Organic Chemistry: Structure and Function

Cover Page......Page 2
IFC......Page 3
About the Authors......Page 5
Title Page......Page 7
Copyright Page......Page 8
Brief Contents......Page 9
Contents......Page 14
Preface: A User’s Guide to Organic Chemistry: Structure and Function......Page 34
Chapter 1 Structure and Bonding in Organic Molecules......Page 60
1-1 The Scope of Organic Chemistry: An Overview......Page 63
Real Life: Nature 1-1 Urea: From Urine to Wöhler’s Synthesis to Industrial Fertilizer......Page 67
1-2 Coulomb Forces: A Simplified View of Bonding......Page 71
1-3 Ionic and Covalent Bonds: The Octet Rule......Page 76
1-4 Electron-Dot Model of Bonding: Lewis Structures......Page 90
1-5 Resonance Forms......Page 101
1-6 Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus......Page 115
1-7 Molecular Orbitals and Covalent Bonding......Page 140
1-8 Hybrid Orbitals: Bonding in Complex Molecules......Page 164
1-9 Structures and Formulas of Organic Molecules......Page 207
1-10 A General Strategy for Solving Problems in Organic Chemistry......Page 214
Worked Examples: Integrating the Concepts......Page 219
Important Concepts......Page 223
Problems......Page 226
Acids and Bases, Polar and Nonpolar Molecules......Page 240
2-1 Kinetics and Thermodynamics of Simple Chemical Processes......Page 244
2-2 Keys to Success: Using Curved “Electron-Pushing” Arrows to Describe Chemical Reactions......Page 261
2-3 Acids and Bases......Page 269
Real Life: Medicine 2-1 Stomach Acid, Peptic Ulcers, Pharmacology, and Organic Chemistry......Page 270
2-4 Functional Groups: Centers of Reactivity......Page 290
2-5 Straight-Chain and Branched Alkanes......Page 296
2-6 Naming the Alkanes......Page 299
2-7 Structural and Physical Properties of Alkanes......Page 313
Real Life: Nature 2-2 “Sexual Swindle” by Means of Chemical Mimicry......Page 318
2-8 Rotation about Single Bonds: Conformations......Page 321
2-9 Rotation in Substituted Ethanes......Page 328
2-10 Worked Examples: Integrating the Concepts......Page 336
Important Concepts......Page 342
Problems......Page 344
Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity......Page 358
3-1 Strength of Alkane Bonds: Radicals......Page 361
3-2 Structure of Alkyl Radicals: Hyperconjugation......Page 371
3-3 Conversion of Petroleum: Pyrolysis......Page 377
Real Life: Sustainability 3-1 Sustainability and the Needs of the 21st Century: “Green” Chemistry......Page 381
3-4 Chlorination of Methane: The Radical Chain Mechanism......Page 384
3-5 Other Radical Halogenations of Methane......Page 396
3-6 Keys to Success: Using the “Known” Mechanism as a Model for the “Unknown”......Page 408
3-7 Chlorination of Higher Alkanes: Relative Reactivity and Selectivity......Page 410
3-8 Selectivity in Radical Halogenation with Fluorine and Bromine......Page 418
3-9 Synthetic Radical Halogenation......Page 422
Real Life: Medicine 3-2 Chlorination, Chloral, and DDT: The Quest to Eradicate Malaria......Page 425
3-10 Synthetic Chlorine Compounds and the Stratospheric Ozone Layer......Page 427
3-11 Combustion and the Relative Stabilities of Alkanes......Page 433
3-12 Worked Examples: Integrating the Concepts......Page 438
Important Concepts......Page 444
Problems......Page 446
Chapter 4 Cycloalkanes......Page 456
4-1 Names and Physical Properties of Cycloalkanes......Page 459
4-2 Ring Strain and the Structure of Cycloalkanes......Page 467
4-3 Cyclohexane: A Strain-Free Cycloalkane......Page 481
4-4 Substituted Cyclohexanes......Page 493
4-5 Larger Cycloalkanes......Page 505
4-6 Polycyclic Alkanes......Page 506
