Process for the preparation of onium salts having a low chloride content

The invention relates to a process for the preparation of onium salts by reaction of an onium halide with an acid, where the hydrohalic acid forming is, in accordance with the invention, removed by coordination to an organic solvent which forms an azeotropic mixture with water.

A large number of onium salts are ionic liquids. Due to their properties, ionic liquids represent an effective alternative to traditional volatile organic solvents for organic synthesis in modern research. The use of ionic liquids as novel reaction medium could furthermore be a practical solution both for solvents emission and also for problems in the reprocessing of catalysts.

Review articles on ionic liquids are, for example, R. Sheldon “Catalytic reactions in ionic liquids”, Chem. Commun., 2001, 2399-2407; M. J. Earle, K. R. Seddon “Ionic liquids. Green solvent for the future”, Pure Appl. Chem., 72 (2000), 1391-1398; P. Wasserscheid, W. Keim “lonische Flüssigkeiten-neue Lösungen für die Übergangsmetallkatalyse” [ionic Liquids—Novel Solutions for Transition-Metal Catalysis], Angew. Chem., 112 (2000), 3926-3945; T. Welton “Room temperature ionic liquids. Solvents for synthesis and catalysis”, Chem. Rev., 92 (1999), 2071-2083 or R. Hagiwara, Ya. Ito “Room temperature ionic liquids of alkylimidazolium cations and fluoroanions”, J. Fluorine Chem., 105 (2000), 221-227).

Ionic liquids or liquid salts are ionic species which consist of an organic cation and a generally inorganic anion. They do not contain any neutral molecules and usually have melting points below 373 K. However, the melting point may also be higher without restricting the usability of the salts in all areas of application. Examples of organic cations are, inter alia, tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, 1,3-dialkyl-imidazolium or trialkylsulfonium. Amongst a multiplicity of suitable anions, mention may be made, for example, of BF 4 − , PF 6 − , SbF 6 − , NO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , arylSO 3 − , CF 3 CO 2 − , CH 3 CO 2 − or Al 2 Cl 7 − .

The properties of ionic liquids, for example the melting point, the thermal and electrochemical stability or the viscosity, are determined by the choice of the cations and anions. Ionic liquids are non-volatile materials and therefore cannot be purified by conventional purification methods, such as, for example, distillation, as developed for most organic solvents. In processes for the preparation of onium salts, in particular ionic liquids, the technology is therefore of crucial importance in order that they can be synthesised with low impurity levels through the reaction per se or the way the reaction is carried out. An impurity which is predominantly present in known ionic liquids are halide ions. If the proportion of halide ions, for example chloride ions, is greater than 1000 ppm (0.1%), the usability of the ionic liquid is reduced, in particular in use for electrochemical processes.

The object of the present invention was accordingly to provide an alternative process for the preparation of onium salts having a low chloride content which results in products of high purity in good yield and is also suitable for large-scale industrial production.

The object is achieved by the process according to the invention.

The process according to the invention is an improvement of the known synthetic processes, which are generally 2-step processes, as described in P. Wasserscheid and W. Keim, Angew. Chem. 112 (2000), 3926-3945. In the first step of the known processes, an organic base, typically an amine, phosphine or a heterocyclic compound, is alkylated using an alkyl halide, and the halide forming is, in the second step, converted into the desired salt via anion exchange.

Typically, ionic liquids having the tetrafluoroborate anion are prepared in this way, where the halide, for example 1-ethyl-3-methylimidazolium chloride or bromide, can be reacted in the second step with NaBF 4 in acetone by the method of S. Park and R. J. Kazlauskas, J. Organic Chemistry, 66 (2001), 8395-8401, with NaBF 4 in water by the method of R. Karmakar and A. Samanta, J. Phys. Chem. A, 106 (2002), 6670-6675, with AgBF 4 or HBF 4 in water by the method of J. D. Holbrey and K. R. Seddon, J. Chem. Soc., Dalton Trans., (1999), 2133-2139, with NH 4 BF 4 in acetone by the method of J. Fuller et al, J. Electrochem. Soc., 144 (1997), 3881-3885, with HBF 4 in methanol by the method of T. Nishida et al, J. of Fluorine Chem., 120 (2003), 135-141 or with NH 4 BF 4 with microwave irradiation by the method of V. V. Namboodiri and R. S. Varma, Tetrahedron Lett., 43 (2002), 5381-5383.

All known processes have a disadvantage, in particular for large-scale industrial synthesis, which can be illustrated by the example of the synthesis of ionic liquids having tetrafluoroborate anions. Silver tetrafluoroborate is, for example, an expensive reagent. The reactions with NaBF 4 , NH 4 BF 4 and HBF 4 in water require a purification step, possibly through the use of AgBF 4 or adsorbents. HBF 4 in methanol is not commercially available and is more expensive than aqueous HBF 4 , which is in turn commercially available.

