Nitrogen trifluoride reactions

Ammonia. Ammonia (qv) reacts with excess fluorine ia the vapor phase to produce N2, NF, N2F2, HF, and NH F. This reaction is difficult to control ia the vapor phase because of the iatense heat of reaction, and ia some cases only N2 and HF are produced. Nitrogen trifluoride was obtained ia 6% yields ia a gas-phase reaction over copper (42). Yields of ca 60% are achieved by the reaction of fluorine and ammonia ia a molten ammonium acid fluoride solution (43,44). 

Massonne, J. et al., Angew. Chem. (Intern. Ed.), 1966, 5, 317 Adsorption of nitrogen trifluoride on to activated granular charcoal at — 100°C caused an explosion, attributed to the heat of adsorption not being dissipated on the porous solid and causing decomposition to nitrogen and carbon tetrafluoride. No reaction occurs at +100°C in a flow system, but incandescence occurs at 150°C. 

Also, nitrogen trifluoride can he prepared by reaction of ammonia with fluorine diluted with nitrogen in a reactor packed with copper. Other nitrogen fluorides, such as N2F2, N2F4, and NHF2 also are produced. The yield of major product depends on fluorine/ammonia ratio and other conditions. 

Nitrogen trifluoride also reacts with fluorine and strong Lewis acids, such as BF3, AsFs and SbFs under pressure. Reactions occur at low temperatures and in the presence of UV radiation to form tetrafluoroamonium salts ... 

Tetrafluorohydraxine or Hydrazine Tetrafluoride, F2N.NF2, mw 104.02 colorless, mobile liq or gas, bp(calcd) —73° crit temp +36°, heat of vaporization 3170cal/mole. Can be prepd by reaction of nitrogen trifluoride with metals at high temp (Ref 3). Ex-... 

The products of the electrochemical perfluorination of aromatic and heteroaromatic compounds are the corresponding perfluorinated cyclic and heterocyclic alkanes.28 and also per-fluorinated derivatives of the heteroaromatic compounds. Perfluorocyclohexane is the principal product from the electrochemical fluorination of benzene and fluorobenzene. Chloro derivatives of perfluorocyclohexane are produced from chlorobenzenes. Anisoles give fully saturated per-fluoro ethers, together with cleavage products. Extensive cleavage is observed in the fluorination of benzenethiols. Chloropyridines, fluorocarbons and sulfur hexafluoride or nitrogen trifluoride are characteristic byproducts from the above scries of reactions. 

Wa.s obtd during the reaction of nitrogen trifluoride (NF3) with As at 250—300° to produce dinitrogen tetrafluoride (N2F4)... 

Nitrogen trifluoride and tetrafluorohydrazine were obtained from Peninsular ChemResearch, Inc., and Air Products Inc., respectively. Difluorodiazine was prepared by the reaction of N2F4 with A1C13 at -78° C. (9). 

Although nitrogen trifluoride can be prepared by several chemical procedures, only two methods are technically and economically feasible for a large-scale production The electrolysis of molten ammonium acid fluoride and the direct fluorination of NH3 in the presence of molten NH4F [71]. The direct fluorination is carried out in specially designed reactor [72] in which NF3 is produced by the reaction of F2 with NH3 in the presence of molten ammonium fluoride. As no hydrogen is generated in the direct fluorination process, it is considered safer than electrolytic process. In the later process, NF3 is produced at the anode and H2 at the cathode. 

These preparations, as well as the reaction of nitrogen trifluoride with mercury vapor in an electric discharge, and the fluorination of sodinm azide yield mixtnres of both isomers. The pure trans isomer is produced in 45% yield by the reaction of tetraflnorohydrazine with alnminnm trichloride, or by the reaction of a mixture of the N2F2 isomers with aluminnm trichloride. 

Preparation. The starting material for the preparation of this reagent is tetra-fluorohydrazine, made by reaction of nitrogen trifluoride with various metals at 375° (I). Conversion into difluoroamine is accomplished by heating tetrufluoro-hydrazine with Ihlophenol In an evacuated bulb yield 74%. ... 

Nitrogen trifluoride is made either by reaction 14.53 which must be carried out in a controlled manner, or by electrolysis of anhydrous NH4F/HF mixtures. 

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