SIXTH EDITION ORGANIC CHEMISTRY T. W. GRAHAM SOLOMONS University of South Florida JOHN WlLEY & SONS, INC. New York Chichester Brisbane Toronto Singapore
CONTENTS CHAPTER 1 CARBON COMPOUNDS AND CHEMICAL BONDS 1.1 Introduction 1 1.2 Development of Organic Chemistry as a Science 2 1.3 The Structural Theory of Organic Chemistry 3 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 12 1.8 Resonance 15 1.9 Energy Changes 18 1.10 Quantum Mechanics 20 1.11 Atomic Orbitals 21 1.12 Molecular Orbitals 23 1.13 The Structure of Methane: sp 3 Hybridization 26 1.14 The Structure of Borane: sp 2 Hybridization 29 1.15 The Structure of Beryllium Hydride: sp Hybridization 31 1.16 A Summary of Important Concepts that Come from Quantum Mechanics 32 1.17 Molecular Geometry: The Valence Shell Electron-Pair Repulsion (VSEPR) Model 34 1.18 Polar Covalent Bonds 38 1.19 Polar and Nonpolar Molecules 39 1.20 Representation of Structural Formulas 41 CHAPTER 2 REPRESENTATIVE CARBON COMPOUNDS 2.1 Carbon-Carbon Covalent Bonds 52 2.2 Methane and Ethane: Representative Alkanes 52 2.3 Alkenes: Compounds Containing the Carbon-Carbon Double Bond; Ethene and Propene 55 2.4 Orbital Hybridization and the Structure of Alkenes 56 2.5 Alkynes: Compounds Containing the Carbon-Carbon Triple Bond; Ethyne (Acetylene) and Propyne 61 2.6 Orbital Hybridization and the Structure of Alkynes 62 2.7 Benzene: A Representative Aromatic Hydrocarbon 64 2.8 Functional Groups 65 2.9 Alkyl Halides or Haloalkanes 66 2.10 Alcohols 67 xvii
XVÜi CONTENTS 2.11 Ethers 69 2.12 Amines 70 2.13 Aldehydes and Ketones 71 2.14 Carboxylic Acids, Amides, and Esters 72 2.15 Summary of Important Families of Organic Compounds 75 2.16 Physical Properties and Molecular Structure 75 2.17 Summary of Attractive Electric Forces 83 CHAPTER3 AN INTRODUCTION TO ORGANIC REACTIONS: ACIDS AND BASES 3.1 Reactions and Their Mechanisms 87 3.2 Acid-Base Reactions 90 3.3 Heterolysis of Bonds to Carbon: Carbocations and Carbanions 94 3.4 The Use of Curved Arrows in Illustrating Reactions 95 3.5 The Strength of Acids and Bases: K a and pk a 96 3.6 Predicting the Outcome of Acid-Base Reactions 100 3.7 The Relationship between Structure and Acidity 102 3.8 The Relationship between the Equilibrium Constant and the Standard Free- Energy Change, AG 0 105 3.9 The Acidity of Carboxylic Acids 106 3.10 The Effect of the Solvent on Acidity 110 3.11 Organic Compounds as Bases 112 3.12 A Mechanism for an Organic Reaction 113 3.13 Acids and Bases in Nonaqueous Solutions 7/5 3.14 Acid-Base Reactions and the Synthesis of Deuterium- and Tritium-Labeled Compounds 117 3.15 Some Important Terms and Concepts 118 CHAPTER 4 ALKANES AND CYCLOALKANES. CONFORMATIONS OF MOLECULES 4.1 Introduction to Alkanes and Cycloalkanes 123 4.2 Shapes of Alkanes 125 4.3 IUPAC Nomenclature of Alkanes, Alkyl Halides, and Alcohols 128 4.4 Nomenclature of Cycloalkanes 136 4.5 Physical Properties of Alkanes and Cycloalkanes 139 4.6 Sigma Bonds and Bond Rotation 142 4.7 Conformational Analysis of Butane 145 4.8 The Relative Stabilities of Cycloalkanes: Ring Strain 147 4.9 The Origin of Ring Strain in Cyclopropane and Cyclobutane: Angle Strain and Torsional Strain 149 4.10 Conformations of Cyclohexane 151 4.11 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Atoms 155 4.12 Disubstituted Cycloalkanes: eis-trans Isomerism 159 4.13 Bicyclic and Polycyclic Alkanes 163 4.14 Chemical Reactions of Alkanes 165 4.15 Synthesis of Alkanes and Cycloalkanes 165
