Organic chemistry / 4th ed.

Table Of Contents:
Preface xxv
About the Author xxxiii

Chemical Bonding and Chemical Structure 1(42)

Introduction 1(2)

What Is Organic Chemistry? 1(1)

Emergence of Organic Chemistry 1(1)

Why Study Organic Chemistry? 2(1)

Classical Theories of Chemical Bonding 3(8)

Electrons in Atoms 3(1)

The Ionic Bond 4(1)

The Covalent Bond 5(4)

The Polar Covalent Bond 9(2)

Structures of Covalent Compounds 11(7)

Methods for Determining Molecular Geometry 12(1)

Prediction of Molecular Geometry 12(6)

Resonance Structures 18(2)

Wave Nature of the Electron 20(1)

Electronic Structure of the Hydrogen Atom 21(6)

Orbitals, Quantum Numbers, and Energy 21(2)

Spatial Characteristics of Orbitals 23(4)

Summary: Atomic Orbitals of Hydrogen 27(1)

Electronic Structures of More Complex Atoms 27(3)

Another Look at the Covalent Bond: Molecular Orbitals 30(5)

Molecular Orbital Theory 30(4)

Molecular Orbital Theory and Lewis Structures 34(1)

Hybrid Orbitals 35(8)

Bonding in Methane 35(2)

Bonding in Ammonia 37(1)

Key Ideas in Chapter 1 38(1)

Additional Problems 39(4)

Alkanes 43(39)

Hydrocarbons 43(2)

Unbranched Alkanes 45(2)

Conformations of Alkanes 47(6)

Conformation of Ethane 47(3)

Conformations of Butane 50(3)

Constitutional Isomers and Nomenclature 53(9)

Isomers 53(1)

Organic Nomenclature 54(1)

Substitutive Nomenclature of Alkanes 54(5)

Highly Condensed Structures 59(2)

Classification of Carbon Substitution 61(1)

Cycloalkanes and Skeletal Structures 62(3)

Physical Properties of Alkanes 65(5)

Boiling Points 65(3)

Melting Points 68(1)

Other Physical Properties 69(1)

Combustion and Elemental Analysis 70(3)

Reactivity of Alkanes: Combustion 70(1)

Elemental Analysis by Combustion 70(3)

Occurrence and Use of Alkanes 73(3)

Functional Groups, Compound Classes, and the ``R'' Notation 76(6)

Functional Groups and Compound Classes 76(1)

``R'' Notation 77(1)

Key Ideas in Chapter 2 78(1)

Additional Problems 78(4)

Acids and Bases: The Curved-Arrow Notation 82(29)

Lewis Acid-Base Association Reactions 82(3)

Electron-Deficient Compounds 82(1)

Reactions of Electron-Deficient Compounds with Lewis Bases 83(1)

The Curved-Arrow Notation for Lewis Acid-Base Association and Dissociation Reactions 84(1)

Electron-Pair Displacement Reactions 85(4)

Electron-Pair Displacement Reactions as Lewis Acid-Base Reactions 85(1)

The Curved-Arrow Notation for Electron-Pair Displacement Reactions 86(3)

Review of the Curved-Arrow Notation 89(2)

Use of the Curved-Arrow Notation to Represent Lewis Acid-Base Reactions 89(1)

Use of the Curved-Arrow Notation to Derive Resonance Structures 89(2)

Brnsted-Lowry Acids and Bases 91(5)

Definition of Brnsted Acids and Bases 91(1)

Strengths of Brnsted Acids 92(1)

Strengths of Brnsted Bases 93(1)

Equilibria in Acid-Base Reactions 94(2)

Free Energy and Chemical Equilibrium 96(3)

Relationship of Structure to Acidity 99(12)

The Element Effect 99(2)

The Polar Effect 101(4)

Key Ideas in Chapter 3 105(1)

Additional Problems 106(5)

Introduction to Alkenes: Structure and Reactivity 111(49)

Structure and Bonding in Alkenes 111(8)

Carbon Hybridization in Alkenes 112(4)

Cis-Trans Isomerism 116(3)

Nomenclature of Alkenes 119(7)

IUPAC Substitutive Nomenclature 119(3)

Nomenclature of Stereoisomers: The E,Z System 122(4)

Unsaturation Number 126(1)

Physical Properties of Alkenes 127(1)

Relative Stabilities of Alkene Isomers 128(5)

Heats of Formation 128(2)

Relative Stabilities of Alkene Isomers 130(3)

Addition Reactions of Alkenes 133(1)

Addition of Hydrogen Halides to Alkenes 134(8)

Regioselectivity of Hydrogen Halide Addition 134(2)

Carbocation Intermediates in Hydrogen Halide Addition 136(2)

Structure and Stability of Carbocations 138(2)

Carbocation Rearrangement in Hydrogen Halide Addition 140(2)

Reaction Rates 142(8)

The Transition State 143(2)

Multistep Reactions and the Rate-Limiting Step 145(2)

Hammond's Postulate 147(3)

Catalysis 150(10)

Catalytic Hydrogenation of Alkenes 150(2)

Hydration of Alkenes 152(2)

Enzyme Catalysis 154(1)

