Rate acceleration and subsequent retardation of Diels-Alder reactions in LiClO4-diethyl ether: an experimental investigation.
The experimental kinetic data for several Diels-Alder reactions show why a 5 M LiClO(4)-diethyl ether (LPDE) solution offers maximum enhancement of reaction rates, endo/exo ratios, and yields. These reactions, if carried out in LPDE solutions of concentrations higher than 5 M, show a substantial decrease in these kinetic parameters. This decrease is attributed to the very high viscosity of LPDE solutions near saturation, though this interpretation is not consistent when considered in terms of sizes of the diene and dienophile. The monoetherates, dietherates, and higher other clusters in LPDE solutions and their relationship with the Lewis acid catalysis by Li+ offer a more plausible explanation of both the enhancement and the decrease of the rate of Diels-Alder reactions in this medium.
Kumar
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A
Physical Chemistry Division, National Chemical Laboratory, Pune 411 008, India. akumar@ems.ncl.res.in
Pawar
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SS