Organic chemistry structure and function, 5th edition

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Tmultimedia
he website found at www.whfreeman.com/vollhardtschore5e is a
learning tool that focuses on molecular visualizations.
“Animations” and “Animated Mechanisms” are two
features of this interactive website that are integrated
seamlessly with the textbook using media icons and
descriptive text. “Animations” allow students to view
motion, three dimensions, atomic and molecular
interactions, and chemical reactions at the atomic
level. Topics focus on orbitals and hybridization.
“Animated Mechanisms” allow students to view
molecular interactions visually as structural formulas and in a ball-and-stick format. Topics include
chemical reactivity and structures and bonding. The
following is a list of selected “Animations” and
“Animated Mechanisms” found in this textbook.

Molecular Visualizations, Text Reference
Stereospecific bromination
of 2-butenes
p. 512 (Ch 12)
Hydroboration–oxidation
p. 521 (Ch 12)
p. 27 (Ch 1)
Oxacyclopropanation
p. 525 (Ch 12)
p. 34 (Ch 1)
Ozonolysis
p. 529 (Ch 12)

p. 34 (Ch 1)
Radical hydrobromination of 1-butene p. 532 (Ch 12)
Radical allylic halogenation
p. 606 (Ch 14)
p. 35 (Ch 1)
Addition of HBr to 1,3-butadiene
p. 614 (Ch 14)
p. 35 (Ch 1)
Diels-Alder cycloaddition (endo rule) p. 630 (Ch 14)
Electrophilic aromatic
p. 37 (Ch 1)
sulfonation of benzene
p. 698 (Ch 15)
p. 105 (Ch 3)
Electrophilic aromatic substitution of
benzenamine (ortho vs meta vs para) p. 729 (Ch 16)
p. 141 (Ch 4)
Electrophilic aromatic substitution of
p. 143 (Ch 4)
benzoic acid (ortho vs meta vs para) p. 732 (Ch 16)
pp. 225, 226, 228,
Acetal formation
p. 781 (Ch 17)
236 (Ch 6)
The Wittig reaction
p. 794 (Ch 17)
Nucleophilic substitution (SN1)
pp. 825, 826 (Ch 18)
of (CH3)3CBr with HOH
pp. 253, 254 (Fig. 7-2), Aldol condensation–dehydration

Robinson annulation
p. 840 (Ch 18)
255 (Ch 7)
Esterification
p. 878 (Ch 19)
Elimination (E2) reaction of
Amide hydrolysis
p. 929 (Ch 20)
2-chloro-2-methylpropane
p. 266 (Ch 7)
Hofmann rearrangement
p. 934 (Ch 20)
Reduction of pentanal with
Reductive amination
p. 973 (Ch 21)
sodium borohydride
p. 297 (Ch 8)
The Mannich reaction
p. 977 (Ch 21)
Reduction of cyclobutanone
Benzylic nucleophilic substitution
pp.1004,1005(Ch 22)
with lithium aluminum hydride
p. 300 (Ch 8)
Nucleophilic aromatic substitution
p. 1015 (Ch 22)
Formation of Grignard reagent
Nucleophilic aromatic
from 1-bromobutane
p. 304 (Ch 8)

substitution via benzynes
p. 1019 (Ch 22)
Reaction of Grignard reagent with
The Claisen condensation
p. 1062 (Ch 23)
acetaldehyde to give 2-hexanol p. 307 (Ch 8)
Alcohol dehydration
p. 336 (Ch 9)
Cyclic hemiacetal formation by glucose p. 1102 (Ch 24)
Carbocation rearrangement
p. 337 (Ch 9)
Methyl glycoside formation
p. 1114 (Ch 24)
Electrophilic addition of HCl
The Strecker synthesis
p. 1200 (Ch 26)
to propene
p. 506 (Ch 12)
Merrifield synthesis of peptides
p. 1219 (Ch 26)

Fig. 1-5, 1s orbital
Fig. 1-7, px orbital;
py orbital; pz orbital
Fig. 1-16, sp hybrids
Fig. 1-17, sp2 hybrids
Fig. 1-18, sp3 hybrids and
methane orbitals
Fig. 1-19, ethane orbitals
Fig. 1-21, ethene and

ethyne orbitals
Chlorination of methane
Fig. 4-9, cyclohexane
potential energy diagram
Fig. 4-11, cyclohexane ring flip
Nucleophilic substitution (SN2)

p. 25 (Ch 1)


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Organic Chemistry

The
, Fifth Edition eBook is a complete
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All of the student media that accompany Organic Chemistry were developed specifically for the book. There is no extraneous material that does not directly support and
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Quick, intuitive navigation to any section or subsection, as well as
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Integration of all student website animated tutorials and activities.

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In-text self quiz questions.

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In-text links to all glossary entries.

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Interactive chapter summary exercises.

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they will see the instructor’s version.

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About the Authors
K. Peter C. Vollhardt

was born in Madrid, raised in Buenos Aires and Munich,
studied at the University of Munich, got his Ph.D. with Professor Peter Garratt at the
University College, London, and was a postdoctoral fellow with Professor Bob
Bergman (then) at the California Institute of Technology. He moved to Berkeley in
1974 when he began his efforts toward the development of organocobalt reagents
in organic synthesis, the preparation of theoretically interesting hydrocarbons, the
assembly of novel transition metal arrays with potential in catalysis, and the discovery of a parking space. Among other pleasant experiences, he was a Studienstiftler,
Adolf Windaus medalist, Humboldt Senior Scientist, ACS Organometallic Awardee,
Otto Bayer Prize Awardee, A. C. Cope Scholar, Japan Society
for the Promotion of Science Prize Holder, and recipient of

the Medal of the University Aix-Marseille and an Honorary
Doctorate from The University of Rome Tor Vergata. He is
the current Chief Editor of Synlett. Among his more than 290
publications, he treasures especially this textbook in organic
chemistry, translated into ten languages. Peter is married to
Marie-José Sat, a French artist, and they have two children,
Paloma (b. 1994) and Julien (b. 1997), whose picture you can
admire on p. 168.

