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Copyright, iv
Preface, xxi
For the Student, xxx
About the Author, xxxviii
Part 1. An Introduction to the Study of Organic Chemistry, 1
1. Electronic Structure and Bonding · Acids and Bases, 2
Natural Versus Synthetic, 3
1.1. The Structure of an Atom, 4
1.2. How the Electrons in an Atom Are Distributed, 5
Albert Einstein, 6
Max Karl Ernst Ludwig Planck, 7
1.3. Ionic and Covalent Bonds, 8
1.4. How the Structure of a Compound Is Represented, 15
Problem-Solving Strategy, 17
1.5. Atomic Orbitals, 21
1.6. An Introduction to Molecular Orbital Theory, 22
1.7. How Single Bonds Are Formed in Organic Compounds, 28
1.8. How a Double Bond Is Formed: The Bonds in Ethene, 32
Diamond, Graphite, and Buckminsterfullerene: Substances Containing Only Carbon Atoms, 33
1.9. How a Triple Bond Is Formed: The Bonds in Ethyne, 34
1.10. The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion, 35
1.11. The Bonds in Water, 37
1.12. The Bonds in Ammonia and in the Ammonium Ion, 38
Water—A Unique Compound, 38
1.13. The Bonds in the Hydrogen Halides, 39
1.14. Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles, 40
Problem-Solving Strategy, 42
1.15. The Dipole Moments of Molecules, 43
1.16. An Introduction to Acids and Bases, 44
1.17. pK_a and pH, 45
Acid Rain, 46
1.18. Organic Acids and Bases, 47
Problem-Solving Strategy, 47
1.19. How to Predict the Outcome of an Acid–Base Reaction, 50
1.20. How the Structure of an Acid Affects Its Acidity, 51
1.21. How Substituents Affect the Strength of an Acid, 55
Problem-Solving Strategy, 56
1.22. An Introduction to Delocalized Electrons, 57
1.23. A Summary of the Factors That Determine Acid Strength, 58
1.24. How the pH Affects the Structure of an Organic Compound, 60
Derivation of the Henderson–Hasselbalch Equation, 60
Problem-Solving Strategy, 61
1.25. Buffer Solutions, 63
1.26. The Second Definition of Acid and Base: Lewis Acids and Bases, 64
Blood: A Buffered Solution, 64
Summary, 65
Key Terms, 66
Problems, 67
2. An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure, 71
2.1. How Alkyl Substituents Are Named, 74
2.2. The Nomenclature of Alkanes, 78
2.3. Nomenclature of Cycloalkanes · Skeletal Structures, 82
Problem-Solving Strategy, 83
2.4. Nomenclature of Alkyl Halides, 85
2.5. Nomenclature of Ethers, 86
2.6. Nomenclature of Alcohols, 87
2.7. Nomenclature of Amines, 89
Bad Smelling Compounds, 90
2.8. The Structures of Alkyl Halides, Alcohols, Ethers, and Amines, 92
2.9. The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines, 94
Problem-Solving Strategy, 97
2.10. Rotation Occurs About Carbon–Carbon Bonds, 101
2.11. Some Cycloalkanes Have Angle Strain, 104
Highly Strained Hydrocarbons, 105
von Baeyer and Barbituric Acid, 106
2.12. Conformations of Cyclohexane, 107
Problem-Solving Strategy, 108
2.13. Conformers of Monosubstituted Cyclohexanes, 110
2.14. Conformers of Disubstituted Cyclohexanes, 113
Problem-Solving Strategy, 113
Summary, 117
Key Terms, 117
Problems, 118
Part 2. Electrophilic Addition Reactions, Stereochemistry, and Electron Delocalization, 123
3. Alkenes: Structure, Nomenclature, and an Introduction to Reactivity · Thermodynamics and Kinetics, 124
3.1. Molecular Formulas and the Degree of Unsaturation, 125
3.2. The Nomenclature of Alkenes, 126
3.3. The Structures of Alkenes, 129
3.4. Alkenes Can Have Cis and Trans Isomers, 130
Cis–Trans Interconversion in Vision, 132
3.5. Naming Alkenes Using the E,Z System, 133
Problem-Solving Strategy, 136
3.6. How Alkenes React · Curved Arrows Show the Flow of Electrons, 137
A Few Words About Curved Arrows, 140
3.7. Thermodynamics and Kinetics, 141
The Difference Between ΔG† and E_a, 151
3.8. Using a Reaction Coordinate Diagram to Describe a Reaction, 152
Summary, 154
Key Terms, 155
Problems, 155
4. The Reactions of Alkenes, 159
4.1. Addition of a Hydrogen Halide to an Alkene, 160
4.2. Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon, 161
4.3. The Structure of the Transition State Lies Partway Between the Structures of the Reactants and Products, 164
