有机化学 原书第7版 英文版PDF|Epub|txt|kindle电子书版本网盘下载

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1 INTRODUCTION AND REVIEW1

1-1 The Origins of Organic Chemistry1

1-2 Principles of Atomic Structure3

1-3 Bond Formation:The Octet Rule6

1-4 Lewis Structures7

1-5 Multiple Bonding8

Summary:Common Bonding Patterns(Uncharged)9

1-6 Electronegativity and Bond Polarity9

1-7 Formal Charges10

1-8 Ionic Structures12

Summary:Common Bonding Patterns in Organic Compounds and Ions13

1-9 Resonance13

1-10 Structural Formulas17

1-11 Molecular Formulas and Empirical Formulas20

1-12 Arrhenius Acids and Bases21

1-13 Br？nsted-Lowry Acids and Bases22

1-14 Lewis Acids and Bases29

Chapter 1 Glossary32

Study Problems34

2 STRUCTURE AND PROPERTIES OF ORGANIC MOLECULES40

2-1 Wave Properties of Electrons in Orbitals40

2-2 Molecular Orbitals42

2-3 Pi Bonding45

2-4 Hybridization and Molecular Shapes46

2-5 Drawing Three-Dimensional Molecules50

2-6 General Rules of Hybridization and Geometry51

2-7 Bond Rotation55

2-8 Isomerism57

2-9 Polarity of Bonds and Molecules59

2-10 Intermolecular Forces62

2-11 Polarity Effects on Solubilities66

2-12 Hydrocarbons69

2-13 Organic Compounds Containing Oxygen72

2-14 Organic Compounds Containing Nitrogen74

Chapter 2 Glossary76

Study Problems79

3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES83

3-1 Classification of Hydrocarbons(Review)83

3-2 Molecular Formulas of Alkanes84

3-3 Nomenclature of Alkanes85

Summary:Rules for Naming Alkanes90

3-4 Physical Properities of Alkanes91

3-5 Uses and Sources of Alkanes93

3-6 Reactions of Alkanes95

3-7 Structure and Conformations of Alkanes96

3-8 Conformations of Butane100

3-9 Conformations of Higher Alkanes102

3-10 Cycloalkanes102

3-11 cis-trans Isomerism in Cycloalkanes105

3-12 Stabilities of Cycloalkanes;Ring Strain105

3-13 Cyclohexane Conformations109

Problem-Solving Strategy:Drawing Chair Conformations112

3-14 Conformations of Monosubstituted Cyclohexanes113

3-15 Conformations of Disubstituted Cyclohexanes116

Problem-Solving Strategy:Recognizing cis and trans Isomers118

3-16 Bicyclic Molecules119

Chapter 3 Glossary121

Study Problems124

4 THE STUDY OF CHEMICAL REACTIONS127

4-1 Introduction127

4-2 Chlorination of Methane127

4-3 The Free-Radical Chain Reaction128

Key Mechanism:Free-Radical Halogenation130

4-4 Equilibrium Constants and Free Energy132

4-5 Enthalpy and Entropy135

4-6 Bond-Dissociation Enthalpies136

4-7 Enthalpy Changes in Chlorination137

4-8 Kinetics and the Rate Equation139

4-9 Activation Energy and the Temperature Dependence of Rates141

4-10 Transition States142

4-11 Rates of Multistep Reactions144

4-12 Temperature Dependence of Halogenation145

4-13 Selectivity in Halogenation146

4-14 The Hammond Postulate151

Problem-Solving Strategy:Proposing Reaction Mechanisms153

4-15 Radical Inhibitors155

4-16 Reactive Intermediates156

Summary:Reactive Intermediates162

Chapter 4 Glossary162

Study Problems165

5 STEREOCH EMISTRY169

5-1 Introduction169

5-2 Chirality170

5-3 (R)and(S)Nomenclature of Asymmetric Carbon Atoms176

5-4 Optical Activity181

5-5 Biological Discrimination of Enantiomers186

5-6 Racemic Mixtures187

5-7 Enantiomeric Excess and Optical Purity188

5-8 Chirality of Conformationally Mobile Systems189

5-9 Chiral Compounds without Asymmetric Atoms191

5-10 Fischer Projections193

Summary:Fischer Projections and Their Use198

5-11 Diastereomers198

Summary:Types of Isomers199

