بسم الله الرحمن الرحيم
Organic_*Chemistry:_Structure_*and_Function_Fifth_Ed
by
K. Peter C. Vollhardt, Neil E. Schore
BooK description
With authors who are both accomplished researchers and educators, Vollhardt and Schore’s Organic Chemistry is proven effective for making contemporary organic chemistry accessible, introducing cutting-edge research in a fresh, student-friendly way. A wealth of unique study tools help students organize and understand the substantial information presented in this course. And this new edition incorporates the most current chemical research and new synthesis and green chemistry applications. New!ChemPortal for Organic Chemistry, Fifth EditionChemPortal provides all necessary multimedia resources in one location, including the eBook,
step-by-step tutorials to illustrate problem-solving skills, and enhanced animations and video lectures.
Table of Contents
CONTENTS
PREFACE - A User’s Guide to ORGANIC CHEMISTRY Structure and Function
1 STRUCTURE AND BONDING IN ORGANIC MOLECULES
1.1 The Scope of Organic Chemistry: An Overview
CHEMICAL HIGHLIGHT 1-1 Saccharin: One of the Oldest Synthetic Organic Compounds in Commercial Use
1.2 Coulomb Forces: A Simplified View of Bonding
1.3 Ionic and Covalent Bonds: The Octet Rule
1.4 Electron-Dot Model of Bonding: Lewis Structures
1.5 Resonance Forms
1.6 Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus
1.7 Molecular Orbitals and Covalent Bonding
1.8 Hybrid Orbitals: Bonding in Complex Molecules
1.9 Structures and Formulas of Organic Molecules
Chapter Integration Problems
Important Concepts
Problems
2 STRUCTURE AND REACTIVITY - Acids and Bases, Polar and Nonpolar Molecules
2.1 Kinetics and Thermodynamics of Simple Chemical Processes
2.2 Acids and Bases; Electrophiles and Nucleophiles
CHEMICAL HIGHLIGHT 2-1 Stomach Acid and Food Digestion
2.3 Functional Groups: Centers of Reactivity
2.4 Straight-Chain and Branched Alkanes
2.5 Naming the Alkanes
2.6 Structural and Physical Properties of Alkanes
CHEMICAL HIGHLIGHT 2-2 “Sexual Swindle” by Means of Chemical Mimicry
2.7 Rotation about Single Bonds: Conformations
2.8 Rotation in Substituted Ethanes
Chapter Integration Problems
Important Concepts
Problems
3 REACTIONS OF ALKANES - Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity
3.1 Strength of Alkane Bonds: Radicals
3.2 Structure of Alkyl Radicals: Hyperconjugation
3.3 Conversion of Petroleum: Pyrolysis resulting delocalization of
CHEMICAL HIGHLIGHT 3-1 Petroleum and Gasoline: Our Main Energy Sources
3.4 Chlorination of Methane: The Radical Chain Mechanism
3.5 Other Radical Halogenations of Methane
3.6 Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
3.7 Selectivity in Radical Halogenation with Fluorine and Bromine
3.8 Synthetic Radical Halogenation
CHEMICAL HIGHLIGHT 3-2 Chlorination, Chloral, and DDT
3.9 Synthetic Chlorine Compounds and the Stratospheric Ozone Layer
3.10 Combustion and the Relative Stabilities of Alkanes
Chapter Integration Problems
Important Concepts
Problems
4 CYCLOALKANES
4.1 Names and Physical Properties of Cycloalkanes
4.2 Ring Strain and the Structure of Cycloalkanes
4.3 Cyclohexane: A Strain-Free Cycloalkane
4.4 Substituted Cyclohexanes
4.5 Larger Cycloalkanes
4.6 Polycyclic Alkanes
CHEMICAL HIGHLIGHT 4-1 Cubane Derivatives with Potential as Explosives: Octanitrocubane
4.7 Carbocyclic Products in Nature
CHEMICAL HIGHLIGHT 4-2 Cholesterol: How Is It Bad and How Bad Is It?
CHEMICAL HIGHLIGHT 4-3 Controlling Fertility: From “the Pill” to RU-486
Chapter Integration Problems
Important Concepts
Problems
5 STEREOISOMERS
5.1 Chiral Molecules
CHEMICAL HIGHLIGHT 5-1 Chiral Substances in Nature
5.2 Optical Activity
5.3 Absolute Configuration: R–S Sequence Rules H
CHEMICAL HIGHLIGHT 5-2 Absolute Configuration: A Historical Note
5.4 Fischer Projections
5.5 Molecules Incorporating Several Stereocenters: Diastereomers
CHEMICAL HIGHLIGHT 5-3 Stereoisomers of Tartaric Acid
5.6 Meso Compounds
5.7 Stereochemistry in Chemical Reactions
CHEMICAL HIGHLIGHT 5-4 Chiral Drugs: Racemic or Enantiomerically Pure?
CHEMICAL HIGHLIGHT 5-5 Why Is Nature “Handed”?
5.8 Resolution: Separation of Enantiomers
Chapter Integration Problems
Important Concepts
Problems
6 PROPERTIES AND REACTIONSOF HALOALKANES - Bimolecular Nucleophilic Substitution
6-1 Physical Properties of Haloalkanes
CHEMICAL HIGHLIGHT 6-1 Halogenated Steroids as Anti-Inflammatory and Anti-Asthmatic Agents
6-2 Nucleophilic Substitution
6-3 Reaction Mechanisms Involving Polar Functional Groups:Using “Electron-Pushing” Arrows
6-4 A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics
6-5 Frontside or Backside Attack? Stereochemistry of the SN2 Reaction
6-6 Consequences of Inversion in SN2 Reactions
6-7 Structure and SN2 Reactivity: The Leaving Group
6-8 Structure and SN2 Reactivity: The Nucleophile
6-9 Structure and SN2 Reactivity: The Substrate
CHEMICAL HIGHLIGHT 6-2 The Dilemma of Bromomethane: Highly Useful but Also Highly Toxic
Chapter Integration Problems
Important Concepts
Problems
7 FURTHER REACTIONS OF HALOALKANES - Unimolecular Substitution and Pathways of Elimination
7.1 Solvolysis of Tertiary and Secondary Haloalkanes
7.2 Unimolecular Nucleophilic Substitution
7-3 Stereochemical Consequences of SN1 Reactions
7-4 Effects of Solvent, Leaving Group, and Nucleophile onUnimolecular Substitution
7-5 Effect of the Alkyl Group on the SN1 Reaction:Carbocation Stability
CHEMICAL HIGHLIGHT 7-1 Unusually Stereoselective SN1 Displacement in Anticancer Drug Synthesis
7-6 Unimolecular Elimination: E1
7-7 Bimolecular Elimination: E2
7-8 Competition Between Substitution and Elimination: StructureDetermines Function
7-9 Summary of Reactivity of Haloalkanes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
8 HYDROXY FUNCTIONAL GROUP: ALCOHOLS - Properties, Preparation, and Strategy of Synthesis
8-1 Naming the Alcohols
8-2 Structural and Physical Properties of Alcohols
8-3 Alcohols as Acids and Bases
8-4 Industrial Sources of Alcohols: Carbon Monoxide and Ethene
8-5 Synthesis of Alcohols by Nucleophilic Substitution
8-6 Synthesis of Alcohols: Oxidation–Reduction RelationBetween Alcohols and Carbonyl Compounds
