Oxidants fluorine-containing

Hydrogen fluoride or compounds that can produce it and fluorine-containing oxidizers should be handled with adequate safety equipment and extreme care by weU-trained personnel. Often the effect of skin exposure is not immediately evident, especially when dilute solutions are handled. Pain may develop several hours later. 

In attempts to further improve the stability of fluorine-containing elastomers Du Pont developed a polymer with no C—H groups. This material is a terpolymer of tetrafluoroethylene, perfluoro(methyl vinyl ether) and, in small amounts, a cure site monomer of undisclosed composition. Marketed as Kalrez in 1975 the polymer withstands air oxidation up to 290-315°C and has an extremely low volume swell in a wide range of solvents, properties unmatched by any other commercial fluoroelastomer. This rubber is, however, very expensive, about 20 times the cost of the FKM rubbers and quoted at 1500/kg in 1990, and production is only of the order of 1 t.p.a. In 1992 Du Pont offered a material costing about 75% as much as Kalrez and marketed as Zalak. Structurally, it differs mainly from Kalrez in the choice of cure-site monomer. 

Polytetrafluoroethylene decomposition products thermal decomposition of the fluorocarbon chain in air leads to the formation of oxidized products containing carbon, fluorine and oxygen. Because these products decompose in part by hydrolysis in alkaline solution, they can be quantitatively determined in air as fluoride to provide an index of exposure. No TLV is recommended pending determination of the toxicity of the products, but air concentration should be minimal. (Trade names Algoflon, Fluon, Teflon, Tetran.)... 

It must be noted that impurities in the ionic liquids can have a profound impact on the potential limits and the corresponding electrochemical window. During the synthesis of many of the non-haloaluminate ionic liquids, residual halide and water may remain in the final product [13]. Halide ions (Cl , Br , I ) are more easily oxidized than the fluorine-containing anions used in most non-haloaluminate ionic liquids. Consequently, the observed anodic potential limit can be appreciably reduced if significant concentrations of halide ions are present. Contamination of an ionic liquid with significant amounts of water can affect both the anodic and the cathodic potential limits, as water can be both reduced and oxidized in the potential limits of many ionic liquids. Recent work by Schroder et al. demonstrated considerable reduction in both the anodic and cathodic limits of several ionic liquids upon the addition of 3 % water (by weight) [14]. For example, the electrochemical window of dry [BMIM][BF4] was found to be 4.10 V, while that for the ionic liquid with 3 % water by weight was reduced to 1.95 V. In addition to its electrochemistry, water can react with the ionic liquid components (especially anions) to produce products... 

The processing of tantalum and niobium begins with the fluorination of the raw material, which always consists of complex oxide compounds containing tantalum and niobium. The main types of tantalum- and niobium-containing minerals are discussed in Chapter 1, and typical compositions of such minerals are presented in Table 2. 

Since the fluorination enables to separate components of complex oxide compounds containing tantalum and niobium, it seems that it is applicable for... 

Uchino and Azuma [504] developed and proposed a two-step calcination process of tantalum and niobium hydroxides to obtain oxides. The first treatment is recommended to be performed at 500-700°C, and the second- at 750-1000°C. It is reported that the above method ensures the production of oxides that contain only negligible concentrations of fluorine and silicon impurities. 

Decomposition Oxidized products containing carbon, fluorine, and oxygen are formed in the air during the thermal decomposition of the fluorocarbon chain. 

With respect to the ring size, it has been stated that neither the redox potentials nor the half-lives of the Ni species are directly correlated to the cavity of the macrocyclic ligand, but the redox potentials are dependent on solvation effects.139 The effect of fused benzene rings and ring conformation has been monitored.140 In Ni complexes of fluorine-containing cyclams (25) the higher oxidation state becomes successively destabilized with respect to Ni, while the lower oxidation state (i.e., Ni1) becomes successively stabilized.141... 

In the fifth paper of this chapter on cathodes, an investigation of thin-film oxide-hydroxide electrodes containing Cr, Ni, and Co compounds was authored by N. Vlasenko et al. The thin-films were produced by electrochemical deposition from transition metal aqueous fluorine-containing electrolytes onto steel substrates. These thin-films were tested in Li coin cells. Electrochemical activity appears to scale with the amount of fluoride used in the deposition the larger concentration of fluoride in the bath, the greater the capacity. One Ni oxide-hydroxide film electrode showed greater than 175 mAh/g reversible capacity on the 50th cycle with excellent coulombic efficiency. 

We managed to obtain dense and solid thin films of 3d-metal oxides using the techniques of electrochemical deposition from aqueous fluorine-containing electrolytes. The films have been studied as a possible cathode material for secondary cells. The best samples show good cycle retention and acceptable specific capacity in the range of 180 mAh/g. They also feature a plateau of electrochemical potential at approximately 3,5 V, which is acceptable for present industrially produced electrochemical devices. 

