Organic Chemistry (Fourth Edition)

Organic Chemistry 4E\r......Page 1
Brief Contents\r......Page 7
Contents\r......Page 9
Selected Applications\r......Page 21
Organic Reaction Animations\r......Page 23
Introduction\r......Page 25
1  Atoms and Molecules; Orbitals and Bonding\r......Page 43
1.1  Preview......Page 44
1.2  Atoms and Atomic Orbitals......Page 46
1.3  Covalent Bonds and Lewis Structures......Page 55
1.4  Resonance Forms\r......Page 64
1.5  Hydrogen (H2): Molecular Orbitals\r......Page 72
1.6  Bond Strength\r......Page 78
1.7  An Introduction to Reactivity: Acids and Bases\r......Page 83
1.8  Special Topic: Quantum Mechanics and Babies\r......Page 84
1.9  Summary\r......Page 85
1.10  Additional Problems\r......Page 87
2  Alkanes......Page 92
2.1 Preview\r......Page 93
2.2 Hyrbid Orbitals: Making a Model for Methane......Page 94
2.3 The Methyl Group (CH3) and Methyl Compunds (CH3X)......Page 102
2.4 The Methyl Cation (+CH3), Anion (-:CH3), and Radical (.CH3)......Page 104
2.5 Ethane (C2H6), Ethyl Compunds (C2H5X), and Newman Projections......Page 106
2.6 Structure Drawings......Page 112
2.7 Propane (C3H8) and Propyl Compunds (C3H7X)......Page 113
2.8 Butanes (C4H10), Butyl Compunds (C4H9X), and Conformational Analysis......Page 115
2.9 Pentanes (C5H12) and Pentyl Compunds (C5H11X)......Page 118
2.10 The Naming Conventions for Alkanes......Page 120
2.11 Drawing Isomers......Page 124
2.12 Rings......Page 125
2.13 Physical Properties of Alkanes and Cycloalkanes......Page 128
2.14 Nuclear Magnetic Resonance Spectroscopy......Page 130
2.15 Acids and Bases Revisited: More Chemical Reactions......Page 132
2.16 Special Topic: Alkanes as Biomolecules......Page 134
2.17 Summary......Page 135
2.18 Additional Problems......Page 136
3  Alkenes and Alkynes\r......Page 139
3.1 Preview......Page 140
3.2 Alkenes: Structure and Bonding......Page 141
3.3 Derivatives and Isomers of Alkenes......Page 149
3.4 Nomenclature......Page 152
3.5 The Cahn-Inglod-Prelog Priority System......Page 154
3.6 Relative Stability of Alkenes: Heats of Formation......Page 157
3.7 Double Bonds in Rings......Page 160
3.9 Alkynes: Structure and Bonding......Page 165
3.11 Derivatives and Isomers of Alkynes......Page 168
3.12 Triple Bonds in Rings......Page 170
3.14 Acidity of Alkynes......Page 171
3.15 Molecular Formulas and Degrees of Unsaturation......Page 172
3.16 An Introduction to Addition Reactions of Alkenes and Alkynes......Page 173
3.17 Mechnism of the Addition of Hydrogen Halides to Alkenes......Page 174
3.18 The Regiochemistry of the Addition Reaction......Page 179
3.19 A Catalyzed Addition to Alkenes: Hydration......Page 181
3.20 Synthesis: A Beginning......Page 183
3.21 Special Topic: Alkenes and Biology......Page 184
3.22 Summary......Page 185
3.23 Additional Problems......Page 186
4  Stereochemistry......Page 189
4.1 Preview......Page 190
4.2 Chirality......Page 191
4.3 The (RIS) Convention......Page 194
4.4 Properties of Enantiomers: Physical Differences......Page 197
4.5 The Physical Basis of Optical Activity......Page 199
4.6 Properties of Enantiomers: Chemical Differences......Page 201
4.7 Interconversion of Enantiomers by Rotation about a Single Bond: gauche-Butance......Page 205
4.8 Diastereomers and Molecules Containing More than One Stereogenic Atom......Page 206
4.9 Physical Properties of Diastereomers: Resolution, a Method of Separating Enantiomers from Each Other......Page 211
4.10 Determination of Absolute Configuration (R or S)......Page 214
4.11 Stereochemical Analysis of Ring Compounds (a Beginning)......Page 215