CHEMICAL HIGHLIGHT 8-1 Biological Oxidation and Reduction
CHEMICAL HIGHLIGHT 8-2 The Breath Analyzer Test
8-7 Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis
8-8 Organometallic Reagents in the Synthesis of Alcohols
CHEMICAL HIGHLIGHT 8-3 Transition Metal-Catalyzed Cross-Coupling Reactions
8-9 Complex Alcohols: An Introduction to Synthetic Strategy
Chapter Integration Problems
New Reactions
Important Concepts
Problems
9 FURTHER REACTIONS OF ALCOHOLS AND THE CHEMISTRY OF ETHERS
9-1 Reactions of Alcohols with Base: Preparation of Alkoxides
9-2 Reactions of Alcohols with Strong Acids: Alkyloxonium Ionsin Substitution and Elimination Reactions of Alcohols
9-3 Carbocation Rearrangements
9-4 Organic and Inorganic Esters from Alcohols
9-5 Names and Physical Properties of Ethers
9-6 Williamson Ether Synthesis
CHEMICAL HIGHLIGHT 9-1 Chemiluminescence of 1,2-Dioxacyclobutanes
9-7 Synthesis of Ethers: Alcohols and Mineral Acids
9-8 Reactions of Ethers
CHEMICAL HIGHLIGHT 9-2 Protecting Groups in Synthesis
9-9 Reactions of Oxacyclopropanes
CHEMICAL HIGHLIGHT 9-3 Hydrolytic Kinetic Resolution of Oxacyclopropanes
9-10 Sulfur Analogs of Alcohols and Ethers
9-11 Physiological Properties and Uses of Alcohols and Ethers
CHEMICAL HIGHLIGHT 9-4 Garlic and Sulfur
Chapter Integration Problems
New Reactions
Important Concepts
Problems
10 USING NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY TO DEDUCE STRUCTURE
10-1 Physical and Chemical Tests
10-2 Defining Spectroscopy
10-3 Hydrogen Nuclear Magnetic Resonance
CHEMICAL HIGHLIGHT 10-1 Recording an NMR Spectrum
10-4 Using NMR Spectra to Analyze Molecular Structure:The Proton Chemical Shift
10-5 Tests for Chemical Equivalence
CHEMICAL HIGHLIGHT 10-2 Magnetic Resonance Imaging in Medicine
10-6 Integration
10-7 Spin–Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens
10-8 Spin–Spin Splitting: Some Complications
CHEMICAL HIGHLIGHT 10-3 The Nonequivalence of Diastereotopic Hydrogens
10-9 Carbon-13 Nuclear Magnetic Resonance
CHEMICAL HIGHLIGHT 10-4 Correlated NMR Spectra: COSY and HETCOR
CHEMICAL HIGHLIGHT 10-5 Structural Characterization of Natural Products: Antioxidants from Grape Seeds
Chapter Integration Problems
Important Concepts
Problems
11 ALKENES; INFRARED SPECTROSCOPY AND MASS SPECTROMETRY
11-1 Naming the Alkenes
11-2 Structure and Bonding in Ethene: The Pi Bond
11-3 Physical Properties of Alkenes
11-4 Nuclear Magnetic Resonance of Alkenes
CHEMICAL HIGHLIGHT 11-1 Prostaglandins
11-5 Infrared Spectroscopy
11-6 Measuring the Molecular Mass of Organic Compounds:Mass Spectrometry
11-7 Fragmentation Patterns of Organic Molecules
11-8 Degree of Unsaturation: Another Aid to IdentifyingMolecular Structure
11-9 Catalytic Hydrogenation of Alkenes: Relative Stability ofDouble Bonds
11-10 Preparation of Alkenes from Haloalkanes and Alkyl Sulfonates: Bimolecular Elimination Revisited
11-11 Preparation of Alkenes by Dehydration of Alcohols
CHEMICAL HIGHLIGHT 11-2 Acid-Catalyzed Dehydration of -Terpineol
Chapter Integration Problems
New Reactions
Important Concepts
Problems
12 REACTIONS OF ALKENES
12-1 Why Addition Reactions Proceed: Thermodynamic Feasibility
12-2 Catalytic Hydrogenation
12-3 Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides
12-4 Alcohol Synthesis by Electrophilic Hydration:Thermodynamic Control
12-5 Electrophilic Addition of Halogens to Alkenes
12-6 The Generality of Electrophilic Addition
12-7 Oxymercuration–Demercuration: A SpecialElectrophilic Addition
CHEMICAL HIGHLIGHT 12-1 Juvenile Hormone Analogs in the Battle against Insect-Borne Diseases
12-8 Hydroboration–Oxidation: A StereospecificAnti-Markovnikov Hydration
12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis
12-10 Oxacyclopropane (Epoxide) Synthesis: Epoxidation byPeroxycarboxylic Acids
12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide
CHEMICAL HIGHLIGHT 12-2 Enantioselective Dihydroxylation in the Synthesis of Antitumor Drugs
12-12 Oxidative Cleavage: Ozonolysis
12-13 Radical Additions: Anti-Markovnikov Product Formation
12-14 Dimerization, Oligomerization, and Polymerizationof Alkenes
12-15 Synthesis of Polymers
CHEMICAL HIGHLIGHT 12-3 Polymers in the Clean-Up of Oil Spills
CHEMICAL HIGHLIGHT 12-4 Polymer-Supported Synthesis of Chemical Libraries
12-16 Ethene: An Important Industrial Feedstock
12-17 Alkenes in Nature: Insect Pheromones
CHEMICAL HIGHLIGHT 12-5 Metal-Catalyzed Alkene Metathesis for Constructing Medium and Large Rings
Chapter Integration Problems
New Reactions
Important Concepts
Problems
13 ALKYNES - The Carbon–Carbon Triple Bond
13-1 Naming the Alkynes
13-2 Properties and Bonding in the Alkynes
13-3 Spectroscopy of the Alkynes
13-4 Preparation of Alkynes by Double Elimination
13-5 Preparation of Alkynes from Alkynyl Anions
13-6 Reduction of Alkynes: The Relative Reactivity of the TwoPi Bonds
13-7 Electrophilic Addition Reactions of Alkynes
13-8 Anti-Markovnikov Additions to Triple Bonds
13-9 Chemistry of Alkenyl Halides
CHEMICAL HIGHLIGHT 13-1 Metal-Catalyzed Stille, Suzuki, and Sonogashira Coupling Reactions
13-10 Ethyne as an Industrial Starting Material
13-11 Naturally Occurring and Physiologically Active Alkynes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
14 DELOCALIZED PI SYSTEMS - Investigation by Ultraviolet and Visible Spectroscopy
14-1 Overlap of Three Adjacent p Orbitals: Electron Delocalizationin the 2-Propenyl (Allyl) System
14-2 Radical Allylic Halogenation
14-3 Nucleophilic Substitution of Allylic Halides: SN1 and SN2
14-4 Allylic Organometallic Reagents: UsefulThree-Carbon Nucleophiles
14-5 Two Neighboring Double Bonds: Conjugated Dienes
14-6 Electrophilic Attack on Conjugated Dienes: Kinetic andThermodynamic Control
CHEMICAL HIGHLIGHT 14-1 Use of a Fungicidal Diene in Making Wine: Sorbic Acid
14-7 Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene
14-8 A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
CHEMICAL HIGHLIGHT 14-1 Use of a Fungicidal Diene in Making Wine: Sorbic Acid
CHEMICAL HIGHLIGHT 14-2 Conducting Organic Polymers: Materials for the Future?
