Flash vacuum pyrolysis - techniques and reactions

While pyrolysis reactions have been performed since ancient times and been crucial for the invention of several technologies, the methodology now commonly known as flash vacuum pyrolysis, FVP (or flash vacuum thermolysis, FVT) had its early beginnings in the 1940s and1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave and millimeterwave spectroscopies, gas-phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution-spray and falling-solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism