Sulphonyl-1,2,4-Triazole Salts

Abstract

The invention relates to triazole salts, to their preparation and to applications thereof. The salts have at least one anionic triazolium group which carries at least one chlorosulphonyl, fluorosulphonyl or alkoxyfluorosulphonyl group, each of the anionic groups being combined with a proton or a cation that has a valency of less than or equal to 4. The salts are useful as synthesis reagents, as chemical-reaction or polymerization catalysts, and as ion-conducting materials for electrochemical generators, supercapacitors and electrochromic devices.

1 . A method using a compound I, comprising at least one anionic part associated with at least one cationic part M in a number which grants electronic neutrality to the compound, wherein M is H+, or a cation of valence m wherein 1≦m≦4, and wherein the anionic part has formula 
       
         
           
           
               
               
           
         
       
       wherein R 1  represents:
 a ClSO 2 — group; 
 a group R F  selected from the group consisting of HCF 2 —, HCF 2 CF 2 —, and linear or branched perfluoroalkyl groups having 1 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; or 
 a group of formula 
 
       
         
           
           
               
               
           
         
         wherein Z is Cl and R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least on divalent oxygen atom linked to two carbon atoms; 
         for the preparation of a compound II comprising at least one anionic part associated with at least one cationic part M′ in a number which grants electronic neutrality to the compound, wherein M′ is H+, or a cation of valence m wherein 1≦m≦4, and wherein the anionic part has formula 
       
       
         
           
           
               
               
           
         
       
       wherein R 3  represents:
 a FSO 2 — group; 
 a group RF selected from HCF 2 —, HCF 2 CF 2 —, and linear or branched perfluoroalkyl groups having 1 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; or 
 a group of formula 
 
       
         
           
           
               
               
           
         
         wherein Z′ is F and R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; 
       
       wherein said method comprises a step of reacting compound I with a fluorine precursor capable of replacing the chlorine atoms of the SO 2 Cl group(s) of compound I with a fluorine atom. 
     
     
         2 . The method according to  claim 1 , wherein compound I is reacted with an alkali metal fluoride, in an organic solvent, in a mixture of water and an organic solvent, or in water. 
     
     
         3 . The method according to  claim 1 , wherein compound I is reacted with ZnF 2  in pyridine. 
     
     
         4 . The method according to  claim 1 , wherein compound I is reacted with a fluorhydric acid onium complex. 
     
     
         5 . The method according to  claim 1 , wherein compound I is reacted with anhydrous HF. 
     
     
         6 . The method according to  claim 1 , wherein compound I is reacted with anhydrous HF in the presence of LiCl. 
     
     
         7 . The method according to  claim 1 , said method comprising a step of ion exchange or a metathesis step. 
     
     
         8 . The method according to  claim 7 , wherein ion exchange or metathesis is carried out with a halogenide, an acetate, a tetrafluoroborate, a perchlorate, a nitrate, a sulfonate, or a sulfamate of an organic cation M′ which is to replace cation M, or with HF. 
     
     
         9 . A method using a compound I comprising at least one anionic part associated with at least one cationic part M in a number which grants electronic neutrality to the compound, wherein M is H+, or a cation of valence m wherein 1≦m≦4, and wherein the anionic part has formula 
       
         
           
           
               
               
           
         
       
       wherein R 1  represents:
 a ClSO 2 — group; 
 a group RF selected from the group consisting of HCF 2 —, HCF 2 CF 2 —, and linear or branched perfluoroalkyl groups having 1 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; or 
 a group of formula 
 
       
         
           
           
               
               
           
         
         wherein Z is Cl and R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least on divalent oxygen atom linked to two carbon atoms; 
         for the preparation of a compound III comprising at least one anionic part associated with at least one cationic part M″ in a number which grants electronic neutrality to the compound, wherein M″ is H+, or a cation of valence m wherein 1≦m≦4, and wherein the anionic part has formula 
       
       
         
           
           
               
               
