Sulfonic acids, trifluoromethylation

Very strongly deactivating 0 II —CCI —C=N —SO3H -CF3 —NO2 (acyl chloride) (cyano) (sulfonic acid) (trifluoromethyl) (nitro) Meta directing... 

T rifi uoro-2 -methyl-4 -(phenylsulfonyl) methanesulfonanilide 1,1,1-Trifluoro-N-[2-methyl-4-(phenylsulfonyl) phenyl] methanesulfonamide. See Perfluidone Trifluoromethyl sulfonic acid. See Trifluoromethane sulfonic acid (Trifluoromethyl) trifluorooxirane. See 1,2-Epoxy-1,1,2,3,3,3-hexafluoropropane (Trifluoromethyl) undecafluorocyclohexane 1-Trifluoromethyl-1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexane. See Perfluoromethylcyclohexane Trifluoromonobromomethane. See Trifluorobromomethane Trifluoromonochlorocarbon. See Chlorotrifluoromethane Trifluoromonochloroethylene. See Chlorotrifluoroethylene... 

Counteranion-bound S-, Se-, and re-(trifluoromethyl)dibenzothiophe-nium-, -selenophenium-, and -tellurophenium-3-sulfonates 42-44, 48, and 49, developed as another series of the electrophilic trifluoromethylating agents, are useful because the resultant trifluoromethylated products are easily separated from the by-product dibenzothiophene-, -selenophene-, or -tellurophene-3-sulfonic acids because these by-products are soluble in water (Eq. 17) (95JFC). 

Finally, a few miscellaneous compounds which were identified in the Delaware River and which have not been previously reported as water contaminants will be discussed Chloro (trifluoromethyl) aniline and chloro (trifluoromethyl) nitrobenzene (no. 55 and 56) were identified in the water, they had maximum concentrations at river mile 78. Both compounds represent common sub-structures in various pesticide and dye molecules, and several of the companies located along the river have patents using these compounds (30-32j. It is possible that these compounds are actually present in the river water as such, but it is also possible that they are formed in the GC injection port by pyrolytic degradation of larger pesticide or dye molecules (see above). All three binaphthyl-sulfone isomers (no. 92) were identified in the river water near Philadelphia. Product literature for one of the companies in the area indicates production of condensed sulfonated polymers derived from naphthalene sulfonic acid and maleic anhydride. It seems likely that the binaphthylsulfones are formed as by-products during preparation of this commercial product. 

Scheme 3.3 Generation of [CI(dppe)2Ru=(C)4HPh]+ by protonation of a phenylbutadiynyl complex with trifluoromethyl sulfonic acid.

This was followed by titration with 0. IN trifluoromethyl sulfonic acid, and the end-point was detected with the use of a glass Ag/AgCl combination electrode [80]. 

The production of industrially important perfluoroalkane sulfonic acids is generally accomplished by electrochemical fluorination. This method of preparation remains expensive and proceeds in good yields only for short hydrocarbon chains.30 Recently however, Wakselman and Tordeux have described a chemical method for the preparation of trifluoromethane sulfonic acid.31 The procedure involves reaction of a metal selected from zinc, cadmium, manganese, and aluminum with sulfur dioxide in DMF, followed by the introduction of trifluoromethyl bromide under slight pressure. The intermediate sulfinate is subsequently oxidized by hydrogen peroxide, and then hydrolyzed which leads to formation of the trifluoromethane sulfonic acid. Successful extension of the sulfination process to the modification of PCTFE should result in the formation of a sulfinated polymer which can ultimately be oxidized to give a sulfonic-acid modified polymer. 

