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(NOTE: Each chapter concludes with Key Terms, Problems, and a Summary.)I. AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY 1. Electronic Structureand Bonding--Acids and Bases. The Structure of an Atom. The Distribution ofElectrons in an Atom. Ionic, Covalent, and Polar Bonds. Representation of aStructure. Atomic Orbitals. An Introduction to Molecular Orbital Theory.Bonding in Methane and Ethane: Single Bonds. Bonding in Ethane: A DoubleBond. Bonding in Ethyne: A Triple Bond. Bonding in the Methyl Cation, theMethyl Radical, and the Methyl Anion. Bonding in Water. Bonding in Ammoniaand the Ammonium Ion. Bonding in the Hydrogen Halides. Summary: OrbitalHybridization, Bond Lengths, Bond Strengths, and Bond Angles. Dipole Momentsof Molecules. An Introduction to Acids and Bases. Organic Acids and Bases; pKa and pH. The Effect of Structure on pK a. An Introduction to DelocalizedElectrons and Resonance. The Effect of pH on the Structure of an OrganicCompound. Lewis Acids and Bases.2. An Introduction to Organic Compounds:Nomenclature, Physical Properties, and Representation of Structure.Nomenclature of Alkyl Substituents. Nomenclature of Alkanes. Nomenclature ofCycloalkanes. Nomenclature of Alkyl Halides. Nomenclature of Ethers.Nomenclature of Alcohols. Nomenclature of Amines. Structures of AlkylHalides, Alcohols, Ethers, and Amines. Physical Properties of Alkanes, AlkylHalides, Alcohols, Ethers, and Amines. Conformations of Alkanes: RotationAbout Carbon-Carbon Bonds. Cycloalkanes: Ring Strain. Conformations ofCyclohexane. Conformations of Monosubstituted Cyclohexanes. Conformations ofDisubstituted Cyclohexanes. Conformations of Fused Rings.II. HYDROCARBONS,STEREOCHEMISTRY, AND RESONANCE. 3. Alkenes: Structure, Nomenclature, and anIntroduction to Reactivity--Thermodynamics and Kinetics. Molecular Formulaand the Degree of Unsaturation. Nomenclature of Alkenes. The Structure ofAlkenes. Cis- Trans Isomerism. The E,Z System of Nomenclature. How AlkenesReact. Curved Arrows. Thermodynamics and Kinetics.4. Reactions of Alkenes.Addition of Hydrogen Halides. Carbocation Stability. The Structure of theTransition State. Regioselectivity of Electophilic Addition Reactions.Addition of Water and Addition of Alcohols. Rearrangement of Carbocations.Addition of Halogens. Oxymercuration-Reduction andAlkoxymercuration-Reduction. Addition of Borane: Hydroboration-Oxidation.Addition of Radicals. The Relative Stabilities of Radicals. Addition ofHydrogen. The Relative Stabilities of Alkenes. Reactions and Synthesis.5.Stereochemistry: The Arrangement of Atoms in Space; The Stereochemistry ofAddition Reactions. Cis-Trans Isomers. Chirality. Asymmetric Carbon,Chirality Centers, and Stereocenters. Isomers with One Asymmetric Carbon.Drawing Enantiomers. Naming Enantiomers: The R, S System of Nomenclature.Optical Activity. Optical Purity and Enantiomeric Excess. Isomers with MoreThan One Asymmetric Carbon. Meso Compounds. The R, S System of Nomenclaturefor Isomers with More Than One Asymmetric Carbon. Reactions of Compounds thatContain an Asymmetric Carbon. The Absolute Configuration of (+)-Glyceraldehyde. Separating Enantiomers. Discrimination of Enantiomers byBiological Molecules. Enantiotopic Hydrogens, Diastereotopic Hydrogens, andProchiral Carbons. Nitrogen and Phosphorus Asymmetric Carbons.Stereochemistry of Reactions: Regioselective, Stereoselective, andStereospecific Reactions. Stereochemistry of