Indian Patents. 269875:A PROCESS FOR THE PREPARATION OF AN IONIC LIQUID

Title of Invention	A PROCESS FOR THE PREPARATION OF AN IONIC LIQUID
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.

Full Text	PCT/GB2005/001364 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, pyrunidinium 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 chromatograpbic 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. WO 2005/097731 PCT/GB2005/001364 The inventors have provided further ionic liquids. According to the present invention there is provided an ionic liquid comprising an aunion 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 in 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 lias 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) NHRR'R" (I) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), thiol, alkythio, sulphonyl, tbiocyanate, 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 di-alkylamino or alkyamido); and R' and R", which may be the same or different, each represent H or R; WO 2005/097731 PCT/GB2005/001364 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 100°C, for example, below 25°C and optionally below 20°C. The boiling point of the ionic liquid may be at least 200°C. It may be above 500°C 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 than 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 30°C 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, cycloalkenyl 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, 6,1, 8 carbon atoois 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, cyclobotyl, cyclopentyl or cyclohexyl. 3 WO 2005/097731 PCT/GB2005/001364 The alkyl group may be substituted with one or more halogen atoms, ha one class of compounds the halogen is fluorine, in another it is chlorine, in a third it is a combination of fluorine and chlorine. "Allcoxy" 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, rnembered hydrocarbon, ring, including cycloalkyl or aryl. "Aryl" means an aromatic, for example, 6-10 membered hydrocarbon containing one, e.g. 6C-10C, 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, t) or S, and containing one ring which is optionally fused to one or more saturated or unsaturated rings. 4 WO 2005/097731 PCT/GB2005/001364 "Heterocyclyl" means, for example, a 3-10 membered ring system containing one or more heteroatorns selected from N, 0 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 rmg-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, ditliiane, dithiazine, dithiazole, ditbiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isooxazole, isothiazole, morphohne, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazne, phthalazine, piperazine, piperidine, pteridine, purine, putrescine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine5 pyridazine, pyridine. pyrimidine, pyrrolidine, pyrrole, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, tbiazine, thiazole, tbiomorpholine, thianaphthalene, thiopyran, triazine, 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 5 WO 2005/097731 PCT/GB2005/001364 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. In 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. In 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 GH3, 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: 6 WO 2005/097731 PCT/GB2005/001364 Ethylammoniurn nitrate Tributylammonium-acetate Tributylammoniuma- cyano-4-hydroxycinnamate Tributylammonium sinapate Dimethylammonium pyridine-2-carboxylate Tributylammonimii pyridine-2-carboxylate Tributylammonium 3 -hydroxypyridine-2-carboxylate Triethylammonium pyidine-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. In 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. 7 WO 2005/0197731 PCT/GB2005/001364 Preferably, the cation is an ethanolammonium, N-(a.UvOxyetliyl)ammomiim, N- memylethanolararaonium, N,N-dim ethyl ethanolammonium, diethanolammonium, N-alkyldiethanolammonium (e.g butyldiethanolammonium), N,N- di(alkoxyalkyl)atrmiomum (e.g di(metlioxyethyl)ammoninm) or triethanolammonium ion. More preferably the cation is a methylethanolammonium, N,N dimethyl ethanolajaunoniiun, N, N- di(metlaoxyetlayl)ammonium) or butyldiemanolarnmonium ion. In another class of compounds, R is an arninoalkyl group having 2 to 8 C atoms, for example, 2, 3, 4, 5, 6, 7 or 8 C atoms. The arninoalkyl may be a di or tri-arrrmoalkyl group. In some compounds, PL is putrescine, piperidine, or tropine. Preferred cations include an. etiianolarnrnonium, diethanolammonium, N-butyldiethanolarjomon ium, N-mem)4e1iianolarnmonivirQ, di(methoxyethyl)arnrnonium, N,N--dixaethylethaiiolariii:aorrium, putrescinium, l-(3- hydroxypropyl)putrescrni"um, or N-(3-hydroxypropyl)-N- methylcyclohexylamraonium ion. Preferably still, .. cations include N-butyldiemanolammoniurn, N-methylethanolammonium, di(methoxyethyl)ajxmionium3 N5N~dimeiiiylethanolamraonium, putrescinium, l-(3- hydroxypropyl)putrescinium, or ¦ N-(3-hydroxypropyl)-N- methylcyclohexylamrnonium 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 .d-esired temperature. 8 WO 2005/097731 PCT/GB2005/001364 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, aUcoxy, alkeneoxy, aryl, arylalkyl, aryloxy, amino, aminoalkyl, tbio, 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(trifluoromethylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, dihydrogen phosphate, rnetaphosphate, 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: EthanolamnLonium formate 9 WO 2005/097731 PCT/GB2005/001364 Ethanolamraonium acetate Ethanolarnmonium propanoate Ethanolammoniuin ptopanedioate Ethanolammonium butanoate Ethanolamronium batenoate Ethanolammonium butanedioate Ethanolammonium pentanoate EtJianolaxnmonium pentanedio ate Ethanolaminoniuni pentenoate Ethanolainmonium hexanoate Ethanolammonium hexanedioate EtJianohummonium hexenoate Ethanolammonium heptanoate Ethanolammonium heptanedioate Etlaanolammonium heptenoate EtJianolammonium octanoate Etlianolammonium octanedioate Ethanolammonium octenoate Ethanolarmnonium nonanoate Etlianolanunonium nonanedioate Etlianolammonium n(3nenoate Ethanolammonium decanoate Etlianolammonium decanedioate Etlianolammonium decenoate Etlianolammonium undecanoate Ethanolgimmonium tmdecanedioate EthanolaLtnmonium uiidecenoate EttianolatDomonium dodecanoate Ethanolammonium dodecanedicarboxylate Etlianolainnionium dodecenecarbo>:ylate Ettianolainiiionium cyclohexanecarboxylate 10 WO 2005/097731 PCT/GB2005/001364 Ethanolammordimi cyclohexenecarboxylate Ethanolammonium phenoxide Emanolarnrnonium benzoate Ethanolammoniura benezenedicarboxylate Ethanolannnonium benzenetricarboxylate Ethanolammonium benzenetetracarboxylate Emanolammonium chlorobenzoate Ethanolammoniirm fluorobenzoate Ethanolammoniiim pentachlorobenzoate Ethanolammoriium pentafluorobenzoate Ethanolammoniitm salicylate Ethanolammonium glycolate Ethanolammonium lactate-Ethanolammonium pantothenate Ethanolammonium tartrate Ethanolammonium hydrogen tartrate Ethanolammonium mandelate Ethanolammonium crotonate Ethanolammordum malate Ethanolammonium pyruvate Ethanolammonium succinate Ethanolammonium citrate Ethanolammonium fumarate Ethanolammonium phenylacetate Ethanolammonium oxalate Emanolamnioniuinbis(trifluoromemylsulphonyl)imide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate 11 WO 2005/097731 PCT/GB2005/001364 Ethanolarnmonium hydrogen phosphate Ethanolammonium dihydrogen phospiiate EthaBolammonium methanesulfonaie Ethanolammonium trifluoromethanesiolphonate Etlianolammonium ethylenediaminetetraacetate Ethanolammonium hexafluorophosphate Ethanolammonium tetrafluoroborate Ethanolammonium trifluoroacetate Etlianolammonium pentafluoropropan.oate Ethanolammonium heptafluorobutcinoate Emanolammoniumphosphoenolpyruvate Ethanolammonium nicotinamide adenine dinucleotide phosphate Ethanolammonium adenosinephosphate Etlianolammonium adenosine diphosphate Ethanolammonium adenosine triphosphate Etlianolammonium oxyniacate Ethanolammonium nitrate Ethanobammonium nitrite Diethaaolammonium 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 12 WO 2005/097731 PCT/GB2005/001364 Diemanolammonrum hexanedioate Diethanolammonium hexenoate Diethanolaminonl"um heptanoate Diethanolammonium heptanedioate Diemanolammonrum heptenoate Diethanolammonixam octanoate Diethanolammonium octanedioate Diethanolammonium octenoate Diethanolammonium nonanoate Diethanolammonium nonanedioate Diethanolammonium nonenoate Diethanolammonium decanoate Diethanolammonium decanedioate Diethanolammonium decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate Diethanolammonium dodecanedicarboxylate Diethanolammonium dodecenecarboxylate Diethanolammonium cyclohexanecarboxylate Diethanolammom'umcyclohexenecarboxylate Diethanolammom'um phenoxide Diethanolammonium benzoate Diethanolammonium benezenedicarboxylate Diethanolammonium benzenetricarboxylate Dietbanolammonium benzenetetracarboxylate Diethanolammonium chlorobenzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate 13 WO 2005/097731 PCT/GB2005/001364 Diethanol ammonium salicylate DiethaD-olammonium glycolate Diethan-olammonium lactate Diethanolammonium pantothenate DiethanolammoniuD3 tartrate Diethanolammonium hydrogen tartrate Diethanolammonium mandelate Diethanolammonium crotonate Diethanolammonium rnalate Diethanolammonium pyruvate Diethanolammonium succinate Diethanolammonium citrate Diethanolammoniuni fumarate Diethanolammonium phenylacetate Diethanolammonium oxalate Diethanolammonium bis(trifluoromethylsulphonyl)imide Diethanolammonium carbonate Diethanolammonium hydrogen carbonate Diethanolammoniuin phosphate Diethanolammonium hydrogen phosphate Diethanolammoniuin dihydrogen phosphate Diethanolamrnoniurainethanesulphonate Diethanolammoniuin trifluoromemanesulphonate Diethanolammoniuin ethylenediaminetetraacetate Diethanolammonium hexafluorophosphate Diethanolammoniuin tetrafluoroborate Dietlianolammonium trifluoro acetate Diethanolammonium pentafluoropropanoate Diemanolammoniurn heptafluoro butanoate Diethanolammonium phosphoenolpynivate Diethanolammonium nicotinamide adenine dinucleotide phosphate 14 WO 2005/097731 PCT/GB2005/001364 Diemanolammonrum adenosinephosphate Diemanolamrnoni-um adenosine diphosphate Diemanolanimonrum adenosine triphosphate Diethanolanimonixim oxyniacate Diethanolanunoni"um nitrate Diethanolammonrum nitrite N-Butyldiethanolaxomonium chloride N-Butyldiethanolammonium bromide N-Butyldiethanolainmonium iodide N-Butyldiethanolainmonium formate N-Butyldiethanolammonium acetate N-Butyldietlianolammonium propanoate N-Butyldiethanolammonium propanedioate N-But3ddiethanolammonium butanoate N-Butyldiethanolammonium butenoate N-Butyldiethanolammonium butanedioate N-Butyldiethanolarnmonium pentanoate N-Butyldiethanolarnmonium pentanedioate N-Butyldiethanolaxnmonium pentenoate N-Butyldiethanolammonium hexanoate N-Butyldiethanolarnmonium hexenoate N-Butyldiethanolarnmonium heptanoate N-Butjddiethanolammonium heptanedioate N-Butyldiethanolammonium heptenoate N-ButyldiethanolammoniuE4 octanoate N-Butyldiethanolammonium octanedioate N-Butyldiethanolammonium octenoate N-Butyldiethanolammomum nonanoate N-Butyldiethanolammonium nonanedioate N-Butyldiethanolammonium nonenoate N-Butyldiethanolammonium decanoate 15 WO 2005/D97731 PCT/GB2005/001364 N-Butyldiethanolauimonium decanedioate N-Buty] diethanolamniooium decenoate N-Buty] diemanolammonium undec anoate N-Butyldiemanolammorriumundecanedioate N-Butyl di ethanolarnmonium undecenoate N-Buty]diethanolainmonium dodec;anoate N-Butyldiethanolainmoniurn dodecanedicarboxylate N-Buty] diethanolanimonium dodecenecarboxylate N-Buty] diethanolammonium cyclohexanecarboxylate N-Buty] di ethanolammoniurn cyclohexenecarboxylate N-Buty] diethanolammonium phenoxide N-Butyldiethanolammonium benzoate N-Buty] diethanolatDmonium benezenedicarboxylate N-Buty] diethanolaaunonium benzenetricarboxylate N-Buty] diethanolammonium benzenetetracarboxyiate N-Buty] diethanolammonium chlorobenzoate N-Buty] diethanolammonium fluorobenzoate N-Buty] diethanolammonium pentachlorobenzoate N-Buty] diethanolammonium pentafhiorobenzoate N-Buty] diethanolammonium salicylate N-Buty] diethanolammonium glycolate N-Buty] diethanolammonium lactate N-Butyldiethanolammonium pantothenate N-Butyldiethanolammonium tartrate N-Buty] diethanolammonium hydrogen tartrate N-Butyldiethanolammonium mandslate N-Buty] diethanolammonium crotonate N-Butyldiethanolammonium malate N-Buty] diethanolammoni'um pyruvate N-Butyldiethanolammonium succinate N-Buty] diethanolammonium citrate 16 WO 2005/097731 PCT/GB2005/001364 N-Butydiemanolammonium fumarate N-Butydiethanolammonium phenylacetate N-Butydiethanolanrmonium oxalate N-Butydiethanolammoniirnibis(trifluoromethylsiilphonyl)iniide N-Butydiethanolammoniurn carbonate N-Butydiethanolammoniiun hydrogen carbonate N-Buiyldiethanolammonirun sulphate N-Biityldiemanolammomum hydrogen sulphate N-Butyldiethanolammonium phosphate N-Butyldiethanolammonium hydrogen phosphate N-Butyldiethanolammonium dihydrogen phosphate N-Butyldiethanolammonium methanesulphonate N-Butyldiemanolammoniumtrifluoromethanesulphonate N-Butyldemanolammomuniemylenediaminetetraacetate N-Butyldiethanolammonium hexafluorophosphate N-Butyldiethanolammonium tetrafluoroborate N-Butyldiethanolammonium trifluoroacetate N-Butyldiethanolammonium pentafluoropropanoate N-Butyldiethanolammonium heptafluorobutanoate N-Butyldiethanolammonium phosphoenolpyruvate 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 N5N-Dimethylethanolammonium formate N,N-Dhnethylethanolammonium acetate 17 WO 2005/097731 PCT/GB2005/001364 N,N-Dinaethylethano]ammonium propanoate NN-DImethylethano] ammonium propanedioate N,N-Diiiaethylethano]ainriioniiimbutanoate N,N-Dimethylethano] ammonium butenoate N,N-Diiiiethylethanolammonium butaoedioate N,N-Dimethylethanolammoiiiumpentanoate N,N-DmiethylethanolammoniumpeDtanedioate N,N-DmiethylethanolammoniumpeQtenoate N,N-Dimethylethanolaramonium bexanoate N,N-Dtmetbylethanolammomumbexenoate N5N-Dimethylethan.olammonium beptanoate N,N-D imethylethanolammonium heptanedioate N,N-Dimethylethanolammoniumheptenoate N,N-DiDaethylethaiiolammonium octanoate N,N -D imethy] ethanolammonium octanedioate N,N-Dtmethylethanolammonium octenoate N,N-Diiiaethylethanolammoniumnonanoate N,N-Dimethylethano lammonium nonauedioate IN ,N-D imetbylethanolammonium