Kinetics and mechanism for the acid‐catalyzed addition of propionic acid to tetradecenes and hexadecenes

Abstract

We developed a kinetic model for the reversible direct addition of propionic acid to linear tetradecences and linear hexadecenes on Amberlyst 15 at 93 • C. The model addresses concurrent double bond isomerization of the olefins and assumes carbenium ion formations to be rate limiting for all conversions; it is detailed enough to include terms for multiple isomers of esters and olefins. The reaction was first order in olefin and in ester but was one-half order in propionic acid. Gas chromatography was the analytical method employed to follow the reactions, and this study represents a novel use of this analytical method to elucidate carbenium ion behavior. The model includes five rate-determining steps and five fast steps.