WO2007147222A9 - Novel ionic liquids - Google Patents

Novel ionic liquids

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Publication number
WO2007147222A9
WO2007147222A9 PCT/BE2007/000062 BE2007000062W WO2007147222A9 WO 2007147222 A9 WO2007147222 A9 WO 2007147222A9 BE 2007000062 W BE2007000062 W BE 2007000062W WO 2007147222 A9 WO2007147222 A9 WO 2007147222A9
Authority
WO
WIPO (PCT)
Prior art keywords
bis
organic
imide
trifluoromethylsulfonyl
water
Prior art date
Application number
PCT/BE2007/000062
Other languages
French (fr)
Other versions
WO2007147222A3 (en
WO2007147222A2 (en
Inventor
Koen Binnemans
Christiane An Goerller-Walrand
Peter Nockemann
Ben Thijs
Original Assignee
Univ Leuven Kath
Koen Binnemans
Christiane An Goerller-Walrand
Peter Nockemann
Ben Thijs
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Univ Leuven Kath, Koen Binnemans, Christiane An Goerller-Walrand, Peter Nockemann, Ben Thijs filed Critical Univ Leuven Kath
Publication of WO2007147222A2 publication Critical patent/WO2007147222A2/en
Publication of WO2007147222A9 publication Critical patent/WO2007147222A9/en
Publication of WO2007147222A3 publication Critical patent/WO2007147222A3/en

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    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
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    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Definitions

  • the present invention provides for novel organic salts, more specifically ionic liquids and for methods for the preparation of such novel ionic liquids.
  • the invention also provides for the use of the ionic liquids in chemistry applications, for example for the solubilization of metal oxides, hydroxides and salts, for the deposition of metals or for extraction procedures, among others.
  • the invention furthermore provides for a method for the solubilization of metal oxides and metal salts, for the deposition of metals and for extraction procedures, this by using the novel ionic liquids.
  • the present invention furthermore provides for materials obtained by the methods hereof.
  • Ionic liquids are an interesting reaction medium for the synthesis of unusual inorganic compounds (Taubert, A.; Li, Z. Dalton Trans. 2007, 723-727). They find use in electrochemical applications, for example as electrolytes in batteries, and in photovoltaic devices, but also as a medium for electrodeposition or electropolishing of metals.
  • ionic liquids should have a high solubilizing power for metal salts, including metal oxides.
  • metal salts including metal oxides.
  • metal oxides To avoid leaching of the metal catalyst in catalytic reactions, it is of importance to have ionic liquids that can keep metals dissolved in them.
  • a good solubility of metal salts is observed for ionic liquids based on aluminum chloride, such as mixtures of l-ethyl-3-methylimidazolium chloride and aluminum chloride ([C 2 InJm]Cl - AlCl 3 ), and mixtures of 1-butylpyridinium chloride and aluminum chloride (BPC - AICI 3 ).
  • aluminum chloride such as mixtures of l-ethyl-3-methylimidazolium chloride and aluminum chloride ([C 2 InJm]Cl - AlCl 3 ), and mixtures of 1-butylpyridinium chloride and aluminum chloride (BPC - AICI 3 ).
  • TSILs task-specific ionic liquids
  • the functional group has the ability to coordinate to the metal ion (preferably as a bidentate or a polydentate ligand)
  • these task-specific ionic liquids are not used as single-component ionic liquids, but they are mixed with more conventional ionic liquids.
  • a rationale to use mixtures rather than pure task-specific ionic liquids is that the task-specific ionic liquids often have a higher melting point and a higher viscosity than conventional ionic liquids. Moreover, the conventional ionic liquids are in general much cheaper than the task-specific ionic liquids.
  • An example of a task- specific ionic liquid is an imidazolium salt incorporating a thiourea moiety, which has been used for the extraction of mercury(H) and cadmium(II) from an aqueous phase (Visser, A. E. et al. Chem. Commun. 2001, 135-136).
  • Choline chloride also known as 2- hydroxyethyltrimethyl ammonium chloride or vitamin B4
  • ionic liquids based on choline chloride have the advantages of being cheap, they are all hydrophilic and miscible with water or with polar solvents. This is a problem for applications like the extraction of metal ions from an aqueous phase or like the electrodeposition of reactive metals (e.g. aluminum, magnesium, tantalum and the rare earths).
  • Metal complexes with the zwitterionic ligand betaine have been investigated for a long time, but none of these complexes contain the bis(trifluoromethylsulfonyl)imide anion.
  • the present invention provides for novel organic salts, more specifically ionic liquids and for methods for the preparation of such novel organic salts, more specifically ionic liquids.
  • the invention also provides for the use of the organic salts, more specifically ionic liquids in chemistry applications.
  • the invention furthermore provides for chemistry applications, like a method for the solubilization of metal oxides, by using the novel organic salts, more specifically ionic liquids.
  • the present invention furthermore relates to compositions, (solutions, complexes or mixtures among others) comprising said organic salts, more specifically ionic liquids and to materials obtained by the methods using said organic salts, more specifically ionic liquids.
  • the present invention also relates to the use of said compositions comprising said organic salts, more specifically ionic liquids or of the materials obtained by the methods using said organic salts, more specifically ionic liquids.
  • a first aspect of the present invention relates to novel organic salts, in a more particular case novel ionic liquids.
  • the organic salts of the present invention have a quaternary ammonium, phosphonium, arsonium, or stibonium structure according to formula (I):
  • each of R 1 , R 2 and R 3 are independently selected from CM 2 alkyl; or C 3- I 2 cycloalkyl; or each of R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 can be taken together to form a substituted or unsubstituted cyclic structure;
  • R 4 is selected from a Cu 2 alkyl-COOH; or C3. 12 cycloalkyl-COOH; wherein alkyl is optionally substituted with at least one OH or comprises at least one carbonyl function;
  • X- is selected from organic sulfonates; organic sulfates; organic carboxylates; organic sulfonylimides; or tetrafluoroborate.
  • R 1 , R 2 , R 3 , R 4 , Y and X " are as described in formula I, but R 4 is not C 3 alkyl-COOH or C 2 alkyl-COOH when Y is N and R 1 , R 2 and R 3 are all methyl and X- is bis(trifluoromethylsulfonyl)imide (Tf 2 N ' ).
  • R 1 , R 2 , R 3 , R 4 , and Y are as described in formula I, and X ' is bis(trifluoromethylsulfonyl)imide but R 4 is not C 3 alkyl- COOH when Y is N and R 1 , R 2 and R 3 are all methyl.
  • each of R 1 , R 2 and R 3 are independently selected from Ci.g alkyl and C 3-J cycloalkyl, yet more in particular are independently selected from Ci -6 alkyl and C 3-6 cycloalkyl, still more particularly are independently selected from C M alkyl, yet more particularly from Ci -3 alkyl.
  • each of R 1 , R 2 and R 3 are the same and more particularly are methyl, ethyl, propyl, butyl, hexyl, or octyl.
  • R 4 is selected from Cj -S alkyl-COOH and C 3 .g cycloalkyl- COOH, still more in particular is selected from Ci -6 alkyl-COOH and C 3-6 cycloalkyl-COOH, yet more particularly is C M alkyl-COOH or Ci -3 alkyl-COOH and yet more preferably is Ci -2 alkyl- COOH and even more preferably is -CH 2 COOH.
  • R 1 , R 2 , R 3 , Y, and X " are as described in formula I, and R 4 is Ci or C 2 alkyl-COOH or C 3-I2 cyclo alkyl, more prefarably is Ci or C 2 alkyl-COOH, even more preferably is -CH 2 COOH.
  • R 1 , R 2 , R 3 , and Y are as described in formula I, and R 4 is Ci or C 2 alkyl- COOH more prefarably is -CH 2 COOH, and X " is Tf 2 N " .
  • the present invention relates to an organic salt of formula I wherein Y is P, As or Sb, and R 1 , R 2 , R 3 and R 4 and X ' are as described in formula I, more preferably X " is Tf 2 N " .
  • R 1 R 2 R 3 R 4 Y + is betaine, wherein Y is N, R 1 is -CH 3 , R 2 is -CH 3 , R 3 is -CH 3 and R 4 is -CH 2 COOH.
  • X " is selected from organic sulfonates, preferably perfluorinated organic sulfonates; organic sulfates, preferably perfluorinated organic sulfates; organic sulfonylimides, preferably perfluorinated organic sulfonylimides ; or organic carboxylates, preferably perfluorinated organic carboxylates, such as methyl sulfonate (CH 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide (Tf 2 N " ), bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, bis(perfluorohexylsulfonyl)imide, triflate (Tf
  • X " is selected from perfluoro-Cu ⁇ alkyl-sulfonylimide (or more particularly from perfluoro-Ci ⁇ alkyl-sulfonylimide, such as bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, or bis(perfluorohexylsulfonyl)imide), more specifically is bis(trifluoromethylsulfonyl)imide (Tf 2 N ).
  • perfluoro-Cu ⁇ alkyl-sulfonylimide or more particularly from perfluoro-Ci ⁇ alkyl-sulfonylimide, such as bis(pentafluoroethylsulfonyl)imide, bis(hepta
  • the organic salt is betaine bis(trifiuoromethylsulfonyl)imide.
  • Such organic salts may be in protonated or unprotonated form.
  • the structure of betaine bis(trifluoromethylsulfonyl)imide in protonated form is according to formula II:
  • the present invention relates to an organic salt of formula I wherein Y is N or P, more preferably wherein Y is N. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P and X ' is Tf 2 N ' . In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is N and X " is Tf 2 N " .
  • the present invention relates to an organic salt of formula I wherein R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 form a substituted or unsubstituted cyclic structure, and wherein Y, R 4 , and X ' are as desribed in formula I, more preferably Y is N or P, even more preferably Y is N.
  • the present invention relates to an organic salt of formula I wherein R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 form a substituted or unsubstituted cyclic structure, and wherein R 4 is as desribed in formula I, and wherein Y is N and X " is Tf 2 N ' .
  • the present invention relates to an organic salt of formula I wherein Y is P, and R 1 , R 2 and R 3 are independently selected from CM 2 alkyl, and R 4 and X " are as desribed in formula I, more preferably X ' is Tf 2 N ' .
  • the present invention relates to an organic salt of formula 1, wherein Y is N and R 4 is selected from a substituted Ci -3 alkyl-COOH wherein at least one OH group is present, or a Ci -3 alkyl-COOH which contains at least one carbonyl group.
  • the present invention relates to an organic salt of formula I wherein Y is N, and R 1 , R 2 and R 3 are as described in formula I, and R 4 is a substituated CM 2 alkyl-COOH, and X " is Tf 2 N " .
  • the present invention relates to an organic salt of formula I wherein Y is P and R 4 is -CH 2 CH 2 COOH or -CH 2 COOH, and even more particularly Y is P and R 4 is -CH 2 COOH.
  • R 1 R 2 R 3 R 4 Y + is carboxymethyl- tributylphosphonium, wherein Y is P and R 1 is butyl, R 2 is butyl, R 3 is butyl and R 4 is - CH 2 COOH.
  • the organic salt is P-carboxymethyl- tributylphosphonium bis(trifluoromethylsulfonyl)imide. The structure of this organic salt is according to formula III:
  • the present invention relates to an organic salt of formula I wherein R 4 is as desribed herein, and Y is N and R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 forms a pyrrolidinium ring structure.
  • R 1 R 2 R 3 R 4 Y 4 is N-carboxymethyl- methylpyrrolidinium, wherein Y is ⁇ and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said ⁇ forms a pyrrolidinium ring structure, and R 4 is -CH 2 COOH.
  • the organic salt is N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula IV:
  • R 1 R 2 R 3 R 4 Y + is N-carboxyethyl-methylpyrrolidinium, wherein Y is N and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said N forms a pyrrolidinium ring structure, and R 4 is -CH 2 CH 2 COOH.
  • the organic salt is N- carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula V:
  • the present invention relates to an organic salt of formula I wherein R 4 is as described herein, and Y is N and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said N forms a morpholinium ring structure.
  • R 1 R 2 R 3 R 4 Y + is JV-carboxymethyl-methylmorpholinium, wherein Y is N and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said N forms a morpholinium ring structure, and R 4 is - CH 2 COOH.
  • the organic salt is N-carboxymethyl- methylmorpholinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula VI:
  • the present invention relates to an organic salt of formula I wherein R 4 is as desribed herein, and Y is N and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said N forms a piperidinium ring structure.
  • R 1 R 2 R 3 R 4 Y + is N-carboxymethyl-methylpiperidinium, wherein Y is ⁇ and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said ⁇ forms a piperidinium ring structure, and R 4 is -CH 2 COOH.
  • the organic salt is N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula VII:
  • the present invention relates to an organic salt of formula I wherein R 1 , R 2 and R 3 are as desribed herein, and R 4 is selected from C M2 hydroxyalkyl-COOH, still more in particular is selected from Ci-3 hydroxyalkyl-COOH, even more particularly is - CH 2 CH 2 OHCH 2 COOH.
  • R 1 R 2 R 3 R 4 Y + is carnitine.
  • the organic salt is carnitine bis(trifiuoromethylsulfonyl)imide, the structure of which is according to formula VIII:
  • carnitine is in L- or D-carnitine or a mixture of L- and D-carnitine, being a racemic mixture.
  • carnitine is L-carnitine.
  • the present invention relates to an organic salt of formula I wherein R 4 is as desribed herein, and Y is N and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said N forms a pyridinium ring structure.
  • R 1 R 2 R 3 R 4 Y + is N- carboxymethyl-methyl pyridinium, wherein Y is ⁇ and together with R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 said ⁇ forms a pyridinium ring structure, and R 4 is -CH 2 COOH.
  • the organic salt is N-carboxymethyl-methylpyridinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula IX:
  • the organic salt is ⁇ -dimethyl- ⁇ -butyl-betainium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula X:
  • the organic salt is N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula XI:
  • X ' is selected from bis(trifluoromethylsulfonyl)imide
  • Tf 2 N " bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, bis(perfluorohexyl- sulfonyl)imide, more preferably X " is bis(trifiuoromethylsulfonyl)imide (Tf 2 N " ).
  • the organic salts of the invention are in a 100% pure form or are not mixed with any other ionic liquids.
  • a second aspect of the present invention relates to a process for the preparation of the ionic liquids described herein, said process comprising the step of performing the metathesis reaction of and salts of - preferably perfluorinated -organic sulfonate, organic sulfate, organic sulfonylimide anions or organic carboxylate anions in water. More particularly, the present invention relates to the preparation of betaine bis(trifluoromethylsulfonyl)imide by the metathesis reaction of betaine chloride or betaine bromide and lithium bis(trifluoromethylsulfonyl)imide in water.
  • the ionic liquid betaine bis(trifluoromethylsulfonyl)imide can also be prepared by the reaction between R'R ⁇ R ⁇ hydroxide and the acid hydrogen bis(trifluoromethylsulfonyl)imide.
  • Another aspect of the present invention relates to the products obtained by the process comprising the step of performing the metathesis reaction of R 1 R 2 R 3 R 4 Y + halogenide and salts of - preferably perfluorinated - organic sulfonate, organic sulfate, organic sulfonylimide or organic carboxylate anions in water as described herein.
  • the present invention relates to the organic salt obtained by mixing betaine halogenide and lithium bis(trifluoromethylsulfonyl)imide in water or by mixing betaine hydroxide and hydrogen bis(trifluoromethylsulfonyl)imide.
  • a third aspect of the present invention relates to the use of the organic salts of the present invention for general chemical applications at higher temperatures such as a solvent, for extraction procedures, as a reaction medium, for electrodeposition, among others.
  • the present invention relates to the use the organic salts, more specifically of betaine bis(trifluoromethylsulfonyl)imide, as an ionic liquid and to the use of said ionic liquids as described herein for industrial applications, more specifically chemical applications, yet more specifically chemical applications involving metals such as:
  • the ionic liquid serves as a solvent or as a catalyst
  • - for electrodeposition of metal ions wherein as an example, the ionic liquid serves as a solvent for the metal precursors
  • Another aspect of the present invention relates to methods for performing chemical applications by using the ionic liquids as described herein.
  • the present invention thus relates to methods for:
  • the ionic liquid serves as a solvent for the metal precursors
  • the present invention furthermore relates to a method for performing chemical reactions and/or extractions by using the ionic liquids, more specifically betaine bis(trifluoromethylsulfonyl)imide ionic liquid and comprising the steps of:
  • the present invention also relates to a method for performing chemical reactions and/or extractions by using the ionic liquids, more specifically betaine bis(trifluoromethylsulfonyl)imide ionic liquid and comprising the steps of:
  • compositions such as solutions, mixtures or complexes, comprising the organic salts, more specifically the ionic liquids described herein, in a particular embodiment comprising betaine bis(trifluoromethylsulfonyl)imide in protonated or unprotonated form.
  • compositions are complexes or solutions of the ionic liquids described herein, which are in a more particular embodiment metal complexes of the ionic liquids such as betaine bis(trifluoromethylsulfonyl)imides with zinc, cadmium, mercury, lead, copper, nickel, silver, gold, palladium, platinum, rhodium, rare earths (scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), thorium, uranium, neptunium, plutonium, americium, curium, californium or berkelium.
  • metal complexes of the ionic liquids such as betaine bis(trifluoromethylsulfonyl)
  • compositions are mixtures of the ionic liquids described herein with one or more other liquids such as water, organic solvents (such as toluene) or other ionic liquids such as bis(trifluoromethylsulfonyl)imide comprising ionic liquids (i.e. choline bis(trifluoromethylsulfonyl)imide), among others.
  • ionic liquids i.e. choline bis(trifluoromethylsulfonyl)imide
  • Such mixtures may be consisting of one phase or may be separated in two or multiple phases, this in a particular embodiment depending on the conditions such as the temperature or the pH.
  • the mixtures may comprise the ionic liquids of the present invention in different ratios, ranging from 0.1% to 99.9%, or from 1% to 99 %, or from 5% to 95%.
  • compositions are solutions of organic or inorganic compounds in the ionic liquids of the present invention.
  • Another aspect relates to the process for the preparation of compositions of the organic salts or ionic liquids described herein, comprising the step of mixing the organic salts or ionic liquids with other liquids, with gases or solid compounds.
  • the invention relates to the process for the preparation of metal complexes of betaine bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with betaine bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-carboxymethyl- methylmorpholinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylpyrrolidinium bis(trifiuoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxyethyl- methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-carboxymethyl- methylpiperidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-rnethylpiperidinium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of P-carboxymethyl-tributylphosphonium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with P-carboxymethyl- tributylphosphonium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N- carboxymethylpyridinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of L-carnitine bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with L-carnitine bis(trifluoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N-dimethyl-N-butyl-betainium bis(trifiuoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-dimethyl-N-butyl-betainium bis(trifiuoromethylsulfonyl)imide.
  • the invention relates to the process for the preparation of metal complexes of N- dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide.
  • compositions obtained by the process of mixing the organic salts or ionic liquids described herein with other liquids, with gases or solid compounds (such as inorganic or organic compounds).
  • the present invention relates to solutions prepared by dissolution of metal salts in the ionic liquids of the present invention.
  • the ionic liquid is betaine bis(trifluoromethylsulfonyl)imide.
  • compositions for industrial applications.
  • a particular embodiment relates to the use of said compositions in chemical applications, more in particular chemical applications involving metals such as metal oxides, metal hydroxides or metal salts.
  • compositions in chemical applications, wherein said chemical applications are selected from the list of as a solvent, for example for the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; for extraction procedures, more in particular for the extraction of metal ions; for decontamination of soils contaminated by heavy metals especially with copper, nickel, zinc, cadmium, mercury or lead; for catalytic reactions wherein the ionic liquid serves as a solvent or as a catalyst; for electrodeposition of metal ions; as a medium for electropolishing or for the cleaning of metal surfaces; for deposition of metals onto conductive surfaces; for the processes of spent nuclear fuel elements; as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices and for recycling of noble metals from used catalysts and electronic circuits.
  • a solvent for example for the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; for extraction procedures, more in particular for the extraction of metal ions
  • One embodiment relates to the use of the lithium complex of betaine bis(trifiuoromethylsulfonyl)imide as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices.
  • Another embodiment relates to the use of lanthanide complexes of betaine bis(trifluoromethylsulfonyl)imide as ionic liquids.
  • FIG. 1 Temperature-dependent phase behavior of a binary [Hbet][Tf 2 N] -water mixture.
  • the bluish [Cu(bipy)Cl 2 ] complex (depicted as dark grey in Figure 1) was dissolved in the ionic liquid to accentuate the phase boundaries.
  • Figure 2 The liquid-liquid equilibrium phase diagram of the binary mixture [Hbet] [Tf 2 N] - water.