nonenoate N,N-Dimethylethano lammonium decanoate N ,N-DirQethylethanolammonium decanedioate •. N,N-Dkaethylethanolammoniuin decenoate N,N-Diraethyletha]aolammoniumui]Ldecanoate N,N-Dimethyletlianolammoniuni undecanedioate N,N-DirQethylethanolammoniumurLdecenoate N,N-Dimethylethaaolammonium dodecanoate N,N-Dixmetbylethaaolammoniumdodecanedicarboxylate N,N-DkmethylethaDiolammoniumdodecenecarboxylate N,N-Dkaethylethanolamraonium cyclohexanecaxboxylate N,N-Dknethyletb.anolammonium cyclohexenecaxboxylate N,N-Dimemylethanolammonitimphenoxide 18 WO 2005/097731 PCT/GB2005/001364 N,N-Dimethylethanolammonium benzoate N,N-Dimefhylethanolammoiiiumbenezenedicarboxylate N,N-Dim.ethylethanolammoniximbenzenetricarboxylate N,N-Dimetiiylethaaolariimoniiimbenzeiietetracarboxy"late N,N-Dimethylethanolammonium chlorobenzoate N,N-Dimethylethanolammoniuiafluoroberizoate NjN-Dimethylethanolammoniumpentachlorobenzoate N,N-DimetiiylethaiLolaminoniurapentafluoroberizoate N,N-Dimethylethanolammonium salicylate N,,N-Dimethylethanolaminoiiium glycolate N,N-Dimethylethanolammonium lactate N,N-Dimethylethanolammoniutn pantothenate N,N-Dimethylethanolammoniuin tartrate N,N-Dimethylethanolammonium hydrogen tartrate N,N-Dimethylethanolarrirnordiim mandelate N,N-Dime1iiylethaiiolaminoniiim crotonate N,N-Dime1hylethanolammomurii malate N,N-Dimethylethanolammoniiim pyruvate N,N-Dimethylethanolammonium succinate N,N-Dimethylethanolanrrnonium citrate NiN-Dimethylethanolammonium fumarate N,N-DimethylethanolaminoiuumpherLylacetate N5N-Dimethylethanolammonium oxalate N,N-Dimethylethanolainmoiumnbis(1xifluoromethylsulphonyl)iirJide N,N-Dimethylethanolammoiuum carbonate N,N-Dimethylethanola.m m onium hydrogen carbonate N,N-Dirnethylethanolammonium sulphate N,N-Dirnethylethanolarnmoniurn hydrogen sulphate N,N-Dirnethylethanolamrnoniurn phosphate N5N-Dimethylethanolammonium hydrogen phosphate N5N-Dirnethylethanolarnmonium dihydrogen phosphate 19 WO 2005/097731 PCT/GB2005/001364 N,N-Dimethylethanolammonium msthanesulphonate N,N-Dinietihylethanolaininoiiiiiin trifluoromethanesulphonate N,N-Dimethylethanolammonium ethylenediaminetetraacetate N,N-Din:iethylethanolammoiiiiimhe:xafluorophosphate N,N-DirriemylethanolammoruumtetTaimoroborate N,N-Dimethylethanolammoniuiii trifluoroacetate N,N-Din:iethylethanolammoniiimpentafluoropropanoate N,N-Ditiiethylethanolammoniiimheptafluorobutanoate N,N-Dirriethylethanolaiiimordiimphosphoenolpyruvate N,N-Dirriemylethanolammonium nicotinamide adenine dinucleotide phosphate N,N-Dimethylethanolammonium adenosiaephosphate NjN-Dimethylethanolammonium adenosme diphosphate N,N-Dimethylethanolainmonium adenosine triphosphate N,N-Dimethylethan.olammoniumo5syniacate N,N-DirrLethylethanolammonium nitrate N,N-Din:Lethylethanolammoniiim nitrite N-Methylethanolammonium bromide N-Methyletb.anolarnmonium iodide N-Methylethanolarninoriium formate N-Methyleth.anolammonium acetate N-Methylethanolammoniumpropanoate N-MethyLethanolammoniumpropanedioate N-Methylethanolammoniumbutanoate N-MethyLethanolammonium butenoate N-Metbylethanolarnmoniumbutanedioate N-Methy!ethanolarimx>murnpentanoate N-Methyl ethanolammonium pentanedioate N-Methylethanolarnmoniumpentenoate N-Methyl ethanolaromoniumhexanc'ate N-Methyl ethanolammoniumhexenoate N-Methyiethanolacomoniumheptanoate 20 WO 2005/097731 PCT/GB2005/001364 N-Methylethanolammonitim heptanedioate N-Methylethsnolammoniuru heptenoate N-Methylethanolammonium octanoate N-Methylethanolammonium octanedioate N-Methyletlianolammonium octenoate N-Methylethanolammoniirtn nonanoate N-Methylethanolammonium nonanedioate N-Methylethanolaimnonium nonenoate N-Metliylethanolammonium decanoate N-Methylethanolammonium decanedioate N-Methylethanolammomumdecenoate N-Methylethanolammom'iun undecanoate N-Methylethanolammomum uadecanedioate N-Methylethanolammom'um undecenoate N-Methylethanolammonium dodecanoate N-Methylethaxiolammonium dodecanedicarboxylate N-Methylethanolammonium dodecenecarboxylate N-Methylethanolammonium cyclohexanecarboxylate N-Methylethanolammonium cyclohexenecarboxylate N-Methylethaolammonium phenoxide N-Methylethanolammonium benzoate N-Methylethaxiolammonium benezenedicarboxylate N-Methylethaolammoniumbenzenetricarboxylate N-Methylethaxiolammoniumbenzenetetracarboxylate N-Methylethaaiolammonium chlorobenzoate N-Methylethaxiolammonium fluorobenzoate N-Methylethaxiolammoniumpentachlorobenzoate N-Methylethanolammonium pentafluorobenzoate N-Methylethanolammomum salicylate N-Methylethanolammonium glycolate N-Methylethanolammonium lactate 21 WO 2005/097731 PCT/GB2005/001364 N-Methylethanolammomiimpantothenate N-Methyletihanolammonium tartrate N-Methylethanolammoniurn hydrogen tartrate N-Methylethanolarmaoniummandelaie N-Methylethanolammonium crotonate N-Methylethanolammonium malate N-Methylethanolammonium pyruvate N-Methylethanolammonium succinate N-Methylethanolammonium citrate N-Methylethanolammonium fumarate N-Methylethanolammonium phenylacetate N-Methy lethanolammonium oxalate N-Methy lethanolammonium bis(triihioromethylsulphony l)imide N-M ethylethanolammonium carboD ate N-Methylethanolammonium hydrogen carbonate N-Methylethanolammonium sulphate N-Methylethanolammonium hydrogen sulphate N-Methylethanolammonium phosphate N-Methylethanolammoniurn hydrogen phiosphate N-Methylethanolammonium dihydrogen phosphate N-Methylethanolammonium methanesulphonate N-Metiiylethanolarnmoniumtrifluoromethanesulphonate N-Methylethanolammomumethylenedicrirriinetetraacetate N-Metihylethanolammonium hexafluoropliosphate • N-Methylethanolammonium tetrafluoroborate N-Methylethanolammonium trifluoroacetate N-Methylethanolammonium pentafluoropropanoate N-Methylethanolammonium heptafluoroh>utanoate N-Methylethanolammonium phosphoenolpyruvate N-Methylethanolammonium nicotinamide adenine dinucleotide phosphate N-Methylethanolammonium adenosinepkosphate 22 WO 2005/097731 PCT/GB2005/001364 N-Memylethanolammonium adenosine diphosphate N-Memylethanolammoiuum adenosine triphosph.a.te 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(methox)rethyl)ammonium propanoate N,N-Di(methoxyethyl)ammoniumpropanedioate N,N-Di(mefhoxyethyl)ammonium butanoate N,N-Di(methoxyethyl)ammonium butenoate N,N-Di(methoxyethyl)ammoniumbutanedioate N,N-Di(methoxyethyl)ammonium pentanoate N,N-Di(methoxyethyl)ammoniumpentanedioate N,N-Di(methoxyethyl)ammoniumpentenoate N,N-Di(methoxyethyl)ammonium hexanoate N,N-Di(niethoxyethyl)ammonium hexenoate N,N-Di(methoxyethyl)arnmonium heptanoate N,N-Di(methoxyethyl)ammoniiimheptanedioate N,N-Di(methoxyethyl)ammoniumheptenoate N,N-Di(methoxyethyl)ammonium octanoate ' N,N-Di(methoxyethyl)ammoniumoctanedioate N,N-Di(methoxyethyl)ammonium octenoate N,N-Di(methoxyethyl)ammonium nonanoate N,N-Di(methoxyethyl)ammonium nonanedioate N,N-Di(methoxyethyl)ammonium nonenoate N,N-Di(methoxyethyl)amm onium decanoate N,N-Di(methoxyethyl)ammonium decanedioate 23 WO 2005/097731 PCT/GB2005/001364 N,N-Di(methoxyethyl)ammoniiiindece.Qoate N,N-Di(me1iioxyethyl)aminoniumui:idecaiioate N,N-Di(methoxyethy] )airunoniuin undecanedioate N,N-Di(metboxyetliyl)airimoniumuiidecenoate N,N-Di(methoxyethyl)ammoniumdodecanoate N,N-Di(methoxyethyl)ammonium dodecanedicarboxylate N,N-Di(methoxyethyl )arnmoniurn dodecenecarboxylate N_,N-Di(methoxye1iiyl)aminoniuin c}rclohexanecarboxylate N,N-Di(methoxyethyl)ammoniumcyclohexenecarboxylate N,N-Di(methoxyeth.yl)ammoniiimphenoxide N,N-Di(rnetboxyetl:iyl)ammoniumbenzoate N,N-Di(inetbox3rettLyl)axaiiioniuinbenezenedicarbo?sylate N,N-Di(me1iioxye1hyl)ammoniuinben2,enetricarboxylate N,N-Di(methoxyeth.yl)ammoniuinbenz,enetetracaxboxylate N,N-Di(inethoxyethyl)ammonium.chlorobenzoate N,N-Di(me1iioxyethyl)aminoniuinfluoroben2;oate N,N-Di(inethoxyethyl)amniordiimpe;ntachlorobenz(>ate N,N-Di(inetboxyethyl)ainmoriiuinpeiitafluorobenzoate "NTjN-Di(inetioxyeijLyl)timinoriiiiinsalicylate N,N-Di(methoxyethyl)ammoniiraig]ycolate N,N-Di(methoxyettiyl)ammoniiun lactate N,N-Di(methoxyethyl)ammoniirai pantothenate N,N-Di(methoxyethyl)aminoriiuintartrate N,N-Di(inethoxyethyl)ammonium hydrogen tartrate ¦ N,N-Di(methoxyethyl)ammonium. m andelate N,N-Di(inethoxyethyl)ammoniuracrotonate N5N-Di(inethoxyethyl)ammoni"Lim. m alate N,N-Di(inethoxyet]:iyl)ammoniumpyruvate N,N-Di(inethoxyettLyl)ammoriiiiin succinate N,N-Di(inethoxyethyl)ammoniton citrate N,N-Di(inethoxyethyl)ctrrxmoniiirnfbirn;jrate 24 WO 2005/097731 PCT/GB2005/001364 N,N-Di(methoxyethyl)ammoniumphenylacetate N,N-Di(methoxyethyl)ammonium oxalate N,N-Di(methoxyet]iyl)aiinnordiimbis(trifluoromethylsulphonyl)iiQiie N,N-Di(methoxyethyl)ammomum carbonate N,N-Di(methoxyethyl)ammonium hydrogen carbonate N,N-Di(metiioxyethyl)arnnioniurn sulphate N,N-Di(methoxyethyl)arnmomum hydrogen sulphate N,N-Di(methoxyethyl)ammonium phosphate N,N-Di(methoxyethyl)arnrrionium hydrogen phosphate N5N-Di(methoxyethyl)arnmoniurn dihydrogen phosphate N,N-Di(methoxyethyl)ammoniurnrjQethanesulphonate N,N-Di(methoxye1iiyl)arrimoriiurntriiluoromethanesulphonate N,N-Di(methoxyethyl)ammornumethylenediaminetetraacetate N,N-Di(methoxyethyl)arnmoniumhexafluorophosphate N,N-Di(methoxye1iiyl)arnrnoniumtetrafluoroborate N,N-Di(methoxyethyl)arrrmoniumtrifluoroacetate N3N-Di(me1iioxye1iyl)aminoriiurnpentafluoropropanoate N,N-Di(methoxyethyl)arnrnoniumheptafluorobutanoate N,N-Di(methoxyethyl)amrnoniumphosphoenolpyruvate N3N-Di(methoxyethyl)arnmonium nicotinamide adenine dinucleotide phosphate N,N-Di(methoxyethyl)aminoiiiurQ adenosinephosphate N,N-Di(me1iioxyethyl)arnrnonium adenosine diphosphate N,N-Di(methoxyethyl)arnmoniurn adenosine triphosphate N,N-Di(methoxyethyl)arnmoniurn oxyniacate N,N-Di(me1iioxye1liyl)arnmoriium nitrate N,N-Di(methoxyethyl)airLmqnium nitrite l-(3-Hydrox5'propyl)putrescrnium chloride l-(3-Hydroxypropyl)putresciruum bromide l-(3-Hydroxypropyl)putrescinium iodide l-(3-Hydroxypropyl)putrescinium formate l-(3-Hydroxypropyl)putrescinium acetate 25 WO 2005/097731 PCT/GB2005/001364 1 -(3-Hydroxypropyl)putrescinium propanoate 1 -(3-Hydroxypropyl)putresciiihirn propanedioate 1 -(3-Hydroxypropyl)putxescinium butanoate 1 -(3-Hydroxypropyl)putrescinium butenoate 1 -(3-Hydroxypropyl)putrescioium butanedioate 1 -(3-Hydroxypropyl)putrescinium pentanoate 1 -(3-Hydroxypropyl)putrescirdum pentanedioate 1 -(3-Hydroxypropyl)putresciniuin pentenoate 1 -(3-Hydroxypropyl)putrescinium hexanoate 1 -(3-Hydroxypropyl)putrescinium hexenoate 1 -(3 -Hy droxypropyl)putresciiiium heptanoate 1 -(3 -Hy droxypropyl)putrescinium heptanedioate 1 -(3-Hydroxypropyl)putrescinium heptenoate 1 -(3-Hydroxypropyl)putrescinimn octanoate 1 -(3-Hydroxypropyl)p"utrescinium octanedioate 1 -(3-Hydroxypropyl)putrescinium octenoate 1 -(3-Hydroxypropyl)putrescinium nonanoate 1 -(3-Hydxoxypropyl)putrescinium nonanedioate 1 -(3-Hydroxypropyl)putresciniiuii nonenoate 1 -(3-HydToxypropyl)putrescinium decanoate 1 -(3-Hydroxypropyl)p"utresciniura decanedioate 1 -(3-Hydroxypropyl)putrescinium decenoate 1 -(3-Hydroxypropyl)putresciiuum undecanoate 1 -(3-Hydroxypropyl)pntrescinium undecanedioate 1 -(3-Hydraxypropyl)putresciniuin 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' 1 -(3-Hydroxypropyl)putrescinium phenoxide 26 WO 2005/097731 PCT/GB2005/001364 l-(3~Hydroxypropyl)putrescimum benzoate 1 -(3-Hydroxypropyl)putresciniuni benezenedicarboxylate 1 -(3-Hydroxypropyl)putresciaiuiii benzenetricarboxylate 1 -(3-Hydroxypropyl)putrescinium benzenetetracarboxylate 1 -(3-Hydroxypropyl)putresciniurn chlorobenzoate 1 -(3-Hydroxypropyl)putresciniuiii fluorobenzoate 1 -(3-Hydroxypropyl)putrescinium pentachlorobenzoate 1 -(3-Hydroxypropyl)putrescinium pentafluorobenzoate 1 -(3-Hydroxyprop5d)putrescinium salicylate 1 -(3 -Hydrox5'propyl)putresciQium glycolate l-(3-Hydroxypropyl)putresciriiurn lactate 1 -(3 -Hydroxypropyl)putxescinium pantothenate l-(3-Hydroxypropyl)putrescinium tartrate l-(3-Hydroxypropyl)putrescinium hydrogen tartrate 1 -(3 -Hydroxypropyl)putrescinium mandelate 1 -(3 -Hydroxypropyl)putrescinium crotonate l-(3-Hydroxypropyl)putrescinium malate l-(3-Hydroxypropyl)putresciniuin pyruvate 1 -(3 -Hydroxypropyl)putrescioium succinate l-(3-Hydroxypropyl)putrescinium citrate l-(3-Hydroxypropyl)putrescinium fumarate 1 -(3 -Hydroxypropyl)putresciaimn phenylacetate l-(3-Hydroxypropyl)putresckiium oxalate 1 -(3-Hydroxypropyl)putrescinium bis(trifluoromethylsulphonyl)irriide 1 -(3-Hydroxypropyl)putrescinium raethanesulphonate 1 -(3-Hydroxypropyl)putrescinium trifluoromethanesulphonate 1 -(3-Hydroxypropyl)putresciniurQ hexafluorophospliate 1 -(3-Hydroxypropyl)putresciniirai tetrafluoroborate 1 -(3-Hydroxypropyl)putescinium trifluoroacetate l-(3-Hydroxypropyl)putrescinium pentafluoropropanoate 1 -(3-Hydroxypropyl)putrescinium heptafluorobutanoate 27 WO 2005/097731 PCT/GB2005/001364 1 -(3-Hyciroxyj)ropyl)putrescinium phosphoenolpyruvate 1 -(3-Hydroxypropyl)putresciniuin nicotmarnide adenine dinucleotide phosphate l-(3-Hydroxypropyl)putresciniumadeno3inephosphate l-(3-Hydroxypropyl)putrescinium adenosine diphosphate l-(3-Hydroxypropyl)putrescinium adenosine triphosphate 1 -(3-Hydroxypropyl)putrescinium carbonate l-(3-Hydroxypropyl)putTesciiiiuiii hydrogen carbonate 1 --(3 --Hydroxypropyl)putresciriiurn sulphate l-(3-Hydroxypropyl)putresciBiiim hydrogen sulphate 1 -(3 -Hydroxypropyl)putxescinium phosphate 1 -(3--Hydroxypropyl)pu1resciniurn hydrogen phosphate , 1 -(3-Hydi'oxypropyl)putrescinium dihydrogen phosphate 1 -(3-Hydioxypropyl)put:esciriium niti'ate 1 -(3-Hydroxypropyl)putrescinium nitrite hi one class of compounds, the invention includes the proviso that the ionic liquid is not ethylarrrmonium nitrate or diethanolamrnonium chloride. In 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 (II) NRR'R" (IT) in. which R, R' and R' have f tie meaning defined herein; and ii.) neutralising the compound in (i) with an acid. 28 WO 2005/097731 PCT/GB2005/001364 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 (II) 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. 