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INTRODUCTION1

The Origins of Organic Chemistry1

Berzelius，Wohler，and Vitalism1

The Structural Theory3

Electronic Theories of Structure and Reactivity3

The Influence of Organic Chemistry4

Computers and Organic Chemistry4

Challenges and Opportunities5

Where Did the Carbon Come From？6

CHAPTER 1 STRUCTURE DETERMINES PROPERTIES7

1.1 Atoms，Electrons，and Orbitals7

1.2 Ionic Bonds10

1.3 Covalent Bonds and the Octet Rule12

1.4 Double Bonds and Triple Bonds14

1.5 Polar Covalent Bonds and Electronegativity14

Electrostatic Potential Maps16

1.6 Formal Charge17

1.7 Structural Formulas of Organic Molecules21

1.8 Constitutional Isomers23

1.9 Resonance24

Learning By Modeling28

1.10 The Shapes of Some Simple Molecules29

1.11 Molecular Dipole Moments31

1.12 Acids and Bases：The Arrhenius View32

1.13 Acids and Bases：The Bronsted-Lowry View33

Curved Arrows34

1.14 What Happened to pKb？37

1.15 How Structure Affects Acid Strength38

1.16 Acid-Base Equilibria43

1.17 Lewis Acids and Lewis Bases45

1.18 SUMMARY47

Problems50

CHAPTER 2 HYDROCARBON FRAMEWORKS.ALKANES57

2.1 Classes of Hydrocarbons57

2.2 Electron Waves and Chemical Bonds58

2.3 Bonding in H2：The Valence Bond Model60

2.4 Bonding in H2：The Molecular Orbital Model61

2.5 Introduction to Alkanes：Methane，Ethane，and Propane63

2.6 sp3 Hybridization and Bonding in Methane63

Methane and the Biosphere66

2.7 Bonding in Ethane67

2.8 Isomeric Alkanes：The Butanes67

2.9 Higher n-Alkanes68

2.10 The C5H12 Isomers69

2.11 IUPAC Nomenclature of Unbranched Alkanes70

2.12 Applying the IUPAC Rules：The Names of the C6H14 Isomers71

2.13 Alkyl Groups73

2.14 IUPAC Names of Highly Branched Alkanes75

2.15 Cycloalkane Nomenclature77

A Brief History of Systematic Organic Nomenclature78

2.16 Sources of Alkanes and Cycloalkanes79

2.17 Physical Properties of Alkanes and Cycloalkanes80

2.18 Chemical Properties.Combustion of Alkanes83

Thermochemistry86

2.19 Oxidation-Reduction in Organic Chemistry87

2.20 sp2 Hybridization and Bonding in Ethylene89

2.21 sp Hybridization and Bonding in Acetylene92

2.22 Which Theory of Chemical Bonding Is Best？93

2.23 SUMMARY95

Problems99

CHAPTER 3 CONFORMATIONS OF ALKANES AND CYCLOALKANES104

3.1 Conformational Analysis of Ethane105

3.2 Conformational Analysis of Butane109

3.3 Conformations of Higher Alkanes110

Molecular Mechanics Applied to Alkanes and Cycloalkanes111

3.4 The Shapes of Cycloalkanes：Planar or Nonplanar？112

3.5 Small Rings：Cyclopropane and Cyclobutane114

3.6 Cyclopentane115

3.7 Conformations of Cyclohexane116

3.8 Axial and Equatorial Bonds in Cyclohexane117

3.9 Conformational Inversion （Ring Flipping） in Cyclohexane119

3.10 Conformational Analysis of Monosubstituted Cyclohexanes120

Enthalpy，Free Energy，and Equilibrium Constant122

3.11 Disubstituted Cycloalkanes：Stereoisomers124

3.12 Conformational Analysis of Disubstituted Cyclohexanes125

3.13 Medium and Large Rings129

3.14 Polycyclic Ring Systems129

3.15 Heterocyclic Compounds131

3.16 SUMMARY132

Problems136

CHAPTER 4 ALCOHOLS AND ALKYL HALIDES142

