Organic Chemistry 4Th Edition David Klein Download PDF Chapter

Organic Chemistry 4th Edition David
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EXAMPLES OF COMMON FUNCTIONAL GROUPS
FUNCTIONAL GROUP* CLASSIFICATION EXAMPLE CHAPTER FUNCTIONAL GROUP* CLASSIFICATION EXAMPLE CHAPTER
O O
R X Cl
Alkyl halide 7 Ketone 19
(X = Cl, Br or ) n-Propyl chloride R R
2-Butanone
R R O
O
C C Alkene 7, 8 Aldehyde 19
1-Butene H
R R R H
Butanal
O
O
Carboxylic H
R C C R Alkyne 9 20
H acid O
1-Butyne R O
Pentanoic acid
O
O
OH
R OH Alcohol 12 Acyl halide Cl 20
1-Butanol R X
Acetyl chloride
O O
O O
O
R O R Ether 13 Anhydride O
20
Diethyl ether R O R
Acetic anhydride
O
O
SH
R SH Thiol 13 R Ester O
20
1-Butanethiol R O
Ethyl acetate
O O
S R
R S R Sulfide 13 R N Amide NH2 20
Diethyl sulfide
R Butanamide
H
R
Aromatic N
17, 18 N Amine 22
(or arene) R R
Methylbenzene Diethylamine
* The “R” refers to the remainder of the compound, usually carbon and hydrogen atoms.
Approximate pKa Values for Commonly Encountered Structural Types
R1 R2 pKa
X pKa
−10 Me H –8.0
–10 H X
Me Me –7.3
Br –9.0 H
+ Me OMe –6.5
Cl –7.0 O
Me Ph –6.2
F 3.2
R1 R2 Me OH –6.1
R pKa O −5 R1 R2 pKa
H
CF3 –14 R S OH Me Me –3.8
O
OH –9.0 O R1 + R2 Et Et –3.6
Me –1.2 Et H –2.4
O
Ph –0.6 Me H –2.2
+N OH (–1.3) –1.7
H H
pKa
0 −O
R
CF3 –0.25 H F (3.2)
H 3.8 −
O N N N H (4.7)
Me 4.8 +
t-Bu 5.0
OH 6.4 R OH
5 N
+
H (5.3)
R1 R2 R3 pKa OH
H S H (7.0)
H H NO2 7.1
H NO2 H 8.4 R1 CH3CO3H (8.2) R1 R2 R3 pKa
H H H 9.9 H H H 9.2
R1
H H OMe 10.2 Me H H 10.5
R3 R2
10 R2
+
N H Me Me H 10.6
O O Me Me Me 9.8
R1 R2 pKa R3
Et Et Et 10.8
Me Me 9.0 R1 R2 Pr Pr H 11.1
OEt Me 11
H H
OMe OMe 13 H
OEt OEt 13.3 (15)
R1 15 H
R1 R2 R3 pKa R2 C O H H O H (15.7)
Me Me Me 18.0 R3 O pKa
R
Me Me H 16.5 16.0
H Ph
Me H H 16.0 R 17.0
H
H H H 15.5
20 H H Me 19.2
CF3 H H 12.5
CF3 CF3 H 9.3
O R pKa
R pKa R C C H Ph 23
t-Bu 24.5 H
RO H 25
Et 25.0
H H
25
O
S H
35 H 3C C (35)
DMSO H H
R1 R2 pKa
H H H (36)
H H 38
Et H 38 N
Et Et 40 R1 R2
40
H H
C C (44)
H H
R1 R2 R3 pKa 45
Ph H H 41
R1
CH=CH2 H H 43
H H H 48 R2 C H
Me H H 50 R3
Me Me H 51
Me Me Me 53 50
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ISBN 978-1-119-659594
Library of Congress Cataloging-in-Publication Data
Names: Klein, David R., 1972- author.

Title: Organic chemistry / David Klein.
Description: Fourth edition. | Hoboken, NJ : Wiley, [2021] | Includes
bibliographical references and index.
Identifiers: LCCN 2020044903 (print) | LCCN 2020044904 (ebook) | ISBN
9781119659594 (paperback) | ISBN 9781119316152 | ISBN 9781119760825
(adobe pdf) | ISBN 9781119659402 (epub)
Subjects: LCSH: Chemistry, Organic—Textbooks.
Classification: LCC QD253.2 .K55 2021 (print) | LCC QD253.2 (ebook) | DDC
547--dc23
LC record available at https://lccn.loc.gov/2020044903
LC ebook record available at https://lccn.loc.gov/2020044904
Printed in the United States of America 10 9 8 7 6 5 4 3 2 1
The inside back cover will contain printing identification and country of origin if omitted from this
page. In addition, if the ISBN on the back cover differs from the ISBN on this page, the one on the
back cover is correct.
Dedication
To my father and mother,
You have saved me (quite literally) on so many occasions, always steering me in the right
direction. I have always cherished your guidance, which has served as a compass for me in all of
my pursuits. You r epeatedly urged me to work on this textbook (“write the book!”, you would say
so often), with full confidence that it would be appreciated by students around the world. I will
forever rely on the life lessons that you have taught me and the values that you have instilled in me.
I love you.
To Larry,
By inspiring me to pursue a career in organic chemistry instruction, you served as the spark
for the creation of this book. You showed me that any subject can be fascinating (even organic
chemistry!) when presented by a masterful teacher. Your mentorship and friendship have pro-
foundly shaped the course of my life, and I hope that this book will always serve as a source of
pride and as a reminder of the impact you’ve had on your students.
To my wife, Vered,
This book would not have been possible without your partnership. As I worked for years in
my office, you shouldered all of our life responsibilities, including taking care of all of the needs
of our five amazing children. This book is our collective accomplishment and will forever serve
as a testament of your constant support that I have come to depend on for everything in life.
You are my rock, my partner, and my best friend. I love you.
Contents Review of Concepts & Vocabulary • SkillBuilder Review
Practice Problems • ACS-Style Problems (Multiple Choice)
Integrated Problems • Challenge Problems
1 3
Acids and Bases 93
A Review of General Chemistry:
Electrons, Bonds, and Molecular Properties 1 3.1 Introduction to Brønsted-Lowry Acids and Bases 94
3.2 Flow of Electron Density: Curved-Arrow Notation 94
1.1 Introduction to Organic Chemistry 2
BioLinks Antacids and Heartburn 96
1.2 The Structural Theory of Matter 3
3.3 Brønsted-Lowry Acidity: Comparing pKa values 97
1.3 Electrons, Bonds, and Lewis Structures 4
1.4 Identifying Formal Charges 7 BioLinks Drug Distribution and pKa 103
1.5 Induction and Polar Covalent Bonds 8 3.4 Brønsted-Lowry Acidity: Factors Affecting the Stability of
Anions 104
1.6 Reading Bond-Line Structures 11
3.5 Brønsted-Lowry Acidity: Assessing the Relative Acidity of
1.7 Atomic Orbitals 14
Cationic Acids 115
1.8 Valence Bond Theory 17
3.6 Position of Equilibrium and Choice of Reagents 120
1.9 Molecular Orbital Theory 18
3.7 Leveling Effect 123
1.10 Hybridized Atomic Orbitals 20
3.8 Solvating Effects 124
1.11 Predicting Molecular Geometry: VSEPR Theory 26
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rchiv
3.9 Counterions 125

on A
1.12 Dipole Moments and Molecular Polarity 30

Keys Images
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WorldLinks Baking Soda versus Baking Powder 125

1.13 Intermolecular Forces and Physical Properties 33
tone
y
Gett
3.10 Lewis Acids and Bases 126

WorldLinks Biomimicry and
Gecko Feet 37 Review of Concepts & Vocabulary • SkillBuilder Review
BioLinks Drug-Receptor Interactions 38
x Pictures

1.14 Solubility 39
k Times/Redu
BioLinks Propofol: The Importance of Drug Solubility 40

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Review of Concepts & Vocabulary • SkillBuilder Review
4
Chang W. Lee
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Integrated
Cole
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Alkanes and Cycloalkanes 138
2
Molecular Representations 50
4.1 Introduction to Alkanes 139
4.2 Nomenclature of Alkanes 139
WorldLinks Pheromones: Chemical Messengers 143
2.1 Molecular Representations 51 BioLinks Naming Drugs 151
2.2 Drawing Bond-Line Structures 53 4.3 Constitutional Isomers of Alkanes 152
2.3 Identifying Functional Groups 55 4.4 Relative Stability of Isomeric Alkanes 153
BioLinks Marine Natural Products 56 4.5 Sources and Uses of Alkanes 154
2.4 Carbon Atoms with Formal Charges 58 WorldLinks An Introduction to Polymers 156
2.5 Identifying Lone Pairs 58 4.6 Drawing Newman Projections 156
2.6 Three-Dimensional Bond-Line Structures 61 4.7 Conformational Analysis of Ethane
and Propane 158
BioLinks The Opioids 62
4.8 Conformational Analysis of Butane 160
2.7 Introduction to Resonance 63
2.8 Curved Arrows 65 BioLinks Drugs and Their Conformations 164
2.9 Formal Charges in Resonance Structures 68 4.9 Cycloalkanes 164
2.10 Drawing Resonance Structures via Pattern Recognition 70 BioLinks Cyclopropane as an Inhalation Anesthetic 166
2.11 Assessing the Relative Importance of Resonance 4.10 Conformations of Cyclohexane 167
Structures 75 4.11 Drawing Chair Conformations 168
2.12 The Resonance Hybrid 79 4.12 Monosubstituted Cyclohexane 170
2.13 Delocalized and Localized Lone Pairs 81 4.13 Disubstituted Cyclohexane 172
iv
CONTENTS v
4.14 cis-trans Stereoisomerism 176 6.12 Reversible and Irreversible Reaction Arrows 268
4.15 Polycyclic Systems 177 Review of Concepts & Vocabulary • SkillBuilder Review
Review of Concepts & Vocabulary • SkillBuilder Review Practice Problems • ACS-Style Problems (Multiple Choice)
Practice Problems • ACS-Style Problems (Multiple Choice) Integrated Problems • Challenge Problems
5
Stereoisomerism 188
7
Alkyl Halides: Nucleophilic Substitution and Elimination
Reactions 280
5.1 Overview of Isomerism 189
7.1 Introduction to Substitution and Elimination Reactions 281
5.2 Introduction to Stereoisomerism 190
7.2 Nomenclature and Uses of Alkyl Halides 282
WorldLinks The Sense of Smell 195
7.3 SN2 Reactions 286
5.3 Designating Configuration Using the
BioLinks Pharmacology and Drug Design 292
Cahn-Ingold-Prelog System 195
7.4 Nucleophilic Strength in SN2 Reactions 294
BioLinks Chiral Drugs 200
BioLinks SN2 Reactions in Biological Systems—Methylation 295
5.4 Optical Activity 201
7.5 Introduction to E2 Reactions 296
5.5 Stereoisomeric Relationships: Enantiomers and
7.6 Stability of Alkenes and Cycloalkenes 299
Diastereomers 207
7.7 Regiochemical and Stereochemical Outcomes for E2
5.6 Symmetry and Chirality 210
Reactions 301
5.7 Fischer Projections 214
7.8 Unimolecular Reactions (SN1 and E1) 311
5.8 Conformationally Mobile Systems 216
7.9 Predicting Products: Substitution vs. Elimination 320
5.9 Chiral Compounds that Lack a Chiral Center 217
7.10 Substitution and Elimination Reactions with Other
5.10 Resolution of Enantiomers 218 Substrates 327
5.11 E and Z Designations for Diastereomeric Alkenes 220 7.11 Synthesis Strategies 331
BioLinks Phototherapy Treatment for Neonatal Jaundice 222 BioLinks Radiolabeled Compounds in Diagnostic Medicine 338
Review of Concepts & Vocabulary • SkillBuilder Review 7.12 Solvent Effects in Substitution Reactions 339
Practice Problems • ACS-Style Problems (Multiple Choice) SpecialTopic Kinetic Isotope Effects 343
Review of Reactions • Review of Concepts & Vocabulary
SkillBuilder Review • Practice Problems
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ACS-Style Problems (Multiple Choice) • Integrated Problems

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Challenge Problems
6
8
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Chemical Reactivity and Mechanisms 233
6.1 Enthalpy 234 Addition Reactions of Alkenes 356

6.2 Entropy 237
6.3 Gibbs Free Energy 239 8.1 Introduction to Addition Reactions 357
WorldLinks Explosives 240 8.2 Alkenes in Nature and in Industry 358
WorldLinks Do Living Organisms Violate the Second Law of WorldLinks Pheromones to Control Insect Populations 358
Thermodynamics? 242 8.3 Nomenclature of Alkenes 359
6.4 Equilibria 242 8.4 Addition vs. Elimination: A Thermodynamic Perspective 361
6.5 Kinetics 244 8.5 Hydrohalogenation 363
BioLinks Nitroglycerin: An Explosive WorldLinks Cationic Polymerization and Polystyrene 370
with Medicinal Properties 247 8.6 Acid-Catalyzed Hydration 371
WorldLinks Beer Making 248 8.7 Oxymercuration-Demercuration 375
6.6 Reading Energy Diagrams 249 8.8 Hydroboration-Oxidation 376
6.7 Nucleophiles and Electrophiles 252 8.9 Catalytic Hydrogenation 382
6.8 Mechanisms and Arrow Pushing 256 WorldLinks Partially Hydrogenated Fats and Oils 387
6.9 Combining the Patterns of Arrow Pushing 261 8.10 Halogenation and Halohydrin Formation 388
6.10 Drawing Curved Arrows 263 8.11 Anti Dihydroxylation 392
6.11 Carbocation Rearrangements 266 8.12 Syn Dihydroxylation 395
vi CONTENTS
8.13 Oxidative Cleavage 396 10.13 Halogenation as a Synthetic

8.14 Predicting the Products of an Addition Reaction 398 Technique 489
8.15 Synthesis Strategies 400 Review of Reactions • Review of Concepts & Vocabulary
Review of Reactions • Review of Concepts & Vocabulary SkillBuilder Review • Practice Problems
SkillBuilder Review • Practice Problems ACS-Style Problems (Multiple Choice)
ACS-Style Problems (Multiple Choice) Integrated Problems • Challenge Problems
9
pokki77/Shutterstock
11
Synthesis 499
Alkynes 417
11.1 One-Step Syntheses 500
9.1 Introduction to Alkynes 418 11.2 Functional Group Transformations 501
BioLinks The Role of Molecular Rigidity 420 11.3 Reactions That Change the Carbon Skeleton 505
WorldLinks Conducting Organic Polymers 421 BioLinks Vitamins 507

