Organic Chemistry 9th Edition, (Ebook

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viii Contents

6-8 Bimolecular Nucleophilic Substitution: The SN2 Reaction 261

6-9 Generality of the SN2 Reaction 263
Summary: SN2 Reactions of Alkyl Halides 264
6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile 265
Summary: Trends in Nucleophilicity 266
6-11 Reactivity of the Substrate in SN2 Reactions 269
6-12 Stereochemistry of the SN2 Reaction 273
6-13 Unimolecular Nucleophilic Substitution: The SN1 Reaction 275
6-14 Stereochemistry of the SN1 Reaction 279
6-15 Rearrangements in SN1 Reactions 281
6-16 Comparison of SN1 and SN2 Reactions 284
Summary: Nucleophilic Substitutions 286
Summary: Reactions of Alkyl Halides 287
Essential Terms 288
Study Problems 291

7 STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION 296

7-1 Introduction 296
7-2 The Orbital Description of the Alkene Double Bond 297
7-3 Elements of Unsaturation 299
7-4 Nomenclature of Alkenes 301
7-5 Nomenclature of Cis-Trans Isomers 303
Summary: Rules for Naming Alkenes 305
7-6 Commercial Importance of Alkenes 306
7-7 Physical Properties of Alkenes 308
squalene 7-8 Stability of Alkenes 310
7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl Halides 318
7-10 Unimolecular Elimination: The E1 Reaction 319
Summary: Carbocation Reactions 323
7-11 Positional Orientation of Elimination: Zaitsev’s Rule 324
7-12 Bimolecular Elimination: The E2 Reaction 326
7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation 328
7-14 Stereochemistry of the E2 Reaction 329
7-15 E2 Reactions in Cyclohexane Systems 332
7-16 Comparison of E1 and E2 Elimination Mechanisms 334
Summary: Elimination Reactions 335
7-17 Competition Between Substitutions and Eliminations 336
Summary: Substitution and Elimination Reactions of Alkyl Halides 338
PROBLEM-SOLVING STRATEGY: Predicting Substitutions and Eliminations 340
7-18 Alkene Synthesis by Dehydration of Alcohols 341
7-19 Alkene Synthesis by High-Temperature Industrial Methods 344
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 346
Summary: Methods for Synthesis of Alkenes 349
Essential Terms 350
Study Problems 353
 Contents ix

8 REACTIONS OF ALKENES 359

8-1 Reactivity of the Carbon–Carbon Double Bond 359
8-2 Electrophilic Addition to Alkenes 360
8-3 Addition of Hydrogen Halides to Alkenes 362
8-4 Addition of Water: Hydration of Alkenes 370
8-5 Hydration by Oxymercuration–Demercuration 372
8-6 Alkoxymercuration–Demercuration 375
8-7 Hydroboration of Alkenes 376
8-8 Addition of Halogens to Alkenes 382
8-9 Formation of Halohydrins 385
8-10 Catalytic Hydrogenation of Alkenes 389
8-11 Addition of Carbenes to Alkenes 391
8-12 Epoxidation of Alkenes 393
8-13 Acid-Catalyzed Opening of Epoxides 395
8-14 Syn Dihydroxylation of Alkenes 398
8-15 Oxidative Cleavage of Alkenes 400
8-16 Polymerization of Alkenes 403
8-17 Olefin Metathesis 407
PROBLEM-SOLVING STRATEGY: Organic Synthesis 410
Summary: Reactions of Alkenes 412
Summary: Electrophilic Additions to Alkenes 415
Summary: Oxidation and Cyclopropanation Reactions of Alkenes 416
Essential Terms 417
Study Problems 421

9 ALKYNES 428
9-1 Introduction 428
9-2 Nomenclature of Alkynes 429
9-3 Physical Properties of Alkynes 431
9-4 Commercial Importance of Alkynes 431
9-5 Electronic Structure of Alkynes 433
9-6 Acidity of Alkynes; Formation of Acetylide Ions 434
9-7 Synthesis of Alkynes from Acetylides 436
9-8 Synthesis of Alkynes by Elimination Reactions 439
Summary: Syntheses of Alkynes 441
9-9 Addition Reactions of Alkynes 441
9-10 Oxidation of Alkynes 450
PROBLEM-SOLVING STRATEGY: Multistep Synthesis 452
Summary: Reactions of Alkynes 454
Summary: Reactions of Terminal Alkynes 455
Essential Terms 456
Study Problems 457
 x Contents

10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 460

10-1 Introduction 460
10-2 Structure and Classification of Alcohols 460
10-3 Nomenclature of Alcohols and Phenols 461
10-4 Physical Properties of Alcohols 466
10-5 Commercially Important Alcohols 468
O 10-6 Acidity of Alcohols and Phenols 470
-menthone
10-7 Synthesis of Alcohols: Introduction and Review 474
Summary: Previous Alcohol Syntheses 474
10-8 Organometallic Reagents for Alcohol Synthesis 475
10-9 Reactions of Organometallic Compounds 478
Summary: Grignard Reactions 484
10-10 Side Reactions of Organometallic Reagents: Reduction
of Alkyl Halides 486
10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2°
Alcohols 489
Summary: Reactions of LiAIH4 and NaBH4 491
Summary: Alcohol Syntheses by Nucleophilic Additions to
Carbonyl Groups 492
10-12 Thiols (Mercaptans) 494
Summary: Synthesis of Alcohols from Carbonyl Compounds 497
Essential Terms 497
Study Problems 499

11 REACTIONS OF ALCOHOLS 505

11-1 Oxidation States of Alcohols and Related Functional Groups 506
11-2 Oxidation of Alcohols 507
11-3 Additional Methods for Oxidizing Alcohols 511
11-4 Biological Oxidation of Alcohols 513
11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 515
Summary: SN2 Reactions of Tosylate Esters 517
11-6 Reduction of Alcohols 518
11-7 Reactions of Alcohols with Hydrohalic Acids 519
11-8 Reactions of Alcohols with Phosphorus Halides 524
11-9 Reactions of Alcohols with Thionyl Chloride 525
11-10 Dehydration Reactions of Alcohols 527
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 531
11-11 Unique Reactions of Diols 534
11-12 Esterification of Alcohols 536
11-13 Esters of Inorganic Acids 537
11-14 Reactions of Alkoxides 540
PROBLEM-SOLVING STRATEGY: Multistep Synthesis 543
Summary: Reactions of Alcohols 546
Summary: Reactions of Alcohols: O ¬ H Cleavage 548
Summary: Reactions of Alcohols: C ¬ O Cleavage 548
Essential Terms 549
Study Problems 551
 Contents xi

12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 556

12-1 Introduction 556
12-2 The Electromagnetic Spectrum 557
12-3 The Infrared Region 558
12-4 Molecular Vibrations 559
12-5 IR-Active and IR-Inactive Vibrations 561
12-6 Measurement of the IR Spectrum 562
12-7 Infrared Spectroscopy of Hydrocarbons 565
12-8 Characteristic Absorptions of Alcohols and Amines 570
12-9 Characteristic Absorptions of Carbonyl Compounds 571
12-10 Characteristic Absorptions of C ¬ N Bonds 576
12-11 Simplified Summary of IR Stretching Frequencies 578
12-12 Reading and Interpreting IR Spectra (Solved Problems) 580
12-13 Introduction to Mass Spectrometry 584
12-14 Determination of the Molecular Formula by
Mass Spectrometry 587
12-15 Fragmentation Patterns in Mass Spectrometry 590
Summary: Common Fragmentation Patterns 596
Essential Terms 597
Study Problems 599

13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 607

13-1 Introduction 607
13-2 Theory of Nuclear Magnetic Resonance 608
13-3 Magnetic Shielding by Electrons 610
13-4 The NMR Spectrometer 612
13-5 The Chemical Shift 613
13-6 The Number of Signals 620
13-7 Areas of the Peaks 622
13-8 Spin-Spin Splitting 625
PROBLEM-SOLVING STRATEGY: Drawing an NMR Spectrum 630
13-9 Complex Splitting 634
13-10 Stereochemical Nonequivalence of Protons 637
13-11 Time Dependence of NMR Spectroscopy 640
PROBLEM-SOLVING STRATEGY: Interpreting Proton NMR Spectra 643
13-12 Carbon-13 NMR Spectroscopy 648
13-13 Interpreting Carbon NMR Spectra 656
13-14 Nuclear Magnetic Resonance Imaging 658
PROBLEM-SOLVING STRATEGY: Spectroscopy Problems 659
Essential Terms 663
Study Problems 665
 xii Contents

14 ETHERS, EPOXIDES, AND THIOETHERS 672

14-1 Introduction 672
14-2 Physical Properties of Ethers 673
14-3 Nomenclature of Ethers 677
14-4 Spectroscopy of Ethers 680
14-5 The Williamson Ether Synthesis 682
14-6 Synthesis of Ethers by Alkoxymercuration–Demercuration 684
14-7 Industrial Synthesis: Bimolecular Condensation of Alcohols 684
Summary: Syntheses of Ethers (Review) 685
14-8 Cleavage of Ethers by HBr and HI 686
14-9 Autoxidation of Ethers 688
Summary: Reactions of Ethers 689
14-10 Thioethers (Sulfides) and Silyl Ethers 689
14-11 Synthesis of Epoxides 693
Summary: Epoxide Syntheses 696
14-12 Acid-Catalyzed Ring Opening of Epoxides 696
14-13 Base-Catalyzed Ring Opening of Epoxides 700
14-14 Orientation of Epoxide Ring Opening 702
Summary: Orientation of Epoxide Ring Opening 703
14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 704
14-16 Epoxy Resins: The Advent of Modern Glues 705
Summary: Reactions of Epoxides 707
Essential Terms 707
Study Problems 710

CONJUGATED SYSTEMS, ORBITAL SYMMETRY, AND

15
alizarin
ULTRAVIOLET SPECTROSCOPY 716
15-1 Introduction 716
15-2 Stabilities of Dienes 717
15-3 Molecular Orbital Picture of a Conjugated System 718
15-4 Allylic Cations 723
15-5 1,2- and 1,4-Addition to Conjugated Dienes 724
15-6 Kinetic Versus Thermodynamic Control in the Addition of
HBr to Buta-1,3-diene 726
15-7 Allylic Radicals 728
15-8 Molecular Orbitals of the Allylic System 730
15-9 Electronic Configurations of the Allyl Radical, Cation, and Anion 732
15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 733
15-11 The Diels–Alder Reaction 734
15-12 The Diels–Alder as an Example of a Pericyclic Reaction 743
15-13 Ultraviolet Absorption Spectroscopy 746
15-14 Colored Organic Compounds 752
15-15 UV-Visible Analysis in Biology and Medicine 754
Essential Terms 756
Study Problems 759
 Contents xiii

16 AROMATIC COMPOUNDS 764

16-1 Introduction: The Discovery of Benzene 764
16-2 The Structure and Properties of Benzene 765
16-3 The Molecular Orbitals of Benzene 769
16-4 The Molecular Orbital Picture of Cyclobutadiene 772
16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds 773
16-6 Hückel’s Rule 774
16-7 Molecular Orbital Derivation of Hückel’s Rule 776
16-8 Aromatic Ions 777
N N
16-9 Heterocyclic Aromatic Compounds 783
O O
16-10 Polynuclear Aromatic Hydrocarbons 787
Zylon®
n
16-11 Aromatic Allotropes of Carbon 789
16-12 Fused Heterocyclic Compounds 791
16-13 Nomenclature of Benzene Derivatives 792
16-14 Physical Properties of Benzene and Its Derivatives 794
16-15 Spectroscopy of Aromatic Compounds 796
Essential Terms 798
Study Problems 800

17 REACTIONS OF AROMATIC COMPOUNDS 809

17-1 Electrophilic Aromatic Substitution 809
17-2 Halogenation of Benzene 811
17-3 Nitration of Benzene 813
17-4 Sulfonation of Benzene 814
17-5 Nitration of Toluene: The Effect of Alkyl Substitution 817
17-6 Activating, Ortho, Para-Directing Substituents 819
Summary: Activating, Ortho, Para-Directors 822
HNO3
NO2 NO2
Fe
NH2 17-7
NH2 Deactivating, Meta-Directing Substituents 822
or or

