EP0567637A1 - Bis(perfluorosulphonyl)methanes, process for preparing same and uses thereof - Google Patents

Bis(perfluorosulphonyl)methanes, process for preparing same and uses thereof

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Publication number
EP0567637A1
EP0567637A1 EP93900221A EP93900221A EP0567637A1 EP 0567637 A1 EP0567637 A1 EP 0567637A1 EP 93900221 A EP93900221 A EP 93900221A EP 93900221 A EP93900221 A EP 93900221A EP 0567637 A1 EP0567637 A1 EP 0567637A1
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EP
European Patent Office
Prior art keywords
group
compound
chosen
bis
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP93900221A
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German (de)
French (fr)
Inventor
Michel Armand
Djamila Benrabah
Jean-Yves Sanchez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hydro Quebec
Centre National de la Recherche Scientifique CNRS
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Hydro Quebec
Centre National de la Recherche Scientifique CNRS
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Publication of EP0567637A1 publication Critical patent/EP0567637A1/en
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
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    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
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Definitions

  • Bis (perfluorosulfonyl) methane derivatives process for their preparation, and their uses.
  • the present invention relates to bis (perfluorosulfonyl) ethan derivatives, a process for their preparation and their applications.
  • these compounds are prepared by reacting perfluoroalkyl sulfonyl halides with a Grignard reagent.
  • the compounds are prepared by reacting an ionic carbide with a sulfonyl halide.
  • Koshar (DE 2,419,274) describes bis- (perfluoroalkylsulfonyl) methanes which correspond to the formula [(RFSO 2) 2CR] y X, in which R represents a lower alkyl radical and X a diazonium cation.
  • R represents a lower alkyl radical
  • X a diazonium cation.
  • the reaction scheme is as follows: 2RFS02 + [(MgCl + ) 2 C (RFS02) 2 ⁇ 2 ] ⁇ MgFCl + (MgCl + ) (RFS02) 2C ⁇ .
  • Treatment with sulfuric acid gives the acid, however, the reaction yield is low, around 20%.
  • ROBINS bis- (perfluoroalkylsulfonyl) methanes which correspond to the formula (RFS02) 2CHR I , in which the group R ′ contains a carbonyl function which is not located directly on the carbon carrying the sylfonyl groups.
  • the group R 'therefore does not have an electro-attracting character.
  • KOSHAR bis- (perfluoro-alkylsulfonyl) methanes which correspond to the formula (RFS02) 2CMCH2CHBr (CH2) mC02R ', in which M represents a metal having a valence of 1 to 4 , or a quaternary ammonium.
  • RFS02 2CMCH2CHBr
  • CH2 mC02R '
  • the object of the present invention is to provide a process for the preparation of bis (perfluorosulfonyl) methane derivatives comprising a strongly electro-attractor group on the methyne carbanion, said process allowing easy obtaining of the derivatives with good yield.
  • a subject of the invention is also new derivatives of bis (perfluorosulfonyl) methanes comprising a strongly electron-withdrawing group on the carbon carrying the sulfonyl groups.
  • the invention also relates to various applications of derivatives.
  • the method of the invention therefore makes it possible to transform an anion (RFS02) 2CH ⁇ into an anion (RFS02) 2CY ⁇ , Y being a strongly electron-attracting group, either -C ⁇ N or RZ as defined above.
  • R is a monovalent organic radical which can comprise various functionalities suited to the application intended for the desired product.
  • the implementation of the invention involves the reaction of a halide with a bis (perfluorosulfonyl) methane derivative.
  • the halide is preferably chosen from F, Cl and Br.
  • the implementation of the process of the invention comprises the reaction of a pseudo-halide with a derivative of bis (perfluorosulfonyl) methane.
  • pseudo-halogen in the present text is meant any group other than a halide which may carry a negative charge.
  • aprotic nucleophilic base Nu is preferably chosen from alkylamines, for example triethylamine, di-isopropylethylamine, quinuclidine; 1,4 diazabicyclo [2,2, 2] octane (TED); pyridines, for example pyridine, alkylpyridines, dialkylaminopyridines; imidazoles, for example N-alkylimidazoles, imidazo [1,2-a] pyridine; amidines
  • a nucleophilic base can be used. fix ée on a macromo ⁇ lecular frame.
  • the RZX compounds of the halide type are advantageously prepared in situ by reaction of the corresponding RZOH or RZOM derivatives with a halogenating agent.
  • condensing agents used in the synthesis of peptides (molecular desiccants).
  • Such agents are described for example in Synthesis p. 453 (1972); and in Ann. Rev. Biochem 3_9, 841 (1970).
  • the compounds of the invention are then prepared from the stoichiometric mixture RCOOH + (1 / nM) [(RFS02) 2CH] in a polar solvent to which the molecular dehydrating agent is added.
  • these condensing agents are chosen from carbodimides, for example cyclohexyl or diisopropyl carbodiimide; alkyl ethynyl ethers RH-0-C ⁇ CH; carbonates and oxalates of succinimidyl, phthalimidyl, 1-benzotriazolyl, nitro-, dinitro- or perhalophenols, trifluoroethyl, trichloroethyl; the P ⁇ 3-diethylazodicarboxylate (DEAD) or P ⁇ 3-dithiodipyridine mixture; carbonyldii idazole (Im) 2CO or phenylphosphoro-diimidazole ⁇ PO (Im) 2; amide acetals, for example, diethylformamide di-neopentyl acetal (CH3) 2NCH [OCH2C (CH2) 2] 2; 2-alkoxy-1-alkoxycarbony
  • reaction medium is lower than that of the compound (NuH) + [(RpS02) 2CY] ⁇ , (M'l / n) + X ⁇ precipitates and the reaction medium contains the compound in solution
  • the method of the invention comprises an additional step during which reacts the compound (NuH) + [(FS02) 2CY] ⁇ with an appropriate salt of the cation M to carry out the cation exchange.
  • This salt can be for example a carbonate, a phosphate, an oxide, a hydroxide.
  • Another solution consists in reacting the compound (NuH) + [(RFS02) 2 C] ⁇ with an anhydrous acid, for example sulfuric acid, to obtain the corresponding acid RFSO 2 ) 2 C HY which can be separated at using an appropriate solvent or by distillation; this acid can itself be converted into a salt by adding an appropriate compound such as a carbonate, a phosphate, an oxide or a hydroxyd.
  • anhydrous acid for example sulfuric acid
  • the compounds of the present invention correspond to the formula (l / nM) + [(RpS02) 2C (Y)] ', in which M, RF, Y and n have the meaning given above, (l / nM) + being different from Li + , K + or a diazonium cation when Y represents CF 3 SO2.
  • R is preferably a C 1 to C 20 perfluoroalkyl group / preferably a C 1 to C 5 -
  • RF can also be chosen from C 6 to C 20 perfluoroaryl groups, preferably from C to C 7 .
  • M can be a metal, chosen from alkaline metals, alkaline earth metals, transition metals at valence 1, 2 or 3, zinc, cadmium, mercury, lanthanides. Particular preferred compounds are those for which M is an alkali metal or Zn or Mg or La.
  • M can also be NuH, Nu being chosen from ammonia, alkyla ines, pyridines, imidazoles, amidines, guanidines, alkaloids, diazonium.
  • M can be a sulfonium, an oxoniu or a phosphonium.
  • the radical Y as defined above has an electro-attracting character, whether it is -C ⁇ N or RZ-.
  • the bifunctional group -Z- (representing -CO-, -SO2- or -R'PO-) has an electro-attractor character sufficiently high so that, whatever the organic group R , the delocalization of the anionic charge on the anion [(RpS02) 2 c ⁇ 3 ⁇ is increased compared to the delocalization of the anionic charge on the anion [(RpS02) 2CH] -.
  • the replacement of the hydrogen atom of the sulfonyl ethane derivative by a radical Y as defined above improves the dissociation power of the salt. Therefore, the compounds of the present invention are particularly useful as ionically conductive materials in electrochemical cells.
  • the compounds of the present invention may constitute the electrolyte or a part of one of the electrodes when a composite electrode is used.
  • the group R can be chosen to confer on the compound of the invention the additional property or properties with a view to its use. The choice for R is therefore very wide.
  • R carries groups capable of reacting themselves during the reaction which is carried out during the implementation of the process of the invention, these groups will be protected before the reagent R2X is introduced into the reaction medium. They will be deprotected by an appropriate treatment of the compound obtained after the reaction.
  • R can be chosen from C1-C30 alkyl or C1-C30 perhaloalkyl radicals, C6-C12 aryl or perhaloaryl radicals, arylalkyl radicals, oxaalkyl, azaalkyl, thiaalkyl and heterocycles.
  • R is an alkyl radical, an aryl-alkyl radical, or a perhalo- radical alkyl having more than 4 carbon atoms
  • the compound of the present invention has surfactant properties.
  • the compound of the invention has the properties of a liquid crystal.
  • R has at least one condensable functional group.
  • the compound of the invention can be incorporated into a network obtained by polycondensation.
  • the group R may consist of a polymer chain carrying grafts comprising one or the other of the biradicals -Z-.
  • the compound of the invention r can then be a polyelectrolyte.
  • the group R can be a hindered phenol or a quinone.
  • the compound of the invention then constitutes a free radical trap and has antioxidant properties.
  • R is a chromophore group, for example Rhodamine B
  • the compound of the invention is a dye.
  • R comprises an amide, nitrile or cyclic ester function
  • the compound of the invention constitutes a dissociating dipole.
  • R can also comprise a redox couple such as for example a disulfide, a thioamide, a ferrocene, a phehiazine, a bis (dialkylamino) aryl, a nitroxide, an aromatic imide.
  • a redox couple such as for example a disulfide, a thioamide, a ferrocene, a phehiazine, a bis (dialkylamino) aryl, a nitroxide, an aromatic imide.
  • R can also be an electronically doped conductive polymer.
  • R can also constitute a complexing ligand or a z itterion.
  • R can also be a hydrolyzable alkoxysilane, an amino acid, an optically or biologically active polypeptide.
  • EXAMPLE 1 This example illustrates the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with a cyanogen halide.
  • Examples 2 to 8 illustrate the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with an RZX halide prepared beforehand.
  • EXAMPLE 2 3.02 g of sodium salt of bis (trifluoromethane ⁇ sulfonyl) methane are dissolved in 10 ml of acetonitrile and 1 ml of pyridine is added. The mixture is cooled to -20 ° C and 1.33 g of trifluoroacetyl chloride is condensed. The reaction is written: Na (CF3S02) 2CH + CF3COCI + C5H5N ⁇
  • EXAMPLE 3 3.02 g of sodium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 15 ml of acetonitrile and 150 ⁇ l of triethylamine and 50 mg of diethylaminopyridine are added. The mixture is cooled to -20 ° C. and 1.52 g of trifluoromethane-sulfonyl fluoride is condensed in the reactor. The temperature is slowly brought back to ambient so that the pressure in the reactor does not exceed 1.5 atmospheres. The reaction can be written: Na (CF3S02) 2CH + CF3SO2F + C2Hs) 3 N ⁇
  • EXAMPLE 5 A 10% solution of poly (acryloyl chloride) in dioxane is obtained by radical polymerization of corresponding monomer. 9.05 g of this solution are added to 3.02 g of sodium salt of bis (trifluoromethane ⁇ sulfonyl) methane dissolved in 5 ml of pyridine and 5 ml of acetonitrile. The sodium chloride precipitate is removed by centrifugation and the supernatant solution is treated with 1.5 g of lithium carbonate with magnetic stirring for 48 h.
  • the lithium salt of a polyelectrolyte which is soluble in polar aprotic solvents, such as DMF, acetonitrile, etc. is obtained, unlike other polymers carrying ionophoric groups of the carboxylate or sulfonate type. . 341 mg of this polymer and 900 mg of polyethylene glycol 400- co-oxymethylene of mass M w ⁇ 10 5 daltons prepared according to the method described in: CV Nicholas, DJ ilson, C. Booth & RJM Giles Brit. Polym. J .. 20 . 289 (1988), are dissolved in 15 ml of acetonitrile.
  • EXAMPLE 6 324 mg of 4- (diethylamino) azobenzene-4 '- sulfonyl chloride in 5 ml of THF are added to 602 mg of sodium salt of bis (nonafluorobutanesulfonyl) methane in 5 ml of THF and 500 ⁇ l of triethylamine. The sodium chloride precipitate is removed and, by evaporation, the triethyla monium salt is obtained which is suspended in 5 ml of water containing in solution 350 mg of tetrabutylammonium bromide. The mixture is stirred for 24 h. An orange-colored powder is obtained, soluble in most organic solvents, and which corresponds to the following formula:
  • This ionic dye is an indicator of pH in a nonaqueous medium (transition from orange to orange
  • EXAMPLE 7 10.8 g of ethoxyacetic acid chloride are diluted in 150 ml of acetonitrile and 15 ml of anhydrous pyridine. The mixture is maintained under a nitrogen atmosphere and magnetic stirring, and 31.8 g of the potassium salt of bis (trifluoromethanesulfonyl) methane are added in portions. When the precipitation of potassium chloride is complete (a few minutes), 25 g of anhydrous K 3 PO 4 tripotassium phosphate are added and the mixture is stirred for 24 hours. Then the mixture is evaporated to dryness. The salt obtained K CH3 ⁇ CH2COC (S ⁇ 2CF3) 2] is purified by recrystallization from the butanone - 1,2-dichloroethane mixture.
  • EXAMPLE 8 3.02 g of sodium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 15 ml of acetonitrile and 5 ml of anhydrous pyridine. 1.48 ml of bis (dimethylamino) phosphorochloroiridate are added. The mixture is stirred for 2 h at ordinary temperature. The sodium chloride precipitate is removed by filtration and the solvent evaporated at 40 ° C in a rotary evaporator. After adding 10 ml of acetone, the solution is stirred for 24 hours with 2.4 g of anhydrous potassium phosphate K 3 PO4. L 1 evaporation of the acetone provides the salt K + ⁇ (CH3) 2N) ⁇ 2PO (CF3S ⁇ 2) C " ⁇ in the form of colorless microcrystals.
  • Examples 9 to 12 illustrate the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with a halide prepared in situ.
  • the solvent is evaporated and the solid residue is dissolved in 100 ml of water supplemented with 20 g of cesium chloride.
  • the precipitate formed Cs (CF3S ⁇ 2) 3C is separated and dried.
  • the acid H (CF3SO2) 3C is obtained by distilling under reduced pressure the cesium salt with an excess of anhydrous sulfuric acid.
  • Treatment of the acid H (CF 3 S0 2 ) 3 C with the hydroxides or carbonates of M makes it possible to prepare the salts M (CF 3 SO 2 ) 3 C.
  • EXAMPLE 10 A sulfonated oligomer of poly (ethylene oxide) PEO is prepared by a procedure similar to that described by T. Hamaide, C. Carré & A. Guyot (Proceedings of the Second International Symposium on Polymer Electrolytes, B. Scrosati ed. Elsevier Applied Science London 1990 page 175): 10 g of POE with a mass of 600 are dried by azeotropic distillation with benzene and lyophilization. After adding 50 ml of THF, the terminal OH groups are metallized with potassium-naphthalene.
  • a chloride precipitate of potassium is formed after approximately 1 hour To this suspension are added 4.4 g of the potassium salt of bis (trifluoromethanesulfonyl) methane and 3 ml of anhydrous pyridine. After filtration, the reaction mixture is stirred in the presence of 2 g of phosphate lithium Li3P0. A new filtration makes it possible to separate a colorless solution which, by concentration, gives a viscous fluid. This material makes it possible to plasticize a large number of polymers containing polar units (ether, amide, nitrile, ester ...), while giving them a high ionic conductivity.
  • EXAMPLE 11 A non-ionic surfactant type BRU 35 ®, polyoxyethylene 23 lauryl ether Ci2H2 5 (OCH2CH2) 3 February ⁇ H is sulfonated by a similar procedure to that described in Example 10: 12 g of BRU 35 ® were dried by azeotropic distilla ⁇ tion "with benzene and lyophilization. After additon of 50 ml of THF, the terminal OH groups are metallized with sodium hydride in the presence of 5 mg of triphenylmethane. the stoichiometry is determined by colorimetry, the end of the reaction being indicated by the persistence of the intense red color of the ⁇ 3 C "anion.
  • EXAMPLE 12 380 mg of ethylenebis (oxyethylenenitrilo) - tetraacetic acid in 10 ml of pyridine are treated with 350 ⁇ l of thionyl chloride at ordinary temperature for 24 h. The excess SOCI 2 and the pyridine are evaporated and 1.208 g of the sodium salt of bis (trifluoromethanesulfonyl) methane is added in 15 ml of an equivolumic mixture of pyridine and acetonitrile. The NaCl precipitate is removed and the solution is stirred with 1 g of anhydrous potassium carbonate K2CO3. After filtration the solution is evaporated and provides colorless crystals of:
  • This compound is a ligand (L) of divalent metals (A 11 ) and trivalents (A 111 ).
