Note: Each chapter concludes with Additional Problems. 1. Bonding and Isomerism 1.1 How Electrons are Arranged in Atoms 1.2 Ionic and Covalent Bonding 1.3 Carbon and the Covalent Bond 1.4 Carbon-Carbon Single Bonds 1.5 Polar Covalent Bonds 1.6 Multiple Covalent Bonds 1.7 Valence 1.8 Isomerism 1.9 Writing Structural Formulas 1.10 Abbreviated Structural Formulas 1.11 Formal Charge 1.12 Resonance 1.13 Arrow Formalism 1.14 The Orbital View of Bonding; the Sigma Bond 1.15 Carbon sp3 Hybrid Orbitals 1.16 Tetrahedral Carbon; the Bonding in Methane 1.17 Classification According to Molecular Framework 1.18 Classification According to Functional Group 2. Alkanes and Cycloalkanes; Conformational and Geometric Isomerism 2.1 The Structures of Alkanes 2.2 Nomenclature of Organic Compounds 2.3 IUPAC Rules for Naming Alkanes 2.4 Alkyl and Halogen Substituents 2.5 Use of the IUPAC Rules A Closer Look at...Natural Gas 2.6 Sources of Alkanes 2.7 Physical Properties of Alkanes and Nonbonding Intermolecular Interactions A Closer Look at...Hydrogen Bonding 2.8 Conformations of Alkanes 2.9 Cycloalkane Nomenclature and Conformation 2.10 Cis-trans Isomerism in Cycloalkanes A Word About: Isomers- Possible and Impossible 2.11 Summary of Isomerism 2.12 Reactions of Alkanes A Word About: Methane, Marsh Gas, and Miller's Experiment 2.13 The Free-Radical Chain Mechanism of Halogenation Reaction Summary Mechanism Summary 3. Alkenes and Alkynes 3.1 Definition and Classification 3.2 Nomenclature 3.3 Some Facts About Double Bonds 3.4 The Orbital Model of a Double Bond; the Pi Bond 3.5 Cis-trans Isomerism in Alkenes A Word About: The Chemistry of Vision 3.6 Addition and Substitution Reactions Compared 3.7 Polar Addition Reactions 3.8 Addition of Unsymmetric Reagents to Unsymmetric Alkenes; Markovnikov's Rule 3.9 Mechanism of Electrophilic Addition to Alkenes 3.10 Markovnikov's Rule Explained 3.11 Reaction Equilibrium: What Makes a Reaction Go? 3.12 Reaction Rates: How Fast Does a Reaction Go? 3.13 Hydroboration of Alkenes 3.14 Addition of Hydrogen 3.15 Additions to Conjugated Systems 3.16 Free-Radical Additions; Polyethylene 3.17 Oxidation of Alkenes A Word About: Ethylene: Raw Material and Plant Hormone 3.18 Some Facts About Triple Bonds 3.19 The Orbital Model of a Triple Bonds 3.20 Additon Reactions of Alkynes A Word About: Petroleum, Gasoline, and Octane Number 3.21 Acidity of Alkynes Reaction Summary Mechanism Summary 4. Aromatic Compounds 4.1 Some Facts About Benzene 4.2 The Kekule Structure of Benzene 4.3 The Resonance Model for Benzene 4.4 Orbital Model for Benzene 4.5 Symbols for Benzene 4.6 Nomenclature of Aromatic Compounds 4.7 The Resonance Energy of Benzene 4.8 Electrophilic Aromatic Substitution 4.9 The Mechanism of Electrophilic Aromatic Substitution 4.10 Ring-Activating and Ring-Deactivating Substituents 4.11 Ortho, Para-Directing, and Meta-Directing Groups 4.12 The Importance of Directing Effects in Synthesis 4.13 Polycyclic Aromatic Hydrocarbons A Word About: Polycyclic Aromatic Hydrocarbons and Cancer A Closer Look at...Polycyclic Aromatic Hydrocarbons A Word About: