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Gas-phase pyrolysis mechanism and kinetics of 3-t-butoxyquadricyclane

✍ Scribed by Angelo J. Alfano

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 537 KB
Volume: 28
Category: Article
ISSN: 0538-8066
DOI: 10.1002/(sici)1097-4601(1996)28:7<481::aid-kin2>3.0.co;2-r

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✦ Synopsis

The gas-phase pyrolysis of 3-t-butoxyquadricyclane [ 1 ] was investigated over the temperature range 51 1-542 K at one atm in helium. The initial pyrolysis step is the isomerization of 3-fbutoxyquadricyclane to 7-f-butoxynorbornadiene (Ea = 38.49 5 0.85 kcalhole. log A = 15.44 ? 0.35). 7-t-butoxynorbornadiene exhibits a single unimolecular reaction pathway which produces a mixture of f-butoxycycloheptatrienes (Ea = 38.44 2 0.63 kcalhole, log A = 15 05 5 0.26). This two-step mechanism affords fewer reactions than unsubstituted quadricyclane in the gas phase and could be useful for its reduced sooting potential. 0 1996 lohn Wiley &Sons, Inc

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