  • the corresponding complexes [A II L] 2 "M + and [A III L]" M + are salts which are soluble in polar aprotic media and in polar polymers, in particular polyethers.
  • Examples 13 to 23 illustrate the process of the invention in which a bis (fluorosulfonyl) ethane salt reacts with a pseudo-halogen prepared in situ.
  • EXAMPLE 13 To 400 mg of lauric acid C11H23COOH in 5 ml of THF and 1 ml of anhydrous pyridine are added to 636 mg of the potassium salt of bis (trifluoromethanesulfonyl) methane and 500 mg of 2-ethoxy-1-ethoxycarbonyl-1,2 -dihydroquinoline (EEDQ). The mixture is stirred for 48 hours and the solvent is evaporated. The residue is treated under primary vacuum at 110 ° C for 20 hours. The salt [CnH23CO (CF3S ⁇ 2) 2C] ⁇ K + is obtained, which has marked surfactant properties, including in solvents and aprotic solvating polymers.
  • EEDQ 2-ethoxy-1-ethoxycarbonyl-1,2 -dihydroquinoline
  • EXAMPLE 14 548 g of acid 1, 1'-ferrocene-dicarboxylic acid and 1.14 g of the lithium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 5 ml of pyridine. 824 mg of dicyclohexylcarbodii ide are added. The mixture is kept under magnetic stirring at room temperature for 75 h. The precipitate of dicyclohexylurea is removed by centrifugation and the solution is evaporated. A hygroscopic dark brown solid of [Li (CF3S ⁇ 2) 2CCOCsH4] Fe is obtained which is soluble in most polar donor solvents.
  • EXAMPLE 16 2.8 g of 4,4'-azobis (4-cyanovaleric) acid are suspended in 20 ml of methyl formate and 5 ml of pyridine. 5.72 g of the lithium salt of bis (trifluoromethanesulfonyl) methane and 4.16 g of di ⁇ cyclohexylcarbodiimide are added. The mixture is kept under agitation. magnetic tation at 0 ° C for 48 hours. The precipitate of di-cyclohexylurea is removed by centrifugation and the solution is evaporated at room temperature. A white crystalline solid is obtained from:
  • EXAMPLE 17 To 858 mg of vinylacetic acid in 10 ml of 1,2-dimethoxyethane (glyme) are added 858 mg of the lithium salt of bis (trifluoromethanesulfonyl) methane, 618 mg of di ⁇ cyclohexyl carbodiimide and 10 mg of 1 , 8-diaza-bicyclo [5,4, 0] undec-7-ene (DBU). The mixture is kept under magnetic stirring at 0 ° C for 48 h. The precipitate of dicyclohexylurea is removed by centrifugation and the salt obtained by evaporation of the solvent under reduced pressure.
  • DBU 8-diaza-bicyclo [5,4, 0] undec-7-ene
  • a network is formed by polycondensation of polyoxyethylene triol of mass 2700 and hexamethylene disocyanate.
  • Crosslinking is carried out by mixing the reagents in 50% solution in dichloromethane with a dilaurate catalyst. dibutyltin. the homogeneous solution is pressed between two flat glass plates kept 300 ⁇ m apart by wedges. The polycondensatipn is complete at ordinary temperature in 72 h. The resulting film is purified by extraction in a Soxhlet type apparatus with acetone.
  • This complex has a significant Kerr effect due to the orientation of the molecules of the zwitterion under the action of an electric field.
  • EXAMPLE 22 The potassium salt of bis (pentafluorobenzene-sulfonyl) ethane was prepared by the action of pentafluorobenzenesulfonyl chloride on aluminum carbide in the presence of anhydrous potassium fluoride in acetonitrile. To 212 mg of pentafluorobenzoxque acid suspended in THF are added 260 mg of N, N'-disuccinimidyl carbonate [(SCO) 2CO] and 1 ml of pyridine. After the end of the reaction followed by the evolution of carbon dioxide, a homogeneous solution is obtained.
  • SCO N, N'-disuccinimidyl carbonate
  • this salt reacts on nucleophilic compounds by substitution of the fluorine atoms in the para position of the sulfonyl group.
  • polyamines containing at least 2 nitrogen groups it is possible to prepare polymers having ion exchange functions, usable for example for the constitution of membranes of fuel cells. Examples 23 to 30 illustrate applications of various compounds of the invention.
  • Example 18 (70%) and 8 g of salt from Example 18 are dissolved in acetone and the solvent is evaporated. The gummy mass is heated to 150 ° C. in a metal mold for 20 min.
  • EXAMPLE 26 1 g of the salt of Example 10 and 1.4 g of poly (ethylene oxide) of mass M w 5.10 6 are dissolved by stirring magnetic in 100ml of methyl formate. The viscous solution is spread on a PTFE plate. By evaporation of the solvent, an elastic film is obtained having a thickness of 120 ⁇ m and an ionic conductivity of 9.10 " 5 ( ⁇ cm" 1 ) at 300 K.
  • An electrochemical generator consists of a negative lithium electrode 45 ⁇ m thick deposited on a polypropylene sheet 8 ⁇ m, metallized with 100 n of nickel.
  • the electrolyte is prepared from the complex of polyethylene glycol 400-co-oxymethylene of mass Mw ⁇ 10 5 daltons prepared according to the method described in: CV Nicholas, DJ Wilson, C. Booth & RJM Giles Brit. Polym. J. 20 . 289 (1988), and the lithium salt of trifluoromethanesulfonimide Li [CF3S ⁇ 2) 2N].
  • the salt concentration is calculated to correspond to a lithium cation for 25 oxygen atoms of the polyether, and the material is prepared in the form of a film 75 ⁇ m thick.
  • This latter material is formed from the polyether constituting the electrolyte and mixed with 35% by weight of the salt of Example 11.
  • the surfactant properties of the salt are used to obtain a homogeneous dispersion of the constituents of the salt.
  • the device is obtained by rolling the components to obtain a flexible generator 210 mm thick,
  • the fem is 3V, the flow rate of 500 mA / cm 2 at 30 ° C for a voltage of 2.8 V.
  • This system is rechargeable.
  • a secondary lithium generator is prepared in a similar manner to Example 27, but by replacing 10 mol% of the salt Li [CF3S ⁇ ) 2 N 3 of the electrolyte the salt of Example 14: Li2 ⁇ Fe [C5H4CO (CF3S ⁇ 2) 2] 2), so as to keep the same O / Li ratio.
  • This generator then has overload protection: for an applied external potential greater than 3.8 V, the ferrocene core of the salt is oxidized to ferriciniu. The corresponding species migrates to the negative electrode where it gives back the initial compound. This mechanism results in a generator leakage current beyond the threshold potential of 3.8 V, avoiding degradation of the system and having the advantage of not inducing self-discharge of the generator in open circuit.
  • This device is particularly advantageous for generators made up of elementary cells connected in series and whose capacities are not exactly identical.
  • a primary generator is made up as follows:
  • Mg polymer electrolyte with composite mechanism anionic vehicular fluoride carrying graphite - electrolyte - black Mg acetylene ions
  • the electrolyte is that described in this example.
  • the composition of the positive electrode corresponds to 42% v / v of the same electrolyte, 8% v / v of acetylene black and 50% v / v of graphite fluoride CF X (x ⁇ 1).
  • the composite material diluted in acetonitrile is spread on a polypropylene sheet 8 ⁇ m thick metallized with 200 nm of copper, so as to form a layer of approximately 80 ⁇ m thick.
  • the negative electrode is a 20 ⁇ m sheet.
  • the battery voltage after assembly by rolling the elements at 80 ° C is 2.5 V and the capacity for a flow rate of 400 ⁇ A / cm 2 is 7 mAh / cm 2 .
  • EXAMPLE 30 426 mg of the monomer of example 20 are dissolved in 5 ml of dried THF to which 42 mg of anhydrous lithium chloride are added. The precipitate of KC1. is removed by centrifugation and the remaining traces of potassium ion is exchanged by stirring with 1 g of NAFION ® resin in Li + form. The substituted pyrrole salt (C 4 H 3 NH) CH2C0C (CF 3 S02) 2 Lx is obtained by evaporation of THF. To 200 mg of this salt in acetonitrile are added 5 g of vanadium pentoxide V2O5 and the suspension is stirred for 48 hours.
  • a deposit of polypyrrole forms on the surface of the oxide grains, the reaction resulting in a change in color from orange to black-green.
  • the particles are separated by filtration; the oxide now has an electronic surface conductivity induced by the deposition of conductive polymer.
  • An electrochemical generator is constructed in a similar manner to that of Example 27, by replacing LiMn2 ⁇ 4 by an equivalent volume of treated vanadium oxide.
  • the generator thus formed has an open circuit voltage of 3.2 V and now has a safety device preventing over-discharge: below a potential of 2.7 V, the poly ⁇ pyrrole undergoes a redox reaction leading to its dedoping and a decrease in its conductivity by 5 orders of magnitude.
  • the V2O5 grains are then isolated and lose their electroactivity.
  • the generator thus assembled also has a safety against over-discharge, an insulating layer of polypyrrole being interposed between the current collector and the positive electrode for a potential lower than 2.7 V.

Abstract

L'invention concerne des dérivés de bis(perfluorosulfonyl)méthanes, un procédé pour leur préparation et leurs applications. Les composés de l'invention répondent à la formule (1/nM)+[(RFSO2)2CY]- dans laquelle Y représente un groupement attracteur d'électrons choisi parmi -C=N et les groupements RZ- dans lesquels Z représente un groupement carbonyle, un groupement sulfonyle ou un groupement phosphonyle et R représente un groupement organique monovalent, M représente un métal ayant la valence n ou un groupe organique pouvant exister sous forme cationique, RF représente un groupement perfluoroalkyle ou perfluoroaryle. Ils sont particulièrement utiles pour la réalisation de dispositifs électrochimiques.The invention relates to bis (perfluorosulfonyl) methane derivatives, a process for their preparation and their applications. The compounds of the invention correspond to the formula (1 / nM) + [(RFSO2) 2CY] - in which Y represents an electron attracting group chosen from -C = N and the groups RZ- in which Z represents a group carbonyl, a sulfonyl group or a phosphonyl group and R represents a monovalent organic group, M represents a metal having the valence n or an organic group which may exist in cationic form, RF represents a perfluoroalkyl or perfluoroaryl group. They are particularly useful for the production of electrochemical devices.

Description

Dérivés de bis(perfluorosulfonyl)méthanes, leur procédé de préparation, et leurs utilisations. La présente invention concerne des dérivés de bis(perfluorosulfonyl) éthanes, un procédé pour leur prépa- ration et leurs applications. Bis (perfluorosulfonyl) methane derivatives, process for their preparation, and their uses. The present invention relates to bis (perfluorosulfonyl) ethan derivatives, a process for their preparation and their applications.
On connaît des composés répondant à la formule géné¬ rale (RFS02)2CH2 et leurs sels nMn+(RpS02) 2CH, Mn+ repré¬ sentant un cation d'un métal (Li, Na, K, Ça, Cu, La...), un cation organique (ammonium, sulfonium... ) , RF repré- sentant un groupe perfluoroal yle (CF3, C2F5, C F9 f C6F13...) , ou -aryle (C6F5...) . Ces composés et leur procédé de préparation sont décrits par exemple dans U.S. 3 776 960 (Koshar) , dans R.J. Koshar & R.A. Mitsch J. Org. Chem. 38 3358 (1973) , ou dans FR 89.04503 (Armand) , ou dans US 3 776 960 (Koshar) . Ces matériaux ont des proprié¬ tés d'acides fort et leurs sels sont très solubles et dissociés dans les solvants organiques polaires ou les polymères solvatants. Néanmoins, l'atome d'hydrogène rési¬ duel sur le carbone possède une certaine acidité et sa réactivité peut être un inconvénient pour de nombreuses applications, en particulier pour l'utilisation de ces sels dans des cellules électrochimiques, et notamment celles qui mettent en jeu des anodes à base de lithium métallique, par formation du dianion : Li+[ (CF3S02)2CH]" + Li° —> 2Li+ (CF3S02)2C2- + 1/2 H2There are known compounds corresponding to the general formula (RFS02) 2CH2 and their nMn + salts (RpS02) 2CH, Mn + representing a cation of a metal (Li, Na, K, Ca, Cu, La ...) , an organic cation (ammonium, sulfonium ...), RF representing a perfluoroal yl group (CF3, C2F5, C F9 f C6F13 ...), or - aryl (C6F5 ...). These compounds and their preparation process are described for example in US 3,776,960 (Koshar), in RJ Koshar & RA Mitsch J. Org. Chem. 38 3358 (1973), or in FR 89.04503 (Armand), or in US 3,776,960 (Koshar). These materials have properties of strong acids and their salts are very soluble and dissociated in polar organic solvents or solvating polymers. However, the residual hydrogen atom on carbon has a certain acidity and its reactivity can be a drawback for many applications, in particular for the use of these salts in electrochemical cells, and in particular those which bring into play set of anodes based on metallic lithium, by formation of the dianion: Li + [(CF3S02) 2CH] " + Li ° -> 2Li + (CF3S02) 2C2- + 1/2 H2
D'une manière générale, la labilité de cet hydrogène peut être mise en évidence dans un milieu très basique (alcoxydes, organo- étalliques) . Selon Koshar, ces composés sont préparés par réaction d'halogénures de perfluoroalkyle sulfonyle avec un réactif de Grignard. Selon Armand, les composés sont préparés par réaction d'un carbure ionique avec un halogénure de sulfonyle.In general, the lability of this hydrogen can be demonstrated in a very basic medium (alkoxides, organo-metallic). According to Koshar, these compounds are prepared by reacting perfluoroalkyl sulfonyl halides with a Grignard reagent. According to Armand, the compounds are prepared by reacting an ionic carbide with a sulfonyl halide.
On connaît également les composés (RFS02)2CHRH et leurs sels M(RFS02)2CRH dans lesquels un hydrogène a été remplacé par un radical RH hydrocarboné tel qu'un méthyle, un allyle, un hydroxyéthyle. Ainsi, Koshar (DE 2 043 381) décrit des bis-(perfluoroalkylsulfonyl) méthanes qui répon¬ dent à la formule [ (RFS02) 2CR]y X, dans laquelle R repré- sente un radical alkyle inférieur et X le cation d'une base azotée (pyridine, guanidine...) . En outre, Koshar (DE 2 419 274) décrit des bis-(perfluoroalkylsulfonyl) méthanes qui répondent à la formule [ (RFS02)2CR]y X, dans laquelle R représente un radical alkyle inférieur et X un cation diazonium. [R.J. Koshar & R.A. Mitsch J. Org. Chem. 38 3358 (1973)] décrit des composés M(RFS02)2CR dans les¬ quels R représente un radical hydrocarboné : méthyle, allyle, ou hydroxyéthyle, ces composés étant généralement préparés avec un faible rendement à partir de M(RFS02)2CH. Dans ces composés, le caractère donneur d'électrons du radical RH diminue la dissociation de la paire d'ions M+[( FS02)2C RH"] et donc la conductivité des électrolytes obtenus par dissolution de ces sels dans un solvant liquide ou polymère. Pour la même raison, l'oxydation de l'anion se produit à des potentiels plus cathodiques, limitant le choix des matériaux d'électrode utilisables dans des cellules électrochimiques. On connaît en outre des composés PhN2+[C(CF3S02)3]~ (Yagupolskii et al, Chemical Abstracts, vol. 113, n°23, 3 décembre 1992, Columbus, Ohio, US; abstract n" 211480 ) . On connaît aussi des composés K+[C(CF3S02)3]"" et Li+[C(CF3S02)3]~, respectivement par L.A. Dominey et al, et al, Chemical Abstracts, vol. 114, n°12, 25 mars 1991, Columbus, Ohio, US; abstract n° 105617G) et L. Turo sky et al, Chemical Abstracts, vol. 109, n°l, 4 juillet 1988, Columbus, Ohio, US; abstract n" 6063P et Inorganic Chemistry .27 page 2135 (1988)). Les composés sont obtenus par une réaction à température élevée. Le schéma réactionnel est le suivant : 2RFS02 + [ (MgCl+)2 C(RFS02)2~2] → MgFCl+(MgCl+) (RFS02)2C~. Un traitement par l'acide sulfurique donne l'acide. Toutefois, le rendement de la réaction est faible, de l'ordre de 20%.Also known are the compounds (RFS02) 2CHRH and their salts M (RFS02) 2CRH in which a hydrogen has been replaced by a hydrocarbon-based RH radical such as methyl, allyl, hydroxyethyl. Thus, Koshar (DE 2 043 381) describes bis- (perfluoroalkylsulfonyl) methanes which correspond to the formula [(RFS02) 2CR] y X, in which R represents smells a lower alkyl radical and X the cation of a nitrogenous base (pyridine, guanidine ...). In addition, Koshar (DE 2,419,274) describes bis- (perfluoroalkylsulfonyl) methanes which correspond to the formula [(RFSO 2) 2CR] y X, in which R represents a lower alkyl radical and X a diazonium cation. [RJ Koshar & RA Mitsch J. Org. Chem. 38 3358 (1973)] describes compounds M (RFS02) 2CR in which R represents a hydrocarbon radical: methyl, allyl, or hydroxyethyl, these compounds generally being prepared with a low yield from M (RFS02) 2CH. In these compounds, the electron donor character of the RH radical decreases the dissociation of the pair of ions M + [(FS02) 2C RH "] and therefore the conductivity of the electrolytes obtained by dissolving these salts in a liquid or polymer solvent For the same reason, the oxidation of the anion occurs at more cathodic potentials, limiting the choice of electrode materials usable in electrochemical cells, and compounds PhN2 + [C (CF3S02) 3] are also known. ~ (Yagupolskii et al, Chemical Abstracts, vol. 113, # 23, December 3, 1992, Columbus, Ohio, US; abstract # 211480). Compounds K + [C (CF3S02) 3] "" and Li + [C (CF3S02) 3] ~ are also known, respectively from LA Dominey et al, et al, Chemical Abstracts, vol. 114, no. 12, March 25, 1991, Columbus, Ohio, US; abstract # 105617G) and L. Turo sky et al, Chemical Abstracts, vol. 109, no. 1, July 4, 1988, Columbus, Ohio, US; Abstract No. 6063P and Inorganic Chemistry. 27 page 2135 (1988)). The compounds are obtained by a reaction at elevated temperature. The reaction scheme is as follows: 2RFS02 + [(MgCl + ) 2 C (RFS02) 2 ~ 2 ] → MgFCl + (MgCl + ) (RFS02) 2C ~. Treatment with sulfuric acid gives the acid, however, the reaction yield is low, around 20%.
