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The 12th edition of Organic Chemistry continues Solomons, Fryhle & Snyders tradition of excellence in teaching and preparing students for success in the organic classroom and beyond.

A central theme of the authors approach to organic chemistry is to emphasize the relationship between structure and reactivity. To accomplish this, the content is organized in a way that combines the most useful features of a functional group approach with one largely based on reaction mechanisms. The authors philosophy is to emphasize mechanisms and their common aspects as often as possible, and at the same time, use the unifying features of functional groups as the basis for most chapters. The structural aspects of the authors approach show students what organic chemistry is. Mechanistic aspects of their approach show students how it works. And wherever an opportunity arises, the authors show students what it does in living systems and the physical world around us.
Year:
2016
Edition:
12th Edition
Publisher:
Wiley
Language:
english
Pages:
1293
File:
PDF, 52.22 MB
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This page intentionally left blank

16
VIA

Lanthanum
138.91

89

Barium
137.33

88

Cesium
132.91

87

Francium
(223)

Actinium
(227)

# Actinide Se ries

*Lanthanide Se ries

Radium
(226)

Ra #Ac

*La

Ba

Cs

Fr

57

56

55

Zr

Y

Yttrium
88.906

Sr

Strontium
87.62

Rb

Rubidium
85.468

40

39

38

37

Ti

59

Pr
Praseodymium

140.91

91

Pa
Protactinium
231.04

58

Ce
Cerium
140.12

90

Th
Thorium
232.04

(261)

Dubnium
(262)

Db

105

Tantalum
180.95

Ta

73

Niobium
92.906

Nb

41

Vanadium
50.942

V

23

Rutherfordium

Rf

104

Hafnium
178.49

Hf

72

Zirconium
91.224

Titanium
47.867

Sc

Scandium
44.956

Ca

Calcium
40.078

K

Potassium
39.098

22

21

20

19

Mn

25

Tc

43

Ru

44

Iron
55.845

Fe

26

62

Hassium
(277)

Hs

108

Osmium
190.23

Os

76

101.07

Pm Sm

61

Bohrium
(264)

Bh

107

Rhenium
186.21

Re

75

(98)

Uranium
238.03

U

92

Neptunium
(237)

Np

93

Plutonium
(244)

Pu

94

Neodymium Promethium Sama rium
(145)
150.36
144.24

Nd

60

Seaborgium
(266)

Sg

106

Tungsten
183.84

W

74

95.94

Molybdenum Technetium Ruthenium

Mo

42

Chromium Manganese
51.996
54.938

Cr

24

Ds

110

Platinum
195.08

Pt

78

Palladium
106.42

Pd

46

Nickel
58.693

Ni

28

Rg

111

Gold
196.97

Au

79

Silver
107.87

Ag

47

Copper
63.546

Cu

29

11
IB

Cn

112

Mercury
200.59

Hg

80

Cadmium
112.41

Cd

48

Zinc
65.409

Zn

30

12
IIB

96

Gadolinium
157.25

Gd

64

Americium
(243)

Curium
(247)

Am Cm

95

Europium
151.96

Eu

63

Berkelium
(247)

Bk

97

Terbium
158.93

Tb

65

Es

99

Holmium
164.93

Ho

67

(284)

Uut

113

Thallium
204.38

Tl

81

Indium
114.82

In

49

Gallium
69.723

Ga

31

Aluminum
26.982

Californium Einsteinium
(251)
(252)

Cf

98

Dysprosium
162.50

Dy

66

Meitnerium Darmstadtium Roentgenium Copernicium
(268)
(281)
(272)
(285)

Mt

109

Iridium
192.22

Ir

77

Rhodium
102.91

Rh

45

Cobalt
58.933

Co

27

10
VIIIB

S

9
VIIIB

P

7
VIIB

8
VIIIB

Si

5
VB

Al

4
IVB

3
IIIB

Mg

Magnesium
24.305

Na

Sodium
22,990

16

15

14

13

Fermium
(257)

Fm

100

Erb; ium
167.26

Er

68

Flerovium
(289)

Fl

114

Lead
207.2

Pb

82

Tin
118.71

Sn

50

Ge rmanium
72.64

Ge

32

Silicon
28.086

116

Polonium
(209)

Po

84

Tellurium
127.60

Te

52

Selenium
78.96

Se

34

Sulfur
32.065

Oxygen
15.999

O

(258)

Mendelevium

Md

101

Thulium
168.93

Tm

69

(288)

Nobelium
(259)

No

102

Ytterbium
173.04

Yb

70

Livermorium
(293)

Uup Lv

115

Bismuth
208.98

Bi

83

Antimony
121.76

Sb

51

Arsenic
74.922

As

33

Phosphorus
30.974

Nitrogen
14.007

N

8

12

Carbon
12.011

C

7

11

B

6

Boron
10.811

Carbon
12.011

5

Berylium
9.0122

6
VIB

15
VA

Lithium
6.941

14
IVA

Be

13
IIIA

LI

IUPAC recommendations:
Chemical Abstracts Service group notation:

4

C

3

Symbol
Name (IUPAC)
Atomic mass

2
IIA

H

Hydrogen
1.0079

6

17
VIIA

118

Radon
(222)

Rn

86

Xenon
131.29

Xe

54

Krypton
83.798

Kr

36

Argon
39.948

Ar

18

Neon
20.180

Ne

10

Lawrencium
(262)

Lr

103

Lutetium
174.97

Lu

71

(294)

(294)

Uus Uuo

117

Astatine
(210)

At

85

Iodine
126.90

I

53

Bromine
79.904

Br

35

Chlorine
35.453

Cl

17

Fluorine
18.998

F

9

Helium
4.0026

He

2

Atomic number

1

EL E M E N T S
18
VIIIA

OF THE

1
IA

PE R I O D I C TA B L E

Table 3.1 Relative Strength of Selected Acids and Their Conjugate Bases
Acid
Strongest acid

Approximate pKa

HSbF6
HI
H2SO4
HBr
HCl
C6H5SO3H
+

(CH3)2OH
+
(CH3)2C=OH

C6H5NH+
3
CH3CO2H
H2CO3
CH3COCH2COCH3
NH+
4
C6H5OH
HCO−
3

Weakest acid

CH3NH+
3
H2O
CH3CH2OH
(CH3)3COH
CH3COCH3
HC≡CH
C6H5NH2
H2
(i-Pr)2NH
NH3
CH2=CH2
CH3CH3

−2.5
−1.74
−1.4
0.18
3.2
4.21
4.63
4.75
6.35
9.0
9.2
9.9
10.2
10.6
15.7
16
18
19.2
25
31
35
36
38
44
50

SbF−
6
I−
HSO−
4
Br−
Cl−
C6H5SO−
3
(CH3)2O
(CH3)2C=O

Weakest base

CH3OH
H2O
NO−
3
CF3CO−
2
F−
C6H5CO−
2
C6H5NH2
CH3CO−
2
HCO−
3
−
CH3COCHCOCH3
NH3

Increasing base strength

Increasing acid strength

+

(CH3)OH2
H3O+
HNO3
CF3CO2H
HF
C6H5CO2H

< −12
−10
−9
−9
−7
−6.5
−3.8
−2.9

Conjugate
Base

C6H5O−
CO32−
CH3NH2
HO−
CH3CH2O−
(CH3)3CO−
−
CH2COCH3
HC≡C−
C6H5NH−
H−
(i-Pr)2N−
−
NH2
CH2=CH−
CH3CH−
2

Strongest base

Organic Chemistry

T.W. Graham Solomons
University of South Florida

Craig B. Fryhle
Pacific Lutheran University

Scott A. Snyder
University of Chicago

12e

For Annabel and Ella. TWGS
For my mother and in memory of my father. CBF
For Cathy and Sebastian. SAS
Vice President and Director: Petra Recter
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Library of Congress Cataloging-in-Publication Data
Names: Solomons, T. W. Graham, author. | Fryhle, Craig B. | Snyder, S. A. (Scott A.)
Title: Organic chemistry.
Description: 12th edition / T.W. Graham Solomons, Craig B. Fryhle, Scott A.
Snyder. | Hoboken, NJ : John Wiley & Sons, Inc., 2016. | Includes index.
Identifiers: LCCN 2015042208 | ISBN 9781118875766 (cloth)
Subjects: LCSH: Chemistry, Organic—Textbooks.
Classification: LCC QD253.2 .S65 2016 | DDC 547—dc23 LC record available at http://lccn.loc.gov/2015042208
ISBN 978-1-118-87576-6
Binder-ready version ISBN 978-1-119-07725-1
The inside back cover will contain printing identification and country of origin if omitted from this page. In
­addition, if the ISBN on the back cover differs from the ISBN on this page, the one on the back cover is correct.
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1

Brief Contents
1		 The Basics Bonding and Molecular Structure 1
2		Families of Carbon Compounds Functional Groups, Intermolecular Forces, and Infrared (IR)
Spectroscopy 55

3		 Acids and Bases An Introduction to Organic R­ eactions and Their Mechanisms 104
4		 Nomenclature and Conformations of Alkanes and Cycloalkanes 144
5		 Stereochemistry Chiral Molecules 193
6		 Nucleophilic Reactions Properties and Substitution Reactions of Alkyl Halides 240
7		 Alkenes and Alkynes I Properties and Synthesis. Elimination Reactions of Alkyl Halides 282
8		 Alkenes and Alkynes II Addition Reactions 337
9		 Nuclear Magnetic Resonance and Mass Spectrometry Tools for Structure Determination 391
10		 Radical Reactions 448
11		 Alcohols and Ethers Synthesis and Reactions 489
12		 Alcohols from Carbonyl Compounds Oxidation–Reduction and O­ rganometallic Compounds 534
13		 Conjugated Unsaturated Systems 572
14		 Aromatic Compounds 617
15		 Reactions of Aromatic Compounds 660
16		 Aldehydes and Ketones Nucleophilic Addition to the C­ arbonyl Group 711
17		 Carboxylic Acids and Their Derivatives Nucleophilic Addition–Elimination at the Acyl Carbon 761
18		 Reactions at the α Carbon of Carbonyl Compounds Enols and Enolates 811
19		Condensation and Conjugate Addition Reactions of Carbonyl Compounds More
Chemistry of Enolates 849

20		
21		
22		
23		
24		
25		

Amines 890
Transition Metal Complexes Promoters of Key Bond-Forming Reactions 938
Carbohydrates 965
Lipids 1011
Amino Acids and Proteins 1045
Nucleic Acids and Protein Synthesis 1090
Glossary GL-1
Index I-1
Answers to Selected Problems can be found at www.wiley.com/college/solomons

iii

Contents

1

2

The Basics

Families of Carbon
Compounds

Bonding and
Molecular
Structure  1

Functional Groups,
Intermolecular Forces, and
Infrared (IR) Spectroscopy 55

1.1	Life and the Chemistry of Carbon
Compounds—We Are Stardust 2
The Chemistry of… Natural Products

2.1	Hydrocarbons: Representative Alkanes, Alkenes,
Alkynes, and Aromatic Compounds 56

3

1.2

Atomic Structure 3

2.2

Polar Covalent Bonds 59

1.3

Chemical Bonds: The Octet Rule 5

2.3

Polar and Nonpolar Molecules 61

1.4

How To Write Lewis Structures

2.4

Functional Groups

1.5

Formal Charges and How To Calculate Them 12

2.5

Alkyl Halides or Haloalkanes 65

2.6

Alcohols and Phenols 67

2.7

Ethers 69

7

1.6	Isomers: Different Compounds that Have the Same
Molecular Formula 14

64

1.7

How To Write and Interpret Structural Formulas

1.8

Resonance Theory

1.9

Quantum Mechanics and Atomic Structure 27

2.8

Amines 70

1.10 Atomic Orbitals and Electron Configuration 28

2.9

Aldehydes and Ketones 71

1.11 Molecular Orbitals

2.10 Carboxylic Acids, Esters, and Amides 73

15

The Chemistry of… Ethers as General

Anesthetics 69

22

30

1.12	The Structure of Methane and Ethane:
sp3 Hybridization 32
The Chemistry of… Calculated Molecular Models:

Electron Density Surfaces 36

2.11 Nitriles 75
2.12	Summary of Important Families of Organic
Compounds 76
2.13	Physical Properties and Molecular Structure 77

1.13	The Structure of Ethene (Ethylene):
sp 2 Hybridization 36

The Chemistry of… Fluorocarbons and Teflon

1.14	The Structure of Ethyne (Acetylene): sp
Hybridization 40
1.15	A Summary of Important Concepts that Come from
Quantum Mechanics 43

2.14 Summary of Attractive Electric Forces 85
The Chemistry of… Organic Templates Engineered to

Mimic Bone Growth 86
2.15	Infrared Spectroscopy: An Instrumental Method
for Detecting Functional Groups 86

