DE102004043632A1 - Process for the preparation of heterocyclic quaternary ammonium and / or guanidinium compounds - Google Patents

Abstract

A process for preparing a heterocyclic quaternary ammonium and / or guanidinium cation-containing intermediate for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds comprising reacting heterocyclic quaternary ammonium and / or guanidinium carboxylates with an oxidizing agent in Presence of a metal from the 8th to 10th group of the periodic table at a temperature of 0 to 250 ° C and a pressure of 0.05 to 20 MPa abs oxidized.

Description

The The present invention relates to a method for producing a a heterocyclic quaternary ammonium and / or guanidinium cation-containing intermediate for the synthesis heterocyclic quaternary Ammonium and / or guanidinium compounds.

Quaternary ammonium compounds are important substances, which find a wide application. So For example, these are used as fabric softeners, in the Hygiene and cosmetics, as phase transfer catalysts or as Conductive salts for electronic applications. Another important application group are ionic liquids with imidazolium or pyridinium as cations.

Quaternary ammonium compounds with freely selectable Anions become common produced in a two-step reaction. In the first synthesis step becomes the corresponding tertiary Alkylated with an alkylating agent, the obtained Anion of the Quaternary Ammonium compound determined by the alkylating agent used is. To the desired Introduce anion will follow carried out in the second synthesis stage, a so-called anion exchange.

The Alkylation (first stage of the synthesis) is usually carried out by reaction the corresponding tertiary Amines / Imines with alkylating agents.

The usual The alkylating agents used are the alkyl esters of strong mineral acids such as especially dimethyl sulfate or methyl chloride (see, e.g., Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume XI / 2, Georg Thieme Verlag, Stuttgart 1958, page 591 to 630). Disadvantage of the use of dimethyl sulfate is its carcinogenic effect, which is a potential hazard represents and elaborate Safety measures requires. A disadvantage of the use of alkyl halides is the introduction of Halide ions, which are usually difficult to replace completely and in particular for use in the electrical industry and in cause problems for catalysis as well as their corrosiveness in handling. Furthermore, the low molecular weight alkyl chlorides, such as methyl chloride and ethyl chloride gaseous and their handling therefore consuming.

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

Of Further, methyl iodide is also shown as a methylating agent quaternary Ammonium compounds known. Disadvantage of the use of methyl iodide However, its carcinogenic effect, which is a potential hazard represents and elaborate Safety measures requires. Furthermore, methyl iodide is required in the technical Quantities not available or opposite the above-mentioned methylating relatively expensive.

WHERE 02/34722 teaches the synthesis of 1,2,3-substituted, 1,2,3,4-substituted and 1,2,3,4,5-substituted imidazolium compounds by reaction of the corresponding substituted imidazole with an alkyl triflate or a trialkyloxonium salt of the desired anion (e.g., triethyloxonium tetrafluoroborate). A disadvantage of the use of Trialkyloxoniumsalzen is their relative complex and expensive manufacturing, which is a technical use both in terms of availability as well as in terms of cost-effectiveness.

Furthermore, the use of alkyl halides, dialkyl sulfates and alkyl triflates as alkylating agents is disadvantageous because of the formation of halide, alkyl sulfate and triflate anions, since these anions require a classical anion exchange to introduce the anion which is actually desired, in which the originally introduced anion 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 unwanted alkyl sulfate remain in the product in 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 follow-up volumes to 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 discloses 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 with formation of the corresponding carboxylates.

WHERE 01/40146 teaches the preparation of 1,3-dialkylimidazolium compounds by reaction of 1-alkylimidazole with alkyl sulfonates or fluorinated Carbonsäureestern, such as ethyl trifluoroacetate, with the corresponding Sulfonate or the fluorinated carboxylate anions formed become. These are for introduction of the actually desired Anions about exchange an anion. In the case of trifluoroacetate anion This anion exchange can be achieved by adding the protic acid of the desired anion and distillative removal of the formed free trifluoroacetic acid. A disadvantage of the use of fluorinated carboxylic acid esters are their technical complex Syntheses for their presentation using electrochemistry and their high prices compared other alkylating agents, making a technical use of fluorinated Carbonsäureester as alkylating agent 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 hydrogen peroxide or oxygen, in the presence of a gp. VIII metal catalyst and subsequent electrolysis to the hydroxide.

task The present invention was to provide a process for the preparation heterocyclic quaternary ammonium and / or to find guanidinium compounds or their precursors, which does not have the disadvantages of the prior art, easy perform the alkylating agent to be used is not or only slightly toxic, technically well available and is inexpensive, and a simple and flexible introduction of the desired Anions allows the product after introduction of the desired Anions in high purity without elaborate purification steps representable and also for should be suitable for use in the electronics industry.

Accordingly, became a process for the preparation of a heterocyclic quaternary ammonium and / or Guanidinium cation-containing intermediate for synthesis heterocyclic quaternary ammonium and / or guanidinium compounds, characterized is that one heterocyclic quaternary ammonium and / or guanidinium carboxylates 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 up to 250 ° C and oxidized to a pressure of 0.05 to 20 MPa abs.

At the inventive method can as oxidizing agent in principle all gaseous, liquid or solid reagents can be used, which are capable of the carboxylates used to oxidize. Hydrogen peroxide is preferably used as the oxidizing agent or oxygen. Hydrogen peroxide is preferred in the form of its aqueous solution used, wherein the preferred Konzentrationsbe rich to be added Hydrogen peroxide is in the range of 1 to 35 wt .-%. oxygen can be in pure form or diluted be added with other gases. Suitable gases for dilution of Oxygen, 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. Such is for example also the oxidation by adding air 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 in the range of the stoichiometric amount up to 4 times the stoichiometric amount. Levels above this range generally lead to disadvantages follow the high dilution of the actual value product. When using gaseous oxidizing agents is generally given to an excess, since the excess gases usually escape from the liquid mixture. The amount of excess is generally determined by the availability of the oxidizing agent, its price, any measures required for waste gas disposal and equipment conditions. If, for example, air is used as the oxidizing agent, it is perfectly possible to use an excess of the order of 1000 times the amount of stoichiometrically required amount. It should be noted, however, that with a very good gas distribution in the reaction mixture, the stoichiometric amount would be sufficient.

The Reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent is used in the process of the invention in the presence of a metal from the 8th to 10th group of the periodic table carried out. Preferably leads the reaction in the presence of palladium, platinum, ruthenium, Rhodium and / or iridium. There is no particular restriction for this metal used in terms of its morphology, the pretreatment conditions or similar. For example, the catalyst may be in a highly active state, such as a powder, or in the form of a so-called supported catalyst be used. The use in the form of a supported catalyst is with regard to his activity generally sufficient and much lighter Handling particularly advantageous compared to the metal powders. As a carrier In principle, all suitable carrier materials come into question. preferred support materials are activated carbon, carbon or activated carbon fibers and inorganic carriers such as such as silica, alumina, aluminosilicates or zeolites. At the inventive method it is particularly preferred to use supported catalysts containing palladium and / or platinum on activated carbon, silica or alumina, in particular palladium on activated carbon. At the Use of supported catalysts is the amount of carried Metal usually 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-% and particularly preferably 1 to 10 wt .-%, based on the mass of finished supported catalyst. Shape and size of the supported catalyst particles is generally immaterial. The supported catalysts can in the form of small irregular particles ranging from a few tenths of a millimeter in diameter up to larger irregular or regular particles be used in the range of several millimeters. suitable supported catalysts are commercially available and their preparation known in the art.

The Reaction is generally carried out in reactors that for the heterogeneous catalytic oxidation in the liquid or in the liquid / gas phase, depending on the state of the oxidizing agent, are suitable. Another criterion for The choice of reactor is the shape and size of the catalyst to be used. Are metal powders or small irregular supported catalyst particles used, so leads the reaction is preferably carried out by suspension catalyzed. In this Case are stirred tank reactors with or without gassing device, depending on the state of aggregation of the oxidizing agent, particularly suitable. Are larger supported catalyst particles used, so leads the reaction is preferably fixed bed catalyzed in a fixed bed reactor by. The implementation is preferred the implementation in suspension-catalyzed driving 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 method according to the invention at a temperature of 0 to 250 ° C, preferably from 10 to 150 ° C and especially preferably from 10 to 120 ° C. The pressure is 0.05 to 20 MPa abs, preferably 0.09 to 10 MPa abs and especially preferably 0.095 to 5 MPa abs.

The Reaction may be batch, semi-continuous or continuous carried out become. In general, the heterocyclic is used for the reaction quaternary Ammonium and / or guanidinium carboxylate together with the catalyst before and gives the oxidizing agent, optionally distributed over several Minutes or hours, too (discontinuous and semi-continuous Mode). In the continuous mode one leads the heterocyclic quaternary Ammonium and / or guanidinium carboxylate and the oxidizing agent at the same time 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, C ₁ - 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 compounds to be used in the process according to the invention and / or guanidinium carboxylates generally have the carboxylate anion of the general formula (I) R'-COO ^- (I), in which R 'is 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 or substituted radical having 1 to 20 carbon atoms.

Suitable heteroatoms for R 'are in principle all heteroatoms in question, which are able to formally replace a -CH ₂ -, a -CH =, a -C≡ or a = C = group. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. 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.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples include -OH (hydroxy), = O (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 alkyloxycarbonyl or C ₁ -C ₄ alkyloxy.

• • Wasserstoff;
• • C₁- bis C₇-Alkyl;
• • ^–OOC-(CH₂)_n- mit n gleich 0, 1 oder 2;
• • R''OOC-(CH₂)_n- mit n gleich 0, 1 oder 2;
• • Ethenyl;
• • 2-Propenyl; oder
• • eine unsubstituierte oder durch eine bis fünf unabhängig voneinander ausgewählte Gruppen aus der Reihe C₁- bis C₆-Alkyl, Hydroxy, Carboxylat, Carboxy und C₁- bis C₆-Alkyloxycarbonyl substituierte Phenylgruppe und

R'' Wasserstoff oder C₁- bis C₆-Alkyl;
bedeuten, enthalten.In the process according to the invention, preference is given to using heterocyclic quaternary ammonium and / or guanidinium carboxylates which contain the carboxylate anion (I) in which R '

• • hydrogen;
• • C ₁ 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;
• • 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.

wobei R¹ für C₁- bis C₆-Alkyl steht.In the unsubstituted or selected from one to five independently selected groups from the series C ₁ - to C ₆ alkyl, hydroxy, carboxylate (-COO ^- ), carboxy (-COOH) and C ₁ - to C ₆ alkyloxycarbonyl (-COOR ² phenyl groups substituted by R ² equal to C ₁ - to C ₆ -alkyl are, for example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl,

wherein R ^{1 is} C ₁ - to C ₆ alkyl.

The in the method according to the invention to be used carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation contains preferably as the carboxylate anion formate, Acetate, propionate, butyrate, pentanoate (valerate), hexanoate, heptanoate, Octanoate, 2-ethylhexanoate, methyl oxalate, ethyl oxalate, 1-propyloxalate, 1-butyloxalate, 1-pentyloxalate, 1-hexyloxalate, 1-heptyloxalate, 1-octyloxalate, 1- (2-ethyl) hexyloxalate, methyl malonate, ethyl malonate, 1-propyl malonate, 1-butylmalonate, 1-pentylmalonate, 1-hexylmalonate, 1-heptylmalonate, 1-octylmalonate, 1- (2-ethyl) hexyl malonate, Methyl succinate, ethyl succinate, 1-propyl succinate, 1-butyl succinate, 1-pentyl succinate, 1-hexyl succinate, 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-heptyl fumarate, 1-octyl fumarate, 1- (2-ethyl) hexyl fumarate, acrylate, Methacrylate, benzoate, 2-methylbenzoate, 3-methylbenzoate, 4-methylbenzoate, 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.

Especially preference is given to heterocyclic in the process according to the invention quaternary Ammonium and / or guanidinium formates, acetate or propionates, especially -formiate.

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 of 20 to 350 °, preferably from 100 to 250 ° C. The reaction is generally carried out at a pressure of 0.05 to 35 MPa abs, preferably from 0.1 to 20 MPa abs.

The Reaction can be in the absence or in the presence of solvents respectively. Suitable solvents are, for example, water, methanol or strongly polar aprotic solvent such as N, N-dimethylformamide. In general, the present works of water or methanol accelerating on the reaction.

