DE102006011077A1 - Process for the degradation of cellulose with nucleophiles - Google Patents

Abstract

The present invention describes a method for breaking down cellulose by dissolving cellulose in an ionic liquid and treating it with a nucleophile.

Description

The The present invention describes a process for the degradation of cellulose by dissolving cellulose in an ionic liquid and using a nucleophile treated.

cellulose is the most important renewable resource and represents an important Starting material for example the textile, paper and nonwovens industries. It also serves as raw material for Derivatives and modifications of cellulose, which include cellulose ethers, such as. Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, such as. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, such as. Cellulose nitrate, and others count. These derivatives and modifications find diverse Application, for example in the food, construction and paint industry.

Cellulose is characterized by insolubility, especially in common solvents of organic chemistry. In general, N-methyl-morpholine-Noxid, anhydrous hydrazine, binary mixtures such as methylamine / dimethylsulfoxide, or ternary mixtures such as ethylenediamine / SO ₂ / dimethyl sulfoxide are used as solvent today. However, it is also possible to use saline systems, such as LiCl / dimethylacetamide, LiCl / N-methylpyrrolidone, potassium thiocyanate / dimethyl sulfoxide, etc.

Rogers et al. have recently reported (J. Am. Chem. Soc., 124, 4974 (2002)) that cellulose in ionic liquids, such as. [1-butyl-3-methyl-imidazolium] chloride is soluble.

Usually becomes cellulose by the average degree of polymerization (DP) characterizes. The DP of cellulose depends on their origin; so the DP can get up from raw cotton at up to 12 000 lie. Usually have cotton linters a DP from 800 to 1800 and wood pulp it is in the range from 600 to 1200. For Many applications, however, it is desirable to use cellulose with one DP to use, which is lower than the above and it is also desirable to have a high proportion of polymers chain length to reduce.

To the Degradation of cellulose are known in four different ways Groups can be classified - the mechanical Degradation, thermal degradation, degradation by the action of radiation and chemical degradation (D. Klemm et al., Comprehensive Cellulose Chemistry, Vol. 1, pp. 83-127, Wiley Verlag, 1998).

At the mechanical degradation, such as dry or wet milling, it is disadvantageous that the DP of the cellulose is reduced only to a small extent. An uncontrolled degradation takes place during the thermal treatment instead, and in addition, the cellulose is modified, in particular dehydrocelluloses be formed. In the degradation by radiation, cellulose with high-energy radiation, such as X-rays are treated. Here, the DP of the cellulose is lowered very quickly. Indeed Also occurs a chemical modification of cellulose by a high number of carboxylic acid or Keto functions are formed. On the other hand, you use less energy-rich Radiation, such as UV / visible light, so it is necessary Use photosensitizers. And here too it comes to one Modification of the cellulose by formation of keto functions, or if oxygen is present during the irradiation, peroxide formation.

When Chemical degradation methods are the acidic, the alkaline and the oxidative Degradation, in addition to the enzymatic known.

At the acid heterogeneous degradation, for example, the cellulose is suspended in dilute mineral acid and at elevated Temperature treated. It is found by this method that the DP of cellulose recovered after working up (degraded cellulose) not among the so-called "level-off DP "(LOPD) drops LODP seems with the size of the crystalline To relate areas of the cellulose used in relation. He is dependent from the cellulose used, but also from the reaction medium, if for example, solvents, such as dimethyl sulfoxide, water, alcohols or methyl ethyl ketone additionally added become. In this method, the yield of degraded cellulose low, because the amorphous areas or the accessible areas of the cellulose Completely be hydrolyzed.

Farther it is also possible Cellulose in a homogeneous system to subject to an acidic degradation. In this case, cellulose is, for example, in a mixture of LiCl / dimethylformamide solved and with an acid treated. In this method, the preparation of the solution is very consuming, the work-up complicated and the yield of degraded Cellulose low.

At the alkaline degradation of cellulose is called reducing Terminus of cellulose gradually cleaved glucose for glucose unit. Here, glucose and degraded cellulose are formed.

Of the Oxidative degradation of cellulose is usually carried out with oxygen. He usually includes the formation of individual as an introductory step Anhydroglucose units, which react further to unstable intermediates and finally lead to a chain break. The control of this Reaction is usually difficult.

The The above methods therefore have various disadvantages and it There is therefore a need for a method for the targeted degradation of cellulose provide.

It a process has now been found for the controlled degradation of cellulose, by dissolving cellulose in an ionic liquid and using a nucleophile treated.

• (A) Salze der allgemeinen Formel (I) [A] + / n[Y]^n– (I)in der n für 1, 2, 3 oder 4 steht, [A]⁺ für ein quartäres Ammonium-Kation, ein Oxonium-Kation, ein Sulfonium-Kation oder ein Phosphonium-Kation und [Y]^n– für ein ein-, zwei-, drei- oder vierwertiges Anion steht;
• (B) gemischte Salze der allgemeinen Formeln (II) [A¹]⁺[A²]⁺[Y]^n– (IIa), wobei n = 2; [A¹]⁺[A²]⁺[A³]⁺[Y]^n– (IIb), wobei n = 3; oder [A¹]⁺[A²]⁺[A³]⁺[A⁴]⁺[Y]^n– (IIc), wobei n = 4 und wobei [A¹]⁺, [A²]⁺, [A³]⁺ und [A⁴]⁺ unabhängig voneinander aus den für [A]⁺ genannten Gruppen ausgewählt sind und [Y]^n– die unter (A) genannte Bedeutung besitzt.

