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Copyright, ii
About the Author, iii
Preface, xxii
1. Introduction and Review, 1
1-1. The Origins of Organic Chemistry, 1
1-2. Principles of Atomic Structure, 3
1-3. Bond Formation: The Octet Rule, 6
1-4. Lewis Structures, 7
1-5. Multiple Bonding, 8
Summary: Common Bonding Patterns (Uncharged), 9
1-6. Electronegativity and Bond Polarity, 9
1-7. Formal Charges, 10
1-8. Ionic Structures, 12
Summary: Common Bonding Patterns in Organic Compounds and Ions, 13
1-9. Resonance, 13
1-10. Structural Formulas, 17
1-11. Molecular Formulas and Empirical Formulas, 20
1-12. Arrhenius Acids and Bases, 21
1-13. Brønsted–Lowry Acids and Bases, 22
1-14. Lewis Acids and Bases, 29
Chapter 1 Glossary, 32
Study Problems, 34
2. Structure and Properties of Organic Molecules, 40
2-1. Wave Properties of Electrons in Orbitals, 40
2-2. Molecular Orbitals, 42
2-3. Pi Bonding, 45
2-4. Hybridization and Molecular Shapes, 46
2-5. Drawing Three-Dimensional Molecules, 50
2-6. General Rules of Hybridization and Geometry, 51
2-7. Bond Rotation, 55
2-8. Isomerism, 57
2-9. Polarity of Bonds and Molecules, 59
2-10. Intermolecular Forces, 62
2-11. Polarity Effects on Solubilities, 66
2-12. Hydrocarbons, 69
2-13. Organic Compounds Containing Oxygen, 72
2-14. Organic Compounds Containing Nitrogen, 74
Chapter 2 Glossary, 76
Study Problems, 79
3. Structure and Stereochemistry of Alkanes, 83
3-1. Classification of Hydrocarbons (Review), 83
3-2. Molecular Formulas of Alkanes, 84
3-3. Nomenclature of Alkanes, 85
Summary: Rules for Naming Alkanes, 90
3-4. Physical Properties of Alkanes, 91
3-5. Uses and Sources of Alkanes, 93
3-6. Reactions of Alkanes, 95
3-7. Structure and Conformations of Alkanes, 96
3-8. Conformations of Butane, 100
3-9. Conformations of Higher Alkanes, 102
3-10. Cycloalkanes, 102
3-11. cis-trans Isomerism in Cycloalkanes, 105
3-12. Stabilities of Cycloalkanes; Ring Strain, 105
3-13. Cyclohexane Conformations, 109
Problem-Solving Strategy: Drawing Chair Conformations, 112
3-14. Conformations of Monosubstituted Cyclohexanes, 113
3-15. Conformations of Disubstituted Cyclohexanes, 116
Problem-Solving Strategy: Recognizing cis and trans Isomers, 118
3-16. Bicyclic Molecules, 119
Chapter 3 Glossary, 121
Study Problems, 124
4. The Study of Chemical Reactions, 127
4-1. Introduction, 127
4-2. Chlorination of Methane, 127
4-3. The Free-Radical Chain Reaction, 128
Key Mechanism 4-1: Free-Radical Halogenation, 130
4-4. Equilibrium Constants and Free Energy, 132
4-5. Enthalpy and Entropy, 135
4-6. Bond-Dissociation Enthalpies, 136
4-7. Enthalpy Changes in Chlorination, 137
4-8. Kinetics and the Rate Equation, 139
4-9. Activation Energy and the Temperature Dependence of Rates, 141
4-10. Transition States, 142
4-11. Rates of Multistep Reactions, 144
4-12. Temperature Dependence of Halogenation, 145
4-13. Selectivity in Halogenation, 146
4-14. The Hammond Postulate, 151
Problem-Solving Strategy: Proposing Reaction Mechanisms, 153
4-15. Radical Inhibitors, 155
4-16. Reactive Intermediates, 156