CHEMICAL HIGHLIGHT 14-3 The Diels-Alder Reaction is “Green”
14-9 Electrocyclic Reactions
CHEMICAL HIGHLIGHT 14-4 An Extraordinary Electrocyclic Reaction of Anticancer Agents
14-10 Polymerization of Conjugated Dienes: Rubber
14-11 Electronic Spectra: Ultraviolet and Visible Spectroscopy
CHEMICAL HIGHLIGHT 14-5 The Contributions of IR, MS, and UV to the Characterization of Viniferone
Chapter Integration Problems
New Reactions
Important Concepts
Problems
INTERLUDE - A Summary of Organic Reaction Mechanisms
15 BENZENE AND AROMATICITY - Electrophilic Aromatic Substitution
15-1 Naming the Benzenes
15-2 Structure and Resonance Energy of Benzene: A First Lookat Aromaticity
15-3 Pi Molecular Orbitals of Benzene
15-4 Spectral Characteristics of the Benzene Ring
15-5 Polycyclic Aromatic Hydrocarbons
CHEMICAL HIGHLIGHT 15-1 The Allotropes of Carbon: Graphite, Diamond, and Fullerenes
15-6 Other Cyclic Polyenes: Hückel’s Rule
CHEMICAL HIGHLIGHT 15-2 Juxtaposing Aromatic and Antiaromatic Rings in Fused Hydrocarbons
15-7 Hückel’s Rule and Charged Molecules
15-8 Synthesis of Benzene Derivatives: ElectrophilicAromatic Substitution
15-9 Halogenation of Benzene: The Need for a Catalyst
15-10 Nitration and Sulfonation of Benzene
15-11 Friedel-Crafts Alkylation
15-12 Limitations of Friedel-Crafts Alkylations
15-13 Friedel-Crafts Alkanoylation (Acylation)
Chapter Integration Problems
New Reactions
Important Concepts
Problems
16 ELECTROPHILIC ATTACK ON DERIVATIVES OF BENZENE - Substituents Control Regioselectivity
16-1 Activation or Deactivation by Substituents on a Benzene Ring
16-2 Directing Inductive Effects of Alkyl Groups
16-3 Directing Effects of Substituents in Conjugation with theBenzene Ring
CHEMICAL HIGHLIGHT 16-1 Explosive Nitroarenes: TNT and Picric Acid
16-4 Electrophilic Attack on Disubstituted Benzenes
16-5 Synthetic Strategies Toward Substituted Benzenes
16-6 Reactivity of Polycyclic Benzenoid Hydrocarbons
16-7 Polycyclic Aromatic Hydrocarbons and Cancer
Chapter Integration Problems
New Reactions
Important Concepts
Problems
17 ALDEHYDES AND KETONES - The Carbonyl Group
17-1 Naming the Aldehydes and Ketones
17-2 Structure of the Carbonyl Group
17-3 Spectroscopic Properties of Aldehydes and Ketones
17-4 Preparation of Aldehydes and Ketones
17-5 Reactivity of the Carbonyl Group: Mechanisms of Addition
17-6 Addition of Water to Form Hydrates
17-7 Addition of Alcohols to Form Hemiacetals and Acetals
17-8 Acetals as Protecting Groups
17-9 Nucleophilic Addition of Ammonia and Its Derivatives
CHEMICAL HIGHLIGHT 17-1 Imines in Biological Transformations
17-10 Deoxygenation of the Carbonyl Group
17-11 Addition of Hydrogen Cyanide to Give Cyanohydrins
17-12 Addition of Phosphorus Ylides: The Wittig Reaction
CHEMICAL HIGHLIGHT 17-2 The Wittig Reaction in Synthesis
17-13 Oxidation by Peroxycarboxylic Acids: TheBaeyer-Villiger Oxidation
17-14 Oxidative Chemical Tests for Aldehydes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
18 ENOLS, ENOLATES, AND THE ALDOL CONDENSATION - Unsaturated Aldehydes and Ketones
18-1 Acidity of Aldehydes and Ketones: Enolate Ions
18-2 Keto–Enol Equilibria
18-3 Halogenation of Aldehydes and Ketones
18-4 Alkylation of Aldehydes and Ketones
18-5 Attack by Enolates on the Carbonyl Function:Aldol Condensation
18-6 Crossed Aldol Condensation
CHEMICAL HIGHLIGHT 18-1 Enzyme-Catalyzed Stereoselective Aldol Condensations in Nature
CHEMICAL HIGHLIGHT 18-2 Enzymes in Synthesis: Stereoselective Crossed Aldol Condensations
18-7 Intramolecular Aldol Condensation
CHEMICAL HIGHLIGHT 18-3 Reactions of Unsaturated Aldehydes in Nature: The Chemistry of Vision
18-8 Properties of ,-Unsaturated Aldehydes and Ketones
18-9 Conjugate Additions to ,-Unsaturated Aldehydesand Ketones
18-10 1,2- and 1,4-Additions of Organometallic Reagents
18-11 Conjugate Additions of Enolate Ions: Michael Addition andRobinson Annulation
CHEMICAL HIGHLIGHT 18-4 Prostaglandins: , -Dialkylation in Synthesis
Chapter Integration Problems
New Reactions
Important Concepts
Problems
19 CARBOXYLIC ACIDS
19-1 Naming the Carboxylic Acids
CHEMICAL HIGHLIGHT 19-1 Toxicity of Oxalic Acid
19-2 Structural and Physical Properties of Carboxylic Acids
19-3 Spectroscopy and Mass Spectrometry of Carboxylic Acids
19-4 Acidic and Basic Character of Carboxylic Acids
19-5 Carboxylic Acid Synthesis in Industry
19-6 Methods for Introducing the Carboxy Functional Group
19-7 Substitution at the Carboxy Carbon: The Addition–Elimination Mechanism
19-8 Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halidesand Anhydrides
19-9 Carboxylic Acid Derivatives: Esters
19-10 Carboxylic Acid Derivatives: Amides
19-11 Reduction of Carboxylic Acids by Lithium Aluminum Hydride
19-12 Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction
19-13 Biological Activity of Carboxylic Acids
CHEMICAL HIGHLIGHT 19-2 Soaps from Long-Chain Carboxylates
CHEMICAL HIGHLIGHT 19-3 Trans Fatty Acids and Your Health
CHEMICAL HIGHLIGHT 19-4 Biodegradable Polyester Plastics
Chapter Integration Problems
New Reactions
Important Concepts
Problems
20 CARBOXYLIC ACID DERIVATIVES
20-1 Relative Reactivities, Structures, and Spectra of CarboxylicAcid Derivatives
20-2 Chemistry of Alkanoyl Halides
20-3 Chemistry of Carboxylic Anhydrides
20-4 Chemistry of Esters
20-5 Esters in Nature: Waxes, Fats, Oils, and Lipids
CHEMICAL HIGHLIGHT 20-1 Alternatives to Petroleum: Fuels from Vegetable Oil
20-6 Amides: The Least Reactive Carboxylic Acid Derivatives
CHEMICAL HIGHLIGHT 20-2 Battling the Bugs: Antibiotic Wars
20-7 Amidates and Their Halogenation: The HofmannRearrangement
CHEMICAL HIGHLIGHT 20-3 Methyl Isocyanate, Carbamate-based Insecticides, and Safety in the Chemical Industry
20-8 Alkanenitriles: A Special Class of Carboxylic Acid Derivatives
Chapter Integration Problems
New Reactions
Important Concepts
Problems
21 AMINES AND THEIR DERIVATIVES - Functional Groups Containing Nitrogen
21-1 Naming the Amines
21-2 Structural and Physical Properties of Amines
CHEMICAL HIGHLIGHT 21-1 Physiologically Active Amines and Weight Control
21-3 Spectroscopy of the Amine Group
