Perfluoroalkanesulfonic acids derivatives: 
synthesis and application

G.G. Furin

Novosibirsky Organic Chemistry Institute of N.N.  Vorozhtsov,  Siberian department of Russian Academy of sciences, 

Abstracts

Information of the last 10 years regarding methods of synthesis and properties of perfluoroalkanesulfonic acids and some of its derivatives is listed and analyzed here. The opportunities of using the perfluoroalkane halides and syntons on the basis of perfluoroalkylsilicon derivatives for these purposes are uncovered. The main attention is paid to practical aspects of perfluoroalkanesulfonic acids salts and bis(perfluoroalkylsulfonyl)imides using as catalysts of different processes, electrolytes, ionic liquids and N-F bond containing compounds as mild fluorinating reagents. The ways of using of perfluoroalkanesulfonic acids derivatives in organic synthesis are discussed.

Table of contents

1.Introduction. The role of organic compounds in the synthesis of semi-products and the creation of new materials on their basis.

2. Perfluoroalkanesulfonic acids synthesis
2.1. Electrochemical fluorination of alkyl derivatives of hexavalent sulfur
2.2. The use of perfluoralkyl iodides in the synthesis of perfluoroalkanesulfonic acids 
2.3. The reactions of fluorocontaining С-nucleophilic reagents with haloid derivatives of sulfur
2.4. The use of trimethyl(trifluoromethyl)silane in the synthesis of trifluoromethylsulfonic acid and its derivatives.

3. The synthesis and characteristics of perfluoroalkanesulfonic acids derivatives

3.1. Haloanhydrides of perfluoroalkanesulfonic acids
3.2. Bis(perfluoroalkylsulfonyl)imides and their use in fluoroorganic synthesis
3.3.  Perfluoroalkanesulfonic acids salts as catalysts of several chemical processes.
3.4. The synthesis of N-F containing compounds.

4.  The new applications of perfluoroalkanesulfonic acids derivatives 
4.1. Electrolytes and ionic liquids on the basis of bis(perfluoroalkylsulfonyl)imides
4.2. Membranes on the basis of perfluoroalkanesulfonic acids

Conclusion

References

3.3. Perfluoroalkanesulfo-acid salts, the catalysts of a number of chemical processes.

The main obtaining methods of perfluoralkanesulfo-acids and bis(perfluoroalkanesulfonyl)imides are their interaction with corresponding oxides of elements. Thus, the reaction with bismuth oxide in the media, containing the mixture of water and ethyl alcohol [110,111] or bismuth compound [112] produces corresponding bismuth derivatives. It's better to use C1 - C3 the alcohol mixable with water, the optimal ratio water/alcohol from 1:1 up to 9:1, and molar ratio of CF₃SO₃H/Bi₂O₃ is 6:1 - 6.5:1 (yield 97 %). Such salts are used as catalysts for carrying out chemical reactions of different types.

They are new ligands for lanthanide complexes creating, especially neodymium 3 [113], ytterbium and yttrium [114,115], lanthanum [116-118], europium [90] and other metals (B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Te) [119,120]. These complexes are excellent catalysts of Friedel-Crafts and in the last years there was found an application for them.. Eu[N(SO₂C₈F₁₇)₂]₃ produces luminescence with quantum yield 56.8 % [90].

As a rule, these complexes are generated during boiling of oxides of these elements with bis(perfluoroalkanesulfonyl)imide in water for example for lanthanum:

The ytterbium salts of tris(perfluoroalkanesulfonyl)methidine were obtained according to the following scheme [121:

The more detailed review of data regarding application of perfluoroalkanesulfoacids is given in review [122]. We will not go beyond few new examples of their application. Thus, trifluoroalkanesulfonates of rare-earth metals are effective catalysts for example of benzyl alcohol etherification using aliphatic alcohols or thiols [123a]. In these reactions RE(OSO₂CF₃)₃ can be easily returned into the process without loss of their catalytic activity.

It is shown [123b], that Bi(OSO₂CF₃)₃is an effective catalyst of acetals and ketals turning into aldehydes.

Bi(OSO₂CF₃)₃ catalyses epoxides turning into thiirans in the presence of ammonium thiocyanate and thiourea [123c,d].

Trifluoromethanesulfonates of scandium, indium and zirconium act as effective catalysts of Friedel-Crafts alkylation of aromatic compounds by derivatives of acetylene [124].

Trifluoromethanesulfonates of scandium, ytterbium and samarium appeared to be rather effective catalysts of reaction of tetrakis(allyl)germanium with carbonyl compounds, for example with benzaldehyde [125].

Other carbonyl compounds also enter into this reaction.

The nature of Lewis acid element is important, affecting the reaction velocity.

Trifluoromethanesulfonates of scandium catalyses the reaction of Diels-Alder between different acrylates and cyclopentadiene in supercritical CO₂ . The reaction passes in a stereo-selective way [126].

Acylation of aromatic compounds is catalysed by bis- (trifluorometansulfonyl)amides of lanthanum, samarium and ytterbium [127a,b]. At this the present catalysts appeared to be more effective compare to trifluorometansulfonates of these elements [128].

Tris(perfluorooctylsulfonyl)methidine of lanthanum and bis(perfluoroctylsulfonyl)amide of lanthanum are not only effective catalysts of alcohols and aromatic compounds acylation, but they are used as Friedel-Crafts catalysts of Diels-Alder reactions.

Instead of organic dissolvents supercritical carbon dioxide was used for these processes [130].

Diels-Alder reaction of different dicarbonyl compounds and 1, 2 - diens passes with high yield in mild conditions when using ytterbium trifluorometansulfonate as catalyst [131].