Neil E. Schore was born in Newark, New Jersey, in 1948.
His education took him through the public schools of the
Bronx, New York, and Ridgefield, New Jersey, after which he
completed a B.A. with honors in chemistry at the University
of Pennsylvania in 1969. Moving back to New York, he worked
with Professor Nicholas Turro at Columbia University, studying photochemical and photophysical processes of organic
compounds for his Ph.D. thesis. He first met Peter Vollhardt
when he and Peter were doing postdoctoral work in Professor Robert Bergman’s laboratory at Cal Tech in the 1970s.
Since joining the U. C. Davis faculty in 1976, he has taught
organic chemistry to more than 10,000 nonchemistry majors,
winning three teaching awards, and has published over 80 papers in various areas related
to organic synthesis. Neil is married to Carrie Erickson, a microbiologist at the U. C. Davis
School of Veterinary Medicine. They have two children, Michael (b. 1981) and Stefanie
(b. 1983), both of whom carried out experiments for this book.


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ORGANIC CHEMISTRY

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O RGANIC C HEMISTRY
Structure and Function

FIFTH EDITION

K. PETER C. VOLLHARDT

University of California at Berkeley

NEIL E. SCHORE

University of California at Davis

W. H. FREEMAN AND COMPANY
New York


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Publishers: Susan Finnemore Brennan, Craig Bleyer
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Composition: TechBooks
Printing and Binding: RR Donnelley

EAN: 9780716799498

Library of Congress Cataloging-in-Publication Data
Vollhardt, K. Peter C.
Organic chemistry : structure and function.— 5th ed. / K. Peter C. Vollhardt, Neil E. Schore.
p. cm.
Includes index.
ISBN 0-7167-9949-9
1. Chemistry, Organic—Textbooks. I. Schore, Neil Eric, 1948– II. Title.
QD251.3.V65 2007
547—dc22
2005025107
©2007
All rights reserved
Printed in the United States of America
First printing
W. H. Freeman and Company

41 Madison Avenue
New York, NY 10010
Houndmills, Basingstoke RG21 6XS, England
www.whfreeman.com


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CONTENTS
Preface: A User’s Guide to Organic Chemistry: Structure and Function

1

Structure and Bonding in Organic Molecules

1-1
The Scope of Organic Chemistry: An Overview
Chemical Highlight 1-1 Saccharin: One of the Oldest Synthetic
Organic Compounds in Commercial Use
1-2
Coulomb Forces: A Simplified View of Bonding
1-3
Ionic and Covalent Bonds: The Octet Rule
1-4
Electron-Dot Model of Bonding: Lewis Structures
1-5
Resonance Forms
1-6
Atomic Orbitals: A Quantum Mechanical Description
of Electrons Around the Nucleus

1-7
Molecular Orbitals and Covalent Bonding
1-8
Hybrid Orbitals: Bonding in Complex Molecules
1-9
Structures and Formulas of Organic Molecules
Chapter Integration Problems
Important Concepts
Problems

2

Structure and Reactivity: Acids and Bases,
Polar and Nonpolar Molecules

2-1
Kinetics and Thermodynamics of Simple Chemical Processes
2-2
Acids and Bases; Electrophiles and Nucleophiles
Chemical Highlight 2-1 Stomach Acid
and Food Digestion
2-3
Functional Groups: Centers of Reactivity
2-4
Straight-Chain and Branched Alkanes
2-5
Naming the Alkanes
2-6
Structural and Physical Properties of Alkanes
2-7

Rotation about Single Bonds: Conformations
Chemical Highlight 2-2 “Sexual Swindle” by Means of
Chemical Mimicry
2-8
Rotation in Substituted Ethanes
Chapter Integration Problems
Important Concepts
Problems

xx

1
2
4
5
7
14
19
23
29
32
38
41
45
46

51
52
58
59

66
69
71
76
79
79
83
87
89
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vi

CONTENTS

3

Reactions of Alkanes: Bond-Dissociation Energies,
Radical Halogenation, and Relative Reactivity

3-1
Strength of Alkane Bonds: Radicals
3-2
Structure of Alkyl Radicals: Hyperconjugation
3-3
Conversion of Petroleum: Pyrolysis
Chemical Highlight 3-1 Petroleum and Gasoline:

Our Main Energy Sources
3-4
Chlorination of Methane: The Radical
Chain Mechanism
3-5
Other Radical Halogenations of Methane
3-6
Chlorination of Higher Alkanes: Relative Reactivity
and Selectivity
3-7
Selectivity in Radical Halogenation with Fluorine
and Bromine
3-8
Synthetic Radical Halogenation
3-9
Synthetic Chlorine Compounds and the
Stratospheric Ozone Layer
Chemical Highlight 3-2 Chlorination, Chloral, and DDT
3-10 Combustion and the Relative Stabilities
of Alkanes
Chapter Integration Problems
Important Concepts
Problems

4

Cycloalkanes

4-1
Names and Physical Properties of Cycloalkanes

4-2
Ring Strain and the Structure of Cycloalkanes
4-3
Cyclohexane: A Strain-Free Cycloalkane
4-4
Substituted Cyclohexanes
4-5
Larger Cycloalkanes
4-6
Polycyclic Alkanes
4-7
Carbocyclic Products in Nature
Chemical Highlight 4-1 Cubane Derivatives with Potential
as Explosives: Octanitrocubane
Chemical Highlight 4-2 Cholesterol: How Is It Bad and
How Bad Is It?
Chemical Highlight 4-3 Controlling Fertility: From “the Pill”
to RU-486
Chapter Integration Problems
Important Concepts
Problems

