WO2006027069A1 - Procede pour produire des composes ammonium et/ou guanidinium quaternaires heterocycliques - Google Patents

Procede pour produire des composes ammonium et/ou guanidinium quaternaires heterocycliques Download PDF

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WO2006027069A1
WO2006027069A1 PCT/EP2005/008605 EP2005008605W WO2006027069A1 WO 2006027069 A1 WO2006027069 A1 WO 2006027069A1 EP 2005008605 W EP2005008605 W EP 2005008605W WO 2006027069 A1 WO2006027069 A1 WO 2006027069A1
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methyl
butyl
carbon
heteroatoms
quaternary ammonium
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PCT/EP2005/008605
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German (de)
English (en)
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Georg Degen
Klaus Ebel
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Basf Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms

Definitions

  • the present invention relates to a process for preparing an intermediate product containing a heterocyclic quaternary ammonium and / or guanidinium cation for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds.
  • Quaternary ammonium compounds are important substances which find wide application. For example, they are used as fabric softeners, in hygiene and cosmetics, as phase transfer catalysts or as conductive salts for electronic applications. Another important group of applications are ionic liquids with imidazolium or pyridinium as cations.
  • Quaternary ammonium compounds with freely selectable anion are usually prepared in a two-step reaction.
  • the corresponding tertiary amine is alkylated with an alkylating agent, the resulting anion of the quaternary ammonium compound being fixed by the alkylating agent used.
  • a so-called anion exchange is subsequently carried out in the second synthesis stage.
  • the alkylation (first stage of the synthesis) is usually carried out by reacting the corresponding tertiary amines / imines with alkylating agents.
  • the alkylating agents customarily used are the alkyl esters of strong mineral acids, in particular dimethyl sulfate or methyl chloride (see, for example, Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Volume XI / 2, Georg Thieme Verlag, Stuttgart 1958, pages 591 to 630).
  • a disadvantage of the use of dimethyl sulfate is its carcinogenic effect, which represents a hazard potential and requires expensive safety measures.
  • a disadvantage of the use of alkyl halides is the introduction of halide ions, which are generally difficult to replace completely and in particular lead to problems when used in the electrical industry and in the catalysis and their corrosivity in handling.
  • the low molecular weight alkyl chlorides such as methyl chloride and ethyl chloride are gaseous and therefore difficult to handle.
  • dimethyl carbonate as a methylating agent is described in JP 04-341, 593 and JP 09-025,173.
  • a disadvantage of this is the occurrence of side reactions, such as, for example, the carboxylation of ring carbon atoms in the reaction of imidazoles with dimethyl carbonate (see M. Aresta et al., In Lonic Liquids as Green Solvents, ACS Symposium Series 856, Ed. R. Rogers and KR Seddon, American Chemical Society 2003, pages 93 to 99).
  • methyl iodide is also known as a methylating agent for the preparation of quaternary ammonium compounds.
  • a disadvantage of the use of methyl iodide is its carcinogenic effect, which represents a potential hazard and requires complex safety measures.
  • methyl iodide is not available in the required technical quantities or is relatively expensive compared to the above-mentioned methylating agents.
  • WO 02/34722 teaches the synthesis of 1, 2,3-substituted, of 1, 2,3,4-substituted and 1, 2,3,4,5-substituted imidazolium compounds by reacting the corre sponding substituted imidazole with an alkyl triflate or a trialkyloxonium salt of the desired anion (eg triethyloxonium tetrafluoroborate).
  • an alkyl triflate or a trialkyloxonium salt of the desired anion eg triethyloxonium tetrafluoroborate.
  • halide, alkyl sulfate and triflate anions is disadvantageous in the use of alkyl halides, dialkyl sulfates and alkyl triflates as alkylating agents, since these anions require a classical anion exchange for the introduction of the anion which is actually desired, in which case the originally introduced anion adjoins together with a suitable cation in liquid or solid form is removed. This replacement is technically complicated and is generally not complete, so that the product still has disturbing contamination. This also applies to chloride-free synthesis routes, such as using dialkyl sulfate as the alkylating agent, since at least small amounts of undesired alkyl sulfate remain in the product during an anion exchange.
  • JP 2003-313,170 teaches the quaternization of cyclic imides such as imidazoles with carboxylic acid esters such as methyl formate or methyl acetate as alkylating agent to form the corresponding carboxylates.
  • WO 01/40146 teaches the preparation of 1,3-dialkylimidazoium compounds by reacting 1-alkylimidazole with alkyl sulfonates or fluorinated carboxylic acid esters, such as ethyl trifluoroacetate, to form the corresponding sulfonate or fluorinated carboxylate anions. These have to be exchanged for the introduction of the actually desired anion via an anion exchange.
