Preview Organic Chemistry, 5th Edition by Janice Gorzynski Smith Dr (2016)

Organic Chemistry
Fifth Edition

Janice Gorzynski Smith
University of Hawai‘i at Ma-noa

TM


TM

ORGANIC CHEMISTRY, FIFTH EDITION
Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121. Copyright © 2017 by McGraw-Hill
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Library of Congress Cataloging-in-Publication Data
Smith, Janice G.
  Organic chemistry / by Janice Gorzynski Smith. — 5th edition.
  p. cm.
  Includes index.
  ISBN 978-0-07-802155-8 — ISBN 0-07-802155-8 (hard copy : alk. paper)  1. Chemistry, Organic—
Textbooks. I. Title
  QD253.2 .S63 2017
 547—dc23
2015037323
The Internet addresses listed in the text were accurate at the time of publication. The inclusion of a website
does not indicate an endorsement by the author or McGraw-Hill Education, and McGraw-Hill Education does
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mheducation.com/highered


About the Author

Janice Gorzynski Smith was born in Schenectady, New York. She became interested
in chemistry in high school and went on to major in chemistry at Cornell University, where
she received an A.B. degree summa cum laude. Jan earned a Ph.D. in Organic Chemistry from
Harvard University under the direction of Nobel Laureate E. J. Corey, and she also spent a year
as a National Science Foundation National Needs Postdoctoral Fellow at Harvard. During her
tenure with the Corey group, she completed the total synthesis of the plant growth hormone
gibberellic acid.
Following her postdoctoral work, Jan joined the faculty of Mount Holyoke College, where
she was employed for 21 years. During this time she was active in teaching organic chemistry lecture and lab courses, conducting a research program in organic synthesis, and serving
as department chair. Her organic chemistry class was named one of Mount Holyoke’s “Don’tmiss courses” in a survey by Boston magazine. After spending two sabbaticals amidst the natural beauty and diversity in Hawai‘i in the 1990s, Jan and her family moved there permanently
in 2000. She is currently a faculty member at the University of Hawai‘i at Mānoa, where she
teaches the two-semester organic chemistry lecture and lab courses. In 2003, she received the
Chancellor’s Citation for Meritorious Teaching.
Jan resides in Hawai‘i with her husband Dan, an emergency medicine physician, pictured
with her hiking in New Zealand in 2015. She has four children and three grandchildren. When
not teaching, writing, or enjoying her family, Jan bikes, hikes, snorkels, and scuba dives in sunny
Hawai‘i, and time permitting, enjoys travel and Hawaiian quilting.

or Megan Sarah


Contents in Brief

Prologue 1
1

Structure and Bonding  7
2
Acids and Bases  61
3
Introduction to Organic Molecules and Functional Groups  91
4
Alkanes 128
5
Stereochemistry 174
6
Understanding Organic Reactions  213
7
Alkyl Halides and Nucleophilic Substitution  247
8
Alkyl Halides and Elimination Reactions  297
9
Alcohols, Ethers, and Related Compounds  331
10
Alkenes 383
11
Alkynes 426
12
Oxidation and Reduction  455
13
Mass Spectrometry and Infrared Spectroscopy  495
14
Nuclear Magnetic Resonance Spectroscopy  527
15
Radical Reactions  570
16

Conjugation, Resonance, and Dienes  604
17
Benzene and Aromatic Compounds  641
18
Reactions of Aromatic Compounds  677
19
Carboxylic Acids and the Acidity of the O–H Bond  729
20
Introduction to Carbonyl Chemistry; Organometallic Reagents;
Oxidation and Reduction  764

21
Aldehydes and Ketones—Nucleophilic Addition  817
22
Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 
23
Substitution Reactions of Carbonyl Compounds at the α Carbon  924
24
Carbonyl Condensation Reactions  962
25
Amines 996
26
Carbon–Carbon Bond-Forming Reactions in Organic Synthesis  1049
27
Pericyclic Reactions  1076
28
Carbohydrates 1106
29
Amino Acids and Proteins  1152
30

Synthetic Polymers  1198
31
Lipids  1231 (Available online)

Appendices A-1

Glossary G-1

Credits C-1

Index I-1
iv

868


Contents

Preface xiii
Acknowledgments xxi
List of How To’s xxiii
List of Mechanisms  xxiv
List of Selected Applications  xxvii

Prologue 1
What Is Organic Chemistry?  1
Some Representative Organic Molecules  2
Organic Chemistry and Malaria  4

1 Structure and Bonding  7

1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14

The Periodic Table  8
Bonding 11
Lewis Structures  13
Isomers 18
Exceptions to the Octet Rule  19
Resonance 19
Determining Molecular Shape  25
Drawing Organic Structures  30
Hybridization 36
Ethane, Ethylene, and Acetylene  40
Bond Length and Bond Strength   45
Electronegativity and Bond Polarity  47
Polarity of Molecules  49
l-Dopa—A Representative Organic Molecule  50

Key Concepts  52
Problems 53

2 Acids and Bases  61
2.1
2.2
2.3
2.4
2.5
2.6

Brønsted–Lowry Acids and
Bases 62
Reactions of Brønsted–Lowry
Acids and Bases  63
Acid Strength and pKa 66
Predicting the Outcome of Acid–Base
Reactions 68
Factors That Determine Acid Strength  70
Common Acids and Bases   78

2.7
2.8

Aspirin 80
Lewis Acids and Bases  81

Key Concepts  84
Problems 85

3 Introduction to Organic
Molecules and Functional
Groups 91
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9

Functional Groups  92
An Overview of Functional Groups  93
Intermolecular Forces  99
Physical Properties  103
Application: Vitamins  109
Application of Solubility: Soap  111
Application: The Cell Membrane  113
Functional Groups and Reactivity  116
Biomolecules 117

Key Concepts  119
Problems 121

4 Alkanes 128
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15

Alkanes—An Introduction  129
Cycloalkanes 132
An Introduction to
Nomenclature 132
Naming Alkanes  133
Naming Cycloalkanes  138
Common Names  141
Fossil Fuels  141

Physical Properties of Alkanes  143
Conformations of Acyclic Alkanes—Ethane  144
Conformations of Butane  148
An Introduction to Cycloalkanes  151
Cyclohexane 152
Substituted Cycloalkanes  156
Oxidation of Alkanes  161
Lipids—Part 1  164




Key Concepts  166
Problems   167

v


vi

Contents

5 Stereochemistry 174
5.1
5.2

5.10
5.11
5.12
5.13

Starch and Cellulose  175
The Two Major Classes of
Isomers 177
Looking Glass Chemistry—Chiral
and Achiral Molecules  178
Stereogenic Centers  181
Stereogenic Centers in Cyclic Compounds  183
Labeling Stereogenic Centers with R or S   185
Diastereomers 190
Meso Compounds  193
R and S Assignments in Compounds with Two or
More Stereogenic Centers  194
Disubstituted Cycloalkanes  195
Isomers—A Summary  196
Physical Properties of Stereoisomers  197
Chemical Properties of Enantiomers  202




Key Concepts  204
Problems 205

5.3
5.4
5.5
5.6
5.7
5.8

5.9

6

Understanding Organic
Reactions 213

6.1

7.4
7.5
7.6

7.11
7.12
7.13
7.14
7.15
7.16
7.17
7.18

Interesting Alkyl Halides  251
The Polar Carbon–Halogen Bond  252
General Features of Nucleophilic
Substitution 253
The Leaving Group  255
The Nucleophile  257
Possible Mechanisms for Nucleophilic
Substitution 261

Two Mechanisms for Nucleophilic
Substitution 262
The SN2 Mechanism  263
The SN1 Mechanism  269
Carbocation Stability  273
The Hammond Postulate  275
When Is the Mechanism SN1 or SN2? 278
Biological Nucleophilic Substitution  283
Vinyl Halides and Aryl Halides  286
Organic Synthesis  286




Key Concepts  288
Problems 290

7.7
7.8
7.9
7.10

8 Alkyl Halides
and Elimination
Reactions 297

Writing Equations for Organic
Reactions 214
6.2 Kinds of Organic Reactions  215
6.3 Bond Breaking and Bond Making  217

6.4 Bond Dissociation Energy  221
6.5 Thermodynamics 225
6.6 Enthalpy and Entropy  227
6.7 Energy Diagrams  229
6.8 Energy Diagram for a Two-Step Reaction
Mechanism 231
6.9 Kinetics 233
6.10 Catalysts 236
6.11 Enzymes 237

General Features of
Elimination 298
8.2 Alkenes—The Products of Elimination
Reactions 299
8.3 The Mechanisms of Elimination  303
8.4 The E2 Mechanism  303
8.5 The Zaitsev Rule  308
8.6 The E1 Mechanism  310
8.7 SN1 and E1 Reactions  314
8.8 Stereochemistry of the E2 Reaction  315
8.9 When Is the Mechanism E1 or E2?  319
8.10 E2 Reactions and Alkyne Synthesis  319
8.11 When Is the Reaction SN1, SN2, E1, or E2?  321

