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Title:
IONIC LIQUIDS COMPRISING NITROGEN CONTAINING CATIONS
Document Type and Number:
WIPO Patent Application WO/2005/097731
Kind Code:
A2
Abstract:
The present invention relates to ionic liquid comprising an anion and a cation wherein the cation is a primary, secondary or tertiary ammonium ion containing a protonated nitrogen atom.

Inventors:
Walker, Adam John (1 Long Row, Welby Grantham, Lincolnshire NG32 3LZ, GB)
Application Number:
PCT/GB2005/001364
Publication Date:
October 20, 2005
Filing Date:
April 07, 2005
Export Citation:
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Assignee:
THE UNIVERSITY OF YORK (Heslington, York YO10 5DD, GB)
Walker, Adam John (1 Long Row, Welby Grantham, Lincolnshire NG32 3LZ, GB)
International Classes:
C07C215/08; C07C215/12; C07C215/40; C07C217/30; (IPC1-7): C07C215/00
Attorney, Agent or Firm:
Greaves, Carol Pauline (Greaves Brewster LLP, Indigo House Cheddar Business Park, Wedmore Roa, Cheddar Somerset BS27 3EB, GB)
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Claims:
CLAIMS
1. An ionic liquid comprising an anion and a cation characterised in that the cation is a nitrogencontaining cation of the formula (I) N+HRR5R" (!) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogencontaining functional groups (including nitrile, nitro or amino or another basic nitrogencontaining functional group), thiol, alkythio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, alkoxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl and substituted amino (e.g. mono or dialkylarnino or alkyamido); and R' and R' ', which may be the same or different, each represent H or R; or any two or three of R, R' and R" may be joined together with the N to form a cyclic group.
2. An ionic liquid as claimed in claim 1 wherein R' and R" are H.
3. An ionic liquid as claimed in claim 1 wherein R' and R" are different and have the same meaning as R.
4. An ionic liquid as claimed in claim 1 wherein the ionic liquid consists of an anion and a cation as defined in claim 1.
5. An ionic liquid as claimed in claim 1 wherein the cyclic group is a cyclohydrocarbyl or heterocyclyl group.
6. An ionic liquid as claimed in claim 5 wherein the cyclic group is not aryl or heteroaryl.
7. An ionic liquid as claimed in claim 1 wherein R is substituted with a moiety selected from the group consisting of alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl groups.
8. An ionic liquid as claimed in claim 7 wherein R is substituted with a hydroxyl or amino group.
9. An ionic liquid as claimed in claim 1 wherein R is a hydroxyalkyl group having 1, 2, 3, 4, 5 or 6 C atoms.
10. An ionic liquid as claimed in claim 9 wherein the hydroxyalkyl group has a hydroxyl moiety on its free, terminal carbon.
11. An ionic liquid as claimed in claim 9 or 10 wherein R is a polyol having 2 to 6 C atoms.
12. An ionic liquid as claimed in claim 11 wherein R is a dialkanol, trialkanol ortetraaikanol group.
13. An ionic liquid as claimed in claim 12 wherein the cation is an ethanolammonium, N(alkoxyethyl)ammonium, Nmethylethanolammonium, N5N dimethylethanolammonium, diethanolammonium, Nalkyldiethanolammonium, N5N di(alkoxyalkyl)ammonium or triethanolammonium ion.
14. An ionic liquid as claimed in claim 13 wherein the cation is a methylethanolammonium, N5Ndimethylethanolammonium, N5 N di(methoxyethyl)ammonium) or butyldiethanolammonium ion.
15. An ionic liquid as claimed in claim 1 wherein R is an aminoalkyl group having 2 to 8 C atoms.
16. An ionic liquid as claimed in claim 15 wherein the aminoalkyl is a di or tri aminoalkyl group.
17. An ionic liquid as claimed in claim 1 wherein R is putrescine, piperidine or tropine.
18. An ionic liquid as claimed in claim 1 wherein the cation is selected from the group consisting of an ethanolammonium, diethanolammonium, N butyldiethanolammonium, Nmethylethanolammonium, N5N dimethylethanolammonium, putrescinium, l(3hydroxypropyl)putrescinium, or N (3hydroxypropy^Nmethylcyclohexylammonium cation.
19. An ionic liquid as claimed in claim 18 wherein the cation is N butyldiethanolammonium, Nmethylethanolammonium, di(methoxyethyl)ammonium, N,Ndimethylethanolammonium, putrescinium, l(3 hydroxypropyl)putrescinium, or N(3hydroxypropyl)N methylcyclohexylammonium ion.
20. An ionic liquid as claimed in claim 1 wherein the anion is selected from the group consisting of halogenated inorganic anions, nitrates, sulphates, phosphates, carbonates, sulphonates and carboxylates.
21. An ionic liquid as claimed in claim 20 wherein the sulphonates and carboxylates are alkylsulphonates and alkylcarboxylates respectively.
22. An ionic liquid as claimed in claim 21 wherein the alkyl group is a moiety selected from alkyl and alkyl substituted at any position with alkenyl, alkoxy, atkeneoxy, aryl, arylalkyl, aryloxy, amino, aminoalkyl, thio, thioalkyl, hydroxyl, hydroxyalkyl, carbonyl, oxoalkyl, carboxyl, carboxyalkyl or halide function.
23. An ionic liquid as claimed in claim 1 wherein the anion is selected from bis(trifluoromethylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, dihydrogen phosphate, metaphosphate, methanesulphonate, trifluoromethanesulphonate, ethylenediaminetetraacetate, chloride, bromide, iodide, hexafluorophosphate, tetrafluoroborate, trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, benezenedicarboxylate, benzenetricarboxylate, benzenetetracarboxylate, chlorobenzoate, fluorobenzoate, pentachlorobenzoate, pentafluorobenzoate salicylate, glycolate lactate, pantothenate, tartrate, hydrogen tartrate, mandelate, crotonate, malate, pyruvate, succinate, citrate, fumarate, phenylacetate.
24. An ionic liquid as claimed in claim 23 wherein the anion is an organic carboxylate.
25. An ionic liquid as claimed in claim 1 wherein the ionic liquid is selected from the group consisting of: \ Ethanolammonium formate Ethanolammonium acetate Ethanolammonium propanoate Ethanolammonium propanedioate Ethanolammonium butanoate Ethanolammonium butenoate Ethanolammonium butanedioate Ethanolammonium pentanoate Ethanolammonium pentanedioate Ethanolammoniutn pentenoate Ethanolammonium hexanoate Emanolammonium. hexanedioate Ethanolammonium hexenoate Ethanolammonium heptanoate Ethanolammonium heptanedioate Ethanolammonium heptenoate Ethanolammonium octanoate Ethanolammonium. octanedioate Ethanolammonium octenoate Ethanolammonium nonanoate Ethanolammonium nonanedioate Ethanolammonium nonenoate Ethanolammonium decanoate Ethanolammonium decanedioate Ethanolammonium decenoate Ethanolammonium υndecanoate Ethanolammonium υndecanedioate Ethanolammonium "undecenoate Ethanolammonium dodecanoate Ethanolammonium dodecanedicarboxylate Ethanolammonium dodecenecarboxylate Ethanolammonium cyclohexanecarboxylate Ethanolammonium cyclohexenecarboxylate Ethanolammonium phenoxide Ethanolammonium benzoate Ethanolammonium benezenedicarboxylate Ethanolammonium benzenetricarboxylate Ethanolammonium benzenetetracarboxylate Ethanolammonium chlorobenzoate Ethanolammonium fluorobenzoate Ethanolammonium pentachlorobenzoate Ethanolammonium pentafluorobenzoate Ethanolammonium salicylate Ethanolammonium glycolate Ethanolammonium lactate Ethanolammonium pantothenate Ethanolammonium tartrate Ethanolammonium hydrogen tartrate Ethanolammonium mandelate Ethanolammonium crotonate Ethanolammonium malate Ethanolammonium pyruvate Ethanolammonium succinate Ethanolammonium citrate Ethanolammonium fumarate Ethanolammonium phenylacetate Ethanolammonium oxalate Emanolanmioniumbis(trifluoromethylsulphonyl)irnide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate Ethanolammonium hydrogen phosphate Ethanolammonium dihydrogen phosphate Ethanolammonium methanesulfonate Ethanolammonium trifluoromethanesulphonate Ethanolammom'um ethylenediaminetetraacetate Ethanolammonium hexafluorophosphate Ethanolammonium tetrafluoroborate Ethanolammonium trifruoroacetate Ethanolammonium pentafluoropropanoate Ethanolammonium heptafluorobutanoate Ethanolammonium phosphoenolpyruvate Ethanolammonium nicotinamide adenine dinucleotide phosphate Ethanolammonium adenosinephosphate Ethanolammonium adenosine diphosphate Ethanolammonium adenosine triphosphate Ethanolammonium oxyniacate Ethanolammonium nitrate Ethanolammonium nitrite Diethanolammonium bromide Diethanolammonium iodide Diethanolammonium formate Diethanolammonium acetate Diethanolammonium propanoate Diethanolammonium propanedioate Diethanolammonium butanoate Diethanolammonium butenoate Diethanolammom'um butanedioate Diethanolammonium pentanoate Diethanolammonium pentanedioate Diethanolammonium pentenoate Diethanolammonium hexanoate Diethanolammonium hexanedioate Diethanolammonium hexenoate Diethanolammonium heptanoate Diethanolammonium heptanedioate Diethanolammonium heptenoate Diethanolammonium octanoate Diethanolammonium octanedioate Diethanolammonium octenoate Diethanolammonium nonanoate Diethanolammonium nonanedioate Diethanolammonium nonenoate Diethanolammomum decanoate Diethanolammonium decanedioate Diethanolammonium decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate Diethanolammonium dodecanedicarboxylate Diethanolammonium dodecenecarboxylate Diethanolammonium cyclohexanecarboxylate Diethanolammonium cyclohexenecarboxylate Diethanolammonium phenoxide Diethanolammonium benzoate Diethanolammonium benezenedicarboxylate Diethanolammonium benzenetricarboxylate Diethanolammonium benzenetetracarboxylate Diethanolammonium chlorobenzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate Diethanolammomum salicylate Diethanolammonium glycolate Diethanolammonium lactate Diethanolammonium pantothenate Diethanolammonium tartrate Diethanolammonium hydrogen tartrate Diethanolammonium mandelate Diethanolammomum crotonate Diethanolammonium malate Diethanolammonium pyruvate Diethanolammonium succinate Diethanolammonium citrate Diethanolammonium fomarate Diethanolammonium phenylacetate Diethanolammonium oxalate Diemaαolammonium bis(trifluoromethylsulphonyl)imide Diethanolammonium carbonate Diethanolammonium hydrogen carbonate Diethanolammonium phosphate Diethanolammonium hydrogen phosphate Diethanolammonium dihydrogen phosphate Diethanolammonium methanesulphonate Diethanolammonium