Real Life: Materials 4-1 Cyclohexane, Adamantane, and Diamandoids: Diamond “Molecules”......Page 511
Real Life: Medicine 4-2 Cholesterol: How Is It Bad and How Bad Is It?......Page 521
Real Life: Medicine 4-3 Controlling Fertility: From “the Pill” to RU-486 to Male Contraceptives......Page 524
4-8 Worked Examples: Integrating the Concepts......Page 529
Important Concepts......Page 535
Problems......Page 537
Chapter 5 Stereoisomers......Page 553
5-1 Chiral Molecules......Page 559
Real Life: Nature 5-1 Chiral Substances in Nature......Page 563
5-2 Optical Activity......Page 566
5-3 Absolute Configuration: R,S Sequence Rules......Page 574
5-4 Fischer Projections......Page 585
5-5 Molecules Incorporating Several Stereocenters: Diastereomers......Page 592
Real Life: Nature 5-2 Stereoisomers of Tartaric Acid......Page 599
5-6 Meso Compounds......Page 604
5-7 Stereochemistry in Chemical Reactions......Page 611
Real Life: Medicine 5-3 Chiral Drugs—Racemic or Enantiomerically Pure?......Page 615
Real Life: Medicine 5-4 Why Is Nature “Handed”?......Page 627
5-8 Resolution: Separation of Enantiomers......Page 632
5-9 Worked Examples: Integrating the Concepts......Page 642
Important Concepts......Page 647
Problems......Page 649
Bimolecular Nucleophilic Substitution......Page 669
6-1 Physical Properties of Haloalkanes......Page 674
Real Life: Medicine 6-1 Fluorinated Pharmaceuticals......Page 679
6-2 Nucleophilic Substitution......Page 682
6-3 Reaction Mechanisms Involving Polar Functional Groups: Using “Electron-Pushing” Arrows......Page 688
6-4 A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics......Page 693
6-5 Frontside or Backside Attack? Stereochemistry of the SN2 Reaction......Page 701
6-6 Consequences of Inversion in SN2 Reactions......Page 709
6-7 Structure and SN2 Reactivity: The Leaving Group......Page 715
6-8 Structure and SN2 Reactivity: The Nucleophile......Page 720
6-9 Keys to Success: Choosing Among Multiple Mechanistic Pathways......Page 743
6-10 Structure and SN2 Reactivity: The Substrate......Page 748
6-11 The SN2 Reaction at a Glance......Page 757
6-12 Worked Examples: Integrating the Concepts......Page 761
Important Concepts......Page 765
Problems......Page 767
Unimolecular Substitution and Pathways of Elimination......Page 779
7-1 Solvolysis of Tertiary and Secondary Haloalkanes......Page 785
7-2 Unimolecular Nucleophilic Substitution......Page 788
7-3 Stereochemical Consequences of SN1 Reactions......Page 797
7-4 Effects of Solvent, Leaving Group, and Nucleophile on Unimolecular Substitution......Page 802
7-5 Effect of the Alkyl Group on the SN1 Reaction: Carbocation Stability......Page 809
Real Life: Medicine 7-1 Unusually Stereoselective SN1 Displacement in Anticancer Drug Synthesis......Page 819
7-6 Unimolecular Elimination: E1......Page 821
7-7 Bimolecular Elimination: E2......Page 830
7-8 Keys to Success: Substitution versus Elimination—Structure Determines Function......Page 839
7-9 Summary of Reactivity of Haloalkanes......Page 845
7-10 Worked Examples: Integrating the Concepts......Page 850
New Reactions......Page 855
Important Concepts......Page 856
Problems......Page 857
Properties, Preparation, and Strategy of Synthesis......Page 879
8-1 Naming the Alcohols......Page 883
8-2 Structural and Physical Properties of Alcohols......Page 887
8-3 Alcohols as Acids and Bases......Page 893
8-4 Synthesis of Alcohols by Nucleophilic Substitution......Page 900
8-5 Synthesis of Alcohols: Oxidation–Reduction Relation Between Alcohols and Carbonyl Compounds......Page 902
Real Life: Medicine 8-1 Oxidation and Reduction in the Body......Page 905
