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A Complication in the thermal reactions of 1,1,2,2-tetramethylcyclopropane

✍ Scribed by C. Blumstein; D. Henfling; C. M. Sharts; H. E. O'Neal

Publisher: John Wiley and Sons
Year: 1970
Tongue: English
Weight: 420 KB
Volume: 2
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550020102

No coin nor oath required. For personal study only.

✦ Synopsis

Reinvestigation of the gas phase thermal reaction of 1,1,2,2-tetramethylcyclopropanr (699--75g0K) gave for the unimolecular disappearance of reactant, l i ( ~1 1 ~) = 1 015.27-63.93/s sec-l, in good agreement with the original results of Frey and Marshall. However, evidence for a high activation energy ( E = 79 & 5 kcalfmole), competitive unimolecular decomposition to 2,3-dimethyl-1 and -2-butenes was also obtained. It is proposed that the serious discrepancy noted [ 11 between the experimentally observed Arrhenius parameters for the overall reaction kinetics, and those predicted by transition state calculations assuming a hiradical mechanism for the isomerization reactions (previously believed to be the only primary reaction mode) can be explained in terms of the increasing importance of the decomposition reactions at higher reaction temperatures.

* r\n error in reporting the A-factor (originally .4 = 10'5**3 sec-l) has been corrected and confirmed by Frey in a personal communication.

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