有机化学 原书第7版 英文版PDF电子书下载

1 INTRODUCTION AND REVIEW 1

1-1 The Origins of Organic Chemistry 1

1-2 Principles of Atomic Structure 3

1-3 Bond Formation:The Octet Rule 6

1-4 Lewis Structures 7

1-5 Multiple Bonding 8

Summary:Common Bonding Patterns(Uncharged) 9

1-6 Electronegativity and Bond Polarity 9

1-7 Formal Charges 10

1-8 Ionic Structures 12

Summary:Common Bonding Patterns in Organic Compounds and Ions 13

1-9 Resonance 13

1-10 Structural Formulas 17

1-11 Molecular Formulas and Empirical Formulas 20

1-12 Arrhenius Acids and Bases 21

1-13 Br？nsted-Lowry Acids and Bases 22

1-14 Lewis Acids and Bases 29

Chapter 1 Glossary 32

Study Problems 34

2 STRUCTURE AND PROPERTIES OF ORGANIC MOLECULES 40

2-1 Wave Properties of Electrons in Orbitals 40

2-2 Molecular Orbitals 42

2-3 Pi Bonding 45

2-4 Hybridization and Molecular Shapes 46

2-5 Drawing Three-Dimensional Molecules 50

2-6 General Rules of Hybridization and Geometry 51

2-7 Bond Rotation 55

2-8 Isomerism 57

2-9 Polarity of Bonds and Molecules 59

2-10 Intermolecular Forces 62

2-11 Polarity Effects on Solubilities 66

2-12 Hydrocarbons 69

2-13 Organic Compounds Containing Oxygen 72

2-14 Organic Compounds Containing Nitrogen 74

Chapter 2 Glossary 76

Study Problems 79

3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 83

3-1 Classification of Hydrocarbons(Review) 83

3-2 Molecular Formulas of Alkanes 84

3-3 Nomenclature of Alkanes 85

Summary:Rules for Naming Alkanes 90

3-4 Physical Properities of Alkanes 91

3-5 Uses and Sources of Alkanes 93

3-6 Reactions of Alkanes 95

3-7 Structure and Conformations of Alkanes 96

3-8 Conformations of Butane 100

3-9 Conformations of Higher Alkanes 102

3-10 Cycloalkanes 102

3-11 cis-trans Isomerism in Cycloalkanes 105

3-12 Stabilities of Cycloalkanes;Ring Strain 105

3-13 Cyclohexane Conformations 109

Problem-Solving Strategy:Drawing Chair Conformations 112

3-14 Conformations of Monosubstituted Cyclohexanes 113

3-15 Conformations of Disubstituted Cyclohexanes 116

Problem-Solving Strategy:Recognizing cis and trans Isomers 118

3-16 Bicyclic Molecules 119

Chapter 3 Glossary 121

Study Problems 124

4 THE STUDY OF CHEMICAL REACTIONS 127

4-1 Introduction 127

4-2 Chlorination of Methane 127

4-3 The Free-Radical Chain Reaction 128

Key Mechanism:Free-Radical Halogenation 130

4-4 Equilibrium Constants and Free Energy 132

4-5 Enthalpy and Entropy 135

4-6 Bond-Dissociation Enthalpies 136

4-7 Enthalpy Changes in Chlorination 137

4-8 Kinetics and the Rate Equation 139

4-9 Activation Energy and the Temperature Dependence of Rates 141

4-10 Transition States 142

4-11 Rates of Multistep Reactions 144

4-12 Temperature Dependence of Halogenation 145

4-13 Selectivity in Halogenation 146

4-14 The Hammond Postulate 151

Problem-Solving Strategy:Proposing Reaction Mechanisms 153

4-15 Radical Inhibitors 155

4-16 Reactive Intermediates 156

Summary:Reactive Intermediates 162

Chapter 4 Glossary 162

Study Problems 165

5 STEREOCH EMISTRY 169

5-1 Introduction 169

5-2 Chirality 170

5-3 (R)and(S)Nomenclature of Asymmetric Carbon Atoms 176

5-4 Optical Activity 181

5-5 Biological Discrimination of Enantiomers 186

5-6 Racemic Mixtures 187

5-7 Enantiomeric Excess and Optical Purity 188

5-8 Chirality of Conformationally Mobile Systems 189

5-9 Chiral Compounds without Asymmetric Atoms 191

5-10 Fischer Projections 193

Summary:Fischer Projections and Their Use 198

5-11 Diastereomers 198

Summary:Types of Isomers 199

5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons 200