4.4. Electrophilic Addition Reactions Are Regioselective, 166
Problem-Solving Strategy, 167
4.5. Acid-Catalyzed Addition Reactions, 169
4.6. A Carbocation Will Rearrange If It Can Form a More Stable Carbocation, 172
4.7. Addition of a Halogen to an Alkene, 175
4.8. Oxymercuration–Reduction and Alkoxymercuration–Reduction Are Other Ways to Add Water or an Alcohol to an Alkene, 180
4.9. Addition of a Peroxyacid to an Alkene, 182
Problem-Solving Strategy, 183
4.10. Addition of Borane to an Alkene: Hydroboration–Oxidation, 184
Borane and Diborane, 185
4.11. Addition of Hydrogen to an Alkene · The Relative Stabilities of Alkenes, 188
Problem-Solving Strategy, 190
Trans Fats, 190
4.12. Reactions and Synthesis, 192
Pesticides: Natural and Synthetic, 193
Summary, 194
Summary of Reactions, 194
Key Terms, 196
Problems, 196
5. Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions, 200
5.1. Cis–Trans Isomers Result from Restricted Rotation, 201
5.2. A Chiral Object Has a Nonsuperimposable Mirror Image, 202
5.3. An Asymmetric Center Is a Cause of Chirality in a Molecule, 203
5.4. Isomers with One Asymmetric Center, 204
5.5. Asymmetric Centers and Stereocenters, 205
5.6. How to Draw Enantiomers, 205
5.7. Naming Enantiomers by the R,S System, 206
Problem-Solving Strategy, 210
Problem-Solving Strategy, 211
5.8. Chiral Compounds Are Optically Active, 212
5.9. How Specific Rotation Is Measured, 213
5.10. Enantiomeric Excess, 215
5.11. Isomers with More than One Asymmetric Center, 216
Problem-Solving Strategy, 220
5.12. Meso Compounds Have Asymmetric Centers but Are Optically Inactive, 221
Problem-Solving Strategy, 223
5.13. How to Name Isomers with More than One Asymmetric Center, 225
Problem-Solving Strategy, 227
5.14. Reactions of Compounds That Contain an Asymmetric Center, 229
5.15. The Absolute Configuration of (+)-Glyceraldehyde, 230
5.16. How Enantiomers Can Be Separated, 232
5.17. Nitrogen and Phosphorus Atoms Can Be Asymmetric Centers, 233
5.18. Stereochemistry of Reactions: Regioselective, Stereoselective, and Stereospecific Reactions, 234
5.19. The Stereochemistry of Electrophilic Addition Reactions of Alkenes, 235
Cyclic Alkenes, 239
Problem-Solving Strategy, 244
5.20. The Stereochemistry of Enzyme-Catalyzed Reactions, 246
5.21. Enantiomers Can Be Distinguished by Biological Molecules, 247
The Enantiomers of Thalidomide, 249
Chiral Drugs, 250
Summary, 250
Key Terms, 251
Problems, 251
6. The Reactions of Alkynes: An Introduction to Multistep Synthesis, 258
Ethyne Chemistry or the Forward Pass?, 259
6.1. The Nomenclature of Alkynes, 260
6.2. How to Name a Compound That Has More than One Functional Group, 261
6.3. The Physical Properties of Unsaturated Hydrocarbons, 263
How a Banana Slug Knows What to Eat, 263
6.4. The Structure of Alkynes, 264
6.5. How Alkynes React, 264
6.6. Addition of Hydrogen Halides and Addition of Halogens to an Alkyne, 266
6.7. Addition of Water to an Alkyne, 269
6.8. Addition of Borane to an Alkyne: Hydroboration–Oxidation, 271
6.9. Addition of Hydrogen to an Alkyne, 272
6.10. A Hydrogen Bonded to an sp Carbon Is “Acidic”, 274
Problem-Solving Strategy, 275
Sodium Amide and Sodium, 275
6.11. Synthesis Using Acetylide Ions, 276
6.12. Designing a Synthesis I: An Introduction to Multistep Synthesis, 277
Identifying Compounds, 281
Summary, 282
Summary of Reactions, 282
Key Terms, 283
Problems, 284
7. Delocalized Electrons and Their Effect on Stability, Reactivity, and pK_a · More About Molecular Orbital Theory, 287
7.1. Benzene Has Delocalized Electrons, 288
Kekulé’s Dream, 290
7.2. The Bonding in Benzene, 291
7.3. Resonance Contributors and the Resonance Hybrid, 291
7.4. How to Draw Resonance Contributors, 293
Peptide Bonds, 295
7.5. The Predicted Stabilities of Resonance Contributors, 296
7.6. Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound, 298
Problem-Solving Strategy, 300
7.7. Examples Illustrating the Effect of Delocalized Electrons on Stability, 301
Problem-Solving Strategy, 304
7.8. A Molecular Orbital Description of Stability, 305
7.9. How Delocalized Electrons Affect pK_a, 312