trifluoromethanesulphonate Diethanolammonium ethyleαediaminetetraacetate Diethanolammonium hexafluorophosphate Diethanolammonium tetrafluoroborate Diethanolammonium trifluoroacetate Diethanolammonium pentafUioropropanoate Diethanolammonium heptafLuorobutanoate Diethanolammonium phosphoenolpyruvate Diethanolammonium nicotinamide adenine dinucleotide phosphate Diethanolammonium adenosinephosphate Diethanolammonium adenosine diphosphate Diethanolammonium adenosine triphosphate Diethanolammonium oxyniacate Diethanolammonium nitrate Diethanolammonium nitrite NButyldiethanolammonium chloride NButyldiethanolammonium bromide NButyldiethanolammoniiim iodide NButyldiemanolammonium formate NButyldiethanolammonium acetate NButyldiethanolammoniumpropanoate NButyldiemanolammonium propanedioate NButyldiethanolammoniutn butanoate NButyldiethanolammonium butenoate NButyldiethanolammomum butanedioate NButyldiethanolammonium pentanoate NButyldiethanolammonium pentanedioate NButyldiethanolammonium pentenoate NButyldiethanolammonium hexanoate NButyldiethanolammonium hexenoate NButyldiethanolammonium heptanoate NButyldiethanolammonium heptanedioate NButyldiethanolammonium heptenoate NButyldiethanolammonium octanoate NButyldiethanolammonium octanedioate NButyldiethanolammonium octenoate NButyldiethanolammonium nonanoate NButyldiethanolammonium nonanedioate NButyldiethanolammonium nonenoate NButyldiethanolammonium decanoate NButyldiethanolammonium decanedioate NButyldiethanolammonium decenoate NButyldiethanolammonium undecanoate NButyldiethanolammonium undecanedioate NButyldietibanolammonium undecenoate NButyldiethanolammonium dodecanoate NButyldiethanolammonium dodecanedicarboxylate NButyldiethanolammonium dodecenecarboxylate NButyldiethanolammoniixm cycloliexanecarboxylate NButyldiethanolammonium cyclohexenecarboxylate NButyldiethanolammoniximphenoxide NButyldiethanolammonium benzoate NButyldiemanolammonimn benezenedicarboxylate NButyldiethanolammoniimi berLzenetricarboxylate NBuiyldiethanolammoήiurαbenzenetetracarboxylate NButyldiethanolanrmonium chlorobenzoate NButyldiethanolammoniurα fluorobenzoate NButyldiethanolammoniitrti pentachlorobenzoate NBulyldiethanolammoniuin pentafluorobenzoate NButyldiethanolammoniιtαa salicylate NButyldiethanolammonixirα glycolate NButyldiethanolanamonium lactate NButyldiethanolammonium pantothenate NButyldiethanolammonium tartrate NButyldiethanolammonium hydrogen tartrate NButyldiethanolammonium mandelate NBulyldiethanolammonium crotonate NButyldiemanolammoniurn malate NButyldiethanolammonium pyruvate \ NButyldiethanolammonium succinate NButyldiethanolammonium citrate NButyldiethanolammonium fumarate NButyldiethanolammonium phenylacetate NButyldiethanolammonium oxalate NButyldiethanolan3moniurn bis(Mfluoromethylsulpbonyl)imide NButyldiethanolammonium carbonate NButyldiethanolammonium hydrogen carbonate NButyldiethanolammonium sulphate NButyldiethanolammonium hydrogen sulphate NButyldiethanolammonium phosphate NButyldiethaBolammonium hydrogen phosphate NBuiyldiethanolamtnonium dihydrogen phosphate NButyldiemanolammonium methanesulphonate NButyldiethanolanijmonium trifluoromethanesulphonate NButyldiethanolaminonixim ethylenediaininetetraacetate NButyldiethanolammonium hexafluorophosphate NButyldiethanolammonium tetrafluoroborate NButyidiethanolammonium trifluoroacetate NButyldiethanolammoniumpentafluoropropanoate NButyldiethanolammoniumheptafluorobutanoate NButyldiethanolaminonium phosphoenolpyruvate NButyldiethanolamnαonium nicotinamide adenine dinucleotide phosphate NButyldiethanolaminonium adenosinephosphate NButyldiethanolammonium adenosine diphosphate NButyldiethanolammonium adenosine triphosphate NButyldiethanolammonium oxyniacate NButyldiethanolammonium nitrate NButyldiethanolammonium nitrite N,NDimethylethanolammonium bromide N,NDimethyle1hanolammonium iodide N,NDhnethylethanolamnionium formate N,NDimethylethanolarnrnonium acetate N,NDhnethylethanolammonium propanoate N,NDimethylethanolammonium propanedioate N,NDimethylethanolamnionium butanoate N,NDήiiethylethanolamnionium butenoate N,NDimethylethanolainmonium butanedioate N,NDimethylethaαolainmonium pentanoate N,NDimethylethanolammonium pentanedioate N,NDimethylethanolamnioniumpentenoate N,NDimethylethanolarnmoniuni hexanoate N,NDimefhylettLanolammonium hexenoate N,NDimethyleth.anolammonium heptanoate N,NDimethyletliaiiolammonium heptanedioate N,NDimethylethLanolammonium heptenoate N,NDimethylethanolammoniuin octanoate N,NDimethylethanolammonium octanedioate N,NDimethyletJianolaminonium octenoate N,NDimethylethanolammonium nonanoate N,NDimethylethaiiolamnionium nonanedioate N,NDimethylethanolammonium nonenoate • N,NDimethylethanolammonium decanoate N,NDimethylethanolammonium decanedioate N,NDimeth.ylethanolammonium decenoate N5NDiinethylethanolammoniuin undecanoate N,NDimethylethanolammonium undecanedioate N,NDimethylethanolaimnonium undecenoate N5NDimethylethanolamnionium dodecanoate NjNDimethylethanolamtnonium dodecanedicarboxylate HNDimethylethanolaπmionium dodecenecarboxylate N,NDimethyle1iiaiiolammonium cyclohexanecarboxylate NjNDimeliLylethaxiolammonium cyclohexenecarboxylate N,NDimethylethaiiolainmonium phenoxide N5NDimethylethanolammonium benzoate NNDimethylethariolaininonium benezenedicarboxylate N,NDimethyleliianolaiiimonium benzenetricarboxylate NjNDimeliiylethaiiolammonium benzenetetracarboxylate N,NDimethylethanolaminonium chlorobenzoate NjNDimethylethanolaimnoniuin fluorobenzoate N5NDimethylethanolammoniumpentachloroberLzoate N,NDimethylethanolammonium penta£luorobenzoate N,NDim.eth.ylethanolammoniuin salicylate N,NDimethylethanolarnmormjrn glycolate N,NDimethyletiianolammonixim lactate N,NDimetliylethanolaπimonium pantothenate N,NDimethyletlianolammonixιm tartrate N,NDimethylethanolammonium hydrogen tartrate N,NDimethyle1±Lanolarnrnoniurn mandelate N,NDimethylethanolammoiiiurn crotonate N,NDimethylethanolarrrmoruurn malate N,NDimethylethanolammonium pyruvate N,NDimethylethanolarrimoniurn succinate N,NDimethylethanolarnrnonium citrate N,NDimetiiylethanolarnmonium fumarate N,NDimetliylethanolarnrnoriiurn phenylacetate N,NDimethylethanolammoniurn oxalate N,NDimetiiyletlianolarrimomurn bis(trifluorometiiylsιdρhonyl)i^ N,NDimetliylethanolammoniurn carbonate N,NDimethylethanolarnrnoriiurri hydrogen carbonate N,NDimethylethanolamrnonium sulphate N,NDimetibyleiJianolarnrnoniurn hydrogen sulphate N,NDime1liylethanolarnmonium phosphate N,NDime1iiyletiianolarnrnorriurn hydrogen phosphate N,NDimelh.yletiιanolarnrnorιiurri dihydrogen phosphate N,NDime1iιylet]ianolarrimoruum rnethanesulphonate N,NDime1iiylethanolaiiαmomumtrMuoromethanesulphonate NjNDrnie&ylethanolanimorύurn etiiylenediaminetetraacetate N,NDimethylethanolanirnorjium hexafluorophosphate N,NDuiiethyletiianolarnniorjiurn tetrafluoroborate NjNDimethylethanolarnmoriium trifluoroacetate N,NDimethylethanolarnrnoniumpentafluoropropanoate N,NDime1iiylethaαolarn2noniurn heptafluorobutanoate N,NDiinet]iyletiianolammoniuinphosphoenolpyruvate N,NDimethylethanolammonium nicotinamide adenine dinucleotide phosphate N,NDirnethylethanolammonium adenosinephosphate N,NDimethylethanolammoniuπi adenosine diphosphate N,NDimethylemanolarnmonium adenosine triphosphate N,NDimethylethanolammonium oxyniacate N,NDimethylethanolammonium nitrate N,NDimethylethanolammonium nitrite NMethylethanolammonium bromide NMethyiethanolammonium iodide NMethylethanolammonium formate NMethyletihanolammonium acetate NMethylethanolammonium propanoate NMethylethanolammonium propanedioate NMethylethanolammonium butanoate NMethylethanolammonium butenoate NMethylethanolammonium butanedioate NMethylethanolammonium pentanoate NMethylethanolammonium pentanedioate NMethylethanolammonium pentenoate NMethylethanolammonium hexanoate % NMethylethanolammonium hexenoate NMethylethanolammonium heptanoate NMethylethanolammonium heptanedioate NMethylethanolammonium heptenoate NMethylethanolammonium octanoate NMethylethanolammonium octanedioate NMethylethanolammonium octenoate NMethylethanolammonium nonanoate NMethylethanolammonium nonanedioate NMethylethanolammonium nonenoate NMethylethanolammonium decanoate NMethylethanolammonium decanedioate NMethylethanolammonium decenoate NMethylethanolammoriium undecanoate NMethylethanolammonium undecanedioate NMethylethanolammonium undecenoate NMethylethanolammonium dodecanoate NMethylethanolammonium dodecanedicarboxylate NMethylethanolammonium dodecenecarboxylate NMethylethanolammonium cyclohexanecarboxylate. NMethylethanolammonium cyclohexenecarboxylate NMethylethanolammonium phenoxide NMethylethanolammonium benzoate NMethylethanolammonium benezenedicarboxylate NMethylethanolammonium benzenetricarboxylate NMethylethanolammonium benzenetetracarboxylate NMethylethanolammonium chlorobenzoate NMethylethanolammonium fluorobenzoate NMethylethanolammoniumpentachlorobenzoate NMethylethanolammonium pentafluorobenzoate NMethylethanolammonium salicylate NMethylethanolammonium glycolate NMethylethanolammonium lactate NMethylethanolammonium pantothenate NMethylethanolammonium tartrate NMethylethanolammonium hydrogen tartrate NMethylethanolammonium mandelate NMethylethanolammonium crotonate NMethylethanolammonium malate NMethylethanolammonium pyruvate NMethylethanolammonium succinate NMethylethanolaαimonium citrate NMethylethanolammonium fumarate NMethylethanolammoniumphenylacetate NMethylethanolammonium oxalate NMemyle1iianolanimomum bis(trifluoromethylsulphonyl)imide NMethylethanolammonium carbonate NMethylethanolarnmonium hydrogen carbonate NMethylethanolammonium sulphate NMethylethanolammonium hydrogen sulphate NMethylethanolammonium phosphate NMethylethanolammonium hydrogen phosphate NMethylethanolammonium dihydrogen phosphate NMethylethanolammonium methanesulphonate NMemylethanolammoniumtrifluoromethanesulphonate NMemylethanolammomum ethylenediaminetetraacetate NMethylethanolammonium hexafluorophosphate NMethylethanolammonium tetrafluoroborate NMethylethanolammonium trifluoroacetate NMemylemanolammonium pentafluoropropanoate NMethylethanolammonium heptafluorobutanoate NMethylethanolammonium phosphoenolpyruvate NMethylethanolammonium nicotinamide adenine dinucleotide phosphate NMethylethanolammonium adenosinephosphate