GB2502607A - Process for the preparation of ionic liquids - Google Patents

Process for the preparation of ionic liquids Download PDF

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GB2502607A
GB2502607A GB1209755.6A GB201209755A GB2502607A GB 2502607 A GB2502607 A GB 2502607A GB 201209755 A GB201209755 A GB 201209755A GB 2502607 A GB2502607 A GB 2502607A
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acid
butyl
ethyl
ethylhexyl
aminium
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Koen Binnemans
Wim Dehaen
Lethesh Kallidanthiyl Chellappan
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Katholieke Universiteit Leuven
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Katholieke Universiteit Leuven
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    • C07C211/62—Quaternary ammonium compounds
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    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
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    • C07C381/12—Sulfonium compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/06—Alkylated phenols
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    • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
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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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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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

Abstract

A method is disclosed to replace halide anions (chloride, bromide, iodide) in ionic liquids by other anions, leading to water-soluble ionic liquids. The halide ionic liquids are first transformed into phenolate ionic liquids by reaction between the halide ionic liquid and a sodium phenolate salt. A solution of the phenolate ionic liquid in a water-immiscible organic solvent is treated with an aqueous solution of a Bronsted acid. This leads to the formation of an ionic liquid with the anion of the Bronsted acid and a phenol. The phenol remains dissolved in the organic phase and can be recycled. The newly formed ionic liquid dissolved in the aqueous phase and can be recovered in a pure state by removal of water. Preferred cations include quaternary ammonium compounds, phosphonium compounds, sulfonium compounds, dialkylimidazolium compounds, 1-alkylpyridinium compounds, 1,1-dialkylpyrrolidinium compounds, 1,1-dialkylpiperidinium compounds and/or 1,1-dialkylmorpholinium compounds.

Description

ANION EXCHANGE IN 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 furthermore provides for a method for the synthesis of ionic liquids in which said method allows replacing halide anions in ionic liquids by other anions, resulting in water-soluble ionic liquids. The invention also provides for the use of the ionic liquids in chemistry applications, for example for the processing of minerals, ores and inorganic waste, among others.
BACKGROUND OF TUE INVENTJON
Ionic liquids are solvents that consist of cations and anions [1]. Typically, they are low-melting organic salts and many of them are liquid at room temperature. Ionic liquids have unique solvent properties, such as a very broad liquidus range, an extremely low vapor presslLre, an intrinsic ionic conductivity and a wide electrochemical window. Their ability to dissolve inorganic and organic compounds, as well as their miscibility with water and organic solvents, strongl)i depends on the alkyl chain length on the cation and especially on the type of anion. For instance, ionic liquids with the bis(trifluoromethylsulfonyl)imide anion (Tf2N) are immiscible with water and are very useful as electrolyte for the electrodeposition of reactive metals [2]. Tonic liquids with acetate anions, for instance l-ethyl-3-methylimidazolium acetate, are excellent solvents for cellulose [3], and ionic liquids with sulfonate anions are able to dissolve lignin [4].
Most ionic liquids are being prepared from precursors with halide counter ions (chloride, bromide or iodide), because haloalkanes are the starting products for the quaternization reaction [5]. The halide counter ions can easily be exchanged via a metathesis reaction by more useful anions, such as Tf2ff or CF3SO. This metathesis reaction is easy to perform, provided that the starting products are soluble in water and that the resulting ionic liquid separates as a hydrophobic phase from the water [6]. A classic example is the straightforward formation of imidazolium ionic liquids with bis(trifluoromethylsulfonyl)imidc counter ions, such as l-butyl-3-methylimidazolium bis(trifluoromcthylsnlfonyDimidc.
I
[C4mim][Tf2N]. These can be synthesized by adding an aqueous solution of LiTf2N to an aqueous solution of [C4thm]Cl. The resulting [C4mim][Tf2N] separates from the aqueous phase and the Lid remains dissolved in water. In contrast, the synthesis of hydrophilic ionic liquids via a metathesis reaction is considerably more difficult, because the resulting water-miscible ionic liquid will remain in the aqueous phase and no phase separation takes place.
The classic method to synthesize hydrophilic ionic liquids was to perform a metathesis reaction using the silver salt of the anion, which results in precipitation of a silver halide [7].
The disadvantages of this method are the high price of silver salts and the risk of contamination of the ionic liquid by silver ions. Addition of an alkali metal salt of the anion to a solution of a chloride or bromide ionic liquid in a dry organic solvent (e.g. acetone) resnlts in an anion exchange and precipitation of an alkali metal salt, but the resulting ionic liquids are often heavily contaminated by halide impurities [8]. An alternative method for the synthesis is the use of alkylating reagents, e.g. dirnethylsulfate or the methyl ester of triflic acid, to synthesize intrinsically halide-free ionic liquids [9]. A few reports describe the use of ion exchange resins for the synthesis of hydrophilic ionic liquids [10]-However, this method is hardly suitable for upscaling, due to the relatively low exchange capacity of the ion-exchange resins. Another method to introduce the anion is by first transforming the ionic liquid into a hydroxide form, followed by addition of a Br�nsted acid [11]. However, the synthesis of the hydroxide ionic liquids often involved multistep reactions and the solutions of the hydroxide ionic liquids easily decompose.
Different patents describe the anion exchange in ionic liquids, but this is by adding a Br�nstcd acid to an aqueous or methanolic solution of salts that decompose to a gas, such as hydrogencarbonate (to C02) or sulfite (to SO2) but not by adding the acid to a solution of an ionic liquid with a basic anion which is dissolved in an organic solvent. Patent PP 0291074 describes the preparation of quatemary ammonium salts in a two-step reaction by reaction of a tertiary amine with a dialkylcarbonate to form a quaternary anmionium carbonate and mixing of the quaternry ainmonium carbonate obtained with a Br�nsted acid to eliminate the carbon dioxide and to form the quaternary amnionium salt [12]. Patent W02009040242 is about the halide-free preparation of 1,3-disubstituted imidazolium ionic liquids by reaction of a 1-substituted imidazole with a dialkylcarbonate and subsequent reaction of the reaction product obtained with the desired acid to introduce the desired anion. A disadvantage of the use of dialkyl carbonates as alkylatiug agent is their relatively low reactivity, so that reaction temperatures of above 1000 C. and superatmospheric pressure (e.g. autoclave) are generally necessary [13]. In patent 1JS200702550M dimethylsulfite is used as the methylating agent instead of dimethylcarbonate. The advantage is that much lower reaction temperatures can be used. The main disadvantage is the formation of toxic SO2 gas [14].
Phenol and its derivatives have been used to extract quaternary ammoniunt salts from aqueous solution. Patent tJS4,487,698 describes a process for removing onium salts from aqueous solutions by a adding a phenol to an aqueous solution containing an oñium salt, followed by contacting die solution with a water-immiscible organic layer, whereby the oniurn salt migrates into the organic phase [15]-However, this method is a water purification method and has not been extended to anion exchange. Patent US2,309,69l describes how quaternary onium phenolates can be made by reaction of an aqueous solution of a quaternary onium salt of an inorganic acid (chloride, bromide, iodide) with sodium hydroxide and a phenol [16]. Excess phenol is used to act as a solvent for extraction of the phenolate from the aqueous solution. Separation of the phenol layer from the aqueous layer and removal of the phenol under reduced pressuth gives the pure quaternary onium phenolate. This can be furth&r transformed to hydroxide or carbonate salts, but not to the salts with anions of our interest.
Therefore, there is still a need for novel water-soluble ionic liquids and novel methods of synthesis for such ionic liquids, which do not possess the disadvantages as described in the prior art, such as high reaction temperatures, high pressure and toxic waste products. The present invention fulfills those needs by providing such new ionic liquids and novel synthesis methods for the generation of such ionic liquids.
SUMMARY OF TIlE INVENTION
In a first aspect, the present invention relates to a new synthesis method for the preparation of Ionic liquids. A new method for the anion exchange in ionic liquids is disclosed. In a first step, a halide ionic liquid is dissolved in a dry organic solvent I and the sodium salt of a phenol derivative is added. Sodium chloride precipitates and can be removed from the solution by filtration. In a second step, the solvent is removed by evaporation at reduced pressure and is replaced by a less polar solvent II, in which the phenolate ionic liquid has a good solubility. Traces of alkali halides still present will precipitate at this stage. In a third step, the organic solution is treated with an aqueous solution of a Br�nsted acid with a hydrophilic anion. The strongly basic phenolate anion gets protonated and the newly formed ionic liquid is transferred to the aqueous phase. In a fourth step, the water is removed (e.g. by evaporation under reduced pressure) which results in the formation of the targeted ionic liquid. Removal of the organic solvent of step 3 allows the recycling of the phenol for re-use.
Because of the important role of the phenolate anion in the anion exchange procedure and because of the versatility of the method, the new method is called the "phenolate platformt'.
Solvent I can be Jichioromethane, chloroform, 1,2-dichioroethane, ethyl acetate, 2-butanone, cyclohexanone, acetone, benzene, xylenes. ortho-xylene, meta-xylene, para-xylene or toluene. Acetone and toluene are preferred. The water content of the solvents has to be as low as possible, preferably below 50 ppm. Solvent II can be hexane, heptane, octane, nonane, decane, undecane, dodecane, toluene, xylenes, ortho-xylene, meta-xylene, para-xylene, benzene, cyclohexane, or ren-butylmethylether. The halide ionic liquid can be a chloride, bromide or iodide salt of a quaternary ammonium, quaternary phosphonium, iinidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium or sulfoniuin cation. Preferred cations are tetrabulylammonium, tetrabutylphosphoniurn, l-ethyl-3-methylinildazoliUm. l-butyl-3- rnethyliniidazolium, 1 -buty!-1 -methylpyrrolidinium and 2-ethyl-N-(2-ethylhexYD-N!V- dimethylhexan-l-aminiunl. The phenol derivative can be 4-rert-butylphenol, 2,4-di-tert-butylphenol, 3,5-dimethylphenol. 2.6di-tert_buty1-4-methylphenol, 2,6-di-tert-butylphenOl, 2,6-dimethyiphenol, 4-nonylphenol and cresol, which is a technical mixture of ortho-rnethylphenol. meta-methyiphenol and para-inethylphenol. The preferred phenol derivative is 4-tert-butyiphenol. The Brsnsted acid can be hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, methanesulfonic acid, trifluoromethanesulfOn-ic acid, para-toluenesulfonic acid, 4-bromobenzenesulfonic acid, 4- nitrobenzenesulfonic acid, 3 -nitrobenzenesulfonic acid, 2-nitrobenzenesulfoflic acid, 2,4- nitrobcnzenesulfonic acid, camphorsulfonic acid, benzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, formic acid, aectig acid, propionic acid, butanoic acid, chloroacetic acid, dichloroacctic acid, trichloroacetic acid, trifluoroacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dialkylphosphoric acids and amino acids. Anions of which the corresponding Bninsted acid is not stable can be introduced via the corresponding ammonium salts. Examples include the thiocyanate and the dieyananiide anion.
A second aspect of the present invention relates to novel ionic liquids having the general formula [Q][Zi, which are further described in the embodiments in this invention.
A third aspect of the present invention relates to the use of the ionic liquids of this invention iii chemistry applications, such as for example in the processing of minerals, ores and inorganic waste. The ionic liquids with thc 1-aminium cation have a good stability against strong bases, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium niethoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium te#- butoxide, potassium tert-butoxide, potassium bis(trimethylsilyl)amide, methyllithium. ii-butyllithium, sec-butyllithium. tert-butyllithium, hexyllithium, lithium diisopropylanhide LDA), potassium dusopropylamide (ICDA), lithium hydride, sodium hydride, potassium hydride, sodium bis(trimethy1silyamide, potassium bis(trimethylsilyl)amide, tetrarnethylpiperidide, ethylmagnesiUm bromide, propylmagnesium bromide, butylmagnesiurn bromide, diethylzinc. l,8diazabicyclo[5.4.0]UndCc-7ene (DBTJ), 1,5- diazabicyclo[4.3.01fl0fl5611e (DBN), 1,5,74riazabicyclo(4.4.O)dec-S-(TBD), 7-Methyl- 1,5,7triazabicyClo(44.O)dec-S-ene (MTBD), and N,NjV',W-Tetramethyl-l.8-naphthaletediarnine (Proton Sponge). Therefore, these ionic liquids can be used as a solvent for organic reactions with strong bases, including organometallie reagents (organolithiumorgaflomagllesium and organozincreagents). The inonic liquids of the present invention and more specifically the ionic liquid 1-aminium hydroxide can be used for the processing of minerals, ores and secondary inorganic waste streams (for instance metallurgical slags, electric arc furnace dust), and especially the aluminium ore bauxite. One embodiment of the present invention concerns the use of said ionic liquids of the present invention in chemistry applications, such as for example in the processing of minerals, ores and inorganic waste. In a preferred embodiment of the present invention, the ionic liquids for said use in chemistry applications arc ionic liquids [Q4Il (fl wherein the cation [QJ is 2-ethyl -N-(2ethylhexy1)NJ dimethy exan-l -aminium. and wherein the anion [Z] can be any anion as described in this invention. In a more preferred embodiment of the present invention1 the ionic liquids for said use in chemistry applications are the ionic liquids [Q'l[Zi, wherein the anion [TI is hydroxide. In certain embodiments of the present invention, the processing of ores is the processinf aluminium ore and in more particular embodiments, said ore is bauxite.
One embodiment of the present invention concerns a solvent J (of stepi) which is selected from the group consisting of dichiorometliafle, chloroform, 1,2.dichloroethane, ethyl 5.
acetate, 2-butanone, cyclohexanone, acetone, benzene, xylenes, ortho-xylene, rneta-xylene, para-xylene and ioluene; preferably said solvent I is acetone or toluene.
One embodiment of the present invention conceits a solvent II (of step2) which is selected from the group consisting of hexane, heptane, octane, nonan, decanc, undecane, dodecane, toluene, xylenes, ortho-xylcne, ,neta-xylene, para-xylenc, benzene, cyclohexane, and tert-butylrnethylether.
In a preferred embodiment of the present invention, said (organic) solvent I (and II) is (are) as dry as possible, meaning that the water content of the solvent has to be as low as possible, preferably below 50 ppm.
One embodiment of the present invention concerns a halide ionic liquid which is selected from the group consisting of chloride, bromide or iodide salt of a quaternary ammonium, quaternary phosphonium, imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium or sulfonium cation. In a preferred embodiment of the present invention, said cation is selected from tetrabutylarrirnonium, tetrabutylphosphonium, 1-ethyl-3- methylimidazolium, 1-butyl-3-methylimidazolium, l-butyl-l -methylpyrrolidinium and 2-ethy1N(2-ethyIhcxyl)-N,N-dimethYlheXan-I -aminium.
One embodiment of the present invention concerns a phenol derivative (HY) which is selected from the group consisting of 4-tert-butyiphenol, 2,4-di-tert-butylphenOl, 3,5- dimethylphenol, 2,6-di-tert-butyl-4-mcthylpheflol, 2,6-di-tert-butyiphenol, 2,6- dimethylphenol, 4-nonylphenol and ciesol, preferably said phenol derivative is 4-ten-butylphenol.
One embodiment of the present invention concerns a Br�nsted acid which is selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulftirc acid, nitric acid, phosphoric acid, perchioric acid, methanesulidnic acid, trifluoromethanesulfonic acid, para-toluenesulfonic acid, 4-bromobenzenesulfonic acid, 4- nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2,4- nitrobenzenesulfonic acid, camphorsulfonic acid, benzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, formic acid, acetic acid, propionic acid, butanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid.
trifluoroacetic acid, picolinic acid, nicotiiiic acid, isonicotinic acid, dipicolinic acid, dialkyiphosphoric acids and amino acids.
One embodiment of the present invention concerns a strong base which is selectcd from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, potassium bis(trimethylsilyl) amide, methyllithium, n-butyllithium, scc-butyllithium, tert-butyllithium, hexyllithium, lithium diisopropylamide LDA), potassium diisopropylamide (KDA), lithium hydride, sodium hydride, potassium hydride, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)aniide, lithium tetramethylpiperidide, ethylmagnesium bromide, propylmagnesium bromide,. butylmagnesium bromide, diethyizinc, 1,8- thazabicyclo[54.O]undec-7-ene (DBU), 1,5-cliazabicyclo[4.3.O]non-5-ene (DBN). 1,5,7-triazabicyclo(4.4.O)dec-5-ene (TBD), 7Mcthy1-1,5,7-triazabicyc1o(4.4.O)dec-5-ene (MTBD), and N,N,LV',M-Tetrainethyl-l,8-naphthalenediamine (Proton Sponge).