  • EP-A 0 608 545 describes the preparation of substituted, sp 3 -hybridized, non-cyclic ammonium hydroxide by oxidation of the corresponding substituted, sp 3 -hybridized ammonium carboxylates, such as the formates or acetates, with an oxidizing agent, such as For example, hydrogen peroxide or oxygen, in the presence of a gp. VIII metal catalyst and subsequent elec trolysis to the hydroxide.
  • an oxidizing agent such as For example, hydrogen peroxide or oxygen
  • the object of the present invention was to find a process for preparing heterocyclic quaternary ammonium and / or guanidinium compounds or their precursors, which does not have the disadvantages of the prior art, is simple to carry out, or does not use the alkylating agent to be used is only slightly toxic, technically readily available and inexpensive, and enables a simple and flexible introduction of the desired anion, wherein the product can be prepared after introduction of the desired anion in high purity without expensive purification steps and also suitable for use in the electronics industry should be.
  • oxidizing agent in principle all gaseous, liquid or solid reagents which are capable of oxidizing the carboxylates used.
  • Hydrogen peroxide is preferably used in the form of its aqueous solution, the preferred concentration being rich of hydrogen peroxide to be added in the range of 1 to 35 wt .-%.
  • Oxygen can be added in pure form or diluted with other gases. Suitable gases for diluting the oxygen are, for example, nitrogen, noble gases or carbon dioxide.
  • the concentration of oxygen in the gas to be added is generally 1 to 100% by volume, preferably 15 to 100% by volume. For example, oxidation by addition of air is also possible.
  • the oxidizing agent is generally added in the process according to the invention in at least stoichiometric amount and preferably in excess.
  • stoichiometric amount In the case of liquid or solid oxidizing agents, they are preferably added in an amount ranging from the stoichiometric amount to 4 times the stoichiometric amount. Quantities above this range generally lead to disadvantages as a result of the high dilution of the actual product of value.
  • gaseous oxidizing agents an excess is generally added, since the excess gases generally escape from the liquid mixture. The amount of excess is generally determined by the availability of the oxidizing agent, its price, any necessary measures for exhaust gas disposal and apparati ⁇ ver conditions.
  • the reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent is carried out in the process according to the invention in the presence of a metal from the 8th to 10th group of the Periodic Table.
  • the reaction is preferably carried out in the presence of palladium, platinum, ruthenium, rhodium and / or iridium.
  • the catalyst can be used, for example, in a highly active state, such as, for example, as a powder, or else in the form of a so-called supported catalyst.
  • Suitable carriers are in principle all suitable carrier materials in question.
  • Preferred support materials are activated carbon, carbon or activated carbon fibers and inorganic carriers such as silica, alumina, aluminosilicates or zeolites.
  • the amount of supported metal is generally from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight and more preferably from 1 to 10% by weight, based on the mass of the finished supported catalyst.
  • the shape and size of the supported catalyst particles is generally negligible.
  • the supported catalysts can be used in the form of small irregular particles ranging from a few tenths of a millimeter in diameter to larger irregular or regular particles in the range of several millimeters. Suitable supported catalysts are commercially available and their preparation is known to the person skilled in the art.
  • the reaction is generally carried out in reactors which are suitable for the heterogeneous catalytic oxidation in the liquid phase or in the liquid / gas phase, depending on the state of aggregation of the oxidizing agent.
  • Another criterion for the choice of the reactor is the shape and size of the catalyst to be used. If metal powders or small irregular supported catalyst particles are used, the reaction is preferably carried out by suspension catalyzed. In this case, stirred tank reactors with or without gassing device, depending on the state of the oxidizing agent, are particularly suitable. If relatively large supported catalyst particles are used, the reaction is preferably carried out in a fixed bed reactor in a fixed bed catalyzed manner. Preference is given to carrying out the reaction in suspension-catalyzed procedure in a tubular reactor or a stirred tank reactor.
  • the reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent takes place in the inventive method at a temperature of 0 to 250 0 C, preferably from 10 to 150 0 C and more preferably be from 10 to 120 0 C.
  • the pressure is from 0.05 to 20 MPa abs, Press ⁇ Trains t 0.09 to 10 MPa abs, and most preferably from 0.095 to 5 MPa abs.
  • the reaction can be carried out batchwise, semicontinuously or continuously.
  • the heterocyclic quaternary ammonium and / or guanidinium carboxylate is used together with the catalyst for the reaction, and the oxidizing agent is added, if appropriate distributed over several minutes or hours (discontinuous and semicontinuous procedure).
  • the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent are added simultaneously to the catalyst.
  • the reaction it is possible to carry out the reaction in the absence or in the presence of a solvent. If a solvent is used, preference is given to choosing water, Cr to C 8 -alkanols, N, N-dimethylformamide or N-methylpyrrolidone and particularly preferably water. If, for example, an oxidizing agent is used which is not present in pure form or is preferably used diluted for other reasons, the reaction is usually carried out in the presence of a solvent. An example of this is the use of aqueous hydrogen peroxide solution.
