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 Br？nsted-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 Properities 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: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 STEREOCH EMISTRY 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 SN2 Reaction 229
Key Mechanism:The SN2 Reaction 230
6-9 Generality of the SN2 Reaction 231
Summary:SN2 Reactions of Alkyl Halides 231
6-10 Factors Affecting SN2 Reactions:Strength of the Nucleophile 233
Summary:Trends in Nucleophilicity 234
6-11 Reactivity of the Substrate in SN2 Reactions 237
6-12 Stereochemistry of the SN2 Reaction 241
6-13 First-Order Nucleophilic Substitution:The SN1 Reaction 243
Key Mechanism:The SN1 Reaction 244
6-14 Stereochemistry of the SN1 Reaction 247
6-15 Rearrangements in SN1 Reactions 249
6-16 Comparison of SN1 and SN2 Reactions 252
Summary:Nucleophilic Substitutions 254
6-17 First-Order Elimination:The E1 Reaction 255
Key Mechanism: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: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: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 ALKEN ES 323
8-1 Reactivity of the Carbon-Carbon Double Bond 323
8-2 Electrophilic Addition to Alkenes 324
Key Mechanism: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:Reacfons 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 E1imination 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: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:SN2 Reactions of Tosylate Esters 475
11-6 Reduction of Alcohols 475
11-7 Reactions of Alcohols witb Hydrohalic Acids 476
11-8 Reactions of Alcohols with Phosphorus Halides 481
11-9 Reactions of Alcohols with Tbionyl 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: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 SN2 Displacement Reactions of Allylic Halides and Tosylates 681
15-11 The Diels-Alder Reaction 682
Key Mechanism: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: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: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: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: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: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: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:Base-Catalyzed Aldol Condensation 1058
22-8 Dehydration of Aldol Products 1061
Key Mechanism: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: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 Deoxvribonucleic 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 Absorption Positions of Protons in Various Structural Environments 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 pKa Values for Representative Compounds 1261
Answers to Selected Problems A 1
Photo Credits PC 1
Index I 1
KEY MECHANISM BOXES 130
CHAPTER 4 Free-Radical Halogenation 130
CHAPTER 6 The SN2 Reaction 230
The SN1 Reaction 244
The E1 Reaction 255
The E2 Reaction 262
CHAPTER 7 Acid-Catalyzed Dehydration of an Alcohol 309
CHAPTER 8 Electrophilic Addition to Alkenes 324
CHAPTER 10 Grignard Reactions 439
CHAPTER 11 The Williamson Ether Synthesis 497
CHAPTER 15 The Diels-Alder Reaction 682
CHAPTER 17 Electrophilic Aromatic Substitution 752
CHAPTER 18 Nucleophilic Additions to Carbonyl Groups 833
Formation of Imines 842
Formation of Acetals 848
CHAPTER 20 Fischer Esterification 961
CHAPTER 21 Addition-Elimination Mechanism of Nucleophilic Acyl Substitution 997
CHAPTER 22 Base-Catalyzed Aldol Condensation 1058
Base-Catalyzed Dehydration of an Aldol 1061
The Claisen Ester Condensation 1068
