Pyrolytic Methods in Organic Chemistry
Application of Flow and Flash Vacuum Pyrolytic Techniques
- 1st Edition - April 28, 1980
- Imprint: Academic Press
- Author: Roger Brown
- Language: English
- Paperback ISBN:9 7 8 - 0 - 1 2 - 4 3 1 6 1 4 - 0
- eBook ISBN:9 7 8 - 0 - 3 2 3 - 1 5 4 1 7 - 8
Pyrolytic Methods in Organic Chemistry: Application of Flow and Flash Vacuum Pyrolytic Techniques is concerned with the use of flow pyrolysis and flash vacuum pyrolysis in… Read more
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Request a sales quotePyrolytic Methods in Organic Chemistry: Application of Flow and Flash Vacuum Pyrolytic Techniques is concerned with the use of flow pyrolysis and flash vacuum pyrolysis in preparative organic chemistry. Topics covered include pyrolytic generation and reactions of free radicals, arynes, and cyclobutadienes; elimination reactions; rearrangements of carbenes and nitrenes in the gas phase; and fragmentation of cyclic and acyclic structures. Examples of the types of reaction for which flow and flash pyrolytic methods are well suited are provided. This book is comprised of nine chapters and begins by discussing the place of flow and flash vacuum pyrolytic methods in organic chemistry. The next chapter gives an account of apparatus and experimental methods, while the remaining chapters focus on pyrolytic reactions that are grouped together according to the nature of the overall process, the formal structure of the starting material, and mechanistic type. Reactions that are formally related because they involve elimination of a small fragment molecule X-X or X-Y from a larger molecular framework are examined, along with cleavage of carbocyclic systems. The final chapter presents examples of high-temperature rearrangements, focusing on electrocyclic reactions and cycloadditions involving mainly four or six electrons; reactions that proceed through diradical intermediates; and isomerizations of heterocyclic rings. This monograph is intended mainly for practicing academic and industrial organic chemists and for advanced and graduate students.
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
- Edition: 1
- Published: April 28, 1980
- No. of pages (eBook): 362
- Imprint: Academic Press
- Language: English
- Paperback ISBN: 9780124316140
- eBook ISBN: 9780323154178
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