Chapter 1 - Structure Determines Properties

1.1 Atoms, Electrons, and Orbitals

1.2 Ionic Bonds

1.3 Covalent Bonds, Lewis Structures, and the Ocelet Rule

1.4 Double Bonds and Triple Bonds

1.5 Polar Covalent Bonds and Electronegativity

Electrostatic Potential Maps

1.6 Structural Formuala of Organic Molecules

1.7 Formal Charge

1.8 Resonance

1.9 The Shape of Some Simple Molecules

Molecular Modeling

1.10 Molecular Dipole Moments

1.11 Curved Arrows and Chemical Reactions

1.12 Acids and Bases: The Arrhenius View

1.13 Acids and Bases: The Brønsted-Lowry View

1.14 What Happened to pKb?

1.15 How Structure Affects Acid Strength

1.16 Acid-Base Equilibria

1.17 Lewis Acids and Lewis Bases

1.18 Summary

Problems

Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures.

Chapter 2 - Alkanes and Cycloakanes: Introduction to Hydrocarbons

2.1 Classes of Hydrocarbons

2.2 Electron Waves and Chemical Bonds

2.3 Bonding in H2: The Valence Bond Model

2.4 Bonding in H2: The Molecular Orbital Model

2.5 Introduction to Alkanes: Methane, Ethane, and Propane

Methane and the Biosphere

2.6 sp3 Hybridization and Bonding in Methane

2.7 Bonding in Ethane

2.8 Isomeric Alkanes: The Butanes

2.9 Higher n -Alkanes

2.10 The C5H12 Isomers

2.11 IUPAC Nomenclature of Unbranched Alkanes

What's in a Name? Organic Nonmenclature

2.12 Applying the IUPAC Rules: The Names of the C6H14 Isomers

2.13 Alkyl Groups

2.14 IUPAC Names of Highly Branched Alkanes

2.15 Cycloalkane Nomenclature

2.16 Sources of Alkanes and Cycloalkanes

2.17 Physical Properties of Alkanes and Cycloalkanes

2.18 Chemical Properties. Combustion of Alkanes

2.19 Oxidation-Reduction in Organic Chemistry

Thermochemistry

2.20 sp2 Hybridization and Bonding in Ethylene

2.21 sp Hybridization and Bonding in Acetylene

2.22 Which Theory of Chemical Bonding is Best?

2.23 Summary

Problems

Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes

Chapter 3 - Alkanes andCycloalkanes: Conformations and cis-trans Stereoisomers

3.1 Conformational Analysis of Ethane

3.2 Conformational Analysis of Butane

Molecular Mechanics Applied to Alkanes and Cycloalkanes

3.3 Conformations of Higher Alkanes

3.4 The Shapes of Cycloalkanes: Planar or Nonplanar

3.5 Small Rings: Cyclopropane and Cyclobutane

3.6 Cyclopentane

3.7 Conformations of Cyclohexane

3.8 Axial and Equatorial Bonds in Cyclohexane

3.9 Conformational Inversion (Ring Flipping) in Cyclohexane

3.10 Conformational Analysis of Monosubstituted Cyclohexanes

3.11 Disubstituted Cycloalkanes. Stereoisomers

Enthalpy, Free Energy, and Equilibrium Constant

3.12 Conformational Analysis of Disubstituted Cyclohexanes

3.13 Medium and Large Rings

3.14 Polycyclic Ring Systems

3.15 Heterocyclic Compounds

3.16 Summary

Problems

Descriptive Passage and Interpretive Problems 3: Cylic Forms of Carbohydrates

Chapter 4 - Alcohols and Alkyl Halides

4.1 Functional Groups

4.2 IUPAC Nomenclature of Alkyl Halides

4.3 IUPAC Nomenclature of Alcohols

4.4 Classes of Alcohols and Alkyl Halides

4.5 Bonding in Alcohols and Alkyl Halides