21-4 Acidity and Basicity of Amines
CHEMICAL HIGHLIGHT 21-2 Separation of Amines from Other Organic Compounds by Aqueous Extraction Techniques
21-5 Synthesis of Amines by Alkylation
21-6 Synthesis of Amines by Reductive Amination
21-7 Synthesis of Amines from Carboxylic Amides
21-8 Quaternary Ammonium Salts: Hofmann Elimination
21-9 Mannich Reaction: Alkylation of Enols by Iminium Ions
21-10 Nitrosation of Amines
CHEMICAL HIGHLIGHT 21-3 N-Nitrosodialkanamines and Cancer
CHEMICAL HIGHLIGHT 21-4 Amines in Industry: Nylon
Chapter Integration Problems
New Reactions
Important Concepts
Problems
22 CHEMISTRY OF BENZENE SUBSTITUENTS - Alkylbenzenes, Phenols, and Benzenamines
22-1 Reactivity at the Phenylmethyl (Benzyl) Carbon: BenzylicResonance Stabilization
22-2 Benzylic Oxidations and Reductions
22-3 Names and Properties of Phenols
CHEMICAL HIGHLIGHT 22-1 Two Phenols in the News: Bisphenol A and Resveratrol
22-4 Preparation of Phenols: NucleophilicAromatic Substitution
22-5 Alcohol Chemistry of Phenols
CHEMICAL HIGHLIGHT 22-2 Aspirin: A Phenyl Alkanoate Drug
22-6 Electrophilic Substitution of Phenols
22-7 An Electrocyclic Reaction of the Benzene Ring: TheClaisen Rearrangement
22-8 Oxidation of Phenols: Benzoquinones
CHEMICAL HIGHLIGHT 22-3 Chemical Warfare in Nature: The Bombardier Beetle
22-9 Oxidation-Reduction Processes in Nature
22-10 Arenediazonium Salts
22-11 Electrophilic Substitution with Arenediazonium Salts
iazo Coupling
CHEMICAL HIGHLIGHT 22-4 William Perkin and the Origins of Industrial and Medicinal Chemistry
Chapter Integration Problems
New Reactions
Important Concepts
Problems
23 ESTER ENOLATES AND THE CLAISEN CONDENSATION - Synthesis of -Dicarbonyl Compounds; Acyl Anion Equivalents
23-1 -Dicarbonyl Compounds: Claisen Condensations
CHEMICAL HIGHLIGHT 23-1 Claisen Condensations in Biochemistry
23-2 -Dicarbonyl Compounds as Synthetic Intermediates
23-3 -Dicarbonyl Anion Chemistry: Michael Additions
23-4 Alkanoyl (Acyl) Anion Equivalents: Preparation of-Hydroxyketones
CHEMICAL HIGHLIGHT 23-2 Thiamine: A Natural, Metabolically Active Thiazolium Salt
Chapter Integration Problems
New Reactions
Important Concepts
Problems
24 CARBOHYDRATES - Polyfunctional Compounds in Nature
24-1 Names and Structures of Carbohydrates
24-2 Conformations and Cyclic Forms of Sugars
24-3 Anomers of Simple Sugars: Mutarotation of Glucose
24-4 Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids
24-5 Oxidative Cleavage of Sugars
24-6 Reduction of Monosaccharides to Alditols
24-7 Carbonyl Condensations with Amine Derivatives
24-8 Ester and Ether Formation: Glycosides
CHEMICAL HIGHLIGHT 24-1 F-Labeled Glucose as a Radiotracer: Imaging the Human Brain
CHEMICAL HIGHLIGHT 24-2 Protecting Groups in Vitamin C Synthesis
24-9 Step-by-Step Buildup and Degradation of Sugars
CHEMICAL HIGHLIGHT 24-3 Sugar Biochemistry
24-10 Relative Configurations of the Aldoses: An Exercise in Structure Determination
24-11 Complex Sugars in Nature: Disaccharides
CHEMICAL HIGHLIGHT 24-4 Carbohydrate-Derived Sugar Substitutes
24-12 Polysaccharides and Other Sugars in Nature
Chapter Integration Problem
New Reactions
Important Concepts
Problems
25 HETEROCYCLES - Heteroatoms in Cyclic Organic Compounds
25-1 Naming the Heterocycles
25-2 Nonaromatic Heterocycles
CHEMICAL HIGHLIGHT 25-1 Azacyclopropene Antibiotics
CHEMICAL HIGHLIGHT 25-2 Smoking, Nicotine, and Cancer
25-3 Structure and Properties of Aromatic Heterocyclopentadienes
25-4 Reactions of the Aromatic Heterocyclopentadienes
25-5 Structure and Preparation of Pyridine: An Azabenzene
25-6 Reactions of Pyridine
CHEMICAL HIGHLIGHT 25-3 Pyridinium Salts in Nature: Nicotinamide Adenine Dinucleotide
25-7 Quinoline and Isoquinoline: The Benzopyridines
CHEMICAL HIGHLIGHT 25-4 Azanaphthalenes in Nature
25-8 Alkaloids: Physiologically Potent Nitrogen Heterocyclesin Nature
CHEMICAL HIGHLIGHT 25-5 Nature Is Not Always Green: Natural Pesticides
Chapter Integration Problems
New Reactions
Important Concepts
Problems
26 AMINO ACIDS, PEPTIDES, PROTEINS, AND NUCLEIC ACIDS - Nitrogen-Containing Polymers in Nature
26-1 Structure and Properties of Amino Acids
CHEMICAL HIGHLIGHT 26-1 Arginine and Nitric Oxide in Biochemistry and Medicine
26-2 Synthesis of Amino Acids: A Combination of Amine andCarboxylic Acid Chemistry
26-3 Synthesis of Enantiomerically Pure Amino Acids
CHEMICAL HIGHLIGHT 26-2 Synthesis of Optically Pure Amino Acids: Phase-Transfer Catalysis
26-4 Peptides and Proteins: Amino Acid Oligomers and Polymers
26-5 Determination of Primary Structure: Amino Acid Sequencing
26-6 Synthesis of Polypeptides: A Challenge in the Application ofProtecting Groups
26-7 Merrifield Solid-Phase Peptide Synthesis
26-8 Polypeptides in Nature: Oxygen Transport by the ProteinsMyoglobin and Hemoglobin
26-9 Biosynthesis of Proteins: Nucleic Acids
CHEMICAL HIGHLIGHT 26-3 Synthetic Nucleic Acid Bases and Nucleosides in Medicine
26-10 Protein Synthesis Through RNA
26-11 DNA Sequencing and Synthesis: Cornerstones of GeneTechnology
CHEMICAL HIGHLIGHT 26-4 DNA Fingerprinting
Chapter Integration Problems
New Reactions
Important Concepts
Problems
MCAT® QUESTIONS
ANSWERS TO EXERCISES
PHOTOGRAPH CREDITS
INDEX
LinK
http://ifile.it/4jml1o
Organic_*Chemistry:_Structure_*and_Function_Fifth_Ed
by
K. Peter C. Vollhardt, Neil E. Schore
BooK description
With authors who are both accomplished researchers and educators, Vollhardt and Schore’s Organic Chemistry is proven effective for making contemporary organic chemistry accessible, introducing cutting-edge research in a fresh, student-friendly way. A wealth of unique study tools help students organize and understand the substantial information presented in this course. And this new edition incorporates the most current chemical research and new synthesis and green chemistry applications. New!ChemPortal for Organic Chemistry, Fifth EditionChemPortal provides all necessary multimedia resources in one location, including the eBook,
step-by-step tutorials to illustrate problem-solving skills, and enhanced animations and video lectures.
