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INTRODUCTION2

The Origins of Organic Chemistry2

Berzelius，Wohler，and Vitalism2

The Structural Theory4

Electronic Theories of Structure and Reactivity4

The Influence of Organic Chemistry5

Computers and Organic Chemistry5

Challenges and Opportunities5

Where Did the Carbon Come From？7

CHAPTER 1 Structure Determines Properties8

1.1 Atoms，Electrons，and Orbitals9

1.2 Ionic Bonds12

1.3 Covalent Bonds，Lewis Structures，and the Octet Rule14

1.4 Double Bonds and Triple Bonds16

1.5 Polar Covalent Bonds and Electronegativity16

Electrostatic Potential Maps19

1.6 Structural Formulas of Organic Molecules19

1.7 Formal Charge22

1.8 Resonance24

1.9 The Shapes of Some Simple Molecules29

Molecular Modeling30

1.10 Molecular Dipole Moments32

1.11 Curved Arrows and Chemical Reactions33

1.12 Acids and Bases：The Arrhenius View35

1.13 Acids and Bases：The Bronsted-Lowry View36

1.14 What Happened to pKb？40

1.15 How Structure Affects Acid Strength41

1.16 Acid-Base Equilibria45

1.17 Lewis Acids and Lewis Bases48

1.18 Summary49

Problems52

Descriptive Passage and Interpretive Problems 1：Amide Lewis Structures57

CHAPTER 2 Alkanes and Cycloalkanes：Introduction to Hydrocarbons58

2.1 Classes of Hydrocarbons59

2.2 Electron Waves and Chemical Bonds60

2.3 Bonding in H2：The Valence Bond Model61

2.4 Bonding in H2：The Molecular Orbital Model63

2.5 Introduction to Alkanes：Methane，Ethane，and Propane64

Methane and the Biosphere65

2.6 sp3 Hybridization and Bonding in Methane66

2.7 Bonding in Ethane68

2.8 Isomeric Alkanes：The Butanes68

2.9 Higher n-Alkanes68

2.10 The C5H12 Isomers69

2.11 IUPAC Nomenclature of Unbranched Alkanes71

What’s In a Name？ Organic Nomenclature72

2.12 Applying the IUPAC Rules：The Names of the C6H14 Isomers73

2.13 Alkyl Groups74

2.14 IUPAC Names of Highly Branched Alkanes76

2.15 Cycloalkane Nomenclature77

2.16 Sources of Alkanes and Cycloalkanes78

2.17 Physical Properties of Alkanes and Cycloalkanes80

2.18 Chemical Properties：Combustion of Alkanes82

2.19 Oxidation-Reduction in Organic Chemistry85

Thermochemistty86

2.20 sp2 Hybridization and Bonding in Ethylene89

2.21 sp Hybridization and Bonding in Acetylene91

2.22 Which Theory of Chemical Bonding Is Best？92

2.23 Summary93

Problems97

Descriptive Passage and Interpretive Problems 2：Some Biochemical Reactions of Alkanes100

