Perfluoro fission

The first step in this pyrolysis consists of the fission of the C-I bond, with formation of a tertiary radical. The collapse of this radical into perfluoro(2-nietliylpropene) and a per-fliioroethyi radical, which recombines with the iodide, gives pentafluoroiodoethane. The homolytic cleavage of the C-C bond seems to be rate determining. 

Perfluoro-(2,5-dimethyl-l-oxa-2,5-diazacyclopentane) (57) decomposes slowly at room temperature in the absence of light to give 1 mol. equiv. of perfluoro-2-azapropene and a quantitative yield of a gum possessing an elemental analysis and F n.m.r. spectral characteristics consistent with the polymer [N(CF3)-0-CF2]n presumably homolytlc ring fission at an N—O bond is followed by j3-scission of the resultant biradical (59) [see Scheme 42 . (CF3)2N-0-N(CF3)2 + heat (CFs)2N-0 + (CFs)2N ->-(CF3)2N-N(CF3)2]. Flow pyrolysis of the diazacyclo-pentane at 150—200 °C and ca. 1 mmHg pressure in platinum yields trifluoronitro-somethane, carbonyl fluoride, perfluoro-2-azaiM opene, and traces of a yellow gas that possesses i.r. spectral characteristics identical with those reported for a... 

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