7.10. Delocalized Electrons Can Affect the Product of a Reaction, 316
7.11. Thermodynamic Versus Kinetic Control of Reactions, 321
7.12. The Diels–Alder Reaction Is a 1,4-Addition Reaction, 326
Problem-Solving Strategy, 334
Summary, 335
Summary of Reactions, 336
Key Terms, 336
Problems, 337
Part 3. Substitution and Elimination Reactions, 343
8. Substitution Reactions of Alkyl Halides, 344
Survival Compounds, 345
8.1. How Alkyl Halides React, 346
8.2. The Mechanism of an S_N2 Reaction, 346
8.3. Factors That Affect S_N2 Reactions, 352
8.4. The Reversibility of an S_N2 Reaction Depends on the Basicities of the Leaving Groups in the Forward and Reverse Directions, 357
8.5. The Mechanism of an S_N1 Reaction, 361
Why Carbon Instead of Silicon?, 361
8.6. Factors That Affect S_N1 Reactions, 364
8.7. More About the Stereochemistry of S_N2 and S_N1 Reactions, 366
8.8. Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides, 368
Problem-Solving Strategy, 370
8.9. Competition Between S_N2 and S_N1 Reactions, 371
Problem-Solving Strategy, 373
8.10. The Role of the Solvent in S_N2 and S_N1 Reactions, 375
Solvation Effects, 376
Environmental Adaptation, 379
8.11. Intermolecular Versus Intramolecular Reactions, 381
8.12. Biological Methylating Reagents Have Good Leaving Groups, 382
Eradicating Termites, 383
S-Adenosylmethionine: A Natural Antidepressant, 384
Summary, 384
Summary of Reactions, 385
Key Terms, 385
Problems, 385
9. Elimination Reactions of Alkyl Halides · Competition Between Substitution and Elimination, 389
9.1. The E2 Reaction, 390
Investigating Naturally Occurring Organohalides, 390
9.2. An E2 Reaction Is Regioselective, 391
9.3. The E1 Reaction, 398
Problem-Solving Strategy, 401
9.4. Competition Between E2 and E1 Reactions, 402
9.5. E2 and E1 Reactions Are Stereoselective, 403
9.6. Elimination from Substituted Cyclohexanes, 408
9.7. A Kinetic Isotope Effect Can Help Determine a Mechanism, 412
9.8. Competition Between Substitution and Elimination, 413
9.9. Substitution and Elimination Reactions in Synthesis, 418
9.10. Consecutive E2 Elimination Reactions, 420
9.11. Designing a Synthesis II: Approaching the Problem, 421
Summary, 423
Summary of Reactions, 424
Key Terms, 425
Problems, 425
10. Reactions of Alcohols, Amines, Ethers, Epoxides, and Sulfur-Containing Compounds · Organometallic Compounds, 429
10.1. Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides, 430
The Lucas Test, 432
10.2. Other Methods for Converting Alcohols into Alkyl Halides, 434
Grain Alcohol and Wood Alcohol, 434
10.3. Converting Alcohols into Sulfonate Esters, 435
10.4. Elimination Reactions of Alcohols: Dehydration, 438
Problem-Solving Strategy, 443
Biological Dehydrations, 443
10.5. Oxidation of Alcohols, 445
10.6. Amines Do Not Undergo Substitution or Elimination Reactions but Are the Most Common Organic Bases, 447
Blood Alcohol Content, 447
Alkaloids, 448
10.7. Nucleophilic Substitution Reactions of Ethers, 449
Anesthetics, 451
10.8. Nucleophilic Substitution Reactions of Epoxides, 452
10.9. Arene Oxides, 455
Benzo[a]pyrene and Cancer, 459
10.10. Crown Ethers, 460
Chimney Sweeps and Cancer, 460
10.11. Thiols, Sulfides, and Sulfonium Salts, 462
An Ionophorous Antibiotic, 462
Mustard—A Chemical Warfare Agent, 464
Antidote to a Chemical Warfare Agent, 464
10.12. Organometallic Compounds, 465
10.13. Coupling Reactions, 469
Summary, 472
Summary of Reactions, 473
Key Terms, 476
Problems, 476
11. Radicals · Reactions of Alkanes, 481
Octane Number, 482
Fossil Fuels: A Problematic Energy Source, 482
11.1. Alkanes Are Unreactive Compounds, 483
11.2. Chlorination and Bromination of Alkanes, 483
11.3. Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron, 485
11.4. The Distribution of Products Depends on Probability and Reactivity, 486
11.5. The Reactivity–Selectivity Principle, 489
Problem-Solving Strategy, 491
11.6. Addition of Radicals to an Alkene, 493
11.7. Stereochemistry of Radical Substitution and Addition Reactions, 496
11.8. Radical Substitution of Benzylic and Allylic Hydrogens, 497
