ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal isomerization of 1,1-divinylcyclopropane has been investigated in the gas phase in the temperature range of 238 to 288°C and for pressures in the range of 4 to 12 torr. The isomerization to 1-vinylcyclopentene is homogeneous and kinetically first order and almost certainly unimolecular. The rate constants yield the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (42.45 \pm 0.33{\rm \,kcal/mole})/RT\,{\rm In 10}$$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (117.6 \pm 1.4{\rm \,kJ/mole})/RT\,{\rm In 10}$$\end{document} The assumption of a similar transition state for this isomerization with that of l-methyl-l-vinylcyclopropane leads to a value for an alkylpentadienyl radical stabilisation energy of 19.2 ± 1.6 kcal/mole (80.4 ± 6.7 kJ/mole), and this value is compared with other estimates.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550060612
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