School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld, 4072, Australia.
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):14808-14835. doi: 10.1002/anie.201705118. Epub 2017 Oct 25.
Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, 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.
闪速真空热解 (FVP) 始于 20 世纪 40 年代和 50 年代，主要通过质谱检测热解形成的自由基。在 20 世纪 60 年代，许多有机化学家开始进行 FVP 实验，目的是分离新的和有趣的化合物并了解热解过程。同时，已经开发出许多不同类型的仪器和技术，本综述的目的是介绍最重要的方法，以及通过各种技术可以实现的典型反应和观察。这包括制备 FVP、化学捕获反应、基质隔离、反应中间体和不稳定分子的低温光谱学、在线质谱、光电离、微波和毫米波光谱学、气相激光热解、超音速射流膨胀的脉冲热解、用于动力学研究的极低压力热解、用于不挥发化合物的溶液喷雾和下落固体 FVP，以及在固体载体和试剂上的热解。此外，FVP 与基质隔离和光化学的结合是研究反应机制的有力工具。