11.9. Designing a Synthesis III: More Practice with Multistep Synthesis, 500
Cyclopropane, 500
11.10. Radical Reactions Occur in Biological Systems, 502
Decaffeinated Coffee and the Cancer Scare, 503
Food Preservatives, 504
11.11. Radicals and Stratospheric Ozone, 505
Artificial Blood, 506
Summary, 506
Summary of Reactions, 507
Key Terms, 508
Problems, 508
Part 4. Identification of Organic Compounds, 511
12. Mass Spectrometry, Infrared Spectroscopy, and Ultraviolet/Visible Spectroscopy, 512
12.1. Mass Spectrometry, 513
12.2. The Mass Spectrum · Fragmentation, 515
12.3. Isotopes in Mass Spectrometry, 518
12.4. High-Resolution Mass Spectrometry Can Reveal Molecular Formulas, 520
12.5. Fragmentation Patterns of Functional Groups, 520
Mass Spectrometry in Forensics, 526
12.6. Spectroscopy and the Electromagnetic Spectrum, 528
12.7. Infrared Spectroscopy, 530
12.8. Characteristic Infrared Absorption Bands, 533
12.9. The Intensity of Absorption Bands, 534
12.10. The Position of Absorption Bands, 535
The Originator of Hooke’s Law, 535
12.11. The Position of an Absorption Band Is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding, 536
Problem-Solving Strategy, 539
12.12. The Shape of Absorption Bands, 544
12.13. The Absence of Absorption Bands, 544
12.14. Some Vibrations Are Infrared Inactive, 545
12.15. A Lesson in Interpreting Infrared Spectra, 546
12.16. Ultraviolet and Visible Spectroscopy, 549
12.17. The Beer–Lambert Law, 551
Ultraviolet Light and Sunscreens, 551
12.18. The Effect of Conjugation on λ_max, 552
12.19. The Visible Spectrum and Color, 554
12.20. Some Uses of UV/Vis Spectroscopy, 555
Anthocyanins: A Colorful Class of Compounds, 555
Summary, 557
Key Terms, 558
Problems, 559
13. NMR Spectroscopy, 569
13.1. An Introduction to NMR Spectroscopy, 569
13.2. Fourier Transform NMR, 572
Nikola Tesla (1856–1943), 572
13.3. Shielding Causes Different Hydrogens to Show Signals at Different Frequencies, 573
13.4. The Number of Signals in an ^1H NMR Spectrum, 574
Problem-Solving Strategy, 575
13.5. The Chemical Shift Tells How Far the Signal Is from the Reference Signal, 577
13.6. The Relative Positions of ^1H NMR Signals, 578
13.7. Characteristic Values of Chemical Shifts, 579
13.8. Diamagnetic Anisotropy, 582
13.9. The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal, 584
13.10. Splitting of the Signals Is Desribed by the N + 1 Rule, 586
13.11. More Examples of ^1H NMR Spectra, 591
13.12. Coupling Constants Identify Coupled Protons, 597
Problem-Solving Strategy, 599
13.13. Splitting Diagrams Explain the Multiplicity of a Signal, 600
13.14. Diastereotopic Hydrogens Are Not Chemically Equivalent, 603
13.15. The Time Dependence of NMR Spectroscopy, 604
13.16. Protons Bonded to Oxygen and Nitrogen, 605
13.17. The Use of Deuterium in ^1H NMR Spectroscopy, 607
13.18. The Resolution of ^1H NMR Spectra, 608
13.19. ^13C NMR Spectroscopy, 610
Problem-Solving Strategy, 614
13.20. DEPT ^13C NMR Spectra, 616
13.21. Two-Dimensional NMR Spectroscopy, 616
13.22. NMR Used in Medicine Is Called Magnetic Resonance Imaging, 619
Summary, 620
Key Terms, 621
Problems, 621
Part 5. Aromatic Compounds, 639
14. Aromaticity · Reactions of Benzene, 640
14.1. Aromatic Compounds Are Unusually Stable, 640
14.2. The Two Criteria for Aromaticity, 642
14.3. Applying the Criteria for Aromaticity, 643
Buckyballs and AIDS, 644
14.4. Aromatic Heterocyclic Compounds, 646
14.5. Some Chemical Consequences of Aromaticity, 647
14.6. Antiaromaticity, 649
Problem-Solving Strategy, 649
14.7. A Molecular Orbital Description of Aromaticity and Antiaromaticity, 650
14.8. Nomenclature of Monosubstituted Benzenes, 651
The Toxicity of Benzene, 652
14.9. How Benzene Reacts, 653
14.10. The General Mechanism for Electrophilic Aromatic Substitution Reactions, 654
14.11. Halogenation of Benzene, 655
14.12. Nitration of Benzene, 657
Thyroxine, 657
14.13. Sulfonation of Benzene, 658
14.14. Friedel–Crafts Acylation of Benzene, 660
14.15. Friedel–Crafts Alkylation of Benzene, 661
Incipient Primary Carbocations, 663
14.16. Alkylation of Benzene by Acylation–Reduction, 664