  • Figure 3 Illustration of the pH-dependent phase behavior of a binary [Hbet] [Tf 2 N] - water mixture. A two-phase system is obtained for acidic and neutral conditions, whereas a one-phase system is observed for alkaline conditions ( pH > 8). The dye methyl red was added to make the phase boundaries better visible (depicted as dark grey in Figure 3).
  • Figure 4 Transfer of copper(II) from the ionic liquid [Hbet][Tf 2 N] to the aqueous phase upon acidification of the aqueous phase by a hydrogen chloride solution.
  • Figure 5 Phase diagram of a water / N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide system.
  • the number of carbon atoms represents the maximum number of carbon atoms generally optimally present in the substituent or linker; it is understood that where otherwise indicated in the present application, the number of carbon atoms represents the optimal maximum number of carbon atoms for that particular substituent or linker.
  • the term "Cu 2 alkyl" as used herein means normal, secondary, or tertiary hydrocarbon having 1 to 12 carbon atoms.
  • Examples are methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-methyl-l-propyl(i- Bu), 2-butyl (s-Bu) 2-methyl-2-propyl (t-Bu), 1-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl-2- butyl, 3-methyl-2-butyl, 3-methyl-l -butyl, 2-methyl-l -butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl- 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3- dimethyl-2-butyl, 3,3-dimethyl-2-butyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the term can also include Ci -I2 haloalkyl, which is a CM 2 alkyl bearing at least one halogen.
  • the term can also include CM 2 hydroxyalkyl, more preferably hydroxyalkyl, even more preferably 2-hydroxypropyl.
  • substituted or unsubstituted cyclic structure as used herein means a monocyclic saturated (aliphatic) or unsaturated (aromatic) or partly unsaturated ring structure having from 3 to 7 carbon atoms wherein at least one N, P, As or Sb atom is present and additionally at least one carbon atom can be replaced with a heteroatom, this heteroatom can be a N, P, As, Sb, O, S, Se, or Te in case of an aliphatic or partly unsaturated ring structure and can be N, P, As, or Sb in case of an aromatic or partly unsaturated ring structure.
  • These cyclic structures can optionally be substituted with C M2 alkyl structures.
  • Examples of this substituted or unsubstituted cyclic structure include, but are not limited to, pyridinium, imidazolium, pyrrolidinium, morpholinium, piperidinium, dihydropyridylium, thiazolylium, pyrrolylium, pyrazolylium, imidazolylium, tetrazolylium, piperidinylium, pyrrolidinylium, 2-pyrrolidonylium, pyrrolinylium, tetrahydropyranylium, bis-tetrahydropyranylium, azocinylium, triazinylium, 6H- 1,2,5- thiadiazinylium, 2H,6H-l,5,2-dithiazinylium, 2H-pyrrolylium, isothiazolylium, isoxazolylium, pyrazinylium, pyridazinylium, pyrimidinyl
  • C3- 12 cycloalkyl means a monocyclic saturated hydrocarbon monovalent radical having from 3 to 12 carbon atoms, such as for instance cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, or a C 7-I2 polycyclic saturated hydrocarbon monovalent radical having from 7 to 12 carbon atoms such as, for instance, norbornyl, fenchyl or adamantyl.
  • Ci -8 , Ci- 6 , C M , Q O or Ci -2 are used herein they respectively refer to structures having from 1 to 8, 1 to 6, 1 to 4, 1 to 3 or 1 to 2 carbon atoms.
  • ionic liquid means molten salts that are liquid at temperatures below
  • halogen means any atom selected from the group consisting of fluorine, chlorine, bromine and iodine. Any substituent designation that is found in more than one site in an organic salt of this invention shall be independently selected.
  • the present invention provides for organic salts having quaternary ammonium or phosphonium structure according to the following formula (I): R 1 R 2 R 3 R 4 Y + X "
  • - Y is selected from N; P; As; or Sb;
  • each of R 1 , R 2 and R 3 are independently selected from CM 2 alkyl; or C 3 . ]2 cycloalkyl; or each of R 1 and R 2 , or R 1 and R 3 , or R 2 and R 3 can be taken together to form a substituted or unsubstituted cyclic structure;
  • R 4 is selected from a C 1-I2 alkyl-COOH; or C 3-I2 cycloalkyl-COOH; wherein alkyl is optionally substituted with at least one OH or comprises at least one carbonyl function;
  • organic sulfonates prefarably perfluorinated organic sulfonates; organic sulfates, preferably perfluorinated organic sulfates; organic carboxylates; organic sulfonylimides, preferably bis(perfluoroalkylsulfonyl)imides; or tetrafluoroborate.
  • organic salts are ionic liquids and can be used as such. More preferably, the present invention provides for the ionic liquid betaine bis(trifluoromethylsulfonyl)imide in protonated or unprotonated form. This invention shows that betaine is a useful starting material for the design of task-specific ionic liquids which can solubilize metal oxides.
  • Betaine is a trivial name for l-carboxy-N,N,N-trimethylmethanaminium (inner salt). It is also known as N,N,N-trimethylglycine, N-trimethylglycine or trimethylglycine. Betaine has a zwitter- ionic structure. Betaine melts with decomposition at 310 0 C. It readily reacts with mineral acids or organic acids whereby the carboxylate group gets protonated and the anionic part of the acid becomes the anion in the betaine salt. For instance betaine reacts with hydrochloric acid to form betaine hydrochloride, a salt with melting point of 232 0 C.
  • Betaine hydrochloride is a water- soluble salt that can be used to prepare hydrophobic salts by a metathesis reaction.
  • the difference between the choline and the betaine cation is that in the betaine cation the hydroxyl group of choline is replaced by a carboxylic acid group.
  • betaine is a metabolite that is formed by oxidation of choline 59 .
  • the carboxylate group of betaine is a very good coordinating group towards metal ions, better than the aliphatic alcohol function of choline.
  • the most important form of betaine on the market is the hydrochloride salt, betaine hydrochloride.
  • the positive charge on the quaternary nitrogen (or phosphor, arsenicum or antimony) atom has an inductive effect on the COOH-group. This effect is affected by the chain length in-between the COOH-group and the positively charged nitrogen (or phosphor, arsenicum or antimony) atom, respectively.
  • the shorter the distance between these functional groups the higher the acidity of the proton of the COOH-function. Therefore, one or two CH 2 groups in-between, and more preferably one CH 2 group in-between is favorable for the application of this invention: these ionic liquids exhibit a significantly higher solubilizing ability for metal oxides than ionic liquids with three or more CH 2 -groups between the positively charged heteroatom and the COOH- function.
  • metal hydroxides can be solubilized in the ionic liquid.
  • the metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse.
  • Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 0 C (temperature switch behavior).
  • the mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions.
  • certain organic salts described herein are not ionic liquids according to the definitions (having melting points under 100 0 C), but still have a melting point around or under 200 0 C and therefore can be used for chemical applications at higher temperatures, such as: as a solvent, as a reaction medium, for electrodeposition of metals, among other applications.
  • Protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet] [Tf 2 N] is accessible via different synthetic routes.
  • the best method is by reaction of the zwitterionic betaine with the acid hydrogen bis(trifluoromethylsulfonyl)imide, Tf 2 NH.
  • This reaction involves a simple proton transfer from the bis(trifluoromethylsulfonyl)imide to the more basic carboxylate group, so that the betaine will be protonated.
  • This method is general applicable for the preparation of other betaine salts. For instance, we prepared by this method protonated betaine hexafluorophosphate, protonated betaine triflate, and protonated betaine pentafluorobenzoate. However, all these salts have melting points above 100 0 C and can therefore not be considered as ionic liquids.
  • a second synthetic route to the protonated betaine bis(trifluoromethylsulfonyl)imide ionic liquid is by the metathesis reaction of betaine hydrochloride and lithium bis(trifluoromethylsulfonyl)imide (in 1 :1 molar ratio) in aqueous solution.
  • An aqueous solution of betaine hydrochloride reacts with an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide to form protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet][Tf 2 N].
  • the ionic liquid easily separates from the aqueous layer (due to its hydrophobicity).
  • the ionic liquid prepared by the metathesis reaction has a melting point of 57 0 C and the compound can easily be supercooled to room temperature.
  • [(Hbet) 3 (bet)][Tf 2 N] 3 is formed besides [Hbet][Tf 2 N]
  • [Hbet][Tf 2 N] is a hydrophobic ionic liquid at room temperature; after addition of water, two separate phases are formed. Heating treatment of a mixture induced the formation of a one-phase-system at a critical temperature of 56 0 C. Cooling of the one-phase mixture resulted again in phase separation. A similar temperature-dependent miscibility was observed for mixtures of [Hbet][Tf 2 N] with toluene.
  • [Hbet][Tf 2 N] is miscible with ethanol, 1- octanol (and other higher alcohols), benzonitrile, acetonitrile, DMSO, acetic acid and ethyl acetate, but also with other ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion like [C O mJm][Tf 2 N].
  • [Hbet][Tf 2 N] is immiscible with hexane, heptane, dichloromethane (DCM), chloroform, benzene, toluene and diethyl ether.
  • a general approach to the synthesis of the other ionic liquids is by first quaternizing a tertiary amine (e.g. N-methylpyrrolidine, tributylamine) or a tertiary phospine (e.g. tributylphosphine) by reaction with an ester of chloroacetic acid or bromoacetic acid (preferentially a methyl ester or an ethyl ester). After quaternization, the ester is converted to the corresponding acid, and the chloride (or bromide) anion is exchanged by a metathesis reaction for a bis(trifluoromethylsulfonyl)imide anion. The ionic liquid separates from the water phase.
  • a tertiary amine e.g. N-methylpyrrolidine, tributylamine
  • a tertiary phospine e.g. tributylphosphine
  • esters of chloroacetic acid or bromoacetic acid can be replaced by other esters of ⁇ - bromoalkanoic acids or ⁇ -chloroalkanoic acids.
  • Lithium bis(trifluoromethylsulfonyl)imide can be replaced by other lithium bis(trifluoroalkylsulfonyl)imides.
  • the phase diagram was measured by equilibrating the [Hbet] [Tf 2 N] - water mixture at a given temperature, followed by analysis of the components in the [Hbet][Tf 2 N] rich phase (lower layer) and in the water-rich phase (upper layer).
  • the composition of the phases was determined by distilling out the water and comparing the original mass with the remaining (non-volatile) ionic liquid mass. At the critical concentration, the mass fraction of the ionic liquid is around 0.519.
  • betaine bis(trifluoromethylsulfonyl)imide is its ability to dissolve metal oxides.
  • the metal oxides react with the carboxylic acid group of the ionic liquid to form carboxylate complexes and water.
  • the following oxides were found to be soluble in the ionic liquid [Hbet][Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , U 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO and MnO.
  • Oxides can be replaced by hydroxides as the starting material.
  • the metal oxide is mixed with [Hbet] [Tf 2 N] and water, and the mixture is stirred for several hours. After evaporation of water under reduced pressure, a solution of the metal betaine complex in [Hbet][Tf 2 N] is obtained.
  • the solubility of metal oxides in protonated betaine bis(trifluoromethylsulfonyl)imide is high because the ionic liquid can form stoichiometric compounds with the metals; i.e. so much metal oxide can be added to the [Hbet][Tf 2 N] ionic liquid until all the ionic liquid is transformed into a metal complex.
  • [Hbet] [Tf 2 N] can dissolve 1.75 mol% of CuCl 2 and 6 mol.% of EuCb (determined titrimetrically by EDTA). The dissolution process can be facilitated by working under moderate to high pressure conditions. Under these experimental conditions, it is possible to dissolve in the ionic liquid oxides that are otherwise insoluble in [Hbet][Tf 2 N]. Examples of such oxides include CO 3 O 4 , CoO, Co 2 C> 3 , Cr 2 O 3 , FeO and Fe 2 O 3 . To perform the experiment, an equimolar ionic liquid/ water mixture is heated with the metal oxide in a PTFE- lined acid digestion bomb.
  • the metals can be stripped from betaine bis(trif!uoromethylsulfonyl)imide by extracting the ionic liquid with an acidified aqueous solution (for instance with diluted hydrochloric acid or diluted nitric acid).
  • an acidified aqueous solution for instance with diluted hydrochloric acid or diluted nitric acid.
  • the metal complex of protonated betaine bis(trifluoromethylsulfonyl)imide is decomposed and the betaine bis(trifluoromethylsulfonyl)- imide ionic liquid is regenerated.
  • the metal ion is thus transferred to the aqueous phase and betaine bis(trifluoromethylsulfonyl)imide is regenerated.
  • the metal complexes of betaine bis(trifluoromethylsulfonyl)imide have in general a high melting point (> 100 0 C), but the rare-earth complexes of betaine bis(trifluoromethylsulfonyl)imide have melting points below 100 °C and can thus be considered as genuine ionic liquids.
  • Table 1 Melting points for the lanthanide complexes of [Hbet] [Tf 2 N].
  • the metal complexes of betaine bis(trifluoromethylsulfonyl)imide can be dissolved in the ionic liquids choline bis(trifluoromethylsulfonyl)imide or the l-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides.
  • Betaine bis(trifluoromethylsulfonyl)imide is also miscible in all molar ratios with choline bis(trifluoromethylsulfonyl)imide or the l-alkyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imides.
  • [Hbet][Tf 2 N] Due to its properties, mainly the metal dissolving properties, [Hbet][Tf 2 N] can be used for multiple purposes.
  • the [Hbet][Tf 2 N] ionic liquid can be used for the selective dissolution of metal oxides in the ionic liquid, extraction and back extraction (stripping) of metals, cleaning of metal surfaces, dissolution of palladium oxide to show the potential for recycling precious metals (platinum group metals) from catalysts and the electrodeposition of metals from the ionic liquid.
  • [Hbet][Tf 2 N] can be used in the following sectors:
  • Metal processing industry electrodeposition of metals, electroplating, electropolishing.
  • metals can be deposited from solutions of the metal salts in protonated betaine bis(trifluoromethylsulfonyl)imide or of the metal complexes of betaine bis(trifluoromethylsulfonyl)imide by electrolysis. After immersion of a zinc plate in an ionic liquid containing copper betaine bis(trifluoromethylsulfonyl)imide, the zinc plate is covered by a coating of metallic copper.
  • a copper plate can be coated with metallic silver by immersion in an ionic liquid containing silver betaine bis(trifluoromethylsulfonyl)imide; • Energy sector: electrolytes for batteries, fuel cells and photovoltaic cells;
  • Nuclear sector processing of spent nuclear fuel elements. Selective extraction of lanthanides and actinides from other fission products and from uranium;
  • protonated betaine bis(trifluoromethylsulfonyl)imide [HbCt][Tf 2 N]
  • HbCt protonated betaine bis(trifluoromethylsulfonyl)imide
  • Tf 2 N protonated betaine bis(trifluoromethylsulfonyl)imide
  • ionic liquid can be switched from a hydrophobic one to a hydrophilic one by temperature or pH control.
  • Elemental analyses (carbon, hydrogen, nitrogen) were made on a CE Instruments EA-1 1 10 elemental analyzer.
  • FTIR spectra were recorded on a Bruker IFS-66 spectrometer. The samples were measured using the KBr pellet method or as a thin film between KBr windows.
  • 1 H NMR spectra were recorded on a Bruker Avance 300 spectrometer (operating at 300 MHz).
  • the water content of the ionic liquids was determined by a coulometric Karl Fischer titrator (Mettler Toledo Coulometric Karl Fischer Titrator, model DL39). The viscosity of the ionic liquids was measured by the falling ball method (Gilmont Instruments).
  • DSC Differential scanning calorimetry
  • EXAMPLE 1 SYNTHESIS AND ANALYSIS OF BETAINE BIS(TRIFLUORO-METHYL- SULFONYDIMIDE.
  • [Hbet][Tf 2 N] and [Choi] [Tf 2 N] are miscible in any molar ratio.
  • a 1 :1 mixture does not crystallize after cooling in a refrigerator at 4°C, so an eutectic mixture is formed.
  • Choline bis(trifluoromethylsulfonyl)imide, [Chol][Tf 2 N] was prepared as described in the prior art.
  • a solution of choline chloride (1 mol, 139.62 g) in 250 mL of water was added under stirring to 500 mL of an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (1 mol, 287.08 g).
  • the mixture was stirred for one hour at room temperature and the aqueous phase separated from the ionic liquid. After separation of the phases the ionic liquid phase was washed three times with small amounts of water until no chloride impurities could be detected after adding silver nitrate.
  • Protonated betaine bis(trifluoromethylsulfonyl)imide [Hbet][Tf 2 N] is completely miscible with e.g. 1-octanol, benzonitrile, DMSO, acetonitrile, acetic acid, ethylacetate, ethanol and methanol.
  • the compound is immiscible with hexane, dichloromethane (DCM), chloroform, benzene, diethylether.
  • DCM dichloromethane
  • Toluene was found to exhibit a temperature dependent miscibility. While the solubility of toluene at room temperature is very low, the solubility increases markedly with temperature..
  • the ionic liquid is also miscible with other ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion, like the l-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides.
  • [Hbet][Tf 2 N] is a hydrophobic ionic liquid at room temperature. After addition of water, two separate phases are formed. Heating treatment of a mixture induced the formation of a one-phase- system at a critical temperature of 56 0 C.
  • the phase diagram of the [Hbet][Tf 2 N]/water system is shown in Figure 2. By cooling down the mixture the two phases are recovered. So the system [Hbet][Tf 2 N] /water is a temperature switchable one-phase/two-phase system.
  • [Hbet] [Tf 2 N] contains an acidic hydrogen atom and can be deprotonated by addition of a base.
  • [Hbet] [Tf 2 N] was mixed with different alkali metal hydroxides. 25 mmol of [Hbet] [Tf 2 N] was mixed with hot water and an aqueous solution of an alkali metal hydroxide was added dropwise until pH 7. The hydrophobic phase disappears. After acidification of the solution, two phase- system was reformed. After evaporation of the water phase under reduced pressure, and after neutralization of the ionic liquid, a hydrophilic salt remained with melting points above 100 0 C.
  • Lithium salt [Hbet][Tf 2 N] (16.63 g; 41.75 mmol) was added to 10 mL of an aqueous solution of LiOH (1 g;
  • the colorless crystals were recrystallized from water and dried at 50 0 C in a vacuum oven.
  • Table 3 Melting points and CHN-results for some alkali metal salts of [Hbet] [Tf 2 N].
  • EXAMPLE 7 SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES IN A THbetl [Tf 7 Nl - WATER MIXTURE
  • the following oxides were found to be soluble in the ionic liquid [Hbet] [Tf 2 Nl: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • hydroxides were found to be soluble in the ionic liquid rHbet!fTf>Nl: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2 , Fe(OH) 3 , Co(OH) 2 , Cr(OH) 3 , Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 and Ba(OH) 2
  • Pr 6 On (1 g; 0.97 mmol) was mixed with [Hbet][Tf 2 N] (7.018 g; 17.6 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
  • Neodymium(III) complex Nd 2 O 3 (1 g; 2.97 mmol) was mixed with [Hbet][Tf 2 N] (7.102 g; 17.8 mmol) and 10 mL of water.
  • Gadolinium(HI) complex Gd 2 O 3 (1 g; 2.75 mmol) was mixed with [Hbet][Tf 2 N] (6.592 g; 16.5 mmol) and 10 mL of water.
  • Ho 2 O 3 (1 g; 2.64 mmol) was mixed with [Hbet][Tf 2 N] (6.319 g; 15.8 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The purple crystals were recrystallized from water 3 times.
  • Tm 2 O 3 (1 g; 2.59 mmol) was mixed with [Hbet][Tf 2 N] (6.193 g; 15.5 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
  • Lu 2 O 3 (1 g; 2.51 mmol) was mixed with [Hbet][Tf 2 N] (6.005 g; 15.7 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
  • Zinc(II) complex ZnO (1 g; 12.3 mmol) was mixed with [Hbet][Tf 2 N] (9.788g; 24.5 mmol) and 10 mL of water.
  • Silver(I) complex Ag 2 O (1 g; 4.35 mmol) was mixed with [Hbet][Tf 2 N] (1.733g; 4.35 mmol) and 10 mL of water.
  • the mixture was stirred at room temperature and protected from light for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized 3 times from water.
  • NiO (1 g; 13.38 mmol) was mixed with [Hbet][Tf 2 N] (10.66 g; 26.7 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The green crystals were recrystallized from water 3 times.
  • the lanthanide-containing complexes described herein may be considered as ionic liquids, because the melting points of the compounds are below 100 0 C, in accordance with the definition of an ionic liquid.
  • the melting points are specified in table 4. At room temperature these complexes can be described as highly viscous supercooled liquids.