1.16 H
 ow To Predict Molecular G
­ eometry: The Valence
Shell Electron Pair R
­ epulsion Model 44

2.16 Interpreting IR Spectra 90

1.17 Applications of Basic Principles 47

2.17 Applications of Basic Principles 97

[ WHY DO THESE TOPICS MATTER? ]

[ WHY DO THESE TOPICS MATTER? ]

iv

48

81

97

3

Acids and Bases

An Introduction to
Organic ­R eactions and
Their Mechanisms 104
Acid–Base Reactions 105

3.2

How To Use Curved Arrows in I­llustrating

107

Reaction of Water
with Hydrogen Chloride: The Use of Curved Arrows 107

[ A MECHANISM FOR THE REACTION ]

3.3

How To Name Alkanes, Alkyl Halides, and Alcohols:
The IUPAC System 148

4.4

How to Name Cycloalkanes 155

4.5

How To Name Alkenes and Cycloalkenes

4.6

How To Name Alkynes

158

160

4.7	Physical Properties of Alkanes and Cycloalkanes 161

3.1

Reactions

4.3

Lewis Acids and Bases 109

The Chemistry of… Pheromones: Communication by

Means of Chemicals 163
4.8

Sigma Bonds and Bond Rotation 164

4.9

Conformational Analysis of Butane 166

The Chemistry of… Muscle Action

168

3.4	Heterolysis of Bonds to Carbon:
Carbocations and Carbanions 111

4.10	The Relative Stabilities of Cycloalkanes: Ring
Strain 168

3.5	The Strength of Brønsted–Lowry Acids
and Bases: Ka and pKa 113

4.11	Conformations of Cyclohexane: The Chair and the
Boat 170

How To Predict the Outcome of Acid–Base
3.6	
Reactions 118

The Chemistry of… Nanoscale Motors and Molecular

3.7

Relationships between Structure and Acidity 120

3.8

Energy Changes

4.12	Substituted Cyclohexanes:
Axial and Equatorial Hydrogen Groups 173

123

Switches 172

3.9	The Relationship between the Equilibrium Constant
and the Standard Free-Energy Change, ∆G ° 125

4.13	Disubstituted Cycloalkanes: Cis–Trans
Isomerism 177

3.10 Acidity: Carboxylic Acids versus Alcohols 126

4.14 Bicyclic and Polycyclic Alkanes 181

3.11 The Effect of the Solvent on Acidity 132

4.15 Chemical Reactions of Alkanes 182

3.12 Organic Compounds as Bases 132

4.16 Synthesis of Alkanes and Cycloalkanes 182

3.13 A Mechanism for an Organic Reaction 134

4.17 H
 ow To Gain Structural Information from
Molecular ­Formulas and the Index of Hydrogen
Deficiency 184

Reaction of
­tert-Butyl Alcohol with Concentrated Aqueous HCl 134

[ A MECHANISM FOR THE REACTION ]

3.14 Acids and Bases in Nonaqueous Solutions 135
3.15	Acid–Base Reactions and the Synthesis of
Deuterium- and Tritium-Labeled Compounds 136
3.16 Applications of Basic Principles 137
[ WHY DO THESE TOPICS MATTER? ]

187

See Special Topic A, 13C NMR Spectroscopy—A Practical
Introduction, in WileyPLUS

5

Stereochemistry

Chiral Molecules  193

Nomenclature and
Conformations
of Alkanes and
Cycloalkanes

5.1

Shapes of Alkanes 146

Chirality and Stereochemistry 194

5.2	Isomerism: Constitutional Isomers
and Stereoisomers 195
5.3

Introduction to Alkanes and Cycloalkanes 145

The Chemistry of… Petroleum Refining

4.2

[ WHY DO THESE TOPICS MATTER? ]

138

4
4.1

4.18 Applications of Basic Principles 186

145

Enantiomers and Chiral Molecules 197

5.4	Molecules Having One Chirality Center
are Chiral 198
5.5	More about the Biological Importance of Chirality 201

v

5.6

How To Test for Chirality: Planes of Symmetry

203

5.7

Naming Enantiomers: The R,S-System 204

5.8

Properties of Enantiomers: Optical Activity 208

5.9

Racemic Forms

the SN1 Reaction 256
6.11 Carbocations 257
6.12 The Stereochemistry of SN1 Reactions 259

213

The

[ A MECHANISM FOR THE REACTION ]

5.10 The Synthesis of Chiral Molecules 214
5.11 Chiral Drugs

Mechanism for

[ A MECHANISM FOR THE REACTION ]

Stereochemistry of an SN1 Reaction

216

The Chemistry of… Selective Binding of Drug

Enantiomers to Left- and Right-Handed Coiled DNA 218

260

6.13	Factors Affecting the Rates of SN1 and SN2
Reactions 262

5.12 Molecules with More than One Chirality Center 218

6.14	Organic Synthesis: Functional Group ­Transformations
­Using SN2 Reactions 272

5.13 Fischer Projection Formulas 224

The Chemistry of… Biological Methylation: A Biological

5.14 Stereoisomerism of Cyclic Compounds 226
5.15	Relating Configurations through Reactions in
Which No Bonds to the Chirality Center Are
Broken 228
5.16 Separation of Enantiomers: Resolution 232
5.17	Compounds with Chirality Centers
Other than Carbon 233

234

275

7

Alkenes and
Alkynes I

7.1

Introduction 283

7.2	The (E )–(Z ) System for Designating Alkene
Diastereomers 283

6

Nucleophilic
Reactions

Properties and Substitution
Reactions of Alkyl Halides  240
6.1

Alkyl Halides 241

6.2

Nucleophilic Substitution Reactions 242

6.3

Nucleophiles 244

6.4

Leaving Groups 246

A Mechanism for the SN2 Reaction

[ A MECHANISM FOR THE REACTION ]

the SN2 Reaction

Relative Stabilities of Alkenes 284

7.4

Cycloalkenes 287

7.5

Synthesis of Alkenes: Elimination Reactions 287

7.6

Dehydrohalogenation

7.7

The E2 Reaction 289

288

[ A MECHANISM FOR THE REACTION ]

Mechanism for

the E2 Reaction 290
E2 Elimination
Where There Are Two Axial β Hydrogens 295

247
Mechanism for

E2 Elimination
Where the Only Axial β Hydrogen Is from a Less Stable
Conformer 296

[ A MECHANISM FOR THE REACTION ]

7.8

The E1 Reaction 297

[ A MECHANISM FOR THE REACTION ]

248

6.7

Transition State Theory: Free-Energy Diagrams 249

6.8

The Stereochemistry of SN2 Reactions

[ A MECHANISM FOR THE REACTION ]

7.3

[ A MECHANISM FOR THE REACTION ]

­ ubstitution Reaction:
6.5	Kinetics of a Nucleophilic S
An SN2 Reaction 246
6.6

[ WHY DO THESE TOPICS MATTER? ]

Properties and
Synthesis. Elimination Reactions
of Alkyl Halides  282

5.18	Chiral Molecules that Do Not Possess
a Chirality Center 233
[ WHY DO THESE TOPICS MATTER? ]

Nucleophilic ­Substitution Reaction 273

252

The

Mechanism for

the E1 Reaction 298
7.9	Elimination and Substitution Reactions Compete
With Each Other 299

Stereochemistry of an SN2 ­Reaction 254

7.10	Elimination of Alcohols: Acid-Catalyzed
Dehydration 303

6.9	The Reaction of tert-Butyl Chloride with Water:
An SN1 Reaction 254

[ A MECHANISM FOR THE REACTION ]

6.10 A Mechanism for the SN1 Reaction

vi

255

Acid-Catalyzed
Dehydration of Secondary or Tertiary Alcohols:
An E1 Reaction 306

Dehydration of a

[ A MECHANISM FOR THE REACTION ]

Primary Alcohol: An E2 Reaction 308
7.11	Carbocation Stability and the Occurrence
of ­Molecular Rearrangements 308

8.5	Alcohols from Alkenes through
Oxymercuration–­Demercuration: Markovnikov
Addition 349
[ A MECHANISM FOR THE REACTION ]

[ A MECHANISM FOR THE REACTION ]

Oxymercuration

7.12 The Acidity of Terminal Alkynes 312

8.6	Alcohols from Alkenes through
Hydroboration–­Oxidation: Anti-Markovnikov Syn
Hydration 352

7.13 Synthesis of Alkynes by Elimination Reactions 313

8.7

[ A MECHANISM FOR THE REACTION ]

[ A MECHANISM FOR THE REACTION ]

Dehydrohalogenation of vic-Dibromides to Form
Alkynes 314

Hydroboration

Formation of
a Rearranged Alkene During Dehydration of a Primary
Alcohol 311

8.8

7.14	Terminal Alkynes Can Be Converted to Nucleophiles
for Carbon–Carbon Bond Formation 315
7.15 Hydrogenation of Alkenes 317
Industry

7.16 Hydrogenation: The Function of the Catalyst 319
7.17 Hydrogenation of Alkynes 320
The Dissolving

Metal Reduction of an Alkyne 321

Oxidation and Hydrolysis of Alkylboranes 355

Trialkylboranes

Oxidation of

356

Summary of Alkene Hydration Methods 358

8.11	Electrophilic Addition of Bromine and Chlorine to
Alkenes 359
Addition of

[ A MECHANISM FOR THE REACTION ]

Bromine to an Alkene 361
The Chemistry of… The Sea: A Treasury of Biologically

7.18 An Introduction to Organic Synthesis 322

Active Natural P
­ roducts 362

The Chemistry of… From the Inorganic to the

Organic

354

8.10 Protonolysis of Alkylboranes 359

318

[ A MECHANISM FOR THE REACTION ]

Hydroboration: Synthesis of Alkylboranes 353

[ A MECHANISM FOR THE REACTION ]

8.9

The Chemistry of… Hydrogenation in the Food

351

8.12	Stereospecific Reactions 363

324

[ The stereochemistry of the Reaction ]
[ WHY DO THESE TOPICS MATTER? ]

326

Addition of Bromine to cis- and trans-2-Butene

364

8.13 Halohydrin Formation 364

8

Halohydrin

[ A MECHANISM FOR THE REACTION ]

Formation from an Alkene 365

Alkenes and
Alkynes II

The Chemistry of… Citrus-Flavored Soft Drinks

366

8.14 Divalent Carbon Compounds: Carbenes 366

Addition
Reactions  337

8.15	Oxidation of Alkenes: Syn 1,2-Dihydroxylation 368

8.1	Addition Reactions of Alkenes 338

The Chemistry of… Catalytic Asymmetric

8.2	Electrophilic Addition of Hydrogen Halides to
Alkenes: Mechanism and Markovnikov’s Rule 340
[ A MECHANISM FOR THE REACTION ]

Addition of a

Hydrogen Halide to an Alkene 341
[ A MECHANISM FOR THE REACTION ]

to 2-Methylpropene

Dihydroxylation 370
8.16 Oxidative Cleavage of Alkenes 371
an Alkene

Addition of HBr

343

8.3	Stereochemistry of the Ionic Addition to an Alkene 345
[ The stereochemistry of the Reaction ]

Ionic

Ozonolysis of

[ A MECHANISM FOR THE REACTION ]

373

8.17	Electrophilic Addition of Bromine
and Chlorine to Alkynes 374
8.18	Addition of Hydrogen Halides to
Alkynes 374

Addition to an Alkene 345

8.19 Oxidative Cleavage of Alkynes 375

8.4	Addition of Water to Alkenes: Acid-Catalyzed
Hydration 346

8.20 H
 ow to Plan a Synthesis: Some Approaches
and Examples 376

[ A MECHANISM FOR THE REACTION ]

Hydration of an Alkene 346

Acid-Catalyzed

[ WHY DO THESE TOPICS MATTER? ]

381

vii

9

Nuclear Magnetic
Resonance and
Mass Spectrometry

10.3

Reactions of Alkanes with Halogens 454

Radical

[ A MECHANISM FOR THE REACTION ]

Chlorination of Methane 456
10.5

Introduction 392

Halogenation of Higher Alkanes 459
Radical

[ A MECHANISM FOR THE REACTION ]

9.2	Nuclear Magnetic Resonance (NMR)
Spectroscopy 392
9.3

Homolytic Bond Dissociation Energies (DH °) 451

10.4	Chlorination of Methane: Mechanism of
Reaction 456

Tools for Structure
Determination  391
9.1

10.2

Halogenation of Ethane 459
10.6

How To Interpret Proton NMR Spectra

398

9.4	Shielding and Deshielding of Protons: More about
Chemical Shift 401
9.5	Chemical Shift Equivalent and Nonequivalent
Protons 403

The Geometry of Alkyl Radicals 462

10.7	Reactions that Generate Tetrahedral Chirality
Centers 462
The
Stereochemistry of Chlorination at C2 of Pentane 463

[ A MECHANISM FOR THE REACTION ]

The

[ A MECHANISM FOR THE REACTION ]