MECHANISM BOXES 225
CHAPTER 6 Allvlic Bromination 225
Inversion of Confiauration in the SN2 Reaction 241
Racemization in the SN1 Reaction 248
Hydride Shift in an SN1 Reaction 250
Methyl Shift in an SN1 Reaction 251
Rearrangement in an E1 Reaction 258
CHAPTER 7 Dehydrohalogenation by the E2 Mechanism 300
Stereochemistry of the E2 Reaction 302
E2 Debromination of a Vicinal Dibromide 306
CHAPTER 8 Ionic Addition of HX to an Alkene 327
Free-Radical Addition of HBr to Alkenes 329
Acid-Catalyzed Hydration of an Alkene 333
Oxymercuration of an Alkene 335
Hvdroboration of an Alkene 340
Addition of Halogens to Alkenes 345
Formation of Halohydrins 347
Epoxidation of Alkenes 356
Acid-Catalyzed Opening of Epoxides 357
Olefin Metathesis 372
CHAPTER 9 Metal-Ammonia Reduction of an Alkyne 404
Acid-Catalyzed Keto-Enol Tautomerism 408
Base-Catalyzed Keto-Enol Tautomerism 410
CHAPTER 10 Hydride Reduction of a Carbonyl Group 450
CHAPTER 11 Reaction of a Tertiary Alcohol with HBr(SN1) 477
Reaction of a Primary Alcohol with HBr(SN2) 477
Reaction of Alcohols with PBr3 481
(Review):Acid-Catalyzed Dehydration of an Alcohol 484
The Pinacol Rearrangement 491
CHAPTER 14 Cleavage of an Ether by HBr or Hl 639
Acid-Catalyzed Opening of Epoxides in Water 648
Acid-Catalyzed Opening of an Epoxide in an Alcohol Solution 649
Base-Catalyzed Opening of Epoxides 651
CHAPTER 15 1,2-and 1,4-Addition to a Coniugated Diene 673
Free-Radical Allylic Bromination 676
CHAPTER 17 Bromination of Benzene 753
Nitration of Benzene 756
Sulfonation of Benzene 757
Friedel-Crafts Alkylation 774
Friedel-Crafts Acylation 778
Nucleophilic Aromatic Substitution(Addition-Elimination) 783
Nucleophilic Aromatic Substitution(Benzyne Mechanism) 786
The Birch Reduction 788
CHAPTER 18 The Wittig Reaction 836
Hydration of Ketones and Aldehydes 839
Formation of Cyanohydrins 840
Wolff-Kishner Reduction 857
CHAPTER 19 Electrophilic Aromatic Substitution of Pyridine 892
Nucleophilic Aromatic Substitution of Pyridine 893
Acylation of an Amine by an Acid Chloride 895
Hofmann Elimination 899
The Cope Elimination of an Amine Oxide 903
Diazotization of an Amine 904
The Hofmann Rearrangement of Amides 921
CHAPTER 20 Nucleophilic Acyl Substitution in the Basic Hydrolysis of an Ester 959
Esterification Using Diazomethane 964
CHAPTER 21 Conversion of an Acid Chloride to an Anhydride 1000
Conversion of an Acid Chloride to an Ester 1000
Conversion of an Acid Chloride to an Amide 1001
Conversion of an Acid Anhydride to an Ester 1001
Conversion of an Acid Anhydride to an Amide 1002
Conversion of an Ester to an Amide(Ammonolysis of an Ester) 1002
Transesterification 1007
Saponification of an Ester 1009
Basic Hydrolysis of an Amide 1011
Acidic Hydrolysis of an Amide 1011
Base-Catalyzed Hydrolysis of a Nitrile 1012
Hydride Reduction of an Ester 1013
Reduction of an Amide to an Amine 1014
Reaction of an Ester with Two Moles of a Grignard Reagent 1016
CHAPTER 22 Alpha Substitution 1043
Addition of an Enolate to Ketones and Aldehydes(a Condensation) 1044
Substitution of an Enolate on an Ester(a Condensation) 1044
Base-Catalyzed Keto-Enol Tautomerism 1044
Acid-Catalyzed Keto-Enol Tautomerism 1045
Base-Promoted Halogenation 1052
Final Steps of the Haloform Reaction 1054
Acid-Catalyzed Alpha Haloaenation 1055
Acid-Catalyzed Aldol Condensation 1060
1,2-Addition and 1,4-Addition(Conjugate Addition) 1082
CHAPTER 23 Formation of a Cyclic Hemiacetal 1104
Base-Catalyzed Epimerization of Glucose 1111
Base-Catalyzed Enediol Rearrangement 1111
CHAPTER 26 Free-Radical Polymerization 1225
Cationic Polymerization 1226
Anionic Polymerization 1228