EP1957472A1 - Procede de production de liquides ioniques - Google Patents

Procede de production de liquides ioniques

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Publication number
EP1957472A1
EP1957472A1 EP06819480A EP06819480A EP1957472A1 EP 1957472 A1 EP1957472 A1 EP 1957472A1 EP 06819480 A EP06819480 A EP 06819480A EP 06819480 A EP06819480 A EP 06819480A EP 1957472 A1 EP1957472 A1 EP 1957472A1
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EP
European Patent Office
Prior art keywords
formula
group
methyl
amine
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06819480A
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German (de)
English (en)
Inventor
Kai Michael Exner
Klemens Massonne
Veit Stegmann
Matthias Maase
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BASF SE
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BASF SE
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Publication date
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Publication of EP1957472A1 publication Critical patent/EP1957472A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms

Definitions

  • the present invention describes a process for the preparation of ionic liquids (I) by reacting ionic liquids whose anion is a halide (II) with an acid (IM), wherein the generated hydrohalic acid is trapped with an amine and the resulting Ammonium halide can be separated.
  • Ionic liquids gain as a solvent, e.g. in the implementation of chemical reactions increasingly important.
  • P. Wasserscheidt in chemistry in our time 37, 52 (2003) gives an overview of the use of ionic liquids in multiphase catalysis.
  • other applications have also been proposed, such as e.g. their use in extraction or separation processes, as heat transfer, etc.
  • the purity of the ionic liquids used is important.
  • impurities can affect the course of chemical reactions.
  • P. Tyson et al Electrochemical Society Proceedings, Vol. 99-41, 161 have pointed out problems with the use of chloride-containing ionic liquids in liquid-phase hydrogenation and Suzuki coupling. Therefore, high demands must be placed on their purity in the production of ionic liquids.
  • ionic liquids are prepared by quaternization of the corresponding nitrogen or phosphorus compounds, alkyl halides generally being used as alkylating reagents.
  • the ionic liquids thus obtained can then be used themselves as solvents, etc.
  • these also serve as starting material for the preparation of ionic liquids whose anion is unlike a halide, by, by the so-called metathesis reaction, the anion is exchanged.
  • the problem frequently arises that the resulting ionic liquid still contains traces of halide, which, as described above, can lead to problems in use as a solvent, etc.
  • the object of the present invention is therefore to provide a technically usable process for the production of ionic liquids, in particular with a reduced halide content. It has been found that ionic liquids of the formula (I)
  • n 1, 2, 3 or 4;
  • n and [Y] n - have the abovementioned meaning
  • R 1 , R 2 and R 3 independently of one another represent hydrogen or C 1 -C 20 -alkyl which may optionally be substituted, the number of carbon atoms of the radicals R 1 , R 2 and R 3 together being at least 10;
  • the reaction of the ionic liquid of the formula II with the acid of the formula III is usually carried out at a temperature of -50 ° C. to 150 ° C., especially at -20 to 120 ° C., in particular at 0 to 100 ° C., preferably at 20 to 60 ° C performed.
  • Formula IM used in the stoichiometric ratio. It may also be beneficial to use one or the other component in excess on a case-by-case basis.
  • the amine of the formula V is used with respect to the acid of the formula IM in the stoichiometric ratio or in excess.
  • the amine is used in the stoichiometric ratio.
  • the amine of formula V is in excess, preferably in the range of 1, 5 to 2.5 times, in particular in the range of 1, 8 to 2.2 times the stoichiometric ratio used.
  • the amine in which the amine is continuously regenerated, it is also possible to use the amine in a deficit based on a snapshot.
  • Suitable solvents are those in which the ammonium halide of the formula VI dissolves or does not dissolve the ionic liquid of the formula I.
  • aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene or p-XyIoI, chlorinated aromatic hydrocarbons such as chlorobenzene, or cyclic hydrocarbons such as cyclohexane, suitable.
  • the amine of the formula V is selected such that it itself or the ammonium halide of the formula VI formed is not or only to a small extent dissolved in the ionic liquid of the formula I.