9.6	Spin–Spin Coupling: More about Signal Splitting and
Nonequivalent or Equivalent Protons 407

Stereochemistry of Chlorination at C3 of
(S)-2-Chloropentane 464

9.7

Proton NMR Spectra and Rate Processes 412

10.8

Allylic Substitution and Allylic Radicals 466

9.8

Carbon-13 NMR Spectroscopy 414

10.9

Benzylic Substitution and Benzylic Radicals 469

9.9

Two-Dimensional (2D) NMR Techniques 420

10.10	Radical Addition to Alkenes: The Anti-Markovnikov
­Addition of Hydrogen Bromide 472

The Chemistry of… Magnetic Resonance Imaging in

Medicine

423

Anti-

[ A MECHANISM FOR THE REACTION ]

9.10 An Introduction to Mass Spectrometry 423

Markovnikov Addition of HBr 472

9.11 Formation of Ions: Electron Impact Ionization 424

10.11	Radical Polymerization of Alkenes:
Chain-Growth Polymers 474

9.12 Depicting the Molecular Ion 424

Radical

[ A MECHANISM FOR THE REACTION ]

9.13 Fragmentation 425

Polymerization of Ethene (Ethylene) 475

9.14 Isotopes in Mass Spectra 432

10.12 Other Important Radical Reactions 478

9.15 GC/MS Analysis

The Chemistry of… Antioxidants

435

480

9.16 Mass Spectrometry of Biomolecules 436

The Chemistry of… Ozone Depletion and

[ WHY DO THESE TOPICS MATTER? ]

Chlorofluorocarbons (CFCs) 481

436

See Special Topic B, NMR Theory and Instrumentation,
in WileyPLUS

[ WHY DO THESE TOPICS MATTER? ]

10

11

10.1	Introduction: How Radicals Form
and How They React 449

Synthesis and
Reactions  489

[ A MECHANISM FOR THE REACTION ]

Hydrogen Atom Abstraction 450
Radical Addition

to a π Bond 450
The Chemistry of… Acne Medications

viii

See Special Topic C, Chain-Growth Polymers, in WileyPLUS

Alcohols and
Ethers

Radical Reactions

[ A MECHANISM FOR THE REACTION ]

482

450

11.1	Structure and
Nomenclature 490
11.2

Physical Properties of Alcohols and Ethers 492

11.3

Important Alcohols and Ethers 494

The Chemistry of… Ethanol as a Biofuel

495

The Chemistry of… Cholesterol and Heart

Disease

496

11.4

Synthesis of Alcohols from Alkenes 496

11.5

Reactions of Alcohols 498

11.6

Alcohols as Acids 500

11.7

Conversion of Alcohols into Alkyl Halides 501

11.8	Alkyl Halides from the Reaction of Alcohols with
­Hydrogen Halides 501
11.9	Alkyl Halides from the Reaction of Alcohols
with PBr3 or SOCl2 504
11.10	Tosylates, Mesylates, and Triflates: Leaving Group
­Derivatives of Alcohols 505
[ A MECHANISM FOR THE REACTION ]

Conversion of an Alcohol into a Mesylate (an Alkyl
Methanesulfonate) 507
11.11 Synthesis of Ethers 507
Intermolecular
Dehydration of A
­ lcohols to Form an Ether 508
[ A MECHANISM FOR THE REACTION ]
[ A MECHANISM FOR THE REACTION ]

Ether Synthesis

The Williamson

509

by Strong Acids

Ether Cleavage

513

11.13 Epoxides 514
[ A MECHANISM FOR THE REACTION ]

Epoxidation

Alkene

515
515

11.14 Reactions of Epoxides 516
[ A MECHANISM FOR THE REACTION ]

Acid-Catalyzed

Ring Opening of an Epoxide 516
[ A MECHANISM FOR THE REACTION ]

Base-Catalyzed

Ring Opening of an Epoxide 517
11.15	Anti 1,2-Dihydroxylation of Alkenes via
Epoxides 519
The Chemistry of… Environmentally Friendly Alkene

Oxidation Methods
11.16 Crown Ethers

521
522

The Chemistry of… Transport Antibiotics and Crown

Ethers

Oxidation–Reduction
and ­O rganometallic
Compounds  534

12.1	Structure of the Carbonyl Group 535

523

PHOTO CREDIT: FSTOP/Image Source Limited

12.2	Oxidation–Reduction Reactions in Organic
­Chemistry 536
12.3	Alcohols by Reduction of Carbonyl Compounds 537
Reduction of
Aldehydes and Ketones by Hydride Transfer 539

[ A MECHANISM FOR THE REACTION ]

The Chemistry of… Alcohol Dehydrogenase—

A Biochemical Hydride Reagent 539
The Chemistry of… Stereoselective Reductions of

Carbonyl Groups 541
12.4

Oxidation of Alcohols 542
The Swern

[ A MECHANISM FOR THE REACTION ]

Oxidation

543
Chromic Acid

[ A MECHANISM FOR THE REACTION ]

12.5

545

Organometallic Compounds 547

12.6	Preparation of Organolithium and
­Organomagnesium Compounds 548
12.7	Reactions of Organolithium
and Organomagnesium Compounds 549
The Grignard

[ A MECHANISM FOR THE REACTION ]

The Chemistry of… The Sharpless Asymmetric

Epoxidation

Alcohols from
Carbonyl Compounds

Oxidation

11.12 Reactions of Ethers 513
[ A MECHANISM FOR THE REACTION ]

12

Reaction

552

12.8

Alcohols from Grignard Reagents 552

12.9

Protecting Groups

561

[ WHY DO THESE TOPICS MATTER? ]

562

See First Review Problem SET in WileyPLUS

13

Conjugated
Unsaturated
Systems
13.1

Introduction 573
PHOTO CREDIT: (house plant) Media Bakery; (carrot) Image Source; (blue jeans) Media Bakery

13.2	The Stability of the Allyl Radical 573

11.17	Summary of Reactions of Alkenes, Alcohols,
and Ethers 523

13.3

The Allyl Cation 577

13.4

Resonance Theory Revisited 578

[ WHY DO THESE TOPICS MATTER? ]

13.5	Alkadienes and Polyunsaturated Hydrocarbons 582

525

ix

13.6

1,3-Butadiene: Electron Delocalization 583

15.3

13.7

The Stability of Conjugated Dienes 586

[ A MECHANISM FOR THE REACTION ]

13.8	Ultraviolet–Visible Spectroscopy 587
13.9	Electrophilic Attack on Conjugated Dienes:
1,4-Addition 595
13.10	The Diels–Alder Reaction: A 1,4-Cycloaddition ­
Reaction of Dienes 599

Halogenation of Benzene 664

Aromatic Bromination
15.4

Nitration of Benzene 665

[ A MECHANISM FOR THE REACTION ]

Benzene
15.5

Sulfonation of Benzene 666

[ A MECHANISM FOR THE REACTION ]

Their Synthetic Lineage 608

Benzene
608

Friedel–Crafts

668

[ A MECHANISM FOR THE REACTION ]

Acylation

The Discovery of Benzene 618

14.2

Nomenclature of Benzene Derivatives 619

14.3

Reactions of Benzene 621

14.4

The Kekulé Structure for Benzene 622

14.5

The Thermodynamic Stability of Benzene 623

14.6

Modern Theories of the Structure of Benzene 625

14.7

Hückel’s Rule: The 4n + 2 π Electron Rule 628

14.8

Other Aromatic Compounds 636

Heterocyclic Aromatic Compounds 639

The Chemistry of… Aryl Halides: Their Uses and

Environmental Concerns 643
14.11 Spectroscopy of Aromatic Compounds 644
The Chemistry of… Sunscreens (Catching the Sun’s

Rays and What ­Happens to Them) 648
[ WHY DO THESE TOPICS MATTER? ]

669

Friedel–Crafts

671

15.7	Synthetic Applications of Friedel–Crafts A
­ cylations:
The Clemmensen and
Wolff–Kishner ­Reductions 673
The Chemistry of… DDT

676

15.8	Existing Substituents Direct the Position of
Electrophilic Aromatic Substitution 677
15.9	Activating and Deactivating Effects: How
Electron-­Donating and Electron-Withdrawing
Groups Affect the Rate of an EAS Reaction 684
15.10 Directing Effects in Disubstituted Benzenes 685

639

14.10 Aromatic Compounds in Biochemistry 641

649

See Special Topic D, Electrocyclic and Cycloaddition
Reactions, in WileyPLUS

15

Reactions
of Aromatic
Compounds
Electrophilic Aromatic Substitution Reactions 661

15.2	A General Mechanism for Electrophilic
Aromatic Substitution 662

x

668

The Chemistry of… Industrial Styrene Synthesis

14.1

15.1

Friedel–Crafts Reactions

Alkylation

Aromatic
Compounds

14.9

Sulfonation of

667

[ A MECHANISM FOR THE REACTION ]

14

The Chemistry of… Nanotubes

15.6

Nitration of

666

The Chemistry of… Molecules with the Nobel Prize in

[ WHY DO THESE TOPICS MATTER? ]

Electrophilic

664

15.11	Reactions of Benzene Ring Carbon Side
Chains 686
15.12 Synthetic Strategies 689
15.13	The SNAr Mechanism: Nucleophilic Aromatic
­Substitution by Addition-Elimination 691
[ A MECHANISM FOR THE REACTION ]

Mechanism

The SNAr

692

The Chemistry of… Bacterial Dehalogenation of a PCB

Derivative 693
15.14	Benzyne: Nucleophilic Aromatic Substitution
by ­Elimination–Addition 694
[ A MECHANISM FOR THE REACTION ]

Elimination–Addition Mechanism

The Benzyne

694

The Chemistry of… Host–Guest Trapping of

Benzyne 697
15.15 Reduction of Aromatic Compounds 697
[ A MECHANISM FOR THE REACTION ]

Reduction

Birch

698

[ WHY DO THESE TOPICS MATTER? ]

699

16

16.10 The Addition of Ylides: The Wittig Reaction 737
Reaction

16.1

Introduction

16.2

Nomenclature of Aldehydes and Ketones 712

16.3

Physical Properties 714

712

The Chemistry of… Aldehydes and Ketones in

16.4

715

16.12 The Baeyer–Villiger Oxidation 741
[ A MECHANISM FOR THE REACTION ]

Villiger Oxidation

The Baeyer–

742

16.13	Chemical Analyses for Aldehydes and
Ketones 743
16.14	Spectroscopic Properties of Aldehydes and
Ketones 743
16.15	S ummary of Aldehyde and Ketone Addition
Reactions 746

Synthesis of Aldehydes 715

[ A MECHANISM FOR THE REACTION ]

739

16.11 Oxidation of Aldehydes 741

Nucleophilic
Addition to the C
­ arbonyl
Group  711

Perfumes

The Wittig

[ A MECHANISM FOR THE REACTION ]

Aldehydes and
Ketones

Reduction of

[ WHY DO THESE TOPICS MATTER? ]

Reduction of an

17

747

an Acyl Chloride to an Aldehyde 718
[ A MECHANISM FOR THE REACTION ]

Ester to an Aldehyde 719
[ A MECHANISM FOR THE REACTION ]

Reduction

of a Nitrile to an Aldehyde 719
16.5

Synthesis of Ketones 720

16.6	Nucleophilic Addition to the Carbon–Oxygen
Double Bond: Mechanistic Themes 723
Addition of a
Strong Nucleophile to an Aldehyde or Ketone 724

[ A MECHANISM FOR THE REACTION ]

Acid-Catalyzed
Nucleophilic Addition to an Aldehyde or Ketone 724

[ A MECHANISM FOR THE REACTION ]

16.7	The Addition of Alcohols: Hemiacetals and
Acetals 726
[ A MECHANISM FOR THE REACTION ]

Hemiacetal Formation

[ A MECHANISM FOR THE REACTION ]

Acetal Formation

Acid-Catalyzed

726
Acid-Catalyzed

728

16.8	The Addition of Primary and Secondary
Amines 731
[ A MECHANISM FOR THE REACTION ]

Formation

Imine

732

Enamine

734

The Chemistry of… A Very Versatile Vitamin, Pyridoxine

(Vitamin B6)

735

Formation

736

Introduction 762

17.2	Nomenclature and Physical Properties 762
17.3

Preparation of Carboxylic Acids 770

17.4	Acyl Substitution: Nucleophilic
Addition–Elimination at the Acyl Carbon 773
Acyl
Substitution by Nucleophilic Addition–Elimination 773

[ A MECHANISM FOR THE REACTION ]

17.5

Acyl Chlorides 775

Synthesis of
Acyl Chlorides Using Thionyl Chloride 776

[ A MECHANISM FOR THE REACTION ]

17.6

Carboxylic Acid Anhydrides 777

17.7

Esters

778

[ A MECHANISM FOR THE REACTION ]

Acid-Catalyzed

779
Base-Promoted

Hydrolysis of an Ester 782
17.8

Amides

784

[ A MECHANISM FOR THE REACTION ]