Real Life: Medicine 8-2 Don’t Drink and Drive: The Breath Analyzer Test......Page 917
8-6 Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis......Page 924
8-7 Organometallic Reagents in the Synthesis of Alcohols......Page 933
8-8 Keys to Success: An Introduction to Synthetic Strategy......Page 937
Real Life: Chemistry 8-3 What Magnesium Does Not Do, Copper Can: Alkylation of Organometallics......Page 939
8-9 Worked Examples: Integrating the Concepts......Page 959
New Reactions......Page 965
Important Concepts......Page 968
Problems......Page 971
Chapter 9 Further Reactions of Alcohols and the Chemistry of Ethers......Page 986
9-1 Reactions of Alcohols with Base: Preparation of Alkoxides......Page 994
9-2 Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols......Page 997
9-3 Carbocation Rearrangements......Page 1003
9-4 Esters from Alcohols and Haloalkane Synthesis......Page 1019
9-5 Names and Physical Properties of Ethers......Page 1029
Real Life: Nature 9-1 Chemiluminescence of 1,2-Dioxacyclobutanes......Page 1036
9-7 Synthesis of Ethers: Alcohols and Mineral Acids......Page 1049
9-8 Reactions of Ethers......Page 1054
Real Life: Medicine 9-2 Protecting Groups in the Synthesis of Testosterone......Page 1058
9-9 Reactions of Oxacyclopropanes......Page 1061
Real Life: Chemistry 9-3 Hydrolytic Kinetic Resolution of Oxacyclopropanes......Page 1068
9-10 Sulfur Analogs of Alcohols and Ethers......Page 1073
9-11 Physiological Properties and Uses of Alcohols and Ethers......Page 1081
9-12 Worked Examples: Integrating the Concepts......Page 1091
New Reactions......Page 1096
Important Concepts......Page 1101
Problems......Page 1103
Chapter 10 Using Nuclear Magnetic Resonance Spectroscopy to Deduce Structure......Page 1127
10-1 Physical and Chemical Tests......Page 1130
10-2 Defining Spectroscopy......Page 1132
10-3 Hydrogen Nuclear Magnetic Resonance......Page 1141
Real Life: Spectroscopy 10-1 Recording an NMR Spectrum......Page 1166
10-4 Using NMR Spectra to Analyze Molecular Structure: The Proton Chemical Shift......Page 1170
10-5 Tests for Chemical Equivalence......Page 1183
Real Life: Medicine 10-2 Magnetic Resonance Imaging (MRI) in Medicine......Page 1193
10-6 Integration of NMR Signals......Page 1196
10-7 Spin–Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens......Page 1202
10-8 Spin–Spin Splitting: Some Complications......Page 1230
Real Life: Spectroscopy 10-3 The Nonequivalence of Diastereotopic Hydrogens......Page 1235
10-9 Carbon-13 Nuclear Magnetic Resonance......Page 1249
Real Life: Spectroscopy 10-4 How to Determine Atom Connectivity in NMR......Page 1276
Real Life: Medicine 10-5 Structural Characterization of Natural and “Unnatural” Products: An Antioxidant from Grape Seeds and a Fake Drug in Herbal Medicines......Page 1280
10-10 Worked Examples: Integrating the Concepts......Page 1286
Important Concepts......Page 1294
Problems......Page 1297
Chapter 11 Alkenes: Infrared Spectroscopy and Mass Spectrometry......Page 1318
11-1 Naming the Alkenes......Page 1322
11-2 Structure and Bonding in Ethene: The Pi Bond......Page 1333
11-3 Physical Properties of Alkenes......Page 1373
11-4 Nuclear Magnetic Resonance of Alkenes......Page 1376
Real Life: Medicine 11-1 NMR of Complex Molecules: The Powerfully Regulating Prostaglandins......Page 1392
11-5 Catalytic Hydrogenation of Alkenes: Relative Stability of Double Bonds......Page 1394
11-6 Preparation of Alkenes from Haloalkanes and Alkyl Sulfonates: Bimolecular Elimination Revisited......Page 1400
11-7 Preparation of Alkenes by Dehydration of Alcohols......Page 1411
11-8 Infrared Spectroscopy......Page 1414
