Kinetics of the thermal decomposition of 3-chlorobut-1-ene and 3-chloro-2-methylbut-1-ene

Abstract

The thermal decompositions of 3-chloro- and 3-chloro-2-methyl-but-1-ene in the range 320–380° are homogeneous and first-order, with rate constants 2·20 × 10¹³ exp (–48,500/RT) and 1·90 × 10¹³ exp (–46,900/RT) sec.^–1, respectively. In each case there is unimolecular elimination of hydrogen chloride. Allylic rearrangement is not rapid under the reaction conditions. In the compounds studied the α-vinyl group does not markedly accelerate the unimolecular elimination of hydrogen chloride. At 385° 3-chlorobut-1-ene decomposes 4·1 times as fast as isopropyl chloride.