96
97
100
101
104
105
110
112

116
118
119
119
122
124
126
127

131
132
134
139
144
148
149
151
151
155
156
158
161
162


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CONTENTS

5

Stereoisomers

5-1
Chiral Molecules
Chemical Highlight 5-1 Chiral Substances in Nature
5-2
Optical Activity
5-3
Absolute Configuration: R–S Sequence Rules
Chemical Highlight 5-2 Absolute Configuration:
A Historical Note
5-4
Fischer Projections
5-5
Molecules Incorporating Several Stereocenters: Diastereomers
Chemical Highlight 5-3 Stereoisomers of Tartaric Acid
5-6
Meso Compounds
5-7
Stereochemistry in Chemical Reactions
Chemical Highlight 5-4 Chiral Drugs: Racemic or
Enantiomerically Pure?
Chemical Highlight 5-5 Why Is Nature “Handed”?
5-8
Resolution: Separation of Enantiomers
Chapter Integration Problems
Important Concepts
Problems

6

Properties and Reactions of Haloalkanes: Bimolecular
Nucleophilic Substitution

6-1
Physical Properties of Haloalkanes
Chemical Highlight 6-1 Halogenated Steroids as Anti-Inflammatory
and Anti-Asthmatic Agents
6-2
Nucleophilic Substitution
6-3
Reaction Mechanisms Involving Polar Functional Groups:
Using “Electron-Pushing” Arrows
6-4
A Closer Look at the Nucleophilic Substitution
Mechanism: Kinetics
6-5
Frontside or Backside Attack? Stereochemistry of
the SN2 Reaction
6-6
Consequences of Inversion in SN2 Reactions
6-7
Structure and SN2 Reactivity: The Leaving Group
6-8
Structure and SN2 Reactivity: The Nucleophile
6-9
Structure and SN2 Reactivity: The Substrate
Chemical Highlight 6-2 The Dilemma of Bromomethane:
Highly Useful but Also Highly Toxic

Chapter Integration Problems
Important Concepts
Problems

168
170
173
174
177
181
182
186
189
190
192
194
198
201
204
206
207

215
215
217
218
221
223
226
228

231
232
239
240
243
245
245

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viii

CONTENTS

7

Further Reactions of Haloalkanes: Unimolecular
Substitution and Pathways of Elimination

250

7-1
7-2
7-3
7-4

Solvolysis of Tertiary and Secondary Haloalkanes

250
Unimolecular Nucleophilic Substitution
252
255
Stereochemical Consequences of SN1 Reactions
Effects of Solvent, Leaving Group, and Nucleophile on
Unimolecular Substitution
256
7-5
Effect of the Alkyl Group on the SN1 Reaction:
Carbocation Stability
258
Chemical Highlight 7-1 Unusually Stereoselective SN1 Displacement
in Anticancer Drug Synthesis
261
7-6
Unimolecular Elimination: E1
262
7-7
Bimolecular Elimination: E2
265
7-8
Competition Between Substitution and Elimination:
Structure Determines Function
268
7-9
Summary of Reactivity of Haloalkanes
271
Chapter Integration Problems
273

New Reactions
275
Important Concepts
276
Problems
276

8
8-1
8-2
8-3
8-4
8-5
8-6

Hydroxy Functional Group: Alcohols: Properties, Preparation,
and Strategy of Synthesis

Naming the Alcohols
Structural and Physical Properties of Alcohols
Alcohols as Acids and Bases
Industrial Sources of Alcohols: Carbon Monoxide and Ethene
Synthesis of Alcohols by Nucleophilic Substitution
Synthesis of Alcohols: Oxidation–Reduction Relation
Between Alcohols and Carbonyl Compounds
Chemical Highlight 8-1 Biological Oxidation and Reduction
Chemical Highlight 8-2 The Breath Analyzer Test
8-7
Organometallic Reagents: Sources of Nucleophilic
Carbon for Alcohol Synthesis

8-8
Organometallic Reagents in the Synthesis of Alcohols
Chemical Highlight 8-3 Transition Metal-Catalyzed
Cross-Coupling Reactions
8-9
Complex Alcohols: An Introduction to Synthetic Strategy
Chapter Integration Problems
New Reactions
Important Concepts
Problems

285
286
287
290
293
294
295
298
301
303
306
308
309
318
321
325
325

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CONTENTS

9

Further Reactions of Alcohols and the Chemistry of Ethers

332

Reactions of Alcohols with Base: Preparation of Alkoxides
Reactions of Alcohols with Strong Acids: Alkyloxonium
Ions in Substitution and Elimination Reactions
of Alcohols
9-3
Carbocation Rearrangements
9-4
Organic and Inorganic Esters from Alcohols
9-5
Names and Physical Properties of Ethers
9-6
Williamson Ether Synthesis
Chemical Highlight 9-1 Chemiluminescence of
1,2-Dioxacyclobutanes
9-7
Synthesis of Ethers: Alcohols and Mineral Acids
9-8
Reactions of Ethers
Chemical Highlight 9-2 Protecting Groups in Synthesis
9-9

Reactions of Oxacyclopropanes
Chemical Highlight 9-3 Hydrolytic Kinetic Resolution of
Oxacyclopropanes
9-10 Sulfur Analogs of Alcohols and Ethers
9-11 Physiological Properties and Uses of Alcohols and Ethers
Chemical Highlight 9-4 Garlic and Sulfur
Chapter Integration Problems
New Reactions
Important Concepts
Problems

333

9-1
9-2

10

Using Nuclear Magnetic Resonance Spectroscopy
to Deduce Structure

10-1 Physical and Chemical Tests
10-2 Defining Spectroscopy
10-3 Hydrogen Nuclear Magnetic Resonance
Chemical Highlight 10-1 Recording an NMR Spectrum
10-4 Using NMR Spectra to Analyze Molecular Structure:
The Proton Chemical Shift
10-5 Tests for Chemical Equivalence
Chemical Highlight 10-2 Magnetic Resonance Imaging in Medicine
10-6 Integration