5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons200

5-13 Meso Compounds201

5-14 Absolute and Relative Configuration203

5-15 Physical Properties of Diastereomers205

5-16 Resolution of Enantiomers206

Chapter 5 Glossary209

Study Problems211

6 ALKYL HALIDES:NUCLEOPHILIC SUBSTITUTION AND ELIMINATION215

6-1 Introduction215

6-2 Nomenclature of Alkyl Halides216

6-3 Common Uses of Alkyl Halides218

6-4 Structure of Alkyl Halides220

6-5 Physical Properties of Alkyl Halides221

6-6 Preparation of Alkyl Halides223

Summary:Methods for Preparing Alkyl Halides226

6-7 Reactions of Alkyl Halides:Substitution and Elimination228

6-8 Second-Order Nucleophilic Substitution:The SN2 Reaction229

Key Mechanism:The SN2 Reaction230

6-9 Generality of the SN2 Reaction231

Summary:SN2 Reactions of Alkyl Halides231

6-10 Factors Affecting SN2 Reactions:Strength of the Nucleophile233

Summary:Trends in Nucleophilicity234

6-11 Reactivity of the Substrate in SN2 Reactions237

6-12 Stereochemistry of the SN2 Reaction241

6-13 First-Order Nucleophilic Substitution:The SN1 Reaction243

Key Mechanism:The SN1 Reaction244

6-14 Stereochemistry of the SN1 Reaction247

6-15 Rearrangements in SN1 Reactions249

6-16 Comparison of SN1 and SN2 Reactions252

Summary:Nucleophilic Substitutions254

6-17 First-Order Elimination:The E1 Reaction255

Key Mechanism:The E1 Reaction255

Summary:Carbocation Reactions259

6-18 Positional Orientation of Elimination:Zaitsev's Rule260

6-19 Second-Order Elimination:The E2 Reaction261

Key Mechanism:The E2 Reaction262

6-20 Stereochemistry of the E2 Reaction264

6-21 Comparison of E1 and E2 Elimination Mechanisms265

Summary:Elimination Reactions267

Problem-Solving Strategy:Predicting Substitutions and Eliminations267

Summary:Reactions of Alkyl Halides270

Chapter 6 Glossary273

Study Problems276

7 STRUCTURE AND SYNTHESIS OF ALKENES281

7-1 Introduction281

7-2 The Orbital Description of the Alkene Double Bond282

7-3 Elements of Unsaturation283

7-4 Nomenclature of Alkenes285

7-5 Nomenclature of Cis-Trans Isomers287

Summary:Rules for Naming Alkenes289

7-6 Commercial Importance of Alkenes290

7-7 Stability of Alkenes292

7-8 Physical Properties of Alkenes298

7-9 Alkene Synthesis by Elimination of Alkyl Halides300

7-10 Alkene Synthesis by Dehydration of Alcohols308

Key Mechanism:Acid-Catalyzed Dehydration of an Alcohol309

7-11 Alkene Synthesis by High-Temperature Industrial Methods311

Problem-Solving Strategy:Proposing Reaction Mechanisms312

Summary:Methods for Synthesis of Alkenes316

Chapter 7 Glossary317

Study Problems319

8 REACTIONS OF ALKEN ES323

8-1 Reactivity of the Carbon-Carbon Double Bond323

8-2 Electrophilic Addition to Alkenes324

Key Mechanism:Electrophilic Addition to Alkenes324

8-3 Addition of Hydrogen Halides to Alkenes326

8-4 Addition of Water:Hydration of Alkenes332

8-5 Hydration by Oxymercuration-Demercuration335

8-6 Alkoxymercuration-Demercuration337

8-7 Hydroboration of Alkenes338

8-8 Addition of Halogens to Alkenes344

8-9 Formation of Halohydrins347

8-10 Catalytic Hydrogenation of Alkenes350

8-11 Addition of Carbenes to Alkenes352

8-12 Epoxidation of Alkenes355

8-13 Acid-Catalyzed Opening of Epoxides357

8-14 Syn Hydroxylation of Alkenes360

8-15 Oxidative Cleavage of Alkenes362

8-16 Polymerization of Alkenes365

8-17 Olefin Metathesis369

Problem-Solving Strategy:Organic Synthesis372

Summary:Reacfons of Alkenes374

Chapter 8 Glossary379

Study Problems382