  • EXAMPLE 8 SOLUBILITY OF METAL OXIDES AND SALTS IN PURE THbetirTf ? N1 AND EXTRACTION PROCEDURES
  • Copper oxide is soluble in pure [Hbet] [Tf 2 N].
  • CuO (Ig) was stirred with 10 g of [Hbet] [Tf 2 N] for 2 hours at 70 0 C. The copper oxide was found to dissolve completely and a blue transparent solution was obtained. Also metal oxides of e.g.
  • Metal salts like CuCl 2 2H 2 O or EuCl 3 -OH 2 O are also soluble in [Hbet][Tf 2 N].
  • a) Solubility Of Cu 2+ An excess of copper chloride was added to [Hbet][Tf 2 N] (5g; 12.5 mmol). The mixture was stirred for 4 hours at 100 °C and the non-dissolved copper chloride was removed from the mixture. The metal content of the resulting solution was determined by titration with EDTA. 1.75 mol% CuCl 2 were found to dissolve in [Hbet][Tf 2 N].
  • the dissolved metals can easily be recovered from the ionic liquid phase by an extraction with an aqueous acid solution.
  • the metals are extracted into the aqueous phase while the ionic liquid phase is recovered and can be separated and reused.
  • Nd 2 O 3 (1 g; 2.97 mmol) was mixed with [Hbet][Tf 2 N] (7.102 g; 17.8 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. The water was evaporated and the ionic liquid phase was extracted twice with a 37% HCl solution. The neodymium ions were almost completely extracted to the aqueous phase after a second extraction with the acid. The same extraction can also be performed with HNO 3 .
  • Copper-containing [Hbet] [Tf 2 N] (100 mL) was heated in a beaker at 70 0 C. A zinc or iron metal plate was immersed into the ionic liquid. After a few minutes the copper metal was deposited on the surface of the zinc or iron plate, respectively.
  • Silver-containing [Hbet][Tf 2 N] (100 mL) was heated in a beaker at 7O 0 C. A copper metal plate was immersed into the ionic liquid. After a few minutes the silver metal was deposited on the surface of the copper plate.
  • EXAMPLE 1 1 SYNTHESIS OF N-CARBOXYMETHYL-METHYLPYRROLIDIUM BIS(TRIFLUOROMETHYLSULFONYLIIMIDE
  • N-methylpyrrolidinium 0.5 mol, 42.5 g
  • ethyl chloroacetate 0.5 mol, 61.2 g
  • the mixture was stirred for 2 days.
  • the crude product was washed with diethyl ether to remove unreacted starting materials.
  • the solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 hours. Water was evaporated under reduced pressure and the hydrochloride N-carboxymethyl-methylpyrrolidinium was recrystallized from a mixture of acetonitrile and methanol.
  • the ionic liquid does not form one phase with water upon heating.
  • the recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • N-methyl morpholinium 0.5 mol, 50.05g
  • ethyl chloroacetate 0.5 mol, 61.2 g
  • the mixture was stirred for 2 days at room temperature.
  • the crude product was washed with diethyl ether to remove unreacted starting materials.
  • the solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the N-carboxymethyl-methylmorpholinium hydrochloride was recrystallized from a mixture of acetonitrile and methanol.
  • the recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • the ionic liquid was then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator. A water content of 320 ppm was determined by coulometric Karl Fischer titration.
  • the recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • the ionic liquid was then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • the compound is a liquid at room temperature.
  • the recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • the ionic liquid was then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • the phosphonium ionic liquid does not form one phase with water upon heating.
  • N-carboxymethylpyridinium (0.5 mol, 86.5) was dissolved in water (100 ml) and an aqueous solution of lithium bis(t ⁇ ifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • the ionic liquid was then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • a mixture of N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide and water forms one phase above 55 0 C. Below 55 0 C, phase separation takes place.
  • EXAMPLE 18 REDUCTION OF THE VISCOSITY OF THE TASK-SPECIFIC IONIC LIQUIDS
  • the task-specific ionic liquids with the COOH functional group are in general viscous liquids. To make these ionic liquids more easy to handle, they can be mixed (diluted) with other ionic liquids. For instance, the task-specific ionic liquid l-carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was found to be miscible in all weight proportions with the ionic liquid 1 -butyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and these mixtures have a lower viscosity than the task-specific ionic liquid itself.
  • This compound was prepared by us a follows:
  • the recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added.
  • the ionic liquid separated from the water phase.
  • the ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test.
  • the ionic liquid was then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator. A water content of 67 ppm was determined by coulometric Karl Fischer titration.
  • M.p. liquid at room temperature.
  • EXAMPLE 19 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-MORPHOLINIUM
  • N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, [MHbetMor] [Tf 2 N] 5 g, 11.35 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • hydroxides were found to be soluble in the ionic liquid [MHbetMor] [Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2, Fe(OH) 3, Co(OH) 2, Cr(OH) 3, Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2, Sr(OH) 2 and Ba(OH) 2 .
  • EXAMPLE 20 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN « THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-PYRROLIDINIUM BISfTRIFLUOROMETHYLSULFONYLMMIDE
  • N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MHbetPyr] [Tf 2 N] 5 g, 11.78 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • hydroxides were found to be soluble in the ionic liquid [MHbetPyr] [Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2, Fe(OH) 3, Co(OH) 2, Cr(OH) 3 , Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2, Sr(OH) 2 and Ba(OH) 2 .
  • N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MEHbetPyr] [Tf 2 N] 5 g, 1 1.05 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • the following oxides were found to be soluble in the ionic liquid [MEHbetPyr] [Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 On, Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • hydroxides were found to be soluble in the ionic liquid [MEHbetPyr] [Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2 , Fe(OH) 3 , Co(OH) 2 , Cr(OH) 3 , Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2, Sr(OH) 2 and Ba(OH) 2
  • EXAMPLE 22 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-PIPERIDINIUM
  • N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, [MHbetPip] [Tf 2 N] 5 g, 11.40 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide, [HbetMIM] [Tf 2 N] 5 g, 11.86 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • the following oxides were found to be soluble in the ionic liquid [HbetMIM] [Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 Ou, Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • hydroxides were found to be soluble in the ionic liquid [HbetMIM] [Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2 , Fe(OH) 3 , Co(OH) 2 , Cr(OH) 3 , Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 and Ba(OH) 2 .
  • EXAMPLE 24 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID P-CARBOXYMETHYL-TRIBUTYL-PHOSPHONIUM
  • the following oxides were found to be soluble in the ionic liquid [HbetPhos] [Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 Ou, Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide, [HbetPy] [Tf 2 N] 5 g, 11.95 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • the following oxides were found to be soluble in the ionic liquid [HbetPy] [Tf 2 N] : Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 On, Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • EXAMPLE 26 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID L-CARNITINE BIS(TRIFLUOROMETHYL-SULFONYLtIMIDE
  • Tb 4 O 7 Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • hydroxides were found to be soluble in the ionic liquid [LCAR][Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2 , Fe(OH) 3, Co(OH) 2 , Cr(OH) 3 , Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 and Ba(OH) 2 .
  • EXAMPLE 27 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- CARBOXYMETHYL-METHYLPIPERIDINIUM BIS(TRIFLUOROMETHYL-
  • N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, [MHbetPip] [Tf 2 N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 140 0 C for 24 hours in a PTFE-Iined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum.
  • EXAMPLE 28 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
  • N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, [MHbetMor] [Tf 2 N] (I g, 2.27 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O 0 C for 24 hours in a PTFE-lined acid digestion bomb (No.
  • EXAMPLE 29 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
  • EXAMPLE 30 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
  • N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MEHbetPyr] [Tf 2 N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 140 0 C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum.
  • N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide [HbetMIM] [Tf 2 N] (1 g, 2.37 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 140 0 C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum.
  • EXAMPLE 33 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID P-
  • EXAMPLE 34 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
  • N-carboxymethyl-pyridinium bis(trifluoromethylsulfonyl)imide, [HbetPy] [NTf 2 ] (1 g, 2.39 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O 0 C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetPy] [Tf 2 N] under high pressure: CO 3 O4, CoO, Co 2 O 3 , Cr 2 O 3 , FeO and Fe 2 O 3 .
  • EXAMPLE 35 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID L- CARNITINE BIS(TRIFLUOROMETHYLSULFONYL)IMIDE UNDER HIGH PRESSURE
  • L-carnitine bis(trifluoromethylsulfonyl)imide, [L-Car] [Tf 2 N] (1 g, 2.26 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 140 0 C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [L-Car][Tf 2 N] under high pressure: Co 3 O 4 , CoO, Co 2 O 3 , Cr 2 O 3 , FeO and Fe 2 O 3 .
  • EXAMPLE 36 SYNTHESIS OF N-DIMETHYL-N-BUTYL-BETAINIUM BIS (TRI- FLUOROMETHYLSULFONYDIMIDE
  • EXAMPLE 38 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN
  • N-imethyl-N-butyl-betainium bis(trifluoromethylsulfonyl)imide, [C4Hbet] [Tf 2 N] 5 g, 1 1.35 mmol was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or metal hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum.
  • the following oxides were found to be soluble in the ionic liquid [C4Hbet] [Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 On, Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • EXAMPLE 39 SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-DIMETHYL-N-HEXYL-BETAINIUM BIS(TRIFLUOROMETHYL- SULFONYLttMIDE
  • the following oxides were found to be soluble in the ionic liquid [C ⁇ Hbet] [Tf 2 N]: Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Pr 6 O n , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , UO 3 , PbO, ZnO, CdO, HgO, CuO, Ag 2 O, NiO, PdO, and MnO.
  • hydroxides were found to be soluble in the ionic liquid [C ⁇ Hbet] [Tf 2 N]: Pb(OH) 2 , Zn(OH) 2 , Cd(OH) 2 , Cu(OH) 2 , Ni(OH) 2 , Fe(OH) 2, Fe(OH) 3, Co(OH) 2, Cr(OH) 3, Mn(OH) 2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2, Sr(OH) 2 and Ba(OH) 2
  • EXAMPLE 40 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- DIMETHYL-N-BUTYL-BETAINIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
  • EXAMPLE 41 SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- DIMETHYL-N-BUTYL-BETAINIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
  • [Hbet][Tf 2 N] and [C 4 HbCt] [Tf 2 N] are insoluble in dichloromethane (DCM)
  • [C 6 Hbet] [Tf 2 N] is soluble in this solvent.
  • [Hbet][Tf 2 N] is insoluble in chloroform
  • [C 4 Hbet][Tf 2 N] is partially soluble
  • [C 6 Hbet] [Tf 2 N] is soluble.
  • R 1 , R 2 , and R 3 are all Ci, C 2 , or C 3 alkyl, in order to obtain ionic liquids with the following properties: miscible with water, in particular above 50 0 C, and insoluble in non- ionic organic solvents, more in particular dichloromethane or chloroform.
  • R 4 is Ci or C 2 alkyl-COOH, when R 1 , R 2 , and R 3 are Ci, C 2 , or C 3 alkyl.
  • the ionic liquids of this invention wherein R 4 is Ci or C 2 alkyl-COOH are easy to synthesize and cheap.
  • the solubilization of metal oxides and metal hydroxides is increased when R 4 is Ci or C 2 alkyl-COOH compared to C 3 or more (>C 3 ) alkyl-COOH, more in particular the solubilization of metal oxides and metal hydroxides is the highest when R 4 is -CH 2 - COOH (Ci alkyl-COOH).
  • the positive charge on the quaternary nitrogen (or phosphor, arsenicum or antimony) atom has an inductive effect on the COOH-group. This effect is affected by the chain length in-between the COOH-group and the positively charged nitrogen (or phosphor, arsenicum or antimony) atom, respectively.
  • the shorter the distance between these functional groups the higher the acidity of the proton of the COOH-function. Therefore, one or two CH 2 groups in-between, and preferably one CH 2 group in-between is favorable for the application of this invention: these ionic liquids exhibit a significantly higher solubilizing ability for metal oxides than ionic liquids with three or more CH2-groups between the positively charged heteroatom and the COOH-function.
  • tributylarsine 0.05 mol, 12.31 g
  • ethyl chloroacetate 0.05 mol, 6.12 g
  • the mixture is stirred for 5 days at room temperature.
  • the crude product is washed with diethyl ether to remove unreacted starting materials.
  • the solid compound is refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water is evaporated under reduced pressure and As-carboxymethyl-tributylarsonium hydrochloride is recrystallized from a mixture of acetonitrile and methanol.
  • the recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added.
  • the ionic liquid separates from the water phase.
  • the ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test.
  • the ionic liquid is then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • the recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added.
  • the ionic liquid separates from the water phase.
  • the ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test.
  • the ionic liquid is then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • the recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added.
  • the ionic liquid separates from the water phase.
  • the ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test.
  • the ionic liquid is then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • the recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added.
  • the ionic liquid separates from the water phase.
  • the ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test.
  • the ionic liquid is then evaporated to dryness at 80 0 C under vacuum on a rotary evaporator.
  • a solution of 3-carboxy-2-oxopropyl-trimethylammonium hydroxide inner salt (dehydrocarnitine) (0.05 mol, 7.96 g) in 100 mL of water is added under stirring to an aqueous solution of hydrogen bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.21 g).
  • the mixture is stirred for one hour in an ice bath.
  • the aqueous phase separated from the ionic liquid. After separation of the phases, the ionic liquid phase is dissolved in acetone, the excess of dehydrocarnitine precipitates.
  • the ionic liquid is evaporated to dryness at 80 0 C in vacuum on a rotary evaporator.

Abstract

The present invention provides for novel organic salts, more specifically ionic liquids and for methods for the preparation of such novel ionic liquids. The invention also provides for the use of the ionic liquids in chemistry applications, for example for the solubilization of metal oxides, hydroxides and salts, for the deposition of metals or for extraction procedures, among others. The invention furthermore provides for a method for the solubilization of metal oxides and metal salts, for the deposition of metals and for extraction procedures, this by using the novel ionic liquids. The present invention furthermore provides for materials obtained by the methods hereof.

Description

NOVEL IONIC LIQUIDS
FIELD OF THE INVENTION
The present invention provides for novel organic salts, more specifically ionic liquids and for methods for the preparation of such novel ionic liquids. The invention also provides for the use of the ionic liquids in chemistry applications, for example for the solubilization of metal oxides, hydroxides and salts, for the deposition of metals or for extraction procedures, among others. The invention furthermore provides for a method for the solubilization of metal oxides and metal salts, for the deposition of metals and for extraction procedures, this by using the novel ionic liquids. The present invention furthermore provides for materials obtained by the methods hereof.
BACKGROUND OF THE INVENTION
There is much current interest in ionic liquids. These compounds are examples of molten salts that are liquid at temperatures below 100 0C or sometimes even at room temperature (Welton, T.
Chem. Rev. 1999, 99, 2071-2083). The much lower melting points of ionic liquids compared to those of inorganic salts can be partially attributed to the bulky cationic groups, i.e. low charge density and incompatibility of Coulombic attraction forces with steric hindrance. Ionic liquids have very low vapor pressures, although it was recently shown that they are distillable (Earle, M.J. Nature 2006, 439, 831-834). Therefore they do not produce hazardous vapors (in contrast to many conventional solvents). Most ionic liquids have high ignition points and they do not generate explosive air-vapor mixtures. They can act as solvents for chemical reactions, including catalytic reactions (Parvulescu, V. I.; Hardacre, C. Chem. Rev. 2007, 707, 2615-2665). Ionic liquids are an interesting reaction medium for the synthesis of unusual inorganic compounds (Taubert, A.; Li, Z. Dalton Trans. 2007, 723-727). They find use in electrochemical applications, for example as electrolytes in batteries, and in photovoltaic devices, but also as a medium for electrodeposition or electropolishing of metals.
Especially for electrochemical applications and for applications in solvent extraction technology, ionic liquids should have a high solubilizing power for metal salts, including metal oxides. To avoid leaching of the metal catalyst in catalytic reactions, it is of importance to have ionic liquids that can keep metals dissolved in them. A good solubility of metal salts is observed for ionic liquids based on aluminum chloride, such as mixtures of l-ethyl-3-methylimidazolium chloride and aluminum chloride ([C2InJm]Cl - AlCl3), and mixtures of 1-butylpyridinium chloride and aluminum chloride (BPC - AICI3). Unfortunately, these systems suffer from extreme water sensitivity. Compounds like the l-alkyl-3-methylimidazolium hexafluorophosphate, [Cnmim][PF6], are room temperature ionic liquids with a much lower sensitivity towards water. Unfortunately, these ionic liquids and related ones like the l-alkyl-3- methylimidazolium tetrafluoroborates or the l-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides have a low solubility for metal salts. This can be explained by the weakly-coordinating properties of the constituting anions and cations, so that the solvation energy is not high enough to break the binding interactions between the ions or molecules of the metal-containing compounds in the solid state.
To overcome the problems with the solubility of metal salts, researchers have developed so-called "task-specific ionic liquids" (TSILs), which are ionic liquids with a functional group covalently tethered to the cationic or anionic part (Davis, J. H. Jr. Chem. Lett. 2004, 33, 1072- 1077). When the functional group has the ability to coordinate to the metal ion (preferably as a bidentate or a polydentate ligand), it is easier to dissolve metal oxides or metal salts into the ionic liquid. As a rule, these task-specific ionic liquids are not used as single-component ionic liquids, but they are mixed with more conventional ionic liquids. A rationale to use mixtures rather than pure task-specific ionic liquids is that the task-specific ionic liquids often have a higher melting point and a higher viscosity than conventional ionic liquids. Moreover, the conventional ionic liquids are in general much cheaper than the task-specific ionic liquids. An example of a task- specific ionic liquid is an imidazolium salt incorporating a thiourea moiety, which has been used for the extraction of mercury(H) and cadmium(II) from an aqueous phase (Visser, A. E. et al. Chem. Commun. 2001, 135-136). Task-specific ionic liquids with appended tertiary phosphine groups have been used to immobilize rhodium(I) organometallic catalysts in [C4mim][PFδ] (Kottsieper, K. W. et al. J. MoI. Catal. A 2001, 175, 285-288).
The major drawback of these task-specific ionic liquids is that they are often only accessible after a multistep synthetic procedure. The time-consuming preparation of these ionic liquids restricts their use in large-scale industrial applications. Therefore, the development of task-specific ionic liquids that can readily be prepared from cheap raw materials is an important research target. Task-specific ionic liquids that can be prepared from renewable natural resources would even be better. Abbott and coworkers obtained ionic liquids by mixing choline chloride with hydrated transition metal salts (Abbott, A. et al. Chem. Eur. J. 2004, 10, 3769-3774), or with anhydrous zinc(II) chloride or tin(II) chloride (Abbott, A. P. et al. Chem. Commun. 2001, 2010- 2011; Abbott, A. P. et al. Inorg. Chem. 2004, 43, 3447-3452). The same research group also prepared ionic liquids by mixing choline chloride with urea in a 1 :2 molar ratio (Abbott, A. P. et al. Chem. Commun. 2003, 70-71). These mixtures of choline chloride and urea are called "deep eutectic solvents". They can dissolve different types of metal oxides as well as metal salts, but the solubility of the metal salts in these ionic-liquid-like mixtures is in general less than 1 wt.% (Abbott, A. P. et al. Inorg. Chem. 2005, 44, 6497-6499). Choline chloride (also known as 2- hydroxyethyltrimethyl ammonium chloride or vitamin B4) is a cheap commodity chemical that is produced annually on a multi-ton scale. Its main use is as an animal feed additive. Choline chloride itself is a solid with a high melting point (m.p. = 298-304 0C). Although ionic liquids based on choline chloride have the advantages of being cheap, they are all hydrophilic and miscible with water or with polar solvents. This is a problem for applications like the extraction of metal ions from an aqueous phase or like the electrodeposition of reactive metals (e.g. aluminum, magnesium, tantalum and the rare earths). Metal complexes with the zwitterionic ligand betaine have been investigated for a long time, but none of these complexes contain the bis(trifluoromethylsulfonyl)imide anion.
The closest prior art (WO 2004/029004) describes the compositions that contain ioniq liquids and their use in organic synthesis, but does not describe the ionic liquids of the present invention.
Therefore, it is clear that there is a need for further alternative ionic liquids, which are cheap, easy to produce, are obtained from renewable natural resources, are water immiscible, have good metal solubilization properties and/or are renewable. The present invention fulfils this need by the provision of novel ionic liquids. SUMMARY OF THE INVENTION
The present invention provides for novel organic salts, more specifically ionic liquids and for methods for the preparation of such novel organic salts, more specifically ionic liquids. The invention also provides for the use of the organic salts, more specifically ionic liquids in chemistry applications. The invention furthermore provides for chemistry applications, like a method for the solubilization of metal oxides, by using the novel organic salts, more specifically ionic liquids. The present invention furthermore relates to compositions, (solutions, complexes or mixtures among others) comprising said organic salts, more specifically ionic liquids and to materials obtained by the methods using said organic salts, more specifically ionic liquids. The present invention also relates to the use of said compositions comprising said organic salts, more specifically ionic liquids or of the materials obtained by the methods using said organic salts, more specifically ionic liquids.
