Chapter 1 Introduction and Review 1
1-1 The Origins of Organic Chemistry 1
1-2 Principles of Atomic Structure 2
1-3 Bond Formation:The Octet Rule 5
1-4 Lewis Structures 6
1-5 Multiple Bonding 7
1-6 Electronegativity and Bond Polarity 8
1-7 Formal Charges 9
1-8 Ionic Structures 11
1-9 Resonance 12
1-10 Structural Formulas 15
1-11 Molecular Formulas and Empirical Formulas 18
1-12 Arrhenius Acids and Bases 19
1-13 Br？nsted-Lowry Acids and Bases 21
1-14 Lewis Acids and Bases 26
Summary in Chinese 28
Study Problems 30
Chapter 2 Structure and Properties of Organic Molecules 34
2-1 Wave Properties of Electrons in Orbitals 34
2-2 Molecular Orbitals 36
2-3 Pi Bonding 39
2-4 Hybridization and Molecular Shapes 41
2-5 Drawing Three-Dimensional Molecules 44
2-6 General Rules of Hybridization and Geometry 45
2-7 Bond Rotation 48
2-8 Isomerism 50
2-9 Polarity of Bonds and Molecules 53
2-10 Intermolecular Forces 56
2-11 Polarity Effects on Solubilities 59
Summary in Chinese 61
Study Problems 63
Chapter 3 Brief Introduction and Nomenclature of Organic Compounds 66
3-1 Hydrocarbons 66
3-2 Organic Compounds Containing Oxygen 69
3-3 Organic Compounds Containing Nitrogen 71
3-4 Nomenclature of Alkanes 72
3-5 Nomenclature of Alkenes 79
3-6 Nomenclature of Alkynes 84
3-7 Nomenclature of Cycloalkanes 85
3-8 Nomenclature of Benzene Derivatives 88
3-9 Nomenclature of Alkyl Halides 90
3-10 Nomenclature of Alcohols and Thiols 92
3-11 Nomenclature of Ethers and Sulfides 95
3-12 Nomenclature of Amines 98
3-13 Nomenclature of Ketones and Aldehydes 101
3-14 Nomenclature of Carboxylic Acids 103
3-15 Structure and Nomenclature of Acid Derivatives 107
Summary in Chinese 113
Study Problems 116
Chapter 4 Structure and Stereochemistry of Alkanes 120
4-1 Physical Properties of Alkanes 120
4-2 Uses and Sources of Alkanes 122
4-3 Reactions of Alkanes 125
4-4 Structure and Conformations of Alkanes 126
4-5 Cycloalkanes 131
4-6 Cyclohexane Conformations 135
4-7 Conformations of Monosubstituted Cyclohexanes 138
4-8 Conformations of Disubstituted Cyclohexanes 141
Summary in Chinese 144
Study Problems 146
Chapter 5 The Study of Chemical Reactions 148
5-1 Introduction 148
5-2 Chlorination of Methane 148
5-3 The Free-Radical Chain Reaction 149
5-4 Equilibrium Constants and Free Energy 152
5-5 Enthalpy and Entropy 154
5-6 Bond-Dissociation Enthalpies 156
5-7 Enthalpy Changes in Chlorination 158
5-8 Kinetics and the Rate Equation 159
5-9 Activation Energy and the Temperature Dependence of Rates 160
5-10 Transition States 162
5-11 Rates of Multistep Reactions 163
5-12 Temperature Dependence of Halogenation 164
5-13 Selectivity in Halogenation 165
5-14 The Hammond Postulate 170
5-15 Radical Inhibitors 172
5-16 Reactive Intermediates 173
Summary in Chinese 179
Study Problems 181
Chapter 6 Stereochemistry 184
6-1 Introduction 184
6-2 Chirality 185
6-3 (R)and(S)Nomenclature of Asymmetric Carbon Atoms 190
6-4 Optical Activity 193
6-5 Racemic Mixtures 196
6-6 Enantiomeric Excess and Optical Purity 197
6-7 Chirality of Conformationally Mobile Systems 198
6-8 Chiral Compounds without Asymmetric Atoms 200
6-9 Fischer Projections 202
6-10 Diastereomers 206
6-11 Stereochemistry of Molecules with Two or More Asymmetric Carbons 208
6-12 Meso Compounds 209
6-13 Absolute and Relative Configuration 211
6-14 Physical Properties of Diastereomers 212
6-15 Resolution of Enantiomers 214
Summary in Chinese 216
Study Problems 218
Chapter 7 Alkyl Halides:Nucleophilic Substitution and Elimination 221