R
alkylbenzene
H2SO4
R
alkylnitrobenzene
R
HCl(aq)
R
alkylated anilines
R Summary: Deactivating, Meta-Directors 825
aniline dyes H2SO4 17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing 826
Summary: Directing Effects of Substituents 827
17-9 Effects of Multiple Substituents on Electrophilic Aromatic
Substitution 827
17-10 The Friedel–Crafts Alkylation 830
17-11 The Friedel–Crafts Acylation 835
Summary: Comparison of Friedel–Crafts Alkylation and Acylation 837
17-12 Nucleophilic Aromatic Substitution 839
17-13 Aromatic Substitutions Using Organometallic Reagents 843
17-14 Addition Reactions of Benzene Derivatives 849
17-15 Side-Chain Reactions of Benzene Derivatives 852
17-16 Reactions of Phenols 856
PROBLEM-SOLVING STRATEGY: Synthesis Using Electrophilic Aromatic
Substitution 859
Summary: Reactions of Aromatic Compounds 863
xiv Contents

Summary: Electrophilic Aromatic Substitution of Benzene 866

Summary: Substitutions of Aryl Halides 866
Essential Terms 867
Study Problems 870

18 KETONES AND ALDEHYDES 876

18-1 Carbonyl Compounds 876
18-2 Structure of the Carbonyl Group 877
18-3 Nomenclature of Ketones and Aldehydes 878
18-4 Physical Properties of Ketones and Aldehydes 880
18-5 Spectroscopy of Ketones and Aldehydes 882
18-6 Industrial Importance
O of Ketones and Aldehydes 888
18-7 Review of Syntheses of Ketones and Aldehydes 889
18-8 Synthesis of Ketones from Carboxylic Acids 893
18-9 Synthesis of Ketones and Aldehydes from Nitriles 893
canthaxanthin

O 18-10 Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 895
Summary: Syntheses of Ketones and Aldehydes 897
18-11 Reactions of Ketones and Aldehydes: Introduction to Nucleophilic
Addition 898
18-12 Hydration of Ketones and Aldehydes 902
18-13 Formation of Cyanohydrins 904
18-14 Formation of Imines 906
18-15 Condensations with Hydroxylamine and Hydrazines 909
Summary: Condensations of Amines with Ketones and Aldehydes 910
18-16 Formation of Acetals 911
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 915
18-17 Use of Acetals as Protecting Groups 916
18-18 The Wittig Reaction 918
18-19 Oxidation of Aldehydes 921
18-20 Reductions of Ketones and Aldehydes 922
Summary: Reactions of Ketones and Aldehydes 925
Summary: Nucleophilic Addition Reactions of Aldehydes and
Ketones 927
Essential Terms 928
Study Problems 931

19 AMINES 941
19-1 Introduction 941
19-2 Nomenclature of Amines 942
19-3 Structure of Amines 945
19-4 Physical Properties of Amines 947
19-5 Basicity of Amines 948
19-6 Factors that Affect Amine Basicity 950
19-7 Salts of Amines 952
O–

H3C
N+
CH3
CH3
H3 C
N
CH3
CH3
+ 1
2 O2
19-8 Spectroscopy of Amines 954
trimethylamine oxide
(TMAO)
trimethylamine
19-9 Reactions of Amines with Ketones and Aldehydes (Review) 958
19-10 Aromatic Substitution of Arylamines and Pyridine 958
 Contents xv

19-11 Alkylation of Amines by Alkyl Halides 962

19-12 Acylation of Amines by Acid Chlorides 963
19-13 Formation of Sulfonamides 965
19-14 Amines as Leaving Groups: The Hofmann Elimination 967
19-15 Oxidation of Amines; The Cope Elimination 970
19-16 Reactions of Amines with Nitrous Acid 973
19-17 Reactions of Arenediazonium Salts 975
Summary: Reactions of Amines 978
19-18 Synthesis of Amines by Reductive Amination 980
19-19 Synthesis of Amines by Acylation–Reduction 982
19-20 Syntheses Limited to Primary Amines 984
Summary: Synthesis of Amines 988
Essential Terms 989
Study Problems 992

20 CARBOXYLIC ACIDS 1002

20-1H Introduction 1002
20-2
H O Nomenclature of Carboxylic Acids 1003

20-3 O
C Structure and Physical Properties of Carboxylic Acids 1006
H 3C C H
20-4 O Acidity of Carboxylic Acids 1007
(S)-lactic acid
20-5 Salts of Carboxylic Acids 1011
20-6 Commercial Sources of Carboxylic Acids 1013
20-7 Spectroscopy of Carboxylic Acids 1015
20-8 Synthesis of Carboxylic Acids 1019
Summary: Syntheses of Carboxylic Acids 1021
20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic Acyl
Substitution 1022
(S)-lactic acid
20-10 Condensation of Acids with Alcohols: The Fischer Esterification 1024
20-11 Esterification Using Diazomethane 1028
20-12 Condensation of Acids with Amines: Direct Synthesis of Amides 1028
20-13 Reduction of Carboxylic Acids 1029
20-14 Alkylation of Carboxylic Acids to Form Ketones 1031
20-15 Synthesis and Use of Acid Chlorides 1031
Summary: Reactions of Carboxylic Acids 1034, 1035
Essential Terms 1036
Study Problems 1037

21 CARBOXYLIC ACID DERIVATIVES 1043

21-1 Introduction 1043
21-2 Structure and Nomenclature of Acid Derivatives 1044
21-3 Physical Properties of Carboxylic Acid Derivatives 1051
21-4 Spectroscopy of Carboxylic Acid Derivatives 1053
21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl
Substitution 1060
21-6 Transesterification 1069
O H O H OH

PhOCH2 C N S CH3 Ph CH C N S CH3CH

SCH2CH2N
NH

C H
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1070
N CH3 NH2 N N
CH3
O O O H
COOH COOH COOH
® ®
penicillin V cephalexin (Keflex ) imipenem (Primaxin )
a penicillin a cephalosporin a carbapenem
xvi Contents

21-7 Hydrolysis of Carboxylic Acid Derivatives 1073

21-8 Reduction of Acid Derivatives 1078
21-9 Reactions of Acid Derivatives with Organometallic Reagents 1081
21-10 Summary of the Chemistry of Acid Chlorides 1083
21-11 Summary of the Chemistry of Anhydrides 1085
21-12 Summary of the Chemistry of Esters 1088
21-13 Summary of the Chemistry of Amides 1091
21-14 Summary of the Chemistry of Nitriles 1094
21-15 Thioesters 1095
21-16 Esters and Amides of Carbonic Acid 1097
Essential Terms 1099
Summary: Reactions of Acid Chlorides 1100
Study Problems 1103

CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL

22 COMPOUNDS 1112
22-1 Introduction 1112
22-2 Enols and Enolate Ions 1114
22-3 Alkylation of Enolate Ions 1117
22-4 Formation and Alkylation of Enamines 1119
22-5 Alpha Halogenation of Ketones 1121
22-6 Alpha Bromination of Acids: The HVZ Reaction 1127
22-7 The Aldol Condensation of Ketones and Aldehydes 1128
22-8 Dehydration of Aldol Products 1132
22-9 Crossed Aldol Condensations 1133
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1134
22-10 Aldol Cyclizations 1136
22-11 Planning Syntheses Using Aldol Condensations 1137
22-12 The Claisen Ester Condensation 1139
22-13 The Dieckmann Condensation: A Claisen Cyclization 1142
22-14 Crossed Claisen Condensations 1143
22-15 Syntheses Using b-Dicarbonyl Compounds 1146
22-16 The Malonic Ester Synthesis 1148
22-17 The Acetoacetic Ester Synthesis 1151
22-18 Conjugate Additions: The Michael Reaction 1154
22-19 The Robinson Annulation 1158
PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1159
Summary: Enolate Additions and Condensations 1161
Summary: Reactions of Stabilized Carbanions 1163
Essential Terms 1163
Study Problems 1166
 Contents xvii

23 CARBOHYDRATES AND NUCLEIC ACIDS 1172

23-1 Introduction 1172
23-2 Classification of Carbohydrates 1173
23-3 Monosaccharides 1174
23-4 Cyclic Structures of Monosaccharides 1178
23-5 Anomers of Monosaccharides; Mutarotation 1182
23-6 Reactions of Monosaccharides: Reduction 1185
23-7 Oxidation of Monosaccharides; Reducing Sugars 1186
OH OH
CH2OH H
O
CH2OH H
O
23-8 Nonreducing Sugars: Formation of Glycosides 1188
H H
HO O HO O
23-9 Ether and Ester Formation 1190
H
H NH
H H
H OH
H
23-10 Chain Shortening: The Ruff Degradation 1193
O C
CH3
23-11 Chain Lengthening: The Kiliani–Fischer Synthesis 1194
N-acetyl-D-galactosamine D-galactose
Summary: Reactions of Sugars 1196
23-12 Disaccharides 1198
23-13 Polysaccharides 1203
23-14 Nucleic Acids: Introduction 1206
23-15 Ribonucleosides and Ribonucleotides 1208
23-16 The Structures of RNA and DNA 1210
23-17 Additional Functions of Nucleotides 1214
Essential Terms 1216
Study Problems 1219

24 AMINO ACIDS, PEPTIDES, AND PROTEINS 1222

24-1 Introduction 1222
24-2 Structure and Stereochemistry of the a-Amino Acids 1223
24-3 Acid–Base Properties of Amino Acids 1227
24-4 Isoelectric Points and Electrophoresis 1229
24-5 Synthesis of Amino Acids 1231
Summary: Syntheses of Amino Acids 1234
24-6 Resolution of Amino Acids 1234
24-7 Reactions of Amino Acids 1235
Summary: Reactions of Amino Acids 1238
24-8 Structure and Nomenclature of Peptides and Proteins 1238
24-9 Peptide Structure Determination 1242
24-10 Laboratory Peptide Synthesis 1247
24-11 Classification of Proteins 1253
24-12 Levels of Protein Structure 1254
24-13 Protein Denaturation 1256
Essential Terms 1259
Study Problems 1261
xviii Contents

25 LIPIDS 1265
25-1 Introduction 1265
25-2 Waxes 1266
25-3 Triglycerides 1266
25-4 Saponification of Fats and Oils: Soaps and Detergents 1270
25-5 Phospholipids 1273
25-6 Steroids 1275
25-7 Prostaglandins 1278
25-8 Terpenes 1279
Essential Terms 1282
Study Problems 1283

26 SYNTHETIC POLYMERS 1286

26-1 Introduction 1286
26-2 Chain-Growth Polymers 1287
26-3 Stereochemistry of Polymers 1293
26-4 Stereochemical Control of Polymerization: Ziegler–Natta Catalysts 1294
26-5 Natural and Synthetic Rubbers 1295
26-6 Copolymers of Two or More Monomers 1297
26-7 Step-Growth Polymers 1297
26-8 Polymer Structure and Properties 1301
26-9 Recycling of Plastics 1303
Essential Terms 1304
Study Problems 1306

APPENDICES 1308
1A NMR: Spin-Spin Coupling Constants 1308
1B NMR: Proton Chemical Shifts 1309
1C NMR: 13C Chemical Shifts in Organic Compounds 1311
2A IR: Characteristic Infrared Group Frequencies 1312
2B IR: Characteristic Infrared Absorptions of Functional Groups 1315
3A Methods and Suggestions for Proposing Mechanisms 1317
3B Suggestions for Developing Multistep Syntheses 1319
4 pKa Values for Representative Compounds 1320
5 Summary of Organic Nomenclature 1322

Brief Answers to Selected Problems A1

Photo Credits PC1

Index I1
 Contents xix

MECHANISMS
CHAPTER 4 Free-Radical Halogenation 159
CHAPTER 6 Allylic Bromination 258
The SN2 Reaction 263
Inversion of Configuration in the SN2 Reaction 273
The SN1 Reaction 276
Racemization in the SN1 Reaction 281
Hydride Shift in an SN1 Reaction 282
Methyl Shift in an SN1 Reaction 283
CHAPTER 7 The E1 Reaction 319
Rearrangement in an E1 Reaction 322
The E2 Reaction 326
Stereochemistry of the E2 Reaction 331
Acid-Catalyzed Dehydration of an Alcohol 342
CHAPTER 8 Electrophilic Addition to Alkenes 361
Ionic Addition of HX to an Alkene 363
Free-Radical Addition of HBr to Alkenes 366
Acid-Catalyzed Hydration of an Alkene 370
Oxymercuration of an Alkene 373
Hydroboration of an Alkene 378
Addition of Halogens to Alkenes 383
Formation of Halohydrins 386
Epoxidation of Alkenes 394
Acid-Catalyzed Opening of Epoxides 395
Olefin Metathesis 409
CHAPTER 9 Metal–Ammonia Reduction of an Alkyne 444
Acid-Catalyzed Keto–Enol Tautomerism 448
Base-Catalyzed Keto–Enol Tautomerism 449
CHAPTER 10 Grignard Reactions 478
Hydride Reduction of a Carbonyl Group 489
CHAPTER 11 Reaction of a Tertiary Alcohol with HBr (SN1) 519
Reaction of a Primary Alcohol with HBr (SN2) 520
Reaction of Alcohols with PBr3 525
(Review): Acid-Catalyzed Dehydration of an Alcohol 527
The Pinacol Rearrangement 535
The Williamson Ether Synthesis 541
xx Contents

