POLYFLUOROAROMATIC COMPOUNDS

This chapter will deal mainly with the chemistry of highly fluorinated compounds, although this will be prefaced by a more general summary of synthetic methods for the introduction of fluorine into an aromatic system. A review of this topic by Brooke [1] covers the area in considerable detail and we can only be selective in our discussion here. 

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Yakobson, G G, Ed Reactivity of PolyfluoroAromatic Compounds (Russ) Nauka, Sib Otd Novosibirsk, USSR 251... 

Homolytic Arylation of Aromatic and Polyfluoroaromatic Compounds Bolton, R Williams, G H Chem Soc Rev 15, 261-289 122... 

Some Peculianties of Radical Reactions of Polyfluoroaromatic Compounds Kobnna, L S J Fluorine Chem 42, 301-344 73 o 5... 

Vibrational Spectra of Polyfluoroaromatic Compounds Korobeimcheva, I K, Fugaeva, O M, Funn, G G J Fluortne Chem 46, 179-209 72 ... 

Kinetics of Nucleophilic Substitution Reactions of Polyfluoroaromatic Compounds Rodionov, P P, Furin, G G J Fluorine Chem 47. 361 34 105 ... 

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

Starichenko and colleagues [185-187] have studied the hydrogenolysis of poly-chloro- and polyfluoroaromatic compounds with the [(NnN)NiCl2]/Zn reducing system (NCN = bpy or phen (phen=l,10-phenanthroline)). Using DMF or DMA... 

Polyfluoroaromatic compounds react with xenon difluoride in the presence of Lewis acids to give the products of regiospecific 1,4-addition of fluorine, i.e. the corresponding fluorinated... 

Zinc can also defluorinate fluorocarbons via a SET pathway. Fluorinated buta-1,2,3-trienes have been stereoselectively defluorinated to divinylalkyne derivatives 6141 and fluorine is eliminated from the CF(CF3)2 group in polyfluoroaromatic compounds.143 The products of the defluorination of perfluoro(l,2,3,4,5,6,7,8-octahydronaphthalene) (7) depend on the polarity of the solvent.142 The higher the polarity of the solvent the more extensive is the defluorination... 

Some Peculiarities of Radical Reactions of Polyfluoroaromatic Compounds ... 

A mechanism postulating formation of a carbocation as an intermediate during oxidative fluorination of the C=C bond was proposed for the reaction of CoF3 with F-benzene and F-pyridine [32], and VF5 with fluoroolefins and polyfluoroaromatic compounds [33] ... 

More data on the reaction of oxidative fluorination of polyfluoroaromatic compounds with halogen fluorides can be found in [86]. 

Fluoroalkenes undergo addition of polyfluoroaromatic compounds in the presence of fluoride ions, c.g. formation of 1. ... 

RpTMS reacts with fluorinated acceptor molecules (A-F) (polyfluoroaromatic compounds. perfluoroalkcnes) to give perfluoroalkylated products and fluorotrimethylsi-lane. ° Periluoroalkylation of hexafluoropropene affords predominantly the ( )-2-cnc product (e.g., 3), but isomerization occurs very easily in the presence of anionic catalysts and the isomeric composition is difficult to control. Moreover, hexafluoropropene undergoes separate dimerization and trimerization processes that result in inefficient use of this component. Nucleophilic addition of periluorooctyl groups via trimethyl(perfluorooctyl)silane to per-lluorocyclopentene involves an addition-elimination mechanism giving perfluoro(l-octylcyclo-pentene) (2). ... 

Reactions of lithium derivatives and Grignard reagents from polyfluoroalkenes or polyfluoroaromatic compounds are often complicated by eliminations but are generally much more useful in synthesis than polyfluoroalkane derivatives. Generation of arynes is discussed later (see Chapter 9). 

The most practicable and versatile laboratory and industrial route to polyfluoroaromatic compounds involves the use of potassium fluoride in nucleophilic displacement of... 

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