part3

3. The synthesis and properties of perfluoroalkanesulfo-acids derivatives.

3.1. Haloidanhydrides of perfluoroalkanesulfo-acids

The main derivatives of perfluoroalkenesulfo-acids are its haloidanhydrides. Their chemistry is rather representative. That's why we give only such examples, that result in formation of strong acids and complexes.
Most reactive derivatives of perfluoroalkenesulfo-acids are their chloroanhydrides. The efforts for creating simple and convenient method of transforming corresponding perfluoroalkenesulfo-acids into their chloroanhydrides were undertaken. The most convenient method is interaction of for example trifluoromethanesulfo-acid with mixture of PCl₃ and Cl₂ (1:1) or PCl₃, POCl₃, Cl₂ (1:1,9:1,1) at 81 ^oC in 4 hours. The yield of CF₃SO₂Cl was 89,7 % [65]. Trifluoromethanesulfonyl fluoride was used for synthesis of Ñ-Í acids : (CF₃SO₂)₂CH₂ [66] (the review of synthesis methods is listed in the work [67]), (CF₃SO₂)₃CH [68] :

Tris(trifluoromethanesulfonyl)methane - is a strong acid in gaseous phase [69].
During action of methyllithium perfluoroalkylsulfonylchloride in diethyl ether the lithium salt of tris(trifluoromethanesulfonyl)methane is formed with the yield 31 % while interaction with anhydrous ammonia in isopropyl ether produces trifluoromethanesulfonamide [70]. During interaction of perfluoroalkanesulfonyl fluorides with dimethylamine or halogensulfonamides the fluorinated sulfonamides X(CYZ)_mSO₂N(CRR¹R²)₂ ( X = H, F, Cl; C_nF_2n+1; m = 1-9) with nearly quantitative yield are produced [71]. These compounds are used as difficult-to flame dissolvents in electrolytes of electrochemical elements, consisting of cathode, anode, separator and electrolyte. Particularly lithium batteries and super condensers are used as such elements.

Since the bond sulfur-chlorine in trifluoromethanesulfochloride is easily is exposed to nucleophilic agents action compare to sulfur-fluorine bond the main chemistry of this class is developed on perfluoroalkenesulfochlorides. It is shown [72-73], that trifluoromethanesulfochloride reacts with bis(-cyclopentadienyl)metal carbonyles in polar medium like tetrahydrofurane and metal complexes are formed .

At the same time the interaction of perfluoroalkenesulfochlorides with carbonyls of V-, VI [74], VIII [74] groups metals results in formation via unstable compound 1 of sulfinate-O,O'-metalchlorides 2.

Direct hydroxylation of olefine, obtained by reaction of perfluoroiodide and allyl-acetate, with further hydrolysis by HSi(OEt)₃ action in presence of palladium catalyst produces sulfofluoride.

The last one at hydrolysis allows to obtain new effective reagent (perfluorosulfonate/trisilanol) which effective as catalyst of alkenes isomerisation, alkylation and acylation reactions etc [75].

Reaction	Product yield, %
Reaction	cat.	Nafion resin NR 50	Amberlyst 15
Alkylation of toluene by heptene (100^oC, 2 hours)	99	5	13
Butene-1 isomerization (50^oC)	95	14	47
Acylation of m-xylene (140^oC, 6 hours)	89	90	-
Alkylation of benzene by dodecene-1 (80^oC, 1 hour)	43	3	5
Constant ([H+]^-1hours^-1) of -methylstyrene dimerization (50^oC)	1000	0,1	0,6