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Kinetics of the reactions of cyclopropane derivatives. III. Gas-phase unimolecular isomerization of cyclopropyl cyanide to the cyanopropenes

✍ Scribed by D. A. Luckraft; P. J. Robinson

Publisher
John Wiley and Sons
Year
1973
Tongue
English
Weight
391 KB
Volume
5
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Cyclopropyl cyanide isomerizes in the gas phase at 660°–760°K and 2–89 torr to give mainly cis‐ and trans‐crotonitrile and allyl cyanide, with traces of methacrylonitrile. The reactions are first order, homogeneous, and unaffected by the presence of radical‐chain inhibitors. The rate constants are given by Overall:
cis‐Crotonitrile:
trans‐Crotonitrile:
Allyl cyanide:

where the error limits are standard deviations. On the basis of a biradical mechanism, it is deduced that the CHCN radical center is resonance stabilized by ca. 30 kJ mole^−1^. Approximate equilibrium data are given for interconversion of the 1‐ and 3‐cyanopropenes.

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