Organic Chemistry

Brief Contents
Detailed Contents
Preface
Ch 1: Structure and Bonding
1-1: Atomic Structure: The Nucleus
1-2: Atomic Structure: Orbitals
1-3: Atomic Structure: Electron Configurations
1-4: Development of Chemical Bonding Theory
1-5: Describing Chemical Bonds: Valence Bond Theory
1-6: sp3 Hybrid Orbitals and the Structure of Methane
1-7: sp3 Hybrid Orbitals and the Structure of Ethane
1-8: sp2 Hybrid Orbitals and the Structure of Ethylene
1-9: sp Hybrid Orbitals and the Structure of Acetylene
1-10: Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur
1-11: Describing Chemical Bonds: Molecular Orbital Theory
1-12: Drawing Chemical Structures
Summary
Exercises
Ch 2: Polar Covalent Bonds; Acids and Bases
2-1: Polar Covalent Bonds: Electronegativity
2-2: Polar Covalent Bonds: Dipole Moments
2-3: Formal Charges
2-4: Resonance
2-5: Rules for Resonance Forms
2-6: Drawing Resonance Forms
2-7: Acids and Bases: The Bronsted-Lowry Definition
2-8: Acid and Base Strength
2-9: Predicting Acid-Base Reactions from pKa Values
2-10: Organic Acids and Organic Bases
2-11: Acids and Bases: The Lewis Definition
2-12: Noncovalent Interactions between Molecules
Summary
Exercises
Ch 3: Organic Compounds: Alkanes and Their Stereochemistry
3-1: Functional Groups
3-2: Alkanes and Alkane Isomers
3-3: Alkyl Groups
3-4: Naming Alkanes
3-5: Properties of Alkanes
3-6: Conformations of Ethane
3-7: Conformations of Other Alkanes
Summary
Exercises
Ch 4: Organic Compounds: Cycloalkanes and Their Stereochemistry
4-1: Naming Cycloalkanes
4-2: Cis-Trans Isomerism in Cycloalkanes
4-3: Stability of Cycloalkanes: Ring Strain
4-4: Conformations of Cycloalkanes
4-5: Conformations of Cyclohexane
4-6: Axial and Equatorial Bonds in Cyclohexane
4-7: Conformations of Monosubstituted Cyclohexanes
4-8: Conformations of Disubstituted Cyclohexanes
4-9: Conformations of Polycyclic Molecules
Summary
Exercises
Ch 5: Stereochemistry at Tetrahedral Centers
5-1: Enantiomers and the Tetrahedral Carbon
5-2: The Reason for Handedness in Molecules: Chirality
5-3: Optical Activity
5-4: Pasteur's Discovery of Enantiomers
5-5: Sequence Rules for Specifying Configuration
5-6: Diastereomers
5-7: Meso Compounds
5-8: Racemic Mixtures and the Resolution of Enantiomers
5-9: A Review of Isomerism
5-10: Chirality at Nitrogen, Phosphorus, and Sulfur
5-11: Prochirality
5-12: Chirality in Nature and Chiral Environments
Summary
Exercises
Ch 6: An Overview of Organic Reactions
6-1: Kinds of Organic Reactions
6-2: How Organic Reactions Occur: Mechanisms
6-3: Radical Reactions
6-4: Polar Reactions
6-5: An Example of a Polar Reaction: Addition of HBr to Ethylene
6-6: Using Curved Arrows in Polar Reaction Mechanisms
6-7: Describing a Reaction: Equilibria, Rates, and Energy Changes
6-8: Describing a Reaction: Bond Dissociation Energies
6-9: Describing a Reaction: Energy Diagrams and Transition States
6-10: Describing a Reaction: Intermediates
6-11: A Comparison between Biological Reactions and Laboratory Reactions
Summary
Exercises
Practice Your Scientific Analysis and Reasoning I: The Chiral Drug Thalidomide
Ch 7: Alkenes: Structure and Reactivity
7-1: Industrial Preparation and Use of Alkenes
7-2: Calculating Degree of Unsaturation
7-3: Naming Alkenes
7-4: Cis-Trans Isomerism in Alkenes