7-1 Introduction 221
7-2 Common Uses of Alkyl Halides 222
7-3 Structure of Alkyl Halides 224
7-4 Physical Properties of Alkyl Halides 225
7-5 Preparation of Alkyl Halides 226
7-6 Reactions of Alkyl Halides:Substitution and Elimination 230
7-7 Second-Order Nucleophilic Substitution:The SN2 Reaction 231
7-8 Generality of the SN2 Reaction 233
7-9 Factors Affecting SN2 Reactions:Strength of the Nucleophile 234
7-10 Reactivity of the Substrate in SN2 Reactions 239
7-11 Stereochemistry of the SN2 Reaction 242
7-12 First-Order Nucleophilic Substitution:The SN1 Reaction 244
7-13 Stereochemistry of the SN1 Reaction 248
7-14 Rearrangements in SN1 Reactions 250
7-15 Comparison of SN1 and SN2 Reactions 253
7-16 First-Order Elimination:The E1 Reaction 254
7-17 Positional Orientation of Elimination:Zaitsev's Rule 259
7-18 Second-Order Elimination:The E2 Reaction 261
7-19 Stereochemistry of the E2 Reaction 263
7-20 Comparison of E1 and E2 Elimination Mechanisms 265
Summary in Chinese 267
Study Problems 272
Chapter 8 Structure and Synthesis of Alkenes 276
8-1 Introduction 276
8-2 The Orbital Description of the Alkene Double Bond 277
8-3 Elements of Unsaturation 278
8-4 Commercial Importance of Alkenes 281
8-5 Stability of Alkenes 282
8-6 Physical Properties of Alkenes 287
8-7 Alkene Synthesis by Elimination of Alkyl Halides 289
8-8 Alkene Synthesis by Dehydration of Alcohols 296
8-9 Alkene Synthesis by High-Temperature Industrial Methods 297
Summary in Chinese 299
Study Problems 301
Chapter 9 Reactions of Alkenes 304
9-1 Reactivity of the Carbon-Carbon Double Bond 304
9-2 Electrophilic Addition to Alkenes 305
9-3 Addition of Hydrogen Halides to Alkenes 306
9-4 Addition of Water:Hydration of Alkenes 311
9-5 Hydration by Oxymercuration-Demercuration 313
9-6 Alkoxymercuration-Demercuration 315
9-7 Hydroboration of Alkenes 316
9-8 Addition of Halogens to Alkenes 321
9-9 Formation of Halohydrins 324
9-10 Catalytic Hydrogenation of Alkenes 326
9-11 Addition of Carbenes to Alkenes 329
9-12 Epoxidation of Alkenes 331
9-13 Acid-Catalyzed Opening of Epoxides 332
9-14 Syn Hydroxylation of Alkenes 334
9-15 Oxidative Cleavage of Alkenes 336
9-16 Polymerization of Alkenes 339
Summary in Chinese 342
Study Problems 345
Chapter 10 Alkynes 349
10-1 Introduction 349
10-2 Physical Properties of Alkynes 350
10-3 Commercial Importance of Alkynes 350
10-4 Electronic Structure of Alkynes 352
10-5 Acidity of Alkynes;Formation of Acetylide Ions 353
10-6 Synthesis of Alkynes from Acetylides 355
10-7 Synthesis of Alkynes by Elimination Reactions 358
10-8 Addition Reactions of Alkynes 360
10-9 Oxidation of Alkynes 369
Summary in Chinese 371
Study Problems 374
Chapter 11 Conjugated Systems and Orbital Symmetry 377
11-1 Introduction 377
11-2 Stabilities of Dienes 377
11-3 Molecular Orbitals of a Conjugated System 379
11-4 Allylic Cations 383
11-5 1,2-and 1,4-Addition to Conjugated Dienes 384
11-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene 385
11-7 Allylic Radicals 388
11-8 Molecular Orbitals of the Allylic System 390
11-9 Electronic Configurations of the Allyl Radical,Cation,and Anion 391
11-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 392
11-11 The Diels-Alder Reaction 393
11-12 The Diels-Alder as an Example of a Pericyclic Reaction 400
Summary in Chinese 404
Study Problems 406
Chapter 12 Infrared and Ultraviolet Spectros-copy 409
12-1 Introduction 409
12-2 The Electromagnetic Spectrum 410
