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Direct and sensitized photolysis of bicyclo[4.2.0]octa-2,4-diene in the gas phase

✍ Scribed by John M. Greathead; S. Walter Orchard

Publisher: John Wiley and Sons
Year: 1987
Tongue: English
Weight: 758 KB
Volume: 19
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550190306

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✦ Synopsis

The direct photolysis of bicyclo[4.2.0locta-2,4-diene in the gas phase at 280-300 nm produces mainly 1,3,5-cyclooctatriene and benzene plus ethylene. The yield of the former product is enhanced by added gases, and it is proposed that it is formed in a vibrationally excited state which can revert to bicyclooctadiene unless the excess energy is removed in collisions. Computer modelling of the direct photolysis yielded quantitative agreement with the experimental results, but only when large, arbitrary adjustments were made to the calculated rate constants for the interconversion of cyclooctratriene and bicyclooctadiene. The Hg(63PI) sensitized reaction of bicyclooctadiene produces mainly benzene plus ethylene, a process which is also enhanced by added gases.

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