1 Structure and Bonding: Acids and Bases

1.1 Atomic Structure

1.2 Electron Configuration of Atoms

1.3 Development of Chemical Bonding Theory

1.4 The Nature of Chemical Bonds: Ionic Bonds

1.5 The Nature of Chemical Bonds: Covalent Bonds

1.6 Formation of Covalent Bonds

1.7 Hybridization: sp3 Orbitals and the Structure of Methane

1.8 The Structure of Ethane

1.9 Hybridization: sp2 Orbitals and the Structure of Ethylene

1.10 Hybridization: sp Orbitals and the Structure of Acetylene

1.11 Bond Polarity and Electronegativity

1.12 Acids and Bases: The Br?nsted-Lowry Definition

1.13 Acids and Bases: The Lewis Definition

Interlude—Chemicals, Toxicity, and Risk

Summary and Key Words

Additional Problems

Working Problems

2 The Nature of Organic Compounds: Alkanes

2.1 Functional Groups

2.2 Alkanes and Alkyl Groups: Isomers

2.3 Naming Branched-Chain Alkanes

2.4 Properties of Alkanes

2.5 Conformations of Ethane

2.6 Drawing Chemical Structures

2.7 Cycloalkanes

2.8 Cis-Trans Isomerism in Cycloalkanes

2.9 Conformations of Some Common Cycloalkanes

2.10 Axial and Equatorial Bonds in Cyclohexane

2.11 Conformational Mobility of Cyclohexane

Interlude—Petroleum

Summary and Key Words

Additional Problems

3 Alkenes: The Nature of Organic Reactions

3.1 Naming Alkenes

3.2 Electronic Structure of Alkenes

3.3 Cis-Trans Isomers of Alkenes

3.4 Sequence Rules: The E,Z Designation

3.5 Kinds of Organic Reactions

3.6 How Reactions Occur: Mechanisms

3.7 An Example of a Polar Reaction: Addition of HCI to Ethylene

3.8 The Mechanism of an Organic Reaction: Addition of HCI to Ethylene

3.9 Describing a Reaction: Rates and Equilibria

3.10 Describing a Reaction: Reaction Energy Diagrams and Transition States

3.11 Describing a Reaction: Intermediates

Interlude--Carrots, Alkenes, and the Chemistry of Vision

Summary and Key Words

Additional Problems

4 Alkenes and Alkynes

4.1 Addition of HX to Alkenes: Hydrohalogenation

4.2 Orientation of Alkene Addition Reactions: Markovnikov s Rule

4.3 Carbocation Structure and Stability

4.4 Addition of H2O to Alkenes: Hydration

4.5 Addition of X2 to Alkenes: Halogenation

4.6 Addition of H2 to Alkenes: Hydrogenation

4.7 Oxidation of Alkenes

4.8 Alkene Polymers

4.9 Preparation of Alkenes: Elimination Reactions

4.10 Conjugated Dienes

4.11 Stability of Allylic Carbocations: Resonance

4.12 Drawing and Interpreting Resonance Forms

4.13 Alkynes

4.14 Reactions of Alkynes: Addition of H2, HX, and X2

4.15 Addition of H2O to Alkynes

4.16 Alkyne Acidity: Formation of Acetylide Anions

Interlude—Natural Rubber

Summary and Key Words

Summary of Reactions

Additional Problems

5 Aromatic Compounds

5.1 Structure of Benzene: The Kekule Proposal

5.2 Stability of Benzene

5.3 Structure of Benzene: The Resonance Proposal

5.4 Naming Aromatic Compounds

5.5 Chemistry of Benzene: Electrophilic Aromatic Substitution Reactions

5.6 Bromination of Benzene

5.7 Other Electrophilic Aromatic Substitution Reactions

5.8 The Friedel-Crafts Alkylation and Acylation Reactions

5.9 Substituent Effects in Electrophilic Aromatic Substitution

5.10 An Explanation of Substituent Effects

5.11 Oxidation and Reduction of Aromatic Compounds

5.12 Polycyclic Aromatic Hydrocarbons

5.13 Organic Synthesis

Interlude—Aspirin and Other Aromatic NSAID s

Summary and Key Words

Summary of Reactions

