Organic Chemistry: Structure and Function, Eighth Edition
By Peter Vollhardt and Neil Schore
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
Real Life: Nature 1-1 Urea: From Urine to Wöhler’s Synthesis to Industrial Fertilizer
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
1-10 A General Strategy for Solving Problems in Organic Chemistry Worked Examples: Integrating the Concepts
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 Keys to Success: Using Curved “Electron-Pushing” Arrows to Describe Chemical Reactions
2-3 Acids and Bases
Real Life: Medicine 2-1 Stomach Acid, Peptic Ulcers,
Pharmacology, and Organic Chemistry
2-4 Functional Groups: Centers of Reactivity
2-5 Straight-Chain and Branched Alkanes
2-6 Naming the Alkanes
2-7 Structural and Physical Properties of Alkanes
Real Life: Nature 2-2 “Sexual Swindle” by Means of Chemical Mimicry
2-8 Rotation about Single Bonds: Conformations
2-9 Rotation in Substituted Ethanes
2-10 Worked Examples: Integrating the Concepts
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
Real Life: Sustainability 3-1 Sustainability and the Needs of the 21st Century: “Green” Chemistry
3-4 Chlorination of Methane: The Radical Chain Mechanism
3-5 Other Radical Halogenations of Methane
3-6 Keys to Success: Using the “Known” Mechanism as a Model for the “Unknown”
3-7 Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
3-8 Selectivity in Radical Halogenation with Fluorine and Bromine
3-9 Synthetic Radical Halogenation
Real Life: Medicine 3-2 Chlorination, Chloral, and DDT: The Quest to Eradicate Malaria
3-10 Synthetic Chlorine Compounds and the Stratospheric Ozone Layer
3-11 Combustion and the Relative Stabilities of Alkanes
3-12 Worked Examples: Integrating the Concepts
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
4-7 Carbocyclic Products in Nature
Real Life: Materials 4-1 Cyclohexane, Adamantane, and Diamandoids: Diamond “Molecules”
Real Life: Medicine 4-2 Cholesterol: How Is It Bad and How Bad Is It?
Real Life: Medicine 4-3 Controlling Fertility: From “the Pill” to
RU-486 to Male Contraceptives
4-8 Worked Examples: Integrating the Concepts
Important Concepts
Problems
5 STEREOISOMERS
5-1 Chiral Molecules
Real Life: Nature 5-1 Chiral Substances in Nature
5-2 Optical Activity
5-3 Absolute Configuration: R,S Sequence Rules
5-4 Fischer Projections
5-5 Molecules Incorporating Several Stereocenters: Diastereomers
Real Life: Nature 5-2 Stereoisomers of Tartaric Acid
5-6 Meso Compounds
5-7 Stereochemistry in Chemical Reactions
Real Life: Medicine 5-3 Chiral Drugs—Racemic or Enantiomerically Pure?
Real Life: Medicine 5-4 Why Is Nature “Handed”?
5-8 Resolution: Separation of Enantiomers
5-9 Worked Examples: Integrating the Concepts
Important Concepts
Problems
6 PROPERTIES AND REACTIONS OF HALOALKANES
Bimolecular Nucleophilic Substitution
6-1 Physical Properties of Haloalkanes
Real Life: Medicine 6-1 Fluorinated Pharmaceuticals
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 Keys to Success: Choosing Among Multiple Mechanistic Pathways
6-10 Structure and SN2 Reactivity: The Substrate
6-11 The SN2 Reaction at a Glance
6-12 Worked Examples: Integrating the Concepts
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 on Unimolecular Substitution
7-5 Effect of the Alkyl Group on the SN1 Reaction: Carbocation Stability
Real Life: Medicine 7-1 Unusually Stereoselective SN1 Displacement in Anticancer Drug Synthesis
7-6 Unimolecular Elimination: E1
7-7 Bimolecular Elimination: E2
7-8 Keys to Success: Substitution versus Elimination—Structure Determines Function
7-9 Summary of Reactivity of Haloalkanes
7-10 Worked Examples: Integrating the Concepts
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 Synthesis of Alcohols by Nucleophilic Substitution
8-5 Synthesis of Alcohols: Oxidation–Reduction Relation Between Alcohols and Carbonyl Compounds
Real Life: Medicine 8-1 Oxidation and Reduction in the Body
Real Life: Medicine 8-2 Don’t Drink and Drive: The Breath Analyzer Test
8-6 Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis
8-7 Organometallic Reagents in the Synthesis of Alcohols
