EP1784380A1

EP1784380A1 - Method for high-purity quaternary ammonium compounds

Info

Publication number: EP1784380A1
Application number: EP05768765A
Authority: EP
Inventors: Laszlo Szarvas; Thorsten Rohde; Lars Wittenbecher; Klemens Massonne
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-08-24
Filing date: 2005-08-03
Publication date: 2007-05-16
Also published as: US20080033209A1; WO2006021304A1; CN101006046A; JP2008510742A; KR20070053783A

Abstract

The invention relates to a method for producing quaternary ammonium compounds by reacting the corresponding tertiary sp3-hybridized amine or sp2-hybridized imine with dimethyl sulfite. The inventive method is characterized by carrying out the reaction (i) in the presence of a solvent selected from the group including aromatic hydrocarbons having 6 to 10 carbon atoms, symmetrical or unsymmetrical dialkyl ethers having a total of 5 to 10 carbon atoms, cycloalkane having 5 to 8 carbon atoms and C5 to C10 alkane; and (ii) at a temperature of 10 to 100 °C.

Description

Process for the preparation of quaternary ammonium compounds of high purity

description

The present invention relates to a process for preparing quaternary ammonium compounds by reacting the corresponding tertiary sp ³ -hybridized amine or sp ² -hybridized imine with dimethyl sulfite.

Quaternary ammonium compounds are important substances which find wide application. For example, they are used as softener

Active ingredients, in hygiene and cosmetics, as phase transfer catalysts or as conductive salts for electronic applications. Another important application group are ionic liquids with alkylammonium, imidazolium or pyridinium as cations.

Quaternary ammonium compounds having at least one methyl group on the nitrogen are usually prepared by alkylating the corresponding tertiary amines with methyl esters of strong mineral acids such as, in particular, dimethyl sulfate or methyl chloride as methylating agent (see, eg, Houben-Weyl, Methoden der Organi see Chemie, 4th Edition, Volume XI / 2, Georg Thieme Verlag, Stuttgart 1958, pages 591 to 630). A disadvantage of the use of dimethyl sulfate is its carcinogenic effect, which represents a hazard potential and requires expensive safety measures. A disadvantage of the use of methyl chloride is its inertness and associated increased reaction temperature and increased reaction pressure. As a result, side reactions take place which make the work-up more difficult and reduce the yield.

Alternatively, the use of dimethyl carbonate as a methylating agent is described in JP 04-341, 593 and JP 09-025,173. A disadvantage of this is its inertness and associated increased reaction temperature of about 100 ⁰ C and an increased reaction pressure of about 1 to 4 MPa abs. As a result, side reactions take place, which complicate the workup and reduce the yield. For example, in the methylation of imidazole under these conditions, the nucleus is carboxylated. When using tertiary alkylamines as starting material, the Hoffmann degradation takes place under these conditions.

Furthermore, methyl iodide is also known as a methylating agent for the preparation of quaternary ammonium compounds. A disadvantage of the use of methyl iodide, however, is its carcinogenic effect, which represents a potential hazard and requires complex safety measures. Furthermore, methyl iodide is not available in the required technical quantities or is relatively expensive compared to the above-mentioned methylating agents. The use of dimethyl sulfite as a methylating agent for the preparation of quaternary ammonium compounds is also known per se. For example, DE-B 228 247 describes the reaction of various alkaloids of the morphine series with dimethyl sulfite in the presence of methanol as solvent by heating in a water bath to give the corresponding morphinium methyl sulfites (according to the old nomenclature "methylatesulfites" used in the German specification). Other suitable solvents include chloroform and nitrobenzene. The isolation of Morphinium methylsulfite er¬ followed by distilling off the solvent and excess dimethyl sulfite in vacuo and subsequent drying. DE 228 247 further discloses the subsequent reaction of the resulting morphinium methylsulfites with metal halide or hydrohalic acids to give the corresponding morphinium halides.

JP 2001-322,970 describes the reaction of aliphatic trialkylamines having di- methylsulfite in the presence of a polar solvent such as an alcohol or acetonitrile Al¬ at 40 to 100 ⁰ C to give the corresponding methyl trialkyl ammonium methylsulfiten. The product was isolated by distilling off the solvent in vacuo. JP 2001-322,970 furthermore discloses the subsequent reaction of the resulting methyl trialkylammonium methyl sulfites with aqueous acid to introduce the desired anion.

Dimethylsulfite possesses the great advantage of sufficient methylation strength over the other methylating agents enumerated above, which allows gentle reaction conditions, and at the same time the relatively easy removability of most of the methylsulfite anion after addition of the acid of the desired anion by heating to form methanol and volatile sulfur dioxide. According to the invention, however, it has been recognized that a sulfur content of the order of> 2% by weight remains in the isolated quaternary ammonium compound after reaction with the acid of the desired anion due to the processes described in DE 228247 and JP 2001-322,970. However, this sulfur content interferes with various applications of the quaternary ammonium compound, especially when used in the electronics industry. The quaternary ammonium compounds prepared by the processes described in the prior art therefore need to be thoroughly cleaned prior to their use, which represents a decisive disadvantage.

The object of the present invention was to find a process for the preparation of quaternary ammonium compounds which does not have the disadvantages of the prior art, is simple to carry out, the alkylating agent to be used is not or only slightly toxic and a simple and flexible introduction of the desired anion with both the direct alkylation product and the product after introduction of the desired anion in high purity without required to be displayed and suitable for use in the electronics industry.

Accordingly, a process for the preparation of quaternary ammonium compounds by reacting the corresponding tertiary sp ³ -hybridized amine or sp ² -hybridized imine with dimethyl sulfite was found, which is characterized in that the reaction

(i) in the presence of a solvent selected from the group of aromatic hydrocarbons having 6 to 10 carbon atoms, symmetrical or asymmetric dialkyl ethers having a total of 5 to 10 carbon atoms, cycloalkane having 5 to 8 carbon atoms and C ₅ - to C ₁₀ -alkane; and

(ii) at a temperature of 10 to 100 ° C

performs.

The common property of the solvents to be used according to the invention is their relatively low polarity, in particular in comparison with the solvents described in the prior art, such as acetonitrile and alcohol in JP 2001-322,970 or methanol, chloroform and nitrobenzene in DE 228 247 Polarity means that the quaternary ammonium methylsulfite formed during the reaction forms its own solid or liquid phase and thus, for example, unconverted educt or possible by-products preferably remain in the solvent phase.