CHAPTER 3 Alkanes and Cycloalkanes：Conformations and cis-trans Stereoisomers102

3.1 Conformational Analysis of Ethane104

3.2 Conformational Analysis of Butane107

Molecular Mechanics Applied to Alkanes and Cycloalkanes109

3.3 Conformations of Higher Alkanes110

3.4 The Shapes of Cycloalkanes：Planar or Nonplanar？110

3.5 Small Rings：Cyclopropane and Cyclobutane111

3.6 Cyclopentane112

3.7 Conformations of Cyclohexane112

3.8 Axial and Equatorial Bonds in Cyclohexane113

3.9 Conformational Inversion （Ring Flipping） in Cyclohexane115

3.10 Conformational Analysis of Monosubstituted Cyclohexanes116

3.11 Disubstituted Cycloalkanes：cis-trans Stereoisomers119

Enthalpy，Free Energy，and Equilibrium Constant120

3.12 Conformational Analysis of Disubstituted Cyclohexanes121

3.13 Medium and Large Rings125

3.14 Polycyclic Ring Systems125

3.15 Heterocyclic Compounds128

3.16 Summary129

Problems132

Descriptive Passage and Interpretive Problems 3：Cyclic Forms of Carbohydrates137

CHAPTER 4 Alcohols and Alkyl Halides138

4.1 Functional Groups139

4.2 IUPAC Nomenclature of Alkyl Halides141

4.3 IUPAC Nomenclature of Alcohols142

4.4 Classes of Alcohols and Alkyl Halides142

4.5 Bonding in Alcohols and Alkyl Halides143

4.6 Physical Properties of Alcohols and Alkyl Halides：Intermolecular Forces144

4.7 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides148

4.8 Mechanism of the Reaction of Alcohols with Hydrogen Halides149

4.9 Potential Energy Diagrams for Multistep Reactions：The SN1 Mechanism154

4.10 Structure，Bonding，and Stability of Carbocations155

4.11 Effect of Alcohol Structure on Reaction Rate158

4.12 Reaction of Methyl and Primary Alcohols with Hydrogen Halides：The SN2 Mechanism159

4.13 Other Methods for Converting Alcohols to Alkyl Halides160

4.14 Halogenation of Alkanes161

4.15 Chlorination of Methane162

4.16 Structure and Stability of Free Radicals162

4.17 Mechanism of Methane Chlorination167

4.18 Halogenation of Higher Alkanes168

From Bond Enthalpies to Heats of Reaction169

4.19 Summary173

Problems176

Descriptive Passage and Interpretive Problems 4：More About PotentialEnergy Diagrams180

CHAPTER 5 Structure and Preparation of Alkenes：Elimination Reactions182

5.1 Alkene Nomenclature183

5.2 Structure and Bonding in Alkenes185

Ethylene186

5.3 Isomerism in Alkenes187

5.4 Naming Stereoisomeric Alkenes by the E-Z Notational System188

5.5 Physical Properties of Alkenes189

5.6 Relative Stabilities of Alkenes191

5.7 Cycloalkenes195

5.8 Preparation of Alkenes：Elimination Reactions196

5.9 Dehydration of Alcohols197

5.10 Regioselectivity in Alcohol Dehydration：The Zaitsev Rule198

5.11 Stereoselectivity in Alcohol Dehydration199

5.12 The E1 and E2 Mechanisms of Alcohol Dehydration200

5.13 Rearrangements in Alcohol Dehydration202

5.14 Dehydrohalogenation of Alkyl Halides205

5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides207

5.16 Anti Elimination in E2 Reactions：Stereoelectronic Effects209

5.17 Isotope Effects and the E2 Mechanism210

5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides211

5.19 Summary213

Problems217

Descriptive Passage and Interpretive Problems 5：A Mechanistic Preview of Addition Reactions222

CHAPTER 6 Addition Reactions of Alkenes224

6.1 Hydrogenation of Alkenes225

6.2 Heats of Hydrogenation226

6.3 Stereochemistry of Alkene Hydrogenation229

6.4 Electrophilic Addition of Hydrogen Halides to Alkenes229

6.5 Regioselectivity of Hydrogen Halide Addition：Markovnikov’s Rule231

6.6 Mechanistic Basis for Markovnikov’s Rule233

Rules，Laws，Theories，and the Scientific Method235

6.7 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes235

6.8 Free-Radical Addition of Hydrogen Bromide to Alkenes236

6.9 Addition of Sulfuric Acid to Alkenes239

6.10 Acid-Catalyzed Hydration of Alkenes241

6.11 Thermodynamics of Addition-Elimination Equilibria243

6.12 Hydroboration-Oxidation of Alkenes246

6.13 Stereochemistry of Hydroboration-Oxidation248

6.14 Mechanism of Hydroboration-Oxidation248

6.15 Addition of Halogens to Alkenes251

6.16 Stereochemistry of Halogen Addition251

6.17 Mechanism of Halogen Addition to Alkenes：Halonium Ions252

6.18 Conversion of Alkenes to Vicinal Halohydrins254

6.19 Epoxidation of Alkenes255

6.20 Ozonolysis of Alkenes257

6.21 Introduction to Organic Chemical Synthesis259

6.22 Reactions of Alkenes with Alkenes：Polymerization260

Ethylene and Propene：The Most Important Industrial Organic Chemicals265

6.23 Summary266

Problems269

Descriptive Passage and Interpretive Problems 6：Some Unusual Electrophilic Additions274