12-3 The Infrared Region 411
12-4 Molecular Vibrations 412
12-5 IR-Active and IR-Inactive Vibrations 413
12-6 Measurement of the IR Spectrum 414
12-7 Infrared Spectroscopy of Hydrocarbons 416
12-8 Characteristic Absorptions of Alcohols and Amines 417
12-9 Characteristic Absorptions of Carbonyl Compounds 417
12-10 Characteristic Absorptions of C—N Bonds 418
12-11 Simplified Summary of IR Stretching Frequencies 419
12-12 Reading and Interpreting IR Spectra 420
12-13 Ultraviolet Absorption Spectroscopy 422
12-14 Ultraviolet Light and Electronic Transitions 423
12-15 Measurement of the UV-Visible Spectrum 424
12-16 Interpreting UV-Visible Spectra 426
Summary in Chinese 429
Study Problems 431
Chapter 13 Nuclear Magnetic Resonance Spectroscopy and Mass Spectrometry 434
13-1 Introduction to Nuclear Magnetic Resonance Spectroscopy 434
13-2 Theory of Nuclear Magnetic Resonance 434
13-3 Magnetic Shielding by Electrons 436
13-4 The NMR Spectrometer 437
13-5 The Chemical Shift 437
13-6 The Number of Signals 441
13-7 Areas of the Peaks 442
13-8 Spin-Spin Splitting 443
13-9 Carbon-13 NMR Spectroscopy 448
13-10 Interpreting Carbon NMR Spectra 451
13-11 Introduction to Mass Spectrometry 452
13-12 Determination of the Molecular Formula by Mass Spectrometry 454
13-13 Fragmentation Patterns in Mass Spectrometry 456
Summary in Chinese 460
Study Problems 462
Chapter 14 Structure and Synthesis of Alcohols 466
14-1 Introduction 466
14-2 Structure and Classification of Alcohols 466
14-3 Physical Properties of Alcohols 467
14-4 Commercially Important Alcohols 470
14-5 Acidity of Alcohols and Phenols 471
14-6 Organometallic Reagents for Alcohol Synthesis 475
14-7 Synthesis of Alcohols:Addition of Organometallic Reagents to Carbonyl Compounds 477
14-8 Side Reactions of Organometallic Reagents:Reduction of Alkyl Halides 484
14-9 Synthesis of 1°and 2°Alcohols:Reduction of the Carbonyl Group 486
14-10 Thiols(Mercaptans) 489
Summary in Chinese 491
Study Problems 494
Chapter 15 Reactions of Alcohols 498
15-1 Oxidation States of Alcohols and Related Functional Groups 498
15-2 Oxidation of Alcohols 499
15-3 Additional Methods for Oxidizing Alcohols 501
15-4 Alcohols as Nucleophiles and Electrophiles;Formation of Tosylates 503
15-5 Reduction of Alcohols 506
15-6 Reactions of Alcohols with Hydrohalic Acids 507
15-7 Reactions of Alcohols with Phosphorus Halides 511
15-8 Reactions of Alcohols with Thionyl Chloride 512
15-9 Dehydration Reactions of Alcohols 514
15-10 Unique Reactions of Diols 517
15-11 Esterification of Alcohols 520
15-12 Reactions of Alkoxides 520
Summary in Chinese 522
Study Problems 525
Chapter 16 Ethers,Epoxides,and Sulfides 529
16-1 Introduction 529
16-2 Physical Properties of Ethers 529
16-3 Spectroscopy of Ethers 534
16-4 Synthesis of Ethers 534
16-5 Cleavage of Ethers by HBr and HI 536
16-6 Autoxidation of Ethers 538
16-7 Synthesis of Epoxides 539
16-8 Acid-Catalyzed Ring Opening of Epoxides 541
16-9 Base-Catalyzed Ring Opening of Epoxides 543
16-10 Orientation of Epoxide Ring Opening 544
16-11 Reactions of Epoxides with Grignard and Organolithium Reagents 546
16-12 Epoxy Resins:The Advent of Modern Glues 547
16-13 Sulfides(Thioethers) 548
Summary in Chinese 550
Study Problems 553
Chapter 17 Aromatic Compounds 556
17-1 Introduction:The Discovery of Benzene 556
17-2 The Structure and Properties of Benzene 556
17-3 The Molecular Orbitals of Benzene 560
17-4 Aromatic,Antiaromatic,and Nonaromatic Compounds 562
17-5 Hückel's Rule 563