14.17. Using Coupling Reactions to Alkylate Benzene, 665
14.18. It Is Important to Have More Than One Way to Carry Out a Reaction, 665
14.19. How Some Substituents on a Benzene Ring Can Be Chemically Changed, 666
Summary, 670
Summary of Reactions, 671
Key Terms, 673
Problems, 673
15. Reactions of Substituted Benzenes, 677
15.1. Nomenclature of Disubstituted and Polysubstituted Benzenes, 678
Measuring Toxicity, 679
15.2. Some Substituents Increase the Reactivity of a Benzene Ring and Some Decrease Its Reactivity, 681
15.3. The Effect of Substituents on Orientation, 687
15.4. The Effect of Substituents on pK_a, 691
15.5. The Ortho–Para Ratio, 693
Problem-Solving Strategy, 693
15.6. Additional Considerations Regarding Substituent Effects, 694
15.7. Designing a Synthesis IV: Synthesis of Monosubstituted and Disubstituted Benzenes, 696
15.8. Synthesis of Trisubstituted Benzenes, 698
15.9. Synthesis of Substituted Benzenes Using Arenediazonium Salts, 699
15.10. The Arenediazonium Ion as an Electrophile, 703
15.11. The Mechanism for the Reaction of Amines with Nitrous Acid, 704
Nitrosamines and Cancer, 706
15.12. Nucleophilic Aromatic Substitution: An Addition–Elimination Mechanism, 707
15.13. Nucleophilic Aromatic Substitution: An Elimination–Addition Mechanism That Forms a Benzyne Intermediate, 709
15.14. Polycyclic Benzenoid Hydrocarbons, 711
Summary, 711
Summary of Reactions, 712
Key Terms, 714
Problems, 714
Part 6. Carbonyl Compounds, 721
16. Carbonyl Compounds I: Nucleophilic Acyl Substitution, 722
16.1. Nomenclature of Carboxylic Acids and Carboxylic Acid Derivatives, 724
16.2. Structures of Carboxylic Acids and Carboxylic Acid Derivatives, 729
16.3. Physical Properties of Carbonyl Compounds, 730
16.4. Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives, 731
The Discovery of Penicillin, 732
16.5. How Class I Carbonyl Compounds React, 733
Dalmatians: The High Cost of Black Spots, 733
Problem-Solving Strategy, 736
16.6. Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives, 737
16.7. General Mechanism for Nucleophilic Acyl Substitution Reactions, 738
16.8. Reactions of Acyl Halides, 739
16.9. Reactions of Acid Anhydrides, 742
16.10. Reactions of Esters, 743
Aspirin, 745
16.11. Acid-Catalyzed Ester Hydrolysis and Transesterification, 746
16.12. Hydroxide-Ion-Promoted Ester Hydrolysis, 751
16.13. How the Mechanism for Nucleophilic Acyl Substitution Reactions Was Confirmed, 752
16.14. Soaps, Detergents, and Micelles, 754
Making Soap, 756
16.15. Reactions of Carboxylic Acids, 757
16.16. Reactions of Amides, 758
Problem-Solving Strategy, 758
16.17. The Hydrolysis of Amides Is Catalyzed by Acids, 760
Nature’s Sleeping Pill, 760
Penicillin and Drug Resistance, 762
Penicillins in Clinical Use, 762
16.18. The Hydrolysis of an Imide: A Way to Synthesize Primary Amines, 763
16.19. The Hydrolysis of Nitriles, 764
16.20. Designing a Synthesis V: The Synthesis of Cyclic Compounds, 765
16.21. How Chemists Activate Carboxylic Acids, 767
16.22. How Cells Activate Carboxylic Acids, 768
Nerve Impulses, Paralysis, and Insecticides, 771
16.23. Dicarboxylic Acids and Their Derivatives, 772
Synthetic Polymers, 774
Dissolving Sutures, 774
Summary, 775
Summary of Reactions, 776
Key Terms, 778
Problems, 779
17. Carbonyl Compounds II: Reactions of Aldehydes and Ketones · More Reactions of Carboxylic Acid Derivatives · Reactions of α,β-Unsaturated Carbonyl Compounds, 788
17.1. Nomenclature of Aldehydes and Ketones, 790
Butanedione: An Unpleasant Compound, 792
17.2. Relative Reactivities of Carbonyl Compounds, 793
17.3. How Aldehydes and Ketones React, 795
17.4. Reactions of Carbonyl Compounds with Grignard Reagents, 796
Problem-Solving Strategy, 799
17.5. Reactions of Carbonyl Compounds with Acetylide Ions, 800
17.6. Reactions of Carbonyl Compounds with Hydride Ion, 800
17.7. Reactions of Aldehydes and Ketones with Hydrogen Cyanide, 805
17.8. Reactions of Aldehydes and Ketones with Amines and Derivatives of Amines, 806
Identifying of Aldehydes and Ketones without Using Spectroscopy, 811
