Oxides of fluorine

The oxides of fluorine are more correctly called oxygen fluorides because of the greater electronegativity of fluorine. 

The halogens form a number of stable oxides, but information on their thermal and photochemical decompositions in the gas phase is limited to two oxides of fluorine and several oxides of chlorine. Little research has been done on the decompositions of bromine, iodine or mixed-halogen oxides. 

Resnick, S.M. and Gibson, D.T. Regio- and stereospecific oxidation of fluorine, dibenzofuran. and dibenzothiophene by... 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

With the exceptions of the oxides of fluorine, GO, N20 and NO, all oxides of the non-metallic elements form complexes with metal... 

Dehydrogenation reactions of ketones have been applied to the aromatization and oxidative coupling of polycycles. High temperature dehydrogenation of 7-fluoro-3,4-dihy-dronaphthalen-l(2/7)-onc with sulfur gives 7-fluoro-1-naphthol in 90% yield.196 During the oxidation of fluorinated anthraccn-9(10//)-one 9 with iron(III) chloride, a radical is formed that collapses by a termination reaction to give the bianthryl derivative 10.197... 

Leitner, N.K.V., Gombert, B., Ben Abdessalem, R., and Dore, M., Kinetics and mechanisms of the photolytic and OH- radical induced oxidation of fluorinated aromatic compounds in aqueous solution, Chemosphere, 32(5), 893-906, 1996. 

Fluorine can be produced only by electrolysis, and then only with difficulty. The complications involved in its production arise from the extreme chemical activity of this element. Of all the known elements, fluorine has the greatest affinity for electrons hence, it is the most powerful oxidizing agent (electron acceptor). Accordingly, fluorine cannot be prepared by the chemical oxidation of fluorine compounds, since this would require an oxidizing agent more powerful than fluorine. This element displaces oxygen from water, attacks all but the very unreactive metals such as platinum, and forms compounds with all ele-... 

Table 1. Fluorinated telechelic diols obtained from the permanganic oxidation of fluorinated alkenes...

For example, oxidation of fluorine-containing stilbenes by oxygen on exposure to UV radiation and in the presence of chlorine or perbenzoic acid leads to epoxidation products. 

In works made under direction of N.M. Emanuel they showed that catalytic system [Cu2+... A. .. 02] where A" - the anion form of substrate (anion form of substrate was formed at the expense of its deprotonation under the action of bases introduced into the system) is extremely effective in reactions of oxidation of fluorinated alcohols with general formula H(CF2CF2)nCH2OH (where n=l-6) [2], camphor [3] and diacetone-L-sorbose [4] with... 

Fluorine-containing cycloalkcncs are cleaved by oxidation to give polyfluoroalkanedicar-boxylic acids with the original number of carbon atoms. Hence, for example, oxidation of fluorinated cyclobutenes gives tetrafluorosuccinic acids, e.g. 7a. Similarly, oxidation of derivatives of perfluorocyclopentene gives perfluoropentanedioic acids, e.g. whilst perfluorocy-... 

Selective oxidation of fluorinated molecules containing both a hydroxy group and a C = C bond is possible due to the mild reaction conditions. The hydroxy group does not react, only the C = C bond is oxidized, e.g. formation of 11. ... 

Tabic 2. Typical Examples of the Oxidation of Fluorinated Alkenes with Potassium Perman-ganate/Acetone... 

Oxidation of fluorinated alkenes with oxygen is possible. The reaction of hexafluoropropene and perfluorohept-l-ene in a solution of perfluoro(dimelhyleyelohexane) has been described. The reaction is carried out with air in a steel autoclave at 200 C and gives perfluoroearbonyl fluoride. 

Oxidation of fluorinated hydrazones with lead tetra-acetate forms a useful method for the synthesis of bis(perfluoroalkyl)diazomethanes [318] (Figure 8.121). 

A number of oxides of fluorine are known. Their preparation, properties, and reactions have been reviewed by Streng. A further description of them will not be given here. 

The oxidation of fluorinated derivatives, which requires chromium trioxide and hot, fuming nitric acid, usually stops at the mono-sulfone stage,although 2,2,4,4-tetrafluoro-l,3-dithietane is converted directly to the disulfone by treatment with chromium trioxide and boiling, fuming nitric acid. The conversion of 2,2,4,4-tetrachloro- or 2,2,4,4-tetrabromo-dithietane to the disulfone may be effected by oxidation to the monosulfone with potassium permanganate followed by treatment which chromium trioxide- nitric acid. Potassium permanganate oxidizes the dimer of thiocyclohexanone to the disulfone in 78% yield. 

The oxides of chlorine, bromine and iodine are listed in Table 16-2. Oxides of fluorine were discussed in Chapter 14 (page 412) while these were called oxygen fluorides because of the greater electronegativity of fluorine,... 

Dicarboxylic Acids.— Perfluoro- -thiaglutaric add has been obtained by permanganate oxidation of fluorinated thiolens (10 X == Y = H X = H, Y = F X = Y = F X = Y = Cl) procured in studies of the fluorination of tetrachlorothiophen, thiophen, and tetrahydrothiophen with cobalt trifluoride, manganese trifluoride, and potassium tetrafluorocobaltate(m). The best route to this acid still appears to be fluorination of tetrachlorothiophen with silver difluoride followed by permanganate oxidation of the 3,4-dichlorotetrafluoro-3-thiolen (10 X = Y = Cl) thus obtained in not less than 45% yield. ... 

Good, D.A., M. Kamoboures, R. Santiano, and J.S. Francisco (1999), Atmospheric oxidation of fluorinated ethers, E143a (CH3OCF3), E134 (CHF2OCHF2), and E125 (CHF2OCF3), J. Phys. Chem. A, 103, 9230-9240. 

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