Additional Problems

6 Stereochemistry

6.1 Stereochemistry and the Tetrahedral Carbon

6.2 The Reason for Handedness in Molecules: Chirality

6.3 Optical Activity

6.4 Specific Rotation

6.5 Pasteur s Discovery of Enantiomers

6.6 Sequence Rules for Specifying Configuration

6.7 Diastereomers

6.8 Meso Compounds

6.9 Molecules with More Than Two Stereocenters

6.10 Racemic Mixtures and the Resolution of Enantiomers

6.11 Physical Properties of Stereoisomers

6.12 A Brief Review of Isomerism

6.13 Stereochemistry of Reactions: Addition of HBr to Alkenes

6.14 Chirality in Nature

Interlude—Chiral Drugs

Summary and Key Words

Additional Problems

7 Alkyl Halides

7.1 Naming Alkyl Halides

7.2 Preparation of Alkyl Halides: Radical Chlorination of Alkanes

7.3 Alkyl Halides from Alcohols

7.4 Reactions of Alkyl Halides: Grignard Reagents

7.5 Nucleophilic Substitution Reactions: The Discovery

7.6 Kinds of Nucleophilic Substitution Reactions

7.7 The SN2 Reaction

7.8 The SN1 Reaction

7.9 Eliminations: The E2 Reaction

7.10 Eliminations: The E1 Reaction

7.11 A Summary of Reactivity: SN1, SN2, E1, E2

7.12 Substitution Reactions in Living Organisms

Interlude—Naturally Occurring Organohalogen Compounds

Summary and Key Words

Summary of Reactions

Additional Problems

8 Alcohols,Ethers,and Phenols

8.1 Naming Alcohols, Phenols, and Ethers

8.2 Properties of Alcohols, Phenols, and Ethers: Hydrogen Bonding

8.3 Properties of Alcohols and Phenols: Acidity

8.4 Synthesis of Alcohols

8.5 Alcohols from Carbonyl Compounds

8.6 Ethers from Alcohols: The Williamson Ether Synthesis

8.7 Reactions of Alcohols

8.8 Synthesis and Reactions of Phenols

8.9 Reactions of Ethers: Acidic Cleavage

8.10 Cyclic Ethers: Epoxides

8.11 Ring-Opening Reactions of Epoxides

8.12 Thiols and Sulfides

Interlude—Ethanol as Chemical, Drug, and Poison

Summary and Key Words

Summary of Reactions

Additional Problems

9 Aldehydes and Ketones: Nucleophilic Addition Reactions

9.1 Kinds of Carbonyl Compounds

9.2 Structure and Properties of Carbonyl Groups

9.3 Naming Aldehydes and Ketones

9.4 Synthesis of Aldehydes and Ketones

9.5 Oxidation of Aldehydes

9.6 Reactions of Aldehydes and Ketones: Nucleophilic Additions

9.7 Nucleophilic Addition of Water: Hydration

9.8 Nucleophilic Addition of Alcohols: Acetal Formation

9.9 Nucleophilic Addition of Amines: Imine Formation

9.10 Nucleophilic Addition of Grignard Reagents: Alcohol Formation

9.11 Some Biological Nucleophilic Addition Reactions

Interlude—Insect Antifeedants

Summary and Key Words

Summary of Reactions

Additional Problems

10 Carboxylic Acids and Derivatives

10.1 Naming Carboxylic Acids and Derivatives

10.2 Occurrence, Structure, and Properties of Carboxylic Acids

10.3 Acidity of Carboxylic Acids

10.4 Synthesis of Carboxylic Acids

10.5 Nucleophilic Acyl Substitution Reactions

10.6 Reactions of Carboxylic Acids

10.7 Chemistry of Acid Halides

10.8 Chemistry of Acid Anhydrides

10.9 Chemistry of Esters

10.10 Chemistry of Amides

10.11 Chemistry of Nitriles

10.12 Nylons and Polyesters: Step-Growth Polymers

Interlude—β-Lactam Antibiotics

Summary and Key Words

Summary of Reactions

Additional Problems

11 Carbonyl Alpha-Substitution Reactions and Condensation Reactions

11.1 Keto-Enol Tautomerism

11.2 Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions

11.3 Alpha Halogenation of Aldehydes and Ketones

11.4 Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation

11.5 Reactivity of Enolate Ions

11.6 Alkylation of Enolate Ions

11.7 Carbonyl Condensation Reactions

11.8 Condensations of Aldehydes and Ketones: The Aldol Reaction

11.9 Dehydration of Aldol Products: Synthesis of Enones

11.10 Condensations of Esters: The Claisen Condensation Reaction

Interlude—Carbonyl Compounds in Metabolism

Summary and Key Words

Summary of Reactions

Additional Problems

12 Amines

12.1 Naming Amines

12.2 Structure and Properties of Amines

12.3 Amine Basicity

12.4 Synthesis of Amines

12.5 Reactions of Amines

12.6 Heterocyclic Amines

Interlude—Naturally Occurring Amines: Morphine Alkaloids

Summary and Key Words

Summary of Reactions

Additional Problems

13 Structure Determination

13.1 Infrared Spectroscopy and the Electromagnetic Spectrum

13.2 Infrared Spectroscopy of Organic Molecules

13.3 Ultraviolet Spectroscopy

13.4 Interpreting Ultraviolet Spectra: The Effect of Conjugation

13.5 Nuclear Magnetic Resonance Spectroscopy

13.6 The Nature of NMR Absorptions

13.7 Chemical Shifts

13.8 Chemical Shifts in 1H NMR Spectra

13.9 Integration of 1H NMR Spectra: Proton Counting

13.10 Spin-Spin Splitting in 1H NMR Spectra

13.11 Uses of 1H NMR Spectra

13.12 13C NMR Spectroscopy

Interlude—Magnetic Resonance Imaging (MRI)

Summary and Key Words

Additional Problems

14 Biomolecules: Carbohydrates

14.1 Classification of Carbohydrates

14.2 Configurations of Monosaccharides: Fischer Projections

14.3 D,L Sugars

14.4 Configurations of Aldoses

14.5 Cyclic Structures of Monosaccharides: Hemiacetal Formation

14.6 Monosaccharide Anomers: Mutarotation

14.8 Reactions of Monosaccharides

14.7 Conformations of Monosaccharides

14.9 Disaccharides

14.10 Polysaccharides

14.11 Other Important Carbohydrates

14.12 Cell-Surface Carbohydrates

Interlude—Sweetness

Summary and Key Words

Additional Problems

15 Biomolecules: Amino Acids,Peptides, and Proteins

15.1 Structures of Amino Acids

15.2 Dipolar Structure of Amino Acids

15.3 Isoelectric Points

15.4 Peptides and Proteins

15.5 Covalent Bonding in Peptides

15.6 Peptide Structure Determination: Amino Acid Analysis

15.7 Peptide Sequencing: The Edman Degradation

15.8 Peptide Synthesis

15.9 Classification of Proteins

15.10 Protein Structure

15.11 Enzymes

15.12 Structure and Classification of Enzymes

Interlude—Protein and Nutrition

Summary and Key Words

Additional Problems

16.1 Lipids

16 Biomolecules: Lipids and Nucleic Acids

16.2 Fats and Oils

16.3 Soaps

16.4 Phospholipids

16.5 Steroids

16.6 Nucleic Acids and Nucleotides

16.7 Structure of DNA

16.8 Base Pairing in DNA: The Watson-Crick Model

16.10 Replication of DNA

16.9 Nucleic Acids and Heredity

16.11 Structure and Synthesis of RNA: Transcription

16.12 RNA and Protein Biosynthesis: Translation

16.13 Sequencing DNA

16.14 The Polymerase Chain Reaction

Interlude—Cholesterol and Heart Disease

Summary and Key Words

Additional Problems

17 The Organic Chemistry of Metabolic Pathways

17.1 An Overview of Metabolism and Biochemical Energy

17.2 Catabolism of Fats: β-Οxidation Pathway

17.3 Catabolism of Carbohydretes: Glycolysis

17.4 The Citric Acid Cycle

17.5 Catabolism of Proteins: Transamination

Interlude—Basal Metabolism

Summary and Key Words

Additional Problems