Key Concepts  239
Problems 240

7 Alkyl Halides
and Nucleophilic
Substitution 247
7.1
7.2
7.3

Introduction to Alkyl
Halides 248
Nomenclature 249
Physical Properties  250

8.1

Key Concepts  325
Problems 326

9 Alcohols, Ethers, and
Related Compounds  331
9.1
9.2
9.3
9.4

Introduction 332
Structure and Bonding  333
Nomenclature 334

Physical Properties  337


Contents

9.5
9.6
9.7
9.8
9.9
9.10
9.11
9.12
9.13
9.14
9.15
9.16
9.17
9.18



Interesting Alcohols, Ethers, and Epoxides  338
Preparation of Alcohols, Ethers, and Epoxides  341
General Features—Reactions of Alcohols,
Ethers, and Epoxides  343
Dehydration of Alcohols to Alkenes  345
Carbocation Rearrangements  348
Dehydration Using POCl3 and Pyridine  351
Conversion of Alcohols to Alkyl Halides

with HX  352
Conversion of Alcohols to Alkyl Halides with
SOCl2 and PBr3 356
Tosylate—Another Good Leaving Group  359
Reaction of Ethers with Strong Acid  362
Thiols and Sulfides  364
Reactions of Epoxides  367
Application: Epoxides, Leukotrienes, and
Asthma 371
Application: Benzo[a]pyrene, Epoxides, and
Cancer 373
Key Concepts  373
Problems 376

10 Alkenes 383
10.1 Introduction 384
10.2 Calculating Degrees of
Unsaturation 385
10.3 Nomenclature 387
10.4 Physical Properties  391
10.5 Interesting Alkenes  391
10.6 Lipids—Part 2   393
10.7 Preparation of Alkenes  395
10.8 Introduction to Addition Reactions  396
10.9 Hydrohalogenation—Electrophilic Addition
of HX  397
10.10 Markovnikov’s Rule  400
10.11 Stereochemistry of Electrophilic Addition
of HX  402
10.12 Hydration—Electrophilic Addition of Water  404

10.13 Halogenation—Addition of Halogen  405
10.14 Stereochemistry of Halogenation   406
10.15 Halohydrin Formation  408
10.16 Hydroboration–Oxidation 411
10.17 Keeping Track of Reactions  415
10.18 Alkenes in Organic Synthesis  417



Key Concepts  418
Problems 419

11 Alkynes 426
11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9
11.10
11.11
11.12

Introduction 427
Nomenclature 428
Physical Properties  429
Interesting Alkynes  430

Preparation of Alkynes  431
Introduction to Alkyne Reactions  432
Addition of Hydrogen Halides  434
Addition of Halogen  436
Addition of Water  437
Hydroboration–Oxidation 439
Reaction of Acetylide Anions  441
Synthesis 444




Key Concepts  447
Problems 448

12 Oxidation and
Reduction 455
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8
12.9
12.10
12.11
12.12
12.13

12.14
12.15

Introduction 456
Reducing Agents  457
Reduction of Alkenes  458
Application: Hydrogenation of Oils  461
Reduction of Alkynes  463
The Reduction of Polar C – X σ Bonds  466
Oxidizing Agents  467
Epoxidation 469
Dihydroxylation 472
Oxidative Cleavage of Alkenes  474
Oxidative Cleavage of Alkynes  476
Oxidation of Alcohols  476
Green Chemistry  479
Biological Oxidation  481
Sharpless Epoxidation  482




Key Concepts  485
Problems 487

13 Mass Spectrometry
and Infrared
Spectroscopy 495
13.1
13.2

13.3
13.4

Mass Spectrometry  496
Alkyl Halides and the M + 2 Peak  500
Fragmentation 501
Other Types of Mass Spectrometry  504

vii


viii

Contents

13.5
13.6
13.7
13.8

Electromagnetic Radiation  506
Infrared Spectroscopy  508
IR Absorptions  510
IR and Structure Determination  517

15.14 Polymers and Polymerization  593

Key Concepts  519
Problems 520

16 Conjugation, Resonance,

14 Nuclear Magnetic
Resonance
Spectroscopy 527
14.1 An Introduction to NMR
Spectroscopy 528
14.2 1H NMR: Number of Signals  531
14.3 1H NMR: Position of Signals  535
14.4 The Chemical Shift of Protons on sp2 and sp
Hybridized Carbons  539
14.5 1H NMR: Intensity of Signals  541
14.6 1H NMR: Spin–Spin Splitting  542
14.7 More Complex Examples of Splitting  546
14.8 Spin–Spin Splitting in Alkenes  549
14.9 Other Facts About 1H NMR Spectroscopy  551
14.10 Using 1H NMR to Identify an Unknown  554
14.11 13C NMR Spectroscopy  556
14.12 Magnetic Resonance Imaging (MRI)  561



Key Concepts  561
Problems 562

Key Concepts  595
Problems 596

and Dienes  604
16.1 Conjugation 605
16.2 Resonance and Allylic
Carbocations 607
16.3 Common Examples of Resonance  608
16.4 The Resonance Hybrid  610
16.5 Electron Delocalization, Hybridization, and
Geometry 612
16.6 Conjugated Dienes  613
16.7 Interesting Dienes and Polyenes  614
16.8 The Carbon–Carbon σ Bond Length in
Buta-1,3-diene 614
16.9 Stability of Conjugated Dienes  615
16.10 Electrophilic Addition: 1,2- Versus
1,4-Addition 616
16.11 Kinetic Versus Thermodynamic Products  618
16.12 The Diels–Alder Reaction  621
16.13 Specific Rules Governing the Diels–Alder
Reaction 623
16.14 Other Facts About the Diels–Alder Reaction  627
16.15 Conjugated Dienes and Ultraviolet Light  630



Key Concepts  632
Problems 634

15 Radical Reactions  570
15.1 Introduction 571
15.2 General Features of Radical
Reactions 572
15.3 Halogenation of Alkanes   574
15.4 The Mechanism of Halogenation  575
15.5 Chlorination of Other Alkanes   578
15.6 Chlorination Versus Bromination  578
15.7 Halogenation as a Tool in Organic Synthesis  581
15.8 The Stereochemistry of Halogenation
Reactions 582
15.9 Application: The Ozone Layer and CFCs  584
15.10 Radical Halogenation at an Allylic Carbon  585
15.11 Application: Oxidation of Unsaturated
Lipids 588
15.12 Application: Antioxidants  589
15.13 Radical Addition Reactions to Double
Bonds 590

17 Benzene and Aromatic
Compounds 641
17.1 Background 642
17.2 The Structure of Benzene  643
17.3 Nomenclature of Benzene
Derivatives 644
17.4 Spectroscopic Properties  647
17.5 Interesting Aromatic Compounds  648
17.6 Benzene’s Unusual Stability  649
17.7 The Criteria for Aromaticity—Hückel’s Rule  651

17.8 Examples of Aromatic Compounds  654
17.9 What Is the Basis of Hückel’s Rule?  660
17.10 The Inscribed Polygon Method for Predicting
Aromaticity 663
17.11 Buckminsterfullerene—Is It Aromatic?  666



Key Concepts  667
Problems 668


Contents

18 Reactions of Aromatic
Compounds 677
18.1 Electrophilic Aromatic
Substitution 678
18.2 The General Mechanism  679
18.3 Halogenation   681
18.4 Nitration and Sulfonation  682
18.5 Friedel–Crafts Alkylation and Friedel–Crafts
Acylation 684
18.6 Substituted Benzenes  691
18.7 Electrophilic Aromatic Substitution of
Substituted Benzenes  694
18.8 Why Substituents Activate or Deactivate a
Benzene Ring  696
18.9 Orientation Effects in Substituted
Benzenes   698

18.10 Limitations on Electrophilic Substitution
Reactions with Substituted Benzenes  701
18.11 Disubstituted Benzenes  703
18.12 Synthesis of Benzene Derivatives  705
18.13 Nucleophilic Aromatic Substitution  706
18.14 Halogenation of Alkyl Benzenes  709
18.15 Oxidation and Reduction of Substituted
Benzenes 711
18.16 Multistep Synthesis  715



Key Concepts  718
Problems   721

19 Carboxylic Acids and
the Acidity of the O–H
Bond 729
19.1
19.2
19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11

