Chapter 1 The Basics: Bonding and Molecular Structure

1.1 Development of the Science of Organic Chemistry

1.2 Atomic Structure

1.3 The Structural Theory of Organic Chemistry

1.4 Chemical Bonds: The Octet Rule

1.5 Resonance Theory

1.6 Hyperconjugation

1.7 The Structure of Methane and Ethane: sp3 Hybridization

1.8 The Structure of Ethene (Ethylene): sp2 Hybridization

1.9 The Structure of Ethyne (Acetylene): sp Hybridization

1.10How to Interpret and Write Structural Formulas

Chapter 2: Families of Carbon Compounds, Functional Groups and Intermolecular Forces

2.1 Hydrocarbons: Representative Alkanes, Alkenes, Alkynes, and Aromatic Compounds

2.2 Polar and Nonpolar Molecules

2.3 Functional Groups

2.4 Alkyl Halides or Haloalkanes

2.5 Alcohols

2.6 Ethers

2.7 Amines

2.8 Aldehydes and Ketones

2.9 Carboxylic Acids, Esters, and Amides

2.10 Nitriles

2.11 Summary of Important Families of Organic Compounds

2.12 Physical Properties and Molecular Structure

2.13 Summary of Attractive Electric Forces

Chapter 3: An Introduction to Organic Reactions and Their Mechanisms: Acids and Bases

3.1 Reactions and Their Mechanisms

3.2 Acid–Base Reactions

3.3 Lewis Acids and Bases

3.4 Heterolysis of Bonds to Carbon: Carbocations and Carbanions

3.5 How to Use Curved Arrows in Illustrating Reactions

3.6 The Strength of Brønsted– Lowry Acids and Bases: Ka and pKa

3.7 How to Predict the Outcome of Acid–Base Reactions

3.8 Relationships between Structure and Acidity

3.9 Energy Changes

3.10 The Relationship between the Equilibrium Constant and the Standard Free-Energy
Change, DG°

3.11 The Acidity of Carboxylic Acids versus Alcohols

3.12 The Effect of the Solvent on Acidity

3.13 Organic Compounds as Bases

3.14 Acids and Bases in Nonaqueous Solutions

3.15 Acid–Base Reactions and the Synthesis of Deuterium-and Tritium-Labeled Compounds

3.16 Reaction of NaHCO3

3.17 Steric Inhibition of Resonance (SIR) Effect

3.18 Ortho and Para Effects

Chapter 4 : Stereochemistry Chiral Molecules

4.1 Chirality and Stereochemistry

4.2 Isomerism: Constitutional Isomers and Stereoisomers

4.3 Enantiomers and Chiral Molecules

4.4 A Single Chirality Center Causes a Molecule to Be Chiral

4.5 More about the Biological Importance of Chirality

4.6 How to Test for Chirality: Planes of Symmetry

4.7 Naming Enantiomers: The R,S-System

4.8 Properties of Enantiomers: Optical Activity

4.9 The Origin of Optical Activity

4.10 The Synthesis of Chiral Molecules

4.11 Chiral Drugs

4.12 Molecules with More than One Chirality Center

4.13 Fischer Projection Formulas

4.14 Stereoisomerism of Cyclic Compounds

4.15 Relating Configurations through Reactions in Which No Bonds to the Chirality Center
Are Broken

4.16 Separation of Enantiomers: Resolution

4.17 Compounds with Chirality Centers Other than Carbon

4.18 Chiral Molecules That Do Not Possess a Chirality Center

4.19 Biphenyl

4.20 Racemization of Biphenyl Compounds

4.21 Tautomerism

4.22 Gero Entropy

Chapter 5 : Nomenclature and Conformations of Alkanes and Cycloalkanes

5.1 Introduction to Alkanes and Cycloalkanes

5.2 Shapes of Alkanes

5.3 HOW TO Name Alkanes, Alkyl Halides, and Alcohols: The IUPAC System

5.4 HOW TO Name Cycloalkanes

5.5 HOW TO Name Alkenes and Cycloalkenes

5.6 HOW TO Name Alkynes

5.7 Physical Properties of Alkanes and Cycloalkanes

5.8 Sigma Bonds and Bond Rotation

5.9 Conformational Analysis of Butane

5.10 The Relative Stabilities of Cycloalkanes: Ring Strain

5.11 Conformations of Cyclohexane: The Chair and the Boat

5.12 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Groups

5.13 Disubstituted Cycloalkanes: cis–trans Isomerism

5.14 Bicyclic and Polycyclic Alkanes

5.15 Chemical Reactions of Alkanes

5.16 Synthesis of Alkanes and Cycloalkanes

5.17 HOW TO Gain Structural Information from Molecular Formulas and the Index of
Hydrogen Deficiency

5.18 Applications of Basic Principles

Chapter 6 Ionic Reactions—Nucleophilic Substitution and Elimination Reactions of Alkyl

