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Copyright, ii
Preface, xvii
1. Structure and Bonding, 1
1.1. Atomic Structure: The Nucleus, 3
1.2. Atomic Structure: Orbitals, 4
1.3. Atomic Structure: Electron Configurations, 6
1.4. Development of Chemical Bonding Theory, 7
1.5. The Nature of Chemical Bonds: Valence Bond Theory, 10
1.6. sp³ Hybrid Orbitals and the Structure of Methane , 12
1.7. sp³ Hybrid Orbitals and the Structure of Ethane , 14
1.8. sp² Hybrid Orbitals and the Structure of Ethylene , 15
1.9. sp Hybrid Orbitals and the Structure of Acetylene , 17
1.10. Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur, 19
1.11. The Nature of Chemical Bonds: Molecular Orbital Theory, 21
1.12. Drawing Chemical Structures, 22
Summary and Key Words, 26
Visualizing Chemistry, 28
Additional Problems, 29
2. Polar Covalent Bonds; Acids and Bases, 35
2.1. Polar Covalent Bonds: Electronegativity, 35
2.2. Polar Covalent Bonds: Dipole Moments, 38
2.3. Formal Charges, 40
2.4. Resonance, 43
2.5. Rules for Resonance Forms, 44
2.6. Drawing Resonance Forms, 46
2.7. Acids and Bases: The Brønsted-Lowry Definition, 49
2.8. Acid and Base Strength, 50
2.9. Predicting Acid-Base Reactions from pK_a Values , 52
2.10. Organic Acids and Organic Bases, 54
2.11. Acids and Bases: The Lewis Definition, 57
2.12. Molecular Models, 61
2.13. Noncovalent Interactions, 61
Summary and Key Words, 65
Visualizing Chemistry, 66
Additional Problems, 68
3. Organic Compounds: Alkanes and Their Stereochemistry, 73
3.1. Functional Groups, 73
3.2. Alkanes and Alkane Isomers, 79
3.3. Alkyl Groups, 83
3.4. Naming Alkanes, 86
3.5. Properties of Alkanes, 91
3.6. Conformations of Ethane, 93
3.7. Conformations of Other Alkanes, 95
Summary and Key Words, 100
Visualizing Chemistry, 101
Additional Problems, 102
4. Organic Compounds: Cycloalkanes and Their Stereochemistry, 107
4.1. Naming Cycloalkanes, 108
4.2. Cis-Trans Isomerism in Cycloalkanes, 110
4.3. Stability of Cycloalkanes: Ring Strain, 113
4.4. Conformations of Cycloalkanes, 115
4.5. Conformations of Cyclohexane, 117
4.6. Axial and Equatorial Bonds in Cyclohexane, 119
4.7. Conformations of Monosubstituted Cyclohexanes, 122
4.8. Conformations of Disubstituted Cyclohexanes, 124
4.9. Conformations of Polycyclic Molecules, 128
Summary and Key Words, 131
Visualizing Chemistry, 132
Additional Problems, 133
5. An Overview of Organic Reactions, 137
5.1. Kinds of Organic Reactions, 137
5.2. How Organic Reactions Occur: Mechanisms, 139
5.3. Radical Reactions, 140
5.4. Polar Reactions, 142
5.5. An Example of a Polar Reaction: Addition of HBr to Ethylene, 147
5.6. Using Curved Arrows in Polar Reaction Mechanisms, 149
5.7. Describing a Reaction: Equilibria, Rates, and Energy Changes, 152
5.8. Describing a Reaction: Bond Dissociation Energies, 155
5.9. Describing a Reaction: Energy Diagrams and Transition States, 157
5.10. Describing a Reaction: Intermediates, 160
5.11. A Comparison between Biological Reactions and Laboratory Reactions, 162
Summary and Key Words, 165
Visualizing Chemistry, 166
Additional Problems, 168
6. Alkenes: Structure and Reactivity, 172
6.1. Industrial Preparation and Use of Alkenes, 173
6.2. Calculating Degree of Unsaturation, 174
6.3. Naming Alkenes, 176
6.4. Cis-Trans Isomerism in Alkenes, 178
6.5. Sequence Rules: the E,Z Designation , 180
