国外名校名著 有机化学 第8版 英文影印版PDF电子书下载

chapter 1 Carbon Compounds and Chemical Bonds 1

“We Are Slardust”1（Molecular graphic：Glycine，an organic molecule found in space） 2

1.1 Introduction 2

1.2 The Development of Organic Chemistry as a Science 3

1.3 The Structural Theory of Organic Chemistry 4

1.4 Chemical Bonds：The Octet Rule 6

1.5 Writing Lewis Structures 8

1.6 Exceptions to the Octet Rule 10

1.7 Formal Charge 11

1.8 Resonance 14

1.9 Quantum Mechanics 19

1.10 Atomic Orbitals 20

1.11 Molecular Orbitals 22

1.12 The Structure of Methane and Ethane：sp3 Hybridization 25

The Chemistry of...Calculated Molecular Models：Electron Density Surfaces 29

1.13 The Structure of Ethene（Ethylene）：sp2 Hybridization 29

1.14 The Structure of Ethyne（Acetylene）：sp Hybridization 34

1.15 A Summary of Important Concepts that Come From Quantum Mechanics 36

1.16 Molecular Geometry：The Valence Shell Electron Pair Repulsion Model 38

1.17 Representation of Structural Formulas 41

Chapter 2 Representative Carbon Compounds：Functional Groups,Intermolecular Forces,and Infrared（IR）Spectroscopy 52

Structure and Function：Organic Chemistry,Nanotechnology,and Bioengineering（Molecular graphic：A molecular template for bone growth） 52

2.1 Carbon-Carbon Covalent Bonds 53

2.2 Hydrocarbons：Representative Alkanes，Alkenes，Alkynes，and Aromatic Compounds 53

2.3 Polar Covalent Bonds 56

The Chemistry of... calculated Molecular Models：Maps of Electrostatic Potentlal 58

2.4 Polar and Nonpolar Molecules 59

2.5 Functional Groups 61

2.6 Alkyl Halides or Haloalkanes 63

2.7 Alcohols 63

2.8 Ehers 65

2.9 Amines 66

2.10 Aldehydes and Ketones 67

2.11 Carboxylic Acids，Esters，and Amides 68

2.12 Nitriles 69

2.13 Summary of Important Families of Organic Compounds 70

2.14 Physical Properties and Molecular Structure 70

2.15 Summary of Attractive Electric Forces 78

The Chemistry of... Organic Templates Engineered to Mimic Bone Growth 78

2.16 Infrared Spectroscopy：An Instrumental Method for Detecting Functional Groups 79

Chapter 3 An Introdution to Organic Reactions：ACIds and Bases 94

Shuttling the Protons（Molecular graphic：Diamox，a drug that prevents altitude sickness） 94

3.1 Reactions and Their Mechanisms 95

3.2 Acid-Base Reactions 97

The Chemistry of...HOMOs and LUMOs in Reactions 101

3.3 Heterolysis of Bonds to Carbon：Carbocations and Carbanions 101

3.4 The Use of Curved Arrows in Illustrating Reactions 102

3.5 The Strength of Acids and Bases：Ka and pKa 104

3.6 Predicting the Outcome of Acid-Base Reactions 107

3.7 The Relationship Between Structure and Acidity 109

3.8 Energy Changes 113

3.9 The Relationship Between the Equilibrium Constant and the Standard Free-Energy Change， △G° 114

3.10 The Acidity of Carboxylic Acids 115

3.11 The Effect of the Solvent on Acidity 120

3.12 Organic Compounds as Bases 121

3.13 A Mechanism for an Organic Reaction 122

The Chemistry of...Carbonic Anhydrase 124

3.14 Acids and Bases in Nonaqueous Solutions 124

3.15 Acid-Base Reactions and the Synthesis of Deuterium-and Tritium-Labeled Compounds 126

Chapter 4 Alkanes：Nomenclature,Conformational Analysis,and an Introduction to Synthesis 134