Halides

6.1 Alkyl Halides

6.2 Nucleophilic Substitution Reactions

6.3 Nucleophiles

6.4 Leaving Groups

6.5 Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction

6.6 A Mechanism for the SN2 Reaction

6.7 Transition State Theory: Free- Energy Diagrams

6.8 The Stereochemistry of SN2 Reactions

6.9 The Reaction of tert-butyl Chloride with Water: an SN1 Reaction

6.10 A Mechanism for the SN1 Reaction

6.11 Carbocations

6.12 The Stereochemistry of SN1 Reactions

6.13 Factors Affecting the Rates of SN1 and SN2 Reactions

6.14 Organic Synthesis: Functional Group Transformations Using SN2 Reactions

6.15 Elimination Reactions of Alkyl Halides

6.16 The E2 Reaction

6.17 The E1 Reaction

6.18 HOW TO Determine Whether Substitution or Elimination is Favored

6.19 Overall Summary

Chapter 7 Alkenes and Alkynes I: Properties and Synthesis. Elimination Reactions of Alkyl
Halides

7.1 Introduction

7.2 The (E )–(Z ) System for Designating Alkene Diastereomers

7.3 Relative Stabilities of Alkenes

7.4 Cycloalkenes

7.5 Synthesis of Alkenes via Elimination Reactions

7.6 Dehydrohalogenation of Alkyl Halides

7.7 Acid-Catalyzed Dehydration of Alcohols

7.8 Carbocation Stability and the Occurrence of olecular Rearrangements

7.9 The Acidity of Terminal Alkynes

7.10 Synthesis of Alkynes by Elimination Reactions

7.11 Terminal Alkynes can be Converted to Nucleophiles for Carbon–Carbon Bond

Formation

7.12 Hydrogenation of Alkenes

7.13 Hydrogenation: The Function of the Catalyst

7.14 Hydrogenation of Alkynes

7.15 An Introduction to Organic Synthesis

Chapter 8 Alkenes and Alkynes II: Addition Reactions

8.1 Addition Reactions of Alkenes

8.2 Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikov’s

Rule

8.3 Stereochemistry of the Ionic Addition to an Alkene

8.4 Addition of Water to Alkenes: Acid-Catalyzed Hydration

8.5 Alcohols from Alkenes through Oxymercuration–Demercuration: Markovnikov Addition

8.6 Alcohols from Alkenes through Hydroboration–Oxidation: Anti-Markovnikov Syn

Hydration

8.7 Hydroboration: Synthesis of Alkylboranes

8.8 Oxidation and Hydrolysis of Alkylboranes

8.9 Summary of Alkene Hydration Methods

8.10 Protonolysis of Alkylboranes

8.11 Electrophilic Addition of Bromine and Chlorine to Alkenes

8.12 Stereospecific Reactions

8.13 Halohydrin Formation

8.14 Oxidation of Alkenes: Syn 1,2-Dihydroxylation

8.15 Oxidative Cleavage of Alkenes

8.16 Electrophilic Addition of Bromine and Chlorine to Alkynes

8.17 Addition of Hydrogen Halides to Alkynes

8.18 Oxidative Cleavage of Alkynes

8.19 HOW TO Plan a Synthesis: Some Approaches and Examples

8.20 Dimerization of Alkene

8.21 Prins Reaction

Chapter 9 Radical Reactions

9.1 Introduction: How Radicals Form and How They React

9.2 Homolytic Bond Dissociation Energies (DH °)

9.3 Reactions of Alkanes with Halogens

9.4 Chlorination of Methane: Mechanism of Reaction

9.5 Halogenation of Higher Alkanes

9.6 Reactions That Generate Tetrahedral Chirality Centers

9.7 Allylic Substitution and Allylic Radicals

9.8 Benzylic Substitution and Benzylic Radicals

9.9 Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide

9.10 Other Important Radical Reactions

Chapter 10 Alcohols and Ethers

10.1 Structure and Nomenclature

10.2 Physical Properties of Alcohols and Ethers

10.3 Synthesis of Alcohols from Alkenes

10.4 Reactions of Alcohols

10.5 Alcohols as Acids

10.6 Conversion of Alcohols into Alkyl Halides

10.7 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides

10.8 Alkyl Halides from the Reaction of Alcohols with PBr3 or SOCl2

10.9 Tosylates, Mesylates, and Triflates: Leaving Group Derivatives of Alcohols

10.10 Synthesis of Ethers

10.11 Reactions of Ethers

10.12 Epoxides

10.13 Reactions of Epoxides

10.14 Anti 1,2-Dihydroxylation of Alkenes via Epoxides

10.15 Crown Ethers

Chapter 11 Alcohols from Carbonyl Compounds. Oxidation–Reduction and Organometallic

Compounds

11.1 Structure of the Carbonyl Group

11.2 Oxidation–Reduction Reactions in Organic Chemistry

11.3 Alcohols by Reduction of Carbonyl Compounds

11.4 Oxidation of Alcohols

11.5 Organometallic Compounds

11.6 Preparation of Organolithium and Organomagnesium Compounds

11.7 Reactions of Organolithium and Organomagnesium Compounds

11.8 Alcohols from Grignard Reagents

11.9 Lithium Dialkylcuprates: The Corey–Posner, Whitesides– House Synthesis

Chapter 12 Conjugated Unsaturated Systems

12.1 Introduction

12.2 Alkadienes and Polyunsaturated Hydrocarbons

12.3 1,3-Butadiene: Electron Delocalization

12.4 Electrophilic Attack on Conjugated Dienes: 1,4-Addition

12.5 The Diels–Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes

Chapter 13 Aromatic Compounds

13.1 The Discovery of Benzene

13.2 Nomenclature of Benzene Derivatives

13.3 Reactions of Benzene

13.4 The Kekulé Structure for Benzene

13.5 The Thermodynamic Stability of Benzene

13.6 Modern Theories of the Structure of Benzene

13.7 Hückel’s Rule: The (4n + 2)p Electron Rule

13.8 Other Aromatic Compounds

13.9 Heterocyclic Aromatic Compounds

Chapter 14 Reactions of Aromatic Compounds

14.1 Electrophilic Aromatic Substitution Reactions

14.2 A General Mechanism for Electrophilic Aromatic Substitution

14.3 Halogenation of Benzene

14.4 Nitration of Benzene

14.5 Sulfonation of Benzene

14.6 Friedel–Crafts Alkylation

14.7 Friedel–Crafts Acylation

14.8 Limitations of Friedel–Crafts Reactions

14.9 Synthetic Applications of Friedel–Crafts Acylations: The Clemmensen and

Wolff–Kishner Reductions

14.10 Substituents Can Affect Both the Reactivity of the Ring and the Orientation of the
Incoming Group

14.11 How Substituents Affect Electrophilic Aromatic Substitution: A Closer Look

14.12 Reactions of the Side Chain of Alkylbenzenes

14.13 Alkenylbenzenes

14.14 Synthetic Applications

14.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions

14.16 Reduction of Aromatic Compounds

Chapter 15 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group

15.1 Introduction

15.2 Nomenclature of Aldehydes and Ketones

15.3 Physical Properties

15.4 Synthesis of Aldehydes

15.5 Synthesis of Ketones

15.6 Nucleophilic Addition to the Carbon–Oxygen Double Bond

15.7 The Addition of Alcohols: Hemiacetals and Acetals

15.8 The Addition of Primary and Secondary Amines

15.9 The Addition of Hydrogen Cyanide: Cyanohydrins

15.10 The Addition of Ylides: The Wittig Reaction

15.11 Oxidation of Aldehydes

15.12 The Baeyer–Villiger Oxidation

15.13 Chemical Analyses for Aldehydes and Ketones

Chapter 16 Aldehydes and Ketones II. Aldol Reactions

16.1 The Acidity of the ` Hydrogens of Carbonyl Compounds: Enolate Anions

16.2 Keto and Enol Tautomers

16.3 Reactions via Enols and Enolates

16.4 Aldol Reactions: Addition of Enolates and Enols to Aldehydes and Ketones

16.5 Crossed Aldol Condensations

16.6 Cyclizations via Aldol Condensation

16.7 Lithium Enolates

Chapter 17 Carboxylic Acids and Their Derivatives. Nucleophilic Addition – Elimination at the
Acyl Carbon

