WO2006027069A1 - Method for producing heterocyclic quaternary ammonium and/or guanidinium compounds - Google Patents

Abstract

The invention relates to a method for producing an intermediate product containing a heterocyclic quarternary ammonium and/or guanidium cation, for the synthesis of heterocyclic quaternary ammonium and/or guanidium compounds. According to said method, heterocyclic quaternary ammonium and/or guanidium carboxylates are oxidised with an oxidising agent in the presence of a metal from groups 8 to 10 of the periodical table, at a temperature of between 0 and 250 °C and a pressure of between 0.05 and 20 MPa abs.

Description

 Process for the preparation of heterocyclic quaternary ammonium and / or guanidinium compounds

description

The present invention relates to a process for preparing an intermediate product containing a heterocyclic quaternary ammonium and / or guanidinium cation for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds.

Quaternary ammonium compounds are important substances which find wide application. For example, they are used as fabric softeners, in hygiene and cosmetics, as phase transfer catalysts or as conductive salts for electronic applications. Another important group of applications are ionic liquids with imidazolium or pyridinium as cations.

Quaternary ammonium compounds with freely selectable anion are usually prepared in a two-step reaction. In the first stage of the synthesis, the corresponding tertiary amine is alkylated with an alkylating agent, the resulting anion of the quaternary ammonium compound being fixed by the alkylating agent used. In order to introduce the desired anion, a so-called anion exchange is subsequently carried out in the second synthesis stage.

The alkylation (first stage of the synthesis) is usually carried out by reacting the corresponding tertiary amines / imines with alkylating agents.

The alkylating agents customarily used are the alkyl esters of strong mineral acids, in particular dimethyl sulfate or methyl chloride (see, for example, Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Volume XI / 2, Georg Thieme Verlag, Stuttgart 1958, pages 591 to 630). A disadvantage of the use of dimethyl sulfate is its carcinogenic effect, which represents a hazard potential and requires expensive safety measures. A disadvantage of the use of alkyl halides is the introduction of halide ions, which are generally difficult to replace completely and in particular lead to problems when used in the electrical industry and in the catalysis and their corrosivity in handling. Furthermore, the low molecular weight alkyl chlorides such as methyl chloride and ethyl chloride are gaseous and therefore difficult to handle.

Alternatively, the use of dimethyl carbonate as a methylating agent is described in JP 04-341, 593 and JP 09-025,173. A disadvantage of this is the occurrence of side reactions, such as, for example, the carboxylation of ring carbon atoms in the reaction of imidazoles with dimethyl carbonate (see M. Aresta et al., In Lonic Liquids as Green Solvents, ACS Symposium Series 856, Ed. R. Rogers and KR Seddon, American Chemical Society 2003, pages 93 to 99).

Furthermore, methyl iodide is also known as a methylating agent for the preparation of quaternary ammonium compounds. A disadvantage of the use of methyl iodide, however, is its carcinogenic effect, which represents a potential hazard and requires complex safety measures. Furthermore, methyl iodide is not available in the required technical quantities or is relatively expensive compared to the above-mentioned methylating agents.

WO 02/34722 teaches the synthesis of 1, 2,3-substituted, of 1, 2,3,4-substituted and 1, 2,3,4,5-substituted imidazolium compounds by reacting the corre sponding substituted imidazole with an alkyl triflate or a trialkyloxonium salt of the desired anion (eg triethyloxonium tetrafluoroborate). A disadvantage of the use of Trialkyloxoniumsalzen is their relatively complex and expensive production, which precludes a technical use both in terms of availability and in terms of cost-effectiveness.

Furthermore, the formation of halide, alkyl sulfate and triflate anions is disadvantageous in the use of alkyl halides, dialkyl sulfates and alkyl triflates as alkylating agents, since these anions require a classical anion exchange for the introduction of the anion which is actually desired, in which case the originally introduced anion adjoins together with a suitable cation in liquid or solid form is removed. This replacement is technically complicated and is generally not complete, so that the product still has disturbing contamination. This also applies to chloride-free synthesis routes, such as using dialkyl sulfate as the alkylating agent, since at least small amounts of undesired alkyl sulfate remain in the product during an anion exchange. An overview of various variants of the anion exchange is in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume XI / 2, Georg Thieme Verlag, Stuttgart 1958, page 591 to 630 and Houben-Weyl, Methods of Organic Chemistry, Extension and following volumes for the 4th edition, volume E16a, part 2, Georg Thieme Verlag, Stuttgart 1990, page 997 to 1017 given.

T. Kametani et al., J. Heterocycl. Chem. 3, 1966, pages 129 to 136 and JP 06 329 603 disclose quaternization of tertiary amines such as trimethylamine or N, N-dimethylethanolamine with carboxylic acid esters such as methyl formate as alkylating agent to form the corresponding carboxylates.

JP 2003-313,170 teaches the quaternization of cyclic imides such as imidazoles with carboxylic acid esters such as methyl formate or methyl acetate as alkylating agent to form the corresponding carboxylates. WO 01/40146 teaches the preparation of 1,3-dialkylimidazoium compounds by reacting 1-alkylimidazole with alkyl sulfonates or fluorinated carboxylic acid esters, such as ethyl trifluoroacetate, to form the corresponding sulfonate or fluorinated carboxylate anions. These have to be exchanged for the introduction of the actually desired anion via an anion exchange. In the case of the trifluoroacetate anion, this anion exchange can take place by addition of the protic acid of the desired anion and distillative removal of the free trifluoroacetic acid formed. Disadvantages of the use of fluorinated carboxylic acid esters are their technically complex syntheses for their preparation using electrochemistry and their high prices compared to other alkylating agents, so that a technical use of fluorinated carboxylic esters as alkylating agents makes sense only in special cases.

EP-A 0 608 545 describes the preparation of substituted, sp ³ -hybridized, non-cyclic ammonium hydroxide by oxidation of the corresponding substituted, sp ³ -hybridized ammonium carboxylates, such as the formates or acetates, with an oxidizing agent, such as For example, hydrogen peroxide or oxygen, in the presence of a gp. VIII metal catalyst and subsequent elec trolysis to the hydroxide.

The object of the present invention was to find a process for preparing heterocyclic quaternary ammonium and / or guanidinium compounds or their precursors, which does not have the disadvantages of the prior art, is simple to carry out, or does not use the alkylating agent to be used is only slightly toxic, technically readily available and inexpensive, and enables a simple and flexible introduction of the desired anion, wherein the product can be prepared after introduction of the desired anion in high purity without expensive purification steps and also suitable for use in the electronics industry should be.

Accordingly, a process for the preparation of an intermediate containing a heterocyclic quaternary ammonium and / or guanidinium cation for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds has been found, which comprises heterocyclic quaternary ammonium - And / or guanidinium carboxylates oxidized with an oxidizing agent in the presence of a metal from the 8th to 10th group of the periodic table at a temperature of 0 to 25O ⁰ C and a pressure of 0.05 to 20 MPa abs.

In the method according to the invention can be used as oxidizing agent in principle all gaseous, liquid or solid reagents which are capable of oxidizing the carboxylates used. Preference is given to using hydrogen peroxide or oxygen as the oxidizing agent. Hydrogen peroxide is preferably used in the form of its aqueous solution, the preferred concentration being rich of hydrogen peroxide to be added in the range of 1 to 35 wt .-%. Oxygen can be added in pure form or diluted with other gases. Suitable gases for diluting the oxygen are, for example, nitrogen, noble gases or carbon dioxide. The concentration of oxygen in the gas to be added is generally 1 to 100% by volume, preferably 15 to 100% by volume. For example, oxidation by addition of air is also possible.

The oxidizing agent is generally added in the process according to the invention in at least stoichiometric amount and preferably in excess. In the case of liquid or solid oxidizing agents, they are preferably added in an amount ranging from the stoichiometric amount to 4 times the stoichiometric amount. Quantities above this range generally lead to disadvantages as a result of the high dilution of the actual product of value. When using gaseous oxidizing agents, an excess is generally added, since the excess gases generally escape from the liquid mixture. The amount of excess is generally determined by the availability of the oxidizing agent, its price, any necessary measures for exhaust gas disposal and apparati¬ ver conditions. If, for example, air is used as the oxidizing agent, then an excess of the order of 1000 times the amount of stoichiometrically required amount can definitely be used. It should be noted, however, that with a very good gas distribution in the reaction mixture, the stoichiometric amount would suffice.

The reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent is carried out in the process according to the invention in the presence of a metal from the 8th to 10th group of the Periodic Table. The reaction is preferably carried out in the presence of palladium, platinum, ruthenium, rhodium and / or iridium. There is no particular restriction on the metal to be used in terms of its morphology, the pretreatment conditions or the like. The catalyst can be used, for example, in a highly active state, such as, for example, as a powder, or else in the form of a so-called supported catalyst. The use in the form of a Trägerkata¬ lysators is generally sufficient in terms of its activity and particularly advantageous in terms of its much easier handling compared to the metal powders. Suitable carriers are in principle all suitable carrier materials in question. Preferred support materials are activated carbon, carbon or activated carbon fibers and inorganic carriers such as silica, alumina, aluminosilicates or zeolites. In the process according to the invention, particular preference is given to using supported catalysts containing palladium and / or platinum on activated carbon, silicon dioxide or aluminum oxide, in particular palladium on activated carbon. When supported catalysts are used, the amount of supported metal is generally from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight and more preferably from 1 to 10% by weight, based on the mass of the finished supported catalyst. The shape and size of the supported catalyst particles is generally negligible. The supported catalysts can be used in the form of small irregular particles ranging from a few tenths of a millimeter in diameter to larger irregular or regular particles in the range of several millimeters. Suitable supported catalysts are commercially available and their preparation is known to the person skilled in the art.

The reaction is generally carried out in reactors which are suitable for the heterogeneous catalytic oxidation in the liquid phase or in the liquid / gas phase, depending on the state of aggregation of the oxidizing agent. Another criterion for the choice of the reactor is the shape and size of the catalyst to be used. If metal powders or small irregular supported catalyst particles are used, the reaction is preferably carried out by suspension catalyzed. In this case, stirred tank reactors with or without gassing device, depending on the state of the oxidizing agent, are particularly suitable. If relatively large supported catalyst particles are used, the reaction is preferably carried out in a fixed bed reactor in a fixed bed catalyzed manner. Preference is given to carrying out the reaction in suspension-catalyzed procedure in a tubular reactor or a stirred tank reactor.

The reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent takes place in the inventive method at a temperature of 0 to 250 ⁰ C, preferably from 10 to 150 ⁰ C and more preferably be from 10 to 120 ⁰ C. The pressure is from 0.05 to 20 MPa abs, bevor¬ Trains t 0.09 to 10 MPa abs, and most preferably from 0.095 to 5 MPa abs.

The reaction can be carried out batchwise, semicontinuously or continuously. In general, the heterocyclic quaternary ammonium and / or guanidinium carboxylate is used together with the catalyst for the reaction, and the oxidizing agent is added, if appropriate distributed over several minutes or hours (discontinuous and semicontinuous procedure). In the continuous procedure, the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent are added simultaneously to the catalyst.

In the process according to the invention, it is possible to carry out the reaction in the absence or in the presence of a solvent. If a solvent is used, preference is given to choosing water, Cr to C ₈ -alkanols, N, N-dimethylformamide or N-methylpyrrolidone and particularly preferably water. If, for example, an oxidizing agent is used which is not present in pure form or is preferably used diluted for other reasons, the reaction is usually carried out in the presence of a solvent. An example of this is the use of aqueous hydrogen peroxide solution. The heterocyclic quaternary ammonium and / or guanidinium carboxylates to be used in the process according to the invention generally have the carboxylate anion of the general formula (I)

R'-COCr (I) ₁

in which R ^{1 represents} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms.

Suitable heteroatoms for R ^{1 are in} principle all heteroatoms in question which are capable of formally replacing a -CH ₂ -, a -CH =, a -C≡ or a = C = group. If the carbon-containing radical contains heteroatoms, then oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. In particular, -O-, -S-, -SO-, -SO ₂ -, -NR-, -N =, -PR-, -PR ₂ and -SiR ₂ - may be mentioned as preferred groups, it being with the radicals R are the remaining part of the carbon-containing radical.

Suitable functional groups are in principle all functional groups which can be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = 0 (especially as carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo ) and -CN (cyano). Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR- (tertiary amide), are included, for example di- (Ci-C ₄ alkyl) amino, Ci-C ₄ alkyloxycarbonyl or Ci-C ₄ alkyloxy.

Preference is given to heterocyclic quaternary in the process according to the invention

Ammonium and / or guanidinium carboxylates which contain the carboxylate anion (I) in which R ¹

• hydrogen; • C ₁ to C ₇ alkyl;

• O0C- (CH _{2) n} - where n is 0, 1 or 2;

• R "OOC- (CH ₂ ) _n - where n is 0, 1 or 2;

OOC-CH = CH-;

• ROOC-CH = CH-; • ethenyl;

• 2-propenyl; or • an unsubstituted or substituted by one to five independently selected groups from the series C ₁ - to C ₆ alkyl, hydroxy, carboxylate, carboxy and C ₁ - to C ₆ alkyloxycarbonyl substituted phenyl group and

R "is hydrogen or C ₁ - to C ₆ -alkyl;

mean, included.

The C ₁ - to C ₇ -alkyl radical are, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2 Methyl 2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3 Methyl 2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1 - pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1 - butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl- 2-butyl, 1-heptyl or 3-heptyl.

In the unsubstituted or by one to five independently selected groups from the series d- to Cβ-alkyl, hydroxy, carboxylate (-COO ^' ), carboxy (-COOH) and C ₁ - to C ₆ alkyloxycarbonyl (-COOR ² with R ² is C ₁ - to C ₆ -alkyl) substituted phenyl, for example phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl,

2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl

wherein R ^{1 is} C ₁ - to C ₆ alkyl. The carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation to be used in the process according to the invention preferably comprises as carboxylate anion formate, acetate, propionate, butyrate, pentanoate (valerate), hexanoate, heptanoate, octanoate, 2-ethylhexanoate, Methyl oxalate, ethyl oxalate, 1-propyl oxalate, 1-butyloxalate, 1-pentyloxalate, 1-hydroxy oxalate, 1-heptyloxalate, 1-octyl oxalate, 1- (2-ethyl) hexyloxalate, methyl malonate, ethyl malonate, 1-propyl malonate, 1-butyl malonate, 1-pentylmalonate, 1-hexylmalonate, 1-heptylmalonate, 1-octylmalonate, 1- (2-ethyl) hexylmalonate, methylsuccinate, ethylsuccinate, 1-propylsuccinate, 1-butylsuccinate, 1-pentylsuccinate, 1-hexylsuccinate, 1- Heptyl succinate, 1-octyl succinate, 1- (2-ethyl) hexyl succinate, methyl maleate, ethyl maleate, 1-propyl maleate, 1-butyl maleate, 1-pentyl maleate, 1-hexyl maleate, 1-heptyl maleate, 1-octyl maleate, 1- (2- Ethyl) hexyl maleate, methyl fumarate, ethyl fumarate, 1-propyl fumarate, 1-butyl fumarate, 1 Pentyl fumarate, 1 -hexyl fumarate, 1-octyl fumarate, 1- (2-ethyl) hexyl fumarate, acrylate, methacrylate, benzoate, 2-methyl benzoate, 3-methyl benzoate, 4-methyl benzoate, 2-hydroxybenzoate ( Salicylate), 3-hydroxybenzoate, 4-hydroxybenzoate, o-hydrogen phthalate, m-hydrogen phthalate, p-hydrogen phthalate, o-phthalate, m-phthalate, p-phthalate, o-methyl phthalate, o-ethyl phthalate, o- (1 - Propyl) phthalate, o- (1-butyl) phthalate, o- (1-pentyl) phthalate, o- (1-hexyl) phthalate, o- (1-heptyl) phthalate, o- (1-octyl) phthalate, o- (1- (2-ethyl) hexyl) phthalate, m-methyl phthalate, m-ethyl phthalate, m- (1-propyl) phthalate, m- (1-butyl) phthalate, m- (1-pentyl) phthalate, m (1-hexyl) phthalate, m- (1-heptyl) phthalate, m- (1-octyl) phthalate, m- (1- (2-ethyl) hexyl) phthalate, p-methyl phthalate, p-ethyl phthalate, p- (1-propyl) phthalate, p- (1-butyl) phthalate, p- (1-pentyl) phthalate, p- (1-hexyl) phthalate, p- (1-heptyl) phthalate, p- (1-octyl) phthalate, p- (1- (2-ethyl) hexyl) phthalate.