4.6 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces

4.7 Preparation of Alkyl Halides From Alcohols and Hydrogen Halides

4.8 Mechanism of the Reaction of Alcohols with Hydrogen Halides

4.9 Potential Energy Diagrams for Multistep Reactions. The SN1 Mechanism

4.10 Structure, Bonding, and Stability of Carbocations

4.11 Effect of Alcohol Structure on Reaction Rate

4.12 Reaction of Primary Alcohols with Hydrogen Halides. The SN2 Mechanism

4.13 Other Methods for Converting Alcohols to Alkyl Halides

4.14 Halogenation of Alkanes

4.15 Chlorination of Methane

4.16 Structure and Stability of Free Radicals

4.17 Mechanism of Methane Chlorination

4.18 Halogenation of Higher Alkanes

From Bond Enthalpies to Heats of Reaction

4.19 Summary

Problems

Descriptive Passage and Interpretive Problems 4: More About Potential Energy Diagrams

Chapter 5 - Structure and Preparation of Alkenes: Elimination Reactions

5.1 Alkene Nomenclature

5.2 Structure and Bonding in Alkenes

Ethylene

5.3 Isomerism in Alkenes

5.4 Naming Stereoisomeric Alkenes by the E-Z Notational System

5.5 Physical Properties on Alkenes

5.6 Relative Stabilities of Alkenes

5.7 Cycloalkenes

5.8 Preparations of Alkenes: Elimination Reactions

5.9 Dehydration of Alcohols

5.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule

5.11 Stereoselectivity in Alcohol Dehydration

5.12 The E1 and E2 Mechanisms of Alcohol Dehydration

5.13 Rearrangements in Alcohol Dehydration

5.14 Dehydrohalogenation of Alkyl Halides

5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides

5.16 Anti Elimination in E2 Reactions: Stereoelectronic Effects

5.17 Isotope Effects and the E2 Mechanism

5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides

5.19 Summary

Problems

Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions

Chapter 6 - Reactions of Alkenes

6.1 Hydrogenation of Alkenes

6.2 Heats of Hydrogenation

6.3 Stereochemistry of Alkene Hydrogenation

6.4 Electrophilic Addition of Hydrogen Halides to Alkenes

6.5 Regioselectivity of Hydrogen Halide Addition: Markovnikov's Rule

6.6 Mechanistic Basis for Markovnikov's Rule

Rules, Laws, Theories, and the Scientific Method

6.7 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes

6.8 Free-Radical Addition of Hydrogen Bromide to Alkenes

6.9 Addition of Sulfuric Acid to Alkenes

6.10 Acid-Catalyzed Hydration of Alkenes

6.11 Thermodynamics of Addition - Elimination Equilibria

6.12 Hydroboration-Oxidation of Alkenes

6.13 Stereochemistry of Hydroboration-Oxidation

6.14 Mechanism of Hydroboration-Oxidation

6.15 Addition of Halogens to Alkenes

6.16 Stereochemistry of Halogen Addition

6.17 Mechanism of Halogen Addition to Alkenes: Halonium Ions

6.18 Conversion of Alkenes to Vicinal Halohydrins

6.19 Epoxidation of Alkenes

6.20 Ozonolysis of Alkenes

6.21 Introduction to Organic Chemical Synthesis

6.22 Reactions of Alkenes with Alkenes: Polymerization

Ethylene and Propane: The Most Important Industrial Organic Chemicals

6.23 Summary

Problems

Descriptive Passage and Interpretive Problems 6: Some Unusual Electrophilic Additions

