Organic chemistry 9e john mcmurry

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7

6

5

4

3

2

1

7B
(7)

8B
(8)

8B
(9)

8B
(10)

1B

(11)

2B
(12)

6

21

72

71

56

Actinides
7

6

V

23

73

24

Cr

25

Mn

43

Tc

Manganese
54.9380

74

75

Re

60

92

91
90

Th
Thorium
232.0381

Ac
Actinium

(227)

89

144.24

140.9076

26

Fe

76

61

Pm

Hassium
(270)

108

Hs

Osmium
190.2

Os

Ruthenium
101.07

44

Ru

Iron
55.847

Protactinium
231.0359

Pa

Uranium
238.00289

U

27

Co

Ir

28

Ni

78

110

Ds

Platinum
195.08

Pt

Palladium
106.42

46

Pd

Nickel
58.693

29

Cu

79

111

Rg

Gold
196.9665

Au

Silver
107.8682

47

Ag

Copper
63.546

30

Zn

80

112

Cn

Mercury
200.59

Hg

Cadmium
112.411

48

Cd

Zinc
65.39

Pu
Plutonium
(244)

Neptunium
(237)

94

Samarium
150.36

62

Sm

Americium
(243)

95

Am

Europium
151.965

63

Eu

Curium
(247)

96

Cm

Gadolium
157.25

64

Gd

Berkelium
(247)

97

Bk

Terbium
158.9253

Tb

65

Meitnerium Darmstadtium Roentgenium Copernicium
(285)
(281)
(280)
(276)

109

Mt

Iridium
192.22

77

Rhodium
102.9055

45

Rh

Cobalt
58.9332

Np

93

(145)

Praseodymium Neodymium Promethium

Cerium
140.115

Lanthanum
138.9055

Nd

59

Pr

Bohrium
(272)

107

Bh

Rhenium
186.207

Seaborgium
(271)

106

Sg

Tungsten
183.85

W

Molybdenum Technetium
95.94
(98)

42

Mo

Chromium
51.9961

Ce

58

Dubnium
(268)

105

Db

Tantalum
180.9479

Ta

Niobium
92.9064

41

Nb

Vanadium
50.9415

La

57

Lawrencium Rutherfordium
(260)
(267)

Lanthanides

Radium
227.0278

Francium
(223)

Rf

104

Lr

103

88

Ra

Fr

87

Hf
Hafnium
178.49

Lu

Lutetium
174.967

Ba
Barium
137.327

Cs
Cesium
132.9054

55

Zirconium
91.224

Yttrium
88.9059

Strontium
87.62

Rubidium
85.4678

40

Zr

Sr

Y

39

38

22

Titanium
47.88

Rb

37

Scandium
44.9559

Sc

20

Calcium
40.078

Ca

19
Potassium

39.0983

K

3B
(3)

Magnesium
24.3050

Sodium
22.9898

Ti

13

31

Californium
(251)

98

Cf

Dysprosium
162.50

Dy

66

Ununtrium

34

84

Lv

116

Polonium
(209)

Po

Tellurium
127.60

52

Te

Selenium
78.96

Se

Sulfur
32.066

S

16

Oxygen
15.9994

8

O

6A
(16)

35

85

117

Uus

Astatine
(210)

At

Iodine
126.9045

I

53

Bromine
79.904

Br

Chlorine
35.4527

17

Cl

Fluorine
18.9984

9

F

7A
(17)

2

36

86

118

Uuo

Radon
(222)

Rn

Xenon
131.29

54

Xe

Krypton
83.80

Kr

Argon
39.948

18

Ar

Neon
20.1797

10

Ne

Helium
4.0026

He

8A
(18)

Einsteinium
(252)

99

Es

Holmium
164.9303

67

Ho

70

(258)

Mendelevium

Fermium
(257)

102

Nobelium
(259)

No

101

Md

Ytterbium
173.04

Yb
Thulium
168.9342

69

Tm

Fm

100

Erbium
167.26

68

Er

7

6

Flerovium Ununpentium Livermorium Ununseptium Ununoctium
(289)
(292)

