1 Structure and Bonding: Acids and Bases 1
1.1 Atomic Structure 3
1.2 Electron Configuration of Atoms 4
1.3 Development of Chemical Bonding Theory 6
1.4 The Nature of Chemical Bonds: Ionic Bonds 7
1.5 The Nature of Chemical Bonds: Covalent Bonds 8
1.6 Formation of Covalent Bonds 11
1.7 Hybridization: sp3 Orbitals and the Structure of Methane 12
1.8 The Structure of Ethane 14
1.9 Hybridization: sp2 Orbitals and the Structure of Ethylene 16
1.10 Hybridization: sp Orbitals and the Structure of Acetylene 18
1.11 Bond Polarity and Electronegativity 20
1.12 Acids and Bases: The Br?nsted-Lowry Definition 23
1.13 Acids and Bases: The Lewis Definition 26
Interlude—Chemicals, Toxicity, and Risk 29
Summary and Key Words 30
Additional Problems 31
Working Problems 31
2 The Nature of Organic Compounds: Alkanes 36
2.1 Functional Groups 36
2.2 Alkanes and Alkyl Groups: Isomers 41
2.3 Naming Branched-Chain Alkanes 47
2.4 Properties of Alkanes 50
2.5 Conformations of Ethane 51
2.6 Drawing Chemical Structures 55
2.7 Cycloalkanes 57
2.8 Cis-Trans Isomerism in Cycloalkanes 58
2.9 Conformations of Some Common Cycloalkanes 60
2.10 Axial and Equatorial Bonds in Cyclohexane 63
2.11 Conformational Mobility of Cyclohexane 65
Interlude—Petroleum 67
Summary and Key Words 69
Additional Problems 70
3 Alkenes: The Nature of Organic Reactions 76
3.1 Naming Alkenes 77
3.2 Electronic Structure of Alkenes 79
3.3 Cis-Trans Isomers of Alkenes 80
3.4 Sequence Rules: The E,Z Designation 83
3.5 Kinds of Organic Reactions 87
3.6 How Reactions Occur: Mechanisms 88
3.7 An Example of a Polar Reaction: Addition of HCI to Ethylene 91
3.8 The Mechanism of an Organic Reaction: Addition of HCI to Ethylene 92
3.9 Describing a Reaction: Rates and Equilibria 93
3.10 Describing a Reaction: Reaction Energy Diagrams and Transition States 96
3.11 Describing a Reaction: Intermediates 98
Interlude--Carrots, Alkenes, and the Chemistry of Vision 100
Summary and Key Words 102
Additional Problems 103
4 Alkenes and Alkynes 108
4.1 Addition of HX to Alkenes: Hydrohalogenation 109
4.2 Orientation of Alkene Addition Reactions: Markovnikov s Rule 110
4.3 Carbocation Structure and Stability 112
4.4 Addition of H2O to Alkenes: Hydration 114
4.5 Addition of X2 to Alkenes: Halogenation 116
4.6 Addition of H2 to Alkenes: Hydrogenation 118
4.7 Oxidation of Alkenes 120
4.8 Alkene Polymers 122
4.9 Preparation of Alkenes: Elimination Reactions 124
4.10 Conjugated Dienes 127
4.11 Stability of Allylic Carbocations: Resonance 129
4.12 Drawing and Interpreting Resonance Forms 131
4.13 Alkynes 134
4.14 Reactions of Alkynes: Addition of H2, HX, and X2 136
4.15 Addition of H2O to Alkynes 137
4.16 Alkyne Acidity: Formation of Acetylide Anions 138
Interlude—Natural Rubber 140
Summary and Key Words 141
Summary of Reactions 142
Additional Problems 145
5 Aromatic Compounds 150
5.1 Structure of Benzene: The Kekule Proposal 151
5.2 Stability of Benzene 152
5.3 Structure of Benzene: The Resonance Proposal 153
5.4 Naming Aromatic Compounds 154
5.5 Chemistry of Benzene: Electrophilic Aromatic Substitution Reactions 157
5.6 Bromination of Benzene 158
5.7 Other Electrophilic Aromatic Substitution Reactions 160
5.8 The Friedel-Crafts Alkylation and Acylation Reactions 163
5.9 Substituent Effects in Electrophilic Aromatic Substitution 164
5.10 An Explanation of Substituent Effects 166
5.11 Oxidation and Reduction of Aromatic Compounds 170
5.12 Polycyclic Aromatic Hydrocarbons 171
5.13 Organic Synthesis 172
Interlude—Aspirin and Other Aromatic NSAID s 175
Summary and Key Words 176
Summary of Reactions 177
Additional Problems 178
6 Stereochemistry 183
