1

Structure Determines Properties

1.1

Atoms, Electrons, and Orbitals

1.10

The Shapes of Some Simple Molecules

1.11

Molecular Dipole Moments

1.12

Curved Arrows and Chemical Reactions

1.13

Acids and Bases: The BrnstedLowry View

1.14

How Structure Affects Acid Strength

1.15

AcidBase Equilibria

1.16

Lewis Acids and Lewis Bases

1.2

Ionic Bonds

1.3

Covalent Bonds, Lewis Formulas, and the Octet Rule

1.4

Double Bonds and Triple Bonds

1.5

Polar Covalent Bonds, Electronegativity, and Bond Dipoles

1.6

Formal Charge

1.7

Structural Formulas of Organic Molecules

1.8

Resonance

1.9

Sulfur and Phosphorus-Containing Organic Compounds and the Octet Rule

---

2

Alkanes and Cycloalkanes: Introduction to Hydrocarbons

2.12

Higher n-Alkanes

2.13

The C5H12 Isomers

2.14

IUPAC Nomenclature of Unbranched Alkanes

2.15

Applying the IUPAC Rules: The Names of the C6H14 Isomers

2.16

Alkyl Groups

2.17

IUPAC Names of Highly Branched Alkanes

2.18

Cycloalkane Nomenclature

2.19

Sources of Alkanes and Cycloalkanes

2.20

Physical Properties of Alkanes and Cycloalkanes

2.21

Chemical Properties: Combustion of Alkanes

2.22

OxidationReduction in Organic Chemistry

2.4

Bonding in H2: The Molecular Orbital Model

2.7

Bonding in Ethane

2.8

sp2 Hybridization and Bonding in Ethylene

2.9

sp Hybridization and Bonding in Acetylene

---

3

Alkanes and Cycloalkanes: Conformations and cistrans Stereoisomers

3.1

Conformational Analysis of Ethane

3.10

Conformational Analysis of Monosubstituted Cyclohexanes

3.11

Disubstituted Cycloalkanes: cistrans Stereoisomers

3.12

Conformational Analysis of Disubstituted Cyclohexanes

3.14

Polycyclic Ring Systems

3.15

Heterocyclic Compounds

3.2

Conformational Analysis of Butane

3.3

Conformations of Higher Alkanes

3.5

Small Rings: Cyclopropane and Cyclobutane

3.8

Axial and Equatorial Bonds in Cyclohexane

---

4

Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms

4.1

Functional Groups

4.11

Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The SN2 Mechanism

4.12

Other Methods for Converting Alcohols to Alkyl Halides

4.15

Structure and Stability of Free Radicals

4.16

Mechanism of Methane Chlorination

4.17

Halogenation of Higher Alkanes

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

Reaction of Alcohols with Hydrogen Halides: The SN1 Mechanism

4.9

Structure, Bonding, and Stability of Carbocations

---

5

Structure and Preparation of Alkenes: Elimination Reactions

5.1

Alkene Nomenclature

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

5.2

Structure and Bonding in Alkenes

5.3

Isomerism in Alkenes

5.4

Naming Stereoisomeric Alkenes by the EZ Notational System

5.5

Physical Properties of Alkenes

5.6

Relative Stabilities of Alkenes

5.7

Cycloalkenes

5.9

Dehydration of Alcohols

---

6

Addition Reactions of Alkenes

6.1

Hydrogenation of Alkenes

6.10

Addition of Halogens to Alkenes

6.11

Epoxidation of Alkenes

6.12

Ozonolysis of Alkenes

6.13

Free-Radical Addition of Hydrogen Bromide to Alkenes

6.14

Free-Radical Polymerization of Alkenes

6.15

Introduction to Organic Chemical Synthesis: Retrosynthetic Analysis

6.2

Stereochemistry of Alkene Hydrogenation

6.3

Heats of Hydrogenation

6.4

Electrophilic Addition of Hydrogen Halides to Alkenes

6.5

Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes

6.6

Acid-Catalyzed Hydration of Alkenes

6.7

Thermodynamics of AdditionElimination Equilibria

6.8

HydroborationOxidation of Alkenes

---

7

Chirality

7.10

Reactions That Create a Chirality Center

7.11

Chiral Molecules with Two Chirality Centers

7.12

Achiral Molecules with Two Chirality Centers

7.13

Molecules with Multiple Chirality Centers

7.14

Reactions That Produce Diastereomers

7.15

Resolution of 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 CahnIngoldPrelog RS Notational System