Chapter 7 - Stereochemistry

7.1 Molecular Chirality: Enantiomers

7.2 The Chirality Center

7.3 Symmetry in Achiral Structures

7.4 Optical Activity

7.5 Absolute and Relative Configuration

7.6 The Cahn-Ingold-Prelog R-S Notation System

7.7 Fischer Projections

7.8 Properties of Enantiomers

Chiral Drugs

7.9 Reactions That Create a Chirality Center

7.10 Chiral Molecules With Two Chirality Centers

7.11 Achiral Molecules With Two Chirality Centers

7.12 Molecules With Multiple Chirality Centers

Chirality of Disubstituted Cyclohexanes

7.13 Reactions That Produce Diastereomers

7.14 Resolution of Enantiomers

7.15 Stereoregular Polymers

7.16 Chirality Centers Other Than Carbon

7.17 Summary

Problems

Descriptive Passage and Interpretive Problems 7: Prochirality

Chapter 8 - Nucleophilic Substitution

8.1 Functional Group Transformation by Nucleophilic Substitution

8.2 Relative Reactivity of Halide Leaving Groups

8.3 The SN2 Mechanism of Nucleophilic Substitution

8.4 Steric Effects and SN2 Reaction Rates

8.5 Nucleophiles and Nucleophilicity

8.6 The SN1 Mechanism of Nucleophilic Substitution

Enzyme-Catalyzed Nucleophilic Substitution of Alkyl Halides

8.7 Carbocation Stability and SN1 Reaction Rates

8.8 Stereochemistry of SN1 Reactions

8.9 Carbocation Rearrangements in SN1 Reactions

8.10 Effect of Solvent on the Rate of Nucleophilic Substitution

8.11 Substitution and Elimination as Competing Reactions

8.12 Nucleophilic Substitution of Alkyl Sulfonates

8.13 Looking Back: Reactions of Alcohols with Hydrogen Halides

8.14 Summary

Problems

Descriptive Passage and Interpretive Problems 8: Nucleophilic Substitution

Chapter 9 - Alkynes

9.1 Sources of Alkynes

9.2 Nomenclature

9.3 Physical Properties of Alkynes

9.4 Structure and Bonding in Alkynes: sp Hybridization

9.5 Acidity of Acetylene and Terminal Alkynes

9.6 Preparation of Alkynes by Alkylation of Acetylene and Terminal Alkynes

9.7 Preparation of Alkynes by Elimination Reactions

9.8 Reactions of Alkynes

9.9 Hydrogenation of Alkynes

9.10 Metal-Ammonia Reduction of Alkynes

9.11 Addition of Hydrogen Halides to Alkynes

9.12 Hydration of Alkynes

9.13 Addition of Halogens to Alkynes

Some Things That Can Be Made From Acetylene...But Aren't

9.14 Ozonolysis of Alkynes

9.15 Summary

Problems

Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes

Chapter 10 - Conjugation in alkadienes and Allylic Systems

10.1 The Allyl Group

10.2 Allylic Carbocations

10.3 SN1 Reactions of Allylic Halides

10.4 SN2 Reactions of Allylic Halides

10.5 Allylic Free Radicals

10.6 Allylic Halogenation

10.7 Allylic Anions

10.8 Classes of Dienes

10.9 Relative Stabilities of Dienes

10.10 Bonding in Conjugated Dienes

10.11 Bonding in Allenes

10.12 Preparation of Dienes

10.13 Addition of Hydrogen Halides to Conjugated Dienes

10.14 Halogen Addition to Dienes

10.15 The Diels-Alder Reaction

Dienes Polymers

10.16 The Molecular Orbitals of Ethylene and 1,3-Butadiene

10.17 A Molecular Orbital Analysis of the Diels-Alder Reaction

10.18 Summary

Problems

Descriptive Passage and Interpretive Passages 10: Intramolecular and Retro Diels-Alder Reactions

