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Kinetics and mechanism of the thermal decomposition reaction of dihydro-3,6-diphenyl-5-benzyl-1,2,4,5-trioxazine

✍ Scribed by Lázaro F. R. Cafferata; Masatomo Nojima; Hideyuki Yamakoshi

Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
295 KB
Volume
28
Category
Article
ISSN
0538-8066

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✦ Synopsis

The thermal decomposition reactions of dihydro-3,6-diphenyl-5-benzyl-1,2.4,5-trioxazine ( D H T ) in the initial concentrations and temperature ranges of 0.004-0.013 M and 353-393 K, respectively, have been investigated in benzene, toluene, and methanol solutions In these solvents the reaction follows a first-order kinetic law up to ca 50% DHT conversions However, at the higher temperatures and higher initial concentrations, an induced decomposition reaction of the DHT molecule is observed, which is suppresed by the addition of a free radical scavenger. The pseudo-first-order rate constant values for the reactions of the trioxazine in acetic acid solution (0004 M ) in the temperature range of 313-323 K. lead to activation parameters significantly different from those of the unimolecular thermolysis in other media This supports a marked effect of the solvent on that reaction. The kinetics and the nature of the products observed in the DHT thermolysis favors a general stepwise mechanism of decomposition which resembles the type of reaction already postulated for other cyclic peroxides in solution.

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