One embodiment of the present invention concerns the ionic liquids of the present invention for the use in processing of minerals, ores and secodary inorganic waste. In a preferred embodiment, the inonic liquid Z-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminiurn hydroxide is used for said processing use. In a yet more prefered embodiment said ore is an aliminium ore, preferably bauxite.
Certain embodiments of the present invention concern a process for the preparation of an ionic liquid having the general formula [Qt][Zi, and other embodiments concern said ionic liquid, wherein the [Q] cation is selected from the group consisting of a quaternary aimnonium [R'R2R3R4N], quatemary phosphonium [R'R2R3R4V'1, sulfonium [R'R2R3S1, 1,3-dialkylimidazolium, 1-alkylpyridinium, 1, 1-dialkylpyrrolidinium, 1,1-dialkylpiperidinium, or 1,1,-dialkylmorpholinium, wherein R', R2, R3 and R4 are alkyl chains.
In certain embodiments of the present invention [Qi is tctrabutylammonium. In other embodiments [Q is tetrabutyiphosphonium. In other embodiments tQI is I -butyl-3-rnethylimidazolium. In other embodiments (Q] is 1-buty1-l-methylpyrrolidinium In other embodiments [Q'] is 2-ethyI-N-(2-cthy1hexy-N,N-dimethylhexan-l-aminium.
Certain embodiments of the present invention concern a process for the preparation of an ionic liquid having the general formula [Q] [Zi, and other embodiments concern said ionic liquid, wherein the [Zi anion is the conjugated base of a Br�nsted acid HZ. In more particular embodiments of the present invention, said Br�nsted acid HZ is selected from the group consistind of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, methanesulfonic acid, trifluoromethanesulfonic acid, para- toluenesulfonic acid, 4-bromobcnzenesulfonic acid, 4-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 2.-nitrobenzenesulfonic acid, 2,4-nitrobenzenesulfonic acid, camphorsulfonic acid, benzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, formic acid, acetic acid, propionic acid, butanoic acid, chioroacetic acid, dichioroacetic acid, trichioroacetic acid, trifluoroacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dialicyiphosphoric acids and an amino acid.
One embodiment of the present invention concern a process for the preparation of an ionic liquid of the present invention wherein the [Xi anion is a halide, more preferably said anion is selected from chloride, bromide or iodide, and more preferably said anion is chloride or bromide. In one embodiment said anion is chloride. In another embodiment said anion is bromide.
One embodiment of the present invention concern a process for the preparation of an ionic liquid of the present invention wherein the [Ati cation is an alkali metal ion, more preferably said cation is selected from a sodium, lithium, potassium, rubidium or cesium ion.
In one embodiment said cation is a sodium ion.
One embodiment of the present invention concern a process for the preparation of an * ionic liquid of the present invention wherein the [TI anion is a phenolate substituted with one, two, three, four or five alkyl chains; In one embodiment said [Yl is the phenolate derived from the phenol MY, wherein HY is selected from 4-tert-butylphenol, 2,4-di-tert- * butylphenol, 3,5-dimethylphenol. 2,6-di-tefl-butyl-4-methylphenol, 2,6-di-tert-butyiphenol, 2,6-dimethylphenol, 4-nonylphenol and cresol. In a prefered embodiment, said [Ti is 4-ten-butylphenolate.
Numbered statements of the invention are as follows.
1. A process for the preparation of ionic liquids having the general formula [Q] [Zi, said process comprising the steps of: (a) conversion of [Q") [Xi to [QJ [T] by reaction with [411 [TI; (I,) conversion of [Q} [TI into [Q'l [Z]; -8 wherein -the [Q] cation is selected from the grolLp consisting of a quaternary ammonium [R'R2R3R4N'1, quaternary phosphonium [R'R2R3R4P], sulfonium [R'R2R3S], 1,3- diallcylimidazolium, 1-alkylpyridinium, 1,1-dialkylpyrrolidinium, 1,1-dialkylpiperidinium, or l,1,-diallcylmorpholinium, wherein R', R2, R3 and R4 are alkyl chains; -the [X] anion is a halide; -the [Al cation is an alkali metal ion; -the [Y] anion is a phenolate substituted with one, two, three, four or five alkyl chains; and the [Z] anion is the conjugated base of a Br�nstcd acid HZ.
2. The process according to statement 1, wherein [QI is tetrabuty1ammonium.
3. The process according to statement 1, wherein [QI is tetrabutylphosphonium.
4. The process according to statement 1, wherein [QI is 1-butyl-3-methylimidazOlium.
5. The process according to statement 1, wherein [Q] is i-butyl-1-methylpyrrolidiflium.
6. The process according to statement 1, wherein [QJ 2-ethyl_N-(2-ethylhexyD-N,N-dimethyihexan-I -aminium.
7. The process according to statements ito 6, wherein [Y] is the phenolate derived from the phenol HY, wherein HY is selected from 4-tert-butylphenol, 2,4-di-tert- butylphenol, 3,5-dixnethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6 -di-tert-butylphenol, 2,6-dimethylphenol, 4-nonylphenol and cresol.
8. The process according to statements 1 to 6, whereiq [TI is 4-tert-butyiphenolate.
9. The process according to statements ito 8, wherein [X] is selected from chloride, bromide or iodide. In a preferred embodiment of statement 9, [Xi is chloride or bromide. In another preferred embodiment [Xi is chloride; and in yet another preferred embodiment of statement 9, [Xi is bromide..
10. The process according to statements Ito 9, wherein [A1 is selected from a sodium, lithium, potassium, rubidium or cesium ion. In a preferred embodiment of statement 10, said alkali metal ion (or said [At]) is preferably a sodium ion.
11. The process according to statements i to 10, wherein [Z] is the anion of the Br�nsted acid HZ, wherein HZ is selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, methanesulfonic acid, trifluoromethanesulfonic acid, para-toluenesulfonic acid, 4-bromobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 3-nitrobenzenesulfoflic acid, 2-nitrobenzenesulfonic acid, 2,4-nitrobenzenesulfonic acid, camphorsulfonic acid, benzoic acid, 2-chlorobcnzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichiorobeuzoic acid, formic acid, acetic acid, propioiilc acid, butanoic acid, chioroacetic acid, dichioroacetic acid, trichioroacetic acid, trifluoroacctic acid, picolinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dialkyiphosphoric acids or an amino acid.
12. The process according to statements 1 to 11, wherein instep (a) [Qi[X] is converted into [Q4][Yi by reaction with [A][Yi in an organic solvent.
13. The process according to statement 12, wherein the organic solvent is selected from dichioromethane, chloroform, 1,2:dichloroethane, ethyl acetate, 2-butanone.
cyclohexanonc, acetone, benzene, xylencs, ortho-xylene, rneta-xylcne, para-xylène or toluene.
14. The process according to statement 13, whcrcin the organic solvent is acctone, having a water content below 200 ppm and preferably below 50 ppm.
15. The process according to statement 13, wherein the organic solvent is toluenc, having a water content below 200 ppm and preferably below 50 ppm.
16 The process according to statements Ito 15, wherein in step (b) [Q][Y] is converted into [Q][Zi by reaction of [Q][Yi dissolved in an organic solvent not miscible with water, with a Br�nsted acid HZ dissolved in water. The chemical entities of statement 16 are chosen so that [Q][Z] will dissolve in water and the phenol HY in the organic phase.
17. The process according to statement 16, wherein organic solvent not miscible with water is selected from toluene, benzene, xylenes, ortho-xylene, meta-xylene, para- xylene, tert-butylmethylether, diethyl ether, hexane, heptane, cyclohexane, 2-butanone, dichlorornethane, chloroform or 1,2-dichloroethane.
18. Tonic liquids [Q] [7] generated according to the processes of statements 1 to 17.
19. Ionic liquids fQ][Z]. wherein [Q] is 2-ethyl-N(2-cthylhexyl)-N,N-dimcthylheXan-1-aminiUm and -[ZTJ is selected from chloride, bromide, iodide, pereblorate, nitrate, hydrogensulfate, dihydrogenphosphate, mcthanesulfonate, trifluoromethanesulfonate (triflate), 4-methylbenzcnesulfonate (tosylate), alkyl sulfonate, bis (trifluoromethylsulfonyl)imi de, hexafluorophosphate, tetrafluorob orate, formate, acetate, propionate, butyrate, pentahoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, decano ate, trifluoroacetate, chioroacetate, dichioroacetate, trichloroacetate, benzoate, chlorobenzoate, dichlorobcnzoate, trichlorobenzoate, picolinate, nicotinate, isonicotinate, 6-carboxypicolinate, carboxylate, aminocarboxylate, phenolat, hydroxide, saccharinate or acesulfamate.
20. The process according to statement 1, for the synthesis of ionic liquids as described in
statement 19.
21. The use of ionic liquids described in statement 18 and 19, as a solvent for organic reactions with strong bases.
22. The use of ionic liquids described in statement 18 and 19 as a solvent for organic reactions with organolithium, organomagnesium or organozinc reagents.
23. The use of the ionic liquid [Q'] [Z], wherein [Q'i is 2-ethyl-N-(2-ethy1hexyl)N,N-dimethylhexan-l-aminium and [Zi is hydroxide for the processing of minerals, ores, and secondary inorganic waste streams.
24. The use according to statement 23, wherein said ores are aluminium ores.
25. Thc use according to statement 23 and 24, wherein said ore is bauxite.
26. An ionic liquid selected from the group consisting of: tetrabutylphosphonium acetate; tetrabutylphosphonium methanesulfonate; tetrabutylphosphonium 4-methylbenzenesulfonate; tetrabutyiphosphonium isonicotinate; tetrabutyiphosphonium nicotinate; tetrabutylphosphonium picolinate; tetrabutylphosphonium 6-carboxypicolinate; tetrabutylphosphonium nitrate; tetrabutylphosphonium hydrogensulfate; tetrabutyiphosphonium dihydiogenphosphaie; tetrabutylphosphonium formate; tetrabutylphosphonium trifluoroacetate; tetrabutylamnioniurn acetate; tetrabutylanmionium methanesulfonate; tetrabutylammonium 4_methylbenzenesulfonate; tetrabutylammoninin isonicotinate; tetrabutylammoniufli nicotinate; tetrabutylanunonium picoliriate; tetrahutylammonium 6-carboxypicolinate; tetrabutylammoniuni nitrate; tetrabutylammonium hydrogensulfate; tetrabutylammonium dihydrogenphosphate; tetrabutylammonium formate; tetrabutyl ammonium trifluoroacetate; I -butyl-3-methylimidazolium acetate; 1-butyl-3-methylimidazolium methanesulfonate; 1-butyl-3-methylimidazolium 4- methylbenzenesulfonate; I -butyl-3-methylimidazoliUm isonicotinate; I -butyl-3- methylimidazolium nicotinate; 1-buty-3-methylimidazoliUm picolinate; 1-butyl-3- methylimidazolium nitrate; 1 -butyl-3-methylimidazolium hydrogensulfate; 1 -butyl-3- methylimidazoliurn dihydrogenphosphate; 1 -butyl--3-methylinhidazoliflm formate; 1-butyl-3-methylintidazolium trifluoroacetate; 1 -butyl-3-methylimidazolium trifluoromethanesulfonate; 1 -butyl-1 -inethylpyrrolidinium 4-tert-butylphenolate; 1-1].
butyl-1-methylpyrrohdinium acetate; 1-buty1-1niethyIpyrro1idiniuni methanesulfonate; 1 -butyl-1-methylpyrrolidinium 4-mcthylbenzenesulfonate; 1-butyh I -methylpyrrolidinium isonicotinate; 1-butyl-1-methylpyrrolidinium nicotinate; 1- butyl-1-methylpyrrolidin.ium picolinate; I-butyl-1-methylpyrrolidinium nitrate; 1-butyl-1. -methylpyrrolidinium hydrogensulfate; 1 -butyl-I -methylpyrrolidinium dihydrogenphosphate; 1-butyl-1-methylpyrroidinium formate; 1-butyl-1-methylpyrrolidinium trifluoroacetate; I -Sty!-1 -methylpyrrolidinium trifluoromethanesulfonate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium methyl sulfate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium 4-tert- butyiphenolate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium acetate; 2- ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -arniniuni propionate; 2-ethyl-N-(2- ethylhexyl)-N,N-dimcthylhexan-1 -amini am trifluoroacetate; 2-ethyl-N42-ethylliexyl)-N,N-dimethylhexan-1 -aminiüm formate; 2-ethy1-N-(2-ethy1hexyI)-N,N dimethyihexan-1 -aminium methanesulfonate; 2-cthyl-N-(2-ethylhexyl)-N,N- dirnethylhexan-1-aminium tosylate; 2-ethyl_N-2-ethylhexyl)-N,N-dimethylhexan-I -aminium chloride; 2-ethy1-N-2-ethy1hexyl)-N,N-cli1nethy1Iiexan-l -aminium bromide; 2-ethyIN-(2-ethy1hexy1)N,N-dirnethy1hexan-1 -aminium iodide; 2-ethyl-N-(2- ethylhexyl) -N,N-dimethylhexan-1 -aminium isonicotinate; 2-ethyl-N-(2-ethylhexyl)- N,N-dimethylhexan-I -aminium nicotinate; 2-ethyl-N-(2-ethylhexyl)-N,N- dimethyihexan-1-antinium picolinate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium hydrogensulfate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium dihydrogenphosphate; 2-ethyl-N-(2-ethylhexyl) -N,N-dimethylhexan-1 -aminium nitrate.
DETAILED DESCRIPTION OF THE INVENTION
Definitions "alicyl chains" means a linear, cyclic, branched, saturated or unsaturated hydrocarbon radicals having from 1 to 20 carbon atoms such as, for example, methyl, ethyl, propyl, n-butyl, 1- methylethyl (isopropyl), 2-methyipropyl (isobutyl), I,1-dimethylethyl (tert-butyl). 2-methylbutyl, n-pentyl, dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, optionally said alkyl chains contain one or more heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, such as oligoethyleneoxides (eg. CH3OCH2CH2 or CH3OCH2CH2OCH2CH2). With regard to the [Q] cation, the alkyl chains of R', and R2, and/or R3, and/or R4 can be identical, partly identical or different. With regard to the alkyl chains as described in the phenolate substituted [Yl anion, said alkyl chains (two, three, four or five) can be identical, partly identical or different.
As used herein with respect to an (organic) solvent used in the process for the preparation of the ionic liquids of the present invention, and unless otherwise stated, the term 1organic solvent" broadly refers to an organic solvent specified as sovent I or solvent II, as further specified in the present invention. Solvent I is used in the step (a) wherein [Q1[X1 is converted into [Q41[Y1, and Solvent II is used in the step (b) wherein [Qi[Yi is converted into [Q] [1].
"Ciesol" is a technical mixture of ortho-methylphenol, mera-methylphenol and para-methylphenol, well known in the art.
Examples of a "strong base" are lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium methoxidc, sodium ethoxide, potassium methoxide, potassium ethoxidc, sodium tert-butoxide, potassium ten-butoxide, potassium bis (trimethylsilyl)amide, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, lithium diisopropylamide LDA), potassium diisopropylamide (KDA), lithium hydride, sodium hydride, potassium hydride, sodium bis(trimethylsilyl)amide, potassium bis (trimethylsilyflamide, lithium tetramethylpiperidide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, diethylzinc, 1,8- diazabicyclo[5.4.O]undec-7-ene (DBU), l,5-diazabicyclo[4.3.Ojnon-5-ene (DBN), 1,5,7-triazabicyclo(4.4.O)dec-5-ene (TBD), 7-Methyl-1,5,7-triazabicyclo(4.4.O)dec-5-ene (MTBD), N,N,N1,IVTetra1flCthyl1,8-naphthalenediamine (Proton Sponge), or other bascs with a similar base strength.