7-5: Alkene Stereochemistry and the E,Z Designation
7-6: Stability of Alkenes
7-7: Electrophilic Addition Reactions of Alkenes
7-8: Orientation of Electrophilic Additions: Markovnikov's Rule
7-9: Carbocation Structure and Stability
7-10: The Hammond Postulate
7-11: Evidence for the Mechanism of Electrophilic Additions: Carbocation Rearrangements
Summary
Exercises
Ch 8: Alkenes: Reactions and Synthesis
8-1: Preparing Alkenes: A Preview of Elimination Reactions
8-2: Halogenation of Alkenes: Addition of X2
8-3: Halohydrins from Alkenes: Addition of HOX
8-4: Hydration of Alkenes: Addition of H2O by Oxymercuration
8-5: Hydration of Alkenes: Addition of H2O by Hydroboration
8-6: Reduction of Alkenes: Hydrogenation
8-7: Oxidation of Alkenes: Epoxidation and Hydroxylation
8-8: Oxidation of Alkenes: Cleavage to Carbonyl Compounds
8-9: Addition of Carbenes to Alkenes: Cyclopropane Synthesis
8-10: Radical Additions to Alkenes: Chain-Growth Polymers
8-11: Biological Additions of Radicals to Alkenes
8-12: Reaction Stereochemistry: Addition of H2O to an Achiral Alkene
8-13: Reaction Stereochemistry: Addition of H2O to a Chiral Alkene
Summary
Summary of Reactions
Exercises
Ch 9: Alkynes: An Introduction to Organic Synthesis
9-1: Naming Alkynes
9-2: Preparation of Alkynes: Elimination Reactions of Dihalides
9-3: Reactions of Alkynes: Addition of HX and X2
9-4: Hydration of Alkynes
9-5: Reduction of Alkynes
9-6: Oxidative Cleavage of Alkynes
9-7: Alkyne Acidity: Formation of Acetylide Anions
9-8: Alkylation of Acetylide Anions
9-9: An Introduction to Organic Synthesis
Summary
Summary of Reactions
Exercises
Ch 10: Organohalides
10-1: Names and Structures of Alkyl Halides
10-2: Preparing Alkyl Halides from Alkanes: Radical Halogenation
10-3: Preparing Alkyl Halides from Alkenes: Allylic Bromination
10-4: Stability of the Allyl Radical: Resonance Revisited
10-5: Preparing Alkyl Halides from Alcohols
10-6: Reactions of Alkyl Halides: Grignard Reagents
10-7: Organometallic Coupling Reactions
10-8: Oxidation and Reduction in Organic Chemistry
Summary
Summary of Reactions
Exercises
Ch 11: Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
11-1: The Discovery of Nucleophilic Substitution Reactions
11-2: The SN2 Reaction
11-3: Characteristics of the SN2 Reaction
11-4: The SN1 Reaction
11-5: Characteristics of the SN1 Reaction
11-6: Biological Substitution Reactions
11-7: Elimination Reactions: Zaitsev's Rule
11-8: The E2 Reaction and the Deuterium Isotope Effect
11-9: The E2 Reaction and Cyclohexane Conformation
11-10: The E1 and E1cB Reactions
11-11: Biological Elimination Reactions
11-12: A Summary of Reactivity: SN1, SN2, E1, E1cB, and E2
Summary
Summary of Reactions
Exercises
Practice Your Scientific Analysis and Reasoning II: From Mustard Gas to Alkylating Anticancer Drugs
Ch 12: Structure Determination: Mass Spectrometry and Infrared Spectroscopy
12-1: Mass Spectrometry of Small Molecules: Magnetic-Sector Instruments
12-2: Interpreting Mass Spectra
12-3: Mass Spectrometry of Some Common Functional Groups
12-4: Mass Spectrometry in Biological Chemistry: Time-of-Flight (TOF) Instruments
12-5: Spectroscopy and the Electromagnetic Spectrum
12-6: Infrared Spectroscopy
12-7: Interpreting Infrared Spectra
