Contents

1Structure and Bonding

2

1.11.21.31.41.51.61.71.81.91.101.111.12

Atomic Structure 3Atomic Structure: Orbitals 3Atomic Structure: Electron Configurations 5Development of Chemical Bonding Theory 6The Nature of Chemical Bonds 7

Valence Bond Theory 10Hybridization: Sp3 Orbitals and the Structure of Methane 11Hybridization: Sp3 Orbitals and the Structure of Ethane 12Hybridization: Sp2 Orbitals and the Structure of Ethylene 13Hybridization: sp Orbitals and the Structure of Acetylene 16Hybridization of Nitrogen and Oxygen 17Molecular Orbital Theory 19

CHEMISTRY@WORK: CHEMICALS, TOXICITY,AND RISK 20

Summary and KeyWords 21 .Exercises 23Building Block Questions 28 . InfoTracCollege Edition 28

Polar Covalent Bonds;Adds and Bases

VI

2.12.22.32.42.52.62.72.82.92.102.112.122.13

Polar Covalent Bonds: Electronegativity 29Polar Covalent Bonds: Dipole Moments 32Formal Charges 34Resonance 37Rules for Resonance Forms 39

Drawing Resonance Forms 40Acids and Bases: The Br0nsted-Lowry Definition 43Acid and Base Strength 45Predicting Acid-Base Reactions from pKaValues 46Organic Acids and Organic Bases 48Acids and Bases: The Lewis Definition 51

Drawing Chemical Structures 55Molecular Models 57

CHEMISTRY@WORK: ALKALOIDS: NATURAllY OCCURRING BASES 58

Summary and KeyWords 59 .Exercises 60BuildingBlockQuestions67 .InfoTracCollegeEdition67

3Contents vii

Organic Compounds:Alkanes and Cycloalkanes

4

3.13.23.33.43.53.63.73.8

Functional Groups 68Alkanes andAlkane Isomers 74

Alkyl Groups 77Naming Alkanes 80Properties of Alkanes 86Cycloalkanes 88

Naming Cycloalkanes 89Cis-Trans Isomerism in Cycloalkanes 92

CHEMISTRY@WORK:GASOLINE 94

Summary and Key Words 96 . Exercises 97

Building Block Questions 102 . InfoTrac College Edition 102

Stereochemistry ofAlkanes and Cycloalkanes

5

4.14.24.34.44.54.64.74.84.94.104.11

4.124.134.14

Conformations of Ethane 103

Conformations of Propane 105Conformations of Butane 106

Stability of Cycloalkanes: The Baeyer Strain Theory 109The Nature of Ring Strain 111Cyclopropane: An Orbital View 112

Conformations of Cyclobutane and Cyclopentane 113Conformations of Cyclohexane 115

Axial and Equatorial Bonds in Cyclohexane 116Conformational Mobility of Cyclohexane 118Conformations of Monosubstituted Cyclohexanes 119

Conformational Analysis of Disubstituted Cyclohexanes 122Boat Cyclohexane 125

Conformations of Polycyclic Molecules 126

CHEMISTRY@WORK:MOLECULARMECHANICS 128

Summary and Key Words 129 . Exercises 130

Building Block Questions 134 . InfoTrac College Edition 134

An Overview

of Organic Reactions

5.15.25.35.45.55.65.75.8

Kinds of Organic Reactions 135How Organic Reactions Occur: Mechanisms 136

Radical Reactions and How They Occur 138Polar Reactions and How They Occur 139

An Example of a Polar Reaction: Addition of HBr to Ethylene 144Using Curved Arrows in Polar Reaction Mechanisms 147

Describing a Reaction: Equilibria, Rates, and Energy Changes 150Describing a Reaction: Bond Dissociation Energies 153

viii Contents

6

5.95.10

Describing a Reaction: Energy Diagrams and Transition States 156

Describing a Reaction: Intermediates 158

CHEMISTRY@WORK: EXPLOSIVES 160

Summary and KeyWords 162 .Exercises 163Building Block Questions 168 . InfoTracCollege Edition 168

