Organic Chemistry, Enhanced Edition

Front Cover......Page 1
Title Page......Page 2
Copyright......Page 3
CONTENTS......Page 10
1.1 Electronic Structure of Atoms......Page 34
1.2 Lewis Model of Bonding......Page 39
How To Draw Lewis Structures from Condensed Structural Formulas......Page 49
1.3 Functional Groups......Page 50
1.4 Bond Angles and Shapes of Molecules......Page 55
1.5 Polar and Nonpolar Molecules......Page 58
1.6 Quantum or Wave Mechanics......Page 60
1.7 A Combined Valence Bond and Molecular Orbital Theory Approach to Covalent Bonding......Page 63
1.8 Resonance......Page 74
How To Draw Curved Arrows and Push Electrons in Creating Contributing Structures......Page 75
1.9 Molecular Orbitals for Delocalized Systems......Page 80
1.10 Bond Lengths and Bond Strengths in Alkanes, Alkenes, and Alkynes......Page 82
Summary......Page 83
Problems......Page 86
2.1 The Structure of Alkanes......Page 94
2.2 Constitutional Isomerism in Alkanes......Page 96
2.3 Nomenclature of Alkanes and the IUPAC System......Page 98
2.4 Cycloalkanes......Page 103
2.5 Conformations of Alkanes and Cycloalkanes......Page 106
How To Draw Alternative Chair Conformations of Cyclohexane......Page 117
2.6 Cis,Trans Isomerism in Cycloalkanes and Bicycloalkanes......Page 119
How To Convert Planar Cyclohexanes to Chair Cyclohexanes......Page 121
Chemical Connections The Poisonous Puffer Fish......Page 126
2.7 Physical Properties of Alkanes and Cycloalkanes......Page 127
2.8 Reactions of Alkanes......Page 130
2.9 Sources and Importance of Alkanes......Page 132
Chemical Connections Octane Rating: What Those Numbers at the Pump Mean......Page 134
Summary......Page 135
Problems......Page 137
3.1 Stereoisomerism......Page 145
3.2 Chirality—The Handedness of Molecules......Page 146
How To Draw Chiral Molecules......Page 147
3.3 Naming Chiral Centers—The R,S Systems......Page 150
How To Assign R or S Configuration to a Chiral Center......Page 151
3.4 Acyclic Molecules with Two or More Chiral Centers......Page 153
3.5 Cyclic Molecules with Two or More Chiral Centers......Page 158
3.6 Properties of Stereoismers......Page 161
3.7 Optical Activity—How Chirality Is Detected in the Laboratory......Page 162
3.8 The Significance of Chirality in the Biological World......Page 166
Connections to Biological Chemistry Chiral Drugs......Page 168
3.9 Separation of Enantiomers—Resolution......Page 169
Summary......Page 173
Problems......Page 175
4.1 Arrhenius Acids and Bases......Page 182
4.2 Brønsted-Lowry Acids and Bases......Page 183
4.3 Acid Dissociation Constants, pK[Sub(a)], and Strengths of Acids and Bases......Page 189
4.4 The Position of Equilibrium in Acid-Base Reactions......Page 191
How To Calculate Equilibrium Constants for Acid-Base Reactions......Page 192
Connections to Biological Chemistry The Ionization of Functional Groups at Physiological pH......Page 193
4.5 Thermochemistry and Mechanism of Acid-Base Reactions......Page 194
4.6 Molecular Structure and Acidity......Page 198
4.7 Lewis Acids and Bases......Page 204
Summary......Page 206
Problems......Page 208
CHAPTER 5 ALKENES......Page 216
5.1 Structure of Alkenes......Page 217
How To Calculate the Index of Hydrogen Deficiency......Page 218
5.2 Nomenclature of Alkenes......Page 220
5.3 Physical Properties of Alkenes......Page 225
Chemical Connections The Case of the Iowa and New York Strains of the European Corn Borer......Page 226
