Kinetics and mechanisms of gas phase elimination of ethyl 1‐piperidine carboxylate,ethyl pipecolinate,and (revisited) ethyl 1‐methyl pipecolinate |
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Authors: | Felix Rosas,Angiebelk Monsalve,Marí a Tosta,Armando Herize,Rosa M. Domí nguez,Doris Brusco,Gabriel Chuchani |
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Abstract: | The kinetics of the gas‐phase elimination of the title compounds has been determined in a static reaction system over the temperature range of 340–420°C and pressure range of 45–96 Torr. The reactions proved to be homogeneous, unimolecular, and obey a first‐order rate law. The estimated rate coefficients are represented by the following Arrhenius expressions: Ethyl 1‐piperidine carboxylate Ethyl pipecolinate Ethyl 1‐methyl pipecolinate The first step of decomposition of these esters is the formation of the corresponding carboxylic acids and ethylene. The acid intermediate undergoes a very fast decarboxylation process. The mechanism of this elimination reactions is suggested on the basis of the kinetic and thermodynamic parameters. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 383–389, 2005 |
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