To Be Flexible or inflexible-Molecular Structure Makes the Difference（Molecular graphic：A portion of the structure of diamond，an exceptionally rigid molecule） 134

4.1 Introduction to Alkanes and Cycloalkanes 135

4.2 Shapes of Alkanes 137

4.3 IUPAC Nomenclature of Alkanes，Alkyl Halides，and Alcohols 139

4.4 Nomenclature of Cycloalkanes 147

4.5 Nomenclature of Alkenes and Cycloalkenes 150

4.6 Nomenclature of Alkynes 152

4.7 Physical Properties of Alkanes and Cycloalkanes 152

4.8 Sigma Bonds and Bond Rotation 154

4.9 Conformational Analysis of Butane 157

4.10 The Relative Stabilities of Cycloalkanes：Ring Strain 159

4.11 The Origin of Ring Strain in Cyclopropane and Cyclobutane：Angle Strain and Torsional Strain 162

4.12 Conformations of Cyclohexane 163

The Chemistry of…Nanoscale Motors and Molecular Switches 166

4.13 Substituted Cyclohexanes：Axial and Equatorial Hydrogen Atoms 167

4.14 Disubstituted Cycloalkanes：Cis-Trans Isomerism 171

4.15 Bicyclic and Polycyclic Alkanes 175

The Chemistry of…Pheromones：Communication by Means of Chemicals 177

4.16 Chemical Reactions of Alkanes 177

4.17 Synthesis of Alkanes and Cycloalkanes 178

4.18 Some General Principles of Structure and Reactivity： A Look toward Synthesis 180

4.19 An Introduction to Organic Synthesis 181

The Chemistry of…From the Inorganic to Organic 185

Chapter 5 Stereochemistry：Chhiral Molecules 193

The Handedness of Life（Molecular graphic：The mirror-image stereoisomners of alanine，a chiral amino acid） 193

5.1 The Biological Significance of Chirality 194

5.2 Isomerism：Constitutional Isomers and Stereoisomers 195

5.3 Enantiomers and Chiral Molecules 196

5.4 More about the Biological Importance of Chirality 200

5.5 Historical Origin of Stereochemist 201

5.6 Tests for Chirality： Planes of Symmetry 202

5.7 Nomenclature of Enantiomers：The R，S System 203

5.8 Properties of Enantiomers：Optical Activity 208

5.9 The Origin of Optical Activity 212

5.10 The Synthesis of Chiral Molecules 215

5.11 Chiral Drugs 217

The Chemmistry of…Selective Binding of Drug Enantiomers to Left-and Right-Hand Coiled DNA 218

5.12 Molecules with More than One Stereogenic Center 219

5.13 Fischer Projection Formulas 223

5.14 Stereoisomerism of Cyclic Compounds 224

5.15 Relating Configurations Through Reactions in Which No Bonds to the Stereogenic Carbon Are Broken 227

5.16 Separation of Enantiomers：Resolution 230

5.17 Compounds with Stereogenic Centers Other than Carbon 231

5.18 Chiral Molecules that Do Not Possess a Tetrahedral Atom with Four Different Groups 231

Chapter 6 Ionic Reactions—Nucleophilic Substitution and Elimination Reactions of Alkyl Halides 238

Breaking Bacterlal Cell Walls with Organic Chemistrry（Molecular graphic：The SN2 transition state resulting from collision of a hydroxide anion with chloromethane） 238