4.1 Functional Groups143

4.2 IUPAC Nomenclature of Alkyl Halides144

4.3 IUPAC Nomenclature of Alcohols145

4.4 Classes of Alcohols and Alkyl Halides146

4.5 Bonding in Alcohols and Alkyl Halides146

4.6 Physical Properties of Alcohols and Alkyl Halides：Intermolecular Forces147

4.7 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides151

4.8 Mechanism of the Reaction of Alcohols with Hydrogen Halides153

4.9 Potential Energy Diagrams for Multistep Reactions：159

The SN1 Mechanism159

4.10 Structure，Bonding，and Stability of Carbocations160

4.11 Effect of Alcohol Structure on Reaction Rate162

4.12 Reaction of Primary Alcohols with Hydrogen Halides：The SN2 Mechanism163

4.13 Other Methods for Converting Alcohols to Alkyl Halides165

4.14 Halogenation of Alkanes166

4.15 Chlorination of Methane166

4.16 Structure and Stability of Free Radicals167

4.17 Mechanism of Methane Chlorination172

4.18 Halogenation of Higher Alkanes173

From Bond Energies to Heats of Reaction174

4.19 SUMMARY178

Problems182

CHAPTER 5 STRUCTURE AND PREPARATION OF ALKENES：ELIMINATION REACTIONS187

5.1 Alkene Nomenclature187

Ethylene189

5.2 Structure and Bonding in Alkenes190

5.3 Isomerism in Alkenes192

5.4 Naming Stereoisomeric Alkenes by the E-Z Notational System193

5.5 Physical Properties of Alkenes196

5.6 Relative Stabilities of Alkenes197

5.7 Cycloalkenes200

5.8 Preparation of Alkenes：Elimination Reactions202

5.9 Dehydration of Alcohols202

5.10 Regioselectivity in Alcohol Dehydration：The Zaitsev Rule204

5.11 Stereoselectivity in Alcohol Dehydration205

5.12 The E1 and E2 Mechanisms of Alcohol Dehydration206

5.13 Rearrangements in Alcohol Dehydration208

5.14 Dehydrohalogenation of Alkyl Halides211

5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides214

5.16 Anti Elimination in E2 Reactions：Stereoelectronic Effects216

5.17 The E1 Mechanism of Dehydrohaloge nation of Alkyl Halides217

5.18 SUMMARY220

Problems223

CHAPTER 6 REACTIONS OF ALKENES：ADDITION REACTIONS230

6.1 Hydrogenation of Alkenes230

6.2 Heats of Hydrogenation231

6.3 Stereochemistry of Alkene Hydrogenation234

6.4 Electrophilic Addition of Hydrogen Halides to Alkenes235

6.5 Regioselectivity of Hydrogen Halide Addition：Markovnikov’s Rule236

6.6 Mechanistic Basis for Markovnikov’s Rule238

Rules，Laws，Theories，and the Scientific Method239

6.7 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes241

6.8 Free-Radical Addition of Hydrogen Bromide to Alkenes242

6.9 Addition of Sulfuric Acid to Alkenes245

6.10 Acid-Catalyzed Hydration of Alkenes247

6.11 Hydroboration-Oxidation of Alkenes250

6.12 Stereochemistry of Hydroboration-Oxidation252

6.13 Mechanism of Hydroboration-Oxidation252

6.14 Addition of Halogens to Alkenes254

6.15 Stereochemistry of Halogen Addition256

6.16 Mechanism of Halogen Addition to Alkenes：Halonium Ions256

6.17 Conversion of Alkenes to Vicinal Halohydrins259

6.18 Epoxidation of Alkenes260

6.19 Ozonolysis of Alkenes262

6.20 Introduction to Organic Chemical Synthesis265

6.21 Reactions of Alkenes with Alkenes：Polymerization266

