Linear‐reactor‐infrared‐matrix and microwave spectroscopy of the cis‐2‐butene gas‐phase ozonolysis

摘要: Investigation of the formation complex products in gas-phase ozonolysis cis,-2-butene by linear-reactor-infrared-matrix and linear-reactor-microwave spectroscopy is reported. The following species have been unequivocally detected: secondary 2-butene ozonide, acetic acid, peracetic glycolaldehyde, dimethyl ketene, simple mixed anhydrides formic 2,3-epoxybutane 2-butanone, besides polyatomic already known. In contrast, primary ozonide has detectable neither LR.-MW. nor LR.-IR. Observation both stereoisomeric epoxides kinetic modelling are used to support intermediate O'Neal-Blumstein radical CH3CH(O2)CH(O)CH3 existence a reaction channel which two carbon atoms C, C double bond olefin remain connected. As dominant path mechanism with Criegee type split into methyldioxirane (ethylidene peroxide) acetaldehyde considered subsequently proposed explain many either unimolecular or bimolecular processes peroxide. For reactions considered, thermochemical estimates enthalpies activation data included. Kinetic for partial involving at least different paths decay biradical Criegee-type intermediates 2, 3-epoxybutanes discussed.