Uup

115

Fl

114

Uut

113

83

Bi

Antimony
121.757

51

Sb

Bismuth
208.9804

82

Pb

Tin
118.710

50

Sn

33

Arsenic
74.9216

As

Phosphorus
30.9738

P

15

Nitrogen
14.0067

Lead
207.2

81

32

Germanium
72.61

Ge

Silicon
28.0855

14

Si

Carbon
12.011

7

N

5A
(15)

Thallium
204.3833

Tl

Indium
114.82

49

In

Gallium
69.723

Ga

Aluminum
26.9815

Al

12

Mg

Na

11

Boron
10.811

Beryllium
9.0122

Lithium
6.941

C

5

4

Be

B

4A
(14)

6B
(6)

Nonmetals

Semimetals

Metals

3A
(13)

5B
(5)

Atomic number
Symbol
Name
Atomic mass

2A
(2)

4B
(4)

Gold
196.9665

79

Au

An element

Key

Li

3

Hydrogen
1.0079

H

1

1A
(1)

Numbers in parentheses
are mass numbers of

radioactive isotopes.

Period
number

Group number,
U.S. system
IUPAC system

Periodic Table of the Elements

7

6

5

4

3

2

1


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Organic Chemistry

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Ninth Edition

Organic Chemistry
John McMurry
C o r ne l l U n i v e r s i t y

Australia • Brazil • Mexico • Singapore • United Kingdom • United States

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Organic Chemistry, Ninth Edition
John McMurry

© 2016, 2012, Cengage Learning

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Brief Contents

1

Structure and Bonding

1

2Polar Covalent Bonds; Acids and Bases

28

3Organic Compounds: Alkanes and Their Stereochemistry

60

4Organic Compounds: Cycloalkanes and Their Stereochemistry

89

5Stereochemistry at Tetrahedral Centers

115

6An Overview of Organic Reactions

149



Practice Your Scientific Analysis and Reasoning I: The Chiral Drug Thalidomide

182

7Alkenes: Structure and Reactivity

185

8Alkenes: Reactions and Synthesis

220

9Alkynes: An Introduction to Organic Synthesis

263

10 Organohalides

287

11 Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

309



 ractice Your Scientific Analysis and Reasoning II: From Mustard Gas
P
to Alkylating Anticancer Drugs

351

12 Structure Determination: Mass Spectrometry and Infrared Spectroscopy

354

13 Structure Determination: Nuclear Magnetic Resonance Spectroscopy

386

14 Conjugated Compounds and Ultraviolet Spectroscopy

420



Practice Your Scientific Analysis and Reasoning III: Photodynamic Therapy (PDT)

15 Benzene and Aromaticity
16

448
451

Chemistry of Benzene: Electrophilic Aromatic Substitution

478

17 Alcohols and Phenols

525

18 Ethers and Epoxides; Thiols and Sulfides

568

•

Preview of Carbonyl Chemistry

595

19 Aldehydes and Ketones: Nucleophilic Addition Reactions


 ractice Your Scientific Analysis and Reasoning IV: Selective Serotonin
P
Reuptake Inhibitors (SSRIs)

604
649

20 Carboxylic Acids and Nitriles

653

21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions

679

22 Carbonyl Alpha-Substitution Reactions

727

v

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Brief Contents
23 Carbonyl Condensation Reactions


753

Practice Your Scientific Analysis and Reasoning V: Thymine in DNA

784

24 Amines and Heterocycles

787

25 Biomolecules: Carbohydrates

832

26 Biomolecules: Amino Acids, Peptides, and Proteins

870

27 Biomolecules: Lipids

907



Practice Your Scientific Analysis and Reasoning VI: Melatonin and Serotonin

939

28 Biomolecules: Nucleic Acids

942

29 The Organic Chemistry of Metabolic Pathways

964

30 Orbitals and Organic Chemistry: Pericyclic Reactions

31

1013

 ractice Your Scientific Analysis and Reasoning VII: The Potent Antibiotic
P
Traits of Endiandric Acid C