  • the heterocyclic quaternary ammonium and / or guanidinium carboxylates to be used in the process according to the invention generally have the carboxylate anion of the general formula (I)
  • R 1 represents a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms.
  • 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 alkyl) amino, Ci-C 4 alkyloxycarbonyl or Ci-C 4 alkyloxy.
  • R is hydrogen or C 1 - to C 6 -alkyl
  • the C 1 - to C 7 -alkyl radical are, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2 Methyl 2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3 Methyl 2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1 - pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1 - butyl, 2,3-dimethyl-1-but
  • hydroxy, carboxylate (-COO ' ), carboxy (-COOH) and C 1 - to C 6 alkyloxycarbonyl (-COOR 2 with R 2 is C 1 - to C 6 -alkyl) substituted phenyl, for example phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl,
  • the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation to be used in the process according to the invention preferably comprises as carboxylate anion formate, acetate, propionate, butyrate, pentanoate (valerate), hexanoate, heptanoate, octanoate, 2-ethylhexanoate, Methyl oxalate, ethyl oxalate, 1-propyl oxalate, 1-butyloxalate, 1-pentyloxalate, 1-hydroxy oxalate, 1-heptyloxalate, 1-octyl oxalate, 1- (2-ethyl) hexyloxalate, methyl malonate, ethyl malonate, 1-propyl malonate, 1-butyl malonate, 1-pentylmalonate
  • the carboxylate of the corresponding heterocyclic quaternary ammonium cation and / or guanidinium cation to be used in the process according to the invention is preferably prepared by reacting the corresponding sp 3 -hybridized amine or sp 2 -hybridized imine with the corresponding ester of the carboxylate anion.
  • the components are generally mixed together in any order over any period of time.
  • the reaction is generally carried out at a temperature from 20 to 350 °, preferably from 100 to 250 0 C.
  • the Umset ⁇ carried wetting generally at a pressure of 0.05 to 35 MPa abs, preferably from 0.1 to 20 MPa abs.
  • the reaction can be carried out in the absence or in the presence of solvents.
  • solvents are, for example, water, methanol or strongly polar aprotic solvents such as N, N-dimethylformamide.
  • the presence of water or methanol accelerates the reaction.
  • the reaction can be worked up after completion of the reaction or used directly for the reaction according to the invention with the oxidizing agent. If the reaction effluent is worked up, this is generally worked up by distillation, extraction and / or crystallization.
  • the formates to be used with particular preference in the reaction according to the invention are thus usually prepared by reacting the corresponding sp 3 -hybridized amine or sp 2 -hybridized imine with methyl formate.
  • the methyl formate required for methylation can also be generated in situ.
  • the corresponding sp 3 -hybridized amine or sp 2 -hybridized imine is reacted with methanol and carbon monoxide, if appropriate in the presence of a solvent, such as water, methanol or strongly polar aprotic solvents such as N, N-dimethylformamide, at a temperature of 20 to 350 ° C, preferably 120 to 250 0 C and a pressure of 0.05 to 35 MPa abs, preferably from 5 to 20 MPa abs.
  • a solvent such as water, methanol or strongly polar aprotic solvents such as N, N-dimethylformamide
  • the preferred heterocyclic quaternary ammonium cation used is an imidazolium, imidazolinium, pyrazolium, pyrazolinium or pyridinium cation.
  • an aromatic heterocyclic quaternary ammonium cation particularly preferably an imidazolium, pyrazolium or pyridinium cation, and very particularly preferably an imidazolium cation.
  • an ammonium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (III)
  • R 7 together with R 8 is a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 30 carbon atoms be ⁇ interpret; or R 7 together with R 8 and R 9 is a trivalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Mean carbon atoms;
  • radicals are 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 or substituted radical having 1 to 20 carbon atoms, where R 6 may additionally stand for hydrogen.
  • an imidazolium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (II)
  • radicals R 2 to R 5 independently of one another a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cycli ⁇ 's, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted 1 to 20 carbon atoms and the radicals R 2 to R 4 additionally, independently of one another, are hydrogen, halogen or a functional group and the radical R 5 may additionally also be hydrogen; or
  • R 2 together with R 3 ; or R 3 together with R 5 ; or R 5 together with R 4 together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 represent carbon atoms and the remaining radicals are as previously defined;
  • radical R 1 is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic see, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups unbere broken or substituted radical having 1 to 20 carbon atoms.
