Contents INTRODUCTION AND REVIEW 1 STRUCTURE AND PROPERTIES OF ORGANIC MOLECULES 42. About the Author. Preface xxv

Transcription

1 Contents About the Author iii Preface xxv INTRODUCTION AND REVIEW The Origins of Organic Chemistry Principles of Atomic Structure Bond Formation: The Octet Rule Lewis Structures Multiple Bonding 8 Summary: Common Bonding Patterns (Uncharged) Electronegativity and Bond Polarity Formal Charges Ionic Structures 13 Summary: Common Bonding Patterns in Organic Compounds and Ions Resonance Structural Formulas Molecular Formulas and Empirical Formulas Arrhenius Acids and Bases Br0nsted-Lowry Acids and Bases Lewis Acids and Bases 31 Essential Terms 34 Study Problems 36 STRUCTURE AND PROPERTIES OF ORGANIC MOLECULES Wave Properties of Electrons in Orbitals Molecular Orbitals Pi Bonding Hybridization and Molecular Shapes DrawingThree-Dimensional Molecules General Rules of Hybridization and Geometry Bond Rotation Isomerism Polarity of Bonds and Molecules Intermolecular Forces Polarity Effects on Solubilities Hydrocarbons Organic Compounds Containing Oxygen Organic Compounds Containing Nitrogen 78 EssentialTerms 81 Study Problems 83

2 VI Contents 3 STRUCTURE AND STEREOCHEMISTRY OFALKANES Classification of Hydrocarbons (Review) Molecular Formulas of Alkanes Nomenclature of Alkanes 89 Summary: Rules for Naming Alkanes Physical Properties of Alkanes Uses and Sources of Alkanes Reactions of Alkanes Structure and Conformations of Alkanes Conformations of Butane Conformations of Higher Alkanes Cycloalkanes Cis-trans Isomerism in Cycloalkanes Stabilities of Cycloalkanes; Ring Strain Cyclohexane Conformations 113 Problem-Solving Strategy: Drawing Chair Conformations Conformations of Monosubstituted Cyclohexanes Conformations of Disubstituted Cyclohexanes 120 Problem-Solving Strategy: Recognizing Cis and Trans Isomers Bicyclic Molecules 123 EssentialTerms 125 Study Problems THE STUDY OF CHEMICAL REACTIONS Introduction Chlorination of Methane The Free-Radical Chain Reaction 134 Key Mechanism 4-1: Free-Radical Halogenation Equilibrium Constants and Free Energy Enthalpy and Entropy Bond-Dissociation Enthalpies Enthalpy Changes in Chlorination Kinetics and the Rate Equation Activation Energy and thetemperature Dependence of Rates Transition States Rates of Multistep Reactions Temperature Dependence of Halogenation Selectivity in Halogenation The Hammond Postulate Radical Inhibitors Reactive Intermediates 162 Summary: Reactive Intermediates 168 EssentialTerms 168 Study Problems 170

3 5 STEREOCHEMISTRY Introduction Chirality (R) and (S) Nomenclature of Asymmetric Carbon Atoms Optical Activity Biological Discrimination of Enantiomers Racemic Mixtures Enantiomeric Excess and Optical Purity Chirality of Conformationally Mobile Systems Chiral Compounds without Asymmetric Atoms Fischer Projections Summary: Fischer Projections andtheir Use 201 Diastereomers 201 Summary:Types of Isomers Stereochemistry of Molecules withtwo or More Asymmetric Carbons Meso Compounds Absolute and Relative Configuration Physical Properties of Diastereomers Resolution of Enantiomers 209 EssentialTerms 213 Study Problems 215 ALKYL HALOES: NUCLEOPHILIC SUBSTITUTION AND ELIMINATION Introduction Nomenclature of Alkyl Halides Common Uses of Alkyl Halides Structure of Alkyl Halides Physical Properties of Alkyl Halides Preparation of Alkyl Halides 226 Mechanism 6-1: Allylic Bromination 228 Summary: Methods for Preparing Alkyl Halides Reactions of Alkyl Halides: Substitution and Elimination Second-Order Nucleophilic Substitution:The SN2 Reaction 232 Key Mechanism 6-2: The S N 2 Reaction Generality of the S N 2 Reaction 234 Summary: SN2 Reactions of Alkyl Halides Factors Affecting S[\j2 Reactions: Strength of the Nucleophile 236 Summary:Trends in Nucleophilicity Reactivity of the Substrate in SN2 Reactions Stereochemistry of the S N 2 Reaction 244 Mechanism 6-3: Inversion of Configuration in the S N 2 Reaction First-Order Nucleophilic Substitution:The S N 1 Reaction 246 Key Mechanism 6-4: The SN1 Reaction Stereochemistry of the S N 1 Reaction Rearrangements in the S[vj1 Reactions 252 Mechanism 6-5: Racemization in the S \ 1 Reaction 252