9 ALKYNES388

9-1 Introduction388

9-2 Nomenclature of Alkynes389

9-3 Physical Properties of Alkynes390

9-4 Commercial Importance of Alkynes390

9-5 Electronic Structure of Alkynes392

9-6 Acidity of Alkynes;Formation of Acetylide Ions393

9-7 Synthesis of Alkynes from Acetylides395

9-8 Synthesis of Alkynes by E1imination Reactions399

Summary:Syntheses of Alkynes400

9-9 Addition Reactions of Alkynes401

9-10 Oxidation of Alkynes411

Problem-Solving Strategy:Multistep Synthesis413

Summary:Reactions of Alkynes414

Chapter 9 Glossary417

Study Problems418

10 STRUCTURE AND SYNTHESIS OF ALCOHOLS421

10-1 Introduction421

10-2 Structure and Classification of Alcohols421

10-3 Nomenclature of Alcohols and Phenols423

10-4 Physical Properties of Alcohols427

10-5 Commercially Important Alcohols429

10-6 Acidity of Alcohols and Phenols431

10-7 Synthesis of Alcohols:Introduction and Review434

Summary:Previous Alcohol Syntheses434

10-8 Organometallic Reagents for Alcohol Synthesis436

10-9 Addition of Organometallic Reagents to Carbonyl Compounds439

Key Mechanism:Grignard Reactions439

Summary:Grignard Reactions446

10-10 Side Reactions of Organometallic Reagents:Reduction of Alkyl Halides447

10-11 Reduction of the Carbonyl Group:Synthesis of 1° and 2° Alcohols449

Summary:Reactions of LiAlH4 and NaBH4452

Summary:Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups453

10-12 Thiols(Mercaptans)455

Chapter 10 Glossary457

Study Problems459

11 REACTIONS OF ALCOHOLS464

11-1 Oxidation States of Alcohols and Related Functional Groups464

11-2 Oxidation of Alcohols466

11-3 Additional Methods for Oxidizing Alcohols469

11-4 Biological Oxidation of Alcohols471

11-5 Alcohols as Nucleophiles and Electrophiles;Formation of Tosylates472

Summary:SN2 Reactions of Tosylate Esters475

11-6 Reduction of Alcohols475

11-7 Reactions of Alcohols witb Hydrohalic Acids476

11-8 Reactions of Alcohols with Phosphorus Halides481

11-9 Reactions of Alcohols with Tbionyl Chloride482

11-10 Dehydration Reactions of Alcohols484

Problem-Solving Strategy:Proposing Reaction Mechanisms488

11-11 Unique Reactions of Diols491

11-12 Esterification of Alcohols493

11-13 Esters of Inorganic Acids494

11-14 Reactions of Alkoxides497

Key Mechanism:The Williamson Ether Synthesis497

Problem-Solving Strategy:Multistep Synthesis499

Summary:Reactions of Alcohols502

Chapter 11 Glossary504

Study Problems506

12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY510

12-1 Introduction510

12-2 The Electromagnetic Spectrum511

12-3 The Infrared Region512

12-4 Molecular Vibrations513

12-5 IR-Active and IR-Inactive Vibrations515

12-6 Measurement of the IR Spectrum516

12-7 Infrared Spectroscopy of Hydrocarbons519

12-8 Characteristic Absorptions of Alcohols and Amines524

12-9 Characteristic Absorptions of Carbonyl Compounds525

12-10 Characteristic Absorptions of C—N Bonds531

12-11 Simplified Summary of IR Stretching Frequencies532

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

12-13 Introduction to Mass Spectrometry539

12-14 Determination of the Molecular Formula by Mass Spectrometry543

12-15 Fragmentation Patterns in Mass Spectrometry546

Summary:Common Fragmentation Patterns551

Chapter 12 Glossary553

Study Problems554

13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY561

13-1 Introduction561

13-2 Theory of Nuclear Magnetic Resonance561

13-3 Magnetic Shielding by Electrons564

13-4 The NMR Spectrometer566