29 WO 2005/097731 PCT/GB2005/001364 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 chrornatographic 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, lite 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 mdefinite article is used, the specification is to be understood as contemplating plurality as well as singulcirity, 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 30 WO 2005/097731 PCT/GB2005/001364 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-dimethylethanola?nmonium glycolate Alcoholic solutions of N,N-dimethylethanolamme (lOO.OOmL, 2.000M concentration) and glycolic acid (lOO.OOmL, 2.000M concentration) were gradually mixed together in a 500mL 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, watsr content 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. WO 2005/097731 PCT7GB2005/001364 FT-IR (cm"1): 1591, 1076, 1358, 687, 993,1468, 909, 1255, 881, 1154,1171, 3240, 2870, 2484,1745 IJV/vis Xmax (nm): 234 ENT (Reichardt): 0.912 Density (g cm"3): 1.146 Preparation ofN-biityldiethanolammonium bis(triflnoromethylsiilphonyl)imide To an alcoholic solution of N-butyldiethanolamine (lOO.OOmL, 2.000M concentration) in a 500mL round-bottomed flask was gradually added 56.232g bis(trifluoromemylsulphonyl)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 98% by ion chromatography . The product was analysed and stored as previously described. FT-IR (cm"1): 1051,1132,1181, 1347,741,791,764,580,960, 1461,2967,3523, 2941,2880,3138, 1632 LTV/vis Xmax (nm): 304 ENT (Reichardt): 0.994 Density (g cm"3): 1,343 APPLICATIONS Enzyme-catalysed reaction in N,N~dimethylethanolammoniwn glycolate Alcohol dehydrogenase: Methanol (50uL) was dissolved in the ionic liquid (6mL) with a net water content of 32 WO 2005/097731 PCT/GB2005/001364 for 24 hours, with vigorous shaking being maintained throughout. Samples (lmL) 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. Biodegi-adation ofN,N-dimethylethanolammoniumglycolate N,N-Dimemyle1ianolarnmonium glycolate (5mM) was used as sole nitrogen and carbon source for the selective enrichment of a mixed community of soil microorganisms 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 30°C, with shaking at llOrpm. Degradation was monitored using ion chromatography. 5mM Ionic liquid was readily degraded (>98% removal) within 48 hours, the final nitrogenous metabolite being ammonia. 33 WO 2005/097731 PCT/GB2005/001364 OAMS 1. Ail ionic liquid comprising an anion and a cation characterised in that the cation is a nitrogen-coataining cation of the formula (I) N+HRR'R" (I) in which R is a hydrocarbyl group optionally substituted witli by one 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, alkoxy, 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 EL" 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 cyclobydxocarbyl or heterocyclyl group. 34 WO 2005/097731 PCT/GB2005/001364 . 6. An ionic liquid as claimed in claim 5 Avherein 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, arnino, 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 di-alkanol, tri-alkanol or tetra-allcanol group. 13. An ionic liquid as claimed in claim 12 wherein the cation is an ethanolammomurn, N-(alkoxyethyl)arnmonium3 N-methylethanolammonium, N,N- dimethylethanolarnmonium, diethanolammonium, N-alkyldiethanolammonium, N,N- di(alkoxyalkyl)ammonium or triethanolammonium ion. 14. An ionic liquid as claimed in claim 13 wherein the cation is a methylethanolammonium, N,N-dimethylethanolamnionium, N, N- di(methoxyethyl)ammonium) or butyldiethanolammonium ion. 35 WO 2005/097731 PCT/GB2005/001364 15. Aa ionic liq[uid as claimed in claim 1 wherein R is an aminoalkyl group having 2 to 8 C atoms 16. AJI 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 tr opine. 18. An ionic liquid as claimed in claim 1 wherein the cation is selected from the group consisting of an ethanolammonium, diethanolammonium, N- butyldietbLanolarnmoniurn, N-rnethylethanolammonium, N,N- dirjQethylethaaiolarniQom'um, puiiescmium, l-(34iydroxypropyl)putrescinium, or N- (3 -hydroxypropyl)-N-methylcyclohexylammonium cation. 19. An ionic liquid as claimed in claim 18 wherein the cation is N- b uty ldiethanolammoni um, N-methylethanol aminonium, di(metho>:yethyl)ammomum., N,N-dimethylethanolamraonium, putrescinium, l-(3- hy"droxypropyl)putrescinium, or N-(3-hydroxypropyl)-N- methylcyclohexylaminoniurja ion. 20. An io:nic liquid as claimed in claim 1 whereia the anion is selected from the group consisting of halogenated inorganic anions, nitrates, sulphates, phosphates, c;arbonates, sulphonates and carboxylates. 21. Aa ionic liquid as claimed in claim 20 wherein the sulphonates and carboxylates .are alkylsulphonates and alkylcarboxylates respectively. 22. Aa ionic liquid as claimed ia claim 21 wherein the alkyl group is a moiety selected from alkyl and alkyl substituted at any position with alkenyl, alkoxy, 36 WO 2005/097731 PCT/GB2005/001364 alkeneoxy, aiyl, arylalkyl, atyloxy, amino, aminoalkyl, thio, thioaUcyl, 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(trifluoromemylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, dfhydrogen phosphate, metaphosphate, methanesulphonate, trifluoromethanesulphonate, ethylenediaminetetraacetate, chloride, bromide, iodide, hexafhiorophosphate, tetrafluoroborate, trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, benzoate, benezenedicarboxylate, benzenetricarboxylate, benzeneterracarboxylate, chlorobenzoate, fluorobenzoate, pentachlorobenzoate, pentafluorobenzoate salicylate, glycolate lactate, pantothenate, tartrate, hydrogen tartrate, mandelate, crotonate, malate, pyruvate, succrnate, 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 37 WO 2005/D97731 PCT/GB2005/001364 Ethanolammoniurn. pentenoate Ethanolammonimn hexaiioate Ethanolatumoninm hexanedioate Ethanolaminomum. hexeaoate EHianolatmnonium heptanoate EUbanolammonium heptanedioate Eilianolammonium. heptenoate Ethanolammonium octanoate Ethanolairimonium. octanedioate Ethanolammonium octenoate Ethanolairimonium. nonanoate Ethanolaminonium nonanedioate Ethanolammonium nonenoate Ethanolammonium decanoate Ethanolammonium decanedioate Ethanolammonium decenoate Ethanolammonium imdecanoate Ethanolammonium undecanedioate Ethanolammonium undecenoate Ethanolammonium dodecanoate Ethanolammonium. dodecanedicarboxylate Ethanolammonium dodecenecarboxylate Ethanolammonium cyclohexanecarboxylate Ethanolaramonium cyclohexenecarboxylate E,thanolammonium phenoxide Ethanolammonium benzoate Ethanolarnmoniuxn benezenedicarboxy] ate Elthanolarnmoniumbenzenetricarboxylate Elthanolammoniumbenzenetetracarboxylate Ethanolammonium chlorobenzoate Ethanolammonium fluorobenzoate 38 WO 2005/097731 PCT/GB2005/001364 Ethanolammoniurn pentachlorobenzoate Ethanolaminonium 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 futnarate Ethanolammonium phenylacetate Ethanolammonium oxalate Emanolaimonumbis(trifluoromethylsulphonyl)imide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate Ethanolammonium hydrogen phosphate Ethanolammonium dihydrogen phosphate Ethanolammomum methanesulfonate Ethanolammonium trifhioromemanesulphonate Ethanolammonium ethy'lenediaminetetraacetate Ethanolammonium hexafluorophosphate Ethanolammonium tetrafluoroborate Ethanolammonium trifluoroacetate 39 WO 2005/097731 PCT7GB2005/001364 EthanolammoniiraipentafluoropropanoaT.e Ethanolammonium heptafluorobutano ate Ethanolammoniumphosphoenolpyruvate Ethanolammonium nicotiaaroide adenine dinucleotide phosphate Ethanolammonium adenosinephosphate Ethanolammonium adenosine diphosphate Ethanolammonium adenosine triphosphate Ethanolammonium oxyniacate Ethanolammonium nitrate Eliianolammonium nitrite Diethanolammonium bromide Diethanolammonium iodide Diethanolammonium formate Diethanolammonium acetate Diethanolammonium propanoate Diethanolammonium propanedioate Diemanolarnmoriium butanoate Diethanolammonium butenoate Diethanolammonium 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 40 WO 2005/097731 PCT/GB2005/001364 DiethanolammoniurQ nonanoate Diemanolammonium nonanedioate Diethanolammonium nonenoate Diethanolammonium decanoate Diemanolammonium decanedioate Diemanolammoniuni decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate ' Diethanolammonium dodecanedicarboxylate Diethanolammonium dodetenecafboxylate Diethanolammonium cyclohexanecarboxylate Diethanolammonium cyclohexenecarboxylate Diethanolammonium phenoxide Diethanolammonium benzoate Diethanolammonium benezenedicarboxylate Diethanolammonium benzenetricarboxylate Diethanolammonium benzenetetracarboxylate Diethanolammonium chlorobemzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate Diethanolammonium salicylate Diethanolammonium glycolate Diethanolammom'um lactate Diethanolammonium pantotkenate Diethanolammonium tartrate Diethanolammonium hydrogen tartrate Diethanolammom'um mandelate Diethanolammonium crotonate 41 WO 2005/097731 PCT/GB2005/001364 Diethanolammonium malate DiethanoLammonium pyruvate Diethanolammonium succinate Diethanolammonium citrate Diethanolammonium fumarate D iethanolemmonium phenylacetate Diethanolammonium oxalate Diemanolammoniumbis(trifluoromethylsulphonyl)imide Diethanolammonium carbonate Diethanolammonium hydrogen carbonate Diemanolammonium phosphate Diethanolammonium hydrogen phosphate Diethanolammonium dihydrogen phosphate Diethanoliammonium methanesulphonate Diethanol;arnmoniuni trifluoromethanesulphonate Diethanolainmonium ethylenediaminetetraacetate D iethanolammoniuni hexafluoropho sphate Diethanolammonium tetrafluoroborate C'iethanolarnmonium uifluoroacetate Diethanolammoniunipentafluoropropanoate Diethanolammoniuniheptafluorobutanoate Diethanolammonium phosphoenolpyruvate Diethanolammonium nicotinamide adenine dinucleotide phosphate Diethanol ammonium adenosinephosphate Diethanolammonium adenosine diphosphate Diethanolammonium adenosine triphosphate Diethanolammoniuna oxyniacate Diethanolammonium nitrate DiethanoLammonium nitrite N-Butyldiethanolammonium chloride N-Butyldiethanolammonium bromide 42 WO 2005/097731 PCT/GB2005/001364 N-Butyldiethanolammonium iodide N-Butyldiethanolarnmonium formate N-Bulyldiemanolammoniuni acetate N-Butyldiethanolamrnonium propanoate N-Butyldiethanolanimonium propanedioate N-Butyldiethanolammordum butanoate N-Butyldiemanolanimonium butenoate N-Butyldiethanolammonium butanedioate N-Butyldiethanolammoniuin pentanoate N-Butyldiethanolammonium pentanedioate N-Butyldiethanolammonium pentenoate N-Butyldiethanolammonium hexanoate N-Butyldiethanolammonium hexenoate N-Butyldiethanolammonium heptanoate N-Butyldiethanolammonium heptanedioate N-Butyldiethanolammonium heptenoate N-Butyldiethanolammonium\)ctanoate N-Butyldiethanolammonium octanedioate N-Butyldiethanolammonium octenoate N-Butyldiethanolammonium nonanoate N-Butyldiethajaolammonium nonanedioate N-Butyldiethanolammonium nonenoate N-Butyldiethanolammonium decanoate N-Butyldiethanolammonium decanedioate N-Butyldiethanolammonium decenoate N-Butyldiethanolammonium undecanoate N-Butyldiethanolammonium undecanedioate N-Butyldiethanolammonium undecenoate N-Butyldiethanolammonium dodecanoate N-Butyldiethanolammonium dodecanedicarboxylate N-Butyldiethanolammonium dodecenecarboxylate 43 WO 21)05/097731 PCT/GB2005/001364 N-Butyldiethaaolamnionitcyclohexanecarboxylate N-Butyldietbanolammoiiiumcyclohexenecarboxylate N-Butyldiethanolammonmmphenoxide N-Butykliethanolammoniumbenzoate N-Butylciiethanolaroxnoniumbenezenedicarboxylate N-Buiykliethanolammonium benzeBetricarboxylate N-Butyldiethanolanmionhmiberizenetetxacarboxylate N-ButyldiethanolammomumcbJorobenzoate N-Butykliethanolammoniurnfluorobenzoate N-Buty ldiethanolammo nixum pentac Morobenzoate N-Bu1yldiethanolaDirri()niunipentafl.uorobenzoate N-Butykiiethanolammonium salicylate N-Butyldiethanolammonium glycolate N-Butyldietbanolammonium lactate N-Butylcliethanolanirrioniurnpantothenate N-Butyldiethanolammonium tartrate N-Butyldiethanolamrtionium hydrogen tartrate N-Butyldietiianolarjmiomummandelate N-Butylfiiethanolaromonium crotonate N-Butyldiethanolanmionium malate: N-Butyldiethanolaranionium pyruvate N-Butyldiethanolammonium succmate N-Butyldiettianolaromoniuni citrate N-Butyldietlianolammonium fumarate N-Butyldiethanolarnmonimxiphenylacetate N-Butyldiethanolamnioniura oxalate N'Butyldiethanolarnnioriiiuribis(trifluoromethylsulphriyl)imide N-Butyldietlianolarnmoniuin carbonate N-Butyldiethanolammonium hydrogen carbonate N'Butyldietlianolammonium sulphate N-Butyldietiianolanimoniitm hydrogen sulphate 44 WO 2005/097731 PCT/GB2005/001364 N-Butyldiethaaolammoniiim phosphate N-Butyldiethanolamrnonium hydrogen phosphate N-Butyldiethanolammomum dihydrogen phosphate N-Buryldiemanolammoin'ummethanesulphonate N-Butyldiethanolaminoniiimtrifluoromethanesulphonate N-Butyldiethanolanitnoniiimethylenediaminetetraacetate N-But}ddiethanolaminoniiimhexafluorophosphate N-Butyldiethanolammoniumtetrafluoroborate N-Butyldiemanolammonium trifluoroacetate N-Butyldiethanolarnrnoripentafluoropropanoate N-Butyldiethanolammonium hep tafluorobutanoate N-Butyldie1iianolaminoniumphosphoenolpyruvate N-Butyldiemanolammonium nicotinamide adenine dinucleotide phosphate N-Butyldiethanolaminoniiiinadenosinephosphate N-Butyldiethanolammonium adenosine diphosphate N-Butyldiethanolaramonium adenosine triphosphate N-Butyldiethanolammonium oxyniacate N-Butyldiethanolammonium nitrate N-Butyldiethanolammonium nitrite N,N-Dimethylethanola.mm onium bromide N,N-Dimethylethanolammonium iodide N,N-Dimethylethanolamnionium formate N,N-Dimeth3flethanola.mjn onium acetate N,N-Dimethylethanolarnmonium propanoate N,N-Dimethylethanolammonium propanedioate N,N-Dimethylethanolammonium butanoate N,N-Dmethylethanolarnrnonium butenoate N,N-Dirnethylethanolainmonium butanedioate N,N-Dimethylethanolammonium pentanoate N,N-Dime1hylethanolamrnonium pentanedioate N;N-Dimethylethanolainmoriium pentenoate 45 WO 2005/097731 PCT/GB2005/001364 N,N-Dimetlayletliaolanunoniuinliexanoate N,N-D imethyletlianol ammonium hexeno ate N,N-Dmie&yle1iianolarnmoniuinlieptanoate N,N-Diriiemylethanolammoniumhe;ptanedioate N\N-Dmiemyletfianolammomumheptenoate N,N-Dimethyletlianolammonium octanoate N,N-Dimethyl ethano lammonium octanedioate N,N-Dimethylethanolammoniuinoctenoate N,N-Dmethylefhanolainmoniumnonanoate N,N-Diraethylethano lammonium nonanedioate 'N,N-Diraethylethanolammoniumnonenoate N,N-Dkaethylethanolammoniiim decanoate N,N-Dimethylethaaolammomumde5canedioate N,N-Direthylethanolammonium decenoate N,N-Dethylethanolammoniumundecanoate N,N-Dethylethajaolamrnonium\iiidecanedioate N,N-Dnethyleti.iaiiolammoniumujidecenoate N,N-Dimethylethanolammoniumdodecanoate N,N-Dknethyle1olammoniitind()decanedicarboxyla_te N,N-Dimethylethariolammonium dodecenecarboxylate N,N-DiinethyletiianolarDinoiiium