  • the solubility of the amine of the formula V or of the ammonium halide of the formula VI in the ionic liquid of the formula I is preferably in each case within a range of less than 10%, especially less than 5%, in particular less than 2% (expressed as the molar ratio between the amine or Ammonium halide and the ionic liquid). This is especially true in the case when working without solvent.
  • the amine of the formula V is selected so that it and the ammonium halide of the formula VI formed are more soluble in the solvent used than in the ionic liquid of the formula I.
  • the ionic liquid of the formula II, the acid of the formula III and the amine of the formula V are combined and the mixture is brought to the desired temperature.
  • One phase contains the ionic liquid of the formula I and the other phase is the formed ammonium halide of formula VI and optionally unreacted amine of formula V (if used in excess).
  • the amine of formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being able to be separated before the additional addition of amine and the ammonium halide of formula VI and, if appropriate, unreacted amine of the formula V being removed can be.
  • the ionic liquid of the formula II and the acid of the formula III are combined.
  • the amine of formula V is added and again after completion of the ammonium halide formation, the phases are separated.
  • One phase contains the ionic liquid of the formula I and the other phase the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous in this case to bring the initially introduced mixture of ionic liquid of the formula II and acid of the formula III to the desired temperature. But it is also possible the desired temperature after addition of the amine
  • the amine of the formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being separated before the further addition of amine and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V being removed ,
  • the ionic liquid of the formula II is initially charged and the acid of the formula III and the amine of the formula V are added in parallel. After completion of the reaction, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous to bring the ionic liquid of the formula II to the desired temperature. However, it is also possible to set the desired temperature after addition of the acid of the formula III and of the amine of the formula V.
  • phase separation and separated ammonium halide of formula VI and optionally unreacted amine of formula V may be advantageous to interrupt the dosing, perform a meantime phase separation and separated ammonium halide of formula VI and optionally unreacted amine of formula V (if this is used in excess) to separate.
  • the separation of the phases is carried out in the presence of a solvent.
  • the reaction mixtures which are described in the embodiments without solvent, are mixed with a solvent before the phase separation and then the phases are separated.
  • One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess).
  • the first phase separation is carried out in the absence of a solvent and then extracted with the solvent.
  • the representation of the ionic liquid of the formula I is carried out in the presence of a solvent.
  • the ionic liquid of the formula II, the acid of the formula IM, the amine of the formula V and the solvent are combined and brought the mixture to the desired temperature.
  • the phases are separated.
  • One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess).
  • the amine of the formula V is added to the reaction mixture in two or more portions, optionally in the solvent, the phases of the reaction mixture being separated before the additional addition of amine and the solvent and the ammonium halide formed Formula VI and possibly unreacted
  • Amine of formula V are separated.
  • the ionic liquid of the formula II and the acid of the formula III are combined.
  • the amine of formula V and the solvent is added and again after completion of the ammonium halide formation, the phases are separated.
  • One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous in this case to bring the initially introduced mixture of ionic liquid of the formula II and acid of the formula III to the desired temperature. But it is also possible to set the desired temperature after addition of the amine of formula V.
  • the amine of formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being separated before the further addition of amine and ammonium halide of formula VI and optionally unreacted amine of formula V removed become.
  • the ionic liquid of the formula II is initially charged and the acid of the formula III and the amine of the formula V are added in parallel.
  • the acid of the formula III and / or the amine of the formula V are metered into the solvent.
  • the phases are separated.
  • One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous to bring the ionic liquid of the formula II to the desired temperature. However, it is also possible to set the desired temperature after addition of the acid of the formula III and of the amine of the formula V.
  • the preparation of the ionic liquid of the formula I can be carried out batchwise, continuously or in a semi-batch mode. Adjusted accordingly, the separation of the resulting ammonium halide of the formula VI.
  • the liquid-liquid phase separation takes place, for example, by such techniques as described in Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2000 electronic release, chapter “Liquid-Liquid Extraction", in particular in subchapter 4 "Phase-Separation Equipment” , are described; preferably by decanting, phase separators, centrifuging or mixer-settler apparatuses, and particularly preferably by phase separators.