MECHANISMS (continued)
CHAPTER 14 Cleavage of an Ether by HBr or HI 686
Acid-Catalyzed Opening of Epoxides in Water 697
Acid-Catalyzed Opening of an Epoxide in an Alcohol
Solution 698
Base-Catalyzed Opening of Epoxides 701
CHAPTER 15 1,2- and 1,4-Addition to a Conjugated Diene 725
Free-Radical Allylic Bromination 728
The Diels–Alder Reaction 734
CHAPTER 17 Electrophilic Aromatic Substitution 810
Bromination of Benzene 811
Nitration of Benzene 813
Sulfonation of Benzene 815
Friedel–Crafts Alkylation 831
Friedel–Crafts Acylation 836
Nucleophilic Aromatic Substitution (Addition–Elimination) 840
Nucleophilic Aromatic Substitution (Benzyne Mechanism) 842
The Suzuki Reaction 849
The Birch Reduction 851
CHAPTER 18 Nucleophilic Additions to Carbonyl Groups 901
Hydration of Ketones and Aldehydes 903
Formation of Cyanohydrins 905
Formation of Imines 907
Formation of Acetals 912
The Wittig Reaction 919
Wolff–Kishner Reduction 924
CHAPTER 19 Electrophilic Aromatic Substitution of Pyridine 960
Nucleophilic Aromatic Substitution of Pyridine 961
Acylation of an Amine by an Acid Chloride 964
Hofmann Elimination 967
The Cope Elimination of an Amine Oxide 971
Diazotization of an Amine 973
CHAPTER 20 Nucleophilic Acyl Substitution in the Basic Hydrolysis of
an Ester 1023
Fischer Esterification 1024
Esterification Using Diazomethane 1028
 Contents xxi

MECHANISMS (continued)
CHAPTER 21 Addition–Elimination Mechanism of Nucleophilic Acyl
Substitution 1060
Conversion of an Acid Chloride to an Anhydride 1063
Conversion of an Acid Chloride to an Ester 1064
Conversion of an Acid Chloride to an Amide 1064
Conversion of an Acid Anhydride to an Ester 1065
Conversion of an Acid Anhydride to an Amide 1065
Conversion of an Ester to an Amide (Ammonolysis of an Ester) 1066
Transesterification 1072
Saponification of an Ester 1074
Basic Hydrolysis of an Amide 1076
Acidic Hydrolysis of an Amide 1076
Base-Catalyzed Hydrolysis of a Nitrile 1078
Hydride Reduction of an Ester 1079
Reduction of an Amide to an Amine 1080
Reaction of an Ester with Two Moles of a Grignard Reagent 1082
CHAPTER 22 Alpha Substitution 1113
Addition of an Enolate to Ketones and Aldehydes (a Condensation) 1113
Substitution of an Enolate on an Ester (a Condensation) 1113
Base-Catalyzed Keto–Enol Tautomerism 1114
Acid-Catalyzed Keto–Enol Tautomerism 1115
Base-Promoted Halogenation 1122
Final Steps of the Haloform Reaction 1124
Acid-Catalyzed Alpha Halogenation 1126
Base-Catalyzed Aldol Condensation 1129
Acid-Catalyzed Aldol Condensation 1131
Base-Catalyzed Dehydration of an Aldol 1132
The Claisen Ester Condensation 1139
1,2-Addition and 1,4-Addition (Conjugate Addition) 1154
CHAPTER 23 Formation of a Cyclic Hemiacetal 1178
CHAPTER 26 Free-Radical Polymerization 1289
Cationic Polymerization 1291
Anionic Polymerization 1293
New to This Edition
1 NEW! Expanded coverage of Acid/Base Chemistry
in chapter 2 and separation of the chapter on
Substitution and Elimination into two distinct
chapters allow students to build upon their
existing knowledge and move through their first
mechanisms with greater clarity and with more
opportunities to test and apply their understanding
without getting overwhelmed by organic chemistry.
New problem-solving strategy spreads have
been added to both corresponding chapters for
additional support.

2 NEW! Reaction Starbursts/Reaction Maps

appear before the end of every ‘reaction-based’
chapter to help students better understand
and mentally organize reactive similarities and
distinctions.

3 NEW! Visual Guides to Organic Reactions place

the reactions covered in each chapter within the
overall context of the reactions covered in the course.

4 NEW! Problem Solving Strategies have been

added and explicitly highlighted in several chapters,
including new strategies for resonance, acid-base
equilibria, and multistep synthesis.

5 NEW! Over 100 New Problems include more

synthesis problems and problems based on
recent literature.
6 NEW! Green Chemistry is emphasized with
presentation of less toxic, environmentally friendly
reagents in many situations, such as oxidation of
alcohols with bleach rather than with chromium
reagents.
8 20 Key Mechanism Boxes highlight the fundamental
mechanistic principles that recur throughout the
course and are the basis for some of the longer, more
complex mechanisms. Each describes the steps of the
reaction in detail with a specific example to reinforce
the mechanism and a concluding problem to help
students absorb these essential reactions.

7 NEW! Chapter Openers focus on organic 9 NEW! Explanations and Annotations to

applications, with introductions and images for a Mechanisms help students better understand how
more enticing, contemporary presentation. each mechanism works.

xxii
Brief Chapter-by-Chapter Changes
Global Changes
Every chapter begins with a new chapter-opening photograph showing an interesting, real-world application of the material
in that chapter. New Problem-Solving Hints and new Applications have been added to each chapter, and all of the chapters
have gone through a careful revision process. All of the structures have been updated to the new IUPAC recommendations
for showing stereochemistry. Green curved arrows are used to show the imaginary flow of electrons in resonance forms, in
contrast to the red curved arrows used to show the actual flow in reactions.
Chapter 1 Structure and Bonding Chapter 7 Structure and Synthesis of Alkenes;
● The material on structure, bonding, and molecular Elimination
geometry has been consolidated into one chapter. A ● This chapter now contains expanded sections on E1
revised discussion of resonance includes a Problem- and E2 eliminations. Several Problem-Solving Hints
Solving Strategy, a Problem-Solving Hint on the types have been added, as well as graphics on the competition
of arrows used in organic chemistry, and several new between substitutions and eliminations. Several new
problems. problems have been added, including two solved
problems.
Chapter 2 Acids and Bases; Functional Groups
● The presentation of acids and bases has been moved from Chapter 8 Reactions of Alkenes
the previous Chapter 1 and greatly enhanced to become ● Several diagrams, applications, problems, and starburst
the main subject in the new Chapter 2. The new material summaries of reactions have been added. The new visual
includes sections on inductive, hybridization, resonance, Guide to Organic Reactions is introduced in Chapter 8,
and solvent effects on acidity and basicity; a section and further updated in Chapters 11, 17, 18, 21, and 22.
and Problem-Solving Strategy on predicting acid-base
equilibrium positions; new Problem-Solving Hints; Chapter 9 Alkynes
new figures; new applications; and 18 new problems. ● New examples and a new starburst summary have
been added. A new Problem-Solving Hint summarizes
Chapter 4 The Study of Chemical Reactions oxidative cleavages of alkynes.
● The values of bond dissociation enthalpies have
been updated to the most recent experimental results Chapter 10 Structure and Synthesis of Alcohols
throughout the chapter. A revised discussion of ● The material on lithium dialkylcuprates has been
Hammond’s postulate includes a figure that has been expanded into a new section. New Problem-Solving
revised for clarity. Hints on Grignard reactions and organometallic reactions
have also been added. A new starburst reaction summary
Chapter 5 Stereochemistry has been added.
● This chapter includes a revised summary of types of
isomers, with revised figures for clarity. There are Chapter 11 Reactions of Alcohols
new Problem-Solving Hints on stereocenters, Fischer ● A newly revised discussion of oxidizing agents
projections, and relative versus absolute configurations. emphasizes “green” reactions with sodium hypochlorite
and acetic acid, or TEMPO, rather than toxic chromium
Chapter 6 Alkyl Halides; Nucleophilic Substitution reagents. A new interim summary compares alcohol
● The sections on E1 and E2 eliminations have been moved oxidations with and without chromium reagents, and a
to Chapter 7. A new graphic showing the strengths of new Problem-Solving Hint discusses ring-size changes
common nucleophiles has been added, and the summary and rearrangements. Two new starburst reaction
of nucleophilic substitution conditions has been summaries have been added.
expanded. Several Problem-Solving Hints have been
added on nucleophiles and bases, acid-base strength in Chapter 14 Ethers, Epoxides, and Thioethers
the SN1 reaction, and carbocation rearrangements. ● New material and a new graphic have been added to
clarify the regiochemistry of the opening of substituted
epoxides. Several new problems have been added.

xxiii
xxiv New to This Edition
Chapter 15 Conjugated Systems, Orbital Symmetry,
and Ultraviolet Spectroscopy
● Several figures have been revised for clarity, and new
applications have been added.
Chapter 16 Aromatic Compounds
● New to this chapter are a Problem-Solving Hint on
drawing energy diagrams for the MOs of cyclic systems,
plus new applications and problems. A new starburst
reaction summary has also been added.
Chapter 17 Reactions of Aromatic Compounds
● A new Problem-Solving Strategy has been added to
explain multistep synthesis using electrophilic aromatic
substitutions. The discussion of the Suzuki reaction
has been expanded, including its mechanism. New
applications, two new starburst reaction summaries, and
several problems have also been added.
Chapter 18 Ketones and Aldehydes
● The discussion of syntheses of ketones and aldehydes
has been revised to emphasize oxidations that use less
toxic reagents such as bleach and TEMPO. Several new
applications have been added, as well as a starburst
reaction summary and several new problems.
Chapter 19 Amines
● A Problem-Solving Hint on pKa of amines has been
added, plus new applications and several new problems.
Chapter 20 Carboxylic Acids
● New problems and applications have been added as well
as a starburst reaction summary.
Chapter 21 Carboxylic Acid Derivatives
● Several new problems and applications have been added,
as well as a starburst reaction summary.
Chapter 22 Condensations and Alpha Substitutions of
Carbonyl Compounds
● A new Problem-Solving Hint on ketone and ester
carbonyl groups has been added, plus a new starburst
reaction summary. Several applications and problems
have been added as well.
Chapter 23 Carbohydrates and Nucleic Acids
● This chapter has been updated with a new application on
glycoproteins. Some of the obsolete older reactions have
been dropped.
Chapter 24 Amino Acids, Peptides, and Proteins
● The material on solid-phase peptide synthesis has been
updated to use current techniques, and some of the
obsolete, older methods have been deleted.
Chapter 26 Synthetic Polymers
● The organization of the chapter has been revised to
emphasize chain-growth versus step-growth polymers,
rather than addition versus condensation polymers. A
new section has been added on the recycling of plastics,
plus applications on 3D printing and PEX pipes.
Preface
To the Student
As you begin your study of organic chemistry, you might feel overwhelmed by the
number of compounds, names, reactions, and mechanisms that confront you. You might
even wonder whether you can learn all this material in a single year. The most important
function of a textbook is to organize the material to show that most of organic chem-
istry consists of a few basic principles and many extensions and applications of these
principles. Relatively little memorization is required if you grasp the major concepts
and develop flexibility in applying those concepts. Frankly, I have a poor memory, and
I hate memorizing lists of information. I don’t remember the specifics of most of the
reactions and mechanisms in this book, but I can work them out by remembering a few
basic principles, such as “alcohol dehydrations usually go by E1 mechanisms.”
Still, you’ll have to learn some facts and fundamental principles to serve as the
working “vocabulary” of each chapter. As a student, I learned this the hard way when I
made a D on my second organic chemistry exam. I thought organic would be like general
chemistry, where I could memorize a couple of equations and fake my way through the
exams. For example, in the ideal gas chapter, I would memorize PV = nRT, and I was
good to go. When I tried the same approach in organic, I got a D. We learn by making
mistakes, and I learned a lot in organic chemistry.
In writing this book, I’ve tried to point out a small number of important facts and
principles that should be learned to prepare for solving problems. For example, of the
hundreds of reaction mechanisms shown in this book, about 20 are the fundamental
mechanistic steps that combine into the longer, more complicated mechanisms. I’ve
highlighted these fundamental mechanisms in Key Mechanism boxes to alert you to
their importance. Similarly, the Guide to Organic Reactions appears in six chapters
that contain large numbers of new reactions. This guide outlines the kinds of reactions
we cover and shows how the reactions just covered fit into the overall organization.
Spectroscopy is another area in which a student might feel pressured to memorize
hundreds of facts, such as NMR chemical shifts and infrared vibration frequencies.
I couldn’t do that, so I’ve always gotten by with knowing about a dozen NMR chemical
shifts and about a dozen IR vibration frequencies, and knowing how they are affected
by other influences. I’ve listed those important infrared frequencies in Table 12-2 and
the important NMR chemical shifts in Table 13-3.
Don’t try to memorize your way through this course. It doesn’t work; you have to
know what’s going on so you can apply the material. Also, don’t think (like I did) that
you can get by without memorizing anything. Read the chapter, listen carefully to the
lectures, and work the problems. The problems will tell you whether or not you know
the material. If you can do the problems, you should do well on the exams. If you can’t
do the problems, you probably won’t be able to do the exams, either. If you keep having
to look up an item to do the problems, that item is a good one to learn.
Here are some hints I give my students at the beginning of the course:
1. Read the material in the book before the lecture (expect 13–15 pages per lecture).
Knowing what to expect and what is in the book, you can take fewer notes and
spend more time listening and understanding the lecture.
2. After the lecture, review your notes and the book, and do the in-chapter
problems. Also, read the material for the next lecture.
3. If you are confused about something, visit your instructor during office hours
immediately, before you fall behind. Bring your attempted solutions to problems
with you to show the instructor where you are having trouble.