6.1 Introduction 239

6.2 Nucleophilic Substitution Reactions 241

6.3 Nucleophiles 241

6.4 Leaving Groups 242

6.5 Kinetics of a Nucleophilic Substitution Reaction：An SN2 Reaction 243

6.6 A Mechanism for the SN2 Reaction 244

6.7 Transition State Theory：Free-Energy Diagrams 245

6.8 The Stereochemistry of SN2 Reactions 249

6.9 The Reaction of tert-Butyl Chloride with Hydroxide Ion：An SN1 Reaction 251

6.10 A Mechanism for the SN1 Reaction 252

6.11 Carbocations 254

6.12 The Stereochemistry of SN1 Reactions 256

6.13 Factors Affecting the Rates of SN1 and SN2 Reactions 258

6.14 Organic Synthesis：Functional Group Transformations Using SN2 Reactions 267

The Chemistry of…Biological Methylation：A Biological Nucleophilic Substitution Reaction 268

6.15 Elimination Reactions of Alkyl Halides 271

6.16 The E2 Reaction 273

6.17 The E1 Reaction 274

6.18 Substitution versus Elimination 275

6.19 Overall Summary 278

Chapter 7 Alkenes and AHkynesⅠ：Properties and Synthesis.Elimination Reactions of Alkyl Halides 287

Cell Membrane Fluidity（Molecular graphic：cis-9-Octadecenoic acid，an unsaturated fatty acid incorporated into cell membrane phospholipids） 287

7.1 Introduction 288

7.2 The（E）-（Z）System for Designating Alkene Diastereomers 288

7.3 Relative Stabilities of Alkenes 290

7.4 Cycloalkenes 292

7.5 Synthesis of Alkenes via Elimination Reactions 292

7.6 Dehydrohalogenation of Alkyl Halides 293

7.7 Acid-Catalyzed Dehydration of Alcohols 298

7.8 Carbocation Stability and the Occurrence of Molecular Rearrangements 303

7.9 Synthesis of Alkynes by Elimination Reactions 307

7.10 The Acidity of Terminal Alkynes 308

7.11 Replacement of the Acetylenic Hydrogen Atom of Terminal Alkynes 309

7.12 Hydrogenation of Alkenes 310

The Chemistry of...Mydrogenation in the Food Industry 311

7.13 Hydrogenation：The Function of the Catalyst 312

The Chemistry of…Homogeneous Asymmetric Catalytic Hydrogenation：Examples Involvlng L-DOPA,（S）-Naproxen,and Aspartame 313

7.14 Hydrogenation of Alkynes 315

7.15 Structural Information from Molecular Formulas and the Index of Hydrogen Deficiency 317

Chapter 8 Alkenes and AlkynesⅡ：Addition Reactions 328

The Sea：A Treasury of Biologically Active Natural Products（Molecular graphic：Dactylyne，a halogenated marine natural product） 328

8.1 Introduction：Addition to Alkenes 329

8.2 Addition of Hydrogen Halides to Alkenes：Markovnikov’s Rule 331

8.3 Stereochemistry of the Ionic Addition to an Alkene 336

8.4 Addition of Sulfuric Acid to Alkenes 337

8.5 Addition of Water to Alkenes：Acid-Catalyzed Hydration 338

8.6 Alcohols from Alkenes through Oxymercuration-Demercuration：Markovnikov Addition 340

8.7 Alcohols from Alkenes through Hydroboration-Oxidation：Anti-Markovnikov Syn Hydration 343

8.8 Hydroboration：Synthesis of Alkylboranes 343

8.9 Oxidation and Hydrolysis of Alkyboranes 346

8.10 Summary of Alkene Hydration Methods 348

8.11 Protonolysis of Alkyboranes 348

8.12 Addition of Bromine and Chlorine to Alkenes 349

8.13 Stereochemistry of the Addition of Halogens to Alkenes 351

8.14 Halohydrin Formation 354

The Chemistry of…Regiospecificity in Unsymmetrically Substituted Bromonium lons：Bromonium lons of Ethene,Propene,and2-Methlypropene 355