Ethylene and Propene：The Most Important Industrial Organic Chemicals269

6.22 SUMMARY271

Problems274

CHAPTER 7 STEREOCHEMISTRY281

7.1 Molecular Chirality：Enantiomers281

7.2 The Chirality Center282

7.3 Symmetry in Achiral Structures286

7.4 Optical Activity287

7.5 Absolute and Relative Configuration289

7.6 The Cahn-Ingold-Prelog R-5 Notational System290

7.7 Fischer Projections293

7.8 Properties of Enantiomers295

Chiral Drugs296

7.9 Reactions That Create a Chirality Center297

7.10 Chiral Molecules with Two Chirality Centers300

7.11 Achiral Molecules with Two Chirality Centers303

Chirality of Disubstituted Cyclohexanes305

7.12 Molecules with Multiple Chirality Centers306

7.13 Reactions That Produce Diastereomers307

7.14 Resolution of Enantiomers310

7.15 Stereoregular Polymers312

7.16 Chirality Centers Other Than Carbon314

7.17 SUMMARY315

Problems318

CHAPTER 8 NUCLEOPHILIC SUBSTITUTION326

8.1 Functional Group Transformation by Nucleophilic Substitution326

8.2 Relative Reactivity of Halide Leaving Groups330

8.3 The SN2 Mechanism of Nucleophilic Substitution330

8.4 Stereochemistry of SN2 Reactions331

8.5 How SN2 Reactions Occur333

8.6 Steric Effects in SN2 Reactions334

8.7 Nucleophiles and Nucleophilicity336

An Enzyme-Catalyzed Nucleophilic Substitution of an Alkyl Halide339

8.8 The SN1 Mechanism of Nucleophilic Substitution339

8.9 Carbocation Stability and SN1 Reaction Rates341

8.10 Stereochemistry of SN1 Reactions342

8.11 Carbocation Rearrangements in SN1 Reactions344

8.12 Effect of Solvent on the Rate of Nucleophilic Substitution345

8.13 Substitution and Elimination as Competing Reactions348

8.14 Sulfonate Esters as Substrates in Nucleophilic Substitution350

8.15 Looking Back：Reactions of Alcohols with Hydrogen Halides354

8.16 SUMMARY355

Problems357

CHAPTER 9 ALKYN ES363

9.1 Sources of Alkynes363

9.2 Nomenclature364

9.3 Physical Properties of Alkynes365

9.4 Structure and Bonding in Alkynes：sp Hybridization365

Natural and “Designed” Enediyne Antibiotics368

9.5 Acidity of Acetylene and Terminal Alkynes368

9.6 Preparation of Alkynes by Alkylation of Acetylene and Terminal Alkynes370

9.7 Preparation of Alkynes by Elimination Reactions372

9.8 Reactions of Alkynes374

9.9 Hydrogenation of Alkynes374

9.10 Metal-Ammonia Reduction of Alkynes376

9.11 Addition of Hydrogen Halides to Alkynes377

9.12 Hydration of Alkynes379

9.13 Addition of Halogens to Alkynes381

9.14 Ozonolysis of Alkynes381

9.15 SUMMARY382

Problems384

CHAPTER 10 CONJUGATION IN ALKADIENES AND ALLYLIC SYSTEMS390

10.1 The Allyl Group390

10.2 Allylic Carbocations391

10.3 Allylic Free Radicals395

10.4 Allylic Halogenation396

10.5 Classes of Dienes398

10.6 Relative Stabilities of Dienes399

10.7 Bonding in Conjugated Dienes400

10.8 Bonding in Allenes402

10.9 Preparation of Dienes404

10.10 Addition of Hydrogen Halides to Conjugated Dienes405

10.11 Halogen Addition to Dienes407

Diene Polymers408

10.12 The Diels-Alder Reaction409

10.13 The π Molecular Orbitals of Ethylene and 1，3-Butadiene412

10.14 A π Molecular Orbital Analysis of the Diels-Alder Reaction414

10.15 SUMMARY415

