Trifluoromethane-sulfonic acid

In contrast to phosphorus esters, sulfur esters are usually cleaved at the carbon-oxygen bond with carbon-fluorine bond formation Cleavage of esteri nf methanesulfonic acid, p-toluenesidfonic acid, and especially trifluoromethane-sulfonic acid (tnflic acid) by fluoride ion is the most widely used method for the conversion of hydroxy compounds to fluoro derivatives Potassium fluoride, triethylamine trihydrofluoride, and tetrabutylammonium fluoride are common sources of the fluoride ion For the cleavage of a variety of alkyl mesylates and tosylates with potassium fluoride, polyethylene glycol 400 is a solvent of choice, the yields are limited by solvolysis of the leaving group by the solvent, but this phenomenon is controlled by bulky substituents, either in the sulfonic acid part or in the alcohol part of the ester [42] (equation 29)... 

Triflucrcrrsethanesuifonate, FNHj FjCSOj, mp subl CA Registry No 42138-65-5. It is prepd by the reaction of N-fluorourethane with trifluoromethanesulfonic acid in methyl chloride (Ref 6). It is more stable than the salts listed above (Ref 6), and upon subln at low press, it dissociates into fluoramine and trifluoromethane-sulfonic acid without further decompn (Ref 7) Refs 1)0. Ruff L. Staub, ZAnorgChem 198, 32 (1931) CA 25, 5105 (1931) 2) O. Ruff... 

Scheme 20. Reaction of 1 with trifluoromethane sulfonic acid.

Sulfenoetherification. The reagent in combination with trifluoromethane-sulfonic acid converts suitably unsaturated alcohols into five- to seven-membered cyclic ethers. The cyclization is considered to involve an intermediate episulfonium ion. 

A. Trifluoromethanesulfonic Anhydride. To a dry, 100-ml., round-bottomed flask are added 36.3 g. (0.242 mole) of trifluoromethane-sulfonic acid (Note 1) and 27.3 g. (0.192 mole) of phosphorus pentoxide (Note 2). The flask is stoppered and allowed to stand at room temperature for at least 3 hours. During this period the reaction changes from a slurry to a solid mass. The flask is fitted with a short-path distilling head and then heated first with a stream of hot air from a heat gun and then with the flame from a small burner. The flask is heated until no more trifluoromethanesulfonic anhydride distills, b.p. 82-115°. The yield of the anhydride, a colorless liquid, is 28.4-31.2 g. (83-91%). Although this product is sufficiently pure for use in the next step of this preparation, the remaining acid may be removed from the anhydride by the following procedure. A slurry of 3.2 g. of phosphorous pentoxide in 31.2 g. of the crude anhydride is stirred at room temperature in a stoppered flask for 18 hours. After the reaction" flask has been fitted with a short-path distilling head, it is heated with an oil bath to distill iD.7 g. of forerun, b.p. 74—81°, followed by 27.9 g. of the pure trifluoromethanesulfonic acid anhydride, b.p. 81-84° (Note 3). 

Figure 27. Defective structure of solid trifluoromethane-sulfonic acid hydrate (CF3S0sH H20)4 found using ab initio molecular dynamics (AIMD see Section 2.2.3 for a description of the technique), showing two hydronium ions hydro-gen-bonded to sulfonate groups (as found in the perfect structure) but, more importantly, two shared protons (one between two sulfonate groups and the other as part of a Zundel ion see text). Note that the energy of the defective structure is only --30 kj/mol higher than that of the perfect structure.

Transalkylation involves the transfer of alkyl groups between aromatic nuclei, usually in the presence of strong Lewis acids. Heredy and Neuworth used this reaction to "depolymerize" coal. As a result of the reaction of coal with BF3 and phenol, the solubility of coal in phenol or pyridine increased substantially. Various modifications of this reaction have since been reported . Transall lation reactions in the presence of trifluoromethane sulfonic acid and aromatic hydrocarbons have recently been used by Benjamin et al. and Farcasiu et al. to identify structural features in coals and heavy petroleum ends, respectively. 

Polymerization Equilibria. As mentioned earlier, esters of strong acids, e.g. trifluoromethane sulfonic acid ("triflates"), are excellent initiators for the polymerization of THF. With such initiators, however, a complication arises. In addition to the normal propagation i depropagation equilibria of oxonium ions, Smith and Hubin postulated that the macroion ( ) may also convert into a corresponding nonpolar macroester ( ) by attack of the anion (14). ... 

The stability of the Cgg -cation can be increased by adding trifluoromethane-sulfonic acid CF3SO3H to the TCE/(TBA)PFg solutions [8]. Under these conditions the life-time of the cation is estimated to be at least some hours. Cgg" is probably stabilized by CF3SO3H because of acid s ability to scavenge water and nucleophiles that would react readily with the cation. The elevated lifetime of the cation made it... 

Zakhari et al. have described the titration of chlorpromazine hydrochloride (in anhydrous acetic acid-acetic anhydride) with O.lM-trifluoromethane sulfonic acid or with 0.1 M HCIO4 [79]. The titrations were conducted in the presence or absence of Hg(II) acetate, with the end point being detected either visually (using crystal violet as the indicator) or potentiometrically. 

Okamoto and co-workers noted that N-phenylhydroxylamine gave predominately diphenylamine on treatment with benzene in TFA but mostly 4-aminobiphenyl and 2-aminobiphenyl in the stronger acid trifluoromethane-sulfonic acid (TFSA). Similar results were obtained if benzene was replaced by toluene or anisole. The authors suggested that the reaction in TFA proceeded through O-protonated hydroxylamine either via a direct Sn2 displacement on N by the aromatic nucleophile or via attack of the aromatic compound on the N of a nitrenium ion. In TFSA they favored a mechanism in which the diprotonated hydroxylamine lost water to generate an iminium-benzenium dication (11, Scheme 5), a protonated nitrenium ion. " This... 

Caution. The reagents trimethyltriazacyclonane and trifluoromethane sulfonic acid are harmful by inhalation and by contact with skin. Potassium cyanide is highly toxic and produces volatile, poisonous hydrogen cyanide on protonation. All operations must be conducted in a well-ventilated fume hood. Wear appropriate protective clothing, gloves, and eye protection. 

We have further examined the effect of initiators and solvents on the equilibrium product distribution. The use of lithium tert-butoxide instead of potassium tert-butoxide and the change of solvent from THF to toluene showed no effect on the product distribution of e-caprolactone oligomers.4 Also we are examining the equilibrium oligomer distribution in cationic system such as trifluoromethane sulfonic acid catalyst.z... 

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. 

P. Konradsson, D. R. Mootoo, R. E. McDevitt, and B. Fraser-Reid, Iodonium ion generated in situ from IV-iodosuccinimide and trifluoromethane-sulfonic acid promotes direct linkage of disarmed pent-4-enyl glycosides, J. Chem. Soc. Chem. Commun. p. 270 (1990). 

All the flexible polyquinolines are readily soluble in chlorinated hydrocarbons such as methylene chloride and chloroform. Semirigid polyquinolines are soluble in tetrachloroethane or / /-cresol, but rigid polyquinolines are soluble only in strong acids like sulfuric and trifluoromethane sulfonic acid. Dilute solution properties of polyquinolines have been investigated by techniques such as membrane osmometry, light scattering, viscometry, and gel-permeation chromatography (96,97). 

F303P6ReSC,9H48, Rhenium(l+), tris[l,2-ethanediylbis[dimethylphosphine]-P,P]-, (OC-6-11)-, salt with trifluoromethane-sulfonic acid (1 1), [154419-20-2],... 

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