A first aspect of the present invention relates to novel organic salts, in a more particular case novel ionic liquids. The organic salts of the present invention have a quaternary ammonium, phosphonium, arsonium, or stibonium structure according to formula (I):
R1R2R3R4Y+X"
I wherein - Y is selected from N; P; As; or Sb;
- each of R1, R2 and R3 are independently selected from CM2 alkyl; or C3-I2 cycloalkyl; or each of R1 and R2, or R1 and R3, or R2 and R3 can be taken together to form a substituted or unsubstituted cyclic structure;
- R4 is selected from a Cu2 alkyl-COOH; or C3.12 cycloalkyl-COOH; wherein alkyl is optionally substituted with at least one OH or comprises at least one carbonyl function;
- X- is selected from organic sulfonates; organic sulfates; organic carboxylates; organic sulfonylimides; or tetrafluoroborate.
In a particular embodiment, R1, R2, R3, R4, Y and X" are as described in formula I, but R4 is not C3 alkyl-COOH or C2 alkyl-COOH when Y is N and R1, R2 and R3 are all methyl and X- is bis(trifluoromethylsulfonyl)imide (Tf2N'). In a more particular embodiment, R1, R2, R3, R4, and Y are as described in formula I, and X' is bis(trifluoromethylsulfonyl)imide but R4 is not C3 alkyl- COOH when Y is N and R1, R2 and R3 are all methyl.
In a particular embodiment, each of R1, R2 and R3 are independently selected from Ci.g alkyl and C3-J cycloalkyl, yet more in particular are independently selected from Ci-6 alkyl and C3-6 cycloalkyl, still more particularly are independently selected from CM alkyl, yet more particularly from Ci-3 alkyl. In a preferred embodiment, each of R1, R2 and R3 are the same and more particularly are methyl, ethyl, propyl, butyl, hexyl, or octyl.
In another particular embodiment, R4 is selected from Cj-S alkyl-COOH and C3.g cycloalkyl- COOH, still more in particular is selected from Ci-6 alkyl-COOH and C3-6 cycloalkyl-COOH, yet more particularly is CM alkyl-COOH or Ci-3 alkyl-COOH and yet more preferably is Ci-2 alkyl- COOH and even more preferably is -CH2COOH. In another particular embodiment, R1, R2, R3, Y, and X" are as described in formula I, and R4 is Ci or C2 alkyl-COOH or C3-I2 cyclo alkyl, more prefarably is Ci or C2 alkyl-COOH, even more preferably is -CH2COOH. In yet another particular embodiment, R1, R2, R3, and Y are as described in formula I, and R4 is Ci or C2 alkyl- COOH more prefarably is -CH2COOH, and X" is Tf2N".
In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P, As or Sb, and R1, R2, R3 and R4 and X' are as described in formula I, more preferably X" is Tf2N". In a more preferred embodiment, R1R2R3R4Y+ is betaine, wherein Y is N, R1 is -CH3, R2 is -CH3, R3 is -CH3 and R4 is -CH2COOH.
In a particular embodiment, X" is selected from organic sulfonates, preferably perfluorinated organic sulfonates; organic sulfates, preferably perfluorinated organic sulfates; organic sulfonylimides, preferably perfluorinated organic sulfonylimides ; or organic carboxylates, preferably perfluorinated organic carboxylates, such as methyl sulfonate (CH3SO3 "), bis(trifluoromethylsulfonyl)imide (Tf2N"), bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, bis(perfluorohexylsulfonyl)imide, triflate (TfO"), pentafluorobenzoate (C6FsCOO") and dodecylsulfate (Ci2H25OSO3 "). In another particular embodiment, X" is selected from perfluoro-Cuπalkyl-sulfonylimide (or more particularly from perfluoro-Ci^alkyl-sulfonylimide, such as bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, or bis(perfluorohexylsulfonyl)imide), more specifically is bis(trifluoromethylsulfonyl)imide (Tf2N ).
In a more preferred embodiment, the organic salt is betaine bis(trifiuoromethylsulfonyl)imide. Such organic salts may be in protonated or unprotonated form. The structure of betaine bis(trifluoromethylsulfonyl)imide in protonated form is according to formula II:
Figure imgf000007_0001
II
In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is N or P, more preferably wherein Y is N. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P and X' is Tf2N'. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is N and X" is Tf2N". In another particular embodiment, the present invention relates to an organic salt of formula I wherein R1 and R2, or R1 and R3, or R2 and R3 form a substituted or unsubstituted cyclic structure, and wherein Y, R4, and X' are as desribed in formula I, more preferably Y is N or P, even more preferably Y is N. In another particular embodiment, the present invention relates to an organic salt of formula I wherein R1 and R2, or R1 and R3, or R2 and R3 form a substituted or unsubstituted cyclic structure, and wherein R4 is as desribed in formula I, and wherein Y is N and X" is Tf2N'. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P, and R1, R2 and R3 are independently selected from CM2 alkyl, and R4 and X" are as desribed in formula I, more preferably X' is Tf2N'. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is N, and R1, R2, R3 and X" are as described in formula I, and R4 is a substituated CM2 alkyl-COOH, more preferably R4 is a CM2 alkyl-COOH wherein at least one OH group is present in alkyl or at least one carbonyl (C=O) group is present in alkyl, more preferably one OH group is present in alkyl or one carbonyl (C=O) group is present in alkyl. In another particular embodiment, the present invention relates to an organic salt of formula 1, wherein Y is N and R4 is selected from a substituted Ci-3 alkyl-COOH wherein at least one OH group is present, or a Ci-3 alkyl-COOH which contains at least one carbonyl group. In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is N, and R1, R2 and R3 are as described in formula I, and R4 is a substituated CM2 alkyl-COOH, and X" is Tf2N". In another particular embodiment, the present invention relates to an organic salt of formula I wherein Y is P and R4 is -CH2CH2COOH or -CH2COOH, and even more particularly Y is P and R4 is -CH2COOH. In a more preferred embodiment, R1R2R3R4Y+ is carboxymethyl- tributylphosphonium, wherein Y is P and R1 is butyl, R2 is butyl, R3 is butyl and R4 is - CH2COOH. In another preferred embodiment, the organic salt is P-carboxymethyl- tributylphosphonium bis(trifluoromethylsulfonyl)imide. The structure of this organic salt is according to formula III:
Figure imgf000008_0001
III
In another particular embodiment, the present invention relates to an organic salt of formula I wherein R4 is as desribed herein, and Y is N and R1 and R2, or R1 and R3, or R2 and R3 forms a pyrrolidinium ring structure. In a more preferred embodiment, R1R2R3R4Y4 is N-carboxymethyl- methylpyrrolidinium, wherein Y is Ν and together with R1 and R2, or R1 and R3, or R2 and R3 said Ν forms a pyrrolidinium ring structure, and R4 is -CH2COOH. In another preferred embodiment, the organic salt is N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula IV:
Figure imgf000009_0001
IV
In another preferred embodiment, R1R2R3R4Y+ is N-carboxyethyl-methylpyrrolidinium, wherein Y is N and together with R1 and R2, or R1 and R3, or R2 and R3 said N forms a pyrrolidinium ring structure, and R4 is -CH2CH2COOH. In another preferred embodiment, the organic salt is N- carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula V:
Figure imgf000009_0002
V In another particular embodiment, the present invention relates to an organic salt of formula I wherein R4 is as described herein, and Y is N and together with R1 and R2, or R1 and R3, or R2 and R3 said N forms a morpholinium ring structure. In a more preferred embodiment, R1R2R3R4Y+ is JV-carboxymethyl-methylmorpholinium, wherein Y is N and together with R1 and R2, or R1 and R3, or R2 and R3 said N forms a morpholinium ring structure, and R4 is - CH2COOH. In another preferred embodiment, the organic salt is N-carboxymethyl- methylmorpholinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula VI:
Figure imgf000010_0001
VI
In another particular embodiment, the present invention relates to an organic salt of formula I wherein R4 is as desribed herein, and Y is N and together with R1 and R2, or R1 and R3, or R2 and R3 said N forms a piperidinium ring structure. In a more preferred embodiment, R1R2R3R4Y+ is N-carboxymethyl-methylpiperidinium, wherein Y is Ν and together with R1 and R2, or R1 and R3, or R2 and R3 said Ν forms a piperidinium ring structure, and R4 is -CH2COOH. In another preferred embodiment, the organic salt is N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula VII:
Figure imgf000010_0002
VII
In yet another particular embodiment, the present invention relates to an organic salt of formula I wherein R1, R2 and R3 are as desribed herein, and R4 is selected from CM2 hydroxyalkyl-COOH, still more in particular is selected from Ci-3 hydroxyalkyl-COOH, even more particularly is - CH2CH2OHCH2COOH. In another preferred embodiment, R1R2R3R4Y+ is carnitine. In another preferred embodiment, the organic salt is carnitine bis(trifiuoromethylsulfonyl)imide, the structure of which is according to formula VIII:
Figure imgf000011_0001
VIII
In a a particular embodiment carnitine is in L- or D-carnitine or a mixture of L- and D-carnitine, being a racemic mixture. In another particular embodiment carnitine is L-carnitine.
In another particular embodiment, the present invention relates to an organic salt of formula I wherein R4 is as desribed herein, and Y is N and together with R1 and R2, or R1 and R3, or R2 and R3 said N forms a pyridinium ring structure. In a more preferred embodiment, R1R2R3R4Y+ is N- carboxymethyl-methyl pyridinium, wherein Y is Ν and together with R1 and R2, or R1 and R3, or R2 and R3 said Ν forms a pyridinium ring structure, and R4 is -CH2COOH. In another preferred embodiment, the organic salt is N-carboxymethyl-methylpyridinium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula IX:
Figure imgf000011_0002
IX
In another particular embodiment, the organic salt is Ν-dimethyl-Ν-butyl-betainium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula X:
Figure imgf000012_0001
X
In another particular embodiment, the organic salt is N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide, the structure of which is according to formula XI:
Figure imgf000012_0002
XI For all embodiments of the invention, X' is selected from bis(trifluoromethylsulfonyl)imide
(Tf2N"), bis(pentafluoroethylsulfonyl)imide, bis(heptafluoropropylsulfonyl)imide, bis(nonafluorobutylsulfonyl)imide, bis(perfluoropentylsulfonyl)imide, bis(perfluorohexyl- sulfonyl)imide, more preferably X" is bis(trifiuoromethylsulfonyl)imide (Tf2N").
The organic salts of the invention are in a 100% pure form or are not mixed with any other ionic liquids.
A second aspect of the present invention relates to a process for the preparation of the ionic liquids described herein, said process comprising the step of performing the metathesis reaction of
Figure imgf000012_0003
and salts of - preferably perfluorinated -organic sulfonate, organic sulfate, organic sulfonylimide anions or organic carboxylate anions in water. More particularly, the present invention relates to the preparation of betaine bis(trifluoromethylsulfonyl)imide by the metathesis reaction of betaine chloride or betaine bromide and lithium bis(trifluoromethylsulfonyl)imide in water. The ionic liquid betaine bis(trifluoromethylsulfonyl)imide can also be prepared by the reaction between R'R^R^hydroxide and the acid hydrogen bis(trifluoromethylsulfonyl)imide. Another aspect of the present invention relates to the products obtained by the process comprising the step of performing the metathesis reaction of R1R2R3R4Y+halogenide and salts of - preferably perfluorinated - organic sulfonate, organic sulfate, organic sulfonylimide or organic carboxylate anions in water as described herein. In a more particular embodiment, the present invention relates to the organic salt obtained by mixing betaine halogenide and lithium bis(trifluoromethylsulfonyl)imide in water or by mixing betaine hydroxide and hydrogen bis(trifluoromethylsulfonyl)imide.
A third aspect of the present invention relates to the use of the organic salts of the present invention for general chemical applications at higher temperatures such as a solvent, for extraction procedures, as a reaction medium, for electrodeposition, among others. In a particular embodiment, the present invention relates to the use the organic salts, more specifically of betaine bis(trifluoromethylsulfonyl)imide, as an ionic liquid and to the use of said ionic liquids as described herein for industrial applications, more specifically chemical applications, yet more specifically chemical applications involving metals such as:
- the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; - extraction procedures, more in particular for the extraction of metal ions from metallurgical slags or from pulverized mixtures of metal oxides with silicate or aluminosilicate rocks;
- decontamination of soils contaminated by heavy metals (especially with copper, nickel, zinc, cadmium, mercury or lead);
- for catalytic reactions wherein the ionic liquid serves as a solvent or as a catalyst; - for electrodeposition of metal ions, wherein as an example, the ionic liquid serves as a solvent for the metal precursors;
- as a medium for electropolishing or for the cleaning of metal surfaces by for example the removal of surface oxidation layers;
- electrodeposition of (thin) metal layers on conductive surfaces; - for the processing of spent nuclear fuel elements: dissolution of MOX or other oxides nuclear fuel elements for separation of fission products and fissile material;
- as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices;
- for recycling of noble metals from used catalysts and electronic circuits.
Another aspect of the present invention relates to methods for performing chemical applications by using the ionic liquids as described herein. The present invention thus relates to methods for:
- the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts;
- extraction procedures, more in particular for the extraction of metal ions from metallurgical slags or from pulverized mixtures of metal oxides with silicate or aluminosilicate rocks;
- decontamination of soils contaminated by heavy metals (especially with copper, nickel, zinc, cadmium, mercury or lead);
- catalytic reactions wherein the ionic liquid serves as a solvent or as a catalyst;
- electrodeposition of metal ions, wherein as an example the ionic liquid serves as a solvent for the metal precursors;
- electropolishing or for the cleaning of metal surfaces, by for example the removal of surface oxidation layers;
- electrodeposition of (thin) metal layers on conductive surfaces;
- the processing of spent nuclear fuel elements: dissolution of MOX or other oxides nuclear fuel elements for separation of fission products and fissile material
- recycling of noble metals from used catalysts and electronic circuits; by using the novel ionic liquids described herein.
The present invention furthermore relates to a method for performing chemical reactions and/or extractions by using the ionic liquids, more specifically betaine bis(trifluoromethylsulfonyl)imide ionic liquid and comprising the steps of:
- mixing betaine bis(trifiuoromethylsulfonyl)imide with one or more other liquids at higher temperatures (for example for a mixture with water at a temperature above 55.5 or 60 0C), alternatively further comprising other organic or inorganic compounds; and
- separating betaine bis(trifluoromethylsulfonyl)imide from the other liquid(s) by cooling the temperature to room temperature or slightly above (i.e. between 25 0C and 40 0C). The present invention also relates to a method for performing chemical reactions and/or extractions by using the ionic liquids, more specifically betaine bis(trifluoromethylsulfonyl)imide ionic liquid and comprising the steps of:
- mixing betaine bis(trifluoromethylsulfonyl)imide with an alkali-hydroxide aqueous solution, alternatively further comprising other organic or inorganic compounds; and - separating betaine bis(trifluoromethylsulfonyl)imide from water by acidification, for example with inorganic acids such as a solution of hydrogen chloride.
Yet another aspect of the present invention relates to compositions, such as solutions, mixtures or complexes, comprising the organic salts, more specifically the ionic liquids described herein, in a particular embodiment comprising betaine bis(trifluoromethylsulfonyl)imide in protonated or unprotonated form.
In a particular embodiment, said compositions are complexes or solutions of the ionic liquids described herein, which are in a more particular embodiment metal complexes of the ionic liquids such as betaine bis(trifluoromethylsulfonyl)imides with zinc, cadmium, mercury, lead, copper, nickel, silver, gold, palladium, platinum, rhodium, rare earths (scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), thorium, uranium, neptunium, plutonium, americium, curium, californium or berkelium. In another particular embodiment, said compositions are mixtures of the ionic liquids described herein with one or more other liquids such as water, organic solvents (such as toluene) or other ionic liquids such as bis(trifluoromethylsulfonyl)imide comprising ionic liquids (i.e. choline bis(trifluoromethylsulfonyl)imide), among others. Such mixtures may be consisting of one phase or may be separated in two or multiple phases, this in a particular embodiment depending on the conditions such as the temperature or the pH. The mixtures may comprise the ionic liquids of the present invention in different ratios, ranging from 0.1% to 99.9%, or from 1% to 99 %, or from 5% to 95%.
Yet in another particular embodiment, said compositions are solutions of organic or inorganic compounds in the ionic liquids of the present invention. Another aspect relates to the process for the preparation of compositions of the organic salts or ionic liquids described herein, comprising the step of mixing the organic salts or ionic liquids with other liquids, with gases or solid compounds. In a particular embodiment, the invention relates to the process for the preparation of metal complexes of betaine bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with betaine bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-carboxymethyl- methylmorpholinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylpyrrolidinium bis(trifiuoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxyethyl- methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-carboxymethyl- methylpiperidinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-rnethylpiperidinium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of P-carboxymethyl-tributylphosphonium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with P-carboxymethyl- tributylphosphonium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N- carboxymethylpyridinium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of L-carnitine bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with L-carnitine bis(trifluoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N-dimethyl-N-butyl-betainium bis(trifiuoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-dimethyl-N-butyl-betainium bis(trifiuoromethylsulfonyl)imide. In another particular embodiment, the invention relates to the process for the preparation of metal complexes of N- dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imides starting from metal oxides or metal hydroxides and mixing them with N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide.
Another particular aspect relates to the compositions (such as solutions, mixtures or complexes) obtained by the process of mixing the organic salts or ionic liquids described herein with other liquids, with gases or solid compounds (such as inorganic or organic compounds). In a particular embodiment, the present invention relates to solutions prepared by dissolution of metal salts in the ionic liquids of the present invention. In a more preferred embodiment, the ionic liquid is betaine bis(trifluoromethylsulfonyl)imide.
Yet another aspect relates to the use of said compositions for industrial applications. A particular embodiment relates to the use of said compositions in chemical applications, more in particular chemical applications involving metals such as metal oxides, metal hydroxides or metal salts.
Another particular embodiment relates to the use of said compositions in chemical applications, wherein said chemical applications are selected from the list of as a solvent, for example for the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; for extraction procedures, more in particular for the extraction of metal ions; for decontamination of soils contaminated by heavy metals especially with copper, nickel, zinc, cadmium, mercury or lead; for catalytic reactions wherein the ionic liquid serves as a solvent or as a catalyst; for electrodeposition of metal ions; as a medium for electropolishing or for the cleaning of metal surfaces; for deposition of metals onto conductive surfaces; for the processes of spent nuclear fuel elements; as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices and for recycling of noble metals from used catalysts and electronic circuits. One embodiment relates to the use of the lithium complex of betaine bis(trifiuoromethylsulfonyl)imide as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices. Another embodiment relates to the use of lanthanide complexes of betaine bis(trifluoromethylsulfonyl)imide as ionic liquids.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 : Temperature-dependent phase behavior of a binary [Hbet][Tf2N] -water mixture. The bluish [Cu(bipy)Cl2] complex (depicted as dark grey in Figure 1) was dissolved in the ionic liquid to accentuate the phase boundaries.
Figure 2: The liquid-liquid equilibrium phase diagram of the binary mixture [Hbet] [Tf2N] - water.
Figure 3: Illustration of the pH-dependent phase behavior of a binary [Hbet] [Tf2N] - water mixture. A two-phase system is obtained for acidic and neutral conditions, whereas a one-phase system is observed for alkaline conditions ( pH > 8). The dye methyl red was added to make the phase boundaries better visible (depicted as dark grey in Figure 3).
Figure 4: Transfer of copper(II) from the ionic liquid [Hbet][Tf2N] to the aqueous phase upon acidification of the aqueous phase by a hydrogen chloride solution.
Figure 5: Phase diagram of a water / N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide system.
DETAILED DESCRIPTION OF THE INVENTION
Definitions and nomenclature. We name the ionic liquid presented in formula I as protonated betaine bis(trifluoromethylsulfonyl)imide, [HbCt][Tf2N]. Here we represent the cation betaine by Hbet rather than by bet, because in [Hbet][Tf2N] the carboxylate group is protonated. Protonated betaine is sometimes also named as betainium58, but this name has not received widespread use. The anion bis(trifluoromethylsulfonyl)imide is also known as (CF3SO2)2N\ PMS, BTFSI, TFSI, Tf2N Or Tf2N". However, it should be clear to a person skilled in the art that the organic salts described in the present invention can be in different forms, protonated or unprotonated or with different counterions.