10-7 Spin–Spin Splitting: The Effect of Nonequivalent
Neighboring Hydrogens
10-8 Spin–Spin Splitting: Some Complications
Chemical Highlight 10-3 The Nonequivalence of Diastereotopic
Hydrogens
10-9 Carbon-13 Nuclear Magnetic Resonance

334
337
342
346
349
350
354
355
357
358
360
364
367
370
371
374
376
377

387
388
388
391

394
396
401
404
405
407
415
418
422

ix


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x

CONTENTS
Chemical Highlight 10-4 Correlated NMR Spectra: COSY
and HETCOR
Chemical Highlight 10-5 Structural Characterization of Natural
Products: Antioxidants from Grape Seeds
Chapter Integration Problems
Important Concepts
Problems

11

Alkenes; Infrared Spectroscopy and Mass Spectrometry

11-1 Naming the Alkenes
11-2 Structure and Bonding in Ethene: The Pi Bond
11-3 Physical Properties of Alkenes
11-4 Nuclear Magnetic Resonance of Alkenes
Chemical Highlight 11-1 Prostaglandins
11-5 Infrared Spectroscopy
11-6 Measuring the Molecular Mass of Organic Compounds:
Mass Spectrometry
11-7 Fragmentation Patterns of Organic Molecules
11-8 Degree of Unsaturation: Another Aid to Identifying
Molecular Structure
11-9 Catalytic Hydrogenation of Alkenes: Relative Stability
of Double Bonds
11-10 Preparation of Alkenes from Haloalkanes and Alkyl
Sulfonates: Bimolecular Elimination Revisited
11-11 Preparation of Alkenes by Dehydration of Alcohols
Chemical Highlight 11-2 Acid-Catalyzed Dehydration of
␣-Terpineol
Chapter Integration Problems
New Reactions
Important Concepts
Problems

12
12-1
12-2
12-3
12-4
12-5
12-6

428
430
432
435
436

446
447
450
453
454
459
460
464
468
473
475
477
481
483
484
486
487
488

Reactions of Alkenes

500

Why Addition Reactions Proceed: Thermodynamic Feasibility
Catalytic Hydrogenation
Nucleophilic Character of the Pi Bond: Electrophilic
Addition of Hydrogen Halides
Alcohol Synthesis by Electrophilic Hydration:
Thermodynamic Control
Electrophilic Addition of Halogens to Alkenes
The Generality of Electrophilic Addition

501
501
504
508
510
513


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CONTENTS
12-7

Oxymercuration–Demercuration: A Special
Electrophilic Addition
Chemical Highlight 12-1 Juvenile Hormone Analogs in the Battle
against Insect-Borne Diseases
12-8 Hydroboration–Oxidation: A Stereospecific
Anti-Markovnikov Hydration
12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis
12-10 Oxacyclopropane (Epoxide) Synthesis: Epoxidation by

Peroxycarboxylic Acids
12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide
Chemical Highlight 12-2 Enantioselective Dihydroxylation in the
Synthesis of Antitumor Drugs
12-12 Oxidative Cleavage: Ozonolysis
12-13 Radical Additions: Anti-Markovnikov Product Formation
12-14 Dimerization, Oligomerization, and Polymerization of Alkenes
12-15 Synthesis of Polymers
Chemical Highlight 12-3 Polymers in the Clean-Up of Oil Spills
Chemical Highlight 12-4 Polymer-Supported Synthesis of
Chemical Libraries
12-16 Ethene: An Important Industrial Feedstock
12-17 Alkenes in Nature: Insect Pheromones
Chemical Highlight 12-5 Metal-Catalyzed Alkene Metathesis for
Constructing Medium and Large Rings
Chapter Integration Problems
New Reactions
Important Concepts
Problems

13
13-1
13-2
13-3
13-4
13-5
13-6

Alkynes: The Carbon–Carbon Triple Bond

Naming the Alkynes
Properties and Bonding in the Alkynes
Spectroscopy of the Alkynes
Preparation of Alkynes by Double Elimination
Preparation of Alkynes from Alkynyl Anions
Reduction of Alkynes: The Relative Reactivity of the
Two Pi Bonds
13-7 Electrophilic Addition Reactions of Alkynes
13-8 Anti-Markovnikov Additions to Triple Bonds
13-9 Chemistry of Alkenyl Halides
13-10 Ethyne as an Industrial Starting Material
Chemical Highlight 13-1 Metal-Catalyzed Stille, Suzuki, and
Sonogashira Coupling Reactions

516
517
520
522
524
526
528
529
531
533
535
536
538
540
541
542

544
546
549
550

561
562
563
565
570
571
572
576
579
580
582
582

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xii

CONTENTS
13-11 Naturally Occurring and Physiologically Active Alkynes
Chapter Integration Problems
New Reactions
Important Concepts

Problems

14

Delocalized Pi Systems: Investigation by Ultraviolet and
Visible Spectroscopy

Overlap of Three Adjacent p Orbitals: Electron
Delocalization in the 2-Propenyl (Allyl) System
14-2 Radical Allylic Halogenation
14-3 Nucleophilic Substitution of Allylic Halides: SN1 and SN2
14-4 Allylic Organometallic Reagents: Useful Three-Carbon
Nucleophiles
14-5 Two Neighboring Double Bonds: Conjugated Dienes
14-6 Electrophilic Attack on Conjugated Dienes:
Kinetic and Thermodynamic Control
Chemical Highlight 14-1 Use of a Fungicidal Diene in Making
Wine: Sorbic Acid
14-7 Delocalization among More than Two Pi Bonds: Extended
Conjugation and Benzene
14-8 A Special Transformation of Conjugated Dienes: Diels-Alder
Cycloaddition
Chemical Highlight 14-2 Conducting Organic Polymers: Materials
for the Future?
Chemical Highlight 14-3 The Diels-Alder Reaction is “Green”
14-9 Electrocyclic Reactions
Chemical Highlight 14-4 An Extraordinary Electrocyclic Reaction
of Anticancer Agents
14-10 Polymerization of Conjugated Dienes: Rubber
14-11 Electronic Spectra: Ultraviolet and Visible Spectroscopy