1034

Synthetic Polymers

1037

Appendix A:

Nomenclature of Polyfunctional Organic Compounds

A-1

Appendix B:

Acidity Constants for Some Organic Compounds

A-9

Appendix C:

Glossary

A-11

Appendix D: Answers to In-Text Problems

A-31

Index

I-1

vi

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D e ta i l e d C o n t e n t s

Structure and Bonding |

c h ap t e r

1

1-1
1-2
1-3
1-4
1-5
1-6
1-7
1-8
1-9
1-10
1-11
1-12

1

Atomic Structure: The Nucleus

Atomic Structure: Orbitals
Atomic Structure: Electron Configurations
Development of Chemical Bonding Theory
Describing Chemical Bonds: Valence Bond Theory
sp3 Hybrid Orbitals and the Structure of Methane
sp3 Hybrid Orbitals and the Structure of Ethane
sp2 Hybrid Orbitals and the Structure of Ethylene
sp Hybrid Orbitals and the Structure of Acetylene
Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur
Describing Chemical Bonds: Molecular Orbital Theory
Drawing Chemical Structures
Something Extra






Organic Foods: Risk versus Benefit

Summary
Key words
Working Problems
Exercises

©Kostyantyn
Ivanyshen/
Shutterstock.com

Polar Covalent Bonds; Acids and Bases |

c h ap t e r

2

2-1
2-2
2-3
2-4
2-5
2-6
2-7

3
4
6
7
10
12
13
14
17
18
20
21
25
26
26
27
27a

28

Polar Covalent Bonds: Electronegativity
Polar Covalent Bonds: Dipole Moments
Formal Charges
Resonance
Rules for Resonance Forms
Drawing Resonance Forms
Acids and Bases: The Brønsted–Lowry Definition
vii

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Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.

28
31
33
36
37
39
42


viiicontents

2-8
2-9
2-10
2-11

2-12

Acid and Base Strength
Predicting Acid–Base Reactions from pKa Values
Organic Acids and Organic Bases
Acids and Bases: The Lewis Definition
Noncovalent Interactions between Molecules
Something Extra





 lkaloids: From Cocaine
A
to Dental Anesthetics 

Summary
Key words
Exercises

44
46
47
50
54
56
58
58
59

©tactilephoto/
Shutterstock.com

Organic Compounds: Alkanes and
Their Stereochemistry | 60

c h ap t e r

3

3-1
3-2
3-3
3-4
3-5
3-6
3-7

Functional Groups
Alkanes and Alkane Isomers
Alkyl Groups
Naming Alkanes
Properties of Alkanes
Conformations of Ethane
Conformations of Other Alkanes
Something Extra

Gasoline

Summary
Key words
Exercises

60
66
70
73
78
80
82
86
87
87
88

Indiapicture /
Alamy

Organic Compounds: Cycloalkanes and
Their Stereochemistry | 89

c h ap t e r

4

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

Naming Cycloalkanes
Cis–Trans Isomerism in Cycloalkanes
Stability of Cycloalkanes: Ring Strain
Conformations of Cycloalkanes
Conformations of Cyclohexane
Axial and Equatorial Bonds in Cyclohexane

90
92
95
97
99
101

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4-7
4-8
4-9

Conformations of Monosubstituted Cyclohexanes

Conformations of Disubstituted Cyclohexanes
Conformations of Polycyclic Molecules
Something Extra





©Bart Brouwer/
Shutterstock.com

c h ap t e r

5

Summary
Key words
Exercises

©Aspen Photo/
Shutterstock.com

c h ap t e r

6

110
113
114
114

114a

115
116
117
121
123
124
131
133
135
138
140
141
145

Chiral Drugs

Summary
Key words
Exercises

An Overview of Organic Reactions |
6-1
6-2
6-3
6-4
6-5
6-6

107

Enantiomers and the Tetrahedral Carbon
The Reason for Handedness in Molecules: Chirality
Optical Activity
Pasteur’s Discovery of Enantiomers
Sequence Rules for Specifying Configuration
Diastereomers
Meso Compounds
Racemic Mixtures and the Resolution of Enantiomers
A Review of Isomerism
Chirality at Nitrogen, Phosphorus, and Sulfur
Prochirality
Chirality in Nature and Chiral Environments
Something Extra