In each of the following definitions, the number of carbon atoms represents the maximum number of carbon atoms generally optimally present in the substituent or linker; it is understood that where otherwise indicated in the present application, the number of carbon atoms represents the optimal maximum number of carbon atoms for that particular substituent or linker. The term "Cu2 alkyl" as used herein means normal, secondary, or tertiary hydrocarbon having 1 to 12 carbon atoms. Examples are methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-methyl-l-propyl(i- Bu), 2-butyl (s-Bu) 2-methyl-2-propyl (t-Bu), 1-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl-2- butyl, 3-methyl-2-butyl, 3-methyl-l -butyl, 2-methyl-l -butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl- 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3- dimethyl-2-butyl, 3,3-dimethyl-2-butyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. In a particular embodiment, the term can also include Ci-I2 haloalkyl, which is a CM2 alkyl bearing at least one halogen. In another particular embodiment, the term can also include CM2 hydroxyalkyl, more preferably
Figure imgf000019_0001
hydroxyalkyl, even more preferably 2-hydroxypropyl. The term "substituted or unsubstituted cyclic structure" as used herein means a monocyclic saturated (aliphatic) or unsaturated (aromatic) or partly unsaturated ring structure having from 3 to 7 carbon atoms wherein at least one N, P, As or Sb atom is present and additionally at least one carbon atom can be replaced with a heteroatom, this heteroatom can be a N, P, As, Sb, O, S, Se, or Te in case of an aliphatic or partly unsaturated ring structure and can be N, P, As, or Sb in case of an aromatic or partly unsaturated ring structure. These cyclic structures can optionally be substituted with CM2 alkyl structures. Examples of this substituted or unsubstituted cyclic structure include, but are not limited to, pyridinium, imidazolium, pyrrolidinium, morpholinium, piperidinium, dihydropyridylium, thiazolylium, pyrrolylium, pyrazolylium, imidazolylium, tetrazolylium, piperidinylium, pyrrolidinylium, 2-pyrrolidonylium, pyrrolinylium, tetrahydropyranylium, bis-tetrahydropyranylium, azocinylium, triazinylium, 6H- 1,2,5- thiadiazinylium, 2H,6H-l,5,2-dithiazinylium, 2H-pyrrolylium, isothiazolylium, isoxazolylium, pyrazinylium, pyridazinylium, pyrimidinylium, furazanylium, imidazolidinylium, imidazolinylium, pyrazolidinylium, pyrazolinylium, piperazinylium, moφholinylium, or oxazolidinylium.
In a particular embodiment of each aspect of the invention the cyclic structures consist of the examples recited above.
As used herein and unless otherwise stated, the term "C3-12 cycloalkyl" means a monocyclic saturated hydrocarbon monovalent radical having from 3 to 12 carbon atoms, such as for instance cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, or a C7-I2 polycyclic saturated hydrocarbon monovalent radical having from 7 to 12 carbon atoms such as, for instance, norbornyl, fenchyl or adamantyl.
For the avoidance of doubt, when the terms Ci-8, Ci-6, CM, QO or Ci-2 are used herein they respectively refer to structures having from 1 to 8, 1 to 6, 1 to 4, 1 to 3 or 1 to 2 carbon atoms.
The term "ionic liquid" as used herein, means molten salts that are liquid at temperatures below
1000C.
As used herein and unless otherwise stated, the term halogen means any atom selected from the group consisting of fluorine, chlorine, bromine and iodine. Any substituent designation that is found in more than one site in an organic salt of this invention shall be independently selected.
It is known to the person skilled in the art that certain isomeric structures like carnitine can have different isomeric forms (e.g. L- and D-form), thus it is clear to the person skilled in the art that these isomeric structures include all possible isomeric forms, including tautomeric and stereochemical forms (stereoisomers) and racemic mixtures which may be present in the cation of the organic salts of the invention and position isomers are not included.
Novel ionic liquids
The present invention provides for organic salts having quaternary ammonium or phosphonium structure according to the following formula (I): R1R2R3R4Y+X"
I Wherein:
- Y is selected from N; P; As; or Sb;
- each of R1, R2 and R3 are independently selected from CM2 alkyl; or C3.]2 cycloalkyl; or each of R1 and R2, or R1 and R3, or R2 and R3 can be taken together to form a substituted or unsubstituted cyclic structure;
- R4 is selected from a C1-I2 alkyl-COOH; or C3-I2 cycloalkyl-COOH; wherein alkyl is optionally substituted with at least one OH or comprises at least one carbonyl function;
- X" is selected from organic sulfonates, prefarably perfluorinated organic sulfonates; organic sulfates, preferably perfluorinated organic sulfates; organic carboxylates; organic sulfonylimides, preferably bis(perfluoroalkylsulfonyl)imides; or tetrafluoroborate.
These organic salts are ionic liquids and can be used as such. More preferably, the present invention provides for the ionic liquid betaine bis(trifluoromethylsulfonyl)imide in protonated or unprotonated form. This invention shows that betaine is a useful starting material for the design of task-specific ionic liquids which can solubilize metal oxides.
In a search for cheap and easily accessible ionic liquids, we turned our attention to betaine. Betaine is a trivial name for l-carboxy-N,N,N-trimethylmethanaminium (inner salt). It is also known as N,N,N-trimethylglycine, N-trimethylglycine or trimethylglycine. Betaine has a zwitter- ionic structure. Betaine melts with decomposition at 310 0C. It readily reacts with mineral acids or organic acids whereby the carboxylate group gets protonated and the anionic part of the acid becomes the anion in the betaine salt. For instance betaine reacts with hydrochloric acid to form betaine hydrochloride, a salt with melting point of 232 0C. Betaine hydrochloride is a water- soluble salt that can be used to prepare hydrophobic salts by a metathesis reaction. The difference between the choline and the betaine cation is that in the betaine cation the hydroxyl group of choline is replaced by a carboxylic acid group. In fact, betaine is a metabolite that is formed by oxidation of choline59. The carboxylate group of betaine is a very good coordinating group towards metal ions, better than the aliphatic alcohol function of choline. The most important form of betaine on the market is the hydrochloride salt, betaine hydrochloride. An aqueous solution of betaine hydrochloride reacts with an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide to form betaine bis(trifluoromethylsulfonyl)imide, [Hbet] [Tf2N]. With this invention, we introduce protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N] (see formula I), as a new ionic liquid, more particularly also as a task-specific ionic liquid for selective solubilization of metal oxides and metal salts. The main physical and structural properties of this organic salt are presented. The temperature dependent miscibility of the ionic liquid with water has been studied. Of importance is the formation of a one-phase binary mixture at high temperature and a two-phase binary mixture at ambient temperatures. It will be shown that the phase behavior of [Hbet] [Tf2N] - water mixtures strongly depends on the pH conditions.
Figure imgf000022_0001
II
The positive charge on the quaternary nitrogen (or phosphor, arsenicum or antimony) atom has an inductive effect on the COOH-group. This effect is affected by the chain length in-between the COOH-group and the positively charged nitrogen (or phosphor, arsenicum or antimony) atom, respectively. The shorter the distance between these functional groups, the higher the acidity of the proton of the COOH-function. Therefore, one or two CH2 groups in-between, and more preferably one CH2 group in-between is favorable for the application of this invention: these ionic liquids exhibit a significantly higher solubilizing ability for metal oxides than ionic liquids with three or more CH2-groups between the positively charged heteroatom and the COOH- function.
Building further on this concept, different other ionic liquids can be obtained, not only by extension of the alkyl chains of the groups R1, R2, R3, R4, but also by making R1 and R2 part of a cyclic system (which can contain in addition a heteroatom). Instead of ammonium cation, the corresponding phosphonium cations can be considered as well. Examples of such ionic liquids are shown in formulae III-IX:
Figure imgf000023_0001
III
10
Figure imgf000023_0002
IV
15
Figure imgf000023_0003
V
Figure imgf000024_0001
VI
10
Figure imgf000024_0002
VII
15
Figure imgf000024_0003
VIII
Figure imgf000025_0001
IX
It has been shown that protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N], and related compounds are ionic liquids with the ability to dissolve large quantities of metal oxides. This metal solubilizing power is selective. Soluble are: oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide and silver(I) oxide. Insoluble or very poorly soluble are iron and manganese oxides, cobalt oxides, as well as aluminum oxide and silicon oxide. Also metal hydroxides can be solubilized in the ionic liquid. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 0C (temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions.
In a particular embodiment, certain organic salts described herein are not ionic liquids according to the definitions (having melting points under 1000C), but still have a melting point around or under 2000C and therefore can be used for chemical applications at higher temperatures, such as: as a solvent, as a reaction medium, for electrodeposition of metals, among other applications.
Synthesis and preliminary analysis of the betaine salts
Protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet] [Tf2N], is accessible via different synthetic routes.
The best method is by reaction of the zwitterionic betaine with the acid hydrogen bis(trifluoromethylsulfonyl)imide, Tf2NH. This reaction involves a simple proton transfer from the bis(trifluoromethylsulfonyl)imide to the more basic carboxylate group, so that the betaine will be protonated. This method is general applicable for the preparation of other betaine salts. For instance, we prepared by this method protonated betaine hexafluorophosphate, protonated betaine triflate, and protonated betaine pentafluorobenzoate. However, all these salts have melting points above 100 0C and can therefore not be considered as ionic liquids. A second synthetic route to the protonated betaine bis(trifluoromethylsulfonyl)imide ionic liquid is by the metathesis reaction of betaine hydrochloride and lithium bis(trifluoromethylsulfonyl)imide (in 1 :1 molar ratio) in aqueous solution. An aqueous solution of betaine hydrochloride reacts with an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide to form protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N]. The ionic liquid easily separates from the aqueous layer (due to its hydrophobicity). The ionic liquid prepared by the metathesis reaction has a melting point of 57 0C and the compound can easily be supercooled to room temperature. The fact that [(Hbet)3(bet)][Tf2N]3 is formed besides [Hbet][Tf2N], depending on the experimental conditions, leads to the assumption that an equilibrium between different species in solution is present. So far, no detailed information on this equilibrium is available yet. The pure [(Hbet)3(bet)][Tf2N]3 compound (m.p. = 70 0C) crystallizes from a solution of the mixture in the [C4inim][Tf2N] ionic liquid. Pure [Hbet][Tf2N], free of [(Hbet)3(bet)] [Tf2N]3, can be obtained by mixing stoichiometric amounts of the betaine inner salt (bet) and the acid hydrogen bis(trifiuromethylsulfonyl)imide, H[Tf2N]. Pure [Hbet][Tf2N] melts at 69 0C. The melting point of protonated betaine bis(trifluoromethylsulfonyl)imide, [HbCt][Tf2N], in equilibrium with [(Hbet)3(bet)] [Tf2N]3, as prepared by the metathesis reaction between lithium bis(trifluromethylsulfonyl)imide and betaine chloride is 57 0C, but the liquid compound can be supercooled to room temperature. [Hbet][Tf2N] shows a tendency to crystallize rather than to form a glass: after some time (hours to weeks) crystallization occurs. The viscosity of [Hbet][Tf2N] is 351 cP at 60 0C. [Hbet][Tf2N] is a hydrophobic ionic liquid at room temperature; after addition of water, two separate phases are formed. Heating treatment of a mixture induced the formation of a one-phase-system at a critical temperature of 56 0C. Cooling of the one-phase mixture resulted again in phase separation. A similar temperature-dependent miscibility was observed for mixtures of [Hbet][Tf2N] with toluene. [Hbet][Tf2N] is miscible with ethanol, 1- octanol (and other higher alcohols), benzonitrile, acetonitrile, DMSO, acetic acid and ethyl acetate, but also with other ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion like [COmJm][Tf2N]. [Hbet][Tf2N] is immiscible with hexane, heptane, dichloromethane (DCM), chloroform, benzene, toluene and diethyl ether.
All trials to obtain ionic liquids of protonated betaine bis(trifluoromethylsulfonyl) imide with counter ions other than bis(trifluoromethylsulfonyl)imide failed and resulted in the formation of solids with a high melting point: (1) protonated betaine hexafluorophosphate, [Hbet][PF6] (m.p. = 159 0C; this compound has been reported earlier); (2) protonated betaine triflate, [Hbet][OTf] (m.p. = 125 0C); (3) protonated betaine pentafluorobenzoate, [HbCt][C6F5COO] (m.p. = 144 0C); (4) betaine tetrafluoroborate (200 0C). Also analogues with non-fluorinated counter ions have widely been described in the literature, but all the reported compounds have a melting point well above 100 0C.
A general approach to the synthesis of the other ionic liquids is by first quaternizing a tertiary amine (e.g. N-methylpyrrolidine, tributylamine) or a tertiary phospine (e.g. tributylphosphine) by reaction with an ester of chloroacetic acid or bromoacetic acid (preferentially a methyl ester or an ethyl ester). After quaternization, the ester is converted to the corresponding acid, and the chloride (or bromide) anion is exchanged by a metathesis reaction for a bis(trifluoromethylsulfonyl)imide anion. The ionic liquid separates from the water phase. The esters of chloroacetic acid or bromoacetic acid can be replaced by other esters of γ- bromoalkanoic acids or γ-chloroalkanoic acids. Lithium bis(trifluoromethylsulfonyl)imide can be replaced by other lithium bis(trifluoroalkylsulfonyl)imides.
Thermomorphic behavior
Although we described hereinabove that [Hbet] [Tf2N] forms a two-phase system with water, this statement is only true for mixtures at room temperature and slightly above. Upon heating the mixture, a one-phase-system with an upper consolute point at around 55.5 0C is formed. Cooling of the one-phase mixture resulted again in phase separation. The phase separation is illustrated in Figure 1. The phase diagram of the binary system [Hbet][Tf2N] - water is shown in Figure 2. The phase diagram was measured by equilibrating the [Hbet] [Tf2N] - water mixture at a given temperature, followed by analysis of the components in the [Hbet][Tf2N] rich phase (lower layer) and in the water-rich phase (upper layer). The composition of the phases was determined by distilling out the water and comparing the original mass with the remaining (non-volatile) ionic liquid mass. At the critical concentration, the mass fraction of the ionic liquid is around 0.519.
pH-dependent phase behavior
When a biphasic mixture of protonated betaine bis(trifluoromethylsulfonyl)imide is treated with (a solution of) alkali hydroxides such as LiOH, NaOH, or KOH, a monophasic mixture is obtained, because the alkali salts of betaine bis(trifluoromethylsulfonyl)imide are water soluble (Figure 3). Acidification of the solution leads to the regeneration of the hydrophobic protonated betaine bis(trifluoromethylsulfonyl)imide ionic liquid and thus to phase separation.
Solubility of metal oxides
An interesting property of betaine bis(trifluoromethylsulfonyl)imide is its ability to dissolve metal oxides. The metal oxides react with the carboxylic acid group of the ionic liquid to form carboxylate complexes and water. The following oxides were found to be soluble in the ionic liquid [Hbet][Tf2N]: Sc2O3, Y2O3, U2O3, Pr6O11, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO and MnO. Oxides can be replaced by hydroxides as the starting material. In a typical experiment, the metal oxide is mixed with [Hbet] [Tf2N] and water, and the mixture is stirred for several hours. After evaporation of water under reduced pressure, a solution of the metal betaine complex in [Hbet][Tf2N] is obtained. The solubility of metal oxides in protonated betaine bis(trifluoromethylsulfonyl)imide is high because the ionic liquid can form stoichiometric compounds with the metals; i.e. so much metal oxide can be added to the [Hbet][Tf2N] ionic liquid until all the ionic liquid is transformed into a metal complex. However, the presence of water is facilitating the dissolution of the metal oxide in the ionic liquid. It is more difficult to dissolve the ionic liquid in direct contact with the metal oxide. This can be due to the fact that most metal oxides have a hydrophilic surface, whereas the ionic liquid is hydrophobic; therefore the wetability of the metal oxide by the pure ionic liquid is lower. Good direct dissolution (i.e. without addition of water) of a metal oxide in [Hbet] [Tf2N] was however also observed, for example for CuO. Not all metal oxides can be solubilized in [Hbet][Tf2N]. Insoluble or very poorly soluble are iron and cobalt oxides, as well as aluminum oxide and silicon oxide. Besides the metal oxides, also different metal salts like CuCl2-2H2O or EuCl3-OH2O are soluble in [Hbet] [Tf2N]. For instance, [Hbet] [Tf2N] can dissolve 1.75 mol% of CuCl2 and 6 mol.% of EuCb (determined titrimetrically by EDTA). The dissolution process can be facilitated by working under moderate to high pressure conditions. Under these experimental conditions, it is possible to dissolve in the ionic liquid oxides that are otherwise insoluble in [Hbet][Tf2N]. Examples of such oxides include CO3O4, CoO, Co2C>3, Cr2O3, FeO and Fe2O3. To perform the experiment, an equimolar ionic liquid/ water mixture is heated with the metal oxide in a PTFE- lined acid digestion bomb.
The metals can be stripped from betaine bis(trif!uoromethylsulfonyl)imide by extracting the ionic liquid with an acidified aqueous solution (for instance with diluted hydrochloric acid or diluted nitric acid). The metal complex of protonated betaine bis(trifluoromethylsulfonyl)imide is decomposed and the betaine bis(trifluoromethylsulfonyl)- imide ionic liquid is regenerated. The metal ion is thus transferred to the aqueous phase and betaine bis(trifluoromethylsulfonyl)imide is regenerated. For instance, a solution of copper(II) in [Hbet][Tf2N] was extracted twice with a 37% HCl solution. The ratio of the metal content in the aqueous phase to the ionic liquid phase was determined by titration to be 82:1 after the first extraction. The metal was almost completely extracted to the aqueous phase after a second extraction with the acidic solution. The transfer of copper(II) from the ionic liquid to the aqueous phase upon acidification of the aqueous layer is shown in Figure 4. The same extraction can also be done with other aqueous acids such as aqueous HNO3 or H2SO4. A nearly quantitative removal of neodymium(III) from [Hbet] [Tf2N] could be obtained by two extractions of the ionic liquid with a 37% HCl solution. The [Hbet][Tf2N] ionic liquid can be reused after stripping of its metal content.
The metal complexes of betaine bis(trifluoromethylsulfonyl)imide have in general a high melting point (> 100 0C), but the rare-earth complexes of betaine bis(trifluoromethylsulfonyl)imide have melting points below 100 °C and can thus be considered as genuine ionic liquids.
Table 1: Melting points for the lanthanide complexes of [Hbet] [Tf2N].
Lanthanide complex Melting point
(0C)
Y2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 109
La2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 78
Pr2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 86
Nd2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)4 90
Sm2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 88
Eu2((CH3)3NCH2COO)8N(Sθ2CF3)2)6(H2O)2 95
Gd2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 94
Tb2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 88
Dy2((CH3)3NCH2COO)8N(Sθ2CF3)2)6(H2O)2 88
Hθ2((CH3)3NCH2COO)8N(Sθ2CF3)2)6(H2O)2 80
Er2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 94
Tm2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 97
Yb2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 89
Lu2((CH3)3NCH2COO)8N(SO2CF3)2)6(H2O)2 88
The metal complexes of betaine bis(trifluoromethylsulfonyl)imide can be dissolved in the ionic liquids choline bis(trifluoromethylsulfonyl)imide or the l-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides. Betaine bis(trifluoromethylsulfonyl)imide is also miscible in all molar ratios with choline bis(trifluoromethylsulfonyl)imide or the l-alkyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imides.