4.16 Planning Organic Syntheses 769 4.17 Pheromones: Communication by Means of Chemicals 172 4.18 Some Important Terms and Concepts 173 CHAPTER 5 STEREOCHEMISTRY. CHIRAL MOLECULES 5.1 Isomerism: Constitutional Isomers and Stereoisomers 778 5.2 Enantiomers and Chiral Molecules 780 5.3 The Biological Importance of Chirality 786 5.4 Historical Origin of Stereochemistry 787 5.5 Tests for Chirality: Planes of Symmetry 788 5.6 Nomenclature of Enantiomers: The (R-S) System 789 5.7 Properties of Enantiomers: Optical Activity 193 5.8 The Origin of Optical Activity 799 5.9 The Synthesis of Enantiomers 202 5.10 Chiral Drugs 204 5.11 Molecules with More than One Stereocenter 205 5.12 Fischer Projection Formulas 270 5.13 Stereoisomerism of Cyclic Compounds 277 5.14 Relating Configurations through Reactions in which No Bonds to the Stereocenter are Broken 214 5.15 Separation of Enantiomers: Resolution 278 5.16 Compounds with Stereocenters Other than Carbon 279 5.17 Chiral Molecules that Do Not Possess a Tetrahedral Atom with Four Different Groups 279 5.18 Some Important Terms and Concepts 220 CHAPTER 6 IONIC REACTIONS NUCLEOPHILIC SUBSTITUTION AND ELIMINATION REACTIONS OF ALKYL HALIDES 6.1 Introduction 224 6.2 Physical Properties of Organic Halides 225 6.3 Nucleophilic Substitution Reactions 227 6.4 Nucleophiles 228 6.5 Leaving Groups 229 6.6 Thermodynamics and Kinetics of Chemical Reactions 229 h.l Kinetics of a Nucleophilic Substitution Reaction: An S N 2 Reaction 230 6.8 A Mechanism for the S N 2 Reaction 232 6.9 Transition State Theory: Free-Energy Diagrams 233 6.10 The Stereochemistry of S N 2 Reactions 237 6.11 The Reaction of terf-butyl Chloride with Hydroxide Ion: An S N 1 Reaction 240 6.12 A Mechanism for the S N 1 Reaction 241 6.13 Carbocations 243 6.14 The Stereochemistry of S N 1 Reactions 246 6.15 Factors Affecting the Rates of S N 1 and S N 2 Reactions 248 6.16 Org anic Synthesis: Functional Group Transformations Using S N 2 Reactions 259 6.17 Elimination Reactions of Alkyl Halides 260
XX CONTENTS 6.18 The E2 Reaction 263 6.19 The El Reaction 264 6.20 Substitution versus Elimination 265 6.21 Overall Summary 268 6.22 Some Important Terms and Concepts 269 SPECIAL TOPIC A BlOLOGICAL A/lETHYLATION. BlOCHEMICAL NUCLEOPHILIC SUBSTITUTION REACTIONS 277 SPECIAL TOPIC ß NEIGHBORING GROUP PARTICIPATION IN NUCLEOPHILIC SUBSTITUTION REACTIONS 280 CHAPTER 7 ALKENES AND ALKYNES l. PROPERTIES AND SYNTHESIS 7.1 Introduction 283 7.2 Nomenclature of Alkenes and Cycloalkenes 284 7.3 Nomenclature of Alkynes 288 7.4 Physical Properties of Alkenes and Alkynes 289 7.5 Hydrogenation of Alkenes 289 7.6 Hydrogenation: The Function of the Catalyst 291 7.7 Hydrogenation of Alkynes 293 7.8 Molecular Formulas of Hydrocarbons: The Index of Hydrogen Deficiency 294 7.9 Relative Stabilities of Alkenes 297 7.10 Cycloalkenes 301 7.11 Synthesis of Alkenes via Elimination Reactions 302 7.12 Dehydrohalogenation of Alkyl Halides 