En outre, DE 2 432 414 (ROBINS) décrit des bis- (perfluoroalkylsulfonyl)méthanes qui répondent à la formule (RFS02)2CHRI, dans laquelle le groupe R' contient une fonc¬ tion carbonyle qui n'est pas située directement sur le carbone portant les groupes sylfonyles. Le groupe R' ne présente donc pas de caractère électro-attracteur.In addition, DE 2,432,414 (ROBINS) describes bis- (perfluoroalkylsulfonyl) methanes which correspond to the formula (RFS02) 2CHR I , in which the group R ′ contains a carbonyl function which is not located directly on the carbon carrying the sylfonyl groups. The group R 'therefore does not have an electro-attracting character.
De même, DE 2 012 011 (KOSHAR) décrit des bis- (perfluoro-alkylsulfonyl) méthanes qui répondent à la formule (RFS02)2CMCH2CHBr(CH2)mC02R' , dans laquelle M repré¬ sente un métal ayant une valence de 1 à 4, ou un ammonium quaternaire. Dans ces composés, la fonction carbonyle qui existe sur l'un dés substituants du méthane, est éloignée du carbone portant les groupes sulfonyles. Ce substituant ne présente donc pas de caractère électro-attracteur. Le procédé de préparation de ces composés met en oeuvre un organomagnésien.Likewise, DE 2,012,011 (KOSHAR) describes bis- (perfluoro-alkylsulfonyl) methanes which correspond to the formula (RFS02) 2CMCH2CHBr (CH2) mC02R ', in which M represents a metal having a valence of 1 to 4 , or a quaternary ammonium. In these compounds, the carbonyl function which exists on one of the methane substituents, is distant from the carbon carrying the sulfonyl groups. This substituent therefore does not have an electro-attracting character. The process for the preparation of these compounds uses an organomagnesium.
La présente invention a pour but de fournir un procédé de préparation de dérivés de bis(perfluorosulfonyl) méthanes comportant un groupe fortement électro-attracteur sur le carbanion méthyne, ledit procédé permettant une obtention aisée des dérivés avec un bon rendement.The object of the present invention is to provide a process for the preparation of bis (perfluorosulfonyl) methane derivatives comprising a strongly electro-attractor group on the methyne carbanion, said process allowing easy obtaining of the derivatives with good yield.
L'invention a également pour objet de nouveaux dérivés de bis(perfluorosulfonyl) méthanes comportant un groupe fortement électro-attracteur sur le carbone portant les groupes sulfonyles.A subject of the invention is also new derivatives of bis (perfluorosulfonyl) methanes comprising a strongly electron-withdrawing group on the carbon carrying the sulfonyl groups.
L'invention a également pour objet diverses applica¬ tions des dérivés.The invention also relates to various applications of derivatives.
Conformément à la présente invention, le procédé de préparation d'un composé répondant à la formule (1/nM)+f (RFS02)2C ]" dans laquelle Y représente un groupe¬ ment attracteur d'électrons choisi parmi -C≡N et les grou¬ pements RZ- dans lesquels Z représente un groupement carbo¬ nyle, un groupement sulfonyle ou un groupement phosphonyle et R représente un groupement organique monovalent, M représente un métal ayant la valence n ou un groupe organique pouvant exister sous forme cationique, Rp repré¬ sente un groupement perfluoroalkyle ou perfluoroaryle, caractérisé en ce qu'il comporte une étape au cours de laquelle on fait réagir un composé (1/n«M')+[ (RpS02)2CH]" avec un composé YX en présence d'une base aprotique nucléo- phile Nu, M' représentant un métal ayant la valence n' ou un groupe organique monovalent et X représentant un halo¬ gène ou un pseudo-halogène.In accordance with the present invention, the process for the preparation of a compound corresponding to the formula ( 1 / n M ) + f ( R FS02) 2C] " in which Y represents an electron-attracting group chosen from -C≡ N and the RZ- groups in which Z represents a carbonyl group, a sulfonyl group or a phosphonyl group and R represents a monovalent organic group, M represents a metal having the valence n or an organic group which may exist in cationic form , Rp represents a perfluoroalkyl or perfluoroaryl group, characterized in that it comprises a step during which a compound ( 1 / n "M ') + [(RpS02) 2 CH]" is reacted with a compound YX in the presence of a nucleotic aprotic base Nu, M 'representing a metal having the valence n' or a monovalent organic group and X representing a halogen gene or a pseudo-halogen.
Le procédé de 1*invention permet par conséquent de transformer un anion (RFS02)2CH~ en un anion (RFS02)2CY~, Y étant un groupe fortement électro-attracteur, soit -C≡N, soit RZ tel que défini ci-dessus. R est un radical organique monovalent qui peut comporter diverses fonction¬ nalités adaptées à l'application prévue pour le produit recherché. Selon une variante, la mise en oeuvre de 1'invention comporte la réaction d'un halogénure avec un dérivé de bis(perfluorosulfonyl)méthane. Dans ce cas, l'halogénure est choisi de préférence parmi F, Cl et Br.The method of the invention therefore makes it possible to transform an anion (RFS02) 2CH ~ into an anion (RFS02) 2CY ~, Y being a strongly electron-attracting group, either -C≡N or RZ as defined above. . R is a monovalent organic radical which can comprise various functionalities suited to the application intended for the desired product. According to a variant, the implementation of the invention involves the reaction of a halide with a bis (perfluorosulfonyl) methane derivative. In this case, the halide is preferably chosen from F, Cl and Br.
Selon une autre variante, la mise en oeuvre du procédé de l'invention comporte la réaction d'un pseudo-halogénure avec un dérivé de bis(perfluorosulfonyl)méthane. Par pseudo-halogène, on entend dans le présent texte, tout groupe autre qu'un halogénure pouvant porter une charge négative. A titre d'exemple, on peut citer les radicaux RSO3-, RCO2', succinimidyloxy (SCO"), phtalimidoxy (PTO-) , 1-benzotriazoloxy (BzO-) , oxynorbornène 2,3-dicarboximide, trifluoroéthoxy, trichloroéthox , imidazolyl, triazolyle, nitrophénoxy, dinitrophénox , perhalophénoxy, O-acylurées. La base nucléophile aprotique Nu est choisie de préférence parmi les alkylamines, par exemple la triéthylamine , la di-isopropyléthylamine, la quinucli- dine ; le 1,4 diazabicyclo[2,2,2]octane (TED) ; les pyridi- nes, par exemple la pyridine, les alkylpyridines, les dialkylaminopyridines ; les imidazoles, par exemple les N- alkylimidazoles, l'imidazo[1,2-a]pyridine ; les amidines, par exemple le 1,5 diazabicyclo[4,3,0]non-5-ène (DBN), le 1,8 diazabicyclo[5, 4, 0]undec-7-ène (DBU) ; les guani- dines, par exemple la tétra éthyl guanidine, la 1,3,4,7,8- hexahydro-l-méthyl-2H-pyrimido[l,2-a]pyrimidine (HPP) . Dans le procédé de la présente invention, on peut utiliser une base nucléophile fixée sur une trame macromo¬ léculaire. Les composés RZX du type halogénure, sont avantageuse¬ ment préparés in-situ par réaction des dérivés RZOH ou RZOM correspondants avec un agent halogénant. Parmi les agents halogénants particulièrement préférés, on peut citer : SOC12, SOBr2, SF4, (C2H5)2NSF3, COCI2, (C0C1)2, (C0Br)2, (CCl3θ)2CO, [ (CH3) 2N=CHCl]+Cl_, le mélange tri- phénylphosphine (Pφ3)/CCl4, le dichlorométhyl-méthyl éther CI2HCOCH3, les sels de 2-chloro-l-méthylpyridinium ou de 2- fluoro-1-méthylpyridinium. Dans le cas particulier où Z = CO, il est particuliè¬ rement avantageux d'utiliser un composé RZX du type pseudo- halogénure préparé directement in-situ (X = RCO2, SCO, PTO, BzO...) à partir de RCOOH par action des agents de conden¬ sation utilisés dans la synthèse des peptides (déshydratants moléculaires) . De tels agents sont décrits par exemple dans Synthesis p. 453 (1972) ; et dans Ann. Rev. Biochem 3_9, 841 (1970) . Les composés de l'invention sont alors préparés à partir du mélange stoechoimétrique RCOOH + (1/nM) [ (RFS02)2CH] dans un solvant polaire auquel est ajouté le déhydratant moléculaire. De préférence, ces agents de condensation sont choisis parmi les carbo- diimides, par exemple le carbodiimide de cyclohexyle ou de diisopropyle ; les éthers d'alkyl-éthynyle RH-0-C≡CH ; les carbonates et les oxalates de succinimidyle, de phtal- imidyle, de 1-benzotriazolyle, de nitro-, de dinitro- ou de perhalo-phénols, de trifluoroéthyle, de trichloro- éthyle ; le mélange PΦ3-diéthylazodicarboxylate (DEAD) ou PΦ3-dithiodipyridine; le carbonyldii idazole (Im)2CO ou le phénylphosphoro-diimidazole ΦPO(Im)2 ; les acétals d'amides, par exemple, le di éthylformamide di-néopentyl acétal (CH3) 2NCH[OCH2C(CH2) 2]2 ; les 2-alcoxy-l-alcoxycar- bonyl-l,2-dihydroquinoline ; les sels de O-benzotriazol-1- yl-N,N,N' ,N'tétraméthyluronium ou de O-benzo triazol-1- yloxytrisdiméthylaminophosphonium ; les sultones aromati- ques, par exemple, l'oxyde de 2,2-(6 nitronapht[l,8-cd]- 1,2-oxathiole) , le chlorofor iate d'isobutyle, le diphé- nylphosphochloroiridate, le chlorophosphite d'éthylène, le pyrophosphite de diéthyléthylène ; le chlorure de bis (2- oxo-3-oxazolidinyl)phosphinyle ; les sels de 2-ter-butyl-5- méthyl ixoaxazolium ( oodward's reagent L) .According to another variant, the implementation of the process of the invention comprises the reaction of a pseudo-halide with a derivative of bis (perfluorosulfonyl) methane. By pseudo-halogen in the present text is meant any group other than a halide which may carry a negative charge. By way of example, mention may be made of the radicals RSO3-, RCO2 ', succinimidyloxy (SCO "), phthalimidoxy (PTO-), 1-benzotriazoloxy (BzO-), oxynorbornene 2,3-dicarboximide, trifluoroethoxy, trichloroethox, imidazolyl, triazolyl, nitrophenoxy, dinitrophenox, perhalophenoxy, O-acylureas The aprotic nucleophilic base Nu is preferably chosen from alkylamines, for example triethylamine, di-isopropylethylamine, quinuclidine; 1,4 diazabicyclo [2,2, 2] octane (TED); pyridines, for example pyridine, alkylpyridines, dialkylaminopyridines; imidazoles, for example N-alkylimidazoles, imidazo [1,2-a] pyridine; amidines, for example 1,5 diazabicyclo [4,3,0] non-5-ene (DBN), 1,8 diazabicyclo [5, 4, 0] undec-7-ene (DBU); guanidines, for example tetra ethyl guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido [1,2-a] pyrimidine (HPP). In the process of the present invention, a nucleophilic base can be used. fix ée on a macromo¬ lecular frame. The RZX compounds of the halide type are advantageously prepared in situ by reaction of the corresponding RZOH or RZOM derivatives with a halogenating agent. Among the particularly preferred halogenating agents, mention may be made of: SOC12, SOBr2, SF4, (C2H5) 2NSF3, COCI2, (C0C1) 2, (C0Br) 2, (CCl3θ) 2CO, [(CH3) 2N = CHCl] + Cl _ , the triphenylphosphine (Pφ3) / CCl4 mixture, the dichloromethyl-methyl ether CI2HCOCH3, the 2-chloro-1-methylpyridinium or 2-fluoro-1-methylpyridinium salts. In the particular case where Z = CO, it is particularly advantageous to use an RZX compound of the pseudo-halide type prepared directly in situ (X = RCO2, SCO, PTO, BzO ...) from RCOOH by action of the condensing agents used in the synthesis of peptides (molecular desiccants). Such agents are described for example in Synthesis p. 453 (1972); and in Ann. Rev. Biochem 3_9, 841 (1970). The compounds of the invention are then prepared from the stoichiometric mixture RCOOH + (1 / nM) [(RFS02) 2CH] in a polar solvent to which the molecular dehydrating agent is added. Preferably, these condensing agents are chosen from carbodimides, for example cyclohexyl or diisopropyl carbodiimide; alkyl ethynyl ethers RH-0-C≡CH; carbonates and oxalates of succinimidyl, phthalimidyl, 1-benzotriazolyl, nitro-, dinitro- or perhalophenols, trifluoroethyl, trichloroethyl; the PΦ3-diethylazodicarboxylate (DEAD) or PΦ3-dithiodipyridine mixture; carbonyldii idazole (Im) 2CO or phenylphosphoro-diimidazole ΦPO (Im) 2; amide acetals, for example, diethylformamide di-neopentyl acetal (CH3) 2NCH [OCH2C (CH2) 2] 2; 2-alkoxy-1-alkoxycarbonyl-1,2-dihydroquinoline; the salts of O-benzotriazol-1-yl-N, N, N ', N'tetramethyluronium or of O-benzo triazol-1-yloxytrisdimethylaminophosphonium; aromatic sultones, for example, 2,2- (6 nitronapht [1,8-cd] - 1,2-oxathiole) oxide, isobutyl chloroforate, diphenylphosphochloroiridate, chlorophosphite d ethylene, diethylene pyrophosphite; bis chloride (2- oxo-3-oxazolidinyl) phosphinyl; 2-ter-butyl-5-methyl ixoaxazolium salts (oodward's reagent L).
Lorsque la solubilité du composé (M'l/n)+X~ dans leWhen the solubility of the compound (M'l / n) + X ~ in the
•milieu réactionnel est inférieure à celle du composé (NuH)+[(RpS02)2CY]~, (M'l/n)+X~ précipite et le milieu réactionnel contient en solution le composé • reaction medium is lower than that of the compound (NuH) + [(RpS02) 2CY] ~, (M'l / n) + X ~ precipitates and the reaction medium contains the compound in solution
(NuH)+[(RFS02)2C ]~- Dans ce cas, si le cation (NuH)+ ne correspond pas au' cation (l/nM)+ souhaité, le procédé de l'invention comporte une étape supplémentaire au cours de laquelle on fait réagir le composé (NuH)+[( FS02)2CY]~ avec un sel approprié du cation M pour réaliser 1'échange de cations. Ce sel peut être par exemple un carbonate, un phosphate, un oxyde, un hydroxyde.(NuH) + [(RFS02) 2C] ~ - In this case, if the cation (NuH) + does not correspond to the 'cation (l / nM) + desired, the method of the invention comprises an additional step during which reacts the compound (NuH) + [(FS02) 2CY] ~ with an appropriate salt of the cation M to carry out the cation exchange. This salt can be for example a carbonate, a phosphate, an oxide, a hydroxide.
Une autre solution consiste à faire réagir le composé (NuH)+[(RFS02) 2C ]~ avec un acide anhydre, par exemple l'acide sulfurique, pour obtenir l'acide correspondant RFSO2)2 CHY qui peut être séparé à l'aide d'un solvant approprié ou par distillation; cet acide pourra lui-même être transformé en sel par addition d'un composé approprié tel qu'un carbonate, un phosphate, un oxyde ou un hydroxyd .Another solution consists in reacting the compound (NuH) + [(RFS02) 2 C] ~ with an anhydrous acid, for example sulfuric acid, to obtain the corresponding acid RFSO 2 ) 2 C HY which can be separated at using an appropriate solvent or by distillation; this acid can itself be converted into a salt by adding an appropriate compound such as a carbonate, a phosphate, an oxide or a hydroxyd.