8.15 Divalent Carbon Compounds：Carbenes 357

8.16 Oxidations of Alkenes：Syn1，2-Dihydroxylation 359

The Chemistry of…Catalytic Asymmetric Dihydroxylation 361

8.17 Oxidative Cleavage of Alkenes 362

8.18 Addition of Bromine and Chlorine to Alkynes 365

8.19 Addition of Hydrogen Halides to Alkynes 366

8.20 Oxidative Cleavage of Alkynes 367

8.21 Synthetic Strategies Revisited 367

The Chemistry 0f…Cholesterol Biosynthesis：Elegant and Familiar Reactions in Nature 370

Chapter 9 Nuclear Magnetic Resonance and Mass Spectrometry：Tools for Structure Determination 383

A Thermos？of Liquid Helium383（Molecular graphic：1-Chloro-2-propanol） 383

9.1 Introduction 384

9.2 The Electromagnetic Spectrum 384

9.3 Nuclear Magnetic Resonance Spectroscopy 386

9.4 Nuclear Spin： The Origin of the Signal 390

9.5 Shielding and Deshielding of Protons 392

9.6 The Chemical Shift 394

9.7 Chemical Shift Equivalent and Nonequivalent Protons 395

9.8 Signal Splitting： Spin-Spin Coupling 397

9.9 Proton NMR Spectra and Rate Processes 406

9.10 Carbon-l3 NMR Spectroscopy 409

9.11 Two-Dimensional（2D）NMR Techniques 414

The Chemistry of...Magnetic Resonance Imaging In Medicine 417

9.12 An Introduction to Mass Spectrometry 418

9.13 The Mass Spectrometer 418

9.14 The Mass Spectrum 421

9.15 Determination of Molecular Formulas and Molecular Weights 423

9.16 Fragmentation 428

9.17 GC/MS Analysis 434

9.18 Mass Spectrometry of Biomolecules 435

Chapter 10 Radical Reactions 447

Calicheamicin γ1:A Radical Device for Slicing the Backbone of DNA447（Molecular graphic：Calicheamicin γ1Ⅰ，a molecule capable of double-strand DNA cleavage，bound to DNA） 447

10.1 Introduction 449

The Chemistry of...Radicals ln Biology,Medicine,and lndustry 450

10.2 Homolytic Bond Dissociation Energies 450

10.3 The Reactions of Alkanes with Halogens 454

10.4 Chlorination of Methane：Mechanism of Reaction 456

10.5 Chlorination of Methane：Energy Changes 459

10.6 Halogenation of Higher Alkanes 466

10.7 The Geometry of Alkyl Radicals 469

10.8 Reactions that Generate Tetrahedral Stereogenic Carbons 469

10.9 Radical Addition to Alkenes：The Anti-Markovnikov Addition of Hydrogen Bromide 472

10.10 Radical Polymerization of Alkenes：Chain-Growth Polymers 474

10.11 Other Important Radical Reactions 476

Special Topic A：Chain-Growth Polymers 485

Chapter 11 Alcohols and Ethers 492

Molecular Hosts（Molecular graphic：Monensin sodium salt，an antibiotic that transports ions across cell membranes） 492

11.1 Structure and Nomenclature 493

11.2 Physical Properties of Alcohols and Ethers 495

11.3 Important Alcohols and Ethers 497

11.4 Synthesis of Alcohols from Alkenes 499

11.5 Reactions of Alcohols 501

11.6 Alcohols as Acids 502

11.7 Conversion of Alcohols into Alkyl Halides 503

11.8 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides 503

11.9 Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl 506

11.10 Tosylates，Mesylates，and Triflates：Leaving Group Derivatives of Alcohols 507

The Chemistry of&Alkyl Phosphates 510

11.11 Synthesis of Ethers 510

11.12 Reactions of Ethers 515

11.13 Epoxides 516

The Chemistry of…The sharpless Asymmetric Epoxidation 517

11.14 Reactions of Epoxides 519

The Chemistry of…Epoxides,Carcinogens,and Biological Oxidation 521

11.15 Anti1，2-Dihydroxylation of Alkenes via Epoxides 523

The Chemistry of…Environmentally Friendly Alkene Oxidatlon Methods 525

11.16 Crown Ethers：Nucleophilic Substitution Reactions in Relatively Nonpolar Aprotic Solvents by Phase-Transfer Catalysis 526