Key Ideas in Chapter 4 155(1)

Additional Problems 156(4)

Addition Reactions of Alkenes 160(41)

Reactions of Alkenes with Halogens 160(4)

Addition of Chlorine and Bromine 160(2)

Halohydrins 162(2)

Writing Organic Reactions 164(1)

Conversion of Alkenes Into Alcohols 165(8)

Oxymercuration-Reduction of Alkenes 165(3)

Hydroboration-Oxidation of Alkenes 168(4)

Comparison of Methods for the Synthesis of Alcohols from Alkenes 172(1)

Ozonolysis of Alkenes 173(4)

Free-Radical Addition of Hydrogen Bromide to Alkenes 177(13)

The Peroxide Effect 177(1)

Free Radicals and the ``Fishhook'' Notation 178(1)

Free-Radical Chain Reactions 179(4)

Explanation of the Peroxide Effect 183(4)

Bond Dissociation Energies 187(3)

Polymers: Free-Radical Polymerization of Alkenes 190(2)

Alkenes in the Chemical Industry 192(9)

Key Ideas in Chapter 5 195(1)

Additional Problems 195(6)

Principles of Stereochemistry 201(43)

Enantiomers, Chirality, and Symmetry 201(5)

Enantiomers and Chirality 201(3)

Asymmetric Carbon and Stereocenters 204(1)

Chirality and Symmetry 205(1)

Nomenclature of Enantiomers: The R,S System 206(3)

Physical Properties of Enantiomers: Optical Activity 209(4)

Polarized Light 209(1)

Optical Activity 210(3)

Optical Activities of Enantiomers 213(1)

Racemates 213(2)

Stereochemical Correlation 215(2)

Diastereomers 217(4)

Meso Compounds 221(3)

Enantiomeric Resolution 224(2)

Chiral Molecules Without Asymmetric Atoms 226(2)

Conformational Stereoisomers 228(3)

Stereoisomers Interconverted by Internal Rotations 228(1)

Asymmetric Nitrogen: Amine Inversion 229(2)

Fischer Projections 231(4)

The Postulation of Tetrahedral Carbon 235(9)

Key Ideas in Chapter 6 239(1)

Additional Problems 239(5)

Cyclic Compounds: Stereochemistry of Reactions 244(57)

Relative Stabilities of the Monocyclic Alkanes 244(1)

Conformations of Cyclohexane 245(8)

The Chair Conformation 245(3)

Interconversion of Chair Conformations 248(3)

Boat and Twist-Boat Conformations 251(2)

Monosubstituted Cyclohexanes: Conformational Analysis 253(4)

Disubstituted Cyclohexanes 257(8)

Cis-Trans Isomerism in Disubstituted Cyclohexanes 257(2)

Conformational Analysis 259(2)

Use of Planar Structures for Cyclic Compounds 261(1)

Stereochemical Consequences of the Chair Flip 262(3)

Cyclopentane, Cyclobutane, and Cyclopropane 265(3)

Cyclopentane 265(1)

Cyclobutane and Cyclopropane 266(2)

Bicyclic and Polycyclic Compounds 268(7)

Classification and Nomenclature 268(2)

Cis and Trans Ring Fusion 270(2)

Trans-Cycloalkenes and Bredt's Rule 272(1)

Steroids 273(2)

Relative Reactivities of Stereoisomers 275(3)

Relative Reactivities of Enantiomers 276(2)

Relative Reactivities of Diastereomers 278(1)

Reactions That Form Stereoisomers 278(5)

Reactions of Achiral Compounds That Give Enantiomeric Products 279(3)

Reactions That Give Diastereomeric Products 282(1)

Stereochemistry of Chemical Reactions 283(18)

Stereochemistry of Addition Reactions 283(1)

Stereochemistry of Substitution Reactions 284(2)

Stereochemistry of Bromine Addition 286(4)

Stereochemistry of Hydroboration-Oxidation 290(1)

Stereochemistry of Other Addition Reactions 291(2)

Key Ideas in Chapter 7 293(1)

Additional Problems 294(7)

Introduction to Alkyl Halides, Alcohols, Ethers, Thiols, and Sulfides 301(50)

Nomenclature 302(8)

Nomenclature of Alkyl Halides 302(2)

Nomenclature of Alcohols and Thiols 304(4)

Nomenclature of Ethers and Sulfides 308(2)

Structures 310(1)

Effect of Molecular Polarity and Hydrogen Bonding on Physical Properties 311(5)

Boiling Points of Ethers and Alkyl Halides 311(2)

Boiling Points of Alcohols 313(1)

Hydrogen Bonding 313(3)

Solvents in Organic Chemistry 316(6)

Classification of Solvents 316(3)

Solubility 319(3)

Applications of Solubility and Solvation Principles 322(6)

Cell Membranes and Drug Solubility 322(3)

Cation-Binding Molecules 325(3)

Acidity of Alcohols and Thiols 328(5)

Formation of Alkoxides and Mercaptides 329(2)

Polar Effects on Alcohol Acidity 331(1)

Role of the Solvent in Alcohol Acidity 332(1)

Basicity of Alcohols and Ethers 333(1)