xxv
xxvi Preface

4. To study for an exam, begin by reviewing each chapter and your notes, and
reviewing any reaction summaries to make sure you can recognize and use those
reactions. The “starburst” summaries are most useful for developing syntheses,
since you can quickly glance at them and see the most useful conversions for that
functional group. Then concentrate on the end-of-chapter problems. In each chapter,
the Essential Problem-Solving Skills (EPSS) outline reviews the important concepts
in the chapter and shows which problems can be used to review each concept. Also
use old exams, if available, for practice. Many students find that working in a study
group and posing problems for each other is particularly helpful.
Remember the two “golden rules” of organic chemistry.
1. Don’t Get Behind! The course moves too fast, and it’s hard to catch up.
2. Work Lots of Problems. Everyone needs the practice, and the problems show
where you need more work.
I am always interested to hear from students using this book. If you have any suggestions
about how the book might be improved, or if you’ve found an error, please let me know
(L. G. Wade, Whitman College, Walla Walla, WA 99362: E-mail wadelg@whitman.
edu). I take students’ suggestions seriously, and hundreds of them now appear in this
book. For example, Whitman student Brian Lian suggested Figure 21-9, and University
of Minnesota student (and race-car driver) Jim Coleman gave me the facts on the fuels
used at Indianapolis.
Good luck with your study of organic chemistry. I’m certain you will enjoy this
course, especially if you let yourself relax and develop an interest in how organic
compounds influence our lives. My goal in writing this book has been to make the
process a little easier: to build the concepts logically on top of each other, so they
flow naturally from one to the next. The hints and suggestions for problem solving
have helped my students in the past, and I hope some of them will help you to learn
and use the material. Even if your memory is worse than mine (highly unlikely), you
should be able to do well in organic chemistry. I hope this will be a good learning
experience for all of us.

To the Instructor
In writing the first edition of this text, my goal was to produce a modern, readable text
that uses the most effective techniques of presentation and review. I wanted a book that
presents organic chemistry at the level needed for chemistry and biochemistry majors,
but one that presents and explains the material in ways that facilitate success for all the
many different kinds of students who take the course. Subsequent editions have extended
and refined these goals, with substantial rewriting and reorganizing and with many new
features. This ninth edition adds several new features to help students organize types of
reactions and mechanisms for easier learning and better understanding, as well as for
reference.

New to This Edition

To help students organize functional group reactions, new Starburst Summaries have
been added that provide visual links between synthetically related functional groups.
This new feature is particularly useful when students are developing multistep synthe-
ses, when the visual links help them to see the possible reactions moving forward from
a reactant or synthetic intermediate. The new Guides to Organic Reactions will help
students to organize mentally the many new reactions they are learning, and where
those reactions fit within the overall scheme of the types of reactions we use in organic
chemistry. Chapter-opening photographs, with captions that explain how the photo-
graph relates to the chemistry presented in that chapter, have been added to all of the
chapters. We have tried to select photos that are remarkable in some way or another and
that grab the viewer’s attention.
 Preface xxvii

All of the features of the earlier editions have been retained in this ninth edition.
In many cases, those that were introduced in earlier editions have been expanded and
refined. Many updated applications have been added, including those relating to medi-
cine, green chemistry, biochemistry, and other contemporary areas of interest. Green
chemistry is emphasized in many areas, most notably in the use of methods that avoid
chromium reagents, which are known to be toxic and carcinogenic. The older, more
toxic reagents are mentioned, but they are no longer given as the first choice for a
reagent. Mechanisms have been provided for the newest reactions, such as the Suzuki
coupling, when they are relevant to the material and studied well enough to be confident
they are correct.

Key Features
Expanded Coverage of Acids and Bases: After reviewing the basics of bonding,
hybridization, and molecular structure in Chapter 1, Chapter 2 is centered around
acids and bases and how these concepts apply to organic compounds. The Arrhenius,
Brønsted-Lowry, and Lewis definitions are introduced and explained. The uses of pKa
and pKb are described, followed by a discussion and a Problem-Solving Strategy feature
on predicting the position of an acid-base equilibrium reaction. Factors that affect acid-
ity and basicity are explained, including solvent effects, size, electronegativity, induc-
tive effects, hybridization effects, and resonance effects. Lewis acid-base reactions are
discussed, with a careful discussion of the correct use of the curved-arrow formalism.

Separation of Substitution and Elimination Reactions: The crucial chapters on sub-

stitution and elimination have been revised, with substitutions covered in Chapter 6
and eliminations in Chapter 7. This organization allows students to become more com-
fortable with the differences between SN1 and SN2 substitutions before the possible
reaction pathways are expanded to include eliminations. Chapter 7 presents complete
coverage of the competition between substitutions and eliminations, and how one can
predict what mechanisms and products are most likely.

Organic Synthesis: Many new synthetic problems have been added, some of them com-
ing from the recent literature. The material on organic synthesis and retrosynthetic analy-
sis has been supplemented, with particular attention to multistep aromatic syntheses.

Nomenclature: We have tried to stay as current as possible with the constantly changing
IUPAC nomenclature, and this edition reflects some of the most recent changes. Begin-
ning with the eighth edition, we have used the 1993 IUPAC positioning of the locants in
names (e.g., but-1-ene), while also showing the names using the older positions of the
locants (e.g., 1-butene). We have also carefully defined stereochemical terms (such as
stereocenter and chiral center) correctly and precisely, and we have endeavored to use
the most precise term in each case.
In this edition, we have adopted three of the newest changes in the IUPAC rules:
1. In showing stereochemistry, IUPAC now recommends the “reverse perspective”
(closer end is smaller) version of wedged dashed bonds. Wedged solid bonds are
still drawn with normal perspective, with their closer end larger.
2. IUPAC now defines hydroxyl as referring only to the radical, not the functional
group. The functional group is the hydroxy group. We have changed these terms
where needed to conform to this rule.
3. At one time, the IUPAC banished the term ketal. It has now been reinstated as a
subclass of acetals, and we have resumed using it.
This ninth edition also includes a new Nomenclature Appendix, which serves as a com-
pact reference to the rules of naming organic compounds. This feature should make it
easier for students to name compounds without always having to find the discussion
pertaining to that particular functional group.
The Keys to Organic Chemistry
340 CHAPTER 7 Structure and Synthesis of Alkenes; Elimination

Among the elimination products, Zaitsev’s rule tells us that the product with the most substituted double bond will predominate.
That is the same product for both the initial carbocation and the rearranged carbocation. However, a substitution product might
Wade & Simek’s ninth edition of Organic Chemistry presents key principles of organic chemistry in the context of
be the major product. Which one depends on whether the rearrangement is faster than attack by the methanol solvent. If the
rearrangement is faster, then we see more rearranged product. This complicated reaction shows why E1 and SN1 reactions of
fundamental reasoning and problem solving. Written to reflect how today’s students use textbooks, this text serves as a
alkyl halides are rarely used for synthesis.
Follow-up question: Show the mechanistic steps that are omitted in the solution to (b) shown above.
primary guide to organic chemistry, as well as a comprehensive study resource when working problems and preparing
for exams.

PROBLEM-SOLVING STRATEGY Predicting Substitutions and Eliminations

The resources in this book
Given a set of reagents and solvents, how can you predict what products will result and which
include Problem-Solving
alkyl halides
mechanisms will be involved? Should you memorize all this theory about substitutions and
eliminations? Students sometimes feel overwhelmed at this point.
Strategies throughout, plus
strong weak
Nuc:/base Nuc:/base Memorizing is not the best way to approach this material because the answers are not absolute Partially Solved Problems,
and too many factors are involved. Besides, the real world with its real reagents and solvents is
not as clean as our equations on paper. Most nucleophiles are also basic, and many solvents can Reaction Summaries, new
SN2 + E2 SN1 + E1 solvate ions or react as nucleophiles or bases.
The first principle you must understand is that you cannot always predict one unique product Starburst Summaries, and new
or one unique mechanism. Often, the best you can do is to eliminate some of the possibilities

H
and make some accurate predictions. Remembering this limitation, here are some general Reaction Guides. Through a
guidelines:
1° alkyl halide R C X
7-18 Alkene Synthesis by Dehydration of Alcohols
1. The strength of the base or nucleophile determines the order of the reaction.
343 careful, refined presentation
Like other E1 reactions,
If a strong nucleophile (or base) is present, it will force second-order kinetics, either SN2 or E2.
H alcohol dehydration
If no strongfollows an order isofpresent,
base or nucleophile reactivity that consider first-order reactions, both SN1
you should and step-by-step guidance, this
reflects carbocationstrong
are the least reactive.
stability: 3° alcohols react
weak
Nuc:/baseRearrangements
Nuc:/base of
and E1.
2.the
faster thanof2°
Addition alcohols,
silver
Primary halides intermediates
salts to and
usually undergoare
1° alcohols
the reaction
thecommon
can force some difficult ionizations.
in occasionally the E2 reaction.
SN2 reaction,
ninth edition gives students
alcohol dehydrations. In most cases, Zaitsev’s Primary
rule halides
applies:rarely
The undergo first-order
major product reactions, unless the carbocation is resonance-
is usually
stabilized. With good nucleophiles, SN2 substitution is usually observed. With a strong base,
a contemporary overview of
the one with the most SN2substituted double bond.
no reaction E2 elimination may occasionally be observed. organic chemistry with tools
3. Tertiary halides usually undergo the E2 reaction (strong base) or a mixture of SN1 and
E1 (weak base). for organizing and understand-
SOLVED PROBLEM 7- 7 Tertiary halides cannot undergo the SN2 reaction. A strong base forces second-order kinet-
(a) Propose a mechanism
R
for the sulfuric ics, resulting in
acid-catalyzed eliminationof
dehydration bytert
the-butyl
E2 mechanism.
alcohol. In the absence of a strong base,
PROBLEM-SOLVING HINTtertiary ing reaction mechanisms and
3° alkyl halide R C X halides react by first-order processes, usually a mixture of SN1 and E1. The specific reaction
S O LU T IO N R
conditions determine the ratio of substitution to elimination.Alcohol dehydrations usually go synthetic organic chemistry.
through E1 elimination of the
The first step is protonation of the hydroxy4.group,The reactions of secondary
which converts halides
it to a good are the
leaving most difficult
group. to predict.
strong weak protonated
With a strong base, either the SN2 or the E2 reaction is possible. Withalcohol.
a weak base and a good
CHNuc:/base Nuc:/base ionizing solvent,CHboth 7 2°Mixtures
7 7 1° of
3 3 the HSN1 and E1 reactions are possible, but bothis:are
Reactivity 3°slow.
products are common. Rearrangements are common.
CH3 C O H + H2SO4 CH3 C O + + HSO4−
E2 SN1 + E1 5. Some nucleophiles and bases favor substitution or elimination. Protonated primary alcohols
CH3 To promote elimination,
CH3 H base should readily abstract
the a protonatbut
dehydrate not readily
elevated attack a
temperatures
carbon atom. A bulky strong base, such as tert-butoxide with [ -OC(CH 3)3], enhances
rearrangement (E1),elimination.
or the
The second step is ionization of the protonated Higher temperatures
alcohol to give aalso favor elimination in most cases. To promote substitution, you need
carbocation.
R a good nucleophile with limited basicity: a highly polarizableadjacentspecies
carbonthatmay is lose a proton
the conjugate
CH3 H base of a strongCHacid. Bromide (Br -) and iodide (I -) areto a weak base
examples of goodat the same timethat
nucleophiles
2° alkyl halide R C X
are weak bases and 3favor substitution. water leaves (E2).
CH3 C
H
O+ CH3 C+ + H2O
CH3 H CH3
strong weak
Nuc:/base Nuc:/base
Abstraction of a proton completes the mechanism.
SN2 + E2 SN1 + E1
H CH3 H CH3
H2O H C C+ C C + H3O+
H CH3 H CH3

(b) Predict the products and propose a mechanism for the acid-catalyzed dehydration of 1-cyclohexylethanol.
PA RT IA L SO LU TI ON:
Protonation of the hydroxy group, followed by loss of water, forms a carbocation.