8-8 Keys to Success: An Introduction to Synthetic Strategy
Real Life: Chemistry 8-3 What Magnesium Does Not Do, Copper Can: Alkylation of Organometallics
8-9 Worked Examples: Integrating the Concepts
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 Ions in Substitution and Elimination Reactions of Alcohols
9-3 Carbocation Rearrangements
9-4 Esters from Alcohols and Haloalkane Synthesis
9-5 Names and Physical Properties of Ethers
9-6 Williamson Ether Synthesis
Real Life: Nature 9-1 Chemiluminescence of 1,2- Dioxacyclobutanes
9-7 Synthesis of Ethers: Alcohols and Mineral Acids
9-8 Reactions of Ethers
Real Life: Medicine 9-2 Protecting Groups in the Synthesis of Testosterone
9-9 Reactions of Oxacyclopropanes
Real Life: Chemistry 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
9-12 Worked Examples: Integrating the Concepts
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
Real Life: Spectroscopy 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
Real Life: Medicine 10-2 Magnetic Resonance Imaging (MRI)
in Medicine
10-6 Integration of NMR Signals
10-7 Spin–Spin Splitting: The Effect of Nonequivalent Neighboring
Hydrogens
10-8 Spin–Spin Splitting: Some Complications
Real Life: Spectroscopy 10-3 The Nonequivalence of
Diastereotopic Hydrogens
10-9 Carbon-13 Nuclear Magnetic Resonance
Real Life: Spectroscopy 10-4 How to Determine Atom
Connectivity in NMR
Real Life: Medicine 10-5 Structural Characterization of Natural
and “Unnatural” Products: An Antioxidant from Grape Seeds
and a Fake Drug in Herbal Medicines
10-10 Worked Examples: Integrating the Concepts
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
Real Life: Medicine 11-1 NMR of Complex Molecules: The Powerfully Regulating Prostaglandins
11-5 Catalytic Hydrogenation of Alkenes: Relative Stability of Double Bonds
11-6 Preparation of Alkenes from Haloalkanes and Alkyl Sulfonates: Bimolecular Elimination Revisited
11-7 Preparation of Alkenes by Dehydration of Alcohols
11-8 Infrared Spectroscopy
11-9 Measuring the Molecular Mass of Organic Compounds: Mass Spectrometry
Real Life: Medicine 11-2 Detecting Performance-Enhancing
Drugs Using Mass Spectrometry
11-10 Fragmentation Patterns of Organic Molecules
11-11 Degree of Unsaturation: Another Aid to Identifying Molecular Structure
11-12 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
12 REACTIONS OF ALKENES
12-1 Why Addition Reactions Proceed: Thermodynamic Feasibility
12-2 Catalytic Hydrogenation
12-3 Basic and 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 Special Electrophilic Addition
Real Life: Medicine 12-1 Juvenile Hormone Analogs in the Battle Against Insect-Borne Diseases
12-8 Hydroboration–Oxidation: A Stereospecific Anti-Markovnikov Hydration
12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis
12-10 Oxacyclopropane (Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids
12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide
Real Life: Medicine 12-2 Synthesis of Antitumor Drugs:
Sharpless Enantioselective Oxacyclopropanation (Epoxidation) and Dihydroxylation
12-12 Oxidative Cleavage: Ozonolysis
12-13 Radical Additions: Anti-Markovnikov Product Formation
12-14 Dimerization, Oligomerization, and Polymerization of Alkenes
12-15 Synthesis of Polymers
12-16 Ethene: An Important Industrial Feedstock
12-17 Alkenes in Nature: Insect Pheromones
Real Life: Medicine 12-3 Alkene Metathesis Transposes the
Termini of Two Alkenes: Construction of Rings
12-18 Worked Examples: Integrating the Concepts
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 Two Pi Bonds
13-7 Electrophilic Addition Reactions of Alkynes
13-8 Anti-Markovnikov Additions to Triple Bonds
13-9 Chemistry of Alkenyl Halides
Real Life: Synthesis 13-1 Metal-Catalyzed Stille, Suzuki, and Sonogashira Coupling Reactions
13-10 Ethyne as an Industrial Starting Material
13-11 Alkynes in Nature and in Medicine
13-12 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
14 DELOCALIZED Pi SYSTEMS
Investigation by Ultraviolet and Visible Spectroscopy
14-1 Overlap of Three Adjacent p Orbitals: Electron Delocalization in 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: Useful Three-Carbon Nucleophiles
