EP2229365A1 - Procédé d'amélioration de la stabilité à l'hydrolyse de liquides ioniques - Google Patents

Procédé d'amélioration de la stabilité à l'hydrolyse de liquides ioniques

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Publication number
EP2229365A1
EP2229365A1 EP08863060A EP08863060A EP2229365A1 EP 2229365 A1 EP2229365 A1 EP 2229365A1 EP 08863060 A EP08863060 A EP 08863060A EP 08863060 A EP08863060 A EP 08863060A EP 2229365 A1 EP2229365 A1 EP 2229365A1
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EP
European Patent Office
Prior art keywords
alkyl
compounds
methyl
ions
butyl
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EP08863060A
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German (de)
English (en)
Inventor
Georg Degen
Veit Stegmann
Klaus Ebel
Klemens Massonne
Laszlo Szarvas
Uwe Vagt
Matthias Maase
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BASF SE
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BASF SE
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Priority to EP08863060A priority Critical patent/EP2229365A1/fr
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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
    • 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
    • C07D233/58—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • 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 improving the stability to hydrolysis of ionic liquids (IL), in which at least one tertiary amine or a quaternary ammonium compound other than the ionic liquid (IL) is added to an ionic liquid (IL).
  • IL ionic liquids
  • Ionic liquids are characterized by a number of interesting properties. They are thermally stable, non-flammable, have a very low, barely measurable vapor pressure, are mostly environmentally friendly, have a large liquid range and very good dissolving properties for numerous substances. In addition, due to their purely ionic structure, ionic liquids also have interesting electrochemical properties, such as electrical conductivity, which is often accompanied by high electrochemical stability. By varying the side chains of the cation and by selecting suitable anions, for example, the solubility in water or organic solvents or the melting point can be determined largely freely.
  • the molecular diversity of ionic liquids allows their use in a variety of technical applications. Examples include the extraction (eg extraction and purification of technical gases, isolation and purification of hydrocarbons in petrochemistry and in organic synthesis or the removal of toxic substances from waste water), sorption, drying, purification and storage of Gases (eg in sorption air conditioners), use as a solvent (eg for organic synthesis), immobilization of catalysts, use as a lubricant, hydraulic fluid or antistatic additive, use as an electrolyte (eg.
  • anions are also frequently used in the ionic liquids subject to hydrolysis under storage and / or use conditions.
  • This hydrolysis can already to a small extent substantially influence the chemical and physical properties of the ionic liquids.
  • An example of this is the change in the melting point of the ionic Liquid or the formation of corrosive hydrolysis products called.
  • An exchange of (partially) hydrolyzed ionic liquids is therefore often mandatory.
  • WO 03022812 describes ionic liquids which have as anion a compound of the formula [R-SO 4 ] in which R is a linear or branched, saturated or unsaturated, aliphatic or alicyclic, functionalized or unsubstituted alkyl radical having 3 to 36 carbon atoms
  • R is a linear or branched, saturated or unsaturated, aliphatic or alicyclic, functionalized or unsubstituted alkyl radical having 3 to 36 carbon atoms
  • the ionic liquids used should be thermally disposable, biodegradable and accessible with little effort without the formation of problematic combustion gases.
  • the present invention therefore provides a process for improving the hydrolytic stability of an ionic liquid (IL), in which at least one tertiary amine and / or a quaternary ammonium compound other than the ionic liquid (IL) are added to the ionic liquid (IL).
  • IL ionic liquid
  • ionic liquids refer to organic salts which are already liquid at temperatures below 180 ° C.
  • the ionic liquids have a melting point of less than 180 0 C.
  • the melting point in a range of -50 0 C to 150 0 C, more preferably in the range of -20 0 C to 120 0 C and most preferably below 100 0 C.
  • Ionic liquids already in liquid state at room temperature are described, for example, by KN Marsh et al., Fluid Phase Equilibria 219 (2004), 93-98 and JG Huddieston et al., Green Chemistry 2001, 3, 156-164.
  • Cations and anions are present in the ionic liquid.
  • a proton or an alkyl radical can be transferred to the anion, resulting in two neutral molecules.
  • alkyl includes straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, in particular C 1 -C -alkyl, and very particularly preferably C 1 -C 12 -alkyl.
  • alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 1-methyl-butyl, tert-pentyl, neopentyl, n-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl,
  • alkyl also encompasses alkyl radicals whose carbon chain is replaced by one or more nonadjacent heteroatoms or heteroatom-containing groups which are preferably selected from -O-, -S-, -NR E -, -PR E -, -SiR E R EE and / or -SO 2 - may be interrupted.
  • R E is preferably H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • R EE is preferably H, alkyl, cycloalkyl, heterocycloalkyl or aryl.
  • alkyl radicals whose carbon chains may be interrupted by one or two nonadjacent heteroatoms -O- are the following:
  • alkyl radicals whose carbon chains may be interrupted by three or more than three nonadjacent heteroatoms -O- are also oligo- and poly- oxyalkylenes, ie compounds having repeating units, which are preferably selected from (CH 2 CH 2 O) Xi, (CH (CH 3 ) CH 2 O) X 2 and ((CH 2 ) 4 O) ⁇ 3, where x1, x2 and x3 independently represent an integer from 0 to 100, preferably from 0 to 80, with the proviso that the sum of x1, x2 and x3 is at least 3.
  • x1, x2 and x3 independently of one another represent an integer from 3 to 100, preferably from 3 to 80.
  • x1, x2 and x3 preferably stands for an integer from 3 to 300, in particular 3 to 100.
  • polyoxyalkylenes which have two or three different repeating units, the order is arbitrary, ie they may be random, alternating or block repeating units. Examples are 3,6,9-trioxadecyl,
  • alkyl radicals whose carbon chains by one or more, for. B. 1, 2, 3, 4 or more than 4, non-adjacent heteroatoms -S- may be interrupted are the following:
  • alkyl radicals whose carbon chains are interrupted by one or two non-adjacent heteroatom-containing groups -NR E - are the following:
  • alkyl radicals whose carbon chains may be interrupted by three or more than three non-adjacent heteroatom-containing groups -NR E - are also oligo- and polyalkyleneimines.
