Thermal decomposition of the diazirines. Part III. 3-Chloro-3-methyldiazirine

Abstract

The thermal decomposition of 3-chloro-3-methyldiazirine has been investigated. The products, vinyl chloride and nitrogen are formed quantitatively by a first order reaction which is probably unimolecular. The high pressure rate constants were determined at a series of temperatures by carrying out runs in the presence of added perfluoropropane whence k_∞= 10^14·135 exp(–31,072/RT) sec.^–1. Arrhenius parameters were also measured at 4 torr at which pressure the rate constants have fallen to about a third of their high pressure limiting value, whence, k_{4 torr}= 10^11·708 exp (–27,177/RT) sec.^–1. Rate constants were also determined at one temperature at various pressures from 6·3 torr to 0·025 torr. The fall-off curve may be fitted approximately by the Kassel integral with s= 9 or 10. The possible structures for the transition complex are discussed.