Atkenes: Structure

and Reactivity

7

6.16.26.36.46.56.66.76.86.96.106.116.12

Industrial Preparation and Use of Alkenes 170Calculating Degree of Unsaturation 171Naming Alkenes 173Electronic Structure of Alkenes 175Cis-Trans Isomerism in Alkenes 176

Sequence Rules: The E,Z Designation 177Stability of Alkenes 181Electrophilic Addition of HXto Alkenes 184Orientation of Electrophilic Addition: Markovnikov's Rule 187Carbocation Structure and Stability 190The Hammond Postulate 192

Evidence for the Mechanism of Electrophilic Addition:Carbocation Rearrangements 195CHEMISTRY@WORK: TERPENES: NATURALLYOCCURRING ALKENES 197

Summary and KeyWords 198 .Exercises 199Building Block Questions 205 . InfoTracCollege Edition 205

Atkenes: Reactionsand Synthesis

7.17.27.37.47.57.67.77.87.97.10

Preparation of Alkenes: A Preview of Elimination Reactions 207Addition of Halogens to Alkenes 208Halohydrin Formation 210Addition of Water to Alkenes: Oxymercuration 212Addition of Water to Alkenes: Hydroboration 215Addition of Carbenes to Alkenes: Cyclopropane Synthesis 219Reduction of Alkenes: Hydrogenation 222Oxidation of Alkenes: Hydroxylation and Cleavage 224Biological Alkene Addition Reactions 227Addition of Radicals to Alkenes: Polymers 228CHEMISTRY@WORK: NATURALRUBBER 233

Summaryand KeyWords234 .Summaryof Reactions235 . Exercises237Building BlockQuestions 245 . InfoTracCollege Edition 245

8Contents ix

Alkynes: An Introductionto Organic Synthesis

9Stereochemistry

8.18.28.38.48.58.68.78.88.98.10

9.19.29.39.49.59.69.79.89.99.109.119.129.139.149.159.169.17

Electronic Structure of Alkynes 246Naming Alkynes 247Preparation of Alkynes: Elimination Reactions of Dihalides 248Reactions of Alkynes: Addition of HXand X2 249Hydration of Alkynes 250Reduction of Alkynes 254Oxidative Cleavage of Alkynes 256Alkyne Acidity: Formation of Acetylide Anions 257Alkylation of Acetylide Anions 258An Introduction to Organic Synthesis 260

CHEMISTRY@WORK:THEARTOFORGANICSYNTHESIS 265

Summary and Key Words 266 .Summary of Reactions 266 . Exercises 268

Building Block Questions 274 . InfoTrac College Edition 274

-Enantiomers and the Tetrahedral Carbon 275

The Reason for Handedness in Molecules: Chirality 277Optical Activity 280Pasteur's Discovery of Enantiomers 281Sequence Rules for Specification of Configuration 282Diastereomers 287

Meso Compounds 288Molecules with More than TwoChirality Centers 290Physical Properties of Stereoisomers 291Racemic Mixtures and Their Resolution 291A Brief Review of Isomerism 293

Stereochemistry of Reactions: Addition of HBrto Alkenes 295Stereochemistry of Reactions: Addition of Br2to Alkenes 296Stereochemistry of Reactions: Addition of HBrto a Chiral Alkene 298Chirality at Atoms Other Than Carbon 299Chirality in Nature 300Prochirality 301

CHEMISTRY@WORK: CHIRAL DRUGS 304

Summary and KeyWords 305 .Exercises 306Building Block Questions 315 . !nfoTracCollege Edition 315

