Organic Chemistry

Cover
Title
Copyright
Contents
List of Important Features
Preface
Acknowledgements
Chapter 1 Structure Determines Properties
	1.1 Atoms, Electrons, and Orbitals
		Organic Chemistry: The Early Days
	1.2 Ionic Bonds
	1.3 Covalent Bonds, Lewis Formulas, and the Octet Rule
	1.4 Double Bonds and Triple Bonds
	1.5 Polar Covalent Bonds, Electronegativity, and Bond Dipoles
		Electrostatic Potential Maps
	1.6 Formal Charge
	1.7 Structural Formulas of Organic Molecules
	1.8 Resonance
	1.9 Sulfur and Phosphorus-Containing Organic Compounds and the Octet Rule
	1.10 The Shapes of Some Simple Molecules
		Molecular Models And Modeling
	1.11 Molecular Dipole Moments
	1.12 Curved Arrows and Chemical Reactions
	1.13 Acids and Bases: The Brønsted–Lowry View
	1.14 How Structure Affects Acid Strength
	1.15 Acid–Base Equilibria
	1.16 Lewis Acids and Lewis Bases
	1.17 Summary
	Problems
	Descriptive Passage and Interpretive Problems 1: Amide Lewis Structural Formulas
Chapter 2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons
	2.1 Classes of Hydrocarbons
	2.2 Electron Waves and Chemical Bonds
	2.3 Bonding in H[sub(2)]: The Valence Bond Model
	2.4 Bonding in H[sub(2)]: The Molecular Orbital Model
	2.5 Introduction to Alkanes: Methane, Ethane, and Propane
	2.6 sp[sup(3)] Hybridization and Bonding in Methane
		Methane and the Biosphere
	2.7 Bonding in Ethane
	2.8 sp[sup(2)] Hybridization and Bonding in Ethylene
	2.9 sp Hybridization and Bonding in Acetylene
	2.10 Which Theory of Chemical Bonding Is Best?
	2.11 Isomeric Alkanes: The Butanes
	2.12 Higher n-Alkanes
	2.13 The C[sub(5)]H[sub(12)] Isomers
	2.14 IUPAC Nomenclature of Unbranched Alkanes
	2.15 Applying the IUPAC Rules: The Names of the C[sub(6)]H[sub(14)] Isomers
		What's in a Name? Organic Nomenclature
	2.16 Alkyl Groups
	2.17 IUPAC Names of Highly Branched Alkanes
	2.18 Cycloalkane Nomenclature
	2.19 Sources of Alkanes and Cycloalkanes
	2.20 Physical Properties of Alkanes and Cycloalkanes
	2.21 Chemical Properties: Combustion of Alkanes
		Thermochemistry
	2.22 Oxidation–Reduction in Organic Chemistry
	2.23 Summary
	Problems
	Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes
Chapter 3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers
	3.1 Conformational Analysis of Ethane
	3.2 Conformational Analysis of Butane
	3.3 Conformations of Higher Alkanes
		Computational Chemistry: Molecular Mechanics and Quantum Mechanics
	3.4 The Shapes of Cycloalkanes: Planar or Nonplanar?
	3.5 Small Rings: Cyclopropane and Cyclobutane
	3.6 Cyclopentane
	3.7 Conformations of Cyclohexane
	3.8 Axial and Equatorial Bonds in Cyclohexane
	3.9 Conformational Inversion in Cyclohexane
	3.10 Conformational Analysis of Monosubstituted Cyclohexanes
		Enthalpy, Free Energy, and Equilibrium Constant
	3.11 Disubstituted Cycloalkanes: cis–trans Stereoisomers
	3.12 Conformational Analysis of Disubstituted Cyclohexanes
	3.13 Medium and Large Rings
	3.14 Polycyclic Ring Systems
	3.15 Heterocyclic Compounds
	3.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 3: Cyclic Forms of Carbohydrates
Chapter 4 Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms
	4.1 Functional Groups
	4.2 IUPAC Nomenclature of Alkyl Halides
	4.3 IUPAC Nomenclature of Alcohols
	4.4 Classes of Alcohols and Alkyl Halides
	4.5 Bonding in Alcohols and Alkyl Halides
	4.6 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces
	4.7 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides
	4.8 Reaction of Alcohols with Hydrogen Halides: The S[sub(N)]1 Mechanism
		Mechanism 4.1 Formation of tert-Butyl Chloride from tert-Butyl Alcohol and Hydrogen Chloride