Problems418

CHAPTER 11 ARENES AND AROMATICITY423

11.1 Benzene424

11.2 Kekule and the Structure of Benzene424

Benzene，Dreams，and Creative Thinking426

11.3 A Resonance Picture of Bonding in Benzene427

11.4 The Stability of Benzene428

11.5 An Orbital Hybridization View of Bonding in Benzene430

11.6 The π Molecular Orbitals of Benzene430

11.7 Substituted Derivatives of Benzene and Their Nomenclature432

11.8 Polycyclic Aromatic Hydrocarbons434

Carbon Clusters，Fullerenes，and Nanotubes436

11.9 Physical Properties of Arenes438

11.10 Reactions of Arenes：A Preview438

11.11 The Birch Reduction438

11.12 Free-Radical Halogenation of Alkylbenzenes439

11.13 Oxidation of Alkylbenzenes443

11.14 Nucleophilic Substitution in Benzylic Halides444

11.15 Preparation of Alkenylbenzenes446

11.16 Addition Reactions of Alkenylbenzenes447

11.17 Polymerization of Styrene449

11.18 Cyclobutadiene and Cyclooctatetraene449

11.19 Huckel’s Rule451

11.20 Annulenes454

11.21 Aromatic Ions456

11.22 Heterocyclic Aromatic Compounds460

11.23 Heterocyclic Aromatic Compounds and Huckel’s Rule462

11.24 SUMMARY463

Problems467

CHAPTER 12 REACTIONS OF ARENES：ELECTROPHILIC AROMATIC SUBSTITUTION473

12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene474

12.2 Mechanistic Principles of Electrophilic Aromatic Substitution474

12.3 Nitration of Benzene477

12.4 Sulfonation of Benzene478

12.5 Halogenation of Benzene480

12.6 Friedel-Crafts Alkylation of Benzene481

12.7 Friedel-Crafts Acylation of Benzene484

12.8 Synthesis of Alkylbenzenes by Acylation-Reduction486

12.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution488

12.10 Rate and Regioselectivity in the Nitration of Toluene489

12.11 Rate and Regioselectivity in the Nitration of （TrifIuoromethyl）benzene492

12.12 Substituent Effects in Electrophilic Aromatic Substitution：Activating Substituents494

12.13 Substituent Effects in Electrophilic Aromatic Substitution：Strongly Deactivating Substituents498

12.14 Substituent Effects in Electrophilic Aromatic Substitution：Halogens500

12.15 Multiple Substituent Effects502

12.16 Regioselective Synthesis of Disubstituted Aromatic Compounds504

12.17 Substitution in Naphthalene506

12.18 Substitution in Hetereocyclic Aromatic Compounds507

12.19 SUMMARY508

Problems512

CHAPTER 13 SPECTROSCOPY519

13.1 Principles of Molecular Spectroscopy：Electromagnetic Radiation520

13.2 Principles of Molecular Spectroscopy：Quantized Energy States521

13.3 Introduction to 1H NMR Spectroscopy522

13.4 Nuclear Shielding and 1H Chemical Shifts525

13.5 Effects of Molecular Structure on 1H Chemical Shifts526

Ring Currents：Aromatic and Antiaromatic530

13.6 Interpreting 1H NMR Spectra532

13.7 Spin-Spin Splitting in 1H NMR Spectroscopy535

13.8 Splitting Patterns：The Ethyl Group538

13.9 Splitting Patterns：The Isopropyl Group540

13.10 Splitting Patterns：Pairs of Doublets541

13.11 Complex Splitting Patterns543

13.12 1H NMR Spectra of Alcohols544

13.13 NMR and Conformations545

Magnetic Resonance Imaging546

13.14 13C NMR Spectroscopy547

13.15 13C Chemical Shifts549