Electrophilic Addition Reactionsof Alkenes. Stereochemistry of Enzyme-Catalyzed Reactions.6. Reactions ofAlkynes--Introduction to Multistep Synthesis. Nomenclature of Alkynes.Physical Properties of Unsaturated Hydrocarbons. The Structure of Alkynes.How Alkynes React. Addition of Hydrogen Halides and Addition of Halogens.Addition of Water. Addition of Borane: Hydroboration-Oxidation. Addition ofHydrogen. Acidity of a Hydrogen Bonded to an SP Hybridized Carbon. SynthesisUsing Acetylide Ions. Designing a Synthesis I: An Introduction to MultistepSynthesis. Commercial Use of Ethyne.7. Electron Delocalization andResonance--More About Molecular Orbital Theory. Delocalized Electrons: theStructure of Benzene. The Bonding In Benzene. Resonance Contributors and theResonance Hybrid. Drawing Resonance Contributors. Predicted Stabilites ofResonance Contributors. Resonance Energy. Stability of Allylic and BenzylicCations. Stability of Allylic and Benzylic Radicals. Some ChemicalConsequences of Electron Delocalization. The Effect of ElectronDelocalization on pK a. A Molecular Orbital Description of Stability.8.Reactions of Dienes--Ultraviolet/Visible Spectroscopy. Nomenclature ofAlkenes with More than One Functional Group. Configurational Isomers ofDienes. Relative Stabilities of Dienes. How Dienes React. ElectrophilicAddition Reactions of Isolated Dienes. Electrophilic Addition Reactions ofConjugated Dienes. Thermodynamic Versus Kinetic Control of Reactions. TheDiels-Alder Reaction: A 1,4-Addition Reaction. Ultraviolet and VisibleSpectroscopy. The Beer-Lambert Law. Effect of Conjugation on Imax. TheVisible Spectrum and Color. Uses of UV/VIS Spectroscopy.III. SUBSTITUTION ANDELIMINATION REACTIONS. 9. Reactions of Alkanes: Radicals. The Low Reactivityof Alkanes. Chlorination and Bromination of Alkanes. Factors that DetermineProduct Distribution. The Reactivity-Selectivity Principle. RadicalSubstitution of Benzylic and Allylic Hydrogens. Stereochemistry of RadicalSubstitution Reactions. Reactions of Cyclic Compounds. Radicals Reactions inBiological Systems. Radicals and Stratospheric Ozone.10. SubstitutionReactions of Alkyl Halides. Reactivity Considerations. The Mechanism of SN2Reactions. The SN2 Reaction. The Reversibility of an SN2 Reaction. TheMechanism of SN1 Reaction. The SN1 Reaction. The Stereochemistry of SN2 andSN1 Reactions. Benzylic Halides, Allylic Halides, Vinylic Halides, and ArylHalides. Competition Between SN2 and SN1 Reactions. The Role of the Solventin SN1 and SN1 Reactions. Biological Methylating Reagents.11. EliminationReactions of Alkyl Halides; Competition Between Substitution and Elimination.The E2 Reaction. The Regioselectivity of the E2 Reaction. The E1 Reaction.Competition Between E2 and E1 Reactions. Stereochemistry of E2 and E1Reactions. Elimination from Cyclic Compounds. A Kinetic Isotope Effect.Competition Between Substitution and Elimination. Substitution andElimination Reactions in Synthesis. Consecutive E2 Elimination Reactions.Intermolecular versus Intramolecular Reactions. Designing a Synthesis II:Approaching the Problem. 12. Reactions of Alcohols, Ethers, Epoxides, andSulfur-Containing Compounds--Organometallic Compounds. SubstitutionReactions of Alcohol. Amines Do Not Undergo Substitution Reactions. OtherMethods Used to Convert Alcohols Into Alkyl Halides. Converting Alcohols intoSulfonates. Dehydration of Alcohols. Substitution Reactions of Ethers.Reactions of Epoxides. Arene Oxides. Crown Ethers. Thiols, Sulfides, andSulfonium Salts. Organometallic Compounds. Coupling Reactions.IV.IDENTIFICATION OF ORGANIC COMPOUNDS. 