cyclohexanecarboxylate N,N-Dunemylethaiiolammoniitm cyclohexenecarboxylate N,N-Diinemylethaiiolammoniumphenoxide N,N-Diinemylethaiiolammoniumberizoate NjN-Dunethylethanolammoniumbenezenedicarboxylate N,N-Diinemylethanolaminoniiimbenzenetricarboxylate N,N-Diineth.ylethaiaolammoniiimbenzenetetracarboxylate N5N-Dunethylemanolammonixtrn.cMorobenzoate N,N-Dimethylethaaolammonium fluorobenzoate N,N-Diinemylethanolammoniumpentachlorobenzoate: N,N-Diinethylethanolammoiiiiim pentafluorobenzoate 46 WO 2005/097731 PCT/GB2005/001364 N,N-Dimeth.ylethanolammonium salicylate NJ^-Dimethylethanolammorniirn glycolate N,N-Dimethylethanolaiiimonium lactate N.N-Dimethyletlianolainnioniiimpantotheriate NjN-Dimethylethanolammomum tartrate N,N-DimethylethaaolaramoniuiQ hydrogen tartrate N,N-Dimethylethanolammoiiium mandelate N,N-Dimetiiylethanolamrnoniurn crotonate N,N-Drrnethylethanolarrrmoniiirn malate N,N-Dimethylethanolamraonium pyruvate N,N-Dimetriylethanolarnmoniiirn succinate N,N-Dimethylethanolarrira.oriiiim. citrate N,N-Dimethyletxianolamrxioriiurn tumarate N,N-Diraethylethanolammonium phenylacetate N,N-Dimethylethanolamrnoiiiurn oxalate N,N-Dimetiiylethanolarrimoniiimbis(triiluoromethylsxilphonyl)imide N,N-Dimethylethaaolamrriorriiim carbonate N,N-Dimethylet±ianolammorjium hydrogen carbonate N,N-Dime1iiylethanolarnrnoriiiuri sulphate N,N-Dimethylethanolarnmomum hydrogen sulphate N,N-Dimethyletiianolarnrnoriium phosphate N;N-Dimethylethanolarrjrnonium hydrogen phosphate N,N-Dimeuiyletlianolamrnorriuni dihydrogen phosphate N,N-Dimethylethaiiolamrnorriurnniethanesulphonate N,N-Dimeuiylet±ianolmrimoniumrrifluoromethanesulphonate N,N-Dimethylethanolammoniumethylenediarriineterraacetate N,N-Dirnethyletlianolainrnorriumhexafluorophosphate N,N-Drmethyle1±ianolairirnoiuumtetrafluoroborate N,N-Dimethyletlianolarnmomurntrifluoroacetate. N,N-Dimethylethanolamrnoniurnpenta£luoropropanoate N,N-Dimethyletkanolarnrnoniurnheptailuorobutanoate 47 WO 2005/097731 PCT/GB2005/001364 N,N-Dime.thylethanolaminoniumphosphoenolpyTuvate N,N-Dirnethylethanolatriinonium nicotinamide adenine dinucleotide phosphate N.N-Dime:thylethanolanuiumadenosiephosphate N;N-Dime:thy]ethanolaromoniiiiii adenosine diphosphate N,.,N-Dime;thy]ethanolammonium adenosine triphosphate N;N-Dimetiby] ethanolammonium oxyniacate N,N-Dimt:th.ylethanolan:anoniiuii nitrate N. N-Dime:thylethanolammonium nitrite N-Methyl N--Methylethanolammonlum iodide N-Methylt;thanolarattionium formate N-Methyl N-MethylethanolairLimomunipropanoate N-Methylethaaolammotniumpropanedioate N-Methylistlianolamjtnoriiuinbutanoate N-Metitiylethaaolamimoniiini butenoate N-Methylethanolanxmordumbutanedioate N-Methylethanolanrmordum pentano ate N-Methyl(3thanolam;[noniiimpentanedioate N-Methylethanolammoniumpentenoate N-Methyl ethanolartimoniuin hexanoate N-MethylethanolaniDioriiirai hexenoate N-Methylethanolaramomuniheptanoate N -Methyl ethanolammonium heptanedioate N-Methylethanolammoniumheptenoate N-Metlaylethanolammonium octanoate N-Methylethanolammoniumoctanedioate N-MethyletlaanolammoniurQ octenoate N-Methyl N-Methylethano lammonium nonanedioate N~MethylethanoLammomumnonenoate 48 WO 2005/097731 PCT/GB2005/001364 N-Methylemanolammonium decanoate N-Methylemanolammorriuni decanedioate N-Methylemanolarnmonium decenoate N-Memylemanolammonium undecanoate N-Methylethanolammom'um undecanedioate N~Memylemanolammonium undecenoate N-Methylethanolammonium dodecanoate N-Methylethanolammonium dodecanedicarboxylate N-Methylethanolammonium dodecenecarboxylate N-Methylethanolammonium cyclohexanecarboxylate. N-Methylethanolammonium cyclohexenecarboxylate N-Methylethanolammonium phenoxide N-Meth5dethanolammonium benzoate N-Methylethanolammonium benezenedicarboxylate N-Methylethanolammonium benzenetricarboxylate N-Methylethanolammonium 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-Me1iiylethanolaminonium crotonate N-Methylethanolammonium malate N-Methylethanolammonium pyruvate N-Methylethanolammonium succinate 49 WO 2005/097731 PCT7GB2005/001364 N -Methyl ethanolanimontum citrate N-Memylethanolammonium funiarate N-Memylethatiolanxmoniumphenylacetate N-Methylethanolammonium oxalate N-MethylethanolamBiorii\imbis(1iifluoromethylsulphonyl)imide N-Methylethanolammo mum carb onate N--Metl"iyk;tliaiiolammomum hydrogen carbonate N-Methylethanolammonium sulphate N-Methylethanolammonium hydrogen sulphate N-Methylethanolammonium phosphate N-Methylethanolammonium hydrogen phosphate N-M ethylethanol ammonium dthydro gen phosphate N-Methylethanolammonium methanesulphonate N-Methylemanolamiiioniiim.trifluoromethanesulphonate N -Methylethanolammordum emylenediaminetetraacetate N-Methyletihanolammonium hexafluorophosphate N-Methylethanolammoniumtet]:afluoroborate N-MethylethanLolammoniumtrifluoroacetate N-Methylethcinolammoniumpentailuoropropanoate N-Methylethanolamnioniuniheptailuorobu.tanoate N-Methylethanolanimomumphosphoenolpyruvate N-Methylethanolamrrj.onium nicotiniamide adenine dinucleotide phosphate N-Methylethianolanunonium adenosinephosphate N-Methylethanolammonium adenosine diphosphate N-Methylethanolammonium adenosine triphosphate N-Meth5rlethanolanimonium oxyniacate N-Methylethanolammonium nitrate N-Methyletbanolai)Qmonium nitrite N,N-Di(memoxyettiyr)ammonium chloride N,N-Di(methoxyethyl)ammonium bromide ]Sr,N-Di(methoxyethyl)ammoniurja iodide 50 WO 2005/097731 PCT/GB2005/001364 N3N-Di(methoxyethyl)ammonium formate N,N-Di(raethoxyeth.yl)ammonium acetate N,N-Di(metlioxyethyl)ammonium propanoate N,N-Di(methoxyethyl)ammoniumpropanedioate N,N-Di(m.ethoxyethyl)ammoniuin butanoate jNf,N-Di(methoxyethyl)amiDonium butenoate N,N-Di(inetb.oxyethyl)amnioniumbutanedioate ]Sf,N-Di(methoxyethyl)ammoniurQ pentanoate 1SI,N-Di(niethoxyetb.yl)amm onium pentanedioate N,N-Di(inethoxyethyl)ammonium pentenoate N,N-Di(methoxyethyl)arnmoiiiiiin hexanoate lNf,N-Di(methoxyetb.yl)ammoniimi hexenoate 2ST,1S[-Di(raethoxyethyl)ammonium heptanoate N,N-Di(methoxyethyl)ammoriitixnheptanedioate N,N-Di(metiioxye&yl)animoidumheptenoate N,N-Di(methoxyethyl)amrQonium octanoate N,N-Di(me1iioxyethyl)ammoiiiumoctanedioate N,N-Di(methoxyethyl)ainmonivun octenoate N,N-Di(methoxyethyl)arnmoiiiiim nonanoate N,N-Di(methoxyethyl)ammoniinnnonanedioate N,N-Di(methoxyethyl)arumoEiium nonenoate N,N-Di(methoxyethyl)ammonium decanoate N,Isf-Di(methoxyetb.yl)amnioriiiimdecanedioate N,N-Di(raetb.oxyethyl)aminomuin decenoate N,N-Di(metibLoxyethyl)anunoiuuin undecanoate N,N-Di(metiioxyet]iyl)arrimoriiumirndecanedioate N?N-Di(methoxyethyl)ainino^iiim undecenoate N,N-Di(methoxyethyl)aminordiini dodecanoate N7N-Di(methoxyethyl)ainjndiiimndodecanedicarboxylate N,N-Di(metb.oxyeth.yl)animoriiiimdodecenecarboxylate N,N-Di(methoxyethyl)aiimioiiiiiincyclob.exaaecarboxylate 51 WO 2005/097731 PCT/GB2005/001364 N,N-Di(methoxyethyl)ammonivim cyclohexenecarboxyjate N,N-Di(methoxyethyl)ammoriiumphenoxide N,N-Di(tue:tibLOX3'ethyl)axrimotiiiiaibenzoate N,N-Di(methoxyethyl)ammonium benezenedicarboxylate N,N-Di(methoxyethyl)aimnoniiunbenzenetricaiboxylate N,N-Di(methoxyethyl)auunoniumberizenetetracarboxylate N,N -Di(methoxyethyl)ammoiii'ura chl orobenzoate N,N-Di(methoxyethyl)axrimoDiiinifluorobenzoate N,N-Di(methoxyethyl)atomoniuinpeiitaclilorobenzoate N,N- Di(niethoxyetliyl)arninonium pentafluorobenzoate N,N-Di(]3iethoxyeth3'l)ammoniimi s;alicylate N,N-Di(methoxy ethyl) ammonium glycolate NjN-Di(m.ethoxyethyl)ammoniumlactate N,N~Di(m.ethoxyethyl)ammoniumpaatotheiiate N,N-Di(methoxyethyl)ammoniuin tartrate N,N-Di(methoxyethyl)atnmonium hydrogen tartrate N,N-Di(meth(3xyethyl)ammoniuni mandelate N,N-Di(rciethoxyethyl)arrirrioiiiurncrotoriate N,N-Di(methoxyethyl)ammoniummalate N,N-Di( nieth.ox>rethyl)ammonium pyruvate N,N-Di(r)iethoxyeth3d)ainmoniiirn succinate N,N-Di(methoxyetliyl)ammoEdtirQ citrate N,N-Di(raethoxye1iiyl)arninoniiirnfltrnarate N,N-Di(rDethoxyethyl)ammoniTHn phenylacetate N,N~Di(methoxyettiy])ammonium oxalate N,N-Di(ine1iioxye1iiyl)ariimordiimb:Ls(1iifluorome1iiylsxilphonyl)im ]sF,N-Di(methoxyethyI)ammoniuinc;3xboBate N,N-Di(methoxyethyl)ammonium hydrogen carbonate N,N-Di(methoxyethyl)aromoiiium sulphate N,N-Di(methoxyethyr)ammoninm hydrogen sulphate N,N-Di(methoxyethyl)ainrnoniurji phosphate 52 WO 2005/097731 PCT/GB2005/001364 N,N-Di(methoxyethyl)ammonium hydrogen phosphate N,N-Di(methoxyethyl)ammbnium dihydrogen phosphate N,N-Di(methoxyethyl)ammoniuriiniethanesiilphonate N,N-Di(methoxyetiiyl)anmioniiimtiifluoromethaiiesulphoria.te N,N-Di(methoxyetliyl)ammoiiiume1iiylenediarQiiietetraacetate N,N-Di(methox}rethyl)ammoniumhexafluorophosphate N,N-Di(methoxyethyl)ammoniumtetrailuoroborate N,N-Di(methoxyethyl)aininoniumtrifluoroacetate N,N-Di(methoxyethyl)ammoniumpentafluoropropanoate N,N-Di (rnethoxyethyl)ammonium heptafluorobutanoate N,N-Di(methoxyethyl)amm oniurn phosphoenolpyruvate N,N-Di(methoxyethyl)aminonitxm nicotinamide adenine dinucleotide phosphate N,N-Di(methoxyethyl)ammordumadenosinephosphate N,N-Di(methoxyethyl)ammonium adenosine diphosphate N,N-Di(methox}rethyl)amrQoniiiin adenosine triphosphate N,N-Di(methoxyethyl)ammoniuin oxyniacate N5N-Di(raethoxyefhyl)amm0niinn nitrate N;N-Di(methoxyethyl)ammoiiitun nitritel-(3-Hydroxypropyl)putrescinium chloride l-(3-Hydrox}'propyl)putrescinium bromide 1 -(3-Hyo!roxypropyl)putrescimirm iodide 1 -(3 -Hydroxypropyl)putrescinium formate l-(3-Hydroxypropyl)putrescinium acetate 1 -(3 -Hydi-ox)'propyl)putrescinium propanoate 1 -(3-Hydroxypropyl)putrescinium propanedioate 1 -(3-Hydroxypropyl)putrescinium butanoate 1 -(3-Hydroxypropyl)putrescinium butenoate 1 -(3-Hydroxypropyl)putrescinimn butanedioate 1 -(3-Hydroxypropyl)putrescinium pentanoate 1 -(3-Hydrox3'propyl)putrescinium pentanedioate 1 -(3-Hydroxypropyl)putrescinium pentenoate 1 -(3-Hydroxypropyl)putresciniiim hexanoate 53 WO 2005/097731 PCT/GB2005/001364 1 -i3-Hydroxypropyl)puti-escinium hexenoate 1 -(3-Hydroxypropyl)putrescinium heptanoate 1 -{3 -Hydroxypropyl)putrescinium heptanedioate l-(3-Hydroxypropyl)putresciniumheptenoate l-(3-Hydroxypropyl)putrescinium octanoate 1 -(3-Hydroxypropyl)putrescinium octanedioate l-(3-Hydroxypropyl)putrescinium octenoate l-(3 -Hydroxypropyl)putrescinium nonanoate 1 - (3 -Hydroxypropyl)putrescinium nonanedioate 1 - (3 -Hydroxypropyl)putrescinium nonenoate 1 -(3 -Hydroxypropyl)putrescinium decanoate 1 -(3 -Hydroxypropyl)putrescinium decanedioate 1 -(3 -Hydroxypropyl)putrescinium decenoate 1 -(3 -Hydroxypropyl)putrescinium undecanoate 1 -(3-Hydioxy;propyr)putresciiiium undecanedioate 1 -(3-Hydi'oxypropyl)putrescinium undecenoate 1 -(3 -Hyd]'oxypropyl)putrescinium dodecanoate 1 -(3 -Hydiroxypropyl)putresciDium dodecaaedicarboxylate 1 -(3-Hydiroxypropyl)putresciDium dodecenecarboxylate 1 -(3-Hydroxypropyl)putresciiiiuiii cyclohexanecarboxylate 1 -(3-Hydroxypropyl)putresciiiium. cyclohexenecarboxylate 1 -(3-Hydroxypropyl)putresciniuni phenoxide ] -(3-Hydroxypropyl)putrescinium benzoate 1 -(3-Hydroxypropyl)putxescinium benezenedicarboxylate 1 -(3-Hydroxypropyl)putrescinium benzenetricarboxylate 1 -(3 -Hydroxypropy l)putrescinitim benzenetetracarboxy] ate 1 -(3-Hydroxypropyl)putrescinium cHorobenzoate l-(3-HydroxypTopyl)putrescinium fluorobenzoate 1 -(3 -Hyclxoxypropyl)putresckii"um pentachlorobenzoate 1 -(3 -Hyclxoxypropyl)putresciniiim pentafluorobenzoate 1 -(3 -Hydroxypropyl)putrescinium salicylate 54 WO 2005/097731 PCT/GB2005/001364 1 -(3 -Hydroxypropyl)putresciniuni glycolate 1 -(3 -Hydrox)'propyl)putresciniimi lactate 1 -(3 -HydroxypropyDputrescinium paiitotlienate l-(3-Hydxoxypropyl)putxescinium tartrate 1-(3-Hydroxypropyl)putresciniurn hydrogen tartrate 1 -(3-HydroxypropyDputrescinium mandelate 1 -(3 -HydroxypropyDputrescinium crotonate l-(3-Hydroxypropyl)putrescinium malate 1-(3-Hydroxypropyl)putrescinium pyruvate 1 -(3 -HydroxypropyDputrescinium succinate 1 -(3-HydroxypropyDputrescinium citrate 1-(3-HydroxypropyDputrescinium fumarate 1 -(3 -HydroxypropyDputrescinium phenylacetate l-(3-HydroxypropyDputrescinium oxalate 1 -(3-HydroxypropyDputrescinium bis(trifluoromethylsulphonyDimide l-(3-HydroxypropyDputrescmium methanesulphonate 1 -(3-HydroxypropyDputrescinium trifluoromethanesulplionate 1 -(3-HydroxypropyDputrescimum hexafluorophosphate 1 -(3-HydroxypropyDputrescinium tetrafluoroborate 1 -(3 -HydroxypropyDputrescinium trifluoroacetate 1 -(3-HydroxypropyDputrescinium penta£Iuoropropanoate1 -(3 -HydroxypropyDputrescinium heptafluorobutanoate ;¦ 1 -(3 -HydroxypropyDputrescinium phosphoenolpyruvate l-(3-HyaoxypropyDputresciniumnicotinamide adenine dinucleotide phosphate 1 -(3-HydroxypropyDputrescinium adenosinephosphate 1-(3-HydroxypropyDputrescinium adenosine diphosphate l-(3-HydroxypropyDputrescinium adenosine triphosphate 1 -(3 -HydroxypropyDputrescinium carbonate 1-(3-HydroxypropyDputrescinium hydrogen carbonate l-(3-HydroxypropyDputrescinium sulphate 1-(3-HydroxypropyDputrescinium hydrogen sulphate 55 WO 2005/097731 PCT7GB2005/001364 I -(3-Hydroxypropyl)putrescimum. phosphate l-(3-Hydroxypropyl)putrescinium hydrogen phosphate l-(3-Hydroxypropyl)putrescinium dihydrogen phosphate 1 -(3-Hydroxypropyl)pufrescmiurn nitrate 1 -(3-Hydroxypropyl)putresciaium 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 nitrogen-containing compound of the formula (11) NRR'R" (II) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), ttuol, alkythio, sulphonyl, thiocyanate, isotbiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, ali:oxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), cacrboxyl, boronate, silyl and substituted amino (e.g. mono- or di-alkylamino-, or afkyamido); 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. 56 WO 2005/097731 PCT/GB2005/001364 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 en2yrne-catalysed reactions, a solvent for organic synthesis, a matrix in matrix-assisted 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 nitrogen-containuag cation of the formula (I) N'HRR'R" (1) in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitro gen-containing functional groups (including nitrile, nitro or amino or another basic rntrogen-conta.in.ing 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 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. 31. A method for carrying out an enzyme-catalysed reaction comprising 57 WO 2005/097731 PCT/GB2005/001364 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. 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.