Structure and Bonding  730
Nomenclature 731
Physical Properties  734
Spectroscopic Properties  735
Interesting Carboxylic Acids  736
Aspirin, Arachidonic Acid, and
Prostaglandins 737
Preparation of Carboxylic Acids  739
Reactions of Carboxylic Acids—General
Features 740
Carboxylic Acids—Strong Organic Brønsted–
Lowry Acids  741
Inductive Effects in Aliphatic Carboxylic
Acids   744
Substituted Benzoic Acids  746

ix

19.12 Extraction 749
19.13 Sulfonic Acids  751
19.14 Amino Acids  752



Key Concepts  755
Problems 756

20 Introduction to
Carbonyl Chemistry;
Organometallic

Reagents; Oxidation and
Reduction 764
20.1
20.2
20.3
20.4
20.5

Introduction 765
General Reactions of Carbonyl Compounds  766
A Preview of Oxidation and Reduction  769
Reduction of Aldehydes and Ketones  771
The Stereochemistry of Carbonyl
Reduction 773
20.6 Enantioselective Carbonyl Reductions  774
20.7 Reduction of Carboxylic Acids and Their
Derivatives 777
20.8 Oxidation of Aldehydes  782
20.9 Organometallic Reagents  782
20.10 Reaction of Organometallic Reagents with
Aldehydes and Ketones  786
20.11 Retrosynthetic Analysis of Grignard
Products 790
20.12 Protecting Groups  792
20.13 Reaction of Organometallic Reagents with
Carboxylic Acid Derivatives  794
20.14 Reaction of Organometallic Reagents with Other
Compounds 797
20.15 α,β-Unsaturated Carbonyl Compounds  799
20.16 Summary—The Reactions of Organometallic

Reagents 802
20.17 Synthesis   802



Key Concepts  805
Problems 808

21 Aldehydes and
Ketones—Nucleophilic
Addition 817
21.1
21.2
21.3
21.4
21.5

Introduction 818
Nomenclature 819
Physical Properties  822
Spectroscopic Properties  823
Interesting Aldehydes and Ketones  825


x

Contents

21.6 Preparation of Aldehydes and Ketones  826
21.7 Reactions of Aldehydes and Ketones—

General Considerations  828
21.8 Nucleophilic Addition of H– and R–—A
Review 831
21.9 Nucleophilic Addition of – CN   833
21.10 The Wittig Reaction  835
21.11 Addition of 1° Amines  840
21.12 Addition of 2° Amines  844
21.13 Addition of H2O—Hydration 845
21.14 Addition of Alcohols—Acetal Formation  849
21.15 Acetals as Protecting Groups  852
21.16 Cyclic Hemiacetals  854
21.17 An Introduction to Carbohydrates  857



Key Concepts  858
Problems 863

22 Carboxylic Acids and
Their Derivatives—
Nucleophilic Acyl
Substitution 868
22.1
22.2
22.3
22.4
22.5
22.6
22.7

Introduction 869
Structure and Bonding  871
Nomenclature 873
Physical Properties  877
Spectroscopic Properties  878
Interesting Esters and Amides  880
Introduction to Nucleophilic Acyl
Substitution 882
22.8 Reactions of Acid Chlorides  885
22.9 Reactions of Anhydrides  887
22.10 Reactions of Carboxylic Acids  889
22.11 Reactions of Esters  894
22.12 Application: Lipid Hydrolysis  896
22.13 Reactions of Amides  899
22.14 Application: The Mechanism of Action
of β-Lactam Antibiotics  900
22.15 Summary of Nucleophilic Acyl Substitution
Reactions 901
22.16 Natural and Synthetic Fibers  902
22.17 Biological Acylation Reactions  904
22.18 Nitriles 906



Key Concepts  911
Problems 914

23 Substitution Reactions
of Carbonyl Compounds
at the 𝛂 Carbon  924

23.1
23.2
23.3
23.4

Introduction 925
Enols 926
Enolates 928
Enolates of Unsymmetrical Carbonyl
Compounds 934
23.5 Racemization at the α Carbon  936
23.6 A Preview of Reactions at the α Carbon  937
23.7 Halogenation at the α Carbon  938
23.8 Direct Enolate Alkylation  942
23.9 Malonic Ester Synthesis  946
23.10 Acetoacetic Ester Synthesis  950



Key Concepts  953
Problems 955

24 Carbonyl Condensation
Reactions 962
24.1
24.2
24.3
24.4
24.5
24.6

24.7
24.8
24.9

The Aldol Reaction  963
Crossed Aldol Reactions  967
Directed Aldol Reactions  971
Intramolecular Aldol Reactions  973
The Claisen Reaction  975
The Crossed Claisen and Related Reactions  977
The Dieckmann Reaction  979
The Michael Reaction  980
The Robinson Annulation  982




Key Concepts  986
Problems   987

25 Amines 996
25.1
25.2
25.3
25.4
25.5
25.6
25.7
25.8
25.9

Introduction 997
Structure and Bonding  997
Nomenclature 999
Physical Properties  1001
Spectroscopic Properties  1002
Interesting and Useful Amines  1004
Preparation of Amines  1007
Reactions of Amines—General Features  1014
Amines as Bases  1014


xi

Contents

25.10 Relative Basicity of Amines and Other
Compounds 1016
25.11 Amines as Nucleophiles 1022
25.12 Hofmann Elimination 1024
25.13 Reaction of Amines with Nitrous Acid 1027
25.14 Substitution Reactions of Aryl Diazonium
Salts 1029
25.15 Coupling Reactions of Aryl Diazonium
Salts 1034
25.16 Application: Synthetic Dyes and Sulfa
Drugs 1036
Key Concepts 1038
Problems 1041

28.5
28.6
28.7
28.8
28.9
28.10
28.11
28.12
28.13

Key Concepts 1144
Problems 1147

26 Carbon–Carbon BondForming Reactions in
Organic Synthesis 1049

29 Amino Acids and
Proteins 1152

26.1

Coupling Reactions of
Organocuprate Reagents 1050
26.2 Suzuki Reaction 1052
26.3 Heck Reaction 1056
26.4 Carbenes and Cyclopropane Synthesis
26.5 Simmons–Smith Reaction 1061
26.6 Metathesis 1062

1058

Key Concepts 1067
Problems 1068

27 Pericyclic

27.2
27.3
27.4
27.5
27.6

Types of Pericyclic
Reactions 1077
Molecular Orbitals 1078
Electrocyclic Reactions 1080
Cycloaddition Reactions 1087
Sigmatropic Rearrangements 1091
Summary of Rules for Pericyclic Reactions
Key Concepts 1098
Problems 1099

28 Carbohydrates 1106
28.1
28.2
28.3
28.4

smi21553_FM.indd 11

Introduction 1107
Monosaccharides 1108
The Family of D -Aldoses 1113
The Family of D -Ketoses 1115

29.1
29.2
29.3
29.4
29.5
29.6
29.7
29.8
29.9
29.10

Amino Acids 1153
Synthesis of Amino Acids 1156
Separation of Amino Acids 1159
Enantioselective Synthesis of Amino Acids
Peptides 1164
Peptide Sequencing 1169
Peptide Synthesis 1172
Automated Peptide Synthesis 1177
Protein Structure 1179
Important Proteins 1186

1163

Key Concepts 1189

Problems 1191

Reactions 1076
27.1

Physical Properties of Monosaccharides 1116
The Cyclic Forms of Monosaccharides 1116
Glycosides 1124
Reactions of Monosaccharides at the OH
Groups 1127
Reactions at the Carbonyl Group—Oxidation
and Reduction 1128
Reactions at the Carbonyl Group—Adding or
Removing One Carbon Atom 1131
Disaccharides 1134
Polysaccharides 1138
Other Important Sugars and Their
Derivatives 1140

30 Synthetic Polymers 1198

1097

30.1 Introduction 1199
30.2 Chain-Growth Polymers—
Addition Polymers 1200
30.3 Anionic Polymerization of
Epoxides 1207
30.4 Ziegler–Natta Catalysts and Polymer
Stereochemistry 1208

30.5 Natural and Synthetic Rubbers 1210
30.6 Step-Growth Polymers—Condensation
Polymers 1211
30.7 Polymer Structure and Properties 1216
30.8 Green Polymer Synthesis 1217
30.9 Polymer Recycling and Disposal 1220
Key Concepts 1223
Problems 1225

12/9/16 4:05 PM


xii

Contents

31 Lipids 1231

Appendix C  Bond Dissociation Energies for Some
Common Bonds [A–B → A• + •B]  A-7

(Available online)

Appendix D  Reactions That Form Carbon–Carbon
Bonds A-8

31.1
31.2
31.3
31.4

31.5
31.6
31.7
31.8

Introduction 1232
Waxes 1233
Triacylglycerols 1234
Phospholipids 1238
Fat-Soluble Vitamins  1241
Eicosanoids 1242
Terpenes 1245
Steroids 1250

Appendix E  Characteristic IR Absorption
Frequencies A-9




Key Concepts  1255
Problems 1256

Glossary G-1
Credits C-1
Index I-1

Appendix A  pKa Values for Selected Compounds  A-1
Appendix B  Nomenclature A-3

Appendix F  Characteristic NMR Absorptions  A-10
Appendix G  General Types of Organic
Reactions A-12
Appendix H  How to Synthesize Particular Functional
Groups A-14


Preface

My goal in writing Organic Chemistry was to create a text that showed students the beauty and
logic of organic chemistry by giving them a book that they would use. This text is based on lecture
notes and handouts that were developed in my own organic chemistry courses over my 30-year
teaching career. I have followed two guiding principles: use relevant and interesting applications
to illustrate chemical phenomena, and present the material in a student-friendly fashion using
bulleted lists, solved problems, and extensive illustrations and summaries. Organic Chemistry
is my attempt to simplify and clarify a course that intimidates many students—to make organic
chemistry interesting, relevant, and accessible to all students, both chemistry majors and those
interested in pursuing careers in biology, medicine, and other disciplines, without sacrificing the
rigor they need to be successful in the future.