4.12 Summary of Isomerism......Page 218
4.13 Special Topic: Chirality without \"Four Different Groups Attached to One Carbon\"......Page 219
4.14 Special Topic: Stereochemistry in the Real World: Thalidomide, the Consequences of Being Wrong-Handed......Page 222
4.15 Summary......Page 223
4.16 Additional Problems......Page 224
5  Rings......Page 227
5.1 Preview......Page 228
5.2 Rings and Strain......Page 229
5.3 Quantitative Evaluation of Strain Energy......Page 235
5.4 Stereochemistry of Cyclohexane: Conformational Analysis......Page 239
5.5 Monosubstituted Cyclohexanes......Page 241
5.6 Disubstituted Ring Compounds......Page 246
5.7 Bicyclic Compounds......Page 253
5.8 Special Topic: Polycyclic Systems......Page 258
5.9 Special Topic: Adamantanes in Materials and Biology......Page 259
5.10 Summary......Page 261
5.11 Additional Problems......Page 262
6  \rAlkyl Halides, Alcohols, Amines, Ethers, and Their Sulfur-Containing Relatives......Page 265
6.1 Preview......Page 266
6.2 Alkyl Halides: Nomenclature and Structure......Page 267
6.3 Alkyl Halides as Sources of Organometallic Reagents: A Synthesis of Hydrocarbons......Page 269
6.4 Alcohols......Page 272
6.5 Solvents in Organic Chemistry......Page 280
6.7 Amines......Page 282
6.8 Ethers......Page 291
6.9 Special Topic: Thiols (Mercaptans) and Thioethers (Sulfides)......Page 293
6.10 Special Topic: Crown Ethers......Page 296
6.11 Special Topic: Complex Nitrogen-Containing Biomolecules-Alkaloids......Page 297
6.12 Summary......Page 298
6.13 Additional Problems......Page 300
7  \rSubstitution and Elimination Reactions: The SN2, SN1, E1, and E2 Reactions......Page 303
7.1 Preview......Page 304
7.2 Review of Lewis Acids and Bases......Page 305
7.3 Reactions of Alkyl Halides: The Substitution Reaction......Page 309
7.4 Substitution, Nucleophilic, Biomolecular: The SN2 Reaction......Page 310
7.5 The SN2 Reaction in Biochemistry......Page 330
7.6 Substitution, Nucleophilic, Unimolecular: The SN1 Reaction......Page 331
7.7 Summary and Overview of the SN2 and SN1 Reactions......Page 338
7.8 The Unimolecular Elimination Reaction: E1......Page 340
7.9 The Biomolecular Elimination Reaction: E2......Page 343
7.10 What Can We Do with These Reactions? How to Do Organic Synthesis......Page 354
7.11 Summary......Page 362
7.12 Additional Problems......Page 365
8  \rEquilibria......Page 373
8.1 Preview......Page 374
8.2 Equilibrium......Page 376
8.3 Entropy in Organic Reactions......Page 379
8.4 Rates of Chemical Reactions......Page 381
8.5 Rate Constant......Page 383
8.6 Energy Barriers in Chemical Reactions: The Transition State and Activation Energy......Page 384
8.7 Reaction Mechanism......Page 391
8.8 The Hammond Postulate: Thermodynamics versus Kinetics......Page 393
8.9 Special Topic: Enzymes and Reaction Rates......Page 399
8.10 Summary......Page 400
8.11 Additional Problems......Page 402
9   Additions to Alkenes 1......Page 405
9.1 Preview......Page 406
9.2 Mechanism of the Addition of Hydrogen Halides to Alkenes......Page 407
9.3 Effects of Resonance on Regiochemistry......Page 408
9.4 Brief Review of Resonance......Page 414
9.5 Resonance and the Stability of Carbocations......Page 416
9.6 Inductive Effects on Addition Reactions......Page 420
9.7 HX Addition Reactions: Hydration......Page 422
9.8 Dimerization and Polymerization of Alkenes......Page 426
9.9 Rearrangements during HX Addition to Alkenes......Page 428
9.10 Hydroboration......Page 432
9.11 Hydroboration in Synthesis: Alcohol Formation......Page 440
9.12 Special Topic: Rearrangements in Biological Processes......Page 443