Ionic liquids in the sense of the present invention are preferred

• (A) Salts of the general formula (I) [A] + / n [Y] ^n- (I) in which n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ^{n- is} a one, two or more -, tri- or tetravalent anion stands;
• (B) mixed salts of the general formulas (II) [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa), where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) wherein n = 4 and wherein [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n -} the ^lower Has (A) meaning.

Preferably own the ionic liquids a melting point of less than 180 ° C. Particularly preferred is the melting point in a range of -50 ° C to 150 ° C, particularly preferably in the range from -20 ° C to 120 ° C and extraordinary preferably below 100 ° C.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are, for example, from DE 102 02 838 A1 known. Thus, such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, more preferably 1 to 5, most preferably 1 to 3 and especially 1 to 2 nitrogen atoms. Optionally, other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included. The nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.

In the event that the nitrogen atom is the carrier of the positive charge in the cation of the ionic liquid, in the synthesis of the ionic liquids, a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle. The quaternization can be carried out by alkylation of the nitrogen atom. Depending on the alkylating reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion already during quaternization, this can be done in a further synthesis step. Starting from, for example, an ammonium halide, the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid. Alternatively, replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt under precipitation tion of the metal halide formed, via an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid) happen. Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.

Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles may be quaternized, for example, are C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₀ -alkyl, more preferably C ₁ -C ₆ -alkyl, and very particularly preferably Methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Prefers are those compounds which contain at least one 5- to 6-membered heterocycle, in particular a five-membered one Heterocycle, containing at least one nitrogen atom as well optionally an oxygen or sulfur atom. Also those compounds which are at least one of them are particularly preferred five to contain six-membered heterocycle, the one, two or three Has nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms. Farther preferred are aromatic heterocycles.

Especially preferred compounds are those having a molecular weight below 1000 g / mol, most preferably below 500 g / mol and in particular below 350 g / mol.

sowie Oligomere, die diese Strukturen enthalten.Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw)

and oligomers containing these structures.

sowie Oligomere, die diese Struktur enthalten.Further suitable cations are compounds of the general formula (IIIx) and (IIIy)

and oligomers containing this structure.

• • der Rest R für Wasserstoff, 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; und
• • die Reste R¹ bis R⁹ unabhängig voneinander für Wasserstoff, eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder ar aliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen, wobei die Reste R¹ bis R⁹, welche in den oben genannten Formeln (III) an ein Kohlenstoffatom (und nicht an ein Heteroatom) gebunden sind, zusätzlich auch für Halogen oder eine funktionelle Gruppe stehen können; oder zwei benachbarte Reste aus der Reihe R¹ bis R⁹ zusammen auch für 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.

In the abovementioned formulas (IIIa) to (IIIy)

• • the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and
• • the radicals R ¹ to R ^{9 are} independently hydrogen, 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 substituted radicals having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or two adjacent radicals from the series R ¹ to R ⁹ together also 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 with 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 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. 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 ' ₃ and -SiR' ₂ -, where the radicals R 'are the remainder of the carbon-containing radical. The radicals R ¹ to R ⁹ are, in the cases in which they are in the above formulas (III) to a carbon atom (and not to a heteroatom) attached, also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = O (especially as carbonyl group), -NH ₂ (amino), -NHR ', -NR ₂ ', = NH (imino), = NR ', -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo) and -CN (cyano) called. 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. The R 'radicals are the remainder of the carbon-containing radical.

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

• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Hydroxy, Halogen, Phenyl, Cyano, C₁-C₆-Alkoxycarbonyl und/oder SO₃H substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie bei spielsweise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 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, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl, Undecylfluorisopentyl, 6-Hydroxyhexyl und Propylsulfonsäure;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten und einem Wasserstoff oder einem C₁-C₈-Alkyl als Endgruppe, wie beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt Wasserstoff, Methyl oder Ethyl und m bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N,N-Di-C₁-C₆-alkyl-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino.

Preferably, the radical R is for

• • straight-chain or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ alkoxycarbonyl and / or SO ₃ H substituted C ₁ -C ₁₈ alkyl having a total of 1 to 20 carbon atoms, as in example Methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl 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, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) - eth yl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
• Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ -C ₈ -alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably hydrogen, methyl or ethyl and m preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12 -Tetraoxatetradecyl;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1 Decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 1-propen-3-yl, in particular methyl, ethyl, 1-butyl and 1-octyl and CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0 to 3.

• • Wasserstoff;
• • Halogen;
• • eine funktionelle Gruppe;
• • 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-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-C₁₈-Alkenyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₆-C₁₂-Aryl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-C₁₂-Cycloalkyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-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 zusammen für
• • 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.

The radicals R ¹ to R ⁹ are preferably each independently

• • hydrogen;
• • halogen;
• • a functional group;
• 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 -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 -C ₁₈ alkenyl;
• Optionally C ₆ -C ₁₂ -aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally C ₅ -C ₁₂ -cycloalkyl 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 -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 together for
• • an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups.