13. Mass Spectrometry and InfraredSpectroscopy. Mass Spectrometry. The Mass Spectrum. Fragmentation. Isotopesin Mass Spectrometry. Determination of Molecular Formulas: High-ResolutionMass Spectrometry. Fragmentation at Functional Groups. Spectroscopy and theElectromagnetic Spectrum. Infrared Spectroscopy. Infrared Absorption Bands.Intensity of Absorption Bands. Position of Absorption Bands. C-H AbsorptionBands. Shape of Absorption Bands. Absence of Absorption Bands. InfraredInactive Vibrations. Identifying Infrared Spectra. 14. NMR Spectroscopy.Introduction to NMR Spectroscopy. Fourier Transform NMR. Shielding. TheNumber of Signals in the 1H NMR Spectrum. The Chemical Shift. The RelativePosition of 1H NMR Signals. Characteristic Values of Chemical Shifts.Integration of the NMR Signals. Diamagnetic Anisotropy. Splitting of theSignals. More Examples of 1H NMR Spectra. Coupling Constants. SplittingDiagrams. Time Dependence of NMR Spectroscopy. Protons Bonded to Oxygen andNitrogen. Use of Deuterium in 1H NMR Spectroscopy. Resolution of 1H NMRSpectra. 13C NMR Spectroscopy. DEPT 13C NMR Spectra. Two-Dimensional NMRSpectroscopy. Magnetic Resonance Imaging.V. AROMATIC COMPOUNDS. 15.Aromaticity--Reactions of Benzene. Criteria for Aromaticity. AromaticHydrocarbons. Aromatic Heterocyclic Compounds. Some Chemical Consequences ofAromaticity. Antiaromaticity. A Molecular Orbital Description of Aromaticityand Antiaromaticity. Nomenclature of Monosubstituted Benzenes. How BenzeneReacts. General Mechanism for Electrophilic Aromatic Substitution Reactions.Halogenation of Benzene. Nitration of Benzene. Sulfonation of Benzene.Friedel-Crafts Alkylation of Benzene. Friedel-Crafts Alkylations of Benzene.Alkylations of Benzene by Acylation-Reduction.16. Reactions of SubstitutedBenzenes. Nomenclature of Diubstituted and Polysubstituted Benzenes.Reactions of Substituents on Benzene. The Effect of Substituents onReactivity. The Effect of Substituents on Orientation. The Effect ofSubstituents on pK a. The Ortho/Para Ratio. Additional ConsiderationsRegarding Substituent Effects. Designing a Synthesis III: Synthesis ofMonosubstituted and Disubstituted Benzenes. Synthesis of TrisubstitutedBenzenes. Synthesis of Substituted Benzenes Using Arenediazonium Salts. TheArenediazonium Ion as an Electrophile. Mechanism for the Reaction of Amineswith Nitrous Acid. Nucleophilic Aromatic Substitution Reactions. Benzyne.Polycyclic Benzenoid Hydrocarbons. Electrophilic Substitution Reactions ofNaphthalene and Substituted Naphthalenes.VI. CARBONYL COMPOUNDS. 17. CarbonylCompounds I: Nucleophilic Acyl Substitution. Nomenclature. Structures ofCarboxylic Acids and Carboxylic Acid Derivatives. Physical Properties ofCarbonyl Compounds. Naturally Occurring Carboxylic Acids and Carobxylic AcidDerivatives. How Class I Carbonyl Compounds React. Relative Reactivities ofCarboxylic Acids, Acyl Halides, and Carboxylic Acid Derivatives. GeneralMechanism for Nucleophilic Acyl Substitution Reactions. Reactions of AcylHalides. Reactions of Acid Anhydrides. Reactions of Esters. Acid-CatalyzedEster Hydrolysis. Hydroxide-Ion-Promotes Ester Hydrolysis. Soaps, Detergents,and Micelles. Reactions of Carboxylic Acids. Reactions of Amides.Acid-Catalyzed Hydrolysis of Amides. Hydrolysis of an Imide- The GabrielSynthesis. Hydrolysis of Nitriles. Designing a Synthesis IV: The Synthesis ofCyclic