Trifluoronitrosomethane

Spectroscopy and photochemistry of CF3NO in the visible region have been extensively studied by Roellig and Houston (113,114), Bower et al. (115), Jones et al. (116), and Spears and Hoffland (117). Trifluoronitrosomethane has a weak structured absorption spectrum in the visible near 700 nm. Absorption of light in this region induced fluorescence as well as dissociation, which is similar to the H2CO photochemistry in the ultraviolet described earlier. 

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Reaction of 2 or 3 aminopyndine with trifluoronitrosomethane forms the trifluoromethaneazo derivative directly 4-Aminopyridine fails to give the azo product [12] (equation 11)... 

Surprisingly, trifluoronitrosomethane and perfluoro(2,5-diazahexane-2,5-dioxyl) 172 react together at 0°C in a sealed tube to form a mixture of products from which an unusual perfluoro furazan 173 was obtained in a moderate yield (76USP3965148) (Scheme 94). 

It was first prepd in low yield by the action of Cl trifluoride on bromodifluoronitroso me thane and by the oxidn of trifluoronitrosomethane with Pb dioxide (Ref 2). The Pb dioxide oxidn of the nitroso compd was repeated by Hazeldine who obtd a 37% yield (Ref 3). This oxidn has also been carried out using dimanganese hcptox-ide (Ref 3), 30% hydrogen peroxide in a sealed tube (Ref 4) and activated C (apparently contg adsorbed 02) in a sealed tube at 150° for 1... 

The same workers also prepd trifluoronitrosomethane by the reaction of Ag trifluoroacetate with nitrosyl chloride (C1NO), yield 13% (Ref... 

Cklorodifluoronitrosomethane. ClCF2NO, mw 115.47 N 8.24% a dark blue liq or gas bp ca -35° (Refs 1, 2 6) CA Registry No 421-13-6 Preparation. It has been prepd by reactions analogous to those for prepn of trifluoronitrosomethane (Refs 2 5). It has also been prepd by the action of 33% aq nitric acid on chloro-difluorosulfenyl chloride (C1CF2SC1) (Ref 3), and by the action of hot coned HC1 on difluoro-nitroacetic acid (Ref 4). Its props and reactions are similar to trifluoronitrosomethane Refs 1) Beil 1, <99) 2) R.N. Hazeldine, JCS... 

The reaction of germane with trifluoronitrosomethane has recently been reported. The first example of a stable N-triIIuoromethylgennaiminc, CF3N=GeH2, was prepared according to equation (19)32 ... 

The [2 + 2]-cycloaddition of trifluoronitrosomethane with tetrafluoroallene (61) (excess) proceeded in the vapor phase to give 1,2-oxazetidine in moderate yield [61]. 

Trifluoronitrosomethane reacts with butadiene at — 78 °C to give 180 (equation 101). Even perfluorobutadiene, which is unreactive toward conventional dienophiles, reacts with trifluoronitrosomethane to give 181 (equation 102)96. 

Trifluoronitrosomethane (b.p. 86.0°C, 767 mm Hg) is of considerable interest as a component of high temperature-resistant elastomers. This compound has been prepared by treatment of trifluoroiodomethane, in the presence of mercury, with nitric oxide in a photochemical reactor whose mercury lamp emitted radiation at 253.7 mp.. The preparation is particularly sensitive to the initial pressure of the gases, reactant ratio, irradiation time, intensity of the ultraviolet radiation, reaction temperature, and method of removal of nitric oxide from the product [60]. 

Triarylmethyl azides, 278 o.tf.T -Trideuterioazobenzene, 301 Tri(2-ethoxyethyl)orthoacetate, 58, 60 1,1,1 -Trifluoromethylazomethane, 301 w-Trifluoromethylnitroso benzene, 409 Trifluoronitrosomethane, 400 Trihalomethyl compounds, 52-53... 

Although the bulk of azo chemistry involves aromatic systems, 1,1,1-tri-fluoromethylazomethane (b.p. 2.6°C) has been prepared by the condensation of methylamine with trifluoronitrosomethane [34], An extension of the reaction to other aliphatic systems would be of considerable interest. 

Oxazetidines have been obtained by [2 + 2] addition of nitroso compounds to appropriate alkenes. Trifluoronitrosomethane reacts with polyhalogenated ethylenes (69JCS(C)2ll9), with styrene (65JGU855) or with allenes (73JCS(Pi)l56l) to give oxazetidines (e.g. Scheme 7). 

Similar phenomena may be observed in some copolymerizations. For example, tetrafluoroethylene, C2F4, and trifluoronitrosomethane, CF3NO, copolymerize spontaneously into a 1 1 copolymer,—[-CF2.CF2.0.. N(CF3).-] —.Its degradation produces, however, a pair of inert... 

Another case of essentially spontaneous copolymerization is the low temperature reaction of trifluoronitrosomethane with tetrafluoroethylene to give a mixture of cyclic adduct and polymer (7). 

What happens if trifluoronitrosomethane is treated with ammonia What is product A and what may be a mechanism of its formation ... 

Ammonia adds across the nitroso group to form an addition product, tri-fluoromethylaminohydroxylamine. This condenses with another molecule of trifluoronitrosomethane to form 3-hydroxy-l,3-bis(trifluoromethyl)-l-tri-azene, which decomposes to nitrogen and bis(trifluoromethyl)hydroxyl-amine A. Another mechanism of the reaction has also been proposed [737]. 

Trifluoronitrosomethane, CFsNO, mw 99.02 bright blue, fairly stable gas, very irritant fr p —150°, bp —84°. Can be prepd by interaction of iodo (or bromo) trifluoromethane with nitric oxide in the presence of UV light. Serves as a monomer for nitroso rubber as a military poison Refs 1) Beil 1, il05i <99 > 2) Cond-... 

Allene 4 reacts with trifluoronitrosomethane (5) under mild conditions to give the 1.2-oxazetidine 6 as the major product... 

Trifluoronitrosomethane may be obtained from photolysis of a mixture of trifluoroiodo-methane and nitric oxide [275, 276] or from pyrolysis of trifluoroacetyl nitrite [277, 278] (Figure 8.108). 

Trifluoronitrosomethane is unusual among nitroso compounds in that it exists as a monomer that is deep blue and is therefore one of the few highly coloured simple polyfluoro compounds. On photolysis, a species derived from radical coupling is formed [276] (Figure 8.109). 

A series of nitroso rubbers has been formed by reaction of trifluoronitrosomethane with fluoroalkenes [279] with tetrafluoroethene an oxazetidine and a 1 1 copolymer are obtained (Figure 8.110), the polymer being formed in preference at lower temperatures [279-281]. It is claimed that the mechanism involves electron transfer [282]. 

The halogenated alkyl nitroso compounds are decomposed by visible light e.g. X 5000-7500 A). Trifluoronitrosomethane has been studied by a number of workers - - > , the major product of decomposition being (Cp3)2 NONO. The primary dissociation step with a quantum efficiency near unity is believed to be... 

A new class of organic NF compounds, N-fluoroazoxy compounds, has recently been reported. Trifluoronitrosomethane reacts with N2F4 under the influence of light or heat to form N-fluoro-N -trifluoromethyldiazine-N -oxide (III) (6). A free radical mechanism for the reaction was proposed and it was sug-... 

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