Grignard and Organolithium Reagents 334(4)

Formation of Grignard and Organolithium Reagents 335(1)

Protonolysis of Grignard and Organolithium Reagents 336(2)

Industrial Preparation and Use of Alkyl Halides, Alcohols, and Ethers 338(13)

Free-Radical Halogenation of Alkanes 338(1)

Uses of Halogen-Containing Compounds 339(3)

Production and Use of Alcohols and Ethers 342(3)

Safety Hazards of Ethers 345(1)

Key Ideas in Chapter 8 346(1)

Additional Problems 347(4)

Chemistry of Alkyl Halides 351(57)

An Overview of Nucleophilic Substitution and -Elimination Reactions 351(5)

Nucleophilic Substitution Reactions 351(2)

β-Elimination Reactions 353(2)

Competition between Nucleophilic Substitution and -Elimination Reactions 355(1)

Equilibrium in Nucleophilic Substitution Reactions 356(1)

Reaction Rates 357(3)

Definition of Reaction Rate 357(1)

The Rate Law 358(1)

Relationship of the Rate Constant to the Standard Free Energy of Activation 359(1)

The SN2 Reaction 360(11)

Rate Law and Mechanism of the SN2 Reaction 360(2)

Stereochemistry of the SN2 Reaction 362(2)

Effect of Alkyl Halide Structure on the SN2 Reaction 364(2)

Nucleophilicity in the SN2 Reaction 366(4)

Leaving-Group Effects in the SN2 Reaction 370(1)

Summary of the SN2 Reaction 371(1)

The E2 Reaction 371(11)

Rate Law and Mechanism of the E2 Reaction 371(1)

Leaving-Group Effects on the E2 Reaction 372(1)

Deuterium Isotope Effects in the E2 Reaction 372(2)

Stereochemistry of the E2 Reaction 374(2)

Regioselectivity of the E2 Reaction 376(1)

Competition between the E2 and SN2 Reactions: A Closer Look 377(5)

Summary of the E2 Reaction 382(1)

The SN1 and E1 Reactions 382(9)

Rate Law and Mechanism of SN1 and E1 Reactions 383(1)

Rate-Limiting and Product-Determining Steps 384(2)

Reactivity and Product Distributions in SN1-E1 Reactions 386(2)

Stereochemistry of the SN1 Reaction 388(3)

Summary of the SN1 and E1 Reactions 391(1)

Summary of Substitution and Elimination Reactions of Alkyl Halides 391(3)

Carbenes and Carbenoids 394(14)

α-Elimination Reactions 394(3)

The Simmons-Smith Reaction 397(2)

Key Ideas in Chapter 9 399(1)

Additional Problems 400(8)

Chemistry of Alcohols and Thiols 408(47)

Dehydration of Alcohols 408(3)

Reactions of Alcohols with Hydrogen Halides 411(3)

Sulfonate and Inorganic Ester Derivatives of Alcohols 414(8)

Sulfonate Ester Derivatives of Alcohols 415(3)

Alkylating Agents 418(1)

Ester Derivatives of Strong Inorganic Acids 419(1)

Reactions of Alcohols with Thionyl Chloride and Phosphorus Tribromide 420(2)

Conversion of Alcohols into Alkyl Halides: Summary 422(1)

Oxidation and Reduction in Organic Chemistry 423(7)

Oxidation Numbers 423(4)

Oxidizing and Reducing Agents 427(3)

Oxidation of Alcohols 430(3)

Oxidation to Aldehydes and Ketones 430(3)

Oxidation to Carboxylic Acids 433(1)

Biological Oxidation of Ethanol 433(3)

Chemical and Stereochemical Group Equivalence 436(7)

Chemical Equivalence and Nonequivalence 437(4)

Stereochemistry of the Alcohol Dehydrogenase Reaction 441(2)

Oxidation of Thiols 443(3)

Synthesis of Alcohols 446(1)

Design of Organic Synthesis 447(8)

Key Ideas in Chapter 10 449(1)

Additional Problems 450(5)

Chemistry of Ethers, Epoxides, Glycols, and Sulfides 455(42)

Synthesis of Ethers and Sulfides 455(6)

Williamson Ether Synthesis 455(2)

Alkoxymercuration-Reduction of Alkenes 457(1)

Ethers from Alcohol Dehydration and Alkene Addition 458(3)

Synthesis of Epoxides 461(3)

Oxidation of Alkenes with Peroxycarboxylic Acids 461(2)

Cyclization of Halohydrins 463(1)

Cleavage of Ethers 464(3)

Nucleophilic Substitution Reactions of Epoxides 467(6)

Ring-Opening Reactions under Basic Conditions 467(2)

Ring-Opening Reactions under Acidic Conditions 469(3)

Reaction of Ethylene Oxide with Grignard Reagents 472(1)

Preparation and Oxidative Cleavage of Glycols 473(6)

Preparation of Glycols 474(3)

Oxidative Cleavage of Glycols 477(2)

Oxonium and Sulfonium Salts 479(2)

Reactions of Oxonium and Sulfonium Salts 479(1)

S-Adenosylmethionine: Nature's Methylating Agent 480(1)