13.16 13C NMR and Peak Intensities551

13.17 13C—1H Coupling552

13.18 Using DEPT to Count Hydrogens Attached to 13C553

Spectra by the Thousands555

13.19 2D NMR：COSY and HETCOR556

13.20 Infrared Spectroscopy559

13.21 Ultraviolet-Visible （UV-VIS） Spectroscopy565

13.22 Mass Spectrometry567

Gas Chromatography，GC/MS，and MS/MS572

13.23 Molecular Formula as a Clue to Structure573

13.24 SUMMARY575

Problems578

CHAPTER 14 ORGANOMETALLIC COMPOUNDS587

14.1 Organometallic Nomenclature588

14.2 Carbon-Metal Bonds in Organometallic Compounds588

14.3 Preparation of Organolithium Compounds589

14.4 Preparation of Organomagnesium Compounds：Grignard Reagents591

14.5 Organolithium and Organomagnesium Compounds as Bronsted Bases592

14.6 Synthesis of Alcohols Using Grignard Reagents594

14.7 Synthesis of Alcohols Using Organolithium Reagents597

14.8 Synthesis of Acetylenic Alcohols597

14.9 Retrosynthetic Analysis598

14.10 Preparation of Tertiary Alcohols from Esters and Grignard Reagents601

14.11 Alkane Synthesis Using Organocopper Reagents602

14.12 An Organozinc Reagent for Cyclopropane Synthesis604

14.13 Carbenes and Carbenoids606

14.14 Transition Metal Organometallic Compounds608

14.15 Ziegler-Natta Catalysis of Alkene Polymerization610

An Organometallic Compound That Occurs Naturally：Coenzyme B12611

14.16 SUMMARY614

Problems617

CHAPTER 15 ALCOHOLS，DIOLS，AND THIOLS623

15.1 Sources of Alcohols623

15.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones627

15.3 Preparation of Alcohols by Reduction of Carboxylic Acids and Esters632

15.4 Preparation of Alcohols from Epoxides632

15.5 Preparation of Diols633

15.6 Reactions of Alcohols：A Review and a Preview635

15.7 Conversion of Alcohols to Ethers635

15.8 Esterification638

15.9 Esters of Inorganic Acids640

15.10 Oxidation of Alcohols641

Economic and Environmental Factors in Organic Synthesis644

15.11 Biological Oxidation of Alcohols645

15.12 Oxidative Cleavage of Vicinal Diols647

15.13 Thiols648

15.14 Spectroscopic Analysis of Alcohols and Thiols651

15.15 SUMMARY653

Problems657

CHAPTER 16 ETHERS，EPOXIDES，AND SULFIDES665

16.1 Nomenclature of Ethers，Epoxides，and Sulfides665

16.2 Structure and Bonding in Ethers and Epoxides667

16.3 Physical Properties of Ethers668

16.4 Crown Ethers668

Polyether Antibiotics670

16.5 Preparation of Ethers671

16.6 The Williamson Ether Synthesis672

16.7 Reactions of Ethers：A Review and a Preview673

16.8 Acid-Catalyzed Cleavage of Ethers674

16.9 Preparation of Epoxides：A Review and a Preview676

16.10 Conversion of Vicinal Halohydrins to Epoxides676

16.11 Reactions of Epoxides：A Review and a Preview678

16.12 Nucleophilic Ring-Opening of Epoxides679

16.13 Acid-Catalyzed Ring-Opening of Epoxides681

16.14 Epoxides in Biological Processes684

16.15 Preparation of Sulfides685

16.16 Oxidation of Sulfides：Sulfoxides and Sulfones685

16.17 Alkylation of Sulfides：Sulfonium Salts686

16.18 Spectroscopic Analysis of Ethers，Epoxides，and Sulfides688

16.19 SUMMARY691

Problems695

CHAPTER 17 ALDEHYDES AND KETONES：NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP703

