ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reaction products and intermediates of the thermal conversions (temperature range: 600 to 1200°C, total pressure about 120 mPa) of phenyl methyl ether (1), phenyl ethyl ether (2), and m-cresyl methyl ether (3) were determined in a pyrolysis apparatur set combined with mass spectral „real time“ analysis. In all cases, the predominant initial process was PhO-R bond homolysis. Phenoxy type radicals thus generated decompose unimolecularly to cyclopentadienyl type radicals and carbon monoxide. In runs with 1 and 2 cyclopentadienyl dimers (C10H10) were formed and, in addition, at temperatures 〉1000°C, naphthalene (C10H8). Under similar conditions the m-methylphenoxy radical (from 3) suffers CO elimination providing the methylcyclopentadienyl radical which chiefly gives benzene instead of the dimers or the products derived from it. Under the applied conditions only bimolecular stabilization of the unsubstituted cyclopentadienyl radical proved possible, whereas the methyl substituted radical has a chance for unimolecular stabilization, too, as a result of which fulvene is formed through the loss of hydrogen. Fulvene is a direct benzene precursor.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19893310606