	4.9 Structure, Bonding, and Stability of Carbocations
	4.10 Effect of Alcohol Structure on Reaction Rate
	4.11 Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The S[sub(N)2 Mechanism
		Mechanism 4.2 Formation of 1-Bromoheptane from 1-Heptanol and Hydrogen Bromide
	4.12 Other Methods for Converting Alcohols to Alkyl Halides
	4.13 Halogenation of Alkanes
	4.14 Chlorination of Methane
	4.15 Structure and Stability of Free Radicals
		From Bond Enthalpies to Heats of Reaction
	4.16 Mechanism of Methane Chlorination
		Mechanism 4.3 Free-Radical Chlorination of Methane
	4.17 Halogenation of Higher Alkanes
	4.18 Summary
	Problems
	Descriptive Passage and Interpretive Problems 4: More About Potential Energy Diagrams
Chapter 5 Structure and Preparation of Alkenes: Elimination Reactions
	5.1 Alkene Nomenclature
	5.2 Structure and Bonding in Alkenes
		Ethylene
	5.3 Isomerism in Alkenes
	5.4 Naming Stereoisomeric Alkenes by the E–Z Notational System
	5.5 Physical Properties of Alkenes
	5.6 Relative Stabilities of Alkenes
	5.7 Cycloalkenes
	5.8 Preparation of Alkenes: Elimination Reactions
	5.9 Dehydration of Alcohols
	5.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule
	5.11 Stereoselectivity in Alcohol Dehydration
	5.12 The E1 and E2 Mechanisms of Alcohol Dehydration
		Mechanism 5.1 The E1 Mechanism for Acid-Catalyzed Dehydration of tert-Butyl Alcohol
	5.13 Rearrangements in Alcohol Dehydration
		Mechanism 5.2 Carbocation Rearrangement in Dehydration of 3,3-Dimethyl-2-butanol
		Mechanism 5.3 Hydride Shift in Dehydration of 1-Butanol
	5.14 Dehydrohalogenation of Alkyl Halides
	5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides
		Mechanism 5.4 E2 Elimination of 1-Chlorooctadecane
	5.16 Anti Elimination in E2 Reactions: Stereoelectronic Effects
	5.17 Isotope Effects and the E2 Mechanism
	5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides
		Mechanism 5.5 The E1 Mechanism for Dehydrohalogenation of 2-Bromo-2-methylbutane
	5.19 Summary
	Problems
	Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions
Chapter 6 Addition Reactions of Alkenes
	6.1 Hydrogenation of Alkenes
	6.2 Stereochemistry of Alkene Hydrogenation
		Mechanism 6.1 Hydrogenation of Alkenes
	6.3 Heats of Hydrogenation
	6.4 Electrophilic Addition of Hydrogen Halides to Alkenes
		Mechanism 6.2 Electrophilic Addition of Hydrogen Bromide to 2-Methylpropene
		Rules, Laws, Theories, and the Scientific Method
	6.5 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes
	6.6 Acid-Catalyzed Hydration of Alkenes
		Mechanism 6.3 Acid-Catalyzed Hydration of 2-Methylpropene
	6.7 Thermodynamics of Addition–Elimination Equilibria
	6.8 Hydroboration–Oxidation of Alkenes
	6.9 Mechanism of Hydroboration–Oxidation
		Mechanism 6.4 Hydroboration of 1-Methylcyclopentene
		Mechanism 6.5 Oxidation of an Organoborane
	6.10 Addition of Halogens to Alkenes
		Mechanism 6.6 Bromine Addition to Cyclopentene
	6.11 Epoxidation of Alkenes
		Mechanism 6.7 Epoxidation of Bicyclo[2.2.1]-2-heptene
	6.12 Ozonolysis of Alkenes
	6.13 Free-Radical Addition of Hydrogen Bromide to Alkenes
		Mechanism 6.8 Free-Radical Addition of Hydrogen Bromide to 1-Butene
	6.14 Free-Radical Polymerization of Alkenes
		Mechanism 6.9 Free-Radical Polymerization of Ethylene
	6.15 Introduction to Organic Chemical Synthesis: Retrosynthetic Analysis
		Ethylene and Propene: The Most Important Industrial Organic Chemicals
	6.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 6: Oxymercuration
Chapter 7 Chirality
	7.1 Molecular Chirality: Enantiomers
	7.2 The Chirality Center
	7.3 Symmetry in Achiral Structures
	7.4 Optical Activity
	7.5 Absolute and Relative Configuration