CHAPTER 7 Stereochemistry276

7.1 Molecular Chirality：Enantiomers277

7.2 The Chirality Center279

7.3 Symmetry in Achiral Structures281

7.4 Optical Activity282

7.5 Absolute and Relative Configuration284

7.6 The Cahn-Ingold-Prelog R-S Notational System285

7.7 Fischer Projections288

7.8 Properties of Enantiomers290

Chiral Drugs291

7.9 Reactions That Create a Chirality Center292

7.10 Chiral Molecules with Two Chirality Centers295

7.11 Achiral Molecules with Two Chirality Centers297

7.12 Molecules with Multiple Chirality Centers299

Chirality of Disubstituted Cyclohexanes300

7.13 Reactions That Produce Diastereomers301

7.14 Resolution of Enantiomers303

7.15 Stereoregular Polymers305

7.16 Chirality Centers Other Than Carbon306

7.17 Summary307

Problems310

Descriptive Passage and Interpretive Problems 7：Prochirality316

CHAPTER 8 Nucleophilic Substitution318

8.1 Functional Group Transformation by Nucleophilic Substitution319

8.2 Relative Reactivity of Halide Leaving Groups322

8.3 The SN2 Mechanism of Nucleophilic Substitution323

8.4 Steric Effects and SN2 Reaction Rates326

8.5 Nucleophiles and Nucleophilicity328

8.6 The SN1 Mechanism of Nucleophilic Substitution330

Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides331

8.7 Carbocation Stability and SN1 Reaction Rates331

8.8 Stereochemistry of SN1 Reactions334

8.9 Carbocation Rearrangements in SN1 Reactions335

8.10 Effect of Solvent on the Rate of Nucleophilic Substitution337

8.11 Substitution and Elimination as Competing Reactions339

8.12 Nucleophilic Substitution of Alkyl Sulfonates342

8.13 Looking Back：Reactions of Alcohols with Hydrogen Halides344

8.14 Summary346

Problems347

Descriptive Passage and Interpretive Problems 8：Nucleophilic Substitution352

CHAPTER 9 Alkynes354

9.1 Sources of Alkynes355

9.2 Nomenclature357

9.3 Physical Properties of Alkynes357

9.4 Structure and Bonding in Alkynes：sp Hybridization357

9.5 Acidity of Acetylene and Terminal Alkynes360

9.6 Preparation of Alkynes by Alkyation of Acetylene and Terminal Alkynes361

9.7 Preparation of Alkynes by Elimination Reactions363

9.8 Reactions of Alkynes364

9.9 Hydrogenation of Alkynes365

9.10 Metal-Ammonia Reduction of Alkynes367

9.11 Addition of Hydrogen Halides to Alkynes368

9.12 Hydration of Alkynes370

9.13 Addition of Halogens to Alkynes371

Some Things That Can Be Made from Acetylenem…But Aren’t372

9.14 Ozonolysis of Alkynes372

9.15 Summary373

Problems376

Descriptive Passage and Interpretive Problems 9：Thinking Mechanistically About Alkynes380

CHAPTER 10 Conjugation in Alkadienes and Allylic Systems382

10.1 The Allyl Group383

10.2 Allylic Carbocations384

10.3 SN1 Reactions of Allylic Halides385

10.4 SN2 Reactions of Allylic Halides388

10.5 Allylic Free Radicals389

10.6 Allylic Halogenation390

10.7 Allylic Anions393

10.8 Classes of Dienes394

10.9 Relative Stabilities of Dienes395

10.10 Bonding in Conjugated Dienes396

10.11 Bonding in Allenes398

10.12 Preparation of Dienes399

10.13 Addition of Hydrogen Halides to Conjugated Dienes400

10.14 Halogen Addition to Dienes403

10.15 The Diels-Alder Reaction403

Diene Polymers404

10.16 The π Molecular Orbitals of Ethylene and 1，3-Butadiene407

10.17 A π Molecular Orbital Analysis of the Diels-Alder Reaction408

10.18 Summary410

Problems413

Descriptive Passage and Interpretive Problems 10：Intramolecular and Retro Diels-Alder Reactions417

