WO2007101813A1 - Method for breaking down cellulose with the aid of nucleophiles - Google Patents

Abstract

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

Description

Process for the degradation of cellulose with nucleophiles

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

Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, such as, for example, Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, e.g. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, e.g. Cellulose nitrate, and others count. These derivatives and modifications find a variety of applications, for example in the food, construction and paint industries.

Cellulose is characterized by insolubility, especially in common solvents of organic chemistry. In general, N-methyl-morpholine-N-oxide, anhydrous hydrazine, binary mixtures such as methylamine / dimethyl sulfoxide, or ternary mixtures such as ethylenediamine / SO 2 / dimethyl sulfoxide are used as solvent today. However, it is also possible to use saline systems, e.g. 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 is oxidized in ionic liquids, such as e.g. [1-butyl-3-methyl-imidazolium] chloride is soluble.

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

For the degradation of cellulose, various methods are known which can be divided into four groups - 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).

In mechanical degradation, such as in dry or wet grinding, it is disadvantageous that the DP reduces the cellulose only to a small extent becomes. An uncontrolled degradation takes place in the thermal treatment and also the cellulose is modified, in particular dehydrocelluloses can be formed. When degraded by radiation, cellulose can be treated with high-energy radiation, such as X-radiation. Here, the DP of the cellulose is lowered very quickly. However, chemical modification of the cellulose also occurs by forming a high number of carboxylic acid or keto functions. On the other hand, if less energy-rich radiation is used, such as UV / visible light, it is necessary to use photosensitizers. And here too there is a modification of the cellulose by the formation of keto functions, or if oxygen is present during the irradiation, to peroxide formation.

As chemical degradation methods, the acidic, the alkaline and the oxidative degradation, in addition to the enzymatic known.

In acidic heterogeneous degradation, for example, the cellulose is suspended in dilute mineral acid and treated at elevated temperature. In this method it is found that the DP of the cellulose (degraded cellulose) obtained after the work-up does not fall under the so-called "level-off DP" (LOPD). The LODP appears to be related to the size of the crystalline regions of the cellulose employed. It depends on the cellulose used, but also on the reaction medium, if, for example, solvents, such as dimethyl sulfoxide, water, alcohols or methyl ethyl ketone are additionally added. In this method, the yield of degraded cellulose is low, because the amorphous regions or the accessible regions of the cellulose are completely hydrolyzed.

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

In the alkaline degradation of cellulose, glucose is gradually split off at the so-called reducing terminus of the cellulose. Here, glucose and degraded cellulose are formed.

The oxidative degradation of cellulose is usually carried out with oxygen. As a preliminary step, it usually involves the formation of individual anhydroglucose units, which react further to form unstable intermediates and ultimately lead to a chain break. The control of this reaction is usually difficult. The abovementioned methods therefore have various disadvantages and there is therefore a need to provide a method for the targeted degradation of cellulose.

A process has now been found for the controlled degradation of cellulose by dissolving cellulose in an ionic liquid and treating it with a nucleophile.

Ionic liquids in the sense of the present invention are preferred

(A) Salts of the general formula (I)

[Ai; [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 J ⁺ [A ² J ⁺ [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 - (Mc), where n = 4 and

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are selected} independently of one another from the groups named for [A] ⁺ and [Y] ^π "that under (A) has meaning.

Preferably, the ionic liquids have a melting point of less than 180 ° C. More preferably, the melting point is in a range of -50 ° C to 150 ° C, more preferably in the range of -20 ° C to 120 ° C, and most preferably below 100 ° C.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are known, for example, from DE 102 02 838 A1. 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 in order to produce an electrically neutral molecule. In the case where 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 with precipitation 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). Suitable methods are, for example, in Angew. Chem. 2000, 12, pp. 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 6 -alkyl, preferably C 1 -C 10 -alkyl, particularly 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.

Preference is given to those compounds which contain at least one five- to six-membered heterocycle, in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom. Also particularly preferred are those compounds containing at least one 5- to 6-membered heterocycle having one, two or three nitrogen atoms and one sulfur or one oxygen atom, most preferably those having two nitrogen atoms. Further preferred are aromatic heterocycles.

Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 350 g / mol.

Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw),

(mg) (mg ¹ ) (MIh)

(MIi) (INJ) (MIj ')

(MIk) (MIk')

(MIk) (MIk ')

(Ulm) (MIm ') (MIn)

(MIn ') (MIo) (MIo')

(MIp) (MIq) (MIq ')

R

(MIq ") Ir) Ir ')

(MIr ") (MIs) (With)

(MIu) (MIv) (MIw)

and oligomers containing these structures.

Further suitable cations are compounds of the general formula (IMx) and (MIy)

R ² R ²

₃ 1 -H ₁ I + ₁

R-P-R S-R

I i

R R

(MIx) (MIy)

and oligomers containing this structure.

In the above formulas (IMa) to (IMy) stand

• 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 independently of one another represent hydrogen, a sulfo

Group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aromatic aliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) may additionally be also halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional

Groups interrupted or substituted radical having 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. Particular preferred groups are -O-, -S-, -SO-, -SO2-, -NR'-, -N =, - PR'-, -PR'3 and -SiRV, where the radicals R 'is the remainder of the carbon-containing residue. The radicals R ¹ to R ⁹ may in the cases in which they are bonded in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) also be bonded 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), = 0 (especially as carbonyl group), -NH 2 (amino), -NHR ', -NR ₂ ', = NH (imino), = NR ', -COOH (carboxy), - CONH ₂ (carboxamide), -SO3H (sulfo) and -CN (cyano). Fractional groups and heteroatoms may also be directly adjacent so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide ) or -CONR'- (tertiary amide), are included, for example, di (Ci-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy. The R 'radicals are the remainder of the carbon-containing radical.

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for

• unbranched or branched, unsubstituted or one to several times with

Hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H-substituted C 1 -C 20 -alkyl having a total of 1 to 20 carbon atoms, such as For 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 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, 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 Ci-Cβ-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 θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and m is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 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-Ci-Cδ-alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

The radical R particularly preferably represents unbranched and unsubstituted C 1 -C 8 -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 also CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH2 and _CH3 CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

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 groups cis-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 groups cis alkenyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-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 containing heterocycle; or

two adjacent radicals together for

An unsaturated, saturated or aromatic, if appropriate by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or

Heterocycles substituted and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups ring.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d-cis-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, Cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p Butyl-phenyl) -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, A-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropy 1, A-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 ( _m -a) + (ib) H 2a + b with m equal to 1 to 30, 0 < a <m and b = 0 or 1 (for example CF3, C2F5, CH2CH2-C ( _m -2) F2 (m-2) + i, C ₆ Fi ₃ , C ₈ Fi ₇ , C10F21, Ci 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- (methoxy - carbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthio - methyl, 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, 1-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, 1 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa -heptyl, 1-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-oxato-tetradecyl.

When 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 C2-Cis Alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F2 (ma) - (ib) H2a-b with im <30, 0 <a < m and b = 0 or 1. When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-Ci2-aryl is preferably phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl, Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl , Ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2.6 Dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F (5- _a ) H _a with 0 <a <5.

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

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclo hexadienyl or C _n F2 _(m -a) -3 (ib) H2a-3b in the <30, 0 <a <m and b = 0 or the first

An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, 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-Ci-C4-alkyl 1-aza-1, 3-propenylene, 1,4-butan-1, 3-dienylene, 1-az-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta-1, 3-dienylene. If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and very particularly preferably not more than 3.

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

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

• hydrogen;

• straight-chain or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, Ci-Cδ-alkoxycarbonyl and / or SO3H Ci-Cis-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-butoxy-carbonyl) -ethyl, 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 1 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 θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably hydrogen, methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 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 are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 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 as well as for CH3O-

(CH ₂ CH2θ) _m -CH ₂ CH 2 and CH ₃ CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

Very particularly preferred pyridinium ions (Ulla) are those 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 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 are} 1, 4-buta-1, 3-dienylene and the remaining 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.

