DE102004043631A1 - Process for the preparation of heterocyclic quaternary ammonium compounds and / or guanidinium compounds of high purity - Google Patents

Abstract

Process for the preparation of heterocyclic quaternary ammonium compounds and / or guanidinium compounds, in which the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation which contains the carboxylate anion of the general formula (I) DOLLAR A R'- COO · - ·, DOLLAR A in the DOLLAR AR 'È hydrogen; DOLLAR A È C¶1¶- to C¶7¶-alkyl; DOLLAR A È · - · OOC- (CH¶2¶) ¶n¶- with n equal to 0, 1 or 2; DOLLAR A È R''OOC- (CH¶2¶) ¶n¶- where n is 0, 1 or 2; DOLLAR A È · - · OOC-CH = CH-; DOLLAR A È R''OOC-CH = CH-; DOLLAR A ethenyl; DOLLAR A È 2-propenyl or DOLLAR A È is an 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 · # · with R · # · equal to C¶1¶- to C¶6¶-alkyl) substituted phenyl group DOLLAR A and DOLLAR A R ' 'Hydrogen or C¶1¶- to C¶6¶-alkyl DOLLAR A contains DOLLAR A with an inorganic or organic protic acid having a pK¶¶¶ value of 14, measured at 25 ° C in aqueous solution, reacted ,

Description

The The present invention relates to a process for producing heterocyclic quaternary Ammonium compounds 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 Episodes 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, methyl acetate, dimethyl phthalate or methyl salicylate as alkylating agent to form 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.

task The present invention was to provide a process for the preparation heterocyclic quaternary ammonium compounds and / or guanidinium compounds, which has the disadvantages of the prior art, is easy to perform 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. Further should the starting materials for the production is not or only slightly toxic, technically good available and be cheap.

• • 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;
• • ^–OOC-CH=CH-;
• • R''OOC-CH=CH-;
• • Ethenyl;
• • 2-Propenyl; oder
• • eine unsubstituierte oder durch eine bis fünf unabhängig voneinander ausgewählte Gruppen aus der Reihe C₁- bis C₆-Alkyl, Hydroxy, Carboxylat (-COO^–), Carboxy (-COOH) und C₁- bis C₆-Alkyloxycarbonyl (-COOR^# mit R^# gleich C₁- bis C₆-Alkyl) substituierte Phenylgruppe

und
R'' Wasserstoff oder C₁- bis C₆-Alkyl;
bedeuten, enthält,
mit einer anorganischen oder organischen Protonensäure mit einem pK_a-Wert von ≤ 14, gemessen bei 25°C in wässriger Lösung, umsetzt.Accordingly, a process for the preparation of heterocyclic quaternary ammonium compounds and / or guanidinium compounds has been found, which is characterized in that the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation, which is the carboxylate anion of the general formula (I) R'-COO - (I) in the
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;
• • ^- OOC-CH = CH-;
• • R''OOC-CH = CH-;
• • ethenyl;
• • 2-propenyl; or
• • an 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 ^# with R ^# equal to C ₁ - to C ₆ alkyl) substituted phenyl group

and
R '' is hydrogen or C ₁ - to C ₆ -alkyl;
mean, contains,
with an inorganic or organic protic acid having a pK _a value of ≤ 14, measured at 25 ° C in aqueous solution, is reacted.

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 in the process of the invention is generally based on the desired degree of conversion of the carboxylate used (ie, whether the carboxylate is to be replaced wholly or partially by another anion), according to specific procedural aspects (such for example, also the nature of the subsequent work-up and the possibility of removing any excess protic acid) and, in the case of polybasic protic acids, according to the number of protons to be released from the inorganic or organic protic acid to form the desired partially or fully deprotonated anion. In general, a molar ratio of the inorganic or organic protic acid to the total amount of the corresponding heterocyclic quaternary ammonium cation and guanidinium cation 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 indicates the number of protons to be delivered by the inorganic or organic protic acid to form the desired partially or fully deprotonated anion. For a monobasic acid such as tetrafluoroboric acid, a is 1. For a dibasic acid such as sulfuric acid, if the monoanion (ie, hydrogen sulfate in the example) is desired, a is 1, and for the Case that the dianion (in the example the sulfate) is desired, a equals 2.