11.17 Summary of Reactions of Alkenes，Alcohols，and Ethers 529

Chapter 12 Alcohols from Carbonyl Compounds. Oxidation-Reduction and Orgganometallic Compounds 537

The Two Aspects of the Coenzyme NADH（Molecular graphic：Nicotinamide [niacin]） 537

12.1 Introduction 538

12.2 Oxidation-Reduction Reactions in Organic Chemistry 539

12.3 Alcohols by Reduction of Carbonyl Compounds 541

The Chemistry of…Alcohol Dehydragenase 544

The Chemistry of…Stereoselective Reductions of Carbonyl Groups 544

12.4 Oxidation of Alcohols 546

12.5 Organometallic Compounds 550

12.6 Preparation of Organolithium and Organomagnesium Compounds 551

12.7 Reactions of Organolithium and Organomagnesium Compounds 553

12.8 Alcohols from Grignard Reagents 556

12.9 Lithium Dialkylcuprates：The Corey-Posner，Whitesides-House Synthesis 564

12.10 Protecting Groups 566

First Review Problem Set 573

Chapter 13 Conjugated Unsaturated Systems 577

MoleCuies with the Nobel Prize in Theirsynthetic Lineage（Molecular graphic：Morphine，the synthesis of which involved the Diels-Alder reaction） 577

13.1 Introduction 578

13.2 Allylic Substitution and the Allyl Radical 578

13.3 The Stability of the Allyl Radical 582

13.4 The Allyl Cation 586

13.5 Summary of Rules for Resonance 587

13.6 Alkadienes and Polyunsaturated Hydrocarbons 591

13.7 1，3-Butadiene：Electron Delocalization 593

13.8 The Stability of Conjugated Dienes 595

13.9 Ultraviolet-Visible Spectroscopy 596

The Chemistry of…The Photochemistry of vision 600

13.10 Electrophilic Attack on Conjugated Dienes：1，4Addition 604

13.11 The Diels-Alder Reaction：A1，4-Cycloaddition Reaction of Dienes 607

Chapter 14 Aromatic Compounds 622

Geen Chemistry（Molecular graphic：Benzene，parent molecule in the family of aromatic hydrocarbons） 622

14.1 Introduction 623

14.2 Nomenclature of Benzene Derivatives 624

14.3 Reactions of Benzene 626

14.4 The Kekule Structure for Benzene 627

14.5 The Stability of Benzene 628

14.6 Modern Theories of the Structure of Benzene 629

14.7 Hiickel’s Rule： The 4n+2πElectron Rule 632

14.8 Other Aromatic Compounds 640

The Chemistry of…Nanotubes 643

14.9 Heterocylic Aromatic Compounds 644

14.10 Aromatic Compounds in Biochemistry 645

14.11 Spectroscopy of Aromatic Compounds 648

The Chemistry of…Sunscreens（Catching the Sun’s Rays and what Happens to Them） 652

Chapter 15 Reactions of Aromatic Compounds 664

Biosynthesis of Thyroxine：Aromatic Substitution lnvolving Iodine（Molecular graphic：Thyroxine，an aromatic iodine-containing hormone associated with regulation of metabolic rate） 664