17.9. Reactions of Aldehydes and Ketones with Water, 814
Preserving Biological Specimens, 815
17.10. Reactions of Aldehydes and Ketones with Alcohols, 816
Problem-Solving Strategy, 818
17.11. Protecting Groups, 819
17.12. Addition of Sulfur Nucleophiles, 822
17.13. The Wittig Reaction Forms an Alkene, 822
β-Carotene, 825
17.14. Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces, 826
17.15. Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents, 827
Enyzme-Catalyzed Carbonyl Additions, 827
Synthesizing Organic Compounds, 829
17.16. Nucleophilic Addition to α,β-Unsaturated Aldehydes and Ketones, 830
Semisynthetic Drugs, 830
Cancer Chemotherapy, 833
17.17. Nucleophilic Addition to α,β-Unsaturated Carboxylic Acid Derivatives, 834
17.18. Enzyme-Catalyzed Additions to α,β-Unsaturated Carbonyl Compounds, 835
Enzyme-Catalyzed Cis-Trans Interconversion, 835
Summary, 836
Summary of Reactions, 836
Key Terms, 840
Problems, 841
18. Carbonyl Compounds III: Reactions at the α-Carbon, 850
18.1. The Acidity of an α-Hydrogen, 851
Problem-Solving Strategy, 854
18.2. Keto–Enol Tautomers, 855
18.3. Enolization, 856
18.4. How Enols and Enolate Ions React, 857
18.5. Halogenation of the α-Carbon of Aldehydes and Ketones, 859
18.6. Halogenation of the α-Carbon of Carboxylic Acids: The Hell–Volhard–Zelinski Reaction, 861
18.7. α-Halogenated Carbonyl Compounds Are Useful in Synthesis, 862
18.8. Using LDA to Form an Enolate Ion, 863
18.9. Alkylation of the α-Carbon of Carbonyl Compounds, 864
The Synthesis of Aspirin, 865
Problem-Solving Strategy, 866
18.10. Alkylation and Acylation of the α-Carbon Using an Enamine Intermediate, 867
18.11. Alkylation of the β-Carbon: The Michael Reaction, 869
18.12. An Aldol Addition Forms β-Hydroxyaldehydes or β-Hydroxyketones, 871
18.13. Dehydration of Aldol Addition Products Forms α,β-Unsaturated Aldehydes and Ketones, 873
18.14. The Mixed Aldol Addition, 874
18.15. A Claisen Condensation Forms a β-Keto Ester, 876
18.16. The Mixed Claisen Condensation, 878
18.17. Intramolecular Condensation and Addition Reactions, 880
Problem-Solving Strategy, 883
18.18. 3-Oxocarboxylic Acids Can Be Decarboxylated, 884
18.19. The Malonic Ester Synthesis: A Way to Synthesize a Carboxylic Acid, 886
18.20. The Acetoacetic Ester Synthesis: A Way to Synthesize a Methyl Ketone, 888
18.21. Designing a Synthesis VII: Making New Carbon–Carbon Bonds, 889
18.22. Reactions at the α-Carbon in Biological Systems, 891
Summary, 895
Summary of Reactions, 896
Key Terms, 899
Problems, 899
Part 7. More About Oxidation–Reduction Reactions and Amines, 907
19. More About Oxidation–Reduction Reactions, 908
19.1. Reduction Reactions, 911
19.2. Oxidation of Alcohols, 917
The Role of Hydrates in the Oxidation of Primary Alcohols, 918
Treating Alcoholism with Antabuse, 919
Fetal Alcohol Syndrome, 919
19.3. Oxidation of Aldehydes and Ketones, 919
19.4. Designing a Synthesis VIII: Controlling Stereochemistry, 922
19.5. Hydroxylation of Alkenes, 923
19.6. Oxidative Cleavage of 1,2-Diols, 925
Problem-Solving Strategy, 925
19.7. Oxidative Cleavage of Alkenes, 926
19.8. Oxidative Cleavage of Alkynes, 931
19.9. Designing a Synthesis IX: Functional Group Interconversion, 932
Summary, 933
Summary of Reactions, 934
Key Terms, 936
Problems, 936
20. More About Amines · Heterocyclic Compounds, 943
20.1. More About Amine Nomenclature, 944
20.2. More About the Acid–Base Properties of Amines, 945
20.3. Amines React as Bases and as Nucleophiles, 946
20.4. Quaternary Ammonium Hydroxides Undergo Elimination Reactions, 947
A Useful Bad-Tasting Compound, 950
20.5. Phase-Transfer Catalysis, 951
20.6. Oxidation of Amines · The Cope Elimination Reaction, 952
20.7. Synthesis of Amines, 953
20.8. Aromatic Five-Membered-Ring Heterocycles, 955
20.9. Aromatic Six-Membered-Ring Heterocycles, 960
20.10. Amine Heterocycles Have Important Roles in Nature, 966
Porphyrin, Bilirubin, and Jaundice, 968
Summary, 969
Summary of Reactions, 969
Key Terms, 972
Problems, 972
Part 8. Bioorganic Compounds, 977
21. Carbohydrates, 978
21.1. Classification of Carbohydrates, 979