5-13 Meso Compounds 201

5-14 Absolute and Relative Configuration 203

5-15 Physical Properties of Diastereomers 205

5-16 Resolution of Enantiomers 206

Chapter 5 Glossary 209

Study Problems 211

6 ALKYL HALIDES:NUCLEOPHILIC SUBSTITUTION AND ELIMINATION 215

6-1 Introduction 215

6-2 Nomenclature of Alkyl Halides 216

6-3 Common Uses of Alkyl Halides 218

6-4 Structure of Alkyl Halides 220

6-5 Physical Properties of Alkyl Halides 221

6-6 Preparation of Alkyl Halides 223

Summary:Methods for Preparing Alkyl Halides 226

6-7 Reactions of Alkyl Halides:Substitution and Elimination 228

6-8 Second-Order Nucleophilic Substitution:The SN2 Reaction 229

Key Mechanism:The SN2 Reaction 230

6-9 Generality of the SN2 Reaction 231

Summary:SN2 Reactions of Alkyl Halides 231

6-10 Factors Affecting SN2 Reactions:Strength of the Nucleophile 233

Summary:Trends in Nucleophilicity 234

6-11 Reactivity of the Substrate in SN2 Reactions 237

6-12 Stereochemistry of the SN2 Reaction 241

6-13 First-Order Nucleophilic Substitution:The SN1 Reaction 243

Key Mechanism:The SN1 Reaction 244

6-14 Stereochemistry of the SN1 Reaction 247

6-15 Rearrangements in SN1 Reactions 249

6-16 Comparison of SN1 and SN2 Reactions 252

Summary:Nucleophilic Substitutions 254

6-17 First-Order Elimination:The E1 Reaction 255

Key Mechanism:The E1 Reaction 255

Summary:Carbocation Reactions 259

6-18 Positional Orientation of Elimination:Zaitsev's Rule 260

6-19 Second-Order Elimination:The E2 Reaction 261

Key Mechanism:The E2 Reaction 262

6-20 Stereochemistry of the E2 Reaction 264

6-21 Comparison of E1 and E2 Elimination Mechanisms 265

Summary:Elimination Reactions 267

Problem-Solving Strategy:Predicting Substitutions and Eliminations 267

Summary:Reactions of Alkyl Halides 270

Chapter 6 Glossary 273

Study Problems 276

7 STRUCTURE AND SYNTHESIS OF ALKENES 281

7-1 Introduction 281

7-2 The Orbital Description of the Alkene Double Bond 282

7-3 Elements of Unsaturation 283

7-4 Nomenclature of Alkenes 285

7-5 Nomenclature of Cis-Trans Isomers 287

Summary:Rules for Naming Alkenes 289

7-6 Commercial Importance of Alkenes 290

7-7 Stability of Alkenes 292

7-8 Physical Properties of Alkenes 298

7-9 Alkene Synthesis by Elimination of Alkyl Halides 300

7-10 Alkene Synthesis by Dehydration of Alcohols 308

Key Mechanism:Acid-Catalyzed Dehydration of an Alcohol 309

7-11 Alkene Synthesis by High-Temperature Industrial Methods 311

Problem-Solving Strategy:Proposing Reaction Mechanisms 312

Summary:Methods for Synthesis of Alkenes 316

Chapter 7 Glossary 317

Study Problems 319

8 REACTIONS OF ALKEN ES 323

8-1 Reactivity of the Carbon-Carbon Double Bond 323

8-2 Electrophilic Addition to Alkenes 324

Key Mechanism:Electrophilic Addition to Alkenes 324

8-3 Addition of Hydrogen Halides to Alkenes 326

8-4 Addition of Water:Hydration of Alkenes 332

8-5 Hydration by Oxymercuration-Demercuration 335

8-6 Alkoxymercuration-Demercuration 337

8-7 Hydroboration of Alkenes 338

8-8 Addition of Halogens to Alkenes 344

8-9 Formation of Halohydrins 347

8-10 Catalytic Hydrogenation of Alkenes 350

8-11 Addition of Carbenes to Alkenes 352

8-12 Epoxidation of Alkenes 355

8-13 Acid-Catalyzed Opening of Epoxides 357

8-14 Syn Hydroxylation of Alkenes 360

8-15 Oxidative Cleavage of Alkenes 362

8-16 Polymerization of Alkenes 365

8-17 Olefin Metathesis 369

Problem-Solving Strategy:Organic Synthesis 372

Summary:Reacfons of Alkenes 374

Chapter 8 Glossary 379

Study Problems 382

9 ALKYNES 388

9-1 Introduction 388