  • the recovery of the amines of formula V can be carried out, for example, by reacting the ammonium halide of the formula VI with a strong base, for example NaOH, KOH, Ca (OH) 2 , lime, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , or KHCO 3 , optionally in a solvent such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol or butanol or pentanol isomer mixtures or acetone releases.
  • a strong base for example NaOH, KOH, Ca (OH) 2 , lime, Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , or KHCO 3
  • a solvent such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol or butanol or pentanol isomer mixtures or
  • the strong base is used in a very concentrated solution, particularly preferably an aqueous solution, for example at least 5% by weight, preferably at least 10% by weight and more preferably at least 15% by weight. ig.
  • the amount of base usually chosen according to the stoichiometry. From case to case it may be beneficial to use a deficit or surplus. As a rule, equimolar is used.
  • the amine of the formula V if it forms a separate phase, can be separated off or else be removed from the mixture by distillation. If necessary, the amine of formula V can be separated by extraction with an extractant.
  • solvents such as aliphatic ethers, for example diethyl ether or methyl tert-butyl ether, cyclic ethers such as tetrahydrofuran, 1, 3-dioxane or 1, 4-dioxane, hydrocarbons such as pentane, hexane, cyclopopentane or cyclohexane, aromatic hydrocarbons such as Benzene, toluene, o-xylene, m-xylene or p-xylene, chlorinated hydrocarbons such as methylene chloride, chloroform or 1, 2-dichloroethane or chlorinated aromatic hydrocarbons such as chlorobenzene into consideration.
  • aliphatic ethers for example diethyl ether or methyl tert-butyl ether
  • cyclic ethers such as tetrahydrofuran, 1, 3-dioxane or 1, 4-dioxane
  • hydrocarbons such
  • the amine of formula V may be further purified before reuse, e.g. by distillation.
  • the amine of the formula V can be obtained by treating the solution of the ammonium halide of the formula VI with the abovementioned bases and the liberated amine of the formula V with the appropriate solution - Are extracted medium in the manner known to those skilled and the amine of the formula V by conventional methods, such as Distillation be recovered.
  • the purification can be carried out, for example, by washing once or several times, drying, filtering, stripping, distilling and / or rectifying.
  • Dried can e.g. by removal of water which may be present by means of distillation or azeotropic distillation with benzene, toluene, xylene, butanol or cyclohexane.
  • Filtration may be useful, for example, to remove precipitated solids or to eliminate any coloration, for example, by filtration over activated carbon, alumina, Celite or silica gel.
  • a distillation for example for the removal of optionally contained solvent, can preferably via a falling or thin film evaporator, optionally under vacuum, carried out, to improve the separation of a column can be placed.
  • the solvent used can, if necessary, be purified and reused if desired.
  • Another object of the present invention is thus a process for the preparation of ionic liquids of the formula I, comprising the following steps:
  • the ionic liquid of the formula II and the acid of the formula III are initially charged and the mixture is extracted continuously with the amine of the formula V, the free amine being regenerated continuously from the separated ammonium halide or the ammonium halide / amine and the Extraction process is fed back.
  • the amine can be used in molar excess with respect to the free acids.
  • the extraction can be assisted by a solvent or can also be carried out completely continuously, the amine phase and the phase with the ionic liquid being continuously conducted past one another.
  • the ionic liquids of the formula I and M, and the ammonium halide of the formula VI independently of one another have a melting point of less than 180 ° C. Furthermore, the melting point in a range from - 50 ° C to 150 ° C, preferably in a range of -20 ° C to 120 ° C and preferably below 100 0 C.
  • ionic liquids of the formula I are prepared which have a molecular weight of less than 1000 g / mol, preferably less than 500 g / mol, in particular less than 250 g / mol.