  • the above for the polyoxyalkylenes applies analogously to polyalkyleneimines, wherein the oxygen atom is replaced in each case by a group NR E , wherein R a is preferably H or CrC 4 -AlkVl.
  • Examples of these are 9-methyl-3,6,9-triazadecyl, 3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl, 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl and like.
  • alkyl radicals whose carbon chains by one or more, for. B. 1 or 2 non-adjacent groups -SO2- are interrupted, are 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-Butylsulfonyl- ethyl, 2-methylsulfonylpropyl, 3-methylsulfonylpropyl, 2-Ethylsulfonylpropyl, 3rd Ethylsulfonylpropyl, 2-propylsulfonylpropyl, 3-propylsulfonylpropyl, 2-butylsulfonylpropyl, 3-butylsulfonylpropyl, 2-methylsulfonylbutyl, 4-methylsulfonylbutyl, 2-ethylsulf
  • alkyl also includes substituted alkyl radicals.
  • Cycloalkyl, cycloalkyloxy, polycycloalkyl, polycycloalkyloxy, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.
  • alkyl also apply in principle to the alkyl moieties in alkoxy, alkylamino, dialkylamino, alkylthio (alkylsulfanyl), alkylsulfinyl, alkylsulfonyl, etc.
  • Suitable substituted alkyl radicals are the following:
  • Alkyl substituted by carboxy such as. Carboxymethyl, 2-carboxyethyl,
  • Alkyl which is substituted by SO 3 H such as. Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 7-sulfoheptyl, 8-sulfooctyl, 9-sulfononyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;
  • Alkyl which is substituted by carboxylate such as.
  • alkoxycarbonylalkyl e.g. Methoxycarbonylmethyl, ethoxycarbonylmethyl, n-butoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-methoxycarbonylpropyl, 2-ethoxycarbonylpropyl, 2- (n-butoxycarbonyl) propyl, 2- (4-n-butoxycarbonyl) propyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 3- (n-butoxycarbonyl) propyl, 3- (4-n-butoxycarbonyl) propyl, aminocarbonylalkyl, e.g.
  • Alkyl substituted by hydroxy such as. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 2-hydroxy-2,2-dimethylethyl,
  • Alkyl which is substituted by amino such as. 2-aminoethyl, 2-aminopropyl,
  • Alkyl which is substituted by cyano such as. 2-cyanoethyl, 3-cyanopropyl, 3-cyanobutyl and 4-cyanobutyl;
  • Alkyl which is substituted by nitro such as. 2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl and the like;
  • Alkyl which is substituted by amino such as. 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl and the like;
  • Alkyl which is substituted by S (thioxo), such as. 2-thioxopropyl, 2-thioxobutyl, 3-thioxobutyl, 1-methyl-2-thioxopropyl, 2-thioxopentyl, 3-thioxopentyl, 1-methyl-2-thioxobutyl, 1-methyl-3-thioxobutyl, 2-thioxohexyl, 3-thioxohexyl, 4-thioxohexyl, 2-thioxoheptyl, 3-thioxoheptyl, 4-thioxoheptyl, 4-thioxoheptyl and the like;
  • Alkyl which is substituted by NR E -, preferably those in which R E is H or Ci-C4-alkyl, such as. 2-iminopropyl, 2-iminopropyl, 2-iminopropyl, 2-iminopropyl, 2-iminopropyl, 2-iminopropyl, 2-iminobutyl, 1-methyl-2-iminobutyl, 1-methyl-3-imino-butyl, 2- isohexyl, 3-iminohexyl, 4-iminohexyl, 2-iminoheptyl, 3-iminoheptyl, 4-iminoheptyl, 4-iminoheptyl, 2-methyliminopropyl, 2-methyliminobutyl, 3-methyliminobutyl, 1-methyl-2-methyliminopropyl, 2-methyliminopentyl, 3-methylimino-pentyl, 1-methyl-2-methyliminobutyl, 1-methyl-3-methyli
  • Alkyl substituted by aryl has at least one unsubstituted or substituted aryl group as defined below. Suitable substituents on the aryl group are the following.
  • the alkyl group in "arylalkyl” may carry at least one further substituent as defined above and / or by one or more nonadjacent heteroatoms or heteroatom-containing groups which are selected from -O-, -S-, -NR E -, and / or -SO2- be interrupted.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C 4 -alkyl, z.
  • benzyl 1-phenethyl, 2-phenethyl, 1-phen-prop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut 1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2 -yl, 1- (phen-meth) -eth-1-yl, 1- (phen-methyl) -1- (methyl) -eth-1-yl or - (phen-methyl) -1- (methyl) -prop-1-yl; preferably for benzyl and 2-phenethyl.
  • Alkoxy is an alkyl group bonded via an oxygen atom.
  • alkoxy are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 , 1-Dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy , 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1 -Ethyl-1-methylpropoxy or 1-ethyl-2
  • Alkylthio (alkylsulfanyl) is an alkyl group bonded via a sulfur atom. Examples of alkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio.
  • alkenyl in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, may carry one or more double bonds (eg 1, 2, 3, 4 or more than 4). Preference is given to C 2 -Cis, particularly preferably C 2 -C 2 -alkenyl groups.
  • alkenyl also includes substituted alkenyl groups which may carry one or more (eg, 1, 2, 3, 4, 5 or more than 5) substituents. Suitable substituents are, for. B.
  • alkenyl also includes alkenyl radicals whose carbon chain may be interrupted by one or more non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from -O-, -S-, -NR E - and / or -SO 2 - ,
  • Alkenyl is then for example ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, penta-1,3-di-en-1-yl, hexa-1, 4-dien-1-yl, hexa-1, 4-dien-3-yl, hexa-1, 4-dien-6-yl, hexa-1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, hexa-1, 5 dien-4-yl, hepta-1, 4-dien-1-yl, Hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-
  • cycloalkyl in the context of the present invention comprises unsubstituted as well as substituted monocyclic saturated hydrocarbon groups having generally 3 to 12 carbon ring members, preferably C3-C12-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl , Cyclodecyl, cycloundecyl or cyclododecyl, in particular C5-Ci2-cycloalkyl.
  • C3-C12-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl , Cyclodecyl, cycloundecyl or cyclododecyl, in particular C5-C
  • Suitable substituents are as a rule selected for alkyl, the substituents mentioned above for the alkyl groups, alkoxy and also alkylthio.