9-2 Nomenclature of Alkynes 389

9-3 Physical Properties of Alkynes 390

9-4 Commercial Importance of Alkynes 390

9-5 Electronic Structure of Alkynes 392

9-6 Acidity of Alkynes;Formation of Acetylide Ions 393

9-7 Synthesis of Alkynes from Acetylides 395

9-8 Synthesis of Alkynes by E1imination Reactions 399

Summary:Syntheses of Alkynes 400

9-9 Addition Reactions of Alkynes 401

9-10 Oxidation of Alkynes 411

Problem-Solving Strategy:Multistep Synthesis 413

Summary:Reactions of Alkynes 414

Chapter 9 Glossary 417

Study Problems 418

10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 421

10-1 Introduction 421

10-2 Structure and Classification of Alcohols 421

10-3 Nomenclature of Alcohols and Phenols 423

10-4 Physical Properties of Alcohols 427

10-5 Commercially Important Alcohols 429

10-6 Acidity of Alcohols and Phenols 431

10-7 Synthesis of Alcohols:Introduction and Review 434

Summary:Previous Alcohol Syntheses 434

10-8 Organometallic Reagents for Alcohol Synthesis 436

10-9 Addition of Organometallic Reagents to Carbonyl Compounds 439

Key Mechanism:Grignard Reactions 439

Summary:Grignard Reactions 446

10-10 Side Reactions of Organometallic Reagents:Reduction of Alkyl Halides 447

10-11 Reduction of the Carbonyl Group:Synthesis of 1° and 2° Alcohols 449

Summary:Reactions of LiAlH4 and NaBH4 452

Summary:Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 453

10-12 Thiols(Mercaptans) 455

Chapter 10 Glossary 457

Study Problems 459

11 REACTIONS OF ALCOHOLS 464

11-1 Oxidation States of Alcohols and Related Functional Groups 464

11-2 Oxidation of Alcohols 466

11-3 Additional Methods for Oxidizing Alcohols 469

11-4 Biological Oxidation of Alcohols 471

11-5 Alcohols as Nucleophiles and Electrophiles;Formation of Tosylates 472

Summary:SN2 Reactions of Tosylate Esters 475

11-6 Reduction of Alcohols 475

11-7 Reactions of Alcohols witb Hydrohalic Acids 476

11-8 Reactions of Alcohols with Phosphorus Halides 481

11-9 Reactions of Alcohols with Tbionyl Chloride 482

11-10 Dehydration Reactions of Alcohols 484

Problem-Solving Strategy:Proposing Reaction Mechanisms 488

11-11 Unique Reactions of Diols 491

11-12 Esterification of Alcohols 493

11-13 Esters of Inorganic Acids 494

11-14 Reactions of Alkoxides 497

Key Mechanism:The Williamson Ether Synthesis 497

Problem-Solving Strategy:Multistep Synthesis 499

Summary:Reactions of Alcohols 502

Chapter 11 Glossary 504

Study Problems 506

12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 510

12-1 Introduction 510

12-2 The Electromagnetic Spectrum 511

12-3 The Infrared Region 512

12-4 Molecular Vibrations 513

12-5 IR-Active and IR-Inactive Vibrations 515

12-6 Measurement of the IR Spectrum 516

12-7 Infrared Spectroscopy of Hydrocarbons 519

12-8 Characteristic Absorptions of Alcohols and Amines 524

12-9 Characteristic Absorptions of Carbonyl Compounds 525

12-10 Characteristic Absorptions of C—N Bonds 531

12-11 Simplified Summary of IR Stretching Frequencies 532

12-12 Reading and Interpreting IR Spectra(Solved Problems) 534

12-13 Introduction to Mass Spectrometry 539

12-14 Determination of the Molecular Formula by Mass Spectrometry 543

12-15 Fragmentation Patterns in Mass Spectrometry 546

Summary:Common Fragmentation Patterns 551

Chapter 12 Glossary 553

Study Problems 554

13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 561

13-1 Introduction 561

13-2 Theory of Nuclear Magnetic Resonance 561

13-3 Magnetic Shielding by Electrons 564

13-4 The NMR Spectrometer 566

13-5 The Chemical Shift 567