6.6. Stability of Alkenes, 185
6.7. Electrophilic Addition Reactions of Alkenes, 188
6.8. Orientation of Electrophilic Additions: Markovnikov’s Rule, 191
6.9. Carbocation Structure and Stability, 195
6.10. The Hammond Postulate, 197
6.11. Evidence for the Mechanism of Electrophilic Additions: Carbocation Rearrangements, 200
Summary and Key Words, 204
Visualizing Chemistry, 205
Additional Problems, 206
7. Alkenes: Reactions and Synthesis, 213
7.1. Preparation of Alkenes: A Preview of Elimination Reactions, 214
7.2. Addition of Halogens to Alkenes, 215
7.3. Addition of Hypohalous Acids to Alkenes: Halohydrin Formation, 218
7.4. Addition of Water to Alkenes: Oxymercuration, 220
7.5. Addition of Water to Alkenes: Hydroboration, 223
7.6. Addition of Carbenes to Alkenes: Cyclopropane Synthesis, 227
7.7. Reduction of Alkenes: Hydrogenation, 229
7.8. Oxidation of Alkenes: Epoxidation and Hydroxylation, 233
7.9. Oxidation of Alkenes: Cleavage to Carbonyl Compounds, 236
7.10. Radical Additions to Alkenes: Polymers, 239
7.11. Biological Additions of Radicals to Alkenes, 243
Summary and Key Words, 246
Summary of Reactions, 247
Visualizing Chemistry, 250
Additional Problems, 251
8. Alkynes: An Introduction to Organic Synthesis, 259
8.1. Naming Alkynes, 259
8.2. Preparation of Alkynes: Elimination Reactions of Dihalides, 261
8.3. Reactions of Alkynes: Addition of HX and X₂, 261
8.4. Hydration of Alkynes, 264
8.5. Reduction of Alkynes, 268
8.6. Oxidative Cleavage of Alkynes, 270
8.7. Alkyne Acidity: Formation of Acetylide Anions, 270
8.8. Alkylation of Acetylide Anions, 272
8.9. An Introduction to Organic Synthesis, 274
Summary and Key Words, 279
Summary of Reactions, 280
Visualizing Chemistry, 282
Additional Problems, 283
9. Stereochemistry, 289
9.1. Enantiomers and the Tetrahedral Carbon, 290
9.2. The Reason for Handedness in Molecules: Chirality, 291
9.3. Optical Activity, 294
9.4. Pasteur’s Discovery of Enantiomers, 296
9.5. Sequence Rules for Specifying Configuration, 297
9.6. Diastereomers, 302
9.7. Meso Compounds, 305
9.8. Racemic Mixtures and the Resolution of Enantiomers, 307
9.9. A Review of Isomerism, 309
9.10. Stereochemistry of Reactions: Addition of H₂O to an Achiral Alkene , 311
9.11. Stereochemistry of Reactions: Addition of H₂O to a Chiral Alkene , 312
9.12. Chirality at Nitrogen, Phosphorus, and Sulfur, 314
9.13. Prochirality, 315
9.14. Chirality in Nature and Chiral Environments, 318
Summary and Key Words, 322
Visualizing Chemistry, 323
Additional Problems, 324
10. Organohalides, 332
10.1. Naming Alkyl Halides, 333
10.2. Structure of Alkyl Halides, 334
10.3. Preparing Alkyl Halides from Alkanes: Radical Halogenation, 335
10.4. Preparing Alkyl Halides from Alkenes: Allylic Bromination, 339
10.5. Stability of the Allyl Radical: Resonance Revisited, 341
10.6. Preparing Alkyl Halides from Alcohols, 344
10.7. Reactions of Alkyl Halides: Grignard Reagents, 345
10.8. Organometallic Coupling Reactions, 346
10.9. Oxidation and Reduction in Organic Chemistry, 348
Summary and Key Words, 352
Summary of Reactions, 353
Visualizing Chemistry, 354
Additional Problems, 355
11. Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations, 359
11.1. The Discovery of Nucleophilic Substitution Reactions, 359
11.2. The S_N2 Reaction , 362
11.3. Characteristics of the S_N2 Reaction , 365