	7.6 The Cahn–Ingold–Prelog R–S Notational System
	7.7 Fischer Projections
	7.8 Properties of Enantiomers
	7.9 The Chirality Axis
		Chiral Drugs
	7.10 Reactions That Create a Chirality Center
	7.11 Chiral Molecules with Two Chirality Centers
	7.12 Achiral Molecules with Two Chirality Centers
		Chirality of Disubstituted Cyclohexanes
	7.13 Molecules with Multiple Chirality Centers
	7.14 Reactions That Produce Diastereomers
	7.15 Resolution of Enantiomers
	7.16 Stereoregular Polymers
	7.17 Chirality Centers Other Than Carbon
	7.18 Summary
	Problems
	Descriptive Passage and Interpretive Problems 7: Prochirality
Chapter 8 Nucleophilic Substitution
	8.1 Functional Group Transformation by Nucleophilic Substitution
	8.2 Relative Reactivity of Halide Leaving Groups
	8.3 The S[sub(N)]2 Mechanism of Nucleophilic Substitution
		Mechanism 8.1 The S[sub(N)]2 Mechanism of Nucleophilic Substitution
	8.4 Steric Effects and S[sub(N)]2 Reaction Rates
	8.5 Nucleophiles and Nucleophilicity
		Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides
	8.6 The S[sub(N)]1 Mechanism of Nucleophilic Substitution
		Mechanism 8.2 The S[sub(N)]1 Mechanism of Nucleophilic Substitution
	8.7 Stereochemistry of S[sub(N)]1 Reactions
	8.8 Carbocation Rearrangements in S[sub(N)]1 Reactions
		Mechanism 8.3 Carbocation Rearrangement in the S[sub(N)]1 Hydrolysis of 2-Bromo-3-methylbutane
	8.9 Effect of Solvent on the Rate of Nucleophilic Substitution
	8.10 Substitution and Elimination as Competing Reactions
	8.11 Nucleophilic Substitution of Alkyl Sulfonates
	8.12 Nucleophilic Substitution and Retrosynthetic Analysis
	8.13 Summary
	Problems
	Descriptive Passage and Interpretive Problems 8: Nucleophilic Substitution
Chapter 9 Alkynes
	9.1 Sources of Alkynes
	9.2 Nomenclature
	9.3 Physical Properties of Alkynes
	9.4 Structure and Bonding in Alkynes: sp Hybridization
	9.5 Acidity of Acetylene and Terminal Alkynes
	9.6 Preparation of Alkynes by Alkylation of Acetylene and Terminal Alkynes
	9.7 Preparation of Alkynes by Elimination Reactions
	9.8 Reactions of Alkynes
	9.9 Hydrogenation of Alkynes
	9.10 Metal–Ammonia Reduction of Alkynes
	9.11 Addition of Hydrogen Halides to Alkynes
		Mechanism 9.1 Sodium–Ammonia Reduction of an Alkyne
	9.12 Hydration of Alkynes
		Mechanism 9.2 Conversion of an Enol to a Ketone
	9.13 Addition of Halogens to Alkynes
		Some Things That Can Be Made from Acetylene … But Aren't
	9.14 Ozonolysis of Alkynes
	9.15 Alkynes in Synthesis and Retrosynthesis
	9.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes
Chapter 10 Conjugation in Alkadienes and Allylic Systems
	10.1 The Allyl Group
	10.2 S[sub(N)]1 and S[sub(N)]2 Reactions of Allylic Halides
		Mechanism 10.1 S[sub(N)]1 Hydrolysis of an Allylic Halide
	10.3 Allylic Free-Radical Halogenation
		Mechanism 10.2 Allylic Chlorination of Propene
	10.4 Allylic Anions
	10.5 Classes of Dienes: Conjugated and Otherwise
	10.6 Relative Stabilities of Dienes
	10.7 Bonding in Conjugated Dienes
	10.8 Bonding in Allenes
	10.9 Preparation of Dienes
		Diene Polymers
	10.10 Addition of Hydrogen Halides to Conjugated Dienes
		Mechanism 10.3 Addition of Hydrogen Chloride to 1,3-Cyclopentadiene
	10.11 Halogen Addition to Dienes
	10.12 The Diels–Alder Reaction
	10.13 Retrosynthetic Analysis and the Diels–Alder Reaction
	10.14 Molecular Orbital Analysis of the Diels–Alder Reaction
	10.15 Summary
	Problems
	Descriptive Passage and Interpretive Problems 10: Intramolecular and Retro Diels–Alder Reactions
Chapter 11 Arenes and Aromaticity
	11.1 Benzene
	11.2 The Structure of Benzene
	11.3 The Stability of Benzene
	11.4 Bonding in Benzene