Applicability of the ionic liquid
Due to its properties, mainly the metal dissolving properties, [Hbet][Tf2N] can be used for multiple purposes. We have shown that the [Hbet][Tf2N] ionic liquid can be used for the selective dissolution of metal oxides in the ionic liquid, extraction and back extraction (stripping) of metals, cleaning of metal surfaces, dissolution of palladium oxide to show the potential for recycling precious metals (platinum group metals) from catalysts and the electrodeposition of metals from the ionic liquid. Subsequently, [Hbet][Tf2N] can be used in the following sectors:
• Ore processing: extraction of precious metals for ores. The selective solubility of metal oxides has advantage for the extraction for metals from ores: valuable metals can be extracted whereas the quartz, silicates, aluminosilicates, aluminum oxides and iron oxides are unaffected;
• Metal processing industry: electrodeposition of metals, electroplating, electropolishing. We have shown that metals can be deposited from solutions of the metal salts in protonated betaine bis(trifluoromethylsulfonyl)imide or of the metal complexes of betaine bis(trifluoromethylsulfonyl)imide by electrolysis. After immersion of a zinc plate in an ionic liquid containing copper betaine bis(trifluoromethylsulfonyl)imide, the zinc plate is covered by a coating of metallic copper. By the same method, a copper plate can be coated with metallic silver by immersion in an ionic liquid containing silver betaine bis(trifluoromethylsulfonyl)imide; • Energy sector: electrolytes for batteries, fuel cells and photovoltaic cells;
• Electrochromic displays;
• Nuclear sector: processing of spent nuclear fuel elements. Selective extraction of lanthanides and actinides from other fission products and from uranium;
• Environmental: cleaning of soils contaminated by heavy metals. The selective solubility of metal oxides is herein also useful;
• Cleaning industry: removal of oxide coating on metals. The cleaning of oxidized metal surfaces is easily done with betaine bis(trifiuoromethylsulfonyl)imide. For instance, we have shown that a copper sheet covered with a black coating of copper(II) oxide could be cleaned after short immersion in protonated betaine bis(trifluoromethyl-sulfonyl)imide; • Recycling: recycling of precious metals (platinum group metals) from used catalysts (three- way catalysts in automobile exhausts);
• Recovery of copper, zinc and lead. As a summary, protonated betaine bis(trifluoromethylsulfonyl)imide, [HbCt][Tf2N], is a versatile ionic liquid that can be used for multiple purposes. It can be looked at as a task-specific ionic liquid that can be used for the selective solubilization of metal oxides, hydroxides and metal salts. Moreover, the ionic liquid can be switched from a hydrophobic one to a hydrophilic one by temperature or pH control. Although the melting point [Hbet] [Tf2N] is above room temperature, it is miscible with room-temperature ionic liquids containing the [Tf2N]" anion and the mixtures are room-temperature ionic liquids as well. This widely broadens the applicability of this ionic liquid.
Examples
GENERAL DESCRIPTION OF THE MATERIALS AND METHODS USED
Elemental analyses (carbon, hydrogen, nitrogen) were made on a CE Instruments EA-1 1 10 elemental analyzer. FTIR spectra were recorded on a Bruker IFS-66 spectrometer. The samples were measured using the KBr pellet method or as a thin film between KBr windows. 1H NMR spectra were recorded on a Bruker Avance 300 spectrometer (operating at 300 MHz). The water content of the ionic liquids was determined by a coulometric Karl Fischer titrator (Mettler Toledo Coulometric Karl Fischer Titrator, model DL39). The viscosity of the ionic liquids was measured by the falling ball method (Gilmont Instruments). Differential scanning calorimetry (DSC) measurements were made on a Mettler-Toledo DSC822e module (scan rate of 10 0C min'1 under helium flow). The organic precursors were purchased from Acros Organics and lithium bis(trifluoromethylsulfonyl)imide from IoLiTec. All chemicals were used as received, without any additional purification step.
EXAMPLE 1 : SYNTHESIS AND ANALYSIS OF BETAINE BIS(TRIFLUORO-METHYL- SULFONYDIMIDE.
A solution of betaine hydrochloride (1 mol, 153.61 g) in 250 mL of water was added under stirring to 500 mL of an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (1 mol, 287.08 g). The mixture was stirred for one hour at room temperature. The aqueous phase S separated from the ionic liquid. After separation of the phases, the ionic liquid phase was washed three times with small amounts of water until no chloride impurities could be detected by the silver nitrate test. The ionic liquid was evaporated to dryness at 120 0C in vacuo on a rotary evaporator. A water content of 35 ppm was determined by coulometric Karl Fischer titration. 1H- NMR (300 MHz, [D6]DMSO, TMS): δ = 4.27 (s, 2H), 3.19 (s, 3 x CH3). 13C-NMR ([D6]DMSO,0 TMS): δ = 167.38 (COO), 125.99, 121.75, 117.52, 1 13.28 (2 x CF3), 64.06 (N-CH2), 54.16 (3 x CH3). Elemental analysis calcd (%) for C7H12N2O6F6S2 (Mw = 398.302 g mol'1): C 21.10, H 3.03, N 7.03; found: C 20.78, H 3.24, N 6.85. M.p. = 57 0C. Density: 1.531 g cm"3 (60 0C). A viscosity of 351 cP (6O0C) of the compound was measured by the falling ball method. Density: 1.554 g em"3. 5
EXAMPLE 2: SYNTHESIS OF BETAINE TETRAFLUOROBORATE
A solution of betaine hydrochloride (32.5 mmol, 5 g) in 20 mL of hot water was added under stirring to an aqueous solution of ammonium tetrafluoroborate (32.5 mmol, 3.412 g, 20 mL). The0 mixture was stirred for one hour at room temperature and no phase separation was observed. The solution was allowed to cool down in the refrigerator at 4°C. White crystals of betaine tetrafluoroborate, [Hbet][BF4] precipitated. The product was filtered, washed with cold water, and dried under vacuum.
Melting point: 200 0C (onset). 5
EXAMPLE 3: SYNTHESIS OF BETAINE HEXAFLUOROPHOSPHATE
A solution of betaine hydrochloride (32.5 mmol, 5 g) in 20 mL of hot water was added under stirring to an aqueous solution of potassium hexafluorophosphate (32.5 mmol, 5.98g, 20 ml). The0 mixture was stirred for one hour at room temperature, no phase separation was observed. The solution was allowed to cool down in the refrigerator at 4°C. White crystals of betaine hexafluorophosphate, [Hbet][PFδ], precipitated. The product was filtered, washed with cold water, and dried under vacuum. Melting point (onset): 159 0C. 5 Note: the synthesis of this compound (but not the thermal behavior) was described by Coronado and coworkers in Eugenio Coronado et al., Angewanώe Chemie International Edition 43 (2004) 6152-6156.
EXAMPLE 4: SYNTHESIS OF BETArNE TRIFLATE
A solution of betaine monohydrate (42.68 mmol, 5 g) in 20 mL of hot water was added under stirring to 20 mL of a hot aqueous solution of trifluoromethanesulfonic acid (42.68 mmol, 6.41 g). The mixture was stirred for one hour at room temperature, no phase separation was observed. The water was evaporated under vacuum. Betaine trifiuoromethanesuifonate , [Hbet][OTfJ was obtained as a white solid.
Melting point (onset): 11 1°C.
EXAMPLE 5: SYNTHESIS OF BETAINE PENTAFLUOROBENZQATE
A solution of betaine monohydrate (42.68 mmol, 5 g) in 20 mL of hot water was added under stirring to 20 mL of a hot aqueous suspension of pentafluorobenzoic acid (42.68 mmol, 9.05 g). The mixture was stirred for one hour at room temperature and phase separation occurred. The aqueous phase was evaporated under vacuum. Betaine pentafluorobenzoate was obtained as a white solid. Melting point (onset): 144 0C.
EXAMPLE 6: MISCIBILITY OF PROTONATED BETAINE BISfTRIFLUORO- METHYLSULFONYL) IMIDE
Figure imgf000034_0001
[Hbet][Tf2N] and [Choi] [Tf2N] are miscible in any molar ratio. A 1 :1 mixture does not crystallize after cooling in a refrigerator at 4°C, so an eutectic mixture is formed.
Choline bis(trifluoromethylsulfonyl)imide, [Chol][Tf2N], was prepared as described in the prior art. A solution of choline chloride (1 mol, 139.62 g) in 250 mL of water was added under stirring to 500 mL of an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (1 mol, 287.08 g). The mixture was stirred for one hour at room temperature and the aqueous phase separated from the ionic liquid. After separation of the phases the ionic liquid phase was washed three times with small amounts of water until no chloride impurities could be detected after adding silver nitrate. Finally the ionic liquid choline bis(trifluoromethylsulfonyl)imide was evaporated to dryness at 1200C on a rotary evaporator. A water content of 25 ppm was determined using a coulometric Karl Fischer Titrator (Mettler Toledo, model DL39). 1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 5.29 (t, IH), 3.84 (m, 2H), 3.39 (m, 2H), 3.10 (s, 9H). 13C-NMR ([D6]DMSO, TMS): δ = 124.27, 121.07, 1 17.87, 114.67 (2 x CF3), 67.01 (N-CH2), 55.13 (CH2), 53.18 (3 x CH3).
• With organic solvents:
Protonated betaine bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N], is completely miscible with e.g. 1-octanol, benzonitrile, DMSO, acetonitrile, acetic acid, ethylacetate, ethanol and methanol. The compound is immiscible with hexane, dichloromethane (DCM), chloroform, benzene, diethylether. Toluene was found to exhibit a temperature dependent miscibility. While the solubility of toluene at room temperature is very low, the solubility increases markedly with temperature.. The ionic liquid is also miscible with other ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion, like the l-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides.
Table 2. Miscibility of [Hbet][Tf2N] with organic solvents
Miscible Immiscible Partially miscible
1-octanol hexane toluene benzonitrile DCM
DMSO chloroform acetonitrile benzene acetic acid diethylether ethylacetate ethanol
With water — dependence of temperature: [Hbet][Tf2N] is a hydrophobic ionic liquid at room temperature. After addition of water, two separate phases are formed. Heating treatment of a mixture induced the formation of a one-phase- system at a critical temperature of 56 0C. The phase diagram of the [Hbet][Tf2N]/water system is shown in Figure 2. By cooling down the mixture the two phases are recovered. So the system [Hbet][Tf2N] /water is a temperature switchable one-phase/two-phase system.
• With water - dependence ofpH:
[Hbet] [Tf2N] contains an acidic hydrogen atom and can be deprotonated by addition of a base. [Hbet] [Tf2N] was mixed with different alkali metal hydroxides. 25 mmol of [Hbet] [Tf2N] was mixed with hot water and an aqueous solution of an alkali metal hydroxide was added dropwise until pH 7. The hydrophobic phase disappears. After acidification of the solution, two phase- system was reformed. After evaporation of the water phase under reduced pressure, and after neutralization of the ionic liquid, a hydrophilic salt remained with melting points above 1000C.
Scheme 1: Neutralization of Betaine Tf2N with an alkaline hydroxide.
hydrophobic hydrophilic
Figure imgf000036_0001
Tf2N" HBetaine+ Tf2N" Betaine
Lithium salt [Hbet][Tf2N] (16.63 g; 41.75 mmol) was added to 10 mL of an aqueous solution of LiOH (1 g;
41.75 mmol) and stirred for 15 minutes. After filtration, the water was evaporated under vacuum.
The colorless crystals were recrystallized from water and dried at 500C in a vacuum oven.
Elemental analysis: calcd (%) for Li((CH3)3NCH2CO2)(N(SO2CF3)2) (Mw= 404.23 g mol 1) C
20.80, H 2.74, N 6.92; found C 20.69, H 3.07, N 6.76. Sodium salt
[Hbet] [Tf2N] (9.96 g; 25.0 mmot) was added to 10 mL of an aqueous solution of NaOH (1 g; 25.0 mmol) and stirred for 15 minutes. After filtration, the water was evaporated under vacuum. The colorless crystals were recrystallized from water and dried at 500C in a vacuum oven. Elemental analysis: calcd (%) for Na((CH3)3NCH2CO2)(N(SO2CF3)2)(H2O) (Mw= 438.2 g mol"1) C 19.18, H 2.98, N 6.39; found C 19.78, H 2.97, N 6.38.
Potassium salt
[Hbet][Tf2N] (7.10 g; 17.82 mmol) was added to 10 mL of an aqueous solution of KOH (1 g; 17.82 mmol) and stirred for 15 minutes. After filtration, the water was evaporated under vacuum. The colorless crystals were recrystallized from water and dried at 500C in a vacuum oven. Elemental analysis: calcd (%) for K((CH3)3NCH2CO2)(N(SO2CF3)2)(H2O) (Mw= 454.41 g moP1) C 18.50, H 2.88, N 6.16; found C 18.83, H 2.82, N 6.18.
Table 3: Melting points and CHN-results for some alkali metal salts of [Hbet] [Tf2N].
Figure imgf000037_0001
EXAMPLE 7: SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES IN A THbetl [Tf7Nl - WATER MIXTURE
The following oxides were found to be soluble in the ionic liquid [Hbet] [Tf2Nl: Sc2O3, Y2O3, La2O3, Pr6O11, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid rHbet!fTf>Nl: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2
Yttrium(III) complex
Y2O3 (1 g; 4.42 mmol) was mixed with [Hbet][Tf2N] (10.583 g; 26.5 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Y2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2831.90 g mor1) C 22.05, H 3.27, N 6.92; found C 21.67, H 3.03, N 6.51.
Lanthanum(III) complex
La2O3 (1 g; 3.06 mmol) was mixed with [Hbet][Tf2N] (7.334 g; 18.4 mmol) and 10 mL of water.
The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for La2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)4 (Mw = 2967.93 g moP1) C 21.04, H 3.24, N 6.60; found C 20.58, H 3.24, N 6.19.
Praseodymium(III) complex
Pr6On (1 g; 0.97 mmol) was mixed with [Hbet][Tf2N] (7.018 g; 17.6 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Pr2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)4 (2971.94 g moK1) C 21.02, H 3.26, N 6.53; found C 20.61, H 4.08, N 6.16.
Neodymium(III) complex Nd2O3 (1 g; 2.97 mmol) was mixed with [Hbet][Tf2N] (7.102 g; 17.8 mmol) and 10 mL of water.
The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The purple crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Nd2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2θ)4 (Mw = 2978.60 g mol 1) C 20.96, H 3.24, N 6.58; found C 20.60, H 3.22, N 6.20. Samarium(III) complex
Sm2O3 (1 g; 2.86 mmol) was mixed with [Hbet][Tf2N] (6.852 g; 17.20 mmol) and 10 mL water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Sm2((CH3)3NCH2CO2)g(N(SO2CF3)2)6(H2O)2 (Mw = 2954.81 g mol 1) C 21.13, H 3.13, N 6.60; found C 21.10, H 3.10, N 6.05.
Europium(III) complex
Eu2O3 (1 g; 2.84 mmol) was mixed with [Hbet][Tf2N] (6.789 g ; 17.04 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Eu2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2958.01 g mol 1) C 21.11, H 3.13, N 6.62; found C 20.25, H 3.08, N 6.32.
Gadolinium(HI) complex Gd2O3 (1 g; 2.75 mmol) was mixed with [Hbet][Tf2N] (6.592 g; 16.5 mmol) and 10 mL of water.
The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Gd2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2968.00 g mol 1) C 21.04, H 3.10, N 6.60; found C 20.31, H 3.03, N 6.21.
Terbium(III) complex
Tb4O7 (1 g; 1.33 mmol) was mixed with [Hbet][Tf2N] (6.398 g; 16.05 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Tb2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2971.94 g mor1) C 21.01, H 3.12, N 6.60; found C 20.70, H 3.17, N 6.18. Dysprosium(III) complex
Dy2O3 (1 g; 2.68 mmol) was mixed with [Hbet][Tf2N] (6.402 g;16.08 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Dy2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2979.09 g mol'1) C 20.93, H 3.1 1, N 6.57; found C 20.74, H 3.69, N 6.20.
Holmium(III) complex
Ho2O3 (1 g; 2.64 mmol) was mixed with [Hbet][Tf2N] (6.319 g; 15.8 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The purple crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Ho2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2983.95 g mol"1) C 20.92, H 3.1 1, N 6.57; found C 20.30, H 3.47, N 6.33.
Erblum(III) complex
Er2O3 (1 g; 2.61 mmol) was mixed with [Hbet][Tf2N] (6.247 g; 15.6 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Er2((CH3)3NCH2CO2)g(N(SO2CF3)2)6(H2O)2 (Mw = 2988.61 g moP1) C 20.90, H 3.10, N 6.56; found C 20.67, H 3.01, N 6.16.
Thulium(III) complex
Tm2O3 (1 g; 2.59 mmol) was mixed with [Hbet][Tf2N] (6.193 g; 15.5 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Tm2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 2991.96 g mol 1) C 20.86, H 3.10, N 6.55; found C 20.54, H 3.26, N 6.13. Ytterbium(III) complex
Yb2O3 (1 g; 2.53 mmol) was mixed with [Hbet][Tf2N] (6.064 g; 15.2 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Yb2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 3000.17 g mol"1) C 20.81, H 3.09, N 6.53; found C 20.60, H 3.22, N 6.20.
Lutetium(III) complex
Lu2O3 (1 g; 2.51 mmol) was mixed with [Hbet][Tf2N] (6.005 g; 15.7 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Lu2((CH3)3NCH2CO2)8(N(SO2CF3)2)6(H2O)2 (Mw = 3004.02 g mol'1) C 20.78, H 3.08, N 6.53; found C 20.61, H 4.08, N 6.16.
Copper(II) complex
CuO (1 g; 12.57 mmol) was mixed with [Hbet][Tf2N] (10.014 g; 25.1 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The green crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Cu((CH3)3CO2)N(SO2CF3)2)2 (Mw = 858.14 g moP1). C 19.59, H 2.58, N 6.52; found C 19.55, H 2.94, N 6.30. Reaction: CuO + 2 (CH3)3NCH2Cθ2)NH(SO2CF3)2 → Cu((CH3)3NCH2CO2)(N(SO2CF3)2)2 + H2O
Zinc(II) complex ZnO (1 g; 12.3 mmol) was mixed with [Hbet][Tf2N] (9.788g; 24.5 mmol) and 10 mL of water.
The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Zn4((CH3)3NCH2Cθ2)io(N(S02CF3)2)8(H20)4 (Mw= 3746.27 g mor1) C 21.15 H 3.17, N 6.72; found C 20.47, H 3.48 N 6.42. Mercury(II) complex
HgO (1 g; 4.6 mmol) was mixed with [Hbet][Tf2N] (3.679g; 9.23 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Hg((CH3)3NCH2Cθ2)2(N(Sθ2CF3)2)2 (Mw= 995.17 g mol"1) C 16.89, H 2.23, N 5.62; found C 17.1 1, H 2.28, N 5.48.
Manganese(II) complex
MnO (1 g; 14.09 mmol) was mixed with [Hbet][Tf2N] (11.2g; 28.1 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The purple crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Mn((CH3)3NCH2Cθ2)2(N(Sθ2CF3)2)2(H2O) (Mw= 867.54 g mor1) C 19.38 H 2.78, N 6.45; found C 19.49, H 2.83, N 6.28.
Silver(I) complex Ag2O (1 g; 4.35 mmol) was mixed with [Hbet][Tf2N] (1.733g; 4.35 mmol) and 10 mL of water.
The mixture was stirred at room temperature and protected from light for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized 3 times from water.
Elemental analysis: calcd(%) for Ag2((CH3)3NCH2Cθ2)2(N(Sθ2CF3)2)2 (Mw= 505,16 g moP1) C 16.64 H 2.19, N 5.54; found C 16.79, H 2.27, N 5.31.
Nickel(II) complex
NiO (1 g; 13.38 mmol) was mixed with [Hbet][Tf2N] (10.66 g; 26.7 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The green crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Ni2((CH3)3NCH2CO2)2(N(SO2CF3)2)2 (Mw = 1895.77 g mol 1). C 20.90, H 3.35, N 6.65; found C 20.93, H 3.23, N 6.46. Palladium(II) complex
PdO (1 g; 8.16 mmol) was mixed with [Hbet] [Tf2N] (6.508 g; 16.3 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The yellow crystals were recrystallized from water 3 times.
Elemental analysis: calcd(%) for Pd((CH3)3NCH2CO2)3(N(SO2CF3)2)2(H2O)2 (Mw= 1054.19 g mol'1) C 21.65, H 3.53, N 6.64; found C 21.31, H 3.02, N 6.80 %.
Lead complex
PbO (1 g; 8.16 mmol) was mixed with [Hbet][Tf2N] (6.507g; 16.3 mmol) and 10 mL of water.
The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The white crystals were recrystallized from water 3 times. Elemental analysis: calcd(%) for Pb5((CH3)3NCH2CO2)7(N(Sθ2CF3)2)8θ(OH)(H2θ)2 (Mw = 4166,24 g mol-1). C 16.76, H
2.21, N 5.54; found C 15.33, H 2.81, N 4.72 %.
Mp.: 177 0C (peak) IR: 3437s, 1632m, 1493m, 1454m, 1397m, 1351m, 1 193m, 1059w, 956w,
933m.