11.4. The S_N1 Reaction , 372
11.5. Characteristics of the S_N1 Reaction , 376
11.6. Biological Substitution Reactions, 381
11.7. Elimination Reactions of Alkyl Halides: Zaitsev’s Rule, 383
11.8. The E2 Reaction and the Deuterium Isotope Effect, 386
11.9. The E2 Reaction and Cyclohexane Conformation, 389
11.10. The E1 and E1cB Reactions, 391
11.11. Biological Elimination Reactions, 393
11.12. A Summary of Reactivity: S_N1, S_N2, E1, E1cB, and E2 , 393
Summary and Key Words, 397
Summary of Reactions, 398
Visualizing Chemistry, 399
Additional Problems, 400
12. Structure Determination: Mass Spectrometry and Infrared Spectroscopy, 408
12.1. Mass Spectrometry of Small Molecules: Magnetic-Sector Instruments, 409
12.2. Interpreting Mass Spectra, 411
12.3. Mass Spectrometry of Some Common Functional Groups, 415
12.4. Mass Spectrometry in Biological Chemistry: Time-of-Flight (TOF) Instruments, 417
12.5. Spectroscopy and the Electromagnetic Spectrum, 418
12.6. Infrared Spectroscopy, 422
12.7. Interpreting Infrared Spectra, 423
12.8. Infrared Spectra of Some Common Functional Groups, 426
Summary and Key Words, 433
Visualizing Chemistry, 434
Additional Problems, 434
13. Structure Determination: Nuclear Magnetic Resonance Spectroscopy, 440
13.1. Nuclear Magnetic Resonance Spectroscopy, 440
13.2. The Nature of NMR Absorptions, 442
13.3. Chemical Shifts, 445
13.4. ¹³C NMR Spectroscopy: Signal Averaging and FT-NMR , 446
13.5. Characteristics of ¹³C NMR Spectroscopy , 448
13.6. DEPT ¹³C NMR Spectroscopy , 451
13.7. Uses of ¹³C NMR Spectroscopy , 453
13.8. ¹H NMR Spectroscopy and Proton Equivalence , 454
13.9. Chemical Shifts in ¹H NMR Spectroscopy , 457
13.10. Integration of ¹H NMR Absorptions: Proton Counting , 459
13.11. Spin-Spin Splitting in ¹H NMR Spectra , 460
13.12. More Complex Spin-Spin Splitting Patterns, 465
13.13. Uses of ¹H NMR Spectroscopy , 467
Summary and Key Words, 469
Visualizing Chemistry, 470
Additional Problems, 471
14. Conjugated Compounds and Ultraviolet Spectroscopy, 482
14.1. Stability of Conjugated Dienes: Molecular Orbital Theory, 483
14.2. Electrophilic Additions to Conjugated Dienes: Allylic Carbocations, 487
14.3. Kinetic versus Thermodynamic Control of Reactions, 490
14.4. The Diels-Alder Cycloaddition Reaction, 492
14.5. Characteristics of the Diels-Alder Reaction, 493
14.6. Diene Polymers: Natural and Synthetic Rubbers, 498
14.7. Structure Determination in Conjugated Systems: Ultraviolet Spectroscopy, 500
14.8. Interpreting Ultraviolet Spectra: The Effect of Conjugation, 502
14.9. Conjugation, Color, and the Chemistry of Vision, 503
Summary and Key Words, 507
Summary of Reactions, 507
Visualizing Chemistry, 508
Additional Problems, 509
15. Benzene and Aromaticity, 516
15.1. Sources and Names of Aromatic Compounds, 517
15.2. Structure and Stability of Benzene: Molecular Orbital Theory, 520
15.3. Aromaticity and the Hückel 4n + 2 Rule , 523
15.4. Aromatic Ions, 525
15.5. Aromatic Heterocycles: Pyridine and Pyrrole, 528
15.6. Why 4n + 2? , 530
15.7. Polycyclic Aromatic Compounds, 531
15.8. Spectroscopy of Aromatic Compounds, 534
Summary and Key Words, 538
Visualizing Chemistry, 539
Additional Problems, 541
16. Chemistry of Benzene: Electrophilic Aromatic Substitution, 547
16.1. Electrophilic Aromatic Substitution Reactions: Bromination, 548