May optionally be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₁ -C _{1 8} alkyl 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, 1,10,3,3-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, cyclohexyl methyl, 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-phenoxybutyne 1, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F _{2 (ma) + (1-b)} H _{2a + b} with m equal to 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _{( m-2)} F _{2 (m-2) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C _{1 2} 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 Butoxythiomethyl, 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-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3, 6,9-trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5- oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

In 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 C ₂ -C _18- alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F _{2 (ma) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

May optionally be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C _{1 2} aryl it is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4 Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2, 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4- Dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₁₂ cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (ma) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

May optionally be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C _{1 2} is cycloalkenyl, it is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5 -Cyclohexadienyl or C _n F _{2 (ma) -3 (1-b)} H _2a-3b with m ≤ 30, 0 ≤ a ≤ m 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.

• • Wasserstoff;
• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Hydroxy, Halogen, Phenyl, Cyano, C₁-C₆-Alkoxycarbonyl und/oder SO₃H substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie beispielsweise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 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, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl, Undecylfluorisopentyl, 6-Hydroxyhexyl und Propylsulfonsäure;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten und einem Wasserstoff oder einem C₁- bis C₈-Alkyl als Endgruppe, wie beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt Wasserstoff, Methyl oder Ethyl und n bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N,N-Di-C₁-C₆-alkyl-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino.

Particularly preferably, the radicals R ¹ to R ⁹ are each independently

• • hydrogen;
• • straight-chain or branched, unsubstituted or mono- to polysubstituted by hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ -alkoxycarbonyl and / or SO ₃ H-substituted C ₁ -C ₁₈ -alkyl having a total of 1 to 20 carbon atoms, such as methyl , Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 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, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl l, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
• Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ - to C ₈ -alkyl as an end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3- Oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, for phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N -Diethylamino, for chlorine and for CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m is 0 to 3.

• • einer der Reste R¹ bis R⁵ Methyl, Ethyl oder Chlor ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind;
• • R³ Dimethylamino ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind;
• • alle Reste R¹ bis R⁵ Wasserstoff sind;
• • R² Carboxy oder Carboxamid ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind; oder
• • R¹ und R² oder R² und R³ 1,4-Buta-1,3-dienylen ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind; und insbesondere solche, bei denen
• • R¹ bis R⁵ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁵ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind.

Very particular preference is given as Pyridiniumionen (IIIIa) such, in which

• • one of the radicals R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining radicals R ¹ to R ^{5 are} hydrogen;
• • R ^{3 is} dimethylamino and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;
• • all of the radicals R ¹ to R ⁵ are hydrogen;
• • R ^{2 is} carboxy or carboxamide and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; or
• • R ¹ and R ² or R ² and R ^{3 is} 1,4-buta-1,3-dienylene and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; and in particular those in which
• • R ¹ to R ^{5 are} hydrogen; or
• • one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen.

When very particularly preferred pyridinium ions (IIIa) are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetra-decyl) -2-methyl-pyridinium, 1- (1-hexadecyl) -2-methyl-pyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-Tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium.

• • R¹ bis R⁴ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁴ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁴ Wasserstoff sind.

Very particularly preferred pyridazinium ions (IIIb) are those in which

• • R ¹ to R ^{4 are} hydrogen; or
• • one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind; oder
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist.

Very particularly preferred pyrimidinium ions (IIIc) are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl; or
• • R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind;
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist;
• • R¹ bis R⁴ Methyl sind; oder
• • R¹ bis R⁴ Methyl Wasserstoff sind.

Very particularly preferred pyrazinium ions (IIId) are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl;
• • R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen;
• • R ¹ to R ^{4 are} methyl; or
• • R ¹ to R ^{4 are} methyl hydrogen.

• • R¹ Wasserstoff, Methyl, Ethyl, 1-Propyl, 1-Butyl, 1-Pentyl, 1-Hexyl, 1-Octyl, 1-Propen-3-yl, 2-Hydroxyethyl oder 2-Cyanoethyl und R² bis R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind.

Very particularly preferred imidazolium ions (IIIe) are those in which

• R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl, 2-hydroxyethyl or 2-cyanoethyl and R ² to R ⁴ independently of one another are hydrogen, methyl or ethyl.

When Very particularly preferred imidazolium ions (IIIe) may be mentioned 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) -3-methyl-imidazolium, 1- (1-Octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-Tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butyl imidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethyl-imidazolium, 1- (1-hexyl) -2,3-dimethyl-imidazolium, 1- (1-octyl) -2,3-dimethyl-imidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 1- (prop-1-en-3-yl) -3-methylimidazolium.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrazolium ions (IIIf), (IIIg) or (IIIg ') are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl.

• • R¹ bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrazolium ions (IIIh) are those in which

• • R ¹ to R ^{4 are} independently hydrogen or methyl.

• • unabhängig voneinander R¹ bis R⁶ Wasserstoff oder Methyl sind.

Very particular preference is given as 1-pyrazolinium (IIIi) such as those in which

• • independently of one another R ¹ to R ^{6 are} hydrogen or methyl.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using 2-pyrazolinium ions (IIIj) or (IIIj ') as those in which

• • R ¹ is hydrogen, methyl, ethyl or phenyl and R ² to R ⁶ are independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as 3-pyrazolinium ions (IIIk) or (IIIk ') those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ³ to R ^{6 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl, 1-Butyl oder Phenyl sind, R³ und R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁵ und R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to imidazolinium ions (IIIl) which are those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ³ and R ^{4 are} independently hydrogen, methyl or ethyl, and R ⁵ and R ^{6 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIm) or (IIIm ') those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl or ethyl and R ³ to R ^{6 are} independently hydrogen or methyl.