CHAPTER 11 Arenes and Aromaticity420

11.1 Benzene421

11.2 Kekule and the Structure of Benzene422

11.3 A Resonance Picture of Bonding in Benzene424

11.4 The Stability of Benzene424

11.5 An Orbital Hybridization View of Bonding in Benzene426

11.6 The π Molecular Orbitals of Benzene427

11.7 Substituted Derivatives of Benzene and Their Nomenclature428

11.8 Polycyclic Aromatic Hydrocarbons430

11.9 Physical Properties of Arenes431

Carbon Clusters，Fullerenes，and Nanotubes432

11.10 Reactions of Arenes：A Preview432

11.11 The Birch Reduction433

11.12 Free-Radical Halogenation of Alkylbenzenes436

11.13 Oxidation of Alkylbenzenes438

11.14 SN1 Reactions of Benzylic Halides440

11.15 SN2 Reactions of Benzylic Halides441

11.16 Preparation of Alkenylbenzenes442

11.17 Addition Reactions of Alkenylbenzenes443

11.18 Polymerization of Styrene445

11.19 Cyclobutadiene and Cyclooctatetraene446

11.20 Huckel’s Rule448

11.21 Annulenes450

11.22 Aromatic Ions452

11.23 Heterocyclic Aromatic Compounds455

11.24 Heterocyclic Aromatic Compounds and Huckel’s Rule457

11.25 Summary459

Problems462

Descriptive Passage and Interpretive Problems 11：The Hammett Equation466

CHAPTER 12 Reactions of Arenes：Electrophilic Aromatic Substitution470

12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene471

12.2 Mechanistic Principles of Electrophilic Aromatic Substitution472

12.3 Nitration of Benzene474

12.4 Sulfonation of Benzene476

12.5 Halogenation of Benzene477

12.6 Friedel-Crafts Alkylation of Benzene478

12.7 Friedel-Crafts Acylation of Benzene481

12.8 Synthesis of Alkylbenzenes by Acylation-Reduction483

12.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution484

12.10 Rate and Regioselectivity in the Nitration of Toluene485

12.11 Rate and Regioselectivity in the Nitration of （Trifluoromethyl）benzene488

12.12 Substituent Effects in Electrophilic Aromatic Substitution：Activating Substituents490

12.13 Substituent Effects in Electrophilic Aromatic Substitution：Strongly Deactivating Substituents493

12.14 Substituent Effects in Electrophilic Aromatic Substitution：Halogens496

12.15 Multiple Substituent Effects498

12.16 Regioselective Synthesis of Disubstituted Aromatic Compounds499

12.17 Substitution in Naphthalene502

12.18 Substitution in Heterocyclic Aromatic Compounds502

12.19 Summary504

Problems507

Descriptive Passage and Interpretive Problems 12：Nucleophilic Aromatic Substitution512

CHAPTER 13 Spectroscopy516

13.1 Principles of Molecular Spectroscopy：Electromagnetic Radiation518

13.2 Principles of Molecular Spectroscopy：Quantized Energy States519

13.3 Introduction to 1H NMR Spectroscopy519

13.4 Nuclear Shielding and 1H Chemical Shifts521

13.5 Effects of Molecular Structure on 1H Chemical Shifts524

Ring Currents：Aromatic and Antiaromatic529

13.6 Interpreting 1H NMR Spectra530

13.7 Spin-Spin Splitting in 1H NMR Spectroscopy532

13.8 Splitting Patterns：The Ethyl Group534

13.9 Splitting Patterns：The Isopropyl Group536

13.10 Splitting Patterns：Pairs of Doublets536

13.11 Complex Splitting Patterns538

13.12 1H NMR Spectra of Alcohols539

Magnetic Resonance Imaging （MRI）540

13.13 NMR and Conformations540

13.14 13C NMR Spectroscopy541

13.15 13C Chemical Shifts543

13.16 13C NMR and Peak Intensities545

13.17 13C— 1H Coupling546

13.18 Using DEPT to Count Hydrogens Attached to 13C546

13.19 2D NMR：COSY and HETCOR547

13.20 Introduction to Infrared Spectroscopy550

Spectra by the Thousands551

13.21 Infrared Spectra552

13.22 Characteristic Absorption Frequencies554

13.23 Ultraviolet-Visible （UV-VIS） Spectroscopy557

13.24 Mass Spectrometry559

13.25 Molecular Formula as a Clue to Structure563

Gas Chromatography，GC/MS，and MS/MS564

13.26 Summary566

Problems569

Descriptive Passage and Interpretive Problems 13：Calculating Aromatic 13C Chemical Shifts575