C60, an Aromatic Sphere: The Fullerenes Reaction Summary Mechanism Summary 5. Stereoisomerism 5.1 Chirality and Enantiomers 5.2 Stereogenic Centers; the Stereogenic Carbon Atom 5.3 Configuration and the R-S Convention 5.4 The E-Z Convention for Cis-trans Isomers 5.5 Polarized Light and Optical Activity A Word About: Pasteur's Experiments and the van't Hoff-LeBel Explanation 5.6 Properties of Enantiomers 5.7 Fischer Projection Formulas 5.8 Compounds with More Than One Stereogenic Center; Diastereomers 5.9 Meso Compounds; the Stereoisomers of Tartaric Acid 5.10 Stereochemistry: a Recap of Definitions 5.11 Stereochemistry and Chemical Reactions A Word About: Enantiomers and Biological Activity 5.12 Resolution of a Racemic Mixture A Closer Look at...Thalidomide 6. Organic Halogen Compounds; Substitution and Elimination Reactions 6.1 Nucleophilic Substitution 6.2 Examples of Nucleophilic Substitution 6.3 Nucleophilic Substitution Mechanism 6.4 The SN2 Mechanism 6.5 The SN1 Mechanism 6.6 The SN1 and SN2 Mechanisms Compared A Word About: SN2 Reactions in Nature: Biological Methylations 6.7 Dehydrohalogenation, an Elimination Reaction; the E2 and E1 Mechanisms 6.8 Substitution and Elimination Competition 6.9 Polyhalogenated Aliphatic Compounds A Word About: CFCs, the Ozone Layer, and Trade-Offs A Word About: Halogenated Organic Compounds from the Sea Reaction Summary Mechanism Summary 7. Alcohols, Phenols, and Thiols 7.1 Nomenclature of Alcohols A Word About: Industrial Alcohols 7.2 Classification of Alcohols 7.3 Nomenclature of Phenols 7.4 Hydrogen Bonding in Alcohols and Phenols 7.5 Acidity and Basicity Reviewed 7.6 The Acidity of Alcohols and Phenols 7.7 The Basicity of Alcohols and Phenols 7.8 Dehydration of Alcohols to Alkenes 7.9 The Reaction of Alcohols with Hydrogen Halides 7.10 Other Ways to Prepare Alkyl Halides from Alcohols 7.11 A Comparison of Alcohols and Phenols 7.12 Oxidation of Alcohols to Aldehydes, Ketones, and Carboxylic Acids A Word About: Biologically Important Alcohols and Phenols 7.13 Alcohols with More Than One Hydroxyl Group 7.14 Aromatic Substitution in Phenols A Word About: Quinones and the Bombardier Beetle 7.15 Oxidation of Phenols 7.16 Phenols As Antioxidants 7.17 Thiols, the Sulfur Analogs of Alcohols and Phenols A Word About: Hair--Curly or Straight Reaction Summary 8. Ethers and Epoxides 8.1 Nomenclature of Ethers 8.2 Physical Properties of Ethers 8.3 Ethers as Solvents 8.4 The Grignard Reagent; an Organometallic Compound 8.5 Preparation of Ethers A Closer Loook at...MTBE 8.6 Cleavage of Ethers A Word About: Ether and Anesthesia 8.7 Epoxides (Oxiranes) A Word About: The Gypsy Moth's Epoxide 8.8 Reactions of Epoxides 8.9 Cyclic Ethers Reaction Summary 9. Aldehydes and Ketones 9.1 Nomenclature of Aldehydes and Ketones 9.2 Some Common Aldehydes and Ketones 9.3 Synthesis of Aldehydes and Ketones 9.4 Aldehydes and Ketones in Nature 9.5 The Carbonyl Group 9.6 Nucleophilic Addition to Carbonyl Groups: An Overview 9.7 Addition of Alcohols: Formation of Hemiacetals and Acetals 9.8 Addition of Water; Hydration of Aldehydes and Ketones 9.9 