Compounds. Synthesis of Carboxylic Acid Derivatives. DicarboxylicAcids and Their Derivatives.18. Carbonyl Compounds II: Nucleophilic AcylAddition, Nucleophilic Acyl Substitution, and NucleophilicAddition-Elimination--Reactions of <F128>a, <F128>b-Unsaturated CarbonylCompounds. Nomenclature. Relative Reactivities of Carbonyl Compounds. HowAldeyhdes and Ketones React. Reactions of Carbonyl Compounds with CarbonNucleophiles. Reactions of Carbonyl Compounds with Hydride Ion. Reactions ofAldehydes and Ketones with Nitrogen Nucleophiles. Reactions of Aldehydes andKetones with Oxygen Nucleophiles. Protecting Groups. Addition of SulfurNucleophiles. The Wittig Reaction. Stereochemistry of Nucleophilic AdditionReactions: Re and Si Faces. Designing a Synthesis V: The Synthesis of CyclicCompounds. Nucleophilic Addition to -Unsaturated Aldehydes and Ketones:Direct Addition Versus Conjugate Addition. Nucleophilic Addition to <F128>a,<F128>b-Unsaturated Carboxylic Acid Derivatives. Enzyme-Catalyzed Additionsto <F128>a, <F128>b-Unsaturated Carbonyl Compounds.19. Carbonyl CompoundsIII: Reactions at the <F128>a-Carbon. Acidity of <F128>a-Hydrogens.Keto-Enol Tautomerism. How Enols and Enolate Ions React. Halogenation of the<F128>a-Carbon of Aldehydes and Ketones. Halogenation of the <F128>a-Carbonof Carboxylic Acids: The Hell-Volhard-Zelinski Reaction. <F128>a-HalogenatedCarbonyl Compounds in Synthesis. Using LDA to Form an Enolate. Alkylation ofthe <F128>a-Carbon of Carbonyl Compounds. Alkylation and Acylation of the<F128>a-Carbon via an Enamine Intermediate. Alkylation of the <F128>b-Carbon:The Michael Reaction. The Aldol Addition. Dehydration of Aldol AdditionProducts: Formation of <F128>a, <F128>b-Unsaturated Aldehydes and Ketones.The Mixed Aldol Addition. The Claisen Condensation. The Mixed ClaisenCondensation. Intramolecular Condensation and Addition Reactions.Decarboxylation of 3-Oxocarboxylic Acids. The Malonic Ester Synthesis:Synthesis of Carboxylic Acids. The Acetoacetic Ester Synthesis: Synthesis ofMethyl Ketones. Designing a Synthesis VI: Making New Carbon-Carbon Bonds.Reactions at the <F128>a-Carbon in Biological Systems.VII. BIOORGANICCOMPOUNDS. 20. More About Oxidation-Reduction Reactions. ReductionReactions. Oxidation of Alcohols. Oxidation of Aldehydes and Ketones.Oxidation of Alkenes with Peroxyacids. Hydroxylation of Alkenes. OxidativeCleavage of 1,2-Diols. Oxidative Cleavage of Alkenes: Ozonolysis. OxidativeCleavage of Alkynes. Designing a Synthesis VII: Functional GroupInterconversion. Biological Oxidation-Reduction Reactions. Oxidation ofHydroquinones/Reduction of Quinones.21. More about Amines--HeterocyclicCompounds. More About Nomenclature. More About Acid-Base Properties. AmineInversion. Synthesis of Amines. Reactions of Amines. Reactions of QuaternaryAmmonium Compounds. Phase-Transfer Catalysis. Unsaturated Five-Membered-RingHeterocycles. Unsaturated Six-Membered-Ring Heterocycles. BiologicallyImportant Heterocycles.22. Carbohydrates. Classification of Carbohydrates.The D and L Notation. Configurations of the Aldoses. Configurations of theKetoses. Redox Reactions of Monosaccharides. Osazone Formation. ChainElongation: The Kiliani-Fischer Synthesis. Chain Shortening: The RuffDegradation. Stereochemistry of Glucose: The Fischer Proof. Cyclic Structureof Monosaccharides: Hemiacetal Formation. Stability of Glucose. Acylation andAlkylation of Monosaccharides. Formation of Glycosides. The Anomeric Effect.Reducing and Nonreducing