Trifluoromethyl hydroperoxide

A direct, but mechanistically obscure, synthesis of trifluoromethyl hydroperoxide has been developed, involving the decomposition of the adduct formed between hexafluoro-acetone and hydrogen peroxide [107] (Figure 8.67). 

Trifluoromethyl peroxynitrate, CF300N02, has been synthesized from the reaction of trifluoromethyl hydroperoxide with N2Os or of fluoroperoxy-trifluoromethane with N204. The vibrational spectrum was assigned based on a molecule of Cs symmetry.155... 

The earliest method for synthesizing perfluorinated oxaziridines entailed addition of trifluoromethyl hydroperoxide (287) to a perfluoroimine, followed by elimination of HF mediated by a metal fluoride. The fluoride of choice was the mild reagent KHF2 because it was basic enough to effect the elimination but too weak to ring open the oxaziridine product. Oxidation of imine 288 by this method gave perfluoro-A-methyloxaziridine (289), the first perfluorooxaziridine. In the case of hindered imine 290, no adduct was obtained with hydroperoxide 287, but oxidation to oxaziridine 291 was successful nonetheless with the hydroperoxide in the presence of KF. Presumably the imine was attacked by the hydroperoxide anion, forming the intermediate anion 292. 

The final section of this Section of the Report is associated with the derivatives of trifluoromethyl hydroperoxide. The new compounds CF3OOPOF2 and CF3OPOF2 have been prepared by the reaction of trifluoromethyl hydroperoxide CF3OOH with iU-oxo-bis(phosphoryl difluoride), P2O3F4, and difluorophosphine-iw-oxo-phosphoryl difluoride, P2O4F4. The i.r. and n.m.r. spectra, physical properties, and some chemical reactions are reported for the new compounds. New synthetic routes to bis(trifluoro-methyl)bis(peroxy)carbonate (CF300>2C0 and trifluoromethyl fluoroformyl peroxide CF300C(0)F, based on the catalytic disproportionation of bis-(fluoroformyl) peroxide FC(0)00C(0)F, have also been derived. ... 

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, - ... 

Other sources of radical CF3, much less expensive than CF3I, have been discovered. These are the anodic oxidation of sodium trifluoroacetate (the decomposition being initated by a hydroperoxide or ruthenium catalyst) and trifluoromethyl bromide (CF3Br) using sodium dithionite as initiating agent. ... 

Bcnzaldehydes with fluoro substituents (monofluoro, trifluoromethyl) on the aromatic ring are readily oxidized to peroxy compounds 1 with 30% hydrogen peroxide, while the oxidation with concentrated hydrogen peroxide leads to geminal hydroxy hydroperoxides 2.185... 

Peroxy esters are a known class of compounds. Fluorinated peroxy esters can be prepared208,209 by the reaction of the hydroperoxides with fluorinated acyl chlorides or acid anhydrides in the presence of pyridine as the base. It has also been demonstrated210 that trifluoromethyl... 

Iodine-catalysed hydroperoxidation of cyclic and acyclic ketones with aqueous hydrogen peroxide in acetonitrile is an efficient and eco-friendly method for the synthesis of gem -dihydroperoxides and the reaction is conducted in a neutral medium with a readily available low-cost oxidant and catalyst.218 Aryl benzyl selenoxides, particularly benzyl 3,5-bis(trifluoromethyl)phenyl selenoxide, are excellent catalysts for the epoxidation of alkenes and Baeyer-Villiger oxidation of aldehydes and ketones with hydrogen peroxide.219 Efficient, eco-friendly, and selective oxidation of secondary alcohols is achieved with hydrogen peroxide using aqueous hydrogen bromide as a catalyst. Other peroxides such as i-butyl hydroperoxide (TBHP), sodium... 

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 other main group elements which form peroxo complexes are d6 and d8 systems in group VIII including iridium, palladium and platinum. The ji-peroxo complexes do not generally catalyse the epoxidation of olefins with hydrogen peroxide,95,96 but it has been found that trifluoromethyl-substituted Pd(II) and Pt(II) hydroperoxides will perform such a transformation.97... 

Further development of the reaction led to zinc bis(sufinate) salts as stable, scalable reagents for this reaction, many of which are now commercially available. Treatment of the zinc salt with t-butyl hydroperoxide generates a trifluoromethyl radical. Heteroaromatic systems can undergo HAS with this electrophilic radical at innately nucleophilic sites in the aromatic ring, though choice of solvent can impact the regioselectivity of this reaction. 

Ye Y, Ktinzi SA, Sanford MS (2012) Practical method for the Cu-mediated trifluoromethylation of arylboronic acids with CF3 radical derived from NaS02Cp3 and tert-butyl hydroperoxide (TDHP). Oig Lett 14 4979-4981... 

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