Chemical Highlight 14-5 The Contributions of IR, MS, and UV
to the Characterization of Viniferone
Chapter Integration Problems
New Reactions
Important Concepts
Problems

585
588
589
593
593

602

14-1

603
606
607
609
610
614
615
618
620
622
628
632
636

638
642
647
648
651
653
653

INTERLUDE: A Summary of Organic Reaction Mechanisms

660

15

Benzene and Aromaticity: Electrophilic Aromatic Substitution

665

Naming the Benzenes
Structure and Resonance Energy of Benzene: A First
Look at Aromaticity

667

15-1
15-2

669

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CONTENTS
15-3 Pi Molecular Orbitals of Benzene
15-4 Spectral Characteristics of the Benzene Ring
15-5 Polycyclic Aromatic Hydrocarbons
Chemical Highlight 15-1 The Allotropes of Carbon: Graphite,
Diamond, and Fullerenes
15-6 Other Cyclic Polyenes: Hückel’s Rule
Chemical Highlight 15-2 Juxtaposing Aromatic and Antiaromatic
Rings in Fused Hydrocarbons
15-7 Hückel’s Rule and Charged Molecules
15-8 Synthesis of Benzene Derivatives: Electrophilic
Aromatic Substitution
15-9 Halogenation of Benzene: The Need for a Catalyst
15-10 Nitration and Sulfonation of Benzene
15-11 Friedel-Crafts Alkylation
15-12 Limitations of Friedel-Crafts Alkylations
15-13 Friedel-Crafts Alkanoylation (Acylation)
Chapter Integration Problems
New Reactions
Important Concepts
Problems

16

Electrophilic Attack on Derivatives of Benzene: Substituents
Control Regioselectivity

672

674
679
680
685
686
690
692
695
696
699
702
704
708
711
713
713

721

16-1

Activation or Deactivation by Substituents on a
Benzene Ring
16-2 Directing Inductive Effects of Alkyl Groups
16-3 Directing Effects of Substituents in Conjugation with
the Benzene Ring
Chemical Highlight 16-1 Explosive Nitroarenes: TNT and Picric Acid
16-4 Electrophilic Attack on Disubstituted Benzenes
16-5 Synthetic Strategies Toward Substituted Benzenes
16-6 Reactivity of Polycyclic Benzenoid Hydrocarbons

16-7 Polycyclic Aromatic Hydrocarbons and Cancer
Chapter Integration Problems
New Reactions
Important Concepts
Problems

728
731
735
738
744
748
750
753
754
755

17

Aldehydes and Ketones: The Carbonyl Group

763

17-1
17-2
17-3

Naming the Aldehydes and Ketones
Structure of the Carbonyl Group
Spectroscopic Properties of Aldehydes and Ketones

764
766
768

722
724

xiii


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xiv

CONTENTS
17-4
17-5

Preparation of Aldehydes and Ketones
Reactivity of the Carbonyl Group:
Mechanisms of Addition
17-6 Addition of Water to Form Hydrates
17-7 Addition of Alcohols to Form Hemiacetals and Acetals
17-8 Acetals as Protecting Groups
17-9 Nucleophilic Addition of Ammonia and Its Derivatives
Chemical Highlight 17-1 Imines in Biological Transformations
17-10 Deoxygenation of the Carbonyl Group
17-11 Addition of Hydrogen Cyanide to Give Cyanohydrins
17-12 Addition of Phosphorus Ylides: The Wittig Reaction

Chemical Highlight 17-2 The Wittig Reaction in Synthesis
17-13 Oxidation by Peroxycarboxylic Acids:
The Baeyer-Villiger Oxidation
17-14 Oxidative Chemical Tests for Aldehydes
Chapter Integration Problems
New Reactions
Important Concepts
Problems

18
18-1
18-2
18-3
18-4
18-5

Enols, Enolates, and the Aldol Condensation:
␣,␤-Unsaturated Aldehydes and Ketones

Acidity of Aldehydes and Ketones: Enolate Ions
Keto–Enol Equilibria
Halogenation of Aldehydes and Ketones
Alkylation of Aldehydes and Ketones
Attack by Enolates on the Carbonyl Function:
Aldol Condensation
18-6 Crossed Aldol Condensation
Chemical Highlight 18-1 Enzyme-Catalyzed Stereoselective
Aldol Condensations in Nature
18-7 Intramolecular Aldol Condensation
Chemical Highlight 18-2 Enzymes in Synthesis: Stereoselective

Crossed Aldol Condensations
18-8 Properties of ␣,␤-Unsaturated Aldehydes and Ketones
Chemical Highlight 18-3 Reactions of Unsaturated Aldehydes
in Nature: The Chemistry of Vision
18-9 Conjugate Additions to ␣,␤-Unsaturated Aldehydes
and Ketones
18-10 1,2- and 1,4-Additions of Organometallic Reagents
18-11 Conjugate Additions of Enolate Ions: Michael Addition
and Robinson Annulation

773
775
778
779
782
784
786
789
791
792
794
795
796
798
800
803
803

814
815

816
819
821
824
828
829
830
830
832
832
834
836
839


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CONTENTS
Chemical Highlight 18-4 Prostaglandins: ␣,␤-Dialkylation
in Synthesis
Chapter Integration Problems
New Reactions
Important Concepts
Problems