9.2 Nomenclature of Alkynes 421 11.4 How to Approach a Synthesis Problem 508
9.3 Acidity of Acetylene and Terminal Alkynes 423 BioLinks The Total Synthesis of Vitamin B12 512
9.4 Preparation of Alkynes 426 11.5 Multi-step Synthesis and Retrosynthetic Analysis 514
9.5 Reduction of Alkynes 428 WorldLinks Retrosynthetic Analysis 519
9.6 Hydrohalogenation of Alkynes 431 11.6 Green Chemistry 519
9.7 Hydration of Alkynes 433 11.7 Practical Tips for Increasing Proficiency 520
9.8 Halogenation of Alkynes 439 BioLinks Total Synthesis of Taxol 521
9.9 Ozonolysis of Alkynes 439
9.10 Alkylation of Terminal Alkynes 440
9.11 Synthesis Strategies 442
ACS-Style Problems (Multiple Choice)
es
ag
Im
ty
Get
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12
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SciePro/Shutterstock
Alcohols and Phenols 529
10
magnetcreative/Getty Images
ki77/Shutterstock
richcano/Getty Images
12.1 Structure and Properties of Alcohols 530

BioLinks Chain Length as a Factor in Drug Design 534
Radical Reactions 454
12.2 Acidity of Alcohols and Phenols 535
10.1 Radicals 455 12.3 Preparation of Alcohols via Substitution or Addition 538
10.2 Common Patterns in Radical Mechanisms 460 12.4 Preparation of Alcohols via Reduction 539
10.3 Chlorination of Methane 463 12.5 Preparation of Diols 546
10.4 Thermodynamic Considerations WorldLinks Antifreeze 547
for Halogenation Reactions 467 12.6 Preparation of Alcohols via Grignard
10.5 Selectivity of Halogenation 469 Reagents 547
10.6 Stereochemistry of Halogenation 472 12.7 Protection of Alcohols 552
10.7 Allylic Bromination 474 12.8 Preparation of Phenols 553
10.8 Atmospheric Chemistry and the Ozone Layer 477 12.9 Reactions of Alcohols: Substitution and Elimination 554
WorldLinks Fighting Fires with Chemicals 479 BioLinks Drug Metabolism 557
10.9 Autooxidation and Antioxidants 480 12.10 Reactions of Alcohols: Oxidation 559
BioLinks Why Is an Overdose of Acetaminophen Fatal? 482 12.11 Biological Redox Reactions 563
10.10 Radical Addition of HBr: Anti-Markovnikov Addition 483 BioLinks Biological Oxidation of Methanol and Ethanol 565
10.11 Radical Polymerization 487 12.12 Oxidation of Phenol 565
10.12 Radical Processes in the Petrochemical Industry 489 12.13 Synthesis Strategies 567
CONTENTS vii
Review of Reactions • Review of Concepts & Vocabulary 14.7 Using IR Spectroscopy to Distinguish between
SkillBuilder Review • Practice Problems Two Compounds 657
ACS-Style Problems (Multiple Choice) 14.8 Introduction to Mass Spectrometry 658
Integrated Problems • Challenge Problems WorldLinks Mass Spectrometry for Detecting Explosives 660
14.9 Analyzing the (M)+• Peak 661
14.10 Analyzing the (M+1)+• Peak 662
14.11 Analyzing the (M+2)+• Peak 664
14.12 Analyzing the Fragments 665
13
14.13 High-Resolution Mass Spectrometry 668
14.14 Gas Chromatography–Mass Spectrometry 670
14.15 Mass Spectrometry of Large Biomolecules 671
Ethers and Epoxides; Thiols and Sulfides 585 BioLinks Medical Applications of Mass Spectrometry 671
14.16 Hydrogen Deficiency Index: Degrees of Unsaturation 672
13.1 Introduction to Ethers 586
13.2 Nomenclature of Ethers 586
13.3 Structure and Properties of Ethers 588
BioLinks Ethers as Inhalation Anesthetics 589
13.4 Crown Ethers 590
WorldLinks Chelating Agents in the Food Industry and in
15
Medicine 592
13.5 Preparation of Ethers 593
13.6 Reactions of Ethers 596
13.7 Nomenclature of Epoxides 599 Nuclear Magnetic Resonance Spectroscopy 684
BioLinks Epothilones as Novel Anticancer Agents 600
15.1 Introduction to NMR Spectroscopy 685
13.8 Preparation of Epoxides 600
15.2 Acquiring a 1H NMR Spectrum 687
BioLinks Active Metabolites and Drug Interactions 603
15.3 Characteristics of a 1H NMR Spectrum 688
13.9 Enantioselective Epoxidation 603
15.4 Number of Signals 689
13.10 Ring-Opening Reactions of Epoxides 605
15.5 Chemical Shift 695
WorldLinks Ethylene Oxide as a Sterilizing Agent for Sensitive 15.6 Integration 702
Medical Equipment 608
15.7 Multiplicity 705
BioLinks Cigarette Smoke and Carcinogenic Epoxides 612 15.8 Drawing the Expected 1H NMR Spectrum of a
13.11 Thiols and Sulfides 613 Compound 713
13.12 Synthesis Strategies Involving Epoxides 617 15.9 Using 1H NMR Spectroscopy to Distinguish between
Review of Reactions • Review of Concepts & Vocabulary Compounds 715
SkillBuilder Review • Practice Problems BioLinks Detection of Impurities in Heparin Sodium Using 1H
ACS-Style Problems (Multiple Choice) NMR Spectroscopy 717
Integrated Problems • Challenge Problems 15.10 Analyzing a 1H NMR Spectrum 718
15.11 Acquiring a 13C NMR Spectrum 721
15.12 Chemical Shifts in 13C NMR Spectroscopy 721
15.13 DEPT 13C NMR Spectroscopy 724
BioLinks Magnetic Resonance Imaging (MRI) 727
14
Infrared Spectroscopy
and Mass Spectrometry 636
14.1 Introduction to Spectroscopy 637

WorldLinks Microwave Ovens 639
14.2 IR Spectroscopy 639
BioLinks IR Thermal Imaging for Cancer Detection 640
14.3 Signal Characteristics: Wavenumber 641
16
Conjugated Pi Systems
14.4 Signal Characteristics: Intensity 646
and Pericyclic Reactions 738
WorldLinks IR Spectroscopy for Testing Blood Alcohol Levels 648
14.5 Signal Characteristics: Shape 648 16.1 Classes of Dienes 739
14.6 Analyzing an IR Spectrum 652 16.2 Conjugated Dienes 740
viii CONTENTS
16.3 Molecular Orbital Theory 742 18.3 Sulfonation 833

16.4 Electrophilic Addition 746 WorldLinks What Are Those Colors
16.5 Thermodynamic Control vs. Kinetic Control 749 in Fruity Pebbles? 834
WorldLinks Natural and Synthetic Rubbers 752 18.4 Nitration 835
16.6 An Introduction to Pericyclic Reactions 753 BioLinks The Discovery of
16.7 Diels–Alder Reactions 754 Prodrugs 837
16.8 MO Description of Cycloadditions 760 18.5 Friedel–Crafts Alkylation 838
16.9 Electrocyclic Reactions 763 18.6 Friedel–Crafts Acylation 840
16.10 Sigmatropic Rearrangements 768 18.7 Activating Groups 842
18.8 Deactivating Groups 846
BioLinks The Photoinduced Biosynthesis of Vitamin D 770
18.9 Halogens: The Exception 848
16.11 UV-Vis Spectroscopy 771
18.10 Determining the Directing Effects of a
WorldLinks Sunscreens 775 Substituent 850
16.12 Color 776 18.11 Multiple Substituents 853
WorldLinks Bleach 777 18.12 Synthesis Strategies 859
16.13 Chemistry of Vision 777 18.13 Nucleophilic Aromatic Substitution 866
Review of Reactions • Review of Concepts & Vocabulary 18.14 Elimination-Addition 868
SkillBuilder Review • Practice Problems 18.15 Identifying the Mechanism of an Aromatic Substitution
ACS-Style Problems (Multiple Choice) Reaction 870
Integrated Problems • Challenge Problems Review of Reactions • Review of Concepts & Vocabulary
17
Aromatic Compounds 788
17.1 Introduction to Aromatic Compounds 789

WorldLinks What Is Coal? 790
17.2 Nomenclature of Benzene Derivatives 790
19
Aldehydes and Ketones 884
JerryB7/Getty Images, Inc
17.3 Structure of Benzene 793

19.1 Introduction to Aldehydes and Ketones 885
17.4 Stability of Benzene 794
19.2 Nomenclature 886
WorldLinks Molecular Cages 798
19.3 Preparing Aldehydes and Ketones: A Review 888
17.5 Aromatic Compounds Other Than Benzene 801
19.4 Introduction to Nucleophilic Addition
BioLinks The Development of Nonsedating Reactions 889
Antihistamines 806 19.5 Oxygen Nucleophiles 892
17.6 Reactions at the Benzylic Position 808
BioLinks Acetals as Prodrugs 898
17.7 Reduction of Benzene and Its Derivatives 813
19.6 Nitrogen Nucleophiles 900
17.8 Spectroscopy of Aromatic Compounds 815
WorldLinks Beta-Carotene and
WorldLinks Buckyballs and Nanotubes 818 Vision 904
Review of Reactions • Review of Concepts & Vocabulary 19.7 Hydrolysis of Acetals, Imines, and Enamines 908
SkillBuilder Review • Practice Problems BioLinks Prodrugs 911
ACS-Style Problems (Multiple Choice) 19.8 Sulfur Nucleophiles 911
19.9 Hydrogen Nucleophiles 912
19.10 Carbon Nucleophiles 913
WorldLinks Organic Cyanide Compounds in Nature 916
19.11 Baeyer–Villiger Oxidation of Aldehydes and
18
Ketones 921
19.13 Spectroscopic Analysis of Aldehydes and
Aromatic Substitution Reactions 828 Courtesy of Andy Washnik
Ketones 925
18.1 Introduction to Electrophilic Aromatic Substitution 829
18.2 Halogenation 829 ACS-Style Problems (Multiple Choice)
BioLinks Halogenation in Drug Design 832 Integrated Problems • Challenge Problems
CONTENTS ix
20
Carboxylic Acids
EduardHarkonen/iStock/Getty Images
22
and Their Derivatives 938
Amines 1054
20.1 Introduction to Carboxylic Acids 939
22.1 Introduction to Amines 1055
20.2 Nomenclature of Carboxylic Acids 939
20.3 Structure and Properties of Carboxylic Acids 941 BioLinks Drug Metabolism Studies 1056
20.4 Preparation of Carboxylic Acids 944 22.2 Nomenclature of Amines 1056
20.5 Reactions of Carboxylic Acids 945 22.3 Properties of Amines 1059
20.6 Introduction to Carboxylic Acid Derivatives 946 BioLinks Fortunate Side Effects 1060
BioLinks Sedatives 948 WorldLinks Chemical Warfare Among Ants 1064
20.7 Reactivity of Carboxylic Acid Derivatives 950 22.4 Preparation of Amines: A Review 1065
20.8 Preparation and Reactions of Acid Chlorides 957 22.5 Preparation of Amines via Substitution
20.9 Preparation and Reactions of Acid Anhydrides 962 Reactions 1066
22.6 Preparation of Amines via Reductive
BioLinks How Does Aspirin Work? 964
Amination 1069
20.10 Preparation of Esters 965
20.11 Reactions of Esters 966
22.8 Acylation of Amines 1074
WorldLinks How Soap Is Made 967 22.9 Hofmann Elimination 1075
BioLinks Esters as Prodrugs 968 22.10 Reactions of Amines with Nitrous Acid 1078
20.12 Preparation and Reactions of Amides 971 22.11 Reactions of Aryl Diazonium Ions 1080
WorldLinks Polyesters and Polyamides 972 22.12 Nitrogen Heterocycles 1084
BioLinks Beta-Lactam Antibiotics 975 BioLinks H2-Receptor Antagonists
20.13 Preparation and Reactions of Nitriles 976 and the Development of Cimetidine 1085
20.14 Synthesis Strategies 979 22.13 Spectroscopy of Amines 1087
Reinhold Leitner/Shutterstock
20.15 Spectroscopy of Carboxylic Acids and Their Derivatives 984 Review of Reactions • Review of Concepts & Vocabulary
21 Daniel Loiselle/iStockphoto
23
Introduction to Organometallic Compounds 1100
Alpha Carbon Chemistry: 23.1 General Properties of Organometallic
Enols and Enolates 996 Compounds 1101
23.2 Organolithium and Organomagnesium
21.1 Introduction to Alpha Carbon Chemistry: Compounds 1102 iSto
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Enols and Enolates 997