Depending on the implementation of the reaction, the nature and amount of any existing excess starting materials or by-products formed and the presence of a catalyst or solvent, the Working up reaction after completion of the reaction worked up 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 needed 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 ° C and a pressure of 0.05 to 35 MPa abs, preferably from 5 to 20 MPa abs.

At the inventive method is preferred as a heterocyclic quaternary ammonium cation an imidazolium, imidazolinium, pyrazolium, pyrazolinium or pyridinium cation one. Particular preference is given to an aromatic heterocyclic quaternary Ammonium cation, particularly preferably an imidazolium, pyrazolium or pyridinium cation, and most preferably an imidazolium cation.

in der
R⁷ zusammen mit R⁸ einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten; oder
R⁷ zusammen mit R⁸ und R⁹ einen dreibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten;
und die verbleibenden Reste einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten, wobei R⁶ zusätzlich auch für Wasserstoff stehen kann.If an ammonium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, 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 radical or substituted radical having 1 to 30 carbon atoms; 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 substituted radical having 1 to 30 carbon atoms ;
and the remaining radicals are 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 or substituted radical having 1 to 20 carbon atoms, wherein R ⁶ additionally also for Hydrogen can stand.

in der
die Reste R² bis R⁵ unabhängig voneinander eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten und die Reste R² bis R⁴ zusätzlich noch unabhängig voneinander Wasserstoff, Halogen oder eine funktionelle Gruppe bedeuten und der Rest R⁵ zusätzlich auch für Wasserstoff stehen kann; oder
zwei benachbarte Reste R² zusammen mit R³; oder R³ zusammen mit R⁵; oder R⁵ zusammen mit R⁴ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R¹ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphati schen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If an imidazolium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (II)

in the
the radicals R ² to R ^{5 are} 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 or 1 to 20 carbon atoms and the radicals R ² to R ⁴ additionally still inde pendent gig each other hydrogen, halogen or a functional group and the radical R ⁵ can 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 denote 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 having 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 rule, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms.

in der
die Reste R¹¹ bis R¹⁴ unabhängig voneinander eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten und die Reste R¹¹ bis R¹³ zusätzlich noch unabhängig voneinander Wasserstoff, Halogen oder eine funktionelle Gruppe bedeuten und der Rest R¹⁴ zusätzlich auch für Wasserstoff stehen kann; oder
zwei benachbarte Reste R¹¹ zusammen mit R¹²; oder R¹² zusammen mit R¹⁴; oder R¹⁴ zusammen mit R¹³ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R¹⁰ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If an imidazolinium cation is used as heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (IV)

in the
the radicals R ¹¹ to R ^{14 are} 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 or 1 to 20 carbon atoms and the radicals R ¹¹ to R ¹³ additionally mean independently of one another 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 denote 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 having 1 to 30 carbon atoms, and the remaining radicals are as previously defined;
and the radical R ^{10 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 radical or 1 to 20 carbon atoms.

in der
die Reste R¹⁶ bis R¹⁹ unabhängig voneinander eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten und die Reste R¹⁶ bis R¹⁸ zusätzlich noch unabhängig voneinander Wasserstoff, Halogen oder eine funktionelle Gruppe bedeuten und der Rest R¹⁹ zusätzlich auch für Wasserstoff stehen kann; oder
zwei benachbarte Reste R¹⁶ zusammen mit R¹⁷; oder R¹⁷ zusammen mit R¹⁸; oder R¹⁸ zusammen mit R¹⁹ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R¹⁵ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If a pyrazolium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, it preferably has the general formula (VI)

in the
the radicals R ¹⁶ to R ^{19 are} 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 or 1 to 20 carbon atoms and the radicals R ¹⁶ to R ¹⁸ additionally independently of one another hydrogen, halogen or a functional group 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 to together represent 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 substituted with 1 to 30 carbon atoms and the remaining radicals are as defined above ;
and the radical R ^{15 is} 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.

in der
die Reste R²¹ bis R²⁴ unabhängig voneinander eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten und die Reste R²¹ bis R²³ zusätzlich noch unabhängig voneinander Wasserstoff, Halogen oder eine funktionelle Gruppe bedeuten und der Rest R²⁴ zusätzlich auch für Wasserstoff stehen kann; oder
zwei benachbarte Reste R²¹ zusammen mit R²²; oder R²² zusammen mit R²⁴; oder R²⁴ zusammen mit R²³ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R²⁰ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If a pyrazolinium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (VII)

in the
the radicals R ²¹ to R ^{24 are} 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 or 1 to 20 carbon atoms and the radicals R ²¹ to R ²³ additionally mean independently of one another of hydrogen, halogen or a functional group and the radical R ^{24 may} additionally 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 denote 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 having 1 to 30 carbon atoms, and the remaining radicals are as previously defined;
and the radical R ^{20 is} 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.

in der
die Reste R²⁶ bis R³⁰ unabhängig voneinander Wasserstoff, Halogen, eine funktionelle Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten; oder
zwei benachbarte Reste R²⁶ zusammen mit R²⁷; oder R²⁷ zusammen mit R²⁸; oder R²⁸ zusammen mit R²⁹ oder R²⁹ zusammen mit R³⁰ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R²⁵ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If a pyridinium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (VIII)

in the
R ²⁶ to R ³⁰ independently of one another are hydrogen, halogen, a functional 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 with 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 with 1 to 30 carbon atoms and the remaining radicals are as previously defined;
and the radical R ^{25 is} 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.

in der
die Reste R³² bis R³⁶ unabhängig voneinander einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeuten und die Reste R³³ und R³⁵ zusätzlich noch unabhängig voneinander Wasserstoff bedeuten; oder
zwei benachbarte Reste R³³ zusammen mit R³⁴; oder R³⁵ zusammen mit R³⁶ zusammen einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen bedeuten und die verbleibenden Reste wie zuvor definiert sind;
und der Rest R³¹ einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphati schen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.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 carbon atoms and the Radicals R ³³ and R ³⁵ additionally independently of one another represent hydrogen; or
two adjacent radicals R ³³ together with R ³⁴ ; or R ³⁵ together with R ³⁶ together denote 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 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 rule, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms.