13-5 The Chemical Shift567

13-6 The Number of Signals574

13-7 Areas of the Peaks575

13-8 Spin-Spin Splitting578

Problem-Solving Strategy:Drawing an NMR Spectrum583

13-9 Complex Splitting587

13-10 Stereochemical Nonequivalence of Protons590

13-11 Time Dependence of NMR Spectroscopy593

Problem-Solving Strategy:Interpreting Proton NMR Spectra596

13-12 Carbon-13 NMR Spectroscopy601

13-13 Interpreting Carbon NMR Spectra609

13-14 Nuclear Magnetic Resonance Imaging611

Problem-Solving Strategy:Spectroscopy Problems612

Chapter 13 Glossary616

Study Problems618

14 ETHERS,EPOXIDES,AND SULFIDES625

14-1 Introduction625

14-2 Physical Properties of Ethers625

14-3 Nomenclature of Ethers630

14-4 Spectroscopy of Ethers633

14-5 The Williamson Ether Synthesis635

14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration636

14-7 Industrial Synthesis:Bimolecular Dehydration of Alcohols637

Summary:Syntheses of Ethers(Review)638

14-8 Cleavage of Ethers by HBr and HI638

14-9 Autoxidation of Ethers641

Summary:Reactions of Ethers641

14-10 Sulfides(Thioethers)642

14-11 Synthesis of Epoxides644

Summary:Epoxide Syntheses647

14-12 Acid-Catalyzed Ring Opening of Epoxides648

14-13 Base-Catalyzed Ring Opening of Epoxides651

14-14 Orientation of Epoxide Ring Opening652

14-15 Reactions of Epoxides with Grignard and Organolithium Reagents654

14-16 Epoxy Resins:The Advent of Modern Glues655

Summary:Reactions of Epoxides657

Chapter 14 Glossary658

Study Problems660

15 CONJUGATED SYSTEMS,ORBITAL SYMMETRY,AND ULTRAVIOLET SPECTROSCOPY665

15-1 Introduction665

15-2 Stabilities of Dienes665

15-3 Molecular Orbital Picture of a Conjugated System667

15-4 Allylic Cations671

15-5 1,2-and 1,4-Addition to Conjugated Dienes672

15-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene674

15-7 Allylic Radicals676

15-8 Molecular Orbitals of the Allylic System678

15-9 Electronic Configurations of the Allyl Radical,Cation,and Anion680

15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates681

15-11 The Diels-Alder Reaction682

Key Mechanism:The Diels-Alder Reaction682

15-12 The Diels-Alder as an Example of a Pericyclic Reaction691

15-13 Ultraviolet Absorption Spectroscopy694

Chapter 15 Glossary701

Study Problems703

16 AROMATIC COMPOUNDS707

16-1 Introduction:The Discovery of Benzene707

16-2 The Structure and Properties of Benzene707

16-3 The Molecular Orbitals of Benzene711

16-4 The Molecular Orbital Picture of Cyclobutadiene714

16-5 Aromatic,Antiaromatic,and Nonaromatic Compounds716

16-6 Hückel's Rule716

16-7 Molecular Orbital Derivation of Hückel's Rule718

16-8 Aromatic Ions719

16-9 Heterocyclic Aromatic Compounds725

16-10 Polynuclear Aromatic Hydrocarbons729

16-11 Aromatic Allotropes of Carbon731

16-12 Fused Heterocyclic Compounds733

16-13 Nomenclature of Benzene Derivatives734

16-14 Physical Properties of Benzene and Its Derivatives736

16-15 Spectroscopy of Aromatic Compounds737

Chapter 16 Glossary740

Study Problems742

17 REACTIONS OF AROMATIC COMPOUNDS751

17-1 Electrophilic Aromatic Substitution751

Key Mechanism:Electrophilic Aromatic Substitution752

17-2 Halogenation of Benzene753

17-3 Nitration of Benzene755

17-4 Sulfonation of Benzene757

17-5 Nitration of Toluene:The Effect of Alkyl Substitution759

17-6 Activating,Ortho,Para-Directing Substituents761

Summary:Activating,Ortho,Para-Directors764

17-7 Deactivating,Meta-Directing Substituents765

Summary:Deactivating,Meta-Directors768