Table 4. Melting points of metal salts of [Hbet] [Tf2N]
Compound Melting point (0C)
[Li(bet)][Tf2N] 127
[Na(bet)][Tf2N] H2O 109
[K(bet)][Tf2N]-H2O 152
[Cu3(bet)8(H2O)4][Tf2N]6 288
[Zn4^eI)10][Tf2N]8(H2O)4 117
[Ag2^eI)2(Tf2N)][Tf2N] 127
[Hg(bet)2][Tf2N]2 111
[Y2(bet)8][Tf2N]6-2H2O 109
[La2(bet)8][Tf2N]6-4H2O 78
[Pr2(bet)8][Tf2N]6-4H2O 86
[Nd2(bet)8][Tf2N]64H2O 90
[Sm2(bet)8][Tf2N]6-2H2O 88 [Eu2(bet)8][Tf2N]6-2H2O 95
[Gd2(bet)8][Tf2N]6-2H2O 94
[Tb2(bet)8][Tf2N]6-2H2O 88
[Dy2(bet)8][Tf2N]6-2H2O 88
[Ho2(bet)8][Tf2N]6-2H2O 88
[Er2(bet)8][Tf2N]6-2H2O 94
[Tm2(bet)8][Tf2N]6-2H2O 97
[Yb2(bet)8][Tf2N]6-2H2O 89
[Lu2(bet)g][Tf2N]6-2H2O 88
The lanthanide-containing complexes described herein may be considered as ionic liquids, because the melting points of the compounds are below 1000C, in accordance with the definition of an ionic liquid. The melting points are specified in table 4. At room temperature these complexes can be described as highly viscous supercooled liquids.
These [Hbet][Tf2N] complexes obtained by procedures described in this example 9 are easily soluble in the [Chol][Tf2N] ionic liquid. As an example, 1.5 g (6.7 mol %) of Cu((CH3)3NCH2CO2)N(SO2CF3)2)2 (1.75 mmol) were stirred with 10 g of [Chol][Tf2N] to give a transparent blue solution. Higher concentrations of the metal betaine complex in the [Choi] [Tf2N] ionic liquid can be achieved. Same concentrations can be dissolved of betaine complexes of e.g. Mn2+, Ni2+, Zn2+, Pd2+, Ag+, Cd2+, Hg2+, Pb2+, Y3+, La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, UO2 2+.
EXAMPLE 8: SOLUBILITY OF METAL OXIDES AND SALTS IN PURE THbetirTf?N1 AND EXTRACTION PROCEDURES
Metal oxides
Copper oxide is soluble in pure [Hbet] [Tf2N]. CuO (Ig) was stirred with 10 g of [Hbet] [Tf2N] for 2 hours at 700C. The copper oxide was found to dissolve completely and a blue transparent solution was obtained. Also metal oxides of e.g. Mn2+, Ni2+, Zn2+, Pd2+, Ag+, Cd2+, Hg2+, Pb2+, Y3+, La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, UO2 2+ can be dissolved in pure [Hbet][Tf2N].
Metal salts Metal salts, like CuCl2 2H2O or EuCl3-OH2O are also soluble in [Hbet][Tf2N]. a) Solubility Of Cu2+: An excess of copper chloride was added to [Hbet][Tf2N] (5g; 12.5 mmol). The mixture was stirred for 4 hours at 100 °C and the non-dissolved copper chloride was removed from the mixture. The metal content of the resulting solution was determined by titration with EDTA. 1.75 mol% CuCl2 were found to dissolve in [Hbet][Tf2N]. b) Solubility Of Eu3+: An excess of europium chloride, EuCl3-OH2O was added to [Hbet][Tf2N] (5g; 12.5 mmol). The mixture was stirred for 4 hours at 100 0C and the non-dissolved europium chloride was removed from the mixture. The metal content of the resulting solution was determined by titration with EDTA. 6 mol% EuCl3-OH2O were found to dissolve in [Hbet][Tf2N]. The same can be performed for the metal chloride salts of e.g. Mn2+, Ni2+, Zn2+, Pd2+, Ag+, Cd2+, Hg2+, Pb2+, Y3+, La3+, Pr3+, Nd3+, Sm3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, UO2 2+.
EXAMPLE 9: RECOVERY OF METALS AND IONIC LIQUIDS
The dissolved metals can easily be recovered from the ionic liquid phase by an extraction with an aqueous acid solution. The metals are extracted into the aqueous phase while the ionic liquid phase is recovered and can be separated and reused.
As an example, CuO (1 g; 12.57 mmol) was mixed with [Hbet][Tf2N] (10 g; 25.1 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. The water was evaporated and the ionic liquid phase was extracted twice with a 37% HCl solution. The ratio of the metal content in the aqueous phase to the ionic liquid phase was determined by titration to be 82:1 after the first extraction. The metal was almost completely extracted to the aqueous phase after a second extraction with the acid. The same extraction can also be performed with HNO3 or H2SO4.
In another example, Nd2O3 (1 g; 2.97 mmol) was mixed with [Hbet][Tf2N] (7.102 g; 17.8 mmol) and 10 mL of water. The mixture was stirred under reflux for 12 hours. The water was evaporated and the ionic liquid phase was extracted twice with a 37% HCl solution. The neodymium ions were almost completely extracted to the aqueous phase after a second extraction with the acid. The same extraction can also be performed with HNO3.
EXAMPLE 10: DISSOLUTION AND DEPOSITION OF METALS
[Hbet] [Tf2N] (100 mL) was heated in a beaker at 700C. An oxidized copper metal plate was immersed into the ionic liquid. After a few minutes the ionic liquid turned slightly blue and the copper plate was found to be bright and reflective all over its surface.
Copper-containing [Hbet] [Tf2N] (100 mL) was heated in a beaker at 70 0C. A zinc or iron metal plate was immersed into the ionic liquid. After a few minutes the copper metal was deposited on the surface of the zinc or iron plate, respectively.
Silver-containing [Hbet][Tf2N] (100 mL) was heated in a beaker at 7O0C. A copper metal plate was immersed into the ionic liquid. After a few minutes the silver metal was deposited on the surface of the copper plate.
EXAMPLE 1 1 : SYNTHESIS OF N-CARBOXYMETHYL-METHYLPYRROLIDIUM BIS(TRIFLUOROMETHYLSULFONYLIIMIDE
To N-methylpyrrolidinium (0.5 mol, 42.5 g), ethyl chloroacetate (0.5 mol, 61.2 g) was slowly added on cooling in an ice bath. The mixture was stirred for 2 days. The crude product was washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 hours. Water was evaporated under reduced pressure and the hydrochloride N-carboxymethyl-methylpyrrolidinium was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. 1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 4.34 (s, 2H), 3.62 (d, 4H), 3.17 (s, N-CH3), 2.09 (s, 4H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 167.1 1 (COOH), 126.22, 121.95, 1 17.69, 1 13.42 (2 x CF3), 65.02 (CH2-N-CH2), 62.15 (CH2-COOH), 49.21 (N- CH3), 21.49 (CH2). Elemental analysis calcd (%) for C9Hi4N2O6F6S2 (Mw = 424.02 g moP1): C 25.47, H 3.33, N 6.60; found: C 26.07, H 4.30, N 6.44. IR (KBr pellet, cm"1): 1747s, 1632w, 1478w, 1462m, 1422m, 1352m, 1062m.
Melting point (M.p.) = 49 0C.
The ionic liquid does not form one phase with water upon heating.
EXAMPLE 12: N-CARBOXYETHYL-METHYLPYRROLIDINIUM BIS(TRIFLUORO- METHYLSULFONYDIMIDE
To N-methylpyrrolidine (0.5 mol, 42.5 g), bromopropionate ethyl ester (0.5 mol, 90.5 g) was slowly added on cooling in an ice bath. The mixture was stirred for 2 days. The crude product was washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the hydrochloride N-carboxyethyl-methylpyrrolidinium was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. Elemental analysis calcd (%) for Ci0Hi6N2O6F6S2 (Mw = 438.36 g mol"1): C 27.40, H 3.68, N 6.39; found: C 27.28, H 3.72, N 6.31. M.p. = liquid at room temperature. The ionic liquid does not form one phase with water upon heating. EXAMPLE 13: N-CARBOXYMETHYL-METHYLMORPHOLINIUM BIS(TRI- FLUOROMETHYLSULFONYDIMIDE
To N-methyl morpholinium (0.5 mol, 50.05g), ethyl chloroacetate (0.5 mol, 61.2 g) was slowly added on cooling in an ice bath. The mixture was stirred for 2 days at room temperature. The crude product was washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the N-carboxymethyl-methylmorpholinium hydrochloride was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. A water content of 320 ppm was determined by coulometric Karl Fischer titration.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 4.43 (s, 2H), 3.93 (s, 4H), 3.60 (m, 4 H), 3.33 (s, 3H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 166.90 (COOH), 126.69, 122.43, 1 18.17, 113.92 (2 x CF3), 62.00 (N-CH2-COOH) 60.59 (4 C), 47.89 (N-CH3).
Elemental analysis calcd (%) for C9Hi4N2O7F6S2 (Mw = 440.01 g moP1): C 24.55, H 3.20, N 6.36; found: C 24.71, H 4.07, N 6.13. IR (KBr-pellet, cm"1): 1745s, 1628m, 1475w, 1426w, 1353m, 1058m. M.p. = 550C (onset).
A mixture of N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide and water (50/50 wt. %) forms one phase above 52 0C. Below 52 0C, phase separation takes place.
EXAMPLE 14: N-CARBOXYMETHYL-METHYLPIPERIDINIUM BISfTRIFLUORO- METHYLSULFONYDIMIDE
To N-methyl piperidinium (0.5 mol, 49.55 g), ethyl chloroacetate (0.5 mol, 61.2 g) was slowly added on cooling. The mixture was stirred for 2 days. The crude product was washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the hydrochloride N-carboxymethyl-methylpiperidinium was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. The compound is a liquid at room temperature.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 4.27 (s, 2H), 3.53 (m, 4H), 3.02 (s, 3H), 1.79 (t, 4H), 1.53 (m, 2H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 166.64 (COOH), 126.22, 121.95, 117.69, 1 13.42 (2 x CF3), 61.25 (N-CH2-COOH), 60.66 (2x CH2), 20.94 (CH2), 19.48 (2 x CH2). The ionic liquid does not form one phase with water upon heating.
EXAMPLE 15: P-CARBOXYMETHYL-TRBUTYLPHOSPHONIUM BIS(TRI- FLUOROMETHYLSULFONYDIMIDE
To tributyl phosphonium (0.5 mol, 101.1 g), ethyl chloroacetate (0.5 mol, 61.2 g) was slowly added on cooling in an ice bath under nitrogen atmosphere. The mixture was stirred for 2 days at room temperature. The crude product was washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the hydrochloride P-carboxymethyl- tributylphosphonium was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 3.62(d, 2H), 2.25 (m, 6H), 1.43 (m,12 H), 0.90 (t, 9H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 167.31 (COOH), 126.24 121.97, 117.70, 113.44 (2 x CF3), 39.01 (CH2-COOH) 26.82 (CH2), 26.15 (CH2), 23.75 (CH2), 23.53 (CH2), 23.32 (CH2), 23.26 (CH2) , 22.98 (CH2), 18.23 (CH2), 18.20 (CH2), 13.51(3xCH3) Elemental analysis calcd (%) for Ci6H30NO6F6S2P (Mw = 541.12 g mol 1): C 35.48, H 5.58, N 2.58; found: C 36.91, H 5.57, N 2.28. IR (KBr-pellet, cm"1): 2967m, 2939s, 2879m, 1712s, 1468w, 1348m, 1059m. M.p. = 55 0C.
The phosphonium ionic liquid does not form one phase with water upon heating.
EXAMPLE 16: L-CARNITINE BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
A solution of L-carnitine (0.6 mol, 96.7g) in 100 mL of water was added under stirring to an aqueous solution of hydrogen bis(trifluoromethylsulfonyl)imide (0.5 mol, 142.1 g). The mixture was stirred for one hour in an ice bath. The aqueous phase separated from the ionic liquid. After separation of the phases, the ionic liquid phase was dissolved in acetone, the excess of L - carnitine precipitates. The ionic liquid was evaporated to dryness at 80 0C in vacuum on a rotary evaporator.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 4.41 (q, IH), 3.35 (d, N-CH2), 3.12 (s, 3 x CH3), 2.41 (m, 2H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 171.56 (COOH), 125.99, 121.75,
117.52, 113.28 (2 x CF3), 69.50 (N-CH2), 62.48 (C-OH), 53.46 (3 x CH3) (40.42 (CH2-COOH).
Elemental analysis calcd (%) for C25H47N5Oi7Fi2S4 (Mw = 1045.17 g mol"1): C 28.67 H 4.62, N
6.69; found: C 28.66, H 4.57, N 6.43. IR (KBr-pellet, cm'1): 1591s, 1481m, 1407m, 1349m,
1056m, 613s. M.p. = 55 0C.
A mixture of l-carnitine bis(trifiuoromethylsulfonyl)imide and water (50/50 wt. %) forms one phase above 8 0C. Below 8 0C, phase separation takes place.
EXAMPLE 17: N-CARBOXYMETHYLPYRIDINIUM BIS(TRIFLUOROMETHYL- SULFONYDIMIDE
N-carboxymethylpyridinium (0.5 mol, 86.5) was dissolved in water (100 ml) and an aqueous solution of lithium bis(tτifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. A water content of
32 ppm was determined by coulometric Karl Fischer titration.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 9.02 (d, 2H), 8.65 (t, IH), 8.19 (t, 2H), 5.52 (s, 2H).
Elemental analysis calcd (%) for C9H8N2O6F6S2 (Mw = 417.97 g mor1): C 25.84, H 1.93, N 6.70; found: C 25.88, H 3.17, N 6.33. IR (KBr-pellet, cm"1): 1747s, 1639m, 1493w, 1426w, 1353m,
1058m.
M.p. = 32 0C (onset temperature).
A mixture of N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide and water (50/50 wt.%) forms one phase above 55 0C. Below 55 0C, phase separation takes place.
EXAMPLE 18: REDUCTION OF THE VISCOSITY OF THE TASK-SPECIFIC IONIC LIQUIDS
The task-specific ionic liquids with the COOH functional group are in general viscous liquids. To make these ionic liquids more easy to handle, they can be mixed (diluted) with other ionic liquids. For instance, the task-specific ionic liquid l-carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was found to be miscible in all weight proportions with the ionic liquid 1 -butyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and these mixtures have a lower viscosity than the task-specific ionic liquid itself.
l-Carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide had been described earlier by Bartsch, Richard A.; Dzyuba, Sergei V. Polarity variation of room temperature ionic liquids and its influence on a Diels-Alder reaction. ACS Symposium Series (2003), 856 (Ionic Liquids as Green Solvents), 289-299.
This compound was prepared by us a follows:
Under an inert atmosphere of dry nitrogen a mixture of 1-methylimidazole (0.5 mol, 41.02 g) and ethyl chloroacetate (0.5 mol, 61.2 g) was stirred at RT for 1 h, during which time the reaction mixture turned to a solid. The solid was washed with diethyl ether (3 x 30 mL). The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water was evaporated under reduced pressure and the l-carboxymethyl-3-methylimidazolium was recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound was redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.5 mol, 143.5 g) was added. The ionic liquid separated from the water phase. The ionic liquid phase was washed several times with water until no chloride impurities could be detected with the silver nitrate test. The ionic liquid was then evaporated to dryness at 80 0C under vacuum on a rotary evaporator. A water content of 67 ppm was determined by coulometric Karl Fischer titration. 1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 9.05 (s, IH), 7.67 (d, 2H), 5.1 1 (s, 2H), 3.90 (s, 3H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 168.58 (COOH), 137.72 (NCN), 123.9 (C-C) 126.21, 121.95, 1 17.68, 113.42 (2 x CF3), 49.97 (N-CH2), 36.11 (N-CH3). Elemental analysis calcd (%) for C8H9N3O6F6S2 (Mw = 420.98 g moP1): C 22.81, H 2.15, N 9.97; found: C 22.22, H 2.12, N 9.17. IR (KBr-pellet, cm"'): 1743s, 1579m, 1478w, 1425w, 1346m, 1056m.
M.p. = liquid at room temperature. A mixture of l-carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and water (50/50 wt. %) forms one phase above 64 0C. Below 64 0C, phase separation takes place.
EXAMPLE 19: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-MORPHOLINIUM
BISfTRIFLUOROMETHYLSULFONYDIMIDE
N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, [MHbetMor] [Tf2N] (5 g, 11.35 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetMor] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6Ou, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [MHbetMor] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2. Characterization of the copper(II) complex: N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, [MHbetMor] [Tf2N] (5 g, 1 1.35 mmol) was mixed with an equimolar amount of copper(II) oxide (1 1.35 mmol, 0.903 g) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. Elemental analysis: calcd(%) for Cu2([MbetMor]4[Tf2N]4 (C9H|4CuF6N2Oi0S2) (Mw = 551.88g moK1) C 19.58, H 2.55, N 5.07; found C 19.70, H 2.45, N 5.25.
EXAMPLE 20: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN « THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-PYRROLIDINIUM BISfTRIFLUOROMETHYLSULFONYLMMIDE
N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MHbetPyr] [Tf2N] (5 g, 11.78 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetPyr] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6On, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [MHbetPyr] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2.
Characterization of the copper(II) complex: N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MHbetPyr] [Tf2N] (5 g, 1 1.78 mmol) was mixed with an equimolar amount of copper oxide (11.78 mmol, 0.936 g) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. Elemental analysis: calcd(%) for Cu2([MbetPyr]4[Tf2N]4 (C36H56Cu2F24N8O26S8) (Mw = 1856.55 mol"1) C 23.29, H 3.04, N 6.03; found C 23.38, H 3.14, N 5.98. EXAMPLE 21 : SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYETHYL-METHYL-PYRROLIDINIUM
BISfTRIFLUOROMETHYLSULFONYL)IMIDE
N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MEHbetPyr] [Tf2N] (5 g, 1 1.05 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MEHbetPyr] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6On, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [MEHbetPyr] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2
EXAMPLE 22: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-PIPERIDINIUM
BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, [MHbetPip] [Tf2N] (5 g, 11.40 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetPip] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6Oi i, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [MHbetPip] [NTf2]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2. EXAMPLE 23: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-CARBOXYMETHYL-METHYL-IMIDAZOLIUM
BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide, [HbetMIM] [Tf2N] (5 g, 11.86 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetMIM] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6Ou, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [HbetMIM] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2.
EXAMPLE 24: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID P-CARBOXYMETHYL-TRIBUTYL-PHOSPHONIUM
BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
P-carboxymethyl-tributylphosphonium bis(trifluoromethylsulfonyl)imide, [HbetPhos] [Tf2N] (5 g, 9.23 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetPhos] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6Ou, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [HbetPhos] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2. EXAMPLE 25: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN
THE IONIC LIQUID N-CARBOXYMETHYL-PYRIDINIUM
BIS(TRIFLUOROMETHYLSULFONYL-)IMIDE
N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide, [HbetPy] [Tf2N] (5 g, 11.95 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetPy] [Tf2N] : Sc2O3, Y2O3, La2O3, Pr6On, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [HbetPy] [Tf2N] : Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2 Characterization of the cadmium complex: N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide, [HBETPy][Tf2N] (5 g, 11.78 mmol) was mixed with an equimolar amount of cadmium oxide (11.78 mmol, 1.534 g) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. Elemental analysis: calcd(%) for Cd([MbetPy] [Tf2N]) (Ci8Hi4CdF12N4Oi4S4) (Mw = 979.02 mol" ') C 22.08, H 1.44, N 5.72; found C 22.38, H 1.54, N 5.78.
EXAMPLE 26: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID L-CARNITINE BIS(TRIFLUOROMETHYL-SULFONYLtIMIDE
L-carnitine bis(trifluoromethylsulfonyl)imide, [LCAR][Tf2N] (5 g, 11.30 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or - hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [LCAR][Tf2N]: Sc2O3, Y2O3, La2O3, Pr6O, ,, Nd2O3, Sm2O3, Eu2O3, Gd2O3,
Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [LCAR][Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2.
EXAMPLE 27: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- CARBOXYMETHYL-METHYLPIPERIDINIUM BIS(TRIFLUOROMETHYL-
SULFONYDIMIDE UNDER HIGH PRESSURE
N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, [MHbetPip] [Tf2N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-Iined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetPip] [Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 28: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYMETHYL-METHYLMORPHOLINIUM BIS(TRIFLUORQMETHYL-
SULFONYDIMIDE UNDER HIGH PRESSURE
N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, [MHbetMor] [Tf2N] (I g, 2.27 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O0C for 24 hours in a PTFE-lined acid digestion bomb (No.
4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum.
