes, Compounds
24 The
Derived from Vitamins 1132
24.1
24.2
24.3
24.4
24.5
24.6
24.7
24.8

Niacin: The Vitamin Needed for Many Redox Reactions 1134
Riboflavin: Another Vitamin Used in Redox Reactions 1140
Vitamin B1: The Vitamin Needed for Acyl Group Transfer 1144
Vitamin H: The Vitamin Needed for Carboxylation of an a-Carbon 1149
Vitamin B6: The Vitamin Needed for Amino Acid Transformations 1151
Vitamin B12: The Vitamin Needed for Certain Isomerizations 1156
Folic Acid: The Vitamin Needed for One-Carbon Transfer 1159
Vitamin K: The Vitamin Needed for Carboxylation of Glutamate 1164
SOME IMPORTANT THINGS TO REMEMBER

1166

■

PROBLEMS

1167

Organic Chemistry of the Metabolic Pathways •
25 The
Terpene Biosynthesis 1170
25.1
25.2
25.3
25.4
25.5
25.6
25.7

ATP Is Used for Phosphoryl Transfer Reactions 1171
ATP Activates a Compound by Giving it a Good Leaving Group 1172
Why ATP Is Kinetically Stable in a Cell 1174
The “High-Energy” Character of Phosphoanhydride Bonds 1174
The Four Stages of Catabolism 1176
The Catabolism of Fats 1177
The Catabolism of Carbohydrates 1180
P R O B L E M - S O LV I N G S T R AT E G Y

25.8
25.9

25.10
25.11
25.12
25.13
25.14
25.15
25.16
25.17

11 8 3

The Fate of Pyruvate 1184
The Catabolism of Proteins 1185
The Citric Acid Cycle 1187
Oxidative Phosphorylation 1191
Anabolism 1192
Gluconeogenesis 1192
Regulating Metabolic Pathways 1194
Amino Acid Biosynthesis 1195
Terpenes Contain Carbon Atoms in Multiples of Five
How Terpenes are Biosynthesized 1197

1195

P R O B L E M - S O LV I N G S T R AT E G Y 1 2 0 0

25.18 How Nature Synthesizes Cholesterol 1202
SOME IMPORTANT THINGS TO REMEMBER

1203

■

PROBLEMS

1204


xix

26 The Chemistry of the Nucleic Acids
26.1
26.2
26.3
26.4
26.5
26.6
26.7
26.8
26.9
26.10
26.11
26.12
26.13
26.14

Nucleosides and Nucleotides 1207
Other Important Nucleotides 1211
Nucleic Acids Are Composed of Nucleotide Subunits 1211
Why DNA Does Not Have A 2¿ –OH Group 1215

The Biosynthesis of DNA Is Called Replication 1215
DNA and Heredity 1216
The Biosynthesis of RNA Is Called Transcription 1217
The RNAs Used for Protein Biosynthesis 1219
The Biosynthesis of Proteins Is Called Translation 1221
Why DNA Contains Thymine Instead of Uracil 1225
Antiviral Drugs 1227
How the Base Sequence of DNA Is Determined 1228
The Polymerase Chain Reaction (PCR) 1230
Genetic Engineering 1231
SOME IMPORTANT THINGS TO REMEMBER

PART 8

PROBLEMS

1233

1235

There Are Two Major Classes of Synthetic Polymers 1237
Chain-Growth Polymers 1238
Stereochemistry of Polymerization • Ziegler–Natta Catalysts 1249
Polymerization of Dienes • The Manufacture of Rubber 1250
Copolymers 1252
Step-Growth Polymers 1253
Classes of Step-Growth Polymers 1254
Physical Properties of Polymers 1258
Recycling Polymers 1261
Biodegradable Polymers 1261

28 Pericyclic Reactions

1262

■

There Are Three Kinds of Pericyclic Reactions 1267
Molecular Orbitals and Orbital Symmetry 1269
Electrocyclic Reactions 1272
Cycloaddition Reactions 1278
Sigmatropic Rearrangements 1281
Pericyclic Reactions in Biological Systems 1286
Summary of the Selection Rules for Pericyclic Reactions

APPENDICES

PROBLEMS

1263

1266

SOME IMPORTANT THINGS TO REMEMBER

I
II
III
IV

■

1236

SOME IMPORTANT THINGS TO REMEMBER

28.1
28.2
28.3
28.4
28.5
28.6
28.7

1232

SPECIAL TOPICS IN ORGANIC CHEMISTRY

27 Synthetic Polymers
27.1
27.2
27.3
27.4
27.5
27.6
27.7
27.8
27.9
27.10

New section on antiviral
drugs and the chemical
reasons for their antiviral
activity. Recently published
information about the
function of segments of DNA
that were thought to contain
no information.

1207

1289

1289
■

PROBLEMS 1290

A-1

pKa Values A-1
Kinetics A-3
Summary of Methods Used to Synthesize a Particular Functional Group
Summary of Methods Employed to Form Carbon-Carbon Bonds A-11

Answers to Selected Problems
Glossary G-1
Photo Credits P-1
Index I-1

A-8

Available in the Study Area in MasteringChemistry


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Preface
TO THE INSTRUCTOR
The guiding principle behind this book is to present organic chemistry as an exciting and
vitally important science. 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, and it emphasizes 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. I also want them to see that organic chemistry is a fascinating discipline that is integral to biology as well as to their daily lives.