16.2. Other Aromatic Substitutions, 550
16.3. Alkylation and Acylation of Aromatic Rings: The Friedel-Crafts Reaction, 554
16.4. Substituent Effects in Substituted Aromatic Rings, 560
16.5. An Explanation of Substituent Effects, 564
16.6. Trisubstituted Benzenes: Additivity of Effects, 570
16.7. Nucleophilic Aromatic Substitution, 572
16.8. Benzyne, 575
16.9. Oxidation of Aromatic Compounds, 576
16.10. Reduction of Aromatic Compounds, 579
16.11. Synthesis of Trisubstituted Benzenes, 581
Summary and Key Words, 587
Summary of Reactions, 588
Visualizing Chemistry, 590
Additional Problems, 591
17. Alcohols and Phenols, 599
17.1. Naming Alcohols and Phenols, 600
17.2. Properties of Alcohols and Phenols, 602
17.3. Preparation of Alcohols: A Review, 607
17.4. Alcohols from Reduction of Carbonyl Compounds, 609
17.5. Alcohols from Reaction of Carbonyl Compounds with Grignard Reagents, 613
17.6. Reactions of Alcohols, 617
17.7. Oxidation of Alcohols, 623
17.8. Protection of Alcohols, 626
17.9. Phenols and Their Uses, 628
17.10. Reactions of Phenols, 631
17.11. Spectroscopy of Alcohols and Phenols, 632
Summary and Key Words, 637
Summary of Reactions, 638
Visualizing Chemistry, 640
Additional Problems, 642
18. Ethers and Epoxides; Thiols and Sulfides, 652
18.1. Names and Properties of Ethers, 653
18.2. Synthesis of Ethers, 654
18.3. Reactions of Ethers: Acidic Cleavage, 657
18.4. Reactions of Ethers: Claisen Rearrangement, 659
18.5. Cyclic Ethers: Epoxides, 660
18.6. Reactions of Epoxides: Ring-Opening, 662
18.7. Crown Ethers, 666
18.8. Thiols and Sulfides, 667
18.9. Spectroscopy of Ethers, 671
Summary and Key Words, 674
Summary of Reactions, 675
Visualizing Chemistry, 676
Additional Problems, 677
A Preview of Carbonyl Compounds, 686
I. Kinds of Carbonyl Compounds, 686
II. Nature of the Carbonyl Group, 688
III. General Reactions of Carbonyl Compounds, 688
IV . Summary, 694
19. Aldehydes and Ketones: Nucleophilic Addition Reactions, 695
19.1. Naming Aldehydes and Ketones, 696
19.2. Preparation of Aldehydes and Ketones, 698
19.3. Oxidation of Aldehydes and Ketones, 700
19.4. Nucleophilic Addition Reactions of Aldehydes and Ketones, 702
19.5. Nucleophilic Addition of H₂O: Hydration , 705
19.6. Nucleophilic Addition of HCN: Cyanohydrin Formation, 707
19.7. Nucleophilic Addition of Grignard and Hydride Reagents: Alcohol Formation, 708
19.8. Nucleophilic Addition of Amines: Imine and Enamine Formation, 710
19.9. Nucleophilic Addition of Hydrazine: The Wolff-Kishner Reaction, 715
19.10. Nucleophilic Addition of Alcohols: Acetal Formation, 717
19.11. Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction, 720
19.12. Biological Reductions, 723
19.13. Conjugate Nucleophilic Addition to α,β-Unsaturated Aldehydes and Ketones, 725
19.14. Spectroscopy of Aldehydes and Ketones, 730
Summary and Key Words, 736
Summary of Reactions, 736
Visualizing Chemistry, 739
Additional Problems, 740
20. Carboxylic Acids and Nitriles, 751
20.1. Naming Carboxylic Acids and Nitriles, 752
20.2. Structure and Properties of Carboxylic Acids, 754
20.3. Biological Acids and the Henderson-Hasselbalch Equation, 758
20.4. Substituent Effects on Acidity, 759
20.5. Preparation of Carboxylic Acids, 762
20.6. Reactions of Carboxylic Acids: An Overview, 764
20.7. Chemistry of Nitriles, 765
