Homogeneous, unimolecular gas‐phase elimination kinetics of ethyl esters of glyoxylic, 2‐oxo‐propanoic, and 3‐methyl‐2‐oxo‐butanoic acids

The rates of elimination of several ethyl esters of 2-oxo-carboxylic acid were determined in a seasoned static reaction vessel over the temperature range 350–430°C and pressure range 33–240 Torr. The reactions, in the presence of a free-radical inhibitor, are homogeneous, unimolecular, and follow a first-order rate law. The overall and partial rate coefficients are expressed by the Arrhenius equation. Ethyl glyoxalate Ethyl 2-oxo-propionate Ethyl 3-methyl-2-oxo-butyrate The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 268–275, 2007