Amide Synthesis

DCC-Promoted

787

The Chemistry of… Some Hot Topics Related to

16.9	The Addition of Hydrogen Cyanide:
Cyanohydrins 736
[ A MECHANISM FOR THE REACTION ]

17.1

[ A MECHANISM FOR THE REACTION ]

The Wolff–Kishner Reduction 733
Formation

Nucleophilic Addition–
Elimination at the Acyl Carbon  761

Esterification

[ A MECHANISM FOR THE REACTION ]
[ A MECHANISM FOR THE REACTION ]

Carboxylic Acids
and Their Derivatives

Structure and Activity 787
Cyanohydrin

[ A MECHANISM FOR THE REACTION ]

Acidic

Hydrolysis of an Amide 789

xi

[ A MECHANISM FOR THE REACTION ]

of an Amide

Basic Hydrolysis

18.7	Synthesis of Substituted Acetic Acids:
The Malonic Ester Synthesis 830

Acidic

[ A MECHANISM FOR THE REACTION ]

Basic Hydrolysis

18.8	Further Reactions of Active Hydrogen
Compounds 833

789

[ A MECHANISM FOR THE REACTION ]

The Malonic
Ester Synthesis of Substituted Acetic Acids 830

Hydrolysis of a Nitrile 791
[ A MECHANISM FOR THE REACTION ]

of a Nitrile 791
The Chemistry of… Penicillins

17.9

18.9	Synthesis of Enamines: Stork Enamine
Reactions 834

792

Derivatives of Carbonic Acid 792

18.10 Summary of Enolate Chemistry 837

17.10	Decarboxylation of Carboxylic Acids 795

[ WHY DO THESE TOPICS MATTER? ]

17.11	P olyesters and Polyamides: Step-Growth
Polymers 797
17.12	Summary of the Reactions of Carboxylic Acids
and Their Derivatives 798
[ WHY DO THESE TOPICS MATTER? ]

19

802

See Special Topic E, Step-Growth Polymers, in WileyPLUS

18

Reactions at
the α Carbon
of Carbonyl
Compounds

19.1

[ A MECHANISM FOR THE REACTION ]

Keto and Enol Tautomers 813

18.3

Reactions via Enols and Enolates 815

Enolization

Base-Catalyzed

β-Dicarbonyl Compounds by Acylation
19.3	
of Ketone Enolates 855

Acid-Catalyzed

19.4	Aldol Reactions: Addition of Enolates
and Enols to Aldehydes and Ketones 856

816

[ A MECHANISM FOR THE REACTION ]

[ A MECHANISM FOR THE REACTION ]

Base-Promoted
Halogenation of Aldehydes and Ketones 817

Addition 857

Acid-Catalyzed
Halogenation of Aldehydes and Ketones 818

the Aldol Addition Product 858

[ A MECHANISM FOR THE REACTION ]

Reaction

The Haloform

819

The Chemistry of… Chloroform in Drinking Water

[ A MECHANISM FOR THE REACTION ]
[ A MECHANISM FOR THE REACTION ]

Dehydration of
An Acid-

The Chemistry of… A Retro-Aldol Reaction in

819

Glycolysis—Dividing Assets to Double the ATP Yield 860
Crossed Aldol Condensations 861

Lithium Enolates 821

19.5

18.5

Enolates of β-Dicarbonyl Compounds 824

[ A MECHANISM FOR THE REACTION ]

18.6	Synthesis of Methyl Ketones:
The Acetoacetic Ester Synthesis 825

The Aldol

Catalyzed Aldol Condensation 858

18.4

xii

The Dieckmann

Condensation 853

815

[ A MECHANISM FOR THE REACTION ]

The Claisen

Condensation 851
[ A MECHANISM FOR THE REACTION ]

18.2

[ A MECHANISM FOR THE REACTION ]

Introduction 850

19.2	The Claisen Condensation: A Synthesis
of β-Keto Esters 850

18.1	The Acidity of the α Hydrogens of Carbonyl
­Compounds: Enolate Anions 812

Enolization

Condensation
and Conjugate
Addition
Reactions of
Carbonyl Compounds

More Chemistry of Enolates  849

Enols and Enolates  811

[ A MECHANISM FOR THE REACTION ]

838

A Directed Aldol

Synthesis Using a Lithium Enolate 865
19.6

Cyclizations via Aldol Condensations 867

[ A MECHANISM FOR THE REACTION ]

Cyclization

20.8

The Aldol

867

­ hlorides 919
20.9	Reactions of Amines with Sulfonyl C

The Chemistry of… Polyketide Anticancer Antibiotic

Biosynthesis

The Chemistry of… Essential Nutrients and

868

Antimetabolites 920

19.7	Additions to α,β-Unsaturated Aldehydes and
Ketones 869
[ A MECHANISM FOR THE REACTION ]

20.10 Synthesis of Sulfa Drugs 921

The Conjugate

Addition of HCN 870
[ A MECHANISM FOR THE REACTION ]

The Conjugate

Addition of an Amine 871
[ A MECHANISM FOR THE REACTION ]

Addition

The Michael

19.8

The Mannich
875

Summary of Important Reactions 876

[ WHY DO THESE TOPICS MATTER? ]

877

See Special TopicS F, Thiols, Sulfur Ylides, and Disulfides,
and G, Thiol Esters and Lipid Biosynthesis, in WileyPLUS

20

Amines

The Chemistry of… Biologically Important Amines

899

Preparation of Amines 901

[ A MECHANISM FOR THE REACTION ]

Reductive

904

Promoters of Key Bond-Forming
Reactions  938
21.1	Organometallic Compounds in Previous
Chapters 939
21.2

Transition Metal Elements and Complexes 939

21.3

How to Count Electrons in a Metal Complex

The Chemistry of… Homogeneous Asymmetric

­ xamples Involving l-DOPA,
Catalytic Hydrogenation: E
(S)-Naproxen, and Aspartame 946

The Hofmann

908

Cross-Coupling Reactions 947

[ A MECHANISM FOR THE REACTION ] The Heck–
Mizoroki Reaction Using an Aryl Halide Substrate 948

20.5

Reactions of Amines 909

The Chemistry of… The Wacker Oxidation

20.6

Reactions of Amines with Nitrous Acid 911

The Chemistry of… Complex Cross Couplings

21.7

[ A MECHANISM FOR THE REACTION ]

Diazotization

912

The Chemistry of… N -Nitrosoamines

940

[ A MECHANISM FOR THE REACTION ] Homogeneous
Hydrogenation Using Wilkinson’s Catalyst 945

21.6

[ A MECHANISM FOR THE REACTION ]

Rearrangement

Transition
Metal
Complexes

21.5	Homogeneous Hydrogenation: Wilkinson’s
Catalyst 944

PHOTO CREDIT: © Eric Isselée/iStockphoto

Basicity of Amines: Amine Salts 894

Amination

21

21.4	Mechanistic Steps in the Reactions of Some
Transition Metal Complexes 942

Nomenclature 891

20.2	Physical Properties and Structure
of Amines 892

20.4

927

See Special Topic H, Alkaloids, in WileyPLUS

874

The Chemistry of… A Suicide Enzyme Substrate

20.3

­ eactions of
20.13	Summary of Preparations and R
Amines 924

The Mannich Reaction 874

[ A MECHANISM FOR THE REACTION ]

20.1

20.12	Eliminations Involving Ammonium
Compounds 923

873

Reaction

19.9

20.11 Analysis of Amines 921

[ WHY DO THESE TOPICS MATTER? ]

871

The Chemistry of… Conjugate Additions to Activate

Drugs

Coupling Reactions of Arenediazonium Salts 917

Olefin Metathesis

20.7	Replacement Reactions of Arenediazonium
Salts 913

Metathesis Reaction

952

955

[ A MECHANISM FOR THE REACTION ]

912

950

The Olefin

955

The Chemistry of… Organic Chemistry Alchemy:

­ lkenes into “Gold” 957
Turning Simple A

xiii

21.8	Transition Metals in Nature: Vitamin B12 and
Vanadium Haloperoxidases 958
[ WHY DO THESE TOPICS MATTER? ]

959

See Second Review Problem SET in WileyPLUS

23

Lipids
23.1

Introduction 1012

23.2	Fatty Acids and
Triacylglycerols 1012

22

The Chemistry of… Olestra and Other Fat

Carbohydrates

Substitutes 1016

22.1

Introduction

966

22.2

Monosaccharides 968

22.3

Mutarotation 973

The Chemistry of… Self-Assembled Monolayers—Lipids
in Materials Science and Bioengineering 1020

22.4

Glycoside Formation 974

23.3

The Chemistry of… Poison Ivy

Formation of a

[ A MECHANISM FOR THE REACTION ]

Glycoside

Hydrolysis of a

975

The Chemistry of… The Bombardier Beetle’s Noxious

23.4

Steroids 1026

The Chemistry of… The Enzyme Aromatase

22.5

Other Reactions of Monosaccharides 976

22.6

Oxidation Reactions of Monosaccharides 979

22.7

Reduction of Monosaccharides: Alditols 984

22.8	Reactions of Monosaccharides with
Phenylhydrazine: Osazones 984
Phenylosazone

[ A MECHANISM FOR THE REACTION ]

Formation

Terpenes and Terpenoids 1021

Spray 1025

974

[ A MECHANISM FOR THE REACTION ]

Glycoside

1019

985

1031

23.5

Prostaglandins

23.6

Phospholipids and Cell Membranes 1036

1035

The Chemistry of… STEALTH® Liposomes for Drug

Delivery 1039
23.7

Waxes

1040

[ WHY DO THESE TOPICS MATTER? ]

1040

22.9	Synthesis and Degradation of Monosaccharides 986
22.10 The

d

Family of Aldoses 988

22.11	F ischer’s Proof of the Configuration of
d -(+)-Glucose
988
22.12 Disaccharides

990

24

Amino Acids and
Proteins

The Chemistry of… Artificial Sweeteners

24.1

Introduction 1046

(How Sweet It Is) 993

24.2

Amino Acids 1047

24.3

Synthesis of α-Amino Acids 1053

22.13 Polysaccharides

994

22.14 Other Biologically Important Sugars 998
22.15 Sugars that Contain Nitrogen 999
­ urface:
22.16	Glycolipids and Glycoproteins of the Cell S
Cell Recognition and the Immune System 1001
The Chemistry of… Patroling Leukocytes and Sialyl

Lewisx Acids

1002

22.17 Carbohydrate Antibiotics

[ A MECHANISM FOR THE REACTION ] Formation of an
α-Aminonitrile ­during the Strecker Synthesis 1054

24.4

Polypeptides and Proteins 1055

24.5	Primary Structure of Polypeptides and
Proteins 1058
24.6	Examples of Polypeptide and Protein Primary
Structure 1062

1003

22.18 Summary of Reactions of Carbohydrates 1004

The Chemistry of… Sickle-Cell Anemia

[ WHY DO THESE TOPICS MATTER? ]

24.7

xiv

1004

1064

Polypeptide and Protein Synthesis 1065

24.8

Secondary, Tertiary, and Quaternary Structures
of Proteins 1071

24.9

Introduction to Enzymes 1075

25.4

Deoxyribonucleic Acid: DNA 1098

25.5

RNA and Protein Synthesis 1105

25.6

Determining the Base Sequence of DNA:
The Chain-Terminating (Dideoxynucleotide)
Method 1113

25.7

Laboratory Synthesis of Oligonucleotides 1116

25.8

Polymerase Chain Reaction 1118

25.9

Sequencing of the Human Genome: An Instruction
Book for the Molecules of Life 1120

24.10 Lysozyme: Mode of Action of an Enzyme 1077
The ChemiSTry oF… Carbonic Anhydrase: Shuttling the

Protons

1079

24.11 Serine Proteases

1079

24.12 Hemoglobin: A Conjugated Protein 1081
The ChemiSTry oF… Some Catalytic Antibodies

1081

[ WHY DO THESE TOPICS MATTER? ]

24.13 Purification and Analysis of Polypeptides and
Proteins 1083

GloSSary

24.14 Proteomics

index

1085

[ WHY DO THESE TOPICS MATTER? ]

1087

1121

Gl-1

i-1

anSWerS To SeleCTed ProBlemS can be found at
www.wiley.com/college/solomons
eula

25

Nucleic Acids
and Protein
Synthesis
25.1

Introduction

1091

25.2

Nucleotides and Nucleosides 1092

25.3

Laboratory Synthesis of Nucleosides
and Nucleotides 1095

xv

Preface
“It’s Organic Chemistry!”
That’s what we want students to exclaim after they become acquainted with our subject. Our
lives revolve around organic chemistry, whether we all realize it or not. When we understand
organic chemistry, we see how life itself would be impossible without it, how the quality of our
lives depends upon it, and how examples of organic chemistry leap out at us from every direction.
That’s why we can envision students enthusiastically exclaiming “It’s organic chemistry!” when,
perhaps, they explain to a friend or family member how one central theme—organic chemistry—
pervades our existence. We want to help students experience the excitement of seeing the world
through an organic lens, and how the unifying and simplifying nature of organic chemistry helps
make many things in nature comprehensible.
Our book makes it possible for students to learn organic chemistry well and to see the marvelous ways that organic chemistry touches our lives on a daily basis. Our book helps students develop
their skills in critical thinking, problem solving, and analysis—skills that are so important in
today’s world, no matter what career paths they choose. The richness of organic chemistry lends
itself to solutions for our time, from the fields of health care, to energy, sustainability, and the
environment. After all, it’s organic chemistry!
Energized by the power of organic chemistry and the goals of making our book an even more
efficient and relevant tool for learning, we have made a number of important changes in this edition.

