Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1990-12-03
1991-12-10
Robinson, Allen J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564 80, C07C31115
Patent
active
050720406
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the synthesis of sulfonylimides and more particularly of symmetrical perfluorosulfonylimides.
The perfluorosulfonylimides of the general formula M[(R.sub.F SO.sub.2).sub.2 N].sub.y, in which M designates a metal or a quaternary or non-quaternary ammonium group, the R.sub.F, which are identical in the case of symmetrical imides or different in the case of unsymmetrical imides, represent monovalent perfluorohydrocarbon radicals and especially perfluoroalkyl radicals, such as CF.sub.3, C.sub.2 F.sub.5, C.sub.4 F.sub.9 or perfluoroaryl radicals, such as C.sub.6 F.sub.5, and y is a number equal to the valence of M, are of interest, due to the properties connected with the corresponding anion. Indeed, delocalization of the charge of the anion over several electronegative centers, i.e. the F, O and N atoms, induces a weak basicity and a weak nucleophilic character. The stability of the covalent bonds moreover extends the range of redox stability, in particular at anodic potentials. Perfluorosulfonylimides of alkali metals and especially of lithium can be used, in particular, for forming solid solutions with macromolecular materials of the polyether type, the said solid solutions being used as solid polymer electrolytes in the manufacture of primary or secondary thin-film all-solid state generators (U.S. Pat. No. 4,505,997). They are likewise useful as salts in liquid electrolytes.
One of these processes described in EP 96,629 consists, at the very beginning, in reacting the anhydride (R.sub.F SO.sub.2).sub.2 O with urea and a sulfonic acid R.sub.F SO.sub.3 H according to the reaction: .fwdarw.(R.sub.F SO.sub.2).sub.2 NH NH.sub.4 CF.sub.3 SO.sub.3 +CO.sub.2 the addition of tetrabutylammonium bromide to the solution obtained precipitates the tetrabutylammonium imide of the formula (Bu).sub.4 NN(R.sub.F SO.sub.2).sub.2.
The sodium imide NaN(R.sub.F SO.sub.2).sub.2 is formed by an ionic exchange reaction between this compound and sodium tetraphenylboron.
The second of these processes consists in reacting the anhydride (R.sub.F SO.sub.2).sub.2 O with pyridine and ammonium chloride according to the reaction scheme: H.sub.5 NH N(R.sub.F SO.sub.2).sub.2 +C.sub.2 H.sub.5 NHCl +2(C.sub.2 H.sub.5 NH)CF.sub.3 SO.sub.3 tetrabutylammonium bromide to the solution obtained leads to the precipitation of tetrabutylammonium imide and then to the salts of other metals as indicated for the first method.
The abovementioned processes are not satisfactory for a large-scale production of the imides, because the overall yields are low and the anhydride precursors (R.sub.F SO.sub.2).sub.2 O are not easily accessible.
The abovementioned imides can also be obtained from the precursors R.sub.F SO.sub.2 F by utilizing the four-step synthetic process proposed by J. FOROPOULOS and D. D. DESMARTEAU in the journal INORGANIC CHEMISTRY, Vol. 23 (1984), No. 23, pages 3720 to 3723. In this process, which leads to sodium imide, the reaction scheme is as follows: ##STR1## As for the fourth step of this process, see DE 2,239,817. Apart from a low yield, which is general below 50%, this process cannot be generally applied to precursors of the sulfonyl chloride type R.sub.F SO.sub.2 Cl, because these compounds do not give, upon reaction with ammonia, the amide H.sub.2 NSO.sub.2 R.sub.F, which is produced in the first step of the method and which is necessary for carrying out the later steps of this method.
Another process consists in obtaining compounds of the N'-substituted N-(amidosulfonyl)sulfonamide type by reacting a sulfonamide with a sulfamoyl chloride.
Another process for the synthesis of sulfonylimides of the formula M[(RSO.sub.2).sub.2 N].sub.y, in which R represents a hydrocarbon radical and more particularly a perfluorohydrocarbon radical R.sub.F, and M and y have the meanings given above, was then developed, starting from the corresponding sulfonyl fluorides or chlorides, which are used as precursors. This process consists in reacting a silazane component with a sulfonyl halide component. The sila
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patent: 3483208 (1969-12-01), Bahr et al.
patent: 4175096 (1979-11-01), Reitz et al.
patent: 4505997 (1985-03-01), Armand et al.
patent: 4697011 (1987-09-01), DesMarteau
Gordon, Arnold J., et al., "Chemistry of imides, etc", CA 74, 41848d (1971).
Chemical Abstracts, vol. 74, No. 9, Mar. 1, 1971, (Columbus, Ohio, U.S.) A. J. Gordon et al.: "Chemistry of imides, II, Cyclic imides and some unusual products from some diacid chlorides and lithium nitride," p. 312.
Centre National de la Recherche Scientifique
Hydro-Quebec
Robinson Allen J.
Tranor Susan P.
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