Particularly preferred pyridinium ions (IIIa) which may be mentioned 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-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-ethyl-pyridinium, 1, 5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethyl -pyridinium, 1- (1-hexyl) -2-methyl-3-ethyl-pyridinium 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.

Very particularly preferred pyridazinium ions (MIb) 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.

Very particularly preferred pyrimidinium ions (MIc) 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.

Very particular preference is given as Pyraziniumionen (IMd) such a, 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.

Very particularly preferred as Imidazoliumionen (Never) 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.

Very particularly preferred imidazolium ions (MIe) which may be mentioned are 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-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 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-methyl imidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3- methyl imidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-H exadecyl) -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-dimethyl-imidazolium, 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 ethyl imidazolium, 1, 4,5-trimethyl-3-butyl imidazolium, 1, 4,5-trimethyl-3-octyl imidazolium and 1- (prop-1 -en-3-yl) -3-methyl imidazolium.

Very particularly preferred pyrazolium ions (MIf), (MIg) or (MIg ') are those in which

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

Very particular preference is given as Pyrazoliumionen (IMh) such, in which

Are • R ¹ to R ⁴ are independently hydrogen or methyl.

Very particular preference is given to using as 1-pyrazolinium (Uli) those in which

• independently of one another R ¹ to R ^{6 are} hydrogen or methyl. Very particularly preferably used as 2-pyrazolinium (IMj) or (MIj ') such, in which

• R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{6 are} independently of one another hydrogen or methyl.

Very particular preference is given as 3-pyrazolinium (MIk) or (IMk ') such, 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.

Very particularly preferred imidazolinium ions (IUI) 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.

Very particularly preferred as Imidazoliniumionen (Ulm) or (MIm ') are 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.

Very particular preference is given to using as imidazolinium ions (IMn) or (MIn ') 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.

Very particular preference is given to using as thiazolium ions (IMO) or (MIo ') and as oxazolium ions (MIp) those in which

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

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

• R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl. Very particular preference is given to using as 1,3,3-triazolium ions (Mir), (IMr ') or (MIr ") those 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.

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

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

With very particular preference one uses as imidazolidinium ions (mit) 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.

Very particular preference is given as ammonium ions (IMu) such, in which

• R ¹ to R ^{3 are} independently of each other Ci-Cis-alkyl; or

• R ¹ and R ² together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R ^{3 is} Ci-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.

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

Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (MIu) are derived 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-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-isopropyl-2-ethylhexyl ) -amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2 ethyl-hexyl) -amine, Nn-butylpyrrolidine, N-sec-butylpyrrolidine, N-tert-butylpyrrolidine, Nn Pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, Nn-propylpiperidine, N-isopropylpiperidine, Nn-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl-Nn-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-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 (MIu) are di-iso-propylethylamine, diethyl-tert-butylamine, di-iso-propylbutylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.

Particularly 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.

Very particularly preferred as guanidinium ions (MIv) are those in which

• R ¹ to R ⁵ are methyl.

As a very particularly preferred guanidinium ion (MIv) may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.

Very particularly preferred as cholinium ions (MIw) are 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 OH or -PO (OH) ₂ are.

Particularly preferred cholinium ions (MIw) are those in which R ^{3 is} selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1 1-methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-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-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-tιϊoxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10- oxetetradecyl.

Very particularly preferred phosphonium ions (IMx) are those in which

• R ¹ to R ^{3 are} independently C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the heterocyclic cations mentioned above, the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazole ions are preferred. Furthermore, ammonium ions are preferred.

Particular preference is given to 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-ethyl-pyridinium, 1- (1-hexadecyl) -2-methyl-3-ethyl-pyri dinium, 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-tetramethyli midazolium, 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. As anions, in principle, all anions can be used.