New To This Edition....
We share the same goals and motivations as our colleagues in wanting to give students the best
experience that they can have in organic chemistry. We also share the challenges of deciding what
students need to know and how the material should be organized. In that spirit, our reviewers and
adopters have helped guide a number of the changes that we have made in this edition.
Simultaneously achieving efficiency and adding breadth We have redistributed and

streamlined material from our old Chapter 21 about phenols, aryl halides, aryl ethers, benzyne,
and nucleophilic aromatic substitution in a way that eliminates redundancy and places it in the
context of other relevant material earlier in the book. At the same time, we wanted to update and
add breadth to our book by creating a new Chapter 21, Transition Metal Complexes about transition
metal organometallic compounds and their uses in organic synthesis. Previously, transformations
like the Heck-Mizoroki, Suzuki-Miyaura, Stille, Sonogashira, and olefin metathesis reactions had
only been part of a special topic in our book, but as the exposure of undergraduates to these processes has become more widespread, we felt it essential to offer instructors a chapter that they could
incorporate into their course if they wished. Streamlining and redistributing the content in our old
Chapter 21 allowed us to do this, and we thank our reviewers for helping to prompt this change.

Transition metal organometallic complexes: Promoters of key bond-forming reactions Our new Chapter 21 brings students a well-rounded and manageable introduction to transition

metal organometallic complexes and their use in organic synthesis. We begin the chapter with an introduction to the structure and common mechanistic steps of reactions involving transition metal organometallic compounds. We then introduce the essentials of important cross-coupling reactions such as the
Heck-Mizoroki, Suzuki-Miyaura, Stille, Sonogashira, ­dialkylcuprate (Gilman), and olefin metathesis
reactions at a level that is practical and useful for undergraduates. We intentionally organized the chapter so that instructors could move directly to the practical applications of these important reactions if
they desire, skipping general background information on transition metal complexes if they wished.

Aromatic efficiency Our coverage of aromatic substitution reactions (Chapter 15) has been
refocused by making our presentation of electrophilic aromatic substation more efficient at
the same time as we included topics of nucleophilic aromatic substation and benzyne that had

xvi

­ reviously been in Chapter 21. Now all types of aromatic substitution reactions are combined in
p
one chapter, with an enhanced flow that is exactly the same length as the old chapter solely on
electrophilic aromatic reactions.
A focus on the practicalities of spectroscopy Students in an introductory organic

chemistry course need to know how to use spectroscopic data to explore structure more than they
need to understand the theoretical underpinnings of spectroscopy. To that end, we have shortened
Chapter 9, Nuclear Magnetic Resonance by placing aspects of NMR instrumentation and theory in
a new special topic that is a standalone option for instructors and students. At the same time, we
maintain our emphasis on using spectroscopy to probe structure by continuing to introduce IR in
Chapter 2, Families of Carbon Compounds: Functional Groups, Intermolecular Forces, and Infrared
(IR) Spectroscopy, where students can learn to easily correlate functional groups with their respective
infrared signatures and use IR data for problems in subsequent chapters.

Organizing nucleophilic substitution and elimination topics Some instructors find

it pedagogically advantageous to present and assess their students’ knowledge of nucleophilic
substitution reactions before they discuss elimination reactions. Following the advice of some
reviewers, we have adjusted the transition between Chapters 6, Nucleophilic Reactions: Properties
and Substitution Reactions of Alkyl Halides and 7, Alkenes and Alkynes I: Properties and Synthesis ;
Elimiantion Reactions of Alkyl Halides so that an instructor can pause cleanly after Chapter 6 to give
an assessment on substitution, or flow directly into Chapter 7 on elimination reactions if they wish.

Synthesizing the Material The double entendre in the name of our new Synthesizing the

Material problems is not lost in the ether. In this new group of problems, found at the end
8.2 ElEctrophilic Addition of hydrogEn hAlidEs to AlkEnEs
343
of Chapters 6-21, students are presented with either multistep synthetic transformations and
Figure 8.2 Free-energy diagrams
unknown products, or target
must deduce by retrosynthetic
Br δ molecules whose precursors they
for the addition of HBr to propene.
∆G (2°) is less than ∆G (1°).
Hδ
analysis. Problems in our Synthesizing
the Material groups often
call upon reagents and transforCH CH CH
This transition
mations covered
in prior chapters.
Thus,+ while students work on synthesizing a chemical material,
state resembles
δ
CH CH CH
a 1° carbocation.
they are also synthesizing
knowledge.
δ
+ Br
−

‡

‡

+

δ+

3

2

Free energy

Br −

δ+

This transition
state resembles
a 2° carbocation.

CH3CH

H +

3

2
−

2

CH2

+
CH3CHCH3
+ Br−

Ongoing Pedagogical Strengths
CH3CH CH2
+
HBr

Mechanisms: Showing
How
Reactions Work
Student success in organic chemistry
𝚫G (2°)
𝚫
G (1°)
CH CH CH Br
hinges on understanding mechanisms. We do all that we can to insure that our mechanism boxes
CH CHBrCH
contain every detail needed Reaction
to help
students learn
and understand how reactions work. Over the
coordinate
years reviewers
that
book
excels(andinultimately
depicting
clear and accurate mechanisms. This
reactionsaid
leading
to theour
secondary
carbocation
to 2-bromo• Thehave
propane) has the lower freethenergy of activation. This is reasonable because its
continues to be
truestate
inresembles
our 12the more
edition,
and it is now augmented by animated mechanism videos
transition
stable carbocation.
the primary carbocation
(and ultimately
to 1-bromopropane) approach when introducing new
• The reaction leading
found in WileyPLUS
withtoORION.
We also
use a mechanistic
has a higher free energy of activation because its transition state resembles a less stable
primary
carbocation.
This
second
reaction
is
much
slower
and
does not compete
reaction types so that students can understand the generalities
and appreciate common themes. For
appreciably with the first reaction.
example, ourThechapters
onwithcarbonyl
chemistry
organized according to the mechanistic themes
2-methylpropene
produces onlyare
2-bromo-2-methylpropane,
reaction of HBr
for the same reason regarding carbocations stability. Here, in the first step (i.e., the attachof nucleophilic
and reactivity
the α-carbon, Mechanistic themes are
ment of addition,
the proton) the acyl
choice substitution,
is even more pronounced—between
a tertiaryat
carbocation and a primary carbocation. Thus, 1-bromo-2-methylpropane is not obtained as a
also emphasized
regarding
alkene
addition
reactions,
oxidation
and reduction, and electrophilic
product of the reaction because its formation would require the formation of a primary
carbocation. Such a reaction would have a much higher free energy of activation than that
aromatic substitution.
leading to a tertiary carbocation.
‡

‡

3

3

2

2

3

• Rearrangements invariably occur when the carbocation initially formed by addition

[

of HX to an alkene can rearrange to a more stable one (see Section 7.11 and Practice
Problem 8.3).

A MechAnisM for the reAction

Addition of HBr to 2-Methylpropene

[

This reaction takes place:

H3C

CH3

H3C
C

C—CH2—H

CH2

H3C

H

+

Br

H3C

Br

CH3

−

3° Carbocation
(more stable carbocation)

C

Major

CH3 product

Br
2-Bromo-2-methylpropane

A Mechanism for the
Reaction Stepped out reactions with just the right amount
of detail provide the tools for students to understand rather than
memorize reaction mechanisms.

This reaction does not occur to any appreciable extent:

CH3

H3C

C
H3C

Br

CH2

CH3

C
H

H

CH3

+

CH3

CH2

Br

−

1° Carbocation
(less stable carbocation)

C

CH2

Br

Little
formed

H
1-Bromo-2-methylpropane

xvii
solom_c08_337-390v3.0.2.indd 343

29/10/15 11:10 am

• Carbon atoms that are electron poor because of bond polarity, but are not carbocations, can also be electrophiles. They can react with the electron-rich centers
of Lewis bases in reactions such as the following:
B

−

δ+

+

C

O

δ−

B

C

−

O

Lewis acid
(electrophile)

Lewis
base

Cementing knowledge
by working
problems:
As athletes
Carbanions
are Lewis bases.
Carbanions seek
a proton orand
some musicians
other positiveknow,
center pracwhich is
they
can donate
their electron
pair and thereby
neutralize
theirtonegative
tice makes perfect. Thetosame
true
with organic
chemistry.
Students
need
workcharge.
all kinds of
When a Lewis base seeks a positive center other than a proton, especially that of a carbon
problems to learn chemistry.
Our
book
has
over
1400
in-text
problems
that
students
can use to
atom, chemists call it a nucleophile (meaning nucleus loving; the nucleo- part of the name
comes
from Problems
nucleus, the positive
center of anlearn
atom).where to begin. Practice Problems
cement their knowledge.
Solved
help students
nucleophile
a Lewis base that
seeks a positive
center
such
as a positively
• Aand
help them hone their skills
commitis knowledge
to memory.
Many
more
problems
at the end
charged carbon atom.
each chapter help students reinforce their learning, focus on specific areas of content, and assess
Since electrophiles are also Lewis acids (electron pair acceptors) and nucleophiles are
their overall skill level with
material.
Learning
Group
in
Lewis that
bases chapter’s
(electron pair
donors), why
do chemists
haveProblems
two terms engage
for them?students
The
answer
that Lewis acid
and throughout
Lewis base are terms
that are used
when
synthesizing information
andis concepts
from
a chapter
andgenerally,
can bebut
used
toone
facilitate
or the other reacts to form a bond to a carbon atom, we usually call it an electrophile or
collaborative learning in
small groups, or serve as a culminating activity that demonstrates stua nucleophile.
dent mastery over an integrated set of principles. Supplementary
material provided
to instructors
δ−
δ+
−
−
Nu
+
C of
O learningNu
C OHundreds more online
includes suggestions about how to orchestrate
the use
groups.
problems are available through WileyPLUS
with Electrophile
ORION, to help students target their learning
Nucleophile
and achieve mastery. Instructors can flip their classroom by doing in-class problem solving using
+
−
Learning Group Problems, clicker questions,
and other
problems, while
allowing our textbook
+
Nu
C Nu
C
and tutorial resources in WileyPlus to provide out of class learning.
Electrophile

SOLVED PROBLEMS
model problem solving
strategies.
PRACTICE
PROBLEMS provides
opportunities to check
progress.

Nucleophile

Solved Problem 3.3

Identify the electrophile and the nucleophile in the following reaction, and add curved arrows to indicate the flow of
electrons for the bond-forming and bond-breaking steps.
O

O
H

−

+

C

−

H

N

N

3.5 the stRength of BRønsted–lowRy Acids And BAses: K a And pK a

113

STRATEgy AND ANSWER: The aldehyde carbon is electrophilic due to the electronegativity of the carbonyl oxygen. The cyanide anion acts as a Lewis base and is the nucleophile, donating an electron pair to the carbonyl carbon, and
causing an electron pair to shift to the oxygen so that no atom has more than an octet of electrons.
c03AcidsandBases_PressOptimized.indd 112
O

δ−

O

25/08/15 6:32 pm

−

δ+

H

−

+

C

N

H
N

Use the curved-arrow notation to write the reaction that would take place between
(ch3)2nh and boron trifluoride. Identify the Lewis acid, Lewis base, nucleophile, and
electrophile and assign appropriate formal charges.