NMethylethanolammonium adenosine diphosphate NMethylethanolammonium adenosine triphosphate NMethylethanolammonium oxyniacate NMethylethanolammonium nitrate NMethylethanolammonium nitrite N,NDi(methoxyethyl)ammonium chloride N,NDi(methoxyethyl)ammonium bromide N,NDi(methoxyethyl)ammonium iodide N,NDi(methoxyethyl)ammonium formate NJvTDi(methoxyethyl)ammonium acetate N,NDi(methoxyethyl)aπimoniuπi propanoate N,NDi(methoxyethyl)ammoniumpropanedioate N,NDi(methoxyethyl)ammonium butanoate N,NDi(methoxyethyl)ammonium butenoate N5NDi(methoxyethyl)amirionium butanedioate N,NDi(methoxyethyl)animonium pentanoate N,NDi(methoxyethyl)ammonium pentanedioate N,NDi(methoxyetiiyl)aminonium pentenoate lSf,NDi(methoxyetiiyl)arQinonium hexanoate N,NDi(metiioxyetliyl)ammoniuni hexenoate N,NDi(methoxye1iiyl)aminonium heptanoate N,NDi(metiioxyetiiyl)ammoniuni heptanedioate N,NDi(mei3ioxyet]iyl)amrnonium lieptenoate N,NDi(methoxyethyl)ammonium octanoate N,NDi(methoxyethyl)animonium octanedioate N,NDi(methoxyethyl)ammonium octenoate N,NDi(methoxye£hyl)amiαonium nonanoate N,NDi(methoxyetαyl)ammonium nonanedioate N,NDi(methoxyethyl)ammonium nonenoate N5NDi(m.ethoxyeth.yl)aminonium decanoate N5NDi(methoxyethyl)aminoniuni decanedioate N,NDi(meth.oxyethyl)arnmonium decenoate N.NDi(methoxyethyl)ammoiiiuni undecanoate N,NDi(methoxyethyl)ammoriium tmdecanedioate N,NDi(methoxye1iiyl)amrnoriium undecenoate N,NDi(meth.oxyethyl)ammoiiiuin dodecanoate N?NDi(methoxye11iyl)aminonium dodecanedicarboxylate N9NDi(me1lioxyethyl)aniinoπiuin dodecenecarboxylate N^NDi^ethoxyeliiy^airimoniuni cyclohexanecarboxylate N^Di^ethoxyethy^ammonium cycloliexenecarboxylate N,NDi(methoxyethyl)ammoniumphenoxide N,NDi(methoxyethyl)ainmoimun benzoate N,NDi(metlioxyethyl)ainmonium benezenedicarboxylate N,NDi(methoxyetliyl)ainmoniunibenzenetricarboxylate N,NDi(methoxyethyl)ammoniιιm benzenetetracarboxylate N,NDi(metb.oxyethyl)aminoiiiυiii cblorobenzoate N,NDi(methoxyethyl)amnionium fluorobenzoate N,NDi(metboxyethyl)ammoiiiumpentachlorobenzoate N,NDi(metlioxyethyl)ainmonium pentafluorobenzoate N,NDi(methoxyethyl)ammonium salicylate N5NDi(methoxyethyl)animonium glycolate N,NDi(methoxyethyl)animoniuin lactate N5NDi(methoxyethyl)ammoniuni pantothenate N.NDi(m.ethoxyethyl)ammoiiiιuii tartrate N,NDi(methoxyethyl)ammomum hydrogen tartrate N5NDi(methoxyethyl)ammonium mandelate N,NDi(m.ethoxyethyl)ammoniυm crotonate N,NDi(methoxyethyl)ammonium malate N,NDi(methoxyethyl)ammomum pyruvate N,NDi(methoxyethyl)ammoniuni succinate N5NDi(me1iioxyethyl)arnmoiiiurn citrate N,NDi(methoxyethyl)ammonium fumarate N,NDi(me1iioxyethyl)ammoniuinphenylacetate N,NDi(methoxyethyl)ammonium oxalate N5NDi(me1±ioxye1liyl)ammoiύum bis(Miluorome1iiylsxilphonyl)imide N,NDi(methoxyethyl)ammonium carbonate N,NDi(meth.oxyethyl)ammonium hydrogen carbonate N,NDi(methoxyethyl)arnmoiiium sulphate N5NDi(methoxyethyl)ammorduni hydrogen sulphate N,NDi(methoxyeth.yl)ammoniuni phosphate N,NDi(methoxyetliyl)aminonium hydrogen phosphate N,NDi(methoxyethyl)ammonium dihydrogen phosphate N,NDi(methoxyetiiyl)ammonium m.ethanesulphonate N,NDi(methoxyethyl)airmioiύumtrifluoromethanesulphonate N,NDi(me1iioxyethyl)atnmordum ethylenediarQinetetraacetate N,NDi(methoxyethyl)ammonium hexafluorophosphate NjNDi^ethoxyet^^aπmioiiutntetrafluoroborate N,NDi(methoxyethyl)ammoniuni trifluoroacetate N,NDi(me1iioxye1liyl)arnmoniiimpentafluoropropanoate N,NDi(methoxye1iιyl)aπimoiiium heptafluorobutanoate N,NDi(methoxyeώyl)arnmoniumphosphoenolpyruvate N,NDi(methoxyemyl)ammonϊum nicotinamide adenine dinucleotide phosphate N,NDi(methoxyethyl)ammonium adenosinephosphate N,NDi(rαethoxyethyl)ammonium adenosine diphosphate N,NDi(methoxyethyl)ammonium adenosine triphosphate N,NDi(methoxyethyl)ammonium oxyniacate N,NDi(methoxyethyl)ammonium nitrate N3NDi(methoxyethyl)ammonium nitritel(3Hydroxypropyl)putresciniuni chloride l(3Hydroxypropyl)putrescinium bromide l(3Hydroxypropyl)putrescinium iodide l(3Hydroxypropyl)putrescinium formate l(3Hydroxypropyl)putresciniimi acetate 1(3Hydroxypropyl)putrescinium propanoate 1(3Hydroxypropyl)putresciαium propanedioate 1(3Hydroxypropyl)putrescinium butanoate 1(3Hydroxypropyl)putrescinium butenoate 1(3Hydroxypropyl)putrescinium butanedioate 1(3Hydroxypropyl)putrescinium pentanoate 1(3Hydroxypropyl)putrescinium pentanedioate 1(3Hydroxypropyl)putrescinium pentenoate 1(3Hydroxypropyl)putrescinium hexanoate 1(3Hydroxypropyl)putrescinium hexenoate 1(3Hydroxypropyl)putrescinium heptanoate 1(3Hydroxypropyl)putrescinium heptanedioate 1(3Hydroxypropyl)putresciαium heptenoate 1(3Hydroxypropyl)putrescinium octanoate 1(3Hydroxypropyl)putrescinium octanedioate 1(3Hydroxypropyl)putresciQium octenoate 1(3Hydroxypropyl)putrescinium nonanoate 1(3Hydroxypropyl)putrescinium nonanedioate 1(3Hydroxypropyl)putrescinium nonenoate l(3Hydroxypropyl)putrescinium decanoate 1(3Hydroxypropyl)putrescinium decanedioate 1(3Hydroxypropyl)putrescirdum decenoate 1(3Hydroxypropyl)putrescimum undecanoate 1(3Hydroxypropyl)putrescinium undecanedioate 1(3Hydroxypropyl)putrescijoiuni undecenoate 1(3Hydroxypropyl)putresciriiuin dodecanoate 1(3Hydroxypropyl)putrescinium dodecanedicarboxylate 1(3Hydroxypropyl)putrescinium dodecenecarboxylate 1(3Hydroxypropyl)putrescinium cyclohexanecarboxylate 1(3Hydroxypropyl)putrescinium cyclohexenecarboxylate 1(3Hydroxypropyl)putrescinium phenoxide l(3Hydroxypropyl)ρutrescinium benzoate 1(3Hydroxypropyl)putresciniuπi benezenedicarboxylate 1(3Hydroxypropyl)putrescinium benzenetricarboxylate 1(3Hydroxypropyl)putrescinmm benzenetetracarboxylate 1(3Hydroxypropyl)putrescinium chlorobenzoate 1(3Hydroxypropyl)ρutrescinium fluorobenzoate 1(3Hydroxypropyl)putrescinium pentachlorobenzoate 1(3Hydroxypropyl)ρutrescinium pentafluorobenzoate 1(3Hydroxypropyl)putrescinium salicylate 1(3Hydroxypropyl)putrescirriurn glycolate l(3Hydroxypropyl)putrescinium lactate 1(3Hydroxypropyl)putrescinium pantothenate l(3Hydroxypropyl)putrescinium tartrate l(3Hydroxypropyl)putresciniυm hydrogen tartrate 1(3Hydroxypropyl)putrescinium maαdelate 1(3Hydroxypropyl)putrescrnium crotonate l(3Hydroxypropyl)putrescinium malate l(3Hydroxypropyl)putrescinium pyruvate 1(3Hydroxypropyl)putrescinium succinate l(3Hydroxypropyl)putrescinitim citrate l(3Hydroxypropyl)putrescinium fumarate 1(3Hydroxypropyl)putrescinium phenylacetate l(3Hydroxypropyl)putrescinium oxalate 1(3Hydroxypropyl)putrescinium bis(trifluoroniethylsulphonyl)imide 1(3Hydroxypropyl)putrescinium methanesulphonate 1(3Hydroxypropyl)putrescinium trifluoromethanesulphonate 1(3Hydroxypropyl)putrescinium hexafluorophosphate 1(3Hydroxypropyl)putrescinium tetrafluoroborate 1(3Hydroxypropyl)putrescinium trifhioroacetate 1(3Hydroxypropyl)putrescinium pentarluoropropanoate•. 1(3Hydroxypropyl)putrescinium heptafluorobutanoate 1(3Hydroxyproρyl)putrescinium phosphoenolpyruvate l(3Hydroxypropyl)putrescMum nicotinamide adenine dinucleotide phosphate 1(3Hydroxypropyl)putrescinium adenosinephosphate l(3Hydroxypropyl)putrescinium adenosine diphosphate l(3Hydroxypropyl)putrescinium adenosine triphosphate 1(3Hydroxyproρyl)putrescinium carbonate l(3Hydroxypropyl)putrescinium hydrogen carbonate 1(3Hydroxypropyl)putrescinium sulphate l(3Hydroxypropyl)putresciniiim hydrogen sulphate 1(3Hydroxypropyl)putrescinium phosphate l(3Hydroxypropyl)putrescinium hydrogen phosphate 1(3Hydroxypropyl)putrescinium dihydrogen phosphate l(3Hydroxypropyl)putrescinium nitrate l(3Hydroxypropyl)putrescinium nitrite .
26. A process for the preparation of an ionic liquid as claimed in claim 1, the process comprising the steps of: i.) providing an organic primary, secondary or tertiary amine; and ii.) neutralising the compound in (i) with an acid.
27. A process as claimed in claim 26 which comprises the steps of: i.) providing a nitrogencontaining compound of the formula (H) NRR'R" (II) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogencontaining functional groups (including nitrile, nitro or amino or another basic nitrogencontaining functional group), thiol, alkythio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, alkoxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl and substituted amino (e.g. mono or dialkylaminό , or alkyamido); and * R' and R' ', which may be the same or different, each represent H or R; or any two or three of R, R' and R" may be joined together with the N to form a cyclic group, ii.) neutralising the compound in (i) with an acid.
28. A process as claimed in claim 26 or 27 wherein the acid includes an anion comprising a halogenated inorganic anion, nitrate, sulphate, carbonate, sulphonate or carboxylate.
29. The use of an ionic liquid comprising an anion and a cation wherein the cation is a primary, secondary or teriary ammonium ion containing a protonated nitrogen atom as a solvent for enzymecatalysed reactions, a solvent for organic synthesis, a matrix in matrixassisted laser desorption/ionisation (MALDI) mass spectrometry, a solvent for extraction, in catalysis or liquefaction, nuclear fuel reprocessing medium, fuel cell, electrochemical applications, pervaporation, drug delivery lubrication, hydraulics, adhesives, sensors, biocides or chromatographic media.
30. The use as claimed in claim 29 wherein the cation is a nitrogencontaining cation of the formula (I) N+EIRR5R" (T) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogencontaining functional groups (including nitrile, nitro or amino or another basic nitrogencontaining functional group), thiol, alkythio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, alkoxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl and substituted amino (e.g. mono or dialkylamino or alkyamido); and R' and R", which may be the same or different, each represent H or R; or any two or three of R, R' and R' ' may be joined together with the N to form a cyclic group.
31. A method for carrying out an enzymecatalysed reaction comprising i.) providing a liquid reaction medium which contains an ionic liquid comprising an anion and a cation wherein the cation is a primary, secondary or teriary ammonium ion containing a protonated nitrogen atom; ii.) providing in the liquid reaction medium an enzyme and a substrate for the enzyme; and iii.) allowing reaction of the substrate to occur.
Description:
LIQUIDS