In principle, heteroatoms in the definition of the radicals R ¹ to R ^{36 are} all heteroatoms which are capable of formally replacing a -CH ₂ -, a -CH =, a -C≡ or a = C = group , When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. 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 include -OH (hydroxy), = O (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 alkyloxycarbonyl or C ₁ -C ₄ alkyloxy.

When Halogens are called fluorine, chlorine, bromine and iodine.

• • Wasserstoff;
• • Halogen; oder
• • eine funktionelle Gruppe;

und die Reste R¹ bis R⁶ und R⁹ bis R³⁶ unabhängig voneinander jeweils

• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₁- bis C₁₈-Alkyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂- bis C₁₈-Alkenyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₆- bis C₁₂-Aryl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅- bis C₁₂-Cycloalkyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅- bis C₁₂-Cycloalkenyl; oder
• • einen gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus bedeuten; oder

zwei benachbarte Reste gemeinsam

• • einen ungesättigten, gesättigten oder aromatischen, gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten und gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenen Ring bilden.

Preferred in the process according to the invention as the heterocyclic quaternary ammonium cation and / or guanidinium cation is 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 (VIII) ) independently of each other and the radicals R ¹ to R ⁶ and R ⁹ to R ³⁶ are each 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, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₁ - bis C ₁₈ alkyl;
• Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ bis C ₁₈ alkenyl;
• Optionally C ₆ - to C ₁₂ -aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally C ₅ -C ₁₂ -cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ - to C ₁₂ cycloalkenyl; or
• • 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 having heterocycle; or

two adjacent remains together

• • an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups form 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-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohex ylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-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- (methoxycarbonyl ) -ethyl, methoxy, ethoxy, 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, C _n F _{2 (n-a) + (1-b)} H _{2a + b} where n is 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) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1 , 1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-Bu toxypropyl, 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-dioxa-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-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15- Methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3, 6-dioxo-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8, 12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

In the case of C ₂ - bis 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 C ₁₈ -alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _n F _{2 (n-a) - (1-b)} H _2a-b with n ≤ 30, 0 ≤ a ≤ n and b = 0 or 1.

When optionally substituted by functional groups, aryl, alkyl, alkyloxy, alkoxy, halogen, heteroatoms and / or heterocycles C ₆ - to C ₁₂ -aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4 Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, 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- Dimethylaminophenyl, 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, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _n F _{2 (n-a) - (1-b)} 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 _n F _{2 (n-a) -3 (1-b)} H _2a-3b with n ≤ 30, 0 ≤ a ≤ n and b = 0 or 1.

at 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, Benzothiazolyl, 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 substituted by one or more oxygen and / or sulfur atoms and / or one or more several 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-C ₁ -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-butane 1.3 dienylene.

Contain the abovementioned radicals oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number is the oxygen and / or Sulfur atoms and / or imino groups not limited. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and more especially preferably not more than 3.

Contain the above-mentioned radicals heteroatoms, so are between two heteroatoms usually 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 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, 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, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, for 6-hydroxyhexyl or propylsulfonic acid. In addition, the radical R ^{7 is} particularly preferably also a sulfo group.

Particularly preferably, 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} independently hydrogen or straight or branched C ₁ - 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, trifluoromethyl, difluoromethane methyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl or 6-hydroxyhexyl.

All Particular preference is given in the inventive method as ammonium cation (II) N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

All Particular preference is given in the process according to the invention as an 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-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-dimethyl-imidazolium, 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 one.

All Particular preference is given in the process according to the invention as imidazolinium 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-methylimidazolinium, 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-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.

All Particular preference is given in the inventive method 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.

All 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-methyl-pyrazolinium, 1- (1-pentyl) -2-methyl-pyrazolinium, 1- (1-hexyl) -2-methyl-pyrazolinium, 1- (1-octyl) -2-methyl-pyrazolinium, 1- (1-decyl) -2-methyl-pyrazolinium, 1- (1-dodecyl) -2-methyl-pyrazolinium and 1- (1-pentadecyl) -2-methylpyrazolinium.

All Particular preference is given in the inventive method as a 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 one.

All Particular preference is given in the process according to the invention as guanidinium cation (IX) N, N, N ', N', N '', N '' - Hexamethylguanidinium one.

That in the reaction between the heterocyclic quaternary ammonium and / or guanidini Carboxylate and the oxidizing agent obtained intermediate for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds can generally be further processed directly without purification to the desired heterocyclic quaternary ammonium and / or guanidinium compound. If necessary, however, a workup and purification of the intermediate product is possible. In the latter case, the oxidation product can be worked up, for example, by phase separation, extraction and / or crystallization.

A Variant for the synthesis of the desired heterocyclic quaternary Ammonium and / or Guanidinium compounds from the inventively formed intermediate is the electrochemical reaction in aqueous solution to the corresponding heterocyclic quaternary Ammonium and / or guanidinium hydroxide.

Around a mixing of the electrochemically formed heterocyclic quaternary Ammonium and / or guanidinium hydroxide with the intermediate used To avoid, split electrolysis cells are preferably used. Particularly preferred are electrolysis cells with a diaphragm from a cation exchange membrane containing the electrolytic cell separates into an anode compartment and a cathode compartment. It is also possible, a multi-chamber electrolysis cell with one or more divided Intermediate chambers by arranging a plurality of cation exchange membranes use. Suitable materials for the cation exchange membrane are, for example, non-corrosive fluorine resins with a cation exchange group, such as a sulfonic acid or carboxylic acid group, in combination with a styrene-divinylbenzene copolymer containing the mentioned above Having ion exchange groups.

When Anode can be used for this electrode Type of electrolysis is suitable, for example, a high purity carbon electrode or a titanium electrode coated with an oxide of a platinum group metal like platinum or iridium is coated. Furthermore, as a cathode An electrode used for this type of electrolysis is suitable, for example, a stainless steel electrode or Nickel. The anodes and cathodes may be in any form as Plates, nets, porous Plates and the like be used.