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23.3 Lithium Dialkyl Cuprates (Gilman Reagents) 1105

os
Pr
21.2 Alpha Halogenation of Enols and Enolates 1004

23.4 The Simmons–Smith Reaction and
21.3 Aldol Reactions 1009 Carbenoids 1109
WorldLinks Muscle Power 1012 23.5 Stille Coupling 1112
21.4 Claisen Condensations 1020 23.6 Suzuki Coupling 1117
21.5 Alkylation of the Alpha Position 1022 23.7 Negishi Coupling 1123
21.6 Conjugate Addition Reactions 1031 23.8 The Heck Reaction 1128
BioLinks Glutathione Conjugation 23.9 Alkene Metathesis 1133
and Biological Michael Reactions 1033 WorldLinks Improving Biodiesel via Alkene
21.7 Synthesis Strategies 1037 Metathesis 1138
Review of Reactions • Review of Concepts & Vocabulary Review of Reactions • Review of Concepts & Vocabulary
SkillBuilder Review • Practice Problems SkillBuilder Review • Practice Problems
ACS-Style Problems (Multiple Choice) ACS-Style Problems (Multiple Choice)
Integrated Problems • Challenge Problems Integrated Problems • Challenge Problems
x CONTENTS
24
Carbohydrates 1153
26
Lipids 1238
24.1 Introduction to Carbohydrates 1154 26.1 Introduction to Lipids 1239
24.2 Classification of Monosaccharides 1154 26.2 Waxes 1240
24.3 Configuration of Aldoses 1157 26.3 Triglycerides 1241
24.4 Configuration of Ketoses 1158 26.4 Reactions of Triglycerides 1244
24.5 Cyclic Structures of Monosaccharides 1160
WorldLinks Soaps Versus Synthetic
24.6 Reactions of Monosaccharides 1167 Detergents 1249
24.7 Disaccharides 1174 26.5 Phospholipids 1253
BioLinks Lactose Intolerance 1177 BioLinks Polyether Antibiotics 1256
WorldLinks Artificial Sweeteners 1178 26.6 Steroids 1257
24.8 Polysaccharides 1179 BioLinks Cholesterol and Heart Disease 1260
24.9 Amino Sugars 1180
BioLinks Anabolic Steroids and Competitive
24.10 N-Glycosides 1181 Sports 1263
BioLinks Aminoglycoside Antibiotics 1182 26.7 Prostaglandins 1263
BioLinks Erythromycin Biosynthesis 1186 BioLinks NSAIDs and COX-2 Inhibitors 1265
Review of Reactions • Review of Concepts & Vocabulary 26.8 Terpenes 1266
SkillBuilder Review • Practice Problems Review of Reactions • Review of Concepts & Vocabulary
ACS-Style Problems (Multiple Choice) SkillBuilder Review • Practice Problems
Integrated Problems • Challenge Problems ACS-Style Problems (Multiple Choice)
25
Amino Acids, Peptides, and Proteins 1194
27
Synthetic Polymers 1277
25.1 Introduction to Amino Acids, Peptides, and
Proteins 1195 27.1 Introduction to Synthetic Polymers 1278
25.2 Structure and Properties of Amino 27.2 Nomenclature of Synthetic Polymers 1279
Acids 1196 27.3 Copolymers 1280
WorldLinks Nutrition and Sources of 27.4 Polymer Classification by Reaction Type 1281
Amino Acids 1198 27.5 Polymer Classification by Mode of
Assembly 1289
WorldLinks Forensic Chemistry and Fingerprint
Detection 1202 27.6 Polymer Classification by Structure 1291
25.3 Amino Acid Synthesis 1203 27.7 Polymer Classification by Properties 1294
25.4 Structure of Peptides 1207 WorldLinks Safety Glass and Car Windshields 1295
BioLinks Polypeptide Antibiotics 1212 27.8 Polymer Recycling 1296
25.5 Sequencing a Peptide 1213 Review of Reactions • Review of Concepts & Vocabulary
25.6 Peptide Synthesis 1216 SkillBuilder Review • Practice Problems
25.7 Protein Structure 1224 ACS-Style Problems (Multiple Choice)
BioLinks Diseases Caused by Misfolded blaneyphoto/iStockphoto
to
ho
Proteins 1227
ckp
Sto
L/i
mm
25.8 Protein Function 1227

To
Appendix: Nomenclature of Polyfunctional Compounds A–1

Review of Reactions • Review of Concepts & Vocabulary Selected Answers ANS–1
SkillBuilder Review • Practice Problems Glossary G–1
ACS-Style Problems (Multiple Choice) Index I–1
Preface
WHY I WROTE THIS BOOK A SKILLS-BASED APPROACH
Students who perform poorly on organic chemistry exams often To address the disconnect in organic chemistry instruction, I have
report having invested countless hours studying. Why do many developed a skills-based approach to instruction. The textbook
students have difficulty preparing themselves for organic chem- includes all of the concepts typically covered in an organic chem-
istry exams? Certainly, there are several contributing factors, istry textbook, complete with conceptual checkpoints that promote
including inefficient study habits, but perhaps the most domi- mastery of the concepts, but special emphasis is placed on skills
nant factor is a fundamental disconnect between what students development through SkillBuilders to support these concepts.
learn in the lecture hall and the tasks expected of them dur- Each SkillBuilder contains three parts:
ing an exam. To illustrate the disconnect, consider the following
Learn the Skill: contains a solved problem that demonstrates a
analogy.
particular skill.
Imagine that a prestigious university offers a course entitled
“Bike-Riding 101.” Throughout the course, physics and engineer- Practice the Skill: includes numerous problems (similar to the
ing professors explain many concepts and principles (for example, solved problem in Learn the Skill) that give students valuable
how bicycles have been engineered to minimize air resistance). opportunities to practice and master the skill.
Students invest significant time studying the information that was
presented, and on the last day of the course, the final exam con- Apply the Skill: contains one or more problems in which the
sists of riding a bike for a distance of 100 feet. A few students may student must apply the skill to solve real-world problems (as
have innate talents and can accomplish the task without falling. reported in the chemical literature). These problems include con-
But most students will fall several times, slowly making it to the ceptual, cumulative, and applied problems that encourage students
finish line, bruised and hurt; and many students will not be able to think outside of the box. Sometimes problems that foreshadow
to ride for even one second without falling. Why? Because there is concepts introduced in later chapters are also included.
a disconnect between what the students learned and what they were At the end of each SkillBuilder, a Need More Practice? refer-
expected to do for their exam. ence suggests end-of-chapter problems that students can work to
Many years ago, I noticed that a similar disconnect exists in practice the skill.
traditional organic chemistry instruction. That is, learning organic This emphasis upon skills development provides students
chemistry is much like bicycle riding; just as the students in the with a greater opportunity to develop proficiency in the key skills
bike-riding analogy were expected to ride a bike after attend- necessary to succeed in organic chemistry. Certainly, not all neces-
ing lectures, it is often expected that organic chemistry students sary skills can be covered in a textbook. However, there are certain
will independently develop the necessary skills for solving prob- skills that are fundamental to all other skills.
lems. While a few students have innate talents and are able to As an example, resonance structures are used repeatedly
develop the necessary skills independently, most students require throughout the course, and students must become masters of
guidance. This guidance was not consistently integrated within resonance structures early in the course. Therefore, a significant
existing textbooks, prompting me to write the first edition of my portion of Chapter 2 is devoted to pattern-recognition for draw-
textbook, Organic Chemistry. The main goal of my text was to ing resonance structures. Rather than just providing a list of rules
employ a skills-based approach to bridge the gap between theory and then a few follow-up problems, the skills-based approach pro-
(concepts) and practice (problem-solving skills). The second and vides students with a series of skills, each of which must be mas-
third editions further supported this goal by introducing hundreds tered in sequence. Each skill is reinforced with numerous practice
of additional problems based on the chemical literature, thereby problems. The sequence of skills is designed to foster and develop
exposing students to exciting real-world examples of chemical proficiency in drawing resonance structures.
research being conducted in real laboratories. The phenomenal The skills-based approach to organic chemistry instruction
success of the first three editions has been extremely gratifying is a unique approach. Certainly, other textbooks contain tips for
because it provided strong evidence that my skills-based approach problem solving, but no other textbook consistently presents skills
is indeed effective at bridging the gap described above. development as the primary vehicle for instruction.
I firmly believe that the scientific discipline of organic chem-
istry is NOT merely a compilation of principles, but rather, it is
a disciplined method of thought and analysis. Students must cer- WHAT’S NEW IN THIS EDITION
tainly understand the concepts and principles, but more impor-
tantly, students must learn to think like organic chemists . . . that Peer review played a very strong role in the development of the first,
is, they must learn to become proficient at approaching new situa- second, and third editions of Organic Chemistry. For each edition,
tions methodically, based on a repertoire of skills. That is the true the manuscript was reviewed by several hundred professors and sev-
essence of organic chemistry. eral thousand students. In preparing the fourth edition, peer review
xi
xii PREFACE
has played an equally prominent role. We have received a tremen- • Biological methylating agents have been moved into a BioLinks
dous amount of input from the market, including surveys, class tests, box (rather than being a numbered section of the chapter).
diary reviews, and phone interviews. All of this input has been care- • Kinetic isotope effects have been moved into a Special Topic
fully culled and has been instrumental in identifying the focus of the box (rather than being a numbered section of the chapter).
fourth edition.
• Solvent effects have been moved to the end of the chapter.
• In Chapter 9, the coverage of dissolving metal reductions has
New Features in the Fourth Edition been revised to show that terminal alkynes cannot be reduced
• Treatment of synthesis was strengthened throughout the text, by this method (only internal alkynes can be reduced with a
with a greater focus on retrosynthetic strategies. The coverage dissolving metal reduction). To reduce a terminal alkyne, it is
of synthesis and retrosynthesis in Chapter 7 has been expanded best to perform hydrogenation with a poisoned catalyst.
(with additional examples and more problems in SkillBuilder • In Chapter 15 (NMR spectroscopy), the discussion of complex
7.8); and in Chapter 8, alkenes are considered both as syn- splitting has been revised to reflect the reality that J values are
thetic targets and possible starting materials. In Chapter 9, the generally similar (~7 Hz), so a triplet of quartets or a quartet
coverage of synthesis with alkynide ions has been expanded, of triplets would be extremely rare. A sextet will be much more
with a focus on retrosynthesis. Indeed, the coverage of retro- common when a signal arises from protons that have three
synthesis has been expanded similarly in each chapter, gradu- neighbors on one side and two neighbors on the other side (for
ally developing a scaffold of advanced synthetic skills. example, the protons on C2 in 1-bromopropane). The entire
• The introduction of bond-line drawings has been moved from discussion of complex splitting has been revised accordingly.
Chapter 2 to Chapter 1. This enables the use of bond-line • In the previous edition (3e), throughout Chapter 21 (alpha
drawings when covering the material in Chapter 1. carbon chemistry), after enolates were first introduced, eno-
• SkillBuilder 2.1 (converting between condensed structures lates were then represented throughout the chapter by showing
and bond-line structures) has been rewritten to show stu- the minor contributor to the resonance hybrid (the resonance
dents how to interpret the condensed structures of aldehydes structure with a negative charge on C, rather than O). While
(RCHO) and carboxylic acids (RCO2H). this simplified the mechanisms for students, it is more accurate
• In Chapter 3 (acids and bases), a new section covers the rela- to show the major contributor. Throughout Chapter 21, all
tive acidity of cationic acids (with a new SkillBuilder), as well instances of enolates (in all mechanisms) have been modified
as the relative basicity of their uncharged conjugate bases. This to show the major contributor to the resonance hybrid (with
new section (Section 3.5) covers the relative acidity of ammo- a negative charge on O), rather than the minor contributor.
nium ions and the relative basicity of amines. • The end of each chapter has been enhanced with additional
• In Chapter 6, the section describing nucleophilic centers and multiple-choice questions that mimic the style of questions
electrophilic centers has been entirely rewritten. The previ- on standardized exams, including the ACS, DAT, and PCAT
ous treatment (3e) would suggest that methyl chloride is a exams. The previous edition (3e) had approximately 3 such
nucleophile, because of the lone pairs on the chlorine atom. questions at the end of each chapter. The new edition (4e)
Furthermore, the previous treatment (3e) would suggest that now has between 7 and 10 such questions per chapter.
methanol is an electrophile, because the carbon atom is con- • Many students have requested that an answer key (for selected
nected directly to an electron-withdrawing element. Both of problems) be included at the end of the text. This much-desired
these conclusions are false, so this section was rewritten so that feature has been provided in the fourth edition. The end of the
students don’t arrive at these false conclusions. book now has a section with answers to selected problems.
• Section 7.2 (nomenclature of alkyl halides) has been revised
to introduce the prefix “n” in alkyl substituents (for example, TEXT ORGANIZATION
n-butyl or n-propyl). This terminology is revisited again in
Section 12.1 (nomenclature of alcohols) as well as throughout The sequence of chapters and topics in Organic Chemistry, 4e does
the text, where appropriate. not differ markedly from that of other organic chemistry textbooks.
• In Chapter 7, when reagents are covered, a discussion has been Indeed, the topics are presented in the traditional order, based on
included to explicitly show that NaOEt/EtOH represents functional groups (alkenes, alkynes, alcohols, ethers, aldehydes and
NaOEt dissolved in EtOH as the solvent. This was not obvi- ketones, carboxylic acid derivatives, etc.). Despite this traditional
ous to students, and it is now explicitly shown. order, a strong emphasis is placed on mechanisms, with a focus on
pattern recognition to illustrate the similarities between reactions
• Sodium hydride is not an appropriate base for performing an
that would otherwise appear unrelated. No shortcuts were taken in
E2 reaction. A quick literature search shows no such examples.
any of the mechanisms, and all steps are clearly illustrated, includ-
NaH has been removed from Chapter 7.
ing all proton transfer steps.
• Chapter 7 (substitution and elimination) has been reorga- Two chapters (6 and 11) are devoted almost entirely to skill
nized in the following ways. development and are generally not found in other textbooks.
• Nomenclature of alkenes has been moved out of Chapter 7 Chapter 6, Chemical Reactivity and Mechanisms, emphasizes skills
and into Chapter 8 (addition reactions of alkenes). that are necessary for drawing mechanisms, while Chapter 11,
PREFACE xiii
Synthesis, prepares the students for proposing syntheses. These Student Partners assist other students in your class and act as
two chapters are strategically positioned within the traditional the main contact for WileyPLUS questions, such as registration or
order described above and can be assigned to the students for course specific functionality.
independent study. That is, these two chapters do not need to be
covered during precious lecture hours, but can be, if so desired. An Easier Way to Succeed
The traditional order allows instructors to adopt the skills-
The features and design of WileyPLUS are molded by what instruc-
based approach without having to change their lecture notes or
tors and students need to succeed. Here are just a few tools that will
methods. For this reason, the spectroscopy chapters (Chapters
help drive achievement in the classroom:
14 and 15) were written to be stand-alone and portable, so that
instructors can cover these chapters in any order desired. In fact, Accessibility is at the forefront of our design. All content and ques-
five of the chapters (Chapters 2, 3, 7, 12, and 13) that precede tions have been audited for accessibility, and anything that does not
the spectroscopy chapters include end-of-chapter spectroscopy meet that standard has been flagged for awareness. WileyPLUS pro-
problems, for those students who covered spectroscopy earlier. vides a learning path that complies with the Americans with Disabilities
Spectroscopy coverage also appears in subsequent functional group Act (ADA) and Web Content Accessibility Guidelines (WCAG 2.1).
chapters, specifically Chapter 17 (Aromatic Compounds), Chapter Mobile Apps for course management meets everyone’s on-the-go
19 (Aldehydes and Ketones), Chapter 20 (Carboxylic Acids and Their demands. Instructors can adjust assignments, grade submissions, or
Derivatives), Chapter 22 (Amines), Chapter 24 (Carbohydrates), message your students all from your mobile device, while students
and Chapter 25 (Amino Acids, Peptides, and Proteins). can study the eTextbook content or submit timely assignments.
Recommended Assignments, based on usage data, empower
THE WileyPLUS ADVANTAGE instructors to choose preloaded assignments that have a proven
path to success. Efficacy studies show that these pre-populated
Discover an Easier Way to Learn assignments are valuable to student engagement and achievement.
The new WileyPLUS gives you the freedom and flexibility to tailor
curated content and easily manage your course in order to engage LMS Integration
and motivate students. Integrate WileyPLUS with Blackboard, Canvas, or Desire2Learn
• Single Sign-On: Providing instructors and students with
An Easier Way to Engage and Keep Students direct access to all WileyPLUS content with the convenience
on Track of one login
To assist instructors with heavy workloads, WileyPLUS offers easy • Integrated Student Registration: Lets students register right
ways for students to keep up with the learning curve, such as: from your Canvas course, no course IDs or special URLs required
Flexible, Linear Learning Paths organize materials, include eText- • Direct Links to Readings and Assignments: Giving instruc-
book content, videos, animations and practice questions into custom- tors greater control over how they deliver information and
izable modules—easy to access and follow for instructors and students. allowing students to conveniently access their course work
Adaptive Practice enables students to identify and focus on areas • Gradebook Synchronization: Offers either total score or
that are particularly challenging to them. These personalized ques- assignment-level grade integration to track all scores in one place
tions engage students in the material and teach them how to study
on their own. New to WileyPLUS for Organic Chemistry, 4e
Reports and Metrics provide insight into each student perfor- Students regularly report that they prefer to work with eBooks and
mance as cumulative class metrics, allowing you to identify and online problems. The ability to receive instant feedback and always
address individual needs in a timely manner. having access to course materials from any mobile device adds to
the appeal of an online environment. Within WileyPLUS, students
An Easier Way to Get Started and Get Help can interact with all (>5,000) problems that appear throughout
Instructors and students shouldn’t spend time on technology ques- the textbook, both within the chapters (SkillBuilder problems and
tions, which is why Wiley is by your side all the way. Here are just Conceptual Checkpoints problems) and at the end of the chap-
some of the ways we can help you: ters (Practice, ACS-style, Integrated, and Challenge problems). For
the 4th edition, all WileyPLUS problems have been reimagined by
The Customer Success Team helps guide instructors through instructional designers to make them as efficient as possible. The
the implementation, course setup, ongoing support, and engage- redesigned problems are more streamlined and better focused on
ment process. the learning objectives being targeted. Improvements include:
Tech Support is available to instructors and students 24/7, because • Clear instructions are provided, and excessive drawing has
we know teaching and studying is not a 9-5 job. been eliminated.
WileyPLUS Studio provides a network of instructors who share • Predict-the-product problems often provide a copy of the
insights, best practices, and product feedback. Best of all, instruc- starting material in the sketch box, so students can focus on
tors can earn rewards. the reactive functional group(s).
xiv PREFACE
• Synthesis problems are open-ended to better reflect classroom Testbank Revised for this edition by Mackay Steffensen, Southern
assessments. Utah University and Ann Paterson, Williams Baptist University.
• Mechanism problems now begin with an overview before PowerPoint Lecture Slides and Clicker Questions Revised for
moving into arrow-pushing. this edition by Michael Cross, Snow College.
• Advanced problems model problem-solving with guided inquiry.
• Feedback is provided to explain each solution, and newly writ- STUDENT RESOURCES
ten hints are now available for each problem.
Student Study Guide and Solutions Manual Authored by David
In addition to the enhancements above, over 100 new videos have Klein. The fourth edition of the Student Study Guide and Solutions
been created by the author using lightboard technology. Each video Manual to accompany Organic Chemistry, 4e contains:
(5–10 minutes in duration) covers one of the boxed (numbered) • More detailed explanations within the solutions.
mechanisms appearing in the text. In each of these mechanism vid-
eos, each step of the mechanism is described in detail, and the stu- • Concept Review Exercises
dent sees the entire mechanism unfolding in a step-by-step fashion. • SkillBuilder Review Exercises
The author shows how to draw the resulting intermediate and how to • Reaction Review Exercises
decide what happens next when drawing the mechanism. The reason • Mechanism Review Exercises
for each step is explained, and experimental observations (regiochem-
ical and stereochemical) are justified. The function of each reagent • A list of new reagents for each chapter, with a description of
is explained, and curved arrows are drawn one at a time, with a dis- their function.
cussion of how each arrow should be drawn. These new mechanism • A list of “Common Mistakes to Avoid” in every chapter.
videos are designed to foster a solid grasp of the skills necessary for Molecular Visions™ Model Kit To support the learning of
drawing mechanisms. Mechanisms are foundational to the study of organic chemistry concepts and allow students the tactile experi-
organic chemistry, and these videos provide students with a step-by- ence of manipulating physical models, we offer a molecular model-
step explanation of each boxed mechanism that appears in the text. ing kit from the Darling Company. The model kit can be bundled
with the textbook or purchased stand alone.
Adaptive Practice for Organic Chemistry, 4e
WileyPLUS for Organic Chemistry, 4e is also supported by an adaptive CONTRIBUTORS TO ORGANIC
practice learning module that provides students with a personalized
learning experience so that they can build and track their proficiency.
CHEMISTRY, 4E
The database has over 25,000 problems, all of which have been vet-
I owe special thanks to my contributors for their collaboration,
ted by the author (a process that took almost a year of work), and are
hard work, and creativity. The expanded coverage of synthesis and
continuously updated based on user feedback. Each problem drills a
retrosynthesis was written by Laurie Starkey, California State Poly-
single concept or skill, so that students can track which concepts and
technic University, Pomona, and many of the new BioLinks and
skills they need to spend more time learning. Once a student’s areas
WorldLinks application boxes throughout the text were written by
of weakness have been identified (all of which are tracked and plot-
Ron Swisher, Oregon Institute of Technology.
ted), the student is provided with links to the relevant portions of the
text, as well as additional problems that will develop proficiency in
those areas of weakness. This provides for a personalized experience ACKNOWLEDGMENTS
that adapts to each student’s needs, thus the term “adaptive practice.”
The feedback received from both faculty and students supported
the creation, development, and execution of each edition of
ADDITIONAL INSTRUCTOR Organic Chemistry. I wish to extend sincere thanks to my col-
RESOURCES leagues (and their students) who have graciously devoted their
time to offer valuable comments that helped shape this textbook.
All resources updated and revised under guidance of Laurie Star-
key, California State Polytechnic University, Pomona.
FOURTH EDITION REVIEWERS: CLASS TEST PARTICIPANTS,

