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The thermal unimolecular decomposition of bromocyclobutane

✍ Scribed by Keith D. King; Robert G. Gilbert

Publisher
John Wiley and Sons
Year
1980
Tongue
English
Weight
326 KB
Volume
12
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The thermal unimolecular decomposition of bromocyclobutane has been investigated over the temperature range of 791–1224 K using the technique of very low‐pressure pyrolysis (VLPP). HBr elimination is the sole mode of decomposition under the experimental conditions. No evidence could be found for the ring‐cleavage pathway to ethylene and vinyl bromide. Assuming a four‐center transition state and an Arrhenius A factor the same as that for HCl elimination from chlorocyclobutane, RRKM calculations show that the experimental unimolecular rate constants are consistent with the Arrhenius expression
where θ = 2.303__RT__ kcal/mol. The activation energy is higher than that for the open‐chain analog, 2bromobutane. This finding is consistent with the results for the corresponding chloro and iodo compounds.

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