Summary: Reactive Intermediates, 162
Chapter 4 Glossary, 162
Study Problems, 165
5. Stereochemistry, 169
5-1. Introduction, 169
5-2. Chirality, 170
5-3. (R) and (S) Nomenclature of Asymmetric Carbon Atoms, 176
5-4. Optical Activity, 181
5-5. Biological Discrimination of Enantiomers, 186
5-6. Racemic Mixtures, 187
5-7. Enantiomeric Excess and Optical Purity, 188
5-8. Chirality of Conformationally Mobile Systems, 189
5-9. Chiral Compounds without Asymmetric Atoms, 191
5-10. Fischer Projections, 193
Summary: Fischer Projections and Their Use, 198
5-11. Diastereomers, 198
Summary: Types of Isomers, 199
5-12. Stereochemistry of Molecules with Two or More Asymmetric Carbons, 200
5-13. Meso Compounds, 201
5-14. Absolute and Relative Configuration, 203
5-15. Physical Properties of Diastereomers, 205
5-16. Resolution of Enantiomers, 206
Chapter 5 Glossary, 209
Study Problems, 211
6. Alkyl Halides: Nucleophilic Substitution and Elimination, 215
6-1. Introduction, 215
6-2. Nomenclature of Alkyl Halides, 216
6-3. Common Uses of Alkyl Halides, 218
6-4. Structure of Alkyl Halides, 220
6-5. Physical Properties of Alkyl Halides, 221
6-6. Preparation of Alkyl Halides, 223
Summary: Methods for Preparing Alkyl Halides, 226
6-7. Reactions of Alkyl Halides: Substitution and Elimination, 228
6-8. Second-Order Nucleophilic Substitution: The S_N2 Reaction, 229
Key Mechanism 6-2: The S_N2 Reaction, 230
6-9. Generality of the S_N2 Reaction, 231
Summary: S_N2 Reactions of Alkyl Halides, 231
6-10. Factors Affecting S_N2 Reactions: Strength of the Nucleophile, 233
Summary: Trends in Nucleophilicity, 234
6-11. Reactivity of the Substrate in S_N2 Reactions, 237
6-12. Stereochemistry of the S_N2 Reaction, 241
6-13. First-Order Nucleophilic Substitution: The S_N1 Reaction, 243
Key Mechanism 6-4: The S_N1 Reaction, 244
6-14. Stereochemistry of the S_N1 Reaction, 247
6-15. Rearrangements in S_N1 Reactions, 249
6-16. Comparison of S_N1 and S_N2 Reactions, 252
Summary: Nucleophilic Substitutions, 254
6-17. First-Order Elimination: The E1 Reaction, 255
Key Mechanism 6-8: The E1 Reaction, 255
Summary: Carbocation Reactions, 259
6-18. Positional Orientation of Elimination: Zaitsev’s Rule, 260
6-19. Second-Order Elimination: The E2 Reaction, 261
Key Mechanism 6-10: The E2 Reaction, 262
6-20. Stereochemistry of the E2 Reaction, 264
6-21. Comparison of E1 and E2 Elimination Mechanisms, 265
Summary: Elimination Reactions, 267
Problem-Solving Strategy: Predicting Substitutions and Eliminations, 267
Summary: Reactions of Alkyl Halides, 270
Chapter 6 Glossary, 273
Study Problems, 276
7. Structure and Synthesis of Alkenes, 281
7-1. Introduction, 281
7-2. The Orbital Description of the Alkene Double Bond, 282
7-3. Elements of Unsaturation, 283
7-4. Nomenclature of Alkenes, 285
7-5. Nomenclature of Cis-Trans Isomers, 287
Summary: Rules for Naming Alkenes, 289
7-6. Commercial Importance of Alkenes, 290
7-7. Stability of Alkenes, 292
7-8. Physical Properties of Alkenes, 298
7-9. Alkene Synthesis by Elimination of Alkyl Halides, 300
7-10. Alkene Synthesis by Dehydration of Alcohols, 308