Neighboring-Group Participation: Intramolecular Reactions 481(3)

Oxidation of Ethers and Sulfides 484(1)

The Three Fundamental Operations of Organic Synthesis 485(12)

Key Ideas in Chapter 11 487(1)

Additional Problems 488(9)

Introduction to Spectroscopy: Infrared Spectroscopy and Mass Spectrometry 497(42)

Introduction to Spectroscopy 497(5)

Electromagnetic Radiation 497(3)

Absorption Spectroscopy 500(2)

Infrared Spectroscopy 502(3)

The Infrared Spectrum 502(1)

Physical Basis of IR Spectroscopy 503(2)

Infrared Absorption and Chemical Structure 505(7)

Factors That Determine IR Absorption Position 506(3)

Factors That Determine IR Absorption Intensity 509(3)

Functional-Group Infrared Absorptions 512(5)

IR Spectra of Alkanes 512(1)

IR Spectra of Alkyl Halides 512(1)

IR Spectra of Alkenes 512(3)

IR Spectra of Alcohols and Ethers 515(2)

The Infrared Spectrometer 517(1)

Introduction to Mass Spectrometry 518(21)

Production of a Mass Spectrum 518(2)

Isotopic Peaks 520(3)

Fragmentation Mechanisms 523(4)

Odd-Electron Ions and Even-Electron Ions 527(1)

Identifying the Molecular Ion 528(1)

The Mass Spectrometer 529(2)

Key Ideas in Chapter 12 531(1)

Additional Problems 531(8)

Nuclear Magnetic Resonance Spectroscopy 539(67)

An Overview of Proton NMR Spectroscopy 539(3)

Physical Basis of NMR Spectroscopy 542(2)

The NMR Spectrum: Chemical Shift and Integral 544(13)

Chemical Shift 544(3)

Chemical Shift Scales 547(1)

Relationship of Chemical Shift to Structure 548(3)

The Number of Absorptions in an NMR Spectrum 551(3)

Counting Protons with the Integral 554(1)

Using the Chemical Shift and Integral to Determine Unknown Structures 555(2)

The NMR Spectrum: Spin-Spin Splitting 557(9)

The n + 1 Splitting Rule 557(4)

Why Splitting Occurs 561(2)

Solving Unknown Structures with NMR Spectra Involving Splitting 563(3)

Complex NMR Spectra 566(7)

Multiplicative Splitting 566(4)

Breakdown of the n + 1 Rule 570(3)

Use of Deuterium in Proton NMR 573(1)

Characteristic Functional-Group NMR Absorptions 574(7)

NMR Spectra of Alkenes 574(3)

NMR Spectra of Alkanes and Cycloalkanes 577(1)

NMR Spectra of Alkyl Halides and Ethers 578(1)

NMR Spectra of Alcohols 579(2)

NMR Spectroscopy of Dynamic Systems 581(3)

Carbon NMR 584(7)

Solving Structure Problems with Spectroscopy 591(3)

The NMR Spectrometer 594(2)

Other Uses of NMR 596(10)

Key Ideas in Chapter 13 597(1)

Additional Problems 597(9)

Chemistry of Alkynes 606(31)

Nomenclature of Alkynes 606(2)

Structure and Bonding in Alkynes 608(3)

Physical Properties of Alkynes 611(3)

Boiling Points and Solubilities 611(1)

IR Spectroscopy of Alkynes 611(1)

NMR Spectroscopy of Alkynes 612(2)

Introduction to Addition Reactions of the Triple Bond 614(1)

Conversion of Alkynes into Aldehydes and Ketones 615(5)

Hydration of Alkynes 615(3)

Hydroboration-Oxidation of Alkynes 618(2)

Reduction of Alkynes 620(3)

Catalytic Hydrogenation of Alkynes 620(1)

Reduction of Alkynes with Sodium in Liquid Ammonia 621(2)

Acidity of 1-Alkynes 623(4)

Acetylenic Anions 623(3)

Acetylenic Anions as Nucleophiles 626(1)

Organic Synthesis Using Alkynes 627(1)

Pheromones 628(2)

Occurrence and Use of Alkynes 630(7)

Key Ideas in Chapter 14 631(1)

Additional Problems 632(5)

Dienes, Resonance, and Aromaticity 637(57)

Structure and Stability of Dienes 638(4)

Structure and Stability of Conjugated Dienes 638(2)

Structure and Stability of Cumulated Dienes 640(2)

Ultraviolet Spectroscopy 642(6)

The UV Spectrum 642(3)

Physical Basis of UV Spectroscopy 645(1)

UV Spectroscopy of Conjugated Alkenes 646(2)

The Diels-Alder Reaction 648(10)

Reaction of Conjugated Dienes with Alkenes 648(4)

Effect of Diene Conformation on the Diels-Alder Reaction 652(2)

Stereochemistry of the Diels-Alder Reaction 654(4)

Addition of Hydrogen Halides to Conjugated Dienes 658(6)

1,2-and 1,4-Additions 658(1)

Allylic Carbocations 659(2)

Kinetic and Thermodynamic Control 661(3)

Diene Polymers 664(2)

Resonance 666(7)

Drawing Resonance Structures 666(1)