• • R¹ bis R³ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁴ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIn) or (IIIn ') those in which

• • R ¹ to R ^{3 are} independently hydrogen, methyl or ethyl and R ⁴ to R ^{6 are} independently hydrogen or methyl.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using thiazolium ions (IIIo) or (IIIo ') and oxazolium ions (IIIp) as those in which

• • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ Wasserstoff, Methyl oder Phenyl ist.

Very particular preference is given to using as 1,2,4-triazolium (IIIq), (IIIq ') or (IIIq''), those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind, oder R² und R³ zusammen 1,4-Buta-1,3-dienylen ist.

Very particular preference is given as 1,2,3-triazolium ions (IIIr), (IIIr ') or (IIIr'') such, in which

• • R ^{1 is} hydrogen, methyl or ethyl, and R ² and R ^{3 are} independently hydrogen or methyl, or R ² and R ³ together are 1,4-buta-1,3-dienylene.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁹ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrrolidinium ions (IIIs) are those in which

• • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl.

• • R¹ und R⁴ unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R² und R³ sowie R⁵ bis R⁸ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred imidazolidinium ions (IIIt) are those in which

• • R ¹ and R ^{4 are} independently hydrogen, methyl, ethyl or phenyl and R ² and R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl sind; oder
• • R¹ und R² zusammen 1,5-Pentylen oder 3-Oxa-1,5-pentylen sind und R³ C₁-C₁₈-Alkyl, 2-Hydroxyethyl oder 2-Cyanoethyl ist.

Very particular preference is given to using as ammonium ions (IIIu) those in which

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl; or
• • R ¹ and R ² together are 1,5-pentylene or 3-oxa-1,5-pentylene and R ^{3 is} C ₁ -C ₁₈ alkyl, 2-hydroxyethyl or 2-cyanoethyl.

As very particularly preferred ammonium ions (IIIu) may be mentioned methyl-tri- (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Examples for the tertiary Amines, of which the quaternary Ammonium ions of the general formula (IIIu) by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, Diethyl-n-pentylamine, diethyl-hexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, Di-n-propyl-n-pentylamine, Di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethylhexyl) amine, Di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropylbutylamine, Di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, Di-iso-propyl (2-ethylhexyl) -amine, Di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, Di-n-butylhexylamine, di-n-butyl-octylamine, di-n-butyl (2-ethylhexyl) -amine, N-n-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butylpyrrolidine, N-n-pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, N-n-propylpiperidine, N-isopropylpiperidine, N-n-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, N-n-pentylpiperidine, N-n-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-n-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl-N-n-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-N-n-butylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di-n-butyl-p-toluidine, diethylbenzylamine, di-n-propylbenzylamine, Di-n-butylbenzylamine, diethylphenylamine, di-n-propylphenylamine and Di-n-butylphenylamine.

preferred tertiary Amines (IIIu) are di-iso-propylethylamine, diethyl-tert-butylamine, Di-iso-propylbutylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine as well as tertiary Amines of pentyl isomers.

Especially preferred tertiary Amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers. Another preferred tertiary Amine having three identical residues is triallylamine.

• • R¹ bis R⁵ Methyl sind.

Very particular preference is given to guanidinium ions (IIIu) as those in which

• • R ¹ to R ^{5 are} methyl.

When very particularly preferred guanidinium ion (IIIv) is N, N, N ', N', N ", N" -hexamethylguanidinium.

• • R¹ und R² unabhängig voneinander Methyl, Ethyl, 1-Butyl oder 1-Octyl sind und R³ Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ ist;
• • R¹ Methyl, Ethyl, 1-Butyl oder 1-Octyl ist, R² eine -CH₂-CH₂-OR⁴-Gruppe ist und R³ und R⁴ unabhängig voneinander Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ sind; oder
• • R¹ eine -CH₂-CH₂-OR⁴-Gruppe ist, R² eine -CH₂-CH₂-OR⁵-Gruppe ist und R³ bis R⁵ unabhängig voneinander Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ sind.

Very particular preference is given to using as cholinium ions (IIIw) those in which

• • R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ;
• • R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁴ group and R ³ and R ^{4 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ; or
• • R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently hydrogen, methyl, ethyl, acetyl, -SO _{2 are} OH or -PO (OH) ₂ .

Particularly preferred cholinium ions (IIIw) are those in which R ^{3 is} selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxo-octyl, 11-ethoxy-3,6,9- trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl, insbesondere Butyl, Isobutyl, 1-Hexyl oder 1-Octyl sind.

Very particularly preferred as phosphonium ions (IIIx) are those in which

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl, especially butyl, isobutyl, 1-hexyl or 1-octyl.

Under the aforementioned heterocyclic cations are the pyridinium ions, Pyrazolinium-, pyrazolium ions and the imidazolinium- and the Imidazoliumionen preferred. Furthermore, ammonium ions are preferred.

Particularly preferred are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-Octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2- methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-Hexyl) -2-ethylpyridinium, 1- (1-Octyl) -2-ethylpyridinium, 1- (1-Dodecyl) -2-ethylpyridinium, 1- (1-Tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethyl- pyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-Dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium, 1- (1-hexadecyl) -2-methyl-3- ethyl-pyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) - imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methyl- imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3- methylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) - 2,3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3 Butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethyl limidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 1- (prop-1-en-3-yl) -3-methylimidazolium.

