ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The kinetics of the gas-phase elimination of two 2-haloethyl methanesulphonates were determined in a static system over the temperature range 310-380°C and pressure range 26-174 Torr. The reactions in seasoned vessels, with the free-radical inhibitor propene and/or toluene always present, are homogeneous and unimolecular, and follow a first-order rate law. The rate coefficients are given by the Arrhenius equations: for 2-bromoethyl methanesulphonate log k1 (s-1) = (11·70 ± 0·43)-(172·8 ± 4·8) kJ mol-1 (2·303RT)-1 and for 2-chloroethyl methanesulphonate log k1 (s-1) = (11·67 ± 0·50)-(173·9 ± 6·0) kJ mol-1 (2·303RT)-1. The bromo compound was found to be more reactive than the chloro compound. At 340°C, for Br k1 = 9·46 × 10-4 s-1 and for Cl k1 = 7·12 × 10-4 s-1. Apparently, electronic factors seem to be operating in these elimination reactions.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610030707