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The thermal isomerization of 1,1‐dimethyl‐2‐vinylcyclopropane to cis ‐2‐methylhexa‐1,4‐diene via 1,5‐hydrogen migration

1969; Wiley; Volume: 1; Issue: 5 Linguagem: Inglês

10.1002/kin.550010506

1097-4601

H. M. Frey, Richard K. Solly,

Synthetic Organic Chemistry Methods

Abstract The gas phase isomerization of 1,1‐dimethyl‐2‐vinylcyclopropane to cis ‐2‐methylhexa‐1,4‐diene has been studied in a static system. The isomerization is homogeneous and kinetically first order. The rate constants were independent of initial reactant pressure in the range 0.6 to 2 torr and of added nitrogen up to 180 torr. Rate constants determined at 10 temperatures in the range 200 to 254°C fitted the Arrhenius equation k = 10 11.41±0.02 exp (−33,540 ± 47 cal/ RT ) sec −1 The low A factor and activation energy are consistent with a concerted 1,5‐hydrogen migration via a “tight” cyclic transition complex.