The Basic Features
• Style   This text is different—by design. Today’s students rely more heavily on visual imag-

ery to learn than ever before. The text uses less prose and more diagrams, equations, tables,
and bulleted summaries to introduce and reinforce the major concepts and themes of organic
chemistry.
• Content  Organic Chemistry accents basic themes in an effort to keep memorization at a
minimum. Relevant examples from everyday life are used to illustrate concepts, and this
material is integrated throughout the chapter rather than confined to a boxed reading. Each
topic is broken down into small chunks of information that are more manageable and easily

learned. Sample problems are used as a tool to illustrate stepwise problem solving. Exceptions to the rule and older, less useful reactions are omitted to focus attention on the basic
themes.
• Organization  Organic Chemistry uses functional groups as the framework within which
chemical reactions are discussed. Thus, the emphasis is placed on the reactions that different
functional groups undergo, not on the reactions that prepare them. Moreover, similar reactions
are grouped together, so that parallels can be emphasized. These include acid–base reactions
(Chapter 2), oxidation and reduction (Chapters 12 and 20), radical reactions (Chapter 15), and
reactions of organometallic reagents (Chapter 20).
By introducing one new concept at a time, keeping the basic themes in focus, and breaking complex problems down into small pieces, I have found that many students find organic chemistry
an intense but learnable subject. Many, in fact, end the year-long course surprised that they have
actually enjoyed their organic chemistry experience.

Organization and Presentation
For the most part, the overall order of topics in the text is consistent with the way most instructors currently teach organic chemistry. There are, however, some important differences in the
way topics are presented to make the material logical and more accessible. This can especially
be seen in the following areas.
• Review material  Chapter 1 presents a healthy dose of review material covering Lewis

structures, molecular geometry and hybridization, bond polarity, and types of bonding. While
many of these topics are covered in general chemistry courses, they are presented here from
an organic chemist’s perspective. I have found that giving students a firm grasp of these fundamental concepts helps tremendously in their understanding of later material.

xiii


xiv

Preface
• Acids and bases  Chapter 2 on acids and bases serves two purposes. It gives students

experience with curved arrow notation using some familiar proton transfer reactions. It also
illustrates how some fundamental concepts in organic structure affect a reaction, in this case
an acid–base reaction. Since many mechanisms involve one or more acid–base reactions, I
emphasize proton transfer reactions early and come back to this topic often throughout the
text.
• Functional groups  Chapter 3 uses the functional groups to introduce important properties of organic chemistry. Relevant examples—PCBs, vitamins, soap, and the cell
membrane—illustrate fundamental solubility concepts. In this way, practical topics that are
sometimes found in the last few chapters of an organic chemistry text (and thus often omitted
because instructors run out of time) are introduced early, so that students can better grasp
why they are studying the discipline.
• Stereochemistry   Stereochemistry (the three-dimensional structure of molecules) is introduced early (Chapter 5) and reinforced often, so students have every opportunity to learn and
understand a crucial concept in modern chemical research, drug design, and synthesis.
• Modern reactions   While there is no shortage of new chemical reactions to present in an
organic chemistry text, I have chosen to concentrate on new methods that introduce a particular three-dimensional arrangement in a molecule, so-called asymmetric or enantioselective
reactions. Examples include Sharpless epoxidation (Chapter 12), CBS reduction (Chapter 20),
and enantioselective synthesis of amino acids (Chapter 29).
• Grouping reactions   Since certain types of reactions have their own unique characteristics and
terminology that make them different from the basic organic reactions, I have grouped these reactions together in individual chapters. These include acid–base reactions (Chapter 2), oxidation
and reduction (Chapters 12 and 20), radical reactions (Chapter 15), and reactions of organometallic reagents (Chapter 20). I have found that focusing on a group of reactions that share a common
theme helps students to better see their similarities.
• Synthesis   Synthesis, one of the most difficult topics for a beginning organic student to
master, is introduced in small doses, beginning in Chapter 7 and augmented with a detailed
discussion of retrosynthetic analysis in Chapter 11. In later chapters, special attention
is given to the retrosynthetic analysis of compounds prepared by carbon–carbon bondforming reactions (for example, Sections 20.11 and 21.10C).
• Spectroscopy   Since spectroscopy is such a powerful tool for structure determination, four
methods are discussed over two chapters (Chapters 13 and 14).
• Key Concepts   End-of-chapter summaries succinctly summarize the main concepts and
themes of the chapter, making them ideal for review prior to working the end-of-chapter
problems or taking an exam.

New to this Edition
• Chemical structures were updated throughout the text for a more modern and consistent look.
• Color has also been used in many areas to help students better understand three-dimensional

structure, stereochemistry, and reactions.
• All nomenclature has been updated in accord with newer IUPAC nomenclature recommendations and the 1993 nomenclature rules.
• The design of the mechanism boxes has been revised, so that students can more readily see
how one intermediate is converted to another.
• In response to reviewer feedback, new material has been added to several chapters. Topics
include a section on biological nucleophilic substitution with phosphorus leaving groups
(Section 7.16) and a section on thiols and sulfides (Section 9.15). The section on biological oxidation was revised to include the oxidizing agent NAD+, with new structures in the
mechanism of oxidation of an alcohol, resulting in a more biological flavor to this material
(Section 12.14). A new section on biological reactions with allylic diphosphates and a new
mechanism on biological reactions with allylic diphosphates have been added to Section 16.2.
New material on biological reduction appears in Section 20.6, and the discussion of ultraviolet
spectroscopy has been expanded in Section 16.15.


Preface

xv

• Material on classifying carbons, hydrogens, alcohols, alkyl halides, amines, and amides was

moved from later chapters to earlier in the text (Section 3.2), so that it is included in the
discussion of functional groups.
• Over 350 new problems have been added to the new edition, increasing the variety of problems for instructors and students alike.
• The chapter on lipids now appears online and is available in customizable versions of the
text in McGraw-Hill Create.
• An online supplement covering imine derivatives is also available on the Online Learning

Center’s Instructor Resources, via the Library tab in Connect.
• New How To’s, Sample Problems, and micro-to-macro illustrations have also been added
throughout the new edition to clarify topics and enhance the student learning experience.


Tools to Make Learning Organic Chemistry Easier
842

Illustrations

Chapter 21

Aldehydes and Ketones—Nucleophilic Addition

Figure 21.9
The key reaction in the
chemistry of vision

Organic Chemistry is supported by a well-developed
illustration program. Besides traditional skeletal (line)
structures and condensed formulas, there are numerous
ball-and-stick molecular models and electrostatic potential
maps to help students grasp the three-dimensional
structure of molecules (including stereochemistry) and to
better understand the distribution of electronic charge.

462

cis
N

hν

opsin

trans

Chapter 12 Oxidation and Reduction

+ nerve impulse

When an unsaturated vegetable
N oil is treated with hydrogen, some (or all) of the π bonds add
rhodopsin
H2, decreasing
the number ofopsin
degrees of unsaturation (Figure 12.4). This increases the melting
point of the oil. For example, margarine is prepared by partially hydrogenating vegetable oil to
give a product having a semi-solid consistency
that more closely
resembles butter. This process
plasma
The nerve impulse travels along
is sometimes called hardening.
membrane
the optic nerve to the brain.
If unsaturated oils 11-cis-retinal
are healthier than saturated fats, why does the food industry hydrogenate
bound
to opsin

oils? There are two
reasons—aesthetics
and shelf life. Consumers prefer the semi-solid
consistency
of margarine to a liquid oil. Imagine pouring vegetable oil on a optic
piecenerve
of toast or
rhodopsin
pancakes.
Furthermore, unsaturated oils are more susceptible than saturated fats to oxidation at the
retina
allylic carbon atoms—the carbons adjacent to the double bond carbons—a process
discussed
in Chapter 15. Oxidation makes the oil rancid and inedible. Hydrogenating the double bonds
reduces the number of allylic carbons (also illustrated in Figure 12.4), thus reducing the likedisc
lihood of oxidation and increasing
food product. This process reflects a
membrane the shelf life of the pupil
delicate balance between providing consumers with healthier food products, while maximizrod cell in
ingrhodopsin
shelf lifeinto
prevent
cross-section of the eye
a rod
cell spoilage. the retina

Peanut butter is a common
consumer product that
contains partially hydrogenated
vegetable oil.