Key Mechanism 7-4: Acid-Catalyzed Dehydration of an Alcohol, 309
7-11. Alkene Synthesis by High-Temperature Industrial Methods, 311
Problem-Solving Strategy: Proposing Reaction Mechanisms, 312
Summary: Methods for Synthesis of Alkenes, 316
Chapter 7 Glossary, 317
Study Problems, 319
8. Reactions of Alkenes, 323
8-1. Reactivity of the Carbon–Carbon Double Bond, 323
8-2. Electrophilic Addition to Alkenes, 324
Key Mechanism 8-1: Electrophilic Addition to Alkenes, 324
8-3. Addition of Hydrogen Halides to Alkenes, 326
8-4. Addition of Water: Hydration of Alkenes, 332
8-5. Hydration by Oxymercuration–Demercuration, 335
8-6. Alkoxymercuration–Demercuration, 337
8-7. Hydroboration of Alkenes, 338
8-8. Addition of Halogens to Alkenes, 344
8-9. Formation of Halohydrins, 347
8-10. Catalytic Hydrogenation of Alkenes, 350
8-11. Addition of Carbenes to Alkenes, 352
8-12. Epoxidation of Alkenes, 355
8-13. Acid-Catalyzed Opening of Epoxides, 357
8-14. Syn Hydroxylation of Alkenes, 360
8-15. Oxidative Cleavage of Alkenes, 362
8-16. Polymerization of Alkenes, 365
8-17. Olefin Metathesis, 369
Problem-Solving Strategy: Organic Synthesis, 372
Summary: Reactions of Alkenes, 374
Chapter 8 Glossary, 379
Study Problems, 382
9. Alkynes, 388
9-1. Introduction, 388
9-2. Nomenclature of Alkynes, 389
9-3. Physical Properties of Alkynes, 390
9-4. Commercial Importance of Alkynes, 390
9-5. Electronic Structure of Alkynes, 392
9-6. Acidity of Alkynes; Formation of Acetylide Ions, 393
9-7. Synthesis of Alkynes from Acetylides, 395
9-8. Synthesis of Alkynes by Elimination Reactions, 399
Summary: Syntheses of Alkynes, 400
9-9. Addition Reactions of Alkynes, 401
9-10. Oxidation of Alkynes, 411
Problem-Solving Strategy: Multistep Synthesis, 413
Summary: Reactions of Alkynes, 414
Chapter 9 Glossary, 417
Study Problems, 418
10. Structure and Synthesis of Alcohols, 421
10-1. Introduction, 421
10-2. Structure and Classification of Alcohols, 421
10-3. Nomenclature of Alcohols and Phenols, 423
10-4. Physical Properties of Alcohols, 427
10-5. Commercially Important Alcohols, 429
10-6. Acidity of Alcohols and Phenols, 431
10-7. Synthesis of Alcohols: Introduction and Review, 434
Summary: Previous Alcohol Syntheses, 434
10-8. Organometallic Reagents for Alcohol Synthesis, 436
10-9. Addition of Organometallic Reagents to Carbonyl Compounds, 439
Key Mechanism 10-1: Grignard Reactions, 439
Summary: Grignard Reactions, 446
10-10. Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides, 447
10-11. Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols, 449
Summary: Reactions of LiAlH₄ and NaBH₄, 452
Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups, 453
10-12. Thiols (Mercaptans), 455
Chapter 10 Glossary, 457
Study Problems, 459
11. Reactions of Alcohols, 464
11-1. Oxidation States of Alcohols and Related Functional Groups, 464
11-2. Oxidation of Alcohols, 466
11-3. Additional Methods for Oxidizing Alcohols, 469
11-4. Biological Oxidation of Alcohols, 471
11-5. Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates, 472
Summary: Reactions S_N2 of Tosylate Esters, 475