17.1 Introduction

17.2 Nomenclature and Physical Properties

17.3 Preparation of Carboxylic Acids

17.4 Acyl Substitution: Nucleophilic Addition– Elimination at the Acyl Carbon

17.5 Acyl Chlorides

17.6 Carboxylic Acid Anhydrides

17.7 Esters

17.8 Amides

17.9 Derivatives of Carbonic Acid

17.10 Decarboxylation of Carboxylic Acids

17.11 Chemical Tests for Acyl Compounds

17.12 Summary of the Reactions of Carboxylic Acids and Their Derivatives

Chapter 18 Amines

18.1 Nomenclature

18.2 Physical Properties and Structure of Amines

18.3 Basicity of Amines: Amine Salts

18.4 Preparation of Amines

18.5 Reactions of Amines

18.6 Reactions of Amines with Nitrous Acid

18.7 Replacement Reactions of Arenediazonium Salts

18.8 Coupling Reactions of Arenediazonium Salts

18.9 Reactions of Amines with Sulfonyl Chlorides

18.10 Synthesis of Sulfa Drugs

18.11 Eliminations Involving Ammonium Compounds

18.12 The Cope Elimination

18.13 Summary of Preparations and Reactions of Amines

Chapter 19 Phenols and Aryl Halides: Nucleophilic Aromatic Substitution

19.1 Structure and Nomenclature of Phenols

19.2 Naturally Occurring Phenols

19.3 Physical Properties of Phenols

19.4 Synthesis of Phenols

19.5 Reactions of Phenols as Acids

19.6 Other Reactions of the O—H Group of Phenols

19.7 Cleavage of Alkyl Aryl Ethers

19.8 Reactions of the Benzene Ring of Phenols

19.9 The Claisen Rearrangement

19.10 Quinones

19.11 Aryl Halides and Nucleophilic Aromatic Substitution

Chapter 20 Carbohydrates

20.1 Introduction

20.2 Monosaccharides

20.3 Mutarotation

20.4 Glycoside Formation

20.5 Other Reactions of Monosaccharides

20.6 Oxidation Reactions of Monosaccharides

20.7 Reduction of Monosaccharides: Alditols

20.8 Reactions of Monosaccharides with henylhydrazine: Osazones

20.9 Synthesis and Degradation of Monosaccharides

20.10 The d Family of Aldoses

20.11 Fischer’s Proof of the Configuration of d-(+)-Glucose

20.12 Disaccharides

20.13 Polysaccharides

20.14 Other Biologically Important Sugars

20.15 Sugars that Contain Nitrogen

20.16 Carbohydrate Antibiotics

Chapter 21 Amino Acids and Proteins

21.1 Introduction

21.2 Amino Acids

21.3 Synthesis of `-Amino Acids

21.4 Polypeptides and Proteins

21.5 Primary Structure of Polypeptides and Proteins

21.6 Secondary, Tertiary, and Quaternary Structures of Proteins

Chapter 22 Carbene and Carbenoids

22.1 Introduction

22.2 Existence of Carbenes

22.3 Formation of Carbenes

22.4 Types of Carbenes

22.5 Reactions of Carbenes

22.6 Rearrangement in Carbenes

Chapter 23 Reaction of Nitrene and Electron Deficient Oxygen

23.1 Migration to Electron Deficient Nitrogen

23.2 Nitrene Formation

23.3 Hofmann—Curtius— Lossen—Schmidt Group of Rearrangements

23.4 Curtius Reaction

23.5 Schmidt Reaction

23.6 Hofmann-Bromamide Reaction or Hofman Rearrangement

23.7 Beckmann Rearrangement

23.8 Stieglitz Rearrangement

Chapter 24 Polymers

24.1 Some Terms Related to Polymers

24.2 Classification of Polymers

24.3 Types of Polymerization Reactions

24.4 Natural Rubber

24.5 Synthetic Rubbers

24.6 Molecular Mass of Polymers

24.7 Biodegradable Polymers

24.8 Polymers of Commercial Importance