Abstract
AbstractThe gas‐phase elimination of ethyl 3‐methylbutanoate and ethyl 3,3‐dimethylbutanoate has been studied, in a static system, over the temperature range of 360–420°C and in the pressure range of 71–286 torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for ethyl 3‐methylbutanoate, log k1 (s−1) = (12.70 ± 0.36) – (202.5 ± 4.4) kJ/mol/2.303RT, and for ethyl 3,3‐dimethylbutanoate, log k1 (s−1) = (13.04 ± 0.08) – (207.1 ± 1.0) kJ/mol/2.303RT. Alkyl substituents at the acyl carbon of ethyl esters yield very close values in rates. Consequently it is rather difficult to offer some conclusion concerning the effect of these substituents.
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