The Gas-Phase Elimination Kinetics of 3-Buten-1-Methanesulphonate and 3-Methyl-3-Buten-1-Methanesulphonate

Article abstract of DOI:10.1002/kin.550270705

The elimination kinetics of the title compounds were carried out in a static system over the temperature range of 290-330 deg 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.