  • Substituted cycloalkyl groups may have one or more (for example 1, 2, 3, 4, 5 or more than 5) substituents, where in the case of halogen the cycloalkyl radical is partially or completely substituted by halogen.
  • cycloalkyl groups are cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, chloropentyl, dichloropentyl, dimethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, chlorhexyl, dimethylcyclohexyl, diethylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, Diethoxycyclohexyl, butoxycyclohexyl, methylthio cyclohexyl, chlorocyclohexyl
  • Cycloalkyloxy is an oxygen-bonded cycloalkyl group as defined above.
  • cycloalkenyl includes unsubstituted and substituted, mono- or diunsaturated hydrocarbon groups having from 3 to 5, to 8, to 12, preferably 5 to 12 carbon ring members, such as cyclopent-1-en-1-yl, cyclopent-2-ene 1-yl, cyclopent-3-en-1-yl, cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, Cyclohexa-2,5-dien-1-yl and the like. Suitable substituents are those previously mentioned for cycloalkyl.
  • Cycloalkenyloxy is an oxygen-bonded cycloalkenyl group as defined above.
  • polycyclyl in the context of the present invention broadly includes compounds containing at least two rings, regardless of how these rings are linked. These may be carbocyclic and / or heterocyclic rings.
  • the rings can be saturated or unsaturated.
  • the rings can be linked via single or double bond ("polynuclear compounds"), linked by annulation (“fused ring systems") or bridged (“bridged ring systems", “cage compounds”).
  • Preferred polycyclic compounds are bridged ring systems and fused ring systems.
  • Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds by annulation. Condensed ring systems consist of two, three or more than three rings.
  • Each ring has one or two atoms in common with each neighboring ring, and a peri-annulation in which one carbon atom belongs to more than two rings.
  • Preferred among the fused ring systems are ortho-fused ring systems.
  • Bridged ring systems in the context of the present invention include those which do not belong to the polynuclear ring systems and not to the fused ring systems and in which at least two ring atoms belong to at least two different rings.
  • bicycloalkyl encompasses bicyclic hydrocarbon radicals having preferably 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] heptane 7-yl, bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like.
  • bicycloalkenyl includes monounsaturated, bicyclic hydrocarbon radicals preferably having 5 to 10 carbon atoms, such as bicyclo [2.2.1] hept-2-en-1-yl.
  • aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • Aryl is usually for hydrocarbon radicals having 6 to 10, to 14, to 18, preferably 6 to 10 carbon ring members.
  • Aryl is preferably unsubstituted or substituted phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and particularly preferably phenyl or naphthyl.
  • Substituted aryls may vary depending on the number and size of their ring systems or more (eg, 1, 2, 3, 4, 5, or more than 5) substituents.
  • Aryl is particularly preferably phenyl, which in the case of a substitution can generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
  • Aryl which carries one or more radicals is, for example, 2-, 3- and
  • B 2,4,6-trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, 2-, 3- and 4-cyanophenyl; 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl; 4-dimethylaminophenyl; 4-acetylphenyl; Methoxyethylphenyl, ethoxymethylphenyl; Methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl; methylnaphthyl; Isopropylnaphthyl or ethoxynaphthyl.
  • substituted aryl wherein two substituents attached to adjacent carbon atoms of the aryl ring form a fused ring or fused ring system are indenyl and fluorenyl.
  • aryloxy in the context of the present invention stands for aryl bound via an oxygen atom.
  • arylthio in the context of the present invention stands for aryl bound via a sulfur atom.
  • heterocycloalkyl in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups with im Generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms are replaced by heteroatoms selected from oxygen, nitrogen, sulfur and a group -NR E - and which is unsubstituted or with one or more , For example, 1, 2, 3, 4, 5 or 6, d-C ⁇ -alkyl groups is substituted.
  • heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothienyl, dihydrothienyl, tetrahydrofuranyl, dihydrofuranyl, Tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl called.
  • Nitrogen-containing heterocycloalkyl can in principle be bound both via a carbon atom and via a nitrogen atom.
  • heteroaryl in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups having generally 5 to 14 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms one, two, three or four heteroatoms selected from O, N, -NR E - and S are substituted, such as furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzofuranyl, benzthiazolyl, benzimidazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl , Pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotri
  • 5- to 7-membered nitrogen-containing heterocycloalkyl or heteroaryl radicals which optionally contain further heteroatoms are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, Piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl, which may be unsubstituted or substituted as mentioned above.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • these include z.
  • esters with Ci-C4-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • acyl denotes alkanoyl, hetaroyl or aroyl groups having generally 1 to 11, preferably 2 to 8, carbon atoms.
  • the radicals E 1 and E 2 , E 3 and E 4 , E 5 and E 6 are independently selected from H, alkyl, cycloalkyl and aryl.
  • the groups NE 1 E 2 , NE 3 E 4 and NE 5 E 6 are preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n -butylamino, N, N-di-tert-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Suitable ionic liquids are selected in the context of the present invention from salts of the general formula (I)
  • [A] + is a quaternary ammonium cation and (1 / n) * [Y] n - is an anion equivalent of an n-charged anion, where n is an integer from 1 to 3.
  • Suitable compounds which are suitable for forming the cation [A] + of ionic liquids are e.g. B. in DE 102 02 838 A1. These compounds preferably contain at least one nitrogen atom, particularly preferably 1 to 10 nitrogen atoms, in particular 1 to 5 nitrogen atoms, very particularly preferably 1 to 3 nitrogen atoms and especially 1 or 2 nitrogen atoms. The latter nitrogen compounds may contain further heteroatoms such as oxygen, sulfur or phosphorus atoms.
  • Nitrogen atoms are, for example, suitable carriers of the positive charge in the cation 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 protonation of the nitrogen atom. Depending on the protonation reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion already during the 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.
  • a halide ion replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt to precipitate the metal halide formed, via an ion exchanger, or by displacing the halide ion with a strong acid (to release the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 1 12, pp. 3926-3945 and the literature cited therein. Preferred cations of the ionic liquids are those compounds which have a molar mass of less than 1000 g / mol, very particularly preferably less than 600 g / mol and in particular less than 400 g / mol.