6.1 Stereochemistry and the Tetrahedral Carbon 183
6.2 The Reason for Handedness in Molecules: Chirality 185
6.3 Optical Activity 190
6.4 Specific Rotation 191
6.5 Pasteur s Discovery of Enantiomers 192
6.6 Sequence Rules for Specifying Configuration 193
6.7 Diastereomers 196
6.8 Meso Compounds 198
6.9 Molecules with More Than Two Stereocenters 200
6.10 Racemic Mixtures and the Resolution of Enantiomers 201
6.11 Physical Properties of Stereoisomers 204
6.12 A Brief Review of Isomerism 205
6.13 Stereochemistry of Reactions: Addition of HBr to Alkenes 206
6.14 Chirality in Nature 208
Interlude—Chiral Drugs 209
Summary and Key Words 211
Additional Problems 211
7 Alkyl Halides 217
7.1 Naming Alkyl Halides 218
7.2 Preparation of Alkyl Halides: Radical Chlorination of Alkanes 219
7.3 Alkyl Halides from Alcohols 222
7.4 Reactions of Alkyl Halides: Grignard Reagents 223
7.5 Nucleophilic Substitution Reactions: The Discovery 225
7.6 Kinds of Nucleophilic Substitution Reactions 226
7.7 The SN2 Reaction 228
7.8 The SN1 Reaction 232
7.9 Eliminations: The E2 Reaction 236
7.10 Eliminations: The E1 Reaction 239
7.11 A Summary of Reactivity: SN1, SN2, E1, E2 239
7.12 Substitution Reactions in Living Organisms 242
Interlude—Naturally Occurring Organohalogen Compounds 243
Summary and Key Words 244
Summary of Reactions 245
Additional Problems 246
8 Alcohols,Ethers,and Phenols 251
8.1 Naming Alcohols, Phenols, and Ethers 252
8.2 Properties of Alcohols, Phenols, and Ethers: Hydrogen Bonding 254
8.3 Properties of Alcohols and Phenols: Acidity 256
8.4 Synthesis of Alcohols 258
8.5 Alcohols from Carbonyl Compounds 259
8.6 Ethers from Alcohols: The Williamson Ether Synthesis 261
8.7 Reactions of Alcohols 263
8.8 Synthesis and Reactions of Phenols 265
8.9 Reactions of Ethers: Acidic Cleavage 267
8.10 Cyclic Ethers: Epoxides 268
8.11 Ring-Opening Reactions of Epoxides 269
8.12 Thiols and Sulfides 270
Interlude—Ethanol as Chemical, Drug, and Poison 272
Summary and Key Words 274
Summary of Reactions 275
Additional Problems 276
9 Aldehydes and Ketones: Nucleophilic Addition Reactions 281
9.1 Kinds of Carbonyl Compounds 282
9.2 Structure and Properties of Carbonyl Groups 283
9.3 Naming Aldehydes and Ketones 284
9.4 Synthesis of Aldehydes and Ketones 286
9.5 Oxidation of Aldehydes 287
9.6 Reactions of Aldehydes and Ketones: Nucleophilic Additions 288
9.7 Nucleophilic Addition of Water: Hydration 290
9.8 Nucleophilic Addition of Alcohols: Acetal Formation 293
9.9 Nucleophilic Addition of Amines: Imine Formation 295
9.10 Nucleophilic Addition of Grignard Reagents: Alcohol Formation 296
9.11 Some Biological Nucleophilic Addition Reactions 299
Interlude—Insect Antifeedants 300
Summary and Key Words 301
Summary of Reactions 302
Additional Problems 303
10 Carboxylic Acids and Derivatives 308
10.1 Naming Carboxylic Acids and Derivatives 309
10.2 Occurrence, Structure, and Properties of Carboxylic Acids 313
10.3 Acidity of Carboxylic Acids 313
10.4 Synthesis of Carboxylic Acids 316
10.5 Nucleophilic Acyl Substitution Reactions 318
10.6 Reactions of Carboxylic Acids 321
10.7 Chemistry of Acid Halides 325
10.8 Chemistry of Acid Anhydrides 327
10.9 Chemistry of Esters 329
10.10 Chemistry of Amides 334
10.11 Chemistry of Nitriles 336
10.12 Nylons and Polyesters: Step-Growth Polymers 339
Interlude—β-Lactam Antibiotics 342
Summary and Key Words 343
Summary of Reactions 344
Additional Problems 346
11 Carbonyl Alpha-Substitution Reactions and Condensation Reactions 352
11.1 Keto-Enol Tautomerism 353
11.2 Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions 356
11.3 Alpha Halogenation of Aldehydes and Ketones 356