FOCUS GROUP PARTICIPANTS, AND ACCURACY CHECKERS
A R I Z O N A Smitha Pillai (Arizona State University, Tempe), Cindy Fresno), Stevan Pecic, (California State University, Fullerton), Yitzhak Tor
Browder (Northern Arizona University) (University of California, San Diego), Haim Weizman (University of Califor-
nia, San Diego)
C A L I F O R N I A Roman Dembinski (Oakland University), Jess Estrada
(Santa Barbara City College), Olga Fryszman (San Diego Miramar College), FLORIDA Kim Fields (University of South Florida), Qun Huo (Univer-
Cynthia Gilley (San Diego Miramar College), Jeremy Klosterman (Univer- sity of Central Florida), Donna Perygin (Jacksonville State University)
sity of California, San Diego), Hubert Muchalski (California State University,
PREFACE xv
GEORGIA Shainaz Landge (Georgia Southern University) NEW MEXICO Lisa Whalen (University of New Mexico)
HAWAII Philip Williams (University of Hawaii, Manoa) NEW YORK Manashi Chatterjee (Hunter College)
IDAHO Don Warner (Boise State University) NORTH CAROLINA Nicholas Shaw (Appalachian State University)
N O R T H D A K O TA Alexey Leontyev (North Dakota State University)
MARYLAND Tiffany Gierasch (University of Maryland, Baltimore
County) OHIO Tevye Celius (Ohio Northern University), James Fletcher
(Creighton University), Kelly Hall (Ohio Northern University)
MASSACHUSETTS Lara Alhariri (University of Massachusetts-Amherst)
P E N N S Y LVA N I A Matthew Betush (Allegheny College). Kevin
MICHIGAN Sean Hickey (Wayne State University), Simona Marincean Minbiole, (Villanova University)
(University of Michigan-Dearborn), Ron Stamper (Mott Community College)
SOUTH CAROLINA Tania Houjeiry (Clemson University)
MISSOURI Erin Whitteck (Saint Louis University), Brian Ganley
TEXAS Dmitriy Khon (St. Mary’s University of Texas)
(University of Missouri)
VIRGINIA Kevin Caran, (James Madison University)
M I N N E S O TA Gabriela Uzcategui White (University of St. Thomas)
CANADA Shegufa Shetranjiwalla (Trent University)
MISSISSIPPI Gerald Rowland (University of Mississippi)
PREVIOUS EDITION REVIEWERS: CLASS TEST PARTICIPANTS,

FOCUS GROUP PARTICIPANTS, AND ACCURACY CHECKERS
Philip Albiniak (Ball State University), Thomas Albright (Uni- Center), Steven Chung (Bowling Green State University), Kimberly Greve (Kalamazoo Valley Community College), Gor-
versity of Houston), Michael Aldersley, (Rensselaer Polytechnic Nagash Clarke (Washtenaw Community College), Beverly don Gribble (Dartmouth College), Ray A. Gross, Jr. (Prince
Institute), David Anderson (University of Colorado, Colorado Clement (Blinn College), Adiel Coca (Southern Connecticut George’s Community College), Nathaniel Grove (University of
Springs), Rodrigo Andrade (Temple University), Jeremy Andre- State University), Jeremy Cody (Rochester Institute of Technol- North Carolina, Wilmington), Yi Guo (Montefiore Medical
atta (Worcester State University), Merritt Andrus (Brigham ogy), Rita Collier (Gadsden State Community College), Lindsay Center), Sapna Gupta (Palm Beach State College), Rich Gurney
Young University), Laura Anna (Millersville University), Cory Comstock (Wake Forest University), John J. Coniglio (Tarrant (Simmons College), Kevin Gwaltney (Kennesaw State Univer-
Antonakos (Diablo Valley College), Ivan Aprahamian (Dart- County College), Phillip Cook (East Tennessee State University), sity), Asif Habib (University of Wisconsin, Waukesha), Laurel
mouth College), Ashley Ayers (Tarrant County College, SE Jeff Corkill (Eastern Washington University), Stephen Corlett Habgood (Rollins College), Donovan Haines (Sam Houston
Campus), Adam Azman (Butler University), Yiyan Bai (Hous- (Laney College), Sergio Cortes (University of Texas at Dallas), State University), Robert Hammer (Louisiana State University),
ton Community College), Satinder Bains (Paradise Valley Com- Philip J. Costanzo (California Polytechnic State University, San Scott Handy (Middle Tennessee State University), Christopher
munity College), Eric Ballard (University of Tampa), Edie Luis Obispo), Wyatt Cotton (Cincinnati State College), Mari- Hansen (Midwestern State University), Kenn Harding (Texas
Banner (University of South Florida, Sarasota), Tim Barker lyn Cox (Louisiana Tech University), David Crich (University A&M University), Matthew Hart (Grand Valley State Univer-
(College of Charleston), Eike Bauer (University of Missouri, St. of Illinois at Chicago), Greg Crouch (Washington State Univer- sity), Jack Lee Hayes (State Fair Community College), Dian He
Louis), Judit Beagle (University of Dayton), James Beil (Lorain sity), Mapi Cuevas (Santa Fe College), Scott Davis (Mercer (Holy Family University), Jason Hein (University of California,
County Community College), Peter Bell (Tarleton State Univer- University, Macon), Frank Day (North Shore Community Col- Merced), Rick Heldrich (College of Charleston), Eric Helms
sity), Dianne Bennet (Sacramento City College), Nicole Ben- lege), Peter de Lijser (California State University, Fullerton), (SUNY Geneseo), Maged Henary (Georgia State University,
nett (Appalachian State University), Thomas Berke (Brookdale Roman Dembinski (Oakland University), Alexei Demchenko Langate), Amanda Henry (Fresno City College), Geneive
Community College), Daniel Bernier (Riverside Community (University of Missouri, St. Louis), Brahmadeo Dewprashad Henry (Susquehanna University), Christine Hermann (Radford
College), Narayan Bhat (University of Texas Pan American), (Borough of Manhattan Community College), Preeti Dhar University), Bruce Hietbrink (University of Delaware), Patricia
Gautam Bhattacharyya (Missouri State University), Pradip (SUNY New Paltz), Martin Di Grandi (Fordham University), Hill (Millersville University), Carl Hoeger (University of Cali-
Bhowmik (University of Nevada, Las Vegas), Silas Blackstock Bonnie Dixon (University of Maryland, College Park), Dono- fornia, San Diego), Ling Huang (Sacramento City College),
(University of Alabama), Lea Blau (Yeshiva University), David van Dixon (University of Central Florida), Theodore Dolter John Hubbard (Marshall University), Thomas Hughes (Siena
Boatright (University of West Georgia), Megan Bolitho (Uni- (Southwestern Illinois College), Jason Dunham (Ball State Uni- College), Roxanne Hulet (Skagit Valley College), Christopher
versity of San Francisco), Marco Bonizzoni (The University of versity), Norma Dunlap (Middle Tennessee State University), Hyland (California State University, Fullerton), Eta Isiorho
Alabama), Charity Brannen (Baptist College), Adam Braunsch- Kay Dutz (Mt. San Antonio College), Joyce Easter (Virginia (Auburn University), Danielle Jacobs (Rider University), Wil-
weig (University of Miami), Kerry Breno (Whitworth Univer- Wesleyan College), Jeffrey Elbert (University of Northern Iowa), lian Jenks (Iowa State University), Christopher S. Jeffrey (Uni-
sity), Matthias Brewer (The University of Vermont), Richard Derek Elgin (Coastal Carolina University), Cory Emal (Eastern versity of Nevada, Reno), Dell Jensen (Augustana College), Ryan
Broene (Bowdoin College), Deborah Bromfield Lee (Florida Michigan University), Jeffrey Engle (Tacoma Community Col- Jeske (Ball State University), Yu Lin Jiang (East Tennessee State
Southern College), David Brook (San Jose State University), lege), Susan Ensel (Hood College), Ishan Erden (San Francisco University), Richard Johnson (University of New Hampshire),
Cindy Browder (Northern Arizona University), Pradip Brow- State University), Brian Esselman (University of Wisconsin Stacey Johnson (Western Piedmont Community College), Mar-
mik (University of Nevada, Las Vegas), Banita Brown (Univer- State), David Flanigan (Hillsborough Community College), lon Jones (Long Beach City College), Paul Jones (Wake Forest
sity of North Carolina Charlotte), David Brown (Florida Gulf James Fletcher (Creighton University), Francis Flores (Califor- University), Reni Joseph (St. Louis Community College), Cyn-
Coast University), Rebecca Brown (West Kentucky Community nia Polytechnic State University, Pomona), John Flygare (Stan- thia Judd (Palm Beach State College), Eric Kantorowski (Cali-
and Technical College), David Brownholland (Carthage Col- ford University), Frantz Folmer-Andersen (SUNY New Paltz), fornia Polytechnic State University, San Luis Obispo), Andrew
lege), Kathleen Brunke (Christopher Newport University), Tim- Raymond Fong (City College of San Francisco), Henry Forman Karatjas (Johnson & Wales University), Amy Keirstead (Univer-
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A Review of
1
General Chemistry 1.1 Introduction to Organic Chemistry
1.2 The Structural Theory of Matter
ELECTRONS, BONDS, AND MOLECULAR PROPERTIES 1.3 Electrons, Bonds, and Lewis Structures
1.4 Identifying Formal Charges
1.5 Induction and Polar Covalent Bonds
DID YOU EVER WONDER . . . 1.6 Reading Bond-Line Structures
what causes lightning? 1.7 Atomic Orbitals
B
1.8 Valence Bond Theory
elieve it or not, the answer to this question is still the subject 1.9 Molecular Orbital Theory
of debate (that’s right … scientists have not yet figured out 1.10 Hybridized Atomic Orbitals
everything, contrary to popular belief ). There are various theories 1.11 Predicting Molecular Geometry:
that attempt to explain what causes the buildup of electric charge in VSEPR Theory
clouds. One thing is clear, though—lightning involves a flow of elec- 1.12 Dipole Moments and Molecular Polarity
trons. By studying the nature of electrons and how electrons flow, it 1.13 Intermolecular Forces and
is possible to control where lightning will strike. A tall building can Physical Properties
be protected by installing a lightning rod (a tall metal column at the 1.14 Solubility
top of the building) that attracts any nearby lightning bolt, thereby
preventing a direct strike on the building itself. The lightning rod on
Top (Key) Gary S Chapman/Photographer’s Choice RF/Getty
the top of the Empire State Building is struck over a hundred times Images; Top (Lightning) Justin Horrocks/Getty Images
each year.
Just as scientists have discovered how to direct electrons in a bolt
of lightning, chemists have also discovered how to direct electrons
in chemical reactions. We will soon see that although
organic chemistry is literally defined as the
ive/
study of compounds containing