4 viii Contents Mechanism 6-6: Hydride Shift in an SN1 Reaction 253 Mechanism 6-7: Methyl Shift in an S N 1 Reaction Comparison of S^l and S N 2 Reactions 255 Summary: Nucleophilic Substitutions First-Order Elimination:The E1 Reaction 258 Key Mechanism 6-8:The E1 Reaction 258 Mechanism 6-9: Rearrangement in an E1 Reaction 261 Summary: Carbocation Reactions Positional Orientation of Elimination: Zaitsev's Rule Second-Order Elimination:The E2 Reaction 265 Key Mechanism 6-10: The E2 Reaction Stereochemistry of the E2 Reaction Comparison of E1 and E2 Elimination Mechanisms 269 Problem-Solving Strategy: Predicting Substitutions and Eliminations 270 Summary: Elimination Reactions 270 Summary: Reactions of Alkyl Halides 273 EssentialTerms 276 Study Problems STRUCTURE AND SYNTHESIS OF ALKENES Introduction The Orbital Description of the Alkene Double Bond Elements of Unsaturation Nomenclature of Alkenes Nomenclature of Cis-Trans Isomers 291 Summary: Rules for Naming Alkenes Commercial Importance of Alkenes Stability of Alkenes Physical Properties of Alkenes Alkene Synthesis by Elimination of Alkyl Halides 304 Mechanism 7-1: Dehydrohalogenation by the E2 Mechanism 304 Mechanism 7-2: Stereochemistry of the E2 Reaction 306 Mechanism 7-3: E2 Debromination of a Vicinal Dibromide Alkene Synthesis by Dehydration of Alcohols 312 Key Mechanism 7-4: Acid-Catalyzed Dehydration of an Alcohol Alkene Synthesis by High-Temperature Industrial Methods 315 Problem-Solving Strategy: Proposing Reaction Mechanisms 316 Summary: Methods for Synthesis of Alkenes 320 EssentialTerms 322 Study Problems 323 REACTIONS OF ALKENES Reactivity of the Carbon-Carbon Double Bond Electrophilic Addition to Alkenes 329 Key Mechanism 8-1: Electrophilic Addition to Alkenes 330

5 8-3 Addition of Hydrogen Halides to Alkenes 331 Mechanism 8-2: Ionic Addition of HX to an Aikene 332 Mechanism 8-3: Free-Radical Addition of HBr to Alkenes Addition of Water: Hydration of Alkenes 337 Mechanism 8-4: Acid-Catalyzed Hydration of an Aikene Hydration by Oxymercuration-Demercuration 340 Mechanism 8-5: Oxymercuration of an Aikene Alkoxymercuration-Demercuration Hydroboration of Alkenes 343 Mechanism 8-6: Hydroboration of an Aikene Addition of Halogens to Alkenes 349 Mechanism 8-7: Addition of Halogens to Alkenes Formation of Halohydrins 352 Mechanism 8-8: Formation of Halohydrins Catalytic Hydrogenation of Alkenes Addition of Carbenes to Alkenes Epoxidation of Alkenes 360 Mechanism 8-9: Epoxidation of Alkenes Epoxidation of Alkenes 361 Mechanism 8-10: Acid-Catalyzed Opening of Epoxides Syn Dihydroxylation of Alkenes Oxidative Cleavage of Alkenes Polymerization of Alkenes Olefin Metathesis 373 Mechanism 8-11: Olefin Metathesis 376 Problem-Solving Strategy: Organic Synthesis 376 Summary: Reactions of Alkenes 378 EssentialTerms 383 Study Problems ALKYNES Introduction Nomenclature of Alkynes Physical Properties of Alkynes Commercial Importance of Alkynes Electronic Structure of Alkynes Acidity of Alkynes; Formation of Acetylide Ions Synthesis of Alkynes from Acetylides Synthesis of Alkynes by Elimination Reactions 403 Summary: Syntheses of Alkynes Addition Reactions of Alkynes 405 Mechanism 9-1: Metal-Ammonia Reduction of an Alkyne 407 Mechanism 9-2: Acid-Catalyzed Keto-EnolTautomerism 411 Mechanism 9-3: Base-Catalyzed Keto-EnolTautomerism Oxidation of Alkynes 414 Problem-Solving Strategy: Multistep Synthesis 416 Summary: Reactions of Alkynes 418 EssentialTerms 421 Study Problems 422

