Journal of the American Chemical Society p. 2697 - 2706 (1987)
Update date:2022-08-22
Topics:
Doering, W. von E.
Ehlhardt, William J.
The Doering-Gilbert-Leermakers strategy for revealing chemical reaction possibly more rapid than internal flow of energy is applied to 1,2-dicyclopropylacetylene by examining addition of dideuteriomethylene to 1-cyclopropyl-2-vinylacetylene and of methylene to 1-(2,2-dideuteriocyclopropyl)-2-vinylacetylene in the gas phase.This reduction to practice of the general strategy has three advantages: one of the three isomers of allylcyclopropylacetylene, itself the key product of chemically activated rearrangement, bears internal witness to the achievement of structural symmetry prior to its generation; the long, linear acetylenic linkage precludes internal energy flow by a mechanism of intramolecular collision; and the activation energy of the cyclopropane-propene rearrangement is lowered significantly.Analysis of the experimental results reveals a small amount of rearrangement at high pressures occurring prior to complete symmetrization of structure and/or energy.If this observation can be ascribed to incomplete symmetrization of energy, the basic premise of the Rice-Ramsperger-Kassel-Marcus theory-that internal energy flow be so much faster than chemical reaction that a structureless statistical treatment is justified-may require reconsideration.
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