17.1 Nomenclature703

17.2 Structure and Bonding：The Carbonyl Group706

17.3 Physical Properties708

17.4 Sources of Aldehydes and Ketones709

17.5 Reactions of Aldehydes and Ketones：A Review and a Preview712

17.6 Principles of Nucleophilic Addition：Hydration of Aldehydes and Ketones712

17.7 Cyanohydrin Formation717

17.8 Acetal Formation720

17.9 Acetals as Protecting Groups723

17.10 Reaction with Primary Amines：Imines724

17.11 Reaction with Secondary Amines：Enamines727

Imines in Biological Chemistry728

17.12 The Wittig Reaction730

17.13 Planning an Alkene Synthesis via the Wittig Reaction732

17.14 Stereoselective Addition to Carbonyl Groups734

17.15 Oxidation of Aldehydes736

17.16 Baeyer-Villiger Oxidation of Ketones736

17.17 Spectroscopic Analysis of Aldehydes and Ketones738

17.18 SUMMARY741

Problems745

CHAPTER 18 ENOLS AND ENOLATES755

18.1 The α-Carbon Atom and Its Hydrogens756

18.2 α Halogenation of Aldehydes and Ketones757

18.3 Mechanism of α Halogenation of Aldehydes and Ketones757

18.4 Enolization and Enol Content759

18.5 Stabilized Enols761

18.6 Base-Catalyzed Enolization.Enolate Anions763

18.7 The Haloform Reaction765

The Haloform Reaction and the Biosynthesis of Trihalomethanes767

18.8 Some Chemical and Stereochemical Consequences of Enolization768

18.9 The Aldol Condensation769

18.10 Mixed Aldol Condensations774

18.11 Effects of Conjugation in α，β-Unsaturated Aldehydes and Ketones775

18.12 Conjugate Addition to α，β-Unsaturated Carbonyl Compounds777

18.13 Addition of Carbanions to α，β-Unsaturated Ketones：779

The Michael Reaction779

18.14 Conjugate Addition of Organocopper Reagents to α，β-Unsaturated Carbonyl Compounds780

18.15 Alkylation of Enolate Anions781

18.16 SUMMARY781

Problems784

CHAPTER 19 CARBOXYLIC ACIDS791

19.1 Carboxylic Acid Nomenclature792

19.2 Structure and Bonding793

19.3 Physical Properties794

19.4 Acidity of Carboxylic Acids795

19.5 Salts of Carboxylic Acids797

Quantitative Relationships Involving Carboxylic Acids798

19.6 Substituents and Acid Strength801

19.7 Ionization of Substituted Benzoic Acids803

19.8 Dicarboxylic Acids804

19.9 Carbonic Acid804

19.10 Sources of Carboxylic Acids806

19.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents806

19.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles808

19.13 Reactions of Carboxylic Acids：A Review and a Preview809

19.14 Mechanism of Acid-Catalyzed Esterification810

19.15 Intramolecular Ester Formation：Lactones814

19.16 α Halogenation of Carboxylic Acids：The Hell-Volhard-Zelinsky Reaction815

19.17 Decarboxylation of Malonic Acid and Related Compounds816

19.18 Spectroscopic Analysis of Carboxylic Acids819

19.19 SUMMARY821

Problems824

CHAPTER 20 CARBOXYLIC ACID DERIVATIVES：NUCLEOPHILIC ACYL SUBSTITUTION830

20.1 Nomenclature of Carboxylic Acid Derivatives831

20.2 Structure and Reactivity of Carboxylic Acid Derivatives833

20.3 General Mechanism for Nucleophilic Acyl Substitution836

20.4 Nucleophilic Substitution in Acyl Chlorides838

20.5 Preparation of Carboxylic Acid Anhydrides841

20.6 Reactions of Carboxylic Acid Anhydrides842

20.7 Sources of Esters845

20.8 Physical Properties of Esters846

20.9 Reactions of Esters：A Review and a Preview846

20.10 Acid-Catalyzed Ester Hydrolysis848

20.11 Ester Hydrolysis in Base：Saponification852