The reaction medium of choice, with respect to large-scale industrial synthesis of onium salts which are water-soluble or partially water-soluble, are water-soluble acids, for example HBF 4 , H 2 SiF 6 , H 2 TiF 6 , H 2 ZrF 6 , HSbF 6 , HAsF 6 , HPF 6 , HN(CN) 2 , HC(CN) 3 , H 2 SO 4 , HNO 3 , alkyl- or perfluoroalkyl-sulfonic acids, aromatic sulfonic acids, perfluoroalkylcarboxylic acids, alkyl- or perfluoroalkylphosphinic acids, alkyl- or perfluoroalkylphosphonic acids, aromatic phosphinic or phosphonic acids or phosphoric acid. However, there is a general problem in the said reaction, which is advantageously carried out in water or also in water-miscible solvents, since the hydrohalic acid which forms cannot be removed completely by distillation. On removal of the solvent, an equilibrium between two salts and two acids always forms. The onium salts obtained inevitably still contain a few percent of halide ions, documented by investigations by N. M. M Mateus et al, Green Chemistry, 5 (2003), 347-352.

Surprisingly, a simple process has been developed. After reaction of an onium halide with an acid, as described above as the second step of the known reactions, the hydrohalic acid forming can, in accordance with the invention, be removed by azeotropic distillation by coordination to an organic solvent which forms an azeotropic mixture with water. The azeoropic distillation shifts the above-described equilibrium, giving, after multiple distillation if the reaction is carried out batchwise or semicontinuously or by continuous distillation if the reaction is carried out continuously, ionic liquids whose halide content can be below 5000 ppm (=0.5%), preferably below 500 ppm, particularly preferably below 100 ppm, very particularly preferably below 20 ppm.

Organic solvents which are able to form an azeotropic mixture with water are, for example, nitroalkanes, nitriles, aromatics, cyclic or linear ethers or esters or alcohols. Without restricting generality, examples of these solvents are 1,4-dioxane, ethanol, propanol, isopropanol, butanol, nitromethane, acetonitrile, dimethoxyethane, tetrahydrofuran, isobutyronitrile, cyclohexanone, benzene or toluene. Particularly suitable for large-scale industrial synthesis is the use of 1,4-dioxane or isopropanol. Very particularly suitable is the use of 1,4-dioxane.

The process according to the invention can be used for the preparation of onium salts whose cation denotes, for example, ammonium, phosphonium, thiouronium, guanidinium or a heterocyclic cation and whose anion is the anion of the corresponding acid.

Suitable acids are, as described above, HBF 4 , H 2 SiF 6 , H 2 TiF 6 , H 2 ZrF 6 , HSbF 6 , HAsF 6 , HPF 6 , HN(CN) 2 , HC(CN) 3 , H 2 SO 4 , HNO 3 , alkyl- or perfluoroalkylsulfonic acids, aromatic sulfonic acids, perfluoroalkylcarboxylic acids, alkyl- or perfluoroalkylphosphinic acids, alkyl- or perfluoroalkylphosphonic acids, aromatic phosphinic or phosphonic acids or phosphoric acid. The process according to the invention is particularly suitable for the reaction with aqueous HBF 4 , H 2 SiF 6 , H 2 TiF 6 , H 2 SO 4 , CF 3 SO 3 H, CF 3 COOH, toluenesulfonic acid monohydrate or CH 3 SO 3 H. As selection from the particularly suitable group of acids, preference is in turn given to the reaction with aqueous HBF 4 , H 2 SO 4 , CF 3 SO 3 H, H 2 SiF 6 or H 2 TiF 6 . The process according to the invention is very particularly suitable for the reaction with HBF 4 in water.