  • Preferred cations of the ionic liquids are furthermore 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 optionally an oxygen or sulfur atom.
  • Particular preference is given to those compounds which have at least one contain five- to six-membered heterocycle having one, two or three nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms.
  • aromatic heterocycles are furthermore 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 optionally an oxygen or sulfur atom.
  • the hydrolysis stability of an ionic liquid (IL) which has a heterocyclic cation will be increased.
  • heterocyclic cation in the context of the present invention encompasses both “heteroaromatic” cations and “partially or completely saturated heterocyclic cations”.
  • heteroaromatic cation includes cations whose structure can be derived, for example, by quaternization of a ring nitrogen atom of a "hetaryl” compound as defined above.
  • Examples of five- or six-membered heteroaromatic cations are pyrazolium, oxazolium, isoxazolium, thiazolium, isothiazolium, imidazolium, 1, 2,4-oxadiazolium, 1, 2,4-thiadiazolium, 1, 3,4-oxadiazolium, 1, 3, 4-thiadiazolium, pyrrolium, 1, 2,3-triazolium, 1, 2,4-triazolium, pyridinium, pyridazinium, pyrimidinium, 2-pyrazinium, 1, 3,5-triazinium and 1, 2,4-triazinium.
  • heterocyclic cation includes cations whose structure can be deduced, for example, by quaternization of a ring nitrogen atom of a "heterocycloalkyl" compound as defined above.
  • examples of five- or six-membered saturated or partially unsaturated heterocyclic cations are pyrrolidinium, pyrazolidinium, oxazolidinium, isoxazolidinium,
  • the ionic liquid IL used according to the invention preferably has at least one cation which is selected from the compounds of the formulas (IV.a) to (IV.v) shown below,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 attached to a ring carbon independently of one another are H, a sulfo group, COOH, carboxylate, sulfonate, acyl , Alkoxycarbonyl, cyano, halogen, hydroxyl, SH, nitro, NE 1 E 2 , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy or Heteroaryl, where E 1 and E 2, independently of one another, are H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 which are bonded to a ring hetero atom, for H, SO 3 H, NE 1 E 2 , alkyl, alkoxy , Alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl, where E 1 and E 2 are each independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or
  • two adjacent radicals R 1 to R 9 together with the ring atoms to which they are attached may stand for at least one fused, saturated, unsaturated or aromatic ring or a ring system having 1 to 30 carbon atoms, the ring or the ring system 1 to 5 non-adjacent heteroatoms or teroatom restroom groups may have and wherein the ring or the ring system may be unsubstituted or substituted,
  • R 1 and R 3 or R 3 and R 5 may also together be the bond moiety of a double bond between the ring atoms which carry these radicals,
  • radicals carboxylate, sulfonate, acyl, alkoxycarbonyl, halogen, NE 1 E 2 , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy, heterocycloalkyl , Aryl, aryloxy or heteroaryl is at the beginning made statements to the full extent.
  • Radicals R 1 to R 9 which are bonded to a carbon atom in the abovementioned formulas (IV) and have a heteroatom or a heteroatom-containing group can also be bonded to the carbon atom directly via a heteroatom.
  • Two adjacent radicals R 1 to R 9, together with the ring atoms to which they are attached, form at least one fused, saturated, unsaturated or aromatic ring or a ring system having from 1 to 30 carbon atoms, the ring or the ring system not being adjacent to 1 to 5 Heteroatoms or heteroatom-containing groups may have and wherein the ring or the ring system may be unsubstituted or substituted, these radicals may together as fused building blocks 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-buta-1, 3-dienylene, 1-az-1, 4-buta-1,
  • the radical R in the compounds of the formulas IV.a to IV.v preferably stands for
  • C 1 -C 18 -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-d
  • Ci-Cis-alkyl especially hydroxy-Ci-Cis-alkyl, such as. 2-hydroxyethyl or 6-hydroxyhexyl; Phenyl-Ci-cis-alkyl, such as. Benzyl,
  • Cyano-Ci-Cis-alkyl such as.
  • Ci-C ⁇ -alkoxy-Ci-Cis-alkyl such as.
  • C 1 -C 6 -fluoroalkyl such as trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl
  • Sulfo-Ci-Cis-alkyl such as.
  • Hydroxyethyloxyalkyl radicals of oligo- and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and their oligomers having 2 to 100 units and an H or a d-Cs-alkyl as an end group, such as R A O- (CH R B -CH 2 -O) n -CH R B -CH 2 - with R A and R B preferably H, methyl or ethyl and n preferably 0 to 3, in particular 3-oxa-butyl, 3-oxa-pentyl, 3,6-dioxa-heptyl, 3,6-dioxa-octyl, 3,6,9-trioxa-decyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxa-tridecyl and 3,6,9,12-tetraoxa tetradecyl; and
  • C2-C6 alkenyl such as vinyl or propenyl.
  • the radical R particularly preferably stands for linear C 1 -C 6 -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, most preferably methyl, ethyl, 1-butyl and 1-octyl and CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) m -CH 2 CH 2 -, wherein m is O to 3.
  • m is O to 3.
  • a to IV.v are each independently H, halogen, hydroxyl, alkoxy, alkylthio, carboxyl, -COOH, sulfonate, CN, NO 2 , acyl, alkoxycarbonyl, NE 1 E 2 , in which E 1 and E 2 have one of the meanings given above,
  • C 1 -C 6 -alkyl which is unsubstituted or substituted and / or which may be interrupted by at least one heteroatom or a heteroatom-containing group
  • C 2 -C 18 -alkenyl which is unsubstituted or substituted and / or may be interrupted by at least one heteroatom
  • C ⁇ -Cio-aryl which is unsubstituted or substituted
  • Heterocycloalkyl having 5 or 6 ring atoms, wherein the ring next to Kohlenstoffringglie- has 1, 2 or 3 heteroatoms or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR E , and which is unsubstituted or substituted, or
  • Heteroaryl having 5 to 10 ring atoms, wherein the ring next to carbon ring members 1, 2 or 3 hetero atoms or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR E , and which is unsubstituted or substituted.