6 STRUCTURE AND SYNTHESIS OF ALCOHOLS Introduction Structure and Classification of Alcohols Nomenclature of Alcohols and Phenols Physical Properties of Alcohols Commercially Important Alcohols Acidity of Alcohols and Phenols Synthesis of Alcohols: Introduction and Review 438 Summary: Previous Alcohol Syntheses Organometallic Reagents for Alcohol Synthesis Addition of Organometallic Reagents to Carbonyl Compounds 443 Key Mechanism 10-1: Grignard Reactions 443 Summary: Grignard Reactions Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides Reduction of the Carbonyl Group: Synthesis of 1 and 2 Alcohols 453 Mechanism 10-2: Hydride Reduction of a Carbonyl Group 454 Summary: Reactions of LiAIH4 and NaBH4 455 Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups Thiols (Mercaptans) 458 EssentialTerms 461 Study Problems 462 REACTIONS OF ALCOHOLS Oxidation States of Alcohols and Related Functional Groups Oxidation of Alcohols Additional Methods for Oxidizing Alcohols Biological Oxidation of Alcohols Alcohols as Nucleophiles and Electrophiles; Formation oftosylates 476 Summary: SN2 Reactions OfTosylate Esters Reduction of Alcohols Reactions of Alcohols with Hydrohalic Acids 479 Mechanism 11-1: Reaction of a Tertiary Alcohol with HBr (S N 1) 480 Mechanism 11-2: Reaction of a Primary Alcohol with HBr(S N 2) Reactions of Alcohols with Phosphorus Halides 484 Reactions of Alcohols withthionyl Chloride Mechanism 11-3: Reaction of Alcohols with PBr Dehydration Reactions of Alcohols 487 Mechanism 11-4: (Review): Acid-Catalyzed Dehydration of an Alcohol 487 Problem-Solving Strategy: Proposing Reaction Mechanisms Unique Reactions of Diols 494 Mechanism 11-5: The Pinacol Rearrangement 495

7 11-12 Esterification of Alcohols Esters of Inorganic Acids Reactions of Alkoxides 500 Key Mechanism 11-6:The Williamson Ether Synthesis 500 Problem-Solving Strategy: Multistep Synthesis 502 Summary: Reactions of Alcohols 505 EssentialTerms 508 Study Problems INFRARED SPECTROSCOPY AND L MASS SPECTROMETRY Introduction The Electromagnetic Spectrum The Infrared Region MolecularVibrations IR-Active and IR-lnactive Vibrations Measurement of the IR Spectrum Infrared Spectroscopy of Hydrocarbons Characteristic Absorptions of Alcohols and Amines Characteristic Absorptions of Carbonyl Compounds Characteristic Absorptions of C N Bonds Simplified Summary of IR Stretching Frequencies Reading and Interpreting IR Spectra (Solved Problems) Introduction to Mass Spectrometry Determination of the Molecular Formula by Mass Spectrometry Fragmentation Patterns in Mass Spectrometry 548 Summary: Common Fragmentation Patterns 553 EssentialTerms 555 Study Problems 556 NUCLEAR MAGNETIC RESONANCE J SPECTROSCOPY Introduction Theory of Nuclear Magnetic Resonance Magnetic Shielding by Electrons The NMR Spectrometer The Chemical Shift The Number of Signals Areas of the Peaks Spin-Spin Splitting 580 Problem-Solving Strategy: Drawing An NMR Spectrum Complex Sitting Stereochemical Nonequivalence of Protons Time Dependence of NMR Spectroscopy 594 Problem-Solving Strategy: Interpreting Proton NMR Sectra 597