H
H H + H
OH O H H +
C C C CH3
CH3
H OSO3H
CH3 + HSO4–
+ H2O

1-cyclohexylethanol carbocation
The carbocation can lose a proton, or it can rearrange to a more stable carbocation.

H H H
H +
C CH3 – + C
˜H CH3

unrearranged 2° carbocation rearranged 3° carbocation

Complete this problem by showing how the unrearranged 2° carbocation can lose either of two protons to give two of the following
products. Also show how the rearranged 3° carbocation can lose either of two protons to give two of the following products.

xxviii
Principles, Preparation, and Problem Solving
8-17 Olefin Metathesis 415

SUMMARY Electrophilic Additions to Alkenes

NEW! Starburst Reaction
Methylcyclopentene is an alkene that displays orientation and stereochemistry of addition reactions. New atoms are shown
Summaries appear before
in color. When reactions create chiral products from achiral reactants, racemic mixtures are produced. N/A means “Not the end-of-chapter material
Applicable to this reaction.”

hydrohalogenation— hydrobromination with peroxides—

of “reaction-based” chapters
Markovnikov orientation;
stereochemistry N/A;
anti-Markovnikov orientation;
stereochemistry N/A; no rearrangement
hydration— to help students mentally
Markovnikov orientation;
rearrangement can occur
Sections 8–2, 8–3
Section 8–3B
OH
CH3 stereochemistry N/A; organize the reactions and
rearrangement can occur
H
CH3 H
Section 8–4 recognize their similarities
X
CH3 H OH
oxymercuration–
demercuration— and differences.
H CH3 Markovnikov orientation;
H Br H OH stereochemistry N/A;
H X H+ catalyst
H H no rearrangement
H Br H Section 8–5
X = Cl, NaBH4
RO OR H OH
Br, I
H Hg(OAc)2 OR alkoxymercuration–
CH3 CH3 CH3
demercuration—
H H H OR NaBH4 Markovnikov
metal Hg(OAc)2 orientation;
H H H stereochemistry N/A;
Pt or Pd or Ni
H H no rearrangement
BH3 • THF Section 8–6
catalytic
X X HO OH
hydrogenation— H
H OH X X
orientation N/A; NaOH
X = Cl, CH3 hydroboration–oxidation—
syn stereochemistry; anti-Markovnikov orientation;
no rearrangement Br
H syn stereochemistry;
Section 8–10 no rearrangement
OH X
OH Section 8–7
CH3 CH3 and enantiomer

X X
H H
and enantiomer and enantiomer
halohydrin formation— halogenation—
Markovnikov orientation; orientation N/A;
anti stereochemistry; anti stereochemistry;
no rearrangement no rearrangement
Section 8–9 Section 8–8

Essential Terms 549

GUIDE TO ORGANIC REACTIONS IN NEW! Visual Guides to

CHAPTER 11 Organic Reactions place
Reactions covered in Chapter 11 are shown in red. Reactions covered in earlier chapters are shown in blue. the reactions covered in each
Substitution Addition Elimination Oxidation/Reduction chapter within the overall
▶ Nucleophilic
at sp3 C (SN1, SN2)
▶ Nucleophilic
at C “ O (Nuc. Addn.)
▶ Basic conditions (E2) ▶ Oxidation
context of the reactions
▶ ▶ ▶ E2 dehydrohalogenation ▶ epoxidation

▶
Ch 6, 10, 14, 22
at sp2 C (Nuc. Arom. Subst.) ▶
Ch 9, 10, 18, 22
at C “ C (conjugate addn.) ▶
Ch 7, 9
tosylate elimination ▶
Ch 8, 10, 14
oxidative cleavage
covered in the course.
Ch 17, 19 Ch 22 Ch 11 Ch 8, 9, 11, 17, 22
▶ at C “ O (Nuc. Acyl Subst.) ▶ Hofmann elimination ▶ oxygen functional groups
Ch 10, 11, 20, 21, 22 ▶ Electrophilic Ch 19 Ch 11, 18, 19, 20
▶ at C “ C (Elect. Addn.)
▶ Electrophilic ▶ Acidic conditions (E1) ▶ Reduction
Ch 8, 9, 10
▶ at sp2 C (Elect. Arom. Subst.) ▶ at C “ C (Carbene Addn.) ▶ E1 dehydrohalogenation ▶ hydride reduction
Ch 17, 19 Ch 8 Ch 7 Ch 8, 10, 11, 17, 18, 19, 20, 21
▶ dehydration of alcohols ▶ hydrogenation
▶ Radical ▶ Radical Ch 11 Ch 8, 9, 17, 18, 19
at sp3 C (alkane halogenation)
▶ metals
▶ ▶ at C “ C (HBr + ROOR) ▶ Pericyclic (Cope elimination) Ch 9, 17, 18, 19
Ch 4, 6, 16, 17 Ch 8
▶ at sp2 C (Sandmeyer rxn) ▶ Ch 19
Ch 19 ▶ Pericyclic

▶ Organometallic ▶ cycloaddition (Diels-Alder)

Ch 15
▶ Gilman
Ch 10, 17 ▶ Oxidation
▶ Suzuki
Ch 17
▶ epoxidation
Ch 8, 10, 14
▶ Heck
Ch 17
▶ Reduction
▶ hydrogenation
Ch 8, 9, 17, 18, 19

xxix

R O H + Na R O − Na+ + 1
2 H2
The Keys to Organic Chemistry
Over 80 Mechanism Boxes help students understand how specific reactions occur by zooming in on each
individual step in detail.
342 CHAPTER 7 Structure and Synthesis of Alkenes; Elimination

18 Key Mechanism
KEY MECHANISM 7-5 Acid-Catalyzed Dehydration of an Alcohol
Boxes highlight the
Alcohol dehydrations usually involve E1 elimination of the protonated alcohol.
Step 1: Protonation of the hydroxy group (fast equilibrium).
fundamental mechanis-
PROBLEM-SOLVING HINT
H
tic principles that recur
In acid-catalyzed mechanisms, the
first step is often addition of H + , H O H O H O+ H HSO4−
throughout the course
and the last step is often loss of H + .
C C H O S O H C C
and are the components
O
of many of the longer,
Step 2: Ionization to a carbocation (slow; rate limiting).
more complex mecha-
H
nisms. Each describes
H O
+
H H
the steps of the reaction
C C C
+
C + H2O in detail with a specific
example to reinforce the
Step 3: Deprotonation to give the alkene (fast). mechanism and a con-
H
cluding problem to help
C C+ + H2O C C + H3O + students absorb these
essential reactions.
EXAMPLE: Acid-catalyzed dehydration of butan-2-ol

Step 1: Protonation of the hydroxy group (fast equilibrium).

NEW! Explanations
OH H O+ H and Annotations
CH3 CH CH2CH3
H2SO4
CH3 CH CH2CH3 to Mechanisms
Step 2: Ionization to a carbocation (slow; rate limiting). help students better
H O+ H understand how each
+
CH3 CH CH2CH3 CH3 C CH2CH3 + H O H mechanism works.
H
Step 3: Deprotonation to give the alkene (fast). NEW! Over 100 New
H H
H H Problems include more
C CH3
H C
+
C C CH3
H2O
H C C + H3O+
synthesis problems
H H H
H H and problems based
major product (cis and trans)
on recent research
H CH3
literature.
H H H C
+ H2O
or H C C C CH3 C C H + H3O+
H H
H H H
minor product

xxx
Principles, Preparation, and Problem Solving

www.masteringchemistry.com

MasteringChemistry motivates students to practice organic chemistry outside of class

and arrive prepared for lecture. The textbook works with MasteringChemistry to guide
students toward what they need to know before testing them on the content. This edition
continually engages students through pre-lecture, during-, and post-lecture activities
that all include real-life applications.

Dynamic Study Modules

Help students understand the concepts more quickly!
Now assignable, Dynamic Study Modules enable your
students to study on their own and be better prepared with
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Activities authored by Mike Huggins, University of West Florida, prompt students to use
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xxxi
Resources in Print and Online
Supplement Available in Available Instructor or Student Description
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xxxii
Acknowledgments
I am pleased to thank the many talented people who helped with this revision. Certainly the largest contribution has come
from Jan William Simek, long-time author of the Solutions Manual and now contributing author for this textbook. Jan has
provided excellent advice and sound judgment through several editions of the book. In this edition, Jan has authored numer-
ous new and revised sections, developed over 100 new problems, constructed the starburst reaction summaries, and authored
the new Nomenclature Appendix.
Jan and I would also like to thank the many reviewers for their valuable insight and commentary. Although we did not
adopt all their suggestions, we adopted most of them; they were helpful and contributed to the quality of the final product.
Ninth Edition Accuracy Reviewers
David A. Boyajian Palomar College
Charles Kingsbury University of Nebraska at Lincoln
Chris Scwhartz Metropolitan Community College
Chad Synder Grace College and Seminary
Ninth Edition Prescriptive Reviewers:
Brad Andersh Bradley University
Anonymous University of Nebraska-Lincoln
Anonymous West Chester University
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David Boyajian Palomar College
Xuefei Huang Michigan State University
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Susan Lever University of Missouri-Columbia
Richard Mullins Xavier University
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Alline Somlai Delta State University
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Additional Reviewers for 9e:
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Ivana Peralta Vincennes University
Suzanne Ruder Virginia Commonwealth University
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Rekha Srinivasan Case Western Reserve University
Eric Trump Emporia State University
Reviewers of Previous Editions
Jung-Mo Ahn University of Texas at Dallas
David Alonso Andrews University
Merritt B. Andrus Brigham Young University
Jon Antilla University of South Florida
Arthur J. Ashe University of Michigan
Bill Baker University of South Florida
xxxiii
xxxiv Acknowledgments

Dan Becker Loyola University

John Berger Montclair State University
Bob Bly University of South Carolina
Mary Boyd Loyola University, Chicago
Hindy Bronstein Fordham College at Lincoln Center
David Brown St. John’s University
Eric Brown Loyola University, Lake Shore
Philip Brown North Carolina State University
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Patrick Buick Florida Atlantic University
David Cantillo Hillsborough Community College
Dee Ann Casteel Bucknell University
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Barry Coddens Northwestern University
Jamie Lee Cohen Pace University
Barbara Colonna University of Miami
Richard Conley Middlesex County College
Robert Crow St. Louis College of Pharmacy
Maria de GracaVicente Louisiana State University
James Fletcher Creighton University
Chris Gorman North Carolina State University
Geneive Henry Susquehanna University
William Jenks Iowa State University
Przemyslaw Maslak Pennsylvania State University
Kristen Meisenheimer Cal Polytechnic at San Luis Obispo
Guillermo Moyna University of the Sciences in Philadelphia
Rabi Musah University at Albany
Stephen A. Miller University of Florida
Hasan Palandoken California Polytechnic State University
Keith Osbourne Pascoe Georgia State University
Anthony J. Pearson Case Western Reserve
Allan Pinhas University of Cincinnati
Owen Priest Northwestern University
Stanley Raucher University ofWashington
Suzanne Ruder Virginia Commonwealth University
K.C. Russell Northern Kentucky University
Alline Somlai Delta State University
Joseph B. Wachter Michigan State University
David Son Southern Methodist University
Solomon Weldegirma University of South Florida

Finally, we want to thank the people at Pearson, whose dedication and commitment contributed to the completion of
this project. Particular thanks are due to Developmental Editor David Chelton, who made thousands of useful suggestions
throughout the writing and revision process, and who helped to shape this new edition. Special thanks are also due to Editor-
in-Chief Jeanne Zalesky, who guided the project from start to finish and made many useful comments and suggestions that
guided the direction of the revision. Director of Development Jennifer Hart and Program Manager Lisa Pierce kept the project
moving and ensured the needed resources were made available. Project Managers Elisa Mandelbaum and Heidi Aguiar, and
Text and Image Research Lead Maya Gomez kept the production process organized, on track, and on schedule. It has been a
pleasure working with all these thoroughly professional and competent people.
We have enjoyed working on this new edition, and we hope that it is a scientific and pedagogical improvement over
the eighth edition. We’ve tried to make this book as error-free as possible, but some errors may have slipped by. If you find
errors, or have suggestions about how the book might be improved, please send those errors and suggestions to me at my
e-mail address: wadelg@whitman.edu. Errors can be fixed quickly in the next printing. Please send any errors you find in
the Solutions Manual, or suggestions for improvements, to Jan Simek at his e-mail address: jsimek@calpoly.edu.
We’ve already started a file of possible changes and improvements for the next edition, and we hope that many of the
current users will contribute suggestions to this file. We hope this book makes the instructor’s job easier and helps more
students to succeed. That’s the most important reason that we continue to work at improving it.