17-8 Halogen Substituents:Deactivating,but Ortho,Para-Directing768

Summary:Directing Effects of Substituents770

17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution770

17-10 The Friedel-Crafts Alkylation773

17-11 The Friedel-Crafts Acylation777

Summary:Comparison of Friedel-Crafts Alkylation and Acylation780

17-12 Nucleophilic Aromatic Substitution782

17-13 Addition Reactions of Benzene Derivatives787

17-14 Side-Chain Reactions of Benzene Derivatives789

17-15 Reactions of Phenols793

Summary:Reactions of Aromatic Compounds796

Chapter 17 Glossary799

Study Problems802

18 KETONES AND ALDEHYDES807

18-1 Carbonyl Compounds807

18-2 Structure of the Carbonyl Group808

18-3 Nomenclature of Ketones and Aldehydes808

18-4 Physical Properties of Ketones and Aldehydes811

18-5 Spectroscopy of Ketones and Aldehydes813

18-6 Industrial Importance of Ketones and Aldehydes820

18-7 Review of Syntheses of Ketones and Aldehydes820

18-8 Synthesis of Ketones and Aldehydes Using 1,3-Dithianes824

18-9 Synthesis of Ketones from Carboxylic Acids825

18-10 Synthesis of Ketones from Nitriles826

18-11 Synthesis of Aldehydes and Ketones from Acid Chlorides827

Summary:Syntheses of Ketones and Aldehydes828

18-12 Reactions of Ketones and Aldehydes:Nucleophilic Addition831

Key Mechanism:Nucleophilic Additions to Carbonyl Groups833

18-13 The Wittig Reaction834

18-14 Hydration of Ketones and Aldehydes838

18-15 Formation of Cyanohydrins840

18-16 Formation of Imines842

Key Mechanism:Formation of Imines842

18-17 Condensations with Hydroxylamine and Hydrazines845

Summary:Condensations of Amines with Ketones and Aldehydes846

18-18 Formation of Acetals847

Key Mechanism:Formation of Acetals848

Problem-Solving Strategy:Proposing Reaction Mechanisms850

18-19 Use of Acetals as Protecting Groups852

18-20 Oxidation of Aldehydes854

18-21 Reductions of Ketones and Aldehydes854

Summary:Reactions of Ketones and Aldehydes857

Chapter 18 Glossary860

Study Problems863

19 AMINES872

19-1 Introduction872

19-2 Nomenclature of Amines873

19-3 Structure of Amines875

19-4 Physical Properties of Amines877

19-5 Basicity of Amines879

19-6 Effects on Amine Basicity880

19-7 Salts of Amines882

19-8 Amine Salts as Phase-Transfer Catalysts884

19-9 Spectroscopy of Amines886

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

19-11 Aromatic Substitution of Arylamines and Pyridine890

19-12 Alkylation of Amines by Alkyl Halides894

19-13 Acylation of Amines by Acid Chlorides895

19-14 Formation of Sulfonamides897

19-15 Amines as Leaving Groups:The Hofmann Elimination898

19-16 Oxidation of Amines;The Cope Elimination902

19-17 Reactions of Amines with Nitrous Acid904

19-18 Reactions of Arenediazonium Salts906

Summary:Reactions of Amines910

19-19 Synthesis of Amines by Reductive Amination912

19-20 Synthesis of Amines by Acylation-Reduction915

19-21 Syntheses Limited to Primary Amines916

Summary:Synthesis of Amines923

Chapter 19 Glossary925

Study Problems928

20 CARBOXYLIC ACIDS937

20-1 Introduction937

20-2 Nomenclature of Carboxylic Acids937

20-3 Structure and Physical Properties of Carboxylic Acids941

20-4 Acidity of Carboxylic Acids942

20-5 Salts of Carboxylic Acids946

20-6 Commercial Sources of Carboxylic Acids949

20-7 Spectroscopy of Carboxylic Acids950

20-8 Synthesis of Carboxylic Acids954

Summary:Syntheses of Carboxylic Acids957

20-9 Reactions of Carboxylic Acids and Derivatives;Nucleophilic Acyl Substitution958