In the process according to the invention, particular preference is given to using heterocyclic quaternary ammonium and / or guanidinium formates, acetate or propionates, in particular formates.

The carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation to be used in the process according to the invention is preferably prepared by reacting the corresponding sp ³ -hybridized amine or sp ² -hybridized imine with the corresponding ester of the carboxylate anion. For this, the components are generally mixed together in any order over any period of time. The reaction is generally carried out at a temperature from 20 to 350 °, preferably from 100 to 250 ⁰ C. The Umset¬ carried wetting generally at a pressure of 0.05 to 35 MPa abs, preferably from 0.1 to 20 MPa abs.

The reaction can be carried out in the absence or in the presence of solvents. Suitable solvents are, for example, water, methanol or strongly polar aprotic solvents such as N, N-dimethylformamide. In general, the presence of water or methanol accelerates the reaction. Depending on the implementation of the reaction, the type and amount of any über¬ schüssiger starting materials or by-products formed and the presence of a Ka¬ talysators or solvent, the reaction can be worked up after completion of the reaction or used directly for the reaction according to the invention with the oxidizing agent. If the reaction effluent is worked up, this is generally worked up by distillation, extraction and / or crystallization.

The formates to be used with particular preference in the reaction according to the invention are thus usually prepared by reacting the corresponding sp ³ -hybridized amine or sp ² -hybridized imine with methyl formate. Alternatively, the methyl formate required for methylation can also be generated in situ. For this purpose, the corresponding sp ³ -hybridized amine or sp ² -hybridized imine is reacted with methanol and carbon monoxide, if appropriate in the presence of a solvent, such as water, methanol or strongly polar aprotic solvents such as N, N-dimethylformamide, at a temperature of 20 to 350 ° C, preferably 120 to 250 ⁰ C and a pressure of 0.05 to 35 MPa abs, preferably from 5 to 20 MPa abs.

In the process according to the invention, the preferred heterocyclic quaternary ammonium cation used is an imidazolium, imidazolinium, pyrazolium, pyrazolinium or pyridinium cation. Particular preference is given to using an aromatic heterocyclic quaternary ammonium cation, particularly preferably an imidazolium, pyrazolium or pyridinium cation, and very particularly preferably an imidazolium cation.

If, in the process according to the invention, an ammonium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (III)

in the

R ⁷ together with R ^{8 is} a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 30 carbon atoms be¬ interpret; or R ⁷ together with R ⁸ and R ^{9 is} a trivalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Mean carbon atoms;

and the remaining radicals are a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aliphatic radical, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms, where R ^{6 may} additionally stand for hydrogen.

If, in the process according to the invention, an imidazolium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (II)

(II).

in the

the radicals R ² to R ⁵ independently of one another a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cycli¬'s, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted 1 to 20 carbon atoms and the radicals R ² to R ⁴ additionally, independently of one another, are hydrogen, halogen or a functional group and the radical R ^{5 may} additionally also be hydrogen; or

two adjacent radicals R ² together with R ³ ; or R ³ together with R ⁵ ; or R ⁵ together with R ⁴ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 represent carbon atoms and the remaining radicals are as previously defined;

and the radical R ^{1 is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic see, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups unbere broken or substituted radical having 1 to 20 carbon atoms.

If an imidazolinium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (IV)

R11 R12

R1CT ^N Ψ ^N -R14

R13

(IV),

in the

the radicals R ¹¹ to R ¹⁴ are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms and the radicals R ¹¹ to R ¹³ additionally, independently of one another, mean hydrogen, halogen or a functional group and the radical R ^{14 may} additionally also be hydrogen; or

two adjacent radicals R ¹¹ together with R ¹² ; or R ¹² together with R ¹⁴ ; or R ¹⁴ together with R ¹³ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Koh ¬ lenstoffatomen mean and the remaining radicals are as defined above;

and the radical R ^{10 is} a carbon-containing organic, saturated or unge¬ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,

If, in the process according to the invention, a pyrazolium cation is used as heterocyclic quaternary ammonium cation, this preferably has the general formula (VI)

in the

the radicals R ¹⁶ to R ¹⁹ are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having from 1 to 20 carbon atoms and the radicals R ¹⁶ to R ¹⁸ additionally independently of one another hydrogen, halogen or a functional group meaning th and the radical R ^{19 may} additionally also be hydrogen; or

two adjacent radicals R ¹⁶ together with R ¹⁷ ; or R ¹⁷ together with R ¹⁸ ; or R ¹⁸ together with R ¹⁹ together represent a divalent, carbon-containing organic see, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Koh ¬ lenstoffatomen mean and the remaining radicals are as defined above;

and the radical R ^{15 is} a carbon-containing organic, saturated or unge¬ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,

If, in the process according to the invention, a pyrazolinium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (VII)

in the R ²¹ to R ²⁴ are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted or substituted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms and the radicals R ²¹ to R ²³ additionally independently of one another hydrogen, halogen or a functional group meaning th and the radical R ^{24 may} additionally also be hydrogen; or

two adjacent radicals R ²¹ together with R ²² ; or R ²² together with R ²⁴ ; or R ²⁴ together with R ²³ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Koh ¬ lenstoffatomen mean and the remaining radicals are as defined above;

and the radical R ^{20 is} a carbon-containing organic, saturated or unge¬ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms ,

If, in the process according to the invention, a pyridinium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (VIII)

in the

the radicals R ²⁶ to R ^{30 are} independently hydrogen, halogen, a functional group or a carbon-containing organic, saturated or ungesättig¬ th, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted or substituted radical having 1 to 20 carbon atoms; or two adjacent radicals R ²⁶ together with R ²⁷ ; or R ²⁷ together with R ²⁸ ; or R ²⁸ together with R ²⁹ or R ²⁹ together with R ³⁰ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Substituted th radical having 1 to 30 carbon atoms and the remaining radicals are as defined above;

and the radical R ^{25 is} a carbon-containing organic, saturated or unge¬ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,

If a guanidinium cation is used in the process according to the invention, this preferably has the general formula (IX)

in the

the radicals R ³² to R ³⁶ independently of one another are carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 Koh¬ mean radicals and R ³³ and R ³⁵ additionally independently of each other hydrogen, - or

two adjacent radicals R ³³ together with R ³⁴ ; or R ³⁵ together with R ³⁶ together menam a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or un interrupted or substituted by 1 to 5 heteroatoms or functional groups Radicals having 1 to 30 carbon atoms and the remaining radicals are as previously defined;

and the radical R ^{31 is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical see, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups unbere broken or substituted radical having 1 to 20 carbon atoms.

As the hetero atoms of the radicals R ¹ to R ³⁶ In the definition principle all heteroatoms in question, which are able to formally replace a -CH ₂ -, a -CH =, a or a -Cs = C = group to replace. If the carbon-containing radical contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. Particularly preferred groups which may be mentioned are -O-, -S-, -SO-, -SO ₂ -, -NR-, -N =, -PR-, -PR ₂ and -SiR ₂ -, where the radicals R is the remainder of the carbon-containing residue. The radical-containing carbon may be in the case of R ² to R ^4, R, R, R to be ¹¹ to R ^{13 16} to R ^{18 21} to R ²³ and R ²⁶ to R ³⁰ bound directly via the heteroatom at the respective Heterocycliumring.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = 0 (especially as carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo ) and -CN (cyano). Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR (tertiary amide), are included, for example di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ -AlkVl- oxycarbonyl or C ₁ -C ₄ -AlkVlOXy.

Halogens are fluorine, chlorine, bromine and iodine.