As we found more recently , these orientation effects can be disguised by mixing effects of the type discussed in Section 4.2. In reactions of 3-trifluoromethyl-benzenediazonium ions with 7-amino-l-naphthol-3-sulfonic acid 154, rates and product ratios which would be predicted from Figure 3 are obtained only in very dilute solutions (<10 mol/1). In systems with higher concentrations of the reactants the product with the 3 -trifluoromethylphenylazo group in the 8-position is not only dominant in acidic solution, as expectal, but also up to pH 9. In this pH range also considerable amounts of bisazo product are obtained. These are observations which are typical for mixing eff ts observed in very fast reactions. With the unsubstituted benzenediazonium ions, a less reactive electrophile, however, rates and products are determined only by equilibria of the type of (70). 

N-trifluoromethyl sulfonic acid. The end-point was detected with use of glass Ag/AgCl combination electrode. Results compared well with those obtained using perchloric acid as titrant. The coefficient of variation were <0.42% and recoveries were >99%. 

C13H8F3NS 2-(trifluoromethyl)phenothiazine 92-30-8 25.00 1.3491 2 25610 C13H10N2O3S 2-phenylbenzimidazole-5-sulfonic acid 27503-81-7 25.00 1.3814 2... 

An alternative mechanism for the formation of the esters is the dissociative mechanism involving RfS02 + and Rf + which was considered to be unlikely104 because of failure to detect Rf + directly and the observation of only a symmetrical anhydride upon the equilibration of a mixture of perfluoroalkanesulfonic acid and triflic anhydride, or a mixture of triflic acid and a perfluoroalkanesulfonic anhydride. However, recent work showed that the unsymmetrical anhydride indeed exists98. The preferential formation of trifluoromethyl esters in the reactions of mixtures of triflic and other perfluoroalkanesulfonic anhydrides in the presence of the corresponding sulfonic acids is consistent with the dissociation mechanism, since trifluoromethyl cation is much more easily formed than its higher analogues. Therefore, the dissociative mechanism (equation 84) cannot be ruled out unequivocally. 

Edwards and colleagues have reported derivatization with 2,4-dinitrobenzene sulfonic acid, a procedure useful for quantification of a number of phenylethylamines, to be unsuitable for analysis of HA. However, Doshi and Edwards discovered that 2,6-dinitro-4-trifluoromethyl benzenesulfonic acid (DNTS) reacts readily with catecholamines, histamines, and related biogenic amines with very suitable properties for GC-ED. Formation of the trifluoroacetyl, trimethylsilyl, and heptafluoro butyryl derivatives of HA for GC have been reported, but these compounds have been found to be unsuitable for quantification of HA because of excess tailoring. 

Synonyms Magic acid Triflic acid Trifluoromethyl sulfonic acid Classification Aliphatic organic compd. 

Heparin sodium salt. See Heparin sodium Heparin sulfate. See Heparin HEPPS HEPPS. See 3-f4-(Hydroxyethyl)-1-piperazinylj-propanesulfonic acid 1,3,4,6,7,9,9b-Heptaazaphenalene-2,5,8-triamine 1,3,4,6,7,9,9b-Heptaazaphenalene, 2,5,8-triamino-. See Cyamelurotriamide Heptacosafluorotributylamine. See Perfluorotributylamine Heptadecafluorodecahydro (trifluoromethyl) naphthalene. See Perfluoromethyidecalin Heptadecafluorooctane-1-sulfonic acid 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluoro-1-octanesulfonic acid. See Perfluorooctanesulfonic acid Hepta decafluoro (trifluoromethyl) decalin. See Perfluoromethyidecalin Heptadecane. See n-Heptadecane n-Heptadecane... 

Another application of trifluoromethyl phenyl sulfone is in the preparation of benzenesulfonic acid (or metal benzenesulfonate) using oxygen nucleophiles. Trifluoromethyl phenyl sulfone is readily transformed into benzenesufonate salt upon treatment with an alkoxide or hydroxide (eq 6). This is particularly useful for the convenient transformation of a polymer-supported trifluoromethyl phenyl sulfone into polymer-supported sulfonic acid (or sufonate) ion-conducting materials. " ... 

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