11-6. Reduction of Alcohols, 475
11-7. Reactions of Alcohols with Hydrohalic Acids, 476
11-8. Reactions of Alcohols with Phosphorus Halides, 481
11-9. Reactions of Alcohols with Thionyl Chloride, 482
11-10. Dehydration Reactions of Alcohols, 484
Problem-Solving Strategy: Proposing Reaction Mechanisms, 488
11-11. Unique Reactions of Diols, 491
11-12. Esterification of Alcohols, 493
11-13. Esters of Inorganic Acids, 494
11-14. Reactions of Alkoxides, 497
Key Mechanism 11-6: The Williamson Ether Synthesis, 497
Problem-Solving Strategy: Multistep Synthesis, 499
Summary: Reactions of Alcohols, 502
Chapter 11 Glossary, 504
Study Problems, 506
12. Infrared Spectroscopy and Mass Spectrometry, 510
12-1. Introduction, 510
12-2. The Electromagnetic Spectrum, 511
12-3. The Infrared Region, 512
12-4. Molecular Vibrations, 513
12-5. IR-Active and IR-Inactive Vibrations, 515
12-6. Measurement of the IR Spectrum, 516
12-7. Infrared Spectroscopy of Hydrocarbons, 519
12-8. Characteristic Absorptions of Alcohols and Amines, 524
12-9. Characteristic Absorptions of Carbonyl Compounds, 525
12-10. Characteristic Absorptions of C—N Bonds, 531
12-11. Simplified Summary of IR Stretching Frequencies, 532
12-12. Reading and Interpreting IR Spectra (Solved Problems), 534
12-13. Introduction to Mass Spectrometry, 539
12-14. Determination of the Molecular Formula by Mass Spectrometry, 543
12-15. Fragmentation Patterns in Mass Spectrometry, 546
Summary: Common Fragmentation Patterns, 551
Chapter 12 Glossary, 553
Study Problems, 554
13. Nuclear Magnetic Resonance Spectroscopy, 561
13-1. Introduction, 561
13-2. Theory of Nuclear Magnetic Resonance, 561
13-3. Magnetic Shielding by Electrons, 564
13-4. The NMR Spectrometer, 566
13-5. The Chemical Shift, 567
13-6. The Number of Signals, 574
13-7. Areas of the Peaks, 575
13-8. Spin-Spin Splitting, 578
Problem-Solving Strategy: Drawing an NMR Spectrum, 583
13-9. Complex Splitting, 587
13-10. Stereochemical Nonequivalence of Protons, 590
13-11. Time Dependence of NMR Spectroscopy, 593
Problem-Solving Strategy: Interpreting Proton NMR Spectra, 596
13-12. Carbon-13 NMR Spectroscopy, 601
13-13. Interpreting Carbon NMR Spectra, 609
13-14. Nuclear Magnetic Resonance Imaging, 611
Problem-Solving Strategy: Spectroscopy Problems, 612
Chapter 13 Glossary, 616
Study Problems, 618
14. Ethers, Epoxides, and Sulfides, 625
14-1. Introduction, 625
14-2. Physical Properties of Ethers, 625
14-3. Nomenclature of Ethers, 630
14-4. Spectroscopy of Ethers, 633
14-5. The Williamson Ether Synthesis, 635
14-6. Synthesis of Ethers by Alkoxymercuration–Demercuration, 636
14-7. Industrial Synthesis: Bimolecular Dehydration of Alcohols, 637
Summary: Syntheses of Ethers (Review), 638
14-8. Cleavage of Ethers by HBr and HI, 638
14-9. Autoxidation of Ethers, 641
Summary: Reactions of Ethers, 641
14-10. Sulfides (Thioethers), 642
14-11. Synthesis of Epoxides, 644
Summary: Epoxide Syntheses, 647
14-12. Acid-Catalyzed Ring Opening of Epoxides, 648
14-13. Base-Catalyzed Ring Opening of Epoxides, 651