	11.5 Substituted Derivatives of Benzene and Their Nomenclature
	11.6 Polycyclic Aromatic Hydrocarbons
		Fullerenes, Nanotubes, and Graphene
	11.7 Physical Properties of Arenes
	11.8 The Benzyl Group
	11.9 Nucleophilic Substitution in Benzylic Halides
	11.10 Benzylic Free-Radical Halogenation
	11.11 Benzylic Anions
	11.12 Oxidation of Alkylbenzenes
	11.13 Alkenylbenzenes
	11.14 Polymerization of Styrene
		Mechanism 11.1 Free-Radical Polymerization of Styrene
	11.15 The Birch Reduction
		Mechanism 11.2 The Birch Reduction
	11.16 Benzylic Side Chains and Retrosynthetic Analysis
	11.17 Cyclobutadiene and Cyclooctatetraene
	11.18 Hückel's Rule
	11.19 Annulenes
	11.20 Aromatic Ions
	11.21 Heterocyclic Aromatic Compounds
	11.22 Heterocyclic Aromatic Compounds and Hückel's Rule
	11.23 Summary
	Problems
	Descriptive Passage and Interpretive Problems 11: The Hammett Equation
Chapter 12 Electrophilic and Nucleophilic Aromatic Substitution
	12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene
	12.2 Mechanistic Principles of Electrophilic Aromatic Substitution
	12.3 Nitration of Benzene
		Mechanism 12.1 Nitration of Benzene
	12.4 Sulfonation of Benzene
		Mechanism 12.2 Sulfonation of Benzene
	12.5 Halogenation of Benzene
		Mechanism 12.3 Bromination of Benzene
		Biosynthetic Halogenation
	12.6 Friedel–Crafts Alkylation of Benzene
		Mechanism 12.4 Friedel–Crafts Alkylation
	12.7 Friedel–Crafts Acylation of Benzene
		Mechanism 12.5 Friedel–Crafts Acylation
	12.8 Synthesis of Alkylbenzenes by Acylation–Reduction
	12.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution
	12.10 Rate and Regioselectivity in the Nitration of Toluene
	12.11 Rate and Regioselectivity in the Nitration of (Trifluoromethyl) benzene
	12.12 Substituent Effects in Electrophilic Aromatic Substitution: Activating Substituents
	12.13 Substituent Effects in Electrophilic Aromatic Substitution: Strongly Deactivating Substituents
	12.14 Substituent Effects in Electrophilic Aromatic Substitution: Halogens
	12.15 Multiple Substituent Effects
	12.16 Retrosynthetic Analysis and the Synthesis of Substituted Benzenes
	12.17 Substitution in Naphthalene
	12.18 Substitution in Heterocyclic Aromatic Compounds
	12.19 Nucleophilic Aromatic Substitution
	12.20 The Addition–Elimination Mechanism of Nucleophilic Aromatic Substitution
		Mechanism 12.6 Nucleophilic Aromatic Substitutionin p-Fluoronitrobenzene by the Addition–Elimination Mechanism
	12.21 Related Nucleophilic Aromatic Substitutions
	12.22 Summary
	Problems
	Descriptive Passage and Interpretive Problems 12: Benzyne
Chapter 13 Spectroscopy
	13.1 Principles of Molecular Spectroscopy: Electromagnetic Radiation
	13.2 Principles of Molecular Spectroscopy: Quantized Energy States
	13.3 Introduction to [sup(1)]H NMR Spectroscopy
	13.4 Nuclear Shielding and [sup(1)]H Chemical Shifts
	13.5 Effects of Molecular Structure on [sup(1)]H Chemical Shifts
		Ring Currents: Aromatic and Antiaromatic
	13.6 Interpreting [sup(1)]H NMR Spectra
	13.7 Spin–Spin Splitting and [sup(1)]H NMR
	13.8 Splitting Patterns: The Ethyl Group
	13.9 Splitting Patterns: The Isopropyl Group
	13.10 Splitting Patterns: Pairs of Doublets
	13.11 Complex Splitting Patterns
	13.12 [sup(1)]H NMR Spectra of Alcohols
		Magnetic Resonance Imaging (MRI)
	13.13 NMR and Conformations
	13.14 [sup(13)]C NMR Spectroscopy
	13.15 [sup(13)]C Chemical Shifts
	13.16 [sup(13)]C NMR and Peak Intensities
	13.17 [sup(13)]C—[sup(1)]H Coupling
	13.18 Using DEPT to Count Hydrogens
	13.19 2D NMR: COSY and HETCOR
	13.20 Introduction to Infrared Spectroscopy
		Spectra by the Thousands
	13.21 Infrared Spectra
	13.22 Characteristic Absorption Frequencies