Les composés de la présente invention répondent à la formule (l/nM)+[(RpS02)2C(Y) ]', dans laquelle M, RF, Y et n ont la signification donnée ci-dessus, (l/nM)+ étant diffé- rent de Li+, K+ ou d'un cation diazonium lorsque Y repré¬ sente CF3SO2.The compounds of the present invention correspond to the formula (l / nM) + [(RpS02) 2C (Y)] ', in which M, RF, Y and n have the meaning given above, (l / nM) + being different from Li + , K + or a diazonium cation when Y represents CF 3 SO2.
R est, de préférence, un groupement perfluoroalkyle en Ci à C20/ de préférence en Ci à Cs-R is preferably a C 1 to C 20 perfluoroalkyl group / preferably a C 1 to C 5 -
RF peut également être choisi parmi les groupements perfluoroaryles en C6 à C20, de préférence en Ce à C7.RF can also be chosen from C 6 to C 20 perfluoroaryl groups, preferably from C to C 7 .
M peut être un métal, choisi parmi les métaux alca¬ lins, les métaux alcalino-terreux, les métaux de transition à la valence 1, 2 ou 3, le zinc, le cadmium, le mercure, les lanthanides. Des composés particuliers préférés sont ceux pour lesquels M est un métal alcalin ou Zn ou Mg ou La.M can be a metal, chosen from alkaline metals, alkaline earth metals, transition metals at valence 1, 2 or 3, zinc, cadmium, mercury, lanthanides. Particular preferred compounds are those for which M is an alkali metal or Zn or Mg or La.
M peut également être NuH, Nu étant choisi parmi l'ammoniac, les alkyla ines, les pyridines, les imidazoles, les amidines, les guanidines, les alcaloïdes, les diazo- nium.M can also be NuH, Nu being chosen from ammonia, alkyla ines, pyridines, imidazoles, amidines, guanidines, alkaloids, diazonium.
En outre M peut être un sulfonium, un oxoniu ou un phosphonium. Le radical Y tel que défini ci-dessus présente un caractère électro-attracteur, qu'il s'agisse de -C≡N ou de RZ-.In addition M can be a sulfonium, an oxoniu or a phosphonium. The radical Y as defined above has an electro-attracting character, whether it is -C≡N or RZ-.
Lorsque Y est du type RZ-, le groupement bifonctionnel -Z- (représentant -CO-, -SO2- ou -R'PO-) présente un carac- tère électro-attracteur suffisamment élevé pour que, quel que soit le groupe organique R, la délocalisation de la charge anionique sur l'anion [ (RpS02) 2cγ3~ soit augmentée par rapport à la délocalisation de la charge anionique sur l'anion [ (RpS02) 2CH]-. Ainsi, le remplacement de l'atome d'hydrogène du dérivé sulfonyl éthane par un radical Y tel que défini ci-dessus améliore le pouvoir de dissociation du sel. De ce fait, les composés de la présente invention sont particulièrement utiles comme matériaux à conduction ionique dans les cellules électrochimiques. Les composés de la présente invention peuvent constituer 1 'électrolyte ou une partie de l'une des électrodes lorsque l'on met en oeuvre une électrode composite.When Y is of the RZ- type, the bifunctional group -Z- (representing -CO-, -SO2- or -R'PO-) has an electro-attractor character sufficiently high so that, whatever the organic group R , the delocalization of the anionic charge on the anion [(RpS02) 2 cγ 3 ~ is increased compared to the delocalization of the anionic charge on the anion [(RpS02) 2CH] -. Thus, the replacement of the hydrogen atom of the sulfonyl ethane derivative by a radical Y as defined above improves the dissociation power of the salt. Therefore, the compounds of the present invention are particularly useful as ionically conductive materials in electrochemical cells. The compounds of the present invention may constitute the electrolyte or a part of one of the electrodes when a composite electrode is used.
Le groupe R peut être choisi pour conférer au composé de l'invention la ou les propriétés additionnelles en vue de son utilisation. Le choix pour R est par conséquent très large. Lorsque R porte des groupes suceptibles de réagir eux-mêmes au cours de la réaction qui est effectuée lors de la mise en oeuvre du procédé de l'invention, ces groupes seront protégés avant que le réactif R2X ne soit introduit dans le milieu réactionnel. Ils seront déprotégés par un traitement approprié du composé obtenu après la réaction.The group R can be chosen to confer on the compound of the invention the additional property or properties with a view to its use. The choice for R is therefore very wide. When R carries groups capable of reacting themselves during the reaction which is carried out during the implementation of the process of the invention, these groups will be protected before the reagent R2X is introduced into the reaction medium. They will be deprotected by an appropriate treatment of the compound obtained after the reaction.
De manière générale, R peut être choisi parmi les radicaux alkyles en C1-C30 ou perhaloalkyles en Ci-Ce, les radicaux aryles ou perhaloaryles en C6-C12, les radicaux arylalkyles, les radicaux oxaalkyles, azaalkyles, thia- alkyles et les hétérocycles.In general, R can be chosen from C1-C30 alkyl or C1-C30 perhaloalkyl radicals, C6-C12 aryl or perhaloaryl radicals, arylalkyl radicals, oxaalkyl, azaalkyl, thiaalkyl and heterocycles.
Plus particulièrement, lorsque R est un radical alkyle, un radical aryle-alkyle, ou un radical perhalo- alkyle ayant plus de 4 atomes de carbone, le composé de la présente invention présente des propriétés tensio-actives.More particularly, when R is an alkyl radical, an aryl-alkyl radical, or a perhalo- radical alkyl having more than 4 carbon atoms, the compound of the present invention has surfactant properties.
Lorsque R représente un groupe mésomorphe, le composé de l'invention présente les propriétés d'un cristal liquide.When R represents a mesomorphic group, the compound of the invention has the properties of a liquid crystal.
Lorsque R comporte des insaturations éthyléniques, par exemple -C=C-, -C=C-C=0, -C=S02~, -C=CΦ, le compo.sé de 1'invention peut être poly érisé.When R contains ethylenic unsaturations, for example -C = C-, -C = C-C = 0, -C = S02 ~, -C = CΦ, the compound of the invention can be poly erized.
Lorsque R comporte au moins un groupe fonctionnel condensable. tel que par exemple -OH, -NH2 ou -COOH, -N≈C≈O, le composé de l'invention peut être incorporé dans un réseau obtenu par polycondensation.When R has at least one condensable functional group. such as for example -OH, -NH2 or -COOH, -N≈C≈O, the compound of the invention can be incorporated into a network obtained by polycondensation.
Lorsque R comporte un groupe dissociable tel que par exemple un groupe peroxyde -0-0-, un groupe diazoïque -N=N, un groupe azo N2=CH-, un groupe -SO2N3, un groupe disulfure -S-S-, le composé de l'invention peut être utilisé comme initiateur radicalaire.When R comprises a dissociable group such as for example a peroxide group -0-0-, a diazo group -N = N, an azo group N 2 = CH-, a group -SO2N3, a disulfide group -SS-, the compound of the invention can be used as a radical initiator.
Le groupe R peut être constitué par une chaîne polymé- rique portant des greffons comportant l'un ou 1*autres des biradicaux -Z-. A titre d'exemple, on peut citer un poly(acryloyle) ou un poly(styrènesulfonyle) . Le composé de lrinvention peut alors constituer un polyélectrolyte.The group R may consist of a polymer chain carrying grafts comprising one or the other of the biradicals -Z-. By way of example, there may be mentioned a poly (acryloyl) or a poly (styrenesulfonyl). The compound of the invention r can then be a polyelectrolyte.
Le groupe R peut être un phénol encombré ou une quinone. Le composé de l'invention constitue alors un piège à radicaux libres et présente des propriétés anti¬ oxydantes.The group R can be a hindered phenol or a quinone. The compound of the invention then constitutes a free radical trap and has antioxidant properties.
Lorsque R est un groupe chromophore, par exemple la Rhodamine B, le composé de l'invention est un colorant.When R is a chromophore group, for example Rhodamine B, the compound of the invention is a dye.
Lorsque R comporte une fonction amide, nitrile ou ester cyclique, le composé de l'invention constitue un dipôle dissociant.When R comprises an amide, nitrile or cyclic ester function, the compound of the invention constitutes a dissociating dipole.
R peut également comporter un couple redox- tel que par exemple un disulfure, un thioamide, un ferrocène, une phé- nothiazine, un bis(dialkylamino)aryle, un nitroxyde, un imide aromatique.R can also comprise a redox couple such as for example a disulfide, a thioamide, a ferrocene, a phehiazine, a bis (dialkylamino) aryl, a nitroxide, an aromatic imide.
R peut également être un polymère conducteur électro¬ niquement dopé. R peut également constituer un ligand complexant ou un z itterion.R can also be an electronically doped conductive polymer. R can also constitute a complexing ligand or a z itterion.
R peut en outre être un alcoxysilane hydrolysable, un acide aminé, un polypeptique optiquement ou biologiquement actif.R can also be a hydrolyzable alkoxysilane, an amino acid, an optically or biologically active polypeptide.
La présente invention est illustrée par les exemples non limitatifs suivants :The present invention is illustrated by the following nonlimiting examples:
EXEMPLE 1 Cet exemple illustre le procédé de 1 ' invention dans lequel un sel de bis(fluorosulfonyl)méthane réagit avec un halogénure de cyanogène.EXAMPLE 1 This example illustrates the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with a cyanogen halide.
A 10 ml d'une solution commerciale 5M de bromure de cyanogène dans 1 'acétonitrile on ajoute 15,9 g du sel de potassium du bis(trifluorométhanesulfonyle)méthane dans 50 ml d'acétonitrile et 10 ml de pyridine. Il se forme un précipité de bromure de potassium qui est éliminé par filtration. La solution incolore résultante est évaporée puis reprise par 70 ml d'acétone et agitée avec 8 g de K2CO3. La suspension est filtrée et évaporée pour donner 14,5 g du sel K+[ (CF3SO2) 2CC≡N]~.To 10 ml of a 5M commercial solution of cyanogen bromide in acetonitrile are added 15.9 g of the potassium salt of bis (trifluoromethanesulfonyl) methane in 50 ml of acetonitrile and 10 ml of pyridine. A precipitate of potassium bromide is formed which is eliminated by filtration. The resulting colorless solution is evaporated and then taken up in 70 ml of acetone and stirred with 8 g of K2CO3. The suspension is filtered and evaporated to give 14.5 g of the K + salt ((CF3SO2) 2CC≡N] ~.
Les exemples 2 à 8 illustrent le procédé de l'inven¬ tion dans lequel un sel de bis(fluorosulfonyl)méthane réagit avec un halogénure RZX préparé au préalable.Examples 2 to 8 illustrate the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with an RZX halide prepared beforehand.
EXEMPLE 2 3,02 g de sel de sodium du bis(trifluorométhane¬ sulfonyle)méthane sont dissous dans 10 ml d'acétonitrile et on ajoute 1ml de pyridine. Le mélange est refroidi à -20°C et on condense 1,33 g de chlorure de trifluoroacétyle. La réaction s'écrit : Na(CF3S02)2CH + CF3COCI + C5H5N →EXAMPLE 2 3.02 g of sodium salt of bis (trifluoromethane¬ sulfonyl) methane are dissolved in 10 ml of acetonitrile and 1 ml of pyridine is added. The mixture is cooled to -20 ° C and 1.33 g of trifluoroacetyl chloride is condensed. The reaction is written: Na (CF3S02) 2CH + CF3COCI + C5H5N →
NaCl + [ (CF3S02)2CCOCF3]~,C5H5NH+ Le précipité de chlorure de sodium est éliminé par filtra¬ tion et le solvant évaporé à 40°C dans un évaporateur rotatif. Après ajout de 10ml d'acétone, la solution est agitée pendant 24 heures avec 1,5 g de phosphate de lithium Li3Pθ . Après évaporation, on obtient un solide blanc dont l'analyse est : C ≈ 13% (12,9) ; F = 45% (46,2) ; S = 22% (23,7) ; Li = 1,9% (1,9) avec un rendement de 91%. Les données théoriques pour Li(CF3S02)2CCOCF3 sont données entre parenthèses.NaCl + [(CF3S02) 2CCOCF3] ~, C5H5NH + The sodium chloride precipitate is removed by filtration and the solvent evaporated at 40 ° C in a rotary evaporator. After adding 10 ml of acetone, the solution is stirred for 24 hours with 1.5 g of lithium phosphate Li3Pθ. After evaporation, a white solid is obtained, the analysis of which is: C ≈ 13% (12.9); F = 45% (46.2); S = 22% (23.7); Li = 1.9% (1.9) with a yield of 91%. The theoretical data for Li (CF3S02) 2CCOCF3 are given in brackets.
EXEMPLE 3 3,02 g de sel de sodium du bis(trifluorométhanesulfo- nyle)méthane sont dissous dans 15 ml d•acétonitrile et on ajoute 150 μl de triéthylaminé et 50 mg de di éthylamino- pyridine. Le mélange est refroidi à -20°C et on condense dans le réacteur 1,52 g de fluorure de trifluorométhane- sulfonyle. La température est lentement ramenée à l'ambiante de manière à ce que la pression dans le réac¬ teur n'excède pas 1,5 atmosphères. La réaction s'écrit : Na(CF3S02)2CH + CF3SO2F + C2Hs)3 N →EXAMPLE 3 3.02 g of sodium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 15 ml of acetonitrile and 150 μl of triethylamine and 50 mg of diethylaminopyridine are added. The mixture is cooled to -20 ° C. and 1.52 g of trifluoromethane-sulfonyl fluoride is condensed in the reactor. The temperature is slowly brought back to ambient so that the pressure in the reactor does not exceed 1.5 atmospheres. The reaction can be written: Na (CF3S02) 2CH + CF3SO2F + C2Hs) 3 N →
NaF + [(CF3θ2)3]~, [(C2H5)3NH]+ La diméthylaminopyridine sert de catalyseur de transfert du groupe trifluorométhanesulfonyle. Le précipité de fluorure de sodium est éliminé par filtration et le solvant évaporé à 40°C dans un évaporateur rotatif. Après ajout de 10ml d'acétone, la solution est agitée pendant 24 heures avec 2,4 g de phosphate de potassium K3PO4 anhydre. Après évapo- ration, on obtient un solide blanc dont l'analyse est C = 11% (théorique pour K(CF3S02)3C : 10,6) ; F = 37% (38) ; S = 20,5% (21,3) ; K = 8,5% (8,6) avec un rendement de 88%.NaF + [(CF 3 θ2) 3] ~, [(C2H5) 3NH] + Dimethylaminopyridine serves as a transfer catalyst for the trifluoromethanesulfonyl group. The sodium fluoride precipitate is removed by filtration and the solvent evaporated at 40 ° C in a rotary evaporator. After adding 10 ml of acetone, the solution is stirred for 24 hours with 2.4 g of anhydrous potassium phosphate K3PO4. After evaporation, a white solid is obtained, the analysis of which is C = 11% (theoretical for K (CF3SO2) 3C: 10.6); F = 37% (38); S = 20.5% (21.3); K = 8.5% (8.6) with a yield of 88%.
EXEMPLE 4 3,3 g de chlorure de l'acide stéarique C17H35COCI dansEXAMPLE 4 3.3 g of chloride of stearic acid C17H35COCI in
25 ml de THF et 5ml de pyridine anhydre sont ajoutés à 3,02 g du sel de sodium du bis(trifluorométhanesulfonyle)méthane dans 25ml de THF. La solution est filtrée pour éliminer le précipité de chlorure de sodium puis mise en contact avec 500 mg de carbonate de lithium Li2C03. Le mélange est agité pendant 24 heures ; l'excès de carbonate est éliminé par centrifugation et le solvant est évaporé. On obtient 4,8 g du sel [Ci7H35C0(CF3S02)2C]~Li+ qui possède des propriétés tensio-actives marquées, y compris dans les solvants et polymères solvatants aprotiques.25 ml of THF and 5 ml of anhydrous pyridine are added to 3.02 g of the sodium salt of bis (trifluoromethanesulfonyl) methane in 25 ml of THF. The solution is filtered to remove the precipitate of sodium chloride and then contacted with 500 mg of lithium carbonate Li2CO3. The mixture is stirred for 24 hours; the excess carbonate is removed by centrifugation and the solvent is evaporated. 4.8 g of the salt [Ci7H35C0 (CF3S02) 2C] ~ Li + are obtained, which has marked surfactant properties, including in solvents and aprotic solvating polymers.