12-8: Infrared Spectra of Some Common Functional Groups
Summary
Exercises
Ch 13: Structure Determination: Nuclear Magnetic Resonance Spectroscopy
13-1: Nuclear Magnetic Resonance Spectroscopy
13-2: The Nature of NMR Absorptions
13-3: The Chemical Shift
13-4: Chemical Shifts in 1H NMR Spectroscopy
13-5: Integration of 1H NMR Absorptions: Proton Counting
13-6: Spin-Spin Splitting in 1H NMR Spectra
13-7: 1H NMR Spectroscopy and Proton Equivalence
13-8: More Complex Spin-Spin Splitting Patterns
13-9: Uses of 1H NMR Spectroscopy
13-10: 13C NMR Spectroscopy: Signal Averaging and FT-NMR
13-11: Characteristics of 13C NMR Spectroscopy
13-12: DEPT 13C NMR Spectroscopy
13-13: Uses of 13C NMR Spectroscopy
Summary
Exercises
Ch 14: Conjugated Compounds and Ultraviolet Spectroscopy
14-1: Stability of Conjugated Dienes: Molecular Orbital Theory
14-2: Electrophilic Additions to Conjugated Dienes: Allylic Carbocations
14-3: Kinetic versus Thermodynamic Control of Reactions
14-4: The Diels-Alder Cycloaddition Reaction
14-5: Characteristics of the Diels-Alder Reaction
14-6: Diene Polymers: Natural and Synthetic Rubbers
14-7: Ultraviolet Spectroscopy
14-8: Interpreting Ultraviolet Spectra: The Effect of Conjugation
14-9: Conjugation, Color, and the Chemistry of Vision
Summary
Summary of Reactions
Exercises
Practice Your Scientific Analysis and Reasoning III : Photodynamic Therapy (PDT)
Ch 15: Benzene and Aromaticity
15-1: Naming Aromatic Compounds
15-2: Structure and Stability of Benzene
15-3: Aromaticity and the Huckel 4n + 2 Rule
15-4: Aromatic Ions
15-5: Aromatic Heterocycles: Pyridine and Pyrrole
15-6: Polycyclic Aromatic Compounds
15-7: Spectroscopy of Aromatic Compounds
Summary
Exercises
Ch 16: Chemistry of Benzene: Electrophilic Aromatic Substitution
16-1: Electrophilic Aromatic Substitution Reactions: Bromination
16-2: Other Aromatic Substitutions
16-3: Alkylation and Acylation of Aromatic Rings: The Friedel-Crafts Reaction
16-4: Substituent Effects in Electrophilic Substitutions
16-5: Trisubstituted Benzenes: Additivity of Effects
16-6: Nucleophilic Aromatic Substitution
16-7: Benzyne
16-8: Oxidation of Aromatic Compounds
16-9: Reduction of Aromatic Compounds
16-10: Synthesis of Polysubstituted Benzenes
Summary
Summary of Reactions
Exercises
Ch 17: Alcohols and Phenols
17-1: Naming Alcohols and Phenols
17-2: Properties of Alcohols and Phenols
17-3: Preparation of Alcohols: A Review
17-4: Alcohols from Carbonyl Compounds: Reduction
17-5: Alcohols from Carbonyl Compounds: Grignard Reaction
17-6: Reactions of Alcohols
17-7: Oxidation of Alcohols
17-8: Protection of Alcohols
17-9: Phenols and Their Uses
17-10: Reactions of Phenols
17-11: Spectroscopy of Alcohols and Phenols
Summary
Summary of Reactions
Exercises
Ch 18: Ethers and Epoxides; Thiols and Sulfides
18-1: Names and Properties of Ethers
18-2: Preparing Ethers
18-3: Reactions of Ethers: Acidic Cleavage
18-4: Reactions of Ethers: Claisen Rearrangement
18-5: Cyclic Ethers: Epoxides
18-6: Reactions of Epoxides: Ring-Opening
18-7: Crown Ethers
18-8: Thiols and Sulfides
18-9: Spectroscopy of Ethers
Summary
Summary of Reactions
Exercises
Preview of Carbonyl Chemistry
Ch 19: Aldehydes and Ketones: Nucleophilic Addition Reactions
19-1: Naming Aldehydes and Ketones
19-2: Preparing Aldehydes and Ketones