17-6 Molecular Orbital Derivation of Hückel's Rule 565
17-7 Aromatic Ions 566
17-8 Heterocyclic Aromatic Compounds 570
17-9 Polynuclear Aromatic Hydrocarbons 573
17-10 Aromatic Allotropes of Carbon 574
17-11 Fused Heterocyclic Compounds 576
17-12 Physical Properties of Benzene and Its Derivatives 576
17-13 Spectroscopy of Aromatic Compounds 578
Summary in Chinese 578
Study Problems 579
Chapter 18 Reactions of Aromatic Compounds 584
18-1 Electrophilic Aromatic Substitution 584
18-2 Halogenation of Benzene 585
18-3 Nitration of Benzene 587
18-4 Sulfonation of Benzene 588
18-5 Nitration of Toluene:The Effect of Alkyl Substitution 591
18-6 Activating,Ortho,Para-Directing Substituents 593
18-7 Deactivating,Meta-Directing Substituents 595
18-8 Halogen Substituents:Deactivating,but Ortho,Para-Directing 598
18-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 600
18-10 The Friedel-Crafts Alkylation 602
18-11 The Friedel-Crafts Acylation 605
18-12 Nucleophilic Aromatic Substitution 609
18-13 Addition Reactions of Benzene Derivatives 613
18-14 Side-Chain Reactions of Benzene Derivatives 615
18-15 Reactions of Phenols 618
Summary in Chinese 621
Study Problems 624
Chapter 19 Ketones and Aldehydes 629
19-1 Carbonyl Compounds 629
19-2 Structure of the Carbonyl Group 630
19-3 Physical Properties of Ketones and Aldehydes 630
19-4 Spectroscopy of Ketones and Aldehydes 633
19-5 Industrial Importance of Ketones and Aldehydes 633
19-6 Syntheses of Ketones and Aldehydes 634
19-7 Reactions of Ketones and Aldehydes:Nucleophilic Addition 639
19-8 Hydration of Ketones and Aldehydes 642
19-9 Formation of Acetals 644
19-10 Formation of Cyanohydrins 648
19-11 Formation of Imines 650
19-12 Condensations with Hydroxylamine and Hydrazines 653
19-13 The Wittig Reaction 654
19-14 Oxidation of Aldehydes 657
19-15 Reductions of Ketones and Aldehydes 658
Summary in Chinese 660
Study Problems 664
Chapter 20 Amines 668
20-1 Introduction 668
20-2 Structure of Amines 669
20-3 Physical Properties of Amines 670
20-4 Basicity of Amines 672
20-5 Effects on Amine Basicity 674
20-6 Salts of Amines 677
20-7 Amine Salts as Phase-Transfer Catalysts 678
20-8 Spectroscopy of Amines 679
20-9 Aromatic Substitution of Arylamines and Pyridine 680
20-10 Alkylation of Amines by Alkyl Halides 683
20-11 Acylation of Amines by Acid Chlorides 684
20-12 Formation of Sulfonamides 685
20-13 Amines as Leaving Groups:The Hofmann Elimination 686
20-14 Oxidation of Amines;The Cope Elimination 689
20-15 Reactions of Amines with Nitrous Acid 690
20-16 Reactions of Arenediazonium Salts 691
20-17 Synthesis of Amines by Reductive Amination 695
20-18 Synthesis of Amines by Acylation-Reduction 697
20-19 Syntheses Limited to Primary Amines 698
Summary in Chinese 703
Study Problems 707
Chapter 21 Carboxylic Acids 712
21-1 Introduction 712
21-2 Structure and Physical Properties of Carboxylic Acids 712
21-3 Acidity of Carboxylic Acids 715
21-4 Salts of Carboxylic Acids 718
21-5 Commercial Sources of Carboxylic Acids 720
21-6 Spectroscopy of Carboxylic Acids 721
21-7 Synthesis of Carboxylic Acids 722
21-8 Condensation of Acids with Alcohols:The Fischer Esterification 723
21-9 Esterification Using Diazomethane 726
21-10 Condensation of Acids with Amines:Direct Synthesis of Amides 726
21-11 Formation of Acid Chlorides 727
21-12 Reduction of Carboxylic Acids 727
21-13 Alkylation of Carboxylic Acids to Form Ketones 728
Summary in Chinese 729
Study Problems 731