Table of Contents
CONTENTS
PREFACE - A User’s Guide to ORGANIC CHEMISTRY Structure and Function
1 STRUCTURE AND BONDING IN ORGANIC MOLECULES
1.1 The Scope of Organic Chemistry: An Overview
CHEMICAL HIGHLIGHT 1-1 Saccharin: One of the Oldest Synthetic Organic Compounds in Commercial Use
1.2 Coulomb Forces: A Simplified View of Bonding
1.3 Ionic and Covalent Bonds: The Octet Rule
1.4 Electron-Dot Model of Bonding: Lewis Structures
1.5 Resonance Forms
1.6 Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus
1.7 Molecular Orbitals and Covalent Bonding
1.8 Hybrid Orbitals: Bonding in Complex Molecules
1.9 Structures and Formulas of Organic Molecules
Chapter Integration Problems
Important Concepts
Problems
2 STRUCTURE AND REACTIVITY - Acids and Bases, Polar and Nonpolar Molecules
2.1 Kinetics and Thermodynamics of Simple Chemical Processes
2.2 Acids and Bases; Electrophiles and Nucleophiles
CHEMICAL HIGHLIGHT 2-1 Stomach Acid and Food Digestion
2.3 Functional Groups: Centers of Reactivity
2.4 Straight-Chain and Branched Alkanes
2.5 Naming the Alkanes
2.6 Structural and Physical Properties of Alkanes
CHEMICAL HIGHLIGHT 2-2 “Sexual Swindle” by Means of Chemical Mimicry
2.7 Rotation about Single Bonds: Conformations
2.8 Rotation in Substituted Ethanes
Chapter Integration Problems
Important Concepts
Problems
3 REACTIONS OF ALKANES - Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity
3.1 Strength of Alkane Bonds: Radicals
3.2 Structure of Alkyl Radicals: Hyperconjugation
3.3 Conversion of Petroleum: Pyrolysis resulting delocalization of
CHEMICAL HIGHLIGHT 3-1 Petroleum and Gasoline: Our Main Energy Sources
3.4 Chlorination of Methane: The Radical Chain Mechanism
3.5 Other Radical Halogenations of Methane
3.6 Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
3.7 Selectivity in Radical Halogenation with Fluorine and Bromine
3.8 Synthetic Radical Halogenation
CHEMICAL HIGHLIGHT 3-2 Chlorination, Chloral, and DDT
3.9 Synthetic Chlorine Compounds and the Stratospheric Ozone Layer
3.10 Combustion and the Relative Stabilities of Alkanes
Chapter Integration Problems
Important Concepts
Problems
4 CYCLOALKANES
4.1 Names and Physical Properties of Cycloalkanes
4.2 Ring Strain and the Structure of Cycloalkanes
4.3 Cyclohexane: A Strain-Free Cycloalkane
4.4 Substituted Cyclohexanes
4.5 Larger Cycloalkanes
4.6 Polycyclic Alkanes
CHEMICAL HIGHLIGHT 4-1 Cubane Derivatives with Potential as Explosives: Octanitrocubane
4.7 Carbocyclic Products in Nature
CHEMICAL HIGHLIGHT 4-2 Cholesterol: How Is It Bad and How Bad Is It?
CHEMICAL HIGHLIGHT 4-3 Controlling Fertility: From “the Pill” to RU-486
Chapter Integration Problems
Important Concepts
Problems
5 STEREOISOMERS
5.1 Chiral Molecules
CHEMICAL HIGHLIGHT 5-1 Chiral Substances in Nature
5.2 Optical Activity
5.3 Absolute Configuration: R–S Sequence Rules H
CHEMICAL HIGHLIGHT 5-2 Absolute Configuration: A Historical Note
5.4 Fischer Projections
5.5 Molecules Incorporating Several Stereocenters: Diastereomers
CHEMICAL HIGHLIGHT 5-3 Stereoisomers of Tartaric Acid
5.6 Meso Compounds
5.7 Stereochemistry in Chemical Reactions
CHEMICAL HIGHLIGHT 5-4 Chiral Drugs: Racemic or Enantiomerically Pure?
CHEMICAL HIGHLIGHT 5-5 Why Is Nature “Handed”?
5.8 Resolution: Separation of Enantiomers
Chapter Integration Problems
Important Concepts
Problems
6 PROPERTIES AND REACTIONSOF HALOALKANES - Bimolecular Nucleophilic Substitution
6-1 Physical Properties of Haloalkanes
CHEMICAL HIGHLIGHT 6-1 Halogenated Steroids as Anti-Inflammatory and Anti-Asthmatic Agents
6-2 Nucleophilic Substitution
6-3 Reaction Mechanisms Involving Polar Functional Groups:Using “Electron-Pushing” Arrows
6-4 A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics
6-5 Frontside or Backside Attack? Stereochemistry of the SN2 Reaction
6-6 Consequences of Inversion in SN2 Reactions
6-7 Structure and SN2 Reactivity: The Leaving Group
6-8 Structure and SN2 Reactivity: The Nucleophile
6-9 Structure and SN2 Reactivity: The Substrate
CHEMICAL HIGHLIGHT 6-2 The Dilemma of Bromomethane: Highly Useful but Also Highly Toxic
Chapter Integration Problems
Important Concepts
Problems
7 FURTHER REACTIONS OF HALOALKANES - Unimolecular Substitution and Pathways of Elimination
7.1 Solvolysis of Tertiary and Secondary Haloalkanes
7.2 Unimolecular Nucleophilic Substitution
7-3 Stereochemical Consequences of SN1 Reactions
7-4 Effects of Solvent, Leaving Group, and Nucleophile onUnimolecular Substitution
7-5 Effect of the Alkyl Group on the SN1 Reaction:Carbocation Stability
CHEMICAL HIGHLIGHT 7-1 Unusually Stereoselective SN1 Displacement in Anticancer Drug Synthesis
7-6 Unimolecular Elimination: E1
7-7 Bimolecular Elimination: E2
7-8 Competition Between Substitution and Elimination: StructureDetermines Function
7-9 Summary of Reactivity of Haloalkanes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
8 HYDROXY FUNCTIONAL GROUP: ALCOHOLS - Properties, Preparation, and Strategy of Synthesis
8-1 Naming the Alcohols
8-2 Structural and Physical Properties of Alcohols
8-3 Alcohols as Acids and Bases
8-4 Industrial Sources of Alcohols: Carbon Monoxide and Ethene
8-5 Synthesis of Alcohols by Nucleophilic Substitution
8-6 Synthesis of Alcohols: Oxidation–Reduction RelationBetween Alcohols and Carbonyl Compounds
CHEMICAL HIGHLIGHT 8-1 Biological Oxidation and Reduction
CHEMICAL HIGHLIGHT 8-2 The Breath Analyzer Test
8-7 Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis
8-8 Organometallic Reagents in the Synthesis of Alcohols
CHEMICAL HIGHLIGHT 8-3 Transition Metal-Catalyzed Cross-Coupling Reactions
8-9 Complex Alcohols: An Introduction to Synthetic Strategy
Chapter Integration Problems
New Reactions