19-3: Oxidation of Aldehydes and Ketones
19-4: Nucleophilic Addition Reactions of Aldehydes and Ketones
19-5: Nucleophilic Addition of H2O: Hydration
19-6: Nucleophilic Addition of HCN: Cyanohydrin Formation
19-7: Nucleophilic Addition of Hydride and Grignard Reagents: Alcohol Formation
19-8: Nucleophilic Addition of Amines: Imine and Enamine Formation
19-9: Nucleophilic Addition of Hydrazine: The Wolff-Kishner Reaction
19-10: Nucleophilic Addition of Alcohols: Acetal Formation
19-11: Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction
19-12: Biological Reductions
19-13: Conjugate Nucleophilic Addition to a,B-Unsaturated Aldehydes and Ketones
19-14: Spectroscopy of Aldehydes and Ketones
Summary
Summary of Reactions
Exercises
Practice Your Scientific Analysis and Reasoning IV: Selective Serotonin Reuptake Inhibitors (SSRIs)
Ch 20: Carboxylic Acids and Nitriles
20-1: Naming Carboxylic Acids and Nitriles
20-2: Structure and Properties of Carboxylic Acids
20-3: Biological Acids and the Henderson-Hasselbalch Equation
20-4: Substituent Effects on Acidity
20-5: Preparing Carboxylic Acids
20-6: Reactions of Carboxylic Acids: An Overview
20-7: Chemistry of Nitriles
20-8: Spectroscopy of Carboxylic Acids and Nitriles
Summary
Summary of Reactions
Exercises
Ch 21: Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
21-1: Naming Carboxylic Acid Derivatives
21-2: Nucleophilic Acyl Substitution Reactions
21-3: Reactions of Carboxylic Acids
21-4: Chemistry of Acid Halides
21-5: Chemistry of Acid Anhydrides
21-6: Chemistry of Esters
21-7: Chemistry of Amides
21-8: Chemistry of Thioesters and Acyl Phosphates: Biological Carboxylic Acid Derivatives
21-9: Polyamides and Polyesters: Step-Growth Polymers
21-10: Spectroscopy of Carboxylic Acid Derivatives
Summary
Summary of Reactions
Exercises
Ch 22: Carbonyl Alpha-Substitution Reactions
22-1: Keto-Enol Tautomerism
22-2: Reactivity of Enols: a-Substitution Reactions
22-3: Alpha Halogenation of Aldehydes and Ketones
22-4: Alpha Bromination of Carboxylic Acids
22-5: Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation
22-6: Reactivity of Enolate Ions
22-7: Alkylation of Enolate Ions
Summary
Summary of Reactions
Exercises
Ch 23: Carbonyl Condensation Reactions
23-1: Carbonyl Condensations: The Aldol Reaction
23-2: Carbonyl Condensations versus Alpha Substitutions
23-3: Dehydration of Aldol Products: Synthesis of Enones
23-4: Using Aldol Reactions in Synthesis
23-5: Mixed Aldol Reactions
23-6: Intramolecular Aldol Reactions
23-7: The Claisen Condensation Reaction
23-8: Mixed Claisen Condensations
23-9: Intramolecular Claisen Condensations: The Dieckmann Cyclization
23-10: Conjugate Carbonyl Additions: The Michael Reaction
23-11: Carbonyl Condensations with Enamines: The Stork Reaction
23-12: The Robinson Annulation Reaction
23-13: Some Biological Carbonyl Condensation Reactions
Summary
Summary of Reactions
Exercises
Practice Your Scientific Analysis and Reasoning V: Thymine in DNA
Ch 24: Amines and Heterocycles
24-1: Naming Amines
24-2: Structure and Properties of Amines
24-3: Basicity of Amines
24-4: Basicity of Arylamines
24-5: Biological Amines and the Henderson-Hasselbalch Equation
24-6: Synthesis of Amines
24-7: Reactions of Amines
24-8: Reactions of Arylamines
