Pyrolytic Methods in Organic Chemistry

Preface

Terminology and Conventions

Chapter 1. The Place of Flow and Flash Vacuum Pyrolytic Methods in Organic Chemistry

I. Historical Introduction

II. Scope of This Book and of Previous Reviews

III. Scope of Pyrolytic Experiments

IV. Thermal, Photochemical, and Mass Spectral Processes and Their Correlation

References

Chapter 2. Apparatus and Methods

I. Introduction

II. Apparatus

III. Choice of Pyrolytic Conditions

References

Chapter 3. Pyrolytic Generation and Reactions of Free Radicals, Arynes, and Cyclobutadienes

I. Introduction

II. Physical Detection, Identification, and Spectroscopic Study of Free Radicals

III. Pyrolytic Generation of Some O-, S-, and N-Centered Radicals

IV. Pyrolytic Formation of Carbon Radicals from Relatively Stable Precursors

V. Trapping of Arynes Formed at High Temperatures

VI. Pyrolytic Generation of Cyclobutadiene and Benzocyclobutadiene

References

Chapter 4. Elimination Reactions

I. Introduction

II. Dehydrogenations and Dealkylations

III. α-Eliminations

IV. β-Eliminations and γ-Eliminations

V. Formation of Ketenes by β-Elimination

VI. 1,4-Eliminations of HX from Systems H — C = C = C — X

References

Chapter 5. Generation of Carbenes and Nitrenes and Their Rearrangements in the Gas Phase

I. Introduction

II. Formation and Rearrangement of Carbenes

III. Rearrangements Involving Aromatic Carbenes and Nitrenes

IV. Sulfonylnitrenes and Carbamoylnitrenes

References

Chapter 6. Fragmentation of Cyclic Structures with Elimination of Small Molecules

I. Introduction

II. Pyrolysis of Carbonyl Compounds and Some Related Thionyl and Sulfonyl Compounds

III. Pyrolysis of Cyclic Sulfoxides and Sulfones

IV. Fragmentation of Various Heterocyclic and Polyheterocyclic Compounds

References

Chapter 7. Fragmentation of Acyclic Structures, and Related Cleavage of Cyclic Structures

I. Decarboxylations and Decarbonylations

II. Fission and Ring Opening of γ ,δ-Unsaturated Alcohols

III. Retro-Ene Reactions

References

Chapter 8. Cleavage of Carbocyclic Systems with Related Heterocyclic Examples

I. Introduction

II. Cleavage of Cyclobutane Derivatives

III. Retro-Diels-Alder Reactions

IV. Miscellaneous Fragmentations

References

Chapter 9. Rearrangements without Fragmentation

I. Introduction

II. Rearrangements with Concerted Four- or Six-Electron Steps

III. Rearrangements with Diradical or Dipolar Intermediates

IV. Concerted Rearrangements of Cyclopropane Derivatives

V. Sigmatropic Rearrangements

VI. Miscellaneous Isomerizations of Heterocyclic Compounds

VII. Rearrangements with Migration of a Coordinated Metal Atom

References

Index