The following oxides were found to be soluble in the ionic liquid [MHbetMor] [Tf2N] under high pressure: CO3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 29: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYMETHYL-METHYLPYRROLIDINIUM BIS(TRIFLUOROMETHYL-
SULFONYUHMIDE UNDER HIGH PRESSURE N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MHbetPyr] [Tf2N] (1 g, 2.35 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetPyr] [Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 30: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYETHYL-METHYLPYRROLIDINIUM BISfTRIFLUOROMETHYL-
SULFONYDIMIDE UNDER HIGH PRESSURE
N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [MEHbetPyr] [Tf2N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MEHbetPyr] [Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 31 : SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYMETHYL-METHYLPIPERIDINIUM BISfTRIFLUOROMETHYL- SULFONYLIIMIDE UNDER HIGH PRESSURE
N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, [MHbetPip] [Tf2N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [MHbetPip][Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3. EXAMPLE 32: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYMETHYL-METHYLIMIDAZOLIUM BIS(TRIFLUOROMETHYL-
SULFONYDIMIDE UNDER HIGH PRESSURE
N-carboxymethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide, [HbetMIM] [Tf2N] (1 g, 2.37 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetMIM] [Tf2N] under high pressure: C03O4, CoO, Co2θ3, Cr2θ3, FeO and Fe2θ3.
EXAMPLE 33: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID P-
CARBOXYMETHYL-TRIBUTYLPHOSPHONIUM BISfTRIFLUOROMETHYL-
SULFONYLtIMIDE UNDER HIGH PRESSURE
P-carboxymethyl-tributylphosphonium bis(trifluoromethylsulfonyl)imide, [HbetPhos] [Tf2N] (1 g, 1.84 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O0C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetPhos] [Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 34: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N-
CARBOXYMETHYL-PYRIDΓNIUM BISΓΓRIFLUOROMETHYLSULFONYDIMIDE UNDER HIGH PRESSURE
N-carboxymethyl-pyridinium bis(trifluoromethylsulfonyl)imide, [HbetPy] [NTf2] (1 g, 2.39 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O0C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [HbetPy] [Tf2N] under high pressure: CO3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 35: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID L- CARNITINE BIS(TRIFLUOROMETHYLSULFONYL)IMIDE UNDER HIGH PRESSURE
L-carnitine bis(trifluoromethylsulfonyl)imide, [L-Car] [Tf2N] (1 g, 2.26 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [L-Car][Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 36: SYNTHESIS OF N-DIMETHYL-N-BUTYL-BETAINIUM BIS (TRI- FLUOROMETHYLSULFONYDIMIDE
1-Bromobutane (0.1 mol, 13.7 g) reacted with the ethyl ester of glycine betaine (0.1 mol 13.1 g) for 7 hours at 50 0C. The product was washed with diethyl ether and refluxed for 7 hours in an aqueous HCl solution (15 %). The hydrobromide salt was recrystallized from methanol and dissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.1 mol, 28.7 g) was added. A hydrophobic phase separated from the water phase.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 3.57 (s, 2H), 3.28 (m, 2H), 3.05 (s, N-CH3), 1.47 (m, 2H), 1.10 (m, 2H), 0.73 (t, 3H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 166.73 (COOH), 126.22, 121.95, 117.69, 1 13.42 (2 x CF3), 64.30 (CH2-COOH), 61.26 (N-CH2), 50.98 (2 x CH3) 24.08 (CH2), 19.42 (CH2), 13.60 (CH3). Elemental analysis calcd (%) for Ci0H18N2O6F6S2 (Mw = 440.38 g moK1): C 27.27, H 4.12, N 6.36; found: C 27.32, H 4.07, N 6.45.
N-dimethyl-N-butyl-betainium bis(tri-fluoromethylsulfonyl)imide ([C4Hbet][Tf2N]) was obtained as a viscous liquid, but the sample crystallized out at room temperature after a few weeks. The melting point of this solid was 58 0C (onset temperature). EXAMPLE 37: SYNTHESIS OF N-DIMETHYL-N-HEXYL-BETAINIUM BISfTRIFLUORO- METHYLSULFONYDIMIDE
1-Bromohexane (0.1 mol, 16.5 g) reacted with the ethyl ester of glycine betaine (0.1 mol 13.1 g) for 7 h at 50 0C. The product was washed with diethyl ether and refluxed for 7 h in a 15 % aqueous HCl solution. The hydrobromide salt was recrystallized from methanol and dissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.1 mol, 28.7 g) was added. A hydrophobic phase separated from the water phase.
1H-NMR (300 MHz, [D6]DMSO, TMS): δ = 4.16 (s, 2H), 3.43 (m, 2H), 3.16 (s, N-CH3), 1.65
(m, 2H), 1.28 (m, 6H), 0.87 (t, 3H). 13C-NMR (100.62 MHz, [D6]DMSO, TMS): δ = 166.72 (COOH), 126.22, 121.95, 1 17.69, 1 13.42 (2 x CF3), 64.44 (N-CH2-COOH), 61.33 (N-CH2),
50.98 (2 x CH3), 30.90 (CH2), 25.66 (CH2), 22.1 1 (CH2), 22.01 (CH2), 14.03 (CH3).
Elemental analysis calcd (%) for CnH22N2O6F6S2 (Mw = 468.08 g moK1): C 30.77, H 4.73, N
5.98; found: C 30.84, H 4.85, N 6.02.
M.p.: below room temperature (higly viscous liquid).
EXAMPLE 38: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN
THE IONIC LIQUID N-DIMETHYL-N-BUTYL-BETAINIUM BISfTRIPLUOROMETHYL-
SULFONYDIMIDE
N-imethyl-N-butyl-betainium bis(trifluoromethylsulfonyl)imide, [C4Hbet] [Tf2N] (5 g, 1 1.35 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or metal hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [C4Hbet] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6On, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [C4Hbet] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2. r υ i # w »- U \/ — —
EXAMPLE 39: SOLUBILIZATION OF METAL OXIDES AND METAL HYDROXIDES IN THE IONIC LIQUID N-DIMETHYL-N-HEXYL-BETAINIUM BIS(TRIFLUOROMETHYL- SULFONYLttMIDE
N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide, [C6Hbet] [Tf2N] (5 g, 1 1.35 mmol) was mixed with an equimolar amount of the metal oxide or -hydroxide (or an excess of the metal oxide or -hydroxide) and 20 mL of water. The mixture was stirred under reflux for 12 hours. After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [CόHbet] [Tf2N]: Sc2O3, Y2O3, La2O3, Pr6On, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb4O7, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, UO3, PbO, ZnO, CdO, HgO, CuO, Ag2O, NiO, PdO, and MnO. The following hydroxides were found to be soluble in the ionic liquid [CόHbet] [Tf2N]: Pb(OH)2, Zn(OH)2, Cd(OH)2, Cu(OH)2, Ni(OH)2, Fe(OH)2, Fe(OH)3, Co(OH)2, Cr(OH)3, Mn(OH)2 LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2
EXAMPLE 40: SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- DIMETHYL-N-BUTYL-BETAINIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
UNDER HIGH PRESSURE
N-dimethyl-N-butyl-betainium bis(trifluoromethylsulfonyl)imide, [C4Hbet] [Tf2N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 14O0C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [C4Hbet] [Tf2N] under high pressure: Co3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 41 : SOLUBILIZATION OF METAL OXIDES IN THE IONIC LIQUID N- DIMETHYL-N-BUTYL-BETAINIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE
UNDER HIGH PRESSURE N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide, [C6Hbet] [Tf2N] (1 g, 2.28 mmol) was mixed with an equimolar amount of metal oxide and 5 mL of water. The mixture was heated in an oven at 1400C for 24 hours in a PTFE-lined acid digestion bomb (No. 4744, 45 ml, Parr Instrument Company). After filtration, water was evaporated under vacuum. The following oxides were found to be soluble in the ionic liquid [C6Hbet] [Tf2N] under high pressure: CO3O4, CoO, Co2O3, Cr2O3, FeO and Fe2O3.
EXAMPLE 42: INFLUENCE OF THE ALKYL CHAIN LENGTH ON THE PHYSICAL PROPERTIES OF BETAINIUM SALTS
Replacement of a methyl group in betainium bis(trifluoromethylsulfonyl)imide by a longer alkyl chain influences the polarity and thus the solubility of the resulting ionic liquids. This affects the solubility of the ionic liquids in water and in some organic solvents, and it also affects the hydropobicity of the ionic liquids. [Hbet][Tf2N] is totally miscible with water at temperatures above 56 0C, but the butyl analogue [C4Hbet] [Tf2N] and the hexyl analogue [C6Hbet] [Tf2N] are at all temperatures insoluble in water. Whereas [Hbet][Tf2N] and [C4HbCt] [Tf2N] are insoluble in dichloromethane (DCM), [C6Hbet] [Tf2N] is soluble in this solvent. [Hbet][Tf2N] is insoluble in chloroform, [C4Hbet][Tf2N] is partially soluble and [C6Hbet] [Tf2N] is soluble. It is preferred that R1, R2, and R3 are all Ci, C2, or C3 alkyl, in order to obtain ionic liquids with the following properties: miscible with water, in particular above 500C, and insoluble in non- ionic organic solvents, more in particular dichloromethane or chloroform.
More in particular, it is preferred that R4 is Ci or C2 alkyl-COOH, when R1, R2, and R3 are Ci, C2, or C3 alkyl. Moreover, the ionic liquids of this invention wherein R4 is Ci or C2 alkyl-COOH are easy to synthesize and cheap. The solubilization of metal oxides and metal hydroxides is increased when R4 is Ci or C2 alkyl-COOH compared to C3 or more (>C3) alkyl-COOH, more in particular the solubilization of metal oxides and metal hydroxides is the highest when R4 is -CH2- COOH (Ci alkyl-COOH). The positive charge on the quaternary nitrogen (or phosphor, arsenicum or antimony) atom has an inductive effect on the COOH-group. This effect is affected by the chain length in-between the COOH-group and the positively charged nitrogen (or phosphor, arsenicum or antimony) atom, respectively. The shorter the distance between these functional groups, the higher the acidity of the proton of the COOH-function. Therefore, one or two CH2 groups in-between, and preferably one CH2 group in-between is favorable for the application of this invention: these ionic liquids exhibit a significantly higher solubilizing ability for metal oxides than ionic liquids with three or more CH2-groups between the positively charged heteroatom and the COOH-function.
EXAMPLE 43: CARBOXYMETHYL-TRIBUTYLARSONIUM BISfTRIFLUORQ- METHYLSULFONYDIMIDE
To tributylarsine (0.05 mol, 12.31 g), ethyl chloroacetate (0.05 mol, 6.12 g) is slowly added on cooling in an ice bath under nitrogen atmosphere. The mixture is stirred for 5 days at room temperature. The crude product is washed with diethyl ether to remove unreacted starting materials. The solid compound is refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water is evaporated under reduced pressure and As-carboxymethyl-tributylarsonium hydrochloride is recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added. The ionic liquid separates from the water phase. The ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test. The ionic liquid is then evaporated to dryness at 80 0C under vacuum on a rotary evaporator.
EXAMPLE 44: CARBOXYMETHYL-TRIOCTYLSTIBONIUM BISfTRIFLUORO- METHYLSULFONYDIMIDE
To trioctyl antimony (0.05 mol, 23.07 g), ethyl chloroacetate (0.05 mol, 6.12 g) is slowly added on cooling in an ice bath under nitrogen atmosphere. The mixture is stirred for 5 days at room temperature. The crude product is washed with diethyl ether to remove unreacted starting materials. The solid compound is refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water is evaporated under reduced pressure and Sb-carboxymethyl-trioctylstibonium hydrochloride is recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added. The ionic liquid separates from the water phase. The ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test. The ionic liquid is then evaporated to dryness at 80 0C under vacuum on a rotary evaporator.
EXAMPLE 45: P-CARBOXYMETHYL-TRIHEXYLPHOSPHONIUM BISfTRI- FLUOROMETHYLSULFONYUIMIDE
To trihexylphosphine (0.5 mol, 14.32 g), ethyl chloroacetate (0.05 mol, 6.12 g) is slowly added on cooling in an ice bath under nitrogen atmosphere. The mixture is stirred for 5 days at room temperature. The crude product is washed with diethyl ether to remove unreacted starting materials. The solid compound is refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water is evaporated under reduced pressure and P-carboxymethyl-trihexylphosphonium hydrochloride is recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added. The ionic liquid separates from the water phase. The ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test. The ionic liquid is then evaporated to dryness at 80 0C under vacuum on a rotary evaporator.
EXAMPLE 46: P-CARBOXYMETHYL-TRIOCTYLPHOSPHONIUM BIS(TRI- FLUOROMETHYLSULFONYDIMIDE
To trioctylphosphine (0.05 mol, 18.53 g), ethyl chloroacetate (0.05 mol, 6.12 g) is slowly added on cooling in an ice bath under nitrogen atmosphere. The mixture is stirred for 5 days at room temperature. The crude product is washed with diethyl ether to remove unreacted starting materials. The solid compound was refluxed in 15% aqueous solution of hydrochloric acid for 7 h. Water is evaporated under reduced pressure and P-carboxymethyl-trioctylphosphonium hydrochloride is recrystallized from a mixture of acetonitrile and methanol. The recrystallized compound is redissolved in water and an aqueous solution of lithium bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.35 g) is added. The ionic liquid separates from the water phase. The ionic liquid phase is washed several times with water until no chloride impurities are detected with the silver nitrate test. The ionic liquid is then evaporated to dryness at 80 0C under vacuum on a rotary evaporator.
EXAMPLE 47: DEHYDROCARMTINIUM BISfTRIFLUOROMETHYLSULFONYLVIMIDE
A solution of 3-carboxy-2-oxopropyl-trimethylammonium hydroxide inner salt (dehydrocarnitine) (0.05 mol, 7.96 g) in 100 mL of water is added under stirring to an aqueous solution of hydrogen bis(trifluoromethylsulfonyl)imide (0.05 mol, 14.21 g). The mixture is stirred for one hour in an ice bath. The aqueous phase separated from the ionic liquid. After separation of the phases, the ionic liquid phase is dissolved in acetone, the excess of dehydrocarnitine precipitates. The ionic liquid is evaporated to dryness at 80 0C in vacuum on a rotary evaporator.

Claims

1. An organic salt according to formula (I):
R1R2R3R4Y+X"
I wherein
- Y is selected from N; P; As; or Sb;
- each of R1, R2 and R3 are independently selected from CM2 alkyl; or Cs-12 cycloalkyl; or each of R1 and R2, or R1 and R3, or R2 and R3 can be taken together to form a substituted or unsubstituted cyclic structure;
- R4 is selected from a C1-)2 alkyl-COOH; or C3-12 cycloalkyl-COOH; wherein alkyl is optionally substituted with at least one OH or comprises at least one carbonyl function;
- X' is selected from organic sulfonates; organic sulfates; organic carboxylates; organic sulfonylimides; or tetrafluoroborate.
2. The organic salt according to claim 1, wherein R4 is selected from C3.12 cycloalkyl- COOH; -CH2CH2COOH; or -CH2COOH and Y = N.
3. The organic salt according to claim 1, wherein R4 is -CH2COOH and Y = N.
4. The organic salt according to claim 1, wherein R4 is selected from C3-I2 cycloalkyl- COOH and Y = N.
5. The organic salt according to claim 1, wherein each of R1, R2 and R3 are independently selected from CM2 alkyl and Y = P.
6. The organic salt according to claim 1, wherein each of R1, R2 and R3 are independently selected from Ci-J2 alkyl, R4 is -CH2COOH and Y = P.
7. The organic salt according to claim 1, wherein Y is N, and R1 and R2, or R1 and R3, or R2 and R3 form a substituted or unsubstituted cyclic structure.
8. The organic salt according to claim 1, wherein Y is N, R1 and R2, or R1 and R3, or R2 and R3 form a substituted or unsubstituted cyclic structure, and R4 is -CH2CH2COOH or - CH2COOH.
9. The organic salt according to claim 1, wherein Y is N and R4 is selected from a substituted C1-12 alkyl-COOH wherein at least one OH group is present, or a Ci-12 alkyl- COOH which contains at least one carbonyl group.
10. The organic salt according to claims 1 to 9, wherein X" is selected from perfluorinated organic sulfonate, perfluorinated organic sulfate, organic bis(perfluoroalkylsulfonyl)imide anions or perfluorinated organic carboxylates.
11. The organic salt according to claims 1 to 9, wherein X" is a bis(perfluoro-C1-12alkyl- sulfonyl)imide.
12. The organic salt according to claims 1 to 9, wherein X" is bis(trifluoromethylsulfonyl)imide.
13. The organic salt according to claim 1, wherein the ionic liquid is selected from the group of betaine bis(trifluoromethylsulfonyl)imide, N-dimethyl-N-butyl-betainium bis(trifluoromethylsulfonyl)imide, N-dimethyl-N-hexyl-betainium bis(trifluoromethylsulfonyl)imide, carboxylmethyl-tributylphosphonium bis(trifluoromethylsulfonyl)imide, N-carboxymethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N-carboxyethyl-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N-carboxymethyl-methylmorpholinium bis(trifluoromethylsulfonyl)imide, N-carboxymethyl-methylpiperidinium bis(trifluoromethylsulfonyl)imide, carnitine bis(trifluoromethylsulfonyl)imide, N- carboxymethyl-methylpyridinium bis(trifluoromethylsulfonyl)imide, carboxymethyl- tributylarsonium bis(trifluoromethylsulfonyl)imide, carboxymethyl-trioctylstibonium bis(trifluoromethylsulfonyl)imide, P-carboxymethyl-trihexylphosphonium bis(trifluoromethylsulfonyl)imide, P-carboxymethyl-trioctylphosphonium bis(trifluoromethylsulfonyl)imide, and dehydrocarnitinium bis(trifluoromethylsulfonyl)imide.
14. A process for the preparation of the organic salts of claims 1 to 13, said process comprising the step of performing the metathesis reaction of R1R2R3R4Y+halogenide and salts of perfluorinated organic sulfonate, organic sulfate, bis(perfluoroalkylsulfonyl)imide or organic carboxylate anions in water.
15. A process for the preparation of the organic salts of claims 1 to 13, said process comprising the step of mixing of
Figure imgf000069_0001
and perfluorinated organic sulfonic acid, organic sulfatic acid, organic carboxylic acids or organic hydrogen sulfonylimide in water.
16. The use of the organic salts according to claims 1 to 13 in chemical applications.
17. The use of organic salts according to claim 16, wherein said chemical applications are chemical applications involving metals such as metal oxides, metal hydroxides or metal salts.
18. The use of the organic salts according to claim 16 and 17, wherein said chemical applications are selected from the list of as a solvent, for example for the solubilization of organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; for extraction procedures, more in particular for the extraction of metal ions; for decontamination of soils contaminated by heavy metals especially with copper, nickel, zinc, cadmium, mercury or lead; for catalytic reactions wherein the organic salt serves as a solvent or as a catalyst; for electrodeposition of metal ions; as a medium for electropolishing or for the cleaning of metal surfaces; for deposition of metals onto conductive surfaces; for the processes of spent nuclear fuel elements; as electrolyte in batteries, fuel cells, photovoltaic devices and electrochromic devices and for recycling of noble metals from used catalysts and electronic circuits.
19. Compositions comprising the organic salts according to claims 1 to 13 and further comprising another liquid, gas or organic or anorganic compound.
20. Compositions according to claim 19, wherein said composition further comprises metals.
21. Compositions according to claim 20, wherein said composition is selected from the list of [Li(bet)][Tf2N], [Na(bet)] [Tf2N] H2O, [K(bet)] [Tf2N] H2O, [Cu3(bet)8(H2O)4][Tf2N]6, [Zn4(bet)10][Tf2N]8(H2O)4, [Ag2O)Ct)2(Tf2N)] [Tf2N], [Hg(bet)2][Tf2N]2, [Y2(bet)8][Tf2N]6-2H2O, [La2(bet)8][Tf2N]6-4H2O, [Pr2(bet)8][Tf2N]6-4H2O, [Nd2(bet)8][Tf2N]6-4H2O, [Sm2(bet)8][Tf2N]6-2H2O, [Eu2(bet)8][Tf2N]6-2H2O, [Gd2(bet)8][Tf2N]6-2H2O, [Tb2(bet)8][Tf2N]6-2H2O, [Dy2(bet)8][Tf2N]6-2H2O, [Ho2(bet)8][Tf2N]6-2H2O, [Er2(bet)8][Tf2N]6-2H2O, [Tm2(bet)8][Tf2N]6-2H2O, [Yb2(bet)8][Tf2N]6-2H2O and [Lu2(bet)8][Tf2N]6-2H2O.
22. Compositions according to claim 19, wherein said compositions are mixtures with other organic salts comprising perfluorinated organic sulfonate, perfluorinated organic sulfate, organic bis(perfluoroalkyl)sulfonylimide, organic carboxylate, or tetrafluoroborate anions.
23. A process for the preparation of compositions according to claim 19, comprising the step of mixing the organic salts with other liquids, with gases or solid compounds.
24. The use of compositions according to claims 19 to 22 in chemical applications.
25. The use of L-carnitine or D-carnitine as a cationic building block for obtaining chiral organic salts.
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