Organic Chemistry

2020·46.4 MB·English

by  Allan D. Headley

Cover Page: iii
Preface Page: xvii
About This Book Page: xvii
To the Student of Organic Chemistry Page: xviii
To the Instructor Page: xxi
About the Companion Website Page: xxiii
1 Bonding and Structure of Organic Compounds Page: 1
1.1 Introduction Page: 1
1.2 Electronic Structure of Atoms Page: 4
1.3 Chemical Bonds Page: 9
1.4 Chemical Formulas Page: 18
1.5 The Covalent Bond Page: 20
1.6 Bonding – Concept Summary and Applications Page: 28
1.7 Intermolecular Attractions Page: 29
1.8 Intermolecular Molecular Interactions – Concept Summary and Applications Page: 31
End of Chapter Problems Page: 34
2 Carbon Functional Groups and Organic Nomenclature Page: 39
2.1 Introduction Page: 39
2.2 Functional Groups Page: 39
2.3 Saturated Hydrocarbons Page: 41
2.4 Organic Nomenclature Page: 45
2.5 Structure and Nomenclature of Alkanes Page: 45
2.6 Unsaturated Hydrocarbons Page: 54
2.7 Structure and Nomenclature of Alkenes Page: 56
2.8 Structure and Nomenclature of Substituted Benzenes Page: 58
2.9 Structure and Nomenclature of Alkynes Page: 60
End of Chapter Problems Page: 61
3 Heteroatomic Functional Groups and Organic Nomenclature Page: 63
3.1 Properties and Structure of Alcohols, Phenols, and Thiols Page: 63
3.2 Nomenclature of Alcohols Page: 66
3.3 Nomenclature of Thiols Page: 68
3.4 Structure and Properties of Aldehydes and Ketones Page: 69
3.5 Nomenclature of Aldehydes Page: 70
3.6 Nomenclature of Ketones Page: 71
3.7 Structure and Properties of Carboxylic Acids Page: 73
3.8 Nomenclature of Carboxylic Acids Page: 75
3.9 Structure and Properties of Esters Page: 78
3.10 Structure and Properties of Acid Chlorides Page: 82
3.11 Structure and Properties of Anhydrides Page: 83
3.12 Structure and Properties of Amines Page: 84
3.13 Structure and Properties of Amides Page: 88
3.14 Structure and Properties of Nitriles Page: 90
3.15 Structure and Properties of Ethers Page: 91
3.16 An Overview of Spectroscopy and the Relationship to Functional Groups Page: 94
End of Chapter Problems Page: 99
4 Alkanes, Cycloalkanes, and Alkenes: Isomers, Conformations, and Stabilities Page: 103
4.1 Introduction Page: 103
4.2 Structural Isomers Page: 103
4.3 Conformational Isomers of Alkanes Page: 104
4.4 Conformational Isomers of Cycloalkanes Page: 108
4.5 Geometric Isomers Page: 114
4.6 Stability of Alkanes Page: 119
4.7 Stability of Alkenes Page: 121
4.8 Stability of Alkynes Page: 122
End of Chapter Problems Page: 123
5 Stereochemistry Page: 125
5.1 Introduction Page: 125
5.2 Chiral Stereoisomers Page: 126
5.3 Significance of Chirality Page: 129
5.4 Nomenclature of the Absolute Configuration of Chiral Molecules Page: 131
5.5 Properties of Stereogenic Compounds Page: 133
5.6 Compounds with More Than One Stereogenic Carbon Page: 134
5.7 Resolution of Enantiomers Page: 137
End of Chapter Problems Page: 140
6 An Overview of the Reactions of Organic Chemistry Page: 145
6.1 Introduction Page: 145
6.2 Acid–Base Reactions Page: 145
6.3 Addition Reactions Page: 149
6.4 Reduction Reactions Page: 150
6.5 Oxidation Reactions Page: 153
6.6 Elimination Reactions Page: 154
6.7 Substitution Reactions Page: 156
6.8 Pericyclic Reactions Page: 158
6.9 Catalytic Coupling Reactions Page: 158
End of Chapter Problems Page: 159
7 Acid–Base Reactions in Organic Chemistry Page: 165
7.1 Introduction Page: 165
7.2 Lewis Acids and Bases Page: 165
7.3 Relative Strengths of Acids and Conjugate Bases Page: 166
7.4 Predicting the Relative Strengths of Acids and Bases Page: 169
7.5 Factors That Affect Acid and Base Strengths Page: 170