The electrochemical conversion can be batchwise or continuous carried out become. The concentration of the product used in the electrolysis, produced according to the invention Intermediate is too Beginning of the electrolysis preferably 1 to 60 wt .-% and particularly preferably 3 to 40 wt .-% in aqueous solution. 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 of 10 to 50 ° C. In addition, it is preferable that, during the electrolysis, the atmosphere on the surface of the electrolyte is made 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, 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 isolated pure substance, but also in the form of the resulting aqueous electrolysis liquid - with an inorganic or organic protic acid having a pK _a 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.

In another preferred variant for the synthesis of the desired heterocyclic quaternary ammonium and / or guanidinium compounds from the intermediate formed according to the invention, this is reacted with an inorganic or organic protic acid having a pK _a value of ≦ 14, measured at 25 ° C. 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 around.

The relative amount of inorganic or organic protic acid in relation to the total amount of the corresponding heterocyclic quaternary ammonium cation and guanidinium cation generally depends on the one desired Degree of conversion of the intermediate used (i.e., whether the intermediate completely or only partially in the desired connection with the desired Anion be transferred should), according to specific procedural aspects (such for example, the nature of the subsequent work-up and the possibility to remove any excess protic acid) as well in polybasic protonic acids according to the number of partially or fully deprotonated to form the desired Anions of the inorganic or organic protic acid to be delivered Protons.

in the Generally one sets a molar ratio of the inorganic or organic protic acid to Total amount of the heterocyclic quaternary ammonium cation and / or Guanidinium cation of the intermediate formed 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 to form the desired partially or fully deprotonated anions of the inorganic or organic proton acid indicating protons to be delivered. For a monobasic acid, such as For example, the tetrafluoroboric acid, a is equal to 1. In a dibasic acid, such as sulfuric acid, is for the case that the monoanion (ie the hydrogen sulfate in the example) it is asked for, a is 1, and for the case that the dianion (in the example the sulfate) is desired, a equals 2.

wobei R^m bis R^o unabhängig voneinander für Wasserstoff oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen Rest mit 1 bis 30 Kohlenstoffatomen, welcher ein oder mehrere Heteroatome enthalten und/oder durch eine oder mehrere funktionelle Gruppen oder Halogen substituiert sein kann, stehen;
organisches Sulfat der allgemeinen Formel (Vi) [R^pO-SO₃]^–, wobei R^p für einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen Rest mit 1 bis 30 Kohlenstoffatomen, welcher ein oder mehrere Heteroatome enthalten und/oder durch eine oder mehrere funktionelle Gruppen oder Halogen substituiert sein kann, steht;
Halometallat der allgemeinen Formel (Vj) [M_qHal_r]^s–, wobei M für ein Metall und Hal für Fluor, Chlor, Brom oder Iod steht, q und r ganze positive Zahlen sind und die Stöchiometrie des Komplexes angeben und s eine ganze positive Zahl ist und die Ladung des Komplexes angibt; oder
Sulfid, Hydrogensulfid, Hydrogenpolysulfid der allgemeinen Formel (Vk) [HS_v]^–, Polysulfid der allgemeinen Formel (Vm) [S_v]^2–, wobei v eine ganze positive Zahl von 2 bis 10 ist, Thiolat der allgemeinen Formel (Vn) [R^sS]^–, wobei R^s für einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acycli-schen oder cyclischen, aliphatischen, aromatischen oder araliphatischen Rest mit 1 bis 30 Kohlenstoffatomen, welcher ein oder mehrere Heteroatome enthalten und/oder durch eine oder mehrere funktionelle Gruppen oder Halogen substituiert sein kann, steht; ist.Preference is given to using an inorganic or organic protic acid in which the partially or fully deprotonated anion
Fluoride; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoroarsenat; 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 ] ^- , 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 from 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 ] ^- , wherein 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 is 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 the general formula (Vd) [PF _x (C _y F _{2y + 1-z} H _z ) _6-x ] ^- , where 1 ≤ x ≤ 6, 1 ≤ y ≤ 8 and 0 ≤ z ≤ 2y + 1 ;
Imide of the general formulas (Ve) [R ^g -SO ₂ -N-SO ₂ -R ^h ] ^- , (Vf) [R ⁱ -SO ₂ -N-CO-R ^j ] ^- or (IVg) [R ^k - CO-N-CO-R ^l ] ^- , wherein R ^g to R ^l independently of one another for 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 contain multiple heteroatoms and / or may be substituted by one or more functional groups or halogen;
Methide of the general formula (Vh)

wherein R ^m to R ^{o 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 contain one or more heteroatoms and / or by one or more functional Groups or halogen may be substituted;
organic sulfate of the general formula (Vi) [R ^p O-SO ₃ ] ^- , wherein R ^{p is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is an or contain several heteroatoms and / or may be substituted by one or more functional groups or halogen;
Halometalat 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 and indicate the stoichiometry of the complex and s a whole is 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 ^s S] ^- , wherein R ^{s is} 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 by one or more a plurality of functional groups or halogen may be substituted; 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. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. 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.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples include -OH (hydroxy), = O (especially as 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,

When Halogens are called fluorine, chlorine, bromine and iodine.