302 7.13 Dehydration of Alcohols 308 7.14 Carbocation Stability and the Transition State 311 7.15 Carbocation Stability and the Occurrence of Molecular Rearrangements 313 7.16 Alkenes by Debromination of Vicinal Dibromides 315 7.17 Summary of Methods for the Preparation of Alkenes 317 7.18 Synthesis of Alkynes by Elimination Reactions 318 7.19 The Acidity of Terminal Alkynes 320 7.20 Replacement of the Acetylenic Hydrogen Atom of Terminal Alkynes 321 CHAPTER 8 ALKENES AND ALKYNES II. ADDITION REACTIONS 8.1 Introduction: Addition to Alkenes 327 8.2 Addition of Hydrogen Halides to Alkenes: Markovnikov's Rule 329 8.3 Stereochemistry of the Ionic Addition to an Alkene 335 8.4 Addition of Sulfuric Acid to Alkenes 335 8.5 Addition of Water to Alkenes: Acid-Catalyzed Hydration 336 8.6 Addition of Bromine and Chlorine to Alkenes 339 8.7 Stereochemistry of the Addition of Halogens to Alkenes 341 8.8 Halohydrin Formation 345 8.9 Oxidations of Alkenes: Syn Hydroxylation 346 8.10 Oxidative Cleavage of Alkenes 348 8.11 Summary of Addition Reactions of Alkenes 351
CONTENTS xxi 12 Addition of Bromine and Chlorine to Alkynes 351 13 Addition of Hydrogen Halides to Alkynes 353 14 Oxidative Cleavage of Alkynes 354 15 Summary of Addition Reactions of Alkynes 354 16 Synthetic Strategies Revisited 354 17 Simple Chemical Tests for Alkanes, Alkenes, Alkynes, Alkyl Halides, and Alcohols 359 CHAPTER9 RADICAL REACTIONS 9.1 Introduction 366 9.2 Homolytic Bond Dissociation Energies 368 9.3 The Reactions of Alkanes with Halogens 373 9.4 Chlorination of Methane: Mechanism of Reaction 375 9.5 Chlorination of Methane: Energy Changes 378 9.6 Halogenation of Higher Alkanes 386 9.7 The Geometry of Alkyl Radicals 390 9.8 Reactions that Generate Tetrahedral Stereocenters 390 9.9 Radical Addition to Alkenes: The An ti-marko vnikov Addition of Hydrogen Bromide 393 9.10 Radical Polymerization of Alkenes: Chain-Growth Polymers 395 9.11 Other Important Radical Chain Reactions 397 9.12 Some Important Terms and Concepts 401 SPECIAL TOPIC c CHAIN-GROWTH POLYMERS 404 SPECIAL TOPIC D DIVALENT CARBON COMPOUNDS: CARBENES 412 CHAPTER 10 ALCOHOLS AND ETHERS 10.1 Structure and Nomenclature 415 10.2 Physical Properties of Alcohols and Ethers 418 10.3 Important Alcohols and Ethers 420 10.4 Synthesis of Alcohols from Alkenes 422 10.5 Alcohols from Alkenes through Oxymercuration-Demercuration 423 10.6 Hydroboration: Synthesis of Organoboranes 426 10.7 Alcohols from Alkenes through Hydroboration-Oxidation 429 10.8 Reactions of Alcohols 432 10.9 Alcohols as Acids 433 10.10 Conversion of Alcohols into Mesylates and Tosylates 435 10.11 Mesylates and Tosylates in S N 2 Reactions 436 10.12 Alkyl Phosphates 437 10.13 Conversion of Alcohols into Alkyl Halides 438 10.14 Alkyl Halides from the Reactions of Alcohols with Hydrogen Halides 439 10.15 Alkyl Halides from the Reactions of Alcohols with PBr 3 or SOCl 2 441 10.16 Synthesis of Ethers 443 10.17 Reactions of Ethers 447 10.18 Epoxides 448