One other fact is worthy of note. Because the steps in hydrogenation are reversible and H
atoms areisadded
in a sequential
rather
than concerted
fashion,
a cisrod
double
can be
•  Rhodopsin
a light-sensitive
compound
located
in the membrane
of the
cells inbond
the retina
of isomthe
eye. Rhodopsin
containsbond.
the protein
bonded
to 11-cis-retinal
via[3]
an in
imine
linkage. When
erized
to a trans double

Afteropsin
addition
of one
H atom (Step
Mechanism
12.1), an
light
strikes this molecule,
crowded atom
11-cisto
double
bond
isomerizes
to the
11-trans
intermediate
can lose athe
hydrogen
re-form
a double
bond
with
either isomer,
the cis and
or trans
a nerve
impulse is transmitted to the brain by the optic nerve.
configuration.
As a result, some of the cis double bonds in vegetable oils are converted to trans double bonds
during hydrogenation, forming so-called “trans fats.” The shape of the resulting fatty acid chain

The complex
process closely
of vision
centers around
this of
imine
derived fatty
fromacid
retinal
(Figure
21.9). Thetrans
is very different,
resembling
the shape
a saturated
chain.
Consequently,
The central role of rhodopsin
11-cis double bond in rhodopsin creates crowding in the rather rigid side chain. When light strikes
in the visual process was
the rod cells of the retina, it is absorbed by the conjugated double bonds of rhodopsin, and the 11-cis
delineated by Nobel Laureate
double bond is isomerized to the 11-trans arrangement. This isomerization is accompanied by a
George Wald of Harvard 
drastic change in shape in the protein, altering the concentration of Ca2+ ions moving across the cell
University.
membrane,
sending a nerve
the brain,
which is then

Figure 12.4
Partial and
hydrogenation
of theimpulse
double to
bonds
in a vegetable
oil processed into a visual image.

21.12 Addition of 2° Amines

Micro-to-Macro Illustrations

O

21.12A Formation of
8 ptEnamines
helvetica roman

Unique to Organic Chemistry are micro-to-macro illustrations,
where line art and photos combine with chemical structures
to reveal the underlying molecular structures giving rise to
macroscopic properties of common phenomena. Examples
include starch and cellulose (Chapter 5), adrenaline (Chapter 7),
partial hydrogenation of vegetable oil (Chapter 12), and dopamine
(Chapter 25).

• lower melting

H

––
–
H2
8.5 pt helvetica
–
–
AddOH2 toroman
one
NR2
OH
(1 equiv)
Chapter 13 Mass Spectrometry and
C Infrared
C only. Spectroscopy
––
–
Pd-C
8.5 pt helvetica bold R2NH
–
–
–H2O
R'
R'
R'
NR2
O 3CH2CH2CH2CH2+ and CH3• . Fragmentation generates a cation and a radical, and
forms CH
––
oil in margarine
– Partially hydrogenated

9 pt helvetica roman
–
cleavage
generally
yields the more stable,
more– substituted
carbocation.
• one C Cenamine
R'
= H or alkyl
carbinolamine
O
– • higher melting
–
–
––
9 pt helvetica bold
• semi-solid
at room temperature
H
Like imines, enamines are also formed by the addition
of a nitrogen
nucleophile
to a carbonyl

502

e–

–

–
+ CH
helvetica lightof water. In thisHcase,
–
––
3
group followed 9bypt elimination
however,
elimination
occurs across
two
H H
adjacent carbon atoms to form a new carbon–carbon π bond.
cation
radical
Cleave the bond
– in red.
shown

10 pt helvetica roman

m/z = 71
–– = an allylic–– carbon—a C adjacent to a C C

• Decreasing the number of degrees of unsaturation
increases
point.
Only
one long

radical
cation
10 pt helvetica
bold the melting
–
–– chain of–– the triacylglycerol is drawn.
m/z = 86 some double bonds remain in the product.
• When an oil is partially hydrogenated, some double bonds react with H2, whereas
• Partial hydrogenation decreases the number of allylic sites (shown in blue), making a triacylglycerol less susceptible to oxidation,
–
pt times
–
–
––
• LossofaCH39groupalwaysformsafragmentwithamass15unitslessthanthe
thereby increasing its shelf life.
molecularion.
––
–
9 pt times bold
–
–

As a result, the mass spectrum of hexane shows a peak at m/z = 71 due to CH3CH2CH2CH2CH2+.
10 pt times
–– rise to other fragments
Figure 13.5 illustrates
how cleavage of other C – C bonds ––in hexane gives
that correspond to peaks in its mass spectrum.
––

10 pt times bold
–
––

smi21553_ch21_817-867.indd 842

Spectra

Figure 13.5

[1]

03/10/15 1:25 PM

[3]

Identifying fragments in the
mass spectrum of hexane
smi21553_ch12_455-494.indd 462

[2]

–

8 pt helvetica bold

–

–[1]
–

8.5 pt helvetica roman

–

CH3CH2
m/z = –
–29

8.5 pt helvetica bold

–

10/20/15 11:49 AM

[4]

–cation derived from hexane
radical –
m/z = 86
–
[2] –
[3]

–
–

8 pt helvetica roman

[4]

+

9 pt helvetica roman

–

9 pt helvetica bold

–

9 pt helvetica light

10 pt helvetica roman
10 pt helvetica bold

m/z = 43
––

50

m/z = 57

m/z = 71

––

––

100

Relative abundance

Over 100 spectra created specifically for Organic Chemistry
are presented throughout the text. The spectra are colorcoded by type and generously labeled. Mass spectra are
green; infrared spectra are red; and proton and carbon nuclear
magnetic resonance spectra are blue.

Unsaturated vegetable oil

–– • two C C’s
––

–

O

–
8 ptwith
helvetica
bold
–
–– • liquidEnamines
A 2° amine reacts
an aldehyde
or ketone to give
an enamine.
have a nitrogen
at–room temperature
atom bonded to a double bond (alkene + amineH= enamine).

–
–

––

–
–

––

9.8 Dehydration of Alcohols to Alkenes

347

The E1 dehydration
of 2°
with acid gives clean elimination products without
–– and 3° alcohols
–
––
by-products formed from an SN1 reaction. This makes the E1 dehydration of alcohols much
more synthetically useful than the E1 dehydrohalogenation of alkyl halides (Section 8.7). Clean
elimination takes
the reaction
mixture contains no good nucleophile to react with
–
– place because
–
––

0
the intermediate carbocation,
so no competing SN1 reaction occurs.
0
–10 20 30–– 40 50 60 70 80 90 100
–
–
m/z

9.8C The• Cleavage
E2 Mechanism
for the Dehydration
of 1°
Alcohols
––– in hexane forms lower
of C – C bonds
molecular weight fragments that
– ––(labeled [1]–[4])

8 pt helvetica roman

9 pt times

–

–

–

correspond to lines in the–mass spectrum.

Although the mass spectrum is complex, possible
1° carbocations
are
the dehydration of 1° alcohols cannot occur by an
–
– highly unstable,
––
structures can be assigned to some of–the fragments, as shown.
– intermediate. With 1° alcohols, therefore, dehydration
E1 mechanism–involving––a carbocation
follows an E2 mechanism.
The two-step
process for the conversion of CH3CH2CH2OH
––
–
8.5 pt helvetica roman
–
–
(a 1o alcohol) to– CH3CH –– CH2 with H––2SO4 as acid catalyst is shown in Mechanism 9.2.
10 pt times
8 pt helvetica boldBecause

9 pt times bold

Sample
13.4
8.5 pt Problem
helvetica bold

Mechanisms

Curved arrow notation is used extensively to help students
follow the movement of electrons in reactions.

10 pt times bold

–– [(CH3)2CHCH(CH3)CH2CH3] shows fragments at
–
The mass spectrum
– of 2,3-dimethylpentane
–
m/z = 85 and 71. Propose–possible structures
for the ions that give rise to these peaks.
–

–

9 pt helvetica roman

–

–

Solution

–
––

–
–

To solve a problem of this sort,
first calculate
the mass of the molecular ion. Draw out the structure
–
9 pt helvetica
bold
– of a 1° –ROH—An
– a C––– CE2
–– – calculate––the mass of the resulting fragments. Repeat this
8 pt helvetica roman
–
–
helvetica
Mechanism
9.28 ptDehydration
Mechanism
ofroman
the compound,
break
bond,
and
–
8 pt helvetica roman
–– of the
process on different
C – C bonds
desired mass-to-charge ratio are formed.
–– –until fragments
–
9

pt
helvetica
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–
–
–
–
–
8
pt
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–
––
8 pt helvetica bold
–
–
8 pt helvetica bold

OH

–

8.5 pt helvetica roman

8.5 pt helvetica bold
––
8.5 pt helvetica bold 10 pt helvetica bold–
smi21553_ch13_495-526.indd 502

1

8.5 pt helvetica bold

––

HSO4

––

––

–

+ 8.5 pt
H helvetica
OSO3Hroman
–– 1

8.5 pt helvetica roman10 pt helvetica roman–

––

–––OH2

–2
––
–

–––

–––

––
–

H–

9 pt helvetica roman

–

–
–
–
–

–

––
––

––
––

+

H2O
+
good

leaving group

H2SO4

––

–
–

06/08/15 9:57 PM

–
Protonation
ofhelvetica
the
atom converts
the
9 ptoxygen
timesroman
– poor
–
–– ( –OH)
–– into a good leaving group (H2O).
–– leaving
–
–
9 pt
– group

