Ethylene oxide pyrolysis, intermediates

The global reactions considered include the conversion by pure pyrolysis of toluene to acetylene and the conversion of isooctane to ethylene, oxidative pyrolysis of the acetylene and ethylene, and partial oxidation of the parent fuels and these hydrocarbon intermediates to CO, H2, and H2O. The specific reactions and rates for this system are given in Table II. Soot formation is assumed to be a function of temperature and oxygen and precursor concentrations. In the present study the soot precursors are taken to be acetylene and toluene, expressed as C2 hydrocarbons. 

Automatic recording infrared apparatus can also be used in studying the kinetics of both complex reactions and intermediates if their concentrations are not less than 1 per cent. In this way, ketene, CH2CO, and acetaldehyde, CIIsCHO, have been identified as intermediates in the pyrolysis of ethylene oxide, C2H40. ... 

Thermolysis of 16e,f in either solution or gas phase (150-350 °C) gave deuteriated ethylenes (i.e. 40e from 16e and 41f from 16f) with about 95% retention of stereochemis-try ". Similarly, pyrolysis of the stereoisomeric 2,3-diphenylthiirane oxides 16g,h proceeded smoothly to yield stilbenes and sulfur monoxide in more than 70% yield . The extrusion of SO from the trans-isomer proceeds almost stereospecifically, while that from the cis-isomer occurs with complete loss of stereochemistry. This indicates the intervention of a stepwise mechanism, and not a symmetry-allowed nonlinear chelatropic reaction . Based on the fact that all attempts to trap the intermediate with 1,3-dipolarophiles were in vain, whereas a 1 1 adduct was obtained in good yield (about 60%) with the carbon radical scavenger di-p-anisyl thioketone, a mechanistic scheme as depicted in equation 10 has been proposed . Although the radical intermediates are capable of internal rotation about the carbon-carbon bond, for the 2,3-diphenyl case (i.e. 16g,h), the rotation would be... 

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