  • R 1 to R 9 in the compounds of the formula IV. A to IV.v are alkoxy, R 1 to R 9 are preferably methoxy or ethoxy or
  • R A O- (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O-, wherein R A and R B are preferably H, methyl or ethyl and n is preferably 0 to 3 ,
  • a to IV.v are acyl, these are preferably selected from formyl and C 1 -C 4 -alkylcarbonyl, in particular formyl or acetyl.
  • Ci-Cis-alkyl these are preferably selected from unsubstituted Ci-Cis-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-9-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,
  • C 1 -C 6 -alkylamino-C 1 -C 8 -alkyl such as 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl;
  • Di- (C 1 -C 6 -alkyl) C 1 -C 8 -alkyl such as 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl;
  • Cyano-Ci-Cis-alkyl such as 2-cyanoethyl, 2-cyanopropyl;
  • C 1 -C 10 -alkoxy-C 1 -C 6 -alkyl such as methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-methoxyisopropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl , 4-ethoxybutyl, 6-ethoxyhexyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 7-methoxy 4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 9-methoxy-5-oxa-nonyl, 9-methoxy
  • a to IV.v are C 2 -C alkenyl, they are preferably selected from C 2 -C 6 alkenyl, such as vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C2-cis-alkenyl which is partially or completely substituted by fluorine.
  • R 1 to R 9 in the compounds of the formula IV. A to IV.v are C ⁇ -Cio-aryl
  • R 1 to R 9 are preferably phenyl or naphthyl, where phenyl or naphthyl is unsubstituted or one or two -, tri- or tetra-substituted, where the substituents independently of one another by halogen, Ci-Cis-alkyl, Ci-C ⁇ -alkoxy, Ci-Ce-alkylsulfanyl, Ci-C 6 -alkoxy-Ci-C 6 -alkyl, Ci -C 6 alkylcarbonyl, amino, Ci-C ⁇ -alkylamino, di- (Ci-C6-dialkyl) amino and nitro are selected, such as phenyl, methylphenyl (ToIyI), dimethylphenyl (XyIyI), such as.
  • 2,6-dimethylphenyl trimethylphenyl
  • B 2,4,6-trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl, Difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, 2,6-dichlorophenyl, 4-bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 2,6-dimethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6- Dinitrophenyl, 4-dimethylaminophenyl, 4-acet
  • a to IV.v are C 5 -C 12 -cycloalkyl
  • R 1 to R 9 are preferably unsubstituted.
  • Cycloalkyl such as cyclopentyl or cyclohexyl;
  • C 5 -C 12 -cycloalkyl which is monosubstituted or disubstituted, wherein the substituents are independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylsulfanyl or chlorine, eg. Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl; C5-C12-cycloalkyl which is completely or completely fluorinated.
  • R 1 to R 9 in the compounds of the formula IV. A to IV.v are polycyclyl
  • R 1 to R 9 are preferably C 5 -C 12 -cycloalkyl, such as norbornyl or C 5 -C 12 -cyclo-alkenyl, such as norbornenyl.
  • R 1 to R 9 in the compounds of the formula IV.a to IV.v are C 5 -C 12 -cycloalkenyl
  • R 1 to R 9 are preferably unsubstituted.
  • Cycloalkenyl such as cyclopent-2-en-1 -yl, cyclopent-3-en-i-yl, cyclohex-2-en-1-yl, cyclohex-1-en-1-yl, cyclohexa-2,5-dien-1-yl or partially or completely fluorinated cycloalkenyl.
  • R 1 to R 9 in the compounds of the formula IV.a to IV.v are heterocycloalkyl having 5 or 6 ring atoms
  • R 1 to R 9 are preferably 1,3-dioxolan-2-yl, 1, 3 Dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl.
  • R 1 to R 9 in the compounds of the formula IV.a to IV.v are heteroaryl
  • R 1 to R 9 are preferably furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl, benzthiazolyl.
  • hetaryl carries 1, 2 or 3 substituents, which are selected independently of one another from C 1 -C 6 -alkyl,
  • C 1 -C 6 -alkoxy and halogen for example dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • the radicals R 1 to R 9 in the compounds of the formula IV.a to IV.v independently of one another are hydrogen; unbranched or branched, unsubstituted or monosubstituted to poly, hydroxyl, halogen, phenyl, cyano, Ci-C ⁇ -alkoxycarbonyl and / or sulfo C 1 -C 18 -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.
  • R A O- (CHR B -CH 2 -O) n -CHR B -CH 2 - OdOR R A O- (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O-, in which R A and R B are preferably H, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,
  • N, N-di-C 1 -C 6 -alkylamino such as N, N-dimethylamino and N, N-diethylamino.
  • the radicals R 1 to R 9 are each independently hydrogen; Ci-Ci ⁇ -alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl; phenyl; 2-hydroxyethyl; 2-cyanoethyl; 2- (alkoxycarbonyl) ethyl such as 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl or 2- (n-butoxycarbonyl) ethyl;
  • N, N- (C 1 -C 4 -dialkyl) amino such as N, N-dimethylamino or N, N-diethylamino
  • Chlorine and for radicals of oligoalkylene glycol such as CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - or CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 -, wherein n stands for 0 to 3
  • Preferred pyridinium ions are compounds of the formula IV.
  • A 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 H.
  • Further preferred pyridinium ions are compounds of the formula IV.
  • Further preferred pyridinium ions are compounds of the formula IV.
  • pyridinium ions are compounds of the formula IV.
  • A in which R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are H.
  • pyridinium ions are compounds of the formula IV.a in which R 1 and R 2 or R 2 and R 3 together are 1,4-buta-1,3-dienylene and the remaining radicals R 1 , R 2 , R 4 and R 5 stands for H.
  • pyridinium ions are pyridinium, 2-methylpyridinium, 2-ethylpyridinium, 5-ethyl-2-methylpyridinium and 2-methyl-3-ethylpyridinium, and 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- ( 1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium,
  • Preferred pyridazinium ions are compounds of the formula IV. B, in which the radicals R 1 to R 4 are H, or in which one of the radicals R 1 to R 4 is methyl or ethyl and the remaining radicals R 1 to R 4 are H.