Addition of Grignard Reagents and Acetylides 9.10 Addition of Hydrogen Cyanide; Cyanohydrins 9.11 Addition of Nitrogen Nucleophiles 9.12 Reduction of Carbonyl Compounds 9.13 Oxidation of Carbonyl Compounds 9.14 Keto-Enol Tautomerism 9.15 Acidity of a-Hydrogens; the Enolate Anion 9.16 Deuterium Exchanges in Carbonyl Compounds 9.17 The Aldol Condensation 9.18 The Mixed Aldol Condensation A Word About: Water Treatment and the Chemistry of Enols/Enolates 9.19 Commercial Synthesis via the Aldol Condensation Reaction Summary Mechanism Summary 10. Carboxylic Acids and their Derivatives 10.1 Nomenclature of Acids 10.2 Physical Properties of Acids 10.3 Acidity and Acidity Constants 10.4 What Makes Carboxylic Acids Acidic? 10.5 Effect of Structure on Acidity; the Inductive Effect Revisited 10.6 Conversion of Acids to Salts 10.7 Preparation of Acids A Word About: Green Chemistry and Ibuprofen: A Case Study A Closer Look at...Green Chemistry 10.8 Carboxylic Acid Derivatives 10.9 Esters 10.10 Preparation of Esters; Fischer Esterification 10.11 The Mechanism of Acid-Catalyzed Esterification; Nucleophilic Acyl Substitution 10.12 Lactones 10.13 Saponification of Esters 10.14 Ammonolysis of Esters 10.15 Reaction of Esters with Grignard Reagents 10.16 Reduction of Esters 10.17 The Need for Activated Acyl Compounds 10.18 Acyl Halides 10.19 Acid Anhydrides A Word About: Thioesters, Nature's Acyl-Activating Groups 10.20 Amides 10.21 A Summary of Carboxylic Acid Derivatives 10.22 The a-Hydrogen of Esters; the Claisen Condensation Reaction Summary Mechanism Summary 11. Amines and Related Nitrogen Compounds 11.1 Classification and Structure of Amines 11.2 Nomenclature of Amines 11.3 Physical Properties and Intermolecular Interactions of Amines 11.4 Preparation of Amines; Alkylation of Ammonia and Amines 11.5 Preparation of Amines; Reduction of Nitrogen Compounds 11.6 The Basicity of Amines 11.7 Comparison of the Basicity and Acidity of Amines and Amides 11.8 Reaction of Amines with Strong Acids; Amine Salts A Word About: Alkaloids and the Dart-Poison Frogs 11.9 Chiral Amines as Resolving Agents 11.10 Acylation of Amines with Acid Derivatives 11.11 Quaternary Ammonium Compounds 11.12 Aromatic Diazonium Compounds 11.13 Diazo Coupling; Azo Dyes Reaction Summary Mechanism Summary 12. Spectroscopy and Structure Determination 12.1 Principles of Spectroscopy 12.2 Nuclear Magnetic Resonance Spectroscopy (NMR) 12.3 13C NMR Spectroscopy A Word About: NMR in Biology and Medicine 12.4 Infrared Spectroscopy 12.5 Visible and Ultraviolet Spectroscopy 12.6 Mass Spectrometry A Closer Look at...Mass Spectrometry and Carbon Dating 13. Heterocyclic Compounds 13.1 Pyridine: Bonding and Basicity 13.2 Substitution in Pyridine 13.3 Other Six-Membered Heterocycles 13.4 Five-Membered Heterocycles: Furan, Pyrrole, and Thiophene 13.5 Electrophilic Substitution in Furan, Pyrrole, and Thiophene 13.6 Other Five-Membered Heterocycles: Azoles A Word About: Porphyrins: What Makes Blood Red and Grass Green? 