Fluoroalkyl cyclopropane

Meagher J F, Chao K J, Barker J R and Rabinovitch B S 1974 Intramolecular vibrational energy relaxation. Decomposition of a series of chemically activated fluoroalkyl cyclopropanes J. Phys. Chem. 78 2535 3... 

Figure A3.12.il. Chemical activation unimolecular rate constants versus co for fluoroalkyl cyclopropanes. The , Oand points are for R=CF2, C Fy, and C Fjj, respectively. (Adapted from [116].)...

To detect the initial apparent non-RRKM decay in a photoactivation or chemical activation experiment, one has to monitor the reaction at short times. This can be performed by studying the unimolecular decomposition at high pressures, where colli-sional stabilization competes with the rate of IVR. The first successful detection of apparent non-RRKM behavior was accomplished by Rynbrandt and Rabinovitch (1971) who used chemical activation to prepare vibrationally excited hexafluoro-bicyclopropyl-dj as described in chapter 1 (Eq. 1.21). Similar studies were also performed (Meagher et al., 1974) on the series of chemically activated fluoroalkyl cyclopropanes ... 

Figure 8.7 Chemical activation unimolecular rate constants vs. lo for fluoroalkyl cyclopropanes see Eq. (8.50) (Meagher et al., 1974). The , O, and A points are for R = CFj,...

In studies of the reactions of 1.1 -difluoroethene, trifluoroethene, and perfluoroethene, the mechanism of ozonide, epoxide, and cyclopropane formation have been studied.84 Unusually stable ozonides 46A and B are prepared by treating mono- and bis(fluoroalkyl)cthenes with ozone85 at room temperature or on heating the substrate to which ozone is introduced. The rates are approximately 1()10 slower than that for the nonfluorinated analogs. Mono-perfluoroalkylated ethene seems to react several times more rapidly than the bis-perfluoroalkylated ethene.85... 

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