EXEMPLE 5 Une solution à 10% de poly(chlorure d'acryloyle) dans le dioxane est obtenue par polymérisation radicalaire du monomère correspondant. 9,05 g de cette solution sont ajoutés à 3,02 g de sel de sodium du bis(trifluorométhane¬ sulfonyle)méthane dissous dans 5 ml de pyridine et 5 ml d'acétonitrile. Le précipité de chlorure de sodium est éliminé par centrifugation et la solution surnageante est traitée par 1,5 g de carbonate de lithium sous agitation magnétique pendant 48 h. Après filtration, on obtient le sel de lithium d'un polyélectrolyte qui est soluble dans les solvants aprotiques polaires, tels le DMF, l'acéto- nitrile..., à la différence des autres polymères portant des groupement ionophores de type carboxylate ou sulfonate. 341 mg de ce polymère et 900 mg de polyéthylène glycol 400- co-oxyméthylène de masse Mw ≡ 105 daltons préparé selon la méthode décrite dans : C.V. Nicholas, D.J. ilson, C. Booth & R.J.M. Giles Brit. Polym. J. .20. 289 (1988), sont dissous dans 15 ml d'acétonitrile. Après épandage de la solution résultante et évaporâtion du solvant, on obtient un film d'un élastomère formé du mélange du polymère solvatant et du polyélectrolyte. Ce matériau présente une conductivité due uniquement au cation Li+ de 1.10"5 (Ωcirr1) à 25"C.EXAMPLE 5 A 10% solution of poly (acryloyl chloride) in dioxane is obtained by radical polymerization of corresponding monomer. 9.05 g of this solution are added to 3.02 g of sodium salt of bis (trifluoromethane¬ sulfonyl) methane dissolved in 5 ml of pyridine and 5 ml of acetonitrile. The sodium chloride precipitate is removed by centrifugation and the supernatant solution is treated with 1.5 g of lithium carbonate with magnetic stirring for 48 h. After filtration, the lithium salt of a polyelectrolyte which is soluble in polar aprotic solvents, such as DMF, acetonitrile, etc., is obtained, unlike other polymers carrying ionophoric groups of the carboxylate or sulfonate type. . 341 mg of this polymer and 900 mg of polyethylene glycol 400- co-oxymethylene of mass M w ≡ 10 5 daltons prepared according to the method described in: CV Nicholas, DJ ilson, C. Booth & RJM Giles Brit. Polym. J .. 20 . 289 (1988), are dissolved in 15 ml of acetonitrile. After spreading the resulting solution and evaporating the solvent, a film of an elastomer formed from the mixture of the solvating polymer and the polyelectrolyte is obtained. This material has a conductivity due solely to the Li + cation of 1.10 " 5 (Ωcirr 1 ) at 25" C.
EXEMPLE 6 324 mg de chlorure de 4-(di éthylamino)azobenzène-4 '- sulfonyle dans 5 ml de THF sont ajoutés à 602 mg de sel de sodium du bis(nonafluorobutanesulfonyle)méthane dans 5 ml de THF et 500 μl de triéthylamine. Le précipité de chlorure de sodium est éliminé et, par évaporation, on obtient le sel de triethyla monium qui est mis en suspen¬ sion dans 5 ml d'eau contenant en solution 350 mg de bromure de tetrabutylammonium. Le mélange est agité pendant 24 h. On obtient une poudre de couleur orange, soluble dans la plupart des solvants organiques, et qui répond à la formule suivante :EXAMPLE 6 324 mg of 4- (diethylamino) azobenzene-4 '- sulfonyl chloride in 5 ml of THF are added to 602 mg of sodium salt of bis (nonafluorobutanesulfonyl) methane in 5 ml of THF and 500 μl of triethylamine. The sodium chloride precipitate is removed and, by evaporation, the triethyla monium salt is obtained which is suspended in 5 ml of water containing in solution 350 mg of tetrabutylammonium bromide. The mixture is stirred for 24 h. An orange-colored powder is obtained, soluble in most organic solvents, and which corresponds to the following formula:
Ce colorant ionique est un indicateur de pH en milieu non aqueux (transition aune-orange | "rouge-violet dans la zone de pH 1-4) . This ionic dye is an indicator of pH in a nonaqueous medium (transition from orange to orange | " red-violet in the zone of pH 1-4).
EXEMPLE 7 10,8 g de chlorure de 1'acide éthoxyacétique sont dilués dans 150 ml d'acétonitrile et 15 ml de pyridine anhydre. Le mélange est maintenu sous atmosphère d'azote et agitation magnétique, et l'on ajoute par portions 31,8 g du sel de potassium du bis(trifluorométhanesulfonyle)méthane. Lorsque la précipitation du chlorure de potassium est terminée (quelques minutes) , on ajoute 25 g de phosphate tripotassique K3PO4 anhydre et le mélange est agité pendant 24 heures. Ensuite, le mélange est évaporé à siccité. Le sel obtenu K CH3θCH2COC(SÛ2CF3)2] est purifié par recristallisation dans le mélange butanone - 1,2-di- chloroéthane.EXAMPLE 7 10.8 g of ethoxyacetic acid chloride are diluted in 150 ml of acetonitrile and 15 ml of anhydrous pyridine. The mixture is maintained under a nitrogen atmosphere and magnetic stirring, and 31.8 g of the potassium salt of bis (trifluoromethanesulfonyl) methane are added in portions. When the precipitation of potassium chloride is complete (a few minutes), 25 g of anhydrous K 3 PO 4 tripotassium phosphate are added and the mixture is stirred for 24 hours. Then the mixture is evaporated to dryness. The salt obtained K CH3θCH2COC (SÛ2CF3) 2] is purified by recrystallization from the butanone - 1,2-dichloroethane mixture.
EXEMPLE 8 3,02 g de sel de sodium du bis(trifluorométhanesulfo¬ nyle)méthane sont dissous dans 15 ml d'acétonitrile et 5 ml de pyridine anhydre. On ajoute 1,48 ml de bis(dimethylamino)phosphorochloroiridate. Le mélange est agité 2 h à température ordinaire. Le précipité de chlorure de sodium est éliminé par filtration et le solvant évaporé à 40°C dans un évaporateur rotatif. Après ajout de 10 ml d'acétone, la solution est agitée pendant 24 heures avec 2,4 g de phosphate de potassium K3PO4 anhydre. L1évapora- tion de l'acétone fournit le sel K+{ (CH3)2N) }2PO(CF3Sθ2)C"} sous forme de microcristaux incolores.EXAMPLE 8 3.02 g of sodium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 15 ml of acetonitrile and 5 ml of anhydrous pyridine. 1.48 ml of bis (dimethylamino) phosphorochloroiridate are added. The mixture is stirred for 2 h at ordinary temperature. The sodium chloride precipitate is removed by filtration and the solvent evaporated at 40 ° C in a rotary evaporator. After adding 10 ml of acetone, the solution is stirred for 24 hours with 2.4 g of anhydrous potassium phosphate K 3 PO4. L 1 evaporation of the acetone provides the salt K + {(CH3) 2N)} 2PO (CF3Sθ2) C "} in the form of colorless microcrystals.
Les exemples 9 à 12 illustrent le procédé de 1'inven- tion dans lequel un sel de bis(fluorosulfonyl)méthane réagit avec un halogénure préparé in situ.Examples 9 to 12 illustrate the process of the invention in which a bis (fluorosulfonyl) methane salt reacts with a halide prepared in situ.
EXEMPLE 9 18,8 g de trifluorométhanesulfonate de potassium sont dissous dans 150ml d'acétonitrile et la solution est refroidie à 0°C. 12,8 g de chlorure de (chlorométhylène)- diméthylammonium [(CH3)2N=CHC1]+,C1" sont additionnés et un précipité de chlorure de potassium se forme. On ajoute 31,8 g du sel de potassium du bis(trifluorométhanesulfonyle)- méthane et 8,5 ml de N-méthylimidazole. Le mélange est agité à 0°C pendant lh, puis 4h à température ordinaire. Après filtration, le solvant est évaporé et le résidu solide est dissous dans 100 ml d'eau additionnés de 20 g de chlorure de césium. Le précipité formé Cs(CF3Sθ2)3C est séparé et séché. L'acide H(CF3S02)3C est obtenu en distillant sous pression réduite le sel de césium ayec un excès d'acide sulfurique anhydre. Un traitement de l'acide H(CF3S02)3C par les hydroxyde ou les carbonates de M permet de préparer les sels M(CF3S02)3C.EXAMPLE 9 18.8 g of potassium trifluoromethanesulfonate are dissolved in 150 ml of acetonitrile and the solution is cooled to 0 ° C. 12.8 g of (chloromethylene) dimethylammonium chloride [(CH3) 2N = CHC1] + , C1 "are added and a precipitate of potassium chloride is formed. 31.8 g of the potassium salt of bis (trifluoromethanesulfonyl) are added ) - methane and 8.5 ml of N-methylimidazole. The mixture is stirred at 0 ° C. for 1 h, then 4 h at ordinary temperature. After filtration, the solvent is evaporated and the solid residue is dissolved in 100 ml of water supplemented with 20 g of cesium chloride. The precipitate formed Cs (CF3Sθ2) 3C is separated and dried. The acid H (CF3SO2) 3C is obtained by distilling under reduced pressure the cesium salt with an excess of anhydrous sulfuric acid. Treatment of the acid H (CF 3 S0 2 ) 3 C with the hydroxides or carbonates of M makes it possible to prepare the salts M (CF 3 SO 2 ) 3 C.
EXEMPLE 10 Un oligomère sulfoné de poly (oxyde d'éthylène) PEO est préparé par une procédure similaire à celle décrite par T. Hamaide, C. Carré & A. Guyot (Proceedings of the Second International Symposium on Polymer Electrolytes, B. Scrosati éd. Elsevier Applied Science London 1990 page 175) : 10 g de POE de masse 600 sont séchés par distilla¬ tion azeotropique avec du benzène et lyophilisation. Après addition de 50 ml de THF, les groupements OH terminaux sont métallés par le potassium-naphtalène. La stoechiométrie est déterminée par colorimétrie, la fin de la réaction étant indiquée par la persistance de la couleur verte intense du radical anion du naphtalène. On ajoute alors 4,10 g de propanesultone. Après évaporâtion du solvant, le polymère α,ω disulfoné est obtenu sous forme de poudre, et le naphtalène résiduel est éliminé par lavage à l'hexane. 5 g du produit ainsi formé, mis en suspension dans 15 ml d'acétonitrile, sont traités par 1,8 g de chlorure de (chlorométhylène)diméthylammonium [ (CH3)2N=CHC1]+,Cl". Un précipité de chlorure de potassium se forme après environ 1 h. A cette suspension sont ajoutés 4,4 g du sel de potas¬ sium du bis(trifluorométhanesulfonyle)méthane et 3 ml de pyridine anhydre. Après filtration, le mélange réactionnel est agité en présence de 2 g de phosphate le lithium Li3P0 . Une nouvelle filtration permet de séparer une solu¬ tion incolore qui, par concentration, donne un fluide visqueux. Ce matériau permet de plastifier un grand nombre de polymères contenant des unités polaires (éther, amide, nitrile, ester...) , tout en leur conférant une conductivité ionique élevée.EXAMPLE 10 A sulfonated oligomer of poly (ethylene oxide) PEO is prepared by a procedure similar to that described by T. Hamaide, C. Carré & A. Guyot (Proceedings of the Second International Symposium on Polymer Electrolytes, B. Scrosati ed. Elsevier Applied Science London 1990 page 175): 10 g of POE with a mass of 600 are dried by azeotropic distillation with benzene and lyophilization. After adding 50 ml of THF, the terminal OH groups are metallized with potassium-naphthalene. The stoichiometry is determined by colorimetry, the end of the reaction being indicated by the persistence of the intense green color of the anion radical of naphthalene. 4.10 g of propanesultone are then added. After evaporating the solvent, the disulfonated α, ω polymer is obtained in the form of a powder, and the residual naphthalene is removed by washing with hexane. 5 g of the product thus formed, suspended in 15 ml of acetonitrile, are treated with 1.8 g of (chloromethylene) dimethylammonium chloride [(CH 3 ) 2 N = CHC1] + , Cl ". A chloride precipitate of potassium is formed after approximately 1 hour To this suspension are added 4.4 g of the potassium salt of bis (trifluoromethanesulfonyl) methane and 3 ml of anhydrous pyridine. After filtration, the reaction mixture is stirred in the presence of 2 g of phosphate lithium Li3P0. A new filtration makes it possible to separate a colorless solution which, by concentration, gives a viscous fluid. This material makes it possible to plasticize a large number of polymers containing polar units (ether, amide, nitrile, ester ...), while giving them a high ionic conductivity.
EXEMPLE 11 Un tensio-actif non-ionique de type BRU® 35, le polyoxyéthylène-23 lauryl éther Ci2H25(OCH2CH2)23θH est sulfoné par une procédure similaire à celle décrite dans l'exemple 10 : 12 g de BRU 35® sont séchés par distilla¬ tion azeotropique "avec du benzène et lyophilisation. Après additon de 50ml de THF, les groupements OH terminaux sont métallés par l'hydrure de sodium en présence de 5 mg de triphénylméthane. La stoechiométrie est déterminée par colorimétrie, la fin de la réaction étant indiquée par la persistance de la couleur rouge intense de 1'anion Φ3C". On ajoute alors 1,4 g de 1,4-butane sultone. Après évapo- ration du solvant, 1Oligomère sulfoné est obtenu sous forme de poudre. 5 g du produit ainsi formé en suspension dans 15 ml d'acétonitrile sont traités par 1 ml de chlo¬ rure de thionyle et 20 μl de diméthylformamide. Un préci¬ pité de chlorure de sodium se forme en 20 min. Après filtration, le solvant et l'excès de SOCI2 sont évaporés sous pression réduite. Le résidu est dissous dans 30 ml de pyridine et ajouté à 1,2 g du sel de sodium du bis(trifluorométhanesulfonyle)méthane. Après filtration, le mélange réactionnel est agité en présence de lg de phosphate le lithium Li3P04. Une nouvelle filtration permet de séparer une solution incolore qui, par concentration, donne une cire. Ce matériau possède des propriétés tensio- actives et plastifiantes.EXAMPLE 11 A non-ionic surfactant type BRU 35 ®, polyoxyethylene 23 lauryl ether Ci2H2 5 (OCH2CH2) 3 February θH is sulfonated by a similar procedure to that described in Example 10: 12 g of BRU 35 ® were dried by azeotropic distilla¬ tion "with benzene and lyophilization. After additon of 50 ml of THF, the terminal OH groups are metallized with sodium hydride in the presence of 5 mg of triphenylmethane. the stoichiometry is determined by colorimetry, the end of the reaction being indicated by the persistence of the intense red color of the Φ 3 C "anion. 1.4 g of 1,4-butane sultone are then added. After evaporation of the solvent, the sulfonated oligomer is obtained in the form of a powder. 5 g of the product thus formed in suspension in 15 ml of acetonitrile are treated with 1 ml of thionyl chloride and 20 μl of dimethylformamide. A precipitate of sodium chloride is formed in 20 min. After filtration, the solvent and excess SOCI2 are evaporated under reduced pressure. The residue is dissolved in 30 ml of pyridine and added to 1.2 g of the sodium salt of bis (trifluoromethanesulfonyl) methane. After filtration, the reaction mixture is stirred in the presence of 1 g of lithium Li 3 P0 4 phosphate. A new filtration makes it possible to separate a colorless solution which, by concentration, gives a wax. This material has surfactant and plasticizing properties.
EXEMPLE 12 380 mg de l'acide éthylènebis(oxyéthylènenitrilo)- tétraacétique dans 10 ml de pyridine sont traités par 350 μl de chlorure de thionyle à température ordinaire pendant 24 h. L'excès de SOCI2 et la pyridine sont évaporés et on ajoute 1,208 g du sel de sodium du bis(trifluorométhanesulfonyle)méthane dans 15 ml d'un mélange équivolumique de pyridine et d'acétonitrile. Le précipité de NaCl est éliminé et la solution est agitée avec 1 g de carbonate de potassium K2CO3 anhydre. Après filtration la solution est évaporée et fournit des cristaux incolores de :EXAMPLE 12 380 mg of ethylenebis (oxyethylenenitrilo) - tetraacetic acid in 10 ml of pyridine are treated with 350 μl of thionyl chloride at ordinary temperature for 24 h. The excess SOCI 2 and the pyridine are evaporated and 1.208 g of the sodium salt of bis (trifluoromethanesulfonyl) methane is added in 15 ml of an equivolumic mixture of pyridine and acetonitrile. The NaCl precipitate is removed and the solution is stirred with 1 g of anhydrous potassium carbonate K2CO3. After filtration the solution is evaporated and provides colorless crystals of:
Ce composé est un ligand (L) des métaux divalents (A11) et trivalentsfA111) . Les complexes correspondants [AIIL]2"M+ et [AIIIL]"M+ sont des sels solubles dans les milieux aproti- ques polaires et dans les polymères polaires, en particulier les polyéthers. Ces complexes dans lesquels le métal central A est protégé des influences électro- statiques extérieures sont intéressants pour la constitu¬ tion de lasers. Il permettent de plus des réactions rédox par changement du degré d'oxydation du métal A.This compound is a ligand (L) of divalent metals (A 11 ) and trivalents (A 111 ). The corresponding complexes [A II L] 2 "M + and [A III L]" M + are salts which are soluble in polar aprotic media and in polar polymers, in particular polyethers. These complexes in which the central metal A is protected from external electrostatic influences are advantageous for the constitution of lasers. They also allow redox reactions by changing the degree of oxidation of metal A.