x Contents

10Alkyl Halides

~~~

11

10.110.210.310.410.510.610.710.810.910.10

Naming Alkyl Halides 317Structure of AlkylHalides 319Preparing AlkylHalides 319Radical Halogenation of Alkanes 320Allylic Bromination of Alkenes 323Stability of the Allyl Radical: Resonance Revisited 325Preparing AlkylHalides from Alcohols 327Reactions of Organohalides: Grignard Reagents 329Organometallic Coupling Reactions 330Oxidation and Reduction in Organic Chemistry 332

CHEMISTRY@WORK: NATURALLY OCCURRING ORGANOHALIDES 335

Summary and Key Words 336 . Summary of Reactions 336 . Exercises 338

Building Block Questions 342 . InfoTracCollege Edition 342

Reactions of AlkylHalides: NucleophilicSubstitutions andEliminations

11.1 The Discovery of the Walden Inversion 34311.2 Stereochemistry of Nucleophilic Substitution 34411.3 Kinetics of Nucleophilic Substitution 34611.4 The SN2Reaction 34711.5 Characteristics of the SN2Reaction 34911.6 The SNlReaction 35611.7 Kinetics of the SNlReaction 35711.8 Stereochemistry of the SNlReaction 35911.9 Characteristics of the SNlReaction 36111.10 Elimination Reactions of Alkyl Halides: Zaitsev's Rule 36711.11 The E2 Reaction 369

11.12 Elimination Reactions and Cyclohexane Conformation 37211.13 The Deuterium Isotope Effect 37411.14 The El Reaction 374

11.15 Summary of Reactivity: SN1,SN2,El, E2 37611.16 Substitution Reactions in Synthesis 378

CHEMISTRY@WORK: SUBSTITUTION REACTIONS IN LIVING ORGANISMS 380

Summary and Key Words 381 . Summary of Reactions 382 . Exercises 383Building Block Questions 392 . InfoTrac College Edition 392

12

Contents xi

Structure Determination:

Mass Spectrometry andInfrared Spectroscopy

13Structure Determination:

Nuclear MagneticResonanceSpectroscopy

14

12.112.212.312.412.512.612.7

12.812.9

13.1

13.213.313.413.5

13.613.713.813.913.1013.11

13.1213.13

Mass Spectrometry 394

Interpreting Mass Spectra 396Interpreting Mass-Spectral Fragmentation Patterns 397Mass-Spectral Behavior of Some Common Functional Groups 400Spectroscopy and the Electromagnetic Spectrum 403Infrared Spectroscopy of Organic Molecules 406Interpreting Infrared Spectra 407Infrared Spectra of Hydrocarbons 411Infrared Spectra of Some Common Functional Groups 412

CHEMISTRY@WORK:CHROMATOGRAPHY:PURIFYINGORGANICCOMPOUNDS 415

Summary and Key Words 417 . Exercises 417Building Block Questions 423 . InfoTrac College Edition 423

-Nuclear Magnetic Resonance Spectroscopy 424

The Nature of NMR Absorptions 426Chemical Shifts 429

13CNMR Spectroscopy: Signal Averaging and FT-NMR 431Characteristics of 13CNMR Spectroscopy 432DEPT13CNMR Spectroscopy 434Uses of 13CNMR Spectroscopy 437lH NMR Spectroscopy and Proton Equivalence 438Chemical Shifts in lH NMR Spectroscopy 440Integration of lH NMR Absorptions: Proton Counting 443Spin-Spin Splitting in lH NMR Spectra 443

More Complex Spin-Spin Splitting Patterns 448Uses oflH NMR Spectroscopy 451

CHEMISTRY@WORK:MAGNETICRESONANCEIMAGING(MRI) 452

Summary and Key Words 452 . Exercises 453Building Block Questions 463 . InfoTrac College Edition 463

Conjugated Dienes andUltraviolet Spectroscopy

14.114.214.314.414.514.614.7

Preparation and Stability of Conjugated Dienes 465Molecular Orbital Description of 1,3-Butadiene 467Electrophilic Additions to Conjugated Dienes: Allylic Carbocations 469Kinetic versus Thermodynamic Control of Reactions 472The Diels-Alder Cycloaddition Reaction 474Characteristics of the Diels-Alder Reaction 475