Chapter 11 - Arenes and Aromaticity

11.1 Benzene

11.2 Kekule and the Structure of Benzene

11.3 A Resonance Picture of Bonding in Benzene

11.4 The stability of Benzene

11.5 An Orbital hybridization View of Bonding in Benzene

11.6 The p Molecular Orbitals of Benzene

11.7 Substituted Derivatives of Benzene and their Nomenclature

11.8 Polycyclic Aromatic Hydrocarbons

11.9 Physical Properties of Arenes

Carbon Clusters, Fullerenes, and Nanotubes

11.10 Reactions of Arenes. A Preview.

11.11 The Birch Reduction

11.12 Free-Radical Halogenation of Alkylbenzenes

11.13 Oxidation of Alkylbenzenes

11.14 SN1 Reactions of Benzylic Halides

11.15 SN2 Reactions of Benzylic Halides

11.16 Preparation of Alkenylbenzenes

11.17 Addition Reactions of Alkenylbenzenes

11.18 Polymerization of Styrene

11.19 Cyclobutadiene and Cyclooctatetraene

11.20 Huckel's Rule

11.21 Annulenes

11.22 Aromatic Ions

11.23 Heterocyclic Aromatic Compounds

11.24 Heterocyclic Aromatic Compounds and Huckel's Rule

11.25 Summary

Problems

Descriptive Passage and Interpretive Problems 11: The Hammett Equation

CHAPTER 12 - Reactions of Arenes: Electrophilic Aromatic Substitution

12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene

12.2 Mechanistic Principles of Electrophilic Aromatic Substitution

12.3 Nitration of Benzene

12.4 Sulfonation of Benzene

12.5 Halogenation of Benzene

12.6 Friedel–Crafts Alkylation of Benzene

12.7 Friedel–Crafts Acylation of Benzene

12.8 Synthesis of Alkylbenzenes by Acylation–Reduction

12.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution

12.10 Rate and Regioselectivity in the Nitration of Toluene

12.11 Rate and Regioselectivity in the Nitration of (Trifluoromethyl)benzene

12.12 Substituent Effects in Electrophilic Aromatic Substitution: Activating Substituents

12.13 Substituent Effects in Electrophilic Aromatic Substitution: Strongly Deactivating Substituents

12.14 Substituent Effects in Electrophilic Aromatic Substitution: Halogens

12.15 Multiple Substituent Effects

12.16 Regioselective Synthesis of Disubstituted Aromatic Compounds

12.17 Substitution in Naphthalene

12.18 Substitution in Heterocyclic Aromatic Compounds

12.19 Summary

Problems

Descriptive Passage and Interpretive Problems 12: Nucleophilic Aromatic Substitution

CHAPTER 13 - Spectroscopy

13.1 Principles of Molecular Spectroscopy: Electromagnetic Radiation

13.2 Principles of Molecular Spectroscopy: Quantized Energy States

13.3 Introduction to 1 H NMR Spectroscopy

13.4 Nuclear Shielding and 1 H Chemical Shifts

13.5 Effects of Molecular Structure on 1 H Chemical Shifts

Ring CurrentsAromatic and Antiaromatic

13.6 Interpreting 1 H NMR Spectra

13.7 Spin–Spin Splitting in 1 H NMR Spectroscopy

13.8 Splitting Patterns: The Ethyl Group

13.9 Splitting Patterns: The Isopropyl Group

13.10 Splitting Patterns: Pairs of Doublets

13.11 Complex Splitting Patterns

13.12 1 H NMR Spectra of Alcohols

Magnetic Resonance Imaging (MRI)

13.13 NMR and Conformations

13.14 13 C NMR Spectroscopy

13.15 13 C Chemical Shifts

13.16 13 C NMR and Peak Intensities

13.17 13 C 1 H Coupling

13.18 Using DEPT to Count Hydrogens Attached to 13C

13.19 2D NMR: COSY and HETCOR

13.20 Introduction to Infrared Spectroscopy

Spectra by the Thousands

13.21 Infrared Spectra

13.22 Characteristic Absorption Frequencies

13.23 Ultraviolet-Visible (UV-VIS) Spectroscopy

13.24 Mass Spectrometry

13.25 Molecular Formula as a Clue to Structure

Gas Chromatography, GC/MS, and MS/MS

13.26 Summary

Problems

Descriptive Passage and Interpretive Problems 13: Calculating Aromatic 13C Chemical Shifts