Relative Importance of Resonance Structures 667(3)

Use of Resonance Structures 670(3)

Introduction to Aromatic Compounds 673(21)

Benzene, a Puzzling ``Alkene'' 673(2)

Structure of Benzene 675(2)

Stability of Benzene 677(1)

Aromaticity and the Huckel 4n + 2 Rule 677(6)

Antiaromatic Compounds 683(1)

Key Ideas in Chapter 15 684(1)

Additional Problems 685(9)

Chemistry of Benzene and Its Derivatives 694(49)

Nomenclature of Benzene Derivatives 694(3)

Physical Properties of Benzene Derivatives 697(1)

Spectroscopy of Benzene Derivatives 698(6)

IR Spectroscopy 698(1)

NMR Spectroscopy 699(3)

CMR Spectroscopy 702(1)

UV Spectroscopy 703(1)

Electrophilic Aromatic Substitution Reactions of Benzene 704(12)

Halogenation of Benzene 704(2)

Electrophilic Aromatic Substitution 706(2)

Nitration of Benzene 708(1)

Sulfonation of Benzene 709(1)

Friedel-Crafts Alkylation of Benzene 710(3)

Friedel-Crafts Acylation of Benzene 713(3)

Electrophilic Aromatic Substitution Reactions of Substituted Benzenes 716(15)

Directing Effects of Substituents 716(7)

Activating and Deactivating Effects of Substituents 723(4)

Use of Electrophilic Aromatic Substitution in Organic Synthesis 727(4)

Hydrogenation of Benzene Derivatives 731(1)

Source and Industrial Use of Aromatic Hydrocarbons 732(11)

Key Ideas in Chapter 16 735(1)

Additional Problems 735(8)

Allylic and Benzylic Reactivity 743(32)

Reactions Involving Allylic and Benzylic Carbocations 744(4)

Reactions Involving Allylic and Benzylic Radicals 748(5)

Reactions Involving Allylic and Benzylic Anions 753(4)

Allylic Grignard Reagents 754(2)

E2 Eliminations Involving Allylic or Benzylic Hydrogens 756(1)

Allylic and Benzylic SN2 Reactions 757(1)

Benzylic Oxidation of Alkylbenzenes 758(1)

Terpenes 759(16)

The Isoprene Rule 759(4)

Biosynthesis of Terpenes 763(3)

Key Ideas in Chapter 17 766(1)

Additional Problems 767(8)

Chemistry of Aryl Halides, Vinylic Halides, and Phenols: Transition-Metal Catalysis 775(61)

Lack of Reactivity of Vinylic and Aryl Halides Under SN2 Conditions 776(2)

Elimination Reactions of Vinylic Halides 778(1)

Lack of Reactivity of Vinylic and Aryl Halides Under SN1 Conditions 779(2)

Nucleophilic Substitution Reactions of Aryl Halides 781(7)

Nucleophilic Aromatic Substitution 781(3)

Substitution by Elimination-Addition: Benzyne 784(3)

Summary: Nucleophilic Substitution Reactions of Aryl Halides 787(1)

Transition-Metal Catalyzed Coupling Reactions 788(19)

Transition Metals and Their Complexes 788(4)

Oxidation State 792(1)

The dn Notation 792(1)

Electron Counting: The 16-and 18-Electron Rules 793(3)

Fundamental Reactions of Transition-Metal Complexes 796(6)

The Heck Reaction 802(3)

Other Examples of Transition-Metal Catalyzed Reactions 805(2)

Acidity of Phenols 807(4)

Resonance and Polar Effects on the Acidity of Phenols 807(2)

Formation and Use of Phenoxides 809(2)

Oxidation of Phenols to Quinones 811(4)

Electrophilic Aromatic Substitution Reactions of Phenols 815(4)

Reactivity of the Aryl-Oxygen Bond 819(4)

Lack of Reactivity of the Aryl-Oxygen Bond in SN1 and SN2 Reactions 819(1)

Substitution at the Aryl-Oxygen Bond: The Stille Reaction 820(3)

Industrial Preparation and Use of Phenol 823(13)

Key Ideas in Chapter 18 824(1)

Additional Problems 825(11)

Chemistry of Aldehydes and Ketones: Carbonyl-Addition Reactions 836(59)

Nomenclature of Aldehydes and Ketones 838(4)

Common Nomenclature 838(2)

Substitutive Nomenclature 840(2)

Physical Properties of Aldehydes and Ketones 842(1)

Spectroscopy of Aldehydes and Ketones 843(8)

IR Spectroscopy 843(2)

Proton NMR Spectroscopy 845(1)

Carbon NMR Spectroscopy 846(1)

UV Spectroscopy 847(2)

Mass Spectrometry 849(2)

Synthesis of Aldehydes and Ketones 851(1)

Introduction to Aldehyde and Ketone Reactions 851(1)

Basicity of Aldehydes and Ketones 852(3)

Reversible Addition Reactions of Aldehydes and Ketones 855(6)

Mechanisms of Carbonyl-Addition Reactions 855(2)

Equilibria in Carbonyl-Addition Reactions 857(3)

Rates of Carbonyl-Addition Reactions 860(1)