           
         
       
       or R F -TrM-SO 2 —O—R 9 —O—SO 2 -TrM-R F  (III′) 
       wherein R 4  represents:
 a group R 5 —O—SO 2 —; 
 a group R F  selected from the group consisting of HCF 2 —, HCF 2 CF 2 —, and linear or branched perfluoroalkyl groups having 1 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; or 
 a group of formula 
 
       
         
           
           
               
               
           
         
       
       wherein Z″ is F and R 5 —O— and R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; 
       wherein R 5  represent a R 6 CH 2 — group, a R 6 R 7 CH— group or a R 6 R 7 R 8 CH— group wherein groups R 6 , R 7  and R 8  represent a perfluorinated linear or branched alkyl group having 1 to 12 carbon atoms, the chain of which is optionally interrupted by at least one divalent oxygen atom linked to two carbon atoms and 
       R 9  represents a perfluorinated linear or branched alkylene group having 2 to 12 carbon atoms, the chain of which is optionally interrupted by at least one divalent oxygen atom linked to two carbon atoms; 
       wherein said method comprises reacting an alcohol R 5 —OH or a corresponding alcoholate with compound I or compound II, or reacting a diol HO—R 9 —OH or the corresponding dialcoolate with a compound I or a compound II having one FSO 2  or ClSO 2  group. 
     
     
         10 . The method of  claim 9 , which comprises reacting a compound ClSO 2 -TrM-R 1  which has one or two SO 2 Cl or SO 2 F groups with an alcoolate R 5 —O—Na in THF. 
     
     
         11 . The method of  claim 9 , which comprises reacting a compound ClSO 2 -TrM-R 1  having a single ClSO 2  group with a diol HO—R 9 —OH. 
     
     
         12 . The method of  claim 9 , which comprises a step of ion exchange or a step of metathesis. 
     
     
         13 . The method of  claim 12 , wherein ion exchange or metathesis is carried out with a halogenide, an acetate, a tetrafluoroborate, a perchlorate, a nitrate, a sulfonate, or a sulfamate of a cation M′ which is to replace cation M, or with HF. 
     
     
         14 . A method using a compound I comprising at least one anionic part associated with at least one cationic part M in a number which grants electronic neutrality to the compound, wherein M is H+, or a cation of valence m wherein 1≦m≦4, and wherein the anionic part has formula 
       
         
           
           
               
               
           
         
       
       wherein R 1  represents:
 a ClSO 2 — group; 
 a group RF selected from the group consisting of HCF 2 —, HCF 2 CF 2 —, and linear or branched perfluoroalkyl groups having 1 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; or 
 a group of formula 
 
       
         
           
           
               
               
           
         
         wherein Z is Cl and R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least on divalent oxygen atom linked to two carbon atoms; 
         for the preparation of a polymer compound IV consisting of repeat units having formula
   [—O 2 S-TrM*-SO 2 OCH 2 —R 9 —CH 2 O—] or
 
   [—O 2 S-TrM*-R 2 -TrM*-SO 2 OCH 2 —R 9 —CH 2 O—]
 
 
       
       wherein:
 R 2  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may optionally be interrupted by at least one divalent oxygen atom linked to two carbon atoms; 
 R 9  is a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms wherein the chain may be optionally interrupted by at least one divalent oxygen atom; 
 M* is H+, or a cation of valence m wherein 1≦m≦4, 
 TrM* represents an anionic triazole-1,2,4 group associated to cation M*; 
 
       wherein said method consists in reacting a compound I having two FSO 2  or ClSO 2  groups, with a difunctional fluoroalcohol HO—CH 2 —R 9 —CH 2 —OH. 
     
     
         15 . The method of  claim 14 , which comprises a step of ion exchange or a step of metathesis. 
     
     
         16 . The method of  claim 15 , wherein ion exchange or metathesis is carried out with a halogenide, an acetate, a tetrafluoroborate, a perchlorate, a nitrate, a sulfonate, or a sulfamate of a cation M′ which is to replace cation M, or with HF.