20.12 Reaction of Esters with Ammonia and Amines857

20.13 Thioesters858

20.14 Preparation of Amides859

20.15 Lactams861

20.16 Imides862

20.17 Hydrolysis of Amides862

20.18 Preparation of Nitriles867

Condensation Polymers：Polyamides and Polyesters868

20.19 Hydrolysis of Nitriles870

20.20 Addition of Grignard Reagents to Nitriles871

20.21 Spectroscopic Analysis of Carboxylic Acid Derivatives872

20.22 SUMMARY874

Problems877

CHAPTER 21 ESTER ENOLATES886

21.1 The Claisen Condensation887

21.2 Intramolecular Claisen Condensation：The Dieckmann Reaction890

21.3 Mixed Claisen Condensations891

21.4 Acylation of Ketones with Esters892

21.5 Ketone Synthesis via β-Keto Esters893

21.6 The Acetoacetic Ester Synthesis894

21.7 The Malonic Ester Synthesis897

21.8 Barbiturates900

21.9 Michael Additions of Stabilized Anions901

21.10 α Deprotonation of Carbonyl Compounds by Lithium Dialkylamides902

21.11 SUMMARY905

Problems908

CHAPTER 22 AMINES913

22.1 Amine Nomenclature913

22.2 Structure and Bonding916

22.3 Physical Properties918

22.4 Basicity of Amines919

22.5 Tetraalkylammonium Salts as Phase-Transfer Catalysts923

Amines as Natural Products924

22.6 Reactions That Lead to Amines：A Review and a Preview926

22.7 Preparation of Amines by Alkylation of Ammonia928

22.8 The Gabriel Synthesis of Primary Alkylamines929

22.9 Preparation of Amines by Reduction931

22.10 Reductive Amination934

22.11 Reactions of Amines：A Review and a Preview935

22.12 Reaction of Amines with Alkyl Halides937

22.13 The Hofmann Elimination938

22.14 Electrophilic Aromatic Substitution in Arylamines939

22.15 Nitrosation of Alkylamines943

22.16 Nitrosation of Arylamines945

22.17 Synthetic Transformations of Aryl Diazonium Salts946

22.18 Azo Coupling950

From Dyes to Sulfa Drugs951

22.19 Spectroscopic Analysis of Amines951

22.20 SUMMARY955

Problems962

CHAPTER 23 ARYL HALIDES971

23.1 Bonding in Aryl Halides971

23.2 Sources of Aryl Halides972

23.3 Physical Properties of Aryl Halides972

23.4 Reactions of Aryl Halides：A Review and a Preview973

23.5 Nucleophilic Substitution in Nitro-Substituted Aryl Halides975

23.6 The Addition-Elimination Mechanism of Nucleophilic Aromatic Substitution977

23.7 Related Nucleophilic Aromatic Substitution Reactions980

23.8 The Elimination-Addition Mechanism of Nucleophilic Aromatic Substitution：Benzyne981

23.9 Diels-Alder Reactions of Benzyne985

23.10 SUMMARY986

Problems988

CHAPTER 24 PHENOLS993

24.1 Nomenclature993

24.2 Structure and Bonding994

24.3 Physical Properties995

24.4 Acidity of Phenols996

24.5 Substituent Effects on the Acidity of Phenols998

24.6 Sources of Phenols999

24.7 Naturally Occurring Phenols1001

24.8 Reactions of Phenols：Electrophilic Aromatic Substitution1002

24.9 Acylation of Phenols1004

24.10 Carboxylation of Phenols：Aspirin and the Kolbe-Schmitt Reaction1006

24.11 Preparation of Aryl Ethers1008

Agent Orange and Dioxin1009

24.12 Cleavage of Aryl Ethers by Hydrogen Halides1010

24.13 Claisen Rearrangement of Allyl Aryl Ethers1011

24.14 Oxidation of Phenols：Quinones1012

24.15 Spectroscopic Analysis of Phenols1014

24.16 SUMMARY1016

Problems1019

CHAPTER 25 CARBOHYDRATES1026

25.1 Classification of Carbohydrates1026

25.2 Fischer Projections and D-L Notation1027

25.3 The Aldotetroses1029