Furthermore, it has surprisingly been found that by employing the solvents to be used according to the invention in conjunction with the temperature range according to the invention, the rearrangement of the methylsulfite anion to the methanesulfonate anion, in contrast to the solvents described in the prior art, is clearly suppressed or even almost completely avoided ,

As aromatic hydrocarbons having 6 to 10 carbon atoms, in general, unsubstituted or with C ₁ - to C ₄ -alkyl, -CH = CH-CH = CH-, 1,4-butylene, -O-CH ₂ -CH ₂ - CH ₂ - substituted benzenes and monohydroxy or monoalkoxy- alkylbenzenes having a number of carbon atoms in the range used. Examples of suitable hydrocarbons having 6 to 10 carbon atoms are benzene, toluene, ethylbenzene, 1-propylbenzene, 2-propylbenzene, 1-butylbenzene, 2-butylbenzene, tert-butylbenzene, xylene (o-, m-, p-) , Methylethylbenzene (o-, m-, p-), diethylbenzene (o-, m-, p-), trimethylbenzene (vic-, sym-, asym-), cresol (o-, m-, p-), ethylphenol (o-, m-, p-), 1, 2,3,4-tetrahydronaphthalene called. Dialkyl ethers with unbranched or branched alkyl groups are generally used as symmetrical or asymmetrical dialkyl ethers having a total of 5 to 10 carbon atoms, where at least one alkyl group is a C ₃ - to C ₉ -alkyl group. The carbon number of the other alkyl group is given by the total number of carbon atoms mentioned. Examples of suitable symmetrical or asymmetric dialkyl ethers having a total of 5 to 10 carbon atoms are diisopropyl ether, methyl tert-butyl ether, di-n-butyl ether and diethylene glycol dimethyl ether.

As cycloalkane having 5 to 8 carbon atoms, unsubstituted or C ₁ - to C ₃ -alkyl-substituted cycloalkanes are generally used. Examples of suitable cycloalkanes having 5 to 8 carbon atoms are cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane.

As C ₅ - to Cio-alkane unbranched or branched alkanes are generally used. Examples of suitable C ₅ - to C ₁₀ -alkanes are n-pentane, 2-methylbutane (isopentane), 2,2-dimethylpropane, n-hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 , 2-dimethylbutane, n-heptane, isomeric heptane, n-octane, isomeric octane, n-nonane, isomeric nonane, n-decane, isomeric decane called.

It is of course also possible to use mixtures of different solvents.

The solvents used in the process according to the invention are preferably toluene, xylene, ethylbenzene, diethylbenzene, methyl tert-butyl ether, cyclohexane, hexane, heptane or octane.

The amount of solvent to be used in the process according to the invention is generally from 10 to 1000% by weight, preferably from 20 to 500% by weight and more preferably from 20 to 200% by weight, based on the amount of tertiary sp ^{3 used} . hybridized amine or sp ² -hybridized imine.

The nature and sequence of the addition of the individual educts and the solvent is immaterial in the process according to the invention. For example, it is possible to add the tertiary sp ³ -hybridized amine or sp ² -hybridized imine, the dimethyl sulfite and the solvent successively in any order or in parallel to the reaction apparatus. It is also possible to add the tertiary sp ³ -hybridized amine or sp ² -hybridized imine and / or the dimethyl sulfite with a part or the total amount of solvent and only then join together both solvent-containing educts. Furthermore, it is also possible to introduce one of the two educts and to drop the other educt over a certain period of time from a few minutes to several hours, at least one of the starting materials is diluted with the solvent. O

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

The molar ratio of dimethyl sulfite to the tertiary sp ³ -hybridized amine or sp ² -hybridized imine in the process according to the invention is generally from 0.9 to 1.5, preferably 0.9 to 1.2, more preferably 0.9 to 1.1 and most preferably 0.95 to 1.05. When dimethylsulfite is added in slight excess, a small amount of unreacted tertiary sp ³ -hybridized amine or sp ² -hybridized imine remains in the solvent phase and can be separated therefrom from the phase containing the reaction product. If dimethyl sulfite is added in excess, the unreacted dimethyl sulfite remains in the solvent phase and can likewise be separated therefrom by the phase containing the reaction product.

The reaction between the tertiary sp ³ -hybridized amine or sp ² -hybridized imine and the dimethyl sulfite takes place in the process according to the invention at a temperature of 10 to 10O ⁰ C and a pressure of 0.05 to 2 MPa abs, preferably 0.09 to 0.5 MPa abs, more preferably 0.09 to 0.2 MPa abs, and most preferably from 0.095 to 0.12 MPa abs.

The time required for the reaction depends primarily on the chemical nature of the educt (reactivity of the tertiary sp ³ -hybridized amine or sp ² -hybridized imine) and the chosen reaction temperature. It can be determined, for example, by preliminary tests in which, for example, the reaction kinetics are determined, the temperature profile of the exothermic reaction is measured and / or the concentrations of the reactants and of the product are determined analytically. In general, the required period of time is in the range of a few minutes to one day, generally of the order of 0.1 to 24 hours, preferably of the order of 0.1 to 10 hours.

After the reaction, the mixing of the reaction mixture is usually completed so that a phase separation can take place. Depending on the type of Reakti¬ onsapparates it may be advantageous to carry out the deposition of both phases in this or in a separate settling tank. After settling of both phases, the resulting liquid or solid phase of the quaternary ammonium methylsulfite is separated off. In general, the quaternary ammonium methyl sulfite phase is at the bottom and the solvent phase at the top. The separated solvent can generally be recycled and used again as solvent for the reaction mentioned. If necessary, it is advisable to take measures against the accumulation of any by-products in the solvent. Possible measures include, for example, (i) the discharge of a small portion of the solvent and its replacement by fresh solvent or (ii) the distillation of at least a small portion of the solvent with subsequent recycling.

Depending on the desired purity of the quaternary ammonium methylsulfite, it may be advantageous to subsequently subject the separated phase to a purification step. If the phase of the quaternary ammonium methylsulfite is liquid at the working temperature, it can be shaken out with a suitable solvent in which the quaternary ammonium methylsulfite does not dissolve or only very slightly dissolves. Suitable solvents for this purpose are, for example, the solvents or esters which can be used for the reaction according to the invention, for example ethyl acetate. If the phase of the quaternary ammonium methylsulfite is fixed at the working temperature, then this can be washed, for example, with a suitable solvent in which the quaternary ammonium methylsulfite does not dissolve or only very slightly dissolves. Suitable solvents for this purpose are, for example, likewise the solvents or esters which can be used for the reaction according to the invention, for example ethyl acetate. Further, the solid quaternary ammonium methylsulfite can also be recrystallized in a suitable solvent. Suitable solvents here are solvents in which the quaternary ammonium methylsulfite dissolves, for example alcohols, acetonitrile, tetrahydrofuran or nitrobenzene.

Depending on the further use of the optionally purified quaternary ammonium methylsulfite, it is advantageous to dry it beforehand. If a drying is carried out, it is preferably carried out in a temperature-saving manner in a vacuum in order to prevent decomposition of the quaternary ammonium methylsulfite and, in particular, isomerization to the quaternary ammonium methanesulfonate.

The process according to the invention can be carried out batchwise, semicontinuously or continuously. In the batchwise reaction, the reactants and the solvent are combined and the reaction is carried out at the desired temperature. After completion of the reaction, the reaction mixture is worked up as described. In the continuous procedure, both starting materials are slowly added to the reaction mixture at the desired temperature for the reaction, it being possible for the solvent to be added together with one of the two starting materials, distributed to both starting materials or separately. The reaction mixture is taken off continuously in accordance with the amounts of starting materials and solvent fed and worked up as described. The workup itself can also be carried out continuously. Semicontinuous variants require at least at least one of the two educts at the desired temperature slowly, wherein the reaction is generally carried out in parallel with the addition. After the desired amount (s) has been added, the reaction mixture is generally left to afterreact for a certain time and then worked up as described.

