Perfluorinated, cleavage

This reaction has often reached explosive proportions in the laboratory. Several methods were devised for controlling it between 1940 and 1965. For fluorination of hydrocarbons of low (1—6 carbon atoms) molecular weight at room temperature or below by these methods, yields as high as 80% of perfluorinated products were reported together with partially fluorinated species (9—11). However, fluorination reactions in that eta involving elemental fluorine with complex hydrocarbons at elevated temperatures led to appreciable cleavage of the carbon—carbon bonds and the yields invariably were only a few percent. 

Fluorination of aliphatic ethers at gentle conditions with cobalt trifluoride or potassium tetrafluorocobaltate do not give perfluorinated products and cause only negligible cleavage of the ether bond. Complex mixtures are formed from ethyl methyl ether and from diethyl ether [9] (equations 16 and 17)... 

Perfluorinated epoxides, which are generally susceptible to C-O cleavage during nucleophihc attack, are cleaved by lithium alummum hydnde Of the available examples, reduction of epoxides from two types of internal olefm to give alcohols IS shown [4S] (equations 37a and 37b)... 

When the reaction of perfluQro-3,4-dimethyl-3-hexene with methanol is performed in the presence of pyridine, a perfluorinated dihydrofuran is formed, probably by a process involving generation of an anionic oxygen atom by nucleophilic cleavage of a supposed intermediate ether [27] (equation 24)... 

Fluonnation and skeletal transformation of fluorinated cycloalkanes occurs in the reaction with antimony pentafluoride at high temperature [777] In the case of perfluorinated benzocyclobutanes, an unexpected alicyclic ring cleavage has been observed Perfluorinated alkyl benzocyclobutanes, when treated with antimony pentafluoride, ean be converted to perfluorinated styrenes and then transformed to perfluorinated indans [77S, 779]... 

Here we would like to emphasize that treatment with XeFj fluorinates the polymer surfaces, with the depth and degree of fluorination depending upon the reaction conditions. We never observed the formation of a perfluorinated surface layer after treatment with XeF,. Results of XPS analysis of XeFj-treated polyethylene film —(—CHj—CHj—) — showed that the maximum degree of fluorination corresponded to the composition —(—CF2—CH2—) —. After that, visible destruction of the polymer surface, i.e., cleavage of C—C bonds in the polymer macromolecule, would start. These results differ from those of the fluorination of polymer powders it was reported by Lagow and Margrave in the early 1970s that polymer powders were fully converted into perfluorinated polymers under the action of a F /N mixture. ... 

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. 

Esters 8 of perfluoroalkanoic acids and perfluorinated or highly fluorinated alcohols react with the sulfur tetrafluoride/hydrogen fluoride mixture without cleavage to give high yields of perfluorinated or highly fluorinated ethers 9.164-165... 

A series of functionalized alkenes has been subjected to selective epoxidation reactions. Oxidation of perfluorinated vinyl polyethers by bubbling oxygen through the liquid that contains a catalytic amount of a Lewis acid, e.g. antimony(V) fluoride, results in the formation of acid fluorides together with a smaller amount of C = C bond cleavage.76 Perfluorinated pentaaIkyI-2.3-dihydrofuran 38, an example of an unsaturated cyclic ether that is quite stable owing to perfluoroalkylation. is epoxidized by hypochlorite to the product 39 at 45 C.62... 

Small heterocycles are of interest in view of their high reactivity and role in biosynthesis. Moreover, for the three-membered ring with an oxygen atom, the ease of ring cleavage creates conditions for polycondensations and heterocyclizations. The former give perfluorinated polyethers with a broad spectrum of practical applications, and the latter affords various heterocyclic compounds. 

Perfluorinated alkanes, alkenes or cycloalkanes show a high thermal stability, heating to temperatures over 1000 C results in radical cleavage to give short chains or alkenes.However, C C bonds which contain quaternary and tertiary carbons are cleaved at lower temperatures than those between secondary carbons. In the presence of bromine, chlorine or toluene, cleav age products are isolated, e.g.Rp—Rp - 2 RpBr Other examples involve pyrolyses. ... 

Hydrolysis of alkyl-substituted phosphine oxides is generally difficult, heating with solid sodium or potassium hydroxide is needed in order to break the P—C bond. Hydrolysis of phosphonates and phos-phinates occurs with P—O cleavage in preference to P—C cleavage. Exceptions have been reported with several aromatic phosphine oxides containing p- and o-nitrobenzyl groups and other stabilized systems. Perfluorinated phosphine oxides can also be hydrolyzed to the phosphinic and phosphonic acids.2 ... 

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