Description
In the present invention, a method is disclosed to replace halide anions (chloride, bromide, iodide) in ionic liquids by other anions, leading to water-soluble ionic liquids The halide ionic liquids are first transformed into phenolate ionic liquids by reaction between the halide iornc liquid and a sodium phenolate salt. A solution of the phenolate ionic liquid in a water-immiscible organic solvent is treated with an aqueous solution of a Br�nsted acid. This leads to the formation of an ionic liquid with the anion of the Br�nsted acid and a phenol. The phenol remains dissolved in the organic phase and can he recycled-The newly formed ionic liquid dissolved in the aqueous phase and can be recovered in a pure state by removal of water.
The first step in the anion exchange process is the synthesis of a hydrophobic ionic liquid precursor, Le. a phenolate compound, via the metathesis reaction between a halide ionic liquid (chloride, bromide or iodide) and the sodium salt of a phenol derivative. The second step is the introduction of the desired anion by the ion-exchange reaction with different Br�nsted acids to form hydrophilic ionic liquids-4-Tert-butylphenolate is preferred as the intermediate anion because of its highly hydrophobic properties, which in turn increases the hydrophobicity of the phenolate intermediate ionic liquid. The hydrophobicity of 4thrt-butyiphenolate is very important in the anion-exchange reaction, because the byproduct after the reactions with Br�nsted acids will be 4-ten-butylphenol, which will stay in the organic layer and ill not interfere with the newly formed hydrophilic, water-soluble ionic liquids. 4-Tert-butylphenol can easily be removed by decantationfseparatioñ of the organic layer (in which the phenol is dissolved) from the water phase.
Initially, it was tried to prepare the phenolate precursors by extraction of quatemary onium salts from the aqueous phase to an organic solvent by thereaction with sodium 4-tert-butylphenolate. Dichloromethane was used as the organic solvent. In the case of tetrabutylphosphoniuni and tetrabutylammonium cations, a highly viscous pale yellow liquid was obtained after the extraction and evaporation of the organic layer. However NMR spectra revealed that not the desired quaternary oniuin 4-ten-butylphenolate salt was formed, but rather 4-tert-butyiphenol. This may be due to the low polarity of the solvent used for the extraction process. Therefore more polar solvents such as chloroform, .1,2-dichloroethanc, ethyl acetate, 2butanone etc, were used for the extraction process instead of dichioromethane.
Ethyl acetate, one of the geener solvents failed to extract the quaternary onium salts to the organic layer.'H NMR spectra showed only the presence of 4-tert-butylphenol in the organic layer. Chloroform, 1.2-dichloroethane and 2-butanone completely extracted tetrabutylammonium and tetrabutylphosphonium salts to the organic layer to form the corresponding phenolate precursor. Ion exchange reaction with different Br�nsted acids were performed Sd the corresponding ionic liquids were obtained in good yield with low halide content (no precipitate with AgNO3 test). However, the use of chloroform and 1,2-dichlowmethane lowers the sustainability of the process. Moreover, when the reaction was scaled up (10 g scale), a precipitate was observed with the AgNO3 test. The miscibility of chloroform and 1,2-dichioroethane with water is 0.815 % and 0.810 % respectively. The solubility of sodium bromide and sodium chloride in water is 36 gIl 00 niL and 90.5 g/100 mL respectively. Thus, even a small percentage of water in the solvent will drastically change the halide content in the final ionic liquid. Another reason for the higher halide content in the final ionic liquids may be the phase transfer ability of the tetrabutylammonium and tetrabutylphosphonium cations.
To overcome these problems, the metathcsis reaction was carried out in a solvent where the solubility of sodium halide is very low, so that removal of sodium halide can be achieved by simple filtration. Dry toluene and dry acetone were employed for the ion exchange reaction of tetrabutylammonium bromide and tetrabutylphosphonium chloride with sodium-4-tert-butylphdnolate. The solubility of sodium chloride and sodium bromide in toluene or acetone is very low and depends on the water content in the solvent. In acetone and toluene both tetrabutylphosphoniuin phenolate and tetrabutylammonium phenolate were obtained in very good yields (above 90 %). Toluene is preferred over acetone because it allows carrying out the ion-exchange reaction with aqueous solutions of Br�nsted acids, without the prior isolation of the corresponding quaternary onium phenolate. Because of the hydrophobieity of 4-tertbutylphenol, it will move to the tolucne layer and the hydrophilic ionic liquid formed will migrate to the aqueous layer. Therefore the isolation of the ionic liquid can be achieved by the simple dccantation of the toluene layer and the evaporation of the water under reduced pressure. 4-Tert-butyipheilol formed after ion-exchange reaction with acids can be recycled and sused for the synthesis of new ionic liquid batches.
The one-pot procedure with toluene as solvent (as described above) was extended to different Br�nsted acids. However in the 1H NMR spectra of the ionic liquids formed, a lower or higher ratio (than the theoretical value) of the protons of the cations and anions were observed. To obtain a perfcct LI ratio between cation and anion, the amount of Br�nsted acids added has to be tuned for every specific acid. The amount of acids used depends on their acidity and polarity. A higher equivalent is needed if the Br�nsted acid has a lower polarity and low acidity. It is also worth noting that Br�nsted acids with low boiling points (preferably lower than 150. °C such as acetic acid) can be used in excess for the ion exchange reaction because the free acids can be removed along with water during the isolation of the ionic liquids.
The extraction of l-butyl-3-methylirnidazolium and 1-butyl-1-methylpyrrolidinium cations from aqueous phase to the organic phase by the reaction with sodium 4-ten-butylphenolate was not successful due to the lower lipophilicity of their phenolate intermediate, i.e. l-butyl-1-methylpyrrolidinium 4-tert-butylphenolate and 3-butyl-1-methylimidazolium 4-tert-butyiphenolate was not lipophilic enough to extract into the organic phase. Solvents such as dichioromethane, 1,2-dichloroethane, chloroform and ethyl acetate were used for the extraction. In order to increase the lipophilicity of the phenolate intermediate, other sodium phenolates such as sodium 2,4-di-tert-butyiphenolate and sodium 2,4,6-tri-tert-butyiphenolate with more carbon atoms were employed for the extraction process. In all above cases only the presence of the corresponding phenol was observed in the organic layer after the extraction. This indicates that even after increasing the number of carbon atoms in the phenol, the lipophilicity of the phenolate precursor was not sufficient to migrate the ionic liquid to the organic layer. When imidazolium arid pyrrolidinium cations with longer alkyl chains (>12) were used, the corresponding phenolate precursor ionic liquids cre formed and extracted to the organic phase. However the ion-exchange reaction with Br�nsted acids in toluene led to the formation of an emulsion. The emulsion formation was due to the presence of a hydrophobic cation with surfactant properties. Jon-exchange reactions were carried out in other solvents, for instance in tert-butyl methyl ether, diethyl ether, n-heptane and cyclohexane, to avoid the emulsion formation. There was no improvement in the results. Even aftei a prolonged centrifugation (lhr, 3600 rpm), the breaking of the emulsion was not accomplished. Due to the failure of the extraction procedure for 1-butyl-3-methylimidazolium and 1-butyl-1-methylpyrrolidiniuifl cations to the organic phase, one-pot procedure for the synthesis of hydrophilic ionic liquids via a phenolate platform was applied.
The metathesis reaction with sodium 4-tert-butylphenolate in toluene was not successful because of the insolubility of imidazolium and pyrrolidinium cations in toluene. 2-Butanone worked as a good solvent for the metathesis and anion exchange reaction with Br�nsted acids for imidazolium cation. The solvent must be as dry as possible to minimize the solubility of the alkali salts (NaCl, NaBr, KC1, KBr) in the solvents. Dissolved water will enhance the solubility of these salts in the organic solvents, and as a consequence the halide impurities can find their way into the final ionic liquid. The one-pot procedure was not successful in the case of 1-butyl-l-methylpyrrolidinium cation because of its insolubility in any of the non-polar organic solvent. This insolubility prevented us from carrying out the ion-exchange reaction with]3r�nsted acids without the isolation of 1-butyl-1-methylpyrrolidinium 4-tert-butylphenolate. 1-Butyl-1-methylpyrrolidiniunt salts are only soluble in polar organic solvents. If the ion-exchange reaction with Br�nsted acids is carried out in poiar solve; ts, the yield of the hydrophilic ionic liquids will be low because of their solubility in those solverns.
A major portion of the ionic liquids will stay in the organic phase. So, a new procedure was employed for the synthesis of hydrophilic ionic liquids based on 1-butyi-1- methylpyrrolidinium cation via the phenolate route. Metathesis reaction of 1 -butyl-1-methylpyrrolidinium bromide with sodium 4L:ert_butylphenolate was carried out in dichioromethane. Sodium bromide formed was filtered off and the solvent was evaporated under vacuum to obtain 1 -butyl-1 -methylpyrrolidinium 4-tert-butylphenolate in quantitative yield. Both the solvents and starting materials should be extremely dry in order to minimize the halide contamination in the final ionic liquids. In the second step, ion-exchange reactions with different Br�nsted acids were carried out in toluene to introduce the desired anion. The phenolate route was extended to other cations such as aUcylpyridinium, nitrile-functionalized pyridiniuin eations and choline chloride. Both the one-pot procedure and two-stage procedure wel-e unsuccessful with those cations. A tarry product was obtained when both synthetic routes applied to alkyl pyridinium and nitrile-functionalized pyridinium cations, because of the decomposition of the pyridine ring. Extraction of choline chloride from the aqueous phase to organic phase by the reaction with different sodium phenolates failed due to the lower lipophilicity of choline chloride. The solubility. of choline chloride in organic solvents is very low, so the two-step process also failed to prepare the phenolate precursor of choline chloride.
The phenolate method has also been used for the synthesis of highly base-stable ionic liquids with the 2-ethyl-N-(2ethylhexyl)-N,N-dimethylhexan-Lamifli11m cation, [BEDMA].
Jn a first step, the secondary amine bis(2-ethylhexyl)aniine was quaternized by the reaction with two equivalents of dimethyl sulphate, in acetonitrile in the presence of potassium carbonate. After 48 hours of heating under reflux, complete conversion of the starting amine was achieved. Potassium salts were removed by filtration and solvent was removed under vacuum. [BBDMA][CH3OSO3] was obtained as a pale yellow liquid in very good yield (96%). The product was characterized by 1H NIVIR, 3C NMR spectroscopy and Cl-IN elemental analysis. Attempts to introduce alkyl groups other than a methyl group, such as an ethyl or butyl group, were made. These a!teirtpts were not successful, because of the steric hindrance due to presence of ethyl group in the 2-position of the bis(2-ethylhexyl)amine. The second step was the synthesis of the phenolate precursor, from which the desired anions were introduced by ion exchange reaction with Br�nsted acids. This was achieved by the extraction of BEDMA from the aqueous phase to the organic phase by stirring with sodium 4-ten-butyiphenolate. The phenol ate precursor ionic liquid, [BEDMA] 41ert-butylphenolate was obtained as a highly viscous liquid with 85 % yield. Sodium 4-tertbuty1phenoIate was prepared by the reaction of 4-rert-butyiphenol and sodium hydroxide in ethanol. Initially we used sodium phenolate instead of sodium 4-tert-butyiphenolate for the extraction of the [BEDMA] cation from the aqueous phase to the organic phase. The intent was to remove the phenol that was formed after the ion exchange reaction with Br�nsted acids in vacuum. Even though extraction of [BEDMA] was achieved, the complete removal of phenol from the ionic liquid formed after the ion exchange with Br�nsted acid& was not successful. The third step was the introduction of different anions by ion exchange of the [BEDMA] [4-ten-butylphenolate] with different Br�nsted acids to obtain the desired ionic liquids. Ton-exchange reaction was carried out by adding an aqueous solution of Br�nsted acid to a solution of [BEDMA] [4-iert--butylphenolate] in toluene. The reaction mixture was vigorously stirred for minutes. The ionic liqliid formed was transferred to the aqueous layer because of its overall hydrophilie nature. The side product of the ion exchange reaction was 4-ten-butyiphenol, which stays in the organic layer. The hydrophilic ionic liquid was isolated by separation of the aqueous layer from the organic phase and the evaporation of water under reduced pressure. The H NMR spectra showed the complete disappearance of the phenolate anion from the final ionic liquids. Because of the hydrophobic nature of the 4-tert-butylphenol, the side product of the ion-exchange reaction, it does not contaminate the hydrophilic ionic liquids formed. It was possible to recover 4-tert-butylphenol after the ion exchange reaction and it could be reused for the preparation Qf sodium-4-tert-butylphenolate for the next stage. The ion exchange reaction is preferably performed in a non-polar organic solvent to avoid the reduction in the yield of the final ionic liquids. Ion exchange reactions in polar solvents lead to lower yields, which are caused by the solubility of these ionic liquids in polar solvents, i.e. a major portion of the ionic liquids formed during the ion exchange reaction would stay in the organic phase together with the 4-tert-butylphenol. A higher or lower relative integration of the protons of the anions was observed in the H NMR spectra when stoichiometric amounts of Br�nsted acids were used for the ion-exchange reaction. To -obtain a perfect 1:1 ratio between cation and anion, the amount of Br�nsted acid used had to be tuned for every specific acid. Ion-exchange reactions were carried out in other non-polar solvents to study the efficiency of the process in other solvent systems. Different solvents such as cyclohexane, m-xylene, tert-butyl methyl ether, n-heptane were used for the ion- exchange reaction. There was not a considerable variation in the yields when different non-polar solvents were used. Hence, different non-polar solvents, which are immiscible with water, can be used for the ion-exchange reaction. The newly synthesized salts have been obtained either as room temperature ionic liquids (RTILs) or as low-melting solids. The base stability of the [BEDMA] cation was studied using H NMR spectroscopy. In a typical procedure, the reaction flask was thermostated at a selected temperature between room temperature and 80 °C and charged with 20 mL of 1,2-dichloroethane solution of [BEDMA][C11 (3.26 mmol) and 20 mL of 50% NaOH solution. Stirring and timings were started. Samples of (1-2 mL) of organic phase were withdrawn at various times by stopping the stirrer for 40 to 60 seconds to allow adequate separation. The organic layer was evaporated and H NMR spectra of the sample were recorded. The possible Hofmann degradation products of [BEDMA] cation is 2-ethyl-hex-1-ene and 2-ethyl-N,N-dtmethylhexan-1-amine. -Even after a long reaction time (120 hours), no evidence for the decomposition of the starting material was observed. Similar results were obtained when the reactions were condacted at higher temperatures, i.e. at 40 °C and 60 °C. The 44 NMR spectra contained only the peaks from the starting material. These results indicate that the [BEDMAJ cation is very stable against strong bases at elevated temperatures. The higher base stability may be due to the higher steric lilndrzince by the ethyl and butyl groups in the J3-position.
EXAMPLES
EXAMPLE 1. Tetrabutylphosphonium acetate To a solution of tetrabutyiphosphonium chloride (10 g, 33.91 mmol) in dry toluene (400 mL) was added sodium 4-tert-butylphenolate (5.83 g, 33.91 mmol). The reaction mixture was stirred vigorously for 12 h and afterwards filtered through Cdite. An aqueous solution (500 mL) of acetic acid (2.84 g. 47.47 mrnol) was added to the reaction mixture and stirred for 30 minutes. The organic phase was separated and washed with 50 mL of H20. The water was removed under vacuum to yield the product as a white solid. Yield: 9.07 g (84%). mp: 57 °C.
H NIvIR (300 MHz, fl20): & 0.82 (t, 1214), 1.37 (m, 161-I), 1.84 (s, 3H), 2-06 (m, 8H). 3C NMR (100 MHz, D20): 6 = 12.55, 17.45 (d), 22.71 (d), 2-2.88,23.22(d), 180.71. CHN: elemental analysis for C,g14390t2Hz0: calculated (%): C 60.98, 14: 12.23, found (%): C: 60.63, H: 12.40.