L. G. Wade, Jr.
Walla Walla, Washington
Jan William Simek
San Luis Obispo, California
 1 Structure and Bonding

Goals for Chapter 1

1 Review concepts from general
chemistry that are essential for
success in organic chemistry, such as
the electronic structure of the atom,
Lewis structures and the octet rule,
types of bonding, electronegativity,
and formal charges.

2 Predict patterns of covalent and

ionic bonding involving C, H, O, N,
and the halogens.

3 Identify resonance-stabilized
structures and compare the relative
importance of their resonance
forms.

4 Draw and interpret the types

of structural formulas commonly
used in organic chemistry, including
condensed structural formulas and
line–angle formulas.

5 Predict the hybridization and

geometry of organic molecules
based on their bonding.
S S SS OH
OH
6 Identify isomers and explain the
differences between them.
O N N NN
O C ◀ Luciferin is the light-emitting
C luciferin compound found in many firefly
luciferin
OH (Lampyridae) species. Luciferin reacts with
luciferin OH atmospheric oxygen, under the control of
an enzyme, to emit the yellow light that
luciferin
Luciferin is the light-emitting compound found in many firefly (Lampyridae) fireflies use to attract mates or prey.
Luciferin is 1-1
species.The Origins
Luciferin
the light-emitting reacts of atmospheric
with Organic
compound Chemistry
found oxygen,
in many under the (Lampyridae)
firefly control of an enzyme,
to emit the yellow light that fireflies use to attract mates and prey.
species. Luciferin reactsdefinition
The modern with atmospheric
of organic oxygen,
chemistryunder the control
is the chemistry of an enzyme,
of carbon compounds.
What islight
to emit the yellow so special about carbon
that fireflies use tothat a whole
attract matesbranch
and of chemistry is devoted to its
prey.
compounds? Unlike most other elements, carbon forms strong bonds to other carbon
atoms and to a wide variety of other elements. Chains and rings of carbon atoms can be
built up to form an endless variety of molecules. This diversity of carbon compounds
provides the basis for life on Earth. Living creatures are composed largely of complex
organic compounds that serve structural, chemical, or genetic functions.
The term organic literally means “derived from living organisms.” Originally, the
science of organic chemistry was the study of compounds extracted from living organ-
isms and their natural products. Compounds such as sugar, urea, starch, waxes, and plant
oils were considered “organic,” and people accepted vitalism, the belief that natural
products needed a “vital force” to create them. Organic chemistry, then, was the study
of compounds having the vital force. Inorganic chemistry was the study of gases, rocks,
and minerals, and the compounds that could be made from them.

1
Another random document with
no related content on Scribd:
 Everything of interest to the Government on the Pennsylvania was
promptly transferred to the Cumberland. On this latter vessel, it was
also said, a large amount of gold from the Custom House at Norfolk
had been in good time placed. Having made safe everything that was
to be brought away, the marines were next set to work to destroy
everything on the Pennsylvania, and the other ships, and in the yard,
that might be of immediate use in waging war upon the government.
Many thousand stands of arms were destroyed. Carbines had their
stocks broken from the barrels by a blow, and were thrown
overboard. A large lot of revolvers shared the like fate. Shot and shell
by thousands went with hurried plunge to the bottom. Most of the
cannon had been spiked the day and night before. There were at least
1,500 pieces in the yard—some elegant Dahlgren guns, and
Columbiads of all sizes.
It is impossible to describe the scene of destruction that was
exhibited. Unweariedly it was continued from 9 o’clock until about
12, during which time the moon gave light to direct the operations.
But when the moon sank behind the western horizon, the barracks
near the centre of the yard were set on fire, that by its illumination
the work might be continued. The crackling flames and the glare of
light inspired with new energies the destroying marines, and havoc
was carried everywhere within the limits of orders. But time was not
left to complete the work. Four o’clock of Sunday morning came, and
the Pawnee was passing down from Gosport harbor with the
Cumberland, the coveted prize of the secessionists, in tow—every
soul from the other ships and the yard being aboard of them, save
two. Just as they left their moorings, a rocket was sent up from the
deck of the Pawnee. It sped high in air, paused a second, and burst in
shivers of many-colored light. As it did so, the well-set trains at the
ship-houses, and on the decks of the fated vessels left behind, went
off as if lit simultaneously by the rocket. One of the ship-houses
contained the old New York, a ship thirty years on the stocks, and yet
unfinished. The other was vacant; but both houses and the old New
York burnt like tinder. The older and unserviceable vessels, the
Pennsylvania, the Raritan, the Columbia, the Dolphin, were fired
without compunction; while the Merrimac, Plymouth and
Germantown were sunk, and the immense lifting shears used for
raising vessels was broken down and rendered useless. The old
Delaware and Columbus, worn out and dismantled seventy-fours,
were scuttled and sunk at the upper docks on Friday.
The grand conflagration now burst in judgment on the startled
citizens of Norfolk, Portsmouth, and all the surrounding country.
The flames leaped from pitchy deck to smoking shrouds, and writhed
to their very tops around the masts that stood like martyrs doomed.
It was not thirty minutes from the time the trains were fired till the
conflagration roared like a hurricane, and the flames from land and
water swayed, and met, and mingled together, and darted high, and
fell, and leaped up again, and by their very motion showed their
sympathy with the crackling, crashing roar of destruction beneath.
But in all this magnificent scene, the old ship Pennsylvania was the
centre-piece. She was a very giant in death, as she had been in life.
She was a sea of flame, and when her bowels were consuming, then
did she spout from every porthole of every deck torrents and
cataracts of fire that, to the mind of Milton, would have represented
her a frigate of hell pouring out unremitting broadsides of infernal
fire. Several of her guns were left loaded, but not shotted, and as the
fire reached them, they sent out on the startled morning air minute
guns of fearful peal, that added greatly to the alarm that the light of
the conflagration had spread through the surrounding country. The
Pennsylvania burnt like a volcano for five hours and a half before her
mainmast fell. At precisely 9½ o’clock the tall tree that stood in her
centre tottered and fell, and crushed deep into her burning sides,
whilst a storm of sparks filled the sky.
As soon as the Pawnee and Cumberland had fairly left the waters,
and were known to be gone, the gathering crowds of Portsmouth and
Norfolk burst open the gates of the Navy Yard and rushed in. They
could do nothing, however, but gaze upon the ruin wrought. The
Commodore’s, residence, left locked but unharmed, was burst open,
and a pillage commenced, which was summarily stopped. As early as
six o’clock a volunteer company had taken possession in the name of
Virginia, and run up her flag from the flagstaff. In another hour
several companies were on hand, and men were at work unspiking
cannon, and by nine o’clock they were moving them to the dock,
whence they were begun to be transferred, on keels, to points below,
where sand batteries were to be built.
 Notwithstanding the splendor of the scene, and the great
destruction of property, the result was incomplete, and a large
amount of artillery and munitions of war fell into the hands of the
Virginians.
 THE STATE OF THE NATION BEFORE ITS
TROOPS ENTERED VIRGINIA.