14-5 Two Neighboring Double Bonds: Conjugated Dienes
14-6 Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control
14-7 Delocalization Among More than Two Pi Bonds: Extended Conjugation and Benzene
14-8 A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
Real Life: Materials 14-1 Organic Polyenes Conduct Electricity
Real Life: Sustainability 14-2 The Diels-Alder Reaction is “Green”
14-9 Electrocyclic Reactions
14-10 Polymerization of Conjugated Dienes: Rubber
14-11 Electronic Spectra: Ultraviolet and Visible Spectroscopy
Real Life: Spectroscopy 14-3 The Contributions of IR, MS, and UV to the Characterization of Viniferone
14-12 Worked Examples: Integrating the Concepts
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 Look at Aromaticity
15-3 Pi Molecular Orbitals of Benzene
15-4 Spectral Characteristics of the Benzene Ring
Real Life: Materials 15-1 Compounds Made of Pure Carbon:
Graphite, Graphene, Diamond, and Fullerenes
15-5 Polycyclic Aromatic Hydrocarbons
15-6 Other Cyclic Polyenes: Hückel’s Rule
15-7 Hückel’s Rule and Charged Molecules
15-8 Synthesis of Benzene Derivatives: Electrophilic Aromatic 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 Acylation
15-14 Worked Examples: Integrating the Concepts
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 Electron-Donating Effects of Alkyl Groups
16-3 Directing Effects of Substituents in Conjugation with the Benzene Ring
Real Life: Materials 16-1 Explosive Nitroarenes: TNT and Picric Acid
16-4 Electrophilic Attack on Disubstituted Benzenes
16-5 Keys to Success: Synthetic Strategies Toward Substituted Benzenes
16-6 Reactivity of Polycyclic Benzenoid Hydrocarbons
16-7 Polycyclic Aromatic Hydrocarbons and Cancer
16-8 Worked Examples: Integrating the Concepts
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
Real Life: Biochemistry 17-1 Imines Mediate the Biochemistry of Amino Acids
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
17-13 Oxidation by Peroxycarboxylic Acids: The Baeyer-Villiger Oxidation
17-14 Oxidative Chemical Tests for Aldehydes
17-15 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
18 ENOLS, ENOLATES, AND THE ALDOL CONDENSATION
α,β -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
Real Life: Biology And Medicine 18-1 Stereoselective Aldol
Reactions in Nature and in the Laboratory: “Organocatalysis”
18-6 Crossed Aldol Condensation
18-7 Keys to Success: Competitive Reaction Pathways and the Intramolecular Aldol Condensation
Real Life: Nature 18-2 Absorption of Photons by Unsaturated Aldehydes Enables Vision
18-8 Properties of α,β -Unsaturated Aldehydes and Ketones
18-9 Conjugate Additions to α,β -Unsaturated Aldehydes and Ketones
18-10 1,2- and 1,4-Additions of Organometallic Reagents
18-11 Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation
18-12 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
19 CARBOXYLIC ACIDS
19-1 Naming the Carboxylic Acids
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: Acyl Halides and 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
Real Life: Materials 19-1 Long-Chain Carboxylates and
Sulfonates Make Soaps and Detergents
Real Life: Health 19-2 Artery-Clogging Trans Fatty Acids Phasing Out
Real Life: Materials 19-3 Green Plastics, Fibers, and Energy
from Biomass-Derived Hydroxyesters
19-14 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
20 CARBOXYLIC ACID DERIVATIVES
20-1 Relative Reactivities, Structures, and Spectra of Carboxylic
Acid Derivatives
20-2 Chemistry of Acyl Halides
20-3 Chemistry of Carboxylic Anhydrides
20-4 Chemistry of Esters
20-5 Esters in Nature: Waxes, Fats, Oils, and Lipids
Real Life: Sustainability 20-1 Moving Away from Petroleum:
Green Fuels from Vegetable Oil
20-6 Amides: The Least Reactive Carboxylic Acid Derivatives
Real Life: Medicine 20-2 Killing the Bugs that Kill the Drugs:
Antibiotic Wars
20-7 Amidates and Their Halogenation: The Hofmann
Rearrangement
20-8 Alkanenitriles: A Special Class of Carboxylic Acid Derivatives
20-9 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
21 AMINES AND THEIR DERIVATIVES
Functional Groups Containing Nitrogen