11.4 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 358
11.5 Reactivity of Enolate Ions 362
11.6 Alkylation of Enolate Ions 362
11.7 Carbonyl Condensation Reactions 365
11.8 Condensations of Aldehydes and Ketones: The Aldol Reaction 366
11.9 Dehydration of Aldol Products: Synthesis of Enones 368
11.10 Condensations of Esters: The Claisen Condensation Reaction 369
Interlude—Carbonyl Compounds in Metabolism 372
Summary and Key Words 373
Summary of Reactions 374
Additional Problems 375
12 Amines 380
12.1 Naming Amines 381
12.2 Structure and Properties of Amines 383
12.3 Amine Basicity 384
12.4 Synthesis of Amines 387
12.5 Reactions of Amines 390
12.6 Heterocyclic Amines 394
Interlude—Naturally Occurring Amines: Morphine Alkaloids 398
Summary and Key Words 400
Summary of Reactions 401
Additional Problems 402
13 Structure Determination 406
13.1 Infrared Spectroscopy and the Electromagnetic Spectrum 407
13.2 Infrared Spectroscopy of Organic Molecules 410
13.3 Ultraviolet Spectroscopy 415
13.4 Interpreting Ultraviolet Spectra: The Effect of Conjugation 416
13.5 Nuclear Magnetic Resonance Spectroscopy 418
13.6 The Nature of NMR Absorptions 419
13.7 Chemical Shifts 421
13.8 Chemical Shifts in 1H NMR Spectra 423
13.9 Integration of 1H NMR Spectra: Proton Counting 424
13.10 Spin-Spin Splitting in 1H NMR Spectra 425
13.11 Uses of 1H NMR Spectra 429
13.12 13C NMR Spectroscopy 430
Interlude—Magnetic Resonance Imaging (MRI) 432
Summary and Key Words 433
Additional Problems 434
14 Biomolecules: Carbohydrates 440
14.1 Classification of Carbohydrates 441
14.2 Configurations of Monosaccharides: Fischer Projections 443
14.3 D,L Sugars 445
14.4 Configurations of Aldoses 447
14.5 Cyclic Structures of Monosaccharides: Hemiacetal Formation 448
14.6 Monosaccharide Anomers: Mutarotation 452
14.8 Reactions of Monosaccharides 454
14.7 Conformations of Monosaccharides 454
14.9 Disaccharides 460
14.10 Polysaccharides 462
14.11 Other Important Carbohydrates 465
14.12 Cell-Surface Carbohydrates 466
Interlude—Sweetness 468
Summary and Key Words 469
Additional Problems 470
15 Biomolecules: Amino Acids,Peptides, and Proteins 474
15.1 Structures of Amino Acids 475
15.2 Dipolar Structure of Amino Acids 478
15.3 Isoelectric Points 480
15.4 Peptides and Proteins 481
15.5 Covalent Bonding in Peptides 484
15.6 Peptide Structure Determination: Amino Acid Analysis 484
15.7 Peptide Sequencing: The Edman Degradation 486
15.8 Peptide Synthesis 488
15.9 Classification of Proteins 491
15.10 Protein Structure 493
15.11 Enzymes 497
15.12 Structure and Classification of Enzymes 497
Interlude—Protein and Nutrition 500
Summary and Key Words 501
Additional Problems 502
16.1 Lipids 507
16 Biomolecules: Lipids and Nucleic Acids 507
16.2 Fats and Oils 508
16.3 Soaps 511
16.4 Phospholipids 513
16.5 Steroids 515
16.6 Nucleic Acids and Nucleotides 517
16.7 Structure of DNA 519
16.8 Base Pairing in DNA: The Watson-Crick Model 522
16.10 Replication of DNA 525
16.9 Nucleic Acids and Heredity 525
16.11 Structure and Synthesis of RNA: Transcription 527
16.12 RNA and Protein Biosynthesis: Translation 528
16.13 Sequencing DNA 532
16.14 The Polymerase Chain Reaction 536
Interlude—Cholesterol and Heart Disease 538
Summary and Key Words 539
Additional Problems 540
17 The Organic Chemistry of Metabolic Pathways 543
17.1 An Overview of Metabolism and Biochemical Energy 543
17.2 Catabolism of Fats: β-Οxidation Pathway 547
17.3 Catabolism of Carbohydretes: Glycolysis 552
17.4 The Citric Acid Cycle 557
17.5 Catabolism of Proteins: Transamination 560
Interlude—Basal Metabolism 562
Summary and Key Words 563
Additional Problems 564