	13.23 Ultraviolet-Visible Spectroscopy
	13.24 Mass Spectrometry
	13.25 Molecular Formula as a Clue to Structure
	13.26 Summary
	Problems
	Descriptive Passage and Interpretive Problems 13: More on Coupling Constants
Chapter 14 Organometallic Compounds
	14.1 Organometallic Nomenclature
	14.2 Carbon–Metal Bonds
	14.3 Preparation of Organolithium and Organomagnesium Compounds
	14.4 Organolithium and Organomagnesium Compounds as Brønsted Bases
	14.5 Synthesis of Alcohols Using Grignard and Organolithium Reagents
	14.6 Synthesis of Acetylenic Alcohols
	14.7 Retrosynthetic Analysis and Grignard and Organolithium Reagents
	14.8 An Organozinc Reagent for Cyclopropane Synthesis
	14.9 Transition-Metal Organometallic Compounds
		An Organometallic Compound That Occurs Naturally: Coenzyme B[sub(12)]
	14.10 Organocopper Reagents
	14.11 Palladium-Catalyzed Cross-Coupling Reactions
	14.12 Homogeneous Catalytic Hydrogenation
		Mechanism 14.1 Homogeneous Catalysis of Alkene Hydrogenation
	14.13 Olefin Metathesis
		Mechanism 14.2 Olefin Cross-Metathesis
	14.14 Ziegler–Natta Catalysis of Alkene Polymerization
		Mechanism 14.3 Polymerization of Ethylene in the Presence of Ziegler–Natta Catalyst
	14.15 Summary
	Problems
	Descriptive Passage and Interpretive Problems 14:Cyclobutadiene and (Cyclobutadiene) tricarbonyliron
Chapter 15 Alcohols, Diols, and Thiols
	15.1 Sources of Alcohols
	15.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones
	15.3 Preparation of Alcohols by Reduction of Carboxylic Acids
	15.4 Preparation of Alcohols from Epoxides
	15.5 Preparation of Diols
	15.6 Reactions of Alcohols: A Review and a Preview
	15.7 Conversion of Alcohols to Ethers
		Mechanism 15.1 Acid-Catalyzed Formation of Diethyl Ether from Ethyl Alcohol
	15.8 Esterification
	15.9 Oxidation of Alcohols
	15.10 Biological Oxidation of Alcohols
		Sustainability and Organic Chemistry
	15.11 Oxidative Cleavage of Vicinal Diols
	15.12 Thiols
	15.13 Spectroscopic Analysis of Alcohols and Thiols
	15.14 Summary
	Problems
	Descriptive Passage and Interpretive Problems 15: The Pinacol Rearrangement
Chapter 16 Ethers, Epoxides, and Sulfides
	16.1 Nomenclature of Ethers, Epoxides, and Sulfides
	16.2 Structure and Bonding in Ethers and Epoxides
	16.3 Physical Properties of Ethers
	16.4 Crown Ethers
	16.5 Preparation of Ethers
		Polyether Antibiotics
	16.6 The Williamson Ether Synthesis
	16.7 Reactions of Ethers: A Review and a Preview
	16.8 Acid-Catalyzed Cleavage of Ethers
		Mechanism 16.1 Cleavage of Ethers by Hydrogen Halides
	16.9 Preparation of Epoxides
	16.10 Conversion of Vicinal Halohydrins to Epoxides
	16.11 Reactions of Epoxides with Anionic Nucleophiles
		Mechanism 16.2 Nucleophilic Ring-Opening of an Epoxide
	16.12 Acid-Catalyzed Ring Opening of Epoxides
		Mechanism 16.3 Acid-Catalyzed Ring Opening of an Epoxide
	16.13 Epoxides in Biological Processes
	16.14 Preparation of Sulfides
	16.15 Oxidation of Sulfides: Sulfoxides and Sulfones
	16.16 Alkylation of Sulfides: Sulfonium Salts
	16.17 Spectroscopic Analysis of Ethers, Epoxides, and Sulfides
	16.18 Summary
	Problems
	Descriptive Passage and Interpretive Problems 16: Epoxide Rearrangements and the NIH Shift
Chapter 17 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group
	17.1 Nomenclature
	17.2 Structure and Bonding: The Carbonyl Group
	17.3 Physical Properties
	17.4 Sources of Aldehydes and Ketones
	17.5 Reactions of Aldehydes and Ketones: A Review and a Preview
	17.6 Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones
		Mechanism 17.1 Hydration of an Aldehyde or Ketone in Basic Solution
		Mechanism 17.2 Hydration of an Aldehyde or Ketone in Acid Solution