13-6 The Number of Signals 574

13-7 Areas of the Peaks 575

13-8 Spin-Spin Splitting 578

Problem-Solving Strategy:Drawing an NMR Spectrum 583

13-9 Complex Splitting 587

13-10 Stereochemical Nonequivalence of Protons 590

13-11 Time Dependence of NMR Spectroscopy 593

Problem-Solving Strategy:Interpreting Proton NMR Spectra 596

13-12 Carbon-13 NMR Spectroscopy 601

13-13 Interpreting Carbon NMR Spectra 609

13-14 Nuclear Magnetic Resonance Imaging 611

Problem-Solving Strategy:Spectroscopy Problems 612

Chapter 13 Glossary 616

Study Problems 618

14 ETHERS,EPOXIDES,AND SULFIDES 625

14-1 Introduction 625

14-2 Physical Properties of Ethers 625

14-3 Nomenclature of Ethers 630

14-4 Spectroscopy of Ethers 633

14-5 The Williamson Ether Synthesis 635

14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration 636

14-7 Industrial Synthesis:Bimolecular Dehydration of Alcohols 637

Summary:Syntheses of Ethers(Review) 638

14-8 Cleavage of Ethers by HBr and HI 638

14-9 Autoxidation of Ethers 641

Summary:Reactions of Ethers 641

14-10 Sulfides(Thioethers) 642

14-11 Synthesis of Epoxides 644

Summary:Epoxide Syntheses 647

14-12 Acid-Catalyzed Ring Opening of Epoxides 648

14-13 Base-Catalyzed Ring Opening of Epoxides 651

14-14 Orientation of Epoxide Ring Opening 652

14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 654

14-16 Epoxy Resins:The Advent of Modern Glues 655

Summary:Reactions of Epoxides 657

Chapter 14 Glossary 658

Study Problems 660

15 CONJUGATED SYSTEMS,ORBITAL SYMMETRY,AND ULTRAVIOLET SPECTROSCOPY 665

15-1 Introduction 665

15-2 Stabilities of Dienes 665

15-3 Molecular Orbital Picture of a Conjugated System 667

15-4 Allylic Cations 671

15-5 1,2-and 1,4-Addition to Conjugated Dienes 672

15-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene 674

15-7 Allylic Radicals 676

15-8 Molecular Orbitals of the Allylic System 678

15-9 Electronic Configurations of the Allyl Radical,Cation,and Anion 680

15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 681

15-11 The Diels-Alder Reaction 682

Key Mechanism:The Diels-Alder Reaction 682

15-12 The Diels-Alder as an Example of a Pericyclic Reaction 691

15-13 Ultraviolet Absorption Spectroscopy 694

Chapter 15 Glossary 701

Study Problems 703

16 AROMATIC COMPOUNDS 707

16-1 Introduction:The Discovery of Benzene 707

16-2 The Structure and Properties of Benzene 707

16-3 The Molecular Orbitals of Benzene 711

16-4 The Molecular Orbital Picture of Cyclobutadiene 714

16-5 Aromatic,Antiaromatic,and Nonaromatic Compounds 716

16-6 Hückel's Rule 716

16-7 Molecular Orbital Derivation of Hückel's Rule 718

16-8 Aromatic Ions 719

16-9 Heterocyclic Aromatic Compounds 725

16-10 Polynuclear Aromatic Hydrocarbons 729

16-11 Aromatic Allotropes of Carbon 731

16-12 Fused Heterocyclic Compounds 733

16-13 Nomenclature of Benzene Derivatives 734

16-14 Physical Properties of Benzene and Its Derivatives 736

16-15 Spectroscopy of Aromatic Compounds 737

Chapter 16 Glossary 740

Study Problems 742

17 REACTIONS OF AROMATIC COMPOUNDS 751

17-1 Electrophilic Aromatic Substitution 751

Key Mechanism:Electrophilic Aromatic Substitution 752

17-2 Halogenation of Benzene 753

17-3 Nitration of Benzene 755

17-4 Sulfonation of Benzene 757

17-5 Nitration of Toluene:The Effect of Alkyl Substitution 759

17-6 Activating,Ortho,Para-Directing Substituents 761

Summary:Activating,Ortho,Para-Directors 764

17-7 Deactivating,Meta-Directing Substituents 765

Summary:Deactivating,Meta-Directors 768