The present invention relates to ionic liquids and uses thereof. The invention also provides processes for the manufacture of ionic liquids.

Ionic liquids are compounds which are composed of ions but which have a melting point below ambient temperature. They can be formed by a suitable combination of charge-delocalised, desymmetrised ions. The degree of order of the resulting salt can be reduced and the melting point lowered to a point where the resultant salt is liquid at ambient temperature. The delocalisation of the charge on the ion is also an important factor in determining the melting point of the resulting salt. Ionic liquids possess a number of remarkable properties, including negligible vapour pressure and high solvation capabilities, which have rendered them interesting alternatives to conventional solvents in a variety of applications.

Ionic liquids may be made up of anions and cations or alternatively consist of zwitterions carrying both a positive and a negative charge on the same molecule. Most commonly the ionic liquid will comprise an anion and a cation.

The prior art comprises liquids composed of a quaternary nitrogen- or phosphorus- based cation, for example, based on a nucleus selected from quaternary ammonium cations, pyrrolidinium cations, imidazolium cations, triazolium cations, pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations and triazinium cations. These types of ionic liquids tend to be highly viscous, potentially hazardous and strongly absorb UV and visible light. Furthermore, the preparation of these ionic liquids involves a number of chemical and chromatographic steps that makes the process time consuming, expensive and inefficient.

Anderson et al., J. Am. Chem. Soc. 124:14247-14254 (2002) discloses ionic liquids composed of a primary or tertiary ammonium based cation for use in certain chemical applications. The inventors have provided further ionic liquids.

According to the present invention there is provided an ionic liquid comprising an anion and a cation wherein the cation is a primary, secondary or tertiary- ammonium ion containing a charged nitrogen atom.

As used herein a "primary ammonium ion" is an ammonium ion in which the nitrogen has 1 carbon atom attached to it.

As used herein a "secondary ammonium ion" is an ammonium ion ira which the nitrogen has 2 carbon atoms attached to it.

As used herein a "tertiary ammonium ion" is an ammonium ion in which the nitrogen has 3 carbon atoms attached to it.

According to a further aspect of the present invention there is provided an ionic liquid comprising an anion and a cation characterised in that the cation is a nitrogen- containing cation of the formula (I)

N1HRR'R" (I)

in which R is a hydrocarbyl group optionally substituted with by o:ne or more substituents selected from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), thiol, alkythio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, atkoxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl and substituted amino (e.g. mono- or di-alkylamino or alkyamido); and

R' and R", which may be the same or different, each represent H or R; or any two or three of R, R' and R" may be joined together with the N to form a cyclic group.

The term "ionic liquid" herein includes, but is not limited to, compounds consisting of ions and liquid at temperatures at which the compound is stable and the ionic liquids may have a melting point below 1000C, for example, b>elow 25°C and optionally below 200C. The boiling point of the ionic liquid may be at least 2000C. It may be above 5000C or even above 1000°C.

The ionic liquids of the invention may consist entirely of ions, which, are liquid at the previously above defined temperatures in the dry state. Such ionic liquids will generally contain less than 1% water, preferably less man lOOOppm water and more preferably still less than lOOppm water by mass.

In a preferred aspect of the invention, ionic liquids are defined- as compounds consisting of a cation and an anion and having a water content of less than 100 parts per million. Preferably still, the ionic liquids have a melting point of 300C or below, and a viscosity of less than 500 centipoise.

For the purposes of this invention hydrocarbyl includes, but is not Limited to, alkyl, alkenyl, alkynyl, cyclohydrocarbyl, for example cycloalkyl, cycloalkeaαyl and moieties containing a combination thereof.

As used herein "alkyl" relates to both straight chain and branched aLkyl radicals, for example, of 1 to 12 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8 carbon atoms including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl. The term alkyl also encompasses cycloalkyl radicals including but not limited to cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The alkyl group may be substituted with one or more halogen atoms. In one class of compounds the halogen is fluorine, in another it is chlorine, in a third it is a combination of fluorine and chlorine.

"Alkoxy" relates to both straight chain and branched alkyl radicals, for example, of 1 to 12 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8 carbon atoms containing one or more oxygen atoms or hydroxyl.

The term "alkenyl" means a straight or branched alkenyl radical of, for example, 2 to 12 carbon atoms, such as 2, 3, 4, 5 or 6 carbon atoms, and containing one or more carbon-carbon double bonds and includes but is not limited to ethylene, n-propyl-1- ene, n-propyl-2-ene, isopropylene etc.

"Alkynyl" relates to a straight or branched alkynyl radical of, for example, 2 to 12 carbon atoms, such as 2, 3, 4, 5 or 6 carbon atoms, and containing one or more triple bonds.

"Cyclohydrocarbyl" relates to a saturated, partly unsaturated or unsaturated 3 - 10, for example, 5, 6, 7, 8, 9 or 10, membered hydrocarbon ring, including cycloalkyl or aryl.

"Aryl" means an aromatic, for example, 6 -10 membered hydrocarbon containing one, e.g. 6C- 1OC, ring which is optionally fused to one or more saturated or unsaturated rings, including phenyl or phenyl substituted by an alkyl or alkoxy group in which alkyl and alkoxy are as described herein.

"Heteroaryl" means an aromatic, for example, 5-10 membered aromatic ring containing one or more heteroatoms selected from N, O or S, and containing one ring which is optionally fused to one or more saturated or unsaturated rings. "Heterocyclyl" means, for example, a 3-10 membered ring system containing one or more heteroatoms selected from N, O or S and includes heteroaryl. The heterocyclyl system may contain one ring or may be fused to one or more saturated or unsaturated rings; the heterocyclyl may be fully saturated, partially saturated or unsaturated.

"Cyclic group" means a ring or ring system, which may be unsaturated or partially unsaturated but is usually saturated, typically containing 5 to 13 ring-forming atoms, for example a 5- or 6- membered ring. Examples include cyclohydrocarbyl or heterocyclyl.

Examples of cyclohydrocarbyl or heterocyclyl groups include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isooxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazne, phthalazine, piperazine, piperidine, pteridine, purine, putrescine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrole, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazino, triazole, trithiane, tropine.

Halogen means F, Cl, Br, or I.

In one class of compounds R' and R" are H. Compounds such as these having 1 R group and 3 hydrogens are referred to herein as primary ammonium ions.