5.4 Naturally Occurring Alkenes—Terpene Hydrocarbons......Page 227
Connections to Biological Chemistry The Importance of Cis Double Bonds in Fats Versus Oils 196......Page 229
Problems......Page 231
6.1 Reactions of Alkenes—An Overview......Page 237
6.2 Organic Reactions Involving Reactive Intermediates......Page 238
6.3 Electrophilic Additions......Page 247
6.4 Hydroboration-Oxidation......Page 265
How To Write a Balanced Half-Reaction......Page 269
6.5 Oxidation......Page 270
6.6 Reduction......Page 274
6.7 Molecules Containing Chiral Centers as Reactants or Products......Page 277
Summary......Page 282
Problems......Page 287
7.1 Structure of Alkynes......Page 295
7.2 Nomenclature of Alkynes......Page 296
7.3 Physical Properties of Alkynes......Page 297
7.4 Acidity of 1-Alkynes......Page 298
7.5 Preparation of Alkynes......Page 299
7.6 Electrophilic Addition to Alkynes......Page 302
7.7 Hydration of Alkynes to Aldehydes and Ketones......Page 304
7.8 Reduction of Alkynes......Page 309
7.9 Organic Synthesis......Page 311
Summary......Page 315
Problems......Page 318
8.1 Structure......Page 325
8.2 Nomenclature......Page 326
8.3 Physical Properties of Haloalkanes......Page 327
8.4 Preparation of Haloalkanes by Halogenation of Alkanes......Page 331
8.5 Mechanism of Halogenation of Alkanes......Page 335
Chemical Connections Freons......Page 338
8.6 Allylic Halogenation......Page 342
8.7 Radical Autoxidation......Page 346
Connections to Biological Chemistry Antioxidants......Page 347
8.8 Radical Addition of HBr to Alkenes......Page 349
Summary......Page 352
Problems......Page 354
CHAPTER 9 NUCLEOPHILIC SUBSTITUTION AND b-ELIMINATION......Page 360
9.1 Nucleophilic Substitution in Haloalkanes......Page 361
9.2 Mechanisms of Nucleophilic Substitution......Page 363
9.3 Experimental Evidence for S[Sub(N)]1 and S[Sub(N)]2 Mechanisms......Page 366
9.4 Analysis of Several Nucleophilic Substitution Reactions......Page 381
9.5 b-Elimination......Page 383
9.6 Mechanisms of b-Elimination......Page 385
9.7 Experimental Evidence for E1 and E2 Mechanisms......Page 387
9.8 Substitution Versus Elimination......Page 392
9.9 Neighboring Group Participation......Page 396
Summary......Page 399
Problems......Page 404
CHAPTER 10 ALCOHOLS......Page 413
10.1 Structure and Nomenclature of Alcohols......Page 414
10.2 Physical Properties of Alcohols......Page 416
Connections to Biological Chemistry The Importance of Hydrogen Bonding in Drug Receptor Interactions......Page 418
10.3 Acidity and Basicity of Alcohols......Page 420
10.4 Reaction of Alcohols with Active Metals......Page 421
10.5 Conversion of Alcohols to Haloalkanes and Sulfonates......Page 422
10.6 Acid-Catalyzed Dehydration of Alcohols......Page 428
10.7 The Pinacol Rearrangement......Page 432
10.8 Oxidation of Alcohols......Page 435
Chemical Connections Blood Alcohol Screening......Page 438
Connections to Biological Chemistry The Oxidation of Alcohols by NAD[Sup(+)]......Page 439
10.9 Thiols......Page 442
Summary......Page 446
Problems......Page 450
11.2 Nomenclature of Ethers......Page 458
11.3 Physical Properties of Ethers......Page 460
11.4 Preparation of Ethers......Page 461
11.5 Reactions of Ethers......Page 465
11.6 Silyl Ethers as Protecting Groups......Page 467
11.7 Epoxides: Structure and Nomenclature......Page 469