21.2. The D and L Notation, 980
21.3. The Configurations of Aldoses, 982
21.4. The Configurations of Ketoses, 983
21.5. Reactions of Monosaccharides in Basic Solutions, 984
21.6. Redox Reactions of Monosaccharides, 985
21.7. Monosaccharides Form Crystalline Osazones, 987
Measuring the Blood Glucose Levels in Diabetes, 988
21.8. Lengthening the Chain: The Kiliani–Fischer Synthesis, 989
21.9. Shortening the Chain: The Wohl Degradation, 990
21.10. Stereochemistry of Glucose: The Fischer Proof, 990
21.11. Monosaccharides Form Cyclic Hemiacetals, 992
Glucose/Dextrose, 992
21.12. Glucose Is the Most Stable Aldohexose, 995
21.13. Formation of Glycosides, 997
21.14. The Anomeric Effect, 999
21.15. Reducing and Nonreducing Sugars, 999
21.16. Disaccharides, 1000
Lactose Intolerance, 1002
Galactosemia, 1002
21.17. Polysaccharides, 1003
Why the Dentist Is Right, 1004
21.18. Some Naturally Occurring Products Derived from Carbohydrates, 1006
Controlling Fleas, 1006
Heparin, 1007
Vitamin C, 1008
21.19. Carbohydrates on Cell Surfaces, 1008
21.20. Synthetic Sweeteners, 1010
The Wonder of Discovery, 1011
Acceptable Daily Intake, 1011
Summary, 1012
Summary of Reactions, 1012
Key Terms, 1014
Problems, 1014
22. Amino Acids, Peptides, and Proteins, 1017
22.1. Classification and Nomenclature of Amino Acids, 1018
Proteins and Nutrition, 1022
22.2. Configuration of the Amino Acids, 1023
Amino Acids and Disease, 1023
A Peptide Antibiotic, 1024
22.3. Acid–Base Properties of Amino Acids, 1024
22.4. The Isoelectric Point, 1026
22.5. Separation of Amino Acids, 1028
22.6. Synthesis of Amino Acids, 1032
Water Softeners: Examples of Cation-Exchange Chromatography, 1032
22.7. Resolution of Racemic Mixtures of Amino Acids, 1035
22.8. Peptide Bonds and Disulfide Bonds, 1035
Hair: Straight or Curly?, 1038
22.9. Some Interesting Peptides, 1039
22.10. The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation, 1040
22.11. Automated Peptide Synthesis, 1043
22.12. An Introduction to Protein Structure, 1045
22.13. How to Determine the Primary Structure of a Peptide or a Protein, 1046
Primary Structure and Evolution, 1046
Problem-Solving Strategy, 1048
22.14. Secondary Structure of Proteins, 1052
22.15. Tertiary Structure of Proteins, 1055
β-Peptides: An Attempt to Improve on Nature, 1055
22.16. Quaternary Structure of Proteins, 1057
22.17. Protein Denaturation, 1058
Summary, 1058
Key Terms, 1059
Problems, 1059
23. Catalysis, 1063
23.1. Catalysis in Organic Reactions, 1065
The Nobel Prize, 1065
23.2. Acid Catalysis, 1066
23.3. Base Catalysis, 1069
23.4. Nucleophilic Catalysis, 1070
23.5. Metal-Ion Catalysis, 1072
23.6. Intramolecular Reactions, 1074
23.7. Intramolecular Catalysis, 1076
23.8. Catalysis in Biological Reactions, 1079
23.9. Enzyme-Catalyzed Reactions, 1081
Summary, 1094
Key Terms, 1094
Problems, 1095
24. The Organic Mechanisms of the Coenzymes, 1098
Vitamin B_1, 1100
“Vitamine”—An Amine Required for Life, 1100
24.1. An Introduction to Metabolism, 1101
24.2. The Vitamin Needed for Many Redox Reactions: Vitamin B_3, 1101
Niacin Deficiency, 1102
24.3. Flavin Adenine Dinucleotide and Flavin Mononucleotide: Vitamin B_2, 1107
24.4. Thiamine Pyrophosphate: Vitamin B_1, 1110
24.5. Biotin: Vitamin H, 1115
24.6. Pyridoxal Phosphate: Vitamin B_6, 1117
Assessing the Damage After a Heart Attack, 1121
24.7. Coenzyme B12: Vitamin B_12, 1124
24.8. Tetrahydrofolate: Folic Acid, 1126
24.9. Vitamin KH_2: Vitamin K, 1131
The First Antibiotics, 1131
Too Much Broccoli, 1133
Summary, 1133
Key Terms, 1134
Problems, 1134
25. The Chemistry of Metabolism, 1137
25.1. The Four Stages of Catabolism, 1138
Differences in Metabolism, 1138
25.2. ATP Is the Carrier of Chemical Energy, 1139
25.3. There Are Three Mechanisms for Phosphoryl Transfer Reactions, 1141
25.4. The “High-Energy” Character of Phosphoanhydride Bonds, 1144
25.5. Why ATP Is Kinetically Stable in a Cell, 1145
25.6. The Catabolism of Fats, 1146
25.7. The Catabolism of Carbohydrates, 1149
25.8. The Fates of Pyruvate, 1152
Problem-Solving Strategy, 1152
25.9. The Catabolism of Proteins, 1153