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.In principle, all inorganic or organic protic acid having a pK _a of ≦ 14, measured at 25 ° C. in aqueous solution, can be used in the process according to the invention. 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 (heptafluoro propyl) trifluorophosphate, bis [oxalato (2 -)] borate, bis [salicylato (2 -)] borate, bis [1,2 benzene diolato (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 ] ^- , wherein 1 ≤ x ≤ 6.1 ≤ 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,
Halogens are 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, C₁₀F₁₇, 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 _17, 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} where 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, fluoromethyl , Ethenyl (vinyl), 2-propenyl, -CH = CH-COO ^- , cis-8-heptadecenyl, -CH ₂ -C (OH) (COOH) -CH ₂ -COO ^- or straight or branched C ₁ -C ₁₈ 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, 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 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, Un decyl 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, Trifuormethyl, 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 -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. Be particularly preferred organic sulfates (Vi) are methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate or octyl sulfate.

If 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, hydrogen sulfate, methyl sulfate, ethyl sulfate , propyl sulfate, butyl sulfate, Pentylsulfat, hexyl sulfate, Heptylsulfat, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, propionate, tetrachloroaluminate, Al ₂ Cl ₇ ^-, chlorozincate, Chloroferrat, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide , Bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato (2 -)] borate, tetracarbonyl cobaltate, dimethylenglycol monomethyl ether sulfate, oyl sulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis [1,2-benzenediolato (2 -) - O, O '] borate, D icyanamide, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyano borate or chlorocobaltate.

The Reaction between the carboxylate of the corresponding heterocyclic quaternary Ammonium cation and / or guanidinium cation and inorganic or organic protic acid takes place in the method according to the invention generally at a temperature of 0 to 350 ° C, preferred from 0 to 200 ° C and more preferably from 10 to 80 ° C. The pressure is generally 0.01 to 10 MPa abs, preferably 0.09 to 0.5 MPa abs and especially preferably 0.09 to 0.2 MPa abs.

When Reaction apparatuses can in the method according to the invention 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 in the process according to the invention immaterial. Thus, it is possible, for example, the carboxylate of the corre sponding heterocyclic quaternary ammonium cation and / or guanidinium cations and the inorganic or organic protic acid in succession in any Sequence or parallel to the reactor. It is also possible, one of the three educts and the other educt over a certain period of time drop from a few seconds to several hours.

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 -C ₈ -alkanols or strongly polar aprotic solvents, such as, for example, 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 process according to the invention 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 thereby continuously removed in accordance with the amounts of educts fed men and worked up as described. The workup itself can also be done continuously. In the case of the semicontinuous variants, one of the two educts is added slowly, the reaction generally taking place in parallel with the addition. After the desired amount has been added, the reaction mixture is subsequently worked up to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound.

• • 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;
• • ^–OOC-CH=CH-;
• • Ethenyl;
• • 2-Propenyl;
• • eine unsubstituierte oder durch eine bis fünf unabhängig voneinander ausgewählte Gruppen aus der Reihe C₁- bis C₆-Alkyl, Hydroxy, Carboxylat (-COO^–), Carboxy (-COON) und C₁- bis C₆-Alkyloxycarbonyl (-COOR^# mit R^# gleich C₁- bis C₆-Alkyl) substituierte Phenylgruppe

und
R'' Wasserstoff oder C₁- bis C₆-Alkyl;
bedeuten.The carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation to be used in the process according to the invention contains the carboxylate anion (I) R'-COO ^- (I), by doing
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;
• • ^- OOC-CH = CH-;
• • ethenyl;
• • 2-propenyl;
• • an unsubstituted or selected from one to five independently selected groups from the series C ₁ - to C ₆ alkyl, hydroxy, carboxylate (-COO ^- ), carboxy (-COON) and C ₁ - to C ₆ alkyloxycarbonyl (-COOR ^# with R ^# equal to C ₁ - to C ₆ alkyl) substituted phenyl group

and
R '' is hydrogen or C ₁ - to C ₆ -alkyl;
mean.