The hetero-cyclic quaternary ammonium cation and / or guanidinium cation used in the process according to the invention is preferably an ammonium (III), imidazolium (II), imidazolinium (IV), pyrazolium (VI), pyrazolinium (VII) , Pyridinium (VIII) or guanidinium cation (IX) in which the radicals R ² to R ⁴ (in the case of an imidazolium cation (II)), R ¹¹ to R ¹³ (in the case of an imidazolinium cation (IV ), R ¹⁶ to R ¹⁸ (in the case of a pyrazolium cation (VI)), R ²¹ to R ²³ (in the case of a pyrazolinium cation (VII)) and R ²⁶ to R ³⁰ (in the case of a pyridinium cation). Cations (VIII)) independently

• hydrogen; • halogen; or

• a functional group;

and the radicals R ¹ to R ⁶ and R ⁹ to R ³⁶ are each independently

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halo, heteroatoms and / or heterocycles and / or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted Cr to C ₁₈ alkyl;

Optionally C ₂ interrupted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to C ₁₈ - alkenyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles C ₆ - to C ₁₂ -aryl; Optionally C ₅ -C ₂ -cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles;

• where appropriate by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halo¬, heteroatoms and / or heterocycles substituted C ₅ - to C ₁₂ - cycloalkenyl; or optionally, a functional group, aryl, alkyl, aryloxy, alkyloxy,

Halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle means; or two adjacent radicals together • an unsaturated, saturated or aromatic, optionally substituted by funk¬ tionelle groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups form an interrupted ring.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₁ - to C ₁₈ -alkyl, it is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2, 3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetra-decyl, 1-pentadecyl, 1-hexadecyl, 1 -heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentene ylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, .alpha.,. alpha.-dimethylbenzyl, p-tolylmethyl, 1 - (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyI) -ethyl, methoxy, ethane oxy, formyl, 1, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2 yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2- Methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3 Ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, CnF ₂ (na) ₊ (ib) H ₂ a ₊ b with n being 1 to 30, 0 <a <n and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C (n. ₂ ) F _{2 (} n. ₂ ) ₊ i, C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl 1, 1, 1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl ) - ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxo-octyl, 11 - Hydroxy-3,6,9-trioxa undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9- Hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy-3,6, 9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxo nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy 5,10-oxa-tetrad ecyl.

C ₂ optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to dβ-alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or CnF _{2 (na)} . _{( 1.b} ) H _2a -b with n <30, 0 <a <n and b = 0 or 1.

C ₆ -C ₁₂ -aryl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, toIyI, xylyl, .alpha.-naphthyl, .beta.-naphthyl , 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, Isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethyl aminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _{(5 ) a)} H _a with 0 <a <5.

C ₅ -C ₁₂ -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl , Dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthio cyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _n F ₂ ( _n ) - (ib) H 2a-b with n <30, 0 <a <n and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ - to C ₁₂ cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5 Cyclohexadienyl or C _π F ₂ (na) -3 (ib) H ₂ a. _3b with n <30, 0 <a <n and b = 0 or 1.

An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or one or more sub¬ substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1 -Oxa- 1, 3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-ci C ₄ alkyl 1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1,3-dienylene or 2-aza-1, 4 -buta-1,3-dienylene.

If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and most preferably not more than 3. If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

Particularly preferably, the radicals R ¹ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹⁴ , R ¹⁵ , R ¹⁹ , R ²⁰ , R ²⁴ , R ²⁵ and R ³¹ to R ³⁶ independently of one another are unbranched or branched C. ₁ - to C ₂ -alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert -Butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2 , 2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2 -pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl 1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-i-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl , 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, vinyl, 2-cyanoethyl, 2- methoxycarbonyl) ethyl,

2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoropropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, for 6 -Hydroxyhexyl or propylsulfonic acid. In addition, the radical R ^{7 is} particularly preferably also a sulfo group.

The radicals R ² to R ⁴ , R ¹¹ to R ¹³ , R ¹⁶ to R ¹⁸ , R ²¹ to R ²³ and R ²⁶ to R ³⁰ are particularly preferably independently of one another hydrogen or unbranched or branched Cr to C ₁₂ -alkyl such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 - Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 - propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3, 3-Dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2- Hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino, chloro, trifluoro methyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl or 6-hydroxyhexyl.

Very particular preference is given in the process according to the invention as ammonium cation (II) to N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Very particular preference is given in the process according to the invention as imidazolium cation (II) 1, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-propyl) -3-methylimidazolium, 1- (1-butyl) 3-methylimidazolium, 1- (1-pentyl) -3-methylimidazolium, 1 - (1-hexyl) -3-methyl-imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-decyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1 - (1-pentadecyl) -3-methylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-propyl) -2,3-dimethylimidazolium, 1- (1-butyl ) -2,3-dimethylimidazolium, 1- (1-pentyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3- dimethyl imidazolium, 1- (1-decyl) -2,3-dimethylimidazolium, 1- (1-dodecyl) -2,3-dimethylimidazolium and 1- (1-pentadecyl) -2,3-dimethylimidazolium.

Very particular preference is given in the process according to the invention as imidazoline cation (IV) 1, 3-dimethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1- (1-propyl) -3-methylimidazolinium, 1- (1-butyl) 3-methylimidazolinium, 1- (1-pentyl) -3-methylimidazolinium, 1- (1-hexyl) -3-methylimidazolinium, 1- (1-octyl) -3-methylimidazoliumium, 1 - (1- Decyl) -3-methylimidazolinium, 1- (1-dodecyl) -3-methylimidazolinium, 1- (1-pentadecyl) -3-methylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium , 1- (1-propyl) -2,3-dimethylimidazolinium, 1- (1-butyl) -2,3-dimethylimidazolinium, 1- (1-pentyl) -2,3-dimethylimidazolinium, 1- (1-naphthyl) -2- Hexyl) -2,3-dimethylimidazolinium, 1- (1-octyl) -2,3-dimethylimidazolinium, 1- (1-decyl) -2,3-dimethylimidazolinium, 1- (1-dodecyl) -2 , 3-dimethylimidazolinium and 1- (1-pentadecyl) -2,3-dimethylimidazolinium.

Very particular preference is given in the process according to the invention as pyrazolium cation (VI) 1, 2-dimethylpyrazolium, 1-ethyl-2-methylpyrazolium, 1- (1-propyl) -2-methylpyrazolium, 1- (1-butyl) 2-methylpyrazolium, 1- (1-pentyl) -2-methylpyrazolium, 1- (1-hexyl) -2-methyl-pyrazolium, 1- (1-octyl) -2-methylpyrazolium, 1- (1-decyl) 2-methylpyrazolium, 1- (1-dodecyl) -2-methylpyrazolium and 1- (1-pentadecyl) -2-methylpyrazolium.

Very particular preference is given in the process according to the invention as pyrazolinium cation (VII) 1, 2-dimethylpyrazolinium, 1-ethyl-2-methylpyrazolinium, 1- (1-propyl) -2-methylpyrazolinium, 1- (1-butyl) 2-methylpyrazolinium, 1- (1-pentyl) -2-methyl-pyrazolinium, 1- (1-hexyl) -2-methyl-pyrazolinium, 1- (1-octyl) -2-methyl-pyrazolinium, 1- (1 Decyl) -2-methylpyrazolinium, 1- (1-dodecyl) -2-methylpyrazolinium and 1- (1-pentadecyl) -2-methylpyrazolinium.

Very particular preference is given in the process according to the invention as pyridinium cation (VIII) 1-methylpyridinium, 1-ethylpyridinium, 1- (1-propyl) pyridinium, 1- (1-butyl) pyridinium, 1- (1-pentyl) pyridinium, 1- (1-hexyl) pyridinium and 1- (1-octyl) pyridinium.

Very particular preference is given in the process according to the invention as guanidinium cation (IX) N ₁ N ₁ N ', N', N " _I N" hexamethylguanidinium. The intermediate product obtained in the reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds can generally be used directly without purification to give the desired heterocyclic quaternary ammonium - And / or guanidinium compound weiterver¬ works. If necessary, however, a workup and purification of the intermediate product is possible. In the latter case, the oxidation product can spielsweise be worked up by phase separation, extraction and / or crystallization.

A variant for the synthesis of the desired heterocyclic quaternary ammonium and / or guanidinium compounds from the intermediate product formed according to the invention is the electrochemical reaction in aqueous solution to give the corresponding heterocyclic quaternary ammonium and / or guanidinium hydroxide.

In order to avoid a mixing of the electrochemically formed heterocyclic quaternary ammonium and / or guanidinium hydroxide with the intermediate used, it is preferred to use divided electrolysis cells. Particular preference is given to electrolysis cells with a diaphragm made of a cation exchange membrane which separates the electrolysis cell into an anode space and a cathode space. However, it is also possible to use a multi-chamber electrolysis cell with one or more separate intermediate chambers by arranging a plurality of cation exchange membranes. Suitable materials for the cation exchange membrane are, for example, non-corrosive fluorine resins having a cation exchange group, such as a sulfonic acid or carboxylic acid group, in combination with a styrene-divinylbenzene copolymer having the above-mentioned ion exchange groups.