EXAMPLE 2. Tetrabutyiphosphofliunl methanesulfonate Tetrabutyiphosphonium methanesulfonate was prepared by the procedure described in Example 1 from tetrabuiylphosphonium chloride (10 g, 33.91 mmdl), sodium 4-ten-butyiphenolate (5.83 g, 33.91 inmol) and methanesulfonic acid (2.93g. 30.51 mmol) to give a colorless solid. Yield: (10.45 g, 87%). mp: 65 °C (lit: 59-62 °C). H NMR (300 MHz, D20): S = 0.84 (t, 121, 1.41 (m, 12H), 2.05 (m, 811), 2.70 (s, 3H). 3C NMR (75 MHz, D20): S = 12.53, 17.95 (d), 22.73 (d), 23.18 (d), 38.44. CHN: elemental analysis for C19H.4102P*1.5H20: calculated (%): C: 63.47, H: 12.34 found (%): C: 63:32, H: 15.54.
EXAMPLE 3. Tetrabutylphosphonium 4-methylbenzenesulfonate Tetrabutyiphosphonium 4-methylbenzenesulfonate was prepared by the general procedure from tetrabuiylphosphoniurn chloride (10 g, 33.91 mmol), sodium 4-sert-butylphenolaw (5.83 g, 33.91 mmol) and 4-methylbenzenesulfonic acid (5.25 g, 30.51 mmol) to give a colorless solid. Yield: (12.70g. 87%). mp: 57°C (lit: 54-57 °C). H NIVIR' (300 MHz, D20): S = 0. 81 (t, 1211,7), 1.32 (m, 16H), 2.01 (m, 811). 2. 31(s, 311), 7.27 (d, 211., 8.44 Eli). 7.59 (d, 2H, 8.44 Hz). 3C NMR (75 MHz, D20): S = 12.51, 17.28 (U), V.64(d), 23.15 (U), 125.35, 129.40. 139.58. :42.32. CHN: elemental analysis for C23I-IO,PS2H2O: calculated (%): C: 59.20, H: 10.15. found (%): C: 59.03, H: 10.61.
EXAJ'vIPLE 4. Tetrabutylphosphonium isonicotinate Tetrabutyiphosphonium isonicotinate was prepared by the procedure described in Example 1 from tetrabutyiphosphonium chloride (10 g, 33.91 mmol), sodium 4-tert-butylphenolate (5.83 g, 33.91 mmol) and isonicotinic acid (4.17 g, 33.91 mmol) to give a colorless solid. Yield: (11.77g, 91 %). mp: 215 °C. 1H NMR (300 MHz, D20): S = 0. 83 (t, 12H), 1.40 (m, 1611), 2.06 (m, 811), 7.87 (d, 211, 5.2 Hz), 8.61 (d, 211, 5.0 Hz). 3C NMR (100 MHz, D20): = 12.56, 17.41 (d), 20.45 (d), 23.20(d), 124.21, 146.48, 148.49, 171.53. CHN: elemental analysis for CFi40NO2P.3HzO: calculated (%): C: 60.66, H: 10.64. N: 3.22, found (%): C: 60.57, H: 8.81, N: 3.22.
EXAMPLE S. Tetrabutylphosphonium nicotiriate Teirabutyiphosplionitim nicotinate was prepared by the proccdure described in Example 1 from tetrabutylphosphonium chloride (10 g, 33.91 mmol). sodium 4-ten-butyl phenolate (5.83 g, 33.91 mmol) and nicotinic acid (4.17 g, 33.91 mmol) to give a colorless solid. Yield: (10.86 g, 84%). mp: 186 °C. H NIvIR (300 MHz, D20): S = 0. 82. (t, 12H), 1.41(m, 16H), 2.05 (m, 811), 7. 98 (m, 1H), 8.75 (m, 2H), 9.05 (s, 1H).'3C NMR (75 MHz, D20): 5 = 12.59, 17.32 (d), 22.68 (d), 23.20 (d), 120.62. 125.94,130.03, 142.19, 153.25, 169.06. CHN: elemental analysis for C2»=H4O2NPH2O: calculated (%): C: 66.13, H: 10.60, N: 3.51, found (%): C: 66.07, H: 10.48, N:3.39.
EXAMPLE 6. Tetrabutylphosphonium picolinate Tetrabutylphosphonium picolinate was prepared by the procedure described in Example 1 from tetrabutyiphosphonium chloride (10 g, 33.91 mmol), sodium 4-ren-butylphenolate (5.83 g, 33.91 mmol) and picolinic acid (3.34 g, 27.12 mmol) to give a colorless solid. Yield:(10.86 g, 84%). mp: 59°C. H NMR (300 MHz, D20): S = o. 80(1, 12H), 1.32 (m, 161-I), 2.01 (m, 8H), 7.98 (m, 1H), 8.25 (ci, 1H, 8.10 Hz), 8.51 (rn, 1H), 8.63 (d, 1H, 5.40 Hz. 3C NMR (75 MHz, D20): S = 12.54, 17.32 (d), 22.67 (d), 23.18 (d), 126.25, 128.30, 141.60, 14630, 146.69, 164.36. CR19: elemental analysis for CnH40 NO2P'3H20: calculated (%): C: 60.66, H: 10.64, N: 3.22, found (%): C: 60.70, H: 10.92, N: 3.27.
EXAMPLE 7. Tetrabutylphosphonium 6-carboxypicolinate Tetrabutylphosphonium 6-carboxypicolinate was prepared by the procedure described in Example 1 from tetrabutylphosphonium chloride (10 g, 33.91 mmol), sodium 4-tert-butyl phenolate (5.83 g, 33,91 mmol) and pyridine-2,6-dicarboxylic acid (5.10 g, 30.51 mmol) to give a colorless solid. Yield: (11.68 g, 81 %). mp: 205 C. H NMR (300 MHz, DzO): S = 0.
81 (t, 12H), 1.32 (m, 16H), 2.02 (m, 8H), 8.33 (m, 3H). 3C NMR (75 MI-I; D20): S = 12.53, 17.32(d), 22.67 (d), 23.18 (d), 128.20, 143.23, 146.37, 165.75. CHN: elemental analysis for C23H40NO4P2HzO: calculated (%): C: 59.85, H: 9.61,N:3.03. found (%): C: 59.79, Fl: i0.32,N:2.58.
EXAMPLE 8. Tetrabutylphosphonium nitratS Tetrabutylphosphonium nitrate was prepared by the procedure described in Example 1 from tetrabutylphosphonium chloride (10 g, 33.91 mmol), sodium 4-tert-butyiphenolate (5.83 g, 33.91 mmol) and nitric acid (65 % solution, 3.29 mL, 2.14 g, 33.91 mmol) to give a colorless solid. Yield: (9.81 g, 90%). mp: 70°C (lit: 70-73 °C). HNMR (300 MHz, D20): S = 0. 80 (t, 12H), 1.32 (in, 16H), 2.01 (m, SH). 3C NMR (75 MHz, D20): S = 12.51, 17.30 (d), 22.66(d), 23.18 (d). CHN:elemental analysis for C16H3&NO3PrH2O: calculated (%): C: 56.61, I-I: 11.28, N: 4.13, found (%): C: 56.87, H:11.61, N: 4.11.
EXAMPLE 9. Tetrabutylphosphonium hydrogensulfate Tetrabutyiphosphonium hydrogensulfate was prepared by the procedure described in Example 1 from tetrabutyiphosphonium chloride (10 g, 33.91 mmol), sodium 4-tcn-butylphenolate (5.83g, 33.91 mmol) and sulphuric acid (95 % solution, 3.49 mL. 3.32 g, 33.91 inmol) to give a colorless solid. Yield: (10.75 g, 90 %). mp: 124°C (lit: 122 °C). H NMR (300 MHz, 6 = 0. 80 (t, 1211), 1.32 (m, 16H), 2.01 (m, 8H). 13C NM_R (75 MHz, D20): 8 = 12.51, 17.28 (d), 22.64 (d), 23.15(d). CHN: elemental analysis for C16113704P35H20: calculated C: 45.80, H: 10.57 found (%): C: 45.84,11: 10.08.
EXAMPLE 10. Tetrabutylphosphonium dihydrogenphosphatc Tetrabutyiphosphonium dihydrogenphosphate was prepared by the procedure described in Example 1 from tetrabutyiphosphonium chloride (10 g, 33.91 rnmol), soditun 4-tert-butyl phenolate (5.83 g, 33.91 mmol) and phosphoric acid (85 % solution, 3.90 mL, 3.32 g, 33.91 mmol) to give a colorless solid. Yield: (10.27 g, 85 %). mp: 149°C (lit: 148-15 1 °). H NMR (300 MJrIz, D20): 6 = 0. 79 (t, 121-I), 1.31 (m, 1611), 2.00 (m, 811). 3C NMR (75 MFIz, D20): 8 = 12.51, 17.29 (d), 22.65 (d), 23.39 (d). CHN: elemental analysis for C16H3504P2.2F120: calculated (%): C: 48.97,11: 10.79 found (%): C: 49.11, H: 11.08.
EXAMPLE 11. Tetrabutylphosphonium formate Tetrabtitylphosphonium formate was prepared by the procedure described in Example 1 from tetrabutylphosphonium chloride (10 g. 33.91 mmofl, sodium 4-tert-butylphenolate (5.83 g, 33.91 mmol) and formic acid (7.80 g, 169.55 inmol) to give a colorless solid. Yield: (8.46 g, 82%). mp: 41 °C.H NMR (300 MHz, D20): 6 = 0. 83 (t, 12H), 1.35 (m, 1611), 2.04 (m, 8H), 8.17 (s, 1H). 3C NMR (75 MHz, D20): 8 = 12.54, 17.32 (d), 22.67 (d). 23.39(d), 166.07.
CHN: elemental analysis for C,7H3702P*3H20: calculated (%): C: 56.96, H: 12.09 found (%): C: 57.13, H: 12.30.
EXAMPLE 12. Tetrabutylphosphonium trffluoroacetate Tetrabutylphosphonium trifluoroacetate was prepared by the procedure described in Example 1 from tetrabutylphosphonium chloride (10g. 33.91 mmol), sodium 4-icrtbuty1phenolate 5.83 g, 33.91 minol) and trifluoroacetic acid (3.86 g, 33.91 mmol) to give a colorless liquid.
Yield: (10.23 g, 81 %). H NMR (300 MHz, D20): 8 0. 83 (t, 1211), 1.35 (ni, 1611), 2.04 (m, BR). 3C NMR (75 MHz, D20): 6 = 12.51, 17.29 (d), 22.65 (d), 23.16 (d), 114.27 (q), 162.44 (q).CHN: elemental analysis for C18H36F302PH20 calculated (%): C: 55.37, H: 9.81 found (%): C: 56;00, H: 10.08.
EXAMPLE 13. Tetrabutylanunoniurn acetate To a solution of tetrabutylammonium bromide (lOg, 31.02 mmol) in dry toluene (400 niL) was added sodium 4-zcrt-butyl phenolate (5.34 g, 31.02 mmol). The reaction mixture was stirred vigorously for 12 h and afterwards filtered through Celite. An aqueous solution (500 mL) of acetic acid (2.84 g, 47.47 mmol) was added to the reaclion mixture and stined for 30 minutes. The organic phase was separated and washed with 50 mL of I-IzO. The solvent was removed under vacuum to yield the product as a white solid. Yield: 8.41 g (90 %). mp: 90°C (lit: 95-98 °C). H NMR (300 MHz, D20): S = 0. 85 (t, 12H), 1.25 (m, SB), 1,55 (m, 811), 2.01 (s, 311), 3.09 (m, SH). 3C NMR (75 MHz, D20): S 12.82, 19.13,20.98, 23.13, 58.08, 177.62. CHN: elemental analysis for C,8H3gO2NH2O: calculated (%): C: 67.66, H:12.93, N:4.38 found (%): C: 67.61, H: 12.89, N:4.41.
EXAMPLE 14. Tetrabutylammoniuni methanesulfonate Tetrabutylammonium methanesulfonate was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10 g, 31.02 mmol), sodium 4-tert-butylphenolate (5.34 g, 31.02 mmol) and methanesulfonic acid (2.l8 g, 27.91 mmol) to give a colorless solid.
Yield: (8.46 g, 82 %). mp: 90°C (lit: 95-98 °C). 1H NMR (300 MHz, D20): 5 0. 81 (t, 12H), 1.22 (m, 8H), 1,52 (m, 8H), 2.69 (s, 3H), 3.06 (iii, 811). 3C NMR (75 MHz, D20): S 12.82, 19.12, 23.12, 38.43, 58.07. CHN: elemental analysis for C,7H39N03S.3H20: calculated (%): C: 52.14, H: 11.58, N: 3.58, found (%): C: 51.71, 1-1: 10.26, N: 3.20.
EXAMPLE 15. Tetrabutylammonium 4-methylbenzenesulfonate Tetrabutytammonium 4-methylbcnzenesulfouatc was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10 g, 31.02 nimol), sodium 4-ten-butylphenolate (5.34 g, 31.02 mniol) and 4-methylbenzenesulfonic acid (4.80 g, 27.90 mmol) to give a colorless solid, Yield: (11.29 g, 88 %). mp: 75 °C (lit: 70-72 °C). H NMR (300 MHz, D20): 5 = 0. 83 (t, 12H), 1.22 (m, BR), 1.52 (m, 811), 2.31(s, 3H), 3.05(m, SH), 7.27(d, 2H, 8.1 Hz), 7.61(d, 2H, 8.1 Hz). 3C NMR (75 MHz, 1J20): 5= 12.84, 19.11, 20.49,23.09, 58.01, 125.37, 129.41, 139.63, 142.30. CHN: elemental analysis for C23H4303N.H20: calculated (%):C:63.99, H:10.51, N:3.24. found(%): C: 64.05, H: 10.59, N: 3.31.
EXAMPLE 16. Tetrabutylammonium isonicotinate Tetrabutylarnntonium isonicotinate was prepared by the procedure described in Example 13 from tetrabutylamrnonium bromide (10g. 31.02 mmol), sodium 4-tert-butylphenolatc (5.34g, 31.02 mmol) and isonicotinic acid (3.81g. 31.02 mmol) to give a colorless solid. Yield: (9.72 g, 86%). mp: 240°c. 1H NMR (300 MHz, D20): S = 0. 82 (t, 12H), 1.19 (ni, 811), 1.52 (m, 8H), 3.04 (m, SB), 8.10 (d, 2H, 6.33 Hz), 8.69 (d, 2H, 6.33 Hz). 3C NMR (75 MHz, D20): 5= 12.83, 19.13,23.13, 58.08, 125,66, 142.71, 152.87, 169.72. CEN: elemental analysis for C22FT40O2NHzO: calculated (%): C: 69.07, H:11.07, N: 7.32,found (%): C: 69.02, H: 11.10, N:7.37.
EXAMPLE 17. Tetrabutylammonium nicotinate Tetrabutylammonium nicotinate was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10g. 31.02 mmol), sodiuin4-i&t-butyIphCflolate (5.34 g, 31.02 nimol) and nicotinic acid (4.20 g, 34.12 mmol) to give a colorless solid. Yield: (9.95 g, 88%). mp: 163 °C. Ji NMR (300 MHz, D20): S = 0. 83 (t, 12H). 1.23 (m, 8H), 1.54 (m, SF1), 3.08 (in, SB), 1.86 (t, IH, 6.53 Hz), 8.66 (m, 2H), 8.97 (s, 111). 3C NIvIR (75 MHz, D20): S = 12.80, 19.13, 23.11, 58,14, 126.33, 135.04. 143.65,144.30. 144.32, 169.26. CHN: elemental analysis for CFLoNiOz'HzO: calculated (%): C: 69.07, H:11.07, N:7.32 found (%): C: 69.13, H: 11.05, N:7.40.
EXAMPLI 18. Tetrabutylainmonium picolinate Tetrabutylammonium picolinate was prepared by the procedure described in Example 13 from tetrabutyiammoniuin bromide (10 g, 31.02 minol), sodium 4-tert-butyiphenolate (5.34 g, 31.02 mmol) and picolinic acid (3.05 g, 24.81 rnmol) to give a colorless solid. Yield: (10.06 g, 89 %). mp: 62 °C H NMR (300 MFTz, D20): 5 = 0.82 (t, 12H), 1.22 (m, 8H), 1,49 (m, 811), 3.01 (m, SF1). 8.26 (m, 1H), 8.29 (d, 1H, 7.8 Hz), 8.50 (rn, 1H), 8.63 (d, 1H, 5.4 Hz). 3C NMR (75 MHz, D20): 5= 12.84, 19.14, 23.14, 58.09. 126.28,128.34,141.53, 146.23, 146.79, 164.27. CHN: elemental analysis for C22H.4oN2Or2HzO: C: 65.96, H: 11.07, N: 6.99, found (%) C: 66.18, Fl: 10.98, N: 6.83.