840
841
844
847
847

19

856

Carboxylic Acids

19-1 Naming the Carboxylic Acids
19-2 Structural and Physical Properties of Carboxylic Acids
Chemical Highlight 19-1 Toxicity of Oxalic Acid
19-3 Spectroscopy and Mass Spectrometry of
Carboxylic Acids
19-4 Acidic and Basic Character of Carboxylic Acids
19-5 Carboxylic Acid Synthesis in Industry
19-6 Methods for Introducing the Carboxy Functional Group
19-7 Substitution at the Carboxy Carbon:
The Addition–Elimination Mechanism
19-8 Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides
and Anhydrides
19-9 Carboxylic Acid Derivatives: Esters
19-10 Carboxylic Acid Derivatives: Amides
19-11 Reduction of Carboxylic Acids by Lithium
Aluminum Hydride
19-12 Bromination Next to the Carboxy Group:
The Hell-Volhard-Zelinsky Reaction
19-13 Biological Activity of Carboxylic Acids
Chemical Highlight 19-2 Soaps from Long-Chain Carboxylates
Chemical Highlight 19-3 Trans Fatty Acids and Your Health
Chemical Highlight 19-4 Biodegradable Polyester Plastics
Chapter Integration Problems

New Reactions
Important Concepts
Problems

857
859
859
861
864
867
867
870
873
876
880
882
882
884
885
887
889
891
894
897
897

20

Carboxylic Acid Derivatives

909

20-1

Relative Reactivities, Structures, and Spectra of
Carboxylic Acid Derivatives
Chemistry of Alkanoyl Halides
Chemistry of Carboxylic Anhydrides
Chemistry of Esters
Esters in Nature: Waxes, Fats, Oils, and Lipids

910
914
918
919
924

20-2
20-3
20-4
20-5

xv


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xvi

CONTENTS

Chemical Highlight 20-1 Alternatives to Petroleum: Fuels from
Vegetable Oil
20-6 Amides: The Least Reactive Carboxylic Acid Derivatives
Chemical Highlight 20-2 Battling the Bugs: Antibiotic Wars
20-7 Amidates and Their Halogenation: The Hofmann
Rearrangement
Chemical Highlight 20-3 Methyl Isocyanate, Carbamate-based
Insecticides, and Safety in the Chemical
Industry
20-8 Alkanenitriles: A Special Class of Carboxylic
Acid Derivatives
Chapter Integration Problems
New Reactions
Important Concepts
Problems

21

926
928
930
933

936
937
941
944
948
948

Amines and Their Derivatives: Functional Groups Containing Nitrogen 956

21-1 Naming the Amines
21-2 Structural and Physical Properties of Amines
Chemical Highlight 21-1 Physiologically Active Amines
and Weight Control
21-3 Spectroscopy of the Amine Group
21-4 Acidity and Basicity of Amines
Chemical Highlight 21-2 Separation of Amines from Other
Organic Compounds by Aqueous
Extraction Techniques
21-5 Synthesis of Amines by Alkylation
21-6 Synthesis of Amines by Reductive Amination
21-7 Synthesis of Amines from Carboxylic Amides
21-8 Quaternary Ammonium Salts: Hofmann Elimination
21-9 Mannich Reaction: Alkylation of Enols by Iminium Ions
21-10 Nitrosation of Amines
Chemical Highlight 21-3 N-Nitrosodialkanamines and Cancer
Chemical Highlight 21-4 Amines in Industry: Nylon
Chapter Integration Problems
New Reactions
Important Concepts
Problems

22

Chemistry of Benzene Substituents: Alkylbenzenes, Phenols,
and Benzenamines

22-1

Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic
Resonance Stabilization

957
958
960
962
965

968
969
972
975
975
977
979
980
982
985
988
993
993

1001
1002


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CONTENTS
22-2 Benzylic Oxidations and Reductions
22-3 Names and Properties of Phenols
Chemical Highlight 22-1 Two Phenols in the News:
Bisphenol A and Resveratrol
22-4 Preparation of Phenols: Nucleophilic Aromatic Substitution
22-5 Alcohol Chemistry of Phenols
Chemical Highlight 22-2 Aspirin: A Phenyl Alkanoate Drug
22-6 Electrophilic Substitution of Phenols
22-7 An Electrocyclic Reaction of the Benzene Ring:
The Claisen Rearrangement
22-8 Oxidation of Phenols: Benzoquinones
Chemical Highlight 22-3 Chemical Warfare in Nature:
The Bombardier Beetle
22-9 Oxidation-Reduction Processes in Nature
22-10 Arenediazonium Salts
22-11 Electrophilic Substitution with Arenediazonium Salts:
Diazo Coupling
Chemical Highlight 22-4 William Perkin and the Origins of
Industrial and Medicinal Chemistry
Chapter Integration Problems
New Reactions
Important Concepts
Problems

23

Ester Enolates and the Claisen Condensation: Synthesis of
␤-Dicarbonyl Compounds; Acyl Anion Equivalents

23-1 ␤-Dicarbonyl Compounds: Claisen Condensations
Chemical Highlight 23-1 Claisen Condensations in Biochemistry
23-2 ␤-Dicarbonyl Compounds as Synthetic Intermediates
23-3 ␤-Dicarbonyl Anion Chemistry: Michael Additions
23-4 Alkanoyl (Acyl) Anion Equivalents: Preparation of
␣-Hydroxyketones
Chemical Highlight 23-2 Thiamine: A Natural, Metabolically
Active Thiazolium Salt
Chapter Integration Problems
New Reactions
Important Concepts
Problems

24

Carbohydrates: Polyfunctional Compounds in Nature

24-1
24-2
24-3

Names and Structures of Carbohydrates
Conformations and Cyclic Forms of Sugars
Anomers of Simple Sugars: Mutarotation of Glucose