	17.7 Cyanohydrin Formation
		Mechanism 17.3 Cyanohydrin Formation
	17.8 Reaction with Alcohols: Acetals and Ketals
		Mechanism 17.4 Acetal Formation from Benzaldehyde and Ethanol
	17.9 Acetals and Ketals as Protecting Groups
	17.10 Reaction with Primary Amines: Imines
		Mechanism 17.5 Imine Formation from Benzaldehyde and Methylamine
		Imines in Biological Chemistry
	17.11 Reaction with Secondary Amines: Enamines
		Mechanism 17.6 Enamine Formation
	17.12 The Wittig Reaction
	17.13 Stereoselective Addition to Carbonyl Groups
	17.14 Oxidation of Aldehydes
	17.15 Spectroscopic Analysis of Aldehydes and Ketones
	17.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 17: The Baeyer–Villiger Oxidation
Chapter 18 Carboxylic Acids
	18.1 Carboxylic Acid Nomenclature
	18.2 Structure and Bonding
	18.3 Physical Properties
	18.4 Acidity of Carboxylic Acids
	18.5 Substituents and Acid Strength
	18.6 Ionization of Substituted Benzoic Acids
	18.7 Salts of Carboxylic Acids
	18.8 Dicarboxylic Acids
	18.9 Carbonic Acid
	18.10 Sources of Carboxylic Acids
	18.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents
	18.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles
	18.13 Reactions of Carboxylic Acids: A Review and a Preview
	18.14 Mechanism of Acid-Catalyzed Esterification
		Mechanism 18.1 Acid-Catalyzed Esterification of Benzoic Acid with Methanol
	18.15 Intramolecular Ester Formation: Lactones
	18.16 Decarboxylation of Malonic Acid and Related Compounds
	18.17 Spectroscopic Analysis of Carboxylic Acids
	18.18 Summary
	Problems
	Descriptive Passage and Interpretive Problems 18: Lactonization Methods
Chapter 19 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution
	19.1 Nomenclature of Carboxylic Acid Derivatives
	19.2 Structure and Reactivity of Carboxylic Acid Derivatives
	19.3 Nucleophilic Acyl Substitution Mechanisms
	19.4 Nucleophilic Acyl Substitution in Acyl Chlorides
	19.5 Nucleophilic Acyl Substitution in Acid Anhydrides
		Mechanism 19.1 Nucleophilic Acyl Substitution in an Anhydride
	19.6 Physical Properties and Sources of Esters
	19.7 Reactions of Esters: A Preview
	19.8 Acid-Catalyzed Ester Hydrolysis
		Mechanism 19.2 Acid-Catalyzed Ester Hydrolysis
	19.9 Ester Hydrolysis in Base: Saponification
		Mechanism 19.3 Ester Hydrolysis in Basic Solution
	19.10 Reaction of Esters with Ammonia and Amines
	19.11 Reaction of Esters with Grignard and Organolithium Reagents and Lithium Aluminum Hydride
	19.12 Amides
	19.13 Hydrolysis of Amides
		Mechanism 19.4 Amide Hydrolysis in Acid Solution
		Mechanism 19.5 Amide Hydrolysis in Basic Solution
	19.14 Lactams
		β-Lactam Antibiotics
	19.15 Preparation of Nitriles
	19.16 Hydrolysis of Nitriles
		Mechanism 19.6 Nitrile Hydrolysis in Basic Solution
	19.17 Addition of Grignard Reagents to Nitriles
	19.18 Spectroscopic Analysis of Carboxylic Acid Derivatives
	19.19 Summary
	Problems
	Descriptive Passage and Interpretive Problems 19: Thioesters
Chapter 20 Enols and Enolates
	20.1 Enol Content and Enolization
		Mechanism 20.1 Acid-Catalyzed Enolization of 2-Methylpropanal
	20.2 Enolates
	20.3 The Aldol Condensation
		Mechanism 20.2 Aldol Addition of Butanal
	20.4 Mixed and Directed Aldol Reactions
		Chalcones as Aromatase Inhibitors: From the Mulberry Tree to Cancer Chemotherapy
	20.5 Acylation of Enolates: The Claisen and Related Condensations
		Mechanism 20.3 Claisen Condensation of Ethyl Propanoate
	20.6 Alkylation of Enolates: The Acetoacetic Ester and Malonic Ester Syntheses
	20.7 The Haloform Reaction
		The Haloform Reaction and the Biosynthesis of Trihalomethanes
		Mechanism 20.4 The Haloform Reaction