Important Concepts
Problems
9 FURTHER REACTIONS OF ALCOHOLS AND THE CHEMISTRY OF ETHERS
9-1 Reactions of Alcohols with Base: Preparation of Alkoxides
9-2 Reactions of Alcohols with Strong Acids: Alkyloxonium Ionsin Substitution and Elimination Reactions of Alcohols
9-3 Carbocation Rearrangements
9-4 Organic and Inorganic Esters from Alcohols
9-5 Names and Physical Properties of Ethers
9-6 Williamson Ether Synthesis
CHEMICAL HIGHLIGHT 9-1 Chemiluminescence of 1,2-Dioxacyclobutanes
9-7 Synthesis of Ethers: Alcohols and Mineral Acids
9-8 Reactions of Ethers
CHEMICAL HIGHLIGHT 9-2 Protecting Groups in Synthesis
9-9 Reactions of Oxacyclopropanes
CHEMICAL HIGHLIGHT 9-3 Hydrolytic Kinetic Resolution of Oxacyclopropanes
9-10 Sulfur Analogs of Alcohols and Ethers
9-11 Physiological Properties and Uses of Alcohols and Ethers
CHEMICAL HIGHLIGHT 9-4 Garlic and Sulfur
Chapter Integration Problems
New Reactions
Important Concepts
Problems
10 USING NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY TO DEDUCE STRUCTURE
10-1 Physical and Chemical Tests
10-2 Defining Spectroscopy
10-3 Hydrogen Nuclear Magnetic Resonance
CHEMICAL HIGHLIGHT 10-1 Recording an NMR Spectrum
10-4 Using NMR Spectra to Analyze Molecular Structure:The Proton Chemical Shift
10-5 Tests for Chemical Equivalence
CHEMICAL HIGHLIGHT 10-2 Magnetic Resonance Imaging in Medicine
10-6 Integration
10-7 Spin–Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens
10-8 Spin–Spin Splitting: Some Complications
CHEMICAL HIGHLIGHT 10-3 The Nonequivalence of Diastereotopic Hydrogens
10-9 Carbon-13 Nuclear Magnetic Resonance
CHEMICAL HIGHLIGHT 10-4 Correlated NMR Spectra: COSY and HETCOR
CHEMICAL HIGHLIGHT 10-5 Structural Characterization of Natural Products: Antioxidants from Grape Seeds
Chapter Integration Problems
Important Concepts
Problems
11 ALKENES; INFRARED SPECTROSCOPY AND MASS SPECTROMETRY
11-1 Naming the Alkenes
11-2 Structure and Bonding in Ethene: The Pi Bond
11-3 Physical Properties of Alkenes
11-4 Nuclear Magnetic Resonance of Alkenes
CHEMICAL HIGHLIGHT 11-1 Prostaglandins
11-5 Infrared Spectroscopy
11-6 Measuring the Molecular Mass of Organic Compounds:Mass Spectrometry
11-7 Fragmentation Patterns of Organic Molecules
11-8 Degree of Unsaturation: Another Aid to IdentifyingMolecular Structure
11-9 Catalytic Hydrogenation of Alkenes: Relative Stability ofDouble Bonds
11-10 Preparation of Alkenes from Haloalkanes and Alkyl Sulfonates: Bimolecular Elimination Revisited
11-11 Preparation of Alkenes by Dehydration of Alcohols
CHEMICAL HIGHLIGHT 11-2 Acid-Catalyzed Dehydration of -Terpineol
Chapter Integration Problems
New Reactions
Important Concepts
Problems
12 REACTIONS OF ALKENES
12-1 Why Addition Reactions Proceed: Thermodynamic Feasibility
12-2 Catalytic Hydrogenation
12-3 Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides
12-4 Alcohol Synthesis by Electrophilic Hydration:Thermodynamic Control
12-5 Electrophilic Addition of Halogens to Alkenes
12-6 The Generality of Electrophilic Addition
12-7 Oxymercuration–Demercuration: A SpecialElectrophilic Addition
CHEMICAL HIGHLIGHT 12-1 Juvenile Hormone Analogs in the Battle against Insect-Borne Diseases
12-8 Hydroboration–Oxidation: A StereospecificAnti-Markovnikov Hydration
12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis
12-10 Oxacyclopropane (Epoxide) Synthesis: Epoxidation byPeroxycarboxylic Acids
12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide
CHEMICAL HIGHLIGHT 12-2 Enantioselective Dihydroxylation in the Synthesis of Antitumor Drugs
12-12 Oxidative Cleavage: Ozonolysis
12-13 Radical Additions: Anti-Markovnikov Product Formation
12-14 Dimerization, Oligomerization, and Polymerizationof Alkenes
12-15 Synthesis of Polymers
CHEMICAL HIGHLIGHT 12-3 Polymers in the Clean-Up of Oil Spills
CHEMICAL HIGHLIGHT 12-4 Polymer-Supported Synthesis of Chemical Libraries
12-16 Ethene: An Important Industrial Feedstock
12-17 Alkenes in Nature: Insect Pheromones
CHEMICAL HIGHLIGHT 12-5 Metal-Catalyzed Alkene Metathesis for Constructing Medium and Large Rings
Chapter Integration Problems
New Reactions
Important Concepts
Problems
13 ALKYNES - The Carbon–Carbon Triple Bond
13-1 Naming the Alkynes
13-2 Properties and Bonding in the Alkynes
13-3 Spectroscopy of the Alkynes
13-4 Preparation of Alkynes by Double Elimination
13-5 Preparation of Alkynes from Alkynyl Anions
13-6 Reduction of Alkynes: The Relative Reactivity of the TwoPi Bonds
13-7 Electrophilic Addition Reactions of Alkynes
13-8 Anti-Markovnikov Additions to Triple Bonds
13-9 Chemistry of Alkenyl Halides
CHEMICAL HIGHLIGHT 13-1 Metal-Catalyzed Stille, Suzuki, and Sonogashira Coupling Reactions
13-10 Ethyne as an Industrial Starting Material
13-11 Naturally Occurring and Physiologically Active Alkynes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
14 DELOCALIZED PI SYSTEMS - Investigation by Ultraviolet and Visible Spectroscopy
14-1 Overlap of Three Adjacent p Orbitals: Electron Delocalizationin the 2-Propenyl (Allyl) System
14-2 Radical Allylic Halogenation
14-3 Nucleophilic Substitution of Allylic Halides: SN1 and SN2
14-4 Allylic Organometallic Reagents: UsefulThree-Carbon Nucleophiles
14-5 Two Neighboring Double Bonds: Conjugated Dienes
14-6 Electrophilic Attack on Conjugated Dienes: Kinetic andThermodynamic Control
CHEMICAL HIGHLIGHT 14-1 Use of a Fungicidal Diene in Making Wine: Sorbic Acid
14-7 Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene
14-8 A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
CHEMICAL HIGHLIGHT 14-1 Use of a Fungicidal Diene in Making Wine: Sorbic Acid
CHEMICAL HIGHLIGHT 14-2 Conducting Organic Polymers: Materials for the Future?
