Preface xvii
About the Campanion Website xxiii
1 Bonding and Structure of Organic Compounds 1
1.1 Introduction 1
1.2 Electronic Structure of Atoms 4
1.3 Chemical Bonds 9
1.4 Chemical Formulas 18
1.5 The Covalent Bond 20
1.6 Bonding Concept Summary and Applications 28
1.7 Intermolecular Attractions 29
1.8 Intermolecular Molecular Interactions Concept Summary and Applications 31
End of Chapter Problems 34
2 Carbon Functional Groups and Organic Nomenclature 39
2.1 Introduction 39
2.2 Functional Groups 39
2.3 Saturated Hydrocarbons 41
2.4 Organic Nomenclature 45
2.5 Structure and Nomenclature of Alkanes 45
2.6 Unsaturated Hydrocarbons 54
2.7 Structure and Nomenclature of Alkenes 56
2.8 Structure and Nomenclature of Substituted Benzenes 58
2.9 Structure and Nomenclature of Alkynes 60
End of Chapter Problems 61
3 Heteroatomic Functional Groups and Organic Nomenclature 63
3.1 Properties and Structure of Alcohols, Phenols, and Thiols 63
3.2 Nomenclature of Alcohols 66
3.3 Nomenclature of Thiols 68
3.4 Structure and Properties of Aldehydes and Ketones 69
3.5 Nomenclature of Aldehydes 70
3.6 Nomenclature of Ketones 71
3.7 Structure and Properties of Carboxylic Acids 73
3.8 Nomenclature of Carboxylic Acids 75
3.9 Structure and Properties of Esters 78
3.10 Structure and Properties of Acid Chlorides 82
3.11 Structure and Properties of Anhydrides 83
3.12 Structure and Properties of Amines 84
3.13 Structure and Properties of Amides 88
3.14 Structure and Properties of Nitriles 90
3.15 Structure and Properties of Ethers 91
3.16 An Overview of Spectroscopy and the Relationship to Functional Groups 94
4 Alkanes, Cycloalkanes, and Alkenes: Isomers, Conformations, and Stabilities 103
4.1 Introduction 103
4.2 Structural Isomers 103
4.3 Conformational Isomers of Alkanes 104
4.4 Conformational Isomers of Cycloalkanes 108
4.5 Geometric Isomers 114
4.6 Stability of Alkanes 119
4.7 Stability of Alkenes 121
4.8 Stability of Alkynes 122
End of Chapter Problems 123
5 Stereochemistry 125
5.1 Introduction 125
5.2 Chiral Stereoisomers 126
5.3 Significance of Chirality 129
5.4 Nomenclature of the Absolute Configuration of Chiral Molecules 131
5.5 Properties of Stereogenic Compounds 133
5.6 Compounds with More Than One Stereogenic Carbon 134
5.7 Resolution of Enantiomers 137
End of Chapter Problems 140
6 An Overview of the Reactions of Organic Chemistry 145
6.1 Introduction 145
6.2 AcidBase Reactions 145
6.3 Addition Reactions 149
6.4 Reduction Reactions 150
6.5 Oxidation Reactions 153
6.6 Elimination Reactions 154
6.7 Substitution Reactions 156
6.8 Pericyclic Reactions 158
6.9 Catalytic Coupling Reactions 158
End of Chapter Problems 159
7 AcidBase Reactions in Organic Chemistry 165
7.1 Introduction 165
7.2 Lewis Acids and Bases 165
7.3 Relative Strengths of Acids and Conjugate Bases 166
7.4 Predicting the Relative Strengths of Acids and Bases 169
7.5 Factors That Affect Acid and Base Strengths 170
7.6 Applications of AcidBases Reactions in Organic Chemistry 176
End of Chapter Problems 180
8 Addition Reactions Involving Alkenes and Alkynes 183
8.1 Introduction 183
8.2 The Mechanism for Addition Reactions Involving Alkenes 183
8.3 Addition of Hydrogen Halide to Alkenes (Hydrohalogenation of Alkenes) 185
8.4 Addition of Halogens to Alkenes (Halogenation of Alkenes) 196
8.5 Addition of Halogens and Water to Alkenes (Halohydrin Formation) 198
8.6 Addition of Water to Alkenes (Hydration of Alkenes) 199
8.7 Addition of Carbenes to Alkenes 207
8.8 The Mechanism for Addition Reactions Involving Alkynes 209
8.9 Applications of Addition Reactions to Synthesis 213
End of Chapter Problems 214
9 Addition Reactions Involving Carbonyls and Nitriles 223
9.1 Introduction 223
9.2 Mechanism for Addition Reactions Involving Carbonyl Compounds 223
9.3 Addition of HCN to Carbonyl Compounds 224
9.4 Addition of Water to Carbonyl Compounds 226
9.5 Addition of Alcohols to Carbonyl Compounds 230
9.6 Addition of Ylides to Carbonyl Compounds (The Wittig Reaction) 235
9.7 Addition of Enolates to Carbonyl Compounds 237
9.8 Addition of Amines to Carbonyl Compounds 240
9.9 Mechanism for Addition Reactions Involving Imines 241
9.10 Mechanism for Addition Reactions Involving Nitriles 242
9.11 Applications of Addition Reactions to Synthesis 244
End of Chapter Problems 246
10 Reduction Reactions in Organic Chemistry 251
10.1 Introduction 251
10.2 Reducing Agents of Organic Chemistry 252
10.3 Reduction of C=O and C=S Containing Compounds 255
10.4 Reduction of Imines 263
10.5 Reduction of Oxiranes 266
10.6 Reduction of Aromatic Compounds, Alkynes, and Alkenes 268
End of Chapter Problems 272