In the process according to the invention, the tertiary sp ³ -hybridized amine or tertiary sp ² -hybridized imine used is preferably an amine, an imidazole, a pyridine or a guanidine.

In the process according to the invention, the tertiary sp ³ -hybridized amine used is preferably an amine of the general formula (I)

R1

^{R2 R3} (I) in which

the radicals R ¹ to R ³ 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 and having 1 to 20 carbon atoms. in addition, the radical R ¹ can also be hydrogen; or

the radical R ^{1 is} as defined above and the radicals R ² and R ³ together form a bivalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituier¬ th or by 1 to 5 Heteroatoms or functional groups mean interrupted or substituted radical having 1 to 30 carbon atoms; or

the radicals R ¹ , R ² and R ³ together form 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 with 1 to 40 carbon atoms mean;

one.

In the process according to the invention, the tertiary sp ² -hybridized imine used is preferably an imidazole of the more general formula (II) in the

the radicals R ⁴ to R ⁷ independently of one another are carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted or substituted by 1 to 5 heteroatoms or functional groups having 1 to 20 carbon atoms. denote fluorine atoms and the radicals R ⁴ to R ⁶ additionally independently of one another mean hydrogen, halogen or a functional group and the radical R ^{7 can} additionally also be hydrogen; or

two adjacent radicals together represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups and having 1 to 30 carbon atoms and the remaining group is as previously defined;

one.

In the process according to the invention, the tertiary sp ² -hybridized imine used is preferably a pyridine of the general formula (III)

in the

the radicals R ⁸ to R ¹² independently of one another hydrogen, halogen, a functional group or a carbon-containing organic, saturated or ungesättig¬ th, ae cyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted or substituted radical having 1 to 20 carbon atoms; or

each independently of one another two adjacent radicals together a zweibindi¬ gene, carbon-containing organic, saturated or unsaturated, aeycli¬ rule or cyclic, aliphatic, aromatic or araliphatic, unsubstituier¬ th or interrupted by 1 to 5 heteroatoms or functional groups substituted radicals having 1 to 30 carbon atoms and the remaining radicals / the remaining radical are as defined above / is;

one.

In the process according to the invention, the tertiary sp ² -hybridized imine used is preferably a guanidine of the general formula (IV)

in the

the radicals R ¹³ to R ¹⁷ are each independently 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 which the radicals R ¹³ and R ¹⁵ independently of one another can also be hydrogen; or

in each case independently of one another the radicals R ¹³ and R ¹⁴ and / or R ¹⁵ and R ¹⁶ together contain a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional groups are interrupted or substituted radicals having 1 to 30 carbon atoms and the remaining radicals / the remaining radical are as defined above; or

the radicals R ¹⁴ and R ¹⁵ together form a divalent, carbon-containing orga¬ African, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Koh ¬ lenstoffatomen mean and the remaining radicals are as defined above;

one.

Suitable hetero atoms in the definition of the radicals R ¹ to R ^{17 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. If the carbon-containing radical contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. Particularly preferred groups which may be mentioned are -O-, -S-, -SO-, -SO ₂ -, -NR-, -N =, -PR-, -PR ₂ and -SiR ₂ -, where the radicals R to the remaining part of Containing carbon. In the case of R ⁴ to R ⁶ and R ⁸ to R ¹² , the carbon-containing radical may also be bonded directly via the heteroatom to the imidazolium or pyridinium ring.

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

Halogens are fluorine, chlorine, bromine and iodine.

In the process according to the invention, preference is given to using amines (I), imidazoles (II), pyridines (III) and guanidines (IV) in which the radicals R ⁴ to R ⁶ and R ⁸ to R ^{12 are} independently of one another

• hydrogen;

• halogen; or

• a functional group;

and the radicals R ¹ to R ¹⁷ are each independently

Optionally C ₁ interrupted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to C ₁₈ -alkyl;

Optionally C ₂ interrupted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to C _1S - alkenyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles Cβ- to C ₁₂ -aryl;

Optionally C ₅ -C 4 -cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles; Optionally C ₅ -C ₁₂ -cycloalkenyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles; 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

adjacent radicals R ¹ and R ² , R ² and R ³ , R ¹ and R ³ , R ⁴ and R ⁵ , R ⁵ and R ⁷ , R ⁷ and R ⁶ ,

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ,

R ¹³ and R ¹⁷ and R ¹⁶ and R ¹⁷ together

• an unsaturated, saturated or aromatic, optionally substituted by funk¬ tionelle groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or one or form a plurality of substituted or unsubstituted imino groups interrupted ring.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles Cr to Ci ₈ -AIkyl 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-cyclopentene tylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, a, a-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-dimethyl aminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxy propyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _n F ₂ ( _n ₊ ) ₊ (ib) H ₂ a ₊ 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) ₊ i, 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-5,10-dioxa-tetradecyl, 5-methoxy-3- oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa- undecyl,

15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxetetradecyl, 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-trioxapentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

C ₂ optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C 1 -C ₈ -alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _n F ₂ ( _n -a) - (ib) H _2a -b with n <30, 0 <a <n and b = 0 or 1.

C ₆ -C ₁₂ -aryl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, toIyI, xylyl, .alpha.-naphthyl, .beta.-naphthyl , 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, Isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4- Dinitrophenyl, 2,6-dinitrophenyl, 4-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 .a ₎ - _(I - _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 (na) -3 (Ib) H2a-3b with n <30, 0 <a <n and b = 0 or 1.

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

Form the adjacent radicals R ¹ and R ² , R ² and R ³ , R ¹ and R ³ , R ⁴ and R ⁵ , R ⁵ and R ⁷ , R ⁷ and R ⁶ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹³ and R ¹⁷ and R ¹⁶ and R ¹⁷ together are an unsaturated, saturated th or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups ring Thus, 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 -za-1, 3-propenylene, 1-Ci-C ₄ -alkyl-1-aza- 1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1, 3-dienylene.

If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.

If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

Particularly preferably, the radicals R ¹ to R ³ , R ⁷ and R ¹³ to R ¹⁷ independently of one another are 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-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-di- methyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-i-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3- Dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3 Phenylpropyl, vinyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, Heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, for 6-hydroxyhexyl or propylsulfonic acid. Furthermore, the radical R ⁷ particularly preferably also a sulfo group or a straight or branched SuIfO-C ₁ - to C ₂ alkyl radical.

Particularly preferably, the radicals R ⁴ to R ⁶ and R ⁸ to R ^{12 are} independently voneinan¬ of hydrogen or unbranched or branched C ₁ - to C ₁₂ -alkyl, such as spielsweise 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, pentafl uorethyl, heptafluoropropyl, heptafluoroisopropyl, No nafluorbutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl or 6-hydroxyhexyl.