Full Text

PCT/GB2005/001364
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, pyrunidinium 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 chromatograpbic 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.

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The inventors have provided further ionic liquids.
According to the present invention there is provided an ionic liquid comprising an aunion 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 in 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 lias 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)
NHRR'R" (I)
in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), thiol, alkythio, sulphonyl, tbiocyanate, 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 di-alkylamino or alkyamido); and
R' and R", which may be the same or different, each represent H or R;

WO 2005/097731 PCT/GB2005/001364
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 100°C, for example, below 25°C and optionally below 20°C. The boiling point of the ionic liquid may be at least 200°C. It may be above 500°C 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 than 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 30°C 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, cycloalkenyl 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, 6,1, 8 carbon atoois 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, cyclobotyl, cyclopentyl or cyclohexyl.
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The alkyl group may be substituted with one or more halogen atoms, ha one class of compounds the halogen is fluorine, in another it is chlorine, in a third it is a combination of fluorine and chlorine.
"Allcoxy" 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, rnembered hydrocarbon, ring, including cycloalkyl or aryl.
"Aryl" means an aromatic, for example, 6-10 membered hydrocarbon containing one, e.g. 6C-10C, 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, t) or S, and containing one ring which is optionally fused to one or more saturated or unsaturated rings.
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"Heterocyclyl" means, for example, a 3-10 membered ring system containing one or more heteroatorns selected from N, 0 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 rmg-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, ditliiane, dithiazine, dithiazole, ditbiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isooxazole, isothiazole, morphohne, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazne, phthalazine, piperazine, piperidine, pteridine, purine, putrescine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine5 pyridazine, pyridine. pyrimidine, pyrrolidine, pyrrole, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, tbiazine, thiazole, tbiomorpholine, thianaphthalene, thiopyran, triazine, 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
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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.
In 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. In 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 GH3, 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:
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Ethylammoniurn nitrate Tributylammonium-acetate Tributylammoniuma- cyano-4-hydroxycinnamate Tributylammonium sinapate Dimethylammonium pyridine-2-carboxylate Tributylammonimii pyridine-2-carboxylate Tributylammonium 3 -hydroxypyridine-2-carboxylate Triethylammonium pyidine-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.
In 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.
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Preferably, the cation is an ethanolammonium, N-(a.UvOxyetliyl)ammomiim, N-
memylethanolararaonium, N,N-dim ethyl ethanolammonium, diethanolammonium,
N-alkyldiethanolammonium (e.g butyldiethanolammonium), N,N-
di(alkoxyalkyl)atrmiomum (e.g di(metlioxyethyl)ammoninm) or triethanolammonium ion.
More preferably the cation is a methylethanolammonium, N,N dimethyl ethanolajaunoniiun, N, N- di(metlaoxyetlayl)ammonium) or butyldiemanolarnmonium ion.
In another class of compounds, R is an arninoalkyl group having 2 to 8 C atoms, for example, 2, 3, 4, 5, 6, 7 or 8 C atoms. The arninoalkyl may be a di or tri-arrrmoalkyl group.
In some compounds, PL is putrescine, piperidine, or tropine.
Preferred cations include an. etiianolarnrnonium, diethanolammonium, N-butyldiethanolarjomon ium, N-mem)4e1iianolarnmonivirQ,
di(methoxyethyl)arnrnonium, N,N--dixaethylethaiiolariii:aorrium, putrescinium, l-(3-
hydroxypropyl)putrescrni"um, or N-(3-hydroxypropyl)-N-
methylcyclohexylamraonium ion. Preferably still, .. cations include N-butyldiemanolammoniurn, N-methylethanolammonium,
di(methoxyethyl)ajxmionium3 N5N~dimeiiiylethanolamraonium, putrescinium, l-(3-
hydroxypropyl)putrescinium, or ¦ N-(3-hydroxypropyl)-N-
methylcyclohexylamrnonium 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 .d-esired temperature.
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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, aUcoxy, alkeneoxy, aryl, arylalkyl, aryloxy,
amino, aminoalkyl, tbio, 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(trifluoromethylsulphonyl)imide,
carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, silicate, phosphate,
hydrogen phosphate, dihydrogen phosphate, rnetaphosphate, 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: EthanolamnLonium formate
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Ethanolamraonium acetate Ethanolarnmonium propanoate Ethanolammoniuin ptopanedioate Ethanolammonium butanoate Ethanolamronium batenoate Ethanolammonium butanedioate Ethanolammonium pentanoate EtJianolaxnmonium pentanedio ate Ethanolaminoniuni pentenoate Ethanolainmonium hexanoate Ethanolammonium hexanedioate EtJianohummonium hexenoate Ethanolammonium heptanoate Ethanolammonium heptanedioate Etlaanolammonium heptenoate EtJianolammonium octanoate Etlianolammonium octanedioate Ethanolammonium octenoate Ethanolarmnonium nonanoate Etlianolanunonium nonanedioate Etlianolammonium n(3nenoate Ethanolammonium decanoate Etlianolammonium decanedioate Etlianolammonium decenoate Etlianolammonium undecanoate Ethanolgimmonium tmdecanedioate EthanolaLtnmonium uiidecenoate EttianolatDomonium dodecanoate Ethanolammonium dodecanedicarboxylate Etlianolainnionium dodecenecarbo>:ylate Ettianolainiiionium cyclohexanecarboxylate
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WO 2005/097731 PCT/GB2005/001364
Ethanolammordimi cyclohexenecarboxylate Ethanolammonium phenoxide Emanolarnrnonium benzoate Ethanolammoniura benezenedicarboxylate Ethanolannnonium benzenetricarboxylate Ethanolammonium benzenetetracarboxylate Emanolammonium chlorobenzoate Ethanolammoniirm fluorobenzoate Ethanolammoniiim pentachlorobenzoate Ethanolammoriium pentafluorobenzoate Ethanolammoniitm salicylate Ethanolammonium glycolate Ethanolammonium lactate-Ethanolammonium pantothenate Ethanolammonium tartrate Ethanolammonium hydrogen tartrate Ethanolammonium mandelate Ethanolammonium crotonate Ethanolammordum malate Ethanolammonium pyruvate Ethanolammonium succinate Ethanolammonium citrate Ethanolammonium fumarate Ethanolammonium phenylacetate Ethanolammonium oxalate
Emanolamnioniuinbis(trifluoromemylsulphonyl)imide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate
11

WO 2005/097731 PCT/GB2005/001364
Ethanolarnmonium hydrogen phosphate
Ethanolammonium dihydrogen phospiiate
EthaBolammonium methanesulfonaie
Ethanolammonium trifluoromethanesiolphonate
Etlianolammonium ethylenediaminetetraacetate
Ethanolammonium hexafluorophosphate
Ethanolammonium tetrafluoroborate
Ethanolammonium trifluoroacetate
Etlianolammonium pentafluoropropan.oate
Ethanolammonium heptafluorobutcinoate
Emanolammoniumphosphoenolpyruvate
Ethanolammonium nicotinamide adenine dinucleotide phosphate
Ethanolammonium adenosinephosphate
Etlianolammonium adenosine diphosphate
Ethanolammonium adenosine triphosphate
Etlianolammonium oxyniacate
Ethanolammonium nitrate
Ethanobammonium nitrite
Diethaaolammonium 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
12

WO 2005/097731 PCT/GB2005/001364
Diemanolammonrum hexanedioate Diethanolammonium hexenoate Diethanolaminonl"um heptanoate Diethanolammonium heptanedioate Diemanolammonrum heptenoate Diethanolammonixam octanoate Diethanolammonium octanedioate Diethanolammonium octenoate Diethanolammonium nonanoate Diethanolammonium nonanedioate Diethanolammonium nonenoate Diethanolammonium decanoate Diethanolammonium decanedioate Diethanolammonium decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate Diethanolammonium dodecanedicarboxylate Diethanolammonium dodecenecarboxylate Diethanolammonium cyclohexanecarboxylate Diethanolammom'umcyclohexenecarboxylate Diethanolammom'um phenoxide Diethanolammonium benzoate Diethanolammonium benezenedicarboxylate Diethanolammonium benzenetricarboxylate Dietbanolammonium benzenetetracarboxylate Diethanolammonium chlorobenzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate
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WO 2005/097731 PCT/GB2005/001364
Diethanol ammonium salicylate
DiethaD-olammonium glycolate
Diethan-olammonium lactate
Diethanolammonium pantothenate
DiethanolammoniuD3 tartrate
Diethanolammonium hydrogen tartrate
Diethanolammonium mandelate
Diethanolammonium crotonate
Diethanolammonium rnalate
Diethanolammonium pyruvate
Diethanolammonium succinate
Diethanolammonium citrate
Diethanolammoniuni fumarate
Diethanolammonium phenylacetate
Diethanolammonium oxalate
Diethanolammonium bis(trifluoromethylsulphonyl)imide
Diethanolammonium carbonate
Diethanolammonium hydrogen carbonate
Diethanolammoniuin phosphate
Diethanolammonium hydrogen phosphate
Diethanolammoniuin dihydrogen phosphate
Diethanolamrnoniurainethanesulphonate
Diethanolammoniuin trifluoromemanesulphonate
Diethanolammoniuin ethylenediaminetetraacetate
Diethanolammonium hexafluorophosphate
Diethanolammoniuin tetrafluoroborate
Dietlianolammonium trifluoro acetate
Diethanolammonium pentafluoropropanoate
Diemanolammoniurn heptafluoro butanoate
Diethanolammonium phosphoenolpynivate
Diethanolammonium nicotinamide adenine dinucleotide phosphate
14