1006
1009
1012
1013
1022

1023
1024
1028
1030
1032
1033
1038
1041
1042
1044
1046
1052
1052

1061
1062
1066
1069
1074
1076
1080
1083
1087
1088
1089

1096
1097
1101
1105

xvii


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xviii

CONTENTS
24-4

Polyfunctional Chemistry of Sugars: Oxidation to
Carboxylic Acids
24-5 Oxidative Cleavage of Sugars
24-6 Reduction of Monosaccharides to Alditols
24-7 Carbonyl Condensations with Amine Derivatives
24-8 Ester and Ether Formation: Glycosides
Chemical Highlight 24-1 18F-Labeled Glucose as a Radiotracer:
Imaging the Human Brain
Chemical Highlight 24-2 Protecting Groups in Vitamin C Synthesis
24-9 Step-by-Step Buildup and Degradation of Sugars
Chemical Highlight 24-3 Sugar Biochemistry
24-10 Relative Configurations of the Aldoses: An Exercise in
Structure Determination
24-11 Complex Sugars in Nature: Disaccharides
Chemical Highlight 24-4 Carbohydrate-Derived Sugar Substitutes
24-12 Polysaccharides and Other Sugars in Nature
Chapter Integration Problem
New Reactions
Important Concepts

Problems

25

1107
1109
1110
1111
1112
1113
1115
1116
1118
1120
1122
1124
1127
1133
1135
1138
1139

Heterocycles: Heteroatoms in Cyclic Organic Compounds

1145

25-1 Naming the Heterocycles
25-2 Nonaromatic Heterocycles
Chemical Highlight 25-1 Azacyclopropene Antibiotics
Chemical Highlight 25-2 Smoking, Nicotine, and Cancer

25-3 Structure and Properties of Aromatic Heterocyclopentadienes
25-4 Reactions of the Aromatic Heterocyclopentadienes
25-5 Structure and Preparation of Pyridine: An Azabenzene
25-6 Reactions of Pyridine
Chemical Highlight 25-3 Pyridinium Salts in Nature:
Nicotinamide Adenine Dinucleotide
25-7 Quinoline and Isoquinoline: The Benzopyridines
Chemical Highlight 25-4 Azanaphthalenes in Nature
25-8 Alkaloids: Physiologically Potent Nitrogen Heterocycles
in Nature
Chemical Highlight 25-5 Nature Is Not Always Green:
Natural Pesticides
Chapter Integration Problems
New Reactions
Important Concepts
Problems

1148
1149
1150
1152
1153
1156
1160
1164
1166
1167
1168
1170
1172

1174
1178
1180
1180


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CONTENTS

26

Amino Acids, Peptides, Proteins, and Nucleic Acids:
Nitrogen-Containing Polymers in Nature

1191

26-1 Structure and Properties of Amino Acids
Chemical Highlight 26-1 Arginine and Nitric Oxide in
Biochemistry and Medicine
26-2 Synthesis of Amino Acids: A Combination of Amine and
Carboxylic Acid Chemistry
26-3 Synthesis of Enantiomerically Pure Amino Acids
Chemical Highlight 26-2 Synthesis of Optically Pure Amino Acids:
Phase-Transfer Catalysis
26-4 Peptides and Proteins: Amino Acid Oligomers
and Polymers
26-5 Determination of Primary Structure:
Amino Acid Sequencing
26-6 Synthesis of Polypeptides: A Challenge in the

Application of Protecting Groups
26-7 Merrifield Solid-Phase Peptide Synthesis
26-8 Polypeptides in Nature: Oxygen Transport by the
Proteins Myoglobin and Hemoglobin
26-9 Biosynthesis of Proteins: Nucleic Acids
Chemical Highlight 26-3 Synthetic Nucleic Acid Bases and
Nucleosides in Medicine
26-10 Protein Synthesis Through RNA
26-11 DNA Sequencing and Synthesis: Cornerstones of
Gene Technology
Chemical Highlight 26-4 DNA Fingerprinting
Chapter Integration Problems
New Reactions
Important Concepts
Problems
MCAT ® Questions

1192
1197
1198
1201
1202
1203
1211
1216
1219
1221
1223
1225
1228

1231
1238
1243
1246
1247
1248

MCAT ®-1

Answers to Exercises

A-1

Photograph Credits

C-1

Index

I-1

xix


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PREFACE
A User’s Guide to

ORGANIC CHEMISTRY S t r u c t u r e a n d F u n c t i o n

I

n this edition of Organic Chemistry: Structure and Function, we maintain our goal
of helping students organize all the information presented in the course and fit it into
a logical framework for understanding contemporary organic chemistry. This framework emphasizes that the structure of an organic molecule determines how that molecule functions in a chemical reaction. By understanding the connection between
structure and function, we can learn to solve practical problems in organic chemistry.
In the fifth edition, we have strengthened the themes of understanding reactivity,
mechanisms, and synthetic analysis to apply chemical concepts to realistic situations.
We incorporated new applications of organic chemistry in the life sciences, industrial
practices, and environmental monitoring and clean-up. This edition includes more than
100 new or substantially revised problems, including new problems on synthesis and
green chemistry, and new “challenging” problems. For the first time, we are offering Organic Chemistry: Structure and Function in an online version to give students
cost-effective access to all content from the text plus all student media resources. For
more information, please visit our Web site at .