  • Preferred pyrimidinium ions are compounds of the formula IV.c in which R 1 is H, methyl or ethyl and R 2 to R 4 independently of one another are H or methyl, or in which R 1 is H, methyl or ethyl, R 2 and R 4 is methyl and R 3 is H.
  • Preferred pyrazinium ions are compounds of the formula IV.
  • D in which R 1 is H, methyl or ethyl and R 2 to R 4 are each independently H or methyl, or in which R 1 is H, methyl or ethyl and R 2 and R 4 is methyl and R 3 is H or wherein R 1 to R 4 are methyl or wherein R 1 to R 4 are H.
  • Preferred imidazolium ions are compounds of the formula IV.e, in which R 1 is H, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are independently H, methyl or ethyl.
  • imidazolium ions of the formula IV.e are 1-methylimidazolium,
  • Preferred pyrazolium ions are compounds of the formulas IV.f, IV. G or IV. G ', wherein R 1 is H, methyl or ethyl and R 2 to R 4 independently of one another are H or methyl.
  • pyrazolium ions are compounds of the formula IV.h in which R 1 to R 4 independently of one another are H or methyl.
  • Particularly preferred pyrazolium ions are 1,4-dimethylpyrazolium and 1,2,4-trimethylpyrazolium.
  • Preferred 1-pyrazolinium ions are compounds of the formula IV. I, in which R 1 to R 6 independently of one another are H or methyl.
  • Preferred 2-pyrazolinium ions are compounds of the formula IV.j or IV.j ", in which R 1 is H, methyl, ethyl or phenyl and R 2 to R 6 are each independently H or methyl.
  • Preferred 3-pyrazolinium ions are compounds of the formula IV. K. or .IV.k ', wherein R 1 and R 2 are independently H, methyl, ethyl or phenyl and R 3 to R 6 are independently H or methyl.
  • Preferred imidazolinium ions are compounds of the formula (IV.1) in which R 1 and R 2 independently of one another are H, methyl, ethyl, 1-butyl or phenyl, R 3 and R 4 independently of one another are H, methyl or ethyl, and R 5 and R 6 are independently H or methyl.
  • imidazolinium ions are compounds of the formula IV.m or
  • imidazolinium ions are compounds of the formula IV.n or IV. N ', where R 1 to R 3 independently of one another are H, methyl or ethyl and R 4 to R 6 independently of one another are H or methyl.
  • Preferred thiazolium ions are compounds of formula IV. O or IV. O ', wherein R 1 is H, methyl, ethyl or phenyl and R 2 and R 3 are independently H or methyl.
  • Preferred oxazolium ions are compounds of formula IV. P, wherein R 1 is H, methyl, ethyl or phenyl and R 2 and R 3 are independently H or methyl.
  • Preferred 1,2,4-triazolium ions are compounds of the formulas IV. Q, IV. Q 'or IV. Q ", in which R 1 and R 2, independently of one another, are H, methyl, ethyl or phenyl and R 3 is H, Methyl or phenyl.
  • Preferred 1,2,3-triazolium ions are compounds of the formulas IV.
  • Preferred pyrrolidinium ions are compounds of the formula IV.
  • S in which R 1 is H, methyl, ethyl or phenyl and R 2 to R 9 independently of one another are H or methyl.
  • Preferred Imidazolidiniumionen are compounds of formula IV.
  • T wherein R 1 and R 4 are independently H, methyl, ethyl or phenyl and R 2 , R 3 and R 5 to R 8 are independently H or methyl.
  • Preferred diazabicycloalkenium ions of the formulas IV.u and IV.v are selected from cationic derivatives of 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1,8-diazabicyclo [5.4.0] undec-7 -en (DBU).
  • the hydrolysis stability of an ionic liquid IL which has at least one cation selected from the aforementioned imidazolium ions and the abovementioned pyrazolium ions is improved.
  • the cation of the ionic liquid is selected from the aforementioned imidazolium ions.
  • the anion [Y] n - of the ionic liquids IL is preferably selected from compounds of the formulas (R a O) SO 3 " , (R a ) SO 3 " , (R 3 O) SO 2 -, (R 3 O ) PO 3 2 " , (R a O) (R b O) PO 2 -, (R a O) (R b ) PO 2 -, (R 3 O) PO 2 2" , (R a O) (R b O) PO " ,
  • C 1 -C 30 -alkyls in particular C 1 -C 6 -alkyls, C 6 -C 14 -aryls, in particular C 6 -C 10 -aryls, C 1 -C 12 -cycloalkyls, heterocycloalkyls having 5 or 6 ring atoms and heteroaryls having 5 or 6 Ring atoms is referred to the statements made at the outset.
  • Ci-C 8 alkyl, C 6 -C 2 aryl, C 5 -C 2 cycloalkyl, heterocycloalkyl with 5 or 6 ring atoms and heteroaryl with 5 or 6 ring atoms also referred to the statements made at the outset to substituents.
  • radicals R a to R d is optionally substituted C 1 -C 18 -alkyl, then it is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, Benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chloro
  • At least one of the radicals R a to R d is interrupted by one or more non-adjacent heteroatoms or heteroatom-containing Ci-Ci8-alkyl, it is preferably 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxa 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-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl,
  • radicals R a to R d 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 mean.
  • the number of non-adjacent heteroatoms or heteroatom-containing groups of the radicals R a to R d is basically not critical and is usually limited only by the size of the respective residue or 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 are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • Preferred functional groups of the radicals R a to R d are carboxy, carboxamide, hydroxy, di (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkoxy.
  • Alkyl of different radicals R c to R f may also be mono- or polysubstituted by Ci-C 4 -alkyl, preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • At least one of the radicals R a to R d is optionally substituted C 6 -C 12 aryl, then it is preferably phenyl, methylphenyl (ToIyI), XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylpheny
  • At least one of the radicals R a to R e is optionally substituted C 5 -C 12 -cycloalkyl, it preferably represents cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl , Diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, Dichlorcyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • radicals R a to R e is an optionally substituted five- or six-membered heterocycle, it preferably represents furyl, thienyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, Dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • radicals R a to R e When in anions which have a plurality of radicals R a to R e , in each case two of these radicals together with the part of the anion to which they are attached represent at least one saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms where the ring or the ring system may have 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR E , the ring or the ring system is unsubstituted or carries 1, 2, 3, 4, 5 or more than 5 substituents.