EXAMPLE 19. Tetrabutylanimonium 6-carboxypicoinate Tetrabutylammonium 6-carboxypicolinate was prepared by the procedure described in Example 13 from tetrabutylamnionium bromide (10 g, 31.02 mmol), sodium 4-ten-butylphenolate (5.34 g, 31.02 mmol) and pyridine-2,6-dicarboXylic acid (4.14 g, 24.81 mmol) to give a colorless solid (10.26 g, 81 %). mp: 219 °C. H NMR (300 MHz, 1JU): S = 0.82 (t, 1211), 1.22 (in, 811), 1,49 (rn, 8H), 3.07 (m, 81-1), 8.26 (m, 111), 8.29 (d, 11-I, 7.8 Hz), 8.50 (m, 1H), 8.63 (d, 1H, 5.4 Hz). 3C NMR (75 MHz, D20): 8= 12.84, 19.14, 23.14, 58.09, 126.28.12834,141.53, 146.23, 146.79, 164.27. CHN: elemental analysis for C23H4004N2.JtO: calculated (%): C: 64.76, H: 9.92, N: 6.57 found (%): C: 64.85, H: 9.79, N: 6.53.
EXAMPLE 20. Tetrabutylammonium nitrate Tetrabutylammonium nitrate was prepared by the procedure described in Example -13 from tetrabutylanimonium bromide (10g, 31.02 mmol), sodium 4-tert-butylphenolate (5.34 g, 31.02 mmol) and nitric acid (65 % solution, 3 mL, 1.95 g, 31.02 mmol) to give a colorless solid. Yield: (8.5 g, 90%). mp: 114°C (lit: 116-118°C). H NMR (300 MHz, D20): 3 0. 83 (t, 1211), 1.23 (in, 81-1), 1,53 (m, 811), 3.08 (m, 8H). 3C NMIR (75 MHz, DzO): ö 12.80, 19.12, 23.12,58.07. CFIN: elemental analysis for C16H36N203*2H20: calculated (%): C: 56.44,11: 11.84, N: .23. found(%): C: 56.42, H: 11.44,8.33.
EXAMPLE 21. Tetrabutylammoniuin hydrogensulfate Tetrabutylammonium hydrogensulfate was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10 g, 31.02 mmol), sodium 4-tert-butyiphenolate (5.34 g, 31.02 minol) and sulfuric acid (95 % solution, 2.88 mL, 3.03 g, 31.02 mmol) to give a colorless solid. Yield: (9.37 g, 89 %). mp: 168°C (lit: 169-171°C). H NMIR (300 MHz, D20): 8 = 0. 82 (t, 12H), 1.21 (m, 8H), 1.50 (in, 8H), 3.05 (m, 81-1). 3C NMR (75 MHz, D20): 8= 12.80, 19.11,23.11,58.06 CFIN: elemental analysis for C,5H37O4NH2O: calculated (%): C: 53.75, H: 10.99, N: 3.92. found (%): C: 53.67, H: 10.79, N: 4.03.
EXAMPLE 22. Tetrabutylaminonium diliydrogenphosphate Tetrabutylammonium dihydrogenphosphate was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10g. 31.02 mmol), sodium 4-tert-butylphenolate (5.34 g, 31.02 mmol) and phosphoric acid (85 % solution, 3.03 g, 3.57 mL) to give a colorless solid. Yield (9.05 g, 86 %). mp: 154°C (lit: 151-154°C). 1H NMR (300 MHz, D20): 8 = 0.81 (t, 1211), 1.23 (m, 81-1), 1,53 (m, 8H), 3.08 (m, SF!). "C NMR (75 MHz, D10): 8= 12.80, 19.12,23.12, 58.06. CHN: elemental analysis for Ci6H38NO4P2H2O: calculated (%): C: 51.18,11: 11.27, N: 3.73. found (%): C: 51.31, H: 11.25, N:3.67.
EXAMPLE 23. Tetrabutylainnionium formate Twabutylammonium forntate was prepared by the procedure described in Example 13 from tetrabutylammoniuin bromide (10 g, 31.02 nmiol), sodium 4-zen-butylphenolate (5.34 g, 31.02 mmol) and formic acid (7.13 g, 155.10 inmol) to give a colorless solid. Yield: (7.40g.
83 %). mp: 69°C. H NMR (300 MHz, D20): S = 0. 68 (t, 12H), 1.07 (m, 811), 1,36 (m, 811), 2.91 (m, 811), 8.07 (s, 111). 13C NMR (75 MHz, D20): a= 12.81, 19.12,23.11,58.13, 169.07.
CFJN: elemental analysis for C,7H37N02P.2H20: calculated (%): C: 63.11, H: 12.77, N: 4.33, found (%): C: 63.05, H: 13.06, N: 4.24.
EXAMPLE 24. Tetrabutylammonium trifluoroacetate Tetrabutylammonium trifluoroacetate was prepared by the procedure described in Example 13 from tetrabutylammonium bromide (10 g, 31.02 rnmol), sodium 4-zert-butylphenolate (5.34 g, 31.02 mmol) and trifluoroacetic acid (3.53 g, 31.02 inrnol) to give a colorless solid Yield: (9.37 g, 85 %). mp: 74°C. H NMR (300 MHz, D20): 6 = 0. 89 (t, 12F1), 129 (m, 811), 1.62 (rn, 811), 3.14 (m, 8H). 3C NMR (75 MHz, D20): 6= 12,80, 19.12,23.12, 58.06, 117.81 (q), 178.20(q). CHN: elemental analysis for C18H,6 F3 NO3 21-J20: calculated (%): C: 53.0;, H: 9.89, N: 3.44, found (%): C: 53.34, H: 9.28, N: 3.61.
EXAMPLE 25. I-Butyl-3-methylimidazoliurn acetate To a solution of 1-butyl-3-methylimidazolium chloride (lOg, 57.25 minol) in dry 2-butanone (500 mL) was added sodium 4-tert-butyiphenolate (9.85 g, 57.25 mmol). The reaction mixture was stirred vigorously for 12 h and afterwards filtered through Celite. An aqueous solution (500 mL) of acetic acid (5.15 g, 85.87 mmol) was added to the reaction mixture and stirred for half an hours. The organic phase was separated and washed with 50 mL of H20.
The water was removed under vacuum to yield the product as a colorless liquid. Yield: 9.08 g (80 %). HNMR (300 MHz, D20): 3 0.80 (t, 3H; 7.37 Hz), 1.21 (m, 211), 1.75 (m, 211), 1.93 (s, 311), 3.79 (s, 31-I), 4.09 (in, 211), 7.32 (m, 211). 8.61 (s, IH). 3C NMR (75 MHz, D20): 3 12.59, 18.70, 23.09. 31.21, 35.56. 49.21, 122.17, 123.43, 135.79, 180.75. CFIN: elemental analysis for C10H18 N202.2H20: calculated (%): C: 51.26,11: 9.46, N: 11.96, found (%): C: 51.20, H: 9.51, N: 12.03.
EXAMPLE 26. 1-B utyl-3-methylimidazolium methanesulfonate 1-Butyl-3-methylimidazolium methanesulfonate was prepared by the procedure described in Example 25 from 1-butyl.3-methylimidazolium chloride (10 g, 57.25 mmol) sodium 4-tert-butylphenolate (9.85 g, 57.25 mmol) and méthanesulfonic acid (4.95g, 51.25 mmol) to give a colorless solid. Yield; (11.40g, 85 %). mp: 76 t (lit: 740). H NMR (300 MHz, D20): 6 = 0.81 (t, 3H; 7.35 Hz), 1.17 (m, 21-I), 1.71 (m, 2H), 2.70 (s, 311), 3.78 (s, 3M), 4.06 (m, 21-1), 7.3! (m, 2H), 8.59 (a, 111). 3C NMR (75 MHz, D20): 5 = 12.62, 18.70, 31.22, 35.59, 38.48.
49.22, 122.18, 123.44, 135.79. CHN: elemental analysis for CHiaN2O3SH2O: calculated (%): C: 42.84, H: 7.99, N: 11.10 found (%): C: 42.81,11: 9.77, N: 11.22.
EXAMPLE 27. 1-Butyl-3-inethyliinidazol.ium 4-methylbeuzenesulfonate 1-B utyl-3-methylimidazolium 4-methylbenzenesulfonate was prepared by the procedure described in Example 25 from 1-b'utyl-3-methylimidazoium chloride (10 g, 57.25 nimol) sodium 4-tert-butylphenolate (9.85 g, 57.25 mmol) and 4-methylbenzenesulfonic acid (8.87 g, 51.52 mmol) to give a colorless solid. Yield: (14.57 g, 82 %). mp: 67 °C (lit: 67 °C). H NMR (300 Mhz, D20); 6 = 0.87 (t, 3H; 7.36 IIz), 1.21 (m, 21-I), 1.69 (m, 211,), 235 (s, 311), 3.82 (s, 311), 7.34 (in, 411), 7.63 (d, 211), 8.7 (a, IH). 3C NMR (75 MHz, D20): 6 = 12.54, 18.67, 20.43, 31.18, 35.52,49.20, 122.13, 123.38, 125.30, 129.39, 135.74, 139.40. 142.41. CHN: elemental analysis for C151122N203.S.H20: calculated (%): C: 54.86, H: 7.37,N 8.53, found (%): C: 54.95, H: 7.21, N: 8.63.
EXAMPLE 28. 1-ButyI-3-methylimidaLoliuim isonicotinate !-Butyl-3-methylimidazolium isoriicotinate was prepared by the procedure described in Example 25 from 1-butyl-3-methylimidazolium chloride (10 g, 57.25 mmol) sodium 4-ten-butyl phenolate (9.85 g, 57.25 mmol) and isonicotinic acid (7.04 g, 57.25 mmol) to give a colorless solid. Yield: (12.41 g, 83 %). mp: 269 °C. H NMR (300 MHz, D20): 6 = 0.80 (t, 3H; 7.35 Hz), 1.16 (m, 2H), 1.72 (m, 211), 3.77(s, 3H), 4.06 (t, 2H, 7.13 Hz), 7.30 (m, 2H), 7.79 (d, 2H, 6.35 Hz), 8.58 (m, 3M). 3C NMR (75 MHz, D20): 6= 12.52, 18.65, 31.16, 35.50, 49.17, 122.11, 123.37,123.89, 135.70, 146.86, 147.77,. 171.89. CHN: elemental analysis for C14H,9N307.P.H20: calculated (%): C: 60.20,11: 7.58, N: 15.04, found (%): C: 60.23, H: 7.61, N: 15.10.
EXAMPLE 29. 1-B utyl-3-niethylimidazoliuin nicotinate 1-Butyl-3-rnethylimidazolium nicotinate was prepared by the procedure described in Example from 1-butyl-3-inethylirnidazclium chloride (10 g, 57.25 mmol) sodium 4-tert-butyl phenolate (9.85 g, 57.25 mmcl) and nicotinic acid (7.04 g, 57.25 mmol) to give a colorless solid. Yield: (12.86g. 86 %). mp: 195 °C. 11 NIvIR (300 MHz, D20): S = 0.87 (t, 311; 7.32 Hz), 1.28 (m. 2H), 1.81 (m, 2H), 4.06 (s, 3H), 4.25 (t, 2H, 7.15 Hz), 7.20 (m, 3M), 8.32 (m, 2H), 8.62 (m, IR), 9.19 (s, 11-I), 10.70 (s, 1H). 3C NMR (75 MHz, D20): 6 =12.54, 18.67, 31.19, 35.53, 49.21, 122.14, 123.40,126.20, 134.89, 13537. 143.86, 144.58, 169.36. CR14: elemental analysis for CJ4H19N,02-H20: calculated (%): C; 60.20, H: 7.58, N: 15.04, found (%): C: 60.13, H: 7.39, N: 15.01.
EXAMPLE 30. 1 Butyl-3-methy1imidaZO1iuIfl picolinaLe 1_Butyl_3-methylinhidaZOliUm picolinate was prepared by the procedure described in Example from 1buty1.3_methylimidaZO1iUni chloride (10 g, 57.25 mmol) sodium 4-tert-butyl phenolate (9.85 g, 57.25 mmol) and picolinic acid (5.63 g, 45.73 mmcl) to give a colorless liquid. Yield: (11.96 g, 80 %). H NMR (300 MHz, D20): 6 = 0.87 (t, 3H; 7.32 Hz), 1.17 (m, 2H), 1.71 (m, 211), 3.78 (s, 311), 4.06 (t, 2.11, 7.15 Hz), 7.32 (m, 2H), 7.91 (t, 111, 6.62 Hz), 8,19 (d, iM, 7.78 Hz), 8.42 (m, 111), 8.63 (m, 2H). 3C NMR (75 MHz, D20): =12.56, 18.68, 31.20, 35.55, 49.22, 122.15, 123.41,125.88, 127.93, 135.79, 142.46, 145.52,147.18, 165.56. CHN: elemental analysis for C!4H,9N3O22HiO: calculated (%): C; 56.55, H: 7.80, N: 14.13, found (%): C: 56.52, H: 7.73, N: 14.19.
EXAMPLE 31. 1 Butyl3-methylimidazOlium nitrate lButy1-3-methylimidaZolium nitrate was prepared by the procedure described in Example 25.
from 1butyl_3methylimidaZo1ium chloride (10 g, 57.25 mmol) sodium 4-tert-butyl phenolate (9.85 g, 57.25 mmol) and nitric acid (65 % solution, 5.55 mL, 3.60 g, 57.25 mmcl) to give a pale yellow liquid. Yield: (9.56g. 83 %). HNMR (300 MHz, D20): S = 0.79 (t, 3H; 7.39 Hz), 1.23 (m, 211), 1.72 (m, 2H), 3.78 (s, 3H), 4.09 (t, 211, 7.13 Hz), 7.36 (m, 211), 8.75 (s, lii). 3C NMR (75 MHz, D20): ö = 12.54, 18.68, 31.20,35.52,49.21, 122.12, 123.38, 135.77.
CUN: elemental analysis for C5H15NaOr 1120: calculated (96): C: 43.83, H: 7.82, N: 19.17, found (96): C; 43.50, H: 7.80, N: 19.31.
EXAMPLE 32. 1Butyl-3-methylimida2olium hydrogensulfate lButyl3methylimidaZolium hydrogensulfate was preparcd by the procedure described in Example 25 from l_butyl_3-methYlimidaZol11m chloride (10 g, 57.25 mmol) sodium 4-ten-butyl phenolate (9.85 g, 57.25 mmol) and sulfuric acid (95 96 solution, 5.90 mL, 5.60 g, 57.25 rnmol) to give a colorless solid. Yield: (10.82 g, 80 %). mp: 30 °C (lit: 29-32 °C). H NMR (300 MHz, D20): 6 = 0.78 (t, 311; 7.39 Hz), 1.18 (m, 211), 1.70 (m, 2H), 3.77 (s, 311), 4.05 (t, ZR, 7.13 Hz), 7.30 (m, 2H), 8.59 (s, 111). 3C NMR (75 MHz, D20): 6 = 12.55, 18.66, 31.18, 35.54, 49.19, 122.13, 123.39, 135.76. CHN: elemental analysis for C8H16N204S.2H20:Calculated (%): C: 35.28, H: 7.40, N: 1019, found (Sb): C: 3519, H: 7.51, N: 10.30.
EXAMPLE 33. hButyl-3-methylimidazolium dihydrogcnphosphate 1-Butyl-3-methylimidazolium dihydrogenphosphate was prepared by the procedure described in Example 25 from 1-butyl-3-methylimidazolium chloride (10 g, 57.25 mmol) sodium 4-ten-butyiphenolate (9.85 g, 57.25 mmol) and phosphoricacid (85 Sb solution, 6.59 mL, 5.60 g, 57.25 mmol) to give a colorless solid. Yield: (11.49 g, 85 %). mp: 165 °C (lit: 167 °C). H NMR (300 MHz, D20): 8 = 0.80 (t, 3H; 7.39 Hz), 1.21 (m, 2H), 1.73 (m, 2H), 3.97 (s, 311), 4.12 (t, 2H, 7.13 Hz). 7.33 (m, 211), 8.7 (s, 1H). 3C NMR (75 MHz, 020): 6=12.53, 18.66, 31.19, 35.52, 49.20, 122.12, 123.38, 135.76. CHN:eleniental analysis for C5H17N204P2F120: calculated (%): C: 35.29, H: 7.78, N: 10.29, found (%): C: 35.33. Fl: 791, N: 10.40.