Diene Polymers: Natural and Synthetic Rubbers 480

xii Contents

15

14.8

14.914.1014.11

Structure Determination in Conjugated Systems:Ultraviolet Spectroscopy 482Ultraviolet Spectrum of 1,3-Butadiene 483Interpreting Ultraviolet Spectra: The Effect of Conjugation 485Conjugation, Color, and the Chemistry of Vision 486

CHEMISTRY@WORK: PHOTOLITHOGRAPHY 488

Summary and KeyWords489 . Summary of Reactions 490 .Exercises 490

Building BlockQuestions 497 . InfoTracCollege Edition 497

Benzene and Aromaticlty

;;,~~

16

15.115.215.315.415.515.615.715.815.915.10

Sources of Aromatic Hydrocarbons 499Naming Aromatic Compounds 500Structure and Stability of Benzene 502Molecular Orbital Description of Benzene 504Aromaticity and the HUckel4n + 2 Rule 505Aromatic Ions 507

Aromatic Heterocycles: Pyridine and Pyrrole 510Why 4n + 2? 512Polycyclic Aromatic Compounds: Naphthalene 514Spectroscopy of Aromatic Compounds 515

CHEMISTRY@WORK: ASPIRIN, NSAlDs, AND COX-2 INHIBITORS 519

Summary and KeyWords 520 . Exercises 521Building Block Questions 527 . InfoTracCollegeEdition527

Chemistry of Benzene:Electrophilic AromaticSubstitution

16.116.216.316.416.516.616.716.816.916.1016.1116.12

Bromination of Aromatic Rings 529Other Aromatic Substitutions 532

Alkylation of Aromatic Rings: The Friedel-Crafts Reaction 535Acylation of Aromatic Rings 538Substituent Effects in Substituted Aromatic Rings 539An Explanation of Substituent Effects 543Trisubstituted Benzenes: Additivity of Effects 549Nucleophilic Aromatic Substitution 551Benzyne 553Oxidation of Aromatic Compounds 555Reduction of Aromatic Compounds 558Synthesis ofTrisubstituted Benzenes 559

CHEMISTRY@WORK:COMBINATORIALCHEMISTRY 564

Summary and Key Words 566 . Summary of Reactions 566 . Exercises 569

Building Block Questions 577 . InfoTrac College Edition 577

Contents xiii

A Brief Review

of Organic Reactions

17

I.II.

A Summaryof the Kindsof OrganicReactions 578A Summaryof OrganicReactionMechanisms 582

Problems586 .BuildingBlockQuestions586 .InfoTracCollegeEdition586

Alcohols and Phenols

18

17.1

17.217.317.417.5

17.6

17.717.8

17.917.1017.1117.12

NamingAlcohols and Phenols 588Propertiesof Alcohols and Phenols:HydrogenBonding 590Propertiesof Alcohols and Phenols:Acidity and Basicity 591Preparationof Alcohols: A Review 596Alcohols from Reductionof CarbonylCompounds 598Alcohols from Reactionof CarbonylCompoundswith Grignard Reagents 601SomeReactionsof Alcohols 605Oxidation of Alcohols 611Protectionof Alcohols 613Preparationand Usesof Phenols 615Reactionsof Phenols 618

Spectroscopyof Alcohols and Phenols 619

CHEMISTRY@WORK: ETHANOL:CHEMICAL, DRUG, AND POISON 623

Summary and KeyWords 624 .Summaryof Reactions625 .Exercises628Building BlockQuestions638 .InfoTracCollegeEdition638

Ethers and Epoxides;Thiols and Sulfides

18.1 NamingEthers 64018.2 Structure, Properties,and Sourcesof Ethers 64018.3 TheWilliamson EtherSynthesis 64218.4 Alkoxymercurationof Alkenes 64318.5 Reactionsof Ethers:AcidicCleavage 64418.6 Reactionsof Ethers:ClaisenRearrangement 64618.7 CyclicEthers:Epoxides 64818.8 Ring-OpeningReactionsof Epoxides 64918.9 CrownEthers 65418.10 Thiols and Sulfides 655