Anions of the onium salts are accordingly [BF 4 ] − , [SiF 6 ] 2− , [TiF 6 ] 2− , [SbF 6 ] − , [AsF 6 ] − , [PF 6 ] − , [N(CN) 2 ] − , [C(CN) 3 ] − , [HSO 4 ] − , [NO 3 ] − , alkyl- or perfluoroalkyl-sulfonate, for example [CH 3 SO 3 ] − , [C 2 H 5 SO 3 ] − , [CF 3 SO 3 ] − , [C 2 F 5 SO 3 ] − , anions of aromatic sulfonic acids, for example tosylate, mesylate or phenylsulfonate, perfluoroalkylcarboxylates, for example [CF 3 CO 2 ] − or [C 2 F 5 CO 2 ] − , anions of alkyl- or perfluoroalkylphosphinic acids, for example (CH 3 ) 2 P(O)O − , (C 2 H 5 ) 2 P(O)O − , (C 3 H 7 ) 2 P(O)O − , (C 4 H 9 ) 2 P(O)O − , (C 2 F 5 ) 2 P(O)O − , (C 3 F 7 ) 2 P(O)O − , (C 4 F 9 ) 2 P(O)O − , anions of alkyl- or perfluoroalkylphosphonic acids, for example [(C 2 F 5 )P(O)O 2 ] 2− , [(C 3 F 7 )P(O)O 2 ] 2− , [[(C 4 F 9 )P(O)O 2 ] 2− , anions of aromatic phosphinic or phosphonic acids, for example (C 6 H 5 ) 2 P(O)O − , or phosphates.

Suitable onium halides are ammonium halides, phosphonium halides, thiouronium halides, guanidinium halides or halides having a heterocyclic cation, where the halides can be selected from the group of chlorides or bromides. Chlorides are particularly suitable.

Ammonium chlorides can be described, for example, by the formula (1)

[NR 4 ] + Cl −   (1),

phosphonium chlorides can be described, for example, by the formula (2)

[PR 4 ] + Cl −   (2),

where

R in each case, independently of one another, denotes H, where all substituents R cannot simultaneously be H, straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, where one or more R may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially by —NO 2 , and where, in the R, one or two non-adjacent carbon atoms which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO 2 — or —P(O)R′—, where R′═non-, partially or perfluorinated C 1 - to C 6 -alkyl, C 3 - to C 7 -cycloalkyl, unsubstituted or substituted phenyl.

However, compounds of the formulae (1) and (2) in which all four or three substituents R are fully substituted by halogens, for example tris(trifluoromethyl)methylammonium chloride, tetra(trifluoromethyl)ammonium chloride or tetra(nonafluorobutyl)ammonium chloride, are excluded.

Thiouronium chlorides can be described by the formula (3)

[(R 1 R 2 N)—C(═SR 7 )(NR 3 R 4 )] + Cl −   (3),

guanidinium chlorides by the formula (4)

[C(NR 1 R 2 )(NR 3 R 4 )(NR 5 R 6 )] + Cl −   (4),

where

R 1 to R 7 each, independently of one another, denote hydrogen, where hydrogen is excluded for R 7 , straight-chain or branched alkyl having 1 to 20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, where one or more of the substituents R 1 to R 7 may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially by —NO 2 , but where all substituents on an N atom cannot be fully substituted by halogens, and where, in the substituents R 1 to R 6 , one or two non-adjacent carbon atoms which are not bonded directly to the heteroatom may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO 2 — or —P(O)R′—, where R′═non-, partially or perfluorinated C 1 - to C 6 -alkyl, C 3 - to C 7 -cycloalkyl, unsubstituted or substituted phenyl.

Chlorides having a heterocyclic cation can be described, for example, by the formula (6)

[HetN] + Cl −   (5),

where

HetN + denotes a heterocyclic cation selected from the group

where the substituents

R 1 ′ to R 4 ′ each, independently of one another, denote hydrogen, straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, saturated, partially or fully unsaturated heteroaryl, heteroaryl-C 1 -C 6 -alkyl or aryl-C 1 -C 6 -alkyl, where the substituents R 1′ , R 2′ , R 3′ and/or R 4′ together may also form a ring system, where one or more substituents R 1 ′ to R 4 ′ may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially by —NO 2 , but where R 1′ and R 4′ cannot simultaneously be fully substituted by halogens, and where, of the substituents R 1 ′ to R 4 ′, one or two non-adjacent carbon atoms which are not bonded to the heteroatom may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO 2 — or —P(O)R′—, where R′═non-, partially or perfluorinated C 1 - to C 6 -alkyl, C 3 - to C 7 -cycloalkyl, unsubstituted or substituted phenyl.

For the purposes of the present invention, fully unsaturated substituents are also taken to mean aromatic substituents.

Besides hydrogen, suitable substituents R and R 1 to R 7 of the compounds of the formulae (1) to (5) are preferably, in accordance with the invention: C 1 - to C 20 -, in particular C 1 - to C 14 -alkyl groups, and saturated or unsaturated, i.e. also aromatic, C 3 - to C 7 -cycloalkyl groups, which may be substituted by C 1 - to C 6 -alkyl groups, in particular phenyl.

The substituents R in the compounds of the formula (1) or (2) may be identical or different here. The substituents R are preferably identical.

The substituent R is particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.