17-8 Halogen Substituents:Deactivating,but Ortho,Para-Directing 768

Summary:Directing Effects of Substituents 770

17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 770

17-10 The Friedel-Crafts Alkylation 773

17-11 The Friedel-Crafts Acylation 777

Summary:Comparison of Friedel-Crafts Alkylation and Acylation 780

17-12 Nucleophilic Aromatic Substitution 782

17-13 Addition Reactions of Benzene Derivatives 787

17-14 Side-Chain Reactions of Benzene Derivatives 789

17-15 Reactions of Phenols 793

Summary:Reactions of Aromatic Compounds 796

Chapter 17 Glossary 799

Study Problems 802

18 KETONES AND ALDEHYDES 807

18-1 Carbonyl Compounds 807

18-2 Structure of the Carbonyl Group 808

18-3 Nomenclature of Ketones and Aldehydes 808

18-4 Physical Properties of Ketones and Aldehydes 811

18-5 Spectroscopy of Ketones and Aldehydes 813

18-6 Industrial Importance of Ketones and Aldehydes 820

18-7 Review of Syntheses of Ketones and Aldehydes 820

18-8 Synthesis of Ketones and Aldehydes Using 1,3-Dithianes 824

18-9 Synthesis of Ketones from Carboxylic Acids 825

18-10 Synthesis of Ketones from Nitriles 826

18-11 Synthesis of Aldehydes and Ketones from Acid Chlorides 827

Summary:Syntheses of Ketones and Aldehydes 828

18-12 Reactions of Ketones and Aldehydes:Nucleophilic Addition 831

Key Mechanism:Nucleophilic Additions to Carbonyl Groups 833

18-13 The Wittig Reaction 834

18-14 Hydration of Ketones and Aldehydes 838

18-15 Formation of Cyanohydrins 840

18-16 Formation of Imines 842

Key Mechanism:Formation of Imines 842

18-17 Condensations with Hydroxylamine and Hydrazines 845

Summary:Condensations of Amines with Ketones and Aldehydes 846

18-18 Formation of Acetals 847

Key Mechanism:Formation of Acetals 848

Problem-Solving Strategy:Proposing Reaction Mechanisms 850

18-19 Use of Acetals as Protecting Groups 852

18-20 Oxidation of Aldehydes 854

18-21 Reductions of Ketones and Aldehydes 854

Summary:Reactions of Ketones and Aldehydes 857

Chapter 18 Glossary 860

Study Problems 863

19 AMINES 872

19-1 Introduction 872

19-2 Nomenclature of Amines 873

19-3 Structure of Amines 875

19-4 Physical Properties of Amines 877

19-5 Basicity of Amines 879

19-6 Effects on Amine Basicity 880

19-7 Salts of Amines 882

19-8 Amine Salts as Phase-Transfer Catalysts 884

19-9 Spectroscopy of Amines 886

19-10 Reactions of Amines with Ketones and Aldehydes(Review) 890

19-11 Aromatic Substitution of Arylamines and Pyridine 890

19-12 Alkylation of Amines by Alkyl Halides 894

19-13 Acylation of Amines by Acid Chlorides 895

19-14 Formation of Sulfonamides 897

19-15 Amines as Leaving Groups:The Hofmann Elimination 898

19-16 Oxidation of Amines;The Cope Elimination 902

19-17 Reactions of Amines with Nitrous Acid 904

19-18 Reactions of Arenediazonium Salts 906

Summary:Reactions of Amines 910

19-19 Synthesis of Amines by Reductive Amination 912

19-20 Synthesis of Amines by Acylation-Reduction 915

19-21 Syntheses Limited to Primary Amines 916

Summary:Synthesis of Amines 923

Chapter 19 Glossary 925

Study Problems 928

20 CARBOXYLIC ACIDS 937

20-1 Introduction 937

20-2 Nomenclature of Carboxylic Acids 937

20-3 Structure and Physical Properties of Carboxylic Acids 941

20-4 Acidity of Carboxylic Acids 942

20-5 Salts of Carboxylic Acids 946

20-6 Commercial Sources of Carboxylic Acids 949

20-7 Spectroscopy of Carboxylic Acids 950

20-8 Synthesis of Carboxylic Acids 954

Summary:Syntheses of Carboxylic Acids 957

20-9 Reactions of Carboxylic Acids and Derivatives;Nucleophilic Acyl Substitution 958