18.11 Spectroscopyof Ethers 658CHEMISTRY@WORK: Epoxy RESINS AND ADHESIVES 660

Summary and KeyWords 661 .Summaryof Reactions662 . Exercises664Building BlockQuestions671 . InfoTracCollegeEdition671

xiv Contents

A Preview of CarbonylCompounds

19

I.II.III.IV.

Kinds of CarbonylCompounds 672Natureof the CarbonylGroup 674GeneralReactionsof CarbonylCompounds 675Summary 680

Problems 680 . Building Block Questions 681 . InfoTrac College Edition 681

Aldehydes andKetones: NucleophilicAddition Reactions

~

20

'.)

19.119.219.319.419.5

19.619.719.8

Naming Aldehydes and Ketones 683Preparation of Aldehydes and Ketones 685Oxidation of Aldehydes and Ketones 687Nucleophilic Addition Reactions of Aldehydes and Ketones 688Relative Reactivity of Aldehydes and Ketones 690

Nucleophilic Addition of H2O:Hydration 691Nucleophilic Addition of HCN: Cyanohydrin Formation 693Nucleophilic Addition of Grignard Reagents and Hydride Reagents:Alcohol Formation 695

Nucleophilic Addition of Amines: Imine and Enamine Formation 696

Nucleophilic Addition of Hydrazine: The Wolff-Kishner Reaction 700Nucleophilic Addition of Alcohols: Acetal Formation 702Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction 706The Cannizzaro Reaction: Biological Reductions 709Conjugate Nucleophilic Addition to a,f3-UnsaturatedAldehydes and Ketones 711Some Biological Nucleophilic Addition Reactions 715Spectroscopy of Aldehydes and Ketones 716

CHEMISTRY@WORK:ENANTIOSELECTIVESYNTHESIS 720

Summary and KeyWords 721 . Summary of Reactions 722 . Exercises 725Building BlockQuestions736 . InfoTrac College Edition 736

Carboxylic Addsand Nitriles

~J

19.919.1019.1119.1219.1319.14

19.1519.16

20.120.220.320.420.520.620.720.820.920.10

Naming Carboxylic Acids and Nitriles 738Structure and Physical Properties of Carboxylic Acids 740Dissociation of Carboxylic Acids 741Substituent Effects on Acidity 743Substituent Effects in Substituted Benzoic Acids 745

Preparation of Carboxylic Acids 746Reactions of Carboxylic Acids: An Overview 749Reduction of Carboxylic Acids 749Chemistry of Nitriles 750Spectroscopy of Carboxylic Acids and Nitriles 755

CHEMISTRY@WORK:VITAMINC 757

Summaryand KeyWords758 . Summaryof Reactions759 . Exercises 761Building Block Questions 769 . InfoTrac College Edition 769

21

Contents xv

Carboxylic AcidDerivatives and

Nucleophilic AcylSubstitution Reactions

22Carbonyl Alpha-Substitution Reactions

23

21.121.221.321.421.521.621.721.8

21.921.10

22.122.222.322.4

22.522.622.722.8

Naming Carboxylic Acid Derivatives 771Nucleophilic AcylSubstitution Reactions 774Nucleophilic AcylSubstitution Reactions of Carboxylic Acids 779Chemistry of Acid Halides 783Chemistry of Acid Anhydrides 788Chemistry of Esters 789Chemistry of Amides 795Thioesters and AcylPhosphates:Biological Carboxylic Acid Derivatives 798Polyamides and Polyesters: Step-Growth Polymers 799Spectroscopy of Carboxylic Acid Derivatives 802

CHEMISTRY@WORK:P-LACTAMANTIBIOTICS 804

Summary and Key Words 805 .Summary of Reactions 806 . Exercises 809

Building Block Questions 819 . InfoTrac College Edition 819

-Keto-Enol Tautomerism 821

Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions 824Alpha Halogenation of Aldehydes and Ketones 824Alpha Bromination of Carboxylic Acids:The Hell-Volhard-Zelinskii Reaction 827

Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation 828Reactivity of Enolate Ions 832Halogenation of Enolate Ions: The Haloform Reaction 833Alkylation of Enolate Ions 834CHEMISTRY@WORK:UNUSUAL ELEMENTSIN ORGANICCHEMISTRY 842

Summary and Key Words 844 . Summary of Reactions 844 .Exercises 846

Building BlockQuestions 853 . InfoTracCollege Edition 853

Carbonyl CondensationReactions

23.123.223.3

23.423.523.623.723.823.923.10

Mechanism of Carbonyl Condensation Reactions 854Condensations of Aldehydes and Ketones: The Aldol Reaction 855Carbonyl Condensation Reactionsversus Alpha-Substitution Reactions 858Dehydration of Aldol Products: Synthesis of Enones 859Using Aldol Reactions in Synthesis 861Mixed Aldol Reactions 862Intramolecular Aldol Reactions 864The Claisen Condensation Reaction 865Mixed Claisen Condensations 867

Intramolecular Claisen Condensations: The Dieckmann Cyclization 869

xvi Contents

24

23.1123.1223.13

23.14

The MichaelReaction 871TheStork EnamineReaction 874CarbonylCondensationReactionsin Synthesis:The RobinsonAnnulation Reaction 876Biological CarbonylCondensationReactions 878

CHEMISTRy@WORK: A PROLOGUE10 METABOLISM 878

Summary and Key Words 880 . Summary of Reactions 881 . Exercises 883

Building Block Questions 891 . InfoTrac College Edition 891

Amines

25

~

24.124.224.324.424.5

24.624.724.824.924.10

NamingAmines 892Structureand Bonding in Amines 895Propertiesand Sourcesof Amines 896Basicityof Amines 897Basicityof SubstitutedArylamines 901Synthesisof Amines 903Reactionsof Amines 912Reactionsof Arylamines 915TetraalkylammoniumSalts as Phase-TransferCatalysts 921Spectroscopyof Amines 923CHEMISTRY@WORK:OPIUM AND OPIATES 927

Summary and Key Words 928 . Summary of Reactions 928 . Exercises932Building Block Questions 941 . InfoTrac College Edition 941

Biomolecules:

Carbohydrates

~

25.125.2

25.325.425.525.625.725.8

25.925.1025.1125.12

'Classification of Carbohydrates 943Depicting Carbohydrate Stereochemistry: Fischer Projections 944D,LSugars 948Configurations of the Aldoses 949Cyclic Structures of Monosaccharides: Hemiacetal Formation 952Monosaccharide Anomers: Mutarotation 954Reactions of Monosaccharides 956

Stereochemistry of Glucose: The Fischer Proof 963Disaccharides 967

Polysaccharides and Their Synthesis 969Other Important Carbohydrates 972Cell-Surface Carbohydrates and Carbohydrate Vaccines 973

CHEMISTRY@WORK:SWEETNESS975

Summaryand KeyWords976 . Summaryof Reactions977 . Exercises 978Building Block Questions 984 . InfoTracCollegeEdition984

26

Contents xvii

Biomolecules: AminoAcids, Peptides, andProteins

27

26.126.226.326.426.526.626.726.826.926.1026.1126.1226.1326.1426.1526.16

Structures of AminoAcids 986Isoelectric Points 991

Synthesis of AminoAcids 994EnantioselectiveSynthesis of AminoAcids 996Peptides and Proteins 998Covalent Bonding in Peptides 999Structure Determinationof Peptides: AminoAcidAnalysis 1000Peptide Sequencing: The Edman Degradation 1001Peptide Sequencing: C-Terminal Residue Determination 1004Peptide Synthesis 1004Automated Peptide Synthesis: The MerrifieldSolid-Phase Technique 1008Protein Classification 1009Protein Structure 1010

Enzymes 1012How Do Enzymes Work? Citrate Synthase 1014Protein Denaturation 1016

CHEMISTRY@WORK:PROTEINANDNUTRITION 1016

Summary and Key Words 1017 .Summary of Reactions 1018Exercises 1020 .Building Block Questions 1026