7.7

Fischer Projections

7.8

Properties of Enantiomers

7.9

The Chirality Axis

---

8

Nucleophilic Substitution

8.1

Functional Group Transformation by Nucleophilic Substitution

8.10

Substitution and Elimination as Competing Reactions

8.11

Nucleophilic Substitution of Alkyl Sulfonates

8.12

Nucleophilic Substitution and Retrosynthetic Analysis

8.2

Relative Reactivity of Halide Leaving Groups

8.3

The SN2 Mechanism of Nucleophilic Substitution

8.4

Steric Effects and SN2 Reaction Rates

8.6

The SN1 Mechanism of Nucleophilic Substitution

8.7

Stereochemistry of SN1 Reactions

8.8

Carbocation Rearrangements in SN1 Reactions

8.9

Effect of Solvent on the Rate of Nucleophilic Substitution

---

9

Alkynes

9.1

Sources of Alkynes

9.10

MetalAmmonia Reduction of Alkynes

9.11

Addition of Hydrogen Halides to Alkynes

9.12

Hydration of Alkynes

9.14

Ozonolysis of Alkynes

9.15

Alkynes in Synthesis and Retrosynthesis

9.2

Nomenclature

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

9.9

Hydrogenation of Alkynes

---

10

Conjugation in Alkadienes and Allylic Systems

10.1

The Allyl Group

10.10

Addition of Hydrogen Halides to Conjugated Dienes

10.11

Halogen Addition to Dienes

10.12

The DielsAlder Reaction

10.13

Retrosynthetic Analysis and the DielsAlder Reaction

10.2

SN1 and SN2 Reactions of Allylic Halides

10.3

Allylic Free-Radical Halogenation

10.4

Allylic Anions

10.5

Classes of Dienes: Conjugated and Otherwise

10.6

Relative Stabilities of Dienes

10.7

Bonding in Conjugated Dienes

10.8

Bonding in Allenes

10.9

Preparation of Dienes

---

11

Arenes and Aromaticity

11.10

Benzylic Free-Radical Halogenation

11.11

Benzylic Anions

11.12

Oxidation of Alkylbenzenes

11.13

Alkenylbenzenes

11.15

The Birch Reduction

11.16

Benzylic Side Chains and Retrosynthetic Analysis

11.17

Cyclobutadiene and Cyclooctatetraene

11.18

Hckels Rule

11.19

Annulenes

11.2

The Structure of Benzene

11.20

Aromatic Ions

11.21

Heterocyclic Aromatic Compounds

11.22

Heterocyclic Aromatic Compounds and Hckels Rule

11.3

The Stability of Benzene

11.5

Substituted Derivatives of Benzene and Their Nomenclature

11.6

Polycyclic Aromatic Hydrocarbons

11.8

The Benzyl Group

11.9

Nucleophilic Substitution in Benzylic Halides

---

12

Electrophilic and Nucleophilic 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