14-14. Orientation of Epoxide Ring Opening, 652
14-15. Reactions of Epoxides with Grignard and Organolithium Reagents, 654
14-16. Epoxy Resins: The Advent of Modern Glues, 655
Summary: Reactions of Epoxides, 657
Chapter 14 Glossary, 658
Study Problems, 660
15. Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy, 665
15-1. Introduction, 665
15-2. Stabilities of Dienes, 665
15-3. Molecular Orbital Picture of a Conjugated System, 667
15-4. Allylic Cations, 671
15-5. 1,2- and 1,4-Addition to Conjugated Dienes, 672
15-6. Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene, 674
15-7. Allylic Radicals, 676
15-8. Molecular Orbitals of the Allylic System, 678
15-9. Electronic Configurations of the Allyl Radical, Cation, and Anion, 680
15-10. S_N2 Displacement Reactions of Allylic Halides and Tosylates, 681
15-11. The Diels–Alder Reaction, 682
Key Mechanism 15-3: The Diels–Alder Reaction, 682
15-12. The Diels–Alder as an Example of a Pericyclic Reaction, 691
15-13. Ultraviolet Absorption Spectroscopy, 694
Chapter 15 Glossary, 701
Study Problems, 703
16. Aromatic Compounds, 707
16-1. Introduction: The Discovery of Benzene, 707
16-2. The Structure and Properties of Benzene, 707
16-3. The Molecular Orbitals of Benzene, 711
16-4. The Molecular Orbital Picture of Cyclobutadiene, 714
16-5. Aromatic, Antiaromatic, and Nonaromatic Compounds, 716
16-6. Hückel’s Rule, 716
16-7. Molecular Orbital Derivation of Hückel’s Rule, 718
16-8. Aromatic Ions, 719
16-9. Heterocyclic Aromatic Compounds, 725
16-10. Polynuclear Aromatic Hydrocarbons, 729
16-11. Aromatic Allotropes of Carbon, 731
16-12. Fused Heterocyclic Compounds, 733
16-13. Nomenclature of Benzene Derivatives, 734
16-14. Physical Properties of Benzene and Its Derivatives, 736
16-15. Spectroscopy of Aromatic Compounds, 737
Chapter 16 Glossary, 740
Study Problems, 742
17. Reactions of Aromatic Compounds, 751
17-1. Electrophilic Aromatic Substitution, 751
Key Mechanism 17-1: Electrophilic Aromatic Substitution, 752
17-2. Halogenation of Benzene, 753
17-3. Nitration of Benzene, 755
17-4. Sulfonation of Benzene, 757
17-5. Nitration of Toluene: The Effect of Alkyl Substitution, 759
17-6. Activating, Ortho, Para-Directing Substituents, 761
Summary: Activating, Ortho, Para-Directors, 764
17-7. Deactivating, Meta-Directing Substituents, 765
Summary: Deactivating, Meta-Directors, 768
17-8. Halogen Substituents: Deactivating, but Ortho, Para-Directing, 768
Summary: Directing Effects of Substituents, 770
17-9. Effects of Multiple Substituents on Electrophilic Aromatic Substitution, 770
17-10. The Friedel–Crafts Alkylation, 773
17-11. The Friedel–Crafts Acylation, 777
Summary: Comparison of Friedel–Crafts Alkylation and Acylation, 780
17-12. Nucleophilic Aromatic Substitution, 782
17-13. Addition Reactions of Benzene Derivatives, 787
17-14. Side-Chain Reactions of Benzene Derivatives, 789
17-15. Reactions of Phenols, 793
Summary: Reactions of Aromatic Compounds, 796
Chapter 17 Glossary, 799
Study Problems, 802
18. Ketones and Aldehydes, 807
18-1. Carbonyl Compounds, 807
18-2. Structure of the Carbonyl Group, 808