11 Oxidation Reactions in Organic Chemistry 275
11.1 Introduction 275
11.2 Oxidation 275
11.3 Oxidation of Alcohols and Aldehydes 279
11.4 Oxidation of Alkenes Without Bond Cleavage 288
11.5 Oxidation of Alkenes with Bond Cleavage 293
11.6 Applications of Oxidation Reactions of Alkenes 296
11.7 Oxidation of Alkynes 299
11.8 Oxidation of Aromatic Compounds 300
11.9 Autooxidation of Ethers and Alkenes 301
11.10 Applications of Oxidation Reactions to Synthesis 302
End of Chapter Problems 304
12 Elimination Reactions of Organic Chemistry 309
12.1 Introduction 309
12.2 Mechanisms of Elimination Reactions 309
12.3 Elimination of Hydrogen and Halide (Dehydrohalogenation) 316
12.4 Elimination of Water (Dehydration) 319
12.5 Applications of Elimination Reactions to Synthesis 323
End of Chapter Problems 326
13 Spectroscopy Revisited, A More Detailed Examination 331
13.1 Introduction 331
13.2 The Electromagnetic Spectrum 331
13.3 UVVis Spectroscopy and Conjugated Systems 334
13.4 Infrared Spectroscopy 337
13.5 Mass Spectrometry 343
13.6 Nuclear Magnetic Resonance (NMR) Spectroscopy 346
End of Chapter Problems 367
14 Free Radical Substitution Reactions Involving Alkanes 369
14.1 Introduction 369
14.2 Types of Alkanes and Alkyl Halides 371
14.3 Chlorination of Alkanes 376
14.4 Bromination of Alkanes 380
14.5 Applications of Free Radical Substitution Reactions 386
14.6 Free Radical Inhibitors 388
14.7 Environmental Impact of Organohalides and Free Radicals 389
End of Chapter Problems 391
15 Nucleophilic Substitution Reactions at sp3 Carbons 393
15.1 Introduction 393
15.2 The Electrophile 393
15.3 The Leaving Group 394
15.4 The Nucleophile 397
15.5 Nucleophilic Substitution Reactions 397
15.6 Bimolecular Substitution Reaction Mechanism (SN2 Mechanism) 400
15.7 Unimolecular Substitution Reaction Mechanism (SN1 Mechanism) 406
15.8 Applications of Nucleophilic Substitution Reactions Synthesis 414
End of Chapter Problems 420
16 Nucleophilic Substitution Reactions at Acyl Carbons 425
16.1 Introduction 425
16.2 Mechanism for Acyl Substitution 426
16.3 Substitution Reactions Involving Acid Chlorides 428
16.4 Substitution Reactions Involving Anhydrides 436
16.5 Substitution Reactions Involving Esters 442
16.6 Substitution Reactions Involving Amides 451
16.7 Substitution Reactions Involving Carboxylic Acids 454
16.8 Substitution Reactions Involving Oxalyl Chloride 458
16.9 Substitution Reactions Involving Sulfur Containing Compounds 458
16.10 Applications of Acyl Substitution Reactions 460
End of Chapter Problems 462
17 Aromaticity and Aromatic Substitution Reactions 467
17.1 Introduction 467
17.2 Structure and Properties of Benzene 468
17.3 Nomenclature of Substituted Benzene 470
17.4 Stability of Benzene 473
17.5 Characteristics of Aromatic Compounds 475
17.6 Electrophilic Aromatic Substitution Reactions of Benzene 478
17.7 Electrophilic Aromatic Substitution Reactions of Substituted Benzene 484
17.8 Applications Synthesis of Substituted Benzene Compounds 491
17.9 Electrophilic Substitution Reactions of Polycyclic Aromatic Compounds 494
17.10 Electrophilic Substitution Reactions of Pyrrole 496
17.11 Electrophilic Substitution Reactions of Pyridine 497
17.12 Nucleophilic Aromatic Substitution 499
End of Chapter Problems 504
18 Conjugated Systems and Pericyclic Reactions 511
18.1 Conjugated Systems 511
18.2 Pericyclic Reactions 513
End of Chapter Problems 522
19 Catalytic CarbonCarbon Coupling Reactions 525
19.1 Introduction 525
19.2 Reactions of Transition Metal Complexes 525
19.3 Palladium Catalyzed Coupling Reactions 528
End of Chapter Problems 535
20 Synthetic Polymers and Biopolymers 537
20.1 Introduction 537
20.2 Cationic Polymerization of Alkenes 537
20.3 Anionic Polymerization of Alkenes 540
20.4 Free Radical Polymerization of Alkenes 540
20.5 Copolymerization of Alkenes 542
20.6 Properties of Polymers 543
20.7 Biopolymers 544
20.8 Amino Acids, Monomers of Peptides and Proteins 545
20.9 AcidBase Properties of Amino Acids 547
20.10 Synthesis of Amino Acids 547
20.11 Reactions of Amino Acids 550
20.12 Primary Structure and Properties of Peptides 556
20.13 Secondary Structure of Proteins 558
20.14 Monosaccharides, Monomers of Carbohydrates 559
20.15 Reactions of Monosaccharides 560
20.16 Disaccharides and Polysaccharides 566
20.17 NGlycosides and Amino Sugars 567
20.18 Lipids 568
20.19 Properties and Reactions of Waxes 569
20.20 Properties and Reactions of Triglycerides 569
20.21 Properties and Reactions of Phospholipids 572
20.22 Structure and Properties of Steroids, Prostaglandins, and Terpenes 572
End of Chapter Problems 573
Index 577
