Trifluoromethyl peroxide

Fluorocarbonyl Trifluoromethyl Peroxide , Univ Wash, Seattle, TR No 63, ONR contract No N00014-67-A-0103-0002 (1967) 16) A.A. 

Trifluoromethyl peroxide, 78 446 Trifluoropropyl groups, in moisture-curing silicones, 22 32... 

Chlorothionitrene complex, osmium, 37 262 Chloro(trifluoromethyl) peroxide, 16 144 Chlorotrimethylsilane, reaction with hexafluoro-acetone, 30 225... 

Difluorophosphoryl(trifluoromethyl) peroxide, 16 135, 136 reactions of, 16 136 Difluoropolysulfanes, 16 302, 325-327 NMR of, 16 325, 326 separation of, 16 327 Difluorosilylene, 29 15-36 alternate layer reactions, 29 26-27 in nuclear recoil systems, 29 22 polymerization, 29 15 reaction mechanisms with alkenes and alkynes, 29 17-19 under co-condensation conditions, 29 28-32, 34-35... 

Nitryl hypofluorite, 26 128, 130 Nitryl(trifluoromethyl) peroxide, 16 135 N—Li bond, 37 63-65 length... 

Dimethylhexan-2,4-diyl dihydroperoxide [3025-88-5] C. Dialkyl peroxides Bis(trifluoromethyl) peroxide [927-84-4] UN2174. f... 

The molecular structure of bis(trifluoromethyl) peroxide can be determined by electron diffraction spectrometry. The following molecular parameters and their estimated standard deviations (3a) are obtained by this method Bond distances in pm units are 0-0 141.9 2.0, C-O 139.9 0.9 and C-F 132.0 0.2 bond angles are ZC-O-O 107.2 1.2°, ZF-C-F 109.0 0.5° and dihedral angle C-O-O-C 123.3 14.0°. A staggered conformation with a small tilt for the group axis is observed for the CF3 groups. A C2 molecular structure may be assumed . ... 

Other compounds for which the most stable conformation is probably because of negative hyperconjugation include difluorodiazene [10], hydrogen peroxide, dioxygen difluoride [14], and bis(trifluoromethyl) peroxide [15] (Scheme 2.5). 

Bis(trifluoromethyl) trioxide is stable in glass at 25°C. with a half-life of many weeks. At 70°C. its decomposition is rapid and results in the formation of bis (trifluoromethyl) peroxide and molecular oxygen. It does not hydrolyze rapidly in pure water at 25°C. and is not destroyed rapidly by mercury although the mercury darkens. 

Photochemical reactions of HFA with perfluorinated carbon-oxygen compounds have been reported (271, 272). HFA serves as a mild source of CO in the reaction with bis(trifluoromethyl) peroxide (271) to yield bis(trifluoromethyl) carbonate with perfluoromethyl oxalate, CF3 radicals are the reactive species to yield perfluoromethyl acetate (272). 

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). 

Trifluoromethyl hypofluorite, CF3OF, is formed by the reaction of fluorine in excess with carbon monoxide, carbon dioxide, methanol, or other compounds containing both carbon and oxygen. In the procedure described below, carbon monoxide first reacts with an excess of fluorine to give largely carbonyl fluoride. The mixture is then passed through a hot tube where nearly all of the carbonyl fluoride reacts with fluorine to give trifluoromethyl hypofluorite. It is desirable to use somewhat more than two volumes of fluorine per volume of carbon monoxide. If this is not done, much perfluorodimethyl peroxide [bis(trifluoromethyl) peroxide] is formed by the combination of carbonyl fluoride with tr fluoromethyl hypofluorite by the reaction ... 

However, in the presence of K[HFj] (or binary Group 1 or Group 2 fluorides) in an autoclave at 250 C, the principal fluorocarbon product of the reaction between CIF 3 and COFj was bis(trifluoromethyl)peroxide, F3COOCF3 (92.3%), with only a small amount of by-product CF., (1.5%) being formed [587] ... 

The formation of the bis(trifluoromethyl peroxide) proceeds according to the following mechanism [444] ... 

Bis(trifluoromethyl) peroxide and disulphide have been used in a novel preparation of the difluorophosphoranes (68) from tertiary phosphines. The phosphetan derivative (69), prepared by this route, has been shown to exist as a mixture of two isomers at —100 °C, one of which has a... 

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