ACCESSIBLE FOR STUDENTS
Review and Extension of General Chemistry Concepts

▼

The first five chapters of the book focus on the general principles of bonding, reactivity, and stereochemistry that enable students to understand the connections
between structure and function. Chapter 1 reviews the
fundamentals of how structure affects bonding, laying
2-1 Kinetics and Thermodynamics of Simple Chemical Processes
The simplest chemical reactions may be described as equilibration between two disthe groundwork for later study of functional groups.
tinct species. Such processes are governed by two fundamental considerations:
Chapter 2 discusses the basics of polar reactions, com1. Chemical thermodynamics, which deals with the changes in energy that take
paring the properties of acids and bases with those of
place when processes such as chemical reactions occur. Thermodynamics controls the extent to which a reaction goes to completion.

nucleophiles and electrophiles, while also presenting
2. Chemical kinetics, which concerns the velocity or rate at which the concentrations of reactants and products change. In other words, kinetics describes the
initial ideas of reaction kinetics and thermodynamics.
speed at which a reaction goes to completion.

Developing the Basic Tools for Understanding Function
An overview of the major functional groups of organic chemistry appears in Chapter 2. Chapter 2 also describes the nonreactive backbone of common organic molecules, as shown by the properties and behavior of the alkanes. Chapter 3 introduces the idea of bond-dissociation energies, illustrated by the radical halogenation
of alkanes. Chapter 4 presents the first cyclic molecules—the cycloalkanes. In Chapter 5 we cover stereochemistry to prepare students for learning the mechanisms of
substitution and elimination reactions of haloalkanes (Chapters 6 and 7) and the
addition reactions of alkenes (Chapter 12).


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PREFACE

xxi

Students must learn so many facts about the structures and
functions of the various families of organic compounds that it
is easy for them to lose sight of the most important concepts
in the course. We include short summaries at the ends of most
sections in the book, emphasizing the main ideas for students
to remember. These have been revised in the new edition to
better reflect the distinction between typical chemical behavior and important exceptions.

▼

Help in Seeing the Big Picture
IN SUMMARY The various hydrogen atoms present in an organic molecule can

be recognized by their characteristic NMR peaks at certain chemical shifts, ␦. An
electron-poor environment is deshielded and leads to low-field (high-␦) absorptions,
whereas an electron-rich environment results in shielded or high-field peaks. The
chemical shift ␦ is measured in parts per million by dividing the difference in hertz
between the measured resonance and that of the internal standard, tetramethylsilane,
(CH3)4Si, by the spectrometer frequency in megahertz. The NMR spectra for the
OH groups of alcohols, the SH groups of thiols, and the NH2 (NHR) groups of
amines exhibit characteristically broad peaks with concentration- and moisturedependent ␦ values.

In addition, the end
of each chapter has
Alkanes lack functional groups, so they do not undergo the kinds of electrophile–
a short section, called
nucleophile reactions typical of functionalized molecules. In fact, alkanes are pretty
unreactive. However, under appropriate conditions, they undergo homolytic bond
The Big Picture, that
cleavage to form radicals, which are reactive species containing odd numbers of electrons. This is another situation in which the structure of a class of compounds
reinforces the connecdetermines their function. Unlike heterolytic processes, which normally proceed via
tions between topics
movement of pairs of electrons to form or break bonds, homolytic chemistry utilizes
the splitting of covalent bonds to give unpaired single electrons, as well as their comwithin chapters and
bination to give new bonds.
In organic chemistry, radical reactions are not encountered as frequently as those
between chapters, and
of polar functional groups. However, radicals play prominent roles in biological,
fits the material into the
environmental, and industrial chemistry.
The halogenation of alkanes, a radical process in which hydrogen is replaced by
overall presentation of
halogen, forms the haloalkane functional group. Examination of halogenation allows

us to learn about several features common to most transformations, including the way
the course. These secinformation about a reaction mechanism may be obtained from experimental obsertions are not summaries,
vations, the relationship between thermodynamics and kinetics, and notions of reactivity and selectivity. The products of halogenation, the haloalkanes, are the starting
but serve to indicate
compounds for a wide variety of reactions, as we will see in Chapters 6 through 9.
Before we examine other classes of compounds and their properties, we need
where we’ve been and
to learn more about the structures and, in particular, the geometric shapes of organic
where we’re going.
molecules. In Chapter 4 we discuss compounds that contain atoms in rings and in
Chapter 5 we study additional forms of isomerism. The ideas we introduce are a necThey have been revised
essary background as we begin a systematic study in the chapters that follow of polar
reactions of haloalkanes and alcohols.
in this edisection number
Reactions of Alcohols
tion to better
reinforce the
O
B
RX
Alkene
RX
R؅COR
themes stated in the chapter-opening introductions, which help set the context for the material in the chapter.
We have retained the Reaction Summary Road Maps, also at the
9-2
7-6,9-2,9-3
9-4,19-9
9-4
9-7,11-11

ends of some chapters, which summarize the principal reactions for
preparation and applications of each major functional group. The PrepaPX
HX
H SO , ∆
R؅COOH
ration maps indicate the possible origins of a functionality—that is, the
i
precursor functional groups. The Reaction maps show what each funcC O OH
L
tional group does. In both maps, reaction arrows are labeled with partic& or
ROH
ular reagents and start from or end at specific reactants or products. The
reaction arrows are also labeled with new section numbers indicating
H ,
O
B
O
GC
where the transformation is discussed in the new edition.
B
G
OH

THE BIG PICTURE

▼

▼

2

3

4

ϩ

G G

C

B

R؅CH(RЉ), Hϩ

Ϫ

C

O
B
R؅CCl

G

Substrate:
NC
OH
D G

C
D G

G

C

C

G

G

G

G

G

H(RЉ)

G

H(RЉ)
OR
RЈCOR

20-2

H

RO

G

We include worked-out solutions to in-chapter exercises, called Working with the Concepts. These solutions emphasize the reasoning
students need to apply in attacking problems, arranging the steps
logically and carefully so students can see potential pitfalls and avoid

O
B
C
D G

G

OH
RЈCOR or

18-9

17-11,24-9

G

Examples of Problem-Solving Approaches

17-7

G

STRONGER PEDAGOGY FOR SOLVING
PROBLEMS

C

O
J
G

O
B
RЈCOR