18-3. Nomenclature of Ketones and Aldehydes, 808
18-4. Physical Properties of Ketones and Aldehydes, 811
18-5. Spectroscopy of Ketones and Aldehydes, 813
18-6. Industrial Importance of Ketones and Aldehydes, 820
18-7. Review of Syntheses of Ketones and Aldehydes, 820
18-8. Synthesis of Ketones and Aldehydes Using 1,3-Dithianes, 824
18-9. Synthesis of Ketones from Carboxylic Acids, 825
18-10. Synthesis of Ketones from Nitriles, 826
18-11. Synthesis of Aldehydes and Ketones from Acid Chlorides, 827
Summary: Syntheses of Ketones and Aldehydes, 828
18-12. Reactions of Ketones and Aldehydes: Nucleophilic Addition, 831
Key Mechanism 18-1: Nucleophilic Additions to Carbonyl Groups, 833
18-13. The Wittig Reaction, 834
18-14. Hydration of Ketones and Aldehydes, 838
18-15. Formation of Cyanohydrins, 840
18-16. Formation of Imines, 842
Key Mechanism 18-5: Formation of Imines, 842
18-17. Condensations with Hydroxylamine and Hydrazines, 845
Summary: Condensations of Amines with Ketones and Aldehydes, 846
18-18. Formation of Acetals, 847
Key Mechanism 18-6: Formation of Acetals, 848
Problem-Solving Strategy: Proposing Reaction Mechanisms, 850
18-19. Use of Acetals as Protecting Groups, 852
18-20. Oxidation of Aldehydes, 854
18-21. Reductions of Ketones and Aldehydes, 854
Summary: Reactions of Ketones and Aldehydes, 857
Chapter 18 Glossary, 860
Study Problems, 863
19. Amines, 872
19-1. Introduction, 872
19-2. Nomenclature of Amines, 873
19-3. Structure of Amines, 875
19-4. Physical Properties of Amines, 877
19-5. Basicity of Amines, 879
19-6. Effects on Amine Basicity, 880
19-7. Salts of Amines, 882
19-8. Amine Salts as Phase-Transfer Catalysts, 884
19-9. Spectroscopy of Amines, 886
19-10. Reactions of Amines with Ketones and Aldehydes (Review), 890
19-11. Aromatic Substitution of Arylamines and Pyridine, 890
19-12. Alkylation of Amines by Alkyl Halides, 894
19-13. Acylation of Amines by Acid Chlorides, 895
19-14. Formation of Sulfonamides, 897
19-15. Amines as Leaving Groups: The Hofmann Elimination, 898
19-16. Oxidation of Amines; The Cope Elimination, 902
19-17. Reactions of Amines with Nitrous Acid, 904
19-18. Reactions of Arenediazonium Salts, 906
Summary: Reactions of Amines, 910
19-19. Synthesis of Amines by Reductive Amination, 912
19-20. Synthesis of Amines by Acylation–Reduction, 915
19-21. Syntheses Limited to Primary Amines, 916
Summary: Synthesis of Amines, 923
Chapter 19 Glossary, 925
Study Problems, 928
20. Carboxylic Acids, 937
20-1. Introduction, 937
20-2. Nomenclature of Carboxylic Acids, 937
20-3. Structure and Physical Properties of Carboxylic Acids, 941
20-4. Acidity of Carboxylic Acids, 942
20-5. Salts of Carboxylic Acids, 946
20-6. Commercial Sources of Carboxylic Acids, 949
20-7. Spectroscopy of Carboxylic Acids, 950
20-8. Synthesis of Carboxylic Acids, 954
Summary: Syntheses of Carboxylic Acids, 957
20-9. Reactions of Carboxylic Acids and Derivatives; Nucleophilic Acyl Substitution, 958
20-10. Condensation of Acids with Alcohols: The Fischer Esterification, 960
Key Mechanism 20-2: Fischer Esterification, 961