9.13 Summary......Page 444
9.14 Additional Problems......Page 446
10  Additions to Alkenes 2 and Additions to Alkynes\r......Page 451
10.2 Addition of H2 and X2 Reagents......Page 452
10.3 Hydration through Mercury Compounds: Oxymercuration......Page 463
10.4 Other Addition Reactions Involving Three-Membered Rings: Oxiranes and Cyclopropanes......Page 465
10.5 Dipolar Addition Reactions: Ozonolysis and the Snythesis of Carbonyl (R2C==O) Compounds......Page 478
10.6 Addition Reactions of Alkynes: HX Addition......Page 486
10.7 Addition of X2 Reagents to Alkynes......Page 489
10.8 Hydration of Alkynes......Page 490
10.9 Hydroboration of Alkynes......Page 492
10.11 Reduction by Sodium in Ammonia: Alkene Synthesis through anti Hydrogenation......Page 494
10.12 Special Topic: Three-Membered Rings in Biochemistry......Page 497
10.13 Summary......Page 498
10.14 Additional Problems......Page 502
11  Radical Reactions\r......Page 509
11.1 Preview......Page 510
11.2 Formation and Simple Reactions of Radicals......Page 511
11.3 Structure and Stability of Radicals......Page 519
11.4 Radical Addition to Alkenes......Page 523
11.5 Other Radical Addition Reactions......Page 529
11.6 Radical-Initiated Addition of HBr to Alkynes......Page 531
11.7 Photohalogenation......Page 532
11.8 Allylic Halogenation: Synthetically Useful Reactions......Page 539
11.9 Special Topic: Rearrangements (and Nonrearrangements) of Radicals......Page 543
11.10 Special Topic: Radicals in Our Bodies; Do Free Radicals Age Us?......Page 546
11.11 Summary......Page 547
11.12 Additional Problems......Page 549
12  Dienes and the Allyl System: 2p Orbitals in Conjugation......Page 553
12.1 Preview......Page 554
12.2 Allenes......Page 555
12.3 Related Systems: Ketenes and Cumulenes......Page 557
12.4 Allenes as Intermediates in the Isomerization of Alkynes......Page 558
12.5 Conjugated Dienes......Page 561
12.6 The Physical Consequences of Conjugation......Page 563
12.7 Molecular Orbitals and Ultraviolent Spectroscopy......Page 567
12.8 Polyenes and Vision......Page 575
12.9 The Chemical Consequences of Conjugation: Addition Reactions of Conjugated Dienes......Page 576
12.10 Thermodynamic and Kinetic Control of Addition Reactions......Page 579
12.11 The Allyl System: Three Overlapping 2p Orbitals......Page 583
12.12 The Diels-Alder Reaction of Conjugated Dienes......Page 586
12.13 Special Topic: Biosynthesis of Terpenes......Page 596
12.14 Special Topic: Steroid Biosynthesis......Page 601
12.15 Summary......Page 605
12.16 Additional Problems......Page 606
13  Conjugation and Aromaticity......Page 613
13.1 Preview......Page 614
13.2 The Structure of Benzene......Page 615
13.3 A Resonance Picture of Benzene......Page 617
13.4 The Molecular Orbital Picture of Benzene......Page 620
13.5 Quantitative Evaluations of Resonance Stabilization in Benzene......Page 622
13.6  A Generalization of Aromaticity: Hückel\'s 4n + 2 Rule\r......Page 624
13.7  Substituted Benzenes\r......Page 637
13.9  Heterobenzenes and Other Heterocyclic Aromatic Compounds\r......Page 640
13.10  Polynuclear Aromatic Compounds\r......Page 644
13.11  Introduction to the Chemistry of Benzene\r......Page 648
13.12  The Benzyl Group and Its Reactivity\r......Page 652
13.13  Special Topic: The Bio-Downside, the Mechanism of Carcinogensis by Polycyclic Aromatic Compounds\r......Page 656
13.14  Summary\r......Page 659
13.15  Additional Problems\r......Page 661
14  Substitution Reactions of Aromatic Compounds\r......Page 665
14.1  Preview\r......Page 666
14.2 Hydrogenation of Aromatic Compounds\r......Page 668