The anion [Y] ⁿ - 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 SOs) ₂ N-, CF ₃ CO ₂ -, CCI 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 ³ OSO ₃ -, R ³ SO ₃ -

The group of phosphates of the general formula PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ³ PO ₄ -, R ³ R ^b PO ₄ -

The group of phosphonates and phosphinates of the general formula: R ³ H PO ₃ -, R ³ R ^b PO ₂ -, R ³ R ^b PO ₃ -

The group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ³ HPO ₃ -, R ³ R ^b PO ₃ -

The group of phosphonites and phosphinites of the general formula: R ³ R ^b PO ₂ -, R ³ HPO ₂ -, R ³ R ^b PO-, R ³ HPO ^"

• the group of carboxylic acids of the general formula: R ³ COO-

The group of borates of the general formula:

BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) ^" , B (HSO ₄ ) ^" , B (R ³ SO ₄ ) -

The group of the boronates of the general formula: R ³ BO ₂ ² -, R ³ 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 ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ^2" , R ³ R ^b R ^ Si0 ₄ ^" , HR ³ SiO ₄ ^2" ,

H ₂ R ³ SiO ₄ ^" , HR ³ R ^b SiO ₄ -

The group of the alkyl or aryl silane salts of the general formula: R ³ SiO ₃ ³ , R ³ R ^b SiO ₂ ² , R ³ R ^b R 1 SiO ³ , R ³ R ^b R 1, SiO ₃ , R ³ R ^b R ^ Si0 ₂ -, R ³ R ^b Si0 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:

SO ₂ -R ³

R ^b -O ₂ S SO ₂ -R ^C

Herein, R ^a, R ^b, R ^c and R ^d are each independently hydrogen, Ci- C3o-alkyl, optionally substituted by one or more nonadjacent oxygen and / or sulfur atoms and / or one or more substituted or the unsubstituted imino groups te 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-containing heterocycle, two of them together having an unsaturated, saturated or aromatic, optionally formed by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups interrupted ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or Heterocycles may be substituted.

In which are optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted Ci-cis-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, heptadyl, 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 interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C2-Ci8-alkyl, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-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, 1-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, 1-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl, 15- Ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

If two radicals form a ring, these radicals can be taken together, for example, as fused building block 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.

The number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.

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

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 C4-alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl. Optionally C6-C4-aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl nyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylsaphthyl, 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 C5-C12-cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles 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.

A five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, 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 ³ OSO ₃ ^" and R ³ SO ₃ -, and the group containing PO ₄ ^3" and R ³ R ^b PO ₄ -.

Particularly preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, C 1 -C ₄ -alkyl sulfates, R ³ -CO 2 ^" , R ³ SO ₃ -, R ³ R ^b PO ₄ -, methanesulfonate, Tosylate or di- (Ci-C ₄ -alkyl) phosphates.

Particularly preferred anions are Ch, 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 ethyl imidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 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-S-octylimidazolium, 1- (1 Tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1 - (1-tetradecyl-S-octylimidazolium, 1 - ( 1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl-S-octylimidazolium, 1, 2-Dimethylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethyl- imidazolium, 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-tetra methylimidazolium, 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 +} 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 ³ PO ₄ -, in particular 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 ethyl imidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 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-ethylimidazolium, 1- (1-tetradecyl) -3-butyl imidazolium, 1- (1-tetradecyl) -S-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3- butyl imidazolium, 1- (1-hexadecyl) -S-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 process according to the invention, an ionic liquid of the formula I is used 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 it is possible to use an ionic liquid of the formula II or a mixture of ionic liquids of the formula II, preferably an ionic liquid of the formula II is used.

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

Nucleophiles in the context of the present invention are preferably compounds of the formula IV,

R ^x - X - H (IV)

With

XO, S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^y -NH, NR ^y -NR ^y , PR ^y -O, NH-O, NR ^y - O, O-NH or 0-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, when X is S, NH, NR ^y , PR ^y , NH-NH, NH-NR ^y , NR ^y -NH,

NR ^{y is} -NR ^y , PR ^{y is} -O or NH-O, NR ^{y is} -O, O-NH or O-NR ^y .