EXAMPLE 34. l-Butyl-3-methylimidazolium formate 1-Butyl-3-methylimidazoliurn formate was prepared by the procedure described in Example from 1-butyl-3-methylimidazolium chloride (10 g, 57.25 mmol) sodium 4-tert-butyl phenolate (9.85 g, 57.25 mmol) and formic acid (13.17 g, 286.25 mmol) to give a colorless liquid. Yield: (11.49 g, 85 %). H NMR (300 MHz, D20): 8 = 0.82 (t, 3H; 7.30 Hz), 1.28 (m, 2H), 1.74 (m, 2H), 3.78 (s, 3H), 4.09 (t, 2H, 7.15 Hz), 7.32 (m, 3H), 8.31 (m, ZH), 8.60 (m, 1H). 3C NMR (75 MHz, D20): S = 12.58, 18.70, 31.22,35.58,49.23, 122.17, 123.42,123.89, 135.79, 167.33 C}{N: elemental analysis for C9H,6N202 *2H20: calculated ç%): C: 49.08, H: 9.15, N: 12.72 found (%): C: 48.95, H: 9.20, N: 12.89.
EXAMPLE 35. 1-Butyl-3-methylimidazolium trifluoroacetate l-Butyl-3-methylimidazoJium irifluoroacetate was prepared by the procedure described in Example 25 from 1-butyl-3-rnethylimidazolium chloride (10 g, 57.25 mmol) sodium 4-ten-butylphenolate (9.85g, 57.25 mmol) and trifluoroacetic acid (6.52 g, 57.25 mmol) to give a colorless liquid. Yield: (11.23 g, 86 %). 1H NMR (300 MHz, Dz0): 6 = 0.75 (t, 3H; 7.35 Hz), 1.16 (in, 2H), 1.68 (iii, 2H), 3.75 (s, 31-1), 4.03 (t, 2H, 7J7 Hz), 7.28 (m, 3M), 8.57 (m, 2H).
°C NMR (75 MHz, D20): 6 = 12.55, 18.68, 31.19, 35.56, 49.22,118.08(q) 122.15, 123.40,123.89, 13535, 162. CHN: elemental analysis for C10H15F3N2OvH2O: calculated (%): C: 44.44, H: 6.34, N: 10.37, found (%): C: 44.62, H: 6.29, N: 10.24.
EXAMPLE 36. 1-Butyl-3 -methylimidazolium trifluoromethaneulfonate 1-l3utyl-3-methylimidazolium frifluoromethanesulfonate was prepared by the procedure described in Example 25 from 1-butyl-3-methylimidazoliurn chloride (10g. 57.25 mmol) sodium 4-ien-butylphenolate (9.85 g, 57.25 mmol) and trifluoromethanesulfonic acid (8.59 g, 57.25 mmol) to give a colorless liquid. Yield: (13.20 g, 80 %). H NMR (300 MHz, D20): S = 0.78 (t, 3H; 7.35 Hz), 1.19 (m, 2H), 1.71 (m, 2F1), 3.77 (s, 3H), 4.05 (t, 2H, 7.17 Hz), 7.35 (m, 311), 8.57 (m, 211). 3C NMIR (75 MHz, D20): 5=12.56, 18.70, 31.21, 35.54, 49.24, 117.53(q) 122.17, 123.43, 135.74. CUN: elemental analysis for CgH,5F3N203S2H2O: calculated (%): C: 33.33, H: 5.90, N: 8.64, found (%): C: 33.32, H: 5.79, N: 8.71.
EXAMPLE 37. 1-Butyl-1-methylpyrrolidiniuin 4-tert-butylphenolatc To a solution of 1-butyl-1-methylpyrrolidinium bromide (10 g, 45.01 mnjol) in dry DcM (500 mL), sodium 4-tert-butylphenolate (7.75 g, 45.01 rmnol) was added and stirred for 12 hours. The reaction mixture was filtered through Celite to remove the precipitated sodium bromide. The solvent was removed under vacuum. l-butyl-l-methylpyrrolidinium 4-ten-bLLtylphenolate was obtained as a white solid. Yield (12.85 g, 98 %). H NMR (300 MHz, CDCI3): 3=0.82 (t, 3H, 7.32 Hz), 1.25 (m, 1111), 1.62 (m, 21-I), 2.54 (m, 4H), 2.92 (a, 3H), 3.55 (m, 211), 3.68 (m, 4H), 6.87 (d, 2H), 7.13 (d, 2H). 3C NMR (75 MHz, CDC13): 6= 13.64, 19.63, 21.52,25.80,29.15,31.71, 33.84, 49.51, 64.39, 115.51, 126.04, 140.85, 156.20. CUN: elemental analysis for C19H33N0: Calculated (%) C: 78.29, H: 11.41, N: 4.81, found (%) C: 78.18, H: 11.53, N: 4.80 EXAMPLE 38. 1-Butyl-1-methylpyrrolidinium acetate To a solution of 1 -butyl-1 -methylpyrrolidinium 4-tcrt-butylphenolate (10 g, 34.30 mmol) in toluene (250 inL), an aqueous solution (500 mL) of acetic acid (3.08 g, 51.45 mmol) was added and stined for 30 minutes. The organic layer was separated and washed with water (50 ml..). The combined aqueous layer was concentrated undcr vacuum to give 1-butyl-1-methylpyrrolidinium acetate as a colorless solid. Yield (5.66 g, 82 %). mp: 78 °C (lit: 81 °C).
H NMIR (300 MHz, 1)20): 8 = 0.88 (t, 311,7.32Hz), 1.25 (m, 2H), 1.62 (m, 211), 1.98 (s, 311), 2.10 (m, 411), 2.70 (s, 3H), 2.94 (s, 3H), 3.19 (m, 2H), 3,40 (m, 411). 3C NMR (75 MHz, D20): 8= 12.86, 19.27,20.75,21.33,25.12,48.05,64.1 l,6430, 177.08. CHN: elemental analysis for C,1H23 N02-2Tr12O: calculated (%): C: 55.67, H: 11.47, N: 5.90 found (%): C: 45.59, H: 11.37, N: 5.83.
EXAMPLE 39. 1-Butyl-1-methylpyrrolidinium methanesulfonate 1Buty11methy1pyrrolidifliUm methanesulfonate was prepared by the procedure described in Example 38 from 1_buty11rnethylpyrrO1id1rnu11t 4-tert-butylpheflolate (10 g, 34.30 mmol) and inethanesulfonic acid (2.96 g, 30.87 mmol) to give a colorless solid. Yield (6.51 g, 80 %).
mp: 65 °C (lit: 63 °C). 1H NMR (300 MHz, D20): 6 = 0.82 (t, 7.32 Hz), 1.28 (m, 2H), 1.65 (m, 2H), 2.10 (m, 411), 2.70 (s, 311), 2.93 (s, 3H), 3.19 (m, 2H), 3.39 (m, 4H). 3C NMR (75 MHz, D20). 6-12.75, 14.80, 19.19, 21.24, 25.04,38.40,49.90, 64.09. CRN. elemental analysis for CjoHs N03SH20: calculated (%): C: 47.03, H: 9.87, N: 5.48 found (96): C: 47.10,11: 8.28, N: 5.30.
EXAMPLE 40. 1 -Butyl-1 -methylp yrrolidiniurn 4methylbeuzeneSUlfOnate 1 -Butyl-1methylpyrrOlidifliUm 4methylbenzeaesulfonat6 was prepared by the procedure described in Example 38 from 1butyl_1-mCthYlPYtTolidithU111 4-terl-butylpheflOlatc (10 g, 34.30 mmol) and 4methylbenZeneSU1fOmC acid (5.31 g, 30.87 rnmol) to give a colorless solid. Yield (8.81 g, 82 96). mpt 114°C (lit: 115 °C). H NMR (300 MI-lz, D20): 6 = 0.83 (t, 21-I, 7.34 Hz), 12.27 (rn, 21-1), 1.67 (m, 2H), 2.13Q, 411), 2.30(s, 31-I), 2.92(s, 311), 3.19 (m, 2ff), 3.38 (m, 4H), 7.29 (d, 2H, 8.16Hz), 7.61 (d, 211, 8.16Hz). SC NMR (75 MHz, D20): 6= 15.26, 21.11,22.96,23.75.27.52,50.52,66.61, 127.85, 131.94, 141.95, 144.96. Cl-IN: elemental analysis for C161127N03S.21120: calculated (%): C: 54.99 H: 8.94, N: 4.01 found (96): C: 55.02, H: 8.60, N: 4.01.
EXAMPLE 41. isdnicotinate lButyl1methy1pYrrolid1111um isonicotinate was prepared by the procedure described in Example 38 from 1-butyl-l -methylpyrrolidifliUlfl 4tert-buty1phenolate (10 g, 34.30 mmcil) and isonicotinic acid (4.22 g, 34.30 mmol) to give a colorless solid. Yield: (8.07 g, 89 %). mp: 227 °C. H NMR (300 MHz, D20): 6 = 0.83 (t, 311, 7.40 Hz), 1.27 (m, 211), 1.68 (m, 211), 2.11 (m, 4H), 2.93 (s, 3H), 3.20 (in, 211), 3.39 (rn, 4H), 8.16 (m, 2H), 8.73 (d, 2H, 6.33 Hz), 8.73 (d, 21-I, 6.33 Hz). 3C NIv1R (75 MHz, D20): S= 12.72, 19.17, 21.22,25.02,47.95, 64.05, 64.20, 125.82, 142.18, 163.34, 169.70. CHN: elemental analysis for C,5H24N202.3H20: calculated (%): C: 56.58, H: 9.50, N: 8.80. found (%): C: 56.26, H: 9.11, N: 9.01.
EXAMPLE 42. 1 -Butyl-1 methylpyrrolidinium nicotinate 1 -Butyl-1 methylpyrrolidinium nicotinate was prepared by the procedure described in Example 38 from _btyllmethylpyrr0lithihlm 4tertbutylphenolate (10 g, 34.30 mrnol) and nicotinie acid (4.22 g, 37.30 mniol) to give a colorless solid. Yield: (7.70 g, 85 96). mp: 174 °C. I-I NMIt (300 Ivll-Iz, D20): 8 0.82 (t, 311, 7.45 FIz), 1.25 (tn, 2H), 1.65 (m, 2H), 2.10 (m, 4H), 2.93 (s, 3H), 3.19 (m, 2H), 3.39 (m, 4H), 7.48 (m, il-fl, 8.68 (d, 211, 6.35), 8.99 (s, Ill). 3C NMR (75 MHz, D20). 8-12.73, 19.18, 21.22, 25.02, 47.95, 64.05, 64.19, 126.43, 135.13,143.33, 143.98, 144.62, 168.99. CHN: elemental analysis for C15H24 N202*H20: calculated (%): C: 63.80, H: 9.28, N: 9.92 found(%): C: 63.78, H: 9.385, N: 9.83.
EXAMPLE 43. 1-Butyl-i-nlethylpyrrolidiniulrk picolinate 1 -Butyl-1-methylpyrrolidinium picolinate was prepared by the procedure described in Example 38 from 1-butyl-1-methylpyrrolidiniuifl 4-tert-butyiphenolate (10 g, 34.30 mmol) and picolinic acid (3.37 g, 27.44 mmol) to give a colorless solid. Yield (7.52 g, 83 %). mp: 78 "C. H NMR (300 MHz, D20): 8 = 1.28 (t, 3H, 7.35 Hz), 1.29 (m, 211), 1.30 (m, 211), 2.11 (m, 411), 2.94 (s, 3H), 3.23 (m, 2.H), 3.40 (m, 4H),*8.04 (ni, 111), 8.33 (t, IH), 8.67 (m, 2H). 3C NMR (75 MHz, D20): 8= 12.77, 19.21,21.26,25.05,47.97,64.06. 64.23, 126.47, 128.54, 140.98, 146.88, 147.48, 163.58. CHN; elemental analysis for C,5H24N202-H20: calculated (%): C: 63.80, H: 9.28, 9.92, found (%): C: 63.69, Fl: 9.39, N: 9.87.
EXAMPLE 44. 1 -Butyl-1 -methylpyrrolidinium nitrate 1-Butyl-1-methylpyrrOlidiflium nitrate was prepared by the procedure described in Example 38 from 1_butyl-1-methylpyrrolidinium 4-ten-butylphenolate (10 g, 34.30 minol) and nitric acid (65 % solution, 3.32 mL, 2.15 g, 34.30 mmol) to give a colorless liquid. Yield: (5.67 g, 81 %). H NMR (300 MHz, D20): 8 = 0.82 (t, 3H, 7.45 Hz), 1.25 (m, 2H), 1.65 (m, 211), 2.10 (m, 4H), 2.93 (s, 3H), 3.19 (in, 2H), 3.39 (m, 411). 3C NMR (75 MHz, D20): 8= 12.73, 19.18, 21.22, 25.02, 47.95, 64.05, 64. 19,CHN: elemental analysis for C9H20 N203 *2H20: calculated (%): C: 44.98, H: 10.07, N: 11.66, found (%): C: 44.87, H: 10.21, N: 11.59.
EXAMPLE 45. 1 -Butyl-I -methylpyrrolidinium hydrogensulfate 1-Butyl-1-methylpyrrolidinium hydrogensulfate was prepared by the procedure described in Example 38 from 1-butyl-l-methylpyrrolidifliuffl 4-rert-butylphenolate (10 g, 34.30 mmol) and sulphuric acid (95 % solution. 3.53 mL, 3.36 g, 34.30 inmol) to give a colorless liquid.
Yield (6.97g. 85 %). H NMR (300 MHz, D20): 8 0.85 (t, 311,7.38Hz), 1.28 (m, 211), 1.67 (m, 2H), 2.10 (111, 411), 2.93 (s, 3H), 3.20 (m, 2H), 3.39 (m, 4H). 3C NMR (75 MHz, D20): 8= 1222, 19.17, 21.22,25.02, 47.95, 64.05, 64.20. CHN: elemental analysis for C9HZ,044S.3H20: calculated (%): C: 36.85, H: 9.28, N: 4.77, found (%): C: 36.20, H: 8.27, N: 4.34.
EXAMPLE 46. 1 Butyl-1 -methylpyrrolidinium dihydrogenphosphate 1 -Butyl-1 -m&hylpyrrolidininm dihydrogenphosphate was prepared by the procedure described in Example 38 from 1-bueyhl-methylpyrrolidinium 4-tert-butyiphenolate (10 g, 34.30 mmol) and phosphoric acid (85 % solution, 3.95 mL, 336 g, 34.30 mrnol) to give a colorless.liquid. Yield (681 g, 83 %). H NI4R (300 MHz, D20): 5 = 0.81 (t, 311,7.31 Hz)! 1.24 (m, 2H), 1.64 (m, 2H), 2.09 (m, 4H), 2.92 (s, 3M), 3.19 (m, 2H), 3.40 (m, 4H). 3C NMR (75 MHz, D20): 5= 12.77, 19.22,21.27,25.06,47.96,64.11, 64.24.CHN: elemental analysis for C9H2204NP*H20: calculated (96): C: 42.02, H: 9.40, N: 5.44 found (%): C: 42.12, H; 9.50, N: 5.40.
EXAMPLE 47. 1 -Butyl-1 -methylpyrrolidinium formate 1-Butyl-1-methylpyrrolidinium formate was prepared by the procedure described in Example 38 from 1-bowl-I -methylpyrrolidinium 4-tert-butylphenolate (10 g, 34.30 mmol) and formic acid (7.89 g, 171.5 mmol) to give a colorless liquid. Yield (5.2 g, 81 %). H NMR (300 M1-Iz, 6=0.81 (t, 3H, 7.31 Hz), 1.24 (m, 2H), 1.64 (m, 2H), 2.09 (in, 4H), 2.92 (s, 3H), 3.19 (m. 211), 3.40 (m, 4H), 8.21 (s, 1H). 3C NMIR (75 MHz, 1J20): 6= 12.77, 19.22, 21.27,25.06, 47.96, 64.11, 64.24, 167.29. CHN: elemental analysis for C,01121N0v2H20: calculated (96): C: 53.78, H:1 1.28, N:6.27, found (%); C: 53.91, H; 11;43, N:6.36.