  • ionic liquids of the formula I are prepared in which the variables, taken alone and in combination, have the following meanings:
  • [A] + is a cation selected from the compounds of the formulas (Ia) to (Iv),
  • 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;
  • radicals R a to R 1 are independently hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 20 carbon atoms, wherein the radicals R a to R 1 , which in the abovementioned formulas (I) are bonded to a carbon atom (and not to a heteroatom), can additionally also stand for halogen or a functional group; or
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R a to R 1 can be present in the cases where they are bonded in the above formulas (I) to a carbon atom (and not to a heteroatom), also be bound directly via the heteroatom.
  • 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 C1-C4alkyloxy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • Is hydrogen, methyl or ethyl and m is preferably 0, 12 or 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9- Trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
  • N 1 N-Di-Cr to C 6 -alkyl-amino such as N, N-dimethylamino and N, N-diethylamino.
  • the radical R is unbranched and unsubstituted Cr to Cis-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, especially for methyl, ethyl, 1-butyl and 1-octyl and also for CH 3 O- (CH 2 CH 2 O) m -CH 2 CH 2 - and CH 3 CH 2 O- ( CH 2 CH 2 O) m -CH 2 CH 2 - with m equal to 0, 1 2 or 3.
  • the radical R is unbranched and unsubstituted Cr to Cis-alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexy
  • radicals R a to R 1 are preferably each independently
  • 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;
  • 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-Ci8- alkenyl;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;
  • C5-C12 cycloalkenyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; or
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d- to 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, 2-methyl-3-pent
  • 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, 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-methoxy-isopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles Ce- to Ci2-aryl is preferably phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl , Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-
  • 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 ⁇ n
  • Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5 Cyclohexadienyl or C m F 2 ( m -a) -3 (ib) H 2a-3b with m ⁇ 30,
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms
  • Heterocycle is preferably furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, 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-C 4 -AlkVl 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-die
  • radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R a to R 1 are particularly preferably each independently
  • N 1 N-di-Ci- to C 6 -alkyl-amino such as N, N-dimethylamino and N, N-diethylamino.
  • radicals R a to R 1 independently of one another are hydrogen or C 1 - to C 6 -alkyl, such as, for example, 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 and for CHaCKCHaCHaCVCHaCHa and CH 3 CH 2 O- (CH 2 CH 2 O) m -CH 2 CH 2 - with m being equal to 0, 1 2 or 3.
  • Very particularly preferred pyridinium ions (Ia) are those in which
  • radicals R a to R e are methyl, ethyl or chlorine and the remaining radicals R a to R e are hydrogen;
  • R c is dimethylamino and the remaining radicals R a , R b , R d and R e are hydrogen;
  • R b is carboxy or carboxamide and the remaining radicals R a , R b , R d and R e are hydrogen; or
  • R a and R b or R b and R c is 1, 4-buta-1, 3-dienylene and the remaining radicals R a , R b , R c and R d are hydrogen;
  • R a to R d are hydrogen
  • radicals R a to R e are methyl or ethyl and the remaining radicals R a to R e are hydrogen.
  • pyridinium ions (IVa) may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1
  • Very particularly preferred pyridazinium ions (Ib) are those in which
  • R a to R d are hydrogen
  • radicals R a to R d are methyl or ethyl and the remaining radicals R a to R d are hydrogen.
  • R a is hydrogen, methyl or ethyl and R b to R d are independently hydrogen or methyl; or R a is hydrogen, methyl or ethyl, R b and R d are methyl and R c is hydrogen.
  • R a is hydrogen, methyl or ethyl and R b to R d are independently hydrogen or methyl;
  • R a is hydrogen, methyl or ethyl, R b and R d are methyl and R c is hydrogen; • R a to R d are methyl; or
  • R a to R d are methyl.
  • Very particularly preferred imidazolium ions are those in which R a is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R b to R d are independently hydrogen, methyl or ethyl ,
  • Very particularly preferred pyrazolium ions are those in which
  • R a is hydrogen, methyl or ethyl and R b to R d are independently hydrogen or methyl.
  • Very particularly preferred pyrazolium ions (Ih) are those in which
  • R a to R d are independently hydrogen or methyl.
  • R a to R f are hydrogen or methyl.
  • R a to R f are hydrogen or methyl.
  • R a is hydrogen, methyl, ethyl or phenyl and R b to R f are independently hydrogen or methyl.