Reduction of Aldehydes and Ketones to Alcohols 861(4)

Reactions of Aldehydes and Ketones with Grignard and Related Reagents 865(3)

Acetals and Their Use as Protecting Groups 868(6)

Preparation and Hydrolysis of Acetals 868(4)

Protecting Groups 872(2)

Reactions of Aldehydes and Ketones with Amines 874(5)

Reaction with Primary Amines and Other Monosubstituted Derivatives of Ammonia 874(3)

Reaction with Secondary Amines 877(2)

Reduction of Carbonyl Groups to Methylene Groups 879(2)

The Wittig Alkene Synthesis 881(3)

Oxidation of Aldehydes to Carboxylic Acids 884(2)

Manufacture and Use of Aldehydes and Ketones 886(9)

Key Ideas in Chapter 19 887(1)

Additional Problems 888(7)

Chemistry of Carboxylic Acids 895(39)

Nomenclature of Carboxylic Acids 895(5)

Common Nomenclature 895(3)

Substitutive Nomenclature 898(2)

Structure and Physical Properties of Carboxylic Acids 900(2)

Spectroscopy of Carboxylic Acids 902(2)

IR Spectroscopy 902(1)

NMR Spectroscopy 902(2)

Acid-Base Properties of Carboxylic Acids 904(4)

Acidity of Carboxylic and Sulfonic Acids 904(3)

Basicity of Carboxylic Acids 907(1)

Fatty Acids, Soaps, and Detergents 908(2)

Synthesis of Carboxylic Acids 910(1)

Introduction to Carboxylic Acid Reactions 911(2)

Conversion of Carboxylic Acids into Esters 913(5)

Acid-Catalyzed Esterification 913(3)

Esterification by Alkylation 916(2)

Conversion of Carboxylic Acids into Acid Chlorides and Anhydrides 918(4)

Synthesis of Acid Chlorides 918(2)

Synthesis of Anhydrides 920(2)

Reduction of Carboxylic Acids to Primary Alcohols 922(1)

Decarboxylation of Carboxylic Acids 923(11)

Key Ideas in Chapter 20 926(1)

Additional Problems 926(8)

Chemistry of Carboxylic Acid Derivatives 934(63)

Nomenclature and Classification of Carboxylic Acid Derivatives 934(6)

Esters and Lactones 934(2)

Acid Halides 936(1)

Anhydrides 936(1)

Nitriles 937(1)

Amides, Lactams, and Imides 937(2)

Nomenclature of Substituent Groups 939(1)

Carbonic Acid Derivatives 939(1)

Structures of Carboxylic acid Derivatives 940(2)

Physical Properties of Carboxylic Acid Derivatives 942(2)

Esters 942(1)

Anhydrides and Acid Chlorides 942(1)

Nitriles 943(1)

Amides 943(1)

Spectroscopy of Carboxylic Acid Derivatives 944(5)

IR Spectroscopy 944(1)

NMR Spectroscopy 945(4)

Basicity of Carboxylic Acid Derivatives 949(1)

Introduction to Reactions of Carboxylic Acid Derivatives 950(1)

Hydrolysis of Carboxylic Acid Derivatives 951(12)

Hydrolysis of Esters 951(3)

Hydrolysis of Amides 954(1)

Hydrolysis of Nitriles 955(2)

Hydrolysis of Acid Chlorides and Anhydrides 957(1)

Mechanisms and Reactivity in Nucleophilic Acyl Substitution Reactions 958(5)

Reactions of Carboxylic Acid Derivatives with Nucleophiles 963(6)

Reactions of Acid Chlorides with Nucleophiles 963(3)

Reactions of Anhydrides with Nucleophiles 966(1)

Reactions of Esters with Nucleophiles 967(2)

Reduction of Carboxylic Acid Derivatives 969(8)

Reduction of Esters to Primary Alcohols 969(1)

Reduction of Amides to Amines 970(2)

Reduction of Nitriles to Primary Amines 972(2)

Reduction of Acid Chlorides to Aldehydes 974(2)

Relative Reactivities of Carbonyl Compounds 976(1)

Reactions of Carboxylic Acid Derivatives with Organometallic Reagents 977(3)

Reaction of Esters with Grignard Reagents 977(1)

Reaction of Acid Chlorides with Lithium Dialkylcuprates 978(2)

Synthesis of Carboxylic Acid Derivatives 980(2)

Use and Occurrence of Carboxylic Acids and Their Derivatives 982(15)

Nylon and Polyesters 982(2)

Waxes, Fats, and Phospholipids 984(2)

Key Ideas in Chapter 21 986(1)

Additional Problems 987(10)

Chemistry of Enolate Ions, Enols, and α,β-Unsaturated Carbonyl Compounds 997(72)

Acidity of Carbonyl Compounds 998(5)

Formation of Enolate Anions 998(3)

Introduction to Reactions of Enolate Ions 1001(2)

Enolization of Carbonyl Compounds 1003(4)

α-Halogenation of Carbonyl Compounds 1007(7)

Acid-Catalyzed α-Halogenation 1007(2)

Halogenation of Aldehydes and Ketones in Base: The Haloform Reaction 1009(2)

