Perfluoro-tert-butyl Hypochlorite

A spun stainless steel Hoke vessel (test pressure 13(X) psi) that is fitted with a stainless steel needle valve [Hoke] is passivated by condensing into it 2 mmol of chlorine monofiuoride and then heating the vessel in an oven at 150° for 24 hr. Any residual gas that remains in the vessel is removed by passing the gas slowly through a tube containing soda lime. Twenty millimoles (4.72 g) of (CF3)3C0H, which is weighed into a vessel that can be attached to the vacuum line, is transferred into the evacuated metal vessel, which is then cooled to —196°. Then 21 mmol (1 mmol excess) of chlorine monofiuoride is condensed into the vessel at —196°. The valve is closed, and the vessel is placed behind a shield, where it is allowed to warm to and remain at 0° for 12 hr. All of the 

Perfluoro-rerr-butyl hypochlorite is a pale yellow liquid at 25°. The F NMR spectrum shows a singlet at 4 - 70.1 ppm, using CCljF as an internal reference. The IR spectrum shows the following absorption bands at 1282 (vs), 1232 (ms), 1190 (mw), 1108 (s), 1003 (s), 983 (s), 788 (w), 758 (m), and 732 (s) cm . The compound slowly decomposes at 25° to (CFjIjCO and CFjCl. Thus, it should be stored at -78°, where it is stable for long periods. 

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A less stable but isolable iodane of this family, C6F5I[OC(CF3)3]2, was prepared from oxidation of the iodide with perfluoro tert-butyl hypochlorite, (CF3)3COCl [39]. The aliphatic CF3I(OMe)2 was obtained from CF3IF2 and Me3SiOMe [40]. 

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

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