CHEMICAL HIGHLIGHT 14-3 The Diels-Alder Reaction is “Green”
14-9 Electrocyclic Reactions
CHEMICAL HIGHLIGHT 14-4 An Extraordinary Electrocyclic Reaction of Anticancer Agents
14-10 Polymerization of Conjugated Dienes: Rubber
14-11 Electronic Spectra: Ultraviolet and Visible Spectroscopy
CHEMICAL HIGHLIGHT 14-5 The Contributions of IR, MS, and UV to the Characterization of Viniferone
Chapter Integration Problems
New Reactions
Important Concepts
Problems
INTERLUDE - A Summary of Organic Reaction Mechanisms
15 BENZENE AND AROMATICITY - Electrophilic Aromatic Substitution
15-1 Naming the Benzenes
15-2 Structure and Resonance Energy of Benzene: A First Lookat Aromaticity
15-3 Pi Molecular Orbitals of Benzene
15-4 Spectral Characteristics of the Benzene Ring
15-5 Polycyclic Aromatic Hydrocarbons
CHEMICAL HIGHLIGHT 15-1 The Allotropes of Carbon: Graphite, Diamond, and Fullerenes
15-6 Other Cyclic Polyenes: Hückel’s Rule
CHEMICAL HIGHLIGHT 15-2 Juxtaposing Aromatic and Antiaromatic Rings in Fused Hydrocarbons
15-7 Hückel’s Rule and Charged Molecules
15-8 Synthesis of Benzene Derivatives: ElectrophilicAromatic Substitution
15-9 Halogenation of Benzene: The Need for a Catalyst
15-10 Nitration and Sulfonation of Benzene
15-11 Friedel-Crafts Alkylation
15-12 Limitations of Friedel-Crafts Alkylations
15-13 Friedel-Crafts Alkanoylation (Acylation)
Chapter Integration Problems
New Reactions
Important Concepts
Problems
16 ELECTROPHILIC ATTACK ON DERIVATIVES OF BENZENE - Substituents Control Regioselectivity
16-1 Activation or Deactivation by Substituents on a Benzene Ring
16-2 Directing Inductive Effects of Alkyl Groups
16-3 Directing Effects of Substituents in Conjugation with theBenzene Ring
CHEMICAL HIGHLIGHT 16-1 Explosive Nitroarenes: TNT and Picric Acid
16-4 Electrophilic Attack on Disubstituted Benzenes
16-5 Synthetic Strategies Toward Substituted Benzenes
16-6 Reactivity of Polycyclic Benzenoid Hydrocarbons
16-7 Polycyclic Aromatic Hydrocarbons and Cancer
Chapter Integration Problems
New Reactions
Important Concepts
Problems
17 ALDEHYDES AND KETONES - The Carbonyl Group
17-1 Naming the Aldehydes and Ketones
17-2 Structure of the Carbonyl Group
17-3 Spectroscopic Properties of Aldehydes and Ketones
17-4 Preparation of Aldehydes and Ketones
17-5 Reactivity of the Carbonyl Group: Mechanisms of Addition
17-6 Addition of Water to Form Hydrates
17-7 Addition of Alcohols to Form Hemiacetals and Acetals
17-8 Acetals as Protecting Groups
17-9 Nucleophilic Addition of Ammonia and Its Derivatives
CHEMICAL HIGHLIGHT 17-1 Imines in Biological Transformations
17-10 Deoxygenation of the Carbonyl Group
17-11 Addition of Hydrogen Cyanide to Give Cyanohydrins
17-12 Addition of Phosphorus Ylides: The Wittig Reaction
CHEMICAL HIGHLIGHT 17-2 The Wittig Reaction in Synthesis
17-13 Oxidation by Peroxycarboxylic Acids: TheBaeyer-Villiger Oxidation
17-14 Oxidative Chemical Tests for Aldehydes
Chapter Integration Problems
New Reactions
Important Concepts
Problems
18 ENOLS, ENOLATES, AND THE ALDOL CONDENSATION - Unsaturated Aldehydes and Ketones
18-1 Acidity of Aldehydes and Ketones: Enolate Ions
18-2 Keto–Enol Equilibria
18-3 Halogenation of Aldehydes and Ketones
18-4 Alkylation of Aldehydes and Ketones
18-5 Attack by Enolates on the Carbonyl Function:Aldol Condensation
18-6 Crossed Aldol Condensation
CHEMICAL HIGHLIGHT 18-1 Enzyme-Catalyzed Stereoselective Aldol Condensations in Nature
CHEMICAL HIGHLIGHT 18-2 Enzymes in Synthesis: Stereoselective Crossed Aldol Condensations
18-7 Intramolecular Aldol Condensation
CHEMICAL HIGHLIGHT 18-3 Reactions of Unsaturated Aldehydes in Nature: The Chemistry of Vision
18-8 Properties of ,-Unsaturated Aldehydes and Ketones
18-9 Conjugate Additions to ,-Unsaturated Aldehydesand Ketones
18-10 1,2- and 1,4-Additions of Organometallic Reagents
18-11 Conjugate Additions of Enolate Ions: Michael Addition andRobinson Annulation
CHEMICAL HIGHLIGHT 18-4 Prostaglandins: , -Dialkylation in Synthesis
Chapter Integration Problems
New Reactions
Important Concepts
Problems
19 CARBOXYLIC ACIDS
19-1 Naming the Carboxylic Acids
CHEMICAL HIGHLIGHT 19-1 Toxicity of Oxalic Acid
19-2 Structural and Physical Properties of Carboxylic Acids
19-3 Spectroscopy and Mass Spectrometry of Carboxylic Acids
19-4 Acidic and Basic Character of Carboxylic Acids
19-5 Carboxylic Acid Synthesis in Industry
19-6 Methods for Introducing the Carboxy Functional Group
19-7 Substitution at the Carboxy Carbon: The Addition–Elimination Mechanism
19-8 Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halidesand Anhydrides
19-9 Carboxylic Acid Derivatives: Esters
19-10 Carboxylic Acid Derivatives: Amides
19-11 Reduction of Carboxylic Acids by Lithium Aluminum Hydride
19-12 Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction
19-13 Biological Activity of Carboxylic Acids
CHEMICAL HIGHLIGHT 19-2 Soaps from Long-Chain Carboxylates
CHEMICAL HIGHLIGHT 19-3 Trans Fatty Acids and Your Health
CHEMICAL HIGHLIGHT 19-4 Biodegradable Polyester Plastics
Chapter Integration Problems
New Reactions
Important Concepts
Problems
20 CARBOXYLIC ACID DERIVATIVES
20-1 Relative Reactivities, Structures, and Spectra of CarboxylicAcid Derivatives
20-2 Chemistry of Alkanoyl Halides
20-3 Chemistry of Carboxylic Anhydrides
20-4 Chemistry of Esters
20-5 Esters in Nature: Waxes, Fats, Oils, and Lipids
CHEMICAL HIGHLIGHT 20-1 Alternatives to Petroleum: Fuels from Vegetable Oil
20-6 Amides: The Least Reactive Carboxylic Acid Derivatives
CHEMICAL HIGHLIGHT 20-2 Battling the Bugs: Antibiotic Wars
20-7 Amidates and Their Halogenation: The HofmannRearrangement
CHEMICAL HIGHLIGHT 20-3 Methyl Isocyanate, Carbamate-based Insecticides, and Safety in the Chemical Industry