Chapter 22 Carboxylic Acid Derivatives 736
22-1 Introduction 736
22-2 Physical Properties of Carboxylic Acid Derivatives 737
22-3 Spectroscopy of Carboxylic Acid Derivatives 739
22-4 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 741
22-5 Transesterification 748
22-6 Hydrolysis of Carboxylic Acid Derivatives 750
22-7 Reduction of Acid Derivatives 753
22-8 Reactions of Acid Derivatives with Organometallic Reagents 755
22-9 Esters and Amides of Carbonic Acid 756
Summary in Chinese 758
Study Problems 761
Chapter 23 Condensations and Alpha Substitutions of Carbonyl Compounds 767
23-1 Introduction 767
23-2 Enols and Enolate Ions 768
23-3 Alpha Halogenation of Ketones 771
23-4 α Bromination of Acids:The HVZ Reaction 775
23-5 Alkylation of Enolate Ions 776
23-6 Formation and Alkylation of Enamines 778
23-7 The Aldol Condensation of Ketones and Aldehydes 779
23-8 Dehydration of Aldol Products 782
23-9 Crossed Aldol Condensations 783
23-10 Aldol Cyclizations 784
23-11 The Claisen Ester Condensation 785
23-12 The Dieckmann Condensation:A Claisen Cyclization 787
23-13 Crossed Claisen Condensations 788
23-14 Syntheses Using β-Dicarbonyl Compounds 791
23-15 The Malonic Ester Synthesis 792
23-16 The Acetoacetic Ester Synthesis 795
23-17 Conjugate Additions:The Michael Reaction 797
23-18 The Robinson Annulation 800
Summary in Chinese 802
Study Problems 805
Chapter 24 Carbohydrates and Nucleic Acids 810
24-1 Introduction 810
24-2 Classification of Carbohydrates 811
24-3 Monosaccharides 812
24-4 Erythro and Threo Diastereomers 815
24-5 Epimers 816
24-6 Cyclic Structures of Monosaccharides 816
24-7 Anomers of Monosaccharides;Mutarotation 818
24-8 Reactions of Monosaccharides:Side Reactions in Base 820
24-9 Reduction of Monosaccharides 822
24-10 Oxidation of Monosaccharides;Reducing Sugars 823
24-11 Nonreducing Sugars:Formation of Glycosides 824
24-12 Ether and Ester Formation 825
24-13 Reactions with Phenylhydrazine:Osazone Formation 827
24-14 Chain Shortening:The Ruff Degradation 827
24-15 Chain Lengthening:The Kiliani-Fischer Synthesis 828
24-16 Fischer's Proof of the Configuration of Glucose 829
24-17 Determination of Ring Size;Periodic Acid Cleavage of Sugars 832
24-18 Disaccharides 833
24-19 Polysaccharides 836
24-20 Nucleic Acids:Introduction 839
24-21 Ribonucleosides and Ribonucleotides 840
24-22 The Structure of Ribonucleic Acid 842
24-23 Deoxyribose and the Structure of Deoxyribonucleic Acid 843
24-24 Additional Functions of Nucleotides 845
Summary in Chinese 847
Study Problems 851
Chapter 25 Amino Acids,Peptides,and Proteins 855
25-1 Introduction 855
25-2 Structure and Stereochemistry of the α-Amino Acids 856
25-3 Acid-Base Properties of Amino Acids 860
25-4 Isoelectric Points 861
25-5 Synthesis of Amino Acids 862
25-6 Resolution of Amino Acids 865
25-7 Reactions of Amino Acids 865
25-8 Structure and Nomenclature of Peptides and Proteins 868
25-9 Peptide Structure Determination 871
25-10 Solution-Phase Peptide Synthesis 875
25-11 Solid-Phase Peptide Synthesis 878
25-12 Classification of Proteins 882
25-13 Levels of Protein Structure 882
25-14 Protein Denaturation 885
Summary in Chinese 885
Study Problems 889
Chapter 26 Lipids 893
26-1 Introduction 893
26-2 Waxes 893
26-3 Triglycerides 894
26-4 Saponification of Fats and Oils;Soaps and Detergents 897
26-5 Phospholipids 899
26-6 Steroids 900
26-7 Terpenes 902
Summary in Chinese 905
Study Problems 906
Answers to Selected Problems 909
Index 919
Vocabulary 925