11-9 Measuring the Molecular Mass of Organic Compounds: Mass Spectrometry......Page 1428
Real Life: Medicine 11-2 Detecting Performance-Enhancing Drugs Using Mass Spectrometry......Page 1435
11-10 Fragmentation Patterns of Organic Molecules......Page 1439
11-11 Degree of Unsaturation: Another Aid to Identifying Molecular Structure......Page 1453
11-12 Worked Examples: Integrating the Concepts......Page 1460
New Reactions......Page 1466
Important Concepts......Page 1468
Problems......Page 1471
Chapter 12 Reactions of Alkenes......Page 1493
12-1 Why Addition Reactions Proceed: Thermodynamic Feasibility......Page 1498
12-2 Catalytic Hydrogenation......Page 1501
12-3 Basic and Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides......Page 1510
12-4 Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control......Page 1520
12-5 Electrophilic Addition of Halogens to Alkenes......Page 1526
12-6 The Generality of Electrophilic Addition......Page 1533
12-7 Oxymercuration–Demercuration: A Special Electrophilic Addition......Page 1541
Real Life: Medicine 12-1 Juvenile Hormone Analogs in the Battle Against Insect-Borne Diseases......Page 1543
12-8 Hydroboration–Oxidation: A Stereospecific Anti-Markovnikov Hydration......Page 1550
12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis......Page 1557
12-10 Oxacyclopropane (Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids......Page 1562
12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide......Page 1567
Real Life: Medicine 12-2 Synthesis of Antitumor Drugs: Sharpless Enantioselective Oxacyclopropanation (Epoxidation) and Dihydroxylation......Page 1569
12-12 Oxidative Cleavage: Ozonolysis......Page 1572
12-13 Radical Additions: Anti-Markovnikov Product Formation......Page 1578
12-14 Dimerization, Oligomerization, and Polymerization of Alkenes......Page 1584
12-15 Synthesis of Polymers......Page 1587
12-16 Ethene: An Important Industrial Feedstock......Page 1595
12-17 Alkenes in Nature: Insect Pheromones......Page 1597
Real Life: Medicine 12-3 Alkene Metathesis Transposes the Termini of Two Alkenes: Construction of Rings......Page 1599
12-18 Worked Examples: Integrating the Concepts......Page 1604
New Reactions......Page 1610
Important Concepts......Page 1615
Problems......Page 1617
The Carbon–Carbon Triple Bond......Page 1639
13-1 Naming the Alkynes......Page 1642
13-2 Properties and Bonding in the Alkynes......Page 1646
13-3 Spectroscopy of the Alkynes......Page 1658
13-4 Preparation of Alkynes by Double Elimination......Page 1672
13-5 Preparation of Alkynes from Alkynyl Anions......Page 1676
13-6 Reduction of Alkynes: The Relative Reactivity of the Two Pi Bonds......Page 1679
13-7 Electrophilic Addition Reactions of Alkynes......Page 1688
13-8 Anti-Markovnikov Additions to Triple Bonds......Page 1697
13-9 Chemistry of Alkenyl Halides......Page 1701
Real Life: Synthesis 13-1 Metal-Catalyzed Stille, Suzuki, and Sonogashira Coupling Reactions......Page 1703
13-10 Ethyne as an Industrial Starting Material......Page 1706
13-11 Alkynes in Nature and in Medicine......Page 1711
13-12 Worked Examples: Integrating the Concepts......Page 1717
New Reactions......Page 1721
Important Concepts......Page 1725
Problems......Page 1727
Investigation by Ultraviolet and Visible Spectroscopy......Page 1746
14-1 Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System......Page 1751
14-2 Radical Allylic Halogenation......Page 1768
14-3 Nucleophilic Substitution of Allylic Halides: SN1 and SN2......Page 1773
14-4 Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles......Page 1777