The anode used may be an electrode which is suitable for this type of electrolysis, for example a high-purity carbon electrode or a titanium electrode which is coated with an oxide of a platinum group metal such as platinum or iridium. Further, as the cathode, an electrode suitable for this type of electrolysis, for example, a stainless steel or nickel electrode, may be used. The anodes and cathodes can be used in any form as plates, nets, porous plates and the like.

The electrochemical reaction can be carried out batchwise or continuously. The concentration of the intermediate used in the electrolysis according to the invention is preferably from 1 to 60 wt .-% and particularly preferably from 3 to 40 wt .-% in aqueous solution at the beginning of the electrolysis. If the conductivity at the beginning of the electrolysis should be very low, for example, a small amount of about 0.01 to 5 wt .-% of the corresponding heterocyclic quaternary ammonium and / or guanidinium hydroxide are added.

The electrolysis can be carried out by applying a DC voltage. The current density is preferably in the range from 1 to 100 A / dm ² and preferably from 3 to 50 A / dm ² . The temperature of the electrolyte is preferably in the range from 10 to 50 ^° C. It is also preferred that during the electrolysis the atmosphere on the surface of the electrolyte consists of an inert gas such as nitrogen or argon.

For purification, the heterocyclic quaternary ammonium and / or guanidinium hydroxide formed can be isolated from the electrolysis liquid, for example by distilling off the water present, preferably under reduced pressure. As a rule, the product is very pure, so that it can be used directly, for example as conductive salt in the electrical industry. If necessary, however, the product can also be further purified, for example by recrystallization or extraction. In a further variant, the heterocyclic quaternary ammonium and / or guanidinium hydroxide - as an isolated pure substance, but also in the form of the resulting aqueous electrolysis liquid - with an inorganic or organic protic acid having a pKa of <14, measured at 25 ° C. in aqueous solution to form the heterocyclic quaternary ammonium and / or guanidinium compound of the partially or fully deprotonated anion of the inorganic or organic protic acid.

In another preferred variant for the synthesis of the desired heterocyclic quaternary ammonium and / or guanidinium compounds from the intermediate product according to the invention, this is reacted with an inorganic or organic protic acid having a pKa value of <14, measured at 25 ° C in aqueous solution to form the heterocyclic quaternary ammonium and / or guanidinium compound of the partially or fully deprotonated anion of inorganic or organic protic acid.

The relative amount of inorganic or organic protic acid relative to the total amount of the corresponding heterocyclic quaternary ammonium cation and guanidinium cation generally depends on the desired degree of conversion of the intermediate used (ie, whether the intermediate is completely or only partially in the desired Compound with the desired anion to be transferred), according to specific procedural aspects (as spielsweise also the nature of the subsequent work-up and the ability to remove any excess protic acid) and ren in polybasic proton acids according to the number of the formation of the desired partially or fully deprotonated anions of protons to be released from the inorganic or organic protic acid. In general, a molar ratio of the inorganic or organic protic acid to the total amount of the heterocyclic quaternary ammonium cation and / or guanidinium cation of the intermediate formed is from 0.9 / a to 1.5 / a, preferably from 0.95 / a to 1, 1 / a and more preferably from 0.99 / a to 1, 02 / a, where a is the number of protons to be released from the inorganic or organic protic acid to form the desired partially or fully deprotonated anion. For a monobasic acid such as tetrafluoroboric acid, a is 1. For a dibasic acid such as sulfuric acid, if the monoanion (ie, hydrogen sulfate in the example) is desired, a is 1, and for the Case that the dianion (in the example the sulfate) is desired, a equals 2.

Preference is given to using an inorganic or organic protic acid in which the partially or fully deprotonated anion

Fluoride; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoroar- genate; Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate; Phosphate;

Hydrogen phosphate; Dihydrogen phosphate, vinyl phosphonate, dicyanamide, bis (pentafluoroethyl) phosphinate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoro-propyl) trifluorophosphate, bis [oxalato (2 -)] borate, bis [salicylato (2 -)] borate, bis [ 1,2-benzenediolato (2 -) - O, O '] borate, tetracyano borate, tetracarbonyl cobaltate;

tetrasubstituted borate of the general formula (Va) [BR ^a R ^b R ^c R ^d ] ^' , wherein R ^a to R ^d independently of one another for fluorine or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

organic sulfonate of the general formula (Vb) [R ^β -SO ₃ ] ^" , where R ^{e is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

Carboxylate of the general formula (Vc) [R ^f -COO] ^' , wherein R ^{f is} hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen; (Fluoroalkyl) fluorophosphate of general formula (Vd) [PF _x (CyF _{2V + I} - _Z Hz) ₆ -J ^" , where 1 <x <6, 1 <y ≤ 8 and O ≤ z <2y + 1;

Imide of the general formulas (Ve) [R 1 SO 2 -N-SOz-R *] ^' , (Vf) [R'-SO 2 -N-CO-R ¹ ] ^' or (IVg) [R ^k -CO-N- CO-R '] ^' , wherein R ⁹ to R ^{1 are} independently hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

Methide of the general formula (Vh)

(Vh),

where R ^m to R ⁰ independently of one another represent hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms which contain one or more heteroatoms and / or one or more heteroatoms a plurality of functional groups or halogen may be substituted;

organic sulfate of the general formula (Vi) [R ¹³ O-SO ₃ ] ^' , where R ^{p is} a carbon-containing organic, saturated or unsaturated, acyclic or cycli¬ rule, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon ¬ atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen, is;

Halometallat of the general formula (Vj) [M _q Hal _r ] ^s' , where M is a metal and Hal for fluorine, chlorine, bromine or iodine, q and r are positive integers indicating the stoichiometry of the complex and s is a whole positive number and indicates the charge of the complex; or

Sulfide, hydrogen sulfide, hydrogen polysulfide of the general formula (Vk) [HS _V ] ^' , polysulfide of the general formula (Vm) [S _v ] ^{2 "} , where v is a whole positive number from 2 to 10, thiolate of the general formula (Vn) [R ⁸ S] ^' , where R ^{s is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms and containing one or more heteroatoms, and or may be substituted by one or more functional groups or halogen; is.

Heteroatoms are in principle all heteroatoms in question, which are able to formally replace a -CH ₂ -, a -CH =, a C≡ or a = C = group. Ent¬ holds the carbon-containing radical heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. Particularly preferred groups are -O-, -S-, -SO-, -SO ₂ -, -NR-, -N =, -PR-, -PR ₂ and -SiR ₂ - called, in particular, where the radicals R are the remaining part of the carbon-containing radical.

Suitable functional groups are in principle all functional groups which can be bonded to a carbon atom or a heteroatom. Suitable examples include -OH (hydroxy), = 0 (especially as the carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide) and -CN (cyano) , Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR- (tertiary amide), are included,

Halogens are fluorine, chlorine, bromine and iodine.

As carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radicals having 1 to 30 carbon atoms, the radicals R ^a to R ^d in tetrasubstituted borate (Va), the radical R ^β in the organic sulfonate (Vb ), the radical R ⁽ in the case of the carboxylate (Vc), the radicals R ⁹ to R ¹ in the imides (Ve), (Vf) and (Vg), the radicals R ^m to R ⁰ in the case of the methide (Vh), the radical R ^p in the case of the organic sulfate (Vi) and the radical R ^s in the thiolate (Vn) independently of one another, preferably for

C 1 -C ₃₀ -alkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO-, -CO-O- or - CO-N <substituted components such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert. Butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2, 2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2- pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl 1-butyl, 3,3-dimethyl-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,

Octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenylmethyl (benzyl), Diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl, acetyl or C _n F _{2 (} na _{) + (} i- _b) H ₂ a _{+ b} with n <30, 0 <a <n and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C ₍ n-2) F 2 (n-) 2) ₊ 1 ι CβFi ₃ , CβFi7, C10F2L C12F25);

C ₃ - to C ₁₂ -cycloalkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components such as cyclopentyl, 2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl, 3-methyl-i-cyclohexyl, 4-methyl-1-cyclohexyl or CnF ₂ (na) - (ib) H2a-b with n <30, 0 <a <n and b = 0 or 1;

C ₂ to C ₃₀ alkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components such as 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or CnF ₂ (na) - (ib) H2a-b with n <30, 0 <a <n and b = 0 or 1 ; • C ₃ - to C ₂ cycloalkenyl and their aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- or -CO-O-substituted Components ¬ th, such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _n F ₂ ( _n . _A ) .3 ( _1-b ) H2 _a -3b with n <30, 0 < a <n and b = 0 or 1; and

Aryl or heteroaryl having 2 to 30 carbon atoms and their alkyl, aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or

-CO-O-substituted components, such as, for example, phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl phenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-dimethylphenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl,

4-pyridinyl or C ₆ F _(S-3 ) H ₃ with 0 <a <5.