Practice Problem 3.4

Laying the foundation earlier, getting to the heart of the matter quickly: Certain

3.5
the
stRength
of
BRønsted–lowRy
Acids
tools
are absolutely
key to
success
in organic chemistry.
Among
And BAses: Ka And pKa

them is the ability to draw structural formulas quickly and correctly. In this edition, we help students learn these skills even sooner
Many
reactionsby
involve
the transfer
of a of
proton
by an acid–base
reaction.
An use curved arrows earlier in the
thanorganic
ever before
moving
coverage
structural
formulas
and the
important consideration, therefore, is the relative strengths of compounds that could
text
(Section
3.2).
We
have
woven
together
instruction
about
Lewis structures, covalent bonds,
potentially act as Brønsted–Lowry acids or bases in a reaction.
hclthat
and h
so
,
acetic
acid
is
a
much
weaker
In contrast
the strong acids,
such asso
and
dash to
structural
formulas,
students
build
their
skills
in these areas as a coherent unit,
2
4
acid. When acetic acid dissolves in water, the following reaction does not proceed to
using
organic
examples
that
include
alkanes,
alkenes,
alkynes,
and
alkyl halides. Similarly, Lewis
completion:
and Brønsted-Lowry acid-base chemistry is fundamental to student success. We present a streamO
O
lined and highly efficient route to student mastery of
these concepts in Chapter 3.
+
CH

C

OH

+ H 2O

CH

C

O−

+ H 3O

3
3
Increased emphasis
on multistep
synthesis: Critical thinking and analysis skills are key

to problem
Multistep
organic
synthesis
Experiments
showsolving
that in a and
0.1 Mlife.
solution
of acetic acid
at 25 °C
only aboutproblems
1% of the are perfectly suited to ­honing
acetic
acidskills.
molecules
transferring
protons to
water.
Therefore, acetic
this by
edition
we their
introduce
new
Synthesizing
theacid
Material problems at the end of
these
In ionize
is a weak acid. As we shall see next, acid strength is characterized in terms of acidity
Chapters
6-21.
These
problems
sharpen
students’
analytical
skills
in synthesis and retrosynthesis,
constant (Ka ) or pKa values.
and help them synthesize their knowledge by integrating chemical reactions that they have learned
throughout the course.

3.5A the Acidity constant, Ka

Because the reaction that occurs in an aqueous solution of acetic acid is an equilibrium,
we can describe it with an expression for the equilibrium constant (Keq):

xviii

Keq =

[h3o+][ch3co2−]
[ch3co2h][h2o]

For dilute aqueous solutions, the concentration of water is essentially constant (∼55.5 M),
so we can rewrite the expression for the equilibrium constant in terms of a new constant
(Ka) called the acidity constant:

A strong balance of synthetic methods Students need to learn methods of organic syn-

thesis that are useful, as environmentally friendly as possible, and that are placed in the best overall
contextual framework. As mentioned earlier, our new Chapter 21 gives mainstream coverage to
reactions that are now essential to practicing organic chemists – transitional metal organometallic
reactions. Other modern methods that we cover include the Jacobsen and Sharpless ­epoxidations
(in The Chemistry of… boxes). In the 11th edition we incorporated the Swern oxidation
(Section 12.4), long held as a useful oxidation method and one that provides a less toxic alternative
to chromate oxidations in some cases. We also restored coverage of the Wolff-Kishner reduction
(Section 16.8C) and the Baeyer-Villiger oxidation (Section 16.12), two methods whose importance
has been proven by the test of time. The chemistry of radical reactions was also refocused and
streamlined by reducing thermochemistry content and by centralizing the coverage of allylic and
benzylic radical substitutions (including NBS reactions) in Chapter 10.
“Why do these topics matter?” is a feature that bookends each chapter with a teaser in the
opener and a captivating example of organic chemistry in the closer. The chapter opener seeks to
whet the student’s appetite both for the core chemistry in that chapter as well as hint at a prize that
comes at the end of the chapter in the form of a “Why do these topics matter?” vignette. These closers consist of fascinating nuggets of organic chemistry that stem from research relating to medical,
environmental, and other aspects of organic chemistry in the world around us, as well as the history
of the science. They show the rich relevance of what students have learned to applications that have
direct bearing on our lives and wellbeing. For example, in Chapter 6, the opener talks about some of
the benefits and drawbacks of making substitutions in a recipe, and then compares such changes to
the nucleophilic displacement reactions that similarly allow chemists to change molecules and their
properties. The closer then shows how exactly such reactivity has enabled scientists to convert simple
table sugar into the artificial sweetener Splenda which is 600 times as sweet, but has no calories!
Key Ideas as Bullet Points The amount of content covered in organic chemistry can be over-

whelming to students. To help students focus on the most essential topics, key ideas are emphasized
as bullet points in every section. In preparing bullet points, we have distilled appropriate concepts
into simple declarative statements that convey core ideas accurately and clearly. No topic is ever
presented as a bullet point if its integrity would be diminished by oversimplification, however.

“How to” Sections Students need to master important skills to support their conceptual learn-

ing. “How to” Sections throughout the text give step-by-step instructions to guide students in
performing important tasks, such as using curved arrows, drawing chair conformations, planning
a Grignard synthesis, determining formal charges, writing Lewis structures, and using 13C and 1H
NMR spectra to determine structure.

The Chemistry of . . . Virtually every instructor has the goal of showing students how organic

chemistry relates to their field of study and to their everyday life experience. The authors assist
their colleagues in this goal by providing boxes titled “The Chemistry of . . .” that provide interesting and targeted examples that engage the student with chapter content.

Summary and Review Tools: At the end of each chapter, Summary and Review Tools

provide visually oriented roadmaps and frameworks that students can use to help organize and
assimilate concepts as they study and review chapter content. Intended to accommodate diverse
learning styles, these include Synthetic Connections, Concept Maps, thematic Mechanism
Review Summaries, and the detailed Mechanism for the Reaction boxes already mentioned. We
also provide Helpful Hints and richly annotated illustrations throughout the text.

Special Topics: Instructors and students can use our Special Topics to augment their coverage in a number of areas. 13C NMR can be introduced early in the course using the special topic
that comes after Chapter 4 on the structure of alkanes and cycloalkanes. Polymer chemistry, now
a required topic by the American Chemistry Society for certified bachelor degrees, can be covered
in more depth than already presented in Chapters 10 and 17 by using the special topics that follow these chapters. Our special topic on electrocyclic and cycloaddition reactions can be used to
augment students’ ­understanding of these reactions after their introduction to conjugated alkenes,

xix

the Diels-Alder ­reaction, and aromatic compounds in Chapters 13-15. In-depth coverage of some
topics in biosynthesis and natural products chemistry can be invoked using our special topics on
biosynthesis and alkaloids.

Organization­—An Emphasis on the
Fundamentals
So much of organic chemistry makes sense and can be generalized if students master and apply
a few fundamental concepts. Therein lays the beauty of organic chemistry. If students learn the
essential principles, they will see that memorization is not needed to succeed.
Most important is for students to have a solid understanding of structure—of hybridization
and geometry, steric hindrance, electronegativity, polarity, formal charges, and resonance —so that
they can make intuitive sense of mechanisms. It is with these topics that we begin in Chapter 1.
In Chapter 2 we introduce the families of functional groups—so that students have a platform
on which to apply these concepts. We also introduce intermolecular forces, and infrared (IR)
spectroscopy—a key tool for identifying functional groups. Throughout the book we include calculated models of molecular orbitals, electron density surfaces, and maps of electrostatic potential.
These models enhance students’ appreciation for the role of structure in properties and reactivity.
We begin our study of mechanisms in the context of acid-base chemistry in Chapter 3.
Acid-base reactions are fundamental to organic reactions, and they lend themselves to introducing
several important topics that students need early in the course: (1) curved arrow notation for illustrating mechanisms, (2) the relationship between free-energy changes and equilibrium constants,
and (3) the importance of inductive and resonance effects and of solvent effects.
In Chapter 3 we present the first of many “A Mechanism for the Reaction” boxes, using an
example that embodies both Brønsted-Lowry and Lewis acid-base principles. All throughout the
book, we use boxes like these to show the details of key reaction mechanisms. All of the Mechanism
for the Reaction boxes are listed in the Table of Contents so that students can easily refer to them
when desired.
A central theme of our approach is to emphasize the relationship between structure and
reactivity. This is why we choose an organization that combines the most useful features of a functional group approach with one based on reaction mechanisms. Our philosophy is to emphasize
mechanisms and fundamental principles, while giving students the anchor points of functional
groups to apply their mechanistic knowledge and intuition. The structural aspects of our approach
show students what organic chemistry is. Mechanistic aspects of our approach show students how
it works. And wherever an opportunity arises, we show them what it does in living systems and the
physical world around us.
In summary, our writing reflects the commitment we have as teachers to do the best we can to
help students learn organic chemistry and to see how they can apply their knowledge to improve
our world. The enduring features of our book have proven over the years to help students learn
organic chemistry. The changes in our 12th edition make organic chemistry even more accessible
and relevant. Students who use the in-text learning aids, work the problems, and take advantage of
the resources and practice available in WileyPLUS with ORION (our online teaching and learning
solution) will be assured of success in organic chemistry.

FOR ORGANIC CHEMISTRY

A Powerful Teaching and Learning Solution
WileyPLUS with ORION provides students with a personal, adaptive learning experience so they can
build their proficiency on topics and use their study time most effectively. WileyPLUS with ORION
helps students learn by working with them as their knowledge grows, by learning about them.

xx

New To WileyPLUS with ORION for Organic Chemistry, 12e

Hallmark review tools in the print version of Organic Chemistry such as Concept Maps and Summaries
of Reactions are also now interactive exercises that help students develop core skills and competencies

• N ew interactive Concept Map exercises
• N ew interactive Summary of Reactions exercises
• N ew interactive Mechanism Review exercises
• N ew video walkthroughs of key mechanisms

NEW INTERACTIVES: Interactive
versions of Concept Maps, Synthetic
Connections, and other review tools
help students test their knowledge and
develop core competencies.

begin

practice

Unique to ORION, students begin by taking a quick diagnostic for any chapter.
This will determine each student’s baseline proficiency on each topic in the chapter.
Students see their individual diagnostic report to help them decide what to do next
with the help of ORION’s recommendations.
For each topic, students can either Study, or Practice. Study directs the students
to the specific topic they choose in WileyPLUS, where they can read from the
e-textbook, or use the variety of relevant resources available there. Students can also
practice, using questions and feedback powered by ORION’s adaptive learn­ing
engine. Based on the results of their diagnostic and ongoing practice, ORION will
present students with questions appropriate for their current level of under­standing,
and will continuously adapt to each student, helping them build their proficiency.

ORION includes a number of reports and ongoing recommendations for students
to help them maintain their proficiency over time for each topic. Students can
easily access ORION from multiple places within WileyPLUS. It does not require
any additional registration, and there will not be any additional charge for students
maintain using this adaptive learning system.

xxi

Breadth and Depth in Available Assessments: Four unique vehicles for assessment are

available to instructors for creating online homework and quizzes and are designed to enable and
support problem-solving skill development and conceptual understanding

w i l e y P l u s a ss e ssm e n t

for organic chemistry

R eact i o n E x pl o rer

Meaningful practice with mechanisms and synthesis
(a ­database of over 100,000 algorithm-generated problems)

I n C hapter / E O C assess m e n t

90-100% of Review Problems and end of chapter
questions are coded for online assessment

C o n cept Mastery

Pre-built concept mastery assignments
(from A ­database of over 25,000 questions)

T est B a n k

Rich Testbank consisting of over 3,000 questions

Reaction Explorer A student’s ability to understand mechanisms and predict synthesis reactions
greatly impacts her/his level of success in the course. Reaction Explorer is an interactive system for
learning and practicing reactions, syntheses and mechanisms in organic chemistry with advanced
­ echanism diagrams.
support for the automatic generation of random problems and curved arrow m

Mechanism Explorer:
valuable practice with reactions
and mechanisms

Synthesis Explorer:
meaningful practice doing single
and multi-step synthesis

End of Chapter Problems. Approximately 90% of the end of chapter problems are included
in WileyPLUS with ORION. Many of the problems are algorithmic and feature structure
­drawing/assessment functionality using MarvinSketch, with immediate answer feedback and
video question assistance. A subset of these end of chapter problems is linked to Guided Online
­tutorials which are stepped-out problem-solving tutorials that walk the student through the
problem, offering individualized feedback at each step.
Prebuilt concept mastery assignments Students must continously practice and work

organic chemistry in order to master the concepts and skills presented in the course. Prebuilt concept mastery assignments offer students ample opportunities for practice, covering all the major
topics and concepts within an organic chemistry course. Each assignment is organized by topic and
features feedback for incorrect answers. These assignments are drawn from a unique database of
over 25,000 questions, over half of which require students to draw a structure using MarvinSketch.

xxii

What do students receive with
WileyPLUS with ORION?

•
•
•
•

 he complete digital textbook, saving students up to 60% off the cost of a printed text.
T
Question assistance, including links to relevant sections in the online digital textbook.
Immediate feedback and proof of progress, 24/7.
Integrated, multi-media resources that address your students’ unique learning styles, levels of
proficiency, and levels of preparation by providing multiple study paths and encourage more
active learning.

WileyPLUS with ORION Student resources
Chapter 0 General Chemistry Refresher. To ensure students have mastered the necessary

prerequisite content from general chemistry, and to eliminate the burden on instructors to review
this material in lecture, WileyPLUS with ORION now includes a complete chapter of core general
chemistry topics with corresponding assignments. Chapter 0 is available to students and can be
assigned in WileyPLUS to ensure and gauge understanding of the core topics required to succeed
in organic chemistry.