α-Bromination of Carboxylic Acids 1011(1)

Reactions of a-Halo Carbonyl Compounds 1012(2)

Aldol Addition and Aldol Condensation 1014(9)

Base-Catalyzed Aldol Reactions 1014(2)

Acid-Catalyzed Aldol Condensation 1016(2)

Special Types of Aldol Reaction 1018(2)

Synthesis with the Aldol Condensation 1020(3)

Condensation Reactions Involving Ester Enolate Ions 1023(9)

Claisen Condensation 1024(3)

Dieckmann Condensation 1027(1)

Crossed Claisen Condensation 1027(2)

Synthesis with the Claisen Condensation 1029(3)

Biosynthesis of Fatty Acids 1032(3)

Alkylation of Ester Enolate Ions 1035(8)

Malonic Ester Synthesis 1036(2)

Direct Alkylation of Enolate Ions Derived from Monoesters 1038(2)

Acetoacetic Ester Synthesis 1040(3)

Conjugate-Addition Reactions 1043(9)

Conjugate Addition to α,β-Unsaturated Carbonyl Compounds 1043(4)

Conjugate Addition Reactions versus Carbonyl-Group Reactions 1047(2)

Conjugate Addition of Enolate Ions 1049(3)

Reduction of α,β-Unsaturated Carbonyl Compounds 1052(1)

Reactions of α,β-Unsaturated Carbonyl Compounds with Organometallic Reagents 1053(2)

Addition of Organolithium Reagents to the Carbonyl Group 1053(1)

Conjugate Addition of Lithium Dialkylcuprate Reagents 1054(1)

Organic Synthesis with Conjugate-Addition Reactions 1055(14)

Key Ideas in Chapter 22 1057(1)

Additional Problems 1058(11)

Chemistry of Amines 1069(51)

Nomenclature of Amines 1070(2)

Common Nomenclature 1070(1)

Substitutive Nomenclature 1070(2)

Structure of Amines 1072(1)

Physical Properties of Amines 1073(1)

Spectroscopy of Amines 1074(2)

IR Spectroscopy 1074(1)

NMR Spectroscopy 1074(1)

Mass Spectrometry 1075(1)

Basicity and Acidity of Amines 1076(7)

Basicity of Amines 1076(1)

Substituent Effects on Amine Basicity 1076(5)

Separations Using Amine Basicity 1081(1)

Acidity of Amines 1082(1)

Summary of Acidity and Basicity 1082(1)

Quaternary Ammonium Salts 1083(1)

Alkylation and Acylation Reactions of Amines 1083(5)

Direct Alkylation of Amines 1084(1)

Reductive Amination 1085(3)

Acylation of Amines 1088(1)

Hofmann Elimination of Quaternary Ammonium Hydroxides 1088(4)

Aromatic Substitution Reactions of Aniline Derivatives 1092(2)

Diazotization: Reactions of Diazonium Ions 1094(6)

Formation and Substitution Reactions of Diazonium Salts 1094(3)

Aromatic Substitution with Diazonium Ions 1097(2)

Reactions of Secondary and Tertiary Amines with Nitrous Acid 1099(1)

Synthesis of Amines 1100(8)

Gabriel Synthesis of Primary Amines 1100(2)

Reduction of Nitro Compounds 1102(1)

Curtius and Hofmann Rearrangements 1103(4)

Synthesis of Amines: Summary 1107(1)

Use and Occurrence of Amines 1108(12)

Industrial Use of Amines and Ammonia 1108(1)

Naturally Occurring Amines 1108(2)

Key Ideas in Chapter 23 1110(1)

Additional Problems 1111(9)

Chemistry of Naphthalene and the Aromatic Heterocycles 1120(52)

Chemistry of Naphthalene 1122(6)

Physical Properties and Structure 1122(1)

Nomenclature 1122(2)

Electrophilic Substitution Reactions 1124(4)

Introduction to the Aromatic Heterocycles 1128(7)

Nomenclature 1128(2)

Structure and Aromaticity 1130(3)

Basicity and Acidity of the Nitrogen Heterocycles 1133(2)

Chemistry of Furan, Pyrrole, and Thiophene 1135(5)

Electrophilic Aromatic Substitution 1135(3)

Addition Reactions of Furan 1138(1)

Side-Chain Reactions 1139(1)

Synthesis of Indoles 1140(4)

Fischer Indole Synthesis 1140(2)

Reissert Indole Synthesis 1142(2)

Chemistry of Pyridine and Quinoline 1144(17)

Electrophilic Aromatic Substitution 1144(3)

Nucleophilic Aromatic Substitution 1147(4)

Pyridinium Salts and Their Reactions 1151(1)

Side-Chain Reactions of Pyridine Derivatives 1152(1)

Pyridinium Ions in Biology: Pyridoxal Phosphate 1153(6)

Skraup Synthesis of Quinolines 1159(2)

Occurrence of Heterocyclic Compounds 1161(11)

Key Ideas in Chapter 24 1162(1)

Additional Problems 1163(9)

Pericyclic Reactions 1172(43)

Molecular Orbitals of Conjugated -Electron Systems 1175(8)