If the anion is a tetrasubstituted borate (Va) [BFY ¹ R ¹ WR ⁰ ] ^' , all four radicals R ^a to R ^d in this case are preferably identical, these preferably being fluorine, trifluoromethyl, pentafluoroethyl, phenyl, 3 , 5-bis (trifluoromethyl) phenyl. Particularly preferred tetrasubstituted borates (Va) are tetrafluoroborate, tetraphenylborate and tetra [3,5-bis (trifluoromethyl) phenyl] borate.

If the anion is an organic sulfonate (Vb) [R ^e -SO ₃ ], the radical R ^{e is} preferably methyl, trifluoromethyl, pentafluoroethyl, p-tolyl or C ₉ F ₁₉ . Particularly preferred organic sulfonates (Vb) are trifluoromethanesulfonate (triflate), methanesulfonate, p-tolylsulfonate, nonadecafluorononanesulfonate (nonaflate), dimethlylene glycol monomethyl ether sulfate and octyl sulfate.

If it ^is', as it is when the anion is a carboxylate (Vc) [R'-COO] R ^f preferably represent hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxy-phenyl-methyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl , Difluoromethyl, Fluids ormethyl, ethenyl (vinyl), 2-propenyl, -CH = CH-COO ^" , cis-8-heptadecenyl, -CH ₂ - C (OH) (COOH) -CH ₂ -COO ^' or unbranched or branched d- to C ₁₈ alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl) , 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-i-butyl, 3 , 3-dimethyl-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, heptadecyl Particularly preferred carboxylates (Vc) are formate, acetate, propionate, butyrate, valerate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.

Is the anion a (fluoroalkyl) fluorophosphate (Vd)

Thus, z is preferably O. Particular preference is given to (fluoroalkyl) fluorophosphates (Vd) ₁ in which z = 0, x = 3 and 1 <y <4, specifically [PF ₃ (CFa) ₃ ] ^" , [PF ₃ (C ₂ Fs) ₃ ] ^" , [PF ₃ (C ₃ F ₇ ) ₃ ] ^" and [PF ₃ (C ₄ F ₇ J ₃ ] ^" .

Is the anion an imide (Ve) [R ⁹ -SO ₂ -N-SO ₂ -R ^h ] (Vf) [R ⁱ -SO ₂ -N-CO-R '] - or (Vg) [ R ^k -CO-N-CO-R '] ^" , the radicals R ⁹ to R ¹ independently of one another preferably represent trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C ₁ - to C ₁₂ -alkyl, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-one propyl (tert -butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2- butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2- Methyl 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2, 3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, Decyl, undecyl or dodecyl. Particularly preferred imides (Ve), (Vf) and (Vg) are [F ₃ C-SO ₂ -N-SO ₂ -CF _3] ^"(bis (trifluoromethylsulfonyl) imide), [F ₅ C ₂ -SO ₂ -N -SO ₂ -C ₂ F _5] ^"(bis (pentafluoroethylsulfonyl) imide), [F ₃ C-SO ₂ -N-CO-CF _3] ^', [F ₃ C-CO-N-CO-CF ^_3]" and those in which the radicals R ⁹ to R ¹ independently of one another are methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.

Is the anion a methide (Vh)?

(Vh), Thus, the radicals R ^m to R ⁰ independently of one another are preferably trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C ₁ - to C ₁₂ -alkyl, such as, for example, methyl, ethyl, 1 Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3 Pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2- Hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl 2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Methides (Vh) Particularly preferred are [(F ₃ C-SO _{2) 3} C] ^* (tris (trifluoromethyl sulfonyl) methide), [(C ₅ F ₂ -SO _{2) S} C] ^"(bis (pentafluoroethylsulfonyl) methide ) and those in which the radicals R ^m to R ⁰ independently of one another are methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.

If the anion is an organic sulfate (Vi) [R ^p O-SO ₃ ] ^' , the radical R ^{p is} preferably a branched or unbranched C ₁ - to C ₃₀ -alklyl radical. Be¬ particularly preferred organic sulfates (Vi) are methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate or octyl sulfate.

If it is, stands When the anion is a halometalate (Vj) [M _q Hal _r] ^{s "as} M preferably represents aluminum, zinc, iron, Cobald, antimony or tin. Hal is preferably chlorine or bromine, and very particularly preferably represents chlorine , q is preferably 1, 2 or 3 and r and s are given according to the stoichiometry and charge of the metal ion.

Wherever the anion is thiolate (Vn) [R ^S S], ^"the radical R ^s is preferably a branched or unbranched C ₁ -. -C ₃₀ -Alklylrest Particularly preferred thiolates (Vn) are methyl sulfide, ethyl sulfide, n Propylsulfide, n-butylsulfide, n-pentylsulfide, n-hexylsulfide, n-heptylsulfide, n-octylsulfide or n-dodecylsulfide.

Very particular preference is given to using an inorganic or organic protic acid in which the partially or fully deprotonated anion tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, formate, acetate, mandelate, nitrate, nitrite, trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, Ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, propionate, tetrachloroaluminate, Al ₂ Cl ₇ ^" , chlorozinc, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato (2 -)] borate, tetracarbonylcobaltate, dimethylenglycolmonomethylethersulfate, octylsulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, Bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis [1, 2-benzene diolato (2 -) - O, O '] borate, dicyanamide, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyano borate or chlorocobaltate.

The reaction between the present invention formed intermediate and the inorganic or organic protonic acid is generally carried out at a Tem¬ temperature of 0 to 35O ⁰ C, preferably from 10 to 200 ⁰ C and more preferably from 10 to 100 ⁰ C. The pressure is generally 0.01 to 10 MPa abs, preferably 0.09 to 0.5 MPa abs and more preferably 0.09 to 0.2 MPa abs.

In principle, all reactors which are suitable for a reaction in the liquid phase can be used as reaction apparatuses. These are in particular reactors which allow a corresponding mixing of the liquid educts, for example stirred tank.

The nature and sequence of the addition of the individual educts is immaterial. Thus, it is possible, for example, to give the intermediate product according to the invention and the inorganic or organic protic acid in succession in any order or in parallel into the reactor. It is also possible to introduce one of the three educts and to drop the other educt over a certain period of time from a few seconds to several hours.

It is possible to carry out the reaction in the absence or in the presence of a solvent. If a solvent is used, preference is given to choosing water, C 1 to C ₈ -alkanols, N, N-dimethylformamide or N-methylpyrrolidone. If, for example, an inorganic or organic protic acid is used which is not present in pure form or is preferably used diluted for other reasons, the reaction is usually carried out in the presence of a solvent.

The reaction between the intermediate product formed according to the invention and the inorganic or organic protic acid can be carried out batchwise, semicontinuously or continuously. In the discontinuous procedure, the starting materials are combined and the reaction is carried out. After completion of the reaction, the reaction mixture is worked up to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound. In the continuous operation, the two starting materials are added slowly to the reaction apparatus for reaction. The reaction mixture is taken off continuously in accordance with the amounts of educts fed in and worked up as described. The workup itself can also be done continuously. In the case of the semicontinuous variants, one of the two educts is added slowly, the reaction generally taking place in parallel with the addition. After the desired amount has been added, the reaction mixture is worked up. then mixed to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound.