20.8. Spectroscopy of Carboxylic Acids and Nitriles, 770
Summary and Key Words, 774
Summary of Reactions, 775
Visualizing Chemistry, 776
Additional Problems, 777
21. Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions, 785
21.1. Naming Carboxylic Acid Derivatives, 786
21.2. Nucleophilic Acyl Substitution Reactions, 789
21.3. Nucleophilic Acyl Substitution Reactions of Carboxylic Acids, 794
21.4. Chemistry of Acid Halides, 800
21.5. Chemistry of Acid Anhydrides, 806
21.6. Chemistry of Esters, 808
21.7. Chemistry of Amides, 813
21.8. Chemistry of Thioesters and Acyl Phosphates: Biological Carboxylic Acid Derivatives, 816
21.9. Polyamides and Polyesters: Step-Growth Polymers, 818
21.10. Spectroscopy of Carboxylic Acid Derivatives, 822
Summary and Key Words, 825
Summary of Reactions, 826
Visualizing Chemistry, 829
Additional Problems, 830
22. Carbonyl Alpha-Substitution Reactions, 841
22.1. Keto-Enol Tautomerism, 842
22.2. Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions, 845
22.3. Alpha Halogenation of Aldehydes and Ketones, 846
22.4. Alpha Bromination of Carboxylic Acids: The Hell-Volhard-Zelinskii Reaction, 849
22.5. Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation, 849
22.6. Reactivity of Enolate Ions, 853
22.7. Alkylation of Enolate Ions, 855
Summary and Key Words, 865
Summary of Reactions, 866
Visualizing Chemistry, 868
Additional Problems, 869
23. Carbonyl Condensation Reactions, 877
23.1. Carbonyl Condensations: The Aldol Reaction, 877
23.2. Carbonyl Condensations versus Alpha Substitutions, 880
23.3. Dehydration of Aldol Products: Synthesis of Enones, 882
23.4. Using Aldol Reactions in Synthesis, 884
23.5. Mixed Aldol Reactions, 885
23.6. Intramolecular Aldol Reactions, 886
23.7. The Claisen Condensation Reaction, 888
23.8. Mixed Claisen Condensations, 890
23.9. Intramolecular Claisen Condensations: The Dieckmann Cyclization, 892
23.10. Conjugate Carbonyl Additions: The Michael Reaction, 894
23.11. Carbonyl Condensations with Enamines: The Stork Reaction, 896
23.12. The Robinson Annulation Reaction, 899
23.13. Some Biological Carbonyl Condensation Reactions, 901
Summary and Key Words, 904
Summary of Reactions, 905
Visualizing Chemistry, 907
Additional Problems, 908
24. Amines and Heterocycles, 916
24.1. Naming Amines, 916
24.2. Properties of Amines, 919
24.3. Basicity of Amines, 921
24.4. Basicity of Substituted Arylamines, 924
24.5. Biological Amines and the Henderson-Hasselbalch Equation, 925
24.6. Synthesis of Amines, 927
24.7. Reactions of Amines, 936
24.8. Reactions of Arylamines, 939
24.9. Heterocycles, 945
24.10. Spectroscopy of Amines, 952
Summary and Key Words, 958
Summary of Reactions, 959
Visualizing Chemistry, 961
Additional Problems, 963
25. Biomolecules: Carbohydrates, 973
25.1. Classification of Carbohydrates, 974
25.2. Depicting Carbohydrate Stereochemistry: Fischer Projections, 975
25.3. D,L Sugars , 980
25.4. Configurations of the Aldoses, 981
25.5. Cyclic Structures of Monosaccharides: Anomers, 984
25.6. Reactions of Monosaccharides, 987
25.7. The Eight Essential Monosaccharides, 996
25.8. Disaccharides, 997
25.9. Polysaccharides and Their Synthesis, 1000
25.10. Some Other Important Carbohydrates, 1002
25.11. Cell-Surface Carbohydrates and Carbohydrate Vaccines, 1003
Summary and Key Words, 1006
Summary of Reactions, 1007
Visualizing Chemistry, 1008