CHAPTER 14 Organometallic Compounds578

14.1 Organometallic Nomenclature580

14.2 Carbon-Metal Bonds in Organometallic Compounds580

14.3 Preparation of Organolithium Compounds581

14.4 Preparation of Organomagnesium Compounds：Grignard Reagents583

14.5 Organolithium and Organomagnesium Compounds as Bronsted Bases584

14.6 Synthesis of Alcohols Using Grignard Reagents586

14.7 Synthesis of Alcohols Using Organolithium Reagents588

14.8 Synthesis of Acetylenic Alcohols588

14.9 Retrosynthetic Analysis589

14.10 Preparation of Tertiary Alcohols from Esters and Grignard Reagents592

14.11 Alkane Synthesis Using Organocopper Reagents593

14.12 An Organozinc Reagent for Cyclopropane Synthesis595

14.13 Carbenes and Carbenoids596

14.14 Transition-Metal Organometallic Compounds599

An Organometallic Compound That Occurs Naturally：Coenzyme B12601

14.15 Homogeneous Catalytic Hydrogenation602

14.16 Olefin Metathesis605

14.17 Ziegler-Natta Catalysis of Alkene Polymerization607

14.18 Summary610

Problems613

Descriptive Passage and Interpretive Problems 14：Oxymercuration617

CHAPTER 15 Alcohols，Diols，and Thiols620

15.1 Sources of Alcohols621

15.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones622

15.3 Preparation of Alcohols by Reduction of Carboxylic Acids and Esters628

15.4 Preparation of Alcohols from Epoxides629

15.5 Preparation of Diols630

15.6 Reactions of Alcohols：A Review and a Preview632

15.7 Conversion of Alcohols to Ethers632

15.8 Esterification635

15.9 Esters of Inorganic Acids637

15.10 Oxidation of Alcohols638

15.11 Biological Oxidation of Alcohols640

Economic and Environmental Factors in Organic Synthesis641

15.12 Oxidative Cleavage of Vicinal Diols643

15.13 Thiols644

15.14 Spectroscopic Analysis of Alcohols and Thiols647

15.15 Summary648

Problems652

Descriptive Passage and Interpretive Problems 15：The Pinacol Rearrangement658

CHAPTER 16 Ethers，Epoxides，and Sulfides662

16.1 Nomenclature of Ethers，Epoxides，and Sulfides663

16.2 Structure and Bonding in Ethers and Epoxides664

16.3 Physical Properties of Ethers665

16.4 Crown Ethers667

16.5 Preparation of Ethers668

Polyether Antibiotics669

16.6 The Williamson Ether Synthesis670

16.7 Reactions of Ethers：A Review and a Preview671

16.8 Acid-Catalyzed Cleavage of Ethers672

16.9 Preparation of Epoxides：A Review and a Preview674

16.10 Conversion of Vicinal Halohydrins to Epoxides675

16.11 Reactions of Epoxides：A Review and a Preview676

16.12 Nucleophilic Ring Opening of Epoxides677

16.13 Acid-Catalyzed Ring Opening of Epoxides679

16.14 Epoxides in Biological Processes682

16.15 Preparation of Sulfides682

16.16 Oxidation of Sulfides：Sulfoxides and Sulfones683

16.17 Alkylation of Sulfides：Sulfonium Salts684

16.18 Spectroscopic Analysis of Ethers，Epoxides，and Sulfides685

16.19 Summary688

Problems692

Descriptive Passage and Interpretive Problems 16：Epoxide Rearrangements and the NIH Shift697

CHAPTER 17 Aldehydes and Ketones：Nucleophilic Addition to the Carbonyl Group700

17.1 Nomenclature701

17.2 Structure and Bonding：The Carbonyl Group704

17.3 Physical Properties706

17.4 Sources of Aldehydes and Ketones707

17.5 Reactions of Aldehydes and Ketones：A Review and a Preview710

17.6 Principles of Nucleophilic Addition：Hydration of Aldehydes and Ketones711

17.7 Cyanohydrin Formation715

17.8 Acetal Formation718

17.9 Acetals as Protecting Groups721

17.10 Reaction with Primary Amines：Imines722

Imines in Biological Chemistry725

17.11 Reaction with Secondary Amines：Enamines727

17.12 The Wittig Reaction728

17.13 Planning an Alkene Synthesis via the Wittig Reaction730

17.14 Stereoselective Addition to Carbonyl Groups732

17.15 Oxidation of Aldehydes733

17.16 Baeyer-Villiger Oxidation of Ketones734

17.17 Spectroscopic Analysis of Aldehydes and Ketones736

17.18 Summary738

Problems742

Descriptive Passage and Interpretive Problems 17：Alcohols，Aldehydes，and Carbohydrates749

