The thermal unimolecular decomposition of t-butylcyclobutane

Abstract

The thermal decomposition of t-butylcyclobutane has been studied in the gas phase from 401 to 478 °C. In an ‘aged’ reaction vessel the decomposition is homogeneous, kinetically of the first order, and yields an equimolar mixture of ethylene and 3,3-dimethylbut-1-ene as primary products. Rate constants were independent of pressure in the range 6–40 Torr and fit the Arrhenius equation (1). Some decomposition of the 3,3-dimethylbut-1-ene k= 10^15·94 exp (–63,860 cal. mole^–1/RT) sec.^–1(1), occurs at the reaction temperatures but is appreciably slower than the primary decomposition.