Arch
carbon atoms, its true essence

on
is actually the study of elec-

one/ s
Hult
age
trons, not atoms. Rather than

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t
Gett
thinking of reactions in terms

Ke y s
of the motion of atoms, we must

continued >
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2 CHAPTER 1 A Review of General Chemistry
recognize that reactions occur as a result of the motion of electrons. For example, in the fol-
lowing reaction the curved arrows represent the motion, or flow, of electrons. This flow of
electrons causes the chemical change shown:
H H
− −
HO + H C HO C H +
H H
Throughout this course, we will learn how, when, and why electrons flow during reac-
tions. We will learn about the barriers that prevent electrons from flowing, and we will learn
how to overcome those barriers. In short, we will study the behavioral patterns of electrons,
enabling us to predict, and even control, the outcomes of chemical reactions.
This chapter reviews some relevant concepts from your general chemistry course that
should be familiar to you. Specifically, we will focus on the central role of electrons in form-
ing bonds and influencing molecular properties.
1.1 Introduction to Organic Chemistry

In the early nineteenth century, scientists classified all known compounds into two categories:
Organic compounds were derived from living organisms (plants and animals), while inorganic com-
pounds were derived from nonliving sources (minerals and gases). This distinction was fueled by
the observation that organic compounds seemed to possess different properties than inorganic
compounds. Organic compounds were often difficult to isolate and purify, and upon heating, they
decomposed more readily than inorganic compounds. To explain these curious observations, many
scientists subscribed to a belief that compounds obtained from living sources possessed a special
“vital force” that inorganic compounds lacked. This notion, called vitalism, stipulated that it should
be impossible to convert inorganic compounds into organic compounds without the introduction
of an outside vital force. Vitalism was dealt a serious blow in 1828 when German chemist Friedrich
Wöhler demonstrated the conversion of ammonium cyanate (a known inorganic salt) into urea,
a known organic compound found in urine:
O
Heat
NH4OCN C
H2N NH2
Ammonium cyanate Urea

(Inorganic) (Organic)
BY THE WAY
There are some carbon‑ Over the decades that followed, other examples were found, and the concept of vitalism was
containing compounds that gradually rejected. The downfall of vitalism shattered the original distinction between organic and
are traditionally excluded inorganic compounds, and a new definition emerged. Specifically, organic compounds became
from organic classification. defined as those compounds containing carbon atoms, while inorganic compounds generally were
For example, ammonium defined as those compounds lacking carbon atoms.
cyanate (seen on this page) Organic chemistry occupies a central role in the world around us, as we are surrounded by
is still classified as inorganic, organic compounds. The food that we eat and the clothes that we wear are comprised of organic
despite the presence of compounds. Our ability to smell odors or see colors results from the behavior of organic com-
a carbon atom. Other
pounds. Pharmaceuticals, pesticides, paints, adhesives, and plastics are all made from organic
exceptions include sodium
carbonate (Na2CO3) and
compounds. In fact, our bodies are constructed mostly from organic compounds (DNA, RNA,
potassium cyanide (KCN), proteins, etc.) whose behavior and function are determined by the guiding principles of organic
both of which are also chemistry. The responses of our bodies to pharmaceuticals are the results of reactions guided by
considered to be inorganic the principles of organic chemistry. A deep understanding of those principles enables the design
compounds. We will not of new drugs that fight disease and improve the overall quality of life and longevity. Accord-
encounter many more ingly, it is not surprising that organic chemistry is required knowledge for anyone entering the
exceptions. health professions.
1.2 The Structural Theory of Matter 3
1.2 The Structural Theory of Matter

In the mid-nineteenth century three individuals, working independently, laid the conceptual foun-
dations for the structural theory of matter. August Kekulé, Archibald Scott Couper, and Alexander
M. Butlerov each suggested that substances are defined by a specific arrangement of atoms. As an
example, consider the following two compounds:
H H H H
H C O C H H C C O H
H H H H
Dimethyl ether Ethanol
Boiling point = –23°C Boiling point = 78.4°C
These compounds have the same molecular formula (C2H 6O), yet they differ from each
other in the way the atoms are connected—that is, they differ in their constitution. As a result,
they are called constitutional isomers. Constitutional isomers have different physical proper-
ties and different names. The first compound is a colorless gas used as an aerosol spray propel-
lant, while the second compound is a clear liquid, commonly referred to as “alcohol,” found in
alcoholic beverages.
According to the structural theory of matter, each element will generally form a predict-
able number of bonds. For example, carbon generally forms four bonds and is therefore said to
be tetravalent. Nitrogen generally forms three bonds and is therefore trivalent. Oxygen forms
two bonds and is divalent, while hydrogen and the halogens form one bond and are monovalent
(Figure 1.1).
Tetravalent Trivalent Divalent Monovalent
C N O H X
FIGURE 1.1 (where X = F, Cl, Br, or )
Valencies of some common Carbon generally Nitrogen generally Oxygen generally Hydrogen and halogens
elements encountered forms four bonds. forms three bonds. forms two bonds. generally form one bond.
in organic chemistry.
SKILLBUILDER
1.1 drawing constitutional isomers of small molecules
LEARN the skill Draw all constitutional isomers that have the molecular formula C3H8O.
SOLUTION
STEP 1 Begin by determining the valency of each atom that appears in the molecular formula.
Determine the valency of Carbon is tetravalent, hydrogen is monovalent, and oxygen is divalent. The atoms with the
each atom that appears
highest valency are connected first. So, in this case, we draw our first isomer by connecting
in the molecular formula.
the three carbon atoms, as well as the oxygen atom, as shown below. The drawing is com‑
STEP 2 pleted when the monovalent atoms (H) are placed at the periphery:
Connect the atoms of H H H
highest valency, and
place the monovalent C C C O C C C O H C C C O H
atoms at the periphery. H H H
This isomer (called 1-propanol) can be drawn in many different ways, some of which are
shown here:
H H O H H H H H H H H H H
H C C C H H C C C O H H C C C H H O C C C H
3 2 1 3 2 1 3 2 1 1 2 3
H H H H H H H H O H H H H
1-Propanol 1-Propanol 1-Propanol 1-Propanol
All of these drawings represent the same isomer. If we number the carbon atoms (C1, C2,
and C3), with C1 being the carbon atom connected to oxygen, then all of the drawings
above show the same connectivity: a three-carbon chain with an oxygen atom attached at
one end of the chain.
STEP 3 Thus far, we have drawn just one isomer that has the molecular formula C3H8O. Other con‑
Consider other ways to stitutional isomers can be drawn if we consider other possible ways of connecting the three car‑
connect the atoms.
bon atoms and the oxygen atom. For example, the oxygen atom can be connected to C2 (rather
than C1), giving a compound called 2-propanol (shown below). Alternatively, the oxygen atom
can be inserted between two carbon atoms, giving a compound called ethyl methyl ether (also
shown below). For each isomer, two of the many acceptable drawings are shown:
H
H
H C H
H O H H 3 H H H H H H
H C C C H H C C O H H C C O C H H C O C C H
1 2 3 1 2
H H H H H H H H H H H
2-Propanol Ethyl methyl ether
If we continue to search for alternate ways of connecting the three carbon atoms and the
oxygen atom, we will not find any other ways of connecting them. So in summary, there are
a total of three constitutional isomers with the molecular formula C3H8O, shown here:
H
H H H H O H H H H
H C C C O H H C C C H H C C O C H
H H H H H H H H H
Oxygen is connected to C1 Oxygen is connected to C2 Oxygen is between two carbon atoms
Additional skills (not yet discussed) are required to draw constitutional isomers of com‑
pounds containing a ring, a double bond, or a triple bond. Those skills will be developed in
Section 14.16.
PRACTICE the skill 1.1 Draw all constitutional isomers with the following molecular formula.
(a) C3H7Cl (b) C4H10 (c) C5H12 (d) C4H10O (e) C3H6Cl2
APPLY the skill 1.2 Chlorofluorocarbons (CFCs) are gases that were once widely used as refrigerants and
propellants. When it was discovered that these molecules contributed to the depletion of
the ozone layer, their use was banned, but CFCs continue to be detected as contaminants
in the environment.1 Draw all of the constitutional isomers of CFCs that have the molecular
formula C2Cl3F3.
need more PRACTICE? Try Problems 1.32, 1.42, 1.51
1.3 Electrons, Bonds, and Lewis Structures

What Are Bonds?
As mentioned, atoms are connected to each other by bonds. That is, bonds are the “glue” that hold
atoms together. But what is this mysterious glue and how does it work? In order to answer this ques-
tion, we must focus our attention on electrons.
The existence of the electron was first proposed in 1874 by George Johnstone Stoney (National
University of Ireland), who attempted to explain electrochemistry by suggesting the existence of
1.3 Electrons, Bonds, and Lewis Structures 5
a particle bearing a unit of charge. Stoney coined the term electron to describe this particle. In 1897,
J. J. Thomson (Cambridge University) demonstrated evidence supporting the existence of Stoney’s
mysterious electron and is credited with discovering the electron. In 1916, Gilbert Lewis (University
of California, Berkeley) defined a covalent bond as the result of two atoms sharing a pair of electrons.
As a simple example, consider the formation of a bond between two hydrogen atoms:
H + H H H △H = –436 kJ/mol
Each hydrogen atom has one electron. When these electrons are shared to form a bond, there is
a decrease in energy, indicated by the negative value of ΔH. The energy diagram in Figure 1.2
plots the energy of the two hydrogen atoms as a function of the distance between them. Focus
H H on the right side of the diagram, which represents the hydrogen atoms separated
Energy by a large distance. Moving toward the left on the diagram, the hydrogen
atoms approach each other, and there are several forces that must be
0.74 Å Internuclear distance taken into account: (1) the force of repulsion between the two neg-
0
atively charged electrons, (2) the force of repulsion between the two
H + H
positively charged nuclei, and (3) the forces of attraction between
H H
the positively charged nuclei and the negatively charged electrons. As
H H the hydrogen atoms get closer to each other, all of these forces get stronger.
–436 kJ/mol Under these circumstances, the electrons are capable of moving in such a way
H H so as to minimize the repulsive forces between them while maximizing their attractive
forces with the nuclei. This provides for a net force of attraction, which lowers the energy of the
FIGURE 1.2
An energy diagram showing
system. As the hydrogen atoms move still closer together, the energy continues to be lowered until
the energy as a function of the the nuclei achieve a separation (internuclear distance) of 0.74 angstroms (Å). At that point, the force
internuclear distance between of repulsion between the nuclei begins to overwhelm the forces of attraction, causing the energy of
two hydrogen atoms. the system to increase if the atoms are brought any closer together. The lowest point on the curve
BY THE WAY represents the lowest energy (most stable) state. This state determines both the bond length (0.74 Å)
1 Å = 10−10 meters. and the bond strength (436 kJ/mol).
Drawing the Lewis Structure of an Atom

Armed with the idea that a bond represents a pair of shared electrons, Lewis then devised a method
for drawing structures. In his drawings, called Lewis structures, the electrons take c enter stage. We
will begin by drawing individual atoms, and then we will draw Lewis structures for small molecules.
First, we must review a few simple features of atomic structure:
• The nucleus of an atom is comprised of protons and neutrons. Each proton has a charge of
+1, and each neutron is electrically neutral.
• For a neutral atom, the number of protons is balanced by an equal number of electrons,
which have a charge of −1 and exist in shells. The first shell, which is closest to the nucleus,
can contain two electrons, and the second shell can contain up to eight electrons.
• The electrons in the outermost shell of an atom are called the valence electrons. The number
of valence electrons in an atom is identified by its group number in the periodic table (Fig-
ure 1.3). So, for example, carbon (C) has four valence electrons because it is in group 4A of
the periodic table.
1A 8A
H 2A 3A 4A 5A 6A 7A He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Ga Ge As Se Br Kr
Transition
Rb Sr Metal n Sn Sb Te Xe
FIGURE 1.3 Elements
A periodic table showing Cs Ba Tl Pb Bi Po At Rn
group numbers.
The Lewis dot structure of an individual atom indicates the number of valence electrons, which are
placed as dots around the periodic symbol of the atom (C for carbon, O for oxygen, etc.). For atoms
with four or fewer valence electrons, each valence electron is drawn by itself (unpaired), as seen in
the following cases:
Li Be B C
For atoms with more than four valence electrons, the first four valence electrons are drawn unpaired
(as seen in the case of carbon above), and then each of the remaining valence electrons is paired up
with an electron already drawn:
N O F Ne
Drawing the Lewis Structure of a Small Molecule