CHAPTER 18 Enols and Enolates752

18.1 The α Hydrogen and Its pKa753

18.2 The Aldol Condensation757

18.3 Mixed Aldol Condensations761

18.4 Alkylation of Enolate Ions763

18.5 Enolization and Enol Content764

18.6 Stabilized Enols766

18.7 α Halogenation of Aldehydes and Ketones768

18.8 Mechanism of α Halogenation of Aldehydes and Ketones768

18.9 The Haloform Reaction770

18.10 Some Chemical and Stereochemical Consequences of Enolization772

The Haloform Reaction and the Biosynthesis of Trihalomethanes773

18.11 Effects of Conjugation in α，β-Unsaturated Aldehydes and Ketones774

18.12 Conjugate Addition to α，β-Unsaturated Carbonyl Compounds775

18.13 Addition of Carbanions to α，β-Unsaturated Ketones：The Michael Reaction778

18.14 Conjugate Addition of Organocopper Reagents to a，β-Unsaturated Carbonyl Compounds778

18.15 Summary779

Problems782

Descriptive Passage and Interpretive Problems 18：Enolate Regiochemistry and Stereochemistry787

CHAPTER 19 Carboxylic Acids790

19.1 Carboxylic Acid Nomenclature791

19.2 Structure and Bonding793

19.3 Physical Properties794

19.4 Acidity of Carboxylic Acids794

19.5 Salts of Carboxylic Acids797

19.6 Substituents and Acid Strength799

19.7 Ionization of Substituted Benzoic Acids801

19.8 Dicarboxylic Acids802

19.9 Carbonic Acid802

19.10 Sources of Carboxylic Acids803

19.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents806

19.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles806

19.13 Reactions of Carboxylic Acids：A Review and a Preview807

19.14 Mechanism of Acid-Catalyzed Esterification808

19.15 Intramolecular Ester Formation：Lactones811

19.16 α Halogenation of Carboxylic Acids：The Hell-Volhard-Zelinsky Reaction813

19.17 Decarboxylation of Malonic Acid and Related Compounds815

19.18 Spectroscopic Analysis of Carboxylic Acids817

19.19 Summary818

Problems821

Descriptive Passage and Interpretive Problems 19：Lactonization Methods825

CHAPTER 20 Carboxylic Acid Derivatives：Nucleophilic Acyl Substitution825

20.1 Nomenclature of Carboxylic Acid Derivatives830

20.2 Structure and Reactivity of Carboxylic Acid Derivatives831

20.3 General Mechanism for Nucleophilic Acyl Substitution834

20.4 Nucleophilic Acyl Substitution in Acyl Chlorides836

20.5 Nucleophilic Acyl Substitution in Acid Anhydrides839

20.6 Sources of Esters842

20.7 Physical Properties of Esters842

20.8 Reactions of Esters：A Review and a Preview844

20.9 Acid-Catalyzed Ester Hydrolysis844

20.10 Ester Hydrolysis in Base：Saponification848

20.11 Reaction of Esters with Ammonia and Amines851

20.12 Amides852

20.13 Hydrolysis of Amides857

20.14 Lactams861

β-Lactam Antibiotics861

20.15 Preparation of Nitriles862

20.16 Hydrolysis of Nitriles863

20.17 Addition of Grignard Reagents to Nitriles864

20.18 Spectroscopic Analysis of Carboxylic Acid Derivatives866

20.19 Summary867

Problems870

Descriptive Passage and Interpretive Problems 20：Thioesters876

CHAPTER 21 Ester Enolates880

21.1 Ester α Hydrogens and Their pKa’s881

21.2 The Claisen Condensation883

21.3 Intramolecular Claisen Condensation：The Dieckmann Cyclization886

21.4 Mixed Claisen Condensations886

21.5 Acylation of Ketones with Esters887

21.6 Ketone Synthesis via β-Keto Esters888

21.7 The Acetoacetic Ester Synthesis889

21.8 The Malonic Ester Synthesis892

21.9 Michael Additions of Stabilized Anions894

21.10 Reactions of LDA-Generated Ester Enolates895

21.11 Summary897

Problems899

Descriptive Passage and Interpretive Problems 21：The Enolate Chemistry of Dianions903