20-11. Esterification Using Diazomethane, 964
20-12. Condensation of Acids with Amines: Direct Synthesis of Amides, 965
20-13. Reduction of Carboxylic Acids, 965
20-14. Alkylation of Carboxylic Acids to Form Ketones, 967
20-15. Synthesis and Use of Acid Chlorides, 968
Summary: Reactions of Carboxylic Acids, 970
Chapter 20 Glossary, 972
Study Problems, 973
21. Carboxylic Acid Derivatives, 980
21-1. Introduction, 980
21-2. Structure and Nomenclature of Acid Derivatives, 981
21-3. Physical Properties of Carboxylic Acid Derivatives, 987
21-4. Spectroscopy of Carboxylic Acid Derivatives, 989
21-5. Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution, 996
Key Mechanism 21-1: Addition–Elimination Mechanism of Nucleophilic Acyl Substitution, 997
21-6. Transesterification, 1005
Problem-Solving Strategy: Proposing Reaction Mechanisms, 1006
21-7. Hydrolysis of Carboxylic Acid Derivatives, 1008
21-8. Reduction of Acid Derivatives, 1013
21-9. Reactions of Acid Derivatives with Organometallic Reagents, 1015
21-10. Summary of the Chemistry of Acid Chlorides, 1017
21-11. Summary of the Chemistry of Anhydrides, 1018
21-12. Summary of the Chemistry of Esters, 1021
21-13. Summary of the Chemistry of Amides, 1024
21-14. Summary of the Chemistry of Nitriles, 1027
21-15. Thioesters, 1028
21-16. Esters and Amides of Carbonic Acid, 1030
Chapter 21 Glossary, 1032
Study Problems, 1034
22. Condensations and Alpha Substitutions of Carbonyl Compounds, 1043
22-1. Introduction, 1043
22-2. Enols and Enolate Ions, 1044
22-3. Alkylation of Enolate Ions, 1048
22-4. Formation and Alkylation of Enamines, 1049
22-5. Alpha Halogenation of Ketones, 1052
22-6. α Bromination of Acids: The HVZ Reaction, 1057
22-7. The Aldol Condensation of Ketones and Aldehydes, 1057
Key Mechanism 22-9: Base-Catalyzed Aldol Condensation, 1058
22-8. Dehydration of Aldol Products, 1061
Key Mechanism 22-11: Base-Catalyzed Dehydration of an Aldol, 1061
22-9. Crossed Aldol Condensations, 1062
Problem-Solving Strategy: Proposing Reaction Mechanisms, 1063
22-10. Aldol Cyclizations, 1065
22-11. Planning Syntheses Using Aldol Condensations, 1066
22-12. The Claisen Ester Condensation, 1067
Key Mechanism 22-12: The Claisen Ester Condensation, 1068
22-13. The Dieckmann Condensation: A Claisen Cyclization, 1070
22-14. Crossed Claisen Condensations, 1071
22-15. Syntheses Using β-Dicarbonyl Compounds, 1074
22-16. The Malonic Ester Synthesis, 1076
22-17. The Acetoacetic Ester Synthesis, 1079
22-18. Conjugate Additions: The Michael Reaction, 1081
22-19. The Robinson Annulation, 1085
Problem-Solving Strategy: Proposing Reaction Mechanisms, 1086
Summary: Enolate Additions and Condensations, 1088
Chapter 22 Glossary, 1090
Study Problems, 1092
23. Carbohydrates and Nucleic Acids, 1097
23-1. Introduction, 1097
23-2. Classification of Carbohydrates, 1098
23-3. Monosaccharides, 1099
23-4. Erythro and Threo Diastereomers, 1102
23-5. Epimers, 1103
23-6. Cyclic Structures of Monosaccharides, 1104
23-7. Anomers of Monosaccharides; Mutarotation, 1108