104

Molecular Mechanics

Stereochemistry at Tetrahedral Centers |
5-1
5-2
5-3
5-4
5-5

5-6
5-7
5-8
5-9
5-10
5-11
5-12

ix



Contents

147
148
148
148a

149

Kinds of Organic Reactions
How Organic Reactions Occur: Mechanisms
Radical Reactions
Polar Reactions
An Example of a Polar Reaction: Addition of HBr to Ethylene
Using Curved Arrows in Polar Reaction Mechanisms

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Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.

149
151
152
155
159
162


xcontents

6-7
6-8
6-9
6-10
6-11

Describing a Reaction: Equilibria, Rates, and Energy Changes
Describing a Reaction: Bond Dissociation Energies
Describing a Reaction: Energy Diagrams and Transition States
Describing a Reaction: Intermediates
A Comparison Between Biological Reactions
and Laboratory Reactions
Something Extra





Where Do Drugs Come From?

Summary
Key words
Exercises

165
169
171
174
177
179
181
181
181a

Practice Your Scientific Analysis and Reasoning I 
The Chiral Drug Thalidomide | 182

©JIANHAO
GUAN/
Shutterstock.com

Alkenes: Structure and Reactivity |

c h ap t e r

7

7-1
7-2

7-3
7-4
7-5
7-6
7-7
7-8
7-9
7-10
7-11

Industrial Preparation and Use of Alkenes
Calculating Degree of Unsaturation
Naming Alkenes
Cis–Trans Isomerism in Alkenes
Alkene Stereochemistry and the E,Z Designation
Stability of Alkenes
Electrophilic Addition Reactions of Alkenes
Orientation of Electrophilic Additions: Markovnikov’s Rule
Carbocation Structure and Stability
The Hammond Postulate
Evidence for the Mechanism of Electrophilic
Additions: Carbocation Rearrangements
Something Extra





185

Summary
Key words
Exercises

Bioprospecting: Hunting
for Natural Products 

186
187
189
192
194
198
201
205
208
211
214
217
218
218
219

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Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.


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Science Faction/
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Alkenes: Reactions and Synthesis |

c h ap t e r

8

8-1
8-2
8-3
8-4
8-5
8-6
8-7
8-8
8-9
8-10
8-11
8-12
8-13






220

Preparing Alkenes: A Preview of Elimination Reactions
Halogenation of Alkenes: Addition of X2

Halohydrins from Alkenes: Addition of HOX
Hydration of Alkenes: Addition of H2O by Oxymercuration
Hydration of Alkenes: Addition of H2O by Hydroboration
Reduction of Alkenes: Hydrogenation
Oxidation of Alkenes: Epoxidation and Hydroxylation
Oxidation of Alkenes: Cleavage to Carbonyl Compounds
Addition of Carbenes to Alkenes: Cyclopropane Synthesis
Radical Additions to Alkenes: Chain-Growth Polymers
Biological Additions of Radicals to Alkenes
Reaction Stereochemistry: Addition of H2O to an Achiral Alkene
Reaction Stereochemistry: Addition of H2O to a Chiral Alkene
Something Extra

©Igor Bulgarin/
Shutterstock.com

c h ap t e r

9

Summary
Key words
Learning Reactions
Summary of Reactions
Exercises

222
225
227
230

235
239
242
245
247
251
252
255
257
259
259
260
260
262

263

Naming Alkynes
Preparation of Alkynes: Elimination Reactions of Dihalides
Reactions of Alkynes: Addition of HX and X2
Hydration of Alkynes
Reduction of Alkynes
Oxidative Cleavage of Alkynes
Alkyne Acidity: Formation of Acetylide Anions
Alkylation of Acetylide Anions
An Introduction to Organic Synthesis
Something Extra