Prelecture Assignments. Preloaded and ready to use, these assignments have been carefully

designed to assess students prior to their coming to class. Instructors can assign these pre-created
quizzes to gauge student preparedness prior to lecture and tailor class time based on the scores
and participation of their students.
Video Mini-Lectures, Office Hour Videos, and Solved Problem Videos In each
chapter, several types of video assistance are included to help students with conceptual understanding and problem solving strategies. The video mini-lectures focus on challenging concepts;
the office hours videos take these concepts and apply them to example problems, emulating the
experience that a student would get if she or he were to attend office hours and ask for assistance
in working a problem. The Solved Problem videos demonstrate good problems solving strategies
for the student by walking through in text solved problems using audio and a whiteboard. The
goal is to illustrate good problem solving strategies.
Skill Building Exercises are animated exercises with instant feedback to reinforce the key
skills required to succeed in organic chemistry.
3D Molecular Visualizations use the latest visualization technologies to help students ­visualize

concepts with audio. Instructors can assign quizzes based on these visualizations in WileyPLUS.

What do instructors receive with
WileyPLUS with ORION?

• Reliable resources that reinforce course goals inside and outside of the classroom.
• T he ability to easily identify students who are falling behind by tracking their progress and

offering assistance easily, even before they come to office hours. Using WileyPLUS with
ORION simplifies and automates such tasks as student performance assessment, creating
assignments, scoring student work, keeping grades, and more.
Media-rich course materials and assessment content that allow you to customize your classroom
presentation with a wealth of resources and functionality from PowerPoint slides to a database
of rich visuals. You can even add your own materials to your WileyPLUS with ORION course.

•

Additional Instructor Resources
All Instructor Resources are available within WileyPLUS with ORION or they can be accessed
by contacting your local Wiley Sales Representative. Many of the assets are located on the book
companion site, www.wiley.com/college/solomons

xxiii

Test Bank Authored by Robert Rossi, of Gloucester County College, Jeffrey Allison, of Austin
Community College, and Gloria Silva, of Carnegie Melon University.
PowerPoint Lecture slides PowerPoint Lecture Slides have been prepared by Professor

William Tam, of the University of Guelph and his wife, Dr. Phillis Chang, and Gary Porter, of
Bergen Community College.

Personal Response System (“Clicker”) Questions
Digital Image Library Images from the text are available online in JPEG format. Instructors

may use these images to customize their presentations and to provide additional visual support
for quizzes and exams.

Additional Student Resources
Study Guide and Solutions Manual (Paperback: 978-1-119-07732-9;
­Binder-Ready: 978-1-119-07733-6)

The Study Guide and Solutions Manual for Organic Chemistry, Twelfth Edition, authored by
Graham Solomons, Craig Fryhle, and Scott Snyder with prior contributions from Robert Johnson
(Xavier University) and Jon Antilla (University of South Florida), contains explained solutions
to all of the problems in the text. The Study Guide also contains:

• A n introductory essay “Solving the Puzzle—or—Structure is Everything” that serves as a bridge
from general to organic chemistry
• Summary tables of reactions by mechanistic type and functional group
• A review quiz for each chapter
• A set of hands-on molecular model exercises
• Solutions to problems in the Special Topics that are found with the text in WileyPLUS.
Molecular Visions™ Model Kits

We believe that the tactile and visual experience of manipulating physical models is key to
­students’ understanding that organic molecules have shape and occupy space. To support our
pedagogy, we have arranged with the Darling Company to bundle a special ensemble of Molecular
Visions™ model kits with our book (for those who choose that option). We use Helpful Hint icons
and margin notes to frequently encourage students to use hand-held models to investigate the
three-dimensional shape of molecules we are discussing in the book.

Customization and Flexible
­Options to Meet Your Needs
Wiley Custom Select allows you to create a textbook with precisely the content you want, in a
simple, three-step online process that brings your students a cost-efficient alternative to a traditional textbook. Select from an extensive collection of content at http://customselect.wiley.com,
upload your own materials as well, and select from multiple delivery formats—full color or black
and white print with a variety of binding options, or eBook. Preview the full text online, get an
instant price quote, and submit your order; we’ll take it from there.
WileyFlex offers content in flexible and cost-saving options to students. Our goal is to deliver
our learning materials to our customers in the formats that work best for them, whether it’s a traditional text, eTextbook, WileyPLUS, loose-leaf binder editions, or customized content through
Wiley Custom Select.

xxiv

Acknowledgments
We are especially grateful to the following
people who provided detailed reviews and
participated in focus groups that helped
us prepare this new edition of Organic
Chemistry.
Arizona

Cindy Browder, Northern Arizona University
Tony Hascall, Northern Arizona University
Arkansas

Kenneth Carter, University of Central
Arkansas
Sean Curtis, University of Arkansas-Fort
Smith
California

Thomas Bertolini, University of Southern
California
Rebecca Broyer, University of Southern
California
Paul Buonora, California State UniveristyLong Beach
Steven Farmer, Sonoma State University
Andreas Franz, University of the Pacific
John Spence, California State Univesity
Sacramento
Daniel Wellman, Chapman University
Pavan Kadandale, University of California
Irvine
Jianhua Ren, University of the Pacific
Harold (Hal) Rogers, California State
University Fullerton
Liang Xue, University of the Pacific
Connecticut

Andrew Karatjas, Southern Connecticut State
University
Florida

Evonne Rezler, Florida Atlantic University
Solomon Weldegirma, University of South
Florida
Georgia

Indiana

Ned Bowden, University of Iowa
Olga Rinco, Luther College

Brian Love, East Carolina University
Jim Parise, Duke University
Cornelia Tirla, University of North CarolinaPembroke
Wei You, University of Norch CarolinaChapel Hill

Kentucky

NORTH DAKOTA

Mark Blankenbuehler, Morehead State
University

Karla Wohlers, North Dakota State
University

Louisiana

Ohio

Marilyn Cox, Louisiana Tech Univeristy
August Gallo, University of LouisianaLafayette
Sean Hickey, University of New Orleans
Kevin Smith, Louisiana State University

Neil Ayres, University of Cincinnati
Benjamin Gung, Miami University
Allan Pinhas, University of Cincinnati
Joel Shulman, University of Cincinnati

Massachusetts

Donna Nelson, University of OklahomaNorman Campus

Paul Morgan, Butler University
Iowa

Philip Le Quesne, Northeastern University
Samuel Thomas, Tufts University
Michigan

Scott Ratz, Alpena Community College
Ronald Stamper, University of Michigan
Minnesota

Eric Fort, University of St. Thomas
Mississippi

Douglas Masterson, University of Southern
Mississippi
Gerald Rowland, Mississippi State University
New Jersey

Bruce Hietbrink, Richard Stockton College
David Hunt, The College of New Jersey
Subash Jonnalagadda, Rowan University
Robert D Rossi, Gloucester County College
New Mexico

Donald Bellew, University of New Mexico
New York

Owen McDougal, Boise State University
Todd Davis, Idaho State University
Joshua Pak, Idaho State University

Brahmadeo Dewprashad, Borough of
Manhattan Community College
Barnabas Gikonyo, State University of New
York-Geneseo
Joe LeFevre, State University of New York-Oswego
Galina Melman, Clarkson University
Gloria Proni, City College of New YorkHunter College

Illinois

North Carolina

Valerie Keller, University of Chicago
Richard Nagorski, Illinois State University

Erik Alexanian, University of North Carolina
-Chapel Hill

Christine Whitlock, Georgia Southern
University
Idaho

Oklahoma

Pennsylvania

Joel Ressner,West Chester University of
Pennsylvania
South Carolina

Carl Heltzel, Clemson University
South Dakota

Grigoriy Sereda, University of South Dakota
Tennessee

Ramez Elgammal, University of Tennessee
Knoxville
Scott Handy, Middle Tennessee State
University
Aleksey Vasiliev, East Tennessee State
University
Texas

Jeff Allison, Austin Community College Hays
Campus
Shawn Amorde, Austin Community College
Jennifer Irvin,Texas State University-San
Marcos
Wisconsin

Elizabeth Glogowski, University of Wisconsin
Eau Claire
Tehshik Yoon, University of WisconsinMadison
Canada

Jeremy Wulff, University of Victoria
France-Isabelle Auzanneau, University of
Guelph

xxv

Many people have helped with this edition, and we owe a great deal of thanks to each one of them.
We thank Sean Hickey (University of New Orleans) for his reviews and assistance with aspects of
WileyPlus. We are grateful to Alan Shusterman (Reed College) and Warren Hehre (Wavefunction,
Inc.) for assistance in prior editions regarding explanations of electrostatic potential maps and other
calculated molecular models. We would also like to thank those scientists who allowed us to use or
adapt figures from their research as illustrations for a number of the topics in our book.

A book of this scope could not be produced without the excellent support we have had from
many people at John Wiley and Sons, Inc. Joan Kalkut, Sponsoring Editor, led the project from
the outset and provided careful oversight and encouragement through all stages of work on the
12th edition. We thank Nick Ferrari, Editor, for his guidance and support as well. Elizabeth Swain
brought the book to print through her incredible skill in orchestrating the production process and
converting manuscript to final pages. Photo Editor MaryAnn Price obtained photographs that so
aptly illustrate examples in our book. Maureen Eide led development of the striking new design
of the 12th edition. Alyson Rentrop coordinated work on the Study Guide and Solutions Manual
as well as WileyPlus components. Mallory Fryc ensured coordination and cohesion among many
aspects of this project, especially regarding reviews and supplements. Kristine Ruff enthusiastically
and effectively helped tell the ‘story’ of our book to the many people we hope will consider using
it. Without the support of Petra Recter, Vice President and Publisher, this book would not have
been possible. We are thankful to all of these people and others behind the scenes at Wiley for the
skills and dedication that they provided to bring this book to fruition.
TWGS with gratitude to my wife Judith for her continuing support. She joins me in dedicating this
edition to our granddaughter, Ella, and her mother, Annabel.
CBF would like to thank Deanna, who has been a steadfast life partner since first studying chemistry
together decades ago. He also thanks his daughter Heather for help with some chemical formulas. His
mother, whose model of scholarly endeavors continues, and father, who shared many science-related
tidbits, have always been inspirational.
SAS would like to thank his parents, his mentors, his colleagues, and his students for all that they have
done to inspire him. Most of all, he would like to thank his wife Cathy for all that she does and her
unwavering support.

T. W. Graham Solomons
Craig B. Fryhle
Scott A. Snyder

xxvi

About the Authors
T. W. Graham Solomons did his undergraduate work at The Citadel and received his ­doctorate
in organic chemistry in 1959 from Duke University where he worked with C. K. Bradsher. Following
this he was a Sloan Foundation Postdoctoral Fellow at the University of Rochester where he worked with
V. Boekelheide. In 1960 he became a charter member of the faculty of the University of South Florida and
became Professor of Chemistry in 1973. In 1992 he was made Professor Emeritus. In 1994 he was a visiting professor with the Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes
(Paris V). He is a member of Sigma Xi, Phi Lambda Upsilon, and Sigma Pi Sigma. He has received research
grants from the Research Corporation and the American Chemical Society Petroleum Research Fund. For
several years he was director of an NSF-sponsored Undergraduate Research Participation Program at USF.
His research interests have been in the areas of heterocyclic chemistry and unusual aromatic compounds.
He has published papers in the Journal of the American Chemical Society, the Journal of Organic Chemistry,
and the Journal of Heterocyclic Chemistry. He has received several awards for distinguished teaching. His
organic chemistry textbooks have been widely used for 30 years and have been translated into French,
Japanese, Chinese, Korean, Malaysian, Arabic, Portuguese, Spanish, Turkish, and Italian. He and his wife
Judith have a daughter who is a building conservator and a son who is a research biochemist.
Craig Barton Fryhle is a Professor of Chemistry at Pacific Lutheran University where he
served as Department Chair for roughly 15 years. He earned his B.A. degree from Gettysburg College
and Ph.D. from Brown University. His experiences at these institutions shaped his dedication to mentoring undergraduate students in chemistry and the liberal arts, which is a passion that burns strongly for
him. His research interests have been in areas relating to the shikimic acid pathway, including molecular
modeling and NMR spectrometry of substrates and analogues, as well as structure and reactivity studies
of shikimate pathway enzymes using isotopic labeling and mass spectrometry. He has mentored many
students in undergraduate research, a number of who have later earned their Ph.D. degrees and gone on
to academic or industrial positions. He has participated in workshops on fostering undergraduate participation in research, and has been an invited participant in efforts by the National Science Foundation
to enhance undergraduate research in chemistry. He has received research and instrumentation grants
from the National Science Foundation, the M J. Murdock Charitable Trust, and other private foundations. His work in chemical education, in addition to textbook coauthorship, involves incorporation
of student-led teaching in the classroom and technology-based strategies in organic chemistry. He has
also developed experiments for undergraduate students in organic laboratory and instrumental analysis
courses. He has been a volunteer with the hands-on science program in Seattle public schools, and Chair
of the Puget Sound Section of the American Chemical Society. His passion for climbing has led to
ascents of high peaks in several parts of the world. He resides in Seattle with his wife, where both enjoy
following the lives of their two daughters as they unfold in new ways and places.
Scott A. Snyder grew up in the suburbs of Buffalo NY and was an undergraduate at Williams
College, where he graduated summa cum laude in 1999. He pursued his doctoral studies at The
Scripps Research Institute in La Jolla CA under the tutelege of K. C. Nicolaou as an NSF, Pfizer, and
­Bristol-Myers Squibb predoctoral fellow. While there, he co-authored the graduate textbook Classics in
Total Synthesis II with his doctoral mentor. Scott was then an NIH postdoctoral fellow with E. J. Corey
at Harvard University. In 2006, Scott began his independent career at Columbia University, moved to
The Scripps Research Institute on their Jupiter FL campus in 2013, and in 2015 assumed his current
position as Professor of Chemistry at the University of Chicago. His research interests lie in the arena
of natural products total synthesis, particularly in the realm of unique polyphenols, alkaloids, and halogenated materials. To date, he has trained more than 60 students at the high school, undergraduate,
graduate, and postdoctoral levels and co-authored more than 50 research and review articles. Scott has
received a number of awards and honors, including a Camille and Henry Dreyfus New Faculty Award,
an Amgen Young Investigator Award, an Eli Lilly Grantee Award, a Bristol-Myers Squibb Unrestricted
Grant Award, an Alfred P. Sloan Foundation Fellowship, a DuPont Young Professor Award, and an
Arthur C. Cope Scholar Award from the American Chemical Society. He has also received awards
­recognizing his teaching, including a Cottrell Scholar Award from the Research Corporation for Science
Advancement. He lives in Chicago with his wife Cathy and son Sebastian where he enjoys gardening,
cooking, cycling, and watching movies.