Very particular preference is given in the process according to the invention as amine (I) trimethylamine, dimethylethylamine, dimethyl-n-propylamine, diethylmethylamine, triethylamine, tri-n-propylamine, di-n-propylmethylamine, tri-n-butylamine, di-n butyl-methylamine, tri-n-pentylamine, N-methylpiperidine, dimethylaniline and N-methylmorpholine.

Very particular preference is given in the process according to the invention as imidazole

(II) N -methylimidazole, N-ethylimidazole, N- (1-propyl) imidazole, N- (1-butyl) imidazole, N- (1-hexyl) imidazole, N- (1-octyl) imidazole, N- ( 1-decyl) imidazole, N- (1-dodecyl) imidazole and N- (1-pentadecyl) imidazole.

Very particular preference is given in the inventive method as pyridine

(III) pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 2-ethylpyridine and 2,6-diethylpyridine.

Very particularly preferably, in the process according to the invention, the guanidine (IV) used is N, N, N ', N', N'-pentamethylguanidine. Be used in the inventive method amines, the reaction takes place between them and the dimethyl sulfite preferably at a temperature of 10 to 80 ⁰ C, particularly preferably from 10 to 60 ⁰ C and most preferably from 10 to 40 ° C.

Are set in the inventive process imidazoles, pyridines or guanidines ein¬, the reaction takes place between them and the dimethyl sulfite preferably at a temperature of 20 to 100 ⁰ C, particularly preferably from 30 to 9O ⁰ C and most preferably from 50 to 8O ⁰ C. ,

If an anion other than methylsulfite is desired, the resulting quaternary ammonium methylsulfite can be further processed in a further reaction stage to introduce the desired anion.

A preferred anion is the hydrogen sulfite anion. In order to obtain the quaternary ammonium hydrogen sulfite, the quaternary ammonium methylsulfite formed is reacted with water with liberation of methanol. In principle, all reaction apparatuses which are suitable for a reaction in the liquid phase can be used as reaction apparatuses. These are, in particular, reaction apparatuses which permit a corresponding mixing of the liquid educts, for example stirred tanks. The molar ratio of water to quaternary ammonium methylsulfite is generally from 0.9 to 1.5, preferably from 0.95 to 1.2, more preferably from 0.95 to 1.1, and most preferably from 0.99 to 1.05 , The reaction is generally carried out at a temperature of 10 to 8O ⁰ C, preferably from 10 to 6O ⁰ C and particularly preferably from 20 to 4O ⁰ C. The pressure is generally 0.05 to 2 MPa abs, preferably 0, 09 to 0.5 MPa abs and more preferably 0.095 to 0.12 MPa abs. The time required for the reaction is generally from a few minutes to several hours, preferably 0.1 to 5 hours, and can for example be determined by the course of the reaction (pH, concentration of the methyl sulfite anion). After the reaction is generally the methanol formed and any¬ existing excess water in vacuo at a temperature of 10 to 80 ⁰ C and preferably from 10 to 60 ⁰ C deducted. The product obtained can be reacted with solvents in which the quaternary ammonium hydrogensulfite does not dissolve or only very slightly, for example an aromatic hydrocarbon having 6 to 10 carbon atoms, a symmetrical or unsymmetrical dialkyl ether having a total of 5 to 10 carbon atoms, a cycloalkane having 5 to 8 carbon atoms or a C ₅ - to C ₁₀ alkane. Furthermore, it is also possible to recrystallize the product in a solvent in which the quaternary ammonium hydrogensulfite dissolves, for example an alcohol, acetonitrile, tetrahydrofuran or nitrobenzene. The product is generally dried in vacuo. In order to introduce anions other than hydrogen sulfite, the quaternary ammonium methylsulfite formed is reacted with an inorganic or organic protic acid having a pK _{a of} from 1.8 to 14, measured at 25 ° C. in aqueous solution, with the release of methanol and Sulfur dioxide and formation of the quaternary ammonium salt of the corresponding partially or fully deprotonated acid anion.

The pKa of the inorganic or organic protic acid to be used is preferably from 1, 8 to 10, particularly preferably 2 to 10 and most vorzugt 3 to 10, measured at 25 ⁰ C in aqueous solution. In principle, all reaction apparatuses which are suitable for a reaction in the liquid phase can be used as reaction apparatuses. These are in particular reactors which allow a corresponding mixing of the liquid educts, for example stirred tank. The molar ratio of the inorganic or organic protic acid to the quaternary ammonium methylsulfite is generally from 0.9 to 1.5, preferably 0.95 to 1.1, more preferably 0.95 to 1.05 and very particularly preferably 0, 99 to 1, 02. The reaction is generally carried out at a temperature of 10 to 80 ⁰ C, preferably from 10 to 60 ⁰ C and particularly preferably from 20 to 40 ⁰ C. The pressure be¬ carries generally 0.05 to 2 MPa abs, preferably 0, From 09 to 0.5 MPa abs and more preferably from 0.095 to 0.12 MPa abs. The time required for the reaction is generally from a few minutes to several hours, preferably 0.1 to 5 hours, and can for example be determined by the course of the reaction (pH, Konzent¬ ration of the methyl sulfite anion). After the reaction, any excess acid which may be present is generally neutralized with a base, for example sodium hydroxide, and the product is subsequently treated with a solvent in which the quaternary ammonium salt does not dissolve, such as, for example, an alcohol, acetonitrile, tetrahydrofuran or Nitrobenzene, washed. The product is generally dried in vacuo.

In the process according to the invention, preference is given to preparing a quaternary ammonium salt in which the partially or fully deprotonated anion

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

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

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

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

(Fluoroalkyl) fluorophosphate of the general formula (Vd) [PF _x (CyF ₂ y ₊ i _-z H _z ) ₆ -x] ^' , where 1 <x <6, 1 <y <8 and O <z <2y + 1 ;

Imide of the general formulas (Ve) [R 1 SO ₂ -N-SO ₂ -R ¹ T, (Vf) [R 1 SO ₂ -N-CO-R ¹ ] - or (IVg) [R ^k -CO-N -CO-R '] ^' , wherein R ^g to R ^{1 are} independently hydrogen or a carbon-containing organic, saturated or unsaturated, acycli¬'s or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;

Methide of the general formula (Vh)

SO ₂ -R ^m

Rn-O ₂ S SO ₂ -R °

(Vh),

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

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

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

Sulfide, hydrosulfide, Hydrogenpolysulf id of the general formula (Vk) [HS _V] ^"Polysul- f id of the general formula (Vm) [S ^{_v] 2-,} where v is a positive integer from 2 to 10, thiolate of the general formula (Vn) [R ^S S] ^", wherein R ^s is a carbon-enthal¬ Tenden organic, saturated or unsaturated, acyclic or cyclic, aliphatic aromatic or araliphatic radical having 1 to 30 carbon atoms which contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

is.

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

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

Halogens are fluorine, chlorine, bromine and iodine.