The invention covers compounds of formula (I) having 2 R groups and 2 hydrogens and which are referred to herein as secondary ammonium ions respectively. The invention further covers compounds having 3 R groups and 1 hydrogen and which are referred to herein as tertiary ammonium ions.

Included is a class of compounds in which R' and R" are different and have the same meaning as R.

In a preferred aspect of the invention there is provided an ionic liquid consisting of an anion and a cation as defined in the first aspect of the invention.

In a preferred aspect of the invention the cyclic group is a cyclohydrocarbyl or hetereocyclyl group, for example cyclohexylammonium.

Ih one class of compounds there are excluded cations wherein any two or three of R, R', R" may be joined together with the N to form an aryl or heteroaryl group. Specifically excluded are pyridinium, pyrrolidinium and imidazolium cations, hi one class of compounds where R is unsubstituted, there are excluded cations where R, R' and R' ' are the same and are ethyl or butyl.

In one class of compounds wherein R, R' and/or R" is an unsubstituted hydrocarbyl group, the invention may include the following provisos:

Where R is ethyl, the invention may include the proviso that R' and/or R' ' are not H.

Where R' and R" are both CH3, the invention may include the proviso that R is not H.

Where one or R' and R" is H and the other is CH3, the invention may include the proviso that R is not CH3. ■

The invention may include the proviso that the ionic liquid is not any of the following: Ethylammonium nitrate Tributylanimonium-acetate Tributylammoniumα-cyano-4-hydroxycinnamate Tributylamnionium sinapate Dimethylammonium pyridine-2-carboxylate Tributylamrtionium pyridine-2-carboxylate Tribulylammoniurn 3-hydroxypyridine-2-carboxylate Triethylammonium pyridine-2-carboxylate

In addition to demonstrating high solvation capability, the ionic liquids of the present invention have a low viscosity, are non-toxic and are colourless. These features make the ionic liquids of the present invention useful in a variety of applications.

Preferably, R is substituted with a moiety selected from the group consisting of alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl groups. More preferably, R is substituted with a hydroxyl or amino group.

hi one class of compounds, where R is substituted with a hydroxyl group, the invention may include the proviso that the ionic liquid is not diethanolammonium chloride.

If more than one substituent group (for example, selected from the group consisting of alkenyl, hydroxyl, amino, thiol, carbonyl and carboxyl groups) is present then more than one substituent group may be present on a single cation.

hi one class of compounds, R is a hydroxyalkyl group having 1, 2, 3, 4, 5 or 6 C atoms. The hydroxyalkyl group may have a hydroxyl moiety on its free, terminal carbon. R may be a polyol having 2 to 6 C atoms, for example, a di-alkanol, tri- alkanol or tetra-alkanol group. Preferably, the cation is an ethanolammonium, N-(alkoxyemyl)ammonrum, N- methylethanolammonium, N,N-α^ethylemanolammonium5 diethanolammonium, N-alkyldiethanolammonium (e.g butyl&emanolammonium), N5N- di(alkoxyalkyl)ammoruum (e.g di(methoxyethyl)ammonium) or triethanolammonium ion.

More preferably the cation is a methylethanolammonium, N5N dimemylemanolanmonium, N, N- di(memoxye1hyl)ammoniurn) or butyldiethanolammonium ion.

In another class of compounds, R is an arninoatkyl group having 2 to 8 C atoms, for example, 2, 3, 4, 5, 6, 7 or 8 C atoms. The aminoalkyl may be a di or iri-arriinoalkyl group.

In some compounds, R is putrescine, piperidine, or tropine.

Preferred cations include an ethanolammonium, diethanolammonium, N- butyldiemanolarnrnoriium, N-memyletiianolammonium, di(methoxyethyl)ammonium, N,N-dimethylethanolammonium, putrescinium, l-(3- hydroxypropyl)putrescinium, or N-(3-hydroxypropyl)~N- methylcyclohexylammonium ion. Preferably still, . cations include N- butyldiethanolammonium, N-methylethanolammonium, » di(methoxyethyl)aramonium, N,N-dimethylethanolammonium, putrescinium, l-(3- hydroxypropyl)putrescinium, or N-(3-hydroxypropyl)-N- methylcyclohexylammonium ion.

Any cation included in the above list may be combined with any disclosed anion.

The identity of the anions in the ionic liquids of the invention is not critical. The only theoretical constraint upon the choice of the anion is its ionic weight in order to keep the melting point of the ionic liquid below the desired temperature. Preferably the anion is selected from halogenated inorganic anions, nitrates, sulphates, phosphates, carbonates, sulphonates and carboxylates. The sulphonates and carboxylates may be alkylsulphonates and alkylcarboxylates, in which the alkyl group is a moiety, for example having 1 to 20 C atoms, selected alkyl and alkyl substituted at any position with alkenyl, alkoxy, alkeneoxy, aryl, arylalkyl, aryloxy, amino, aniinoalkyl, thio, thioalkyl, hydroxyl, hydroxyalkyl, carbonyl, oxoalkyl, carboxyl, carboxyalkyl or halide function, including all salts, ethers, esters, pentavalent nitrogen or phosphorus derivatives or stereoisomers thereof. For example, the anion may be selected from bis(trifiuoromethylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, dihydrogen phosphate, metaphosphate, methanesulphonate, trifluoromethanesulphonate, ethylenediaminetetraacetate, chloride, bromide, iodide, hexafluorophosphate, tetrafluoroborate, trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, benezenedicarboxylate, benzenetricarboxylate, benzenetetracarboxylate, chlorobenzoate, fluorobenzoate, pentachlorobenzoate, pentafluorobenzoate salicylate, glycolate lactate, pantothenate, tartrate, hydrogen tartrate, mandelate, crotonate, malate, pyruvate, succinate, citrate, fumarate, phenylacetate. An especially preferred anion is an organic carboxylate. When the anion is required to include a labile proton then glycolate, tartrate and lactate anions are preferred. These contain both acid and hydroxyl functional groups.

The ionic liquid according to the invention may contain cations which are all the same or which are different. In the same way, the ionic liquids may contain anions which are all the same or which are different. Thus the invention encompasses ionic liquids including a mixture of different cations and/or different anions.