Molecular Orbitals of Conjugated Alkenes 1175(4)

Molecular Orbitals of Conjugated Ions and Radicals 1179(3)

Excited States 1182(1)

Electrocyclic Reactions 1183(5)

Thermal Electrocyclic Reactions 1183(2)

Excited-State (Photochemical) Electrocyclic Reactions 1185(1)

Selection Rules and Microscopic Reversibility 1186(2)

Cycloaddition Reactions 1188(4)

Sigmatropic Reactions 1192(11)

Classification and Stereochemistry 1192(8)

[3,3] Sigmatropic Reactions 1200(1)

Summary: Selection Rules for Sigmatropic Reactions 1201(2)

Summary of the Pericyclic Selection Rules 1203(1)

Fluxional Molecules 1204(1)

Formation of Vitamin D 1205(10)

Key Ideas in Chapter 25 1207(1)

Additional Problems 1208(7)

Amino Acids, Peptides, and Proteins 1215(76)

Nomenclature of Amino Acids and Peptides 1216(4)

Nomenclature of Amino Acids 1216(1)

Nomenclature of Peptides 1217(3)

Stereochemistry of the α-Amino Acids 1220(1)

Acid-Base Properties of Amino Acids and Peptides 1221(8)

Zwitterionic Structures of Amino Acids and Peptides 1221(2)

Isoelectric Points of Amino Acids and Peptides 1223(4)

Separations of Amino Acids and Peptides Using Acid-Base Properties 1227(2)

Synthesis and Enantiomeric Resolution of -Amino Acids 1229(3)

Alkylation of Ammonia 1229(1)

Alkylation of Aminomalonate Derivatives 1230(1)

Strecker Synthesis 1230(2)

Enantiomeric Resolution of α-Amino Acids 1232(1)

Acylation and Esterification Reactions of Amino Acids 1232(1)

Determination of Peptide Structure 1233(13)

Hydrolysis of Peptides: Amino Acid Analysis 1233(4)

Sequential Degradation of Peptides 1237(3)

Specific Cleavage of Peptides 1240(6)

Solid-Phase Peptide Synthesis 1246(9)

Combinatorial Chemistry 1255(6)

The Premise of Combinatorial Chemistry 1255(1)

An Example of Combinatorial Chemistry 1256(4)

Some Fundamental Ideas of Combinatorial Chemistry 1260(1)

Structures of Peptides and Proteins 1261(9)

Primary Structure 1261(1)

Secondary Structure 1262(3)

Tertiary and Quaternary Structure 1265(5)

Enzymes: Biological Catalysts 1270(9)

The Catalytic Action of Enzymes 1270(4)

Enzymes as Drug Targets: Enzyme Inhibition 1274(5)

Occurrence of Peptides and Proteins 1279(12)

Key Ideas in Chapter 26 1280(1)

Additional Problems 1281(10)

Carbohydrates and Nucleic Acids 1291

Classification and Properties of Carbohydrates 1292

Structures of the Monosaccharides 1293

Stereochemistry and Configuration 1293

Cyclic Structures of the Monosaccharides 1297

Mutarotation of Carbohydrates 1302

Base-Catalyzed Isomerization of Aldoses and Ketoses 1306

Glycosides 1308

Ether and Ester Derivatives of Carbohydrates 1311

Oxidation and Reduction Reactions of Carbohydrates 1314

Oxidation to Aldonic Acids 1314

Oxidation to Aldaric Acids 1315

Periodate Oxidation 1317

Reduction to Alditols 1318

Kiliani-Fischer Synthesis 1319

Proof of Glucose Stereochemistry 1320

Which Diastereomer? The Fischer Proof 1320

Which Enantiomer? The Absolute Configuration of D-(+)-Glucose 1325

Disaccharides and Polysaccharides 1326

Disaccharides 1326

Polysaccharides 1329

Nucleosides, Nucleotides, and Nucleic Acids 1333

Nucleosides and Nucleotides 1333

Structures of DNA and RNA 1336

DNA, RNA, and the Genetic Code 1341

Role of DNA and RNA in Protein Synthesis 1341

DNA Modification and Chemical Carcinogenesis 1343

Key Ideas in Chapter 27 1345

Additional Problems 1346
Appendixes A-1

Appendix I: Substitutive Nomenclature of Organic Compounds A-1

Appendix II: Infrared Absorptions of Organic Compounds A-2

Appendix III: Proton NMR Chemical Shifts in Organic Compounds A-5

Protons within Functional Groups A-5

Protons Adjacent to Functional Groups A-5

Appendix IV: 13C NMR Chemical Shifts in Organic Compounds A-7

Chemical Shifts of Carbons within Functional Groups A-7

Chemical Shifts of Carbons Adjacent to Functional Groups A-7

Appendix V: Summary of Synthetic Methods A-8

Appendix VI: Reactions Used to Form Carbon-Carbon Bonds A-13

Appendix VII: Typical Acidities and Basicities of Organic Functional Groups A-14

Acidities of Groups That Ionize to Give Anionic Conjugate Bases A-14

Basicities of Groups That Protonate to Give Cationic Conjugate Acids A-15
Credits C-1
Index I-1