Trifluoromethyl sulphones, reactions

However, the discovery with the most far-reaching consequences arose from the close scrutiny of the results of Kunitake and Takarabe on the polymerisation of styrene by trifluoromethyl sulphonic acid. It became evident to the reviewer that in these reactions an important contribution to monomer consumption must have been made by the ester, and he was able to extract from the results the corresponding propagation rate-constants, kpu, for that cationoid insertion polymerisation. This became one of the most convincing supports for the author s views on cationoid insertions. 

To the new heterogeneous systems used to initiate the cationic polymerization belong perchlorates and trifluoromethyl sulphonates of magnesium, aluminum, cobalt, nickel and gallium. In contrast the lithiiun and silver salts do not show any catalytic activity. Initiating mechanism of this reaction relies on creation of an appropriate ion pair ... 

Trifluoromethyl sulphones, neologized as triflones , are particularly reactive compared with other sulphones towards a-alkylation, and towards elimination reactions. ... 

The kinetics of protodeboronation of a range of substituted benzeneboronic acids in aqueous sulphuric acid mixtures were also examined. Good first-order kinetics were obtained in all cases except for the 3-fluoro compound (due to the sulphonation side reaction) and the 3-trifluoromethyl compound, which hydrolysed, hydrogen fluoride being produced the rates with this latter compound were only followed to 30 % reaction. The kinetic details are summarised in Table 190, from... 

The Russians have been q>loring reactions between bis(trifluoromethyl)keten and carboxylic and sulphonic amides. Such additions proceed straightforwardly and lead to hexahuoroisobutyiylamide derivatives. Urea and sulpham may be used in the same way the derived ureides and sulpham bis-amides decompose thermally to 2/f-hexafluoroisobutyromtrile, which is also obtained by P2O5-dehydration of the keten-ammonia adduct. (For these and other additions to the keten see Scheme 52.)... 

Ring Substitution of Aryl Sulphones.—The influence of the sulphonyl group on reactions of substituted phenyl sulphones has been studied in relation to nucleophilic substitution of p-h dogenophenyl aryr or trifluoromethyl aryl sulphones/ by phenoxide anions and other species. 

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