Trifluoromethyl hypofluorite difluoride

In addition, fluonne [97, 98], trifluoromethyl hypofluorite [99, 100], bisftri-fluoromethyOperoxide [100, 101], trifluoromethyl disulfide [100]. and xenon difluoride [102, lOi, 104] react with phosphines to give the corresponding diflu-orophosphoranes in yields ranging from 25% to near quantitative. Phosphites are fluorinated by carbonyl fluoride [95, 96] or 2-hydroperfIuoropropyl azide [f05J (equation 15). 

Tetrafluoroammonium hexafluoromanganate, 4384 Tetrafluoroammonium hexafluoronickelate, 4385 Tetrafluoroammonium hexafluoroxenate Tetranitromethane, 0546 Titanium tetraperchlorate, 4170 1,1,1 -Triacetoxy-1,2-benziodoxol-3-one, 3610 Trifluoromethyl hypofluorite, 0353 Trimethylsilyl chlorochromate, 1301 Trioxygen difluoride , 4323 Uranium hexafluoride, 4375 Vanadium(V) oxide, 4866 Vanadium trinitrate oxide, 4763 Vanadyl perchlorate, 4152 Xenon hexafluoride, 4377 Xenon(II) pentafluoroorthoselenate, 4382 Xenon(II) pentafluoroorthotellurate, 4383 Xenon tetrafluoride, 4353 Xenon tetrafluoride oxide, 4346 Xenon tetraoxide, 4863 Xenon trioxide, 4857 Zinc permanganate, 4710... 

Trifluoromethyl hypofluorite was first made by Cady by passing methanol [184] or carbon monoxide [185, 186] with fluorine over silver difluoride at elevated temperatures. Later, trifluoromethyl hypofluorite and higher perfluoroalkyl hypofluorites were prepared by treating the appropriate carbonyl compound with fluorine in the presence of dry caesium fluoride at sub-zero temperatures (Fig. 81) [187-189]. 

Barton and co-workers have studied30 the reactions of trifluoromethyl hypofluorite with various alkenes and found that (Z)- and (T -stilbene give vicinal fluoro trifluoromclhoxy products and vicinal difluorides in chlorotrifluoromethane or diethyl ether, while vicinal fluoro methoxy adducts predominate when the reaction is carried out in methanol at —78 C. svn Addition predominates in all cases on the basis of the fluorination regioselectivity of many alkenes, the formation of a /1-fluoro carbcnium ion is proposed.30... 

Tetrafluoroammonium hexafluoromanganate, 4378 Tetrafluoroammonium hexafluoronickelate, 4379 Tetrafluoroammonium hexafluoroxenate, 4380 Tetranitromethane, 0543 Titanium tetraperchlorate, 4164 1,1,1 -Triacetoxy-1,2-benziodoxol-3-one, 3604 Trifluoromethyl hypofluorite, 0352 Trimethylsilyl chlorochromate, 1297 Trioxygen difluoride , 4317 Uranium hexafluoride, 4369 Vanadium trinitrate oxide, 4758 Vanadium(V) oxide, 4860 Vanadyl perchlorate, 4146 Xenon hexafluoride, 4371 Xenon tetrafluoride, 4347 Xenon tetrafluoride oxide, 4340 Xenon tetraoxide, 4857 Xenon trioxide, 4851 Xenon(II) pentafluoroorthoselenate, 4376 Xenon(II) pentafluoroorthotellurate, 4377 Zinc permanganate, 4705 ACETYLENIC PEROXIDES ACYL HYPOHALITES ALKYL HYDROPEROXIDES ALKYL TRIALKYLLEAD PEROXIDES AMINIUM IODATES AND PERIODATES AMMINECHROMIUM PEROXOCOMPLEXES BIS (FLUOROOXY)PERHALOALKANES BLEACHING POWDER CHLORITE SALTS... 

The electrophihc nature of COF2 is beneficial in the reaction of carbonyl difluoride with CsF, which produces trifluoromethyl hypofluorite (CF3OF) with fluorine and triflnoromethyl hypochlorite (CF3OCI) with chlorine monoflnoride. Both reactions imply the presence of the triflnoromethoxide anion as an intermediate. 

Trifluoromethyl hypofluorite can be reacted with carbonyl difluoride to yieldbis(trifluoromethyl) peroxide, CF3OOCF3, a colorless gas, bp -37 °C, which is quite stable up to 220 °C and chemically relatively inert (equation 53). At high temperatures the peroxide appears to be in equilibrium with COF2 and CF3OF. The peroxide is best prepared by reaction of CO and F2 over AgF2 at 220 °C (equation 54). 

In an attempt to prepare trifluoromethanoi, CF3OH, trifluoromethyl hypofluorite was treated with an equal flow rate of dihydrogen at about 160 C in a reaction vessel packed with copper ribbon [1078e]. However, the reaction proceeded to give carbonyl difluoride in accordance with ... 

Ultraviolet photolysis (230-400 nm) of trifluoromethyl hypofluorite in dilute argon matrices at 8 K gave carbonyl difluoride as the only product observable by infrared spectroscopy, equation (13.9), and with no evidence for the formation of the peroxide CF3OOCF3. The subsequent photodissociation of the molecular fluorine produced results in the production of fluorine atoms, which are sufficiently mobile to escape the argon matrix cage [1902]. 

Titauiuiu tetraperchlorate, 4170 1,1.1 -Triaceto -1.2-beuziodoxol-3 -oue, 3610 Trifluoromethyl hypofluorite, 0353 Trimethylsilyl chlorochromate, 1301 Trioxygeu difluoride , 4323... 

Several reagents were used for the electrophilic fluorination of indole. The first one used for this aim was trifluoromethyl hypofluorite (CF3OF). Treatment of V-acylindole 1 with trifluoromethyl hypofluorite in CF3CI at -78 °C afforded a mixture of 2-fluoro-3-trifluoromethoxy- and 2,3-difluoroindoline derivatives 2-4 in high combined yield. Subsequent treatment of difluoride 4 with potassium hydroxide in methanol afforded quantitatively 3-fluoroindole 5. Similarly, starting from l-formyl-2-methylindole reaction with trifluoromethyl hypofluorite resulted in formation of 2-methyl-3-fluoroindole 7 in low yield in mixture with 2-methyl-3-trifluormethoxyindole 8 [7]. 

Studies on the well known reaction between fluorine and carbon monoxide have revealed that a film of silver fluoride(s) on copper truly is a catalyst for the reaction Fj + CO - COFa, and for subsequent changes producing bistrifluoromethyl peroxide and trifluoromethyl hypofluorite, whereas caesium fluoride is not and since neither copper nor silver iluoride(s) appears to be a good catalyst for the reaction CF3 OF + COFj CFa O O CFg, it has been suggested that the fluorination of carbon monoxide or carbonyl fluoride in the presence of silver difluoride may possibly involve the steps... 

Trifluoromethyl hypofluorite has been shown to be the major product of the reaction between caesium trifluoromethoxide and CFa(OF)g (see above), and also to occur in the products from the electrochemical fluorination of phosgene (ca. 7% yield) and A/-fluoroformyliminosulphur difluoride. ... 

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