CHAPTER 22 Amines908

22.1 Amine Nomenclature909

22.2 Structure and Bonding911

22.3 Physical Properties913

22.4 Basicity of Amines914

Amines as Natural Products919

22.5 Tetraalkylammonium Salts as Phase-Transfer Catalysts921

22.6 Reactions That Lead to Amines：A Review and a Preview922

22.7 Preparation of Amines by Alkylation of Ammonia923

22.8 The Gabriel Synthesis of Primary Alkylamines924

22.9 Preparation of Amines by Reduction926

22.10 Reductive Amination928

22.11 Reactions of Amines：A Review and a Preview929

22.12 Reaction of Amines with Alkyl Halides931

22.13 The Hofmann Elimination931

22.14 Electrophilic Aromatic Substitution in Arylamines932

22.15 Nitrosation of Alkylamines935

22.16 Nitrosation of Arylamines937

22.17 Synthetic Transformations of Aryl Diazonium Salts938

22.18 Azo Coupling942

From Dyes to Sulfa Drugs943

22.19 Spectroscopic Analysis of Amines944

22.20 Summary947

Problems953

Descriptive Passage and Interpretive Problems 22：Synthetic Applications of Enamines960

CHAPTER 23 Aryl Halides964

23.1 Bonding in Aryl Halides965

23.2 Sources of Aryl Halides966

23.3 Physical Properties of Aryl Halides966

23.4 Reactions of Aryl Halides：A Review and a Preview966

23.5 Nucleophilic Substitution in Nitro-Substituted Aryl Halides968

23.6 The Addition-Elimination Mechanism of Nucleophilic Aromatic Substitution971

23.7 Related Nucleophilic Aromatic Substitution Reactions973

23.8 The Elimination-Addition Mechanism of Nucleophilic Aromatic Substitution：Benzyne974

23.9 Diels-Alder Reactions of Benzyne978

23.10 m-Benzyne and p-Benzyne979

23.11 Summary980

Problems982

Descriptive Passage and Interpretive Problems 23：The Heck Reaction986

CHAPTER 24 Phenols990

24.1 Nomenclature991

24.2 Structure and Bonding992

24.3 Physical Properties993

24.4 Acidity of Phenols994

24.5 Substituent Effects on the Acidity of Phenols995

24.6 Sources of Phenols996

24.7 Naturally Occurring Phenols998

24.8 Reactions of Phenols：Electrophilic Aromatic Substitution999

24.9 Acylation of Phenols1001

24.10 Carboxylation of Phenols：Aspirin and the Kolbe-Schmitt Reaction1002

24.11 Preparation of Aryl Ethers1004

Agent Orange and Dioxin1005

24.12 Cleavage of Aryl Ethers by Hydrogen Halides1006

24.13 Claisen Rearrangement of Allyl Aryl Ethers1006

24.14 Oxidation of Phenols：Quinones1007

24.15 Spectroscopic Analysis of Phenols1009

24.16 Summary1010

Problems1013

Descriptive Passage and Interpretive Problems 24：Directed Metalation of Aryl Ethers1018

CHAPTER 25 Carbohydrates1022

25.1 Classification of Carbohydrates1023

25.2 Fischer Projections and D-L Notation1024

25.3 The Aldotetroses1025

25.4 Aldopentoses and Aldohexoses1026

25.5 A Mnemonic for Carbohydrate Configurations1028

25.6 Cyclic Forms of Carbohydrates：Furanose Forms1029

25.7 Cyclic Forms of Carbohydrates：Pyranose Forms1032

25.8 Mutarotation and the Anomeric Effect1035

25.9 Ketoses1037

25.10 Deoxy Sugars1038

25.11 Amino Sugars1039

25.12 Branched-Chain Carbohydrates1040

25.13 Glycosides1040

25.14 Disaccharides1042

25.15 Polysaccharides1044

How Sweet It Is！1045

25.16 Reactions of Carbohydrates1047

25.17 Reduction of Monosaccharides1047

25.18 Oxidation of Monosaccharides1047

25.19 Cyanohydrin Formation and Chain Extension1049

25.20 Epimerization，Isomerization，and Retro-Aldol Cleavage1050

25.21 Acylation and Alkylation of Hydroxyl Groups1052

25.22 Periodic Acid Oxidation1053

25.23 Summary1054

Problems1057

Descriptive Passage and Interpretive Problems 25：Emil Fischer and the Structure of （＋）-Glucose1061