CHAPTER 14 - Organometallic Compounds

14.1 Organometallic Nomenclature

14.2 Carbon–Metal Bonds in Organometallic Compounds 14.3 Preparation of Organolithium Compounds

14.4 Preparation of Organomagnesium Compounds: Grignard Reagents

14.5 Organolithium and Organomagnesium Compounds as Brønsted Bases

14.6 Synthesis of Alcohols Using Grignard Reagents

14.7 Synthesis of Alcohols Using Organolithium Reagents

14.8 Synthesis of Acetylenic Alcohols

14.9 Retrosynthetic Analysis

14.10 Preparation of Tertiary Alcohols from Esters and Grignard Reagents

14.11 Alkane Synthesis Using Organocopper Reagents

14.12 An Organozinc Reagent for Cyclopropane Synthesis

14.13 Carbenes and Carbenoids

14.14 Transition-Metal Organometallic Compounds

An Organometallic Compound That Occurs Naturally: Coenzyme B12

14.15 Homogeneous Catalytic Hydrogenation

14.16 Olefin Metathesis

14.17 Ziegler–Natta Catalysis of Alkene Polymerization

14.18 Summary

Problems

Descriptive Passage and Interpretive Problems 14: Oxymercuration

CHAPTER 15 - Alcohols, Diols, and Thiols

15.1 Sources of Alcohols

15.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones

15.3 Preparation of Alcohols by Reduction of Carboxylic Acids and Esters

15.4 Preparation of Alcohols from Epoxides

15.5 Preparation of Diols

15.6 Reactions of Alcohols: A Review and a Preview

15.7 Conversion of Alcohols to Ethers

15.8 Esterification

15.9 Esters of Inorganic Acids

15.10 Oxidation of Alcohols

15.11 Biological Oxidation of Alcohols

Economic and Environmental Factors in Organic Synthesis

15.12 Oxidative Cleavage of Vicinal Diols

15.13 Thiols

15.14 Spectroscopic Analysis of Alcohols and Thiols

15.15 Summary

Problems

Descriptive Passage and Interpretive Problems 15: The Pinacol Rearrangement

CHAPTER 16 - Ethers, Epoxides, and Sulfides

16.1 Nomenclature of Ethers, Epoxides, and Sulfides

16.2 Structure and Bonding in Ethers and Epoxides

16.3 Physical Properties of Ethers

16.4 Crown Ethers

16.5 Preparation of Ethers

Polyether Antibiotics

16.6 The Williamson Ether Synthesis

16.7 Reactions of Ethers: A Review and a Preview

16.8 Acid-Catalyzed Cleavage of Ethers

16.9 Preparation of Epoxides: A Review and a Preview

16.10 Conversion of Vicinal Halohydrins to Epoxides

16.11 Reactions of Epoxides: A Review and a Preview

16.12 Nucleophilic Ring Opening of Epoxides

16.13 Acid-Catalyzed Ring Opening of Epoxides

16.14 Epoxides in Biological Processes

16.15 Preparation of Sulfides

16.16 Oxidation of Sulfides: Sulfoxides and Sulfones

16.17 Alkylation of Sulfides: Sulfonium Salts

16.18 Spectroscopic Analysis of Ethers, Epoxides, and Sulfides

16.19 Summary

Problems

Descriptive Passage and Interpretive Problems 16: Epoxide Rearrangements and the NIH Shift

CHAPTER 17 - Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group

17.1 Nomenclature

17.2 Structure and Bonding: The Carbonyl Group

17.3 Physical Properties

17.4 Sources of Aldehydes and Ketones

17.5 Reactions of Aldehydes and Ketones: A Review and a Preview

17.6 Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones

17.7 Cyanohydrin Formation

17.8 Acetal Formation

17.9 Acetals as Protecting Groups

17.10 Reaction with Primary Amines: Imines

Imines in Biological Chemistry

17.11 Reaction with Secondary Amines: Enamines

17.12 The Wittig Reaction

17.13 Planning an Alkene Synthesis via the Wittig Reaction

17.14 Stereoselective Addition to Carbonyl Groups

17.15 Oxidation of Aldehydes

17.16 Baeyer–Villiger Oxidation of Ketones

17.17 Spectroscopic Analysis of Aldehydes and Ketones

17.18 Summary

Problems

Descriptive Passage and Interpretive Problems 17: Alcohols, Aldehydes, and Carbohydrates