• • C₁- bis C₃₀-Alkyl und deren aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO-, -CO-O- oder -CO-N< substituierte Komponenten, wie beispielsweise 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, 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 oder C_nF_{2(n–a)+(1–b)}H_2a+b mit n ≤ 30, 0 ≤ a ≤ n und b = 0 oder 1 (beispielsweise CF₃, C₂F₅, CH₂CH₂-C_(n–2)F_2(n–2)+1, C₆F₁₃, C₈F₁₇, C₁₀F₂₁, C₁₂F₂₅);
• • C₃- bis C₁₂-Cycloalkyl und deren aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- oder -CO-O-substituierte Komponenten, wie beispielsweise Cyclopentyl, 2-Methyl-1-cyclopentyl, 3-Methyl-1-cyclopentyl, Cyclohexyl, 2-Methyl-1-cyclohexyl, 3-Methyl-1-cyclohexyl, 4-Methyl-1-cyclohexyl oder C_nF_{2(n–a)–(1–b)}H_2a–b mit n ≤ 30, 0 ≤ a ≤ n und b = 0 oder 1;
• • C₂- bis C₃₀-Alkenyl und deren aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- oder -CO-O-substituierte Komponenten, wie beispielsweise 2-Propenyl, 3-Butenyl, cis-2-Butenyl, trans-2-Butenyl oder C_nF_{2(n–a)–(1–b)}H_2a–b mit n ≤ 30, 0 ≤ a ≤ n und b = 0 oder 1;
• • C₃- bis C₁₂-Cycloalkenyl und deren aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- oder -CO-O-substituierte Komponenten, wie beispielsweise 3-Cyclopentenyl, 2-Cyclohexenyl, 3-Cyclohexenyl, 2,5-Cyclohexadienyl oder C_nF_{2(n–a)-3(1–b)}H_2a–3b mit n ≤ 30, 0 ≤ a ≤ n und b = 0 oder 1; und
• • Aryl oder Heteroaryl mit 2 bis 30 Kohlenstoffatomen und deren alkyl-, aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- oder -CO-O-substituierte Komponenten, wie beispielsweise Phenyl, 2-Methyl-phenyl (2-Tolyl), 3-Methyl-phenyl (3-Tolyl), 4-Methyl-phenyl, 2-Ethyl-phenyl, 3-Ethyl-phenyl, 4-Ethyl-phenyl, 2,3-Dimethyl-phenyl, 2,4-Dimethyl-phenyl, 2,5-Dimethyl-phenyl, 2,6-Dimethyl-phenyl, 3,4-Dimethyl-phenyl, 3,5-Dimethyl-phenyl, 4-Phenyl-phenyl, 1-Naphthyl, 2-Naphthyl, 1-Pyrrolyl, 2-Pyrrolyl, 3-Pyrrolyl, 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl oder C₆F_(5–a)H_a mit 0 ≤ a 5.

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 ^e in the organic sulfonate (Vb), the radical R ^f in the case of the carboxylate (Vc), the radicals R ^g to R ^l in the imides (Ve), (Vf) and (Vg), the radicals R ^m to R ^o in the case of the methide (Vh), the radical R ^p in organic sulfate (Vi) and the radical R ^s in the thiolate (Vn) independently of each other preferably for

• C ₁ - to 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-1-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 (Be nzyl), 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 (n- a) + (1-b)} H _{2a + 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} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ );
• 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-1-cyclohexyl, 4-methyl-1-cyclohexyl or C _n F _{2 (n-a) - (1-b)} H _2a-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 C _n F _{2 (n-a) - (1-b)} H _2a-b with n ≤ 30, 0 ≤ a ≤ n and b = 0 or 1;
• C ₃ - to C ₁₂ -cycloalkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _n F _{2 (n-a) -3 (1-b)} H _2a-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 phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4- Ethyl phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethyl phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl or C ₆ F _(5-a) H _a with 0 ≤ a 5.

If the anion is a tetrasubstituted borate (Va) [BR ^a R ^b R ^c R ^d ] ^- , 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-toluenesulfonate, nonadecafluorononanesulfonate (nonaflate), dimethylenglycol monomethyl ether sulfate and octyl sulfate.

When the anion is a carboxylate (Vc) [R ^f -COO] ^- , the radical R ^{f is} preferably hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxy-phenylmethyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, Flu ormethyl, ethenyl (vinyl), 2-propenyl, -CH = CH-COO ^- , cis-8-heptadecenyl, -CH ₂ -C (OH) (COOH) -CH ₂ -COO ^- or unbranched or branched C ₁ - bis 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 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, heptadecyl. Particularly preferred carboxylates (Vc) are formate, acetate, propionate, butyrate, valerate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.

When the anion is a (fluoroalkyl) fluorophosphate (Vd) [PF _x (C _y F _{2y + 1-z} H _z ) _6-x ] ^- , z is preferably 0. Particularly preferred are (fluoroalkyl) fluorophosphates (Vd ), in which z = 0, x = 3 and 1 ≦ y ≦ 4, specifically [PF ₃ (CF ₃ ) ₃ ] ^- , [PF ₃ (C ₂ F ₅ ) ₃ ] ^- , [PF ₃ (C ₃ F ₇ ) ₃ ] ^- and [PF ₃ (C ₄ F ₇ ) ₃ ] ^- .

Is the anion an imide (Ve) [R ^g -SO ₂ -N-SO ₂ -R ^h ] ^- , (Vf) [R ⁱ -SO ₂ -N-CO-R ^j ] ^- or (Vg) [R ^k -CO-N-CO-R ^l ] ^- , the radicals R ^g to R ^l 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 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 , And ecyl 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 ^g to R ^l independently of one another are methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.

so stehen die Reste R^m bis R^o unabhängig voneinander bevorzugt für Trifluormethyl, Pentafluorethyl, Phenyl, Trichlormethyl, Dichlormethyl, Chlormethyl, Trifluormethyl, Difluormethyl, Fluormethyl oder unverzweigtes oder verzweigtes C₁- bis C₁₂-Alkyl, wie beispielsweise 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 oder Dodecyl. Besonders bevorzugte Methide (Vh) sind [(F₃C-SO₂)₃C]^– (Tris(trifluoromethylsulfonyl)methid), [(F₅C₂-SO₂)₃C]^– (Bis(pentafluoroethylsulfonyl)methid) und jene, in denen die Reste R^m bis R^o unabhängig voneinander für Methyl, Ethyl, Propyl, Butyl, Phenyl, Trichlormethyl, Dichlormethyl, Chlormethyl, Trifluormethyl, Difluormethyl oder Fluormethyl stehen.Is the anion a methide (Vh)?

Thus, the radicals R ^m to R ^o 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. Particularly preferred methides (Vh) are [(F ₃ C-SO ₂ ) ₃ C] ^- (tris (trifluoromethylsulfonyl) methide), [(F ₅ C ₂ -SO ₂ ) ₃ C] ^- (bis (pentafluoroethylsulfonyl) methide) and those in which the radicals R ^m to R ^o independently of Me ethyl, 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. Particularly preferred organic sulfates (Vi) are methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate or octyl sulfate.

If the anion is a halometalate (Vj) [M _q Hal _r ] ^s- , M is preferably aluminum, zinc, iron, cobalt, antimony or tin. Hal is preferably chlorine or bromine and most preferably chlorine. q is preferably 1, 2 or 3 and r and s are given according to the stoichiometry and charge of the metal ion.