20-8 Alkanenitriles: A Special Class of Carboxylic Acid Derivatives
Chapter Integration Problems
New Reactions
Important Concepts
Problems
21 AMINES AND THEIR DERIVATIVES - Functional Groups Containing Nitrogen
21-1 Naming the Amines
21-2 Structural and Physical Properties of Amines
CHEMICAL HIGHLIGHT 21-1 Physiologically Active Amines and Weight Control
21-3 Spectroscopy of the Amine Group
21-4 Acidity and Basicity of Amines
CHEMICAL HIGHLIGHT 21-2 Separation of Amines from Other Organic Compounds by Aqueous Extraction Techniques
21-5 Synthesis of Amines by Alkylation
21-6 Synthesis of Amines by Reductive Amination
21-7 Synthesis of Amines from Carboxylic Amides
21-8 Quaternary Ammonium Salts: Hofmann Elimination
21-9 Mannich Reaction: Alkylation of Enols by Iminium Ions
21-10 Nitrosation of Amines
CHEMICAL HIGHLIGHT 21-3 N-Nitrosodialkanamines and Cancer
CHEMICAL HIGHLIGHT 21-4 Amines in Industry: Nylon
Chapter Integration Problems
New Reactions
Important Concepts
Problems
22 CHEMISTRY OF BENZENE SUBSTITUENTS - Alkylbenzenes, Phenols, and Benzenamines
22-1 Reactivity at the Phenylmethyl (Benzyl) Carbon: BenzylicResonance Stabilization
22-2 Benzylic Oxidations and Reductions
22-3 Names and Properties of Phenols
CHEMICAL HIGHLIGHT 22-1 Two Phenols in the News: Bisphenol A and Resveratrol
22-4 Preparation of Phenols: NucleophilicAromatic Substitution
22-5 Alcohol Chemistry of Phenols
CHEMICAL HIGHLIGHT 22-2 Aspirin: A Phenyl Alkanoate Drug
22-6 Electrophilic Substitution of Phenols
22-7 An Electrocyclic Reaction of the Benzene Ring: TheClaisen Rearrangement
22-8 Oxidation of Phenols: Benzoquinones
CHEMICAL HIGHLIGHT 22-3 Chemical Warfare in Nature: The Bombardier Beetle
22-9 Oxidation-Reduction Processes in Nature
22-10 Arenediazonium Salts
22-11 Electrophilic Substitution with Arenediazonium Salts
iazo CouplingCHEMICAL HIGHLIGHT 22-4 William Perkin and the Origins of Industrial and Medicinal Chemistry
Chapter Integration Problems
New Reactions
Important Concepts
Problems
23 ESTER ENOLATES AND THE CLAISEN CONDENSATION - Synthesis of -Dicarbonyl Compounds; Acyl Anion Equivalents
23-1 -Dicarbonyl Compounds: Claisen Condensations
CHEMICAL HIGHLIGHT 23-1 Claisen Condensations in Biochemistry
23-2 -Dicarbonyl Compounds as Synthetic Intermediates
23-3 -Dicarbonyl Anion Chemistry: Michael Additions
23-4 Alkanoyl (Acyl) Anion Equivalents: Preparation of-Hydroxyketones
CHEMICAL HIGHLIGHT 23-2 Thiamine: A Natural, Metabolically Active Thiazolium Salt
Chapter Integration Problems
New Reactions
Important Concepts
Problems
24 CARBOHYDRATES - Polyfunctional Compounds in Nature
24-1 Names and Structures of Carbohydrates
24-2 Conformations and Cyclic Forms of Sugars
24-3 Anomers of Simple Sugars: Mutarotation of Glucose
24-4 Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids
24-5 Oxidative Cleavage of Sugars
24-6 Reduction of Monosaccharides to Alditols
24-7 Carbonyl Condensations with Amine Derivatives
24-8 Ester and Ether Formation: Glycosides
CHEMICAL HIGHLIGHT 24-1 F-Labeled Glucose as a Radiotracer: Imaging the Human Brain
CHEMICAL HIGHLIGHT 24-2 Protecting Groups in Vitamin C Synthesis
24-9 Step-by-Step Buildup and Degradation of Sugars
CHEMICAL HIGHLIGHT 24-3 Sugar Biochemistry
24-10 Relative Configurations of the Aldoses: An Exercise in Structure Determination
24-11 Complex Sugars in Nature: Disaccharides
CHEMICAL HIGHLIGHT 24-4 Carbohydrate-Derived Sugar Substitutes
24-12 Polysaccharides and Other Sugars in Nature
Chapter Integration Problem
New Reactions
Important Concepts
Problems
25 HETEROCYCLES - Heteroatoms in Cyclic Organic Compounds
25-1 Naming the Heterocycles
25-2 Nonaromatic Heterocycles
CHEMICAL HIGHLIGHT 25-1 Azacyclopropene Antibiotics
CHEMICAL HIGHLIGHT 25-2 Smoking, Nicotine, and Cancer
25-3 Structure and Properties of Aromatic Heterocyclopentadienes
25-4 Reactions of the Aromatic Heterocyclopentadienes
25-5 Structure and Preparation of Pyridine: An Azabenzene
25-6 Reactions of Pyridine
CHEMICAL HIGHLIGHT 25-3 Pyridinium Salts in Nature: Nicotinamide Adenine Dinucleotide
25-7 Quinoline and Isoquinoline: The Benzopyridines
CHEMICAL HIGHLIGHT 25-4 Azanaphthalenes in Nature
25-8 Alkaloids: Physiologically Potent Nitrogen Heterocyclesin Nature
CHEMICAL HIGHLIGHT 25-5 Nature Is Not Always Green: Natural Pesticides
Chapter Integration Problems
New Reactions
Important Concepts
Problems
26 AMINO ACIDS, PEPTIDES, PROTEINS, AND NUCLEIC ACIDS - Nitrogen-Containing Polymers in Nature
26-1 Structure and Properties of Amino Acids
CHEMICAL HIGHLIGHT 26-1 Arginine and Nitric Oxide in Biochemistry and Medicine
26-2 Synthesis of Amino Acids: A Combination of Amine andCarboxylic Acid Chemistry
26-3 Synthesis of Enantiomerically Pure Amino Acids
CHEMICAL HIGHLIGHT 26-2 Synthesis of Optically Pure Amino Acids: Phase-Transfer Catalysis
26-4 Peptides and Proteins: Amino Acid Oligomers and Polymers
26-5 Determination of Primary Structure: Amino Acid Sequencing
26-6 Synthesis of Polypeptides: A Challenge in the Application ofProtecting Groups
26-7 Merrifield Solid-Phase Peptide Synthesis
26-8 Polypeptides in Nature: Oxygen Transport by the ProteinsMyoglobin and Hemoglobin
26-9 Biosynthesis of Proteins: Nucleic Acids
CHEMICAL HIGHLIGHT 26-3 Synthetic Nucleic Acid Bases and Nucleosides in Medicine
26-10 Protein Synthesis Through RNA
26-11 DNA Sequencing and Synthesis: Cornerstones of GeneTechnology
CHEMICAL HIGHLIGHT 26-4 DNA Fingerprinting
Chapter Integration Problems
New Reactions
Important Concepts
Problems
MCAT® QUESTIONS
ANSWERS TO EXERCISES
PHOTOGRAPH CREDITS
INDEX
LinK
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