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.

und
R'' C₁- bis C₄-Alkyl;
bedeuten, enthält.The carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation is particularly preferably used in the process according to the invention as a carboxylate which contains the carboxylate anion (I) in which
R 'is hydrogen;
Methyl;
ethyl;

and
R "C ₁ to C ₄ alkyl;
mean, contains.

All Particular preference is given in the inventive method as a carboxylate the corresponding heterocyclic quaternary ammonium cation and / or of the guanidinium cation formate, acetate or propionate, in particular Formate.

The in the reaction according to the invention The reaction mixture obtained can be prepared in various ways for isolation of the desired heterocyclic quaternary Ammonium compound and / or guanidinium compounds worked up become.

In a variant of the work-up, the carboxylic acid formed in the reaction is distilled off. This variant is particularly advantageously used for the separation of low-boiling carboxylic acids having a boiling point of below 150 ° C. (1013 hPa abs), such as formic acid (bp 101 ° C), acetic acid (bp 116-118 ° C) and propionic acid (bp. 141 ° C). In this variant, it is thus preferable to use the formate, acetate or propionate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation and separates the formed in the reaction formic, acetic or propionic acid by distillation of the heterocyclic quaternary ammonium compound formed and / or guanidinium compounds. When distilling off the carboxylic acid formed at the same time also possibly existing What removed by distillation. Furthermore, any solvent or any by-products formed may also be removed by distillation.

In another variant, the carboxylic acid formed in the reaction is removed by extraction with a suitable extraction agent. Examples of suitable extractants are C ₅ - to C ₁₂ -alkanols, methyl tert-butyl ether or ethyl acetate. In yet another variant, the carboxylic acid formed in the reaction is removed by crystallization. Extraction and crystallization are preferably used in higher-boiling carboxylic acids having a boiling point above 200 ° C (1013 hPa abs).

In Another variant of the workup is in the implementation formed reaction mixture with an alcohol to form the corresponding Esters added the set carboxylate anion. Alternatively The alcohol may also be equal in the reaction between the carboxylate the corresponding heterocyclic quaternary ammonium cation and / or Guanidinium cation and the inorganic or organic protic acid added for example, as a solvent in the implementation to act. In this variant, it is therefore preferable to give an alcohol to form the corresponding ester of the carboxylate anion used to and separates the formed ester by distillation from the formed heterocyclic quaternary Ammonium compound and / or guanidinium compound. alternative However, the ester formed may also be by extraction or crystallization be separated.

Suitable alcohols in this variant are preferably C ₁ -C ₈ -alkanols, such as, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol , 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 1-octanol or 2-ethyl-1-hexanol.

advantage This variant is that carboxylic acids with a higher boiling point be converted into esters can, which have a much lower boiling point and therefore also can be easily separated by distillation.

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.

ever after execution the implementation, the type and amount of any existing excess feedstocks or by-products formed and the presence of a catalyst or solvent the reaction can be worked up after completion of the reaction or directly to the reaction according to the invention the inorganic or organic protic acid can be used. Becomes worked up the reaction, so 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 R^e 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 ara liphatischen, 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 ^{e 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 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 ara liphatischen, 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 can stand for hydrogen.

in er
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 araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen bedeutet.If, in the process according to the invention, an imidazolium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general meaning in the

in he
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 mean independently of one another of hydrogen, halogen or a functional group and the radical R ^{5 may} additionally 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 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 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 R¹²zusammen 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, in the process according to the invention, a pyrazolium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general structure

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 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 ^{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 R²⁷zusammen 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 araliphati schen, 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 rule, 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 araliphatischen, 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, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups, 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.