7.6 Applications of Acid–Bases Reactions in Organic Chemistry Page: 176
End of Chapter Problems Page: 180
8 Addition Reactions Involving Alkenes and Alkynes Page: 183
8.1 Introduction Page: 183
8.2 The Mechanism for Addition Reactions Involving Alkenes Page: 183
8.3 Addition of Hydrogen Halide to Alkenes (Hydrohalogenation of Alkenes) Page: 185
8.4 Addition of Halogens to Alkenes (Halogenation of Alkenes) Page: 196
8.5 Addition of Halogens and Water to Alkenes (Halohydrin Formation) Page: 198
8.6 Addition of Water to Alkenes (Hydration of Alkenes) Page: 199
8.7 Addition of Carbenes to Alkenes Page: 207
8.8 The Mechanism for Addition Reactions Involving Alkynes Page: 209
8.9 Applications of Addition Reactions to Synthesis Page: 213
End of Chapter Problems Page: 214
9 Addition Reactions Involving Carbonyls and Nitriles Page: 223
9.1 Introduction Page: 223
9.2 Mechanism for Addition Reactions Involving Carbonyl Compounds Page: 223
9.3 Addition of HCN to Carbonyl Compounds Page: 224
9.4 Addition of Water to Carbonyl Compounds Page: 226
9.5 Addition of Alcohols to Carbonyl Compounds Page: 230
9.6 Addition of Ylides to Carbonyl Compounds (The Wittig Reaction) Page: 235
9.7 Addition of Enolates to Carbonyl Compounds Page: 237
9.8 Addition of Amines to Carbonyl Compounds Page: 240
9.9 Mechanism for Addition Reactions Involving Imines Page: 241
9.10 Mechanism for Addition Reactions Involving Nitriles Page: 242
9.11 Applications of Addition Reactions to Synthesis Page: 244
End of Chapter Problems Page: 246
10 Reduction Reactions in Organic Chemistry Page: 251
10.1 Introduction Page: 251
10.2 Reducing Agents of Organic Chemistry Page: 252
10.3 Reduction of C=O and C=S Containing Compounds Page: 255
10.4 Reduction of Imines Page: 263
10.5 Reduction of Oxiranes Page: 266
10.6 Reduction of Aromatic Compounds, Alkynes, and Alkenes Page: 268
End of Chapter Problems Page: 272
11 Oxidation Reactions in Organic Chemistry Page: 275
11.1 Introduction Page: 275
11.2 Oxidation Page: 275
11.3 Oxidation of Alcohols and Aldehydes Page: 279
11.4 Oxidation of Alkenes Without Bond Cleavage Page: 288
11.5 Oxidation of Alkenes with Bond Cleavage Page: 293
11.6 Applications of Oxidation Reactions of Alkenes Page: 296
11.7 Oxidation of Alkynes Page: 299
11.8 Oxidation of Aromatic Compounds Page: 300
11.9 Autooxidation of Ethers and Alkenes Page: 301
11.10 Applications of Oxidation Reactions to Synthesis Page: 302
End of Chapter Problems Page: 304
12 Elimination Reactions of Organic Chemistry Page: 309
12.1 Introduction Page: 309
12.2 Mechanisms of Elimination Reactions Page: 309
12.3 Elimination of Hydrogen and Halide (Dehydrohalogenation) Page: 316
12.4 Elimination of Water (Dehydration) Page: 319
12.5 Applications of Elimination Reactions to Synthesis Page: 323
End of Chapter Problems Page: 326
13 Spectroscopy Revisited, A More Detailed Examination Page: 331
13.1 Introduction Page: 331
13.2 The Electromagnetic Spectrum Page: 331
13.3 UV‐Vis Spectroscopy and Conjugated Systems Page: 334
13.4 Infrared Spectroscopy Page: 337
13.5 Mass Spectrometry Page: 343
13.6 Nuclear Magnetic Resonance (NMR) Spectroscopy Page: 346
End of Chapter Problems Page: 367
14 Free Radical Substitution Reactions Involving Alkanes Page: 369
14.1 Introduction Page: 369
14.2 Types of Alkanes and Alkyl Halides Page: 371
14.3 Chlorination of Alkanes Page: 376
14.4 Bromination of Alkanes Page: 380
14.5 Applications of Free Radical Substitution Reactions Page: 386
14.6 Free Radical Inhibitors Page: 388
14.7 Environmental Impact of Organohalides and Free Radicals Page: 389
