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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
Author(s) -
Frey H. M.,
Solly R. K.
Publication year - 1969
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550010506
Subject(s) - isomerization , chemistry , arrhenius equation , reaction rate constant , diene , activation energy , torr , hydrogen , arrhenius plot , atmospheric temperature range , photochemistry , kinetics , medicinal chemistry , thermodynamics , organic chemistry , catalysis , physics , natural rubber , quantum mechanics
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.