The reaction mixture obtained in the reaction between the intermediate product formed according to the invention and the inorganic or organic protic acid can be worked up in various ways to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compounds. Generally suitable methods are the extraction and the crystallization of the desired product. Suitable extraction agents are for example C ₅ - to C ₂ alkanols, methyl tert-butyl ether and ethyl acetate. If, in the reaction between the intermediate formed according to the invention and the inorganic or organic protic acid, gaseous or at least readily distillate components are formed from the anion of the intermediate product, then it is generally sufficient to remove these components from the Reaction mixture by distillation, preferably under vacuum to remove. An example of this procedure is the reaction of the carbonate / bicarbonate obtained with the reaction according to the invention between the heterocyclic quaternary ammonium and / or guanidinium formate and the oxidizing agent with the inorganic or organic protic acid in which carbon dioxide escapes and The water formed can be easily removed by distillation.

In a preferred embodiment, an N-alkylated and optionally also substituted on one or more ring carbon atoms imidazole with methyl formate to the corresponding 1-methyl-3-alkyl-imidazolium formate. This is then oxidized to the desired intermediate with an aqueous hydrogen peroxide solution or air over a catalyst containing palladium and / or platinum.

In one variant, this intermediate product is converted electrochemically into the corresponding 1-methyl-3-alkylimidazolium hydroxide, which can be obtained by distilling off the water present and, if appropriate, extraction and / or crystallization in pure form. The 1-methyl-3-alkyl-imidazolium hydroxide is obtained in high purity.

In another preferred variant, this intermediate is reacted with the organic or organic protic acid of the desired anion to give the 1-methyl-3-alkylimidazolium compound of the desired anion, which is removed by removing the carbon dioxide formed and distilling off the water present if appropriate, extraction and / or crystallization in pure form can be obtained. The 1-methyl-3-alkyl-imidazolium compound of the desired anion is obtained in high purity. The process according to the invention makes it possible to prepare simply an intermediate containing a heterocyclic quaternary ammonium and / or guanidinium cation for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds which can be converted into the desired process in a simple and flexible manner heterocyclic quaternary ammonium and / or guanidinium compound of high purity can be converted. The desired anion can be introduced simply and flexibly in the case of the hydroxide anion by electrolysis and in the case of other anions by reacting the intermediate formed according to the invention with an inorganic or organic protic acid of the desired anion and the resulting reaction mixture to isolate the desired heterocyclic quaternary ammonium Compound and / or guanidinium compound easy to work up. The particular advantage of using the carboxylate as the starting compound is the simple preparation of the carboxylates, the starting materials used for their preparation being not or only slightly toxic, technically readily available and inexpensive.

In this context, the use of the formates of the corresponding heterocyclic quaternary ammonium compounds and / or guanidinium compound is particularly advantageous, since these are very simply prepared by reacting the corresponding amines or imines with the inexpensive and very readily available methyl formate can be represented and the carbonates / bicarbonates formed in the subsequent reaction with the oxidizing agent by the an¬ closing reaction with the inorganic or organic protic acid readily decomposable and the reaction products of carbon dioxide and water are easily separated.

The heterocyclic quaternary ammonium and guanidinium compounds which can be prepared from the intermediate products prepared by the process according to the invention are particularly suitable for use in the electronics industry because of their high purity.

Examples

Example 1 (1, 3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were in 40 g of methanol in an autoclave with 91 g (1, 5 mol) of methyl formate and stirred for 18 hours under autogenous pressure at 130 ⁰ C ge. From the reaction, the volatile, excess feedstocks and methanol were distilled off. According to the NMR spectrum of the crude product, the structure of the product was confirmed to be 1, 3-dimethylimidazolium formate. The conversion of the reaction was 43% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and filtered with suction in the form of colorless crystals. Example 2 (1, 3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were mixed in 40 g of methanol in an autoclave with 91 g (1, 5 mol) of methyl formate and stirred for 12 hours under autogenous pressure at 150 ⁰ C ge. From the reaction, the volatile, excess feedstocks and methanol were distilled off. According to the NMR spectrum of the crude product, the structure of the product was confirmed to be 1, 3-dimethylimidazolium formate. The conversion of the reaction was 73% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and filtered with suction in the form of colorless crystals.

Example 3 (1,3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were mixed in 40 g of methanol in an autoclave with 91 g (1, 5 mol) of methyl formate and stirred for 12 hours under autogenous pressure at 14O ⁰ C ge. From the reaction, the volatile, excess feedstocks and methanol were distilled off. According to the NMR spectrum of the crude product, the structure of the product was confirmed to be 1, 3-dimethylimidazolium formate. The conversion of the reaction was 55% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and filtered with suction in the form of colorless crystals.

Example 4 (1,3-dimethylimidazolium formate via in-situ preparation of methyl formate)

33 g (0.4 mol) of 1-methylimidazole were dissolved in 50 ml of methanol. In an autoclave 10 MPa abs carbon monoxide were injected at 150 ⁰ C and stirred for 40 hours. From the reaction, the volatiles excess starting materials and methanol were distilled off. According to the NMR spectrum of the crude product, the structure of the product was confirmed to be 1, 3-dimethylimidazolium formate. The conversion of the reaction was 21% based on 1-methylimidazole.

Example 4 demonstrates that a methylation to the 1, 3-dimethylimidazolium formate is also possible by the in-situ representation of methyl formate.

Example 5 (1-ethyl-3-methylimidazolium acetate)

33 g (0.4 mol) of 1-ethylimidazole were added in 45 g of methanol in an autoclave with 111 g (1, 5 mol) of methyl acetate and stirred under autogenous pressure at 16O ⁰ C for 20 hours. From the reaction, the volatile, excess feedstocks and methanol were distilled off. According to the NMR spectrum of the crude product, the structure of the product was confirmed to be 1-methyl-3-ethylimidazolium acetate. The conversion of the reaction was 24% based on 1-ethylimidazole. The product mixture was extracted three times with 1: 1 by volume of methyl tert-butyl ether (MTBE) and the MTBE phase concentrated separately from the product phase. The residue of the MTBA phase contained> 95% 1-ethylimidazole, the product phase contained 65% of 1-ethyl-3-methylimidazoium acetate and 35% of 1-ethylimidazole. The remaining 1-ethylimidazole from the product phase was distilled off in vacuo (5 hPa abs), leaving 15.7 g (97%) of 1-ethyl-3-methylimidazolium acetate.

Example 6: (1-Butyl-3-methylimidazolium formate)

373 g (3.0 mol) of 1-butylimidazole were mixed in 300 ml of methanol in an autoclave with 685 g (11, 4 mol) of methyl formate and 18 hours under autogenous pressure at 14O ⁰ C stirred. From the reaction, the volatile, excess Einsatz¬ substances and methanol were distilled off. The conversion of the reaction was 78% based on 1-butylimidazole. Excess 1-butylimidazole was removed by distillation in vacuo (8 hPa abs). According to the NMR spectrum of the liquid, brownish colored crude product, the structure was confirmed to be 1-methyl-3-butylimidazolium formate. The yield was 76%.

Example 7 (1,2,3-trimethylimidazolium formate)

28.8 g (0.299 mol) of 1,2-dimethylimidazole and 68.4 g (1.14 mol) of methyl formate were dissolved in 20 g of methanol and stirred under autogenous pressure (3 MPa abs) at 14O ⁰ C for 18 hours. The volatiles, excess feedstocks and methanol were distilled off. The conversion of the reaction was 90% based on 1, 2-dimethylimidazole. Excess 1,2-dimethylimidazole was distilled off and the product, 1,3,3-trimethylimidazolium formate, was obtained as a slightly yellow-colored solid (37.5 g, 99% yield).

Example 8 (according to the invention)

20 g (0.109 mol) of 1-butyl-3-methylimidazolium formate were added together with 1 g Kata¬ lyst (10 wt .-% Pd on activated carbon) were introduced into 80 g of water and heated to 60 ⁰ C. Within 40 minutes, 24.7 g of 30 wt .-% hydrogen peroxide solution (corresponding to 0.218 mol H ₂ O ₂ ) were metered in and stirred for 1 hour. The catalyst was filtered off and the water was distilled off from the filtrate under vacuum (to 100 ⁰ C, 5 hPa abs). 19.2 g of a product were isolated whose structure was confirmed according to the NMR spectrum as 1-butyl-3-methylimidazolium carbonate / bicarbonate.