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

»C _r to C ₃₀ alkyl and their aryl, heteroaryl, cycioalkyl, halogeno, 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 (benzyl), diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl , Methoxy, ethoxy, formyl, acetyl or C _n F ₂ ( _n -a) ₊ (Ib) H ₂ a ₊ b with n <30, 0 <a <n and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ ,

CH2CH2-C _(n-2) F2 _(n-2) +1, CβFi3, CEFI _7, C10F21, C12F25);

• C ₃ - to Ci ₂ cycloalkyl, and whose aryl, heteroaryl, cycioalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -O-, -CO- or -CO-O-substituted derivatives 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 (na) - (ib) H2a-b with n <30, 0 <a <n and b = 0 or 1;

C ₂ to C ₃₀ alkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components such as 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or CnF ₂ (na) - (ib) H2a-b with n <30, 0 <a <n and b = 0 or 1 ;

C ₃ - to C ₁₂ -cycloalkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components ¬ th, such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _n F ₂ (n..a) - ₃ (ib) H2a-3b with n <30, 0 <a < n and b = 0 or 1; and

Aryl or heteroaryl having 2 to 30 carbon atoms and their alkyl, aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO -O-substituted components, such as, for example, phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-toiyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 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)} Ha with 0 <a <5.

Is When the anion is a tetra-substituted borate (Va) [BR ^a R ^b R c R ^d] ^~, so, in this preferred all four groups R ^a to R ^d are the same, which preferably represents 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 it is [R ₃ -SO ^Θ] \ is so When the anion is an organic sulfonate (Vb) of the radical R ^e preferably represents methyl, trifluoromethyl, pentafluoroethyl, p-tolyl or C ₉ F _19th Particularly preferred organic sulfonates (Vb) are trifluoromethanesulfonate (triflate), methanesulfonate, p-tolylsulfonate, nonadecafluorononanesulfonate (nonaflate), dimethlylene glycol monomethyl ether sulfate and octyl sulfate.

If the anion is a carboxylate (Vc) [R ^f -COO] ^' , the radical R ^{f is} preferably hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxyphenylmethyl, 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 unbranched or branched C _r to C ₈ alkyl such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl ( tert -butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3- Dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl , Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, heptadecyl. Particularly preferred carboxylates (Vc) are formate, acetate, propionate, butyrate, valerate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.

If the anion is a (fluoroalkyl) fluorophosphate (Vd) [PF _x (C _y F _{2y + 1-z} H _z ) _6-x ] ^" , then z is preferably 0. Particular preference is given to (fluoroalkyl) fluorophosphates (Vd ), where z = 0, x = 3 and 1 <y <4, specifically [PF ₃ (CF ₃₎ S] ^", [PF ₃ (C ₂ F) _^3]," [PF ₃ (C ₃ F ₇ ) ₃ ] ^' and [PF ₃ (C ₄ Fr) ₃ ] ^" .

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

Is the anion a methide (Vh)?

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

Wherever the anion is an organic sulfate (Vi) [R ¹³ O-SO _3] ^", represents the radical R ^p is preferably a branched or unbranched C _r to C ₃₀ -Alklylrest. Sawn Sonders preferred organic sulfates (Vi ) are methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate or octyl sulfate. If it is, stands When the anion is a halometalate (Vj) [M _q Hal _r] ^{s "as} M preferably represents aluminum, zinc, iron, Cobald, antimony or tin. Hal is preferably chlorine or bromine, and very particularly preferably represents chlorine , q is preferably 1, 2 or 3 and r and s are given according to the stoichiometry and charge of the metal ion.

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

Quaternary ammonium salt 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, pentyl sulfate, hexyl sulfate, hydrogen sulfate, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, propionate, tetrachloroaluminate, Al ₂ Cl _? ^' , Chlorozincate, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato (2 -)] borate, tetracarbonylcobaltate, dimethylenglycolmonomethylethersulfate, Octyl sulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis [1,2-benzenediolato (2 -) - O, O ' ] borate, dicyanamide, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, tetracyano borate or chlorocobaltate.

In a general embodiment, the corresponding tertiary sp ³ -hybridized amine or sp ² -hybridized imine, the solvent and the dimethyl sulfite are combined and reacted with mixing, for example while stirring, at the desired temperature and pressure. After completion of the reaction, the mixing is stopped so that both phases separate. Now you separate the two phases from each other. The liquid or solid phase containing the quaternary ammonium methylsulfite is preferably washed with a suitable solvent and then dried in vacuo. The resulting quaternary ammonium methylsulfite has a high purity and can be used if necessary for the preparation of quaternary ammonium salts of other anions.

In a preferred embodiment, the resulting quaternary ammonium methylsulfite is mixed with, for example, with stirring, with an inorganic or organic protic acid having a pK _a value of <14, measured at 25 ° C in aqueous solution, with release of methanol and sulfur dioxide and forming the quaternary ammonium salt of the corresponding partially or fully deprotonated acid anion. After completion of the reaction neutralizes any existing -SO excess acid with a base, wash the resulting quaternary ammonium salt with a suitable solvent and then dried in vacuo.

The process according to the invention makes it possible to prepare quaternary ammonium compounds in high purity without complicated purification steps, is easy to carry out and requires no toxic substances due to the use of dimethyl sulfite as methylating agent. As a result of the process characteristics according to the invention, the rearrangement of the methylsulfite formed to form the methanesulfonate is almost completely avoided or at least significantly suppressed, which makes possible the high purity, also with regard to the isomeric secondary component methanesulfonate. Furthermore, the process according to the invention makes it possible to introduce other anions by the possible reaction of the primary reaction product quaternary ammonium methylsulfite with water or an inorganic or organic protic acid and is therefore very flexible in the choice of the available anion. The particular advantage of the use of pure quaternary ammonium methylsulfite in the further reaction with water or an inorganic or organic protonic acid is the easy and complete removal of the methyl sulfite anion to form volatile methanol (in the reaction with water to the hydrogen sulfite) or to form volatile methanol and volatile sulfur dioxide (when reacted with an inorganic or organic protic acid). In contrast, the quaternary ammonium methyl sulfites prepared according to the prior art contain significant amounts of isomeric methanesulfonate, which can no longer be decomposed into readily volatile components. Thus, even after introduction of the desired anion, the methanesulfonate would remain in the reaction mixture and contaminate the final product.

The quaternary ammonium compounds which can be prepared by the process according to the invention are therefore also suitable for use in the electronics industry without problems.

Examples

Example 1 (according to the invention)

21, 11 g (0.192 mol) of dimethyl sulfite were initially charged in 100 ml of toluene and a solution of 23.8 g (0.192 mol) of N-butylimidazole in 25 ml of toluene was added. The solution was stirred at 60 ^° C. for 15 hours. During the reaction, a second liquid phase was formed by the resulting N, N'-butylmethylimidazolium methylsulfite. Upon completion of the stirring, both phases separated. The lower, N.N'-butyl-methyl-imidazolium-methyl sulfite-containing phase was separated and extracted by shaking twice with ethyl acetate. N, N'-butyl-methylirnidazolium methylsulfite was on closing (mbar 3) vacuum dried at 0.3 kPa at 40 ⁰ C. The balance was 37.5 g, corresponding to 83% overall theoretical yield (N, N'-butylmethylimidazolium methylsulfite and methanesulfonate).

