Trifluoromethyl hypochlorite

The vessel is then cooled to - 196°, and 20 mmol of carbonyl fluoride [PCR, Inc.] is condensed into the vessel. 

To this is added 21 mmol (1 mmol excess) of chlorine monofluoride by condensing the premeasured gas into the metal vessel. The reaction valve is closed, and the vessel is removed from the vacuum line and placed behind a shield. The vessel is allowed to warm slowly to and to remain at 25° for 12 hr. 

The product is purified by trap-to-trap distillation using traps at — 137° and —196°. The nearly pure CF3OCI condenses in the trap at — 137° (30°/60° petroleum ether/liquid N2 slush) while any unreacted CIF or COF2 passes into the trap at —1%°. The yield is 19.8 mmol (99%). The product contains traces of chlorine, which is an impurity in the commercially available chlorine monofiuoride. 

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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). 

Further evidence of facile substitution on sulfur is shown by the reaction with trifluoromethyl hypochlorite. The sulfurane is stable to 100 °C where it reverts to 1,3-dithietane and peroxide (Scheme 30) (77JA4194). 

The photolytic reaction of trifluoromethyl hypochlorite gives s-bis(trifluoromethoxy)sulfur tetrafluoride (11) in very high yield.216... 

SF4 (0.5 g, 5 mmol) was condensed into a 150-mL quartz vessel, followed by trifluoromethyl hypochlorite (1.2 g, 10 mmol). The mixture was allowed to warm to 25 °C and was photolyzed for 24 h with a Hanovia utility UV quartz lamp. After this period the remaining material was vacuum distilled and c -bis(trifluoro-methoxy)sulfur tetrafluoride was retained in a trap at — 78°C yield 90-95%. 

TRIFLUOROMETHYL HYPOCHLORITE AND PERFLUORO-tert-BUTYL HYPOCHLORITE (2,2,2-TRIFLUORO-l,l-BIS(TRIFLUOROMETHYL)ETHYL HYPOCHLORITE)... 

Trifluoromethyl hypochlorite allowed to react at -80° with 1,1-difluoroethylene in a stainless-steel cylinder -> product. Y >90%. - The Cl-atom of the hypochlorite adds to that olefinic C-atom which has the greatest electron density. F. e. s. L. R. Anderson et al., J. Org. Chem. 35, 3730 (1970). 

Reactions of 1,3-Dithietans.—Monothiobenzil can be generated by photolysis of its dithietan dimer.Dithietanones (121) can be used as thioketen equivalents. Tetrafluoro-l,3-dithietan reacts with oxygen atoms to give CFj, SO, and CFjS as primary products, and with trifluoromethyl hypochlorite to give (122). With tris(trifluoromethyl)methyl hypochlorite it gives (123). The 1,1-dioxides and the 1,1,3,3-tetroxides of tetrafluoro-, tetrachloro-, and tetrabromo-l,3-dithietans have been reported. ... 

One may determine whether additions to alkenes are syn, anti, or mixed. For example, trifluoromethyl hypochlorite adds to alkenes and one may propose the mechanisms in Equations 4.2,4.3, and 4.4. 

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... 

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