Ionic liquids of the invention may include any of the following: Ethanolammonium formate Emanolammonium acetate Ethanolammonium propanoate Ethanolammoniumpropanedioate Ethanolammonium butanoate Ethanolammonium butenoate Ethanolammonium butanedioate Ethanolammonium pentanoate Ethanolammonium pentanedioate Ethanolammonium pentenoate Ethanolammonium hexanoate Ethanolammonium hexanedioate Ethanolammonium hexenoate Ethanolammonium heptanoate Ethanolammonium heptanedioate Ethanolammonium heptenoate Ethanolammonium octanoate Ethanolammonium octanedioate Ethanolammonium octenoate Ethanolammonium nonanoate Ethanolanunonium nonanedioate Ethanolammonium nonenoate Ethanolammonium decanoate Ethanolammonium decanedioate Ethanolammonium decenoate Ethanolammonium undecanoate Ethanolammonium undecanedioate Ethanolammonium undecenoate Ethanolammonium dodecanoate Ethanolammonium dodecanedicarboxylate Ethanolammonium dodecenecarboxylate Ethanolammonium cyclohexanecarboxylate Ethanolammoiiium cyclohexenecarboxylate Ethanolammouium phenoxide Ethanolammoiiium benzoate Ethanolammouium benezenedicarboxylate Ethanolammoiiium benzenetricarboxylate Ethanolammouium benzenetetracarboxylate Ethanolammouium chlorobenzoate Ethanolammouium fluorobenzoate Ethanolammoiύum pentachlorobenzoate Ethanolammoiiium pentafluorobenzoate Ethanolammouium salicylate Ethanolammoiiium glycolate Ethanolammouium lactate Ethanolammonium pantothenate Ethanolammoiiium tartrate Ethanolammoiiium hydrogen tartrate Ethanolammonium mandelate Ethanolammoiiium crotonate Ethanolammonium malate Ethanolammonium pyruvate Ethanolammonium succinate • Ethanolammonium citrate Ethanolammonium fumarate Ethanolammonium phenylacetate Ethanolammonium oxalate Ethanolammonium bis(trifluoromethylsulphonyl)imide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate Eώanolammonium hydrogen phosphate Ethanolammonium dihydrogen phosphate Ethanolammonium methanesulfonate Ethanolammonium trifluoromethanesulphonate Ethanolammonium ethylenediaminetetraacetate Ethanolammonium hexafluorophosphate Ethanolammonium tetrafluoroborate Ethanolammonium trifluoroacetate Ethanolammonium pentafluoropropanoate Ethanolammonium heptafluorobutanoate Ethanolammonium phosphoenolpyruvate Ethanolammonium nicotinamide adenine dinucleotide phosphate Ethanolammonium adenosinephosphate Ethanolammonium adenosine diphosphate Ethanolammonium adenosine triphosphate Ethanolammonium oxyniacate Ethanolammonium nitrate Ethanolammonium nitrite Diethanolammonium bromide Diethanolammonium iodide Diethanolammonium formate Diethanolammonium acetate Diethanolammonium propanoate Diethanolammonium propanedioate Diethanolammonium butanoate Diethanolammonium butenoate Diethanolammonium butanedioate Diethanolammonium pentanoate Diethanolammonium pentanedioate Diethanolammonium pentenoate Diethanolammonium hexanoate Diethaαolammonitmi hexanedioate Diethanolammonixun hexenoate Diethanolammonixrai heptanoate Diemanolanimonmm heptanedioate Diethanolammoniumheptenoate Diethanolammoniυin octanoate Diethanolammonium octanedioate Diethanolammoniυm octenoate Diethanolammoniυm nonanoate Diethanolammonixun nonanedioate Diethanolammonium nonenoate Diethanolammonium decanoate Diethanolammonium decanedioate Diethanolammonium decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate Diethanolammonium dodecanedicarboxylate Diethanolammonium dodecenecarboxylate Diethanolammomum cyclohexanecarboxylate Dietiianolammonium cyclohexenecarboxylate Diethanolammonium phenoxide Diethanolammomum benzoate Diethanolammonium benezenedicarboxylate Diethanolammomum benzenetricarboxylate Diethanolammonium benzenetetracarboxylate Diethanolammonium chlorobenzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate Diethanolammonium salicylate Diethanolammonium glycolate Diethanolammoriium lactate Diethanolammonium pantothenate Diethanolammoriium tartrate Diemanolammonium hydrogen tartrate Diethanolammonium mandelate Diethanolammonium crotonate Diethanolammonium malate Diethanolammonium pyruvate Diethanolammonium succinate Diethanolammonium citrate Diethanolammonium fumarate Diethanolammonium phenylacetate Diethanolammomum oxalate Diemanolammomuin bis(trifluoromethylsulphonyl)imide Diethanolammonium carbonate Diethanolammomum hydrogen carbonate Diethanolammomum phosphate Diethanolammonium hydrogen phosphate Diethanolammonium dihydrogen phosphate Diethanolammonium methanesulphonate J Diethanolammonium trifluoromethanesulphonate Diemanolammonium ethylenediaminetetraacetate Diethanolammonium hexafluorophosphate Diethanolammonium tetrafluoroborate Diethanolammonium trifluoroacetate Diethanolammonium pentafluoropropanoate Diethanolammonium heptafluorobutanoate Diethanolammonium phosphoenolpyruvate Diethanolammonium nicotinamide adenine dinucleotide phosphate Dieώanolammonmm. adenosinephosphate Dieraanolarnmonrum adenosine diphosphate Diemanolammonmm adenosine triphosphate Diemanolarnmonmm oxyniacate Diemanolammonmm nitrate Diethanolammoniυm nitrite N-Butyldiethanolammonium chloride N-Butyldiethanolammonium bromide N-Butyldiethanolarnmonium iodide N-Butyldiethanolammonium formate N-Butyldiethanolammonium acetate N-Butyldiethanolammonium propanoate N-Butyldiethanolammonium propanedioate N-Butyldiethanolammonium butanoate N-Butyldiethanolammonium butenoate N-Butyldiethanolammonium butanedioate N-Bulyldiethanolammonium pentanoate N-Butyldiethanolammonium pentanedioate N-Butyldiethanolammonium pentenoate N-Butyldiethanolammonium hexanoate N-Butyldiethanolarnmonium hexenoate N-Butyldiethanolarnmonium heptanoate N-Butyldiethanolarnmonium heptanedioate N-Butyldiethanolammonium heptenoate N-Butyldiethanolammonium octanoate N-Butyldiethanolammonium octanedioate N-Butyldiethanolammonium octenoate N-Butyldiethanolammonium nonanoate N-Butyldiethanolammonium nonanedioate N-Butyldiethanolammonium nonenoate N-Butyldiethanolammonium decanoate N-Butyldiethanolammonium decanedioate N-Butyl&emanolammonium decenoate N-Butyldiethanolammonium υndecanoate N-Butyldiethanolammonium undecanedioate N-Butyldiethanolammonium undecenoate N-Butyldiethanolammonium dodecanoate N-Butyldiethanolammonium dodecanedicarboxylate N-Butyldiethanolammonium dodecenecarboxylate N-Butyldiethanolammonium cyclohexanecarboxylate N-Butyldiethanolammonium cyclohexenecarboxylate N-Butyldiethanolammonium phenoxide N-Butyldiethanolammonium benzoate N-Butyldiethanolammonium benezenedicarboxylate N-Butyldiethanolammonium benzenetricarboxylate N-Butyldiethanolammonium benzenetetracarboxylate N-Butyldiethanolammonium chlorobenzoate N-Butyldiethanolammoniυm fluorobenzoate N-Butyldiethanolammonium pentachlorobenzoate N-Butyldiethanolammonium pentafluorobenzoate N-Butyldiethanolammonium salicylate N-Butyldiethanolammonium glycolate N-Butyldiethanolammonium lactate ; N-Butyldiethanolammonium pantothenate N-Butyldiethanolammonium tartrate N-Butyldiethanolammonium hydrogen tartrate N-Butyldiethanolammonium mandelate N-Butyldiethanolammonium crotonate N-Butyldiethanolammonium malate N-Butyldiethanolammonium pyruvate N-Butyldiethanolammonium succinate N-Butyldiethanolammonium citrate N-Butyldiethanolammonium fumarate N-Butyldiethanolammonium phenylacetate N-Butyldiethanolammonium oxalate N-Bu1yldiethanolammordum bis(trifluoromethylsulphonyl)imde N-Butyldiethanolammonium carbonate N-Butyldiethanolammonium hydrogen carbonate N-Butyldiethanolammonium sulphate N-Butyldiethanolammonium hydrogen sulphate N-Butyldiethanolammonium phosphate N-Butyldiethanolammonium hydrogen phosphate N-Butyldiethanolammonium dihydrogen phosphate N-Butyldiethanolammonium methanesulphonate N-Butyldiethanolammonium trifluoromethanesulphonate N-Butyldiemanolammonium emylenediaminetetraacetate N-Butyldiethanolammoniumhexafluorophosphate N-Butyldiethanolammonium tetrafluoroborate N-Butyldiethanolammonium trifluoroacetate N-Butyldiethanolammoniunipentafliioropropanoate N-Butyldiethanolammonium heptafluorobutanoate N-Bu1yldiethanolammoniumphosptioenolpyruvate N-Butyldiethanolammonium nicotinamide adenine dinucleotide phosphate N-Butyldiethanolammonium adenosinephosphate N-Butyldiethanolammonium adenosine diphosphate N-Butyldiethanolammonium adenosine triphosphate N-Butyldiethanolammonium oxyniacate N-Butyldiethanolammonium nitrate N-Butyldiethanolammonium nitrite N,N-Dimethylethanolammonium bromide N,N-Dimethylethanolammonium iodide N,N-Dimethylethanolammonium formate N,N-Dimethylethanolammonium acetate N,N-Dimethylethanolaminoniuin propanoate N,N-Dime1hylethanolarnmorrium propanedioate N,N-Dimethylethanolammonium butanoate N,N-Dimethylethaαolammoniuin butenoate N,N-Dimethylethanolamiiioniuin butanedioate N,N-Dimethyleihanolammonium pentanoate N,N-Dimethyletiianolaπimonium pentanedioate N,N-Dimethyle1iιanolamrnoniuin pentenoate N,N-Dimethylethanolammonium hexanoate N,N-Dimethylethanolammonium hexenoate N,N-Dύnethyle1iιanolarninonium heptanoate N,N-Dimethylethanolammonium heptanedioate N,N-Dimethylethanolammoniuin heptenoate N,N-Dime1iιylethanolarnrnonium octanoate N,N-Dimethyletibanolammonium octanedioate N,N-Dimethylethanolammonium octenoate N,N-Dimethylethanolammonium nonanoate N,N-Dimethylethanolammonium nonanedioate N,N-Dimethylethanolammonium nonenoate N,N-Dimethylethanolamnionium decanoate N,N-Diinethylethanolammoniuni decanedioate■ . N,N-Dimethylethanolammoniuni decenoate s N-N-Dimetiiylethanolammonium undecanoate N5N-Dimethyletlιanolammoniιiin undecanedioate N,N-Dimethylethanolammonium undecenoate N,N-Dimeth.ylethanolammoniuin dodecanoate NjN-Dimethyletiianolammonium dodecanedicarboxylate NjN-Dirαethylethanolarnmoniunα dodecenecarboxylate NjN-Dimethylethanolammonium cyclohexanecarboxylate ^N-Dimethylethanolammonium cyclohexenecaurboxylate N,N-Dimethyle1iianolaminoniιιm phenoxide N,N-Dimethylethaαolammonium benzoate NsN-Dimeliiylethanolainnionium benezenedicarboxylate N5N-Dimethylethanolammonium benzenetricarboxylate benzenetetracarboxylate N,N-Dimethylethanolainmonium cblorobenzoate N,N-Dimethylethanolammoiuurn fluorobenzoate NjN-Dimethyletiianolainnioniumpentachlorobenzoate N,N-Dime1hylethanolaninioniumpentafluorobenzoate N,N-Dimethylethanolammonium salicylate N,N-Dimethylethanolanmomum glycolate N,N-Dimethylethanolaπunonium lactate N,N-Dimethylethanolammonium pantothenate N,N-Dimethylethanolammonium tartrate N,N-Dimethylethanolammonium hydrogen tartrate N,N-Dimethyle1iιanolarnmoniuin mandelate N,N-Dimethylethanolarnmoniurn crotonate N,N-Dimethylethanolamrnoniurn malate N,N-Dimeώyletiianolarnmoniιun pyruvate N,N-Dimethylethanolammonium succinate N,N-Dimethylethanolammonium citrate NiN-Dimetibylethanolammonium fumarate N,N-Dimethylethanolarnmonium phenylacetate ; N,N-Dimethyle1hanolarnrnonium oxalate N,N-Dimethylethanolammordum bis(trifluorometiiylsulphonyl)iniide N,N-Dimethylethanolarnmonium carbonate N,N-Dimethylethanolammonium hydrogen carbonate N,N-Dimethylethanolarnmoniuni sulphate N,N-Dimethylethanolammonium hydrogen sulphate N,N-Dimethylethanolarnmonium phosphate N,N-Dimethylethanolarnmonium hydrogen phosphate N,N-Duiiethylethanolarnmoniurn dihydrogen phosphate N5N-Dirne1liyletiianolainmonium methanesulplionate N,N-Dirnethyle1iianolamϋtnoiύιim trifluoromethanesulphonate NjN-Dirnethylethanolammonium