XXÜ CONTENTS 10.19 Reactions of Epoxides 450 10.20 Anti Hydroxylation of Alkenes via Epoxides 453 10.21 Summary of Reactions of Alcohols and Ethers 454 10.22 Crown Ethers: Nucleophilic Substitution Reactions in Relatively Nonpolar Aprotic Solvents by Phase-Transfer Catalysis 458 CHAPTER 1 1 ALCOHOLS FROM CARBONYL COMPOUNDS, OXIDATION- REDUCTION AND ORGANOMETALLIC COMPOUNDS 11.1 Introduction 466 11.2 Oxidation-Reduction Reactions in Organic Chemistry 468 11.3 Alcohols by Reduction of Carbonyl Compounds 470 11.4 Oxidation of Alcohols 473 11.5 Organometallic Compounds 478 11.6 Preparation of Organolithium and Organomagnesium Compounds 479 11.7 Reactions of Organolithium and Organomagnesium Compounds 481 11.8 Alcohols from Grignard Reagents 484 CHAPTER 1 2 CONJUGATED UNSATURATED SYSTEMS 12.1 Introduction 496 12.2 Allylic Substitution and the Allyl Radical 497 12.3 The Stability of the Allyl Radical 501 12.4 The Allyl Cation 505 12.5 Summary of Rules for Resonance 506 12.6 Alkadienes and Polyunsaturated Hydrocarbons 577 12.7 1,3-Butadiene: Electron Delocalization 512 12.8 The Stability of Conjugated Dienes 514 12.9 Electrophilic Attack on Conjugated Dienes: 1,4 Addition 516 12.10 The Diels-Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes 520 FIRST REVIEW PROBLEM SET 530 CHAPTER 1 3 SPECTROSCOPIC METHODS OF STRUCTURE DETERMINATION 13.1 Introduction. The Electromagnetic Spectrum 534 13.2 Visible and Ultraviolet Spectroscopy 536 13.3 Infrared Spectroscopy 541 13.4 Nuclear Magnetic Resonance Spectroscopy 548 13.5 Nuclear Spin: The Origin of the Signal 552 13.6 Shielding and Deshielding of Protons 554 13.7 The Chemical Shift 556 13.8 Chemical Shift Equivalent and Nonequivalent Protons 558 13.9 Signal Splitting: Spin-Spin Coupling 560 13.10 Proton NMR Spectra and Rate Processes 570 13.11 Carbon-13 NMR Spectroscopy 573 13.12 Magnetic Resonance Imaging in Medicine 577
CONTENTS XXÜi SPECIAL TOPic E TWO-DIMENSIONAL (2D) NMR TECHNIQUES 585 SPECIAL TOPIC F MASS SPECTROMETRY 589 SPECIAL TOPIC G THE PHOTOCHEMISTRY OF VISION 610 CHAPTER 14 AROMATIC COMPOUNDS 14.1 Introduction 614 14.2 Nomenclature of Benzene Derivatives 615 14.3 Reactions of Benzene 617 14.4 The Kekule Structure for Benzene 679 14.5 The Stability of Benzene 620 14.6 Modern Theories of the Structure of Benzene 627 14.7 Hückel's Rule: The {An + 2) TT Electron Rule 624 14.8 Other Aromatic Compounds 633 14.9 Heterocyclic Aromatic Compounds 637 14.10 Aromatic Compounds in Biochemistry 639 14.11 Spectroscopy of Aromatic Compounds 641 14.12 A Summary of Important Terms and Concepts 646 CHAPTER 1 5 REACTIONS OF AROMATIC COMPOUNDS 15.1 Electrophilic Aromatic Substitution Reactions 655 15.2 A General Mechanism for Electrophilic Aromatic Substitution: Arenium Ions 656 15.3 Halogenation of Benzene 658 15.4 Nitration of Benzene 660 15.5 Sulfonation of Benzene 667 15.6 Friedel-Crafts Alkylation 663 15.7 Friedel-Crafts Acylation 664 15.8 Limitations of Friedel-Crafts Reactions 667 15.9 Synthetic Applications of Friedel-Crafts Acylations. The Clemmensen Reduction 669 15.10 Effect of Substituents on Reactivity and Orientation 670 15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution 674 15.12 Reactions of the Side Chain of Alkylbenzenes 684 15.13 Alkenylbenzenes 689 15.14 Synthetic Applications 697 15.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions 695 15.16 Reduction of Aromatic Compounds: The Birch Reduction 697 CHAPTER 16 ALDEHYDES AND KETONES I. NUCLEOPHILIC ADDITIONS TO THE CARBONYL GROUP 16.1 Introduction 704 16.2 Nomenclature of Aldehydes and Ketones 705 16.3 Physical Properties 706