WO 2005/097731 PCT/GB2005/001364
Diemanolammonrum adenosinephosphate Diemanolamrnoni-um adenosine diphosphate Diemanolanimonrum adenosine triphosphate Diethanolanimonixim oxyniacate Diethanolanunoni"um nitrate Diethanolammonrum nitrite N-Butyldiethanolaxomonium chloride N-Butyldiethanolammonium bromide N-Butyldiethanolainmonium iodide N-Butyldiethanolainmonium formate N-Butyldiethanolammonium acetate N-Butyldietlianolammonium propanoate N-Butyldiethanolammonium propanedioate N-But3ddiethanolammonium butanoate N-Butyldiethanolammonium butenoate N-Butyldiethanolammonium butanedioate N-Butyldiethanolarnmonium pentanoate N-Butyldiethanolarnmonium pentanedioate N-Butyldiethanolaxnmonium pentenoate N-Butyldiethanolammonium hexanoate N-Butyldiethanolarnmonium hexenoate N-Butyldiethanolarnmonium heptanoate N-Butjddiethanolammonium heptanedioate N-Butyldiethanolammonium heptenoate N-ButyldiethanolammoniuE4 octanoate N-Butyldiethanolammonium octanedioate N-Butyldiethanolammonium octenoate N-Butyldiethanolammomum nonanoate N-Butyldiethanolammonium nonanedioate N-Butyldiethanolammonium nonenoate N-Butyldiethanolammonium decanoate
15

WO 2005/D97731 PCT/GB2005/001364
N-Butyldiethanolauimonium decanedioate N-Buty] diethanolamniooium decenoate N-Buty] diemanolammonium undec anoate N-Butyldiemanolammorriumundecanedioate N-Butyl di ethanolarnmonium undecenoate N-Buty]diethanolainmonium dodec;anoate N-Butyldiethanolainmoniurn dodecanedicarboxylate N-Buty] diethanolanimonium dodecenecarboxylate N-Buty] diethanolammonium cyclohexanecarboxylate N-Buty] di ethanolammoniurn cyclohexenecarboxylate N-Buty] diethanolammonium phenoxide N-Butyldiethanolammonium benzoate N-Buty] diethanolatDmonium benezenedicarboxylate N-Buty] diethanolaaunonium benzenetricarboxylate N-Buty] diethanolammonium benzenetetracarboxyiate N-Buty] diethanolammonium chlorobenzoate N-Buty] diethanolammonium fluorobenzoate N-Buty] diethanolammonium pentachlorobenzoate N-Buty] diethanolammonium pentafhiorobenzoate N-Buty] diethanolammonium salicylate N-Buty] diethanolammonium glycolate N-Buty] diethanolammonium lactate N-Butyldiethanolammonium pantothenate N-Butyldiethanolammonium tartrate N-Buty] diethanolammonium hydrogen tartrate N-Butyldiethanolammonium mandslate N-Buty] diethanolammonium crotonate N-Butyldiethanolammonium malate N-Buty] diethanolammoni'um pyruvate N-Butyldiethanolammonium succinate N-Buty] diethanolammonium citrate
16

WO 2005/097731 PCT/GB2005/001364
N-Butydiemanolammonium fumarate N-Butydiethanolammonium phenylacetate N-Butydiethanolanrmonium oxalate
N-Butydiethanolammoniirnibis(trifluoromethylsiilphonyl)iniide N-Butydiethanolammoniurn carbonate N-Butydiethanolammoniiun hydrogen carbonate N-Buiyldiethanolammonirun sulphate N-Biityldiemanolammomum hydrogen sulphate N-Butyldiethanolammonium phosphate N-Butyldiethanolammonium hydrogen phosphate N-Butyldiethanolammonium dihydrogen phosphate N-Butyldiethanolammonium methanesulphonate N-Butyldiemanolammoniumtrifluoromethanesulphonate N-Butyldemanolammomuniemylenediaminetetraacetate N-Butyldiethanolammonium hexafluorophosphate N-Butyldiethanolammonium tetrafluoroborate N-Butyldiethanolammonium trifluoroacetate N-Butyldiethanolammonium pentafluoropropanoate N-Butyldiethanolammonium heptafluorobutanoate N-Butyldiethanolammonium phosphoenolpyruvate 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 N5N-Dimethylethanolammonium formate N,N-Dhnethylethanolammonium acetate
17

WO 2005/097731 PCT/GB2005/001364
N,N-Dinaethylethano]ammonium propanoate
NN-DImethylethano] ammonium propanedioate
N,N-Diiiaethylethano]ainriioniiimbutanoate
N,N-Dimethylethano] ammonium butenoate
N,N-Diiiiethylethanolammonium butaoedioate
N,N-Dimethylethanolammoiiiumpentanoate
N,N-DmiethylethanolammoniumpeDtanedioate
N,N-DmiethylethanolammoniumpeQtenoate
N,N-Dimethylethanolaramonium bexanoate
N,N-Dtmetbylethanolammomumbexenoate
N5N-Dimethylethan.olammonium beptanoate
N,N-D imethylethanolammonium heptanedioate
N,N-Dimethylethanolammoniumheptenoate
N,N-DiDaethylethaiiolammonium octanoate
N,N -D imethy] ethanolammonium octanedioate
N,N-Dtmethylethanolammonium octenoate
N,N-Diiiaethylethanolammoniumnonanoate
N,N-Dimethylethano lammonium nonauedioate
IN ,N-D imetbylethanolammonium nonenoate
N,N-Dimethylethano lammonium decanoate
N ,N-DirQethylethanolammonium decanedioate •.
N,N-Dkaethylethanolammoniuin decenoate
N,N-Diraethyletha]aolammoniumui]Ldecanoate
N,N-Dimethyletlianolammoniuni undecanedioate
N,N-DirQethylethanolammoniumurLdecenoate
N,N-Dimethylethaaolammonium dodecanoate
N,N-Dixmetbylethaaolammoniumdodecanedicarboxylate
N,N-DkmethylethaDiolammoniumdodecenecarboxylate
N,N-Dkaethylethanolamraonium cyclohexanecaxboxylate
N,N-Dknethyletb.anolammonium cyclohexenecaxboxylate
N,N-Dimemylethanolammonitimphenoxide
18

WO 2005/097731 PCT/GB2005/001364
N,N-Dimethylethanolammonium benzoate N,N-Dimefhylethanolammoiiiumbenezenedicarboxylate N,N-Dim.ethylethanolammoniximbenzenetricarboxylate N,N-Dimetiiylethaaolariimoniiimbenzeiietetracarboxy"late N,N-Dimethylethanolammonium chlorobenzoate N,N-Dimethylethanolammoniuiafluoroberizoate NjN-Dimethylethanolammoniumpentachlorobenzoate N,N-DimetiiylethaiLolaminoniurapentafluoroberizoate N,N-Dimethylethanolammonium salicylate N,,N-Dimethylethanolaminoiiium glycolate N,N-Dimethylethanolammonium lactate N,N-Dimethylethanolammoniutn pantothenate N,N-Dimethylethanolammoniuin tartrate N,N-Dimethylethanolammonium hydrogen tartrate N,N-Dimethylethanolarrirnordiim mandelate N,N-Dime1iiylethaiiolaminoniiim crotonate N,N-Dime1hylethanolammomurii malate N,N-Dimethylethanolammoniiim pyruvate N,N-Dimethylethanolammonium succinate N,N-Dimethylethanolanrrnonium citrate NiN-Dimethylethanolammonium fumarate N,N-DimethylethanolaminoiuumpherLylacetate N5N-Dimethylethanolammonium oxalate
N,N-Dimethylethanolainmoiumnbis(1xifluoromethylsulphonyl)iirJide N,N-Dimethylethanolammoiuum carbonate N,N-Dimethylethanola.m m onium hydrogen carbonate N,N-Dirnethylethanolammonium sulphate N,N-Dirnethylethanolarnmoniurn hydrogen sulphate N,N-Dirnethylethanolamrnoniurn phosphate N5N-Dimethylethanolammonium hydrogen phosphate N5N-Dirnethylethanolarnmonium dihydrogen phosphate
19

WO 2005/097731 PCT/GB2005/001364
N,N-Dimethylethanolammonium msthanesulphonate N,N-Dinietihylethanolaininoiiiiiin trifluoromethanesulphonate N,N-Dimethylethanolammonium ethylenediaminetetraacetate N,N-Din:iethylethanolammoiiiiimhe:xafluorophosphate N,N-DirriemylethanolammoruumtetTaimoroborate N,N-Dimethylethanolammoniuiii trifluoroacetate N,N-Din:iethylethanolammoniiimpentafluoropropanoate N,N-Ditiiethylethanolammoniiimheptafluorobutanoate N,N-Dirriethylethanolaiiimordiimphosphoenolpyruvate
N,N-Dirriemylethanolammonium nicotinamide adenine dinucleotide phosphate N,N-Dimethylethanolammonium adenosiaephosphate NjN-Dimethylethanolammonium adenosme diphosphate N,N-Dimethylethanolainmonium adenosine triphosphate N,N-Dimethylethan.olammoniumo5syniacate N,N-DirrLethylethanolammonium nitrate N,N-Din:Lethylethanolammoniiim nitrite N-Methylethanolammonium bromide N-Methyletb.anolarnmonium iodide N-Methylethanolarninoriium formate N-Methyleth.anolammonium acetate N-Methylethanolammoniumpropanoate N-MethyLethanolammoniumpropanedioate N-Methylethanolammoniumbutanoate N-MethyLethanolammonium butenoate N-Metbylethanolarnmoniumbutanedioate N-Methy!ethanolarimx>murnpentanoate N-Methyl ethanolammonium pentanedioate N-Methylethanolarnmoniumpentenoate N-Methyl ethanolaromoniumhexanc'ate N-Methyl ethanolammoniumhexenoate N-Methyiethanolacomoniumheptanoate
20

WO 2005/097731 PCT/GB2005/001364
N-Methylethanolammonitim heptanedioate N-Methylethsnolammoniuru heptenoate N-Methylethanolammonium octanoate N-Methylethanolammonium octanedioate N-Methyletlianolammonium octenoate N-Methylethanolammoniirtn nonanoate N-Methylethanolammonium nonanedioate N-Methylethanolaimnonium nonenoate N-Metliylethanolammonium decanoate N-Methylethanolammonium decanedioate N-Methylethanolammomumdecenoate N-Methylethanolammom'iun undecanoate N-Methylethanolammomum uadecanedioate N-Methylethanolammom'um undecenoate N-Methylethanolammonium dodecanoate N-Methylethaxiolammonium dodecanedicarboxylate N-Methylethanolammonium dodecenecarboxylate N-Methylethanolammonium cyclohexanecarboxylate N-Methylethanolammonium cyclohexenecarboxylate N-Methylethaolammonium phenoxide N-Methylethanolammonium benzoate N-Methylethaxiolammonium benezenedicarboxylate N-Methylethaolammoniumbenzenetricarboxylate N-Methylethaxiolammoniumbenzenetetracarboxylate N-Methylethaaiolammonium chlorobenzoate N-Methylethaxiolammonium fluorobenzoate N-Methylethaxiolammoniumpentachlorobenzoate N-Methylethanolammonium pentafluorobenzoate N-Methylethanolammomum salicylate N-Methylethanolammonium glycolate N-Methylethanolammonium lactate
21

WO 2005/097731 PCT/GB2005/001364
N-Methylethanolammomiimpantothenate
N-Methyletihanolammonium tartrate
N-Methylethanolammoniurn hydrogen tartrate
N-Methylethanolarmaoniummandelaie
N-Methylethanolammonium crotonate
N-Methylethanolammonium malate
N-Methylethanolammonium pyruvate
N-Methylethanolammonium succinate
N-Methylethanolammonium citrate
N-Methylethanolammonium fumarate
N-Methylethanolammonium phenylacetate
N-Methy lethanolammonium oxalate
N-Methy lethanolammonium bis(triihioromethylsulphony l)imide
N-M ethylethanolammonium carboD ate
N-Methylethanolammonium hydrogen carbonate
N-Methylethanolammonium sulphate
N-Methylethanolammonium hydrogen sulphate
N-Methylethanolammonium phosphate
N-Methylethanolammoniurn hydrogen phiosphate
N-Methylethanolammonium dihydrogen phosphate
N-Methylethanolammonium methanesulphonate
N-Metiiylethanolarnmoniumtrifluoromethanesulphonate
N-Methylethanolammomumethylenedicrirriinetetraacetate
N-Metihylethanolammonium hexafluoropliosphate •
N-Methylethanolammonium tetrafluoroborate
N-Methylethanolammonium trifluoroacetate
N-Methylethanolammonium pentafluoropropanoate
N-Methylethanolammonium heptafluoroh>utanoate
N-Methylethanolammonium phosphoenolpyruvate
N-Methylethanolammonium nicotinamide adenine dinucleotide phosphate
N-Methylethanolammonium adenosinepkosphate
22

WO 2005/097731 PCT/GB2005/001364
N-Memylethanolammonium adenosine diphosphate N-Memylethanolammoiuum adenosine triphosph.a.te 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(methox)rethyl)ammonium propanoate N,N-Di(methoxyethyl)ammoniumpropanedioate N,N-Di(mefhoxyethyl)ammonium butanoate N,N-Di(methoxyethyl)ammonium butenoate N,N-Di(methoxyethyl)ammoniumbutanedioate N,N-Di(methoxyethyl)ammonium pentanoate N,N-Di(methoxyethyl)ammoniumpentanedioate N,N-Di(methoxyethyl)ammoniumpentenoate N,N-Di(methoxyethyl)ammonium hexanoate N,N-Di(niethoxyethyl)ammonium hexenoate N,N-Di(methoxyethyl)arnmonium heptanoate N,N-Di(methoxyethyl)ammoniiimheptanedioate N,N-Di(methoxyethyl)ammoniumheptenoate N,N-Di(methoxyethyl)ammonium octanoate ' N,N-Di(methoxyethyl)ammoniumoctanedioate N,N-Di(methoxyethyl)ammonium octenoate N,N-Di(methoxyethyl)ammonium nonanoate N,N-Di(methoxyethyl)ammonium nonanedioate N,N-Di(methoxyethyl)ammonium nonenoate N,N-Di(methoxyethyl)amm onium decanoate N,N-Di(methoxyethyl)ammonium decanedioate
23