NEW TO THIS EDITION
In planning the changes to this edition, our focus was on two questions:
1. What is the best way to help students learn and study organic chemistry?
2. How can we prepare students for the new MCAT while still meeting the needs of students majoring in chemistry and chemical engineering?

HELPING STUDENTS LEARN AND STUDY ORGANIC CHEMISTRY.
As each student generation evolves and becomes increasingly diverse, we are challenged
as teachers to support the unique ways students acquire knowledge, study, practice, and
master a subject. In order to support contemporary students who are often visual learners, with preferences for interactivity and small ‘bites’ of information, I have revisited
this edition with the goal of helping students organize the vast amount of information
that comprises organic chemistry. Through significant changes to the organization,
a new and modern design, and new pedagological tools, the Seventh Edition helps
students focus on fundamental concepts and skills, make connections from one topic

to the next, and review the material visually through the guidance of an annotated
art program and new tutorial spreads. Details about the many changes to this text are
outlined below:
A New Feature, “Organizing What We Know About Organic Chemistry”, 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 (other than an acid-base reaction) of an organic
compound, they are told that all organic compounds can be divided into families and all
members of a family react in the same way. And 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: compounds with an electronegative
group attached to an sp3 carbon; Group III: carbonyl compounds; and Group IV: aromatic
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
381, 524, 894, and 1010) that they can compare with the summary of the characteristic
reactions of the groups studied previously.
New Tutorials spreads following relevant chapters give students extra practice so they
can better master important topics: acid-base chemistry, interconverting chemical structures, building molecular models, drawing curved arrows, drawing contributing resonance structures, drawing curved arrows in radical systems, synthesis and retrosynthetic
xxi


xxii

Preface

analysis. MasteringChemistry includes additional online tutorials on each of these topics
that can be assigned as homework or for test preparation.
New Modern Design and Streamlined narrative allow students to navigate through

content and study more efficiently with the text. With three fewer chapters than the
previous edition, an updated organization and presentation allows for a more efficient
path through the content and ultimately the course.
An Enhanced Art program with new annotations provides key information to students so that they can review important parts of the chapter with the support of the visual
program. New margin notes throughout the book succinctly repeat key points and help
students review important material at a glance.
Cutting Edge Content—The chapters on nucleophilic substitution and elimination
have been rewritten to incorporate the new finding that secondary alkyl halides do not
undergo SN1/E1 reactions. You will be surprised at how much easier the addition of this
one new fact makes this topic. I feel badly that students have been tortured for so long by
misinformation!
The discussion of palladium-catalyzed coupling reactions and their mechanisms has
been expanded while Solved problems and problem-solving strategies were added to
facilitate understanding.
Many of the sections on bioorganic chemistry were rewritten to emphasize the connection between the organic reactions that occur in the laboratory and those that occur
in cells.
Many new interest boxes have been added to intrigue students and reinforce their
appreciation for how organic chemistry relates to biological systems. Some examples:
Why Did Nature Choose Phosphates?, What Drug Enforcement Dogs are Really Detecting, Synthetic Alkynes are Used to Treat Parkinson’s Disease, Influenza Pandemics.

ORGANIZATIONAL CHANGES
Stereoisomers are now covered (Chapter 4) before the students see any reactions. Therefore, the Reactions of Alkenes (Chapter 6) now covers both the reactions of alkenes and
the stereochemistry of those reactions. This reorganization also allows the compounds in
Group I (alkenes, alkynes, and dienes) to be covered sequentially.
The concepts of electronic effects and aromaticity have been moved up (Chapter 8) to
allow them to be carried though the text starting at an earlier point.
The reactions of benzene and substituted benzenes now come after carbonyl chemistry.
This allows the two chapters that discuss compounds in Group IV (aromatic compounds)
to be adjacent. Coverage of oxidation-reduction reactions, lipids, and drug discovery and
design have been integrated into early chapters where appropriate.

PROBLEM SOLVING SUPPORT
Fifty new spectroscopy problems—in addition to the many spectroscopy problems
in the text—have been added to the Study Guide/Solutions Manual.The spectroscopy
chapters (Chapters 14 and 15) are written so they can be covered at any time during the
course, For those who prefer to teach spectroscopy at the beginning of the course—or
in a separate laboratory course—there is a table of functional groups at the beginning
of Chapter 14.
Because many students enjoy the challenge of designing multistep syntheses and find
them to be a good test of their understanding of reactivity, many new examples of retrosynthetic analysis have been added. There are also new solved problems and problemsolving strategies on multistep synthesis.
This edition has more than 200 new problems, both in-chapter and end-of-chapter.
They include new solved problems, new problem-solving strategies, and new problems
incorporating information from more than one chapter. I keep a list of questions my students have when they come to office hours. Many of the new problems were created as a
result of these questions.