End of Chapter Problems Page: 391
15 Nucleophilic Substitution Reactions at sp3 Carbons Page: 393
15.1 Introduction Page: 393
15.2 The Electrophile Page: 393
15.3 The Leaving Group Page: 394
15.4 The Nucleophile Page: 397
15.5 Nucleophilic Substitution Reactions Page: 397
15.6 Bimolecular Substitution Reaction Mechanism (SN2 Mechanism) Page: 400
15.7 Unimolecular Substitution Reaction Mechanism (SN1 Mechanism) Page: 406
15.8 Applications of Nucleophilic Substitution Reactions – Synthesis Page: 414
End of Chapter Problems Page: 420
16 Nucleophilic Substitution Reactions at Acyl Carbons Page: 425
16.1 Introduction Page: 425
16.2 Mechanism for Acyl Substitution Page: 426
16.3 Substitution Reactions Involving Acid Chlorides Page: 428
16.4 Substitution Reactions Involving Anhydrides Page: 436
16.5 Substitution Reactions Involving Esters Page: 442
16.6 Substitution Reactions Involving Amides Page: 451
16.7 Substitution Reactions Involving Carboxylic Acids Page: 454
16.8 Substitution Reactions Involving Oxalyl Chloride Page: 458
16.9 Substitution Reactions Involving Sulfur Containing Compounds Page: 458
16.10 Applications of Acyl Substitution Reactions Page: 460
End of Chapter Problems Page: 462
17 Aromaticity and Aromatic Substitution Reactions Page: 467
17.1 Introduction Page: 467
17.2 Structure and Properties of Benzene Page: 468
17.3 Nomenclature of Substituted Benzene Page: 470
17.4 Stability of Benzene Page: 473
17.5 Characteristics of Aromatic Compounds Page: 475
17.6 Electrophilic Aromatic Substitution Reactions of Benzene Page: 478
17.7 Electrophilic Aromatic Substitution Reactions of Substituted Benzene Page: 484
17.8 Applications – Synthesis of Substituted Benzene Compounds Page: 491
17.9 Electrophilic Substitution Reactions of Polycyclic Aromatic Compounds Page: 494
17.10 Electrophilic Substitution Reactions of Pyrrole Page: 496
17.11 Electrophilic Substitution Reactions of Pyridine Page: 497
17.12 Nucleophilic Aromatic Substitution Page: 499
End of Chapter Problems Page: 504
18 Conjugated Systems and Pericyclic Reactions Page: 511
18.1 Conjugated Systems Page: 511
18.2 Pericyclic Reactions Page: 513
End of Chapter Problems Page: 522
19 Catalytic Carbon–Carbon Coupling Reactions Page: 525
19.1 Introduction Page: 525
19.2 Reactions of Transition Metal Complexes Page: 525
19.3 Palladium‐Catalyzed Coupling Reactions Page: 528
End of Chapter Problems Page: 535
20 Synthetic Polymers and Biopolymers Page: 537
20.1 Introduction Page: 537
20.2 Cationic Polymerization of Alkenes Page: 537
20.3 Anionic Polymerization of Alkenes Page: 540
20.4 Free Radical Polymerization of Alkenes Page: 540
20.5 Copolymerization of Alkenes Page: 542
20.6 Properties of Polymers Page: 543
20.7 Biopolymers Page: 544
20.8 Amino Acids, Monomers of Peptides and Proteins Page: 545
20.9 Acid–Base Properties of Amino Acids Page: 547
20.10 Synthesis of α‐Amino Acids Page: 547
20.11 Reactions of α‐Amino Acids Page: 550
20.12 Primary Structure and Properties of Peptides Page: 556
20.13 Secondary Structure of Proteins Page: 558
20.14 Monosaccharides, Monomers of Carbohydrates Page: 559
20.15 Reactions of Monosaccharides Page: 560
20.16 Disaccharides and Polysaccharides Page: 566
20.17 N‐Glycosides and Amino Sugars Page: 567
20.18 Lipids Page: 568
20.19 Properties and Reactions of Waxes Page: 569
20.20 Properties and Reactions of Triglycerides Page: 569
20.21 Properties and Reactions of Phospholipids Page: 572
20.22 Structure and Properties of Steroids, Prostaglandins, and Terpenes Page: 572
End of Chapter Problems Page: 573
Index Page: 577
End User License Agreement Page: 595