15.1 Electrophilic Aromatic Substitution Reactions 665

15.2 A General Mechanism for Electrophilic Aromatic Substitution：Arenium Ions 666

15.3 Halogenation of Benzene 668

15.4 Nitration of Benzene 669

15.5 Sulfonation of Benzene 670

15.6 Friedel-Crafts Alkylation 671

15.7 Friedel-Crafts Acylation 673

15.8 Limitations of Friedel-Crafts Reactions 675

15.9 Synthetic Applications of Friedel-Crafts Acylations：The Clemmensen Reduction 677

15.10 Effect of Substituents on Reactivity and Orientation 679

15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution 681

The Chemistry of…Iodine lncorporatlon In Thyroxine Biosynthesis 681

15.12 Reactions of the Side Chain of Alkylbenzenes 693

The Chemistry of…Industrial Styrene synthesis 694

15.13 Alkenylbenzenes 697

15.14 Synthetic Applications 699

15.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions 703

15.16 Reduction of Aromatic Compounds 705

Chapter 16 Aldehydes and KetonesI.Nucleophilic Addition to the Carbonyl Group 716

A Very Versatile Vitamin,Pyridoxine（Vitamin B6）（Molecular graphic：Pyridoxal phosphate[vitamin B6]） 716

16.1 Introduction 717

16.2 Nomenclature of Aldehydes and Ketones 717

16.3 Physical Properties 719

16.4 Synthesis of Aldehydes 720

16.5 Synthesis of Ketones 724

16.6 Nucleophilic Addition to the Carbon-Oxygen Double Bond 728

16.7 The Addition of Alcohols： Hemiacetals and Acetals 731

16.8 The Addition of Primary and Secondary Amines 738

The Chemistry of…Pyridoxal Phosphate 741

16.9 The Addition of Hydrogen Cyanide 743

16.10 The Addition of Ylides：The Wittig Reaction 745

16.11 The Addition of Organometallic Reagents：The Reformatsky Reaction 749

16.12 Oxidation of Aldehydes and Ketones 751

16.13 Chemical Analyses for Aldehydes and Ketones 753

16.14 Spectroscopic Properties of Aldehydes and Ketones 754

Chaptet 17 Aldehydes and KetonesⅡ.Aldol Reactions 769

TIM（Triose Phosphate Isomerase）Recycles Carbon via an Enol（Molecular graphic：Glyceraldehyde-3-phosphate， a key intermediate in metabolic energy production） 769

17.1 The Acidity of the α Hydrogens of Carbonyl Compounds：Enolate Anions 770

17.2 Keto and Enol Tautomers 772

17.3 Reactions Via Enols and Enolate Anions 773

17.4 The Aldol Reaction：The Addition of Enolate Anions to Aldehydes and Ketones 779

The Chemistry of…A Retro-Aldol Reaction In Glycolysls—Dividing Assets to Double the ATP yield 782

17.5 Crossed Aldol Reactions 784

17.6 Cyclizations via Aldol Condensations 789

17.7 Lithium Enolates 791

The Chemistry of…Silyl Fnol Ethers 795

17.8 α-Selenation：A Synthesis of α，β-Unsaturated Carbonyl Compounds 796

17.9 Additions to α，β3-Unsaturated Carbonyl Compounds 797

The Chemistry of…Calicheamicin γ1ⅠActivation for Cleavage of DNA 801

Chapter 18 Carboxylic Acids and Their Derivatives.Nucleophilic Addition-Elimination at the Acyl Carbon 813

A Common Bond（Molecular graphic：A portion of nylon 6，6，a polyamide） 813

18.1 Introduction 814

18.2 Nomenclature and Physical Properties 814

18.3 Preparation of Carboxylic Acids 823

18.4 Nucleophilic Addition-Elimination at the Acyl Carbon 826

18.5 Acyl Chlorides 828

18.6 Carboxylic Acid Anhydrides 830

18.7 Esters 832

18.8 Amides 838

The Chemistry of…Penicillins 845

18.9 Derivatives of Carbonic Acid 846

18.10 Decarboxylation of Carboxylic Acids 848

The Chemistry of…Thiamine 849

18.11 Chemical Tests for Acyl Compounds 851

Special TopicB：Step-Growth Polymers 867

Chapter 19 Synthesis and Reactions of β-Dicarbonyl Compounds：More Chemistry of Enolate Ions 878