  • the substituents are preferably independently selected from alkyl, alkoxy, alkylsulfanyl, cycloalkyl, cycloalkoxy, polycyclyl, heterocycloalkyl, aryl, aryloxy, arylthio and heteroaryl.
  • the abovementioned anions or anion equivalents are generally at least partially subject to hydrolysis in ionic liquids.
  • the anion [Y] n - of the ionic liquid (IL) is selected from compounds of the formulas (R a O) SO 3 " , (R a ) SO 3 " , (R 3 O) PO 3 2 " and (R a O) (R b O) PO 2 " in which R a and R b independently of one another are alkyl, cycloalkyl or aryl, especially unsubstituted C 1 -C 4 -alkyl.
  • the anion [Y] n - the ionic liquid (IL) is selected from compounds of the formula (R a O) SO 3 ", especially mono-C 1 -C 4 -alkyl sulfates, such as, for example, ethyl sulfate.
  • the anions mentioned as being particularly preferred are subject to hydrolysis in ionic liquids to a particular degree.
  • hydrolysis of compounds of formula (R a O) SO 3 "get sulfuric acid may have a damaging effect on chemical compounds, chemical reactions and apparatus by their corrosive properties with which an ionic liquid containing them is brought into contact.
  • tertiary amines or mixtures of tertiary amines are used to increase the hydrolytic stability of the ionic liquid (IL).
  • Suitable tertiary amines are compounds of the formula NR 1 R 2 R 3 , wherein R 1 , R 2 and R 3 have one of the previously given for R 1 to R 9 , different meanings of H.
  • the tertiary amines used according to the invention are selected from compounds of the formula NR 1 R 2 R 3 , where R 1 , R 2 and R 3 independently of one another are each optionally substituted C 1 -C 30 -alkyl, C 5 -C 8 -cycloalkyl or aryl where C 1 -C 30 -alkyl can also be interrupted as defined above by one or more nonadjacent heteroatoms or heteroatom-containing groups.
  • Suitable unsubstituted tertiary amines are triethylamine, diethyl-n-propylamine, diethylisopropylamine, diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, diethylcyclohexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, diethyldodecylamine Tri-n-propylamine, di-n-propylethylamine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine,
  • Suitable substituted tertiary amines are tri (2-hydroxyethyl) amine, di (2-hydroxyethyl) n-propylamine, di (2-hydroxyethyl) isopropylamine, di (2-hydroxyethyl) -n-butylamine, di (2-hydroxyethyl) tert-butylamine, di (2-hydroxyethyl) -n-pentylamine,
  • the abovementioned alkoxylated derivatives of the tertiary amines are present as mixtures and have on average 1 to 50, preferably 1 to 20 and more preferably 2 to 10 alkylene oxide units per 2-hydroxyethyl group.
  • Preferred substituted tertiary amines are di (2-hydroxyethyl) (Ci-Ci2-alkyl) amines and Tri (2-hydroxyethyl) amine and their alkoxylated derivatives.
  • a particularly preferred substituted tertiary amine is tri (2-hydroxyethyl) amine.
  • mixtures of tertiary amines of the formula NR 1 R 2 R 3 in which the meanings of at least one of the radicals R 1 , R 2 or R 3 of a mixture of straight-chain and branched Ci-C3o-alkyl, especially Cs-ds Alkyl, and Ci-C3o-alkenyl, especially Cs-ds-alkenyl, as it is accessible from natural or synthetic fatty acids and fatty alcohols and from oxo alcohols derives.
  • the tertiary amines used according to the invention are selected from compounds of the formula NR 1 R 2 R 3 , in which R 1 together with R 2 and together with the nitrogen atom to which they are bonded represent a five- to six-membered heterocycle R 3 has one of the meanings given above or may stand together with an adjacent substituent of the heterocycle for the single bond moiety of a chemical double bond.
  • Heterocyclic tertiary amines NR 1 R 2 R 3 are preferred in which at least one ring carbon atom adjacent to a ring nitrogen atom has a substituent other than H, in particular a C 1 -C 4 -alkyl substituent.
  • Suitable heterocyclic tertiary amines NR 1 R 2 R 3 are pyridine compounds, pyridazine compounds, pyrimidine compounds, pyrazine compounds, imidazole compounds, pyrazole compounds, 1, 2,4-triazole compounds or 1,2,4-triazole compounds, in particular those which in adjacent position to a ring nitrogen atom have at least one substituent.
  • Suitable pyridine compounds are 2-methylpyridine, 2-ethylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine and 2-methyl-3- ethylpyridine.
  • Suitable pyridazine compounds are, for example, 3-methylpyridazine, 3-ethylpyridazine, 3,4-dimethylpyridazine, 3,5-dimethylpyridazine, 3,6-dimethylpyridazine.
  • Suitable pyrimidine compounds are, for example, 2-methylpyrimidine, 4-methylpyrimidine, 2,4-dimethylpyrimidine, 2,5-dimethylpyrimidine, 4,5-dimethylpyrimidine, 4,6-dimethylpyrimidine, 2,4,5-trimethylpyrimidine, 2,4,6- Trimethylpyrimidine, 2-ethyl-pyrimidine, 2-ethyl-4-methylpyrimidine, 2-ethyl-5-methylpyrimidine, 2-ethyl-4,5-dimethylpyrimidine or 2-ethyl-4,6-dimethylpyrimidine.
  • Suitable pyrazine compounds are, for example, 2-methylpyrazine,
  • 2,3-dimethylpyrazine 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,6-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine, 2-ethylpyrazine, 2- Ethyl 3-methylpyrazine, 2-ethyl-5-methylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 2-ethyl-3,6-dimethylpyrazine or 2,3,5, 6-tetramethylpyrazine.
  • Examples of suitable imidazole compounds are 1, 2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-n-propyl-2-methylimidazole, 1-isopropyl-2-methylimidazole, 1-n-butyl-2-methylimidazole, 1-sec.
  • Suitable pyrazole compounds are 1, 3-dimethylpyrazole, 1-ethyl-3-methylpyrazole, 1-n-propyl-3-methylpyrazole, 1-isopropyl-3-methylpyrazole, 1-n-butyl-3-methylpyrazole, 1-sec.