  • an imidazolinium cation is used as the heterocyclic quaternary ammonium cation in the process according to the invention, this preferably has the general formula (IV)
  • the radicals R 11 to R 14 are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms and the radicals R 11 to R 13 additionally, independently of one another, mean hydrogen, halogen or a functional group and the radical R 14 may additionally also be hydrogen; or
  • radical R 10 is a carbon-containing organic, saturated or unge ⁇ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati ⁇ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,
  • a pyrazolium cation is used as heterocyclic quaternary ammonium cation, this preferably has the general formula (VI)
  • the radicals R 16 to R 19 are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having from 1 to 20 carbon atoms and the radicals R 16 to R 18 additionally independently of one another hydrogen, halogen or a functional group meaning th and the radical R 19 may additionally also be hydrogen; or
  • R 16 together with R 17 ; or R 17 together with R 18 ; or R 18 together with R 19 together represent a divalent, carbon-containing organic see, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 30 Koh ⁇ lenstoffatomen mean and the remaining radicals are as defined above;
  • radical R 15 is a carbon-containing organic, saturated or unge ⁇ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati ⁇ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,
  • a pyrazolinium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (VII)
  • R 21 to R 24 are each independently a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted or substituted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms and the radicals R 21 to R 23 additionally independently of one another hydrogen, halogen or a functional group meaning th and the radical R 24 may additionally also be hydrogen; or
  • radical R 20 is a carbon-containing organic, saturated or unge ⁇ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati ⁇ rule, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups interrupted or substituted radical having 1 to 20 carbon atoms ,
  • a pyridinium cation is used as the heterocyclic quaternary ammonium cation, this preferably has the general formula (VIII)
  • the radicals R 26 to R 30 are independently hydrogen, halogen, a functional group or a carbon-containing organic, saturated or ungesquestionedtig ⁇ th, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted or substituted radical having 1 to 20 carbon atoms; or two adjacent radicals R 26 together with R 27 ; or R 27 together with R 28 ; or R 28 together with R 29 or R 29 together with R 30 together form a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Substituted th radical having 1 to 30 carbon atoms and the remaining radicals are as defined above;
  • radical R 25 is a carbon-containing organic, saturated or unge ⁇ saturated, acyclic or cyclic, aliphatic, aromatic or araliphati ⁇ rule, unsubstituted or by 1 to 5 heteroatoms or functional groups un interrupted or substituted radical having 1 to 20 carbon atoms ,
  • radicals R 32 to R 36 independently of one another are carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 Koh ⁇ mean radicals and R 33 and R 35 additionally independently of each other hydrogen, - or
  • R 33 together with R 34 ; or R 35 together with R 36 together menam a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphati ⁇ rule, unsubstituted or un interrupted or substituted by 1 to 5 heteroatoms or functional groups Radicals having 1 to 30 carbon atoms and the remaining radicals are as previously defined;
  • radical R 31 is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical see, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups unbere broken or substituted radical having 1 to 20 carbon atoms.
  • the carbon-containing radical contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred.
  • the radical-containing carbon may be in the case of R 2 to R 4, R, R, R to be 11 to R 13 16 to R 18 21 to R 23 and R 26 to R 30 bound directly via the heteroatom at the respective Heterocycliumring.
  • 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 -AlkVl- oxycarbonyl or C 1 -C 4 -AlkVlOXy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the hetero-cyclic quaternary ammonium cation and / or guanidinium cation used in the process according to the invention is preferably an ammonium (III), imidazolium (II), imidazolinium (IV), pyrazolium (VI), pyrazolinium (VII) , Pyridinium (VIII) or guanidinium cation (IX) in which the radicals R 2 to R 4 (in the case of an imidazolium cation (II)), R 11 to R 13 (in the case of an imidazolinium cation (IV ), R 16 to R 18 (in the case of a pyrazolium cation (VI)), R 21 to R 23 (in the case of a pyrazolinium cation (VII)) and R 26 to R 30 (in the case of a pyridinium cation).
  • Cations (VIII)) independently
  • radicals R 1 to R 6 and R 9 to R 36 are each independently
  • C 2 interrupted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to C 18 - alkenyl;
  • aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles C 6 - to C 12 -aryl;
  • C 5 -C 2 -cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogens, heteroatoms and / or heterocycles;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C 1 - to C 18 -alkyl it is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl
  • C 2 optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - to d ⁇ -alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or CnF 2 (na) .
  • ( 1.b ) H 2a -b with n ⁇ 30, 0 ⁇ a ⁇ n and b 0 or 1.
  • C 6 -C 12 -aryl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, toIyI, xylyl, .alpha.-naphthyl, .beta.-naphthyl , 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, Isopropylnap
  • C 5 -C 12 -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl , Dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthio cyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C n F 2 ( n ) - (ib) H 2a-b with n ⁇ 30, 0 ⁇ a ⁇ n
  • An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • 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 by one or more oxygen and / or sulfur atoms and / or one or more sub ⁇ 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 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 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 most 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.
  • the radicals R 1 , R 5 , R 6 , R 9 , R 10 , R 14 , R 15 , R 19 , R 20 , R 24 , R 25 and R 31 to R 36 independently of one another are unbranched or branched C.