23-8. Reactions of Monosaccharides: Side Reactions in Base, 1110
23-9. Reduction of Monosaccharides, 1112
23-10. Oxidation of Monosaccharides; Reducing Sugars, 1113
23-11. Nonreducing Sugars: Formation of Glycosides, 1115
23-12. Ether and Ester Formation, 1117
23-13. Reactions with Phenylhydrazine: Osazone Formation, 1119
23-14. Chain Shortening: The Ruff Degradation, 1120
23-15. Chain Lengthening: The Kiliani–Fischer Synthesis, 1121
Summary: Reactions of Sugars, 1122
23-16. Fischer’s Proof of the Configuration of Glucose, 1124
23-17. Determination of Ring Size; Periodic Acid Cleavage of Sugars, 1127
23-18. Disaccharides, 1129
23-19. Polysaccharides, 1134
23-20. Nucleic Acids: Introduction, 1137
23-21. Ribonucleosides and Ribonucleotides, 1139
23-22. The Structure of Ribonucleic Acid, 1141
23-23. Deoxyribose and the Structure of Deoxyribonucleic Acid, 1141
23-24. Additional Functions of Nucleotides, 1145
Chapter 23 Glossary, 1147
Study Problems, 1149
24. Amino Acids, Peptides, and Proteins, 1153
24-1. Introduction, 1153
24-2. Structure and Stereochemistry of the α-Amino Acids, 1154
24-3. Acid–Base Properties of Amino Acids, 1158
24-4. Isoelectric Points and Electrophoresis, 1160
24-5. Synthesis of Amino Acids, 1161
Summary: Syntheses of Amino Acids, 1166
24-6. Resolution of Amino Acids, 1167
24-7. Reactions of Amino Acids, 1167
Summary: Reactions of Amino Acids, 1170
24-8. Structure and Nomenclature of Peptides and Proteins, 1170
24-9. Peptide Structure Determination, 1174
24-10. Solution-Phase Peptide Synthesis, 1180
24-11. Solid-Phase Peptide Synthesis, 1183
24-12. Classification of Proteins, 1188
24-13. Levels of Protein Structure, 1188
24-14. Protein Denaturation, 1191
Chapter 24 Glossary, 1193
Study Problems, 1196
25. Lipids, 1200
25-1. Introduction, 1200
25-2. Waxes, 1200
25-3. Triglycerides, 1201
25-4. Saponification of Fats and Oils; Soaps and Detergents, 1205
25-5. Phospholipids, 1208
25-6. Steroids, 1210
25-7. Prostaglandins, 1213
25-8. Terpenes, 1214
Chapter 25 Glossary, 1217
Study Problems, 1219
26. Synthetic Polymers, 1222
26-1. Introduction, 1222
26-2. Addition Polymers, 1223
26-3. Stereochemistry of Polymers, 1229
26-4. Stereochemical Control of Polymerization; Ziegler–Natta Catalysts, 1230
26-5. Natural and Synthetic Rubbers, 1230
26-6. Copolymers of Two or More Monomers, 1232
26-7. Condensation Polymers, 1232
26-8. Polymer Structure and Properties, 1236
Chapter 26 Glossary, 1238
Study Problems, 1239
Appendices, 1243
1A. NMR: Proton Chemical Shifts, 1244
1B. Spin-Spin Coupling Constants, 1246
1C. ¹³C Chemical Shifts in Organic Compounds, 1247
2A. Characteristic Infrared Group Frequencies, 1248
2B. IR: Characteristic Infrared Absorptions of Functional Groups, 1251
3. UV: The Woodward–Fieser Rules for Predicting UV-Visible Spectra, 1253
4A. Methods and Suggestions for Proposing Mechanisms, 1257
4B. Suggestions for Developing Multistep Syntheses, 1260
5. pK_a Values for Representative Compounds, 1261
Answers to Selected Problems, A1
Photo Credits, PC1
Index, I1
End Papers, EP-1

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