EXAMPLE 48. 1-Butyl-1.-methylpyrrolidiniuni trifluoroacetate 1-B utyl-i-methylpyrrolidiniulfl trifluoroacetate was prepared by the procedure described in Example 38 from 1-butyl-l -methylpyrrolidinium 4-tert-butylphenolate (10 g, 34.30 mmol) and trifluoroacetic acid (3.91 g, 34.3 rnmol) to give a colorless liquid. Yield (7 g, 80 %). H NMR (300 MHz, D20): S = 0.81 (t, 31-I, 7.31 Hz), 1.24 (m, 211), 1.64 (m, 211), 2.09 (in, 411), 2.92 (s, 3H), 3.19 (m, 2H), 3.40 (in, 411). 3C NMR (75 MHz, D20); 6= 12.77, 19.18, 21.24, 21.95, 25.04, 47.98, 64.11, 64.23, 117.98(q), 162.55(q). CHN: elemental analysis for C,lH2c, P3NO»= HO: calculated (%): C: 45.35, H: 8.30, N: 4.81. found (%): C: 45.45, H: 8.04, N: 5.49.
EXAMPLE 49. 1 -Butyl-I -methylpyrrolidiniulu trifluoromethanesulfonate LButyl-1-methylpyrrolldiflium trifluoromethanesulfonate was prepared by the procedure described in Example 38 from 1-butyl-1-rnethylpyrrolidiniulfl 4-tert-butylphenolate (10 g, 34.30 rnmol) and trifluorornethanesulphonic acid (5.14 g, 34.3 mrnol) to give a colorless liquid. Yield: (8.19 g, 82%). H NMR (300 MHz, D20): 5 = 0.81 (t, 311,7.31 Hz), 1.24 (m, 211), 1.64 (m, 211), 2.09 (m, 411), 2.92 (s, 311), 3.19 (m, 2F1), 3.40 (rn, 4H)1 8.21 (s, 111). 13C NMR (75 MHz, D20): 5= 12.66, 19.1],21.16,21.87, 24.97, 47.88, 64.11, 64.04, 1 17.47(q).
CHN: elemental analysis for C10H20F3N03S'2H20: calculated (%): C: 36.69, 7.39,N: 4.28 found (%): C: 37.01, H: 7.61, N:4.50.
EXAMPLE 50. 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aniiniuin methyl sulfate To a suspension of potassium carbonate (45.79 g, 331.13 mmol) in acetonitrile (250 mL), bis(2-ethylhexyl)amine (20 g, 82.82 mmol) was added followed by dimethyl sulphate (20.89 g, 165.65 mmol). The reaction mixture was refluxed for 48 hours. Potassium carbonate was removed by filtration and the solvent removed under vacuum to yield 2-ethyl-N-(2-cthylhexyl)-N,N-dimethylhexan-1-aminium methyl sulfate as a pale yellow liquid. Yield: (26.84 g, 85 %)ifl NMR (300 MHz, D20): 5=0.85 (in, 12 H), 1.25 (m, 1611), 1.81(s, 211), 3.02 (s, 6H), 3.20 (m, 411), 3.66 (s, 31-I). 3C NMR (75 MI-li, D20): S 8.72, 12.45,21.33, 24.97, 26.86, 31.53, 3148, 48.83, 54.54,70.19. CHN: elemental analysis for C19H43N04S: Calculated (%): C: 59.80, H: 11.36. N: 3.67: found (%): C: 59.60, Fl: 11.24, N: 3.52.
EXAMPLE 51. Synthesis of 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aininium 4-ien-butylphenolate To a solution of 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium methyl sulfate (15 g, 39.34 mmol) in water (100 mL) sodium-4-ten-butylphenolate (6.77 g, 39.34 mmol) was added followed by diehloromethane (200 mL). The mixture was vigorously sthred at room temperature for five hours. The organic layer was separated and evaporated under vacuum to give 2-ethyl-N-(2.ethylhexyl)-N,N-dimethylhexan-1 -aminium 4-tert-butylphenolate as a highly viscous liquid. Yield: (13.20g, 80 %).H NMR (300 MHz, DMSO[D6]): 3=0.850, 1211), 12.95 (iii, 2511), l.4l(m, 2H), 3.01(s, 6H), 3.19(m, 4H), 7.08 (ci. 211.8.74Hz). 7.15 (ci, 2H, 8.74 Hz).'3C NMR (75 MHz, DMSO[DG]): 5= 10.07, 13.89, 22.34, 25.71, 27.58, 31.24, 32.45, 33.55, 52.78, 68.92, 114;68, 125.78, 140.55, l55.12.CHN: elemental analysis for C28M53N0 Calculated (%) C: 72.94, H: 10.62, N: 5.00 Calculated (%) C: 72.88, H: 10.41, N: 4.94, EXAMPLE 52. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhex-an-1 -aminium acetate An aqueous solution (250 mL) of glacial acetic acid (6.43 g, 107.21 mmol) was added to 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium 4-tert-butylphenolate (15 g, 35.74 rnmol) in toluene (50 mL). The reaction mixture was stirred vigorously at room temperature for half an hour. The aqueous layer was separated and evaporated under vacuum to give 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-l-aminium acetate as a colonrless liquid. Yield: (11.42 g, 97 %). H NMR (300 MHz, D20): 8= 0.85 (in, 12H), 1.28 (m, 16H), 1.88 (s, 3H), 1.92 (m, 2H), 2.92 (s, 6H), 3.06 (in, 4H). 3C NMR (75 MHz, D20): S = 9.74, 13.54, 21. 68, 22.34, 25.65, 27.82, 32.34, 33.32, 50.38, 69.66, 178.77.CHN: elemental analysis for C20 H43N023.5H20: Calculated (%) C: 61.34, H: 12.61, 3.57, found(%), C: 61.13, H: 12.35, N: 3.54.
EXAMPLE 53. 2..Ethyl-N-(2-ethylhexyl)-N,N-dirnethylhexan-1 -aminium propionate 2-Ethyl-N-(2-ethylhexyl)-N,N-diinethylhexan-1 -arninium propionate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-l-aminium 4-tcrt-butylphenolate (15 g, 35.74 imnol) and propioinic acid 3.97 g, 53.61 mmol), to give a colourless liquid.Yield: (10.80 g, 88 %). H NMR (300 MHz, D20): 5= 0.79 (m, 12H), 0.93 (t. 3H, 7.64Hz), 1.21 (m, 16H), 1.90 (m, 2H), 2.12 (in, 211), 2.95 (s, 6W, 3.09 (m, 4H). 3C NMR (75 MHz, D20): 6= 9.49, 9.65,22.14,25.80, 27.67,29.71, 32.34, 33.30, 49.70, 70.25, 183.46. CHN: elemental analysis for C21H45N02 2H20 Calculated (%) C: 66.44; H: 13.01; N: 3.69 found (%) C: 66.53, H: 13.23, N: 3.61.
EXAMPLE 54. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium trifluoroacetate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium trifluoroacetate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-JV,N-dimethylhexan-1-aniinium 4-ten-butylphenolate (15 g, 35.74 mmol) and trifluoroacetic acid (6.11 g, 53.61 mmol), to give a colourless liquid.Yield: (11.10 g, 81 %).H NMR (300 MHz, D0): 8=0.85 (m, l2H), 1.29 (m, 16H). 1.92 (m, 2H), 3.00 (s, 6H), 3.20 (m, 4H.'3C NMR (75 MHz, 1)20): 8=9.74,13,54,22.34,25.65,27.82.32.34,33.32,50.38,69.66, 117. 98(q), 169.32(q). CHN: elemental analysis for C20H40F3N02F120 calculated (%) C: 59.82; H: 10.54; N: 3.49 found (%) C: 59.90, H: 10.67, N: 3.37.
EXAMPLE 55. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aniinium formate 2-Bthyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium formate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-anilnium 4-tert-butylpheuolate (15 g, 35.74 mmol) and formic acid (8.22 g, 178.70 mmol), to give a colourless liquid,Yield: (10.48g, 93 %). H NMR (300 MHz, DzO): S = 0.87 (m, 1211), 1.31 (m, 16 H), 1.89 (in, 2F1), 3.05 (s, 611), 3.22 (m, 411). 3C NMR (75 MHz, D20): 6= 9.11, 12.84, 21.71, 25.37, 27.24, 31.90, 32.89, 49.32, 69.81, 169.08. CHN: elemental analysis for C19H41N023.5 H20, calculated (%) C: 60.27, 11: 12.79, N: 3.69, found (%) C: 60.32, H: 12.64, N: 3.71.
EXAMPLE 56. 2-Ethyl-N-(2-ethylhexyl)-N,N-dirnethylhcxan-1 -aminium mcthancsulfonate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-I -aminium methanesulfonate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium 4-ten-butyiphenolate (15 g, 35.74 mmol) and methanesulfonic acid (3.09 g, 32.17 mmol), to give a colourless liquid. Yield: (11.23 g, 86%). 11 NMR (300 MHz, DzO): 6=0.91 (in, 12 H), 1.31 (m, 16H), 1.50 (m, 211), 2.18 (s, 3H), 3.02 (s, 611), 3.20 (s, 4H). 3C MAR (75 MHz, D20): 3=9.54, 13.24, 22.10, 25.76, 27.64, 31, 17, 32.30, 38.39, 49.56, 70.19.CFIN: elemental analysis for C19H43N03S 21120, Calculated (%) C: 56.82, H: 11.79, N: 3.49, found (%) C: 56.60, H: 11.85, N: 3.42.
EXAMPLE 57. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium tosylate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-l -aminium tosylate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl) -IV,N-dimethylhexan-1-anlinium 4-tert-butylphenolate (15 g, 35.74 nunol) and 4-methylbenzenesulfonic acid (5.84 g, 33.95 mmol), to give a colourless solid. Yield: (12.63 g, 80%). mp: 78 °C. 111 NMR (300 MHz, D20): 6=0.80 (m, 12H), 1.38 (in, 1611), 1.42 (m, 2H), 2.31 (s, 311), 2.94 (s, 611), 3.12 (m, 4H), 7.27 (d, 2H), 7.61 (d, 2H). 3C NMR (75 MHz, D20): 6=9.45, 13.19, 20.37, 22.06, 25.68,27.58, 32.24,33.20,70.15, 125.24, 129.32, 139.32, 142.33. CHN: elemental analysis for C25 H47N038 211z0, C: 62.29; H: 18.19; N: 2.91 found (%) C: 62.21, H: 18.31, N: 3.00.
EXAMPLE 58. 2-Ethyl-N.-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium chloride 2-Ethyl-N-(2-cthylhexyl)-N,N-dimethylhexan-1 -aminium chloride was prepared by the procedure described in ExampJe 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium 4-ten-butylphenolate (15 g, 35.74 mniol) and hydrochloric acid (37 % solution, 3.52 mL, 1.30 g. 35.74 mmol), to give a colourless solid. Yield: (9.18 g, 84%). mp: 84°C. H NMR (300 MHz, D20): 5=0.87 (m, 1211), 1.35 (m, 1611), 1.45 (m, 2H), 2.9 (s, 6H), 3.15 (m, 4H). 13C NMR (75 MHz, D20): 6 = 9.74, 13.54, 22.34, 25.65, 27.82, 32.34, 33.32, 50.38, 69.66. CHN: elemental analysis for C1gHC1N 3.5 1120, Calculated (%) C: 58.58, H: 12.83, N: 3.79, found (%) C: 58.74, 12.16, N: 3.81.
EXAMPLE 59. 2-EthyI--N-(2ethy1hexyl)-N,N-dirnethylhexan-1 -aininium bromide 2-Ethyl*N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium bromide was prepared by the procedure described in Example 52 from 2-cthyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium 4-ren-butylphenolate (15 g, 35.74 miuol) and hydrobromic acid (48 % solution, 6.02 mL, 2.89 g, 35.74 nunol), to give a colourless solid.Yield: (10.14 g, 81%). mp: 90°C. H NMR (300 MHz, D20): 6=0.85 (m, 12.H), 1.32 (m, 1611), 1.45 (rn, 2H), 2.93 (s, 6H), 3.14 Cm, 4H). 3C NMR (75 MFIz, D20): 6= 9.74, 13.54, 22.34, 25.65, 27.82, 32.34, 33.32, 50.38, 69.66. GUN: elemental analysis for Ci5HBrN l1O, calculated (%) C: .58.67, Fl: 11.49, N: 3.80, found (%) C: 58.55, Fl: 11.33. N: 3.80.
EXAMPLE 60. 2-Ethyl-N-(2-cthylhexyl)-N,N-dirnethylhexan-1 -aminium iodide 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium iodide was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhekan-1 -aminium 4-tert-butylphenolate (15 g, 35.74 mmol) and hydrogen iodide (57 % solution, 8.02 mL, 4.57 g, 35.74 mmol), to give a colourless solid. Yield: (11.36 g, 80%). mp: 73°C. H NMR (300 MHz, D20): 6=0.80 (m, 1211), 1.22 (m, 16H), 1.42 (m, 2H), 2.96 (s, 6H), 3.13 (m, 411). 13C NMR (75 MHz, D20): 5=9.73, 13.54, 22.31, 25.60, 27.82,32.34,33.32, 50.38, 69.66. CHN: elemental analysis for C1811401N Calculated (%) C: 40.18; H: 9.05; N: 2.47 found (%) C: 40.12, H: 9.50, N: 2.40.
EXAMPLE 61. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium isonicotinate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhcxan-1 -aminium isonicotinate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyfl-N,N-dimethylhexan-1-anilnium 4-tert-butylphenolate (15 g, 35.74 mmol) and isonicotinic acid (5.49 g, 44.68 minol), to give a colourless solid. Yield: (11.508, 82%). mp: 266 °C. H NMR (300 MHz, D20): 6=0.82 (m, 12H), 1.27 (m, 1211), 1.85 (m, 2H), 3.01 (s, 6H), 3.19 (m, 4H). C NMR (75MHz, D20): 5=9.50, 13.26, 22.15, 25.79, 27.68, 32.35, 32.41, 55.41, 70.27, 124.24, 146.15, 148.76, 171.66. CFIN: elemental analysis for C24iaN202Hz0 Calculated (%) C: 70.20, H: 11.29, N: 6.82, found (%) C: 70.26, Fl: 11.32, N: 6.75.
EXAMPLE 62. 2-Ethyl-W-(2-ethylhexyl) -N,N-dimethyihexan-1 -aminium nicotinate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-l-aminium nicotinate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-cthylliexyl)-N,IV-dimethylhexan-1-aminium 4-tert-butylphenolate (15 g, 35.74 mmol) and nicotinic acid (3.96 g, 32.16 mmol), to give a colourless solid.Yield: (11.22g, 80%). mp: 224 C. 111 NMR (300 MHz, 1320): 8= 0.77 (m, 1211), 1.26 (m, 1ÔH), 1.70 (m, 2H), 2.96 (s, 611), 3.15 (in, 411), 7.38 (in, 1H), 8.20 (d, 111,7.98Hz), 8.48 (d, 111,7.14Hz), 8.92 (s, 1H). 13C NMR (75 MHz, D20): 8=9.50, 13.31, 22.14,25.70,27.65,32.29, 33.27, 49.81, 70.07, 125.82, 134.42, 142.89, 144.76, 145.57, 169.53. CFIN: elemental analysis for C24 HN2022H20 calculated (%)C: 67.25,11: 11.29, N: 6.54 found (%) C: 67.15, 11. 10, N: 6.60.