President Lincoln, on the 15th of April, issued a proclamation

stating that the laws of the United States had been and are opposed
in several States, by combinations too powerful to be suppressed by
the ordinary course of judicial proceedings; he therefore called for
75,000 troops from the several States. The first service assigned to
this force would probably be to repossess the forts and other places
and property which had been seized from the Union. An extra
session of Congress was also to meet on the 4th of July.
When President Lincoln issued his proclamation on the 15th of
April, dispatches were sent from the Secretary of War, addressed to
the Governors of the several States, designating the quotas assigned
to each State, under this proclamation. The Executives of the
slaveholding States, with the exception of Maryland and Delaware,
peremptorily refused to comply with this requisition. Governor Ellis,
of North Carolina, replied, “I regard the levy of troops made by the
Administration for the purpose of subjugating the States of the South
as in violation of the Constitution, and a usurpation of power. I can
be no party to this wicked violation of the laws of the country, and to
this war upon the rights of a free people. You can get no troops from
North Carolina.” Governor Jackson, of Missouri, answered, “There
can be, I apprehend, no doubt but these men are intended to form
part of the President’s army to make war upon the people of the
seceding States. Your requisition, in my judgment, is illegal,
unconstitutional and revolutionary in its objects, altogether inhuman
and diabolical, and cannot be complied with. Not one man will
Missouri furnish to carry on such an unholy crusade.” Governor
Magoffin, of Kentucky, replied, “In answer, I say emphatically, that
Kentucky will furnish no troops for the wicked purpose of subduing
her sister Southern States.” Governor Letcher, of Virginia, answered,
“I have only to say that the militia of Virginia will not be furnished to
the powers at Washington for any such use or purpose as they have
in view. Your object is to subjugate the Southern States, and a
requisition made upon me for such an object—an object, in my
judgment, not within the purview of the Constitution, or the Act of
1795—will not be complied with. You have chosen to inaugurate civil
war, and having done so, we will meet it in a spirit as determined as
the Administration has exhibited toward the South.” Governor
Harris, of Tennessee, refused, in terms equally explicit, to comply
with the requisition of the Government. In his Message to the
Legislature, dated April 25, he takes strong ground against the action
of the Administration, which he says is designed for the subjugation
of the Southern States. He recommended the immediate passage of
an Act of Secession, and an Act for the union of Tennessee with the
Southern Confederacy, both to be submitted separately to the people
at an early day. He also recommended an appropriation for arming
the State, and the creation of a large military fund, to be placed
under the direction of a special board.
The position of Virginia is of the greatest importance to a thorough
understanding of the difficulties in which the country was placed. At
the breaking out of hostilities, the State Convention was in session. A
resolution was passed, expressing an earnest desire for the re-
establishment of the Union in its former integrity: an amendment,
declaring that Virginia ought not to accept a form of adjustment
which would not be acceptable to the seceding States, was rejected.
Commissioners were appointed to wait on the President, and
ascertain the policy which he intended to pursue. An amendment,
denying the right of the Federal Government to deal with the
question of secession, was rejected. A resolution was adopted,
expressing a willingness that the independence of the seceding States
should be acknowledged. An amendment, declaring that Virginia
would secede in case the proposed amendments to the Constitution
were rejected by the non-slaveholding States, was lost. And
resolutions were adopted, opposing any action on the part of the
Federal Government for retaining or retaking forts in the seceding
States, and affirming, that any measures of the Government, tending
to produce hostilities with the Confederate States, would leave
Virginia free to determine her own future policy. When the
proclamation of the President, calling for troops, was issued, the
Convention went into secret session, on the 17th of April, passed an
ordinance to repeal the ratification of the Constitution of the United
States, by the State of Virginia, and to resume all the rights and
powers granted under such Constitution.
When the proclamation was received at Montgomery, President
Davis issued a proclamation, dated on the 17th of April, inviting all
persons to apply for letters of marque and reprisal, to be issued
under the seal of the Confederate States. President Lincoln
thereupon, on the 19th, issued a proclamation, announcing the
blockade of all the ports of the seceding States, and that a competent
force would be stationed to prevent the entrance and exit of vessels
at these ports. On the 27th, the President issued a proclamation
extending the blockade to the ports of North Carolina and Virginia. It
was announced that the blockade would be maintained by at least
fifty vessels of war, accompanied by a fleet of steam transports,
capable of conveying an army of 20,000 men. On the 3d of May the
President issued another proclamation, calling into service 42,000
volunteers to serve for a period of three years, unless sooner
discharged; ordering that the regular army should be increased by
22,714 men; and directing the enlistment, for the naval force of the
United States, of 18,000 seamen, for a period of not less than one or
more than three years.
The Congress of the Confederate States met at Montgomery on the
29th of April. The message of President Davis announced that the
permanent Constitution had been ratified by a sufficient number of
States to render it valid, and that it only remained to elect officers
under its provisions. The message of President Lincoln, calling for
volunteers, was characterized as a declaration of war, which will
render it necessary to adopt measures to replenish the treasury of the
Confederation, and provide for the defence of the country. Proposals
had been issued, inviting subscriptions for a loan of five millions;
more than eight millions was subscribed for, none under par. The
whole amount had been ordered to be accepted; and it was now
necessary to raise a much larger sum. The Confederate States had in
the field, at Charleston, Pensacola, and different forts, 19,000 men,
and 16,000 were on route for Virginia. It was proposed to organize
and hold in readiness an army of 100,000 men. “We seek no
conquest,” says Mr. Davis, “no aggrandizement, no concession from
the Free States. All that we ask is to be let alone; that none shall
attempt our subjugation by arms. This we will, and must, resist to
the direst extremity. The moment this pretension is abandoned, the
sword will drop from our grasp, and we shall be ready to enter into
treaties of amity and commerce mutually beneficial.” In the
meanwhile warlike and aggressive measures had been pushed
forward with all possible activity. The forces besieging Fort Pickens
had been augmented, and new batteries had been constructed
against it. Vessels belonging to the government and to individuals
had been seized. Among these was the steamer Star of the West,
which had been dispatched to Indianola, Texas, to bring away the
United States troops collected at that port. The vessel was lying at
anchor, awaiting the arrival of the troops. At midnight, of the 19th of
April, the steamer Rusk approached, and the captain of the Star of
the West was informed that she had on board 320 United States
troops, which were to be embarked.
Every assistance was given for the reception of the supposed
soldiers, who, however, proved to be Texan troops. As soon as they
were on board they took possession of the steamer, which was taken
to New Orleans, the crew being detained as prisoners of war. Shortly
after, 450 of the United States troops attempted to make their escape
from Indianola on board of two sailing vessels. They were pursued by
two armed steamers, manned by the Texans, overtaken, and made
prisoners.
The loyal States had not only been patriotic in sending troops to
the capital, but in supplying money also. The Legislature of New
York appropriated three millions of dollars for arming and equipping
troops; Connecticut appropriated two millions; Vermont one million;
New Jersey two millions, and other States in proportion. The
Common Council of the city of New York appropriated one million.
Besides the public appropriations, in every considerable town and
city private subscriptions were made for the same purposes, and to
support the families of volunteers. The aggregate of the sums thus
furnished was estimated at twenty-five millions—all raised in a few
days.
Meantime the Confederate government had adjourned on the 20th
of May to meet in Richmond, Virginia, on the 20th of July, or some
other convenient place to be selected by the President.
On the 6th of May an act was passed “recognizing the existence of
war between the United States and the Confederate States, and
concerning letters of marque, prizes, and prize goods.” This act gave
the President of the Confederate States authority to use the whole
land and naval forces of the Confederacy to meet the war thus
commenced, and to issue letters of marque and reprisal against the
vessels and property of the United States and their citizens, with the
exception of the States belonging to the Confederation or expected to
join it.
An act was passed prohibiting the export of cotton or cotton yarn
from any of the Confederate States except through the sea-ports. It
was proposed in Congress that the cotton planters should be invited
to put their crops in the hands of the government, receiving bonds
for its value, the government to dispose of it in Europe for cash. The
Postmaster-General, on the 1st of June, took charge of the
transmission of the mails in the Confederate States; and the
Postmaster-General of the United States announced that on that day
postal communication would close with the seceding States, with the
exception of some counties in Western Virginia. All letters for these
States were sent to the Dead Letter Office at Washington.
Two more States—Arkansas and North Carolina—had formally
seceded from the Union, and joined the Confederate States. In
Arkansas the State Convention, on the 18th of April, had passed an
ordinance submitting the question of secession to the people, at an
election to be held on the 3d of August. When the requisition of
President Lincoln was received, Governor Rector, on the 22d of
April, replied to the Secretary of War, “In answer to your requisition
for troops from Arkansas to subjugate the Southern States, I have to
say that none will be furnished. The demand is only adding insult to
injury. The people of this Commonwealth are freemen and not
slaves, and will defend to the last extremity their honor, lives and
property against Northern mendacity and usurpation.” On the same
day the Governor gave orders for the seizure at Napoleon of a large
quantity of military supplies belonging to the United States. On the
6th of May, the Convention, which had re-assembled, unanimously
passed an ordinance of secession.
 Tennessee also virtually, though not in form, joined the Southern
Confederacy. The Legislature passed a Declaration of Independence,
which was to be submitted to the people on the 8th of June.
Meanwhile a military league had been formed with the Confederate
government, in virtue of which the forces of Tennessee were to be
employed to aid the Confederate States.
In Kentucky a determined effort was made to preserve a strict
neutrality. Governor Magoffin, as before noted, refused peremptorily
to comply with the President’s requisition for troops. On the 20th of
May he issued a proclamation declaring that every indication of
public sentiment in Kentucky showed a fixed determination of the
people to take neither side, but to maintain a posture of self-defence,
forbidding the quartering upon her soil of troops from either section,
in the hope that the State might yet become a mediator between the
parties. He therefore warned all States, whether separate or united,
and especially the Confederate and the United States, against any
armed occupation within the State of Kentucky, without the
permission of the Legislature and Executive authorities. All citizens
of Kentucky were forbidden to make any demonstration against
either of the sovereignties, but were directed to make prompt and
efficient preparations for the defence of the State. Of similar purport
were the proceedings of the “Border States Convention,” held at
Frankfort. Virginia, North Carolina and Arkansas, having joined the
Southern Confederacy, of course sent no delegates; none appeared
from Maryland, and only one from Tennessee, and four from
Missouri. The remainder were from Kentucky. Senator Crittenden
was chosen President. Two addresses, one to the people of the
United States, and the other to the people of Kentucky, were
adopted. The essential point in the first address is the
recommendation that Congress would propose such Constitutional
amendments as should secure the legal rights of slaveholders; and if
this should fail to bring about a pacification, that a Convention be
called composed of delegates from all the States, to devise measures
of peaceable adjustment.
The address to the people of Kentucky defended the action of the
Executive in refusing troops to the Federal Government, as called for
by the peculiar circumstances in which the State was placed. “In all
things,” says the address, “she is as loyal as ever to the constitutional
administration of the government. She will follow the stars and
stripes to the utmost regions of the earth, and defend it from foreign
insult. She refuses alliance with any who would destroy the Union.
All she asks is permission to keep out of this unnatural strife. She has
announced her intention to refrain from aggression upon others, and
she must protest against her soil being made the theatre of military
operations by any belligerent.” The address goes on to censure the
conduct of the States who have withdrawn from the Union, affirming
that there was in the Constitution a remedy for every wrong, and
provisions to check every encroachment by the majority upon the
minority. In withdrawing the States committed “a great wrong, for
which they must answer to posterity. But Kentucky remained true to
herself, contending with all her might for what were considered to be
the rights of the people, and although one after another of the States
that should have been by her side ungenerously deserted her, leaving
her almost alone in the field, yet she did not surrender her rights
under the Constitution, and never would surrender them. She would
appear again in the Congress of the United States, not having
conceded the least atom of power to the Government that had not
heretofore been granted, and retaining every power she had
reserved. She would insist upon her constitutional rights in the
Union, and not out of it.” The address went on to say that if the war
should be transferred to Kentucky, her destruction would be the
inevitable result; “and even the institution to preserve or control
which the wretched war was undertaken, would be exterminated in
the general ruin.”
In Virginia the vote upon secession resulted in a large majority in
its favor. In the north-western part of the State the vote was largely
in favor of the Union. A Convention of the Western Counties
convened at Wheeling on the 13th of May, at which resolutions were
passed pronouncing the ordinance of secession null and void. The
Convention adjourned to meet on the 11th of June.
The position of Missouri was similar to that of Kentucky. The State
endeavored to avoid taking part in the war. Troops had been
organized with hostile designs against the Government. These were
forced to surrender by Captain Lyon, (afterward appointed General).
At St. Louis an attack was made by the populace, on the 10th of May,
upon the United States volunteers; they returned the fire, killing
some twenty; an émeute on the next day resulted in the loss of
several lives. General Harney, who had been put in command of this
district, entered into an agreement with the State authorities, that
was disapproved by the Government, and he relieved from the
command, which was then given to General Lyon.
The attitude assumed by the great powers of Europe in relation to
the American war was important. That of England, indicated by the
royal proclamation issued on the 14th of May a determination to
maintain a strict neutrality in the contest between the contending
parties. The proclamation went on to forbid all British subjects from
taking part in any way in the contest, by enlisting in the army or navy
of either party; by fitting out or arming any vessel; by breaking any
lawfully established blockade, or carrying to either, troops or any
articles contraband of war. This proclamation, taken in connection
with the explanations of the Ministers and the speeches in
Parliament, had an unfriendly aspect toward the United States,
recognizing, as it did, the Confederate States as belligerents, and, by
implication, entitled equally to the right of carrying prizes into the
ports of Great Britain. In the House of Commons, Lord John Russell
said that the character of belligerency was not so much a principle as
a fact; that a certain amount of force and consistency acquired by any
mass of population engaged in war entitled them to be treated as a
belligerent. A power or a community which was at war with another,
and which covered the sea with its cruizers, must either be
acknowledged as a belligerent or dealt with as a pirate. The
Government had come to the opinion that the Southern Confederacy,
according to those principles which were considered just, must be
treated as belligerent. In this critical condition was the country when
the Government prepared to advance its armies into Virginia.
 OCCUPATION OF ALEXANDRIA, Va.