xxvii

To the Student
Contrary to what you may have heard, organic chemistry does not
have to be a difficult course. It will be a rigorous course, and it will
offer a challenge. But you will learn more in it than in almost any
course you will take—and what you learn will have a special relevance to life and the world around you. However, because organic
chemistry can be approached in a logical and systematic way, you
will find that with the right study habits, mastering organic chemistry can be a deeply satisfying experience. Here, then, are some suggestions about how to study:
1. Keep up with your work from day to day—never let
yourself get behind. Organic chemistry is a course in which
one idea almost always builds on another that has gone before.
It is essential, therefore, that you keep up with, or better yet,
be a little ahead of your instructor. Ideally, you should try to
stay one day ahead of your instructor’s lectures in your own
class preparations. Your class time, then, will be much more
helpful because you will already have some understanding of
the assigned material. Use WileyPlus study tools (Including
ORION) to help with your pre-class learning.
2. Study material in small units, and be sure that you
understand each new section before you go on to
the next. Again, because of the cumulative nature of organic
chemistry, your studying will be much more effective if you
take each new idea as it comes and try to understand it completely before you move on to the next concept.
3. Work all of the in-chapter and assigned problems.
One way to check your progress is to work each of the inchapter problems when you come to it. These problems have
been written just for this purpose and are designed to help you
decide whether or not you understand the material that has
just been explained. You should also carefully study the Solved
Problems. If you understand a Solved Problem and can work
the related in-chapter problem, then you should go on; if you
cannot, then you should go back and study the preceding material again. Work all of the problems assigned by your instructor
from the text and WileyPlus. A notebook for homework is
helpful. When you go to your instructor for help, show her/
him your attempted homework, either in written form or in
WileyPlus online format.
4. Write when you study. Write the reactions, mechanisms,
structures, and so on, over and over again. Organic chemistry
is best assimilated through the fingertips by writing, and not
through the eyes by simply looking, or by highlighting mate-

xxviii

rial in the text, or by referring to flash cards. There is a good
reason for this. Organic structures, mechanisms, and reactions
are complex. If you simply examine them, you may think you
understand them thoroughly, but that will be a misperception.
The reaction mechanism may make sense to you in a certain
way, but you need a deeper understanding than this. You need
to know the material so thoroughly that you can explain it to
someone else. This level of understanding comes to most of us
(those of us without photographic memories) through writing.
Only by writing the reaction mechanisms do we pay sufficient
attention to their details, such as which atoms are connected
to which atoms, which bonds break in a reaction and which
bonds form, and the three-dimensional aspects of the structures. When we write reactions and mechanisms, connections
are made in our brains that provide the long-term memory
needed for success in organic chemistry. We virtually guarantee
that your grade in the course will be directly proportional to the
number of pages of paper that your fill with your own writing
in studying during the term.
5. Learn by teaching and explaining. Study with your student peers and practice explaining concepts and mechanisms
to each other. Use the Learning Group Problems and other
exercises your instructor may assign as vehicles for teaching and
learning interactively with your peers.
6. Use the answers to the problems in the Study Guide
in the proper way. Refer to the answers only in two circumstances: (1) When you have finished a problem, use the
Study Guide to check your answer. (2) When, after making
a real effort to solve the problem, you find that you are completely stuck, then look at the answer for a clue and go back to
work out the problem on your own. The value of a problem is
in solving it. If you simply read the problem and look up the
answer, you will deprive yourself of an important way to learn.
7. Use molecular models when you study. Because of the
three-dimensional nature of most organic molecules, molecular
models can be an invaluable aid to your understanding of them.
When you need to see the three-dimensional aspect of a particular topic, use the Molecular Visions™ model set that may have
been packaged with your textbook, or buy a set of models separately. An appendix to the Study Guide that accompanies this
text provides a set of highly useful molecular model exercises.
8. Make use of the rich online teaching resources in
WileyPLUS including ORION’s adaptive learning system.

c h a p t e r

1

The Basics
Bonding and Molecular Structure

O

rganic chemistry plays a role in all aspects of our lives, from the clothing we wear, to the pixels of our t­elevision

and computer screens, to preservatives in food, to the inks that color the pages of this book. If you take the time to understand organic chemistry, to learn its overall logic, then you will truly have the power to change society. Indeed, organic
chemistry provides the power to synthesize new drugs, to engineer molecules that can make computer processors run
more quickly, to understand why grilled meat can cause cancer and how its effects can be combated, and to design ways
to knock the calories out of sugar while still making food taste deliciously sweet. It can explain biochemical processes like
aging, neural functioning, and cardiac arrest, and show how we can prolong and improve life. It can do almost anything.
In this chapter we will consider:
• what kinds of atoms make up organic molecules
• the principles that determine how the atoms in organic molecules are bound together
• how best to depict organic molecules

[ WHY DO THESE TOPICS MATTER? ] At the end of the chapter, we will see how some of the unique organic
­structures that nature has woven together possess amazing properties that we can harness to aid human health. See
for additional examples, videos, and practice.

photo credits: computer screen: Be Good/Shutterstock; capsules: Ajt/Shutterstock

1

2  Chapter 1 The Basics: Bonding and Molecular Structure

NASA/Photo Researchers, Inc.

1.1 Life and the Chemistry of Carbon
Compounds—We are Stardust

Supernovae were the crucibles in
which the heavy elements were
formed.

Organic chemistry is the chemistry of compounds that contain the element carbon.
If a compound does not contain the element carbon, it is said to be inorganic.
Look for a moment at the periodic table inside the front cover of this book. More than
a hundred elements are listed there. The question that comes to mind is this: why should
an entire field of chemistry be based on the chemistry of compounds that contain this
one element, carbon? There are several reasons, the primary one being this: carbon compounds are central to the structure of living organisms and therefore to the existence
of life on Earth. We exist because of carbon compounds.
What is it about carbon that makes it the element that nature has chosen for living
organisms? There are two important reasons: carbon atoms can form strong bonds to
other carbon atoms to form rings and chains of carbon atoms, and carbon atoms can also
form strong bonds to elements such as hydrogen, nitrogen, oxygen, and sulfur. Because
of these bond-forming properties, carbon can be the basis for the huge diversity of compounds necessary for the emergence of living organisms.
From time to time, writers of science fiction have speculated about the possibility of
life on other planets being based on the compounds of another element—for example,
silicon, the element most like carbon. However, the bonds that silicon atoms form to each
other are not nearly as strong as those formed by carbon, and therefore it is very unlikely
that silicon could be the basis for anything equivalent to life as we know it.

1.1A What Is the Origin of the Element Carbon?
Through the efforts of physicists and cosmologists, we now understand much of how
the elements came into being. The light elements hydrogen and helium were formed at
the beginning, in the Big Bang. Lithium, beryllium, and boron, the next three elements,
were formed shortly thereafter when the universe had cooled somewhat. All of the heavier
elements were formed millions of years later in the interiors of stars through reactions in
which the nuclei of lighter elements fuse to form heavier elements.
The energy of stars comes primarily from the fusion of hydrogen nuclei to produce
helium nuclei. This nuclear reaction explains why stars shine. Eventually some stars begin
to run out of hydrogen, collapse, and explode—they become supernovae. Supernovae
explosions scatter heavy elements throughout space. Eventually, some of these heavy elements drawn by the force of gravity became part of the mass of planets like the Earth.

1.1B How Did Living Organisms Arise?
This question is one for which an adequate answer cannot be given now because there
are many things about the emergence of life that we do not understand. However, we do
know this. Organic compounds, some of considerable complexity, are detected in outer
space, and meteorites containing organic compounds have rained down on Earth since it
was formed. A meteorite that fell near Murchison, Victoria, Australia, in 1969 was found
to contain over 90 different amino acids, 19 of which are found in living organisms on
Earth. While this does not mean that life arose in outer space, it does suggest that events
in outer space may have contributed to the emergence of life on Earth.
In 1924 Alexander Oparin, a biochemist at the Moscow State University, ­postulated that
life on Earth may have developed through the gradual evolution of carbon-based molecules
in a “primordial soup” of the compounds that were thought to exist on a ­prebiotic Earth:
methane, hydrogen, water, and ammonia. This idea was tested by experiments carried out
at the University of Chicago in 1952 by Stanley Miller and Harold Urey. They showed that
amino acids and other complex organic compounds are synthesized when an electric spark
(think of lightning) passes through a flask containing a mixture of these four compounds
(think of the early atmosphere). Miller and Urey reported in their 1953 publication that
five amino acids (essential constituents of proteins) were formed. In 2008, examination
of archived solutions from Miller and Urey’s original experiments revealed that 22 amino
acids, rather than the 5 amino acids originally reported, were actually formed.

3

1.2 Atomic Structure

Similar experiments have shown that other precursors of biomolecules can also arise
in this way—compounds such as ribose and adenine, two components of RNA. Some
RNA molecules can not only store genetic information as DNA does, they can also act
as catalysts, as enzymes do.
There is much to be discovered to explain exactly how the compounds in this soup
became living organisms, but one thing seems certain. The carbon atoms that make up
our bodies were formed in stars, so, in a sense, we are stardust.

1.1C Development of the Science of Organic Chemistry
The science of organic chemistry began to flower with the demise of a nineteenth century
theory called vitalism. According to vitalism, organic compounds were only those that
came from living organisms, and only living things could synthesize organic compounds
through intervention of a vital force. Inorganic compounds were considered those compounds that came from nonliving sources. Friedrich Wöhler, however, discovered in
1828 that an organic compound called urea (a constituent of urine) could be made by
evaporating an aqueous solution of the inorganic compound ammonium cyanate. With
this discovery, the synthesis of an organic compound, began the evolution of organic
chemistry as a scientific discipline.

An RNA molecule

O
NH4+NCO−
Ammonium cyanate

heat

H 2N

C

NH2

Urea

Despite the demise of vitalism in science, the word “organic” is still used today by some
people to mean “coming from living organisms” as in the terms “organic vitamins” and
“organic fertilizers.” The commonly used term “organic food” means that the food was
grown without the use of synthetic fertilizers and pesticides. An “organic vitamin” means
to these people that the vitamin was isolated from a natural source and not synthesized by
a chemist. While there are sound arguments to be made against using food contaminated
with certain pesticides, while there may be environmental benefits to be obtained from organic farming, and while “natural” vitamins may contain beneficial substances not present
in synthetic vitamins, it is impossible to argue that pure
OH
“natural” vitamin C, for example, is healthier than pure
O
CH—CH2OH
“synthetic” vitamin C, since the two substances are iden- O
C
CH
tical in all respects. In science today, the study of compounds from living organisms is called natural products
C C
chemistry. In the closer to this chapter we will consider
HO
OH
more about why natural products chemistry is important.

FOODCOLLECTION/Image Source

The Chemistry of... Natural Products

Vitamin C is found in various
citrus fruits.

Vitamin C

1.2 Atomic Structure
Before we begin our study of the compounds of carbon we need to review some basic but
familiar ideas about the chemical elements and their structure.
• The compounds we encounter in chemistry are made up of elements combined in
different proportions.
• Elements are made up of at