有机化学 第6版 改编版PDF电子书下载

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