The resulting liquid product was analyzed by NMR spectroscopy and identified as N, N'-butyl-methylimidazolium methylsulfite:

[1 H-NMR, 400Mhz], D ₂ O: 0.9 ppm (t-3H); 1.3 ppm (m - 2H); 1.8 ppm (m - 2H); 2.8 ppm (s-3H-methanesulfonate); 3.4 ppm (s - 3H); 3.8 ppm (s - 3H); 4.2 ppm (t - 2H); 7.4 ppm (d - 2H); 8.7 ppm (s -1 H).

A quantitative evaluation of the NMR spectrum showed from the signal ratio 2.8 ppm (3H-methanesulfonate): 3.8 ppm (3H-methyl group on the imidazolium nitrogen) that the proportion of methanesulfonate formed was below the detection limit. This is 3 mol%. The purity of the N.N'-butyl-methylimidazolium methylsulfite was thus> 97%.

Example 2 (comparative example without solvent)

62 g (0.5 mol) of N-butylimidazole were treated with 55 g (0.5 mol) of dimethyl sulfite and heated to 8O ⁰ C with stirring. The reaction was highly exothermic. The solution was stirred for 5 hours at 80 ⁰ C, then abge¬ to about room temperature is cooled and extracted twice with ethyl acetate. N.N'-butyl-methyl-imidazolium-methylsulfite was then dried in vacuo at 0.3 kPa (3 mbar) at 40 ⁰ C. The balance was 108.6 g, corresponding to 92% theoretical Gesamt¬ yield (N.N'-butyl-methylimidazolium-methyl sulfite and methanesulfonate).

The resulting liquid product was analyzed by NMR spectroscopy and identified as the mixture of N.N'-butylmethylimidazolium methylsulfite and N, N'-butyl-methylimidazolium methanesulfonate. [1 H-NMR, 400Mhz], D ₂ O: 0.9 ppm (t-3H); 1.3 ppm (m - 2H); 1.8 ppm (m - 2H);

2.8 ppm (s-3H-methanesulfonate); 3.4 ppm (s - 3H); 3.8 ppm (s - 3H); 4.2 ppm (t - 2H); 7.4 ppm (d - 2H); 8.7 ppm (s - 1 H)

In addition, a quantitative evaluation of the NMR spectrum from the signal ratio 2.8 ppm (3H-methanesulfonate): 3.8 ppm (3H-methyl group on imidazolium nitrogen) determined the proportion of methanesulfonate formed to be 16 mol%. The purity of N, N'-butyl-methylimidazolium methylsulfite was thus only 84%.

Even if a higher yield was achieved in Comparative Example 2 without the use of a solvent, it was possible to obtain the N, N'-butyl-methylimidazolium methylsulfite in only 84% purity, which corresponds to a calculated yield of N, N'-butyl - Methylimidazolium methylsulfite of only about 77% corresponds. In contrast, Example 1 of the invention shows a significantly higher purity of> 97%, which corresponds to a calculated yield of N, N'-butyl-methylimidazolium methylsulfite of about 80 to 83%.

Example 3 (Comparative Example with acetonitrile as solvent)

Example 3 was essentially carried out analogously to Example 1 of JP 2001-322,970.

20.0 g (0.198 mol) of ^{"methylamine,} 21, 8 g (0.198 mol) of dimethyl sulfite and 40 mL acetonitrile were combined and heated under atmospheric pressure and with stirring for 2 hours under reflux. Thereafter, the acetonitrile was distilled off under reduced pressure, and the liquid triethylmethylammonium obtain salt. This was dissolved in 100 mL of water and 38.0 g of 50% aqueous tetrafluoroboric acid, accordingly entspre¬ 0.198 mol HBF _4, was added. The solution was heated to 70 ⁰ C, while formed sulfur dioxide evolved. After completion In the evolution of sulfur dioxide, water and methanol were distilled off under vacuum, and the overall theoretical yield was 92% (triethylmethylammonium tetrafluoroborate and methanesulfonate).

Compared to Example 1 of JP 2001-322,970, wherein a yield of 96% is described ben, the yield in the experimental adjustment was only 92%.

The resulting liquid product was analyzed by NMR spectroscopy and the following

Signals identified:

[1 H-NMR, 400Mhz], D ₂ O: 1.3 ppm (t-9H); 2.8 ppm (s-3H-methanesulfonate);

2.9 ppm (s - 3H); 3.3 ppm (q - 6H)

In addition, quantitative analysis of the NMR spectrum from the signal ratio 2.8 ppm (3H-methanesulfonate): 2.9 ppm (3H-methyl group on the amino group). nium-nitrogen), the proportion of formed methanesulfonate to 6.1 mol% determined. The purity of triethylmethylammonium tetrafluoroborate was thus only 93.9%.

Example 4 (according to the invention)

Example 4 is based on the above Vergleichsbeispie 3, but with the main difference that according to the invention was used as a solvent toluene, with a correspondingly altered workup, and a lower reaction temperature was selected.

20.0 g (0.198 mol) of triethylamine were initially charged at room temperature and a solution of 21.8 g (0.198 mol) of dimethyl sulfite in 30 g of toluene was added dropwise. The mixture was heated to 50 ^° C. and left under atmospheric pressure and with stirring for 12 hours under these conditions. During the reaction, a second liquid phase was formed by the resulting triethylmethylammonium methylsulfite. Upon completion of the stirring, both phases separated. The lower phase containing triethylmethylammonium methylsulfite was separated and 38.0 g of 50% strength aqueous tetrafluoroboric acid, corresponding to 0.198 mol of HBF ₄ , were added dropwise. The solution was heated to 7O ⁰ C, with evolved sulfur dioxide escaped. After completion of the sulfur dioxide evolution, it was cooled and the product was concentrated in vacuo to remove water and methanol. The balance was 33.36 g, corresponding to 85% theoretical total yield (triethylmethylammonium methyl sulfite and methanesulfonate).

The resulting liquid product was analyzed by NMR spectroscopy and identified the following signals:

[1 H-NMR, 400Mhz], D ₂ O: 1.3 ppm (t-9H); 2.8 ppm (s-3H-methanesulfonate); 2.9 ppm (s-3H); 3.3 ppm (q - 6H)

In addition, a quantitative evaluation of the NMR spectrum from the signal ratio of 2.8 ppm (3H-methanesulfonate): 2.9 ppm (3H-methyl group on the ammonium nitrogen) resulted in the proportion of formed methanesulfonate being 4.6 mol -% determined. The purity of triethylmethylammonium tetrafluoroborate was thus 95.4%.