If the anion is thiolate (Vn) [R ^s S] ^- , the radical R ^{s is} preferably a branched or unbranched C ₁ - to C ₃₀ -alklyl radical. Particularly preferred thiolates (Vn) are methylsulfide, ethylsulfide, 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, ethylsulfate, propylsulfate, Butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen 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, dimethylenglycol monomethyl ether sulfate, octyl sulfate, 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) tr ifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyano borate or chlorocobaltate.

The Reaction between the intermediate product formed according to the invention and the inorganic or organic protic acid is generally at a temperature of 0 to 350 ° C, preferably from 10 to 200 ° C and especially preferably from 10 to 100 ° 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.

When Reaction apparatuses can in principle, all reactors are used, which for a reaction in the liquid phase are suitable. These are in particular reactors, which allow appropriate mixing of the liquid reactants, for example, stirred tank.

The The nature and sequence of the addition of the individual educts is immaterial. For example, it is possible the inventively formed Intermediate and the inorganic or organic protic acid in succession in any order or parallel to the reactor to give. It is also possible, to submit one of the three educts and the other educt via a certain period of time from a few seconds to several hours zuzutropfen.

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 -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 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 slowly added to the reaction apparatus for reaction. The reaction mixture is continuously removed according to the amounts of starting materials fed 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 you work the reaction mixture is then mixed to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound.

The reaction mixture obtained in the reaction between the intermediate 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 extractants are, for example, C ₅ - to C ₁₂ -alkanols, methyl tert-butyl ether and ethyl acetate. If exclusively gaseous or at least readily distillative components are formed in the reaction between the intermediate formed according to the invention and the inorganic or organic protic acid from the anion of the intermediate product, then it is sufficient in this case to remove these components from the reaction mixture by distillation, preferably under reduced pressure , 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 is light can be removed by distillation.

In a preferred embodiment If one sets an N-alkylated and optionally also at one or substituted imidazole with methyl formate with several ring carbon atoms to the corresponding 1-methyl-3-alkyl-imidazolium formate. This then oxidized with an aqueous Hydrogen peroxide solution or air on a palladium and / or platinum-containing catalyst to the desired Intermediate.

In In one variant, this intermediate is added electrochemically to the corresponding 1-methyl-3-alkyl-imidazolium hydroxide, which by distilling off the water present and optionally Extraction and / or crystallization can be obtained in pure form can. The 1-methyl-3-alkyl-imidazolium hydroxide is in high purity receive.

In another preferred variant is this intermediate with the inorganic or organic protic acid of the desired anion to the 1-methyl-3-alkyl-imidazolium compound of the desired Anions, which by removing the formed carbon dioxide and distilling off the water present and optionally extraction and / or crystallization can be obtained in pure form. The 1-methyl-3-alkyl-imidazolium compound of the desired Anions is obtained in high purity.

The inventive method allows the easy to perform Preparation of a, a heterocyclic quaternary ammonium and / or guanidinium cation containing intermediate for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds, which in a simple and flexible manner in the desired heterocyclic quaternary Ammonium and / or guanidinium compound high purity is convertible. The wished Anion is simple and flexible in the case of the hydroxide anion by electrolysis and in the case of other anions by reaction of the formed according to the invention Intermediate with an inorganic or organic protic acid of the desired Anions insertable 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 starting compound is the simple preparation of the carboxylates, wherein for their Representation to be used starting materials not or only slightly toxic, technically well available and are inexpensive.

In In this context, in particular the use of formates the corresponding heterocyclic quaternary ammonium compounds and / or Guanidine compound Particularly advantageous, since this very easy by implementing the corresponding amines or imines with the cheap and very well available Methyl formate can be displayed and in the subsequent implementation carbonates / bicarbonates formed with the oxidizing agent through the subsequent Reaction with the inorganic or organic protic acid easily decomposable and the reaction products carbon dioxide and water well are separable.

The from that according to the inventive method produced intermediate heterocyclic quaternary ammonium and guanidinium compounds are particularly due to their high purity for use suitable in the electronics industry.

Example 1 (1,3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were dissolved in 40 g of methanol in an autoclave with 91 g (1.5 mol) of methyl formate and 18 hours under autogenous pressure at 130 ° C touched. From the reaction effluent, the volatile, excess feedstocks and methanol distilled off. According to the NMR spectrum of the crude product was the structure of the product as 1,3-dimethylimidazolium formate approved. The conversion of the reaction was 43% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and vacuumed in the form of colorless crystals.

Example 2 (1,3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were dissolved in 40 g of methanol in an autoclave with 91 g (1.5 mol) of methyl formate and 12 hours under autogenous pressure at 150 ° C touched. From the reaction effluent, the volatile, excess feedstocks and methanol distilled off. According to the NMR spectrum of the crude product was the structure of the product as 1,3-dimethylimidazolium formate approved. The conversion of the reaction was 73% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and vacuumed in the form of colorless crystals.

Example 3 (1,3-dimethylimidazolium formate)

33.0 g (0.4 mol) of 1-methylimidazole were dissolved in 40 g of methanol in an autoclave with 91 g (1.5 mol) of methyl formate and 12 hours under autogenous pressure at 140 ° C touched. From the reaction effluent, the volatile, excess feedstocks and methanol distilled off. According to the NMR spectrum of the crude product was the structure of the product as 1,3-dimethylimidazolium formate approved. The conversion of the reaction was 55% based on 1-methylimidazole. The product was precipitated by the addition of ethyl acetate and vacuumed in the form of colorless crystals.

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

33 g (0.4 mol) of 1-methylimidazole was dissolved in 50 ml of methanol. In one Autoclaves were at 150 ° C 10 MPa abs carbon monoxide and pressed for 40 hours. from The reaction effluent was the volatile excess feedstock and methanol distilled off. According to the NMR spectrum of the crude product was the structure of the product as 1,3-dimethylimidazolium formate approved. The conversion of the reaction was 21% based on 1-methylimidazole.