InfoTrac College Edition 1026

Biomolecules: Lipids 27.127.227.327.427.527.627.727.827.9

Waxes, Fats, and Oils 1027Soap 1030Phospholipids 1032Prostaglandins 1033Terpenoids 1035Biosynthesis ofTerpenoids 1038Steroids 1045

Stereochemistry of Steroids 1047Steroid Biosynthesis 1049

CHEMISTRY@WORK: CHOLESTEROL AND HEART DISEASE 1052

Summary and KeyWords 1053 . Exercises 1053Building Block Questions 1059 . InfoTracCollege Edition 1059

xviii Contents

28Biomolecules:Heterocyclesand Nucleic Acids

29

28.1 Five-Membered Unsaturated Heterocycles 106128.2 Structures of Pyrrole, Furan, and Thiophene 106228.3 ElectrophilicSubstitution Reactions of Pyrrole, Furan,and Thiophene 106328.4 Pyridine, a Six-Membered Heterocycle 106428.5 Electrophilic Substitution of Pyridine 106528.6 Nucleophilic Substitution of Pyridine 106628.7 Fused-Ring Heterocycles 106728.8 Nucleic Acids and Nucleotides 106928.9 Structure of Nucleic Acids 1071

28.10 Base Pairing in DNA:The Watson-Crick Model 107228.11 Nucleic Acids and Heredity 107428.12 Replication of DNA 107528.13 Structure and Synthesis of RNA:Transcription 107728.14 RNAand Protein Biosynthesis: Translation 107828.15 DNASequencing 108128.16 DNASynthesis 108328.17 The Polymerase Chain Reaction 1086

CHEMISTRY@WORK: DNA FINGERPRINTING 1087

Summary and KeyWords 1088 .Summary of Reactions 1089Exercises 1090 . Building Block Questions 1093InfoTracCollege Edition 1093

The Organic Chemistryof Metabolic Pathways

29.129.229.329.429.529.629.729.829.9

An Overview of Metabolism and Biochemical Energy 1094Catabolism of Fats: f3-0xidation 1098Catabolism of Carbohydrates: Glycolysis 1104The Conversion of Pyruvate to Acetyl CoA 1110The CitricAcid Cycle 1113Catabolism of Proteins: Transamination 1116

Fatty Acid Biosynthesis 1118Carbohydrate Biosynthesis: Gluconeogenesis 1122Some Conclusions About Biological Chemistry 1125CHEMISTRY@WORK: BASAL METABOLISM 1126

Summary and KeyWords 1126 .Exercises 1127Building Block Questions 1133 . InfoTracCollege Edition 1133

.....

30Contents xix

Orbitals and OrganicChemistry: PericyclicReactions

31

30.1 Molecular Orbitals of Conjugated 7T Systems 113430.2 Molecular Orbitals and Pericyclic Reactions 113530.3 Electrocyclic Reactions 113730.4 Stereochemistry of Thermal Electrocyclic Reactions 113930.5 Photochemical Electrocyclic Reactions 114130.6 Cycloaddition Reactions 114230.7 Stereochemistry of Cycloadditions 114430.8 Sigmatropic Rearrangements 114630.9 Some Examples of Sigmatropic Rearrangements 114830.10 A Summary of Rules for Pericyclic Reactions 1150

CHEMISTRY@WORK: VITAMIN D, THE SUNSHINE VITAMIN 1151

Summaryand KeyWords1152 . Exercises1152Building Block Questions 1158 . InfoTrac College Edition 1158

Synthetic Polymers

"""0

31.1

31.2

31.3

31.4

31.5

Chain-Growth Polymers 1160Stereochemistry of Polymerization: Ziegler-Natta Catalysts 1161Copolymers 1163Step-Growth Polymers 1165Polymer Structure and Physical Properties 1167CHEMISTRY@WORK: BIODEGRADABLE POLYMERS 1170

Summary and KeyWords 1172 . Exercises 1172Building Block Questions 1176 . InfoTracCollege Edition 1176

Appendix A: Nomenclature of Polyfunctional Organic Compounds A-1

Appendix B:Acidity Constants for Some Organic Compounds A-7

Appendix C: Glossary A-9

Appendix D:Answers to Selected In-TextProblems A-31

Index 1-1