The heterocyclic quaternary ammonium cation and / or guanidinium cation used is preferably an ammonium (III), imidazolium (II), imidazolinium (IV), pyrazolium (VI), pyrazolinium (VII), pyridinium (VIII) or guanidinium cation (IX) in which the radicals R ² to R ⁴ (in the case of an imidazolium cation (II)), R ¹¹ to R ¹³ (in the case of an imidazolinium cation (IV)), R ¹⁶ to R ¹⁸ (in the case of a pyrazolium cation (VI)), R ²¹ to R ²³ (in the case of a pyrazolinium cation (VII)) and R ²⁶ to R ³⁰ (in the case of a pyridinium cation (VIII)) independently of each other

• • 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 -Al -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 radicals in common
• • 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-phenoxybu tyl, 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} with n equal to 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-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- ( n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxo-octyl, 11-hydroxy-3,6,9-trioxa -undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14 -Hydroxy-5,1O-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-di oxo-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-5,1-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-5,1O-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, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₆ - to C ₁₂ -aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4th -Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaph ethyl, 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, butylthio cyclohexyl, 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) - (31-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-butox y-carbonyl) -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, difluoromethyl, 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-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.

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-dimethyl-imidazolinium, 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 one.

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.

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 you then set with the inorganic or organic protic acid of the desired anion and separates the formed formic acid by distillation or after esterification with methanol as methyl formate from. The 1-methyl-3-alkyl-imidazolium compound of the desired anion is in high Purity received.

The process according to the invention makes it possible to prepare heterocyclic quaternary ammonium compounds and guanidinium compounds in high purity without any need to purify the product by complex purification steps. The desired anion is simple and flexible by reacting the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation with an inorganic or organic proton acid of the desired anion insertable and easily work up the resulting reaction mixture to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound. The particular advantage of using the carboxylate as the starting compound is the formation of the corresponding carboxylic acid, which can then be easily removed. Furthermore, the carboxylates to be used are likewise easy to prepare, the starting materials to be used for their presentation being not or only slightly toxic, technically readily available and 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 Formic acid formed with the inorganic or organic protic acid very easy and complete is separable from the reaction mixture, preferably by distillation the free formic acid or after esterification with a low molecular weight alcohol, in particular Methanol, by distilling off the formed methyl formate, which returned and can be used again as a methylating agent.

The according to the inventive method can be prepared heterocyclic quaternary ammonium compounds and Guanidinium compounds are particularly due to their high Purity for suitable for use 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)

In To a 3-neck flask was added 20 g (0.1 mol) of 1-butyl-3-methylimidazolium formate (prepared analogously to Example 6) in 50 mL of water and inside 30 minutes at approx. 25 ° C with 9.8 g (0.1 mol) of 37% aqueous HCl solution added. At 70 ° C and 35 hPa abs were distilled off water and formic acid. This distillation was repeated three times to complete the resulting formic acid remove. The residue was 4 hours at 150 ° C and 5 hPa abs dried and from the NMR spectrum as 1-butyl-3-methylimidazolium chloride identified (purity> 95%). The yield was 17.4 g (95%).

Example 9 (according to the invention)

In a 3-neck flask, 20 g (0.1 mol) of 1-butyl-3-methylimidazolium formate (prepared analogously to Example 6) in 50 mL of water and within 30 minutes at about 25 ° C with 17.6 g ( 0.1 mol) of 50% aqueous HBF ₄ solution. At 70 ° C and 35 hPa abs of water and formic acid were distilled off. This distillation was repeated three times to completely remove the resulting formic acid. The residue was dried for 4 hours at 150 ° C. and 5 hPa abs and identified on the basis of the NMR spectrum as 1-butyl-3-methylimidazolium tetrafluoroborate (purity> 95%). The yield was 21.5 g (95%).

