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Thermal rearrangements of 1,1,2,2- and 1,1,4,4-tetrafluorospiropentanes

โœ Scribed by Dolbier, William R.; Sellers, Simon F.; Al-Sader, Basil H.; Fielder, Thomas H.


Book ID
125999554
Publisher
American Chemical Society
Year
1981
Tongue
English
Weight
303 KB
Volume
103
Category
Article
ISSN
0002-7863

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The thermal rearrangements of 1,1,2,2,4,
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The title compounds were synthesized via CF2: addition to the respective methylenecyclopropanes. The hexafluorospiropentane thermally rearranges to 2,2,4,4-tetrafluoro-l-(difluoromethyiene)cyclobutane in competition with CF2: extrusion, whereas perfluorospiropentane decomposes exclusively by CF2: e

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energy (2 x 12 kcal mo1-l). the removal of allene strain ( 2 x 13 kcal mol-l 163). and the observed activation energy.

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The thermal isomerization of the title compounds was studied in the vapor phase. Over the temperature range from 445.1 to 477.5"K7 1,4-dimethylbicyclo[2.2.O]hexane underwent a homogeneous unimolecular reaction to 2,5-dimethyl-175-hexadiene, the rate constants being represented by the equation: k =