The Lewis dot structures of individual atoms are combined to
produce Lewis dot structures of small molecules. These drawings H
H
are constructed based on the observation that atoms tend to bond H C H HC H
in such a way so as to achieve an electron configuration with a full H
valence shell, just like that of a noble gas. For example, hydro- H
gen will form one bond to achieve the electron configuration of
helium (two valence electrons), while second-row elements (C, N, O, and F) will form the necessary
number of bonds so as to achieve the electron configuration of neon (eight valence electrons).
This observation, called the octet rule, explains why carbon is tetravalent. As just shown, it can
achieve an octet of electrons by using each of its four valence electrons to form a bond. The octet
rule also explains why nitrogen is trivalent. Specifically, it has five
valence electrons and requires three bonds in order to achieve an H N H HN H
octet of electrons. Notice that the nitrogen atom contains one H
H
pair of unshared, or nonbonding, electrons, called a lone pair.
In Chapter 2, we will discuss the octet rule in more detail; in particular, we will explore when
it can be violated and when it cannot be violated. For now, let’s practice drawing Lewis structures.
SKILLBUILDER
1.2 drawing the lewis structure of a small molecule
LEARN the skill Draw the Lewis structure of CH2O.
SOLUTION
There are four discrete steps when drawing a Lewis structure: First determine the number of
valence electrons for each atom.
STEP 1
Draw all individual C H H O
atoms.
Then, connect any atoms that form more than one bond. Hydrogen atoms only form
one bond each, so we will save those for last. In this case, we connect the C and the O.
STEP 2
Connect atoms that C O
form more than one
bond. Next, connect all hydrogen atoms. We place the hydrogen atoms next to carbon,
because carbon has more unpaired electrons than oxygen.
STEP 3 H C O
Connect the H
hydrogen atoms.
Finally, check to see if each atom (except hydrogen) has an octet. In fact, neither the carbon
nor the oxygen has an octet, so in a situation like this, the unpaired electrons are shared as
a double bond between carbon and oxygen.
STEP 4
Pair any unpaired H C O H C O
electrons so that each H H
atom achieves an octet.
1.4 Identifying Formal Charges 7
Now all atoms have achieved an octet. When drawing Lewis structures, remember that
you cannot simply add more electrons to the drawing. For each atom to achieve an octet,
the existing electrons must be shared. The total number of valence electrons should be
correct when you are finished. In this example, there was one carbon atom, two hydrogen
atoms, and one oxygen atom, giving a total of 12 valence electrons (4 + 2 + 6). The drawing
above MUST have 12 valence electrons, no more and no less.
PRACTICE the skill 1.3 Draw a Lewis structure for each of the following compounds:
(a) C2H6 (b) C2H4 (c) C2H2 (d) C3H8 (e) CH3OH
1.4 Borane (BH3) is very unstable and quite reactive. Draw a Lewis structure of borane and
explain the source of the instability.
1.5 There are four constitutional isomers with the molecular formula C3H9N. Draw a Lewis
structure for each isomer and determine the number of lone pairs on the nitrogen atom in
each case.
APPLY the skill 1.6 Smoking tobacco with a water pipe, or hookah, is often perceived as being less
angerous than smoking cigarettes, but hookah smoke has been found to contain the
d
same variety of toxins and carcinogens (cancer-causing compounds) as cigarette smoke.2
Draw a Lewis structure for each of the following dangerous compounds found in tobacco
smoke:
(a) HCN (hydrogen cyanide) (b) CH2CHCHCH2 (1,3-butadiene)
need more PRACTICE? Try Problem 1.35
1.4 Identifying Formal Charges

A formal charge is associated with any atom that does not exhibit the appropriate number of
valence electrons. When such an atom is present in a Lewis structure, the formal charge must be
drawn. Identifying a formal charge requires two discrete tasks:
1. Determine the appropriate number of valence electrons for an atom.
2. Determine whether the atom exhibits the appropriate number of electrons.
The first task can be accomplished by inspecting the periodic table. As mentioned earlier, the
group number indicates the appropriate number of valence electrons for each atom. For example,
carbon is in group 4A and therefore has four valence electrons. Oxygen is in group 6A and has six
valence electrons.
O
After identifying the appropriate number of electrons for each atom in a Lewis
structure, the next task is to determine if any of the atoms exhibit an unexpected num- H C H
ber of electrons. For example, consider the structure shown on the right: H
O
Each line represents two shared electrons (a bond). For our purposes, we must split H C H
each bond apart equally, and then count the number of electrons on each atom.
H
Each hydrogen atom has one valence electron, as expected. The carbon atom also has −
O
the appropriate number of valence electrons (four), but the oxygen atom does not. The
oxygen atom in this structure exhibits seven valence electrons, but it should only have H C H
six. In this case, the oxygen atom has one extra electron, and it must therefore bear a H
negative formal charge, which is indicated as shown:
SKILLBUILDER
1.3 calculating formal charge
LEARN the skill Consider the nitrogen atom in the structure below and determine if it has a formal charge:
H
H N H
SOLUTION
STEP 1 We begin by determining the appropriate number of valence electrons for a nitrogen atom.
Determine the Nitrogen is in group 5A of the periodic table, and it should therefore have five valence
appropriate number electrons.
of valence electrons.
Next, we count how many valence electrons are exhibited by the nitrogen atom in this par‑
STEP 2 ticular example.
Determine the actual
number of valence H
electrons in this case. H N H
STEP 3 In this case, the nitrogen atom exhibits only four valence electrons. It is missing one elec‑
Assign a formal tron, so it must bear a positive charge, which is shown like this:
charge.
H
+
H N H
PRACTICE the skill 1.7 Identify any formal charges in the structures below:
H H H H
H O
H Al H H C N C H H C H
O C
(a) H (b) H H (c) H H (d) H H (e) H
H Cl H H O
H C H H C C O Cl Al Cl Cl H N C C O
(f ) H (g) H (h) Cl (i) H H
1.8 Draw a structure for each of the following ions; in each case, indicate which atom pos‑
sesses the formal charge:
(a) BH4− (b) NH2− (c) C2H5+
APPLY the skill 1.9 If you are having trouble paying attention during a long H
H
H
lecture, your levels of acetylcholine (a neurotransmitter) may H O H H C H
be to blame.3 Identify any formal charges in acetylcholine. H C C O C C N C H
H H H C H
need more PRACTICE? Try Problem 1.66, 1.81a H H
H
Acetylcholine
1.5 Induction and Polar Covalent Bonds

Chemists classify bonds into three categories: (1) covalent, (2) polar covalent, and (3) ionic. These
categories emerge from the electronegativity values of the atoms sharing a bond. Electronegativity
is a measure of the ability of an atom to attract electrons. Table 1.1 gives electronegativity values for
elements commonly encountered in organic chemistry.
1.5 Induction and Polar Covalent Bonds 9
TABLE 1.1 electronegativity values of some common elements

TABLE 1.1 ELECTRONEGATIVITY VALUES OF SOME COMMON ELEMENTS
Increasing electronegativity
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Increasing
Na Mg Al Si P S Cl electronegativity
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Br
0.8 2.8
When two atoms form a bond, one critical consideration allows us to classify the bond: What
is the difference in the electronegativity values of the two atoms? Below are some rough guidelines:
shared between the two atoms, resulting in a covalent bond. Examples include CC and CH:
If the difference in electronegativity is less than 0.5, the electrons are considered to be equally
C C C H
The CCbond is clearly covalent, because there is no difference in electronegativity between the
two atoms forming the bond. Even a C Hbond is considered to be covalent, because the differ-
ence in electronegativity between C and H is less than 0.5.
If the difference in electronegativity is between 0.5 and 1.7, the electrons are not shared
between carbon and oxygen (CO). Oxygen is significantly more electronegative (3.5) than carbon
equally between the atoms, resulting in a polar covalent bond. For example, consider a bond
(2.5), and therefore oxygen will more strongly attract the electrons of the bond. The withdrawal of
electrons toward oxygen is called induction, which is often indicated with an arrow like this.
C O
Induction causes the formation of partial positive and partial negative charges, symbolized by
the Greek symbol delta (δ). The partial charges that result from induction will be very important in
upcoming chapters.
δ+ δ–
C O
If the difference in electronegativity is greater than 1.7, the electrons are not shared at all. For
example, consider the bond between sodium and oxygen in sodium hydroxide (NaOH).
+ −
Na OH
The difference in electronegativity between O and Na is so great that both electrons of the bond
are possessed solely by the oxygen atom, rendering the oxygen negatively charged and the sodium
positively charged. The bond between oxygen and sodium, called an ionic bond, is the result of the
force of attraction between the two oppositely charged ions.
The cutoff numbers (0.5 and 1.7) should be thought of as rough guidelines. Rather than view-
ing them as absolute, we must view the various types of bonds as belonging to a spectrum without
clear cutoffs (Figure 1.4).
Covalent Polar covalent Ionic

FIGURE 1.4 C C C H N H C O Li C Li N NaCl
The nature of various bonds
commonly encountered Small difference Large difference
in organic chemistry. in electronegativity in electronegativity
This spectrum has two extremes: covalent bonds on the left and ionic bonds on the right.
such as CCbonds (covalent), CObonds (polar covalent), or NaCl bonds (ionic). However,
Between these two extremes are the polar covalent bonds. Some bonds fit clearly into one category,
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gobbling season, and the Stag in autumn, may also be drawn within
shot by the same means. I once “tolled” two Loons with my hat from
a distance of nearly half a mile, and although they were at one time
so near to me that I could clearly perceive the colour of their eyes, I
had no sure opportunity of firing at them, as it was in the pairing
season, and they never once dived, or raised their wings to flap
them, so that, knowing the extreme agility with which they disappear
when they have seen a gun snap, I judged it useless to shoot. Until
my visit to Labrador I had supposed, agreeably to the common
belief, that the Loons always repose at night on the water, which,
however, I have since assured myself they rarely if ever do.
Colonel Montagu, than whom none has written more correctly on
the habits of the birds of Great Britain, having procured a wounded
Loon, placed it in a pond, and observed the manner in which it made
its way under the surface of the water. “In swimming and diving,” he
remarks, “only the legs are used and not the wings, as in the
Guillemot and Auk tribes, and by their position so far behind, and
their little deviation from the line of the body, the bird is enabled to
propel itself in the water with great velocity, in a straight line, as well
as turn with astonishing quickness.” This I have no doubt was the
case with the individual observed; but that this is not the usual mode
of proceeding of the species is equally true. Having myself seen
Loons pass and repass under boats, at the distance of several feet
from the surface, and propel themselves both with their feet, and
their half-extended wings, I am inclined to believe that when not
wounded, and when pursuing their prey, they usually employ all the
limbs.
My friend Thomas Nuttall, who kept one for some time, gives the
following account of its manners while in his possession. “A young
bird of this kind which I obtained in the Salt Marsh at Chelsea Beach,
and transferred to a fish-pond, made a good deal of plaint, and
would sometimes wander out of his more natural element, and hide
and bask in the grass. On these occasions he lay very still until
nearly approached, and then slid into the pond and uttered his usual
plaint. When out at a distance he made the same cautious efforts to
hide, and would commonly defend himself in great anger, by darting
at the intruder, and striking powerfully with his dagger-like bill. This
bird, with a pink-coloured iris-like albinos, appeared to suffer from
the glare of broad day-light, and was inclined to hide from its effects,
but became very active towards the dusk of the evening. The pupil of
the eye in this individual, like that of nocturnal animals, appeared
indeed dilatable; and the one in question often put down his head
and eyes into the water to observe the situation of his prey. This bird
was a most expert and indefatigable diver, and remained down
sometimes for several minutes, often swimming under water, and as
it were flying with the velocity of an arrow in the air. Though at length
inclining to become docile, and shewing no alarm when visited, it
constantly betrayed its wandering habits, and every night was found
to have waddled to some hiding place, where it seemed to prefer
hunger to the loss of liberty, and never could be restrained from
exercising its instinct to move onwards to some secure or more
suitable asylum.”
The same valued friend has corroborated the result of my
observations respecting the number of eggs usually laid by this
species, by stating as follows: “About the 11th of June, through the
kindness of Dr J. W. Harris, I received three eggs, which had been
taken from the nest of a Loon, made in a hummock, or elevated
grassy hillock, at Sebago Pond, in New Hampshire.”
The range of this species is immense. It occurs on the waters that
fall into the Pacific Ocean, and has been observed on the Columbia
River. In the Fur Countries it is plentiful; and, as I have already
stated, it breeds in many parts of the United States. It is found
equally in Europe, and the northern parts of Asia. In all these
countries it moves southward on the approach of winter, and returns
when the mild weather commences in spring.
Unlike the Cormorant, the Loon usually swallows its food under the
water, unless when it happens to bring up a shell-fish or a
crustaceous animal, which it munches for a while before it swallows
it. Fishes of numerous kinds, aquatic insects, water-lizards, frogs,
and leeches, have been found by me in its stomach, in which there is
also generally much coarse gravel, and sometimes the roots of
fresh-water plants.
Although the flesh of the Loon is not very palatable, being tough,
rank, and dark coloured, I have seen it much relished by many lovers
of good-living, especially at Boston, where it was not unfrequently
served almost raw at the table of the house where I boarded.
A female bird particularly examined by me presented the following
appearances. From the point of the bill to the end of the tail it
measured 34 inches; to the claws 41; the extended wings were 71;
the bill measured 5 inches along the gape; the breadth of the body
was 8 inches, its depth only four; the wings were 2 inches shorter
than the tail; and the weight was 10 lb. 11 oz. avoirdupois. The first
primary was longest. The trachea, which was even and flattened,
being in diameter about 5/8 of an inch by 1/2 inch, was 16 inches
long. The eggs were numerous. The gizzard was moderate, and
contained many large pebbles. The intestines were 7 feet long, and
about the same size as a Swan’s quill. Every bone and sinew was
strong and tough. The tongue resembled in shape and size that of
the Ivory-billed Woodpecker. The bones of the wing and leg were
almost solid, the cavity for the marrow being very small. All the
bones of this specimen were presented to Mr Thomas Allis, of the
Friend’s Retreat, near York.
My friend Captain James Clark Ross, of the Royal Navy of
England, once placed at my disposal a specimen of the Loon
procured in a very high latitude, and which, having closely inspected
it, I found to differ from the one represented in the plate, only in
having the point of the bill slightly elevated or recurved, and of a fine
yellow tint. Dr Richardson informed me that, on one of his arduous
northern journeys, he saw a very large and handsomely crested
Diver, which, although somewhat prematurely, I propose honouring
with the name of Colymbus Richardsoni.
Colymbus glacialis, Linn. Syst. Nat. vol. i. p. 221. Adult.—Lath. Ind. Ornith.
p. 799.
Colymbus Immer, Linn. Syst. Nat. vol. i. p. 222. Young.—Lath. Ind. Ornith. p.
800.
Colymbus glacialis, Ch. Bonaparte, Synopsis of Birds of United States, p.
420.
Great Northern Diver or Loon, Wils. Amer. Ornith. vol. ix. pl. 74, fig. 3.
Colymbus glacialis, Richards. and Swains. Fauna Bor. Amer. vol. ii. p. 474.
Loon, or Great Northern Diver, Nuttall, Manual, vol. ii. p. 513.
Adult Male. Plate CCCVI. Fig. 1.