9 pt helvetica roman

–

–

–

–

––

–

–
–
–– – or H ––O) removes a proton from the β carbon; the
9 pt helvetica
bold
2 Two bonds9 are
broken
two
bonds are –formed. The
(HSO
2
– base
boldand
–
– 4 ––
–
–

9 pt
pt times
bold
––π bond
–
–H
–
9 pt helvetica bold
electron pair
inhelvetica
the9 β C
bond forms
the new–
and
the–– leaving
group
(H2O) departs.
––
pt helvetica light
–
––
910
pt pt
helvetica
––
times light
– –– ––
––

9 pt helvetica light

10 pt helvetica roman
10 pt helvetica bold

xvi

–––
10times
pt helvetica
roman
––––
10 pt
bold
–
–– ––
pt helvetica
helvetica roman
108pt
roman
––
–
––
–
10 pt helvetica
bold–
–
–The dehydration
–1° alcohol
–
of

a
begins
pt helvetica
helvetica bold
108pt
bold
––
–– –

––

––

–
–

–

–– protonation of the OH group to form a good
with
the
–– –
leaving group, just as –in the dehydration of a 2° or 3° alcohol. With 1° alcohols, however, loss of
– 9 pt times–
–
–
–
– of a β
–
––

the leaving group and removal
proton
occur
at the same time, so that no highly unstable
– –
pt times
––
–
––
8.5 pt helvetica9roman
– –
–––
carbocation
is generated.
9 pt1°times
bold
–
–
–

–
––
– –
9 pt times
–bold
–
––– –
9 pt times
bold
–

8.5 pt helvetica
–
––
––
10 pt times–
–
––
Draw the structure
of each
state in–the two-step mechanism for the reaction,
9 pt times bold Problem 9.13
–
––– transition
10 pt–times
––
– –
– – 2 + H2O.––
9 pt helvetica
– CH
3CH
2CH2OH + H2SO4 →
10 roman
pt CH
times
bold
– 3CH – CH
–
–
––
–

10 pt times– bold
––
–
10 pt times
–
–– –
–
–
––
9 pt helvetica bold


Several additional examples of alkane nomenclature are given in Figure 4.1.

Figure 4.1
Examples of alkane
nomenclature
2,3-dimethylpentane

4-ethyl-5-methyloctane

Number to give the 1st methyl group
the lower number.

Assign the lower number to the 1st substituent
alphabetically: the e of ethyl before the m of methyl.

Problem Solving

4-ethyl-3,4-dimethyloctane

2,3,5-trimethyl-4-propylheptane

Alphabetize the e of ethyl
before the m of methyl.

Pick the long chain with more substituents.

• The carbon atoms of each long chain are drawn in red.

Sample Problems

Sample Problem 4.1

Give the IUPAC name for the following compound.

Sample Problems show students how to solve organic
chemistry problems in a logical, stepwise manner. More
than 800 follow-up problems are located throughout the
chapters to test whether students understand concepts
covered in the Sample Problems.

Solution
To help identify which carbons belong to the longest chain and which are substituents, box in or
highlight the atoms of the long chain. Every other carbon atom then becomes a substituent that
needs its own name as an alkyl group.
Step 1: Name the parent.

Step 3: Name and number the substituents.
tert-butyl at C5

methyl at C3
5

3

9 C’s in the longest chain
nonane
Step 2: Number the chain.

5

Step 4: Combine the parts.

• Alphabetize: the b of butyl

3

4

before the m of methyl

2

9

Answer: 5-tert-butyl-3-methylnonane

1

first substituent at C3

Problem 4.7

Give the IUPAC name for each compound.

a.

b.

c.

d.

smi21553_ch04_128-173.indd 137

874

23/07/15 11:15 AM

Chapter 22

Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution

How To Name an Ester (RCO2R') Using the IUPAC System

How To’s

Example Giveasystematicnameforeachester:

How To’s provide students with detailed instructions on

how to work through key processes.

O

O

a.

b.

8 pt helvetica roman

O

O

8 pt helvetica bold

Step [1]

–

––

––

–

––

––

NametheR'groupbondedtotheoxygenatomasanalkylgroup.

• The name of the alkyl group, ending in the suffix -yl, becomes the first part of the ester name.
––
8.5 pt helvetica roman
–
––
O

8.5 pt helvetica bold

9 pt helvetica roman

8 pt helvetica
8 ptbold
helvetica bold

8 pt helvetica
––– bold

10 pt helvetica roman

tert-butyl

–––

O

–

–

–
–

–
–––

–
–––

8.5 pt helvetica bold

–
– –
–

––

– ––
–

–––

–
–
––

–

–
–

–

––

–

– times
––
9 pt

9 pt helvetica
9 pt times
bold
– roman

–

––

9 pt helvetica bold

9 pt helvetica
9 ptlight
helvetica light

–

–times
10 pt––

9 pt helvetica light

–––

acetate
–

––

Answer: ethyl acetate

–

–
–

–

O

derived from
––
cyclohexanecarboxylic
acid
–

–
–
––
–

–
–
–

–
–

All 1°–amides are
– named by––replacing the -ic acid, -oic acid, or -ylic acid ending with the suffix
–
amide.
–––
––
–
–

– ––
–

Chapter 22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution
166

cyclohexanecarboxylate

–

Answer: tert-butyl cyclohexanecarboxylate

––
22.3D
Naming
–– –
–
– an ––Amide

10 pt times bold

–roman
– helvetica––
10 pt

–

O

derived from
acetic acid

O

––

––
–

–– ––

–

––

––

–

–– ––

– helvetica–– bold
10 8.5
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pt helvetica roman

9 pt helvetica
9 pt helvetica
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bold

10 pt helvetica
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O

––

• The
name of the acyl group–becomes –
–– of the name.
9 pt helvetica
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–the second part

–

9 pt helvetica
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898

–
–

–

8 pt helvetica roman

8.5 pt helvetica
8.5 pt bold
helvetica bold

O

group

ethyl group
–
–––
–– ––
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–
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–
9Step
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[2] Nametheacylgroup(RCO
–
–––
–– ––
––

8 pt helvetica
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8.5 pt helvetica
8.5 ptroman
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––

O–
–

–

O

Chapter 4 Alkanes

O

–– –
10–pt helvetica
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–
– –
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8 pt
helvetica
–
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NH2
10 pt helvetica
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––
–
NH2
–
–

– –
Olestra is a polyester formed
and
sucrose,
the ––sweet-tasting
8 ptfrom
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–
–
–
NH
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Key
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–
–
9
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–
–
carbohydrate in table sugar. Naturally
occurring
triacylglycerols
are also polyesters formed from
–
–

–
–
9 pt times 9 pt times
–
––
– –
–
derived from
derived
from
derived from
–– in close
–
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proximity
Alkanes
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–

–
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–
– acid
– –– benzoic
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2-methylcyclopentanecarboxylic acid
– As
– olestra
that
they
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to8.5bept–––hydrolyzed.
a result,
is
Instead,
it
– –
––
–
–
–
General
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Alkanes
(4.1–4.3)
9 pt times 9bold

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–
–
–
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8.5 pt bold
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–acetamide
– not metabolized.
– benzamide
–
2-methylcyclopentanecarboxamide
–
–
3
10 pt times
–
– spconsumer.
– C atoms.
• providing
Alkanesarecomposedoftetrahedral,
hybridized
passes through the body unchanged,
no calories
to the
A 2° or 3° amide
has–– two parts–– to

annHacyl
group that contains the carbonyl group
•9 Therearetwotypesofalkanes:acyclicalkaneshavingmolecularformulaC
2n + 2, and
9 pt helvetica
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–– its structure:
––
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10 pt times
10 pt olestra’s
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–
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and
one–– or

two
bonded to triacylthe nitrogen atom.
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bonds
it (RCO
similar
solubility
naturally
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2nto

Applications and Summaries
Key Concept Summaries

Succinct summary tables reinforcing important principles
and
glycerols,
but its three-dimensional structure makes it inert to hydrolysis because of steric hindrance.
–
–
10 pt times
10 bold
pt times bold
–
––
–
– –
–
–

concepts are provided at the end of each chapter.
How To Name a 2° or 3° Amide

–– no functional
––
– H bonds––and
9 pt helvetica
pt helvetica
bold
bold
group, so they undergo
•9Alkaneshaveonlynonpolar
C – C and C –
few reactions.

9 pt helvetica
9 ptlight
helvetica light
–
––
• Alkanesarenamedwiththesuffix-ane.

Problem 22.22

How would you synthesize olestra from
sucrose?
Names
of Alkyl Groups (4.4A)

–

10 pt helvetica
10 pt helvetica
roman roman
–
–
CH3–
=
Example Giveasystematicnameforeachamide:
methyl
–
10 pt helvetica
10Opt helvetica
bold
bold
–
O–

22.12B The Synthesis of Soap
Soap has been previously
discussed in Section 3.6.