20-10 Condensation of Acids with Alcohols:The Fischer Esterification960

Key Mechanism:Fischer Esterification961

20-11 Esterification Using Diazomethane964

20-12 Condensation of Acids with Amines:Direct Synthesis of Amides965

20-13 Reduction of Carboxylic Acids965

20-14 Alkylation of Carboxylic Acids to Form Ketones967

20-15 Synthesis and Use of Acid Chlorides968

Summary:Reactions of Carboxylic Acids970

Chapter 20 Glossary972

Study Problems973

21 CARBOXYLIC ACID DERIVATIVES980

21-1 Introduction980

21-2 Structure and Nomenclature of Acid Derivatives981

21-3 Physical Properties of Carboxylic Acid Derivatives987

21-4 Spectroscopy of Carboxylic Acid Derivatives989

21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution996

Key Mechanism:Addition-Elimination Mechanism of Nucleophilic Acyl Substitution997

21-6 Transesterification1005

Problem-Solving Strategy:Proposing Reaction Mechanisms1006

21-7 Hydrolysis of Carboxylic Acid Derivatives1008

21-8 Reduction of Acid Derivatives1013

21-9 Reactions of Acid Derivatives with Organometallic Reagents1015

21-10 Summary of the Chemistry of Acid Chlorides1017

21-11 Summary of the Chemistry of Anhydrides1018

21-12 Summary of the Chemistry of Esters1021

21-13 Summary of the Chemistry of Amides1024

21-14 Summary of the Chemistry of Nitriles1027

21-15 Thioesters1028

21-16 Esters and Amides of Carbonic Acid1030

Chapter 21 Glossary1032

Study Problems1034

22 CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL COMPOUNDS1043

22-1 Introduction1043

22-2 Enols and Enolate Ions1044

22-3 Alkylation of Enolate Ions1048

22-4 Formation and Alkylation of Enamines1049

22-5 Alpha Halogenation of Ketones1052

22-6 α Bromination of Acids:The HVZ Reaction1057

22-7 The Aldol Condensation of Ketones and Aldehydes1057

Key Mechanism:Base-Catalyzed Aldol Condensation1058

22-8 Dehydration of Aldol Products1061

Key Mechanism:Base-Catalyzed Dehydration of an Aldol1061

22-9 Crossed Aldol Condensations1062

Problem-Solving Strategy:Proposing Reaction Mechanisms1063

22-10 Aldol Cyclizations1065

22-11 Planning Syntheses Using Aldol Condensations1066

22-12 The Claisen Ester Condensation1067

Key Mechanism:The Claisen Ester Condensation1068

22-13 The Dieckmann Condensation:A Claisen Cyclization1070

22-14 Crossed Claisen Condensations1071

22-15 Syntheses Using β-Dicarbonyl Compounds1074

22-16 The Malonic Ester Synthesis1076

22-17 The Acetoacetic Ester Synthesis1079

22-18 Conjugate Additions:The Michael Reaction1081

22-19 The Robinson Annulation1085

Problem-Solving Strategy:Proposing Reaction Mechanisms1086

Summary:Enolate Additions and Condensations1088

Chapter 22 Glossary1090

Study Problems1092

23 CARBOHYDRATES AND NUCLEIC ACIDS1097

23-1 Introduction1097

23-2 Classification of Carbohydrates1098

23-3 Monosaccharides1099

23-4 Erythro and Threo Diastereomers1102

23-5 Epimers1103

23-6 Cyclic Structures of Monosaccharides1104

23-7 Anomers of Monosaccharides:Mutarotation1108

23-8 Reactions of Monosaccharides:Side Reactions in Base1110

23-9 Reduction of Monosaccharides1112

23-10 Oxidation of Monosaccharides:Reducing Sugars1113

23-11 Nonreducing Sugars:Formation of Glycosides1115

23-12 Ether and Ester Formation1117

23-13 Reactions with Phenylhydrazine:Osazone Formation1119

23-14 Chain Shortening:The Ruff Degradation1120

23-15 Chain Lengthening:The Kiliani-Fischer Synthesis1121

