Helvetica Chimica Acta p. 1971 - 1999 (1980)
Update date:2022-08-17
Topics:
Kuehne, Heinz
Forster, Martin
Hulliger, Juerg
Ruprecht, Heidi
Bauder, Alfred
Guenthard, Hans-Heinrich
Investigation of the formation of complex products in the gas-phase ozonolysis of 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 acid, glycolaldehyde, dimethyl ketene, the simple mixed anhydrides of formic and acetic acid, 2,3-epoxy-butane and 2-butanone, besides polyatomic products alredy known.In contrast, the primery ozonide has been detectable neither by LR.-MW. nor by LR.-IR.Observation of both stereoisomeric epoxides and kinetic modelling are used to support the intermediate formation of the O'Neal-Blumstein radical CH3CH(O2)CH(O)CH3 and the existence of a reaction channel in which the two carbon atoms of the C,C double bond of the olefin remain connected.As the dominant reaction path a mechanism with a Criegee type split into methyldioxirane (ethylidene peroxide) and acetaldehyde is considered and subsequently proposed to explain formation of many complex products by either unimolecular or bimolecular processes of the peroxide.For the reactions considered, thermochemical estimates of reaction enthalpies and activation data are included.Kinetic modelling for a partial reaction mechanism involving at least two different paths of decay of the O'Neal-Blumstein biradical into Criegee-type intermediates and the 2,3-epoxy-butanes is discussed.
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