14-5 Two Neighboring Double Bonds: Conjugated Dienes......Page 1779
14-6 Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control......Page 1796
14-7 Delocalization Among More than Two Pi Bonds: Extended Conjugation and Benzene......Page 1807
14-8 A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition......Page 1812
Real Life: Materials 14-1 Organic Polyenes Conduct Electricity......Page 1828
Real Life: Sustainability 14-2 The Diels-Alder Reaction is “Green”......Page 1837
14-9 Electrocyclic Reactions......Page 1843
14-10 Polymerization of Conjugated Dienes: Rubber......Page 1859
14-11 Electronic Spectra: Ultraviolet and Visible Spectroscopy......Page 1867
Real Life: Spectroscopy 14-3 The Contributions of IR, MS, and UV to the Characterization of Viniferone......Page 1880
14-12 Worked Examples: Integrating the Concepts......Page 1886
New Reactions......Page 1893
Important Concepts......Page 1896
Problems......Page 1898
Interlude......Page 1914
A Summary of Organic Reaction Mechanisms......Page 1915
Electrophilic Aromatic Substitution......Page 1921
15-1 Naming the Benzenes......Page 1926
15-2 Structure and Resonance Energy of Benzene: A First Look at Aromaticity......Page 1933
15-3 Pi Molecular Orbitals of Benzene......Page 1946
15-4 Spectral Characteristics of the Benzene Ring......Page 1956
Real Life: Materials 15-1 Compounds Made of Pure Carbon: Graphite, Graphene, Diamond, and Fullerenes......Page 1976
15-5 Polycyclic Aromatic Hydrocarbons......Page 1981
15-6 Other Cyclic Polyenes: Hückel’s Rule......Page 1995
15-7 Hückel’s Rule and Charged Molecules......Page 2008
15-8 Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution......Page 2015
15-9 Halogenation of Benzene: The Need for a Catalyst......Page 2022
15-10 Nitration and Sulfonation of Benzene......Page 2027
15-11 Friedel-Crafts Alkylation......Page 2034
15-12 Limitations of Friedel-Crafts Alkylations......Page 2042
15-13 Friedel-Crafts Acylation......Page 2046
15-14 Worked Examples: Integrating the Concepts......Page 2055
New Reactions......Page 2061
Important Concepts......Page 2063
Problems......Page 2066
Substituents Control Regioselectivity......Page 2087
16-1 Activation or Deactivation by Substituents on a Benzene Ring......Page 2091
16-2 Directing Electron-Donating Effects of Alkyl Groups......Page 2097
16-3 Directing Effects of Substituents in Conjugation with the Benzene Ring......Page 2107
Real Life: Materials 16-1 Explosive Nitroarenes: TNT and Picric Acid......Page 2111
16-4 Electrophilic Attack on Disubstituted Benzenes......Page 2123
16-5 Keys to Success: Synthetic Strategies Toward Substituted Benzenes......Page 2130
16-6 Reactivity of Polycyclic Benzenoid Hydrocarbons......Page 2143
16-7 Polycyclic Aromatic Hydrocarbons and Cancer......Page 2149
16-8 Worked Examples: Integrating the Concepts......Page 2156
New Reactions......Page 2162
Important Concepts......Page 2164
Problems......Page 2166
The Carbonyl Group......Page 2186
17-1 Naming the Aldehydes and Ketones......Page 2189
17-2 Structure of the Carbonyl Group......Page 2196
17-3 Spectroscopic Properties of Aldehydes and Ketones......Page 2200
17-4 Preparation of Aldehydes and Ketones......Page 2216
17-5 Reactivity of the Carbonyl Group: Mechanisms of Addition......Page 2221
17-6 Addition of Water to Form Hydrates......Page 2227
17-7 Addition of Alcohols to Form Hemiacetals and Acetals......Page 2232
17-8 Acetals as Protecting Groups......Page 2239
17-9 Nucleophilic Addition of Ammonia and Its Derivatives......Page 2247
Real Life: Biochemistry 17-1 Imines Mediate the Biochemistry of Amino Acids......Page 2250
17-10 Deoxygenation of the Carbonyl Group......Page 2260