21-1 Naming the Amines
Real Life: Medicine 21-1 Physiologically Active Amines and
Weight Control
21-2 Structural and Physical Properties of Amines
21-3 Spectroscopy of the Amine Group
21-4 Acidity and Basicity of Amines
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 Reactions of Quaternary Ammonium Salts: Hofmann
Elimination
21-9 Mannich Reaction: Alkylation of Enols by Iminium Ions
21-10 Nitrosation of Amines
Real Life: Medicine 21-2 Sodium Nitrite as a Food Additive,
N-Nitrosodialkanamines, and Cancer
Real Life: Materials 21-3 Amines in Industry: Nylon, the
“Miracle Fiber”
21-11 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
22 CHEMISTRY OF BENZENE SUBSTITUENTS
Alkylbenzenes, Phenols, and Anilines
22-1 Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic
Resonance Stabilization
22-2 Oxidations and Reductions of Substituted Benzenes
22-3 Names and Properties of Phenols
Real Life: Medicine 22-1 Two Phenols in the News: Bisphenol
A and Resveratrol
22-4 Preparation of Phenols: Nucleophilic Aromatic Substitution
22-5 Alcohol Chemistry of Phenols
Real Life: Medicine 22-2 Aspirin: The Miracle Drug
22-6 Electrophilic Substitution of Phenols
22-7 An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement
22-8 Oxidation of Phenols: Benzoquinones
Real Life: Biology 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: Diazo Coupling
22-12 Worked Examples: Integrating the Concepts
New Reactions
Important Concepts
Problems
23 ESTER ENOLATES AND THE CLAISEN CONDENSATION
Synthesis of β-Dicarbonyl Compounds; Acyl Anion Equivalents
23-1 β -Dicarbonyl Compounds: Claisen Condensations
Real Life: Nature 23-1 Claisen Condensations Assemble Biological Molecules
23-2 β -Dicarbonyl Compounds as Synthetic Intermediates
23-3 β -Dicarbonyl Anion Chemistry: Michael Additions
23-4 Acyl Anion Equivalents: Preparation of α -Hydroxyketones
Real Life: Nature 23-2 Thiamine: A Natural, Metabolically Active Thiazolium Salt
23-5 Worked Examples: Integrating the Concepts
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
24-9 Step-by-Step Buildup and Degradation of Sugars
Real Life: Nature 24-1 Biological Sugar Synthesis
24-10 Relative Configurations of the Aldoses: An Exercise in Structure Determination
24-11 Complex Sugars in Nature: Disaccharides
Real Life: Food Chemistry 24-2 Manipulating Our Sweet Tooth
24-12 Polysaccharides and Other Sugars in Nature
Real Life: Medicine 24-3 Sialic Acid, “Bird Flu,” and Rational Drug Design
24-13 Worked Example: Integrating the Concepts
New Reactions
Important Concepts
Problems
25 HETEROCYCLES
Heteroatoms in Cyclic Organic Compounds
25-1 Naming the Heterocycles
25-2 Nonaromatic Heterocycles
Real Life: Medicine 25-1 Smoking, Nicotine, Cancer, and Medicinal Chemistry
25-3 Structures 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
Real Life: Biochemistry 25-2 Lessons from Redox-Active
Pyridinium Salts in Nature: Nicotinamide Adenine
Dinucleotide, Dihydropyridines, and Synthesis
25-7 Quinoline and Isoquinoline: The Benzopyridines
Real Life: Biology 25-3 Folic Acid, Vitamin D, Cholesterol, and the Color of Your Skin
25-8 Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature
Real Life: Nature 25-4 Nature is Not Always Green: Natural Pesticides
25-9 Worked Examples: Integrating the Concepts
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
Real Life: Medicine 26-1 Arginine and Nitric Oxide in Biochemistry and Medicine
26-2 Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry
26-3 Synthesis of Enantiomerically Pure Amino Acids
Real Life: Chemistry 26-2 Enantioselective 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 of Protecting Groups
26-7 Merrifield Solid-Phase Peptide Synthesis
26-8 Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
26-9 Biosynthesis of Proteins: Nucleic Acids Real Life: Medicine 26-3 Synthetic Nucleic Acid Bases and
Nucleosides in Medicine
26-10 Protein Synthesis Through RNA
26-11 DNA Sequencing and Synthesis: Cornerstones of Gene Technology Real Life: Forensics 26-4 DNA Fingerprinting
26-12 Worked Examples: Integrating the Concepts New Reactions
Important Concepts
Problems
Answers to Exercises
Index