The effect of ring size on the gas phase elimination kinetics of cycloalkyl acetates

The rates of elimination of seven cycloalkyl acetates containing between 5 and 15 ring carbons have been determined in a static system over a temperature range 280–370°C and a pressure range 35–234 torr. The unimolecular reactions, carried out in the presence of the inhibitor cyclohexene, are homogeneous in seasoned vessels and follow a first-order rate law. The rate coefficients are exemplified by that found for cyclopentyl acetate: The sequence of relative rates is analogous to that found in most solution reactions of these compounds. The contribution of ring strain to energy barriers of these compounds is described.