XXJV CONTENTS 16.4 Synthesis of Aldehydes 708 16.5 Synthesis of Ketones 712 16.6 Nucleophilic Addition to the Carbon-Oxygen Double Bond 776 16.7 The Addition of Water and Alcohols: Hydrates and Acetals 720 16.8 The Addition of Derivatives of Ammonia 728 16.9 The Addition of Hydrogen Cyanide 732 16.10 The Addition of Ylides: The Wittig Reaction 734 16.11 The Addition of Organometallic Reagents: The Reformatsky Reaction 738 16.12 Oxidation of Aldehydes and Ketones 740 16.13 Chemical Analysis of Aldehydes and Ketones 742 16.14 Spectroscopic Properties of Aldehydes and Ketones 742 16.15 Summary of the Addition Reactions of Aldehydes and Ketones 745 CHAPTER 1 7 ALDEHYDES AND KETONES II. ALDOL REACTIONS 17.1 The Acidity of the a Hydrogens of Carbonyl Compounds: Enolate Ions 753 17.2 Keto and Enol Tautomers 755 17.3 Reactions via Enols and Enolate Ions 756 17.4 The Haloform Reaction 759 17.5 The Aldol Reaction: The Addition of Enolate Ions to Aldehydes and Ketones 762 17.6 Crossed Aldol Reactions 765 17.7 Cyclizations via Aldol Condensations 772 17.8 Acid-Catalyzed Aldol Condensations 773 17.9 Additions to a,/3-unsaturated Aldehydes and Ketones 774 SPECIAL TOPIC H LITHIUM ENOLATES IN ORGANIC SYNTHESIS 784 CHAPTER 1 8 CARBOXYLIC ACIDS AND THEIR DERIVATIVES. NUCLEOPHILIC SUBSTITUTION AT THE ACYL CARBON 18.1 Introduction 792 18.2 Nomenclature and Physical Properties 792 18.3 Preparation of Carboxylic Acids 803 18.4 Nucleophilic Substitutions at the Acyl Carbon 805 18.5 Acyl Chlorides 808 18.6 Carboxylic Acid Anhydrides 810 18.7 Esters 812 18.8 Amides 820 18.9 a-halo Acids: The Hell-Volhard-Zelinski Reaction 828 18.10 Derivatives of Carbonic Acid 830 18.11 Decarboxylation of Carboxylic Acids 833 18.12 Chemical Tests for Acyl Compounds 835 18.13 Summary of the Reactions of Carboxylic Acids and Their Derivatives 835 SPECIAL TOPIC i STEP-GROWTH POLYMERS 849
CONTENTS XXV CHAPTER 1 9 SYNTHESIS AND REACTIONS OF /3-DICARBONYL COMPOUNDS: MORE CHEMISTRY OF ENOLATE IONS 19.1 Introduction 859 19.2 The Claisen Condensation: The Synthesis of /3-Keto Esters 860 19.3 The Acetoacetic Ester Synthesis: Synthesis of Substituted Acetones 19.4 The Malonic Ester Synthesis: Synthesis of Substituted Acetic Acids 19.5 Further Reactions of Active Hydrogen Compounds 877 19.6 Direct Alkylation of Esters and Nitriles 879 19.7 Alkylation of 1,3-Dithianes 880 19.8 The Knoevenagel Condensation 882 19.9 Michael Additions 882 19.10 The Mannich Reaction 884 19.11 Synthesis of Enamines: Stork Enamine Reactions 885 19.12 Barbiturates 889 19.13 Summary of Important Reactions 890 CHAPTER 2 0 AMINES 20.1 Nomenclature 899 20.2 Physical Properties and Structure of Amines 901 20.3 Basicity of Amines: Amine Salts 903 20.4 Some Biologically Important Amines 910 20.5 Preparation of Amines 913 20.6 Reactions of Amines 921 20.7 Reactions of Amines with Nitrous Acid 923 20.8 Replacement Reactions of Arenediazonium Salts 926 20.9 Coupling Reaction of Arenediazonium Salts 930 20.10 Reactions of Amines with Sulfonyl Chlorides 932 20.11 The