Up to four substituents of the guanidinium cation [C(NR 1 R 2 )(NR 3 R 4 )(NR 5 R 6 )] + may also be connected in pairs in such a way that mono-, bi- or polycyclic cations are formed.

Without restricting generality, examples of such guanidinium cations are:

where the substituents R 1 to R 3 and R 6 may have an above-mentioned or particularly preferred meaning.

The carbocycles or heterocycles of the above-mentioned guanidinium cations may optionally also be substituted by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 NR″ 2 , SO 2 X′ or SO 3 H, where X′ and R″ have a meaning indicated above or below, substituted or unsubstituted phenyl or an unsubstituted or substituted heterocycle.

Up to four substituents of the thiouronium cation [(R 1 R 2 N)—C(═SR 7 )(NR 3 R 4 )] + may also be connected in pairs in such a way that mono-, bi- or polycyclic cations are formed.

Without restricting generality, examples of such cations are indicated below, where Y═S:

where the substituents R 1 , R 3 and R 7 may have an above-mentioned or particularly preferred meaning.

The carbocycles or heterocycles of the above-mentioned cations may optionally also be substituted by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 NR″ 2 , SO 2 X′ or SO 3 H or substituted or unsubstituted phenyl or an unsubstituted or substituted heterocycle, where X′ and R″ have an above-mentioned meaning.

The substituents R 1 to R 7 are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R 1 and R 2 , R 3 and R 4 and R 5 and R 6 in compounds of the formulae (3) to (5) may be identical or different here.

R 1 to R 7 are particularly preferably each, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, phenyl or cyclohexyl, very particularly preferably methyl, ethyl, n-propyl, isopropyl or n-butyl.

Besides hydrogen, suitable substituents R 1′ to R 4′ of compounds of the formula (6) are preferably, in accordance with the invention: C 1 - to C 20 -, in particular C 1 - to C 12 -alkyl groups, and saturated or unsaturated, i.e. also aromatic, C 3 - to C 7 -cycloalkyl groups, which may be substituted by C 1 - to C 6 -alkyl groups, in particular phenyl.

The substituents R 1′ and R 4′ are each, independently of one another, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly preferably methyl, ethyl, n-butyl or hexyl. In pyrrolidinium, piperidinium or indolinium compounds, the two substituents R 1′ and R 4′ are preferably different.

The substituent R 2′ or R 3′ is in each case, independently of one another, in particular, hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, cyclohexyl, phenyl or benzyl. R 2′ is particularly preferably hydrogen, methyl, ethyl, isopropyl, propyl, butyl or sec-butyl. R 2′ and R 3′ are very particularly preferably hydrogen.

The C 1 -C 12 -alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Optionally difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.

A straight-chain or branched alkenyl having 2 to 20 C atoms, where a plurality of double bonds may also be present, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, —C 9 H 17 , —C 10 H 19 to —C 20 H 39 ; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, preference is furthermore given to 4-pentenyl, isopentenyl or hexenyl.

A straight-chain or branched alkynyl having 2 to 20 C atoms, where a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl, —C 9 H 15 , —C 10 H 17 to —C 20 H 37 , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.

Aryl-C 1 -C 6 -alkyl denotes, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and also the alkylene chain may be partially or fully substituted, as described above, by halogens, in particular —F and/or —Cl, or partially by —NO 2 .

Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, which may be substituted by C 1 - to C 6 -alkyl groups, where the cycloalkyl group or the cycloalkyl group which is substituted by C 1 - to C 6 -alkyl groups may in turn also be substituted by halogen atoms, such as F, Cl, Br or I, in particular F or Cl, or NO 2 .

In the substituents R, R 1 to R 6 or R 1′ to R 4′ , one or two non-adjacent carbon atoms which are not bonded in the α-position to the heteroatom may also be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO 2 — or —P(O)R′—, where R′═non-, partially or perfluorinated C 1 - to C 6 -alkyl, C 3 - to C 7 -cycloalkyl, unsubstituted or substituted phenyl.

Without restricting generality, examples of substituents R, R 1 to R 6 and R 1′ to R 4′ which have been modified in this way are: —OCH 3 , —OCH(CH 3 ) 2 , —CH 2 OCH 3 , —CH 2 —CH 2 —O—CH 3 , —C 2 H 4 OCH(CH 3 ) 2 , —C 2 H 4 SC 2 H 5 , —C 2 H 4 SCH(CH 3 ) 2 , —S(O)CH 3 , —SO 2 CH 3 , —SO 2 C 6 H 5 , —SO 2 C 3 H 7 , —SO 2 CH(CH 3 ) 2 , —SO 2 CH 2 CF 3 , —CH 2 SO 2 CH 3 , —O—C 4 H 8 —O—C 4 H 9 , —CF 3 , —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —C(CF 3 ) 3 , —CF 2 SO 2 CF 3 , —C 2 F 4 N(C 2 F 5 )C 2 F 5 , —CHF 2 , —CH 2 CF 3 , —C 2 F 2 H 3 , —C 3 FH 6 , —CH 2 C 3 F 7 , —CH 2 C(O)OH, —CH 2 C 6 H 5 , —C(O)C 6 H 5 or P(O)(C 2 H 5 ) 2 .