20-10 Condensation of Acids with Alcohols:The Fischer Esterification 960

Key Mechanism:Fischer Esterification 961

20-11 Esterification Using Diazomethane 964

20-12 Condensation of Acids with Amines:Direct Synthesis of Amides 965

20-13 Reduction of Carboxylic Acids 965

20-14 Alkylation of Carboxylic Acids to Form Ketones 967

20-15 Synthesis and Use of Acid Chlorides 968

Summary:Reactions of Carboxylic Acids 970

Chapter 20 Glossary 972

Study Problems 973

21 CARBOXYLIC ACID DERIVATIVES 980

21-1 Introduction 980

21-2 Structure and Nomenclature of Acid Derivatives 981

21-3 Physical Properties of Carboxylic Acid Derivatives 987

21-4 Spectroscopy of Carboxylic Acid Derivatives 989

21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 996

Key Mechanism:Addition-Elimination Mechanism of Nucleophilic Acyl Substitution 997

21-6 Transesterification 1005

Problem-Solving Strategy:Proposing Reaction Mechanisms 1006

21-7 Hydrolysis of Carboxylic Acid Derivatives 1008

21-8 Reduction of Acid Derivatives 1013

21-9 Reactions of Acid Derivatives with Organometallic Reagents 1015

21-10 Summary of the Chemistry of Acid Chlorides 1017

21-11 Summary of the Chemistry of Anhydrides 1018

21-12 Summary of the Chemistry of Esters 1021

21-13 Summary of the Chemistry of Amides 1024

21-14 Summary of the Chemistry of Nitriles 1027

21-15 Thioesters 1028

21-16 Esters and Amides of Carbonic Acid 1030

Chapter 21 Glossary 1032

Study Problems 1034

22 CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL COMPOUNDS 1043

22-1 Introduction 1043

22-2 Enols and Enolate Ions 1044

22-3 Alkylation of Enolate Ions 1048

22-4 Formation and Alkylation of Enamines 1049

22-5 Alpha Halogenation of Ketones 1052

22-6 α Bromination of Acids:The HVZ Reaction 1057

22-7 The Aldol Condensation of Ketones and Aldehydes 1057

Key Mechanism:Base-Catalyzed Aldol Condensation 1058

22-8 Dehydration of Aldol Products 1061

Key Mechanism:Base-Catalyzed Dehydration of an Aldol 1061

22-9 Crossed Aldol Condensations 1062

Problem-Solving Strategy:Proposing Reaction Mechanisms 1063

22-10 Aldol Cyclizations 1065

22-11 Planning Syntheses Using Aldol Condensations 1066

22-12 The Claisen Ester Condensation 1067

Key Mechanism:The Claisen Ester Condensation 1068

22-13 The Dieckmann Condensation:A Claisen Cyclization 1070

22-14 Crossed Claisen Condensations 1071

22-15 Syntheses Using β-Dicarbonyl Compounds 1074

22-16 The Malonic Ester Synthesis 1076

22-17 The Acetoacetic Ester Synthesis 1079

22-18 Conjugate Additions:The Michael Reaction 1081

22-19 The Robinson Annulation 1085

Problem-Solving Strategy:Proposing Reaction Mechanisms 1086

Summary:Enolate Additions and Condensations 1088

Chapter 22 Glossary 1090

Study Problems 1092

23 CARBOHYDRATES AND NUCLEIC ACIDS 1097

23-1 Introduction 1097

23-2 Classification of Carbohydrates 1098

23-3 Monosaccharides 1099

23-4 Erythro and Threo Diastereomers 1102

23-5 Epimers 1103

23-6 Cyclic Structures of Monosaccharides 1104

23-7 Anomers of Monosaccharides:Mutarotation 1108

23-8 Reactions of Monosaccharides:Side Reactions in Base 1110

23-9 Reduction of Monosaccharides 1112

23-10 Oxidation of Monosaccharides:Reducing Sugars 1113

23-11 Nonreducing Sugars:Formation of Glycosides 1115

23-12 Ether and Ester Formation 1117

23-13 Reactions with Phenylhydrazine:Osazone Formation 1119

23-14 Chain Shortening:The Ruff Degradation 1120

23-15 Chain Lengthening:The Kiliani-Fischer Synthesis 1121

Summary:Reactions of Sugars 1122