Suitable heteroatoms here are in principle all heteroatoms which are capable of formally replacing a -CH ₂ -, a -CH =, a -C≡ or a = C = group. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Preferred groups which may be mentioned are in particular -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -PR ' ₃ and -SiRV, where the R 'is the remainder of the carbon-containing residue.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = 0 (especially as carbonyl group), -NH ₂ (amino), -NHR ', -NR ₂ ', = NH (imino), = NR ', -COOH (carboxy), -CONH ₂ (carboxamide), -SO 3 H (sulfo), -CN (cyano) and -NO ₂ (nitro), preferably -OH, = 0 (in particular as carbonyl group), -NH ₂ , -NHR ', - NR ₂ ', = NH, = NR', -COOH, - CONH ₂ , -SO 3 H and -CN. Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide), are included, for example di- (Ci-C ₄ -AlkVl) - amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy. The radicals R 'are the remaining part of the carbon-containing radical.

Halogens are 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 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 Ci-Cis alkyl;

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 one or more substituted or unsubstituted imino groups interrupted C2-C18 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 C2-Cis alkynyl;

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkyl;

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkenyl; or

an optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyl oxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d-cis-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, cyclohexylmethyl, 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-cyano-propyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- Butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, methoxy, ethoxy, formyl, 1, 3-dioxo lan-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 F2 (ma) + (ib) H2a + b, with the same 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) ₊ i, C ₆ Fi _3, C ₈ Fi _7, C10F21, C 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-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxo-octyl, 1 1-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1-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, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-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-oxapentyl, 8-ethoxy-3, 6-dioxo-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8 , 12-trioxa-pentadecyl,

9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

When 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 C2-C18- Alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F 2 ( _m -a) - (ib) H 2a-b with m <30, 0 < a <m and b = 0 or 1.

When 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 C2-C18- 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 C6-Ci2-aryl is preferably phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, A-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, A-

Acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F (5- _a ) H _a with 0 <a <5.

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

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-C12-CVCI0 alkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5- cyclohexadienyl or C _n F2 _(m -a) -3 (ib) H2a-3b where m <30, 0 <a <m and b = 0 or the first

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

If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms. XO, S, NH, NR ^y , NH-NH, NR ^y -NH, NH-NR ^y or NR ^y -NR ^y , wherein for R ^y the preferred radical meanings mentioned for R ^x are analogous and wherein R ^{y is} preferably hydrogen ; preferably O, S, NH or NH-NH.

Particular 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} phenyl which is unsubstituted or substituted by 1 to 5 halogens and / or by 1 to 3 radicals selected from the group consisting of C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -alkyoxycarbonyl, cyano or nitro,

X is NH or NH-NH.

Celluloses from a variety of sources, such as e.g. cotton, flax, ramie, straw, bacteria etc., or wood or bagasse, in the cellulose-enriched form.

However, the process according to the invention can be used not only for the degradation of cellulose but generally for the cleavage or degradation of poly-, oligo- and disaccharides, as well as derivatives thereof. As examples of polysaccharides, in addition to cellulose and hemicellulose, starch, glycogen, dextran and tunicin may be mentioned. Likewise, these include the polycondensates of D-fructose, such as inulin, and 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 senitrate. The corresponding explanations apply accordingly.

In the process according to the invention, a solution of cellulose in ionic liquid is prepared. The concentration of cellulose can be varied within wide ranges. Usually, it is in the range of 0.1 to 50 wt .-%, based on the total weight of the solution, preferably 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% by weight.

This dissolution 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, particularly preferably at 50 to 150 ° C. , But it is also possible to accelerate the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by combining them. To this solution thus obtained, the nucleophile of formula IV is added.

The nucleophile of formula IV can be added in bulk, dissolved in an ionic liquid or in a suitable solvent. Suitable solvents are 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 solvent used to dissolve the nucleophile of formula IV should be such that no precipitation of the cellulose occurs during the addition. As ionic liquid is preferably the one in which the cellulose itself - as described above - is dissolved.

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

In a further particular embodiment, the nucleophile of the formula IV is added dissolved in an ionic liquid, with particular preference being given to using the ionic liquid which is also used to dissolve the cellulose.

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

There is also the possibility that one or more further solvents are added to the reaction mixture or already supplied with the ionic liquid or the nucleophile of the formula IV. Suitable solvents in this case are those solvents which do not adversely affect the solubility of the cellulose, such as aprotic dipolar solvents, for example dimethylsulfoxide, dimethylformamide, dimethylacetamide or sulfolane. Furthermore, nitrogen-containing bases, such as pyridine, etc., can also be added.