etiiylenediaininetetraacetate N,N-Dirαethyleihanolammoniuni hexafluoroρhosphate N,N-Dinaethylethanolammoniuni tetrafluoroborate N,N-Dmαemylemanolammonium Mfluoroacetate N,N-Dirrie1iiylethanolammonii]mpentafluoropropanoate N,N-Diirιethylethanolanimoniuni heptafluorobutanoate N,N-Diinethylethanolammoniuin phosp]ioenolpyruvate N5N-Diinethylethanolainmonium nicotinamide adenine dinucleoti&e phosphate N,N-Dinαethylethanolammonium adenosinephosphate NjN-Dinα.ethylethanolammonium adenosine diphosphate N,N-Dinαethylethanolammonium adenosine triphosphate N,N-Dinxethylethanolamnioniuni oxyniacate N5N-Dήn.ethylethanolammonium nitrate N,N-DitrLethylethanolammonium nitrite N-Methylethanolammonium bromide N-Methylethanolammonium iodide N-Methylethanolammonium formate N-Methylethanolammonium acetate N-Methylethanolammonium propanoate N-Methylethanolammonium propanedioate N-Methylethanolammonium butanoate N-Methylethanolammonium butenoate N-Methylethanolammonium butanedioate N-Methylethanolammonium pentanoate N-Methylethanolammonium pentanedioate N-Methylethanolammonium pentenoate N-Methylethanolammonium hexanoate N-Methylethanolammonium hexenoate N-Methylethanolammonium heptanoate N-Memylethanolammonium heptanedioate N-Memylethanolammonium heptenoate N-Memylethanolammonium octanoate N-Methylethanolamtnonium octanedioate N-Methylethanolamtnonium octenoate N-Meώyleihanolammoniuπi nonanoate N-Methylethanolammonium nonanedioate N-Methylethanolammonium nonenoate N-Methylethanolammonium decanoate N-Methylethanolammonium decanedioate N-Methylethanolammonium decenoate N-Methylethanolammonium undecanoate N-Methylethanolammonium undecanedioate N-Methylethanolammonium undecenoate N-Methylethanolammonium dodecanoate N-Methylethanolammonium dodecanedicarboxylate N-Methylethanolammonium dodecenecarboxylate N-Methylethanolammonium cyclohexanecarboxylate N-Methylethanolammonium cyclohexenecarboxylate N-Methylethanolammonium phenoxide N-Methylethanolammonium benzoate N-Methylethanolammonium benezenedicarboxylate •< N-Methylethaαiolammonium benzenetricarboxylate N-Methylethaaiolammonium benzenetetracarboxylate N-Methylethanolammonium chlorobenzoate N-Methylethanolammonium fluorobenzoate N-Methylethanolammonium pentachlorobenzoate N-Methylethanolammonium pentafluorobenzoate N-Methylethanolammonium salicylate N-Methylethanolammonium glycolate N-Methylethanolammonium lactate N-Methylethanolammonium pantothenate N-Methylethanolammonium tartrate N-Methylethanolammonium hydrogen tartrate N-Methylethanolammonium mandelate N-Methylethanolammonium crotonate N-Methylethanolammonium malate N-Methylethanolammonium pyruvate N-Methylethanolammonium succinate N-Methylethanolammonium citrate N-Methylethanolammonium fumarate N-Methylethanolammonium phenylacetate N-Methylethanolammonium oxalate N-Methylethanolammonium bis(trifluoromethylsulphonyl)imide N-Methylethanolammonium carbonate N-Methylethanolammonium hydrogen carbonate N-Methylethanolammonium sulphate N-Methylethanolammonium hydrogen snlphate N-Methylethanolammonium phosphate N-Methylethanolammonium hydrogen phosphate N-Methylethanolammonium dihydrogen phosphate N-Methylethanolammonium methanesulphonate N-Methylethanolammoniumtrifluoromethanesulphonate N-Methylethanolammomum N-Methylethanolammonium hexafluoroplhosphate N-Methylethanolammonium tetrafluoroborate N-Methylethanolammonium trifluoroacetate N-Methylethanolammoniumpentafluoropropanoate N-Methylethanolammonium heptafluorobutanoate N-Methylethanolammoniumphosphoenolpyruvate N-Methylethanolammonium nicotinamide adenine dinucleotide phosphate N-Methylethanolammonium adenosinepkosphate N-Methylethanolammonium adenosine diphosphate N-Methylethanolammonium adenosine triphosphate N-Methylethanolammonium oxyniacate N-Methylethanolammonium nitrate N-Methylethanolammonium nitrite N,N-Di(methoxyethyl)ammonium chloride N,N-Di(methoxyethyl)ammonium bromide N,N-Di(methoxyethyl)ammonium iodide N,N-Di(methoxyethyl)ammonium formate N,N-Di(methoxyethyl)ammonium acetate N,N-Di(methoxyethyl)ammoniumpropanoate N,N-Di(methoxyethyl)ammonium propanedioate N,N-Di(methoxyethyl)ammonium butanoate N,N-Di(methoxyethyl)ammonium butenoate N,N-Di(methoxyethyl)ammonium butanedioate N,N-Di(methoxyethyl)ammonium pentanoate N,N-Di(methoxyethyl)ammonium pentanedioate N,N-Di(methoxyemyl)arnmonium pentenoate N,N-Di(methoxyethyl)ammonium hexanoate N,N-Di(methoxyethyl)ammonium hexenoate N,N-Di(methoxyethyl)ammonium heptanoate N,N-Di(methoxyethyl)ammonium heptanedioate N,N-Di(metiioxyethyl)animoniumheptenoate N,N-Di(methoxyethyl)ammonium octanoate N.N-Di(methoxyethyl)ammonium octanedioate N,N-Di(methoxyethyl)ammonium octenoate N,N-Di(methoxyethyl)ammonium nonanoate N,N-Di(methoxye1iiyl)ammonium nonanedioate N,N-Di(methoxyethyl)ammonium nonenoate N,N-Di(methoxyethyl)ammonium decanoate N,N-Di(methoxyethyl)ammonium decanedioate N,N-Di(methoxyethyl)amjmonium decenoate N,N-Di(methoxyethyl)animoiύum undecanoate N,N-Di(methoxyethyl)ammonium undecanedioate N,N-Di(methoxyethyl)ammonium undecenoate N,N-Di(methoxyethyl)ammonium dodecanoate N,N-Di(metiioxyetliyl)aπunonium dodecanedicarboxylate N,N-Di(methoxyethyl)ammonium dodecenecarboxy^late N,N-Di(me1iιoxyethyl)ammonium cyclohexanecarboxylate cyclohexenecarboxylate N,N-Di(methoxyethyl)ammoniumphenoxide N,N-Di(methoxyethyl)ammonium benzoate N,N-Di(metiioxyethyl)ammonium benezenedicarboxylate N,N-Di(methoxyethyl)ammonium benzenetricarboxylate N,N-Di(metiιoxye1byl)ammonium benzenetetracarboxylate N,N-Di(methoxyethyl)ammonium chlorobenzoate N,N-Di(methoxyethyl)ammonium fluorobenzoate N,N-Di(methoxyethyl)ammonium pentachlorobenzo>ate N,N-Di(methoxyethyl)ammonium pentafluorobenzoate N,N-Di(methoxyethyl)ammonium salicylate N,N-Di(methoxyethyl)ammonium glycolate N,N-Di(methoxyethyl)ammonium lactate N,N-Di(metiioxyethyl)animoniuin pantothenate N,N-Di(methoxyethyl)ammonium tartrate N,N-Di(methoxyethyl)ammonium hydrogen tartrate N,N-Di(methoxyethyl)ammonium mandelate N,N-Di(methoxyethyl)amrnonium crotonate N,N-Di(methoxyethyl)ammonium malate N,N-Di(methoxyethyl)ammoniurn pyruvate N,N-Di(methoxyethyl)arnmonium succinate N,N-Di(methoxyethyl)arnmoniurn citrate N,N-Di(methoxyethyl)arnmonium fumarate N,N-Di(methoxyethyl)ammonium plienylacetate N,N-Di(methoxyethyl)ammonium oxalate N,N-Di(methoxyetiiyl)ammoniιmi bis(Mfluorome11iylsulphonyl)imii€ N,N-Di(methoxyeth.yl)ammonium carbonate N,N-Di(memoxyemyl)ammonium hydrogen carbonate N,N~Di(memoxyemyl)ammonium sulphate N,N-Di(me1hoxyethyl)arnmonium hydrogen sulphate N,N-Di(methoxyethyl)arnrnoniurn phosphate N,N-Di(methoxyethyl)arnmonium hydrogen phosphate N5N-Di(methoxyethyl)ammonium dihydrogen phosphate N,N-Di(me1hoxyethyl)arnmoniurn methanesulphonate N,N-Di(methoxye1hyl)arnmonium trifluoromethanesulphonate N,N-Di(methoxye1hyl)animonium ethylenediarninetetraacetate N5N-Di(rnethoxyethyl)ammoniurn hexafluorophosphate N,N-Di(me1hoxyethyl)arnmonium tetrafluoroborate N,N-Di(me11ioxyethyl)arnmoniurn trifluoroacetate N,N-Di(methoxyethyl)arnmoniurn pentafluoropropanoate N,N-Di(me1hoxyethyl)arnmonium heptafluorobutanoate N,N-Di(me1hoxyethyl)amrnonium phosphoenolpyruvate N,N-Di(methoxyethyl)arnmonium nicotinamide adenine dinucleotide phosphate N5N-Di(me1hoxyethyl)arnmonium adenosinephosphate N,N-Di(methoxyethyl)ammonium adenosine diphosphate N,N-Di(methoxyethyl)ammonium adenosine triphosphate N,N-Di(me1hoxyethyl)ammonium oxyniacate N,N-Di(methoxyethyl)ammonium nitrate N,N-Di(methoxyethyl)ammonium nitrite l-(3-Hydroxypropyl)putrescinium chloride l-(3-Hydroxypropyl)putrescinium bromide l-(3-Hydroxypropyl)putrescinium iodide l-(3-Hydroxypropyl)putrescinium formate l-(3-Hydroxypropyl)putrescinium acetate 1-(3-Hydroxypropyl)putrescinium propanoate 1-(3-Hydroxypropyl)puttescinium propanedioate 1-(3-Hydroxypropyl)putrescinium butanoate 1-(3-Hydroxypropyl)putrescinium butenoate l-(3-Hydroxypropyl)putrescinium butanedioate 1-(3-Hydroxypropyl)putrescinium pentanoate 1-(3-Hydroxypropyl)putrescinium pentanedioate 1-(3-Hydroxypropyl)putrescinium pentenoate 1-(3-Hydroxypropyl)putrescMum hexanoate 1-(3-Hydroxypropyl)putrescinium hexenoate 1-(3-Hydroxypropyl)putrescinium heptanoate ■ 1-(3-Hydroxypropyl)putrescinium heptanedioate 1-(3-Hydroxypropyl)putrescinium heptenoate 1-(3-Hydroxypropyl)putrescinium octanoate 1-(3-Hydroxypropyl)putrescinium octanedioate 1-(3-Hydroxypropyl)putrescinium octenoate 1-(3-Hydroxypropyl)putresciniuni nonanoate 1-(3-Hydroxypropyl)putrescinium nonanedioate 1-(3-Hydroxypropyl)putrescinium nonenoate 1-(3-Hydroxypropyl)putrescinium decanoate l-(3-Hydroxypropyl)putrescinium decanedioate l-(3-Hydroxypropyl)putrescinium decenoate « 1-(3-Hydroxypropyl)putresciniuin undecanoate 1-(3-Hydroxypropyl)putrescinium undecanedioate 1-(3-Hydroxypropyl)putrescinium undecenoate 1-(3-Hydroxypropyl)putrescinium dodecanoate 1-(3-Hydroxypropyl)putrescinium dodecanedicarboxylate 1-(3-Hydroxypropyl)putrescinium dodecenecarboxylate 1-(3-Hydroxypropyl)putrescinium cyclohexanecarboxylate 1-(3-Hydroxypropyl)putrescinium cyclohexenecarboxylate l-(3-Hydroxypropyl)putrescinium phenoxide l-(3-Hydroxypropyl)putrescinium benzoate 1-(3-Hydroxypropyl)putrescinium benezenedicarboxylate 1-(3-Hydroxypropyl)putrescinium benzenetricarboxylate 1-(3-Hydroxypropyl)putrescinium benzenetetracarboxylate 1-(3-Hydroxypropyl)putrescinium chlorobenzoate 1-(3-Hydroxypropyl)putrescinium fluorobenzoate 1-(3-Hydroxypropyl)putrescinium pentachlorobenzoate 1-(3-Hydroxypropyl)putrescinium pentafluorobenzoate 1-(3-Hydroxypropyl)putrescinium salicylate 1-(3-Hydroxypropyl)putrescinium glycolate l-(3-Hydroxypropyl)putrescinium lactate 1-(3-Hydroxypropyl)putrescinium pantothenate l-(3-Hydroxypropyl)putrescinium tartrate l-(3-Hydroxypropyl)putrescinium hydrogen tartrate 1-(3-Hydroxypropyl)putrescinium mandelate 1-(3-Hydroxypropyl)putreschiiurn crotonate l-(3-Hydroxypropyl)putrescinium malate l-(3-Hydroxypropyl)putrescinium pyruvate 1-(3-Hydroxypropyl)putresciniuni succinate l-(3-Hydroxypropyl)putrescinium citrate 1-(3-Hydroxypropyl)putrescinium fumarate 1-(3-Hydroxypropyl)putrescinium phenylacetate l-(3-Hydroxypropyl)putrescinium oxalate 1-(3-Hydroxypropyl)putrescinium bis(trifluoromethylsulphonyl)imide 1-(3-Hydroxyρropyl)putrescinium methanesulphonate 1-(3-Hydroxypropyl)putrescinium trifluoromethanesulphonate 1-(3-Hydroxypropyl)putrescinium hexafluorophosphate 1-(3-Hydroxypropyl)putrescinium tetrafluoroborate 1-(3-Hydroxypropyl)putrescinium trifluoroacetate 1-(3-Hydroxypropyl)putrescinium pentafluoropropanoate 1-(3-Hydroxypropyl)putrescinium heptafluorobutanoate 1-(3-Hydroxypropyl)putrescinium phosphoenolpyruvate l-(3-Hydroxypropyl)putresciniumnicotinamide adenine dinucleotide phosphate l-(3-Hydroxypropyl)putrescinium adenosinephosphate l-(3-Hydroxypropyl)putrescinium adenosine diphosphate l-(3-Hydroxypropyl)putrescinium adenosine triphosphate l-(3-Hydroxypropyl)putrescinium carbonate l-(3-Hydroxypropyl)putrescinium hydrogen carbonate l-(3-Hydroxypropyl)putrescinium sulphate l-(3-Hydroxypropyl)putrescinium hydrogen sulphate 1-(3-Hydroxypropyl)putrescinium phosphate 1-(3-Hydroxypropyl)putrescinium hydrogen phosphate 1-(3-Hydroxypropyl)putrescinium dihydrogen phosphate 1-(3-Hydroxypropyl)putrescinium nitrate \ 1-(3-Hydroxypropyl)putrescinium nitrite