11.8 Synthesis of Epoxides......Page 470
11.9 Reactions of Epoxides......Page 474
11.10 Ethylene Oxide and Epichlorohydrin: Building Blocks in Organic Synthesis......Page 477
11.11 Crown Ethers......Page 479
11.12 Sulfides......Page 480
Summary......Page 482
Problems......Page 486
12.1 Electromagnetic Radiation......Page 495
12.3 Infrared Spectroscopy......Page 496
12.4 Interpreting Infrared Spectra......Page 502
12.5 Solving Infrared Spectral Problems......Page 510
Summary......Page 511
Problems......Page 513
13.1 Nuclear Spin States......Page 516
13.2 Orientation of Nuclear Spins in an Applied Magnetic Field......Page 517
13.3 Nuclear Magnetic Resonance......Page 518
13.4 An NMR Spectrometer......Page 520
13.5 Equivalent Hydrogens......Page 522
13.6 Signal Areas......Page 524
13.7 Chemical Shift......Page 525
13.8 Signal Splitting and the (n + 1) Rule......Page 529
13.9 The Origins of Signal Splitting......Page 530
13.10 Stereochemistry and Topicity......Page 538
Chemical Connections Magnetic Resonance Imaging......Page 540
13.11 [Sup(13)]C-NMR......Page 541
13.12 Interpretation of NMR Spectra......Page 543
How To Solve NMR Spectral Problems......Page 546
Summary......Page 549
Problems......Page 551
14.1 A Mass Spectrometer......Page 559
14.2 Features of a Mass Spectrum......Page 562
14.3 Interpreting Mass Spectra......Page 566
Connections to Biological Chemistry Mass Spectrometry of Biological Macromolecules......Page 573
14.4 Mass Spectrometry in the Organic Synthesis Laboratory and Other Applications......Page 574
Summary......Page 575
Problems......Page 576
15.1 Organomagnesium and Organolithium Compounds......Page 581
15.2 Lithium Diorganocopper (Gilman) Reagents......Page 586
15.3 Carbenes and Carbenoids......Page 589
Summary......Page 592
Problems......Page 595
16.1 Structure and Bonding......Page 599
16.2 Nomenclature......Page 600
16.3 Physical Properties......Page 603
16.4 Reactions......Page 604
16.5 Addition of Carbon Nucleophiles......Page 606
16.6 The Wittig Reaction......Page 610
16.7 Addition of Oxygen Nucleophiles......Page 614
16.8 Addition of Nitrogen Nucleophiles......Page 622
16.9 Keto-Enol Tautomerism......Page 627
Connections to Biological Chemistry Pyridoxine (Vitamin B6), a Carrier of Amino Groups......Page 625
16.10 Oxidation......Page 630
16.11 Reduction......Page 632
Connections to Biological Chemistry NADH: The Biological Equivalent of a Hydride Reducing Agent......Page 634
16.12 Reactions at an a-Carbon......Page 638
Summary......Page 641
Problems......Page 647
17.2 Nomenclature......Page 661
17.3 Physical Properties......Page 665
Chemical Connections From Willow Bark to Aspirin and Beyond......Page 666
17.4 Acidity......Page 667
17.5 Preparation of Carboxylic Acids......Page 670
17.6 Reduction......Page 672
17.7 Esterification......Page 673
Chemical Connections The Pyrethrins: Natural Insecticides of Plant Origin......Page 675
Chemical Connections Esters as Flavoring Agents......Page 677
17.8 Conversion to Acid Chlorides......Page 678
17.9 Decarboxylation......Page 679
Connections to Biological Chemistry Ketone Bodies and Diabetes Mellitus......Page 681
Summary......Page 682
Problems......Page 685
18.1 Structure and Nomenclature......Page 694
Chemical Connections From Cocaine to Procaine and Beyond......Page 697
Chemical Connections From Moldy Clover to a Blood Thinner......Page 698