17-11 Addition of Hydrogen Cyanide to Give Cyanohydrins......Page 2265
17-12 Addition of Phosphorus Ylides: The Wittig Reaction......Page 2267
17-13 Oxidation by Peroxycarboxylic Acids: The Baeyer-Villiger Oxidation......Page 2274
17-14 Oxidative Chemical Tests for Aldehydes......Page 2277
17-15 Worked Examples: Integrating the Concepts......Page 2281
New Reactions......Page 2285
Important Concepts......Page 2290
Problems......Page 2294
þÿ±......Page 2313
18-1 Acidity of Aldehydes and Ketones: Enolate Ions......Page 2318
18-2 Keto–Enol Equilibria......Page 2326
18-3 Halogenation of Aldehydes and Ketones......Page 2335
18-4 Alkylation of Aldehydes and Ketones......Page 2339
18-5 Attack by Enolates on the Carbonyl Function: Aldol Condensation......Page 2345
Real Life: Biology And Medicine 18-1 Stereoselective Aldol Reactions in Nature and in the Laboratory: “Organocatalysis”......Page 2353
18-6 Crossed Aldol Condensation......Page 2357
18-7 Keys to Success: Competitive Reaction Pathways and the Intramolecular Aldol Condensation......Page 2361
Real Life: Nature 18-2 Absorption of Photons by Unsaturated Aldehydes Enables Vision......Page 2365
18-8 Properties of [H9251],[H9252]-Unsaturated Aldehydes and Ketones......Page 2369
18-9 Conjugate Additions to [H9251],[H9252]-Unsaturated Aldehydes and Ketones......Page 2375
18-10 1,2- and 1,4-Additions of Organometallic Reagents......Page 2380
18-11 Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation......Page 2387
18-12 Worked Examples: Integrating the Concepts......Page 2396
New Reactions......Page 2401
Important Concepts......Page 2406
Problems......Page 2407
Chapter 19 Carboxylic Acids......Page 2426
19-1 Naming the Carboxylic Acids......Page 2429
19-2 Structural and Physical Properties of Carboxylic Acids......Page 2435
19-3 Spectroscopy and Mass Spectrometry of Carboxylic Acids......Page 2439
19-4 Acidic and Basic Character of Carboxylic Acids......Page 2451
19-5 Carboxylic Acid Synthesis in Industry......Page 2457
19-6 Methods for Introducing the Carboxy Functional Group......Page 2459
19-7 Substitution at the Carboxy Carbon: The Addition–Elimination Mechanism......Page 2465
19-8 Carboxylic Acid Derivatives: Acyl Halides and Anhydrides......Page 2473
19-9 Carboxylic Acid Derivatives: Esters......Page 2480
19-10 Carboxylic Acid Derivatives: Amides......Page 2488
19-11 Reduction of Carboxylic Acids by Lithium Aluminum Hydride......Page 2492
19-12 Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction......Page 2494
Real Life: Materials 19-1 Long-Chain Carboxylates and Sulfonates Make Soaps and Detergents......Page 2497
Real Life: Health 19-2 Artery-Clogging Trans Fatty Acids Phasing Out......Page 2503
Real Life: Materials 19-3 Green Plastics, Fibers, and Energy from Biomass-Derived Hydroxyesters......Page 2507
19-14 Worked Examples: Integrating the Concepts......Page 2513
New Reactions......Page 2519
Important Concepts......Page 2523
Problems......Page 2526
Chapter 20 Carboxylic Acid Derivatives......Page 2545
20-1 Relative Reactivities, Structures, and Spectra of Carboxylic Acid Derivatives......Page 2548
20-2 Chemistry of Acyl Halides......Page 2558
20-3 Chemistry of Carboxylic Anhydrides......Page 2567
20-4 Chemistry of Esters......Page 2571
20-5 Esters in Nature: Waxes, Fats, Oils, and Lipids......Page 2585
Real Life: Sustainability 20-1 Moving Away from Petroleum: Green Fuels from Vegetable Oil......Page 2587
20-6 Amides: The Least Reactive Carboxylic Acid Derivatives......Page 2591
Real Life: Medicine 20-2 Killing the Bugs that Kill the Drugs: Antibiotic Wars......Page 2595