Additional Problems, 1009
26. Biomolecules: Amino Acids, Peptides, and Proteins, 1016
26.1. Structures of Amino Acids, 1017
26.2. Amino Acids, the Henderson-Hasselbalch Equation, and Isoelectric Points, 1022
26.3. Synthesis of Amino Acids, 1025
26.4. Peptides and Proteins, 1027
26.5. Amino Acid Analysis of Peptides, 1030
26.6. Peptide Sequencing: The Edman Degradation, 1031
26.7. Peptide Synthesis, 1033
26.8. Automated Peptide Synthesis: The Merrifield Solid-Phase Method, 1036
26.9. Protein Structure, 1038
26.10. Enzymes and Coenzymes, 1040
26.11. How Do Enzymes Work? Citrate Synthase, 1043
Summary and Key Words, 1049
Summary of Reactions, 1050
Visualizing Chemistry, 1052
Additional Problems, 1053
27. Biomolecules: Lipids, 1060
27.1. Waxes, Fats, and Oils, 1061
27.2. Soap, 1064
27.3. Phospholipids, 1066
27.4. Prostaglandins and Other Eicosanoids, 1067
27.5. Terpenoids, 1070
27.6. Steroids, 1079
27.7. Biosynthesis of Steroids, 1084
Summary and Key Words, 1091
Visualizing Chemistry, 1092
Additional Problems, 1093
28. Biomolecules: Nucleic Acids, 1100
28.1. Nucleotides and Nucleic Acids, 1100
28.2. Base Pairing in DNA: The Watson-Crick Model, 1103
28.3. Replication of DNA, 1106
28.4. Transcription of DNA, 1107
28.5. Translation of RNA: Protein Biosynthesis, 1109
28.6. DNA Sequencing, 1112
28.7. DNA Synthesis, 1114
28.8. The Polymerase Chain Reaction, 1117
Summary and Key Words, 1119
Visualizing Chemistry, 1120
Additional Problems, 1121
29. The Organic Chemistry of Metabolic Pathways, 1125
29.1. An Overview of Metabolism and Biochemical Energy, 1126
29.2. Catabolism of Triacylglycerols: The Fate of Glycerol, 1130
29.3. Catabolism of Triacylglycerols: β-Oxidation, 1133
29.4. Biosynthesis of Fatty Acids, 1138
29.5. Catabolism of Carbohydrates: Glycolysis, 1143
29.6. Conversion of Pyruvate to Acetyl CoA, 1150
29.7. The Citric Acid Cycle, 1154
29.8. Carbohydrate Biosynthesis: Gluconeogenesis, 1159
29.9. Catabolism of Proteins: Transamination, 1165
29.10. Some Conclusions about Biological Chemistry, 1169
Summary and Key Words, 1170
Visualizing Chemistry, 1171
Additional Problems, 1172
30. Orbitals and Organic Chemistry: Pericyclic Reactions, 1178
30.1. Molecular Orbitals and Pericyclic Reactions of Conjugated Pi Systems, 1178
30.2. Electrocyclic Reactions, 1181
30.3. Stereochemistry of Thermal Electrocyclic Reactions, 1183
30.4. Photochemical Electrocyclic Reactions, 1185
30.5. Cycloaddition Reactions, 1186
30.6. Stereochemistry of Cycloadditions, 1188
30.7. Sigmatropic Rearrangements, 1191
30.8. Some Examples of Sigmatropic Rearrangements, 1192
30.9. A Summary of Rules for Pericyclic Reactions, 1196
Summary and Key Words, 1198
Visualizing Chemistry, 1199
Additional Problems, 1200
31. Synthetic Polymers, 1206
31.1. Chain-Growth Polymers, 1207
31.2. Stereochemistry of Polymerization: Ziegler-Natta Catalysts, 1209
31.3. Copolymers, 1210
31.4. Step-Growth Polymers, 1212
31.5. Polymer Structure and Physical Properties, 1215
Summary and Key Words, 1220
Visualizing Chemistry, 1221
Additional Problems, 1221
Appendix A. Nomenclature of Polyfunctional Organic Compounds, A-1
Appendix B. Acidity Constants for Some Organic Compounds, A-8
Appendix C. Glossary, A-10
Appendix D. Answers to In-Text Problems, A-30
Index, I-1

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