Sulfa Drugs: Sulfanilamide 934 20.12 Analysis of Amines 938 20.13 Eliminations Involving Ammonium Compounds 940 20.14 Summary of Preparations and Reactions of Amines 942 SPECIAL TOPIC J REACTIONS AND SYNTHESIS OF HETEROCYCLIC AMINES 952 CHAPTER 2 1 PHENOLS AND ARYL HALIDES: NUCLEOPHILIC AROMATIC SUBSTITUTION 21.1 Structure and Nomenclature of Phenols 963 21.2 Naturally Occurring Phenols 965 21.3 Physical Properties of Phenols 965 21.4 Synthesis of Phenols 966 21.5 Reactions of Phenols as Acids 970 21.6 Other Reactions of the O H Group of Phenols 973 21.7 Cleavage of Alkyl Aryl Ethers 973
XXVi CONTENTS 21.8 Reactions of the Benzene Ring of Phenols 974 21.9 The Claisen Rearrangement 976 21.10 Quinones 978 21.11 Aryl Halides and Nucleophilic Aromatic Substitution 980 21.12 Spectroscopic Analysis of Phenols and Aryl Halides 986 21.13 Summary of Important Reactions 986 SECOND REVIEW PROBLEM SET 993 SPECIAL TOPIC K ALKALOIDS 999 SPECIAL TOPIC L THIOLS, THIOETHERS, AND THIOPHENOLS 1006 SPECIAL TOPIC M COMPOUNDS 1012 TRANSITION METAL ORGANOMETALLIC SPECIAL TOPIC N ORGANIC HALIDES AND ORGANOMETALLIC COMPOUNDS IN THE ENVIRONMENT 1024 SPECIAL TOPIC O ELECTROCYCLIC AND CYCLOADDITION REACTIONS 1030 CHAPTER 22 CARBOHYDRATES 22.1 Introduction 1046 22.2 Monosaccharides 1049 22.3 Mutarotation 1055 22.4 Glycoside Formation 1056 22.5 Reactions of Monosaccharides 1059 22.6 Oxidation Reactions of Monosaccharides 1061 22.7 Reduction of Monosaccharides: Alditols 7067 22.8 Reactions of Monosaccharides with Phenylhydrazine: Osazones 1067 22.9 Synthesis and Degradation of Monosaccharides 1069 22.10 The D-Family of Aldoses 1071 22.11 Fischer's Proof of the Configuration of D-(+)-Glucose 1073 22.12 Disaccharides 1075 22.13 Polysaccharides 7079 22.14 Other Biologically Important Sugars 1084 22.15 Sugars That Contain Nitrogen 1085 22.16 Glycolipids and Glycoproteins of the Cell Surface 1086 22.17 Carbohydrate Antibiotics 7087 CHAPTER 23 LlPIDS 23.1 Introduction 7093 23.2 Fatty Acids and Triacylglycerols 1094 23.3 Terpenes and Terpenoids 7702 23.4 Steroids 7706 23.5 Prostaglandins 7777
CONTENTS XXVÜ 23.6 Phospholipids and Cell Membranes 1118 23.7 Waxes 1122 SPECIAL TOPIC P THIOL ESTERS AND LIPID BIOSYNTHESIS 1128 CHAPTER 24 AMINO ACIDS AND PROTEINS 24.1 Introduction 1142 24.2 Amino Acids 1143 24.3 Laboratory Synthesis of a-amino Acids 1148 24.4 Analysis of Polypeptides and Proteins 1153 24.5 Amino Acid Sequence of Polypeptides and Proteins 1156 24.6 Primary Structures of Polypeptides and Proteins 7760 24.7 Polypeptide and Protein Synthesis 1164 24.8 Secondary and Tertiary Structures of Proteins 7769 24.9 Introduction to Enzymes 7776 24.10 Lysozyme: Mode of Action of an Enzyme 1178 24.11 Serine Proteases 1181 24.12 Hemoglobin: A Conjugated Protein 1183 CHAPTER 25 NUCLEIC ACIDS AND PROTEIN SYNTHESIS 25.1 Introduction 1188 25.2 Nucleotides and Nucleosides 1188 25.3 Laboratory Synthesis of Nucleosides and Nucleotides 7792 25.4 Deoxyribonucleic Acid: DNA 7/96 25.5 RNA and Protein Synthesis 7203 25.6 Determining the Base Sequence of DNA 1211 25.7 Laboratory Synthesis of Oligonucleotides 1214 25.8 The Polymerase Chain Reaction 1216 ANSWERS TO SELECTED PROBLEMS A-l GLOSSARY G-1 INDEX i-i