In R′, C 3 - to C 7 -cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

In R′, substituted phenyl denotes phenyl which is substituted by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 X′, SO 2 NR″ 2 or SO 3 H, where X′ denotes F, Cl or Br and R″ denotes a non-, partially or perfluorinated C 1 - to C 6 -alkyl or C 3 - to C 7 -cyclo-alkyl, as defined for R′, for example o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-, p-(trifluoromethyl)-phenyl, o-, m-, p-(trifluoromethoxy)phenyl, o-, m-, p-(trifluoromethylsulfonyl)phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodophenyl, furthermore preferably 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-di-hydroxyphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-difluorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-di-bromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl or 2,4,5-trimethylphenyl.

In R 1′ to R 4′ , heteroaryl is taken to mean a saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13 ring members, in which 1, 2 or 3 N and/or 1 or 2 S or O atoms may be present and the heterocyclic radical may be mono- or polysubstituted by C 1 - to C 6 -alkyl, C 1 - to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 X′, SO 2 NR″ 2 or SO 3 H, where X′ and R″ have an above-mentioned meaning.

The heterocyclic radical is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, furthermore preferably 1,2,3-triazol-1-, 4- or -5-yl, 1,2,4-triazol-1-, -4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 2-, 3-, 4-, 5- or 6-2H-thiopyranyl, 2-, 3- or 44H-thiopyranyl, 3- or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6- or 7-benzofuryl, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-1 H-indolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl or 1-, 2- or 3-pyrrolidinyl.

Analogously to aryl-C 1 -C 6 -alkyl, heteroaryl-C 1 -C 6 -alkyl is taken to mean, for example, pyridinylmethyl, pyridinylethyl, pyridinylpropyl, pyridinylbutyl, pyridinylpentyl, pyridinylhexyl, where the above-described heterocycles may furthermore be linked to the alkylene chain in this manner.

HetN + is preferably

where the substituents R 1′ to R 4′ each, independently of one another, have a meaning described above.

HetN + is particularly preferably imidazolium, pyrrolidinium or pyridinium, as defined above, where the substituents R 1′ to R 4′ each, independently of one another, have a meaning described above. HetN + is very particularly preferably imidazolium, where the substituents R 1′ to R 4′ each, independently of one another, have a meaning described above.

A general scheme summarises the process according to the invention, where the arrow in the case of the hydrochloric acid HCl forming represents a symbol for azeotropic distillation:

The substituents R, R 1 to R 7 and HetN + of the compounds of the formulae (1) to (10) correspond to the meanings as described above.

The anion exchange is carried out under reaction conditions which are known to the person skilled in the art. The solvent used is preferably water. However, it is also possible to employ solvents which are miscible with water, for example dimethoxyethane, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, propionitrile, methanol, ethanol or isopropanol, or mixtures with one another or with water.

The reaction can be carried out, for example, at temperatures of 0° C. to 100° C., preferably at 10° to 50° C., particularly preferably at room temperature. The reaction is carried out with an excess or equimolar amount of acid. An excess of 0.1 to 5 mol % of acid is preferably used. The azeotropic distillation is carried out a number of times under atmospheric pressure or under reduced pressure. Under reduced pressure here is taken to mean pressures of 0.1 Pa to atmospheric pressure. The low chloride content is preferably achieved if the azeotropic distillation is carried out five times. The low chloride content is particularly preferably achieved if the azeotropic distillation is carried out three times.

Even without further comments, it is assumed that a person skilled in the art will be able to utilise the above description in the broadest scope. The preferred embodiments and examples should therefore merely be regarded as descriptive disclosure which is absolutely not limiting in any way.

The NMR spectra were measured on solutions in deuterated solvents at 20° C. in a Bruker Avance 300 spectrometer with a 5 mm 1 H/BB broad-band head with deuterium lock, if not indicated in the examples. The measurement frequencies of the various nuclei are: 1 H: 300.13 MHz, 11 B: 96.92 MHz, 19 F: 282.41 MHz and 31 P: 121.49 MHz. The referencing method is indicated separately for each spectrum or each data set.