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Kinetics and mechanism of the thermal reactions of endo- and exo-5-cyanobicyclo[2.2.2]oct-2-ene and methyl-substituted derivatives in the gas phase

✍ Scribed by B. Van Mele; G. Huybrechts

Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
364 KB
Volume
19
Category
Article
ISSN
0538-8066

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✦ Synopsis

The thermal reactions of endoand ao-5-cyanobicyclo-[2.2.2loct-2-ene and their transand cis-6-methyl-substituted derivatives have been investigated in the gas phase between 518 and 630 K. Each product decomposes by two parallel first-order retro-Diels-Alder reactions, a main one with formation of cyclohexa-1,3-diene and a minor one with elimination of ethene. Slight isomerizations are also observed. The kinetic results can be explained in terms of a biradical mechanism. The rate-determining step is shown to depend on the amount of resonance energy in the biradical. Heats of formation and entropies of the bicyclo[2.2.2]oct-2-enes studied are estimated.

*From Table I and known values of rate constants [6]

, one calculates that the back Diels-Alder reactions of CHD are negligible.

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