23-16 Fischer's Proof of the Configuration of Glucose 1124

23-17 Determination of Ring Size;Periodic Acid Cleavage of Sugars 1127

23-18 Disaccharides 1129

23-19 Polysaccharides 1134

23-20 Nucleic Acids:Introduction 1137

23-21 Ribonucleosides and Ribonucleotides 1139

23-22 The Structure of Ribonucleic Acid 1141

23-23 Deoxyribose and the Structure of Deoxvribonucleic Acid 1141

23-24 Additional Functions of Nucleotides 1145

Chapter 23 Glossary 1147

Study Problems 1149

24 AMINO ACIDS,PEPTIDES,AND PROTEINS 1153

24-1 Introduction 1153

24-2 Structure and Stereochemistry of the α-Amino Acids 1154

24-3 Acid-Base Properties of Amino Acids 1158

24-4 Isoelectric Points and Electrophoresis 1160

24-5 Synthesis of Amino Acids 1161

Summary:Syntheses of Amino Acids 1166

24-6 Resolution of Amino Acids 1167

24-7 Reactions of Amino Acids 1167

Summary:Reactions of Amino Acids 1170

24-8 Structure and Nomenclature of Peptides and Proteins 1170

24-9 Peptide Structure Determination 1174

24-10 Solution-Phase Peptide Synthesis 1180

24-11 Solid-Phase Peptide Synthesis 1183

24-12 Classification of Proteins 1188

24-13 Levels of Protein Structure 1188

24-14 Protein Denaturation 1191

Chapter 24 Glossary 1193

Study Problems 1196

25 LIPIDS 1200

25-1 Introduction 1200

25-2 Waxes 1200

25-3 Triglycerides 1201

25-4 Saponification of Fats and Oils;Soaps and Detergents 1205

25-5 Phospholipids 1208

25-6 Steroids 1210

25-7 Prostaglandins 1213

25-8 Terpenes 1214

Chapter 25 Glossary 1217

Study Problems 1219

26 SYNTHETIC POLYMERS 1222

26-1 Introduction 1222

26-2 Addition Polymers 1223

26-3 Stereochemistry of Polymers 1229

26-4 Stereochemical Control of Polymerization;Ziegler-Natta Catalysts 1230

26-5 Natural and Synthetic Rubbers 1230

26-6 Copolymers of Two or More Monomers 1232

26-7 Condensation Polymers 1232

26-8 Polymer Structure and Properties 1236

Chapter 26 Glossary 1238

Study Problems 1239

APPENDICES 1243

1A NMR Absorption Positions of Protons in Various Structural Environments 1244

1B Spin-Spin Coupling Constants 1246

1C 13C Chemical Shifts in Organic Compounds 1247

2A Characteristic Infrared Group Frequencies 1248

2B IR:Characteristic Infrared Absorptions of Functional Groups 1251

3 UV:The Woodward-Fieser Rules for Predicting UV-Visible Spectra 1253

4A Methods and Suggestions for Proposing Mechanisms 1257

4B Suggestions for Developing Multistep Syntheses 1260

5 pKa Values for Representative Compounds 1261

Answers to Selected Problems A 1

Photo Credits PC 1

Index I 1

KEY MECHANISM BOXES 130

CHAPTER 4 Free-Radical Halogenation 130

CHAPTER 6 The SN2 Reaction 230

The SN1 Reaction 244

The E1 Reaction 255

The E2 Reaction 262

CHAPTER 7 Acid-Catalyzed Dehydration of an Alcohol 309

CHAPTER 8 Electrophilic Addition to Alkenes 324

CHAPTER 10 Grignard Reactions 439

CHAPTER 11 The Williamson Ether Synthesis 497

CHAPTER 15 The Diels-Alder Reaction 682

CHAPTER 17 Electrophilic Aromatic Substitution 752

CHAPTER 18 Nucleophilic Additions to Carbonyl Groups 833

Formation of Imines 842

Formation of Acetals 848

CHAPTER 20 Fischer Esterification 961

CHAPTER 21 Addition-Elimination Mechanism of Nucleophilic Acyl Substitution 997

CHAPTER 22 Base-Catalyzed Aldol Condensation 1058

Base-Catalyzed Dehydration of an Aldol 1061

The Claisen Ester Condensation 1068

MECHANISM BOXES 225

CHAPTER 6 Allvlic Bromination 225

Inversion of Confiauration in the SN2 Reaction 241

Racemization in the SN1 Reaction 248

Hydride Shift in an SN1 Reaction 250