  • C 2 -alkyl such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert -Butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2 , 2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2 -pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl 1-butyl, 3,3-dimethyl
  • radical R 7 is particularly preferably also a sulfo group.
  • the radicals R 2 to R 4 , R 11 to R 13 , R 16 to R 18 , R 21 to R 23 and R 26 to R 30 are particularly preferably independently of one another hydrogen or unbranched or branched Cr to C 12 -alkyl such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 - Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 - propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-penty
  • ammonium cation (II) to N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • imidazolium cation (II) 1, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-propyl) -3-methylimidazolium, 1- (1-butyl) 3-methylimidazolium, 1- (1-pentyl) -3-methylimidazolium, 1 - (1-hexyl) -3-methyl-imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-decyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1 - (1-pentadecyl) -3-methylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-propyl) -2,3-dimethylimidazolium, 1- (1-(-dimethylimidazolium, 1-
  • imidazoline cation (IV) 1, 3-dimethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1- (1-propyl) -3-methylimidazolinium, 1- (1-butyl) 3-methylimidazolinium, 1- (1-pentyl) -3-methylimidazolinium, 1- (1-hexyl) -3-methylimidazolinium, 1- (1-octyl) -3-methylimidazoliumium, 1 - (1- Decyl) -3-methylimidazolinium, 1- (1-dodecyl) -3-methylimidazolinium, 1- (1-pentadecyl) -3-methylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium , 1- (1-propyl) -2,3-dimethylimidazolinium, 1- (1-butyl)
  • pyrazolium cation (VI) 1, 2-dimethylpyrazolium, 1-ethyl-2-methylpyrazolium, 1- (1-propyl) -2-methylpyrazolium, 1- (1-butyl) 2-methylpyrazolium, 1- (1-pentyl) -2-methylpyrazolium, 1- (1-hexyl) -2-methyl-pyrazolium, 1- (1-octyl) -2-methylpyrazolium, 1- (1-decyl) 2-methylpyrazolium, 1- (1-dodecyl) -2-methylpyrazolium and 1- (1-pentadecyl) -2-methylpyrazolium.
  • pyrazolinium cation (VII) 1, 2-dimethylpyrazolinium, 1-ethyl-2-methylpyrazolinium, 1- (1-propyl) -2-methylpyrazolinium, 1- (1-butyl) 2-methylpyrazolinium, 1- (1-pentyl) -2-methyl-pyrazolinium, 1- (1-hexyl) -2-methyl-pyrazolinium, 1- (1-octyl) -2-methyl-pyrazolinium, 1- (1 Decyl) -2-methylpyrazolinium, 1- (1-dodecyl) -2-methylpyrazolinium and 1- (1-pentadecyl) -2-methylpyrazolinium.
  • pyridinium cation VIII
  • guanidinium cation (IX) N 1 N 1 N ', N', N " I N" hexamethylguanidinium The intermediate product obtained in the reaction between the heterocyclic quaternary ammonium and / or guanidinium carboxylate and the oxidizing agent for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds can generally be used directly without purification to give the desired heterocyclic quaternary ammonium - And / or guanidinium compound emergever ⁇ works. If necessary, however, a workup and purification of the intermediate product is possible. In the latter case, the oxidation product can spielnem be worked up by phase separation, extraction and / or crystallization.
  • a variant for the synthesis of the desired heterocyclic quaternary ammonium and / or guanidinium compounds from the intermediate product formed according to the invention is the electrochemical reaction in aqueous solution to give the corresponding heterocyclic quaternary ammonium and / or guanidinium hydroxide.
  • electrolysis cells In order to avoid a mixing of the electrochemically formed heterocyclic quaternary ammonium and / or guanidinium hydroxide with the intermediate used, it is preferred to use divided electrolysis cells. Particular preference is given to electrolysis cells with a diaphragm made of a cation exchange membrane which separates the electrolysis cell into an anode space and a cathode space. However, it is also possible to use a multi-chamber electrolysis cell with one or more separate intermediate chambers by arranging a plurality of cation exchange membranes.
  • Suitable materials for the cation exchange membrane are, for example, non-corrosive fluorine resins having a cation exchange group, such as a sulfonic acid or carboxylic acid group, in combination with a styrene-divinylbenzene copolymer having the above-mentioned ion exchange groups.
  • the anode used may be an electrode which is suitable for this type of electrolysis, for example a high-purity carbon electrode or a titanium electrode which is coated with an oxide of a platinum group metal such as platinum or iridium.
  • an electrode suitable for this type of electrolysis for example, a stainless steel or nickel electrode, may be used.
  • the anodes and cathodes can be used in any form as plates, nets, porous plates and the like.
  • the electrochemical reaction can be carried out batchwise or continuously.
  • concentration of the intermediate used in the electrolysis according to the invention is preferably from 1 to 60 wt .-% and particularly preferably from 3 to 40 wt .-% in aqueous solution at the beginning of the electrolysis. If the conductivity at the beginning of the electrolysis should be very low, for example, a small amount of about 0.01 to 5 wt .-% of the corresponding heterocyclic quaternary ammonium and / or guanidinium hydroxide are added.