13.7 Fused-Ring, Five-Membered Heterocycles: Indoles and Purines A Word About: Morphine and Other Nitrogen-Containing Drugs Reaction Summary Mechanism Summary 14. Synthetic Polymers 14.1 Classification of Polymers 14.2 Free-Radical Chain-Growth Polymerization 14.3 Cationic Chain-Growth Polymerization 14.4 Anionic Chain-Growth Polymerization 14.5 Stereoregular Polymers; Ziegler-Natta Polymerization A Word About: Polyacetylene and Conducting Polymers 14.6 Diene Polymers: Natural and Synthetic Rubber 14.7 Copolymers 14.8 Step-Growth Polymerization: Dacron and Nylon A Word About: Degradable Polymers A Word About: Aramids, the Latest in Polyamides A Closer Look at...Nylon 14.9 Polyurethanes and Other Step-Growth Polymers Reaction Summary Mechanism Summary 15. Lipids and Detergents 15.1 Fats and Oils; Triesters of Glycerol 15.2 Hydrogenation of Vegetable Oils 15.3 Saponification of Fats and Oils; Soap 15.4 How Do Soaps Work? 15.5 Synthetic Detergents (Syndets) A Word About: Commercial Detergents 15.6 Phospholipids 15.7 Prostaglandins, Leukotrienes, and Lipoxins A Word About: Prostaglandins, Aspirin, and Pain 15.8 Waxes 15.9 Terpenes and Steroids Reaction Summary 16. Carbohydrates 16.1 Definitions and Classification 16.2 Monosaccharides 16.3 Chirality in Monosaccharides; Fischer Projection Formulas and D,L-Sugars 16.4 The Cyclic Hemiacetal Structures of Monosaccharides 16.5 Anomeric Carbons; Mutarotation 16.6 Pyranose and Furanose Structures 16.7 Conformations of Pyranoses 16.8 Esters and Ethers from Monosaccharides 16.9 Reduction of Monosaccharides 16.10 Oxidation of Monosaccharides 16.11 Formation of Glycosides from Monosaccharides 16.12 Disaccharides A Word About: Sweetness and Sweeteners 16.13 Polysaccharides A Word About: Fat Substitutes from Carbohydrates 16.14 Sugar Phosphates 16.15 Deoxy Sugars 16.16 Amino Sugars 16.17 Ascorbic Acid (Vitamin C) Reaction Summary 17. Amino Acids, Peptides, and Proteins 17.1 Naturally Occurring Amino Acids 17.2 The Acid-Base Properties of Amino Acids 17.3 The Acid-Base Properties of Amino Acids with More Than One Acidic or Basic Group 17.4 Electrophoresis 17.5 Reactions of Amino Acids 17.6 The Ninhydrin Reaction 17.7 Peptides A Word About: Some Naturally Occurring Peptides 17.8 The Disulfide Bond 17.9 Proteins 17.10 The Primary Structure of Proteins 17.11 The Logic of Sequence Determination A Word About: Protein Sequencing and Evolution 17.12 Peptide Synthesis 17.13 Secondary Structure of Proteins 17.14 Tertiary Structure: Fibrous and Globular Proteins 17.15 Quaternary Protein Structure A Closer Look at...Nobel Laureates and Protein Chemistry Reaction Summary 18. Nucleotides and Nucleic Acids 18.1 The General Structure of Nucleic Acids 18.2 Components of Deoxyribonucleic Acid (DNA) 18.3 Nucleosides 18.4 Nucleotides 18.5 The Primary Structure of DNA 18.6 Sequencing Nucleic Acids A Word About: DNA and Crime 18.7 Laboratory Synthesis of Nucleic Acids 18.8 Secondary DNA Structure; the Double Helix 18.9 DNA Replication 18.10 Ribonucleic Acids; RNA 18.11 The Genetic Code and Protein Biosynthesis A Word About: The Human Genome A Word About: Nucleic Acids and Viruses 18.12 Other Biologically Important Nucleotides Reaction Summary