Margin Notes
Margin notes are placed
carefully throughout
the chapters, providing
interesting information
relating to topics covered
in the text. Some margin
notes are illustrated
with photos to make the

chemistry more relevant.

––

–
––
–

–
–

––
–

–

=

CH3CH2CH2CH2–
butyl
–
–

=

CH3CH2–

–– ––

=

CH3CH2CHCH3

N
a. H 9 N
b.
––
pt times 9 ethyl
pt
–
–– a triacylglycerol.
––sec-butyl
––
Soap is prepared by the basic
hydrolysis
ortimes
saponification
of
Heating
H
an animal fat or vegetable oil with
aqueous
base
the ––three esters
to form
glycerol
9 pt times
bold
9 pt times
boldhydrolyzes

–
–– ––
––
(CH3)2CHCH2–
=
=
CH3CH2CH2–
and sodium salts of three fatty acids. These carboxylate
salts are soaps, which
isobutyl clean away dirt
propyl
–
–
–
––
10 pt times
10 pt timesThe nonpolar
–
–
–
–
because of their two structurally different
regions.
tail
dissolves
grease
and oil and
=
(CH3)3C–
(CH3)2CH–

=
the polar head makes it soluble10in
water
(Figure
3.5).
Most
triacylglycerols
tert-butyl
isopropyl
–
–
pt times
10bold
pt times bold
–
–
––
– have–
–two or three
different R groups in their hydrocarbon chains, so soaps are usually mixtures of two or three difConformations in Acyclic Alkanes (4.9, 4.10)
ferent carboxylate salts.
• Alkaneconformationscanbeclassifiedaseclipsed, staggered, anti, or gauche depending on
the relative orientation of the groups on adjacent carbons.

O
O

smi21553_ch22_868-923.indd 874

R

O
O
R'

NaOH

H

OHH

H2O

R''

O

eclipsed
H
H

OH

OH

+

staggered

anti

H
H

Na

O
O

• dihedral angle = 0°

R

H

H

+

H

H

O

O
HNa
• dihedral angle = 60°

R'

+H

30/07/15 9:23 PM

gauche

CH3

H
H

H
H

O

H

Na
CH3 O

H

H

H

CH3

R"

CH3
• dihedral angle of two
• dihedral angle of two
CH3 from
groupsfatty
= 180°acids.
CH3 groups = 60°
derived

Soaps are carboxylate salts
glycerol• Astaggeredconformationislower in energy than an eclipsed conformation.
• Ananticonformationislower
in energy than a gauche conformation.
For example:

O
triacylglycerol

Types of Strain

O

• Torsional strain—an increase in energy caused by eclipsing interactions (4.9).
• Steric strain—an
in energy when atoms are forced too close to each other (4.10).
–
Na+ increase
O
• Angle strain—an increase in energy when tetrahedral bond angles deviate from 109.5° (4.11).

All soaps are salts of fatty
acids. The main difference
between soaps is the addition
of other ingredients that do not
alter their cleaning properties:
dyes for color, scents for a
pleasing odor, and oils for
lubrication. Soaps that float are
aerated, so that they are less
dense than water.

Two Types of Isomers
polar head
nonpolar tail
[1] Constitutional isomers—isomers that differ in the way the atoms are connected to each other
(4.1A).
[2] Stereoisomers—isomers that differ only in the way the atoms are oriented in space (4.13B).

Na+

–

cis

trans

3-D structure
stereoisomers
Soaps are typically made from lard (from hogs), tallowconstitutional
(from

isomerscattle or sheep), coconut oil, or
palm oil. All soaps work in the same way, but have somewhat different properties depending on
the lipid source. The length of the carbon chain in the fatty acids and the number of degrees of
unsaturation affect the properties of the soap to some extent.

Problem 22.23

xvii

What is the composition of the soap prepared by hydrolysis of the following triacylglycerol?
smi21553_ch04_128-173.indd 166

O

23/07/15 11:18 AM


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Learning Resources for Instructors and Students
The following items may accompany this text. Please consult your McGraw-Hill representative
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Presentation Tools
Within the Instructor’s Presentation Tools, instructors have access to editable PowerPoint lecture outlines, which appear as ready-made presentations that combine art and lecture notes for
each chapter of the text. For instructors who prefer to create their lecture notes from scratch, all
illustrations, photos, tables, How To’s, and Sample Problems are pre-inserted by chapter into a
separate set of PowerPoint slides. They are also available as individual .jpg files.
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Student Study Guide/Solutions Manual 
Written by Janice Gorzynski Smith and Erin R. Smith, the Student Study Guide/Solutions Manual
provides step-by-step solutions to all in-chapter and end-of-chapter problems. Each chapter begins
with an overview of key concepts and includes a short-answer practice test on the fundamental
principles and new reactions.


Acknowledgments

When I started working on the first edition of Organic Chemistry in the fall of 1999, I had no sense of the magnitude of the
task, or any idea of just how many people I would rely upon
to complete it. Fortunately, I have had the steadfast support of
a dedicated team of publishing professionals at McGraw-Hill.
I am especially thankful for the opportunity to work with
Senior Product Developer Mary Hurley, who skillfully and
efficiently guided me through the process of updating this fifth
edition. Mary has been my rock through the many months of
re-drawing chemical structures and re-designing mechanisms
and art. I am grateful to once again work with Lead Content
Project Manager Peggy Selle, who managed the production of
this updated and re-designed text. Organic Chemistry has also
benefited greatly from the expertise and market-based feedback
provided by Marketing Manager Matthew Garcia.
Special thanks go out to Brand Manager Andrea P
­ ellerito,
who gave me the day-to-day editorial support crucial in
producing a revision of Organic Chemistry. Thanks also to

Managing Director Thomas Timp, who efficiently directed the
editorial team that produced this revision. I also appreciate the
work of Matt Backhaus (Designer) and Carrie Burger (Photo
Researcher) who are responsible for the visually pleasing
appearance of this edition. Thanks are again due to freelance
Developmental Editor John Murdzek for his meticulous editing
and humorous insights on my project.
My immediate family has experienced the day-to-day
demands of living with a busy author. Thanks go to my husband Dan, my children Erin, Jenna, Matthew, and Zachary, and
my grandchildren Max, Koa, and Alijah, all of whom keep me
grounded during the time-consuming process of writing and
publishing a textbook.
Among the many others that go unnamed but who have
profoundly affected this work are the thousands of students I
have been lucky to teach over the last 30 years. I have learned
so much from my daily interactions with them, and I hope that
the wider chemistry community can benefit from this experience by the way I have presented the material in this text.
This fifth edition has evolved based on the helpful feedback of many people who reviewed the fourth edition text
and digital products, class-tested the book, and attended focus
groups or symposiums. These many individuals have collectively provided constructive improvements to the project.
Listed below are the reviewers of the fourth edition text:
Steven Castle, Brigham Young University
Ihsan Erden, San Francisco State University
Andrew Frazer, University of Central Florida, Orlando
Tiffany Gierasch, University of Maryland, Baltimore County

Anne Gorden, Auburn University
Michael Lewis, Saint Louis University
Eugene A. Mash, Jr., University of Arizona
Mark McMills, Ohio University

Joan Mutanyatta–Comar, Georgia State University
Felix Ngassa, Grand Valley State University
Michael Rathke, Michigan State University
Jacob Schroeder, Clemson University
Keith Schwartz, Portland State University
John Selegue, University of Kentucky
Paul J. Toscano, University at Albany, SUNY
Jane E. Wissinger, University of Minnesota

The following contributed to the editorial direction of the
fifth edition text by responding to our survey on the MCAT and
the organic chemistry course student population:
Chris Abelt, College of William and Mary
Orlando Acevedo, Auburn University
Kim Albizati, University of California, San Diego
Merritt Andrus, Brigham Young University
Ardeshir Azadnia, Michigan State University
Susan Bane, Binghamton University
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Sulekha Coticone, Florida Gulf Coast University
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Chapel Hill
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Tammy Davidson, University of Florida
Brenton DeBoef, University of Rhode Island
Amy Deveau, University of New England
Kenneth M. Doxsee, University of Oregon
xxi


xxii

Acknowledgments

Larissa D’Souza, Johns Hopkins University
Philip Egan, Texas A&M University, Corpus Christi
Seth Elsheimer, University of Central Florida
John Esteb, Butler University
Steve Fleming, Temple University
Marion Franks, North Carolina A&T State University
Andy Frazer, University of Central Florida
Brian Ganley, University of Missouri, Columbia
Robert Giuliano, Villanova University

