THE GAS-PHASE ELIMINATION KINETICS OF 3-BUTEN-1-METHANESULFONATE AND 3-METHYL-3-BUTEN-1-METHANESULFONATE

The elimination kinetics of the title compounds were carried out in a static system over the temperature range of 290-330 degrees C and pres sure range of 29.5-124 torr. The reactions, carried out in seasoned ve ssels with allyl bromide, obey first-order rate law, are homogeneous a nd unimolecular. The temperature dependence of the rate coefficients i s given by the following Arrhenius equations: for 3-buten-1-methanesul phonate, log k(1)(s(-1)) = (12.95+/-0.53)-(175.3+/-5.9)kJ mol(-1) (2.3 03RT)(-1); and for 3-methyl-3-buten-1-methanesulphonate, log k(1)(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.