	20.8 Conjugation Effects in α β-Unsaturated Aldehydes and Ketones
	20.9 Summary
	Problems
	Descriptive Passage and Interpretive Problems 20: The Enolate Chemistry of Dianions
Chapter 21 Amines
	21.1 Amine Nomenclature
	21.2 Structure and Bonding
	21.3 Physical Properties
	21.4 Basicity of Amines
		Amines as Natural Products
	21.5 Tetraalkylammonium Salts as Phase-Transfer Catalysts
	21.6 Reactions That Lead to Amines: A Review and a Preview
	21.7 Preparation of Amines by Alkylation of Ammonia
	21.8 The Gabriel Synthesis of Primary Alkylamines
	21.9 Preparation of Amines by Reduction
		Mechanism 21.1 Lithium Aluminum Hydride Reduction of an Amide
	21.10 Reductive Amination
	21.11 Reactions of Amines: A Review and a Preview
	21.12 Reaction of Amines with Alkyl Halides
	21.13 The Hofmann Elimination
	21.14 Electrophilic Aromatic Substitution in Arylamines
	21.15 Nitrosation of Alkylamines
	21.16 Nitrosation of Arylamines
	21.17 Synthetic Transformations of Aryl Diazonium Salts
	21.18 Azo Coupling
		From Dyes to Sulfa Drugs
	21.19 Spectroscopic Analysis of Amines
	21.20 Summary
	Problems
	Descriptive Passage and Interpretive Problems 21: Synthetic Applications of Enamines
Chapter 22 Phenols
	22.1 Nomenclature
	22.2 Structure and Bonding
	22.3 Physical Properties
	22.4 Acidity of Phenols
	22.5 Substituent Effects on the Acidity of Phenols
	22.6 Sources of Phenols
	22.7 Naturally Occurring Phenols
	22.8 Reactions of Phenols: Electrophilic Aromatic Substitution
	22.9 Acylation of Phenols
	22.10 Carboxylation of Phenols: Aspirin and the Kolbe–Schmitt Reaction
	22.11 Preparation of Aryl Ethers
		James Bond, Oxidative Stress, and Antioxidant Phenols
	22.12 Cleavage of Aryl Ethers by Hydrogen Halides
	22.13 Claisen Rearrangement of Allyl Aryl Ethers
	22.14 Oxidation of Phenols: Quinones
	22.15 Spectroscopic Analysis of Phenols
	22.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 22: Directed Metalation of Aryl Ethers
Chapter 23 Carbohydrates
	23.1 Classification of Carbohydrates
	23.2 Fischer Projections and D,L Notation
	23.3 The Aldotetroses
	23.4 Aldopentoses and Aldohexoses
	23.5 A Mnemonic for Carbohydrate Configurations
	23.6 Cyclic Forms of Carbohydrates: Furanose Forms
	23.7 Cyclic Forms of Carbohydrates: Pyranose Forms
	23.8 Mutarotation
		Mechanism 23.1 Acid-Catalyzed Mutarotation of D-Glucopyranose
	23.9 Carbohydrate Conformation: The Anomeric Effect
	23.10 Ketoses
	23.11 Deoxy Sugars
	23.12 Amino Sugars
	23.13 Branched-Chain Carbohydrates
	23.14 Glycosides: The Fischer Glycosidation
		Mechanism 23.2 Preparation of Methyl D-Glucopyranosides by Fischer Glycosidation
	23.15 Disaccharides
	23.16 Polysaccharides
		How Sweet It Is!
	23.17 Application of Familiar Reactions to Monosaccharides
	23.18 Oxidation of Monosaccharides
	23.19 Glycosides: Synthesis of Oligosaccharides
		Mechanism 23.3 Silver-Assisted Glycosidation
	23.20 Glycobiology
	23.22 Summary
	Problems
	Descriptive Passage and Interpretive Problems 23: Emil Fischer and the Structure of (+)-Glucose
Chapter 24 Lipids
	24.1 Acetyl Coenzyme A
	24.2 Fats, Oils, and Fatty Acids
	24.3 Fatty Acid Biosynthesis
	24.4 Phospholipids
	24.5 Waxes
	24.6 Prostaglandins
		Nonsteroidal Antiinflammatory Drugs (NSAIDs) and COX-2 Inhibitors
	24.7 Terpenes: The Isoprene Rule
	24.8 Isopentenyl Diphosphate: The Biological Isoprene Unit
	24.9 Carbon–Carbon Bond Formation in Terpene Biosynthesis
	24.10 The Pathway from Acetate to Isopentenyl Diphosphate
	24.11 Steroids: Cholesterol
		Mechanism 24.1 Biosynthesis of Cholesterol from Squalene
	24.12 Vitamin D
		Good Cholesterol? Bad Cholesterol? What's the Difference?
