Thermolytic reactions of esters part I: Allyl acetate

Within the scope of a general study on the gas phase chemistry of esters, the thermolysis of allyl acetate was investigated, using a stirred‐flow type (“tank‐flow”‐) reactor operating at atmospheric pressure in the presence of nitrogen as the carrier gas. Rate and product studies, including the use of toluene or cyclohexene as scavengers and the application of selectively deuterated compounds, demonstrated that under our conditions (400‐500°C) the reaction mainly proceeds via. free radicals, allyl‐oxygen homolysis probably being the intial step. The main decomposition products formed are carbon dioxide, 1‐butene, carbon monoxide and methane; formation of these and other (minor) products may be accounted for in terms of an induced decomposition mainly effected by methyl radicals.