Polyfluorinated

With an amine reactant, it has been shown that roughly one-third of the current passed makes Hquid product, one-third gas, and one-third goes to HF-soluble polyfluorinated products (24). The ether perfluoro(2-butyltetrahydrofuran) [335-36-4] is made from a cyclization process during the ECF of perfluorooctanoyl chloride other cycHc ethers have been prepared from certain ester reactants by a similar cyclization (25). Perfluoroaminoethers have been prepared by ECF (26). 

Fluorinated diacids offer a convenient method for introducing a perfluoro moiety into organic molecules. They are of potential interest in the preparation of polyamides and other fluorinated polymers. A detailed description of the perfluorocarboxyUc acids and their derivatives has been pubflshed (1), and a review article on polyfluorinated linear biflmctional compounds has appeared (35). 

Hydroxyalkyl Alkyl Peroxides and Hydroxyalkyl Peroxyesters. The same stmctural restrictions discussed for the hydroxyhydroperoxides apply for the hydroxyalkyl alkyl peroxides, and those that exist are derived from aldehydes and certain ketones having electron-withdrawing groups, eg, polyfluorinated a,P-unsaturated ketones (136). 

Preparation and Reactions of Polyfluorinated Aromatic Heterocyclic Compounds Yakobson G G, Petrova, T D, Kobnna, L S Fluorine Chem Rev 7, 115-223 285... 

Cesium fluoroxysulfate reacts with derivatives ot porphyrin to give i-fluoro-porphynns accompanied by polyfluorinated products [35, 36]... 

The amine hydrogens of polyfluorinated anilines can be replaced with chlorine by using tert-butyl hypochlorite [65,66]... 

Diacetato(l, 10-phenanthroline)palladium(II)-catalyzed transetheriflcation of polyfluorinated alcohols with enol ethers leads to the corresponding fluormated vinylic ethers [14] (equation 13)... 

This reaction has received especial attention for the stereocontrolled synthesis of polyfluorinated artrfieial pyrethroids [65, 66] (equation 52). 

A polyfluorinated P,y-unsaturated ketone is formed m situ from tributylamine and 3,4-bis(tnfluoromethyl)-3-(pentafluoroethyl)-5,5,6,6,6-pentafluoro-2-hex-anone. The enol form of the unsaturated ketone cyclizes via an intermolecular addition-elimination reaction that involves exclusive attack by oxygen rather than by carbon. This reaction demonstrates the hardness of a F-C= site toward... 

Polyfluorinated a-diketones react with 1,2-diainino compounds, such as ortlio-phenylenediamine, to give 2,3-substituted quinoxalmes [103] Furthermore, the carboxyl function of trifluoropyruvates offers an additional electrophilic center. Cyclic products are obtained with binucleophiles [13, 104] With aliphatic or aromatic 1,2-diamines, six-memhered heterocycles are formed Anilines and phenols undergo C-alkylation with trifluoropyruvates in the ortho position followed by ring closure to form y-lactams and y-lactones [11, 13, 52, 53, 54] (equation 23). 

The addition of diazo compounds generally leads to three membered tings, although in special cases, linear adducts with an intact diazo group [110] or l,3,4-oxadiazol-3-ines [111] can be isolated Most diazo compounds are unstable and yield oxirans and aziridines [112,113,114] Aziridines are obtained exclusively on reaction of certain polyfluorinated acyl imines with diazomethane [115]... 

With linear immophosphoranes and alkyltdenephosphoranes, polyfluorinated ketones readily undergo aza-Wittig and Witlig reactions, respectively [5] In these caseSr the-(2+2] cycloadducts [49, 50, 122] are usually not isolated, instead. 

Similar dehydrofluorination occurs with polyfluorinated heterocycles. 2,2-Bis(trifluoromethyl)-3,4-difluorooxetane gives 3-fluoro-4,4-bis(trifluoromethyl)-2-oxete [19] (equation 17), and heptafluoro-p-dioxane yields hexafluoro-p dioxene [20] (equation 18)... 

NMR data on the most common fluorinated aromatics are presented in three categories. Monofluorophenyls and pentafluorophenyls have found the greatest application in synthesis and spectroscopy. Data for polyfluorinated benzenes are also presented. 

Alty et al. (1988) found that polyfluorinated arenediazonium ions are much less reactive in azo coupling reactions, but they did not investigate this effect mechanistically. 

This methodology is worthy of wider exploitation in the study of other groups of organofluorine compounds that are of industrial importance as agrochemicals and pharmaceuticals and fluorinated componnds snch as polyfluorinated octanoates and sulfonates that have awakened increasing environmental interest. 

Carbon tetrafluoride and all polyfluorinated hydrocarbons are very stable and inert molecules. This inertness can be attributed to the strength of the CF bonds and the close packing of the inert fluoride-like ligands around the carbon atom, which effectively prevent attack by a nucleophile on the carbon atom. In contrast, even though BF3 has stronger bonds than CF4, it is more reactive, forming adducts such as BF3-NH3 because the boron atom is only three-coordinated and there is space around it for an additional ligand. 

Polyfluorinated chemicals now dominate in the fields of oil-repellent and water-repellent finishes. The earlier so-called conventional polyfluorinated products were of the type represented by poly(N-methylperfluoro-octanesulphonamidoethyl acrylate) (10.248) [499]. Such products presented a shield of closely packed fluoroalkyl groups at the fibre-air interface, thus giving low-energy surfaces with excellent oleophobicity. These showed excellent resistance to oil-based stains but were less satisfactory as soil-release agents during... 

Markovskii, L.N., Furing, G.G., Shermolovich, Y.G., and Yakobson, G.G., Phosphorylation of polyfluorinated compounds. 3. Michaelis-Becker reaction in a series of polyfluoro-substituted benzene derivatives, Izv. Akad. Nauk S.S.S.R., 646, 1981. 

In electrochemical oxidation of l-hydroxy-3-imidazoline-3-oxides containing one to four H atoms at a-C, one observes in ESR-spectra not only triplet splitting of the nucleus 14N of the nitroxyl group (a v 15-16 G) but also splitting of the neighboring protons (a// 18-20 G), with multiplets corresponding to their number (from doublet to quintet) (101). Unlike spatially hindered hydroxylamines which show reversibility in electrochemical oxidation, hydroxylamines with H at a-C are oxidized irreversibly. Oxidation of hydroxylamines with nitroxyl radical proceeds easily and with quantitative yields (102). In the oxidation of asymmetric polylluorinated hydroxylamines with Mn02, isomeric polyfluorinated nitrones have been obtained (103). 

The exact mass of an ion (4 to 6 decimal points) reliably defines its elemental and isotopic composition, while the method is called high resolution mass spectrometry. The measurements are conducted manually or automatically (computerized). Manual measurements are based on the parallel acquisition of the peak of interest with the closest peak of an ion with the known composition. Any compound with an intense ion peak with m/z value in the region +10% may serve as a marker. The most widespread markers are perfluorokerosene, perfluorotributylamine, and other polyfluorinated compounds. The use of these compounds is based on their volatility, as well as on the fact that fluorine is a monoisotopic element. In the spectra of these compounds intense ion peaks randomly cover all the range between m/z 19 and M+. ... 

Conductive polymers have attracted increasing attention because they have wide applications. Recently, very stable poly(thiophenes) with polyfluorinated side chains have been electrochemically synthesized and characterized [81]. Furthermore, notably novel conductive materials have been prepared by cathodic electropolymerization of perfluoro cvclobutene and cyclopentene [82]. 

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