221

Terpenes: Naturally Occurring Alkenes

Alkynes: An Introduction to Organic Synthesis |
9-1
9-2
9-3
9-4
9-5
9-6
9-7
9-8
9-9

xi



Contents

The Art of Organic Synthesis

264
265
265
268
272
275
275
277
279

283

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xiicontents






Sebastián Crespo
Photography/
Getty Images

Organohalides |

c h ap t e r

10

Summary
Key words
Summary of Reactions
Exercises

284
284

285
286a

287

1 0-1
10-2
10-3
10-4
10-5
10-6
10-7
10-8

Names and Structures of Alkyl Halides
Preparing Alkyl Halides from Alkanes: Radical Halogenation
Preparing Alkyl Halides from Alkenes: Allylic Bromination
Stability of the Allyl Radical: Resonance Revisited
Preparing Alkyl Halides from Alcohols
Reactions of Alkyl Halides: Grignard Reagents
Organometallic Coupling Reactions
Oxidation and Reduction in Organic Chemistry

288

Naturally Occurring Organohalides

305

Something Extra

Summary
Key words
Summary of Reactions
Exercises

290
292
294
297
298
300
303

307
307
307
308

Martin Harvey/
Getty Images

Reactions of Alkyl Halides: Nucleophilic
Substitutions and Eliminations | 309

c h ap t e r

11

11-1
11-2
11-3
11-4
11-5
11-6
11-7
11-8
11-9
11-10
11-11
11-12

The Discovery of Nucleophilic Substitution Reactions
The SN2 Reaction
Characteristics of the SN2 Reaction
The SN1 Reaction
Characteristics of the SN1 Reaction
Biological Substitution Reactions
Elimination Reactions: Zaitsev’s Rule
The E2 Reaction and the Deuterium Isotope Effect
The E2 Reaction and Cyclohexane Conformation
The E1 and E1cB Reactions
Biological Elimination Reactions
A Summary of Reactivity: SN1, SN2, E1, E1cB, and E2

310
313
316
323
327
333
335
338
341
343
345
345

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Something Extra






xiii



Contents

Green Chemistry

347

Summary
Key words
Summary of Reactions
Exercises

349
349
350
350a

Practice Your Scientific Analysis and Reasoning II 
From Mustard Gas to Alkylating Anticancer Drugs |

351

Structure Determination: Mass Spectrometry
and Infrared Spectroscopy | 354
MakiEni’s photo/
Getty Images

12-1

c h ap t e r

12

1 2-2
12-3
12-4
1 2-5
12-6
12-7
12-8

Mass Spectrometry of Small Molecules:
Magnetic-Sector Instruments
Interpreting Mass Spectra
Mass Spectrometry of Some Common Functional Groups
Mass Spectrometry in Biological Chemistry:
Time-of-Flight (TOF) Instruments
Spectroscopy and the Electromagnetic Spectrum
Infrared Spectroscopy
Interpreting Infrared Spectra
Infrared Spectra of Some Common Functional Groups
Something Extra





355
357
362
367
368
371

373
376

X-Ray Crystallography

Summary
Key words
Exercises

384
385
385
385

©EM Karuna/
Shutterstock.com

Structure Determination: Nuclear Magnetic
Resonance Spectroscopy | 386

c h ap t e r

13

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

Nuclear Magnetic Resonance Spectroscopy
The Nature of NMR Absorptions
The Chemical Shift
Chemical Shifts in 1H NMR Spectroscopy
Integration of 1H NMR Absorptions: Proton Counting

386
389
392
394
396

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xivcontents

1 3-6
13-7
13-8
13-9
13-10
13-11
13-12
13-13

Spin–Spin Splitting in 1H NMR Spectra
1H NMR Spectroscopy and Proton Equivalence
More Complex Spin–Spin Splitting Patterns

Uses of 1H NMR Spectroscopy
13C NMR Spectroscopy: Signal Averaging and FT–NMR
Characteristics of 13C NMR Spectroscopy
DEPT 13C NMR Spectroscopy
Uses of 13C NMR Spectroscopy
Something Extra