  • Suitable 1,2,4-triazole compounds are, for example, 1,3-dimethyl-1, 2,4-triazole, 1-ethyl-3-methyl-1, 2,4-triazole, 1 -n-propyl-3-methyl- 1, 2,4-triazole, 1-isopropyl-3-methyl-1, 2,4-triazole, 1-n-butyl-3-methyl-1, 2,4-triazole, 1-sec-butyl-3 -methyl-1, 2,4-triazole, 1-tert-butyl-3-methyl-1, 2,4-triazole, 1- (2-hydroxyethyl) -3-methyl-1,2,4-triazole, 1 , 5-Dimethyl-1, 2,4-triazole, 1-ethyl-5-methyl-1, 2,4-triazole, 1-n-propyl-5-methyl-1, 2,4-triazole, 1-iso propyl-5-methyl-1, 2,4-triazole, 1-n-butyl-5-methyl-1, 2,4-triazole, 1-sec-but
  • Suitable 1,2,3-triazole compounds are, for example, 1,4-dimethyl-1,3,3-triazole, 1-ethyl-4-methyl-1,3,3-triazole, 1-n-propyl-4-methyl- 1, 2,3-triazole, 1-isopropyl-4-methyl-1,2,3-triazole, 1-n-butyl-4-methyl-1,2,3-triazole, 1-sec-butyl-4 -methyl-1,2,3-triazole, 1-tert-butyl-4-methyl-1,2,3-triazole, 1- (2-hydroxyethyl) -4-methyl-1,2,3-triazole, 1 , 5-Dimethyl-1, 2,3-triazole, 1-ethyl-5-methyl-1,2,3-triazole, 1-n-propyl-5-methyl-1,2,3-triazole, 1-isopropyl 5-methyl-1,2,3-triazole, 1-n-butyl-5-methyl-1,2,3-triazole, 1-sec-butyl-5
  • DBN 1, 5-diazabicyclo [4.3.0] non-5-ene
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • the heterocyclic tertiary amines of the formula NR 1 R 2 R 3 used according to the invention are preferably selected from the abovementioned imidazole and pyrazole compounds. Particularly preferably, the heterocyclic tertiary amine is 1, 2-dimethylimidazole.
  • various quaternary ammonium compounds or mixtures of quaternary ammonium compounds are used to increase the hydrolytic stability of the ionic liquid (IL) from the ionic liquid (IL).
  • Suitable quaternary ammonium compounds for example, by quaternization tion of the aforementioned tertiary amines NR 1 R 2 R 3 be provided, wherein compounds of the formula [NR 1 R 2 R 3 R] + (1 / n) * [Y '] n ⁇ Get in which R has one of the meanings given with respect to the ionic liquids and (1 / n) * [Y '] n - represents an anion equivalent.
  • R in the quaternary ammonium compounds of the formula [NR 1 R 2 R 3 R] + (1 / n) * [Y '] n ⁇ is C 1 -C 4 -alkyl, particularly preferably methyl.
  • Suitable methods for quaternization of tertiary amines are known to the person skilled in the art. Suitable methods include, in particular, the reaction of tertiary amines of the formula NR 1 R 2 R 3 with C 1 -C 4 -alkyl halides, such as methyl iodide, or with di-C 1 -C 4 -alkyl sulfates, such as dimethyl sulfate or diethyl sulfate.
  • Preferred quaternary ammonium compounds are (C 1 -C 4 -alkyl) (C 1 -C 8 -alkyl) -di (2-hydroxyethyl) ammonium compounds and (C 1 -C 4 -alkyl) tri (2-hydroxyethyl) ammonium compounds and their alkoxylated derivatives, in particular those which have as counterion a Ci-C4 Alkylsulfatanion.
  • Particularly preferred quaternary Ammonium compounds are methyltri (2-hydroxyethyl) ammonium compounds, in particular their methyl or ethyl sulfates, and also the alkoxylated derivatives of methyltri (2-hydroxyethyl) ammonium compounds.
  • mixtures are preferred quaternary ammonium compounds in which the meanings of at least one of the radicals R 1, R 2 or R 3 of a mixture of overall radkettigem and branched Ci-C3o-alkyl, especially Cs-ds-alkyl, and Ci-C3o- Alkenyl, especially Cs-C-is-alkenyl, as it is accessible from natural or synthetic fatty acids and fatty alcohols and from oxo alcohols derives.
  • mixtures of quaternary ammonium compounds in which at least one of the radicals R 1 , R 2 or R 3 is a mixture of straight-chain and branched C 1 -C 30 -alkyl and C 1 -C 30 -alkenyl and at least one further, especially two, of the radicals R 1 , R 2 or R 3 is 2-hydroxyethyl or alkoxylated 2-hydroxyethyl.
  • Such mixtures are commercially available, for example, under the trade name Ammoeng TM 100 (Solvent Solution).
  • the tertiary amines and / or quaternary ammonium compounds used according to the invention are preferably used in an amount of from 0.01 to 50% by weight, preferably in an application rate of from 0.05 to 30% by weight and more preferably 0.1 to
  • the ionic liquids IL used according to the invention and the tertiary amines and / or quaternary ammonium compounds used according to the invention are advantageously completely miscible with one another, ie. H. Addition of the tertiary amine and / or the quaternary ammonium compound to an ionic liquid IL produces a homogeneous liquid composition.

Abstract

La présente invention concerne un procédé d'amélioration de la stabilité à l'hydrolyse d'un liquide ionique (IL), selon lequel au moins une amine tertiaire ou un composé d'ammonium quaternaire différent du liquide ionique (IL) est ajouté à un liquide ionique (IL).
EP08863060A 2007-12-14 2008-12-12 Procédé d'amélioration de la stabilité à l'hydrolyse de liquides ioniques Withdrawn EP2229365A1 (fr)

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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
US9777074B2 (en) 2008-02-13 2017-10-03 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US8188267B2 (en) 2008-02-13 2012-05-29 Eastman Chemical Company Treatment of cellulose esters
US8354525B2 (en) 2008-02-13 2013-01-15 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US8158777B2 (en) 2008-02-13 2012-04-17 Eastman Chemical Company Cellulose esters and their production in halogenated ionic liquids
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