Related to the nitrile oxide cycloadditions presented in Scheme 6.206 are 1,3-dipolar cycloaddition reactions of nitrones with alkenes leading to isoxazolidines. The group of Comes-Franchini has described cycloadditions of (Z)-a-phenyl-N-methylnitrone with allylic fluorides leading to enantiopure fluorine-containing isoxazolidines, and ultimately to amino polyols (Scheme 6.207) [374]. The reactions were carried out under solvent-free conditions in the presence of 5 mol% of either scandium(III) or indium(III) triflate. In the racemic series, an optimized 74% yield of an exo/endo mixture of cycloadducts was obtained within 15 min at 100 °C. In the case of the enantiopure allyl fluoride, a similar product distribution was achieved after 25 min at 100 °C. Reduction of the isoxazolidine cycloadducts with lithium aluminum hydride provided fluorinated enantiopure polyols of pharmaceutical interest possessing four stereocenters. 

Oxidative Fluorination of Nitrones to a-Fluorosubstituted Nitroxyl Radicals Formation of nitroxyl radicals by the radical cation route was observed in reactions of various nitrones with xenon difluoride in dry methylene chloride (520, 523). In this reaction, more than 40 nitrones, including 4H -imidazole N,N -dioxides (219), 4H -imidazole TV-oxides (223) and (224), 2H -imidazole N -oxides (225), 2H -imidazole TV,TV-dioxides (226), 3,3,5,5-tetramethylpyrroline N -oxide (TMPO), derivatives of 3-imidazoline-3-oxides (231) and (232), have been examined. ESR spectra of nitroxyl radicals containing one or two fluorine atoms at a-C have been registered (Scheme 2.108) (523). In the case of... 

The fluorine-containing members of this group are oxidants almost as powerful as fluorine itself. Individually indexed compounds are ... 

It has to be considered that titanium - at least without special protection layers - will be attacked by several chemicals for example, fluorides, fluorine-containing substances, such as tetrafluo-roborates BF4, or oxalates, and possibly by other organic acids, which may be formed during anodic oxidation reactions. An application of titanium in nonaqueous media is not suitable (instability of the passivating oxide layer). 

The incorporation of magnesium particles into fluorine-containing polymeric materials, such as polyfluoroethylene (Tf) or vinyUdene fluoride hexafluoropropene polymer (Vt), generates energetic pyrolants. The magnesium particles are oxidized by fluorine molecules eliminated from these polymers to produce high-tempera-ture magnesium fluoride. 

Hydrogenated isoxazole derivatives were obtained by single electron transfer (SET) cyclization of /9,y-unsaturated oximes , by thermal [4- -2] cycloaddition of aldox-imes or ketoximes to conventional dienophiles or isomerization/cyclization of an ortho halogeno or nitro-substituted amidoximes. Preparation of 1,4-disubstituted 3-hydroximino-2-nitro-l-butenes and their oxidative cyclization to 4-nitroisoxazoles are reported " . Synthesis of fluorine-containing substituted isoxazolidines as well as isoxazoles by ultrasonic methods has been also described. 

In similar transformations, agriculturally and medicinally significant fluorine-containing quinazolines 101, isolated as the hydrates, were produced in good yields from 100 after condensation with various aldehydes in the presence of ammonia followed by oxidation with DDQ <99H2471>. 

Oxidative Fluorination of Sulfur-, Selenium-, and Tellurium-Containing Compounds... 

Methods have been developed for the introduction of fluoro groups into TV-alkylsulfonamidcs by reaction with fluorine-containing inorganic oxides (1 -3 % F2/argon or XeF2) iY-fluorobis-(alkylsulfonyl)amines la and b are formed in > 70% yield.105... 

Much attention has been paid to the synthesis of fluorine-containing condensation polymers because of their unique properties (43) and different classes of polymers including polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, and epoxy prepolymers containing pendent or backbone-incorporated bis-trifluoromethyl groups have been developed. These polymers exhibit promise as film formers, gas separation membranes, seals, soluble polymers, coatings, adhesives, and in other high temperature applications (103,104). Such polymers show increased solubility, glass-transition temperature, flame resistance, thermal stability, oxidation and environmental stability, decreased color, crystallinity, dielectric constant, and water absorption. 

A 2-alkoxyethanol with a fluorine-containing alkoxy group can be selectively oxidized by nitric acid to the 2-alkoxyacetic acid without cleavage of the ether bond, e.g. oxidation of 9 to 10.148... 

Perfluorinated organic bromides can be oxidatively fluorinated with elemental fluorine to derivatives containing tn- [124] and pentavalent [725 126 127] bromine in yields up to 42% Perfluoroheptylbromine tetrafluoride has been used to fluonnate double bonds in halogenated alkenes [127]... 

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