  • the electrolysis can be carried out by applying a DC voltage.
  • the current density is preferably in the range from 1 to 100 A / dm 2 and preferably from 3 to 50 A / dm 2 .
  • the temperature of the electrolyte is preferably in the range from 10 to 50 ° C. It is also preferred that during the electrolysis the atmosphere on the surface of the electrolyte consists of an inert gas such as nitrogen or argon.
  • the heterocyclic quaternary ammonium and / or guanidinium hydroxide formed can be isolated from the electrolysis liquid, for example by distilling off the water present, preferably under reduced pressure.
  • the product is very pure, so that it can be used directly, for example as conductive salt in the electrical industry. If necessary, however, the product can also be further purified, for example by recrystallization or extraction.
  • the heterocyclic quaternary ammonium and / or guanidinium hydroxide - as an isolated pure substance, but also in the form of the resulting aqueous electrolysis liquid - with an inorganic or organic protic acid having a pKa of ⁇ 14, measured at 25 ° C. in aqueous solution to form the heterocyclic quaternary ammonium and / or guanidinium compound of the partially or fully deprotonated anion of the inorganic or organic protic acid.
  • this is reacted with an inorganic or organic protic acid having a pKa value of ⁇ 14, measured at 25 ° C in aqueous solution to form the heterocyclic quaternary ammonium and / or guanidinium compound of the partially or fully deprotonated anion of inorganic or organic protic acid.
  • the relative amount of inorganic or organic protic acid relative to the total amount of the corresponding heterocyclic quaternary ammonium cation and guanidinium cation generally depends on the desired degree of conversion of the intermediate used (ie, whether the intermediate is completely or only partially in the desired Compound with the desired anion to be transferred), according to specific procedural aspects (as spielnem also the nature of the subsequent work-up and the ability to remove any excess protic acid) and ren in polybasic proton acids according to the number of the formation of the desired partially or fully deprotonated anions of protons to be released from the inorganic or organic protic acid.
  • a molar ratio of the inorganic or organic protic acid to the total amount of the heterocyclic quaternary ammonium cation and / or guanidinium cation of the intermediate formed is from 0.9 / a to 1.5 / a, preferably from 0.95 / a to 1, 1 / a and more preferably from 0.99 / a to 1, 02 / a, where a is the number of protons to be released from the inorganic or organic protic acid to form the desired partially or fully deprotonated anion.
  • a monobasic acid such as tetrafluoroboric acid, a is 1.
  • a 1, and for the Case that the dianion (in the example the sulfate) is desired, a equals 2.
  • Hydrogen phosphate Dihydrogen phosphate, vinyl phosphonate, dicyanamide, bis (pentafluoroethyl) phosphinate, tris (pentafluoroethyl) trifluorophosphate, tris (heptafluoro-propyl) trifluorophosphate, bis [oxalato (2 -)] borate, bis [salicylato (2 -)] borate, bis [ 1,2-benzenediolato (2 -) - O, O '] borate, tetracyano borate, tetracarbonyl cobaltate;
  • organic sulfonate of the general formula (Vb) [R ⁇ -SO 3 ] " , where R e is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
  • Carboxylate of the general formula (Vc) [R f -COO] ' wherein R f is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;
  • R m to R 0 independently of one another represent hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms which contain one or more heteroatoms and / or one or more heteroatoms a plurality of functional groups or halogen may be substituted;
  • organic sulfate of the general formula (Vi) [R 13 O-SO 3 ] ' where R p is a carbon-containing organic, saturated or unsaturated, acyclic or cycli ⁇ rule, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon ⁇ atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen, is;
  • Halometallat of the general formula (Vj) [M q Hal r ] s' where M is a metal and Hal for fluorine, chlorine, bromine or iodine, q and r are positive integers indicating the stoichiometry of the complex and s is a whole positive number and indicates the charge of the complex; or
  • Ent ⁇ holds the carbon-containing radical heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • Octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenylmethyl (benzyl), Diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl, acetyl or C n F 2 ( na ) + ( i- b) H 2 a + b with n ⁇ 30, 0 ⁇ a ⁇ n and b 0 or 1 (for example CF 3 , C 2
  • -CO-O-substituted components such as, for example, phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl phenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-dimethylphenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl,
  • tetrasubstituted borate (Va) [BFY 1 R 1 WR 0 ] '
  • all four radicals R a to R d in this case are preferably identical, these preferably being fluorine, trifluoromethyl, pentafluoroethyl, phenyl, 3 , 5-bis (trifluoromethyl) phenyl.
  • Particularly preferred tetrasubstituted borates (Va) are tetrafluoroborate, tetraphenylborate and tetra [3,5-bis (trifluoromethyl) phenyl] borate.
