Kinetics of the thermal decomposition of 2,3-epoxy-2,3-dimethylbutane

Abstract

2,3-Epoxy-2,3-dimethylbutane decomposes in the gas phase between 388 and 456° by three competing homogeneous, first-order, nonradical reactions to give 3,3-dimethylbutan-2-one, propene, acetone, and 2,3-dimethylbut-3-en-2-ol. k(3,3-dimethylbutan-2-one)= 10^13·83±^0·43 exp (–56,700 ± 1360/RT) sec.^–1, k(propene)= 10^14·77±^0·76 exp (–59,220 ± 2400/RT) sec.^–1, k(alcohol)= 10^10·88±^0·65 exp (–47,500 ± 2050/RT) sec.^–1. Reaction mechanisms are discussed in which the initial step is fission of the ring at either a C–C or a C–O bond to give a short-lived biradical intermediate that may rearrange or decompose to give the observed products.