WO 2005/097731 PCT/GB2005/001364
N,N-Di(methoxyethyl)ammoniiiindece.Qoate
N,N-Di(me1iioxyethyl)aminoniumui:idecaiioate
N,N-Di(methoxyethy] )airunoniuin undecanedioate
N,N-Di(metboxyetliyl)airimoniumuiidecenoate
N,N-Di(methoxyethyl)ammoniumdodecanoate
N,N-Di(methoxyethyl)ammonium dodecanedicarboxylate
N,N-Di(methoxyethyl )arnmoniurn dodecenecarboxylate
N_,N-Di(methoxye1iiyl)aminoniuin c}rclohexanecarboxylate
N,N-Di(methoxyethyl)ammoniumcyclohexenecarboxylate
N,N-Di(methoxyeth.yl)ammoniiimphenoxide
N,N-Di(rnetboxyetl:iyl)ammoniumbenzoate
N,N-Di(inetbox3rettLyl)axaiiioniuinbenezenedicarbo?sylate
N,N-Di(me1iioxye1hyl)ammoniuinben2,enetricarboxylate
N,N-Di(methoxyeth.yl)ammoniuinbenz,enetetracaxboxylate
N,N-Di(inethoxyethyl)ammonium.chlorobenzoate
N,N-Di(me1iioxyethyl)aminoniuinfluoroben2;oate
N,N-Di(inethoxyethyl)amniordiimpe;ntachlorobenz(>ate
N,N-Di(inetboxyethyl)ainmoriiuinpeiitafluorobenzoate
"NTjN-Di(inetioxyeijLyl)timinoriiiiinsalicylate
N,N-Di(methoxyethyl)ammoniiraig]ycolate
N,N-Di(methoxyettiyl)ammoniiun lactate
N,N-Di(methoxyethyl)ammoniirai pantothenate
N,N-Di(methoxyethyl)aminoriiuintartrate
N,N-Di(inethoxyethyl)ammonium hydrogen tartrate ¦
N,N-Di(methoxyethyl)ammonium. m andelate
N,N-Di(inethoxyethyl)ammoniuracrotonate
N5N-Di(inethoxyethyl)ammoni"Lim. m alate
N,N-Di(inethoxyet]:iyl)ammoniumpyruvate
N,N-Di(inethoxyettLyl)ammoriiiiin succinate
N,N-Di(inethoxyethyl)ammoniton citrate
N,N-Di(inethoxyethyl)ctrrxmoniiirnfbirn;jrate
24

WO 2005/097731 PCT/GB2005/001364
N,N-Di(methoxyethyl)ammoniumphenylacetate N,N-Di(methoxyethyl)ammonium oxalate
N,N-Di(methoxyet]iyl)aiinnordiimbis(trifluoromethylsulphonyl)iiQiie N,N-Di(methoxyethyl)ammomum carbonate N,N-Di(methoxyethyl)ammonium hydrogen carbonate N,N-Di(metiioxyethyl)arnnioniurn sulphate N,N-Di(methoxyethyl)arnmomum hydrogen sulphate N,N-Di(methoxyethyl)ammonium phosphate N,N-Di(methoxyethyl)arnrrionium hydrogen phosphate N5N-Di(methoxyethyl)arnmoniurn dihydrogen phosphate N,N-Di(methoxyethyl)ammoniurnrjQethanesulphonate N,N-Di(methoxye1iiyl)arrimoriiurntriiluoromethanesulphonate N,N-Di(methoxyethyl)ammornumethylenediaminetetraacetate N,N-Di(methoxyethyl)arnmoniumhexafluorophosphate N,N-Di(methoxye1iiyl)arnrnoniumtetrafluoroborate N,N-Di(methoxyethyl)arrrmoniumtrifluoroacetate N3N-Di(me1iioxye1iyl)aminoriiurnpentafluoropropanoate N,N-Di(methoxyethyl)arnrnoniumheptafluorobutanoate N,N-Di(methoxyethyl)amrnoniumphosphoenolpyruvate N3N-Di(methoxyethyl)arnmonium nicotinamide adenine dinucleotide phosphate N,N-Di(methoxyethyl)aminoiiiurQ adenosinephosphate N,N-Di(me1iioxyethyl)arnrnonium adenosine diphosphate N,N-Di(methoxyethyl)arnmoniurn adenosine triphosphate N,N-Di(methoxyethyl)arnmoniurn oxyniacate N,N-Di(me1iioxye1liyl)arnmoriium nitrate N,N-Di(methoxyethyl)airLmqnium nitrite l-(3-Hydrox5'propyl)putrescrnium chloride l-(3-Hydroxypropyl)putresciruum bromide l-(3-Hydroxypropyl)putrescinium iodide l-(3-Hydroxypropyl)putrescinium formate l-(3-Hydroxypropyl)putrescinium acetate
25

WO 2005/097731 PCT/GB2005/001364
1 -(3-Hydroxypropyl)putrescinium propanoate
1 -(3-Hydroxypropyl)putresciiihirn propanedioate
1 -(3-Hydroxypropyl)putxescinium butanoate
1 -(3-Hydroxypropyl)putrescinium butenoate
1 -(3-Hydroxypropyl)putrescioium butanedioate
1 -(3-Hydroxypropyl)putrescinium pentanoate
1 -(3-Hydroxypropyl)putrescirdum pentanedioate
1 -(3-Hydroxypropyl)putresciniuin pentenoate
1 -(3-Hydroxypropyl)putrescinium hexanoate
1 -(3-Hydroxypropyl)putrescinium hexenoate
1 -(3 -Hy droxypropyl)putresciiiium heptanoate
1 -(3 -Hy droxypropyl)putrescinium heptanedioate
1 -(3-Hydroxypropyl)putrescinium heptenoate
1 -(3-Hydroxypropyl)putrescinimn octanoate
1 -(3-Hydroxypropyl)p"utrescinium octanedioate
1 -(3-Hydroxypropyl)putrescinium octenoate
1 -(3-Hydroxypropyl)putrescinium nonanoate
1 -(3-Hydxoxypropyl)putrescinium nonanedioate
1 -(3-Hydroxypropyl)putresciniiuii nonenoate
1 -(3-HydToxypropyl)putrescinium decanoate
1 -(3-Hydroxypropyl)p"utresciniura decanedioate
1 -(3-Hydroxypropyl)putrescinium decenoate
1 -(3-Hydroxypropyl)putresciiuum undecanoate
1 -(3-Hydroxypropyl)pntrescinium undecanedioate
1 -(3-Hydraxypropyl)putresciniuin 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'
1 -(3-Hydroxypropyl)putrescinium phenoxide
26

WO 2005/097731 PCT/GB2005/001364
l-(3~Hydroxypropyl)putrescimum benzoate
1 -(3-Hydroxypropyl)putresciniuni benezenedicarboxylate
1 -(3-Hydroxypropyl)putresciaiuiii benzenetricarboxylate
1 -(3-Hydroxypropyl)putrescinium benzenetetracarboxylate
1 -(3-Hydroxypropyl)putresciniurn chlorobenzoate
1 -(3-Hydroxypropyl)putresciniuiii fluorobenzoate
1 -(3-Hydroxypropyl)putrescinium pentachlorobenzoate
1 -(3-Hydroxypropyl)putrescinium pentafluorobenzoate
1 -(3-Hydroxyprop5d)putrescinium salicylate
1 -(3 -Hydrox5'propyl)putresciQium glycolate
l-(3-Hydroxypropyl)putresciriiurn lactate
1 -(3 -Hydroxypropyl)putxescinium pantothenate
l-(3-Hydroxypropyl)putrescinium tartrate
l-(3-Hydroxypropyl)putrescinium hydrogen tartrate
1 -(3 -Hydroxypropyl)putrescinium mandelate
1 -(3 -Hydroxypropyl)putrescinium crotonate
l-(3-Hydroxypropyl)putrescinium malate
l-(3-Hydroxypropyl)putresciniuin pyruvate
1 -(3 -Hydroxypropyl)putrescioium succinate
l-(3-Hydroxypropyl)putrescinium citrate
l-(3-Hydroxypropyl)putrescinium fumarate
1 -(3 -Hydroxypropyl)putresciaimn phenylacetate
l-(3-Hydroxypropyl)putresckiium oxalate
1 -(3-Hydroxypropyl)putrescinium bis(trifluoromethylsulphonyl)irriide
1 -(3-Hydroxypropyl)putrescinium raethanesulphonate
1 -(3-Hydroxypropyl)putrescinium trifluoromethanesulphonate
1 -(3-Hydroxypropyl)putresciniurQ hexafluorophospliate
1 -(3-Hydroxypropyl)putresciniirai tetrafluoroborate
1 -(3-Hydroxypropyl)putescinium trifluoroacetate
l-(3-Hydroxypropyl)putrescinium pentafluoropropanoate
1 -(3-Hydroxypropyl)putrescinium heptafluorobutanoate
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WO 2005/097731 PCT/GB2005/001364
1 -(3-Hyciroxyj)ropyl)putrescinium phosphoenolpyruvate 1 -(3-Hydroxypropyl)putresciniuin nicotmarnide adenine dinucleotide phosphate l-(3-Hydroxypropyl)putresciniumadeno3inephosphate l-(3-Hydroxypropyl)putrescinium adenosine diphosphate l-(3-Hydroxypropyl)putrescinium adenosine triphosphate 1 -(3-Hydroxypropyl)putrescinium carbonate l-(3-Hydroxypropyl)putTesciiiiuiii hydrogen carbonate 1 --(3 --Hydroxypropyl)putresciriiurn sulphate l-(3-Hydroxypropyl)putresciBiiim hydrogen sulphate 1 -(3 -Hydroxypropyl)putxescinium phosphate 1 -(3--Hydroxypropyl)pu1resciniurn hydrogen phosphate , 1 -(3-Hydi'oxypropyl)putrescinium dihydrogen phosphate 1 -(3-Hydioxypropyl)put:esciriium niti'ate 1 -(3-Hydroxypropyl)putrescinium nitrite
hi one class of compounds, the invention includes the proviso that the ionic liquid is not ethylarrrmonium nitrate or diethanolamrnonium chloride. In 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 (II)
NRR'R" (IT)
in. which R, R' and R' have f tie meaning defined herein; and ii.) neutralising the compound in (i) with an acid.
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WO 2005/097731 PCT/GB2005/001364
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 (II) 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.
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WO 2005/097731 PCT/GB2005/001364
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 chrornatographic 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, lite 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 mdefinite article is used, the specification is to be understood as contemplating plurality as well as singulcirity, 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
30

WO 2005/097731 PCT/GB2005/001364
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-dimethylethanola?nmonium glycolate
Alcoholic solutions of N,N-dimethylethanolamme (lOO.OOmL, 2.000M concentration) and glycolic acid (lOO.OOmL, 2.000M concentration) were gradually mixed together in a 500mL 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, watsr content 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.

WO 2005/097731 PCT7GB2005/001364
FT-IR (cm"1): 1591, 1076, 1358, 687, 993,1468, 909, 1255, 881, 1154,1171, 3240, 2870, 2484,1745 IJV/vis Xmax (nm): 234 ENT (Reichardt): 0.912 Density (g cm"3): 1.146
Preparation ofN-biityldiethanolammonium bis(triflnoromethylsiilphonyl)imide
To an alcoholic solution of N-butyldiethanolamine (lOO.OOmL, 2.000M concentration) in a 500mL round-bottomed flask was gradually added 56.232g bis(trifluoromemylsulphonyl)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 98% by ion chromatography . The product was analysed and stored as previously described.
FT-IR (cm"1): 1051,1132,1181, 1347,741,791,764,580,960, 1461,2967,3523, 2941,2880,3138, 1632 LTV/vis Xmax (nm): 304 ENT (Reichardt): 0.994 Density (g cm"3): 1,343
APPLICATIONS
Enzyme-catalysed reaction in N,N~dimethylethanolammoniwn glycolate
Alcohol dehydrogenase: Methanol (50uL) was dissolved in the ionic liquid (6mL) with a net water content of 32

WO 2005/097731 PCT/GB2005/001364
for 24 hours, with vigorous shaking being maintained throughout. Samples (lmL) 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.
Biodegi-adation ofN,N-dimethylethanolammoniumglycolate
N,N-Dimemyle1ianolarnmonium glycolate (5mM) was used as sole nitrogen and carbon source for the selective enrichment of a mixed community of soil microorganisms 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 30°C, with shaking at llOrpm. Degradation was monitored using ion chromatography. 5mM Ionic liquid was readily degraded (>98% removal) within 48 hours, the final nitrogenous metabolite being ammonia.
33

