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Effect of substituents in the gas-phase elimination kinetics of β-substituted ethyl acetates

✍ Scribed by Gabriel Chuchani; Ignacio Martin; Irama Avila

Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
353 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The kinetics of gas‐phase elimination of 3‐methyl‐1‐butyl acetate and 3,3‐dimethyl‐1‐butyl acetate into acetic acid and the corresponding substituted butenes have been measured over the temperature range of 360–420°C and the pressure range of 63–250 Torr. The reactions are homogeneous in both clean and seasoned vessels, obey first‐order law, and are unimolecular. The temperature dependence of the rate constants is given by the Arrhenius equation

3‐methyl‐1‐butyl acetate:

3,3‐dimethyl‐1‐butyl acetate:
The points in a plot of log (k/k~0~) of β‐alkyl and several β‐substituted ethyl acetates against E~s~ values appear aligned in an approximate linear relationship. These results may be interpreted as a consequence of steric effects, namely, steric accelerations.

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