14.3  Diels-Alder Reactions\r......Page 670
14.4  Substitution Reactions of Aromatic Compounds\r......Page 673
14.5  Carbon-Carbon Bond Formation: Friedel-Crafts Alkylation\r......Page 681
14.6  Friedel-Crafts Acylation\r......Page 685
14.7  Synthetic Reactions We Can Do So Far\r......Page 688
14.8  Electrophilic Aromatic Substitution of Heteroaromatic Compounds\r......Page 694
14.9  Disubstituted Benzenes: Ortho, Meta, and Para Substitution......Page 697
14.10  Inductive Effects in Aromatic Substitution\r......Page 708
14.11  Synthesis of Polysubstituted Benzenes\r......Page 710
14.12  Nucleophilic Aromatic Substitution\r......Page 716
14.13  Special Topic: Stable Carbocations in \"Superacid\"\r......Page 721
14.14  Special Topic: Benzyne\r......Page 722
14.15  Special Topic: Biological Synthesis of Aromatic Rings, Phenylalanine\r......Page 724
14.16  Summary\r......Page 727
14.17  Additional Problems\r......Page 730
15  Analytical Chemistry: Spectroscopy\r......Page 736
15.1  Preview\r......Page 737
15.2  Chromatography\r......Page 739
15.3  Mass Spectrometry (MS)\r......Page 741
15.5  1H Nuclear Magnetic Resonance Spectroscopy (NMR)\r......Page 755
15.6  NMR Measurements\r......Page 759
15.7  13C NMR Spectroscopy\r......Page 782
15.8  Problem Solving: How to Use Spectroscopy to Determine Structure\r......Page 784
15.9  Special Topic: Dynamic NMR\r......Page 788
15.10  Summary\r......Page 792
15.11  Additional Problems\r......Page 793
16  Carbonyl Chemistry 1: Addition Reactions\r......Page 804
16.1  Preview\r......Page 805
16.2  Structure of the Carbon-Oxygen Double Bond\r......Page 806
16.3  Nomenclature of Carbonyl Compounds\r......Page 809
16.4  Physical Properties of Carbonyl Compounds\r......Page 812
16.5  Reactions of Carbonyl Compounds: Simple Reversible Additions\r......Page 815
16.7  Equilibrium in Addition Reactions\r......Page 819
16.8  Other Addition Reactions: Additions of Cyanide and Bisulfite\r......Page 823
16.9  Additional Reactions Followed by Water Loss: Acetal Formation\r......Page 825
16.10  Protecting Groups in Synthesis\r......Page 830
16.11  Addition Reactions of Nitrogen Base: Imine and Enamine Formation\r......Page 832
16.12  Organometallic Reagents\r......Page 839
16.13  Irreversible Addition Reactions: A General Synthesis of Alcohols\r......Page 841
16.14  Oxidation of Alcohols to Carbonyl Compounds\r......Page 844
16.15  Retrosynthetic Alcohol Synthesis\r......Page 849
16.16  Oxidation of Thiols and Other Sulfur Compounds\r......Page 851
16.17  The Wittig Reaction\r......Page 853
16.18  Special Topic: Biological Oxidation\r......Page 855
16.19  Summary\r......Page 858
16.20  Additional Problems\r......Page 863
17  Carboxylic Acids......Page 870
17.1  Preview\r......Page 871
17.2  Nomenclature and Properties of Carboxylic Acids\r......Page 872
17.3  Structure of Carboxylic Acids\r......Page 874
17.4  Infrared and Nuclear Magnetic Resonance Spectra of Carboxylic Acids\r......Page 875
17.5  Acidity and Basicity of Carboxylic Acids\r......Page 876
17.6  Synthesis of Carboxylic Acids\r......Page 881
17.7  Reactions of Carboxylic Acids\r......Page 883
17.8  Special Topic: Fatty Acids\r......Page 904
17.9  Summary\r......Page 909
17.10  Additional Problems\r......Page 912
18  Derivatives of Carboxylic Acids: Acyl Compounds\r......Page 918
18.1  Preview\r......Page 919
18.2  Nomenclature\r......Page 921
18.3  Physical Properties and Structures of Acyl Compounds\r......Page 926
18.4  Acidity and Basicity of Acyl Compounds\r......Page 927
18.5  Special Characteristics\r......Page 929