Chemical Connections The Penicillins and Cephalosporins: b-Lactam Antibiotics......Page 700
18.2 Acidity of Amides, Imides, and Sulfonamides......Page 701
18.3 Characteristics of Reactions......Page 703
18.4 Reaction with Water: Hydrolysis......Page 705
18.5 Reaction with Alcohols......Page 715
18.6 Reactions with Ammonia and Amines......Page 718
18.8 Interconversion of Functional Derivatives......Page 720
18.9 Reactions with Organometallic Compounds......Page 721
How To Write Mechanisms for Interconversions of Carboxylic Acid Derivatives......Page 724
18.10 Reduction......Page 726
Summary......Page 730
Problems......Page 736
19.1 Formation and Reactions of Enolate Anions: An Overview......Page 750
19.2 Aldol Reaction......Page 752
19.3 Claisen and Dieckmann Condensations......Page 758
19.4 Claisen and Aldol Condensations in the Biological World......Page 764
Chemical Connections Drugs that Lower Plasma Levels of Cholesterol......Page 765
19.5 Enamines......Page 767
19.6 Acetoacetic Ester Synthesis......Page 771
19.7 Malonic Ester Synthesis......Page 775
Chemical Connections Ibuprofen: The Evolution of an Industrial Synthesis......Page 777
19.8 Conjugate Addition to a,b-Unsaturated Carbonyl Compounds......Page 779
19.9 Crossed Enolate Reactions using LDA......Page 787
Summary......Page 791
Problems......Page 798
20.1 Stability of Conjugated Dienes......Page 815
20.2 Electrophilic Addition to Conjugated Dienes......Page 819
20.3 UV-Visible Spectroscopy......Page 824
Chemical Connections Curry and Cancer......Page 828
Summary......Page 829
Problems......Page 831
CHAPTER 21 BENZENE AND THE CONCEPT OF AROMATICITY......Page 833
21.1 The Structure of Benzene......Page 834
21.2 The Concept of Aromaticity......Page 838
21.3 Nomenclature......Page 847
21.4 Phenols......Page 850
Chemical Connections Capsaicin, for Those Who Like It Hot......Page 852
21.5 Reactions at a Benzylic Position......Page 859
Summary......Page 863
Problems......Page 868
CHAPTER 22 REACTIONS OF BENZENE AND ITS DERIVATIVES......Page 885
22.1 Electrophilic Aromatic Substitution......Page 886
22.2 Disubstitution and Polysubstitution......Page 896
22.3 Nucleophilic Aromatic Substitution......Page 903
Summary......Page 906
Problems......Page 911
23.1 Structure and Classification......Page 925
23.2 Nomenclature......Page 926
23.3 Chirality of Amines and Quaternary Ammonium Ions......Page 929
23.4 Physical Properties......Page 930
Chemical Connections The Poison Dart Frogs of South America......Page 931
23.5 Basicity......Page 932
Connections to Biological Chemistry The Planarity of -NH[Sub(2)] Groups on Aromatic Rings......Page 935
23.6 Reactions with Acids......Page 939
23.7 Preparation......Page 942
23.8 Reaction with Nitrous Acid......Page 944
23.9 Hofmann Elimination......Page 951
23.10 Cope Elimination......Page 953
Summary......Page 954
Problems......Page 959
24.1 Carbon–Carbon Bond-Forming Reactions from Earlier Chapters......Page 975
24.2 Organometallic Compounds......Page 976
24.3 Organopalladium Reagents—The Heck Reaction......Page 977
24.4 Organopalladium Reagents—The Suzuki Coupling......Page 983
24.5 Alkene Metathesis......Page 985
24.6 The Diels-Alder Reaction......Page 988
24.7 Pericyclic Reactions and Transition State Aromaticity......Page 996
24.8 The Synthesis of Enantiomerically Pure Target Molecules......Page 999
