Trifluoromethyl hypochlorite decomposition

In contrast to the alkyl hypochlorites, the fluoroalkyl hypochlorites are extremely susceptible to hydrolysis but are much more thermally stable. Trifluoromethyl hypochlorite, eg, showed no decomposition when heated for several days at 100°C. When decomposition does occur, several products are formed C2F OCl gives COF2, CF Cl, CF COF, and GIF, whereas (GF2)3GOGl gives (GF2)2GO, GI2, GF Gl, and G2F (40). 

Thermal or photolytic cleavage of the O—Cl bond in a perfluoroalkyl hypochlorite is readily effected, but in general members of this class are much more stable thermally than their hydrocarbon analogues. Trifluoromethyl hypochlorite is the most stable of the series (thermolysis occurs only slowly at 150°C ), rupture of the O—Cl bond becoming easier as the perfluoroalkyl chain lengthens or branches > decomposition occurs in a manner apparently analogous to that of perfluoroalkyl hypofluorites, e.g. 

U.v. irradiation of trifluoromethyl hypochlorite gives bistrifluoromethyl peroxide in 91% yield, together with chlorine and carbonyl fluoride, but similar decomposition of the next higher homologue yields essentially an equimolar mixture of carbonyl fluoride and chlorotrifluoromethane. Carbon monoxide, - sulphur dioxide, - and olefins - insert readily into the O—Cl bonds of polyfluoroalkyl hypochlorites to yield chloroformates, chlorosulphates, and ethers, respectively treatment of... 

Extension of the RpOH-CIF route to polyfluoroalkyl hypochlorites (see Vol. 1, p. 149) to trifluoromethyl hydroperoxide has provided the first stable chloroperoxide, CFj-O-oa, a stable yellow gas (b.p. —22 °C) at room temperature the peroxide decomposes completely in glass within 5 min at 100 °C to give COFj, OOgF, CO2, and SiF , yields bistrifluoromethyl peroxide when photolysed, reacts explosively with tetrafluoroethylene at ca. —110 °C, and yields a product that may be CFj-O O-COF when treated with carbon monoxide. The trifluoromethyl hydroperoxide used in this work was obtained via the slow decomposition that hexafluoro-2-hydro-peroxypropan-2-ol undergoes at 25 °C in glass (CF,)jCO + HjO, - ... 

Decomposition of bis(trifluoromethyl)diazomethane or bis(trifluoro-methyl)diazirine in carbon disulphide at 150—175 °C produces the cyclic polysulphides (29) and (30), but bis(chlorodifluoromethyl)diazirine, prepared by treatment of the diamine (CFjCl)jC(NH,)2 with alkaline hypochlorite, yields only the carbene rearrangement product CF, CCl CFja when heated with the disulphide. ... 

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