Summary:Reactions of Sugars1122

23-16 Fischer's Proof of the Configuration of Glucose1124

23-17 Determination of Ring Size;Periodic Acid Cleavage of Sugars1127

23-18 Disaccharides1129

23-19 Polysaccharides1134

23-20 Nucleic Acids:Introduction1137

23-21 Ribonucleosides and Ribonucleotides1139

23-22 The Structure of Ribonucleic Acid1141

23-23 Deoxyribose and the Structure of Deoxvribonucleic Acid1141

23-24 Additional Functions of Nucleotides1145

Chapter 23 Glossary1147

Study Problems1149

24 AMINO ACIDS,PEPTIDES,AND PROTEINS1153

24-1 Introduction1153

24-2 Structure and Stereochemistry of the α-Amino Acids1154

24-3 Acid-Base Properties of Amino Acids1158

24-4 Isoelectric Points and Electrophoresis1160

24-5 Synthesis of Amino Acids1161

Summary:Syntheses of Amino Acids1166

24-6 Resolution of Amino Acids1167

24-7 Reactions of Amino Acids1167

Summary:Reactions of Amino Acids1170

24-8 Structure and Nomenclature of Peptides and Proteins1170

24-9 Peptide Structure Determination1174

24-10 Solution-Phase Peptide Synthesis1180

24-11 Solid-Phase Peptide Synthesis1183

24-12 Classification of Proteins1188

24-13 Levels of Protein Structure1188

24-14 Protein Denaturation1191

Chapter 24 Glossary1193

Study Problems1196

25 LIPIDS1200

25-1 Introduction1200

25-2 Waxes1200

25-3 Triglycerides1201

25-4 Saponification of Fats and Oils;Soaps and Detergents1205

25-5 Phospholipids1208

25-6 Steroids1210

25-7 Prostaglandins1213

25-8 Terpenes1214

Chapter 25 Glossary1217

Study Problems1219

26 SYNTHETIC POLYMERS1222

26-1 Introduction1222

26-2 Addition Polymers1223

26-3 Stereochemistry of Polymers1229

26-4 Stereochemical Control of Polymerization;Ziegler-Natta Catalysts1230

26-5 Natural and Synthetic Rubbers1230

26-6 Copolymers of Two or More Monomers1232

26-7 Condensation Polymers1232

26-8 Polymer Structure and Properties1236

Chapter 26 Glossary1238

Study Problems1239

APPENDICES1243

1A NMR Absorption Positions of Protons in Various Structural Environments1244

1B Spin-Spin Coupling Constants1246

1C 13C Chemical Shifts in Organic Compounds1247

2A Characteristic Infrared Group Frequencies1248

2B IR:Characteristic Infrared Absorptions of Functional Groups1251

3 UV:The Woodward-Fieser Rules for Predicting UV-Visible Spectra1253

4A Methods and Suggestions for Proposing Mechanisms1257

4B Suggestions for Developing Multistep Syntheses1260

5 pKa Values for Representative Compounds1261

Answers to Selected Problems A1

Photo Credits PC1

Index I1

KEY MECHANISM BOXES130

CHAPTER 4 Free-Radical Halogenation130

CHAPTER 6 The SN2 Reaction230

The SN1 Reaction244

The E1 Reaction255

The E2 Reaction262

CHAPTER 7 Acid-Catalyzed Dehydration of an Alcohol309

CHAPTER 8 Electrophilic Addition to Alkenes324

CHAPTER 10 Grignard Reactions439

CHAPTER 11 The Williamson Ether Synthesis497

CHAPTER 15 The Diels-Alder Reaction682

CHAPTER 17 Electrophilic Aromatic Substitution752

CHAPTER 18 Nucleophilic Additions to Carbonyl Groups833

Formation of Imines842

Formation of Acetals848

CHAPTER 20 Fischer Esterification961

CHAPTER 21 Addition-Elimination Mechanism of Nucleophilic Acyl Substitution997

CHAPTER 22 Base-Catalyzed Aldol Condensation1058

Base-Catalyzed Dehydration of an Aldol1061

The Claisen Ester Condensation1068

MECHANISM BOXES225

CHAPTER 6 Allvlic Bromination225

Inversion of Confiauration in the SN2 Reaction241

