Premium
The Gas‐phase thermal unimolecular isomerization of n‐propylidenecyclopropylamine to 5‐ethyl‐1‐pyrroline
Author(s) -
Cocks Alan T.,
Egger Kurt W.
Publication year - 1972
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.550040205
Subject(s) - chemistry , isomerization , arrhenius equation , torr , activation energy , pyrroline , gas phase , reaction rate constant , homogeneous , atmospheric temperature range , radical , medicinal chemistry , kinetics , organic chemistry , thermodynamics , catalysis , physics , quantum mechanics
The gas‐phase thermal isomerization of N‐propylidenecyclopropylamine has been studied in the temerature range of 573° to 635°K. The reaction is homogeneous and kinetically first order and yields 5‐ethyl‐1‐pyrroline as the sole product. The rate constants are independent of pressure in the range of 2.5 to 55 torr and fit the Arrhenius relationship log k (sec −1 ) = (14.05 ± 0.06) ‐ (47.77 ± 0.16)/θ where θ = 2.303 RT in units of kcal/mole, or log k (sec −1 ) = (14.05 ± 0.06) ‐ (199.9 ± 0.7)/θ, where θ = 2.303 RT in kJ/mole. From considerations of a biradical pathway it is concluded that the resonance stabilization energy of the substituted 2‐aza‐allyl radical is very similar to that of the methallyl radical.