8 13-12 Carbon-13 NMR Spectroscopy Interpreting Carbon NMR Spectra Nuclear Magnetic Resonance Imaging 611 Problem-Solving Strategy: Spectroscopy Problems 612 EssentialTerms 617 Study Problems ETHERS, EPOXIDES, AND THIOETHERS Introduction Physical Properties of Ethers Nomenclature of Ethers Spectroscopy of Ethers The Williamson Ether Synthesis Synthesis of Ethers by Alkoxymercuration-Demercuration Industrial Synthesis: Bimolecular Condensation of Alcohols 637 Summary: Syntheses of Ethers (Review) Cleavage of Ethers by HBr and HI 638 Mechanism 14-1: Cleavage of an Ether by HBr or HI Autoxidation of Ethers 641 Summary: Reactions of Ethers Thioethers (Sulfides) and Silyl Ethers Synthesis of Epoxides 646 Summary: Epoxide Syntheses Acid-Catalyzed Ring Opening of Epoxides 649 Mechanism 14-2: Acid-Catalyzed Opening of Epoxides in Water 649 Mechanism 14-3: Acid-Catalyzed Opening of an Epoxide in an Alcohol Solution Base-Catalyzed Ring Opening of Epoxides 652 Mechanism 14-4: Base-Catalyzed Opening of Epoxides Orientation of Epoxide Ring Opening Reactions of Epoxides with Grignard and Organolithium Reagents Epoxy Resins:The Advent of Modern Glues 656 Summary: Reactions of Epoxides 658 EssentialTerms 660 Study Problems CONJUGATED SYSTEMS, ORBITAL SYMMETRY, AND ULTRAVIOLET SPECTROSCOPY Introduction Stabilities of Dienes Molecular Orbital Picture of a Conjugated System Allylic Cations ,2- and 1,4-Addition to Conjugated Dienes 674 Mechanism 15-1: 1,2- and 1,4-Addition to a Conjugated Diene 675

9 15-6 Kinetic versusthermodynamic Control in the Addition of HBr to Buta-1,3-diene Allylic Radicals 678 Mechanism 15-2: Free-Radical Allylic Bromination Molecular Orbitals of the Allylic System Electronic Configurations of the Allyl Radical, Cation, and Anion SN2 Displacement Reactions of Allylic Halides and Tosylates The Diels-Alder Reaction 684 Key Mechanism 15-3:The Diels-Alder Reaction The Diels-Alder as an Example of a Pericyclic Reaction Ultraviolet Absorption Spectroscopy Colored Organic Compounds UV-Visible Analysis in Biology and Medicine 704 EssentialTerms 706 Study Problems AROMATIC COMPOUNDS lntroduction:the Discovery of Benzene The Structure and Properties of Benzene The Molecular Orbitals of Benzene The Molecular Orbital Picture of Cyclobutadiene Aromatic, Antiaromatic, and Nonaromatic Compounds Huckel's Rule Molecular Orbital Derivation of Huckel's Rule Aromatic Ions Heterocyclic Aromatic Compounds Polynuclear Aromatic Hydrocarbons Aromatic Allotropes of Carbon Fused Heterocyclic Compounds Nomenclature of Benzene Derivatives Physical Properties of Benzene and Its Derivatives Spectroscopy of Aromatic Compounds 743 EssentialTerms 746 Study Problems 748 REACTIONS OF AROMATIC COMPOUNDS Electrophilic Aromatic Substitution 756 Key Mechanism 17-1: Electrophilic Aromatic Substitution Halogenation of Benzene 758 Mechanism 17-2: Bromination of Benzene Nitration of Benzene 760 Mechanism 17-3: Nitration of Benzene Sulfonation of Benzene 761 Mechanism 17-4: Sulfonation of Benzene Nitration oftoluene:the Effect of Alkyl Substitution 763

