Gas-Phase Pyrolytic Reactions: Synthesis, Mechanisms, and Kinetics

ISBN-13: 9781118057476 / Angielski / Twarda / 2019 / 304 str.

Nouria A. Al–Awadi; Osman M.E. El–Dusouqui

Opis

This book covers a chemical processing technique, gas–phase pyrolysis, that has garnered great interest in recent years as a benign synthetic method for green chemistry. The book looks at all aspects of gas–phase pyrolysis: structure, kinetics, mechanisms, empirical and theoretical investigations, synthesis, materials, and potential applications.

Spis treści

Preface xiList of Abbreviations xiiiAbout the Author xv1 Methodologies and Reactors 11.1 Static Pyrolysis 11.1.1 Sealed-Tube Reactor 21.1.1.1 Pyrolyzer 21.1.1.2 Reaction Tube 31.1.1.3 Kinetic Studies 31.1.1.4 Treatment of Kinetic Results 41.1.2 Static Apparatus 51.1.2.1 Reaction Chamber 61.1.2.2 The Pyrolysis Method 71.1.2.3 Treatment of the Results 71.2 Dynamic Flow Pyrolysis 81.2.1 Flash Vacuum Pyrolysis 81.2.2 Synthetic Applications of FVP 101.2.3 Gas-Flow Pyrolysis vs. STP 131.2.4 Limitations of FVP 131.2.5 Spray Pyrolysis 141.2.6 Falling-Solid Pyrolysis 171.3 Analytical Pyrolysis 191.3.1 Pyrolysis Gas Chromatography (Py-GC) 191.3.1.1 Online Py-GC 201.3.2 Pyrolysis Mass Spectrometry 221.3.2.1 Online Pyrolysis Gas Chromatography/Mass Spectrometry (Py-GC/MS) 221.3.3 FVP with Spectroscopy 221.3.4 Catalytic Gas-Phase Pyrolysis 24References 272 Synthesis and Applications 312.1 Flash Vacuum Pyrolysis in Organic Synthesis 312.2 Elimination of HX 342.3 Elimination of CO and CO2 382.4 Pyrolysis of Meldrum's Acid Derivatives 542.5 Elimination of N2 602.5.1 Deazetization Reactions of Allylic Diazenes 632.5.2 Pyrolysis of Benzotriazole Derivatives 652.5.3 Pyrolysis of Triazine Derivatives 68References 723 Reaction Mechanism 793.1 Retro-ene Reactions 793.1.1 Acetylenic Compounds 803.1.2 Acyl Group Participation 823.1.3 Cyanates and Isocyanates 823.1.4 Esters 833.1.5 Amides 883.1.5.1 Acetamides and Thioacetamides 883.1.5.2 Benzamides 923.1.5.3 N-Substituted Amides 933.2 Reactive Intermediates 943.2.1 Radicals 943.2.2 Diradicals 973.2.3 Benzynes 983.2.3.1 o-Benzynes 993.2.3.2 m- and p-Benzynes 1013.2.4 Carbenes 1013.2.5 Nitrenes 108References 1204 Structure/Reactivity Correlation 1274.1 Diketones 1274.2 Cyanoketones 1334.3 Ketoamides 1354.4 Benzotriazoles 1364.5 Hammett Correlation in Gas-Phase Pyrolysis 1484.6 Alkoxy versus Amino Group 1534.6.1 Neighboring Group Participation 1554.6.2 Amino Esters 158References 1625 Functional Group and Structural Frame Interconversions 1675.1 Functional Group Interconversion 1675.1.1 Thermal Retro-Ene Reactions 1675.1.1.1 alpha-Substituted Carboxylic Acids 1735.1.1.2 2-Hydroxycarboxylic Acids 1755.1.1.3 2-Alkoxycarboxylic Acids 1765.1.1.4 2-Phenoxycarboxylic Acids 1775.1.1.5 2-Aminocarboxylic Acids 1805.1.1.6 2-Acetooxycarboxylic Acids 1825.1.1.7 2-Ketocarboxylic Acids 1845.1.1.8 alpha-Substituted Esters 1865.1.1.9 ß-Substituted Carboxylic Acids 1885.2 Structural Frame Interconversion 1915.2.1 Alkyl Heterocycles 195References 1976 Gas-Phase Pyrolysis of Hydrazones 2016.1 Substituted Phenylhydrazones 2036.2 N-Arylidineamino Heterocycles 2136.3 Arylidene Hydrazine Heterocycles 221References 2317 Gas-Phase Pyrolysis of Phosphorus Ylides 2357.1 Synthetic Applications 2357.2 Haloalkynes 2417.3 Terminal Alkynes 2447.4 Diynes 2477.5 Enynes and Dienes 2507.6 Selective Elimination of Ph3PO from Di- and Tri-oxo-stabilized Phosphorus Ylides 2527.7 Sulfonyl-Stabilized Phosphorus Ylides 2577.8 Sulfinyl-Stabilized Phosphorus Ylides 2627.9 Kinetic andThermal Reactivity of Carbonyl-Stabilized Phosphonium Ylides 266References 277Index 281

O autorze

NOURIA A. AL-AWADI is Professor of Organic Chemistry at Kuwait University, Safat, State of Kuwait. She is a Chartered Chemist and Fellow of the Royal Society of Chemistry and has over 150 peer-reviewed journal papers published.