Anne Gorden, Auburn University
Carlos G. Gutierrez, California State University, Los Angeles
Scott Handy, Middle Tennessee State University
Rick Heldrich, College of Charleston
James Herndon, New Mexico State University
Kathleen Hess, Brown University
Sean Hickey, University of New Orleans
Carl Hoeger, University of California, San Diego
Javier Horta, University of Massachusetts, Lowell
Bob A. Howell, Central Michigan University
Jennifer Irvin, Texas State University
Phil Janowicz, Cal State, Fullerton
Mohamad Karim, Tennessee State University
Mark L. Kearley, Florida State University
Amy Keirstead, University of New England
Margaret Kerr, Worcester State University
James Kiddle, Western Michigan University
Jisook Kim, University of Tennessee at Chattanooga
Angela King, Wake Forest University
Margaret Kline, Santa Monica College
Dalila G. Kovacs, Grand Valley State University
Deborah Lieberman, University of Cincinnati
Carl Lovely, University of Texas, Arlington
Kristina Mack, Grand Valley State University
Daniel Macks, Towson University
Vivian Mativo, Georgia Perimeter College, Clarkston
Mark McMills, Ohio University
Stephen Mills, Xavier University
Robert Minto, Indiana University–Purdue University,
Indianapolis

Debbie Mohler, James Madison University
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Anne Padias, University of Arizona
Dan Paschal, Georgia Perimeter College
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Claudia Taenzler, University of Texas at Dallas

Robin Tanke, University of Wisconsin, Stevens Point
Richard T. Taylor, Miami University, Oxford
Edward Turos, University of South Florida
Ted Wood, Pierce College
Kana Yamamoto, University of Toledo

The following individuals helped write and review learning
goal-oriented content for LearnSmart for Organic Chemistry:
David G. Jones, Vistamar School; Adam I. Keller, Columbus
State Community College; and Parul D. Root, Henry Ford
Community College. Harpreet Malhotra of Florida State College at Jacskonville reviewed the Connect content for accuracy, and Ujjwal Chakraborty, also of Florida State College at
Jacksonville, revised the PowerPoint Lectures and Test Bank
for the fifth edition.
Although every effort has been made to make this text and
its accompanying Student Study Guide/Solutions Manual as
error-free as possible, some errors undoubtedly remain and,
for them, I am solely responsible. Please feel free to email me
about any inaccuracies, so that subsequent editions may be
further improved.
With much aloha,
Janice Gorzynski Smith



List of How To’s
How To boxes provide detailed instructions for key procedures that students need to master. Below is a list of each How To and where it is
presented in the text.


Chapter 1

Chapter 2



Chapter 4



Chapter 5



Chapter 7



Chapter 9



Chapter 10



Chapter 11

Chapter 13



Chapter 14



Chapter 16



Chapter 17



Chapter 18



Chapter 21



Chapter 22



Chapter 24

Chapter 25



Chapter 28



Chapter 29

Structure and Bonding
How To  Draw a Lewis Structure  14
How To  Interpret a Skeletal Structure  33
Acids and Bases
How To  Determine Relative Acidity of Protons  77
Alkanes
How To  Name an Alkane Using the IUPAC System  135
How To  Name a Cycloalkane Using the IUPAC System  139
How To  Draw a Newman Projection  145
How To  Draw the Chair Form of Cyclohexane  154
How To  Draw the Two Conformations for a Substituted Cyclohexane  156
How To  Draw Two Conformations for a Disubstituted Cyclohexane   159
Stereochemistry
How To Assign R or S to a Stereogenic Center  187
How To  Find and Draw All Possible Stereoisomers for a Compound with Two Stereogenic Centers  191
Alkyl Halides and Nucleophilic Substitution
How To  Name an Alkyl Halide Using the IUPAC System  249

Alcohols, Ethers, and Related Compounds
How To  Name an Alcohol Using the IUPAC System  334
Alkenes
How To  Name an Alkene  387
How To  Assign the Prefixes E and Z to an Alkene  389
Alkynes
How To  Develop a Retrosynthetic Analysis  445
Mass Spectrometry and Infrared Spectroscopy
How To  Use MS and IR for Structure Determination  518
Nuclear Magnetic Resonance Spectroscopy
How To Use 1H NMR Data to Determine a Structure  554
Conjugation, Resonance, and Dienes
How To  Draw the Product of a Diels–Alder Reaction  622
Benzene and Aromatic Compounds
How To Use the Inscribed Polygon Method to Determine the Relative Energies of MOs for Cyclic,
Completely Conjugated Compounds  664
Reactions of Aromatic Compounds
How To  Determine the Directing Effects of a Particular Substituent  698
Aldehydes and Ketones—Nucleophilic Addition
How To  Determine the Starting Materials for a Wittig Reaction Using Retrosynthetic Analysis  838
Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution
How To  Name an Ester (RCO2R') Using the IUPAC System  874
How To  Name a 2° or 3° Amide  874
Carbonyl Condensation Reactions
How To  Synthesize a Compound Using the Aldol Reaction  967
How To  Synthesize a Compound Using the Robinson Annulation  985
Amines
How To  Name 2° and 3° Amines with Different Alkyl Groups  999
Carbohydrates
How To  Draw a Haworth Projection from an Acyclic Aldohexose  1119

Amino Acids and Proteins
How To  Use (R)-α-Methylbenzylamine to Resolve a Racemic Mixture of Amino Acids  1161
How To  Synthesize a Dipeptide from Two Amino Acids   1173
How To  Synthesize a Peptide Using the Merrifield Solid Phase Technique  1178

xxiii


List of Mechanisms
Mechanisms are the key to understanding the reactions of organic chemistry. For this reason, great care has been given to present mechanisms
in a detailed, step-by-step fashion. The list below indicates when each mechanism in the text is presented for the first time.


Chapter 7

Alkyl Halides and Nucleophilic Substitution
7.1 The SN2 Mechanism  264
7.2 The SN1 Mechanism  269

Chapter 8

Alkyl Halides and Elimination Reactions
8.1 The E2 Mechanism  304
8.2 The E1 Mechanism  310

Chapter 9

Alcohols, Ethers, and Related Compounds
9.1 Dehydration of 2° and 3° ROH—An E1 Mechanism  346
9.2 Dehydration of a 1° ROH—An E2 Mechanism  347

9.3 A 1,2-Methyl Shift—Carbocation Rearrangement During Dehydration  349
9.4 Dehydration Using POCl3 + Pyridine—An E2 Mechanism  351
9.5 Reaction of a 1° ROH with HX—An SN2 Mechanism  353
9.6 Reaction of 2° and 3° ROH with HX—An SN1 Mechanism  354
9.7 Reaction of ROH with SOCl2 + Pyridine—An SN2 Mechanism  356
9.8 Reaction of ROH with PBr3—An SN2 Mechanism  357
9.9 Mechanism of Ether Cleavage in Strong Acid—
(CH3)3COCH3 + HI → (CH3)3CI + CH3I + H2O 363


















Chapter 10

Alkenes
10.1 Electrophilic Addition of HX to an Alkene  399
10.2 Electrophilic Addition of H2O to– an Alkene—Hydration 
404
––
8 pt helvetica roman
–
–
10.3 Addition of X2 to an Alkene—Halogenation  406
10.4 Addition of X and OH—Halohydrin
Formation 
408
8pthelveticabold
–
––
––
10.5 Addition of H and BH2—Hydroboration 411

Chapter 11

11.2 Addition of X2 to an Alkyne—Halogenation 
–– 436
–
––
11.3 Tautomerization in Acid  438
11.4 Hydration of an Alkyne  438
–
–
9Chapter
pt helvetica
roman
–
–
12 Oxidation and Reduction–
8.5pthelveticabold

12.1
9pthelveticabold
12.2
9 pt helvetica12.3
light
12.4

12.5
12.6

10 pt helvetica roman
Chapter 15







Alkynes

––
8.5 pt helvetica roman
– of HX to––an Alkyne  435
11.1 Electrophilic Addition

Addition of H2 to an Alkene—Hydrogenation 
459
–
–
–
–
–
Dissolving Metal Reduction of an Alkyne to a Trans Alkene   465
Reduction of RX with
–
–

– LiAlH4 467
–
Epoxidation of an Alkene with a Peroxyacid  469
Oxidation of an Alcohol with CrO3   478
Oxidation of a 1° Alcohol to a Carboxylic
Acid
–   478
–

–

–

Radical Reactions
15.1 Radical Halogenation
– 576
10pthelveticabold
– of Alkanes 
–
15.2 Allylic Bromination with NBS  586
15.3 Radical Addition of HBr to an Alkene  591
9 pt 15.4
times Radical Polymerization
– of CH2 –
– CHZ 595

–
–
–
–

–




Chapter 16 Conjugation, Resonance, and Dienes
–
–
9 pt times16.1
bold Biological Formation– of Geranyl
– Diphosphate 
– 608
16.2 Electrophilic Addition of HBr to a 1,3-Diene—1,2- and 1,4-Addition  617






10 pt Reactions
times
–
–
–
Chapter 18
of Aromatic Compounds
18.1 General Mechanism—Electrophilic Aromatic Substitution  679
–
–
10 pt times 18.2

bold Bromination of Benzene 
–
–
681 –
+
18.3 Formation of the Nitronium Ion ( NO2) for Nitration  682
18.4 Formation of the Electrophile +SO3H for Sulfonation  683



xxiv

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–