Compared with Comparative Example 3 with acetonitrile as the solvent, the inventive method achieved a purity which was higher by 1.5% (95.4% vs. 93.9%). This corresponds to a reduction of undesirable triethylmethylammonium methanesulfonate of 1.5 mol%, which corresponds to a relative reduction of 24.6 rel% to 75.4 rel% (4.6 mol% vs. 6.1 mol%). The inventive method leads to the quaternization of triethylamine and subsequent exchange of the anion to triethylmethylammonium tetrafluoroborate to a significantly purer product.

Example 5 (according to the invention)

14.6 g (0.2 mol) of N, N-dimethylethylamine in 150 ml of n-heptane introduced and it was added dropwise within 10 minutes 22.0 g (0.2 mol) Dimethylsulf at 10 ⁰ C. After dropwise addition, the solution was slowly warmed to room temperature and stirred for 4 hours. During the reaction, a white precipitate was precipitated. This was filtered off with suction, washed with a little heptane and dried. The balance was 31.5 g, corresponding to 86% overall theoretical yield (trimethylethylammonium methylsulfite and methanesulfonate).

The resulting solid product was analyzed by NMR spectroscopy. The 1 H-NMR spectrum (400 Mhz, D ₂ O) with signals at 1.4 ppm (t-3H), 3.3 ppm (s-3H-methyl sulfite anion) and 3.4 ppm (q-2H ) shows a mixture of the desired product trimethylethylammonium methylsulfite and trimethylethylammonium hydrogensulfite, which is formed by hydrolysis by the presence of D ₂ O.

After aqueous workup of trimethylethylammonium methylsulfite, the secondary product trimethylethylammonium hydrogensulfite was isolated and identified by elemental analysis.

Example 6 (according to the invention)

49.3 g (0.21 mol) of N, N'-butyl-methylimidazolium methylsulfite, which was prepared by the preparation according to Example 1, was initially charged at room temperature and, while stirring, 13 g (0.21 mol) of acetic acid were slowly added dropwise. The reaction mixture was carefully placed between 40 and 65 ° C under a vacuum of 50 to 0.2 kPa abs (500 to 2 mbar abs), wherein formed methanol were distilled off. After the methanol formation and distillation was complete, the reaction mixture was heated to 140 ⁰ C, and under vacuum 0.3 kPa abs (3 mbar abs) of sulfur dioxide freed. The latter was caught in a cold trap. The yield of reaction product was 37.2 g, corresponding to 90% overall theoretical yield.

The resulting liquid product was analyzed by NMR spectroscopy and identified as N ₁ N ¹ -butyl-methylimidazolium acetate.

[1 H-NMR, 400 MHz], D ₂ O: 0.9 ppm (t-3H); 1.3 ppm (m - 2H); 1.8 ppm (m - 2H); 1.9 ppm (s - 3H CH ₃ COO-); 3.4 ppm (s - 3H); 3.8 ppm (s - 3H); 4.2 ppm (t - 2H); 7.4 ppm (d - 2H); 8.7 ppm (s - 1 H)

Example 7 (comparative example with acetonitrile as solvent)

Example 7 was carried out essentially analogously to Example 1 of JP 2001-322,970, wherein pyridine was used instead of triethylamine.

15.66 g (0.198 mol) of pyridine, 21.8 g (0.198 mol) of dimethyl sulfite and 40 mL of acetonitrile were combined and heated under atmospheric pressure with stirring for 2 hours under reflux. Subsequently, the acetonitrile was distilled off under reduced pressure to obtain the liquid methylpyridinium salt. This was dissolved in 100 ml of water and mixed with 38.0 g of 50% aqueous tetrafluoroboric acid, corresponding to 0.198 mol of HBF ₄ . The solution was heated to 70 ⁰ C, while formed sulfuric dioxide evolved. After completion of the sulfur dioxide evolution, water and methanol were distilled off under vacuum. The overall theoretical yield was 86.8% (methylpyridinium methylsulfite and methanesulfonate).

[1 H-NMR, 400Mhz], D ₂ O: 2.8 ppm (s-3H-methanesulfonate); 4.4 ppm (s - 3H); 4.45 ppm (s - 3H - minor components); 8.0 ppm (m, 2H); 8.5 ppm (m-1H); 8.8 ppm (m - 2H)

In addition, a quantitative evaluation of the NMR spectrum from the signal ratio 2.8 ppm (3H-methanesulfonate): 4.4 ppm (3H-methyl group on pyridinium nitrogen) showed that the proportion of methanesulfonate formed was 10.5 mol -% determined. The purity of the pyridinium tetrafluoroborate was thus only 89.5%.

Example 8 (according to the invention)

15.82 g (0.2 mol) of pyridine were initially charged at room temperature and a mixture of 22 g (0.2 mol) Dimethylsulft and 30 g of toluene was slowly added dropwise. The resulting mixture was warmed to 50 ^° C. and stirred for 12 hours. After cooling the reaction mixture, the lower, containing methylpyridinium methylsulfite Pha¬ se was separated and to this 39 g of 50% aqueous tetrafluoroboric acid, accordingly 0.2 mol of HBF ₄ , added dropwise. This gas evolution was observed. The Reakti¬ onsgemisch was then stirred for 2 hours at 7O ⁰ C and then at 12O ⁰ C and 0.2 kPa abs (2 mbar abs) concentrated. The balance was 28.5 g, corresponding to 85% overall theoretical yield (methylpyridinium tetrafluoroborate and methanesulfonate).

[1 H-NMR, 400Mhz], D ₂ O: 2.8 ppm (s-3H, methanesulfonate); 4.4 ppm (s, 3H-methyl group on pyridinium nitrogen); 8.1 ppm (m, 2H); 8.5 ppm (m, 1H); 8.8 ppm (m, 2H)

A quantitative evaluation of the NMR spectrum showed from the signal ratio of 2.8 ppm (3H-methanesulfonate): 4.4 ppm (3H-methyl group on pyridinium nitrogen) that the proportion of methanesulfonate formed was below the detection limit. This is 3 mol%. The purity of the methylpyridinium tetrafluoroborate was thus> 97%.

Claims

claims

1. A process for preparing quaternary ammonium compounds by reacting the corresponding tertiary sp ³ -hybridized amine or sp ² -hybridized imine with dimethyl sulfite, characterized in that the reaction

(i) in the presence of a solvent selected from the group aromatic hydrocarbon having 6 to 10 carbon atoms, symmetrical or unsymmetrical dialkyl ethers having a total of 5 to 10 carbon atoms, cycloalkane having 5 to 8 carbon atoms and C ₅ - to C ₁₀ -alkane; and

(ii) at a temperature of 10 to 100 ° C

performs.

2. The method according to claim 1, characterized in that the Lösungs¬ medium in an amount of 10 to 1000 wt .-%, based on the amount of ein¬ set tertiary sp ³ -hybridized amine or sp ² -hybridized imine, a ¬ sets.

3. Process according to claims 1 to 2, characterized in that the solvent used is toluene, xylene, ethylbenzene, diethylbenzene, methyl tert-butyl ether, cyclohexane, hexane, heptane or octane.

4. The method according to claims 1 to 3, characterized in that one uses a molar ratio of dimethyl sulfite to the tertiary sp ³ -hybridized amine or sp ² -hybridized imine from 0.9 to 1, 5.