In a particular embodiment, the reaction mixture in addition to the ionic liquid and optionally the solvent in which the nucleophile of the formula IV is dissolved, less than 5 wt.%, Preferably less than 2 wt.%, In particular less than 0.1 wt. %, based on the total weight of the reaction mixture, of further solvents and / or additional nitrogen-containing bases.

The degradation is usually carried out at a temperature of melting point of the ionic liquid to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C, depending on the ionic liquid used and the nucleophile used. Usually, the reaction is carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially if a volatile nucleophile is used.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example under N2, a noble gas, CO2 or mixtures thereof to work.

From case to case, the acid-catalyzed reaction with the nucleophile of the formula IV may be advantageous. As acids here come inorganic acids such as HCl, H2SO4, etc., or organic acids such as acetic acid, trifluoroacetic acid, p-Tolulosulfonsäure etc. into consideration.

In a particular embodiment, the reaction is carried out acid-catalyzed. The acid is used here in an amount of 1 mol% up to 100 mol% based on the nucleophile.

In a further embodiment, the reaction is carried out in the absence of added acid.

Depending on the desired degree of degradation, the amount of nucleophile used, in each case in relation to the cellulose used, the reaction time and optionally the reaction temperature is set.

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 / riNucieophi ^ 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 of u anhydroglucose units on average in a cellulose, the number of anhydroglucose units is less than u, the amount to be üblicherwese adapted to the inserted nucleophile (nAnhydrogiucoseemheiten / nNucieophii ⁵ '1) - the larger the ratio of anhydroglucose units / nucleases is lower, the lower the average degradation of cellulose will be under otherwise the same conditions and the same reaction time.

Furthermore, it is possible to stop the degradation reaction when the desired degree of degradation is achieved by separating the cellulose from the reaction mixture. This can be done, for example, by adding an excess of water or other suitable solvent in which the degraded cellulose is insoluble, such as a lower alcohol such as methanol, ethanol, propanol or butanol, or with a ketone, for example, acetone, etc., or mixtures thereof. Preferably, an excess of water or methanol is used.

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 dissolving the volatile components, such as benzene. the precipitant, any added water or excess nucleophile, etc. are distilled off. The remaining ionic liquid can be used again in the process according to the invention. In another embodiment, excess nucleophile may also remain in the ionic liquid and be reused in the process of the invention.

Due to the statistical degradation of cellulose, the ionic liquid to be regenerated contains only a small amount of glucose, its oligomers or, if appropriate, corresponding reaction products with the nucleophile of the formula IV thereof. Any existing amounts of these compounds can be separated by extraction with a solvent or by adding a precipitant from the ionic liquid.

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

However, it is also possible the reaction mixture in water or in another suitable solvent in which the degraded cellulose is not soluble, such. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example acetone, etc., or mixtures thereof, and, depending on the embodiment, for example, obtaining fibers, films of degraded cellulose or optionally derivatized degraded cellulose or mixtures thereof. The filtrate is worked up as described above.

Furthermore, it is possible to stop the degradation reaction when the desired degree of degradation is achieved by cooling and working up the reaction mixture. The work-up can be carried out according to the methods described above.

In the event that reaction conditions are chosen so that the cellulose is completely degraded, the glucose or optionally according to derivatized glucose resulting from the reaction with the nucleophile of formula IV by conventional methods, such as precipitation with ethanol from the ionic Liquid to be separated. In the event that the ionic liquid is circulated, the ionic liquid may contain up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above , contain.

The process can be carried out batchwise, semicontinuously or continuously.

If amines or hydrazines are used as nucleophiles of the formula IV, then the terminal glucose unit of the "degraded" cellulose with the amine or hydrazine can form an imine or hydrazone.

The following examples serve to illustrate the invention.

Preliminary note

Cotton linters (hereinafter Linters) and Avicel PH 101 (microcrystalline cellulose) were dried overnight at elevated temperature in vacuo.

The ionic liquids were dried overnight at 120 ° C and 0.1 to 0.05 mbar with stirring.