Les exemples 13 à 23 illustrent le procédé de l'inven¬ tion dans lequel un sel de bis(fluorosulfonyl) éthane réagit avec un pseudo-halogène préparé in situ.Examples 13 to 23 illustrate the process of the invention in which a bis (fluorosulfonyl) ethane salt reacts with a pseudo-halogen prepared in situ.
EXEMPLE 13 A 400 mg d'acide laurique C11H23COOH dans 5 ml de THF et 1ml de pyridine anhydre sont ajoutés à 636 mg du sel de potassium du bis(trifluorométhanesulfonyle)méthane et 500 mg de 2-éthoxy-l-éthoxycarbonyl-l,2-dihydroquinoline (EEDQ) . Le mélange est agité pendant 48 heures et le solvant est évaporé. Le résidu est traité sous vide primaire à 110°C pendant 20 heures. On obtient le sel [CnH23CO(CF3Sθ2) 2C]~K+ qui possède des propriétés tensio- actives marquées, y compris dans les solvants et polymères solvatants aprotiques. EXEMPLE 14 548 g d'acide l,l'-ferrocène-dicarboxylique et 1,14 g du sel de lithium du bis(trifluorométhanesulfonyle)méthane sont dissous dans 5 ml de pyridine. On ajoute 824 mg de dicyclohexylcarbodii ide. Le mélange est maintenu sous agitation magnétique à température ambiante pendant 75 h. Le précipité de dicyclohexylurée est éliminé par centrifu- gation et la solution est évaporée. On obtient un solide brun foncé hygroscopique de [Li(CF3Sθ2)2CCOCsH4]Fe qui est soluble dans la plupart des solvants polaires donneurs.EXAMPLE 13 To 400 mg of lauric acid C11H23COOH in 5 ml of THF and 1 ml of anhydrous pyridine are added to 636 mg of the potassium salt of bis (trifluoromethanesulfonyl) methane and 500 mg of 2-ethoxy-1-ethoxycarbonyl-1,2 -dihydroquinoline (EEDQ). The mixture is stirred for 48 hours and the solvent is evaporated. The residue is treated under primary vacuum at 110 ° C for 20 hours. The salt [CnH23CO (CF3Sθ2) 2C] ~ K + is obtained, which has marked surfactant properties, including in solvents and aprotic solvating polymers. EXAMPLE 14 548 g of acid 1, 1'-ferrocene-dicarboxylic acid and 1.14 g of the lithium salt of bis (trifluoromethanesulfonyl) methane are dissolved in 5 ml of pyridine. 824 mg of dicyclohexylcarbodii ide are added. The mixture is kept under magnetic stirring at room temperature for 75 h. The precipitate of dicyclohexylurea is removed by centrifugation and the solution is evaporated. A hygroscopic dark brown solid of [Li (CF3Sθ2) 2CCOCsH4] Fe is obtained which is soluble in most polar donor solvents.
EXEMPLE 15 324 g de d'acide 6-hydroxy-2,5,7,8-tétraméthyl- chroman2-carboxylique(Trolox®) :EXAMPLE 15 324 g of 6-hydroxy-2,5,7,8-tetramethyl- chroman2-carboxylic acid (Trolox ®):
sont mis en suspension dans 10 ml d'acétate d'éthyle et lml de pyridine. A ce mélange sont ajoutés 836 mg du sel de potassium du bis(pentafluoroéthanesulfonyle)méthane et are suspended in 10 ml of ethyl acetate and 1 ml of pyridine. To this mixture are added 836 mg of the potassium salt of bis (pentafluoroethanesulfonyl) methane and
313 μl de 1,3 diisopropylcarbodiimide. Après 24 h, le précipité de diisopropylurée est filtré et le volume de la solution est réduit à 2ml à l'aide d'un évaporateur rotatif. On ajoute 20 ml d'hexane et le mélange est refroidi à -10βC. Le précipité blanc est collecté par filtration. L'analyse correspond à C19H17F10KO7S2. Ce produit possède des propriétés anti-oxidantes, en particu- lier pour les polymères. Il en est de même pour les dérivés d'autres cations, y compris de cations organiques tels que les tétraalkylammonium.313 μl of 1.3 diisopropylcarbodiimide. After 24 h, the precipitate of diisopropylurea is filtered and the volume of the solution is reduced to 2 ml using a rotary evaporator. 20 ml of hexane and the mixture is cooled to -10 β C. The white precipitate is collected by filtration. The analysis corresponds to C19H1 7 F1 0 KO7S2. This product has antioxidant properties, especially for polymers. The same is true for derivatives of other cations, including organic cations such as tetraalkylammonium.
EXEMPLE 16 2,8 g d'acide 4,4'-azobis(4-cyanovalérique) sont mis en suspension dans 20 ml de formiate de méthyle et 5 ml de pyridine. On ajoute 5,72 g du sel de lithium du bis(trifluorométhanesulfonyle)méthane et 4,16 g de di¬ cyclohexylcarbodiimide. Le mélange est maintenu sous agi- tation magnétique à 0°C pendant 48h. Le précipité de di- cyclohexylurée est éliminé par centrifugation et la solu¬ tion est évaporée à température ordinaire. On obtient un solide cristallin blanc de :EXAMPLE 16 2.8 g of 4,4'-azobis (4-cyanovaleric) acid are suspended in 20 ml of methyl formate and 5 ml of pyridine. 5.72 g of the lithium salt of bis (trifluoromethanesulfonyl) methane and 4.16 g of di¬ cyclohexylcarbodiimide are added. The mixture is kept under agitation. magnetic tation at 0 ° C for 48 hours. The precipitate of di-cyclohexylurea is removed by centrifugation and the solution is evaporated at room temperature. A white crystalline solid is obtained from:
[Li(CF3S02)2CC0CH2CH2(CN) (CH)3CN=] qui est soluble en particulier dans l'éther, l'acétone, 1 'acétonitrile, l'acétate d'éthyle. Ce sel peut servir d'initiateur radi- calaire pour amorcer des réactions de polymérisation ou de réticulation dès 60°C.[Li (CF3S02) 2CC0CH2CH2 (CN) (CH) 3CN =] which is soluble in particular in ether, acetone, acetonitrile, ethyl acetate. This salt can be used as a radical initiator to initiate polymerization or crosslinking reactions from 60 ° C.
EXEMPLE 17 A 258 mg d'acide vinylacétique dans 10 ml de 1,2-dimé- thoxyethane (glyme) sont ajoutés 858 mg du sel de lithium du bis(trifluorométhanesulfonyle)méthane, 618 mg de di¬ cyclohexyl carbodiimide et 10 mg de 1,8-diaza- bicyclo[5,4, 0]undec-7-ène (DBU) . Le mélange est maintenu sous agitation magnétique à 0°C pendant 48 h. Le précipité de dicyclohexylurée est éliminé par centrifugation et le sel obtenu par évaporation du solvant sous pression réduite.EXAMPLE 17 To 858 mg of vinylacetic acid in 10 ml of 1,2-dimethoxyethane (glyme) are added 858 mg of the lithium salt of bis (trifluoromethanesulfonyl) methane, 618 mg of di¬ cyclohexyl carbodiimide and 10 mg of 1 , 8-diaza-bicyclo [5,4, 0] undec-7-ene (DBU). The mixture is kept under magnetic stirring at 0 ° C for 48 h. The precipitate of dicyclohexylurea is removed by centrifugation and the salt obtained by evaporation of the solvent under reduced pressure.
EXEMPLE 18EXAMPLE 18
76 g de carboxypropyl disulfure [-S (CH2) 3COOHJ2 sont dissous dans 100ml de pyridine avec 12,08 g du sel de sodium du bis(trifluorométhanesulfonyle)méthane et 8,24 g de dicyclohexyl carbodiimide. Après 48 h sous agitation, le mélange est filtré est évaporé. Le solide résiduel est dissous dans 50 ml d'eau et 12 g de bromure de tétrapropyl- ammonium sont ajoutés. Le précipité est filtré et séché76 g of carboxypropyl disulfide [-S (CH2) 3COOHJ2 are dissolved in 100 ml of pyridine with 12.08 g of the sodium salt of bis (trifluoromethanesulfonyl) methane and 8.24 g of dicyclohexyl carbodiimide. After 48 h with stirring, the mixture is filtered and evaporated. The residual solid is dissolved in 50 ml of water and 12 g of tetrapropylammonium bromide are added. The precipitate is filtered and dried
(20 g). EXEMPLE 19 479 mg de Rhodamine B sont mis en suspension dans 10 ml de pyridine et on ajoute 802 mg de sel de potassium du bis(tridécafluorohexylsulfonyle)méthane et 206 mg de dicyclohexyl carbodiimide. Après 48 h sous agitation, le mélange est filtré pour éliminer la dicyclohexylurée et évaporé. Le z itterion obtenu :(20 g). EXAMPLE 19 479 mg of Rhodamine B are suspended in 10 ml of pyridine and 802 mg of potassium salt of bis (tridecafluorohexylsulfonyl) methane and 206 mg of dicyclohexyl carbodiimide are added. After 48 h with stirring, the mixture is filtered to remove the dicyclohexylurea and evaporated. The z itterion obtained:
possède des propriétés colorantes intenses. Il est soluble dans les polymères polaires et permet la constitution de lasers à colorants. EXEMPLE 20has intense coloring properties. It is soluble in polar polymers and allows the creation of dye lasers. EXAMPLE 20
L'acide pyrryl-3 acétique (M = 122) est préparé selon la méthode de D. Delabouglise (Thèse Université de Paris- Nord, février 1991, "Contrôle Moléculaire des propriétés des polymères") . 488 mg de ce composé sont dissous dans un mélange de 5 ml d'acétonitrile et 1 ml de pyridine. A la solution homogène on ajoute 1,272 g du sel de potassium du bis(trifluorométhanesulfonyle)méthane et 1,1 g. de di- cyclohéxylecarbodiimide. Le mélange est agité pendant 48 h à température ordinaire, puis le précipité de dicyclo- hexylurée est éliminé par centrifugation. Le solvant est évaporé et le sel est purifié par recristallisation dans le mélange butanone -1,2 dichloroéthane.The pyrryl-3 acetic acid (M = 122) is prepared according to the method of D. Delabouglise (Thesis University of Paris-Nord, February 1991, "Molecular Control of the Properties of Polymers"). 488 mg of this compound are dissolved in a mixture of 5 ml of acetonitrile and 1 ml of pyridine. To the homogeneous solution is added 1.272 g of the potassium salt of bis (trifluoromethanesulfonyl) methane and 1.1 g. of di-cyclohexylecarbodiimide. The mixture is stirred for 48 h at ordinary temperature, then the precipitate of dicyclohexylurea is removed by centrifugation. The solvent is evaporated off and the salt is purified by recrystallization from a butanone -1.2 dichloroethane mixture.
On prépare 10 ml d'une solution 5.10"2 M du sel dans 1'acétonitrile et 1 'on effectue une électropolymérisation dans le compartiment anodique d'une cellule électrochimi¬ que sur électrode de platine. On obtient un film souple conducteur de : 10 ml of a 5.10 " 2 M solution of salt in acetonitrile are prepared and electropolymerization is carried out in the anode compartment of an electrochemical cell on a platinum electrode. A flexible conductive film is obtained:
dont le dopage (oxydation) est assuré par échange de cations et d'électrons avec l'extérieur. La conductivité de ce matériau est de l'ordre de 10 (Ωcm) _1 et est stable à l'atmosphère ambiante. L1électropolymérisation effectuée en présence de pyrrole non substitué ou possédant des chaînons oxyéthylène en position N ou 3 donne des copolymères égale¬ ment stables dont le changement de couleur peut-être utili¬ sé pour la constitution de systèmes électrochromes. EXEMPLE 21whose doping (oxidation) is ensured by exchange of cations and electrons with the outside. The conductivity of this material is of the order of 10 (Ωcm) _1 and is stable at ambient atmosphere. L 1 electropolymerization carried out in the presence of unsubstituted pyrrole or having oxyethylene links in position N or 3 gives copolymers also stable, the color change of which may be used for the formation of electrochromic systems. EXAMPLE 21
137 mg d'acide p-aminobenzoïque (PABA) sont traités par 250 μl de dicarbonate de di-tert-butyle dans la pyri¬ dine. Le solvant est évaporé et le résidu de t-BOC-PABA est mis en suspension dans 4 ml d'acétonitrile et 1 ml de pyri- dine. On ajoute à cette suspension 302 mg du sel de sodium du bis(trifluorométhanesulfonyle)méthane et 165 mg de 1,1'- carbonyle-diimidazole. Le mélange est agité pendant 48 h et l'excès de réactif est éliminé par 10 μl d'eau. Le solvant est éliminé à l'aide d'un évaporateur rotatif. Le groupement protecteur t-BOC est éliminé par addition de 5 ml d'une solution 0,2 M de HBr dans le dioxane. La suspension résultante est filtrée et le zwitterion :137 mg of p-aminobenzoic acid (PABA) are treated with 250 μl of di-tert-butyl dicarbonate in pyri¬ dine. The solvent is evaporated off and the residue of t-BOC-PABA is suspended in 4 ml of acetonitrile and 1 ml of pyridine. 302 mg of the sodium salt of bis (trifluoromethanesulfonyl) methane and 165 mg of 1,1'-carbonyl-diimidazole are added to this suspension. The mixture is stirred for 48 h and the excess reagent is removed with 10 μl of water. The solvent is removed using a rotary evaporator. The protective group t-BOC is removed by adding 5 ml of a 0.2 M solution of HBr in dioxane. The resulting suspension is filtered and the zwitterion:
est purifié par recristallisation dans l'eau. Ce composé forme des complexes avec les polyéthers : un réseau est formé par polycondensation de polyoxyéthylène triol de masse 2700 et de disocyanate d'hexaméthylene. La réticula-^ tion est effectuée par mélange des réactifs en solution à 50% dans le dichlorométhane avec un catalyseur de dilaurate de dibutylétain. la solution homogène est pressée entre deux plaques de verre planes maintenues distantes de 300 μm par des cales. La polycondensatipn est complète à tempéra¬ ture ordinaire en 72 h. Le film résultant est purifié par extraction dans un appareil de type Soxhlet avec de l'acétone. Le complexe polymère-zwitterion est ensuite formé par imprégnation d'un disque (φ= 1 cm) du polymère par 80 mg du sel' en solution dans 1*acétonitrile. Ce complexe possède un effet Kerr important du à 1'orientation des molécules du zwitterion sous l'action d'un champ élec¬ trique.is purified by recrystallization from water. This compound forms complexes with polyethers: a network is formed by polycondensation of polyoxyethylene triol of mass 2700 and hexamethylene disocyanate. Crosslinking is carried out by mixing the reagents in 50% solution in dichloromethane with a dilaurate catalyst. dibutyltin. the homogeneous solution is pressed between two flat glass plates kept 300 μm apart by wedges. The polycondensatipn is complete at ordinary temperature in 72 h. The resulting film is purified by extraction in a Soxhlet type apparatus with acetone. The polymer-zwitterion complex is then formed by impregnating a disc (φ = 1 cm) of the polymer with 80 mg of the salt ' in solution in 1 * acetonitrile. This complex has a significant Kerr effect due to the orientation of the molecules of the zwitterion under the action of an electric field.