CHAPTER 26 Lipids1064

26.1 Acetyl Coenzyme A1066

26.2 Fats，Oils，and Fatty Acids1067

26.3 Fatty Acid Biosynthesis1070

26.4 Phospholipids1073

26.5 Waxes1075

26.6 Prostaglandins1076

Nonsteroidal Anti inflammatory Drugs （NSAIDs） and COX-2 Inhibitors1078

26.7 Terpenes：The Isoprene Rule1079

26.8 Isopentenyl Diphosphate：The Biological Isoprene Unit1082

26.9 Carbon-Carbon Bond Formation in Terpene Biosynthesis1082

26.10 The Pathway from Acetate to Isopentenyl Diphosphate1086

26.11 Steroids：Cholesterol1087

26.12 Vitamin D1090

Good Cholesterol？ Bad Cholesterol？ What’s the Difference？1091

26.13 Bile Acids1092

26.14 Corticosteroids1092

26.15 Sex Hormones1093

26.16 Carotenoids1093

Anabolic Steroids1094

Crocuses Make Saffron from Carotenes1095

26.17 Summary1096

Problems1098

Descriptive Passage and Interpretive Problems 26：Polyketides1101

CHAPTER 27 Amino Acids，Peptides，and Proteins1106

27.1 Classification of Amino Acids1108

27.2 Stereochemistry of Amino Acids1113

27.3 Acid-Base Behavior of Amino Acids1114

27.4 Synthesis of Amino Acids1117

Electrophoresis1117

27.5 Reactions of Amino Acids1119

27.6 Some Biochemical Reactions of Amino Acids1120

27.7 Peptides1127

27.8 Introduction to Peptide Structure Determination1130

27.9 Amino Acid Analysis1130

27.10 Partial Hydrolysis of Peptides1131

27.11 End Group Analysis1132

27.12 Insulin1133

27.13 The Edman Degradation and Automated Sequencing of Peptides1134

Peptide Mapping and MALDI Mass Spectrometry1136

27.14 The Strategy of Peptide Synthesis1137

27.15 Amino Group Protection1138

27.16 Carboxyl Group Protection1140

27.17 Peptide Bond Formation1141

27.18 Solid-Phase Peptide Synthesis：The Merrifield Method1143

27.19 Secondary Structures of Peptides and Proteins1145

27.20 Tertiary Structure of Polypeptides and Proteins1148

27.21 Coenzymes1152

Oh NO！ It’s Inorganic！1153

27.22 Protein Quaternary Structure：Hemoglobin1153

27.23 Summary1154

Problems1156

Descriptive Passage and Interpretive Problems 27：Amino Acids in Enantioselective Synthesis1159

CHAPTER 28 Nucleosides，Nucleotides，and Nucleic Acids1162

28.1 Pyrimidines and Purines1163

28.2 Nucleosides1166

28.3 Nucleotides1167

28.4 Bioenergetics1170

28.5 ATP and Bioenergetics1170

28.6 Phosphodiesters，Oligonucleotides，and Polynucleotides1172

28.7 Nucleic Acids1173

28.8 Secondary Structure of DNA：The Double Helix1174

“It Has Not Escaped Our Notice…”1175

28.9 Tertiary Structure of DNA：Supercoils1177

28.10 Replication of DNA1178

28.11 Ribonucleic Acids1180

28.12 Protein Biosynthesis1183

RNA World1184

28.13 AIDS1184

28.14 DNA Sequencing1185

28.15 The Human Genome Project1187

28.16 DNA Profiling and the Polymerase Chain Reaction1188

28.17 Summary1191

Problems1194

Descriptive Passage and Interpretive Problems 28：Oligonucleotide Synthesis1195

CHAPTER 29 Synthetic Polymers1200

29.1 Some Background1201

29.2 Polymer Nomenclature1202

29.3 Classification of Polymers：Reaction Type1203

29.4 Classification of Polymers：Chain Growth and Step Growth1204

29.5 Classification of Polymers：Structure1205

29.6 Classification of Polymers：Properties1207

29.7 Addition Polymers：A Review and a Preview1209

29.8 Chain Branching in Free-Radical Polymerization1211

29.9 Anionic Polymerization：Living Polymers1214

29.10 Cationic Polymerization1216

29.11 Polyamides1217

29.12 Polyesters1218

29.13 Polycarbonates1219

29.14 Polyurethanes1220

29.15 Copolymers1221

29.16 Summary1223

Problems1225

Descriptive Passage and Interpretive Problems 29：Chemical Modification of Polymers1227