When Anions are in principle all anions usable.

• • der Gruppe der Halogenide und halogenhaltigen Verbindungen der Formel: F^–, Cl^–, Br^–, I^–, BF₄ ^–, PF₆ ^–, CF₃SO₃ ^–, (CF₃SO₃)₂N^–, CF₃CO₂ ^–, CCl₃CO₂ ^–, CN^–, SCN^–, OCN^–
• • der Gruppe der Sulfate, Sulfite und Sulfonate der allgemeinen Formel: SO₄ ^2–, HSO₄ ^–, SO₃ ^2–, HSO₃ ^–, R^aOSO₃ ^–, R^aSO₃ ^–
• • der Gruppe der Phosphate der allgemeinen Formel PO₄ ^3–, HPO₄ ^2–, H₂PO₄ ^–, R^aPO₄ ^2–, HR^aPO₄ ^–, R^aR^bPO₄ ^–
• • der Gruppe der Phosphonate und Phosphinate der allgemeinen Formel: R^aHPO₃ ^–, R^aR^bPO₂ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphite der allgemeinen Formel: PO₃ ^3–, HPO₃ ^2–, H₂PO₃ ^–, R^aPO₃ ^2–, R^aHPO₃ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphonite und Phosphinite der allgemeinen Formel: R^aR^bPO₂ ^–, R^aHPO₂ ^–, R^aR^bPO^–, R^aHPO^–
• • der Gruppe der Carbonsäuren der allgemeinen Formel: R^aCOO^–
• • der Gruppe der Borate der allgemeinen Formel: BO₃ ^3–, NBO₃ ^2–, H₂BO₃ ^–, R^aR^bBO₃ ^–, R^aHBO₃ ^–, R^aBO₃ ^2–, B(OR^a)(OR^b)(OR^c)(OR^d)^–, B(HSO₄)^–, B(R^aSO₄)^–
• • der Gruppe der Boronate der allgemeinen Formel: R^aBO₂ ^2–, R^aR^bBO^–
• • der Gruppe der Silikate und Kieselsäuresäureester der allgemeinen Formel: SiO₄ ^4–, HSiO₄ ^3–, H₂SiO₄ ^2–, H₃SiO₄ ^–, R^aSiO₄ ^3–, R^aR^bSiO₄ ^2–, R^aR^bR^cSiO₄ ^–, HR^aSiO₄ ^2–, H₂R^aSiO₄ ^–, HR^aR^bSiO₄ ^–
• • der Gruppe der Alkyl- bzw. Arylsilan-Salze der allgemeinen Formel: R^aSiO₃ ^3–, R^aR^bSiO₂ ^2–, R^aR^bR^cSiO^–, R^aR^bR^cSiO₃ ^–, R^aR^bR^cSiO₂ ^–, R^aR^bSiO₃ ^2–
• • der Gruppe der Carbonsäureimide, Bis(sulfonyl)imide und Sulfonylimide der allgemeinen Formel:
  
• • der Gruppe der Methide der allgemeinen Formel:
  

The anion [Y] ^{n of} the ionic liquid is for example selected from

• The group of halides and halogen ^- containing compounds of the formula: F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^-, CCl ₃ CO ₂ ^-, CN ^-, SCN ^-, OCN ^-
• • the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^-
• • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^-
• The group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^-
• • the group of carboxylic acids of the general formula: R ^a COO ^-
• • the group of borates of the general formula: BO ₃ ^3- , NBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^-
• The group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^-
• The group of silicates and silicic acid esters of the general formula: SiO ₄ ^4- , HSiO ₄ ^3- , H ₂ SiO ₄ ^2- , H ₃ SiO ₄ ^- , R ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^-
• • the group of alkylsilane and arylsilane salts of the general formula: R ^a SiO ₃ ^3-, R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2-
• The group of the carboxylic imides, bis (sulfonyl) imides and sulfonyl imides of the general formula:
  
• The group of methides of the general formula:
  

In this R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C _{1 2-cycloalkyl} or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-comprising heterocycle, where two of them together form an unsaturated, saturated or aromatic, optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more unsubstitu ierte or substituted imino groups can form interrupted ring, wherein said radicals may each be additionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.

Therein, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted C ₁ -C ₁₈ -alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3, 3-tetramethylbutyl, benzyl, 1-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 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-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2- chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2- Aminoethyl, 2-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl.

Optionally C ₂ -C ₁₈ -alkyl which is interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups are, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5- oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy 4-oxaheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy 3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4, 8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

When two radicals form a ring, these radicals can be taken together, for example, as fused building blocks, 1,3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1,3-propenylene, 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-buta-1,3-dienylene mean.

The Number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited or limited automatically by the size of the rest or the ring module. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or especially preferably not more than 3. Furthermore, there are between two Heteroatoms usually at least one, preferably at least two Carbon atom (s).

substituted and unsubstituted imino groups may be, for example, imino, Methylimino, iso-propylimino, n-butylimino or tert-butylimino be.

The term "functional groups" is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C ₁ -C ₄ -alkyl) -amino, C ₁ -C ₄ -alkyloxycarbonyl, cyano or C ₁ -C ₄ - Alkoxy, where C ₁ -C ₄ -alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C ₆ -C ₁₄ -aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2 , 4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl.

Optionally, by functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or He terocyclene-substituted C ₅ -C ₁₂ -cycloalkyl are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic System such as norbornyl or norbornenyl.