The average degree of polymerization DP of the cellulose used as well as the degraded cellulose was determined in each case by measuring the viscosity in Cuen solution.

Abbreviations

BMIM Cl 1-butyl-3-methylimidazolium chloride

DNP 2,4-dinitrophenylhydrazine

DP Average degree of polymerization N Nitrogen content of degraded cellulose determined by elemental analysis

4-NA 4-nitroaniline

4-NA HCl 4-nitroaniline hydrochloride

Examples 1 and 2

0.5 g of dried linters having a DP of 3252 were dissolved in 19.5 g of BMIM Cl at 110 ° C. After the quantities of DNP indicated in Table 1 were added, the mixture was stirred for the time indicated in Table 1 at the temperature also indicated in Table 1. The resulting dark red solution was then added with vigorous stirring to methanol and the filtered precipitate filtered off, washed and dried at 80 ° C and 1 mbar in vacuo.

Example 3

0.5 g of dried linters having a DP of 3252 were dissolved in 19.5 g of BMIM Cl at 110 ° C. After 59.7 mg of DNP was added, the mixture was stirred for 24 h at 120 ° C. The forming dark red solution was then added with vigorous stirring to methanol and the precipitate formed filtered off, washed and dried at 80 ° C and 1 mbar in vacuo. This gave a "degraded" cellulose with a DP of 145 and a nitrogen content of 0.237.

Example 4

0.5 g of dried Avicel PH 101, which has a DP of 463, was dissolved in 10 g of BMIM Cl at 100 ° C. It was then cooled to 80 ° C, 38.3 mg of 4-NA and 5.4 mg of 4-NA HCl added and stirred at this temperature for 96 h. The reaction mixture was then added with vigorous stirring in methanol, the precipitate formed filtered off, washed and dried at 80 ° C and 0.1 mbar in vacuo. The resulting "degraded" cellulose has a DP of 263. Elemental analysis has not detected nitrogen, and the theoretical nitrogen content of degraded cellulose with a DP of 263 is below the detection limit of nitrogen by elemental analysis.

Claims

claims 1. A process for the degradation of poly-, oligo- or disaccharides, or derivatives thereof, which comprises dissolving the polysaccharide, oligosaccharide or disaccharide, or the corresponding derivative, in at least one ionic liquid and reacting with a nucleophile, treated. 2. The method according to claim 1, characterized in that one uses as polylactic, oligo- or disaccharide, or a derivative thereof, a polysaccharide, or a derivative thereof. 3. The method according to claim 2, characterized in that one uses as polysaccharide, or a derivative thereof, cellulose, or a cellulose derivative. 4. The method according to claim 3, characterized in that one uses as polysaccharide, or a derivative thereof, cellulose. 5. Process according to claims 1 to 4, characterized in that the ionic liquid, or mixtures thereof, are selected from the compounds of the formulas I, [A]; [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] ^p - for a mono-, di-, tri- or tetravalent anion; stand; or the compounds of the formula II [A ¹ J ⁺ [A ² J ⁺ [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 - (Mc), where n = 4 and where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ⁺ independently of one another are those mentioned for [A] ⁺ Groups are selected; and [Y] ^p - have the abovementioned meaning. 6. The method according to claim 5, characterized in that [A] ⁺ for a cation selected from the compounds of the formulas (IIIa) to (MIy)

Ia) (MIb) (MIc)

(UId) (MIe) (MIf)

Ciig> (mg ¹ ) (MIh)

(H) (inj) (MIj ')

(MIm) (MIm ') (MIn)

(MIn ') lo) (MIo')

(MIp) (MIq) (MIq ') R

(HIq ") Ir) (MIr ')

(MIr ") (MIs) (With)