Magnetic Resonance Imaging (MRI)

Summary
Key words
Exercises

397
402
404
407
408
410
413
416
417
418
418
419

Conjugated Compounds and Ultraviolet
Spectroscopy | 420
©DemarK/
Shutterstock.com

1 4-1
14-2
c h ap t e r

14

1 4-3
14-4
14-5
14-6
14-7
14-8
14-9

Stability of Conjugated Dienes: Molecular Orbital Theory
Electrophilic Additions to Conjugated Dienes:
Allylic Carbocations
Kinetic versus Thermodynamic Control of Reactions
The Diels–Alder Cycloaddition Reaction
Characteristics of the Diels–Alder Reaction
Diene Polymers: Natural and Synthetic Rubbers
Ultraviolet Spectroscopy
Interpreting Ultraviolet Spectra: The Effect of Conjugation
Conjugation, Color, and the Chemistry of Vision
Something Extra

Photolithography

Summary
Key words
Summary of Reactions
Exercises

421
425
428
430
431
437
438
441
442
444
446
446
447
447a

Practice Your Scientific Analysis and Reasoning III 
Photodynamic Therapy (PDT) | 448

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©Handmade
Pictures/
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Benzene and Aromaticity |

c h ap t e r

15

1 5-1
15-2
15-3
15-4
15-5
15-6
15-7

451

Naming Aromatic Compounds
Structure and Stability of Benzene
Aromaticity and the Hückel 4n 1 2 Rule
Aromatic Ions
Aromatic Heterocycles: Pyridine and Pyrrole

Polycyclic Aromatic Compounds
Spectroscopy of Aromatic Compounds
Something Extra





xv



Contents

452
456
459
461
464
467
469

Aspirin, NSAIDs, and COX-2 Inhibitors

474

Summary
Key words
Exercises

476
476
477

Niday Picture
Library / Alamy

Chemistry of Benzene: Electrophilic
Aromatic Substitution | 478

c h ap t e r

16

1 6-1
16-2
16-3
1 6-4
16-5
16-6
16-7
16-8
16-9
16-10

Electrophilic Aromatic Substitution Reactions: Bromination
Other Aromatic Substitutions
Alkylation and Acylation of Aromatic Rings:
The Friedel–Crafts Reaction
Substituent Effects in Electrophilic Substitutions

Trisubstituted Benzenes: Additivity of Effects
Nucleophilic Aromatic Substitution
Benzyne
Oxidation of Aromatic Compounds
Reduction of Aromatic Compounds
Synthesis of Polysubstituted Benzenes
Something Extra






Summary
Key words
Summary of Reactions
Exercises

479
482
488
493
503
505
508
510
513
514

Combinatorial Chemistry

519
521
521
522

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524


xvicontents

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Murillo/
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Alcohols and Phenols |

c h ap t e r

17

1 7-1
17-2
17-3
17-4
17-5
17-6

17-7
17-8
17-9
17-10
17-11

525

Naming Alcohols and Phenols
Properties of Alcohols and Phenols
Preparation of Alcohols: A Review
Alcohols from Carbonyl Compounds: Reduction
Alcohols from Carbonyl Compounds: Grignard Reaction
Reactions of Alcohols
Oxidation of Alcohols
Protection of Alcohols
Phenols and Their Uses
Reactions of Phenols
Spectroscopy of Alcohols and Phenols
Something Extra






Ethanol: Chemical, Drug, Poison

Summary
Key words

Summary of Reactions
Exercises

©Heiko Kiera/
Shutterstock.com

c h ap t e r

18






Summary
Key words
Summary of Reactions
Exercises

533
535
539
543
550
553
555
557
559
563

564
565
567

568

Names and Properties of Ethers
Preparing Ethers
Reactions of Ethers: Acidic Cleavage
Reactions of Ethers: Claisen Rearrangement
Cyclic Ethers: Epoxides
Reactions of Epoxides: Ring-Opening
Crown Ethers
Thiols and Sulfides
Spectroscopy of Ethers
Something Extra