EXEMPLE 22 Le sel de potassium du bis(pentafluorobenzène-sulfo- nyle) éthane a été préparé par action du chlorure de penta- fluorobenzènesulfonyle sur le carbure d'aluminium en présence de fluorure de potassium anhydre dans l'acéto¬ nitrile. A 212 mg d'acide pentafluorobenzoxque en suspen¬ sion dans le THF sont ajoutés 260 mg de carbonate de N,N'- disuccinimidyle [(SCO)2CO] et 1 ml de pyridine. Après la fin de la réaction suivie par le dégagement de dioxyde de carbone, on obtient une solution homogène. A cette solution de l'ester activé sont ajoutés 515 mg de sel de potassium du bis(pentafluorobenzènesulfonyle)méthane. Après réaction (totale en 1 h à 27°C), le solvant est évaporé et le sel K+tC6F5Sθ2)2CCOCgF5]~, insoluble dans l'eau, est séparé par lavage de l'hydroxy-succinimide formé au cours de la réaction. Le composé préparé peut être utilisé comme anion dopant de polymères conducteurs électroniques, de type polypyrrole ou polyaniline, auxquels il confère une stabilité vis à vis de l'action de l'eau et de l'oxygène. Par ailleurs, ce sel réagit sur les composés nucléophiles par substitution des atomes de fluor en position para du groupement sulfonyle. En particulier, par action de polyamines contenant au moins 2 groupements azotés, il est possible de préparer des polymères présentant des fonctions d'échange ionique, utilisables par exemple pour la consti¬ tution de membranes de piles à combustibles. Les exemples 23 à 30 illustrent des applications de divers composés de l'invention.EXAMPLE 22 The potassium salt of bis (pentafluorobenzene-sulfonyl) ethane was prepared by the action of pentafluorobenzenesulfonyl chloride on aluminum carbide in the presence of anhydrous potassium fluoride in acetonitrile. To 212 mg of pentafluorobenzoxque acid suspended in THF are added 260 mg of N, N'-disuccinimidyl carbonate [(SCO) 2CO] and 1 ml of pyridine. After the end of the reaction followed by the evolution of carbon dioxide, a homogeneous solution is obtained. To this solution of the activated ester are added 515 mg of potassium salt of bis (pentafluorobenzenesulfonyl) methane. After reaction (total in 1 h at 27 ° C), the solvent is evaporated and the salt K + tC 6 F 5 Sθ2) 2CCOCgF5] ~, insoluble in water, is separated by washing the hydroxy-succinimide formed in during the reaction. The compound prepared can be used as a doping anion of electronic conductive polymers, of the polypyrrole or polyaniline type, to which it confers stability with respect to the action of water and oxygen. Furthermore, this salt reacts on nucleophilic compounds by substitution of the fluorine atoms in the para position of the sulfonyl group. In particular, by the action of polyamines containing at least 2 nitrogen groups, it is possible to prepare polymers having ion exchange functions, usable for example for the constitution of membranes of fuel cells. Examples 23 to 30 illustrate applications of various compounds of the invention.
EXEMPLE 23 6,6 g d'un copolymère d'oxyde d'éthylène contenant des doubles liaisons >C=C< et ayant une masse Mw = 2,5.105 sont mis en solution dans l'acétonitrile. On y ajoute 1,77 g du sel de l'exemple 17 et 165 mg de l'initiateur radica,laire préparé selon l'exemple 16. La solution est évaporée dans une coupelle de PTFE à fond plat, et le récipient est mis dans un four sous vide primaire à 80°C pendant 12 h. On obtient un élastomère réticulé dans lequel le groupement - COC(Sθ2CF3) 2Li est fixé, provenant soit du monomère, soit de l'initiateur. Ce matériau possède une conduction par les ions lithium de 1,2.10~5 (Ωcm) _1 à 26°C. EXEMPLE 24EXAMPLE 23 6.6 g of an ethylene oxide copolymer containing double bonds> C = C <and having a mass M w = 2.5 × 10 5 are dissolved in acetonitrile. 1.77 g of the salt of example 17 and 165 mg of the radica initiator are added thereto, the milk prepared according to example 16. The solution is evaporated in a PTFE dish with a flat bottom, and the container is placed in a primary vacuum oven at 80 ° C for 12 h. A crosslinked elastomer is obtained in which the group - COC (Sθ2CF3) 2Li is fixed, originating either from the monomer or from the initiator. This material has a conduction by lithium ions of 1.2.10 ~ 5 (Ωcm) _1 at 26 ° C. EXAMPLE 24
531 mg du sel de l'exemple 17 sont dissous dans 5ml de THF auquel sont ajoutés : 1 ml de l 'éther diallylique du poly(éthylène glycol) 400, 5 mg d'acide chloroplatinique et 1,2 ml de triéthoxysilane. Le mélange est maintenu à 60°C jusqu'à disparition des bandes caractéristiques de la liaison Si-H à 2250 cm-1. Le mélange est filtré et le filtrat ajouté à 19,5 ml de méthanol et 500μl d'eau. Une plaque de verre décapée à 1 'acide nitrique puis séchée à 100°C est trempée dans la solution pendant 4 mn. Après rinçage au méthanol et séchage, la conductivité de surface est de 4.10"5 Ω(carré) .531 mg of the salt of example 17 are dissolved in 5 ml of THF to which are added: 1 ml of the diallyl ether of poly (ethylene glycol) 400, 5 mg of chloroplatinic acid and 1.2 ml of triethoxysilane. The mixture is maintained at 60 ° C. until the bands characteristic of the Si-H bond at 2250 cm −1 disappear. The mixture is filtered and the filtrate added to 19.5 ml of methanol and 500 μl of water. A glass plate pickled with nitric acid and then dried at 100 ° C. is soaked in the solution for 4 min. After rinsing with methanol and drying, the surface conductivity is 4.10 "5 Ω (square).
EXEMPLE 25EXAMPLE 25
100 g d'un copolymère acrylonitrile (30%) -butadiène100 g of an acrylonitrile (30%) -butadiene copolymer
(70%) et 8 g de sel de l'exemple 18 sont dissous dans l'acétone et le solvant est évaporé. La masse gommeuse est chauffée à 150"C dans un moule métallique pendant 20 mn.(70%) and 8 g of salt from Example 18 are dissolved in acetone and the solvent is evaporated. The gummy mass is heated to 150 ° C. in a metal mold for 20 min.
Après refroidissement et démoulage, on obtient un polymère réticulé de bonne tenue mécanique et possédant de bonnes propriétés antistatiques, exprimées par une conductivité de 10"^ (Ωcm) _1 à température ordinaire.After cooling and demolding, a crosslinked polymer is obtained with good mechanical strength and having good antistatic properties, expressed by a conductivity of 10 "^ (Ωcm) _1 at ordinary temperature.
EXEMPLE 26 1 g du sel de l'exemple 10 et 1,4 g de poly(oxyde d'éthylène) de masse Mw 5.106 sont dissous par agitation magnétique dans 100ml de formiate de méthyle. La solution visqueuse est épandue sur une plaque de PTFE. Par évapora- tion du solvant, on obtient un film élastique ayant une épaisseur de 120 μm et une conductivité ionique de 9.10"5(Ωcm"1) à 300 K.EXAMPLE 26 1 g of the salt of Example 10 and 1.4 g of poly (ethylene oxide) of mass M w 5.10 6 are dissolved by stirring magnetic in 100ml of methyl formate. The viscous solution is spread on a PTFE plate. By evaporation of the solvent, an elastic film is obtained having a thickness of 120 μm and an ionic conductivity of 9.10 " 5 (Ωcm" 1 ) at 300 K.
EXEMPLE 27 Un générateur électrochimique est constitué d'une électrode négative de lithium de 45μm d'épaisseur déposée sur une feuille de polypropylène de 8 μm, métallisé par 100 n de nickel. L•électrolyte est préparé à partir du complexe du polyéthylène glycol 400-co-oxyméthylène de masse Mw ≡ 105 daltons préparés selon la méthode décrite dans : C.V. Nicholas, D.J. Wilson, C. Booth & R.J.M. Giles Brit. Polym. J. 20. 289 (1988) , et du sel de lithium de la trifluorométhanesulfonimide Li[CF3Sθ2)2N] . La concentration du sel est calculée pour correspondre à un cation lithium pour 25 atomes d'oxygène du polyéther, et le matériau est préparé sous forme de film de 75 μm d'épaisseur. L'élec¬ trode positive est un matériau composite contenant 45% en volume de manganite de lithium de structure spinelle iMn2θ4, broyé en grain de =8 μm, 5% v/v de noir d'acéty¬ lène et 50% v/v d'un conducteur ionique. Ce dernier maté¬ riau est ormé à partir du polyéther constituant 1'élec¬ trolyte et mélangé à 35% en poids du sel de l'exemple 11. Les propriétés tensioactives du sel sont mises à profit pour obtenir une dispersion homogène des constituants de l'électrode positive dans l'acétonitrile, permettant, par une technique d'epandage, d'obtenir des films de 80 μm d'épaisseur sur un collecteur de courant similaire à celui de l'électrode négative. Le dispositif est obtenu par laminage des composants pour obtenir un générateur souple de 210 mm d'épaisseur, La f.e.m. est de 3V, le débit de 500 mA/cm2 à 30°C pour une tension de 2,8 V. Ce système est rechargeable. EXEMPLE 28EXAMPLE 27 An electrochemical generator consists of a negative lithium electrode 45 μm thick deposited on a polypropylene sheet 8 μm, metallized with 100 n of nickel. The electrolyte is prepared from the complex of polyethylene glycol 400-co-oxymethylene of mass Mw ≡ 10 5 daltons prepared according to the method described in: CV Nicholas, DJ Wilson, C. Booth & RJM Giles Brit. Polym. J. 20 . 289 (1988), and the lithium salt of trifluoromethanesulfonimide Li [CF3Sθ2) 2N]. The salt concentration is calculated to correspond to a lithium cation for 25 oxygen atoms of the polyether, and the material is prepared in the form of a film 75 μm thick. The positive electrode is a composite material containing 45% by volume of lithium manganite with a spinel structure iMn2θ4, ground into a grain of = 8 μm, 5% v / v of acetylene black and 50% v / v of an ionic conductor. This latter material is formed from the polyether constituting the electrolyte and mixed with 35% by weight of the salt of Example 11. The surfactant properties of the salt are used to obtain a homogeneous dispersion of the constituents of the salt. positive electrode in acetonitrile, allowing, by a spreading technique, to obtain films of 80 μm thickness on a current collector similar to that of the negative electrode. The device is obtained by rolling the components to obtain a flexible generator 210 mm thick, The fem is 3V, the flow rate of 500 mA / cm 2 at 30 ° C for a voltage of 2.8 V. This system is rechargeable. EXAMPLE 28
Un générateur secondaire au lithium est préparé d'une manière similaire à l'exemple 27, mais en remplaçant 10% molaire du sel Li[CF3Sθ )2N3 de 1'électrolyte le sel de l'exemple 14 : Li2{Fe[C5H4CO(CF3Sθ2) 2]2) , de manière à con¬ server le même rapport O/Li. Ce générateur possède alors une protection à la surcharge : pour un potentiel exté¬ rieur appliqué supérieur à 3,8 V, le noyau ferrocène du sel est oxydé en ferriciniu . L'espèce correspondante migre jusqu'à l'électrode négative ou elle redonne le composé initial. Ce mécanisme se traduit par un courant de fuite du générateur au delà du potentiel seuil de 3,8 V, évitant une dégradation du système et ayant 1 'avantage de ne pas induire d'auto-décharge du générateur en circuit ouvert. Ce dispositif est particulièrement avantageux pour les générateurs constitués de cellules élémentaires connectées en série et dont les capacités ne sont pas exactement identiques. EXEMPLE 29A secondary lithium generator is prepared in a similar manner to Example 27, but by replacing 10 mol% of the salt Li [CF3Sθ) 2 N 3 of the electrolyte the salt of Example 14: Li2 {Fe [C5H4CO (CF3Sθ2) 2] 2), so as to keep the same O / Li ratio. This generator then has overload protection: for an applied external potential greater than 3.8 V, the ferrocene core of the salt is oxidized to ferriciniu. The corresponding species migrates to the negative electrode where it gives back the initial compound. This mechanism results in a generator leakage current beyond the threshold potential of 3.8 V, avoiding degradation of the system and having the advantage of not inducing self-discharge of the generator in open circuit. This device is particularly advantageous for generators made up of elementary cells connected in series and whose capacities are not exactly identical. EXAMPLE 29
390 mg du sel K[CH3θCH2COC(SO2CF3) 2] obtenu à l'exemple 7 sont dissous dans 5 ml d'acétonitrile séché et auquel sont ajoutés 15 mg de chlorure de magnésium anhydre. Le mélange est agité pendant 4 h et le précipité de chlorure de potassium est éliminé par centrifugation. A la solution surnageante sont ajoutés 800 mg de copolymère statistique oxyde d'éthylène (80%) - méthyl-glycidyl-éther (20%) de masse M ≡2,5.105. Par épandage et évaporation de la solution visqueuse, on obtient un film d'électrolyte polymère contenant le magnésium sous forme de complexe390 mg of salt K [CH3θCH2COC (SO2CF3) 2] obtained in Example 7 are dissolved in 5 ml of dried acetonitrile and to which are added 15 mg of anhydrous magnesium chloride. The mixture is stirred for 4 h and the precipitate of potassium chloride is removed by centrifugation. To the supernatant solution are added 800 mg of random copolymer of ethylene oxide (80%) - methyl-glycidyl-ether (20%) of mass M ≡2.5.10 5 . By spreading and evaporating the viscous solution, a film of polymer electrolyte containing magnesium is obtained in the form of a complex.
{Mg[CH3θCH2COC(Sθ2CF3)2]3}".{Mg [CH3θCH2COC (Sθ2CF3) 2] 3} " .
Un générateur primaire est constitué comme suit :A primary generator is made up as follows:
Mg électrolyte polymère à mécanisme composite : fluorure de véhiculaire anionique transportant graphite - électrolyte - noir les ions Mg d'acétylèneMg polymer electrolyte with composite mechanism: anionic vehicular fluoride carrying graphite - electrolyte - black Mg acetylene ions
L'électrolyte est celui décrit dans cet exemple. La composition de l'électrode positive correspond à 42% v/v du même électrolyte, 8% v/v de noir d'acétylène et 50% v/v de fluorure de graphite CFX (x ≡ 1) . Le matériau composite dilué dans l 'acétonitrile est épandu sur une feuille de polypropylène de 8 μm d'épaisseur métallisé par 200 nm de cuivre, de manière à former une couche d'environ 80 μm d'épaisseur. L'électrode négative est une feuille de 20 μm. La tension de la batterie après assemblage par laminage des éléments à 80°C est de 2,5 V et la capacité pour un débit de 400 μA/cm2 est de 7 mAh/cm2.The electrolyte is that described in this example. The composition of the positive electrode corresponds to 42% v / v of the same electrolyte, 8% v / v of acetylene black and 50% v / v of graphite fluoride CF X (x ≡ 1). The composite material diluted in acetonitrile is spread on a polypropylene sheet 8 μm thick metallized with 200 nm of copper, so as to form a layer of approximately 80 μm thick. The negative electrode is a 20 μm sheet. The battery voltage after assembly by rolling the elements at 80 ° C is 2.5 V and the capacity for a flow rate of 400 μA / cm 2 is 7 mAh / cm 2 .
EXEMPLE 30 426 mg du monomère de l'exemple 20 sont dissous dans 5 ml de THF desséché auxquels sont ajouté 42 mg de chlorure de lithium anhydre. Le précipité de KC1. est éliminé par centrifugation et les traces d'ions potassium restantes sont échangées par agitation avec 1 g de résine NAFION® sous forme Li+. Le sel de pyrrole substitué (C4H3NH)CH2C0C(CF3S02)2Lx est obtenu par évaporation du THF. A 200 mg de ce sel dans 1'acétonitrile sont ajoutés 5 g de penta-oxyde de vanadium V2O5 et la suspension est agitée pendant 48 heures. Un dépôt de polypyrrole se forme à la surface des grains de l'oxide, la réaction se tradui¬ sant par un changement de couleur de l'orange au noir- vert. Les particules sont séparées par filtration ; l'oxyde possède maintenant une conductivité électronique de surface induite par le dépôt de polymère conducteur. Un générateur électrochimique est construit d'une manière similaire à celle de l'exemple 27, en remplaçant LiMn2θ4 par un volume équivalent d'oxyde de vanadium traité. Le générateur ainsi constitué a une tension en circuit ouvert de 3,2 V et possède maintenant une sécurité évitant la sur- décharge : en dessous d'un potentiel de 2,7 V, le poly¬ pyrrole subit une réaction rédox amenant son dédopage et une diminution de sa conductivité de 5 ordres de grandeur. Les grains de V2O5 se trouvent alors isolés et perdent leur électroactivité. Dans une variante, le collecteur de courant de l'électrode positive du générateur de l'exemple 28 est recouvert d'un film de =1 μm de polypyrrole modifié, déposé par électropolymérisation à partir d'une solution aqueuse du sel de lithium. Le générateur ainsi assemblé possède aussi une sécurité contre la sur-décharge, une couche isolante de polypyrrole étant interposée entre le collecteur de courant et l'électrode positive pour un potentiel inférieur à 2,7 V. EXAMPLE 30 426 mg of the monomer of example 20 are dissolved in 5 ml of dried THF to which 42 mg of anhydrous lithium chloride are added. The precipitate of KC1. is removed by centrifugation and the remaining traces of potassium ion is exchanged by stirring with 1 g of NAFION ® resin in Li + form. The substituted pyrrole salt (C 4 H 3 NH) CH2C0C (CF 3 S02) 2 Lx is obtained by evaporation of THF. To 200 mg of this salt in acetonitrile are added 5 g of vanadium pentoxide V2O5 and the suspension is stirred for 48 hours. A deposit of polypyrrole forms on the surface of the oxide grains, the reaction resulting in a change in color from orange to black-green. The particles are separated by filtration; the oxide now has an electronic surface conductivity induced by the deposition of conductive polymer. An electrochemical generator is constructed in a similar manner to that of Example 27, by replacing LiMn2θ 4 by an equivalent volume of treated vanadium oxide. The generator thus formed has an open circuit voltage of 3.2 V and now has a safety device preventing over-discharge: below a potential of 2.7 V, the poly¬ pyrrole undergoes a redox reaction leading to its dedoping and a decrease in its conductivity by 5 orders of magnitude. The V2O5 grains are then isolated and lose their electroactivity. In a variant, the current collector of the positive electrode of the generator of Example 28 is covered with a film of = 1 μm of modified polypyrrole, deposited by electropolymerization from an aqueous solution of the lithium salt. The generator thus assembled also has a safety against over-discharge, an insulating layer of polypyrrole being interposed between the current collector and the positive electrode for a potential lower than 2.7 V.