5. The method according to claims 1 to 4, characterized in that separated after the reaction of the corresponding tertiary sp ³ -hybridized amine or sp ² -hybridized imine with dimethyl sulfite, the resulting liquid or solid phase of the quaternary ammonium methylsulfite.

6. Process according to claims 1 to 5, characterized in that the tertiary sp ³ -hybridized amine is an amine of the general formula (I)

^{R2 R3} (I) in which

the radicals R ¹ to R ³ are each independently of one another carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic see, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms, wherein the radical R ^{1 may} additionally be hydrogen; or

the radical R ¹ is as defined above and the radicals R ² and R ³ together form a divalent, carbon-comprising organic, saturated or ungesät¬ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati¬ rule, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups are interrupted or substituted radicals having 1 to 30 carbon atoms; or

the radicals R ¹ , R ² and R ³ together form a trivalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or from 1 to 5

Heteroatoms or functional groups mean interrupted or substituted radical having 1 to 40 carbon atoms;

starts.

7. Process according to claims 1 to 5, characterized in that the tertiary sp ² -hybridized imine is an imidazole of the general formula (II)

in the

the radicals R ⁴ to R ^{7 are} independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituier¬ th or interrupted or substituted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms and the radicals R ⁴ to R ⁶ additionally independently of one another denote hydrogen, halogen or a functional group and the radical R ^{7 may} additionally also be hydrogen; or

two adjacent radicals together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted radical having 1 to 30 carbon atoms and the remaining radical is as defined above;

starts.

8. Process according to claims 1 to 5, characterized in that the tertiary sp ² -hybridized imine is a pyridine of the general formula (III)

in the

the radicals R ⁸ to R ¹² 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 by 1 to 5 hetero atoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms; or

in each case independently of one another, two adjacent radicals together represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical, unsubstituted or interrupted or substituted by 1 to 5 heteroatoms or functional groups with 1 to 30 carbon atoms, and the remaining radicals / the remaining radical are as defined above;

starts.

9. Process according to claims 1 to 5, characterized in that the tertiary sp ² -hybridized imine is a guanidine of the general formula (IV)

_{(| V)>} in the

the radicals R ¹³ to R ^{17 are} independently of one another carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 hetero atoms or functional groups radical or 1 to 20 Carbon atoms, wherein the radicals R ¹³ and R ¹⁵ independently of one another may additionally be hydrogen; or

each independently of one another the radicals R ¹³ and R ¹⁴ and / or R ¹⁵ and R ¹⁶ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional groups are interrupted or substituted radicals having 1 to 30 carbon atoms and the remaining radicals / the remaining radical are as defined above; or

the radicals R ¹⁴ and R ¹⁵ together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 30 carbon atoms and the remaining radicals are as previously defined;

starts.

10. The method according to claims 1 to 9, characterized in that as a tertiary sp ³ -hybridized amine or sp ² -hybridized imine trimethylamine, dimethyl- methylethyl, Dimethyi- n-propylamine, diethylmethylamine, triethylamine, tri-n- propylamine, di-n-propylmethylamine, tri-n-butylamine, di-n-butylmethylamine, tri-n-pentylamine, N-methylpiperidine, dimethylaniline, N-methylmorpholine, N-methyl-midazole, N-ethylimidazole, N- (1 Propyl) imidazole, N- (1-butyl) imidazole, N- (1-hexyl) midazole, N- (1-octyl) imidazole, N- (1-decyl) imidazole, N- (1-dodecyl) imidazole , N- (1-

Pentadecyl) imidazole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 2-ethylpyridine, 2,6-diethylpyridine or N, N, N ¹ , N ', N "-pentamethylguanidine.

11. The method according to claims 1 to 10, characterized in that the formed quaternary ammonium methylsulfit with water to release Reacting methanol and formation of the quaternary ammonium hydrogensulfite.

12. The method according to claims 1 to 10, characterized in that the formed quaternary ammonium methylsulfit with an inorganic or organic protic acid having a pK _a value of <14, measured at 25 ⁰ C in aqueous solution, with release of methanol and sulfur dioxide and Bil¬ formation of the quaternary ammonium salt of the corresponding partially or fully deprotonated acid anion.

13. The method according to claim 12, characterized in that the quaternary ammonium compound is prepared as a quaternary ammonium salt in which the partially or fully deprotonated anion

Fluoride; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoro- arsenate; Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate;

Phosphate; Hydrogen phosphate; Dihydrogen phosphate, vinyl phosphonate, dicyanamide, bis (pentafluoroethyl) phosphinate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoropropyl) trifluorophosphate, bis [oxalato (2 -)] borate, bis [salicylato (2-)] borate, bis [1, 2-benzenediolato (2 -) - 0,0 '] borate, tetracyano borate, tetracarbonyl cobalada;

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 represent fluorine or a carbon-containing orga African, saturated or unsaturated, acyclic or cyclic, aliphatic see, aromatic or araliphatic radical having 1 to 30 carbon atoms, which contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;

organic sulfonate of the general formula (Vb) [R ^e -Sθ _3] ^", wherein R ^e is a carbon-comprising organic, saturated or unsaturated acycli¬, rule or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is a or more heteroatoms may enthal¬ and / or tuiert by one or more functional groups or halogen substituted may be;

Carboxylate of the general formula (Vc) [R'-COO] ^' , wherein R ^{f is} hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen; (Fluoroalkyl) fluorophosphate of the general formula (Vd) [PF _x (C _y F _{2V + I-2} Hz) _6-X] ^"where 1 <x <6, 1 <y <8 and O <z <2y + 1 ;

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

Methide of the general formula (Vh)

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

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

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

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

is.

14. The method according to claim 13, characterized in that the quaternary ammonium compound is prepared as a quaternary ammonium salt in which the partially or fully deprotonated anion Tetraf luoroborat, Hexaf luorophosphat, Trif luor- methanesulfonate, methanesulfonate, formate, acetate, mandelate, nitrate, nitrite , Trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, propylsulfate, butylsulfate, pentylsulfate, hexylsulfate, heptylsulfate, octylsulfate, phosphate, dihydrogenphosphate, hydrogenphosphate, propionate, tetrachloroaluminate, Al ₂ Cl ₇ ^" , chlorozincate, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, bis (pentafluoroethylsulfonyl) methide, p-tolylsulfonate, bis [salicylato (2 -)] borate, tetracarbonyl cobaltate, dimethylenglycol monomethyl ether sulfate, octylsulfate , Oleate, stearate, acrylate, methacrylate, maleate, hydrogen citrate, vinyl phosphonate, bis (pentafluoroethyl) phosphinate, bis [oxalato (2 -)] borate, bis [1, 2-benzenediolato (2 -) - O, O ^l] borate, dicyanomaleic amide, tris (pentafluoroethyl) trif luorophosphat, tris (heptafluoropropyl) trif luoro¬ phosphate, is tetracyanoborate or Chlorocobaltat.