20-7 Amidates and Their Halogenation: The Hofmann Rearrangement......Page 2604
20-8 Alkanenitriles: A Special Class of Carboxylic Acid Derivatives......Page 2610
20-9 Worked Examples: Integrating the Concepts......Page 2619
New Reactions......Page 2625
Important Concepts......Page 2631
Problems......Page 2633
Functional Groups Containing Nitrogen......Page 2652
21-1 Naming the Amines......Page 2656
Real Life: Medicine 21-1 Physiologically Active Amines and Weight Control......Page 2659
21-2 Structural and Physical Properties of Amines......Page 2665
21-3 Spectroscopy of the Amine Group......Page 2669
21-4 Acidity and Basicity of Amines......Page 2681
21-5 Synthesis of Amines by Alkylation......Page 2691
21-6 Synthesis of Amines by Reductive Amination......Page 2697
21-7 Synthesis of Amines from Carboxylic Amides......Page 2704
21-8 Reactions of Quaternary Ammonium Salts: Hofmann Elimination......Page 2706
21-9 Mannich Reaction: Alkylation of Enols by Iminium Ions......Page 2709
Real Life: Medicine 21-2 Sodium Nitrite as a Food Additive, N-Nitrosodialkanamines, and Cancer......Page 2716
Real Life: Materials 21-3 Amines in Industry: Nylon, the “Miracle Fiber”......Page 2726
21-11 Worked Examples: Integrating the Concepts......Page 2732
New Reactions......Page 2738
Important Concepts......Page 2743
Problems......Page 2744
Alkylbenzenes, Phenols, and Anilines......Page 2764
22-1 Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization......Page 2767
22-2 Oxidations and Reductions of Substituted Benzenes......Page 2779
Real Life: Medicine 22-1 Two Phenols in the News: Bisphenol A and Resveratrol......Page 2789
22-4 Preparation of Phenols: Nucleophilic Aromatic Substitution......Page 2799
22-5 Alcohol Chemistry of Phenols......Page 2818
Real Life: Medicine 22-2 Aspirin: The Miracle Drug......Page 2820
22-6 Electrophilic Substitution of Phenols......Page 2824
22-7 An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement......Page 2833
22-8 Oxidation of Phenols: Benzoquinones......Page 2840
Real Life: Biology 22-3 Chemical Warfare in Nature: The Bombardier Beetle......Page 2841
22-9 Oxidation-Reduction Processes in Nature......Page 2845
22-10 Arenediazonium Salts......Page 2855
22-11 Electrophilic Substitution with Arenediazonium Salts: Diazo Coupling......Page 2863
22-12 Worked Examples: Integrating the Concepts......Page 2868
New Reactions......Page 2872
Important Concepts......Page 2880
Problems......Page 2881
þÿ......Page 2906
þÿ......Page 2910
Real Life: Nature 23-1 Claisen Condensations Assemble Biological Molecules......Page 2919
þÿ......Page 2929
þÿ......Page 2939
23-4 Acyl Anion Equivalents: Preparation of [H9251]-Hydroxyketones......Page 2944
Real Life: Nature 23-2 Thiamine: A Natural, Metabolically Active Thiazolium Salt......Page 2951
23-5 Worked Examples: Integrating the Concepts......Page 2957
New Reactions......Page 2963
Important Concepts......Page 2966
Problems......Page 2967
Polyfunctional Compounds in Nature......Page 2983
24-1 Names and Structures of Carbohydrates......Page 2987
24-2 Conformations and Cyclic Forms of Sugars......Page 2998
24-3 Anomers of Simple Sugars: Mutarotation of Glucose......Page 3008
24-4 Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids......Page 3013
24-5 Oxidative Cleavage of Sugars......Page 3016
24-6 Reduction of Monosaccharides to Alditols......Page 3020
24-7 Carbonyl Condensations with Amine Derivatives......Page 3022
24-8 Ester and Ether Formation: Glycosides......Page 3024
24-9 Step-by-Step Buildup and Degradation of Sugars......Page 3030
Real Life: Nature 24-1 Biological Sugar Synthesis......Page 3033