Methyl Shift in an SN1 Reaction 251

Rearrangement in an E1 Reaction 258

CHAPTER 7 Dehydrohalogenation by the E2 Mechanism 300

Stereochemistry of the E2 Reaction 302

E2 Debromination of a Vicinal Dibromide 306

CHAPTER 8 Ionic Addition of HX to an Alkene 327

Free-Radical Addition of HBr to Alkenes 329

Acid-Catalyzed Hydration of an Alkene 333

Oxymercuration of an Alkene 335

Hvdroboration of an Alkene 340

Addition of Halogens to Alkenes 345

Formation of Halohydrins 347

Epoxidation of Alkenes 356

Acid-Catalyzed Opening of Epoxides 357

Olefin Metathesis 372

CHAPTER 9 Metal-Ammonia Reduction of an Alkyne 404

Acid-Catalyzed Keto-Enol Tautomerism 408

Base-Catalyzed Keto-Enol Tautomerism 410

CHAPTER 10 Hydride Reduction of a Carbonyl Group 450

CHAPTER 11 Reaction of a Tertiary Alcohol with HBr(SN1) 477

Reaction of a Primary Alcohol with HBr(SN2) 477

Reaction of Alcohols with PBr3 481

(Review):Acid-Catalyzed Dehydration of an Alcohol 484

The Pinacol Rearrangement 491

CHAPTER 14 Cleavage of an Ether by HBr or Hl 639

Acid-Catalyzed Opening of Epoxides in Water 648

Acid-Catalyzed Opening of an Epoxide in an Alcohol Solution 649

Base-Catalyzed Opening of Epoxides 651

CHAPTER 15 1,2-and 1,4-Addition to a Coniugated Diene 673

Free-Radical Allylic Bromination 676

CHAPTER 17 Bromination of Benzene 753

Nitration of Benzene 756

Sulfonation of Benzene 757

Friedel-Crafts Alkylation 774

Friedel-Crafts Acylation 778

Nucleophilic Aromatic Substitution(Addition-Elimination) 783

Nucleophilic Aromatic Substitution(Benzyne Mechanism) 786

The Birch Reduction 788

CHAPTER 18 The Wittig Reaction 836

Hydration of Ketones and Aldehydes 839

Formation of Cyanohydrins 840

Wolff-Kishner Reduction 857

CHAPTER 19 Electrophilic Aromatic Substitution of Pyridine 892

Nucleophilic Aromatic Substitution of Pyridine 893

Acylation of an Amine by an Acid Chloride 895

Hofmann Elimination 899

The Cope Elimination of an Amine Oxide 903

Diazotization of an Amine 904

The Hofmann Rearrangement of Amides 921

CHAPTER 20 Nucleophilic Acyl Substitution in the Basic Hydrolysis of an Ester 959

Esterification Using Diazomethane 964

CHAPTER 21 Conversion of an Acid Chloride to an Anhydride 1000

Conversion of an Acid Chloride to an Ester 1000

Conversion of an Acid Chloride to an Amide 1001

Conversion of an Acid Anhydride to an Ester 1001

Conversion of an Acid Anhydride to an Amide 1002

Conversion of an Ester to an Amide(Ammonolysis of an Ester) 1002

Transesterification 1007

Saponification of an Ester 1009

Basic Hydrolysis of an Amide 1011

Acidic Hydrolysis of an Amide 1011

Base-Catalyzed Hydrolysis of a Nitrile 1012

Hydride Reduction of an Ester 1013

Reduction of an Amide to an Amine 1014

Reaction of an Ester with Two Moles of a Grignard Reagent 1016

CHAPTER 22 Alpha Substitution 1043

Addition of an Enolate to Ketones and Aldehydes(a Condensation) 1044

Substitution of an Enolate on an Ester(a Condensation) 1044

Base-Catalyzed Keto-Enol Tautomerism 1044

Acid-Catalyzed Keto-Enol Tautomerism 1045

Base-Promoted Halogenation 1052

Final Steps of the Haloform Reaction 1054

Acid-Catalyzed Alpha Haloaenation 1055

Acid-Catalyzed Aldol Condensation 1060

1,2-Addition and 1,4-Addition(Conjugate Addition) 1082

CHAPTER 23 Formation of a Cyclic Hemiacetal 1104

Base-Catalyzed Epimerization of Glucose 1111

Base-Catalyzed Enediol Rearrangement 1111

CHAPTER 26 Free-Radical Polymerization 1225

Cationic Polymerization 1226

Anionic Polymerization 1228