One five to six-membered, oxygen, nitrogen and / or sulfur atoms heterocycle having, for example, furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, Benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, Methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, Isopropylthiophenyl or tert-butylthiophenyl.

Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- .

Preferred anions are in particular chloride, bromide, iodide, SCN ^-, OCN ^-, CN ^-, acetate, C ₁ -C ₄ alkyl sulfates, R ^a -COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^-, methanesulfonate , Tosylate or di (C ₁ -C ₄ alkyl) phosphates.

Particularly preferred anions are Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- .

In a further preferred embodiment, ionic liquids of the formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium , 1- (1-Hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) 3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3 ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3 ethyl imidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) 3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2 3 dimethyl imidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1.4 Dimethyl imidazolium, 1,3,4-trimethyl imidazolium, 1,4-dimethyl-3-ethyl imidazolium, 1,4-dimethyl-3-butyl imidazolium, 1,4-dimethyl-3-octyl imidazolium, 1,4,5-trimethyl imidazolium, 1 , 3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (propyl 1-en-3-yl) -3-methylimidazolium; and
[Y] ^{n +} Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- ;
used.

In a further preferred embodiment, ionic liquids are used whose anions are selected from the group comprising HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- and HR ^a PO ₄ ^- ; especially HSO ₄ ^- .

In particular, ionic liquids of formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium , 1- (1-Hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) 3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3 ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3 ethyl imidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) 3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2 . 3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1, 4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (prop-1-en-3-yl) -3-methylimidazolium; and
[Y] ^{n +} HSO ₄ ^- ;
used.

In the method according to the invention becomes an ionic liquid of formula I or a mixture of ionic liquids of the formula I, preferably an ionic liquid of the formula I is used.

In a further embodiment of the invention Is it possible an ionic liquid of formula II or a mixture of ionic liquids of formula II, preferably becomes an ionic liquid of the formula II used.

In a further embodiment of the invention Is it possible a mixture of ionic liquids of formulas I and II.

Nucleophiles in the context of the present invention are preferably compounds of the formula IV, R ^x -XH (IV) With
X is O, S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^y -NH, NR ^y -NR ^y , PR ^{y is} -O, NH-O, NR ^{y is} -O, O-NH or O-NR ^y ; wherein in the nine latter groups, the left-hand atom with the radical R ^x and the right-hand atom is connected to the hydrogen of formula IV and wherein R ^{y is} hydrogen or a radical described under R ^x .
R ^{x is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or having 1 to 20 carbon atoms; or additionally hydrogen if X is S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^y -NH, NR ^y -NR ^y , PR ^{y is} -O or NH-O, NR ^{y is} -O, O-NH or O-NR ^y stands.

In principle, all heteroatoms which are capable of formally replacing a -CH ₂ -, a -CH =, a -C≡ or a = C =-group are suitable as heteroatoms. 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 ' ₃ and -SiR' ₂ -, where the radicals R 'are the remainder of the carbon-containing radical.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = O (especially as carbonyl group), -NH ₂ (amino), -NHR ', -NR ₂ ', = NH (imino), = NR ', -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo) and -CN (cyano) called. 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. The radicals R 'are the remaining part of the carbon-containing radical.

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

Preference is given to using nucleophiles of the formula IV in which the variables, taken alone or in combination, have the following meaning:
R ^{x is} optionally C ₁ - interrupted 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 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 -C ₁₈ alkenyl;
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 -C ₁₈ alkynyl;
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl;
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ -cycloalkyl;
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -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.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₁ -C ₁₈ alkyl 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, cyclohexylmet hyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl ) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl ) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1, 3-dioxolan-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2- Methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2- Phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F _{2 (ma) + (1-b)} H _{2a + b} with m equal to 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _{(m-) 2)} F _{2 (m-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-oxaheptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5 , 10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11- Methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9- Methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-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-oxo nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

In 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 C ₂ -C _18- alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F _{2 (ma) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

In 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 C ₂ -C ₁₈ -alkynyl is preferably ethynyl, 1-propyn-3-yl, 1-propyn-1-yl, or 3-methyl-1-propyn-3-yl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4 -Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2, 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4- Dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₁₂ cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (ma) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

C ₅ -C ₁₂ -cycloalkenyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5- Cyclohexadienyl or C _n F _{2 (ma) -3 (1-b)} H _2a-3b with m ≤ 30, 0 ≤ a ≤ m 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.

Contain the above-mentioned radicals heteroatoms, so are between two heteroatoms usually at least one carbon atom, preferably at least two carbon atoms.

X is O, S, NH, NR ^y , NH-NH, NR ^y -NH, NH-NR ^y or NR ^y -NR ^y , where R ^{y is} the preferred radical meaning mentioned for R ^x analogously and wherein R ^{y is} preferably hydrogen ; preferably O, S, NH or NH-NH.

For the degradation of the invention of cellulose Celluloses from a variety of sources are used such as. made of cotton, flax, ramie, straw, bacteria etc., or made of wood or bagasse, in the cellulose-enriched form.