24-10 Relative Configurations of the Aldoses: An Exercise in Structure Determination......Page 3037
24-11 Complex Sugars in Nature: Disaccharides......Page 3043
Real Life: Food Chemistry 24-2 Manipulating Our Sweet Tooth......Page 3049
24-12 Polysaccharides and Other Sugars in Nature......Page 3055
Real Life: Medicine 24-3 Sialic Acid, “Bird Flu,” and Rational Drug Design......Page 3067
24-13 Worked Example: Integrating the Concepts......Page 3073
New Reactions......Page 3079
Important Concepts......Page 3083
Problems......Page 3085
Heteroatoms in Cyclic Organic Compounds......Page 3099
25-1 Naming the Heterocycles......Page 3108
25-2 Nonaromatic Heterocycles......Page 3110
Real Life: Medicine 25-1 Smoking, Nicotine, Cancer, and Medicinal Chemistry......Page 3114
25-3 Structures and Properties of Aromatic Heterocyclopentadienes......Page 3119
25-4 Reactions of the Aromatic Heterocyclopentadienes......Page 3131
25-5 Structure and Preparation of Pyridine: An Azabenzene......Page 3140
Real Life: Biochemistry 25-2 Lessons from Redox-Active Pyridinium Salts in Nature: Nicotinamide Adenine Dinucleotide, Dihydropyridines, and Synthesis......Page 3154
25-7 Quinoline and Isoquinoline: The Benzopyridines......Page 3160
Real Life: Biology 25-3 Folic Acid, Vitamin D, Cholesterol, and the Color of Your Skin......Page 3163
25-8 Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature......Page 3168
Real Life: Nature 25-4 Nature is Not Always Green: Natural Pesticides......Page 3171
25-9 Worked Examples: Integrating the Concepts......Page 3178
New Reactions......Page 3184
Important Concepts......Page 3187
Problems......Page 3188
Nitrogen-Containing Polymers in Nature......Page 3210
26-1 Structure and Properties of Amino Acids......Page 3214
Real Life: Medicine 26-1 Arginine and Nitric Oxide in Biochemistry and Medicine......Page 3221
26-2 Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry......Page 3228
26-3 Synthesis of Enantiomerically Pure Amino Acids......Page 3234
Real Life: Chemistry 26-2 Enantioselective Synthesis of Optically Pure Amino Acids: Phase-Transfer Catalysis......Page 3236
26-4 Peptides and Proteins: Amino Acid Oligomers and Polymers......Page 3240
26-5 Determination of Primary Structure: Amino Acid Sequencing......Page 3258
26-6 Synthesis of Polypeptides: A Challenge in the Application of Protecting Groups......Page 3269
26-7 Merrifield Solid-Phase Peptide Synthesis......Page 3276
26-8 Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin......Page 3280
26-9 Biosynthesis of Proteins: Nucleic Acids......Page 3285
Real Life: Medicine 26-3 Synthetic Nucleic Acid Bases and Nucleosides in Medicine......Page 3290
26-10 Protein Synthesis Through RNA......Page 3299
26-11 DNA Sequencing and Synthesis: Cornerstones of Gene Technology......Page 3305
Real Life: Forensics 26-4 DNA Fingerprinting......Page 3321
26-12 Worked Examples: Integrating the Concepts......Page 3328
New Reactions......Page 3334
Important Concepts......Page 3337
Problems......Page 3339
Footnotes......Page 3352
Answers to Exercises......Page 3380
Index......Page 3692
A......Page 3693
B......Page 3716
C......Page 3724
D......Page 3739
E......Page 3745
F......Page 3753
G......Page 3756
H......Page 3759
I......Page 3767
J......Page 3770
K......Page 3771
L......Page 3774
M......Page 3777
N......Page 3786
O......Page 3792
P......Page 3796
Q......Page 3807
R......Page 3808
S......Page 3815
T......Page 3829
U......Page 3833
V......Page 3835
W......Page 3837
X......Page 3839
Y......Page 3840
Z......Page 3841
Inside Back Cover......Page 3842
Back Cover......Page 3843