(MIu) Iv) (MIw) R ^z R ^z 3 ' ⁺ 1 ^{1 +} 1 R-PR ¹ SR ¹ RR Ix) (MIy) and oligomers containing this structure, wherein 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 independently of one another represent 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 with 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ which in the abovementioned formulas (III) are attached to a carbon atom (and not to a heteroatom) may additionally be halogen or a functional group; or two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted 1 to 30 carbon atoms, can stand. 7. Process according to claims 5 or 6, characterized in that [Y] ⁿ "is selected from an anion 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 SOs) ₂ N-, CF ₃ CO ₂ - , CCI 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 ³ OSO ₃ -, R ³ SO ₃ - The group of phosphates of the general formula PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ³ PO ₄ -, R ³ R ^b PO ₄ - The group of phosphonates and phosphinates of the general formula: R ³ HPO ₃ -, R ³ R ^b PO ₂ -, R ³ R ^b PO ₃ - The group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ³ HPO ₃ -, R ³ R ^b PO ₃ - The group of phosphonites and phosphinites of the general formula: R ³ R ^b PO ₂ -, R ³ HPO ₂ -, R ³ R ^b P0-, R ³ HPO ^" • the group of carboxylic acids of the general formula: R ³ COO- The group of borates of the general formula: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) -, B (HSO ₄ ) -, B (R ³ SO ₄ ) - The group of boronates of the general formula: R ³ BO ₂ ² -, R ³ R ^b B0- 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 ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ² -, R ³ R ^b R ^c Si0 ₄ -, HR ³ - SiO ₄ ² -, H ₂ R ³ SiO ₄ -, HR ^a R ^b Si0 ₄ - The group of the alkyl or aryl silane salts of the general formula: R ³ SiO ₃ ^{3 "} , R ³ R ^b Si0 ₂ ² -, R ³ R ^b R ^c Si0 ^" , R ³ R ^b R ^c Si0 ₃ -, R ³ R ^b R ^c Si0 ₂ -, R ³ R ^b Si0 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: SO ₂ -R ³ R ^{b is} -O ₂ S SO ₂ -R ^C ; wherein the radicals R ³ , R ^b , R ^c and R ^d are each independently hydrogen, Ci-C ₃ o-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 8 -alkyl, C ₆ -C 14 -aryl, Cs Ci ₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally by one or more oxygen and / or sulfur atoms and / or a or a plurality of unsubstituted or substituted imino groups can form an interrupted ring, where the radicals mentioned can each additionally be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; stands. 8. Process according to claims 5 to 7, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IMa, Nie, Nif; IMg, IMg, MIh, Uli, MIj, MIj, MIk, IMk, IUI, Ulm, Ulm, IMn or IMn. 9. Process according to claims 5 to 8, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IMa, Nie or Nif. 10. Process according to claims 5 to 9, characterized in that [Y] ⁿ - for an anion selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^{2 "} , SO3 ^2" , R ³ OSO ₃ - and R ³ SO ₃ -, as well as the group containing PO ₄ ^{3 "} and R ³ R ^b PO ₄ -, stands. 1 1. A process according to claims 1 to 10, characterized in that as nucleophile a compound of formula IV R ^x - X - H (IV) With XO, 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 0-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 aliphatic radical, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; or additionally hydrogen when X is S, NH, NR ^{y, y} PR, NH-NH, NH-NR ^y, NR ^y - NH, NR ^{y y} NR, PR ^y -O or NH-O, NR ^y -O-, O-NH or O-NR ^y is. 12. The method according to claim 1 1, characterized in that X is O, S, NH or NH-NH; means. 13. The method according to claims 1 1 or 12, characterized in that R ^{x is} optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, C 1 -C 18 -alkyl which is substituted by 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; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, 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 C2-cis-alkenyl ; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, 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 C2-Cis-alkynyl ; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-C12-cycloalkyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-C12-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 containing heterocycle ;; means. 14. The method according to claims 1 to 13, characterized in that the concentration of poly-, oligo- or disaccharide, or a derivative thereof, in ionic liquid in a range of 0.1 to 50 wt .-% based on the total weight the solution lies. 15. The method according to claims 1 to 14, characterized in that the degradation is carried out at a temperature of the melting point of the ionic liquid to 200 ° C. 16. The method according to claims 1 to 15, characterized in that the quenching by the addition of a solvent in which the degradation products of the polysaccharide are not soluble quenches. 17. degraded cellulose obtainable by the process according to claims 1 to 16.