Retrosynthetic Analysis and the Synthesis of Substituted Benzenes

12.17

Substitution in Naphthalene

12.18

Substitution in Heterocyclic Aromatic Compounds

12.19

Nucleophilic Aromatic Substitution

12.2

Mechanistic Principles of Electrophilic Aromatic Substitution

12.20

The AdditionElimination Mechanism of Nucleophilic Aromatic Substitution

12.21

Related Nucleophilic Aromatic Substitutions

12.3

Nitration of Benzene

12.4

Sulfonation of Benzene

12.5

Halogenation of Benzene

12.6

FriedelCrafts Alkylation of Benzene

12.7

FriedelCrafts Acylation of Benzene

12.8

Synthesis of Alkylbenzenes by AcylationReduction

---

13

Spectroscopy

13.11

Complex Splitting Patterns

13.12

1 H NMR Spectra of Alcohols

13.14

13C NMR Spectroscopy

13.15

13C Chemical Shifts

13.16

13C NMR and Peak Intensities

13.18

Using DEPT to Count Hydrogens

13.20

Introduction to Infrared Spectroscopy

13.21

Infrared Spectra

13.22

Characteristic Absorption Frequencies

13.23

Ultraviolet-Visible Spectroscopy

13.24

Mass Spectrometry

13.25

Molecular Formula as a Clue to Structure

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

13.6

Interpreting 1 H NMR Spectra

13.7

SpinSpin Splitting and 1 H NMR

13.8

Splitting Patterns: The Ethyl Group

---

14

Organometallic Compounds

14.1

Organometallic Nomenclature

14.10

Organocopper Reagents

14.11

Palladium-Catalyzed Cross-Coupling

14.12

Homogeneous Catalytic Hydrogenation

14.13

Olefin Metathesis

14.3

Preparation of Organolithium and Organomagnesium Compounds

14.4

Organolithium and Organomagnesium Compounds as Brnsted Bases

14.5

Synthesis of Alcohols Using Grignard and Organolithium Reagents

14.7

Retrosynthetic Analysis and Grignard and Organolithium Reagents

14.8

An Organozinc Reagent for Cyclopropane Synthesis

14.9

Transition-Metal Organometallic Compounds

---

15

Alcohols, Diols, and Thiols

15.10

Biological Oxidation of Alcohols

15.11

Oxidative Cleavage of Vicinal Diols

15.12

Thiols

15.2

Preparation of Alcohols by Reduction of Aldehydes and Ketones

15.4

Preparation of Alcohols from Epoxides

15.5

Preparation of Diols

15.7

Conversion of Alcohols to Ethers

15.8

Esterification

15.9

Oxidation of Alcohols

---

16

Ethers, Epoxides, and Sulfides

16.1

Nomenclature of Ethers, Epoxides, and Sulfides

16.10

Conversion of Vicinal Halohydrins to Epoxides

16.11

Reactions of Epoxides with Anionic Nucleophiles

16.12

Acid-Catalyzed Ring Opening of Epoxides

16.14

Preparation of Sulfides

16.15

Oxidation of Sulfides: Sulfoxides and Sulfones

16.16

Alkylation of Sulfides: Sulfonium Salts

16.17

Spectroscopic Analysis 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

16.6

The Williamson Ether Synthesis

16.8

Acid-Catalyzed Cleavage of Ethers

16.9

Preparation of Epoxides

---

17

Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group

17.1

Nomenclature

17.10

Reaction with Primary Amines: Imines

17.11

Reaction with Secondary Amines: Enamines

17.12

The Wittig Reaction

17.13

Stereoselective Addition to Carbonyl Groups

17.3

Physical Properties

17.4

Sources of Aldehydes and Ketones

17.6

Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones

17.7

Cyanohydrin Formation

17.8

Reaction with Alcohols: Acetals and Ketals

17.9

Acetals and Ketals as Protecting Groups

---

18

Carboxylic Acids

18.1

Carboxylic Acid Nomenclature

18.11

Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents

18.12

Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles

18.4

Acidity of Carboxylic Acids

18.5

Substituents and Acid Strength

18.6

Ionization of Substituted Benzoic Acids

18.7

Salts of Carboxylic Acids

18.9

Carbonic Acid

---

19

Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution

19.1

Nomenclature of Carboxylic Acid Derivatives

19.10

Reaction of Esters with Ammonia and Amines

19.11

Reaction of Esters with Grignard and Organolithium Reagents and Lithium Aluminum Hydride