Racemization in the SN1 Reaction248

Hydride Shift in an SN1 Reaction250

Methyl Shift in an SN1 Reaction251

Rearrangement in an E1 Reaction258

CHAPTER 7 Dehydrohalogenation by the E2 Mechanism300

Stereochemistry of the E2 Reaction302

E2 Debromination of a Vicinal Dibromide306

CHAPTER 8 Ionic Addition of HX to an Alkene327

Free-Radical Addition of HBr to Alkenes329

Acid-Catalyzed Hydration of an Alkene333

Oxymercuration of an Alkene335

Hvdroboration of an Alkene340

Addition of Halogens to Alkenes345

Formation of Halohydrins347

Epoxidation of Alkenes356

Acid-Catalyzed Opening of Epoxides357

Olefin Metathesis372

CHAPTER 9 Metal-Ammonia Reduction of an Alkyne404

Acid-Catalyzed Keto-Enol Tautomerism408

Base-Catalyzed Keto-Enol Tautomerism410

CHAPTER 10 Hydride Reduction of a Carbonyl Group450

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

Reaction of a Primary Alcohol with HBr(SN2)477

Reaction of Alcohols with PBr3481

(Review):Acid-Catalyzed Dehydration of an Alcohol484

The Pinacol Rearrangement491

CHAPTER 14 Cleavage of an Ether by HBr or Hl639

Acid-Catalyzed Opening of Epoxides in Water648

Acid-Catalyzed Opening of an Epoxide in an Alcohol Solution649

Base-Catalyzed Opening of Epoxides651

CHAPTER 15 1,2-and 1,4-Addition to a Coniugated Diene673

Free-Radical Allylic Bromination676

CHAPTER 17 Bromination of Benzene753

Nitration of Benzene756

Sulfonation of Benzene757

Friedel-Crafts Alkylation774

Friedel-Crafts Acylation778

Nucleophilic Aromatic Substitution(Addition-Elimination)783

Nucleophilic Aromatic Substitution(Benzyne Mechanism)786

The Birch Reduction788

CHAPTER 18 The Wittig Reaction836

Hydration of Ketones and Aldehydes839

Formation of Cyanohydrins840

Wolff-Kishner Reduction857

CHAPTER 19 Electrophilic Aromatic Substitution of Pyridine892

Nucleophilic Aromatic Substitution of Pyridine893

Acylation of an Amine by an Acid Chloride895

Hofmann Elimination899

The Cope Elimination of an Amine Oxide903

Diazotization of an Amine904

The Hofmann Rearrangement of Amides921

CHAPTER 20 Nucleophilic Acyl Substitution in the Basic Hydrolysis of an Ester959

Esterification Using Diazomethane964

CHAPTER 21 Conversion of an Acid Chloride to an Anhydride1000

Conversion of an Acid Chloride to an Ester1000

Conversion of an Acid Chloride to an Amide1001

Conversion of an Acid Anhydride to an Ester1001

Conversion of an Acid Anhydride to an Amide1002

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

Transesterification1007

Saponification of an Ester1009

Basic Hydrolysis of an Amide1011

Acidic Hydrolysis of an Amide1011

Base-Catalyzed Hydrolysis of a Nitrile1012

Hydride Reduction of an Ester1013

Reduction of an Amide to an Amine1014

Reaction of an Ester with Two Moles of a Grignard Reagent1016

CHAPTER 22 Alpha Substitution1043

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 Tautomerism1044

Acid-Catalyzed Keto-Enol Tautomerism1045

Base-Promoted Halogenation1052

Final Steps of the Haloform Reaction1054

Acid-Catalyzed Alpha Haloaenation1055

Acid-Catalyzed Aldol Condensation1060

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

CHAPTER 23 Formation of a Cyclic Hemiacetal1104

Base-Catalyzed Epimerization of Glucose1111

Base-Catalyzed Enediol Rearrangement1111

CHAPTER 26 Free-Radical Polymerization1225

Cationic Polymerization1226

Anionic Polymerization1228