18.6  Reactions of Acid Chlorides: Synthesis of Acyl Compounds......Page 931
18.7  Reactions of Anhydrides\r......Page 936
18.8  Reaction of Esters\r......Page 937
18.9  Reactions of Amides\r......Page 943
18.10  Reactions of Nitriles\r......Page 946
18.12  Special Topic: Other Synthetic Routes to Acid Derivatives\r......Page 949
18.13  Special Topic: Thermal Elimination Reactions of Esters\r......Page 954
18.14  Special Topic: A Family of Concerted Rearrangements of Acyl Compounds\r......Page 956
18.15  Summary\r......Page 963
18.16  Additional Problems\r......Page 967
19   Carbonyl Chemistry 2: Reactions at the α Position......Page 973
19.1  Preview\r......Page 974
19.2  Many Carbonyl Compounds Are Weak Brønsted Acids\r......Page 975
19.3  Racemization of Enols and Enolates\r......Page 986
19.4  Halogenation in the a Position\r......Page 988
19.5  Alkylation in a Position\r......Page 996
19.6  Addition of Carbonyl Compounds to the a Position: The Aldol Condensation\r......Page 1007
19.7  Reactions Related to the Adol Condensation\r......Page 1022
19.8  Addition of Acid Derivatives to the a Position: The Claisen Condensation\r......Page 1027
19.10  Special Topic: Forward and Reverse Claisen Condensation in Biology\r......Page 1038
19.11  Condensation Reactions in Combination\r......Page 1040
19.12  Special Topic: Alkylation of Dithianes\r......Page 1043
19.13  Special Topic: Amines in Condensation Reactions, the Mannich Reaction\r......Page 1045
19.14  Special Topic: Carbonyl Compounds without a Hydrogens\r......Page 1046
19.15  Special Topic: The Aldol Condensation in the Real World, an Introduction to Modern Synthesis\r......Page 1049
19.16  Summary\r......Page 1052
19.17  Additional Problems\r......Page 1059
20  Special Topic: Reactions Controlled by Orbital Symmetry\r......Page 1072
20.1  Preview\r......Page 1073
20.2  Concerted Reactions\r......Page 1074
20.3  Electrocyclic Reactions\r......Page 1076
20.4  Cycloaddition Reactions\r......Page 1085
20.5  Sigmatropic Shift Reactions\r......Page 1090
20.6  The Cope Rearrangement\r......Page 1101
20.7  A Molecule with  Fluxional Structure\r......Page 1105
20.8  How to Work Orbital Symmetry Problems\r......Page 1113
20.9  Summary\r......Page 1115
20.10  Additional Problems\r......Page 1116
21  Special Topic: Intramolecular Reactions and Neighboring Group Participation......Page 1122
21.1  Preview\r......Page 1123
21.2  Heteratoms as Neighboring Groups\r......Page 1125
21.3  Neighboring pi \rSystems......Page 1138
21.4  Single Bonds as Neighboring Groups\r......Page 1150
21.5  Coates\' Cation\r......Page 1159
21.7 Additional Problems......Page 1160
22  Special Topic: Carbohydrates\r......Page 1166
22.1  Preview\r......Page 1167
22.2  Nomenclature and Structure of Carbohydrates\r......Page 1168
22.3  Formation of Carbohydrates\r......Page 1180
22.4  Reactions of Carbohydrates\r......Page 1182
22.5  The Fischer Determination of the Structure of D-Glucose (and the 15 Other Aldohexoses\r......Page 1195
22.6  Special Topic: An Introduction to Di-and Polysaccharides\r......Page 1203
22.7  Summary\r......Page 1210
22.8  Additional Problems\r......Page 1212
23  Special Topic: Amino Acids and Polyamino Acids (Peptides and Proteins)\r......Page 1215
23.1  Preview\r......Page 1216
23.2  Amino Acids\r......Page 1217
23.3 Reactions of Amino Acids\r......Page 1228
23.4  Peptide Chemistry\r......Page 1231
23.5  Nucleosides, Nucleotides, and Nucleic Acids\r......Page 1252
23.6  Summary\r......Page 1257
23.7  Additional Problems\r......Page 1260
Glossary\r......Page 1263
Credits\r......Page 1279
Index\r......Page 1281