10 17-6 Activating, Ortho, Para-Directing Substituents 766 Summary: Activating, Ortho, Para-Directors Deactivating, Meta-Directing Substituents 769 Summary: Deactivating, Meta-Directors Halogen Substituents: Deactivating, but Ortho, Para-Directing 772 Summary: Directing Effects of Substituents Effects of Multiple Substituents on Electrophilic Aromatic Substitution The Friedel-Crafts Alkylation 777 Mechanism 17-5: Friedel-Crafts Alkylation The Friedel-Crafts Acylation 781 Mechanism 17-6: Friedel-Crafts Acylation 782 Summary: Comparison of Friedel-Crafts Alkylation and Acylation Nucleophilic Aromatic Substitution 786 Mechanism 17-7: Nucleophilic Aromatic Substitution (Addition-Elimination) 787 Mechanism 17-8: Nucleophilic Aromatic Substitution (Benzyne Mechanism) Aromatic Substitutions Using Organometallic Reagents Addition Reactions of Benzene Derivatives 796 Mechanism 17-9:The Birch Reduction Side-Chain Reactions of Benzene Derivatives Reactions of Phenols 802 Summary: Reactions of Aromatic Compounds 805 Essential Terms 808 Study Problems KETONES AND ALDEHYDES Carbonyl Compounds Structure of the Carbonyl Group Nomenclature of Ketones and Aldehydes Physical Properties of Ketones and Aldehydes Spectroscopy of Ketones and Aldehydes Industrial Importance of Ketones and Aldehydes Review of Syntheses of Ketones and Aldehydes Synthesis of Ketones from Carboxylic Acids Synthesis of Ketones and Aldehydes from Nitriles Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 835 Summary: Syntheses of Ketones and Aldehydes Reactions of Ketones and Aldehydes: Introduction to Nucleophilic Addition 839 Key Mechanism 18-1: Nucleophilic Additions to Carbonyl Groups The Wittig Reaction 843 Mechanism 18-2: The Wittig Reaction Hydration of Ketones and Aldehydes 847 Mechanism 18-3: Hydration of Ketones and Aldehydes 847

11 18-14 Formation of Cyanohydrins 849 Mechanism 18-4: Formation of Cyanohydrins Formation of Imines 850 Key Mechanism 18-5: Formation of Imines Condensations with Hydroxylamine and Hydrazines 853 Summary: Condensations of Amines with Ketones and Aldehydes Formation of Acetals 855 Key Mechanism 18-6: Formation of Acetals 856 Problem-Solving Strategy: Proposing Reaction Mechanisms Use of Acetals as Protecting Groups Oxidation of Aldehydes Reductions of Ketones and Aldehydes 862 Mechanism 18-7: Wolff-Kishner Reduction 864 Summary: Reactions of Ketones and Aldehydes 865 EssentialTerms 868 Study Problems AMINES Introduction Nomenclature of Amines Structure of Amines Physical Properties of Amines Basicity of Amines Effects on Amine Basicity Salts of Amines Spectroscopy of Amines Reactions of Amines with Ketones and Aldehydes (Review) Aromatic Substitution of Arylamines and Pyridine 896 Mechanism 19-1: Electrophilic Aromatic Substitution of Pyridine 897 Mechanism 19-2: Nucleophilic Aromatic Substitution of Pyridine Alkylation of Amines by Alkyl Halides Acylation of Amines by Acid Chlorides 900 Mechanism 19-3: Acylation of an Amine by an Acid Chloride Formation of Sulfonamides Amines as Leaving Groups:The Hofmann Elimination 904 Mechanism 19-4: Hofmann Elimination Oxidation of Amines;The Cope Elimination 907 Mechanism 19-5: The Cope Elimination of an Amine Oxide Reactions of Amines with Nitrous Acid 910 Mechanism 19-6: Diazotization of an Amine Reactions of Arenediazonium Salts 911 Summary: Reactions of Amines Synthesis of Amines by Reductive Amination Synthesis of Amines by Acylation-Reduction 920

