The gas‐phase elimination kinetics of 3‐buten‐1‐methanesulphonate and 3‐methyl‐3‐buten‐1‐methanesulphonate

AbstractThe elimination kinetics of the title compounds were carried out in a static system over the temperature range of 290–330°C and pressure range of 29.5–124 torr. The reactions, carried out in seasoned vessels with allyl bromide, obey first‐order rate law, are homogeneous and unimolecular. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3‐buten‐1‐methanesulphonate, log k1(s−1) = (12.95 ± 0.53) − (175.3 ± 5.9)kJ mol−1(2.303RT)−1; and for 3‐methyl‐3‐buten‐1‐methanesulphonate, log k1(s−1) = (12.98 ± 0.40) − (174.7 ± 4.5)kJ mol−1(2.303RT)−1. The olefinic double bond appears to assist in the rate of pyrolysis. The mechanism is described in terms of an intimate ion‐pair intermediate. © 1995 John Wiley & Sons, Inc.