CHAPTER 18 - Enols and Enolates

18.1 The -Hydrogen and Its pKa

18.2 The Aldol Condensation

18.3 Mixed Aldol Condensations

18.4 Alkylation of Enolate Ions

18.5 Enolization and Enol Content

18.6 Stabilized Enols

18.7 Halogenation of Aldehydes and Ketones

18.8 Mechanism of Halogenation of Aldehydes and Ketones

18.9 The Haloform Reaction

18.10 Some Chemical and Stereochemical Consequences of Enolization

The Haloform Reaction and the Biosynthesis of Trihalomethanes

18.11 Effects of Conjugation in ,-Unsaturated Aldehydes and Ketones

18.12 Conjugate Addition to ,-Unsaturated Carbonyl Compounds

18.13 Addition of Carbanions to ,-Unsaturated Ketones: The Michael Reaction

18.14 Conjugate Addition of Organocopper Reagents to ,-Unsaturated Carbonyl Compounds

18.15 Summary

Problems

Descriptive Passage and Interpretive Problems 18: Enolate Regiochemistry and Stereochemistry

CHAPTER 19 - Carboxylic Acids

19.1 Carboxylic Acid Nomenclature

19.2 Structure and Bonding

19.3 Physical Properties

19.4 Acidity of Carboxylic Acids

19.5 Salts of Carboxylic Acids

19.6 Substituents and Acid Strength

19.7 Ionization of Substituted Benzoic Acids

19.8 Dicarboxylic Acids

19.9 Carbonic Acid

19.10 Sources of Carboxylic Acids

19.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents

19.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles

19.13 Reactions of Carboxylic Acids: A Review and a Preview

19.14 Mechanism of Acid-Catalyzed Esterification

19.15 Intramolecular Ester Formation: Lactones

19.16 Alpha Halogenation of Carboxylic Acids: The Hell–Volhard–Zelinsky Reaction

19.17 Decarboxylation of Malonic Acid and Related Compounds

19.18 Spectroscopic Analysis of Carboxylic Acids

19.19 Summary

Problems

Descriptive Passage and Interpretive Problems 19: Lactonization Methods

CHAPTER 20 - Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution

20.1 Nomenclature of Carboxylic Acid Derivatives

20.2 Structure and Reactivity of Carboxylic Acid Derivatives

20.3 General Mechanism for Nucleophilic Acyl Substitution

20.4 Nucleophilic Acyl Substitution in Acyl Chlorides

20.5 Nucleophilic Acyl Substitution in Acid Anhydrides

20.6 Sources of Esters

20.7 Physical Properties of Esters

20.8 Reactions of Esters: A Review and a Preview

20.9 Acid-Catalyzed Ester Hydrolysis

20.10 Ester Hydrolysis in Base: Saponification

20.11 Reaction of Esters with Ammonia and Amines

20.12 Amides

20.13 Hydrolysis of Amides

20.14 Lactams

Lactum Antibiotics

20.15 Preparation of Nitriles

20.16 Hydrolysis of Nitriles

20.17 Addition of Grignard Reagents to Nitriles 901

20.18 Spectroscopic Analysis of Carboxylic Acid Derivatives

20.19 Summary

Problems

Descriptive Passage and Interpretive Problems 20: Thioesters

CHAPTER 21 - Ester Enolates

21.1 Ester Hydrogens and Their pKa s

21.2 The Claisen Condensation

21.3 Intramolecular Claisen Condensation: The Dieckmann Reaction

21.4 Mixed Claisen Condensations

21.5 Acylation of Ketones with Esters

21.6 Ketone Synthesis via -Keto Esters

21.7 The Acetoacetic Ester Synthesis

21.8 The Malonic Ester Synthesis

21.9 Michael Additions of Stabilized Anions

21.10 Reactions of LDA-Generated Ester Enolates

21.11 Summary

Problems

Descriptive Passage and Interpretive Problems 21: The Enolate Chemistry of Dianions