12 19-20 Syntheses Limited to Primary Amines 922 Summary Synthesis of Amines 926 EssentialTerms 929 Study Problems CARBOXYLIC ACIDS Introduction Nomenclature of Carboxylic Acids Structure and Physical Properties of Carboxylic Acids Acidity of Carboxylic Acids Salts of Carboxylic Acids Commercial Sources of Carboxylic Acids Spectroscopy of Carboxylic Acids Synthesis of Carboxylic Acids 956 Summary: Syntheses of Carboxylic Acids Reactions of Carboxylic Acids and Derivatives; Nucleophilic Acyl Substitution 960 Mechanism 20-1: Nucleophilic Acyl Substitution in the Basic Hydrolysis of an Ester Condensation of Acids with Alcohols: The Fischer Esterification 961 Key Mechanism 20-2: Fischer Esterification Esterification Using Diazomethane 965 Mechanism 20-3: Esterification Using Diazomethane Condensation of Acids with Amines: Direct Synthesis of Amides Reduction of Carboxylic Acids Alkylation of Carboxylic Acids to Form Ketones Synthesis and Use of Acid Chlorides 969 Summary: Reactions of Carboxylic Acids 972 EssentialTerms 974 Study Problems 975 CARBOXYLIC ACID DERIVATIVES Introduction Structure and Nomenclature of Acid Derivatives Physical Properties of Carboxylic Acid Derivatives Spectroscopy of Carboxylic Acid Derivatives Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 997 Key Mechanism 21-1: Addition-Elimination Mechanism of Nucleophilic Acyl Substitution 998 Mechanism 21-2: Conversion of an Acid Chloride to an Anhydride 1001 Mechanism 21-3: Conversion of an Acid Chloride to an Ester 1001 Mechanism 21-4: Conversion of an Acid Chloride to an Amide 1002 Mechanism 21-5: Conversion of an Acid Anhydride to an Ester 1002

13 Mechanism 21-6: Conversion of an Acid Anhydride to an Amide 1003 Mechanism 21-7: Conversion of an Ester to an Amide (Ammonolysis of an Ester) Transesterification 1006 Problem-Solving Strategy: Proposing Reaction Mechanisms 1007 Mechanism 21-8:Transesterification Hydrolysis of Carboxylic Acid Derivatives 1009 Mechanism 21-9: Saponification of an Ester 1010 Mechanism 21-10: Basic Hydrolysis of an Amide 1012 Mechanism 21-11: Acidic Hydrolysis of an Amide 1012 Mechanism 21-12: Base-Catalyzed Hydrolysis of a Nitrile Reduction of Acid Derivatives 1014 Mechanism 21-13: Hydride Reduction of an Ester 1015 Mechanism 21-14: Reduction of an Amide to an Amine Reactions of Acid Derivatives with Organometallic Reagents 1017 Mechanism 21-15: Reaction of an Ester withtwo Moles of a Grignard Reagent Summary of the Chemistry of Acid Chlorides Summary of the Chemistry of Anhydrides Summary of the Chemistry of Esters Summary of the Chemistry of Amides Summary: of the Chemistry of Nitriles Thioesters Esters and Amides of Carbonic Acid 1032 EssentialTerms 1035 Study Problems 1037 CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL COMPOUNDS Introduction 1045 Mechanism 22-1: Alpha Substitution 1045 Mechanism 22-2: Addition of an Enolate to Ketones and Aldehydes (a Condensation) 1046 Mechanism 22-3: Substitution of an Enolate on an Ester (a Condensation) Enols and Enolate Ions 1046 Mechanism 22-4: Base-Catalyzed Keto-EnolTautomerism 1047 Mechanism 22-5: Acid-Catalyzed Keto-EnolTautomerism Alkylation of Enolate Ions Formation and Alkylation of Enamines Alpha Halogenation of Ketones 1054 Mechanism 22-6: Base-Promoted Halogenation 1054 Mechanism 22-7: Final Steps of the Haloform Reaction 1056 Mechanism 22-8: Acid-Catalyzed Alpha Halogenation Alpha Bromination of Acids:The HVZ Reaction The Aldol Condensation of Ketones and Aldehydes 1060 Key Mechanism 22-9: Base-Catalyzed Aldol Condensation 1061 Mechanism 22-10: Acid-Catalyzed Aldol Condensation 1063