528

564

Ethers and Epoxides; Thiols and Sulfides |
1 8-1
18-2
18-3
18-4
18-5
18-6
18-7

18-8
18-9

526

Epoxy Resins and Adhesives

569
570
573
575
577
578
583
584
588
591
592
592
593
594a

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Preview of Carbonyl Chemistry |
I
II
III

IV

xvii



Contents

595

Kinds of Carbonyl Compounds
Nature of the Carbonyl Group
General Reactions of Carbonyl Compounds
Summary

595
597
597
603

©Loskutnikov/
Shutterstock.com

Aldehydes and Ketones: Nucleophilic
Addition Reactions | 604

c h ap t e r

19

1 9-1
19-2
19-3
19-4
19-5
19-6
19-7
1 9-8
19-9
19-10
19-11
19-12
19-13
19-14

Naming Aldehydes and Ketones
Preparing Aldehydes and Ketones
Oxidation of Aldehydes and Ketones
Nucleophilic Addition Reactions of Aldehydes and Ketones
Nucleophilic Addition of H2O: Hydration
Nucleophilic Addition of HCN: Cyanohydrin Formation
Nucleophilic Addition of Hydride and Grignard Reagents:
Alcohol Formation
Nucleophilic Addition of Amines: Imine and Enamine Formation
Nucleophilic Addition of Hydrazine: The Wolff–Kishner Reaction
Nucleophilic Addition of Alcohols: Acetal Formation
Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction
Biological Reductions
Conjugate Nucleophilic Addition to a,b-Unsaturated
Aldehydes and Ketones

Spectroscopy of Aldehydes and Ketones
Something Extra






605
607
609
610
614
616
617
619
624
626
630
633
635
640

Enantioselective Synthesis

Summary
Key words
Summary of Reactions
Exercises

644
646
646
646
648a

Practice Your Scientific Analysis and Reasoning IV 
Selective Serotonin Reuptake Inhibitors (SSRIs) | 649

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xviiicontents

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Carboxylic Acids and Nitriles |

c h ap t e r

20

2 0-1
20-2
20-3
20-4
20-5
20-6

20-7
20-8

653

Naming Carboxylic Acids and Nitriles
Structure and Properties of Carboxylic Acids
Biological Acids and the Henderson–Hasselbalch Equation
Substituent Effects on Acidity
Preparing Carboxylic Acids
Reactions of Carboxylic Acids: An Overview
Chemistry of Nitriles
Spectroscopy of Carboxylic Acids and Nitriles
Something Extra






Vitamin C

Summary
Key words
Summary of Reactions
Exercises

654
656
660

661
664
667
668
672
674
676
676
677
678

©Greg Epperson/
Shutterstock.com

Carboxylic Acid Derivatives: Nucleophilic Acyl
Substitution Reactions | 679

c h ap t e r

21

2 1-1
21-2
21-3
21-4
21-5
21-6
21-7
21-8
2 1-9

21-10

Naming Carboxylic Acid Derivatives
Nucleophilic Acyl Substitution Reactions
Reactions of Carboxylic Acids
Chemistry of Acid Halides
Chemistry of Acid Anhydrides
Chemistry of Esters
Chemistry of Amides
Chemistry of Thioesters and Acyl Phosphates:
Biological Carboxylic Acid Derivatives
Polyamides and Polyesters: Step-Growth Polymers
Spectroscopy of Carboxylic Acid Derivatives
Something Extra






Summary
Key words
Summary of Reactions
Exercises

b-Lactam Antibiotics

680
683
688

696
701
703
709
713
715
718
721
723
723
723
726

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Carbonyl Alpha-Substitution Reactions |

c h ap t e r

22

22-1
22-2
22-3
22-4

22-5
22-6
22-7





Picturebank /
Alamy

23

Barbiturates

Summary
Key words
Summary of Reactions
Exercises

Carbonyl Condensation Reactions |

c h ap t e r

727

Keto–Enol Tautomerism
Reactivity of Enols: a-Substitution Reactions
Alpha Halogenation of Aldehydes and Ketones
Alpha Bromination of Carboxylic Acids

Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation
Reactivity of Enolate Ions
Alkylation of Enolate Ions
Something Extra

730
731
734
735
738
739
748

750
751
752

753

Carbonyl Condensations: The Aldol Reaction
Carbonyl Condensations versus Alpha Substitutions
Dehydration of Aldol Products: Synthesis of Enones
Using Aldol Reactions in Synthesis
Mixed Aldol Reactions
Intramolecular Aldol Reactions
The Claisen Condensation Reaction
Mixed Claisen Condensations
Intramolecular Claisen Condensations:
The Dieckmann Cyclization
23-10 Conjugate Carbonyl Additions: The Michael Reaction

2 3-11 Carbonyl Condensations with Enamines: The Stork
Reaction
23-12 The Robinson Annulation Reaction
23-13 Some Biological Carbonyl Condensation Reactions





728

750

2 3-1
23-2
23-3
23-4
23-5
23-6
23-7
23-8
23-9

Something Extra

xix



Contents

A Prologue to Metabolism

Summary
Key words
Summary of Reactions
Exercises

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753
756
757
760
761
762
764
766
768
770
773
776
777
779
781
781
782
783

xxcontents

Practice Your Scientific Analysis and Reasoning V 
Thymine in DNA | 784

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Shutterstock.com

Amines and Heterocycles |

c h ap t e r

24

24-1
24-2
24-3
24-4
24-5
24-6
24-7
24-8
24-9
24-10

787

Naming Amines
Structure and Properties of Amines

Basicity of Amines
Basicity of Arylamines
Biological Amines and the Henderson–Hasselbalch Equation
Synthesis of Amines
Reactions of Amines
Reactions of Arylamines
Heterocyclic Amines
Spectroscopy of Amines
Something Extra






Summary
Key words
Summary of Reactions
Exercises

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Shutterstock.com

Biomolecules: Carbohydrates |

c h ap t e r

25

2 5-1

25-2
25-3
25-4
25-5
25-6
25-7
25-8
25-9
25-10
25-11

Green Chemistry II: Ionic Liquids

787
790
792
795
797
798
806
810
816
823
826
828
828
830
831a

832

Classification of Carbohydrates
Representing Carbohydrate Stereochemistry: Fischer Projections
d,l Sugars
Configurations of the Aldoses
Cyclic Structures of Monosaccharides: Anomers
Reactions of Monosaccharides
The Eight Essential Monosaccharides
Disaccharides
Polysaccharides and Their Synthesis
Some Other Important Carbohydrates
Cell-Surface Carbohydrates and Influenza Viruses
Something Extra

Sweetness

833
834
838
840
844
848
856
858
861
864
864
866

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Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.







Summary
Key words
Summary of Reactions
Exercises

xxi



Contents

868
868
869
869

Biomolecules: Amino Acids, Peptides,
and Proteins | 870
Stuart Cox/V&A
Images / Alamy

2 6-1

26-2

c h ap t e r

26

Structures of Amino Acids
Amino Acids and the Henderson–Hasselbalch Equation:
Isoelectric Points
26-3 Synthesis of Amino Acids
26-4 Peptides and Proteins
26-5 Amino Acid Analysis of Peptides
26-6 Peptide Sequencing: The Edman Degradation
26-7
Peptide Synthesis
26-8 Automated Peptide Synthesis: The Merrifield
Solid-Phase Method
26-9 Protein Structure
26-10 Enzymes and Coenzymes
2 6-11 How Do Enzymes Work? Citrate Synthase
Something Extra






Summary
Key words
Summary of Reactions

Exercises

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Biomolecules: Lipids |

c h ap t e r

27

2 7-1
27-2
27-3
27-4
27-5
27-6
27-7

The Protein Data Bank

871
876
879
881
884
885
888
890
893

895
898
903
904
904
905
906a

907

Waxes, Fats, and Oils
Soap
Phospholipids
Prostaglandins and Other Eicosanoids
Terpenoids
Steroids
Biosynthesis of Steroids

908
911
913
915
917
926
930

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