ASSASSINATION OF COLONEL
ELLSWORTH.
May 24, 1861.
The defenders of the Union had been gathering at Washington and
in its vicinity for more than a month, in answer to the call for troops,
that rang through the land clear as clarion notes. The arduous labor
of providing for and disciplining the large number of untrained
recruits, collected in such haste, had been met with energy and
perseverance by the officers of the government. Very much had been
accomplished, notwithstanding all the embarrassments incident to
an extensive and untried field of labor.
The heart of the country was beating restively at delay, and
popular feeling, as it found its voice through the press, thundered
anathemas, and clamored for a forward movement. Nothing but
prompt and decisive action would satisfy the people that the
government was sturdily bending its whole energies to strangle the
monster treason in its youth. The people had not yet learned the first
great secret of success—how to wait. They saw the ship of state
struggling fiercely amid the rocks of an untried ocean, and
worshiping the flag at her mast-head, grew clamorous for its
protection. Every newspaper, and almost every household, had its
own ideas of how this was to be accomplished. The government,
unused to war, and anxious to gratify the spirit of patriotism that had
supported it so nobly, was ready to answer the rash clamor; and so
this long, loud cry of ignorant impatience became words of fate, and
ended in giving us the defeat of Bull Run.
 The people, the generous loyal people, ever dissatisfied with
anything but lightning speed, in peace or war, clamored for action,
and must be appeased. Under this pressure, events forced each other
on, culminating in action.
Though an act of secession had been passed by a State Convention,
held at Richmond on the 17th of April, it was professedly to be
submitted to the people of the State of Virginia for their approval on
the 23d of May; and though it had been determined by the United
States Government to take possession of, and fortify the Virginia
hills, in front of the capital, it was deemed advisable to await that
event before making any military movement into that State which
could be interpreted into an attempt to influence or control the
popular vote. The conspirators, however, without waiting for any
ratification of their secession act by the people, immediately made a
conveyance of the State to the Confederate government, and claimed
its protection; thus effectually leaving the “mother of States” to
associate with the disobedient daughters.
In consequence of the action of Governor Letcher, Confederate
troops from Georgia, Mississippi, and other Southern States, were
sent rapidly into Virginia, and located at various points, where it was
deemed that they could be of the most use, and best serve the
interests of the Confederacy. The result of this movement could
easily have been foretold. The election was held under military
regime and terrorism, and loyal men, having been warned of the
penalty of voting against secession, either feared to do so, or
neglected to vote altogether; a majority was secured for the
ordinance, and Virginia, “mother of Presidents,” had taken her
second grand step in the downward path of disunion.
The people of the city of Alexandria were generally infected with
disloyalty, and rebel flags floated boldly from many of the principal
buildings. A detachment of Confederate troops was at all times
quartered within its limits, and with the hope of capturing them and
their supplies, it was determined to occupy the city by a surprise
movement. The result of the election clearly foreshadowed,
arrangements were made for action—prompt and decisive action—to
follow immediately upon the closing of the polls, where disunionists
had played a mere farce, and disloyal bayonets had fettered the
freedom of the ballot-box.
 On the night of May 23d, orders were given for an advance to the
troops designed for this expedition, numbering in all about 13,000,
and at ten o’clock an advance guard of picked men moved cautiously
over the bridge. Sent to reconnoitre, their commands were
imperative that if assaulted they were to signalize for reinforcements,
which would be speedily furnished by a corps of infantry and a
battery. At twelve o’clock the regiment of infantry, the artillery and
the cavalry corps began to muster, and as fast as they were prepared,
proceeded to the Long Bridge, the portion of the force then in
Washington being directed to take that route. The troops quartered
at Georgetown, comprising the Fifth, Eighth, Twenty-eighth and
Sixty-ninth New York, also proceeded across the Chain Bridge, under
the command of General McDowell.
At half-past one o’clock, six companies of District Volunteers,
including the National Rifles, and Turners, stepped from the Long
Bridge upon Virginia soil. To capture the enemy’s patrols by the
means of boats had been the original plan, but the bright moonlight
prevented it. This vanguard was commanded by Inspector-General
Stone, under whom Captain Smead led the centre, Adjutant Abbott
the left, and Captain Stewart the right wing. When within half a mile
of Alexandria, they halted and awaited the arrival of the main body.
The remainder of the army crossed in the following order: The
Twelfth and Twenty-fifth New York, First Michigan, and First,
Second, Third, and Fourth New Jersey; two regular cavalry corps of
eighty men each, and Sherman’s two batteries; next and last came
the New York Seventh. General Mansfield directed the movements of
the troops. At a quarter to four the last of the forces left, and fifteen
minutes later Major-General Sanford, accompanied by his staff,
proceeded to Virginia to assume the command.
The famous Sixty-ninth New York, after crossing the river below
Georgetown, took position on the Orange and Manassas Gap
railroad, and surrounded and captured the train from Alexandria,
with a large number of passengers, of which a few, known to be
violent secession partizans, were retained as prisoners.
As the Michigan regiment, accompanied by two guns of Sherman’s
renowned battery, and a company of regular cavalry, marched into
the town, a detachment of thirty-five rebel horsemen were found
preparing to mount. The battery came up the street towards them
like a whirlwind, and they soon surrendered.
The New York Fire Zouaves, under the command of Colonel E. E.
Ellsworth, were conveyed in steamers, and as the day was dawning
their dashing uniform and fearless faces flashed upon the citizens of
Alexandria. Not until they had landed did the rebel sentinels discover
them, and then, after firing their muskets as a signal of warning, they
hastened to alarm the sleeping city.
Little need had those brave and untameable “fire fighters” of
directions. The master spirit of all their movements had imbued
them with feelings akin to his own. They knew their duty, and men
trained as they had been in a severe school of danger, could never be
backward in performing it. Ellsworth, who, as it might seem, with the
shadows of death already gathering around him, could sit calmly
down in the dim midnight, after addressing his men in a brief and
stirring speech, announcing the orders to march on Alexandria,
closing with the well remembered words, “Now boys, go to bed and
wake up at two o’clock for a sail and a skirmish;” and after arranging
the business of his regiment, pen letters that seemed “as if the
mystical gales from the near eternity must have breathed for a
moment over his soul, freighted with the odor of amaranths and
asphodels”—needed none to tell him of his duty or to urge him to its
even rash fulfilment.
In the early light of morning he entered the rebel town. A secession
flag waved defiantly from the Marshall House, and with the fiery
enthusiasm of his nature, Ellsworth rushed to tear down the hated
emblem of enmity to the Union he loved so well. With his own hand
he tore the flag from its fastening, and descending the stairs flushed
with the pride of success, came upon his fate. A musket in the hands
of the proprietor, J. W. Jackson, pealed his death-knell, and he
sealed the glories of that too well remembered morning, with his
heart’s blood.
 ASSASSINATION OF COLONEL ELLSWORTH.

Brownell, a name now linked with Ellsworth’s in all history, was

his prompt avenger, and the blood of patriot and assassin ran
commingled, a ghastly stream. Both will be long remembered—will
stand shadowed forth to the future from the past—one a brave,
tender, chivalric heart; and the other, reckless in his courage,
vindictive in his passions, and terrible in his cruelty.
And the morning of that day, now lined upon the page of history
with letters of blood, that never to be forgotten 24th of May, re-
awoke the enthusiasm and stern resolve of Sumter—caused the finest
strings of a nation’s heart to vibrate with sorrow, and hosts that
never before unsheathed a sabre, shouldered a gun or helmeted their
brows, had never marched beneath a banner, or given a thought to
the glories of war, leaped forth, Minerva-like, fully armed for the
strife. Swift vengeance, indeed, followed the death of Ellsworth, but
what was that compared to the iron hate of such hearts?
Not here, truly, is the proper place to write the life-history of
Ephraim Elmer Ellsworth, but this much it is fitting—necessary
almost to recapitulate. Born in the little village of Mechanicsville, on
the banks of the Hudson, on the 23d of April, A.D. 1837, he, after
passing through trials that would have utterly discouraged a less
ambitious and sanguine man, rendered himself famous by the
inauguration, drill, and marche de triomphe of the Chicago Zouaves.
All the country remembers the bloodless march of those young men
—the “crimson phantoms” that blazed comet-like before their eyes
and secured the championship, without a struggle. When the war
broke out, when the knell of Sumter’s fall shook the very corner-
stone of the nation, Ellsworth sought a place in the army. Jealousy
and fear of the youthful aspirant impeded him, and turning his back
upon Washington, he hastened to New York, organized the Fire
Zouaves, and rushed to his fate.
One who knew him well, and has written a glorious prose-poem to
his memory, thus briefly described him. “His person was strikingly
prepossessing. His form, though slight, exactly the Napoleonic size,
was very compact and commanding: the head statuesquely poised
and crowned with a luxuriance of curling black hair; a hazel eye,
bright though serene, the eye of a gentleman as well as a soldier; a
nose such as you see on Roman medals; a light moustache, just
shading the lips, that were continually curving into the sunniest
smiles. His voice, deep and musical, instantly attracted attention,
and his address, though not without soldierly brusqueness, was
sincere and courteous.”
And thus, in the very prime of manhood and vigor, with one of the
military insignia he sometimes wore—a golden circle, inscribed with
the legend “Non nobis, sed pro patria,” driven into his heart by the
bullet of his assassin, perished a brave spirit—an ambitious follower
after the “pride, pomp, and circumstance of glorious war”—a soul
devoted to his country and his country’s honor—an eagle struck in its
high soaring, down—a spirit of fire, fretting at causeless delay,
burning against useless restraints, and rushing on to snatch success
even from the cannon’s mouth.
A nation mourned him long—has not yet forgotten him, and green
will ever be the laurel she entwines around the name of the boy-
martyr of Alexandria! “Remember Ellsworth” became a watchword
with the volunteers, who pledged themselves to avenge his death,
and well they redeemed it. His life was stainless and loyal—his death,
sealed with his blood the holy bond of his noble faith.
 When Lincoln saw this young man lying in his coffin, it is said that
he wept over him. It was the first shock and horror of war brought
home to the chief magistrate. Alas! if he has wept for all the brave
that have since fallen, his days and nights must have been given up to
tears.
Alexandria and its neighborhood were occupied by the Federal
troops, and a company of Virginia cavalry were captured; after a
detention of some days they were released upon taking the oath of
allegiance to the United States. Intrenchments were thrown up
around Alexandria, and upon Arlington Heights, which commanded
a portion of the capital. Bodies of troops were pushed forward
toward Manassas Junction, with the object of interrupting the
communication between Richmond and Harper’s Ferry.
A detachment took possession of Arlington, the old Curtis
Mansion, which had been deserted by its owner, General Lee, when
he gave up his flag and took sides with its enemies.
It is said that General Scott held this officer in such high
appreciation that he offered him the chance of any position under
himself in the Union army. When the letter reached Lee, containing
this noble proposition, he was sitting with his family at Arlington. He
read the letter in silence, and laying it on the table, covered his face
with one hand. When he looked up traces of tears were in his eyes,
and he said in a broken voice, “What am I to do? If I take up arms for
the Union it must be to turn them on my native State, my own
neighbors, dear relations. If I do not, they will brand me as a traitor!”
Again he fell into thought. The result was that he abandoned the
home consecrated by Washington, and turned upon the flag that
great man had planted.
On the 1st of June, a company of cavalry set out on a scouting
expedition to Fairfax Court House, about twenty miles beyond the
outposts. Some hundreds of Virginia troops were stationed here, and
a sharp skirmish ensued. Several of the Virginians were reported to
have been killed; one of the United States troops was killed, and four
or five wounded, among whom was the commander, Lieutenant
Tompkins. The cavalry withdrew, having made five prisoners, and
leaving two of their own number as captives. On the following day
the same cavalry company made another dash to Fairfax, and
rescued their comrades who had been left behind.
 BATTLE OF GREAT BETHEL.

June 10, 1861.

The first engagement on the field occurred at Great Bethel, about

ten miles north of Newport News, on the road from Hampton to
Yorktown, Virginia, the place having derived its name from a large
church, near which the rebels had an entrenched camp.
Under cover of night, the forces, who were under the command of
General B. F. Butler, had been repeatedly annoyed by the secession
forces, whose rendezvous was Little Bethel, distant about eight miles
from Newport News, and the same distance from Hampton, where,
also, a church was used as the headquarters of their cavalry, thus
literally putting “holy things to an unholy use.” The Union-loving, or,
at least, Union-respecting citizens, were continually robbed—slaves
were impressed to work upon their fortifications, and all that
forethought could suggest was recklessly accomplished.
Determined to put a stop to these forays, General Butler organized
an expedition for the purpose of surprising the rebels at Little Bethel,
giving to the officers commanding discretionary powers, as no
positive information could be obtained with regard to their defences
or forces.
General Pierce, of Massachusetts, who had the command at
Hampton, was instructed to detach Colonels Duryea and Townsend’s
New York regiments, and Colonel Phelps, commanding at Newport
News, was also commanded to start an equal force, about an hour
later, to make a demonstration in front. One regiment from each
command was directed to repair to a point about one mile from Little
Bethel, and there await further orders. Should the design prove
successful, they were, when directed, to follow close upon the enemy,
drive them into their entrenchments at Big Bethel and attack them.
A naval brigade—a new volunteer organization, stationed at
Hampton Roads, had been exercised in the management of scows,
with capacity for carrying about one hundred and thirty men, besides
those at the oars, and when the night came settling down in
darkness, they set out, with muffled oars, passed the mouth of
Hampton river, and silently proceeded up the stream. Moored at the
hither shore of Hampton, at midnight they awaited the time when
the blow was to be struck.
Three companies of Duryea’s New York Fifth, under the command
of Captain Kilpatrick, crossed and went forward on the Bethel road,
followed soon after by the remainder of the regiment, and Colonel
Townsend’s New York Third. One hour later, five companies, each of
the Vermont First and Massachusetts Fourth, under Lieutenant-
Colonel Washburne; six companies of the New York Seventh, Colonel
Bendix, and a squad of regulars, with three small field pieces under
Lieutenant Greble, moved forward from Newport News.
At about one o’clock, A. M., the three companies under Captain
Kilpatrick reached New Market Bridge—at about three o’clock they
were joined by the main body and started for Little Bethel. The
pickets of the enemy were surprised, the officer in command
captured, and the Union forces, flushed with success, were pushing
forward, when the sound of heavy firing in their rear checked them.
Meantime, the force from Newport News came up the road from
that place, and took the road from Hampton to Bethel, not far behind
the Fifth; but they left at the junction of the roads, under Colonel
Bendix, a rear guard of one hundred and seventy men and one field
piece, with the order to hold this position at all hazards, where they
were to be joined by Colonel Townsend’s regiment from Hampton.
Almost immediately after, the Third New York regiment came up the
Hampton road. It was still dark, and their colors could not be seen.
Their approach also was over a ridge, and as General Pierce and staff,
and Colonel Townsend and staff, in a body, rode in front of their
troops, and without any advance guard thrown out, as customary, to
reconnoitre, they appeared from Colonel Bendix’s position to be a
troop of cavalry. It was known that the Federal force had no cavalry,
and the fire of this rear guard was poured into the advancing body, at