Bill as long as the head, straight, stout, much compressed, tapering
to a point. Upper mandible with the dorsal line descending and
slightly convex towards the end, the ridge convex, narrowed towards
the point, the sides convex beyond the nostrils, the edges sharp and
considerably inflected, the tip narrow and sharpish. Nasal groove
short, nostrils basal, linear, direct, pervious. Lower mandible with the
angle extremely narrow, and extending beyond the middle, the
dorsal line straight and sloping upwards to the point, the ridge
convex and narrow, the edges sharp and involute; the tip attenuated.
Head of moderate size, oblong, narrowed before. Neck rather long
and thick. Eyes of moderate size. Body elongated, much depressed,
of an elliptical form viewed from above. Wings small. Feet short,
rather large, placed very far back; tibia almost entirely concealed;
tarsus short, exceedingly compressed, sharp-edged before and
behind, covered all over with reticulated angular scales; hind toe
extremely small, connected with the second by a very small
membrane; the anterior toes united by articulated membranes, the
fourth or outer longest, the third a little shorter, the second
considerably shorter than the third, all covered above with very
numerous narrow scutella, the second toe with a free two-lobed
membrane; claws very small, depressed, blunt.
Plumage short and dense; of the head and neck very short, and
blended; of the lower parts blended, short, with slight gloss; of the
upper compact, glossy; the feathers in general oblong, those of the
upper parts with the extremity abrupt. Wings proportionally very
small and narrow, curved; primaries strong, tapering, the first
longest, the second almost as long, the rest rapidly graduated;
secondaries broad, and rounded. Tail extremely short, rounded, of
twenty feathers.
Bill black. Iris deep bright red. Feet, tarsi, and toes, of a livid greyish-
blue, their inner sides tinged with pale yellowish flesh-colour; claws
black, lighter at the base; webs brownish-black, lighter in the middle.
Head and neck dark greenish-blue, with purple reflections. On the
throat a small transverse patch of white, longitudinally striated with
dusky; about the middle of the neck, two large patches of the same,
separated in front to the distance of an inch, behind continuous, but
when the feathers are laid close, appearing as if separated by a
longitudinal dark band about half an inch in breadth. The under parts
glossy white, excepting the feathers on the sides under the wing,
which are black, each with two, three, or four elliptical white spots, a
faint dusky band across the vent, the lower tail-coverts, which are
brownish-black tipped with white, and the axillar feathers and larger
wing-coverts, which have a dusky streak along the middle. The sides
of the neck at its lower part are longitudinally streaked with black and
white, there being two oblong spots of the latter on each feather
towards the end. The upper parts are glossy black, variegated with
spots of white in regular transverse slightly-curved lines having the
convexity backwards. These spots vary in form and size, being small
and roundish towards the neck and sides, larger and somewhat four-
sided along the middle of the back: largest and rectangular on the
scapulars, very small and roundish on the hind part of the back and
tail-coverts. The upper part of the wing is similar, with smallish spots;
the alula and quill brownish-black, a few of the inner secondaries
only having two white spots at their extremity. Tail brownish-black,
paler at the tip.
Adult Male. Adult Male. Young.

Length to the end of tail, 32 7/8 36 31 1/4
................................claws, 39 1/4 40 1/2 36
................................wings, 31 1/4 — 29 3/4
carpal joint, 16 3/4 — 16 1/4
Extent of wings, 57 1/2 52 54 1/2
Wing from flexure, 15 1/2 — 14 1/4
Depth of body, — 6 —
Breadth, — 9 1/2 —
Bill along the ridge, — 3 4/12 —
Gape-line, — 4 1/2 —
Tarsus, — 3 5/12 —
Hind toe, — 9 1/2 —
Its claw, — 2/
12 —
Outer toe and claw, — 4 1/2 —
Middle toe, — 4 1/4 —
Inner, — 3 9/12 —
Tail, — 29 1/12 —
Wing from flexure, — 14 1/2 —
Weight, 8 3/4 8 1/2 9
The female is generally smaller, but in all other respects resembles

the male. Weight 10 lb. 11 oz.
Young in winter. Plate, CCCVI. Fig. 2.
Bill pale yellowish-green, the ridge and tip of the upper mandible
dusky. Iris brown. Feet dusky externally, pale yellowish flesh-colour
internally, webs dusky, but yellow in the middle. Claws yellowish-
brown. All the upper parts are of a uniform dark greyish-brown, each
feather margined with lighter, the lower parts white; the sides of the
neck at the lower part whitish, streaked with dusky; the sides dusky,
without spots.
Towards spring the eye assumes a redder tint, and the plumage of
the upper parts gradually becomes spotted with white; and when the
moult is completed about the end of summer, the plumage is as in
the adult, although the tints are improved at each successive moult
for several years.
A fine male killed at Boston, 34 inches in length, with an alar extent
of 56, presents the following characters. There is a general layer of
subcutaneous adipose tissue, and the skin is very tenacious. The
external aperture of the ear roundish, very small, having a diameter
of only 2 lines. The tongue is 2 inches 1 line in length, fleshy, as high
as broad, slightly concave and longitudinally grooved above,
tapering to a horny point. On the palate are 6 rows of papillæ; the
posterior aperture of the nares is linear 2 1/2 inches in length. The
aperture of the glottis is 1/2 an inch long, with numerous papillæ
along its sides and behind. The pharynx is extremely dilatable, as is
the œsophagus, which is 17 inches long, passes along the right side
of the neck, together with the trachea, and when distended has an
average diameter of 2 1/2 inches, but on entering the thorax
contracts to 1 1/2. The structure of the œsophagus in birds may be
very conveniently examined in this species, the different layers being
remarkably developed in it. Properly speaking, it has only two coats,
—the outer muscular, its external layer composed of transverse or
circular fibres, the internal of equally distinct longitudinal fibres,
which are not straight, but irregularly undulated. The inner, or
mucous coat, when contracted falls into longitudinal plaits. The
proventriculus is 2 3/4 inches long, the glandules large, roundish,
simple, and disposed in a continuous belt. Over this part, the
transverse muscular fibres are remarkably developed. The right lobe
of the liver is 5 3/4 inches long, the left lobe 5 1/2. The heart is very
large, of a broadly conical form, 3 inches long, 2 3/4 inches in
breadth. The stomach is three inches long, 2 1/2 in breadth, of an
elliptical form, a little compressed; its lateral muscles 9 lines in
thickness, and composed of strong large fasciculi; the tendons 1 1/2
inch in diameter; the cuticular lining thick, its upper and lower parts
marked with strong longitudinal ridges having numerous transverse
fissures; the grinding surfaces irregularly wrinkled, with a deep
fissure down the middle of each. The pylorus is 8 lines in diameter
when distended, and is destitute of valve, but has a strong prominent
rim. In the stomach were remains of fishes, and some pebbles,
chiefly quartz, the largest 4 lines long. The intestine measures 6 feet
6 inches in length, and varies in diameter from 8 to 6 lines. The
rectum is 3 1/2 inches long, the cloaca extremely large, forming a
cavity about 3 inches in diameter. The cæca are 1 3/4 inch long,
cylindrical, rounded at the extremity; one of them 7 lines, the other 9
lines, in diameter.
The trachea, when moderately extended, measures 13 1/2 inches in

length, inconsiderably depressed, its transverse diameter at the
upper part 9 1/2 lines, at the lower 6 1/2 lines; the rings cartilaginous,
of moderate breadth, uniform, with a contraction in the middle before
and behind, their number 134, the four lowest united. The bronchi
are composed of about 20 narrow cartilaginous half rings. The
contractor muscles are very broad but thin, their fibres irregularly
disposed in front; they become thicker and narrower toward the
lower part, and are continued beyond the sterno-tracheal muscles,
which come off from the 20th ring from the inferior larynx, to the
membrane between the last tracheal and first bronchial ring.
BLUE HERON.
Ardea cœrulea, Linn.

PLATE CCCVII. Adult Male and Young.
Along with a few other Herons, this is, comparatively speaking,