14 22-8 Dehydration of Aldol Products 1063 Key Mechanism 22-11: Base-Catalyzed Dehydration of an Aldol Crossed Aldol Condensations 1065 Problem-Solving Strategy: Proposing Reaction Mechanisms Aldol Cyclizations Planning Syntheses Using Aldol Condensations The Claisen Ester Condensation 1070 Key Mechanism 22-12: The Claisen Ester Condensation The Dieckmann Condensation: A Claisen Cyclization Crossed Claisen Condensations Syntheses Using /3-Dicarbonyl Compounds The Malonic Ester Synthesis The Acetoacetic Ester Synthesis Conjugate Additions:The Michael Reaction 1085 Mechanism 22-13: 1,2-Addition and (Conjugate Addition) The Robinson Annulation ,4-Addition Problem-Solving Strategy: Proposing Reaction Mechanisms 1089 Summary: Enolate Additions and Condensations 1092 Essential Terms 1094 Study Problems 1096 CARBOHYDRATES AND NUCLEIC ACIDS Introduction Classification of Carbohydrates Monosaccharides Erythro andthreo Diastereomers Epimers Cyclic Structures of Monosaccharides 1108 Mechanism 23-1: Formation of a Cyclic Hemiacetal Anomers of Monosaccharides; Mutarotation Reactions of Monosaccharides: Side Reactions in Base 1114 Mechanism 23-2: Base-Catalyzed Epimerization of Glucose 1115 Mechanism 23-3: Base-Catalyzed Enediol Rearrangement Reduction of Monosaccharides Oxidation of Monosaccharides; Reducing Sugars Nonreducing Sugars: Formation of Glycosides Ether and Ester Formation Reactions with Phenylhydrazine: Osazone Formation Chain Shortening:The Ruff Degradation Chain Lengthening:The Kiliani Fischer Synthesis Determination of Ring Size; Periodic Acid Cleavage of Sugars 1128 Summary: Reactions of Sugars Disaccharides Polysaccharides Nucleic Acids: Introduction 1140

15 23-20 Ribonucleosides and Ribonucleotides The Structures of RNA and DNA Additional Functions of Nucleotides 1147 EssentialTerms 1149 Study Problems AMINO ACIDS, PEPTIDES, AND PROTEINS Introduction Structure and Stereochemistry of the a-amino Acids Acid-Base Properties of Amino Acids Isoelectric Points and Electrophoresis Synthesis of Amino Acids 1164 Summary: Syntheses of Amino Acids Resolution of Amino Acids Reactions of Amino Acids 1170 Summary: Reactions of Amino Acids Structure and Nomenclature of Peptides and Proteins Peptide Structure Determination Solution-Phase Peptide Synthesis Solid-Phase Peptide Synthesis Classification of Proteins Levels of Protein Structure Protein Denaturation 1193 EssentialTerms 1195 Study Problems LIPIDS Introduction Waxes Triglycerides Saponification of Fats and Oils; Soaps and Detergents Phospholipids Steroids Prostaglandins Terpenes 1215 EssentialTerms 1218 Study Problems SYNTHETIC POLYMERS Introduction Addition Polymers 1223 Mechanism 26-1: Free-Radical Polymerization 1225 Mechanism 26-2: Cationic Polymerization 1226 Mechanism 26-3: Anionic Polymerization 1228

16 26-3 Stereochemistry of Polymers Stereochemical Control of Polymerization; Ziegler-NattaCatalysts Natural and Synthetic Rubbers Copolymers of Two or More Monomers Condensation Polymers Polymer Structure and Properties 1236 Essential Terms 1239 Study Problems 1240 APPENDICES A NMR: Proton Chemical Shifts 1244 IB NMR: Spin-Spin Coupling Constants C NMR: Chemical Shifts in Organic Compounds A IR: Characteristic Infrared Group Frequencies B IR: Characteristic Infrared Absorptions of Functional Groups A Methods and Suggestions for Proposing Mechanisms B Suggestions for Developing Multistep Syntheses p/c a Values for Representative Compounds 1257 Answers A1 Photo Credits PC1 Index 11