Imposters（Molecular graphic：5-Fluorouracil， an enzyme inhibitor that has anticancer activity by masquerading as a natural substrate） 878

19.1 Introduction 879

19.2 The Claisen Condensation：The Synthesis of β-Keto Esters 880

19.3 The Acetoacetic Ester Synthesis： Synthesis of Methyl Ketones（Substituted Acetones） 885

19.4 The Malonic Ester Synthesis： Synthesis of Substituted Acetic Acids 891

19.5 Further Reactions of Active Hydrogen Compounds 895

19.6 Direct Alkylation of Esters and Nitriles 896

19.7 Alkylation of 1，3-Dithianes 897

19.8 The Knoevenagel Condensation 898

19.9 Michael Additions 898

19.10 The Mannich Reaction 900

The Chenmistry of…A suicide Enzyme substrate 901

19.11 Synthesis of Enamines：Stork Enamine Reactions 902

The Chemistry of…Antibody-Catalyzed Aldol Condensations 906

19.12 Barbiturates 907

Special Topic C：Thiols，Sulfur Ylides，and Disulfides 922

Special Topic D：Thiol Esters and Lipid Biosynthesis 927

Chapter 20 Amines 940

Neurotoxins and Neurotransmitters（Molecular graphic：Histrionicatoxin，a paralyzing neurotoxin from certain dart frogs） 940

20.1 Nomenclature 941

20.2 Physical Properties and Structure of Amines 943

20.3 Basicity of Amines：Amine Salts 945

The Chemistry of…HPLC Resolution of Enantiomers 951

20.4 Some Biologically Important Amines 952

20.5 Preparation of Amines 954

20.6 Reactions of Amines 962

20.7 Reactions of Amines with Nitrous Acid 963

The Chemistry of…N-Nitrosoamines 965

20.8 Replacement Reactions of Arenediazonium Salts 966

20.9 Coupling Reactions of Arenediazonium Salts 969

20.10 Reactions of Amines with Sulfonyl Chlorides 972

20.11 The Sulfa Drugs： Sulfanilamide 974

20.12 Analysis of Amines 977

20.13 Eliminations Involving Ammonium Compounds 979

Special TopicE：Alkaloids 994

Chapter 21 Phenols and Aryl Halides：Nucleophilic Aromatic Substitution 1000

A Silver Chalice（Molecular graphic：4-tert-Butylcalix[4]arene， a chalice-shaped molecule） 1001

21.1 Structure and Nomenclature of Phenols 1001

21.2 Naturally Occurring Phenols 1002

21.3 Physical Properties of Phenols 1003

21.4 Synthesis of Phenols 1003

The Chemistry of…Polyketide Anticancer Antiblotic Biosynthesis 1004

21.5 Reactions of Phenols as Acids 1008

21.6 Other Reactions of the O—H Group of Phenols 1010

21.7 Cleavage of Alkyl Aryl Ethers 1011

21.8 Reactions of the Benzene Ring of Phenols 1012

21.9 The Claisen Rearrangement 1014

21.10 Quinones 1015

21.11 Aryl Halides and Nucleophilic Aromatic Substitution 1016

The Chemistry of…The Bombardier Beetles’s Noxious spray 1017

The Chemistry of…Bacterlal Dehalogenatlon of a PCB Derivative 1020

21.12 Spectroscopic Analysis of Phenols and Aryl Halides 1025

Second Review：Problem Set 1035

Special Topic F：Electrocyclic and Cycloaddition Reactions 1041

Special Topic G：Transition Metal Organometallic Compounds 1055

Special Topic H：Organic Halides and Organometallic Compounds In the Environment 1066

Chapter 22 Carbohydrates 1072

Carhohydrate ReCOgnition in Healing and Disease（Molelcular graphic：Sialyl Lewis，x a carbohydrate that is important in the recognition and healing of traumatized tissue） 1072