EXAMPLE 63. 2-Bthyl-N-(2-ethylhexyfl-N,N-dimethylhexan-1-aminiurn picolinate 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-aminium picolinate was prepared by the procedure described in Example 52. from 2-ethyl-N-(2.-ethy1hexyfl-N,N-dimethylhexan-1 anñnium 4-tert-butylplienolate (15 g, 35.74 minol) and picolinic acid (4.39 g, 35.74 mniol), to give a colourless liquid. Yield: (11.92 g, 85%). H NMR (300 MHz, D20): 8= 0.77 (m, 1211), 1.22 (m, 16H), 1.79 (m, 2H), 2.95 (s, 6H). 3.13 (m, 4H), 7.81 (m, IF!), 8.13 (d, 111,7.88Hz), 8.31 (m, 111), 8.60 (d, 111, 5;07 Hz). 3C NMR (75MHz, DO): &9.53, 13.26, 22.15,25.82, 27.68, 32.35, 33.30, 49.60, 55.40,70.26, 125.53, 127.31, 143.43, 144.29, 148.19, 166.81.
CHN: elemental analysis for CM RN202.31120 calculated (%) C: 63.62; 11:23.14; N: 6.1 8 found (%) C: 63.51, H: 23.28, N: 6.11.
EXAMPLE 64. 2-Ethyl-N-(2-ethylhexyl)-N,N-diinethylhexan-1 -aminium hydroge.nsulfatc 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium hydrogensulfate was prepared by the procedure described in Example 52 from 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1-antinium 4-tert-butylphenolate (15 g, 35.74 mmol) and sulphuric acid (95 % solution, 3.68 mL, 3.50g. 35.74 mmol), to give a colourless liquid.Yield: (10.64 g, 81%). 11 NMR (300 MHz, D20): 6=0.89 (m, 12H), 1.30 (in, 16H), 1.43 (m, 211), 3.00 (s, 6H), 3.20 (m, 411). 3C NMR (75 MHz, 1320): 8=9.45, 13.26, 22.11, 25.69, 27.63, 32.25, 33.23, 49.99, 69.90. CHN: elemental analysis for C18H41N04S31120 Calculated (%) C: 51.28, 11: 11.24, N: 3.32 found (%) C: 5122, H: 11.35, N: 3.18.
EXAMPLE 65. 2-Ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1.-aminium dihydrogenphosphate 2-Bthyl-N-(2-ethylhexyl)-N,N-dimethylhexam 1 -aminium dihydrogenphosphate was prepared by the procedure described in Example 52 front 2-ethyl-N-(2-ethylhexyl)-N,N-diniethylhexan- 1-aminium 4-tert-butyiphenolate (15 g, 35.74 mmol) and phosphoric acid (85 % solution, 4.12 niL, 3.50 g, 35.74 mine!), to give a colourless liquid. Yield: (10.50 g, 80%)-HNMR (300 MHz, D20): 6 0.86 (m, 12H). 1.28 (m, 16H), 1.45 (m, 211), 3.02 (a, 6H), 3.20 (m, 411).
3C NMR (75 MHz, D20): = 9.45, 13.29,22.11, 25.69, 27.63. 3223, 33.23. 49.99, 69.93.
CnN: elemental analysis for Ci1L2NO4P2HzO calculated (%) C: 53.57, H: 11.49, N: 3.47 found (%) C: 53. 46, H: 11.37, N: 3.60.
EXAMPLE 66. 2Ethy1N(2ethy1heXYl)-N,N-dilflethYIheXa11 1 -aminium nitrate 2-Ethyl-N-(2ethylhexyl)-N,N-dimethYlheXa114 -aminium nitrate was prepared by the procedure described in Example 52 from 1-aminium 4-tert-butylphenolate (15 g, 35.74 mmol) and nitric acid (65 % solution, 3.46 mL, 2.25 g, 35.74 mmol), to give a colourless liquid. Yield: (10.10 g, 85%). 111 NMR (300 MHz, D20): = 0.88 (in, 12H), 1.25 (m, 161-1), 1.45 (m, 2H), 3.02 (s, 611), 3.20 (m, 411). 13C NIVIR (75 MHz, D20): 9.45, 13.29, 22.11, 25.69, 27.63,32.23,33.23,49.99,69.93. CUN: elerSntal analysis for CLSH.40N20y2H2O, Calculated (%) C: 58.66, H: 12.03, N: 7.60 found (%) C: 58i2, H: 12.10, N: 7,57.
EXAMPLE 67. Test of base stability of the aminiuni cation The reaction flask was thermostated at 60 °C and charged with 20 mL of 1,2-dichloroethane solution of [BEDMAI[C!I (3.26 mmol) and 20 niL of 50% NaOH solution. Stirring and timings were started. Samples of (1-2 mL) of organic phase were withdrawn at various times by stopping the stirrer for 40 to 60 seconds to allow adequate separation. The organic layer * was evaporated and 1H NMR spectra of the sample were recorded. Even after a long reaction time (120 hours), no evidence for the decomposition of' the starting material was observed.
The 111 NMR spectra contained only the peaks from the starting material.
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[15] K. Idel, D. Freitag, B. Ostlinning, "Extraction of onium salts from process waters and waste waters", US Patent 4,487,698 (Dec 11, 1984) [16] J.L. Brairnon, "Preparation of quaternary oniurn salts", US Patent 2,309,691 (Feb 2. 1943)

Claims (26)

  1. CLAIMS1. A process for the preparation of ionic liquids having the general formula [Q] [TI, said process comprising the steps of: (a) conversion of [Q][Xi to [QI[Yi by reaction with [AH1[Yi; (b) conversion of [Q][Yi into [QI[Zi; wherein -the [Q'i cation is selected from the group consisting of a quatemary ammonium [R'R2R3R4N], quaternary phosphonium [R'R2R3R4P]. sulfonium [R'R2R3S], 1,3- diaWyhmidazolium, I -alkylpyridiniurn, 1,1 -dialkylpyrrolidiniuni, 1,1 -diaWypiperidiniurn, or 1.1.-dialkylmorpholiniurn, wherein R1. R2. R3 and R4 are alkyl chains; -the [Xi anion is a halide; -the [A] cation is an ailcali metal ion; -the [Yi anion is a phenolate substituted with one, two, three, four or five alkyl chains; and -the [TI anion is the conjugated base of a Br�nsted acid HZ.
  2. 2. The process according to claim I, wherein [Q] is tetrabutyammonium.
  3. 3. The process according to claim I, wherein [Q] is tetrabutyphosphonium.
  4. 4. The process according to claim 1, wherein [Q] is l-butyi-3-methylimidazolium.
  5. 5. The process according to claim 1, wherein [Q] is i-butyl-i-methylpyrrolidinium.
  6. 6. The process according to claim I, wherein [Q] 2-ethyl-N-2-ethy1hexy1)-N,N-dimethylhexan-I -arninium.
  7. 7. The process according to claims ito 6, wherein [Yl is the phenolate derived from the phenol BY, wherein HY is selected from 4-tert-butyiphenol, 2,4-di-tert-butylphenol, 3,5-dimethyiphenol, 2.6-di-tert-butyl-4-methylphenol. 2,6-di-tert-butyiphenol, 2,6-dimethylphenol. 4-nonyiphenol and cresol.
  8. 8. The process according to claims ito 6, wherein [Yl is 4-tert-butylphenolate.
  9. 9. The process according to claims 1 to 8, wherein [Xi is selected from chloride, bromide or iodide.
  10. 10. The process according to claims 1 to 9, wherein [At] is selected from a sodium, lithium, potassium, rubidium or cesium ion.
  11. 11. The process according to claims I to 10, wherein [ZJ is the anion of the Brpnsted acid HZ, wherein HZ is selected from hydrochloric acid, hydrobrornic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, perchioric acid, methanesulfonic acid, tnfluoromethanesulfonic acid, para-toluenesulfonic acid, 4-bromobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 2-nitrobenzenesuffonic acid, 2,4-nitrobenzenesuifonic acid, camphorsulfonic acid, benzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, formic acid, acetic acid, propionic acid, butanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dialkylphosphoric acids or an amino acid.
  12. 12. The process according to claims ito 11, wherein in step (a) [Q'i[Xi is converted into [Q] [Yl by reaction with [Ai [Yl in an organic solvent.
  13. 13. The process according to claim 12, wherein the organic solvent is sdected from dichloromethane, chloroform, I,2-dichloroethane, ethyl acetate, 2-butanone, cyclohexanone, acetone, benzene, xylenes, ortho-xyiene, meea-xylene, para-xylene or toluene.
  14. 14. The process according to claim 13, wherein the organic solvent is acetone, having a water content below 200 ppm and preferably below 50 ppm.
  15. 15. The process according to claim 13, wherein the organic solvent is toluene, having a water content below 200 ppm and preferably below 50 ppm.
  16. 16. The process according to claims Ito 15, wherein in step (b) [Q][i is converted into [Q][Zi by reaction of [Q][Yi dissolved in an organic solvent not miscible with water, with a Br�nsted acid HZ dissolved in water.
  17. 17. The process according to claim 16, wherein organic solvent not miscible with water is selected from toluene, benzene, xylenes, ortho-xylene, meea-xylene, para-xylene. len-butylmethylether. diethyl ether, hexane, heptane. cyclohexane, 2-butanone, dichloromethane, chloroform or 1,2-dichloroethane.
  18. 18. Ionic liquids [Q4][Zi, generated according to the processes of claims Ito 17.
  19. 19. Ionic liquids [Qi[Zi, wherein -[Q] is 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-i-aminium; and -[TI is selected from chloride, bromide, iodide, perchlorate, nitrate, hydrogensulfate, dihydrogenphosphate, methanesulfonate, trifluoromethanesulfonate (tritlate), 4-methylbenzenesulfonate (tosylate), a&yhulfonate. bis(trifiuoromethylsulfonyl)imide, hexafluorophosphate, tetrafluoroborate, formate, acetate, propionate, butyrate, pentanoate. hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, decanoate, trifluoroacetate. cifioroacetate. dichloroacetate, trichloroacetate, benzoate, chlorobenzoate, dichlorobenzoate, trichlorobenzoate, picolinate, nicotinate, isonicotinate, 6-carboxypicolinate, carboxylate, aminocarboxylate, phenolat, hydroxide, saccharinate or acesulfarnate.
  20. 20. The process according to claim 1, for the synthesis of ionic liquids as described in claim 19.
  21. 21. The use of ionic liquids described in claim 18 and 19, as a solvent for organic reactions with strong bases.
  22. 22. The use of ionic liquids described in claim 18 and 19 as a s&vent for organic reactions with organolithium, organomagnesiurn or organozinc reagents.
  23. 23. The use of the ionic liquid [Q] [LI. wherein [Q] is 2-ethyl-N-(2-ethylhexyl)-N,N-dirnethylhexan-1-arninium and [Zi is hydroxide for the processing of minerals, ores.and secondary inorganic waste streams.
  24. 24. The use according to claim 23, wherein said ores are aluminium ores.
  25. 25. The use according to claim 23 and 24, wherein said ore is bauxite.
  26. 26. An ionic liquid selected from the group consisting of: tetrabutylphosphoniurn acetate; tetrabutylphosphonium methanesulfonate; tetrabutylphosphonium 4-methylbenzenesulfonate; tetrabutylphosphonium isonicotinate; tetrabutylphosphonium nicotinate; tetrabutylphosphonium picolinate; tetrabutylphosphoniurn 6-carboxypicolinate; tetrabutyiphosphonium nitrate; tetrabutylphosphonium hydrogensulfate; tetrabutylphosphonium dihydrogenphosphate; tetrabutylphosphonium formate; tetrabutylphosphonium tnfluoroacetate; tetrabutylammonium acetate; tetrabutylammonium methanesulfonate; tetrabutylammoniurn 4-rnethylbenzenesulfonate; tetrabutylammoniurn isonicotinate; tetrabutylammoni urn nicotinate; tetrabutylamrnoni urn picolinate; tetrabutylammoni urn 6-carboxypicolinate; tetrabutylammonium nitrate; tetrabutylammonium hydrogensulfate; tetrabutyl arnmonium dihydrogenphosphate; tetrabutylarnrnoni urn formate; tetrabutylammonium trifluoroacetate; 1 -butyl-3-methylimidazolium acetate; 1 -butyl-3-methylimidazolium methanesulfonate; 1 -butyl-3-methyliniidazolium 4- methylbenzenesulfonate; 1 -butyl-3-rnethylimidazolium isonicotinate; l-butyl-3- methylinñdazolium nicotinate; 1-butyl-3-rnethylimidazolium picolinate; 1-butyl-3- methyfimidazolium nitrate; I -butyl-3-methylimidazolium hydrogensulfate; I -butyl-3- methylirnidazolium dihydrogenphosphate; 1-butyl-3-methylimidazolium formate; 1-butyl-3-methyfimidazofium trifluoroacetate; I -butyL-3-methylimidazolium trifluoromethanesulfonate; I -butyl-I -methylpyrrolidiniurn 4-tert-butylphenolate; I-butyl-1 -methylpyrrolidinium acetate; 1-butyl-1-methylpyrrolidinium methanesulfonate; 1-butyl-1-methylpyrrolidinium 4-rnethylbenzenesulfonate; 1-butyl- I -methylpyrrolidinium isonicotinate; I -butyl-I -methylpyrrolidinium nicotinate; 1- butyl-1-methylpyrrolidiniurn picolinate; 1-butyl-1 -methylpyrrolidiniurn nitrate; 1-butyl-I -methylpyrrol idinium hydrogensuffate; I -butyl-I -methylpyrrofidinium dihydrogenphosphate; 1 -butyl-1-methylpyrrolidiniurn formate; 1 -butyl-1-methypyrroI idi n ium trifluoroacetate; I -butyl-I -methylpyrrol idi n ium trifluoromethanesulfonate; 2-ethyl-N-( -ethylhexyl)-N,N-dimethylhexan-I -aminium methyl sulfate; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-1 -aminium 4-tert- butyiphenolate; 2-ethyl-N-(2-ethylhexyl)-N.N-dirnethythexan-1-arniniurn acetate; 2- ethyl-N-(2-ethythexyl)-N,N-dimethylhexan-I -aminiurn propionate; 2-ethyl-N-(2- ethylhexyl)-N.N-diniethylhexan-I -aminium trifluoroacetate; 2-ethyI-N-t-ethyIhexy)- N,N-dimethylhexan-1 -aminium formate; 2-ethyl-N-(2-ethylhexyl)-N,N- dirnethyffiexan-1-aminium methanesulfonate; 2-ethyl-N-(2-ethylhexyl)-N,N- dimethylhexan-I -arninium tosylate; 2-ethyl-N-(2-ethylhexyl)-N,N-dirnethylhexan-I-aminium chloride; 2-ethyl-N-(2-ethylhexyl)-N,N-dimethylhexan-I-aminium bromide; 2-ethyl-N-(2-ethylhexyl)-N,N-dirnethylhexan-1-aminium iodide; 2-ethyl-N-(2- ethylhexyl)-N,N-dirnethylhexan-1-aminium isonicotinate; 2-ethyl-N-K2-ethylhexyl)- N.N-dimethylhexan-I -aminium nicotinate; 2-ethyl-N-(2-ethylhexyl)-N,N- dimethylhexan-I -aminium picol mate; 2-ethyl-N-(2-ethythexyl)-N,N-dimethylhexan-I-arniniurn hydrogensulfate; 2-ethyl-N-(2-ethylhexyl)-N,N-dirnethylhexan-1 -arniniurn dihydrogenphosphate; 2-ethyl-N-(2-ethylhexyl)-N.N-dirnethylhexan-1 -aminiurn nitrate.
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JP2016175882A (en) * 2015-03-20 2016-10-06 東洋合成工業株式会社 Ammonium cation-containing organic salt
CN109180495A (en) * 2018-11-01 2019-01-11 江西肯特化学有限公司 A method of 4-butyl ammonium hydrogen sulfate is synthesized by aerosol processing
WO2020028684A1 (en) * 2018-08-01 2020-02-06 Jumpstart Fertility Pty Ltd Salts of nicotinic acid and nicotinamide as anti-aging agents

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016175882A (en) * 2015-03-20 2016-10-06 東洋合成工業株式会社 Ammonium cation-containing organic salt
WO2020028684A1 (en) * 2018-08-01 2020-02-06 Jumpstart Fertility Pty Ltd Salts of nicotinic acid and nicotinamide as anti-aging agents
CN109180495A (en) * 2018-11-01 2019-01-11 江西肯特化学有限公司 A method of 4-butyl ammonium hydrogen sulfate is synthesized by aerosol processing

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