Example 10 (according to the invention)

In To a 3-neck flask was added 20 g (0.1 mol) of 1-butyl-3-methylimidazolium formate (prepared analogously to Example 6) in 50 mL of water and inside 30 minutes at approx. 25 ° C with 9.6 g (0.1 mol) of methanesulfonic acid. At 70 ° C and 35 hPa abs were distilled off water and formic acid. This distillation was repeated three times to completely remove the resulting formic acid. The residue was 4 hours at 150 ° C and 5 hPa abs dried and from the NMR spectrum as 1-butyl-3-methylimidazolium methanesulfonate identified (purity> 95%). The yield was 22.9 g (98%).

Claims (14)

Process for the preparation of heterocyclic quaternary ammonium compounds and / or guanidinium compounds, characterized in that the carboxylate of the corresponding heterocycli quaternary ammonium cation and / or guanidinium cation which contains the carboxylate anion of the general formula (I) R'-COO ^- (I), in the R '• hydrogen; • C ₁ to C ₁ 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; , is reacted with an inorganic or organic protic acid having a pK _a value of ≦ 14, measured at 25 ° C. in aqueous solution. Method according to claim 1, characterized in that that you have a molar ratio of the inorganic or organic protic acid to the total amount of the corresponding heterocyclic quaternary ammonium cation and guanidinium cation from 0.9 / a to 1.5 / a, where a is the number of to form the desired partially or fully deprotonated anions of the inorganic or organic proton acid indicating protons to be given. Process according to claims 1 to 2, 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 ≤ 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 a plurality of 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 a 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 of 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 is an or is more heteroatoms and / or may be substituted by one or more functional groups or halogen; A method according to claim 3, characterized in that one uses an inorganic or organic protic acid in which the partially or fully deprotonated anion tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, Me thansulfonat, formate, acetate, almond, nitrate, nitrite, trifluoroacetate, sulfate, hydrogen sulfate, Methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, propionate, tetrachloroaluminate, Al ₂ Cl ₇ ; Chlorozincate, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato (2 -)] borate, tetracarbonylcobaltate, dimethylenglycolmonomethylethersulfate, octylsulfate, oleate, Stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis (1,2-benzenediolato (2 -) - O, O '] borate, dicyanamide, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyanoborate or chlorocobaltate. Process according to Claims 1 to 4, characterized in that the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation used is a carboxylate which contains the carboxylate anion (I) in which R 'is hydrogen; Methyl; ethyl;

and R "is C ₁ to C ₄ alkyl; mean, contains. Method according to claim 5, characterized in that that as a carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation formate. Process according to Claims 5 to 6, characterized in that the formate, acetate or propionate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation is used and the formic, acetic or propionic acid formed in the reaction is distilled from the structure separated heterocyclic quaternary ammonium compound and / or guanidinium compound. Process according to claims 1 to 7, characterized that by adding an alcohol, the corresponding ester of used car boxylate anions and this distillative of the formed heterocyclic quaternary ammonium compound and / or Guanidinium compound separates. A method according to claim 8, characterized in that one uses as alcohol a C ₁ - to C ₈ -alkanol. Process according to claims 1 to 10, characterized in that the carboxylate to be used of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation by reacting the corresponding sp ³ -hybridized amine or sp ² -hybridized imine with the corresponding ester of the carboxylate -Anions manufactures. Process according to claims 1 to 10, characterized that the heterocyclic quaternary ammonium cation is an imidazolium, Imidazolinium, pyrazolium, pyrazolinium or pyridinium cation starts. Process according to claims 1 to 10, characterized that is a heterocyclic quaternary ammonium cation an aromatic heterocyclic quaternary Ammonium cation. Process according to Claim 12, characterized in that the aromatic heterocyclic quaternary ammonium cation used 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 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 having 1 to 20 carbon atoms; starts. Method according to claim 14, characterized in that that as imidazolium cation (II) 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-propyl) -3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-pentyl) -3-methylimidazolium, 1- (1-hexyl) -3-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 starts.