24-9: Heterocyclic Amines
24-10: Spectroscopy of Amines
Summary
Summary of Reactions
Exercises
Ch 25: Biomolecules: Carbohydrates
25-1: Classification of Carbohydrates
25-2: Representing Carbohydrate Stereochemistry: Fischer Projections
25-3: D,L Sugars
25-4: Configurations of the Aldoses
25-5: Cyclic Structures of Monosaccharides: Anomers
25-6: Reactions of Monosaccharides
25-7: The Eight Essential Monosaccharides
25-8: Disaccharides
25-9: Polysaccharides and Their Synthesis
25-10: Some Other Important Carbohydrates
25-11: Cell-Surface Carbohydrates and Influenza Viruses
Summary
Summary of Reactions
Exercises
Ch 26: Biomolecules: Amino Acids, Peptides, and Proteins
26-1: Structures of Amino Acids
26-2: Amino Acids and the Henderson-Hasselbalch Equation: Isoelectric Points
26-3: Synthesis of Amino Acids
26-4: Peptides and Proteins
26-5: Amino Acid Analysis of Peptides
26-6: Peptide Sequencing: The Edman Degradation
26-7: Peptide Synthesis
26-8: Automated Peptide Synthesis: The Merrifield Solid-Phase Method
26-9: Protein Structure
26-10: Enzymes and Coenzymes
26-11: How Do Enzymes Work? Citrate Synthase
Summary
Summary of Reactions
Exercises
Ch 27: Biomolecules: Lipids
27-1: Waxes, Fats, and Oils
27-2: Soap
27-3: Phospholipids
27-4: Prostaglandins and Other Eicosanoids
27-5: Terpenoids
27-6: Steroids
27-7: Biosynthesis of Steroids
Summary
Exercises
Practice Your Scientific Analysis and Reasoning VI: Melatonin and Serotonin
Ch 28: Biomolecules: Nucleic Acids
28-1: Nucleotides and Nucleic Acids
28-2: Base Pairing in DNA: The Watson-Crick Model
28-3: Replication of DNA
28-4: Transcription of DNA
28-5: Translation of RNA: Protein Biosynthesis
28-6: DNA Sequencing
28-7: DNA Synthesis
28-8: The Polymerase Chain Reaction
Summary
Exercises
Ch 29: The Organic Chemistry of Metabolic Pathways
29-1: An Overview of Metabolism and Biochemical Energy
29-2: Catabolism of Triacylglycerols: The Fate of Glycerol
29-3: Catabolism of Triacylglycerols: B-Oxidation
29-4: Biosynthesis of Fatty Acids
29-5: Catabolism of Carbohydrates: Glycolysis
29-6: Conversion of Pyruvate to Acetyl CoA
29-7: The Citric Acid Cycle
29-8: Carbohydrate Biosynthesis: Gluconeogenesis
29-9: Catabolism of Proteins: Deamination
29-10: Some Conclusions about Biological Chemistry
Summary
Exercises
Ch 30: Orbitals and Organic Chemistry: Pericyclic Reactions
30-1: Molecular Orbitals of Conjugated Pi Systems
30-2: Electrocyclic Reactions
30-3: Stereochemistry of Thermal Electrocyclic Reactions
30-4: Photochemical Electrocyclic Reactions
30-5: Cycloaddition Reactions
30-6: Stereochemistry of Cycloadditions
30-7: Sigmatropic Rearrangements
30-8: Some Examples of Sigmatropic Rearrangements
30-9: A Summary of Rules for Pericyclic Reactions
Summary
Exercises
Practice Your Scientific Analysis and Reasoning VII: The Potent Antibiotic Traits of Endiandric Acid C
Ch 31: Synthetic Polymers
31-1: Chain-Growth Polymers
31-2: Stereochemistry of Polymerization: Ziegler-Natta Catalysts
31-3: Copolymers
31-4: Step-Growth Polymers
31-5: Olefin Metathesis Polymerization
31-6: Polymer Structure and Physical Properties
Summary
Exercises
A: Nomenclature of Polyfunctional Organic Compounds
B: Acidity Constants for Some Organic Compounds
C: Glossary
D: Answers to In-Text Problems
Index