CHAPTER 22 - Amines

22.1 Amine Nomenclature

22.2 Structure and Bonding

22.3 Physical Properties

22.4 Basicity of Amines

Amines as Natural Products

22.5 Tetraalkylammonium Salts as Phase-Transfer Catalysts

22.6 Reactions That Lead to Amines: A Review and a Preview

22.7 Preparation of Amines by Alkylation of Ammonia

22.8 The Gabriel Synthesis of Primary Alkylamines

22.9 Preparation of Amines by Reduction

22.10 Reductive Amination

22.11 Reactions of Amines: A Review and a Preview

22.12 Reaction of Amines with Alkyl Halides

22.13 The Hofmann Elimination

22.14 Electrophilic Aromatic Substitution in Arylamines

22.15 Nitrosation of Alkylamines

22.16 Nitrosation of Arylamines

22.17 Synthetic Transformations of Aryl Diazonium Salts

22.18 Azo Coupling

From Dyes to Sulfa Drugs

22.19 Spectroscopic Analysis of Amines

22.20 Summary

Problems

Descriptive Passage and Interpretive Problems 22: Synthetic Applications of Enamines

CHAPTER 23 - Aryl Halides

23.1 Bonding in Aryl Halides

23.2 Sources of Aryl Halides

23.3 Physical Properties of Aryl Halides

23.4 Reactions of Aryl Halides: A Review and a Preview

23.5 Nucleophilic Substitution in Nitro-Substituted Aryl Halides

23.6 The Addition–Elimination Mechanism of Nucleophilic Aromatic Substitution

23.7 Related Nucleophilic Aromatic Substitution Reactions

23.8 The Elimination–Addition Mechanism of Nucleophilic Aromatic Substitution: Benzyne

23.9 Diels–Alder Reactions of Benzyne

23.10 m-Benzyne and p-Benzyne

23.11 Summary

Problems

Descriptive Passage and Interpretive Problems 23: The Heck Reaction

CHAPTER 24 - Phenols

24.1 Nomenclature

24.2 Structure and Bonding

24.3 Physical Properties

24.4 Acidity of Phenols

24.5 Substituent Effects on the Acidity of Phenols

24.6 Sources of Phenols

24.7 Naturally Occurring Phenols

24.8 Reactions of Phenols: Electrophilic Aromatic Substitution

24.9 Acylation of Phenols

24.10 Carboxylation of Phenols: Aspirin and the Kolbe–Schmitt Reaction

24.11 Preparation of Aryl Ethers

Agent Orange and Dioxin

24.12 Cleavage of Aryl Ethers by Hydrogen Halides

24.13 Claisen Rearrangement of Allyl Aryl Ethers

24.14 Oxidation of Phenols: Quinones

24.15 Spectroscopic Analysis of Phenols

24.16 Summary

Problems

Descriptive Passage and Interpretive Problems 24: Directed Metalation of Aryl Ethers

CHAPTER 25 - Carbohydrates

25.1 Classification of Carbohydrates

25.2 Fischer Projections and D–L Notation

25.3 The Aldotetroses

25.4 Aldopentoses and Aldohexoses

25.5 A Mnemonic for Carbohydrate Configurations

25.6 Cyclic Forms of Carbohydrates: Furanose Forms

25.7 Cyclic forms of Carbohydrates: Pyranose Forms

25.8 Mutarotation and the Anomeric Effect

25.9 Ketoses

25.10 Deoxy Sugars

25.11 Amino Sugars

25.12 Branched-Chain Carbohydrates

25.13 Glycosides

25.14 Disaccharides

25.15 Polysaccharides

How Sweet It Is!