	24.13 Bile Acids
	24.14 Corticosteroids
	24.15 Sex Hormones
	24.16 Carotenoids
		Crocuses Make Saffron from Carotenes
	24.17 Summary
	Problems
	Descriptive Passage and Interpretive Problems 24: Polyketides
Chapter 25 Amino Acids, Peptides, and Proteins
	25.1 Classification of Amino Acids
	25.2 Stereochemistry of Amino Acids
	25.3 Acid–Base Behavior of Amino Acids
		Electrophoresis
	25.4 Synthesis of Amino Acids
	25.5 Reactions of Amino Acids
	25.6 Some Biochemical Reactions of Amino Acids
		Mechanism 25.1 Pyridoxal 5'-Phosphate-Mediated Decarboxylation of an α-Amino Acid
		Mechanism 25.2 Transamination: Biosynthesis of l-Alanine from l-Glutamic Acid and Pyruvic Acid
	25.7 Peptides
	25.8 Introduction to Peptide Structure Determination
	25.9 Amino Acid Analysis
	25.10 Partial Hydrolysis and End Group Analysis
	25.11 Insulin
	25.12 Edman Degradation and Automated Sequencing of Peptides
		Mechanism 25.3 The Edman Degradation
		Peptide Mapping and MALDI Mass Spectrometry
	25.13 The Strategy of Peptide Synthesis
	25.14 Amino and Carboxyl Group Protection and Deprotection
	25.15 Peptide Bond Formation
		Mechanism 25.4 Amide Bond FormationBetween a Carboxylic Acid and an Amine Using N,N'-Dicyclohexylcarbodiimide
	25.16 Solid-Phase Peptide Synthesis: The Merrifield Method
	25.17 Secondary Structures of Peptides and Proteins
	25.18 Tertiary Structure of Polypeptides and Proteins
		Mechanism 25.5 Carboxypeptidase-Catalyzed Hydrolysis
	25.19 Coenzymes
		Oh NO! It's Inorganic!
	25.20 Protein Quaternary Structure: Hemoglobin
	25.21 G-Coupled Protein Receptors
	25.22 Summary
	Problems
	Descriptive Passage and Interpretive Problems 25: Amino Acids in Enantioselective Synthesis
Chapter 26 Nucleosides, Nucleotides, and Nucleic Acids
	26.1 Pyrimidines and Purines
	26.2 Nucleosides
	26.3 Nucleotides
	26.4 Bioenergetics
	26.5 ATP and Bioenergetics
	26.6 Phosphodiesters, Oligonucleotides, and Polynucleotides
	26.7 Nucleic Acids
	26.8 Secondary Structure of DNA: The Double Helix
		It Has Not Escaped Our Notice…
	26.9 Tertiary Structure of DNA: Supercoils
	26.10 Replication of DNA
	26.11 Ribonucleic Acids
	26.12 Protein Biosynthesis
	26.13 AIDS
	26.14 DNA Sequencing
	26.15 The Human Genome Project
	26.16 DNA Profiling and the Polymerase Chain Reaction
	26.17 Recombinant DNA Technology
	26.18 Summary
	Problems
	Descriptive Passage and Interpretive Problems 26: Oligonucleotide Synthesis
Chapter 27 Synthetic Polymers
	27.1 Some Background
	27.2 Polymer Nomenclature
	27.3 Classification of Polymers: Reaction Type
	27.4 Classification of Polymers: Chain Growth and Step Growth
	27.5 Classification of Polymers: Structure
	27.6 Classification of Polymers: Properties
	27.7 Addition Polymers: A Review and a Preview
	27.8 Chain Branching in Free-Radical Polymerization
		Mechanism 27.1 Branching in Polyethylene Caused by Intramolecular Hydrogen Transfer
		Mechanism 27.2 Branching in Polyethylene Caused by Intermolecular Hydrogen Transfer
	27.9 Anionic Polymerization: Living Polymers
		Mechanism 27.3 Anionic Polymerization of Styrene
	27.10 Cationic Polymerization
		Mechanism 27.4 Cationic Polymerization of 2-Methylpropene
	27.11 Polyamides
	27.12 Polyesters
	27.13 Polycarbonates
	27.14 Polyurethanes
	27.15 Copolymers
		Conducting Polymers
	27.16 Summary
	Problems
	Descriptive Passage and Interpretive Problems 27: Chemically Modified Polymers
Glossary
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Credits
Index
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