Sugars. Determination of Ring Size. Disaccharides.Polysaccharides. Some Naturally Occurring Products Derived fromCarbohydrates. Carbohydrates on Cell Surfaces. Synthetic Sweeteners.23. AminoAcids, Peptides, and Proteins. Classification and Nomenclature of AminoAcids. Configuration of Amino Acids. Acid-Base Properties of Amino Acids. TheIsoelectric Point. Separation of Amino Acids. Resolution of Racemic Mixturesof Amino Acids. Peptide Bonds and Disulfide Bonds. Some Interesting Peptides.Strategy of Peptide Bond Synthesis: N-Protection and C-Activation. AutomatedPeptide Synthesis. Protein Structure. Determining the Primary Structure of aProtein. Secondary Structure of Proteins. Tertiary Structure of Proteins.Quaternary Structure of Proteins. Protein Denaturation.24. Catalysis.Catalysis in Organic Reactions. Nucleophilic Catalysis. Acid Catalysis. BaseCatalysis. Metal-Ion Catalysis. Intramolecular Reactions. IntramolecularCatalysis. Catalysis in Biological Reactions. Enzyme-Catalyzed Reactions.Catalytic Antibodies and Artificial Enzymes.25. The Organic Mechanisms of theCoenzymes--Metabolism. Overall View of Metabolism. Niacin: The VitaminNeeded for Many Redox Reactions. Flavin Adenine Dinucleotide and FlavinMononucleotide: Vitamin B2. Thiamine Pyrophosphate: Vitamin B1. Biotin:Vitamin H. Pyridoxal Phosphate: Vitamin B6. Coenzyme B12: Vitamin B12.Tetrahydrofolate: Folic Acid. Vitamin KH2: Vitamin K.VIII: SPECIAL TOPICS INORGANIC CHEMISTRY. 26. Lipids. Fatty Acids. Waxes. Fats and Oils. Membranes.Prostaglandins. Terpenes. Vitamin A. Biosynthesis of Terpenes. Steroids.Biosynthesis of Cholesterol. Synthetic Steroids.27. Nucleosides, Nucleotides,and Nucleic Acids I. Nucleosides and Nucleotides. ATP: The Carrier ofChemical Energy. Three Mechanisms for Phosphoryl Transfer Reactions. The"High-Energy" Character of Phosphoanhydride Bonds. Kinetic Stability of ATPin the Cell. Other Important Nucleotides. The Nucleic Acids. Helical Forms ofDNA. Biosynthesis of DNA: Replication. Biosynthesis of Messenger RNA:Transcription. Ribosomal RNA. Transfer RNA. Biosynthesis of Proteins:Translation. Why DNA Contains Thymine Instead of Uracil. Determining the BaseSequence of DNA. Laboratory Synthesis of DNA Strands. Rational DrugDesign.28. Synthetic Polymers. General Classes of Synthetic Polymers.Chain-Growth Polymers. Stereochemistry of Polymerization. Ziegler-NattaCatalysts. Polymerization of Dienes. The Manufacture of Rubber. Copolymers.Step-Growth Polymers. Physical Properties of Polymers. BiodegradablePolymers.29. Pericyclic Reactions. Three Kinds of Pericyclic Reactions.Molecular Orbitals and Orbital Symmetry. Electrocyclic Reactions.Cycloaddition Reactions. Sigmatropic Rearrangements. Pericyclic Reactions inBiological Systems. Summary of the Selection Rules for PericyclicReactions.30. The Organic Chemistry of Drugs: Discovery and Design. NamingDrugs. Lead Compounds. Molecular Modification. Random Screening. Serendipityin Drug Development. Receptors. Drugs as Enzyme Inhibitors. Designing aSuicide Substrate. Quantitative Structure-Activity Relation-ships (QSAR).Molecular Modeling. Combinatorial Organic Synthesis. Antiviral Drugs.Economics of Drugs. Governmental Regulations.Appendices. Physical Propertiesof Organic Compounds. Values. Derivations of Rate Laws. Summary of MethodsUsed to Synthesize a Particular Functional Group. Summary of Methods Used toForm Carbon-Carbon Bonds. Spectroscopy Tables.Answers to Selected Problems.Glossary. Photo Credits.