  • the anion is an organic sulfonate (Vb) [R e -SO 3 ], the radical R e is preferably methyl, trifluoromethyl, pentafluoroethyl, p-tolyl or C 9 F 19 .
  • Particularly preferred organic sulfonates (Vb) are trifluoromethanesulfonate (triflate), methanesulfonate, p-tolylsulfonate, nonadecafluorononanesulfonate (nonaflate), dimethlylene glycol monomethyl ether sulfate and octyl sulfate.
  • z is preferably O.
  • R 9 to R 1 independently of one another preferably represent trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C 1 - to C 12 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-one propyl (tert -butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-
  • Particularly preferred imides (Ve), (Vf) and (Vg) are [F 3 C-SO 2 -N-SO 2 -CF 3] "(bis (trifluoromethylsulfonyl) imide), [F 5 C 2 -SO 2 -N -SO 2 -C 2 F 5] "(bis (pentafluoroethylsulfonyl) imide), [F 3 C-SO 2 -N-CO-CF 3] ', [F 3 C-CO-N-CO-CF 3]" and those in which the radicals R 9 to R 1 independently of one another are methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.
  • the radicals R m to R 0 independently of one another are preferably trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C 1 - to C 12 -alkyl, such as, for example, methyl, ethyl, 1 Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3 Pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2- Hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 3-
  • Methides (Vh) Particularly preferred are [(F 3 C-SO 2) 3 C] * (tris (trifluoromethyl sulfonyl) methide), [(C 5 F 2 -SO 2) S C] "(bis (pentafluoroethylsulfonyl) methide ) and those in which the radicals R m to R 0 independently of one another are methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.
  • the radical R p is preferably a branched or unbranched C 1 - to C 30 -alklyl radical.
  • Be ⁇ particularly preferred organic sulfates (Vi) are methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate or octyl sulfate.
  • M preferably represents aluminum, zinc, iron, Cobald, antimony or tin.
  • Hal is preferably chlorine or bromine, and very particularly preferably represents chlorine , q is preferably 1, 2 or 3 and r and s are given according to the stoichiometry and charge of the metal ion.
  • the anion is thiolate (Vn) [R S S]
  • the radical R s is preferably a branched or unbranched C 1 -. -C 30 -Alklylrest
  • Particularly preferred thiolates (Vn) are methyl sulfide, ethyl sulfide, n Propylsulfide, n-butylsulfide, n-pentylsulfide, n-hexylsulfide, n-heptylsulfide, n-octylsulfide or n-dodecylsulfide.
  • an inorganic or organic protic acid in which the partially or fully deprotonated anion tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, formate, acetate, mandelate, nitrate, nitrite, trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, Ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, propionate, tetrachloroaluminate, Al 2 Cl 7 " , chlorozinc, chloroferrate, bis (trifluoromethylsulfonyl) imide, bis
  • the reaction between the present invention formed intermediate and the inorganic or organic protonic acid is generally carried out at a Tem ⁇ temperature of 0 to 35O 0 C, preferably from 10 to 200 0 C and more preferably from 10 to 100 0 C.
  • the pressure is generally 0.01 to 10 MPa abs, preferably 0.09 to 0.5 MPa abs and more preferably 0.09 to 0.2 MPa abs.
  • reactors which are suitable for a reaction in the liquid phase can be used as reaction apparatuses. These are in particular reactors which allow a corresponding mixing of the liquid educts, for example stirred tank.
  • reaction it is possible to carry out the reaction in the absence or in the presence of a solvent. If a solvent is used, preference is given to choosing water, C 1 to C 8 -alkanols, N, N-dimethylformamide or N-methylpyrrolidone. If, for example, an inorganic or organic protic acid is used which is not present in pure form or is preferably used diluted for other reasons, the reaction is usually carried out in the presence of a solvent.
  • the reaction between the intermediate product formed according to the invention and the inorganic or organic protic acid can be carried out batchwise, semicontinuously or continuously.
  • the starting materials are combined and the reaction is carried out.
  • the reaction mixture is worked up to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound.
  • the two starting materials are added slowly to the reaction apparatus for reaction.
  • the reaction mixture is taken off continuously in accordance with the amounts of educts fed in and worked up as described.
  • the workup itself can also be done continuously.
  • one of the two educts is added slowly, the reaction generally taking place in parallel with the addition.
  • the reaction mixture is worked up. then mixed to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compound.
  • the reaction mixture obtained in the reaction between the intermediate product formed according to the invention and the inorganic or organic protic acid can be worked up in various ways to isolate the desired heterocyclic quaternary ammonium compound and / or guanidinium compounds.
  • suitable methods are the extraction and the crystallization of the desired product.