hi one class of compounds, the invention includes the proviso that the ionic liquid is not ethylammoniurn nitrate or diethanolammonium chloride, hi a further class of compounds, the invention includes the proviso that the ionic liquid is not a N- protonated pyridimium or pyrrolidinium salt.

According to a further aspect, the present invention provides a process for the preparation of an ionic liquid according to the invention, the process comprising the steps of: i.) providing an organic primary, secondary or tertiary amine; and ii.) neutralising the compound in (i) with an acid.

The process according to the invention may comprise the steps of: i.) providing a nitrogen-containing compound of the formula (H) NRR'R" (ET) in which R, R' and R' ' have the meaning defined herein; and ii.) neutralising the compound in (i) with an acid. The process of the present invention provides an economical route to the manufacture of ionic liquids since the process involves only a single step and uses starting materials that are generally readily available.

During the process of the invention, the nitrogen atom of the primary, secondary or tertiary amine is protonated to provide a protonated ammonium ion.

Preferably, the acid includes an anion as defined herein.

Preferably the acid anion comprises a halogenated inorganic anion, nitrate, sulphate, carbonate, sulphonate or carboxylate.

The invention also encompasses compounds of formula (IT) and their use in the preparation of one or more ionic liquids.

The invention further provides the use of a cation as defined in the ionic liquids of the present invention in a solvent for enzyme-catalysed reactions. Further provided is the use of an ionic liquid according to the present invention as a solvent for enzyme- catalysed reactions.

The use of ionic liquids in certain biological and/or chemical reactions has several advantages over traditional aqueous solutions. Ionic liquids have an ability to dissolve a wide range of inorganic, organic, polymeric and biological materials, often to a very high concentration. They have a wide liquid range, allowing both high and low temperature processes to be carried out in the same solvent. They do not elicit solvolysis phenomena and most stabilise short-lived reactive intermediates. There are no pH effects in the solvents and there is practically zero vapour pressure over much of the liquid range. Ionic liquids also exhibit excellent electrical and thermal conductivity whilst being non-flammable, recyclable and generally of low toxicity. The invention further provides the use of an ionic liquid, or of a cation as defined in an ionic liquid, according to the present invention in a solvent for organic synthesis, matrixes in matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry, solvent extraction (e.g to remove desired components from an immiscible liquid or solid) or gas chromatography, catalysis, liquefaction, nuclear fuel reprocessing, fuel cells, electrochemical applications, pervaporation, drug delivery, lubrication, hydraulic fluids, adhesives, sensors, biocides and chromatographic media.

Further provided is a method for carrying out an enzyme-catalysed reaction comprising i.) providing a liquid reaction medium which comprises an ionic liquid according to the present invention; ii.) providing in the liquid reaction medium an enzyme and a substrate for the enzyme; and iii.) allowing reaction of the substrate to occur.

Further provided is a method for the synthesis of one or more organic compounds, the method comprising carrying out an organic synthesis reaction in an ionic liquid according to the present invention.

Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", means "including but not limited to", and is not intended to (and does not) exclude other moieties, additives, components, integers or steps.

Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires, hi particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

The invention will now be described by way of the following, non-limiting examples:

MATERIALS AND METHODS

Preparation of ammonium-based ionic liquids bearing one or more ammoniacal protons

The requisite stoichiometric equivalents of the parent amine and complementary acid were dissolved independently in water, methanol or ethanol to give solutions of equal concentrations. Equal volumes of these two solutions were mixed together in a flask, with stirring and cooling, at a rate sufficiently slow as to prevent the temperature of the reaction from exceeding 60°C. When neutralization was complete, the excess solvent was removed in vacuo, at temperatures not exceeding 60°C. The product was then freeze-dried, analysed and stored in a desiccated condition.

Preparation ofN,N-dimethylethanolammonium glycolate

Alcoholic solutions of N,N-dimethylethanolamine (100.0OmL, 2.000M concentration) and glycolic acid (lOO.OOmL, 2.000M concentration) were gradually mixed together in a 50OmL round-bottomed flask, with external cooling and stirring. After completion of the neutralisation reaction, the cold alcoholic solution was filtered, transferred to a clean flask and the solvent was removed on a rotary evaporator. The reaction product was frozen in liquid nitrogen and lyophilised in vacuo, being gradually permitted to rise to room temperature, to yield 32.85g (99%) of a pale yellow liquid, water content <100ppm by Karl Fischer titration, purity > 99.9% by ion chromatography. The product was analysed by elemental analysis and by infra-red, ultra-violet/visible and nuclear magnetic resonance spectroscopy and was stored over anhydrous calcium chloride in a vacuum desiccator. FT-IR (cm"1): 1591, 1076, 1358, 687, 993, 1468, 909, 1255, 881, 1154, 1171, 3240, 2870, 2484, 1745 UV/vis λmax (nm): 234 ENτ (Reichardt): 0.912 Density (g cm'3): 1.146

Preparation ofN-butyldiethanolammonium bis(trifluoromethylsulphonyl)imide

To an alcoholic solution of N-butyldiethanolamine (100.0OmL, 2.000M concentration) in a 50OmL round-bottomed flask was gradually added 56.232g bis(trifluoromethylsulplionyl)imide, with vigorous stirring and external cooling, over a period of 30 minutes. After completion of the reaction, the solution was filtered and the solvent was removed in vacuo. The product was dried as above to yield 87.2g (98%) of a pale yellow liquid, water content <100ppm by Karl Fischer titration, purity >98% by ion chromatography . The product was analysed and stored as previously described.

FT-IR (cm^lOSl, 1132, 1181, 1347, 741, 791, 764, 880, 960, 1461, 2967, 3523, 2941, 2880, 3138, 1632 UV/vis λmax (nm): 304 ENτ (Reichardt): 0.994 Density (g cm"3): 1.343

APPLICATIONS

Enzyme-catalysed reaction in N,N-dimethylethanolammonium glycolate

Alcohol dehydrogenase: Methanol (50μL) was dissolved in the ionic liquid (6mL) with a net water content of <100ppm by Karl Fischer titration. Nicotinamide adenine dinucleotide (lOOmg) was added along with lyophilised Saccharomyces cerevisiae alcohol dehydrogenase (lmg). The reaction vessel was sealed and incubated at 300C for 24 hours, with vigorous shaking being maintained throughout. Samples (ImL) were extracted at time points of 0, 2, 4, 8, 12 and 24 hours and were analysed by means of the chromotropic acid assay. The absorbance of the analyte samples at 560nm was measured against enzyme-free standards and correlated with the concentration of formaldehyde by comparison with a standard curve. The accumulation of formaldehyde was observed up to an equilibrium concentration of 20+/-2mM.

Biodegradation ofN,N-dimethylethanolammonium glycolate

N,N-Dimethylethanolammonium glycolate (5mM) was used as sole nitrogen and carbon source for the selective enrichment of a mixed community of soil micro¬ organisms collected from waste ground. Individual organisms were isolated from the mixed culture and were screened for their capability to metabolise the ionic liquid at varying concentrations in aqueous phosphate buffer. Experiments were performed in Erlenmeyer flasks at 300C, with shaking at l lOrpm. Degradation was monitored using ion chromatography. 5mM Ionic liquid was readily degraded (>98% removal) within 48 hours, the final nitrogenous metabolite being ammonia.