25.4 Aldopentoses and Aldohexoses1030

25.5 A Mnemonic for Carbohydrate Configurations1032

25.6 Cyclic Forms of Carbohydrates：Furanose Forms1032

25.7 Cyclic Forms of Carbohydrates：Pyranose Forms1036

25.8 Mutarotation1040

25.9 Ketoses1041

25.10 Deoxy Sugars1042

25.11 Amino Sugars1042

25.12 Branched-Chain Carbohydrates1043

25.13 Glycosides1043

25.14 Disaccharides1046

25.15 Polysaccharides1048

25.16 Cell-Surface Glycoproteins1050

How Sweet It Is！1051

25.17 Carbohydrate Structure Determination1052

25.18 Reduction of Carbohydrates1052

25.19 Oxidation of Carbohydrates1053

25.20 Cyanohydrin Formation and Chain Extension1055

25.21 Epimerization，Isomerization，and Retro-Aldol Cleavage1056

25.22 Acylation and Alkylation of Hydroxyl Groups in Carbohydrates1058

25.23 Periodic Acid Oxidation of Carbohydrates1059

25.24 SUMMARY1061

Problems1065

CHAPTER 26 LIPIDS1069

26.1 Acetyl Coenzyme A1070

26.2 Fats，Oils，and Fatty Acids1071

26.3 Fatty Acid Biosynthesis1075

26.4 Phospholipids1077

26.5 Waxes1079

26.6 Prostaglandins1080

Nonsteroidal Antiinflammatory Drugs （NSAIDs） and COX-2 Inhibitors1083

26.7 Terpenes：The Isoprene Rule1084

26.8 Isopentenyl Pyrophosphate：The Biological Isoprene Unit1087

26.9 Carbon-Carbon Bond Formation in Terpene Biosynthesis1087

26.10 The Pathway from Acetate to Isopentenyl Pyrophosphate1091

26.11 Steroids：Cholesterol1093

Good Cholesterol？ Bad Cholesterol？ What’s the Difference？1096

26.12 Vitamin D1096

26.13 Bile Acids1097

26.14 Corticosteroids1098

26.15 Sex Hormones1098

Anabolic Steroids1099

26.16 Carotenoids1100

26.17 SUMMARY1101

Problems1103

CHAPTER 27 AMINO ACIDS，PEPTIDES，AND PROTEINS1109

27.1 Classification of Amino Acids1110

27.2 Stereochemistry of Amino Acids1115

27.3 Acid-Base Behavior of Amino Acids1117

Electrophoresis1120

27.4 Synthesis of Amino Acids1121

27.5 Reactions of Amino Acids1123

27.6 Some Biochemical Reactions of Amino Acids1123

27.7 Peptides1126

27.8 Introduction to Peptide Structure Determination1129

27.9 Amino Acid Analysis1130

27.10 Partial Hydrolysis of Peptides1130

27.11 End Group Analysis1131

27.12 Insulin1131

27.13 The Edman Degradation and Automated Sequencing of Peptides1133

27.14 The Strategy of Peptide Synthesis1135

27.15 Amino Group Protection1137

27.16 Carboxyl Group Protection1138

27.17 Peptide Bond Formation1139

27.18 Solid-Phase Peptide Synthesis：The Merrifield Method1141

27.19 Secondary Structures of Peptides and Proteins1143

27.20 Tertiary Structure of Peptides and Proteins1145

27.21 Coenzymes1147

27.22 Protein Quaternary Structure：Hemoglobin1148

Oh NO！ It’s Inorganic！1149

27.23 SUMMARY1150

Problems1152

CHAPTER 28 NUCLEOSIDES，NUCLEOTIDES，AND NUCLEIC ACIDS1155

28.1 Pyrimidines and Purines1155

28.2 Nucleosides1158

28.3 Nucleotides1160

28.4 Bioenergetics1162

28.5 ATP and Bioenergetics1162

28.6 Phosphodiesters，Oligonucleotides，and Polynucleotides1164

28.7 Nucleic Acids1165

28.8 Secondary Structure of DNA：The Double Helix1166

“It Has Not Escaped Our Notice…”1167

28.9 Tertiary Structure of DNA：Supercoils1170

28.10 Replication of DNA1172

28.11 Ribonucleic Acids1172

RNA World1177

28.12 Protein Biosynthesis1178

28.13 AIDS1179

28.14 DNA Sequencing1180

28.15 The Human Genome Project1182

28.16 DNA Profiling and the Polymerase Chain Reaction1183

28.17 SUMMARY1186

Problems1189