19.12

Amides

19.13

Hydrolysis of Amides

19.14

Lactams

19.15

Preparation of Nitriles

19.16

Hydrolysis of Nitriles

19.17

Addition of Grignard Reagents to Nitriles

19.2

Structure and Reactivity of Carboxylic Acid Derivatives

19.3

Nucleophilic Acyl Substitution Mechanisms

19.4

Nucleophilic Acyl Substitution in Acyl Chlorides

19.5

Nucleophilic Acyl Substitution in Acid Anhydrides

19.8

Acid-Catalyzed Ester Hydrolysis

19.9

Ester Hydrolysis in Base: Saponification

---

20

Enols and Enolates

20.1

Enol Content and Enolization

20.2

Enolates

20.3

The Aldol Condensation

20.4

Mixed and Directed Aldol Reactions

20.5

Acylation of Enolates: The Claisen and Related Condensations

20.6

Alkylation of Enolates: The Acetoacetic Ester and Malonic Ester Syntheses

20.7

The Haloform Reaction

20.8

Conjugation Effects in ,-Unsaturated Aldehydes and Ketones

---

21

Amines

21.1

Amine Nomenclature

21.10

Reductive Amination

21.13

The Hofmann Elimination

21.14

Electrophilic Aromatic Substitution in Arylamines

21.15

Nitrosation of Alkylamines

21.17

Synthetic Transformations of Aryl Diazonium Salts

21.18

Azo Coupling

21.2

Structure and Bonding

21.4

Basicity of Amines

21.7

Preparation of Amines by Alkylation of Ammonia

21.8

The Gabriel Synthesis of Primary Alkylamines

21.9

Preparation of Amines by Reduction

---

22

Phenols

22.1

Nomenclature

22.11

Preparation of Aryl Ethers

22.13

Claisen Rearrangement of Allyl Aryl Ethers

22.3

Physical Properties

22.4

Acidity of Phenols

22.5

Substituent Effects on the Acidity of Phenols

22.6

Sources of Phenols

22.8

Reactions of Phenols: Electrophilic Aromatic Substitution

22.9

Acylation of Phenols

---

23

Carbohydrates

23.10

Ketoses

23.11

Deoxy Sugars

23.12

Amino Sugars

23.14

Glycosides: The Fischer Glycosidation

23.15

Disaccharides

23.17

Application of Familiar Reactions to Monosaccharides

23.18

Oxidation of Monosaccharides

23.2

Fischer Projections and D,L Notation

23.20

Glycobiology

23.3

The Aldotetroses

23.4

Aldopentoses and Aldohexoses

23.6

Cyclic Forms of Carbohydrates: Furanose Forms

23.7

Cyclic Forms of Carbohydrates: Pyranose Forms

23.8

Mutarotation

23.9

Carbohydrate Conformation: The Anomeric Effect

---

24

Lipids

24.10

The Pathway from Acetate to Isopentenyl Diphosphate

24.11

Steroids: Cholesterol

24.12

Vitamin D

24.16

Carotenoids

24.2

Fats, Oils, and Fatty Acids

24.3

Fatty Acid Biosynthesis

24.4

Phospholipids

24.5

Waxes

24.6

Prostaglandins

24.7

Terpenes: The Isoprene Rule

24.9

CarbonCarbon Bond Formation in Terpene Biosynthesis

---

25

Amino Acids, Peptides, and Proteins

25.1

Classification of Amino Acids

25.10

Partial Hydrolysis and End Group Analysis

25.12

Edman Degradation and Automated Sequencing of Peptides

25.15

Peptide Bond Formation

25.16

Solid-Phase Peptide Synthesis: The Merrifield Method

25.17

Secondary Structures of Peptides and Proteins

25.18

Tertiary Structure of Polypeptides and Proteins

25.2

Stereochemistry of Amino Acids

25.3

AcidBase Behavior of Amino Acids

25.4

Synthesis of Amino Acids

25.5

Reactions of Amino Acids

25.6

Some Biochemical Reactions of Amino Acids

25.7

Peptides

25.9

Amino Acid Analysis

---

26

Nucleosides, Nucleotides, and Nucleic Acids

26.1

Pyrimidines and Purines

26.10

Phosphodiesters, Oligonucleotides, and Polynucleotides

26.12

Protein Biosynthesis

26.13

AIDS

26.2

Nucleosides

26.3

Nucleotides

26.5

ATP and Bioenergetics

26.7

Nucleic Acids

26.9

Tertiary Structure of DNA: Supercoils

---

27

Synthetic Polymers

27.11

Polyamides

27.12

Polyesters

27.13

Polycarbonates

27.14

Polyurethanes

27.2

Polymer Nomenclature

27.3

Classification of Polymers: Reaction Type

27.4

Classification of Polymers: Chain Growth and Step Growth

27.7

Addition Polymers: A Review and a Preview

27.8

Chain Branching in Free-Radical Polymerization

27.9

Anionic Polymerization: Living Polymers