Claims

REVENDICATIONS
1. Procédé de préparation d'un composé répondant à la formule (l/nM)+[ (RpS02)2C(Y) ]" dans laquelle Y représente un groupement attracteur d'électrons choisi parmi -C≡N et les groupements RZ- dans lesquels Z représente un groupe¬ ment carbonyle, un groupement sulfonyle ou un groupement phosphonyle et R représente un groupement organique mono¬ valent, M représente un métal ayant la valence n ou un groupe organique pouvant exister sous forme cationique, Rp représente un groupement perfluoroalkyle ou perfluoroaryle, caractérisé en ce qu'il comporte une étape au cours de laquelle on fait réagir un composé (1/nM')+[ (RpS02)2CH]" avec un composé YX en présence d'une base aprotique nucléo- phile Nu, M' représentant un métal ayant la valence n ou un groupe organique pouvant exister sous forme cationique et X représentant un halogène ou un pseudo-halogène lorsque Y est RZ, et X représentant un halogène lorsque Y est -CN.1. Process for the preparation of a compound corresponding to the formula (l / nM) + [(RpS0 2 ) 2 C (Y)] "in which Y represents an electron attractor group chosen from -C≡N and the groups RZ- in which Z represents a carbonyl group, a sulfonyl group or a phosphonyl group and R represents a mono¬ valent organic group, M represents a metal having the valence n or an organic group which may exist in cationic form, Rp represents a perfluoroalkyl or perfluoroaryl group, characterized in that it comprises a step during which a compound (1 / nM ') + [(RpS0 2 ) 2 CH] "is reacted with a compound YX in the presence of an aprotic base nucleophile Nu, M 'representing a metal having the valence n or an organic group which can exist in cationic form and X representing a halogen or a pseudo-halogen when Y is RZ, and X representing a halogen when Y is -CN.
2. Procédé selon la revendication 1, caractérisé en ce que le pseudo-halogène est choisi parmi RSO3-, RCO2-, les radicaux succinimidyloxy (SCO-) , phtalimidoxy (PTO-) , 1-benzotriazoloxy (BzO-) , oxynorbornène 2,3-dicarboximide, trifluoroéthoxy, trichloroéthoxy, imidazolyl, triazolyle, nitrophénoxy, dinitrophénoxy, perhalophénoxy, O-acylurées. 2. Method according to claim 1, characterized in that the pseudo-halogen is chosen from RSO 3 -, RCO2-, succinimidyloxy (SCO-), phthalimidoxy (PTO-), 1-benzotriazoloxy (BzO-), oxynorbornene 2 radicals , 3-dicarboximide, trifluoroethoxy, trichloroethoxy, imidazolyl, triazolyl, nitrophenoxy, dinitrophenoxy, perhalophenoxy, O-acylureas.
3. Procédé selon la revendication 1, caractérisé en ce que la base aprotique nucléophile Nu est choisie parmi les trialkylamines, les pyridineε, les imidazoles, les amidines et les guanidines.3. Method according to claim 1, characterized in that the nucleotic aprotic base Nu is chosen from trialkylamines, pyridineε, imidazoles, amidines and guanidines.
4. Procédé selon la revendication 3, caractérisé en ce que la base nucléophile est choisie parmi la triéthyl- amine, la di-isopropyléthyla ine, la quinuclidine et le 1,4 diazabicyclo[2,2,2]octane (TED) ; la pyridine, les alkyl- pyridines et les dialkyla inopyridines ; les N-alkylimida- zoles et 1'imidazo[1,2-a]pyridine ; le 1,5 diazabicyclo- [4,3,0]non-5-ène (DBN) et le 1,8 diazabicyclo[5,4,0]undec- 7-ène (DBU) ; la tétra méthyl guanidine et la 1,3,4,7,8 hexahydro-lméthyl-2H-pyrimido [1,2-a]pyrimidine (HPP) . 4. Method according to claim 3, characterized in that the nucleophilic base is chosen from triethylamine, di-isopropylethylamine, quinuclidine and 1,4 diazabicyclo [2,2,2] octane (TED); pyridine, alkyl pyridines and dialkyla inopyridines; N-alkylimidazoles and imidazo [1,2-a] pyridine; 1.5 diazabicyclo [4.3.0] non-5-ene (DBN) and 1.8 diazabicyclo [5.4.0] undec 7-ene (DBU); tetra methyl guanidine and 1,3,4,7,8 hexahydro-1-methyl-2H-pyrimido [1,2-a] pyrimidine (HPP).
5. Procédé selon la revendication 1, caractérisé en ce que la base nucléophile est fixée sur une trame macromo¬ léculaire.5. Method according to claim 1, characterized in that the nucleophilic base is fixed to a macromo¬ lecular frame.
6. Procédé selon la revendication 1, caractérisé en ce que le dérivé XY est un halogénure préparé in-situ à partir de l'acide RZOH ou du dérivé RZOM correspondant par action d'un agent halogénant.6. Method according to claim 1, characterized in that the derivative XY is a halide prepared in situ from the acid RZOH or the corresponding derivative RZOM by the action of a halogenating agent.
7. Procédé selon la revendication 6, caractérisé en ce que l'agent halogénant est choisi parmi SOCI2, SOBr2, SF4, (C2H5)2NSF3, COCl2, (C0C1)2, (COBr)2 (CC130)2C0, [(CH3)2N=CHC1]+C1~, le mélange triphénylphosphine (PΦ3)/CCl4, le dichlorométhyl-méthyl éther CI2HCOCH3, les sels de 2-chloro-l-méthylpyridinium ou de 2-fluoro-l- méthylpyridinium. 7. Method according to claim 6, characterized in that the halogenating agent is chosen from SOCI2, SOBr2, SF4, (C 2 H 5 ) 2NSF 3 , COCl 2 , (C0C1) 2, (COBr) 2 (CC1 3 0 ) 2C0, [(CH 3 ) 2N = CHC1] + C1 ~, the triphenylphosphine (PΦ 3 ) / CCl 4 mixture, dichloromethyl-methyl ether CI2HCOCH3, the salts of 2-chloro-1-methylpyridinium or 2-fluoro- l- methylpyridinium.
8. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que lorsque Z représente un carbonyle, le réactif RZX est l'anhydride RCO-O-COR.8. Method according to one of claims 1 or 2, characterized in that when Z represents a carbonyl, the reagent RZX is the anhydride RCO-O-COR.
9. Procédé selon la revendication 8, caractérisé en ce que l'anhydride RCO-O-COR est obtenu in-situ par réaction de l'acide RCOOH correspondant avec un agent de déshydratation moléculaire.9. Method according to claim 8, characterized in that the anhydride RCO-O-COR is obtained in situ by reaction of the corresponding RCOOH acid with a molecular dehydrating agent.
10. Procédé selon la revendication 9, caractérisé en ce que l'agent de déshydratation moléculaire est choisi parmi les carbodiimides, les éthers d'alkyl-éthynyle, les carbonates et les oxalates de succini idyle £(SCO)2CO),10. Method according to claim 9, characterized in that the molecular dehydrating agent is chosen from carbodiimides, alkyl ethynyl ethers, carbonates and oxinates of succinyl idyl (SCO) 2CO),
(SCO)2C2θ2) ], de phtalimidyle [(PTO)2CO), (PTO)2C2θ2) ] , de(SCO) 2C2θ2)], phthalimidyl [(PTO) 2CO), (PTO) 2C2θ2)],
1-benzotriazolyle [(BzO)2CO), (BzO)2C2O2) ] , les oxalates et les carbonates de nitro-, de dinitro- ou de perhalo- phénols, les carbonates et les oxalates de trifluoroéthyle [(CF3CH2θ)2CO) , (CF3CH2θ)2C2θ2] ou de trichloroéthyle [(CCl3CH2θ)2CO) , (CCI3CH2O)2C2O2], le mélange PΦ3-diéthyl- azodicarboxylate (DEAD) ou PΦ3~dithiodipyridine, le carbo- nyldiimidazole (Im)2CO, le phénylphosphoro-diimidazole ΦPO(Im)2 t les acétals d'amides, les 2-alcoxy-l-alcoxy- carbonyl-l,2-dihydroquinoline (EEDQ, IIDQ) , les sels de O- benzotriazol-lyl- N,N,N' ,N'tétraméthyluronium ou de O- benzotriazol-1-yloxytrisdiméthylaminophosphonium, les sultones aromatiques, le chloroformxate d'isobutyle, le diphénylphosphochloroiridate, le chlorophosphite d'éthy¬ lène, le pyrophosphite de diéthyléthylène, le chlorure de bis(2-oxo-3oxazolidinyl)phosphinyle, les sels de 2-ter- butyl-5-méthylixoaxazolium. 1-benzotriazolyle [(BzO) 2CO), (BzO) 2 C 2 O2)], oxalates and carbonates of nitro-, dinitro- or perhalophenols, carbonates and oxalates of trifluoroethyl [(CF3CH2θ) 2CO ), (CF3CH2θ) 2C2θ2] or trichloroethyl [(CCl3CH2θ) 2CO), (CCI3CH 2 O) 2C2O2], the mixture PΦ 3 -diethyl- azodicarboxylate (DEAD) or PΦ 3 ~ dithiodipyridine, carbo- nyldiimidazole (Im) , phenylphosphoro-diimidazole ΦPO (Im) 2 t acetals of amides, 2-alkoxy-1-alkoxycarbonyl-1,2-dihydroquinoline (EEDQ, IIDQ), O-benzotriazol-lyl- N salts, N, N ', N'tetramethyluronium or O-benzotriazol-1-yloxytrisdimethylaminophosphonium, aromatic sultones, isobutyl chloroformxate, diphenylphosphochloroiridate, ethylene chlorophosphite, diethylene pyrophosphite, bis (2-oxo-3oxazolidinyl) phosphinyl chloride, 2-tert-butyl-5-methylixoaxazolium salts.
11. Procédé selon la revendication 1, caractérisé en ce que M' est tel que la solubilité du composé M'1/πX dans le milieu réactionnel est plus faible que celle du composé (NuH)+[ (RFS02) 2CY]~, et en ce que le procédé comporte une étape supplémentaire au cours de laquelle on fait réagir le produit obtenu avec un sel approprié de M.11. Method according to claim 1, characterized in that M 'is such that the solubility of the compound M' 1 / π X in the reaction medium is lower than that of the compound (NuH) + [(RFS02) 2CY] ~, and in that the process comprises an additional step during which the product obtained is reacted with an appropriate salt of M.
12. Procédé selon la revendication 11, caractérisée en ce que le sel de M est choisi parmi le carbonate, le phos¬ phate, le chlorure et l'hydroxyde de M.12. Method according to claim 11, characterized in that the salt of M is chosen from carbonate, phos¬ phate, chloride and hydroxide of M.
13. Composé répondant à la formule (1/nM)+[ (RpSθ2) 2 Y] " dans laquelle Y représente un groupement attracteur d'électrons choisi parmi -C=N et les groupements RZ- dans lesquels Z représente un groupement carbonyle, un groupe¬ ment sulfonyle ou un groupement phosphonyle et R représente un groupement organique monovalent, M représente un métal ayant la valence n ou un groupe organique pouvant exister sous forme cationique, RF représente un groupement per¬ fluoroalkyle ou perfluoroaryle, (l/nM)+ étant différent d'un cation Li+, K+ ou d'un cation diazoniu lorsque RZ re¬ présente CF3SO2. 13. Compound corresponding to the formula (1 / nM) + [(RpSθ2) 2 Y] "in which Y represents an electron attracting group chosen from -C = N and the RZ- groups in which Z represents a carbonyl group, a sulfonyl group or a phosphonyl group and R represents a monovalent organic group, M represents a metal having the valence n or an organic group which may exist in cationic form, RF represents a per¬ fluoroalkyl or perfluoroaryl group, (l / nM) + being different from a Li + , K + cation or from a diazoniu cation when RZ presents CF3SO2.
14. Composé selon la revendication 13, caractérisé en ce que RF représente un groupement perfluoroalkyle en Ci à C20 ou un groupement perfluoroaryle en Cξ, à C20-14. Compound according to claim 13, characterized in that RF represents a C 1 to C 20 perfluoroalkyl group or a Cξ, C 20- perfluoroaryl group
15. Composé selon la revendication 13, caractérisé en ce que M représente un métal choisi parmi les métaux alca- lins, les métaux alcalino-terreux, les métaux de transi¬ tion, le zinc, le magnésium, les lanthanides ; un groupe NuH, Nu étant choisi parmi l'ammoniac, les alkylamines, les pyridines, les imidazoles, les amidines, les guanidines, les alcaloïdes, les diazonium, les sulfonium, les oxonium, les phosphonium.15. Compound according to claim 13, characterized in that M represents a metal chosen from alkali metals, alkaline earth metals, transition metals, zinc, magnesium, lanthanides; a NuH group, Nu being chosen from ammonia, alkylamines, pyridines, imidazoles, amidines, guanidines, alkaloids, diazonium, sulfonium, oxonium, phosphonium.
16. Composé selon la revendication 13, caractérisé en ce que R est choisi parmi les radicaux alkyles en C1-C30 ou perhaloalkyles en Ci-Cβ, les radicaux aryles ou perhalo- aryles en C6-C12, les radicaux arylalkyles, les radicaux oxaalkyles, azaalkyles, thiaalkyles et les hétérocycles.16. A compound according to claim 13, characterized in that R is selected from alkyl C 1 -C 30 perhaloalkyl or Ci-C β, aryl radicals or perhalo- aryl, C 6 -C 12 arylalkyl radicals, oxaalkyl radicals, azaalkyl, thiaalkyl and heterocycles.
17. Composé selon la revendication 13, caractérisé en ce que R comporte au moins une insaturation éthylénique et/ou un groupe condensable et/ou un groupe dissociable.17. Compound according to claim 13, characterized in that R comprises at least one ethylenic unsaturation and / or a condensable group and / or a dissociable group.
18. Composé selon la revendication 13, caractérisé en ce que R représente un groupe mesomorphe ou un groupe chromophore ou un polymère conducteur électronique autodopé ou un alcoxysilane hydrolysable. 18. Compound according to claim 13, characterized in that R represents a mesomorphic group or a chromophore group or a self-doped electronic conductive polymer or a hydrolysable alkoxysilane.
19. Composé selon la revendication 13, caractérisé en ce que R constitue une chaîne polymérique portant des greffons comportant un groupe carbonyle, un groupe sulfonyle ou un groupe phosphonyle.19. Compound according to claim 13, characterized in that R constitutes a polymer chain carrying grafts comprising a carbonyl group, a sulfonyl group or a phosphonyl group.
20. Composé selon la revendication 13, caractérisé en ce que R comporte un piège à radicaux libres tel qu'un phénol encombré, ou une quinone ; ou un dipôle dissociant tel qu'une amide ou un nitrile ; ou un couple rédox tel qu'un disulfure, un thioamide, un ferrocène, une phéno- thiazine, un groupe bis(dialkylaminoaryle) , un nitroxyde, un imide aromatique ; ou un ligand complexant ; ou un zwitterion.20. Compound according to claim 13, characterized in that R comprises a free radical trap such as a hindered phenol, or a quinone; or a dissociating dipole such as an amide or a nitrile; or a redox couple such as a disulfide, a thioamide, a ferrocene, a phenothiazine, a bis (dialkylaminoaryl) group, a nitroxide, an aromatic imide; or a complexing ligand; or a zwitterion.
21. Composé selon la revendication 13, caractérisé en ce que RZ représente un acide aminé, ou un polypeptide optiquement ou biologiquement actif. 21. Compound according to claim 13, characterized in that RZ represents an amino acid, or an optically or biologically active polypeptide.
22. Application d'un composé selon l'une quelconque des revendications 13 à 21, à la réalisation de dispositifs électrochimiques.22. Application of a compound according to any one of claims 13 to 21, in the production of electrochemical devices.
23. Application selon la revendication 22, caracté¬ risée en ce que le dispositif électrochimique est un géné- rateur primaire ou secondaire, ou une supercapacité, ou un dispositif permettant la modulation de la transmission ou de la réflexion de la lumière. 23. Application according to claim 22, characterized in that the electrochemical device is a primary or secondary generator, or a supercapacitor, or a device allowing the modulation of the transmission or the reflection of light.
EP93900221A 1991-11-08 1992-11-04 Bis(perfluorosulphonyl)methanes, process for preparing same and uses thereof Ceased EP0567637A1 (en)

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