  • R a and R b are independently hydrogen, methyl, ethyl or phenyl and R c to R d are independently hydrogen or methyl.
  • R a and R b are independently hydrogen, methyl, ethyl, 1-butyl or phenyl
  • R c and R d are independently hydrogen, methyl or ethyl
  • R e and R f are independently hydrogen or methyl.
  • R a and R b are independently hydrogen, methyl or ethyl and R c to R f are independently hydrogen or methyl.
  • R a to R c are independently hydrogen, methyl or ethyl and R d to R f are independently hydrogen or methyl.
  • R a is hydrogen, methyl, ethyl or phenyl
  • R b and R c are independently hydrogen or methyl
  • R a is hydrogen, methyl or ethyl and R b and R c are independently hydrogen or methyl, or R b and R c together are 1, 4-buta-1, 3-dienylene.
  • R a is hydrogen, methyl, ethyl or phenyl and R b to R 1 are independently hydrogen or methyl.
  • R a and R d are independently hydrogen, methyl, ethyl or phenyl and R b and R c and R e to R h are independently hydrogen or methyl.
  • R a to R c independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the pyridine ions, pyrazolinium, pyrazolium ions, and imidazolinium and imidazolium ions are preferable.
  • R A # and R B # are each independently hydrogen, C 1 -C 30 -alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 - Ci8-alkyl, C6-Ci 4 -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 a or several oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups can form interrupted ring, wherein the radicals mentioned in each case additionally by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles len may be substituted.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C1-C18 alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl , Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl,
  • C2-Cis-alkyl for example, 5-hydroxy-3 oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1 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 1-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-t ⁇ oxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.
  • radicals can be taken together, for example, as fused radical 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, where C 1 to C 4 -Alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • C6-C4-aryl substituted by functional groups are, for example, phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaph
  • 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, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl, dimethoxypyridyl , Diflorurpyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates, in particular selected from the group of sulfates, the group of carboxylic acids and the group of sulfonates or NO3 " .
  • SO 4 2 " 'HSO 4 " are SO 4 2 " 'HSO 4 " ; Ci-C 4 alkyl-COO ', particularly acetate and propionate, preferably acetate; Ci-C 4 haloalkyl-COO', in particular trifluoroacetate, or perfluoropropionate, preferably trifluoroacetate; C 1 -C 4 -alkyl-SO 3 " , preferably methylsulfonate, ethylsulfonate or butylsulfonate, preferably methylsulfonate; or C 1 -C 4 -haloalkyl-SO 3 " , preferably trifluoromethylsulfonate or perfluoroethylsulfonate, preferably trifluoromethylsulfonate.
  • ionic liquids of the formula II are used in which the variables [A] + as defined for the ionic liquids of the formula I and X 'is chloride or bromide, preferably represents CHIO chloride.
  • the preferences for [A ] + apply accordingly.
  • amines of the formula V are used in which the radicals
  • R 1 to R 3 are independently of each other Ci-Cis-alkyl
  • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is d-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • One of the radicals R 1 to R 3 is hydrogen and the other two radicals independently of one another are C 1 -C 6 -alkyl;
  • R 2 and R 3 together is at least 10 but not more than 30.

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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de production de liquides ioniques [A]+n[Y]n- par mise en réaction de liquides ioniques, dont l'anion est un halogénure [A]+[X]-, avec un acide H+n[Y]n-, l'acide halohydrique formé étant piégé avec une amine et l'halogénure d'ammonium ainsi formé pouvant être séparé.
EP06819480A 2005-11-21 2006-11-15 Procede de production de liquides ioniques Withdrawn EP1957472A1 (fr)

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DE102005055815A DE102005055815A1 (de) 2005-11-21 2005-11-21 Verfahren zur Herstellung von ionischen Flüssigkeiten
PCT/EP2006/068465 WO2007057403A1 (fr) 2005-11-21 2006-11-15 Procede de production de liquides ioniques

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KR20080079271A (ko) 2008-08-29
CN101309914A (zh) 2008-11-19

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