The inventive method But not only for the degradation of cellulose but generally for cleavage or for the degradation of poly-, oligo- and disaccharides, as well as derivatives thereof, used. As examples of polysaccharides are besides Cellulose and hemicellulose, starch, To name glycogen, dextran and tunicin. Likewise count to this the polycondensates of D-fructose, such as inulin, as well as u.a. chitin, and alginic acid. Sucrose is an example of a disaccharide. As cellulose derivatives, i.a. cellulose ethers, such as methylcellulose and carboxymethylcellulose, cellulose esters, such as cellulose acetate, cellulose butyrate and cellulose nitrate, in Consideration. The corresponding explanations apply accordingly.

at the method according to the invention becomes a solution of cellulose in ionic liquid, produced. The concentration of cellulose can be in large areas be varied. Usually it is in the range of 0.1 to 50 wt .-%, based on the total weight the solution, preferably at 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% wt .-%.

This solution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic Liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, especially preferably at 50 to 150 ° C. It is also possible the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by speeding up their combination.

To this solution thus obtained Now the nucleophile of formula IV is added.

The Nucleophile of formula IV may be in bulk, in an ionic liquid or in a suitable solvent solved be added. As a solvent Alcohols, such as methanol or ethanol, ethers, such as diethyl ether, Methyl tert-butyl ether, Terahydrofuran or dioxane or ketones, such as dimethyl ketone. The amount of solvents, which should be used to solve the nucleophile of formula IV should be sized so that no precipitation of the cellulose in the Addition occurs. As an ionic liquid Preferably, the one in which the cellulose yourself - like described above - is solved.

In a particular embodiment the nucleophile of formula IV is added in bulk.

In another particular embodiment becomes the nucleophile of formula IV in an ionic liquid solved added, with particular preference the ionic liquid which is also used to solve the cellulose is used.

In another embodiment become the ionic liquid and the nucleophile of the formula IV are premixed and the cellulose in solved this mixture.

It there is also the possibility that one or more further solvents, be added to the reaction mixture, or already with the ionic liquid or the nucleophile of formula IV. As a solvent come here in such solvents in question, what the solubility do not adversely affect the cellulose, such as aprotic dipolar Solvent, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane. Furthermore you can also nitrogenous bases, such as pyridine, etc., additionally added become.

In a particular embodiment contains the reaction mixture in addition to the ionic liquid and possibly the solvent, in which the nucleophile of the formula IV is dissolved, less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, based on the total weight of the reaction mixture, on further solvents and / or additional nitrogenous bases.

Of the Degradation becomes dependent from the ionic liquid used and the used Nucleophile usually at a temperature of melting point of the ionic liquid up to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

Usually the reaction takes place at ambient pressure. It may be case by case but also be advantageous in case of overpressure to work, especially if a volatile Nucleophile can be used.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example under N ₂ , a noble gas, CO ₂ or mixtures thereof, to work.

In dependence from the desired Degradation degree is the amount of nucleophile used - respectively in relation to to the cellulose used - the Reaction time and optionally set the reaction temperature.

For example, if it is desired to completely degrade the cellulose, which is composed on average of u anhydroglucose units, to glucose, u equivalents of nucleophile are needed. Preferably, the stoichiometric amount of nucleophile (n _{anhydroglucose units /} n _nucleophile = 1) or an excess is used, preferably an excess of up to 1000 mol%, based on u.

If it is desired to convert the cellulose, which is composed on average of u anhydroglucose units, into a cellulose whose number of anhydroglucose units is smaller than u, the amount of nucleophile used is usually adjusted (n _{anhydroglucose units /} n _nucleophile > 1). The larger the quotient n _{anhydroglucose units / nucleophile} , the lower will be the average degradation of cellulose under otherwise identical conditions and the same reaction time.

Farther Is it possible to stop the degradation reaction when the desired degree of degradation is reached is by separating the cellulose from the reaction mixture. This can be done, for example, by adding an excess of water or a other suitable solvents, in which the degraded cellulose is not soluble, e.g. a low one Alcohol, such as methanol, ethanol, propanol or butanol, or with a Ketone, for example acetone etc., or mixtures thereof. Preferably, an excess used on water or methanol.

The workup of the reaction mixture is usually carried out by the cellulose is precipitated as described above and the cellulose is filtered off. From the filtrate, the ionic liquid can be recovered by conventional methods by the volatile components, such as the precipitant, the optionally added water or excess nucleophile, etc. are distilled off. The remaining ionic liquid can be reused in the process according to the invention. In another embodiment, excess nucleophile may also remain in the ionic liquid and back into the ionic liquid inventive method can be used.

by virtue of of the statistical degradation of cellulose, contains the ionic to be regenerated Liquid only low glucose, its oligomers or optionally corresponding reaction products with the nucleophile of the formula IV thereof. Any existing quantities of these compounds can by extraction with a solvent or by adding a precipitant from the ionic liquid be separated.

The If necessary, cellulose degraded by this process may be in the form of its Reaction products with the nucleophile of the formula IV or as a mixture of degraded and derivatized as described above Cellulose present.

It but it is also possible the reaction mixture in water or in another suitable solvent, in which the degraded cellulose is not soluble, e.g. a low one Alcohol, such as methanol, ethanol, propanol or butanol, or a Ketone, for example, acetone, etc., or mixtures thereof, initiate and depending on the embodiment, for example, fibers, films of degraded Cellulose or optionally derivatized degraded cellulose or mixtures to obtain from this. The filtrate is worked up as described above.

Farther Is it possible to stop the degradation reaction when the desired degree of degradation is reached is by cooling the reaction mixture and worked up. The workup can be done according to the methods described above.