confined within narrow limits along our southern coast in winter. It
occurs, however, in most parts of the Floridas, where it is a constant
resident, and whence, at the approach of summer, vast multitudes
are seen proceeding northward, in search of suitable places in which
they may rear their young in security. Many, however, go southward,
beyond the limits of the United States, and proceed coastwise to
Texas and Mexico to spend the winter, especially the younger birds,
when still in that singular white plumage which differs so much from
that of the young of every other known species of this genus, except
that of the Reddish Egret (A. rufescens). At New Orleans, where it
arrives at the same period, both from Mexico and the Floridas, its
first appearance in spring is about the beginning of March; at which
time also multitudes leave the Floridas on their way eastward, to
settle in Georgia, the Carolinas, and other States farther east, as far
as Long Island in that of New York. Beyond this, I believe, no birds of
the species have been met with. They rarely, if ever, proceed far
inland, or leave the shores of our large rivers and estuaries. On the
Mississippi, the swamps and lakes on the borders of which are so
well adapted to the habits of these birds, few individuals are ever
seen above Natchez. About the beginning of September, by which
time the young are able to shift for themselves, they return
southward.
When in the Floridas, during winter, I observed that the Blue Herons
associated with other species, particularly the White Heron, Ardea
alba, and the Louisiana Heron, Ardea Ludoviciana, all of which were
in the habit of roosting together in the thick evergreen low bushes
that cover the central parts of the islands along the coast. Their
passage to and from their feeding places, is as regular as the rising
and setting of the sun, and, unless frequently disturbed, they betake
themselves every night to the same locality, and almost to the same
spot. In the morning, they rise with one accord from the roosts on
which they have been standing all night on one leg, the other drawn
up among the feathers of the abdomen, their neck retracted, and
their head and bill buried beneath their scapulars. On emerging from
their retreats, they at once proceed to some distant place in search
of food, and spend the day principally on the head waters of the
rivers, and the fresh-water lakes of the interior, giving a decided
preference to the soft mud banks, where small crabs or fiddlers are
abundant, on which they feed greedily, when the inland ponds have
been dried up, and consequently no longer supply them with such
fishes as they are wont to feed upon.
There, and at this season, Reader, you may see this graceful Heron,
quietly and in silence walking along the margins of the water, with an
elegance and grace which can never fail to please you. Each
regularly-timed step is lightly measured, while the keen eye of the
bird seeks for and watches the equally cautious movements of the
objects towards which it advances with all imaginable care. When at
a proper distance, it darts forth its bill with astonishing celerity, to
pierce and secure its prey; and this it does with so much precision,
that, while watching some at a distance with a glass, I rarely
observed an instance of failure. If fish is plentiful, on the shallows
near the shore, when it has caught one, it immediately swallows it,
and runs briskly through the water, striking here and there, and thus
capturing several in succession. Two or three dashes of this sort,
afford sufficient nourishment for several hours, and when the bird
has obtained enough it retires to some quiet place, and remains
there in an attitude of repose until its hunger returns. During this
period of rest, however, it is as watchful as ever, and on hearing the
least noise, or perceiving the slightest appearance of danger,
spreads its wings, and flies off to some other place, sometimes to a
very distant one. About an hour before sunset, they are again seen
anxiously searching for food. When at length satisfied, they rise
simultaneously from all parts of the marsh, or shore, arrange
themselves into loose bodies, and ascending to the height of fifty or
sixty yards in the air, fly in a straight course towards their roosting
place. I saw very few of these birds during the winter, on or near the
river St John in Florida; but on several occasions met with some on
small ponds in the pine barrens, at a considerable distance from any
large stream, whither they had been attracted by the great number of
frogs.
The flight of the Blue Heron is rather swifter than that of the Egret,
Ardea candidissima, and considerably more so than that of the Great
Blue Heron, Ardea Herodias, but very similar to that of the Louisiana
Heron, Ardea Ludoviciana. When the bird is travelling, the motion is
performed by flappings in quick succession, which rapidly propel it in
a direct line, until it is about to alight, when it descends in circular
sailings of considerable extent towards the spot selected. During
strong adverse winds, they fly low, and in a continuous line, passing
at the necessary distance from the shores to avoid danger, whether
at an early or a late hour of the day. I recollect that once, on such an
occasion, when, on the 15th of March, I was in company with my
friend John Bachman, I saw a large flock about sunset arising from
across the river, and circling over a large pond, eight miles distant
from Charleston. So cautious were they, that although the flock was
composed of several hundred individuals, we could not manage to
get so much as a chance of killing one. I have been surprised to see
how soon the Blue Herons become shy after reaching the districts to
which they remove for the purpose of breeding from their great
rendezvous the Floridas, where I never experienced any difficulty in
procuring as many as I wished. In Louisiana, on the other hand, I
have found them equally vigilant on their first arrival. On several
occasions, when I had placed myself under cover, to shoot at some,
while on their way to their roosts or to their feeding grounds, I found
it necessary to shift from one place to another, for if one of them had
been fired at and had fallen in a particular place, all that were in its
company took care not to pass again near it, but when coming up
diverged several hundred yards, and increased their speed until
past, when they would assume their more leisurely flappings. In
South Carolina, where they are very shy on their arrival, I have seen
them fly off on hearing the very distant report of a gun, and alight on
the tops of the tallest trees, where they would congregate in
hundreds, and whence they would again fly off on the least
apprehension of danger. But when once these Herons have chosen
a place to nestle in, or reached one in which they bred the preceding
year, they become so tame as to allow you to shoot as many as you
are disposed to have.
While on Cayo Island, in the Gulf of Mexico, on the 10th of April
1837, I observed large flocks of the Blue and Green Herons, Ardea
cœrulea and A. virescens, arriving from the westward about the
middle of the day. They flew at a considerable height, and came
down like so many hawks, to alight on the low bushes growing
around the sequestered ponds; and this without any other noise than
the rustling of their wings as they glided through the air towards the
spot on which they at once alighted. There they remained until
sunset, when they all flew off, so that none were seen there next
day. This shews that although these species migrate both by day
and night, they are quite diurnal during the period of their residence
in any section of the country which they may have chosen for a
season. It is more than probable that it has been from want of
personal knowledge of the habits of these birds, that authors have
asserted that all Herons are nocturnally inclined. This certainly is by
no means the case, although they find it advantageous to travel by
night during their migrations, which is a remarkable circumstance as
opposed to their ordinary habits. In the instance above mentioned, I
found the birds remarkably gentle, which was probably owing to
fatigue.
The Blue Heron breeds earlier or later according to the temperature
of the district to which it resorts for that purpose, and therefore
earlier in Florida, where, however, considerable numbers remain,
during the whole year than in other parts of the United States. Thus I
have found them in the southern parts of that country, sitting on their
eggs, on the 1st of March, fully a month earlier than in the vicinity of
Bayou Sara, on the Mississippi, where they are as much in advance
of those which betake themselves, in very small numbers indeed, to
our Middle Districts, in which they rarely begin to breed before the
fifteenth of May.
The situations which they choose for their nests are exceedingly
varied. I have found them sitting on their eggs on the Florida Keys,
and on the islands in the Bay of Galveston, in Texas, in nests placed
amidst and upon the most tangled cactuses, so abundant on those
curious isles, on the latter of which the climbing Rattlesnake often
gorges itself with the eggs of this and other species of Heron, as well
as with their unfledged young. In the Lower parts of Louisiana, it
breeds on low bushes of the water-willow, as it also does in South
Carolina; whereas, on the islands on the coast of New Jersey, and
even on the mainland of that State, it places its nest on the branches
of the cedar and other suitable trees. Wherever you find its breeding
place, you may expect to see other birds in company with it, for like
all other species, excepting perhaps the Louisiana Heron, it rarely
objects to admit into its society the Night Heron, the Yellow-crowned
Heron, or the White Egret.
The heronries of the southern portions of the United States are often
of such extraordinary size as to astonish the passing traveller. I
confess that I myself might have been as sceptical on this point as
some who, having been accustomed to find in all places the Heron to
be a solitary bird, cannot be prevailed on to believe the contrary, had
I not seen with my own eyes the vast multitudes of individuals of
different species breeding together in peace in certain favourable
localities. Such persons may be excused from giving that credit to
my account of the Passenger Pigeon which posterity will, I trust,
accord to it.
The nest of the Blue Heron, wherever situated, is loosely formed of
dry sticks, sometimes intermixed with green leaves of various trees,
and with grass or moss, according as these materials happen to be
plentiful in the neighbourhood. It is nearly flat, and can scarcely be
said to have a regular lining. Sometimes you see a solitary nest fixed
on a cactus, a bush, or a tree; but a little beyond this you may
observe from six to ten, placed almost as closely together as you
would have put them had you measured out the space necessary for
containing them. Some are seen low over the water, while others are
placed high; for, like the rest of its tribe, this species is rather fond of
placing its tenement over or near the liquid element.
The eggs are usually three, rarely four; and I have never found a
nest of this species containing five eggs, as is stated by Wilson,
who, probably found a nest of the Green Heron containing that
number among others of the present species. They measure an inch
and three quarters in length, by an inch and a quarter in breadth,
being about the size of those of Ardea candidissima, though rather
more elongated, and precisely of the same colour.
The young bird is at first almost destitute of feathers, but scantily
covered with yellowish-white down. When fully fledged, its bill and
legs are greenish-black, and its plumage pure white, or slightly
tinged with cream-colour, the tips of the three outer primaries light
greyish-blue. Of this colour the bird remains until the breeding
season, when, however, some individuals exhibit a few straggling
pale blue feathers. When they have entered on their second year,
these young birds become spotted with deeper blue on some parts
of the body, or on the head and neck, thus appearing singularly
patched with that colour and pure white, the former increasing with
the age of the bird in so remarkable a manner, that you may see
specimens of these birds with portions even of the pendant feathers
of their head or shoulders so marked. And these are produced by full
moultings, by which I mean the unexpected appearance, as it were,
of feathers growing out of the skin of the bird coloured entirely blue,
as is the case in many of our land birds. In all these stages of
plumage, and from the first spring after birth, the young birds breed
with others, as is equally the case with Ardea rufescens. You may
see a pure white individual paired with one of a full blue colour, or
with one patched with blue and white. The young, after leaving their
parents, remain separate from the old birds until the next breeding
season. At no period can the young of this species be confounded
with, or mistaken for that of the Ardea candidissima, by a person
really acquainted with these birds, for the Blue Heron is not only
larger than the latter, but the very colour of its feet and legs is
perfectly distinctive. Indeed, during the time when the young Blue
Heron is quite white (excepting on the tips of the outer primaries), it
would be easier to confound it with the young of the Reddish Egret,
Ardea rufescens, than with that of any other, were the feathers of its
hind head and neck of the same curious curled appearance as those
of that species.
My friend John Bachman informs me, that in South Carolina, this
species not unfrequently breeds in the company of the Louisiana
Heron, the nests and eggs of which, he adds, are very similar. He
has specimens of these birds in all the different stages which I have
described. At New Orleans, the Blue Herons, during the transition of
their plumage from white to blue, are called “Egrettes folles,” or
foolish Egrets, on account of their unusual tameness. My friend
Bachman and I, shot, on the 6th and 9th of April, several specimens
spotted with blue feathers, and having their crests and trains
similarly mixed, although of full length; but in most of the specimens
obtained, the white was still prevalent. I have shot some in
Louisiana, in autumn, in the same curious dress.
This species, though larger than the Snowy Heron, Ardea
candidissima, is considerably inferior to it in courage; and I was
much amused as well as surprised, when at Galveston Bay, on the
24th of April 1837, to see one of that species alight near a Purple
Heron, attack it, and pursue it as far as I could follow them with my
eyes. When the Blue Herons are on the sea-coast they not
unfrequently repose on the large mud or sand bars, at some
distance from the adjacent marshes; but they generally prefer
roosting on trees or bushes, when there are any in their
neighbourhood. The Creoles of Louisiana not unfrequently eat the
flesh of this species, and although they by no means consider it
equal to that of the Night Heron, some of them have assured me that
it is not bad food. Like other birds of this family, they become larger
with age, and the male is usually somewhat superior in size to the
female; but, with this exception, no difference can be perceived in
the external appearance of the sexes.
Ardea cœrulea, Linn. Syst. Nat. vol. 1. p. 238.—Lath. Ind. Ornith. vol. ii. p.
689.
Ardea cœrulea, Ch. Bonaparte, Synopsis, p. 300.
Blue Heron, Ardea cœrulea, Wils. Amer. Ornith. vol. vii. p. 117. pl. 62. fig.
3. Adult.
Blue Heron, Nuttall, Manual, vol. ii. p. 58.
Adult Male in full plumage. Plate CCCVI. Fig. 1.

Bill much longer than the head, rather slender, very slightly
decurved, compressed, tapering to a point. Upper mandible with the
dorsal line nearly straight for two-thirds of its length, then slightly
decurved, the ridge convex, broad at the base, gradually narrowed to
the point; a groove from the base to near the end, the sides convex
beneath, the edges thin and sharp, with a slight notch close to the
tips. Nostrils basal, linear, longitudinal, with a membrane above and
behind. Lower mandible with the angle extremely narrow and
elongated, the dorsal line beyond it ascending and almost straight,
the sides sloping outwards, and flattened, the edges sharp and
slightly inflected, the tip acuminate.
Head rather small, oblong, compressed. Neck very long and slender.
Body slender and compressed. Feet very long; tibia elongated, its
lower half bare, very slender, covered all round with angular scales,
of which the posterior are large; tarsus elongated, slender,
compressed, anteriorly covered with numerous broad scutella,
laterally and behind with angular scales. Toes long, slender, with
numerous broad scutella above, flattened and reticularly granulate
beneath. Claws rather long, arched, compressed, acute, that of hind
toe much larger and more curved, the inner edge of that of the third
finely and regularly pectinate.
Space between the bill and eye, and around the latter, bare.
Plumage soft, thin, and blended. Feathers of the upper and hind part
of the head very long, linear, with loose barbs; of the sides of the
neck loose and inclined obliquely backwards, of its lower part much
elongated, narrow, and tapering to a point; of the middle of the back
extremely long, linear, acuminate, their tips projecting about five
inches beyond the tail. Wings long, and very broad; primaries broad,
tapering, and rounded, the first, second and third almost equal, the
latter being only a twelfth of an inch longer; secondaries broad and
rounded; some of the inner only half an inch shorter than the longest
primary, when the wing is closed. Tail very short, small, even, of
twelve rather weak feathers.
Bill ultramarine blue at the base, gradually shaded into black towards
the point; the bare space between it and the eye, as well as the
edges of the eyelids, ultramarine. Iris pale yellow. Legs, tarsi, toes,
and claws, black. Head and neck of a rich deep purple, inclining to
vinaceous; the lower part of the neck and all the other parts deep
greyish-blue, the edges of the feathers lighter.
Length to end of tail 24 1/2 inches, to end of wings 25, to end of
elongated dorsal feathers 26 1/2, to end of claws 30 3/4; wing from
flexure 11 1/2; tail 4 2/12; extent of wings 42; bill along the ridge 3 4/12
along the edge of lower mandible 4; bare part of tibia 2 2/12; tarsus
3 5/12; first toe 11/12, its claw 2/12; middle toe 2 1/4, its claw 7/12.
Weight 1 lb.
The female is similar to the male, but smaller. Weight 11 oz.
The young are at first sparely covered with yellowish-white down.
When a fortnight old, the bill is yellow, with the tips greenish-black;
the feet greenish-yellow, the claws dusky, with the tips greyish-
yellow. The general colour of the plumage is pure white, but the
down which tips the feathers of the head is brownish-white; two of
the alular feathers are tinged with dull bluish-grey, and the outer
seven or eight primaries are broadly margined on both sides to the
length of about an inch and a half with the same colour of a deeper
tint, the extreme tip white.
When fully fledged, the bare parts at the base of the bill, and the
basal half of the upper mandible, are light greenish-blue, the rest
black; the lower mandible yellow, with a patch of black, an inch and a
quarter in length on each side at the end. Legs, tarsi, and toes
greenish-blue, the sides yellowish; claws dusky. The feathers of the
head are slightly elongated; those of the back are also elongated,
but much broader and shorter than in the adult. The feathers on the
upper part of the head are of a faint bluish-grey; and the alular
feathers and eight outer primaries are tinged with the same colour.
At this period, the length to the end of the tail is 22 inches, to end of
claws 28 1/2; bill along the ridge 2 7/8; wing from flexure 11; tail 4 2/12.
In November, when the moult is advanced. The bill is black, dull blue
at the base. The feet are nearly black, as are the claws. The occipital
feathers are now two inches and a half in length, and some of the
dorsal feathers extend as far as the tips of the wings; those of the
lower part of the neck have also a length of about three inches. The
general colour of the plumage is white; the upper part of the head,
the hind neck, back, anterior edge of the wing, and outer primaries at
the end, of a faint bluish-grey tint; some of the elongated feathers of
the back darker.
Length to end of tail 22 inches; to end of claws 29 1/2; bill 3; wing
from flexure 11 1/4.
A year old. Bill nearly as in the adult; feet bluish-black, the plumage
is white, with the upper parts pale greyish-blue as in November, but
the whole interspersed with numerous feathers of a deep greyish-
blue, similar to that of the adult; the primaries and tail being still
white.
Length to end of tail 23 1/4; extent of wings 32 1/2; bill 3 1/8. Weight 9
oz.

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Organic Chemistry 4th Edition David

Library of Congress Cataloging-in-Publication Data

Names: Klein, David R., 1972- author.

Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

3.9 Counterions 125

1.12 Dipole Moments and Molecular Polarity 30

WorldLinks Baking Soda versus Baking Powder 125

3.10 Lewis Acids and Bases 126

Integrated Problems • Challenge Problems

BioLinks Propofol: The Importance of Drug Solubility 40

Review of Concepts & Vocabulary • SkillBuilder Review

Alkanes and Cycloalkanes 138

ACS-Style Problems (Multiple Choice) • Integrated Problems

Chemical Reactivity and Mechanisms 233

6.1 Enthalpy 234 Addition Reactions of Alkenes 356

8.13 Oxidative Cleavage 396 10.13 Halogenation as a Synthetic

WorldLinks Conducting Organic Polymers 421 BioLinks Vitamins 507

Alcohols and Phenols 529

12.1 Structure and Properties of Alcohols 530

and Mass Spectrometry 636

14.1 Introduction to Spectroscopy 637

16.3 Molecular Orbital Theory 742 18.3 Sulfonation 833

17.1 Introduction to Aromatic Compounds 789

17.3 Structure of Benzene 793

Enols and Enolates 997

23.3 Lithium Dialkyl Cuprates (Gilman Reagents) 1105

21.2 Alpha Halogenation of Enols and Enolates 1004

25.8 Protein Function 1227

Appendix: Nomenclature of Polyfunctional Compounds A–1

FOURTH EDITION REVIEWERS: CLASS TEST PARTICIPANTS,

PREVIOUS EDITION REVIEWERS: CLASS TEST PARTICIPANTS,

study of compounds containing

carbon atoms, its true essence

is actually the study of elec-

trons, not atoms. Rather than

thinking of reactions in terms

of the motion of atoms, we must

1.1 Introduction to Organic Chemistry

Ammonium cyanate Urea

1.2 The Structural Theory of Matter

Tetravalent Trivalent Divalent Monovalent

need more PRACTICE? Try Problems 1.32, 1.42, 1.51

1.3 Electrons, Bonds, and Lewis Structures

Drawing the Lewis Structure of an Atom

Drawing the Lewis Structure of a Small Molecule

LEARN the skill Draw the Lewis structure of CH2O.

(a) HCN (hydrogen cyanide) (b) CH2CHCHCH2 (1,3-butadiene)

need more PRACTICE? Try Problem 1.35

1.4 Identifying Formal Charges

(f ) H (g) H (h) Cl (i) H H

(a) BH4− (b) NH2− (c) C2H5+

1.5 Induction and Polar Covalent Bonds

TABLE 1.1 electronegativity values of some common elements

Covalent Polar covalent Ionic

Adult Male. Plate CCCVI. Fig. 1.

Adult Male. Adult Male. Young.

The female is generally smaller, but in all other respects resembles

The trachea, when moderately extended, measures 13 1/2 inches in

Ardea cœrulea, Linn.

Along with a few other Herons, this is, comparatively speaking,

Adult Male in full plumage. Plate CCCVI. Fig. 1.

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