25.16 Reactions of Carbohydrates

25.17 Reduction of Monosaccharides

25.18 Oxidation of Monosaccharides

25.19 Cyanohydrin Formation and Chain Extension

25.20 Epimerization, Isomerization, and Retro-Aldol Cleavage

25.21 Acylation and Alkylation of Hydroxyl Groups

25.22 Periodic Acid Oxidation

25.23 Summary

Problems

Descriptive Passage and Interpretive Problems 25: Emil Fisher and the structure of (+) - Glucose

CHAPTER 26 - Lipids

26.1 Acetyl Coenzyme A

26.2 Fats, Oils, and Fatty Acids

26.3 Fatty Acid Biosynthesis

26.4 Phospholipids

26.5 Waxes

26.6 Prostaglandins

Nonsteroidal Antiinflammatory Drugs (NSAIDS) and COX-2 Inhibitors

26.7 Terpenes: The Isoprene Rule

26.8 Isopentenyl Diphosphate: The Biological Isoprene Unit

26.9 Carbon–Carbon Bond Formation in Terpene Biosynthesis

26.10 The Pathway from Acetate to Isopentenyl Diphosphate

26.11 Steroids: Cholesterol

26.12 Vitamin D

Good Cholesterol? Bad Cholesterol? Whats the Difference? 26.13 Bile Acids

26.14 Corticosteroids

26.15 Sex Hormones

26.16 Carotenoids

Anabolic Steroids

Crocuses Make Saffron from Carotenes

26.17 Summary

Problems

Descriptive Passage and Interpretive Problems 26: Polyketides

CHAPTER 27 - Amino Acids, Peptides, and Proteins

27.1 Classification of Amino Acids

27.2 Stereochemistry of Amino Acids

27.3 Acid–Base Behavior of Amino Acids

27.4 Synthesis of Amino Acids

Electrophoresis

27.5 Reactions of Amino Acids

27.6 Some Biochemical Reactions of Amino Acids

27.7 Peptides

27.8 Introduction to Peptide Structure Determination

27.9 Amino Acid Analysis

27.10 Partial Hydrolysis of Peptides

27.11 End Group Analysis

27.12 Insulin

27.13 The Edman Degradation and Automated Sequencing of Peptides

Peptide Mapping and MALDI Mass Spectrometry

27.14 The Strategy of Peptide Synthesis

27.15 Amino Group Protection

27.16 Carboxyl Group Protection

27.17 Peptide Bond Formation

27.18 Solid-Phase Peptide Synthesis: The Merrifield Method

27.19 Secondary Structures of Peptides and Proteins

27.20 Tertiary Structure of Polypeptides and Proteins

27.21 Coenzymes

Oh NO! Its Inorganic!

27.22 Protein Quaternary Structure: Hemoglobin

27.23 Summary

Problems

Descriptive Passage and Interpretive Problems 27: Amino Acids in Enantioselective Synthesis

CHAPTER 28 - Nucleosides, Nucleotides, and Nucleic Acids

28.1 Pyrimidines and Purines

28.2 Nucleosides

28.3 Nucleotides

28.4 Bioenergetics

28.5 ATP and Bioenergetics

28.6 Phosphodiesters, Oligonucleotides, and Polynucleotides

28.7 Nucleic Acids

28.8 Secondary Structure of DNA: The Double Helix

“It Has Not Escaped Our Notice . . .”

28.9 Tertiary Structure of DNA: Supercoils

28.10 Replication of DNA

28.11 Ribonucleic Acids

28.12 Protein Biosynthesis

RNA World

28.13 AIDS

28.14 DNA Sequencing

28.15 The Human Genome Project

28.16 DNA Profiling and the Polymerase Chain Reaction

28.17 Summary

Problems

Descriptive Passage and Interpretive Problems 28: Oligonucleotide Synthesis

CHAPTER 29 - Synthetic Polymers

29.1 Some Background

29.2 Polymer Nomenclature

29.3 Classification of Polymers: Reaction Type

29.4 Classification of Polymers: Chain-Growth and Step-Growth

29.5 Classification of Polymers: Structure

29.6 Classification of Polymers: Properties

29.7 Addition Polymers: A Review and a Preview

29.8 Chain Branching in Free-Radical Polymerization

29.9 Anionic Polymerization: Living Polymers

29.10 Cationic Polymerization

29.11 Polyamides

29.12 Polyesters

29.13 Polycarbonates

29.14 Polyurethanes

29.15 Copolymers

29.16 Summary

Problems

Descriptive Passage and Interpretive Problems 29: Chemical Modification of Polymers

GLOSSARY

CREDITS

INDEX