In the case, that selected reaction conditions be that the cellulose is completely degraded, so can the glucose or optionally derivatized glucose resulting from the reaction with the nucleophile of the formula IV results according to common methods, such as. precipitation with ethanol from the ionic liquid be separated.

In the case, that the ionic liquid guided in circulation mode is, the ionic liquid can up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above.

The Method may be discontinuous, semi-continuous or continuous, carried out become.

The The following examples serve to illustrate the invention.

Claims (17)

Process for the degradation of poly-, oligo- or disaccharides, or derivatives thereof, characterized in that one dissolves the poly-, oligo- or disaccharide, or the corresponding derivative, in at least one ionic liquid and treated with a nucleophile. Method according to claim 1, characterized in that that as poly, oligo- or Disaccharide, or a derivative thereof, a polysaccharide, or a derivative thereof. Method according to claim 2, characterized in that that as polysaccharide, or a derivative thereof, cellulose, or a cellulose derivative. Method according to claim 3, characterized that as polysaccharide, or a derivative thereof, cellulose starts. Process according to Claims 1 to 4, characterized in that the ionic liquid, or mixtures thereof, are chosen from the compounds of the formulas I, [A] + / n [Y] ^n- (I), where n is 1, 2, 3 or 4; [A] ⁺ for a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation; and [Y] ^n- for a mono-, di-, tri- or tetravalent anion; stand; or the compounds of the formula II [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa), where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) wherein n = 4 and wherein [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ ; and [Y] ^{n- have} the abovementioned meaning. A method according to claim 5, characterized in that [A] ⁺ for a cation selected from the compounds of formulas (IIIa) to (IIIy)

and oligomers containing this structure, wherein • the radical R is hydrogen 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 with 1 to 20 carbon atoms; and • the radicals R ¹ to R ⁹ independently of one another are hydrogen, 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 substituted radical having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) ge connected, may additionally be halogen or a functional group ; or two adjacent radicals from the series R ¹ to R ⁹ together also 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 with 1 to 30 carbon atoms, can stand. Process according to claims 5 or 6, characterized in that [Y] ^n- for an anion is selected from • the group of halides and halogen-containing compounds of the formula: F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^- , • the group of sulfates, sulfites. and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ^4- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- • the group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^- • the group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^- • the group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^- • the group of carboxylic acids of the general formula: R ^a COO ^- • the group of borates of the general formula: BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (B) R ^a SO ₄ ) ^- • the group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^- • the group of silicates and silicic acid esters of the general formula: SiO ₄ ^4- , HSiO ₄ ^3- , H ₂ SiO ₄ ^2- , H ₃ SiO ₄ ^- , R ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a -SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^- • the group of alkyl or aryl silane salts of the general formula: R ^a SiO ₃ ^3- , R ^a R ^b SiO ₂ ^2- , R ^a R ^b R ^c SiO ^- , R ^a R ^b R ^c SiO ₃ ^- , R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2- • the group of carboximides, bis (sulfonyl) imides and sulfonyl imides of the general formula:

The group of methides of the general formula:

wherein the radicals R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally substituted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, two of them together may form an unsaturated, saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkyloxy , Halogen, heteroatoms and / or heterocycles may be substituted; stands. Process according to claims 5 to 7, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IIIa, IIIe, IIIf; IIIg, IIIg ', IIIh, IIIi, IIIj, IIIj', IIIk, IIIk ', IIIl, IIIm, IIIm', IIIn or IIIn '. Process according to claims 5 to 8, characterized in that [A] ^{+ is} a cation selected from the group of compounds IIIa, IIIe or IIIf. Process according to Claims 5 to 9, characterized in that [Y] ^{n- represents} an anion selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, of the group comprising SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- stands. Process according to claims 1 to 10, characterized in that the nucleophile is a compound of formula IV R ^x -XH (IV) with X is O, S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^{y is} -NH, NR ^{y is} -NR ^y , PR ^{y is} -O, NH-O, NR ^{y is} -O, O-NH or O-NR ^y ; wherein in the nine latter groups, the left-hand atom with the radical R ^x and the right-hand atom is connected to the hydrogen of formula IV and wherein R ^{y is} hydrogen or a radical described under R ^x . R ^{x is} a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or having 1 to 20 carbon atoms; or additionally hydrogen if X is S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^y -NH, NR ^y -NR ^y , PR ^{y is} -O or NH-O, NR ^{y is} -O, O-NH or O-NR ^y stands. Method according to claim 11, characterized in that that X is O, S, NH or NH-NH; means. Process according to claims 11 or 12, characterized in that R ^{x is} optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or by one or more oxygen and / or sulfur atoms and / or or one or more substituted or unsubstituted imino groups interrupted C ₁ -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 -C ₁₈ alkenyl; 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 -C ₁₈ alkynyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ -cycloalkyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C _{1 2} cycloalkenyl; or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; means. Process according to claims 1 to 13, characterized that the concentration of poly, oligo- or disaccharide, or one Derivatives thereof, in ionic liquid in a range of 0.1 to 50 wt .-% based on the total weight of the solution. Process according to claims 1 to 14, characterized that the degradation at a temperature from the melting point of the ionic liquid up to 200 ° C carried out becomes. Process according to claims 1 to 15, characterized that the degradation by addition of a solvent in which the degradation products of polysaccharide insoluble are, quenching. Degraded cellulose obtainable by the processes according to claims 1 to 16th