Summary......Page 1001
Problems......Page 1005
CHAPTER 25 CARBOHYDRATES......Page 1021
25.1 Monosaccharides......Page 1022
25.2 The Cyclic Structure of Monosaccharides......Page 1026
Chemical Connections L-Ascorbic Acid (Vitamin C)......Page 1028
25.3 Reactions of Monosaccharides......Page 1030
Chemical Connections Testing for Glucose......Page 1035
25.4 Disaccharides and Oligosaccharides......Page 1036
Chemical Connections A, B, AB, and O Blood Group Substances......Page 1039
25.5 Polysaccharides......Page 1040
Chemical Connections High-Fructose Corn Syrup......Page 1041
25.6 Glucosaminoglycans......Page 1042
Summary......Page 1043
Problems......Page 1047
26.1 Triglycerides......Page 1055
26.2 Soaps and Detergents......Page 1058
Connections to Biological Chemistry FAD/FADH[Sub(2)]: Agents for Electron Transfer in Biological Oxidation-Reductions, Fatty Acid Oxidation......Page 1061
26.3 Prostaglandins......Page 1062
26.4 Steroids......Page 1065
Chemical Connections Drugs that Lower Plasma Levels of Cholesterol......Page 1069
26.5 Phospholipids......Page 1070
Chemical Connections Snake Venom Phospholipases......Page 1072
26.6 Fat-Soluble Vitamins......Page 1073
Chemical Connections Vitamin K, Blood Clotting, and Basicity......Page 1075
Summary......Page 1077
Problems......Page 1079
27.1 Amino Acids......Page 1084
27.2 Acid-Base Properties of Amino Acids......Page 1087
27.3 Polypeptides and Proteins......Page 1092
27.4 Primary Structure of Polypeptides and Proteins......Page 1093
27.5 Synthesis of Polypeptides......Page 1099
27.6 Three-Dimensional Shapes of Polypeptides and Proteins......Page 1103
Chemical Connections Spider Silk......Page 1109
Summary......Page 1110
Problems......Page 1114
CHAPTER 28 NUCLEIC ACIDS......Page 1120
28.1 Nucleosides and Nucleotides......Page 1121
28.2 The Structure of DNA......Page 1123
Chemical Connections The Search for Antiviral Drugs......Page 1125
28.3 Ribonucleic Acids......Page 1129
Chemical Connections The Fountain of Youth......Page 1130
28.4 The Genetic Code......Page 1132
28.5 Sequencing Nucleic Acids......Page 1134
Summary......Page 1138
Problems......Page 1140
CHAPTER 29 ORGANIC POLYMER CHEMISTRY......Page 1143
29.2 Polymer Notation and Nomenclature......Page 1144
29.3 Molecular Weights of Polymers......Page 1145
29.4 Polymer Morphology—Crystalline Versus Amorphous Materials......Page 1146
29.5 Step-Growth Polymerizations......Page 1147
Chemical Connections Stitches That Dissolve......Page 1153
29.6 Chain-Growth Polymerizations......Page 1154
Chemical Connections Organic Polymers That Conduct Electricity......Page 1157
Chemical Connections The Chemistry of Superglue......Page 1164
Chemical Connections Recycling of Plastics......Page 1169
Summary......Page 1171
Problems......Page 1174
1. Thermodynamics and the Equilibrium Constant......Page 1180
2. Major Classes of Organic Acids......Page 1181
3. Bond Dissociation Enthalpies......Page 1182
4. Characteristic [Sup(1)]H-NMR Chemical Shifts......Page 1183
5. Characteristic [Sup(13)]C-NMR Chemical Shifts......Page 1184
6. Characteristic IR Absorption Frequencies......Page 1185
7. Electrostatic Potential Maps......Page 1186
8. Summary of Stereochemical Terms......Page 1187
9. Summary of the Rules of Nomenclature......Page 1191
10. Common Mistakes in Arrow Pushing......Page 1199
GLOSSARY......Page 1204
INDEX......Page 1218