  • Suitable extraction agents are for example C 5 - to C 2 alkanols, methyl tert-butyl ether and ethyl acetate. If, in the reaction between the intermediate formed according to the invention and the inorganic or organic protic acid, gaseous or at least readily distillate components are formed from the anion of the intermediate product, then it is generally sufficient to remove these components from the Reaction mixture by distillation, preferably under vacuum to remove.
  • an N-alkylated and optionally also substituted on one or more ring carbon atoms imidazole with methyl formate to the corresponding 1-methyl-3-alkyl-imidazolium formate. This is then oxidized to the desired intermediate with an aqueous hydrogen peroxide solution or air over a catalyst containing palladium and / or platinum.
  • this intermediate product is converted electrochemically into the corresponding 1-methyl-3-alkylimidazolium hydroxide, which can be obtained by distilling off the water present and, if appropriate, extraction and / or crystallization in pure form.
  • the 1-methyl-3-alkyl-imidazolium hydroxide is obtained in high purity.
  • this intermediate is reacted with the organic or organic protic acid of the desired anion to give the 1-methyl-3-alkylimidazolium compound of the desired anion, which is removed by removing the carbon dioxide formed and distilling off the water present if appropriate, extraction and / or crystallization in pure form can be obtained.
  • the 1-methyl-3-alkyl-imidazolium compound of the desired anion is obtained in high purity.
  • the process according to the invention makes it possible to prepare simply an intermediate containing a heterocyclic quaternary ammonium and / or guanidinium cation for the synthesis of heterocyclic quaternary ammonium and / or guanidinium compounds which can be converted into the desired process in a simple and flexible manner heterocyclic quaternary ammonium and / or guanidinium compound of high purity can be converted.
  • the desired anion can be introduced simply and flexibly in the case of the hydroxide anion by electrolysis and in the case of other anions by reacting the intermediate formed according to the invention with an inorganic or organic protic acid of the desired anion and the resulting reaction mixture to isolate the desired heterocyclic quaternary ammonium Compound and / or guanidinium compound easy to work up.
  • the particular advantage of using the carboxylate as the starting compound is the simple preparation of the carboxylates, the starting materials used for their preparation being not or only slightly toxic, technically readily available and inexpensive.
  • the use of the formates of the corresponding heterocyclic quaternary ammonium compounds and / or guanidinium compound is particularly advantageous, since these are very simply prepared by reacting the corresponding amines or imines with the inexpensive and very readily available methyl formate can be represented and the carbonates / bicarbonates formed in the subsequent reaction with the oxidizing agent by the an ⁇ closing reaction with the inorganic or organic protic acid readily decomposable and the reaction products of carbon dioxide and water are easily separated.
  • heterocyclic quaternary ammonium and guanidinium compounds which can be prepared from the intermediate products prepared by the process according to the invention are particularly suitable for use in the electronics industry because of their high purity.
  • Example 4 demonstrates that a methylation to the 1, 3-dimethylimidazolium formate is also possible by the in-situ representation of methyl formate.
  • the residue of the MTBA phase contained> 95% 1-ethylimidazole
  • the product phase contained 65% of 1-ethyl-3-methylimidazoium acetate and 35% of 1-ethylimidazole.
  • the remaining 1-ethylimidazole from the product phase was distilled off in vacuo (5 hPa abs), leaving 15.7 g (97%) of 1-ethyl-3-methylimidazolium acetate.

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Abstract

La présente invention concerne un procédé pour produire un produit intermédiaire contenant un cation ammonium et/ou guanidinium quaternaire hétérocyclique pour la synthèse de composés d'ammonium et/ou de guanidinium quaternaires hétérocycliques. Ce procédé consiste à oxyder des carboxylates d'ammonium et/ou de guanidinium quaternaires hétérocycliques avec un agent oxydant, en présence d'un métal issu du groupe 8 à 10 du système de tableau périodique, à une température allant de 0 à 250 °C et à une pression allant de 0,05 à 20 MPa abs.
PCT/EP2005/008605 2004-09-07 2005-08-09 Procede pour produire des composes ammonium et/ou guanidinium quaternaires heterocycliques WO2006027069A1 (fr)

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WO2008052863A3 (fr) * 2006-10-10 2008-09-18 Proionic Production Of Ionic S Procédé de mise en réaction de 2-carboxylates 1,3 hétéroaromatiques avec de l'eau
US8148518B2 (en) 2007-02-14 2012-04-03 Eastman Chemical Company Cellulose esters and their production in carboxylated ionic liquids
US9834516B2 (en) 2007-02-14 2017-12-05 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US10174129B2 (en) 2007-02-14 2019-01-08 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US7919631B2 (en) 2007-02-14 2011-04-05 Eastman Chemical Company Production of ionic liquids
US8153782B2 (en) 2007-02-14 2012-04-10 Eastman Chemical Company Reformation of ionic liquids
WO2009074535A2 (fr) * 2007-12-12 2009-06-18 Basf Se Procédé de production de sels d'imidazolium disubstitués
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