25.10. The Citric Acid Cycle, 1155
Phenylketonuria: An Inborn Error of Metabolism, 1155
Alcaptonuria, 1155
25.11. Oxidative Phosphorylation, 1158
25.12. Anabolism, 1159
Basal Metabolic Rate, 1159
Summary, 1159
Key Terms, 1160
Problems, 1160
26. Lipids, 1162
26.1. Fatty Acids Are Long-Chain Carboxylic Acids, 1163
26.2. Waxes Are High-Molecular-Weight Esters, 1165
26.3. Fats and Oils, 1165
Omega Fatty Acids, 1165
Olestra: Nonfat with Flavor, 1169
Whales and Echolocation, 1169
26.4. Phospholipids and Sphingolipids Are Components of Membranes, 1170
Snake Venom, 1172
Is Chocolate a Health Food?, 1172
26.5. Prostaglandins Regulate Physiological Responses, 1173
Multiple Sclerosis and the Myelin Sheath, 1173
26.6. Terpenes Contain Carbon Atoms in Multiples of Five, 1177
26.7. Vitamin A Is a Diterpene, 1179
26.8. How Terpenes Are Biosynthesized, 1180
26.9. Steroids Are Chemical Messengers, 1186
Cholesterol and Heart Disease, 1189
Clinical Treatment of High Cholesterol, 1190
26.10. How Nature Synthesizes Cholesterol, 1190
26.11. Synthetic Steroids, 1192
Summary, 1192
Key Terms, 1193
Problems, 1193
27. Nucleosides, Nucleotides, and Nucleic Acids, 1197
27.1. Nucleosides and Nucleotides, 1198
The Structure of DNA: Watson, Crick, Franklin, and Wilkins, 1199
27.2. Other Important Nucleotides, 1202
27.3. Nucleic Acids Are Composed of Nucleotide Subunits, 1202
27.4. DNA Is Stable but RNA Is Easily Cleaved, 1207
27.5. Biosynthesis of DNA Is Called Replication, 1207
27.6. Biosynthesis of RNA Is Called Transcription, 1209
27.7. There Are Three Kinds of RNA, 1210
27.8. Biosynthesis of Proteins Is Called Translation, 1212
27.9. Why DNA Contains Thymine Instead of Uracil, 1216
Sickle Cell Anemia, 1216
Antibiotics That Act by Inhibiting Translation, 1216
27.10. How the Base Sequence of DNA Is Determined, 1217
27.11. Polymerase Chain Reaction (PCR), 1220
27.12. Genetic Engineering, 1221
DNA Fingerprinting, 1221
27.13. Laboratory Synthesis of DNA Strands, 1222
Resisting Herbicides, 1222
Summary, 1227
Key Terms, 1228
Problems, 1228
Part 9. Special Topics in Organic Chemistry, 1231
28. Synthetic Polymers, 1232
28.1. There Are Two Major Classes of Synthetic Polymers, 1233
28.2. Chain-Growth Polymers, 1234
Recycling Symbols, 1239
28.3. Stereochemistry of Polymerization · Ziegler–Natta Catalysts, 1245
28.4. Polymerization of Dienes · The Manufacture of Rubber, 1246
28.5. Copolymers, 1248
28.6. Step–Growth Polymers, 1249
28.7. Physical Properties of Polymers, 1254
Designing a Polymer, 1255
Summary, 1257
Key Terms, 1258
Problems, 1258
29. Pericyclic Reactions, 1262
29.1. Three Kinds of Pericyclic Reations, 1263
29.2. Molecular Orbitals and Orbital Symmetry, 1265
29.3. Electrocyclic Reactions, 1269
29.4. Cycloaddition Reactions, 1275
Luminescence, 1278
29.5. Sigmatropic Rearrangements, 1279
29.6. Pericyclic Reactions in Biological Systems, 1284
The Sunshine Vitamin, 1286
29.7. Summary of the Selection Rules for Pericyclic Reactions, 1287
Summary, 1287
Key Terms, 1288
Problems, 1288
30. The Organic Chemistry of Drugs: Discovery and Design, 1293
30.1. Naming Drugs, 1297
30.2. Lead Compounds, 1297
30.3. Molecular Modification, 1298
30.4. Random Screening, 1300
30.5. Serendipity in Drug Development, 1302
Drug Safety, 1302
30.6. Receptors, 1304
30.7. Drugs as Enzyme Inhibitors, 1307
30.8. Designing a Suicide Substrate, 1311
30.9. Quantitative Structure–Activity Relationships (QSAR), 1312
30.10. Molecular Modeling, 1314
30.11. Combinatorial Organic Synthesis, 1314
30.12. Antiviral Drugs, 1316
30.13. Economics of Drugs · Governmental Regulations, 1317
Orphan Drugs, 1317
Summary, 1317
Key Terms, 1318
Problems, 1318
Appendices, A-1
I. Physical Properties of Organic Compounds, A-1
II. pK_a Values, A-8
III. Derivations of Rate Laws, A-10
IV. Summary of Methods Used to Synthesize a Particular Functional Group, A-13
V. Summary of Methods Employed to Form Carbon–Carbon Bonds, A-17
VI. Spectroscopy Tables, A-18
Answers to Selected Problems, A-24
Glossary, G-1
Photo Credits, P-1
Index, I-1

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