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

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

33 g (0.4 mol) of 1-ethylimidazole were dissolved in 45 g of methanol in an autoclave with 111 g (1.5 mol) of methyl acetate and 20 hours under autogenous pressure at 160 ° C touched. From the reaction effluent, the volatile, excess feedstocks and methanol distilled off. According to the NMR spectrum of the crude product was the structure of the product as 1-methyl-3-ethylimidazolium acetate approved. The conversion of the reaction was 24% based on 1-ethylimidazole. The product mixture was treated with 1: 1 by volume of methyl tert-butyl ether (MTBE) extracted three times and the MTBE phase separately from the product phase concentrated. The residue the MTBA phase contained> 95% 1-ethylimidazole, the product phase contained 65% 1-ethyl-3-methylimidazolium acetate and 35% 1-ethylimidazole. The remaining 1-ethylimidazole from the product phase was distilled off in vacuo (5 hPa abs) to give 15.7 g (97%) 1-ethyl-3-methylimidazolium acetate remained.

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

373 g (3.0 moles) of 1-butylimidazole were dissolved in 300 ml of methanol in an autoclave with 685 g (11.4 mol) of methyl formate and 18 hours under Autogenous pressure at 140 ° C touched. From the reaction effluent, the volatile, excess feedstocks and methanol 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 was the structure as 1-methyl-3-butylimidazolium formate approved. 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 under autogenous pressure (3 MPa abs) for 18 hours at 140 ° C stirred. The Volatile, excess feedstocks and methanol were distilled off. The conversion of the reaction was at 90% based on 1,2-dimethylimidazole. Excess 1,2-dimethylimidazole was distilled off and the product, 1,2,3-trimethylimidazolium formate, as 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 initially charged together with 1 g of catalyst (10% by weight of Pd on activated charcoal) in 80 g of water and heated to 60.degree. 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 ° C, 5 hPa abs). There were isolated 19.2 g of a product 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 admixed with 14.5 g of 50% strength by weight aqueous tetrafluoroboric acid (ent speaking 0.082 mol of HBF ₄ ) at about 25 ° C. within 15 minutes, 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 (14)

A process for the preparation of a heterocyclic quaternary ammonium and / or guanidinium cation-containing intermediate for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds, which comprises reacting heterocyclic quaternary ammonium and / or guanidinium carboxylates with an oxidizing Agent oxidized in the presence of a metal from the 8th to 10th group of the Periodic Table at a temperature of 0 to 250 ° C and a pressure of 0.05 to 20 MPa abs. Method according to claim 1, characterized in that that as oxidizing agent hydrogen peroxide or oxygen starts. Process according to claims 1 to 2, characterized that the oxidation in the presence of palladium, platinum, ruthenium, Rhodium and / or iridium. Process according to Claims 1 to 3, characterized in that heterocyclic quaternary ammonium and / or guanidinium carboxylates are used which contain the carboxylate anion of the general formula (I) R ¹ -COO ^- (I), in the R ¹ • hydrogen; • C ₁ 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-; • 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. Process according to Claim 4, characterized in that heterocyclic quaternary ammonium and / or guanidinium formate. 641/2004 Gmy / cz 07.09.2004 Process according to claims 1 to 5, characterized that an intermediate product is prepared in which the cation is an imidazolium, Imidazolinium, pyrazolium, pyrazolinium or pyridinium cation. Process according to claims 1 to 5, characterized to produce an intermediate in which the cation is an aromatic heterocyclic quaternary Ammonium cation is. Process according to Claim 7, characterized in that an intermediate is prepared in which the cation is an imidazolium cation of the general formula (II)

in which the radicals R ² to R ^{5 are} 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 1 to 20 carbon atoms and the radicals R ² to R ⁴ additionally mean independently of one another 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 denote 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 having 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 interrupted by 1 to 5 heteroatoms or funktionel le groups radical having 1 to 20 carbon atoms; is. Method according to claim 8, characterized in that that an intermediate is prepared in which the cation 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-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 is. Process according to claims 1 to 9, characterized that the resulting intermediate in aqueous solution electrochemically to the corresponding heterocyclic quaternary Ammonium and / or guanidinium hydroxide implements. Process according to claims 1 to 9, characterized in that the intermediate formed with an inorganic or organic protic acid having a pK _a 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. 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 is from 0.9 / a to 1.5 / a, where a is the Number of to Formation of the desired partially or fully deprotonated anion of the inorganic or organic protic acid protons to give to be used. Process 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; Trifluoroarsenat; 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 ] ^- , 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 from 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 ] ^- , wherein 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 is 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 the general formula (Vd) [PF _x (C _y F _{2y + 1-z} H _z ) _6-x ] ^- , where 1 ≦ x ≦ 6, 1 ≦ y ≦ 8 and 0 ≦ z ≦ 2 y + 1; Imide of the general formulas (Ve) [R ^g -SO ₂ -N-SO ₂ -R ^h ] ^- , (Vf) [R ⁱ -SO ₂ -N-CO-R ^j ] ^- or (IVg) [R ^k - CO-N-CO-R ^l ] ^- , wherein R ^g to R ^l independently of one another for 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 contain multiple heteroatoms and / or may be substituted by one or more functional groups or halogen; Methide of the general formula (Vh)

wherein R ^m to R ^{o 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 contain one or more heteroatoms and / or by one or more functional Groups or halogen may be substituted; organic sulfate of the general formula (Vi) [R ^p O-SO ₃ ] ^- , wherein R ^{p is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is an or contain multiple heteroatoms and / or may be substituted by one or more functional groups or halogen; Halometalat 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 and indicate the stoichiometry of the complex and s a whole is 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- , wherein v is a whole positive number from 2 to 10, thiolate of the general formula (Vn ) [R ^s S] ^- , wherein R ^{s is} 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 by one or more is functional groups or halogen may be substituted; A method according to claim 13, characterized in that one uses an inorganic or organic protic acid, wherein the partially or fully deprotonated anion tetrafluoroborate, hexafluorophosph phat, trifluoromethanesulfonate, methanesulfonate, formate, acetate, mandelate, nitrate, nitrite, trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, propylsulfate, butylsulfate, pentylsulfate, hexylsulfate, heptylsulfate, octylsulfate, phosphate, dihydrogenphosphate, hydro genphosphate, 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, dimethylenglycol monomethyl ether sulfate , Octylsulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinylphosphonate, bis (pentafluoroethyl) phosphinate, bis (oxalato (2 -)] borate, bis [1,2-benzenediolato (2 -) - O, O '] borate, dicyanamide, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyano borate or chlorocobaltate.