22.1 Introduction 1073

22.2 Monosaccharides 1076

22.3 Mutarotation 1081

22.4 Glycoside Formation 1082

22.5 Other Reactions of Monosaccharides 1085

22.6 Oxidation Reactions of Monosaccharides 1088

22.7 Reduction of Monosaccharides：Alditols 1093

22.8 Reactions of Monosaccharides with Phenylhydrazine：Osazones 1094

22.9 Synthesis and Degradation of Monosaccharides 1095

22.10 The D Family of Aldoses 1097

22.11 Fischer’s Proof of the Configuration of D-（+）-Glucose 1099

The Chemistry of…Stereoselective synthesis of All the L-Aldohexoses 1101

22.12 Disaccharides 1102

The Chemistry of…Artificial Sweeteners（How sweet it is） 1106

22.13 Polysaccharides 1107

The Chemistry of…Oligosaccharldes synthesis on a Solid Support-The Glycal Assembly Approach 1112

22.14 Other Biologically Important Sugars 1113

22.15 Sugars that Contain Nitrogen 1114

22.16 Glycolipids and Glycoproteins of the Cell Surface：Cell Recognition and the Immune System 1116

The Chemistry of…Vacclnes Agalnst CanCer 1118

22.17 Carbohydrate Antibiotics 1119

Chapter 23 Lipids 1129

lnsulation for Nerves（Molecular graphic：A sphingomyelin molecule，found in myelin sheath membranes） 1129

23.1 Introduction 1130

23.2 Fatty Acids and Triacylglycerols 1131

The Chemistry of…Olestra and Other Fat Substitutes 1135

Thhe Chemistry of…Self-Assembled Monolayers—Lipids in Materials SCienCe and Bioengineering 1138

23.3 Terpenes and Terpenoids 1139

23.4 Steroids 1143

23.5 Prostaglandins 1153

23.6 Phospholipids and Cell Membranes 1154

The Chemistry of…Stealth? Lipesomes for Drug Delivery 1157

23.7 Waxes 1158

Chapter 24 Amino Acids and Proteins 1166

Catalytic Antibodies：Designer Catalysts（Molecular graphic：A synthetic Diels-Alderase catalytic antibody with a bound hapten） 1166

24.1 Introduction 1167

24.2 Amnino Acids 1168

24.3 Synthesis of α-Amino Acids 1173

24.4 Polypeptides and Proteins 1177

24.5 Primary Structure of Polypeptides and Proteins 1181

24.6 Examples of Polypeptide and Protein Primary Structure 1185

The Chemistry of…Sickle-Cell Anemia 1188

24.7 Polypeptide and Protein Synthesis 1189

24.8 Secondary，Tertiary， and Quaternary Structure of Proteins 1195

24.9 Introduction to Enzymes 1200

24.10 Lysozyme：Mode of Action of an Enzyme 1202

24.11 Serine Proteases 1203

The Chemistry of…Some CatalytiC Antibodies 1208

24.12 Hemoglobin：A Conjugated Protein 1210

24.13 Purification and Analysis of Polypeptides and Proteins 1211

24.14 Proteomics 1213

Chapter 25 NUCleic Acids and Protein Synthesis 1220

Tools for Finding Families（Molecular graphic：A cytosine-guanine base pair， depicting the van der Waals surface as an electrostatic potential map） 1220

25.1 Introduction 1221

25.2 Nucleotides and Nucleosides 1222

25.3 Laboratory Synthesis of Nucleosides and Nucleotides 1225

25.4 Deoxyribonucleic Acid：DNA 1228

25.5 RNA and Protein Synthesis 1236

25.6 Determining the Base Sequence of DNA：The Chain Terminating （Dideoxynucleotide Method） 1243

25.7 Laboratory Syntesis of Oligonucleotides 1247

25.8 The Polymerase Chain Reaction 1249

25.9 Sequencing of the Human Genome：An Instruction Book for the Molecules of Life 1251