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