The Principles of Heterocyclic Chemistry

The Principles of Heterocyclic Chemistry presents a unified account of fundamental heterocyclic chemistry with the emphasis placed on the correlations between the methods of preparation and the properties of the various ring systems. This book opens with an introductory chapter that discusses fundamental concepts of the electronic theory of organic chemistry and the relationship of heterocyclic and carbocyclic aromatic compounds. This is followed by separate chapters on the chemistry of the six-membered ring compounds containing one or more heteroatoms, five-membered ring compounds, three- and four-membered rings, and the physical properties of representative heterocyclic compounds.
Each chapter begins with introductory section that surveys the various ring types, gives the systems of nomenclature and numbering, and mentions a few important natural and synthetic compounds. Syntheses starting from aliphatic and carbocyclic compounds are then given. The preparation of one heterocyclic compound from another is considered as a reaction of the starting material. The reactions of aromatic and non-aromatic compounds are discussed separately. This book contains the essential heterocyclic chemistry required by an Undergraduate or Graduate student for his course-work, and it is hoped that it will be found stimulating by many a more senior teacher and researcher.

Preface

1. Introduction

1. Use of this Book by the Undergraduate Student

2. Fundamental Concepts of the Electronic Theory of Organic Chemistry

3. Relationship of Heterocyclic and Carbocyclic Aromatic Compounds

4. Arrangement of the Book

5. Conventions

6. Nomenclature

7. The Literature of Heterocyclic Chemistry

2. Six-Membered Rings with One Heteroatom

I. Nomenclature and Important Compounds

1. Monocyclic Nitrogen-Containing Compounds

2. Benzopyridines

3. Monocyclic Oxygen- and Sulphur-Containing Compounds

4. Monobenzo-Pyrones and -Pyrylium Salts

5. Dibenzo-Pyrones and -Pyrylium Salts

II. Ring Syntheses

A. General Survey

B. Preparation of Monocyclic Compounds (Pyridines, Pyridones, Pyrylium Salts, etc.)

C. Preparation of 2,3-Benzo Derivatives (Quinolines, Quinolones, Chromans, etc.)

D. Preparation of 3,4-Benzo Derivatives (Isoquinolines, etc.)

III. Reactions Of The Aromatic Nuclei

A. General Survey of Reactivity

B. Electrophilic Attack at the Pyridine Nitrogen Atom

C. Electrophilic Attack at the Ring Carbon Atoms

D. Nucleophilic Attack at the Ring Carbon Atoms

E. Free Radical Attack at the Ring Carbon Atoms

F. Miscellaneous Reactions

IV. The Reactions of Substituents Attached to Aromatic Rings

A. Substituents on Carbon

B. Substituents on the Ring Nitrogen Atom

C. Summary of Synthetic Routes to Substituted Pyridines

V. Reactions of Non-Aromatic Compounds

A. Dihydro Compounds

B. Tetra- and Hexa-hydro Compounds

3. Six-Membered Rings with Two or More Heteroatoms

I. Nomenclature and Important Compounds

1. Diazines

2. Other Compounds

II. Ring Syntheses

A. Heteroatoms in the 1,2-Positions

B. Heteroatoms in the 1,3-Positions

C. Heteroatoms in the 1,4-Positions

D. Compounds with Three or Four Heteroatoms

III. Reactions of the Aromatic Rings

1. General Survey

2. Electrophilic Attack on the Ring Nitrogen Atoms

3. Electrophilic Attack on the Ring Carbon Atoms

4. Nucleophilic Attack on the Ring Carbon Atoms

IV. Reactions of Substituents on Aromatic Rings

1. General Survey

2. Carbon-Containing Substituents

3. Halogen Atoms

4. Oxygen-Containing Functional Groups

5. Nitrogen- and Sulphur-Containing Functional Groups

V. Reactions of Non-Aromatic Compounds

1. Reactions Involving 'Reversion to Type'

2. Aromatization

3. Other Reactions

4. Five-Membered Rings with One Heteroatom

I. Nomenclature and Important Compounds

1. Aromatic Monocyclic Compounds

2. Non-Aromatic Monocyclic Compounds

3. 2,3-Benzo Derivatives

4. Other Compounds

II. Ring Syntheses

1. General Survey

2. Formation of C-Z Bonds

3. Formation of the C3-C4 Bond

III. Reactions of the Aromatic Nuclei

A. General Survey of Reactivity

B. Reactions with Electrophilic Reagents

C. Other Reactions of the Aromatic Nuclei

IV. Reactions of Substituents on Aromatic Nuclei

1. General Survey of Reactivity

2. Fused Benzene Rings

3. Alkyl and Substituted-Alkyl Groups

4. Carboxylic Acids

5. Formyl and Acyl Groups

6. Halogen

7. Nitro, Sulphonic Acid, and Mercuri Groups

8. N-Substituents on Pyrroles

V. Reactions of Hydroxyl, Amino, and Related Compounds

1. Survey of Reactivity

2. Reactions with Electrophiles

3. Reactions of Carbonyl Compounds with Nucleophiles

4. Reduction of Carbonyl and Hydroxyl Compounds

5. Reactions at Other Sites in the Ring

6. Amino and Imino Compounds

VI. Reactions of Other Non-Aromatic Compounds

1. Pyrrolenines and Indolenines

2. Thiophene Sulphones

3. Dihydro Compounds

4. Tetrahydro Compounds

5. Five-Membered Rings Containing Two or More Heteroatoms

I. Nomenclature and Important Compounds

1. Monocyclic Compounds Containing Annular Nitrogen Atoms Only

2. Monocyclic Compounds Containing Annular Nitrogen and Oxygen or Sulphur Atoms

3. Polycyclic Derivatives

II. Ring Syntheses

A. Heteroatoms in the 1,2-Positions

B. Heteroatoms in the 1,3-Positions

C. Compounds Containing Three or More Heteroatoms

III. Reactions of the Aromatic Rings

A. General Survey

B. Electrophilic Attack at a Multiply-Bonded Ring Nitrogen Atom

C. Electrophilic Attack at a Ring Carbon Atom

D. Nucleophilic Attack at the Ring Carbon Atoms

E. Other Reactions of the Aromatic Nuclei 152

IV. Reactions of Substituents on Aromatic Nuclei

1. General Survey

2. Carbon-Containing Substituents

3. Halogens

4. Potential Hydroxy Compounds

5. Amino Groups

V. Reactions of Non-Aromatic Compounds

(a) Dihydro Compounds

(b) Tetrahydro Compounds

(c) Non-Aromatic Derivatives of Azolinones

6. Heterocyclic Compounds with Three- and Four-Membered Rings

I. Three-Membered Rings

A. Three-Membered Rings with One Heteroatom

B. Three-Membered Rings Containing Two Heteroatoms

II. Four-Membered Rings

A. Four-Membered Rings Containing One Heteroatom

B. Four-Membered Rings Containing Two Heteroatoms

7. Physical Properties

1. Melting Points and Boiling Points

(a) Unsubstituted Compounds

(b) Effect oj Substituents

2. Refractive Indices, Specific Gravities, and Viscosities

3. Dipole Moments

4. pKa Values

5. Ultraviolet Spectra

6. Infrared Spectra

7. Nuclear Magnetic Resonance Spectra

8. Mass Spectra

Index