Example 9 (according to the invention)

16.5 g of the product from Example 8 were dissolved in 50 g of water and, at about 25 ° C., dissolved within 15 minutes with 14.5 g of 50% strength by weight aqueous tetrafluoroboric acid ( 0.082 mole of HBF ₄ ) is added, with a gas evolution (CO ₂ ) was observed. After the end of the dropping time, the water was distilled off, and according to the NMR spectrum, the structure was confirmed to be 1-butyl-3-methylimidazolium tetrafluoroborate. The yield was 18.5 g, corresponding to 99%.

Claims

claims

1. A process for the preparation of a, a heterocyclic quaternary ammonium and / or guanidinium cation-containing intermediate for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds, characterized in that heterocyclic quaternary ammonium and / or guanidinium carboxylates with oxidized an oxidizing agent in the presence of a metal from the 8th to 10th group of the periodic table at a Tempe¬ temperature of 0 to 250 ⁰ C and a pressure of 0.05 to 20 MPa abs.

2. The method according to claim 1, characterized in that one uses as the oxidizing agent hydrogen peroxide or oxygen.

3. Process according to claims 1 to 2, characterized in that the oxidation in the presence of palladium, platinum, ruthenium, rhodium and / or

Iridium performs.

4. Process according to claims 1 to 3, characterized in that one uses heterocyclic quaternary ammonium and / or guanidinium carboxylates, which is the carboxylate anion of the general formula (I)

R'-COCT (I),

in the R ¹ • hydrogen;

• Cr to C ₇ alkyl;

• OOC- (CH ₂ ) _n - where n is 0, 1 or 2;

• R "OOC- (CH ₂ ) _n - where n is 0, 1 or 2;

OOC-CH = CH-; • ROOC-CH = CH-;

• ethenyl;

• 2-propenyl; or

• an unsubstituted or substituted by one to five independently selected groups from the series C ₁ to C ₆ alkyl, hydroxy, carboxyl, carboxyl and C ₁ - to Cβ-alkyloxycarbonyl substituted phenyl group and

R "is hydrogen or Ci- to C ₆ -alkyl;

5. The method according to claim 4, characterized in that one uses heterocyclic quaternary ammonium and / or guanidinium formate. Process according to Claims 1 to 5, characterized in that an intermediate is prepared in which the cation is an imidazolium, imidazolinium, pyrazolium, pyrazolinium or pyridinium cation.

Process according to Claims 1 to 5, characterized in that an intermediate is prepared in which the cation is an aromatic heterocyclic quaternary ammonium cation.

A process according to claim 7, characterized in that an intermediate product is prepared in which the cation is an imidazolium cation of the general formula (II)

OD.

in the

the radicals R ² to R ⁵ independently of one another sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted or substituted by 1 to 5 heteroatoms or functional groups Radical having from 1 to 20 carbon atoms and the radicals R ² to R ⁴ additionally mean, independently of one another, of hydrogen, halogen or a functional group and the radical R ^{5 may} additionally also be hydrogen; or

two adjacent radicals R ² together with R ³ ; or R ³ together with R ⁵ ; or R ⁵ together with R ⁴ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 carbon atoms and the remaining radicals are as previously defined;

and the radical R ^{1 is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional Ie groups interrupted or substituted radical having 1 to 20 Kohlenstoff¬ atoms means;

is.

9. The method according to claim 8, characterized in that one prepares a Zwischen¬ product in which the cation 1, 3-dimethylimidazolium, 1-ethyl-3-methyl-imidazolium, 1 - (1-propyl) -3-methylimidazolium, 1 - (1-Butyl) -3-methylimidazolium, 1- (1-pentyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1 - (1-Decyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-pentadecyl) -3-methylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl 2,3-dimethylimidazolium, 1- (1-propyl) -2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-pentyl) -2,3-dimethylimidazolium, 1 - (1-Hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1- (1-decyl) -2,3-dimethylimidazolium, 1- (1-dodecyl) - 2,3-dimethylimidazolium and 1 - (1 -

Pentadecyl) -2,3-dimethylimidazolium.

10. Process according to claims 1 to 9, characterized in that the intermediate formed in an aqueous solution is electrochemically reacted to give the corresponding heterocyclic quaternary ammonium and / or guanidinium hydroxide.

11. The method according to claims 1 to 9, characterized in that the formed intermediate with an inorganic or organic protic acid having a pKg of <14, measured at 25 ° C in aqueous solution, to form the heterocyclic quaternary ammonium and / or guanidinium compound of the partially or fully deprotonated anion of inorganic or organic protic acid.

12. Process according to claim 11, characterized in that a molar ratio of the inorganic or organic protic acid to the total amount of the heterocyclic quaternary ammonium and / or guanidinium cation of the intermediate formed from 0.9 / a to 1.5 / a where a denotes the number of protons to be released from the inorganic or organic protic acid to form the desired partially or fully deprotonated anion.

13. The method according to claims 11 to 12, characterized in that one uses an inorganic or organic protic acid in which the partially or fully deprotonated anion

Fluoride; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoro- arsenate; Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate; Phosphate; Hydrogen phosphate; Dihydrogen phosphate, vinyl phosphonate, dicyanamide, bis (pentafluoroethyl) phosphinate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, bis [oxalato (2 -)] borate, bis [salicylato (2 -)] borate, bis [1 , 2-benzenediolato (2 -) - O, O '] borate, tetracyano borate, tetracarbonyl cobaltate;

tetrasubstituted borate of the general formula (Va) [BR ^a R ^b R ^c R ^d ] ^' , where R ^a to R ^d independently of one another represent fluorine or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

organic sulfonate of the general formula (Vb) [R ^e -SO ₃ ] \ where R ^{e is} a carbon-containing organic, saturated or unsaturated, acycli¬'s or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which one or contains a plurality of heteroatoms and / or may be substituted by one or more functional groups or halogen;

Carboxylate of the general formula (Vc) [R'-COO] ^" , wherein R ^{f is} hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;

(Fluoroalkyl) fluorophosphate of the general formula (Vd) [PF _x (CyF _{2x + IZ} Hz) ₆ - _X ] ^' , where 1 <x <6, 1 <y <8 and 0 <z <2y + 1;

Imide of general formulas (Ve)

(Vf) [R ⁱ -SO ₂ -N-CO-R '] - or (IVg) [R ^k -CO-N-CO-R'] \ where R ⁹ to R ¹ independently of one another for hydrogen or a Carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen , stand;

Methide of the general formula (Vh) SO ₂ -R ^m

I

R ⁿ -O ₂ S '^" SO ₂ -R ⁰

(Vh),

where R ^m to R ⁰ independently of one another are hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms which contain one or more heteroatoms and / or one or more functional groups or halogen may be substituted;

organic sulfate of the general formula (Vi) [R ^P O-SO ₃ ] ^' , where R ^{p is} a

Carbon-containing organic, saturated or unsaturated, acycli¬ rule or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or tuiert by one or more functional groups or halogen tuiert , stands;

Halometalate of the general formula (Vj) [M _q Hal _r ] ^s \ where M is a metal and Hal is fluorine, chlorine, bromine or iodine, q and r are positive integers indicating the stoichiometry of the complex and s is a whole positive Number is and indicates the charge of the complex; or

Sulfide, hydrogen sulfide, hydrogen polysulfide of the general formula (Vk) [HS _V ] ^' , polysulfide of the general formula (Vm) [S _v ] ^2' , where v is a whole positive number from 2 to 10, thiolate of the general formula (Vn) [R ^S S] ^' , where R ^{s is} a carbon-containing organic, saturated or unsaturated, acycli¬'s or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, the one or more heteroatoms enthal¬ th and / or by one or more functional groups or halogen may be substituted;

is.

14. The method according to claim 13, characterized in that one uses a anorgani¬ rule or organic protic acid, wherein the partially or fully deprotonated anion tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, formate, acetate, almond, nitrate, nitrite , Trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, propylsulfate, butylsulfate, pentylsulfate, hexylsulfate, heptylsulfate, octylsulfate, phosphate, dihydrogenphosphate, hydroxysulfate, sodium phosphate, propionate, tetrachloroaluminate, Al ₂ Cl ₇ ^" , chlorozincate, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato ( 2 -)] borate, tetracarbonyl cobaltate, dimethyl glycol monomethyl ether sulfate, octyl sulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis [1, 2-benzenediolato (2 -) - O, O ^I] borate, dicyanamide trifluorophosphate, tris (pentafluoroethyl), tris (heptafluoropropyl) trifluorophosphate, tetracyanoborate or is Chlorocobaltat.