WO 2005/097731 PCT/GB2005/001364
OAMS
1. Ail ionic liquid comprising an anion and a cation characterised in that the
cation is a nitrogen-coataining cation of the formula (I)
N+HRR'R" (I)
in which R is a hydrocarbyl group optionally substituted witli by one 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, alkoxy, 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 EL" 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
cyclobydxocarbyl or heterocyclyl group.
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WO 2005/097731 PCT/GB2005/001364
. 6. An ionic liquid as claimed in claim 5 Avherein 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, arnino, 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 di-alkanol, tri-alkanol
or tetra-allcanol group.
13. An ionic liquid as claimed in claim 12 wherein the cation is an
ethanolammomurn, N-(alkoxyethyl)arnmonium3 N-methylethanolammonium, N,N-
dimethylethanolarnmonium, diethanolammonium, N-alkyldiethanolammonium, N,N-
di(alkoxyalkyl)ammonium or triethanolammonium ion.
14. An ionic liquid as claimed in claim 13 wherein the cation is a
methylethanolammonium, N,N-dimethylethanolamnionium, N, N-
di(methoxyethyl)ammonium) or butyldiethanolammonium ion.
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WO 2005/097731 PCT/GB2005/001364
15. Aa ionic liq[uid as claimed in claim 1 wherein R is an aminoalkyl group
having 2 to 8 C atoms
16. AJI 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
tr opine.
18. An ionic liquid as claimed in claim 1 wherein the cation is selected from the
group consisting of an ethanolammonium, diethanolammonium, N-
butyldietbLanolarnmoniurn, N-rnethylethanolammonium, N,N-
dirjQethylethaaiolarniQom'um, puiiescmium, l-(34iydroxypropyl)putrescinium, or N-
(3 -hydroxypropyl)-N-methylcyclohexylammonium cation.
19. An ionic liquid as claimed in claim 18 wherein the cation is N-
b uty ldiethanolammoni um, N-methylethanol aminonium,
di(metho>:yethyl)ammomum., N,N-dimethylethanolamraonium, putrescinium, l-(3-
hy"droxypropyl)putrescinium, or N-(3-hydroxypropyl)-N-
methylcyclohexylaminoniurja ion.
20. An io:nic liquid as claimed in claim 1 whereia the anion is selected from the
group consisting of halogenated inorganic anions, nitrates, sulphates, phosphates,
c;arbonates, sulphonates and carboxylates.
21. Aa ionic liquid as claimed in claim 20 wherein the sulphonates and
carboxylates .are alkylsulphonates and alkylcarboxylates respectively.
22. Aa ionic liquid as claimed ia claim 21 wherein the alkyl group is a moiety
selected from alkyl and alkyl substituted at any position with alkenyl, alkoxy,
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WO 2005/097731 PCT/GB2005/001364
alkeneoxy, aiyl, arylalkyl, atyloxy, amino, aminoalkyl, thio, thioaUcyl, 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(trifluoromemylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate,
hydrogen sulphate, silicate, phosphate, hydrogen phosphate, dfhydrogen phosphate,
metaphosphate, methanesulphonate, trifluoromethanesulphonate,
ethylenediaminetetraacetate, chloride, bromide, iodide, hexafhiorophosphate,
tetrafluoroborate, trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate,
oxalate, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, heptanoate,
octanoate, nonanoate, decanoate, benzoate, benezenedicarboxylate,
benzenetricarboxylate, benzeneterracarboxylate, chlorobenzoate, fluorobenzoate,
pentachlorobenzoate, pentafluorobenzoate salicylate, glycolate lactate, pantothenate,
tartrate, hydrogen tartrate, mandelate, crotonate, malate, pyruvate, succrnate, 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
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WO 2005/D97731 PCT/GB2005/001364
Ethanolammoniurn. pentenoate Ethanolammonimn hexaiioate Ethanolatumoninm hexanedioate Ethanolaminomum. hexeaoate EHianolatmnonium heptanoate EUbanolammonium heptanedioate Eilianolammonium. heptenoate Ethanolammonium octanoate Ethanolairimonium. octanedioate Ethanolammonium octenoate Ethanolairimonium. nonanoate Ethanolaminonium nonanedioate Ethanolammonium nonenoate Ethanolammonium decanoate Ethanolammonium decanedioate Ethanolammonium decenoate Ethanolammonium imdecanoate Ethanolammonium undecanedioate Ethanolammonium undecenoate Ethanolammonium dodecanoate Ethanolammonium. dodecanedicarboxylate Ethanolammonium dodecenecarboxylate Ethanolammonium cyclohexanecarboxylate Ethanolaramonium cyclohexenecarboxylate E,thanolammonium phenoxide Ethanolammonium benzoate Ethanolarnmoniuxn benezenedicarboxy] ate Elthanolarnmoniumbenzenetricarboxylate Elthanolammoniumbenzenetetracarboxylate Ethanolammonium chlorobenzoate Ethanolammonium fluorobenzoate
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WO 2005/097731 PCT/GB2005/001364
Ethanolammoniurn pentachlorobenzoate Ethanolaminonium 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 futnarate Ethanolammonium phenylacetate Ethanolammonium oxalate
Emanolaimonumbis(trifluoromethylsulphonyl)imide Ethanolammonium carbonate Ethanolammonium hydrogen carbonate Ethanolammonium sulphate Ethanolammonium hydrogen sulphate Ethanolammonium phosphate Ethanolammonium hydrogen phosphate Ethanolammonium dihydrogen phosphate Ethanolammomum methanesulfonate Ethanolammonium trifhioromemanesulphonate Ethanolammonium ethy'lenediaminetetraacetate Ethanolammonium hexafluorophosphate Ethanolammonium tetrafluoroborate Ethanolammonium trifluoroacetate
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WO 2005/097731 PCT7GB2005/001364
EthanolammoniiraipentafluoropropanoaT.e
Ethanolammonium heptafluorobutano ate
Ethanolammoniumphosphoenolpyruvate
Ethanolammonium nicotiaaroide adenine dinucleotide phosphate
Ethanolammonium adenosinephosphate
Ethanolammonium adenosine diphosphate
Ethanolammonium adenosine triphosphate
Ethanolammonium oxyniacate
Ethanolammonium nitrate
Eliianolammonium nitrite
Diethanolammonium bromide
Diethanolammonium iodide
Diethanolammonium formate
Diethanolammonium acetate
Diethanolammonium propanoate
Diethanolammonium propanedioate
Diemanolarnmoriium butanoate
Diethanolammonium butenoate
Diethanolammonium 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
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WO 2005/097731 PCT/GB2005/001364
DiethanolammoniurQ nonanoate Diemanolammonium nonanedioate Diethanolammonium nonenoate Diethanolammonium decanoate Diemanolammonium decanedioate Diemanolammoniuni decenoate Diethanolammonium undecanoate Diethanolammonium undecanedioate Diethanolammonium undecenoate Diethanolammonium dodecanoate ' Diethanolammonium dodecanedicarboxylate Diethanolammonium dodetenecafboxylate Diethanolammonium cyclohexanecarboxylate Diethanolammonium cyclohexenecarboxylate Diethanolammonium phenoxide Diethanolammonium benzoate Diethanolammonium benezenedicarboxylate Diethanolammonium benzenetricarboxylate Diethanolammonium benzenetetracarboxylate Diethanolammonium chlorobemzoate Diethanolammonium fluorobenzoate Diethanolammonium pentachlorobenzoate Diethanolammonium pentafluorobenzoate Diethanolammonium salicylate Diethanolammonium glycolate Diethanolammom'um lactate Diethanolammonium pantotkenate Diethanolammonium tartrate Diethanolammonium hydrogen tartrate Diethanolammom'um mandelate Diethanolammonium crotonate
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WO 2005/097731 PCT/GB2005/001364
Diethanolammonium malate
DiethanoLammonium pyruvate
Diethanolammonium succinate
Diethanolammonium citrate
Diethanolammonium fumarate
D iethanolemmonium phenylacetate
Diethanolammonium oxalate
Diemanolammoniumbis(trifluoromethylsulphonyl)imide
Diethanolammonium carbonate
Diethanolammonium hydrogen carbonate
Diemanolammonium phosphate
Diethanolammonium hydrogen phosphate
Diethanolammonium dihydrogen phosphate
Diethanoliammonium methanesulphonate
Diethanol;arnmoniuni trifluoromethanesulphonate
Diethanolainmonium ethylenediaminetetraacetate
D iethanolammoniuni hexafluoropho sphate
Diethanolammonium tetrafluoroborate
C'iethanolarnmonium uifluoroacetate
Diethanolammoniunipentafluoropropanoate
Diethanolammoniuniheptafluorobutanoate
Diethanolammonium phosphoenolpyruvate
Diethanolammonium nicotinamide adenine dinucleotide phosphate
Diethanol ammonium adenosinephosphate
Diethanolammonium adenosine diphosphate
Diethanolammonium adenosine triphosphate
Diethanolammoniuna oxyniacate
Diethanolammonium nitrate
DiethanoLammonium nitrite
N-Butyldiethanolammonium chloride
N-Butyldiethanolammonium bromide
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WO 2005/097731 PCT/GB2005/001364
N-Butyldiethanolammonium iodide N-Butyldiethanolarnmonium formate N-Bulyldiemanolammoniuni acetate N-Butyldiethanolamrnonium propanoate N-Butyldiethanolanimonium propanedioate N-Butyldiethanolammordum butanoate N-Butyldiemanolanimonium butenoate N-Butyldiethanolammonium butanedioate N-Butyldiethanolammoniuin pentanoate N-Butyldiethanolammonium pentanedioate N-Butyldiethanolammonium pentenoate N-Butyldiethanolammonium hexanoate N-Butyldiethanolammonium hexenoate N-Butyldiethanolammonium heptanoate N-Butyldiethanolammonium heptanedioate N-Butyldiethanolammonium heptenoate N-Butyldiethanolammonium\)ctanoate N-Butyldiethanolammonium octanedioate N-Butyldiethanolammonium octenoate N-Butyldiethanolammonium nonanoate N-Butyldiethajaolammonium nonanedioate N-Butyldiethanolammonium nonenoate N-Butyldiethanolammonium decanoate N-Butyldiethanolammonium decanedioate N-Butyldiethanolammonium decenoate N-Butyldiethanolammonium undecanoate N-Butyldiethanolammonium undecanedioate N-Butyldiethanolammonium undecenoate N-Butyldiethanolammonium dodecanoate N-Butyldiethanolammonium dodecanedicarboxylate N-Butyldiethanolammonium dodecenecarboxylate
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N-Butyldiethaaolamnionitcyclohexanecarboxylate N-Butyldietbanolammoiiiumcyclohexenecarboxylate N-Butyldiethanolammonmmphenoxide N-Butykliethanolammoniumbenzoate N-Butylciiethanolaroxnoniumbenezenedicarboxylate N-Buiykliethanolammonium benzeBetricarboxylate N-Butyldiethanolanmionhmiberizenetetxacarboxylate N-ButyldiethanolammomumcbJorobenzoate N-Butykliethanolammoniurnfluorobenzoate N-Buty ldiethanolammo nixum pentac Morobenzoate N-Bu1yldiethanolaDirri()niunipentafl.uorobenzoate N-Butykiiethanolammonium salicylate N-Butyldiethanolammonium glycolate N-Butyldietbanolammonium lactate N-Butylcliethanolanirrioniurnpantothenate N-Butyldiethanolammonium tartrate N-Butyldiethanolamrtionium hydrogen tartrate N-Butyldietiianolarjmiomummandelate N-Butylfiiethanolaromonium crotonate N-Butyldiethanolanmionium malate: N-Butyldiethanolaranionium pyruvate N-Butyldiethanolammonium succmate N-Butyldiettianolaromoniuni citrate N-Butyldietlianolammonium fumarate N-Butyldiethanolarnmonimxiphenylacetate N-Butyldiethanolamnioniura oxalate
N'Butyldiethanolarnnioriiiuribis(trifluoromethylsulphriyl)imide N-Butyldietlianolarnmoniuin carbonate N-Butyldiethanolammonium hydrogen carbonate N'Butyldietlianolammonium sulphate N-Butyldietiianolanimoniitm hydrogen sulphate
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WO 2005/097731 PCT/GB2005/001364
N-Butyldiethaaolammoniiim phosphate N-Butyldiethanolamrnonium hydrogen phosphate N-Butyldiethanolammomum dihydrogen phosphate N-Buryldiemanolammoin'ummethanesulphonate N-Butyldiethanolaminoniiimtrifluoromethanesulphonate N-Butyldiethanolanitnoniiimethylenediaminetetraacetate N-But}ddiethanolaminoniiimhexafluorophosphate N-Butyldiethanolammoniumtetrafluoroborate N-Butyldiemanolammonium trifluoroacetate N-Butyldiethanolarnrnoripentafluoropropanoate N-Butyldiethanolammonium hep tafluorobutanoate N-Butyldie1iianolaminoniumphosphoenolpyruvate N-Butyldiemanolammonium nicotinamide adenine dinucleotide phosphate N-Butyldiethanolaminoniiiinadenosinephosphate N-Butyldiethanolammonium adenosine diphosphate N-Butyldiethanolaramonium adenosine triphosphate N-Butyldiethanolammonium oxyniacate N-Butyldiethanolammonium nitrate N-Butyldiethanolammonium nitrite N,N-Dimethylethanola.mm onium bromide N,N-Dimethylethanolammonium iodide N,N-Dimethylethanolamnionium formate N,N-Dimeth3flethanola.mjn onium acetate N,N-Dimethylethanolarnmonium propanoate N,N-Dimethylethanolammonium propanedioate N,N-Dimethylethanolammonium butanoate N,N-Dmethylethanolarnrnonium butenoate N,N-Dirnethylethanolainmonium butanedioate N,N-Dimethylethanolammonium pentanoate N,N-Dime1hylethanolamrnonium pentanedioate N;N-Dimethylethanolainmoriium pentenoate
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WO 2005/097731 PCT/GB2005/001364
N,N-Dimetlayletliaolanunoniuinliexanoate
N,N-D imethyletlianol ammonium hexeno ate
N,N-Dmie&yle1iianolarnmoniuinlieptanoate
N,N-Diriiemylethanolammoniumhe;ptanedioate
N\N-Dmiemyletfianolammomumheptenoate
N,N-Dimethyletlianolammonium octanoate
N,N-Dimethyl ethano lammonium octanedioate
N,N-Dimethylethanolammoniuinoctenoate
N,N-Dmethylefhanolainmoniumnonanoate
N,N-Diraethylethano lammonium nonanedioate
'N,N-Diraethylethanolammoniumnonenoate
N,N-Dkaethylethanolammoniiim decanoate
N,N-Dimethylethaaolammomumde5canedioate
N,N-Direthylethanolammonium decenoate
N,N-Dethylethanolammoniumundecanoate
N,N-Dethylethajaolamrnonium\iiidecanedioate
N,N-Dnethyleti.iaiiolammoniumujidecenoate
N,N-Dimethylethanolammoniumdodecanoate
N,N-Dknethyle1olammoniitind()decanedicarboxyla_te
N,N-Dimethylethariolammonium dodecenecarboxylate
N,N-DiinethyletiianolarDinoiiium cyclohexanecarboxylate
N,N-Dunemylethaiiolammoniitm cyclohexenecarboxylate
N,N-Diinemylethaiiolammoniumphenoxide
N,N-Diinemylethaiiolammoniumberizoate
NjN-Dunethylethanolammoniumbenezenedicarboxylate
N,N-Diinemylethanolaminoniiimbenzenetricarboxylate
N,N-Diineth.ylethaiaolammoniiimbenzenetetracarboxylate
N5N-Dunethylemanolammonixtrn.cMorobenzoate
N,N-Dimethylethaaolammonium fluorobenzoate
N,N-Diinemylethanolammoniumpentachlorobenzoate:
N,N-Diinethylethanolammoiiiiim pentafluorobenzoate
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WO 2005/097731 PCT/GB2005/001364
N,N-Dimeth.ylethanolammonium salicylate NJ^-Dimethylethanolammorniirn glycolate N,N-Dimethylethanolaiiimonium lactate N.N-Dimethyletlianolainnioniiimpantotheriate NjN-Dimethylethanolammomum tartrate N,N-DimethylethaaolaramoniuiQ hydrogen tartrate N,N-Dimethylethanolammoiiium mandelate N,N-Dimetiiylethanolamrnoniurn crotonate N,N-Drrnethylethanolarrrmoniiirn malate N,N-Dimethylethanolamraonium pyruvate N,N-Dimetriylethanolarnmoniiirn succinate N,N-Dimethylethanolarrira.oriiiim. citrate N,N-Dimethyletxianolamrxioriiurn tumarate N,N-Diraethylethanolammonium phenylacetate N,N-Dimethylethanolamrnoiiiurn oxalate
N,N-Dimetiiylethanolarrimoniiimbis(triiluoromethylsxilphonyl)imide N,N-Dimethylethaaolamrriorriiim carbonate N,N-Dimethylet±ianolammorjium hydrogen carbonate N,N-Dime1iiylethanolarnrnoriiiuri sulphate N,N-Dimethylethanolarnmomum hydrogen sulphate N,N-Dimethyletiianolarnrnoriium phosphate N;N-Dimethylethanolarrjrnonium hydrogen phosphate N,N-Dimeuiyletlianolamrnorriuni dihydrogen phosphate N,N-Dimethylethaiiolamrnorriurnniethanesulphonate N,N-Dimeuiylet±ianolmrimoniumrrifluoromethanesulphonate N,N-Dimethylethanolammoniumethylenediarriineterraacetate N,N-Dirnethyletlianolainrnorriumhexafluorophosphate N,N-Drmethyle1±ianolairirnoiuumtetrafluoroborate N,N-Dimethyletlianolarnmomurntrifluoroacetate. N,N-Dimethylethanolamrnoniurnpenta£luoropropanoate N,N-Dimethyletkanolarnrnoniurnheptailuorobutanoate
47

WO 2005/097731 PCT/GB2005/001364
N,N-Dime.thylethanolaminoniumphosphoenolpyTuvate
N,N-Dirnethylethanolatriinonium nicotinamide adenine dinucleotide phosphate
N.N-Dime:thylethanolanuiumadenosiephosphate
N;N-Dime:thy]ethanolaromoniiiiii adenosine diphosphate
N,.,N-Dime;thy]ethanolammonium adenosine triphosphate
N;N-Dimetiby] ethanolammonium oxyniacate
N,N-Dimt:th.ylethanolan:anoniiuii nitrate
N. N-Dime:thylethanolammonium nitrite
N-Methyl N--Methylethanolammonlum iodide
N-Methylt;thanolarattionium formate
N-Methyl N-MethylethanolairLimomunipropanoate
N-Methylethaaolammotniumpropanedioate
N-Methylistlianolamjtnoriiuinbutanoate
N-Metitiylethaaolamimoniiini butenoate
N-Methylethanolanxmordumbutanedioate
N-Methylethanolanrmordum pentano ate
N-Methyl(3thanolam;[noniiimpentanedioate
N-Methylethanolammoniumpentenoate
N-Methyl ethanolartimoniuin hexanoate
N-MethylethanolaniDioriiirai hexenoate
N-Methylethanolaramomuniheptanoate
N -Methyl ethanolammonium heptanedioate
N-Methylethanolammoniumheptenoate
N-Metlaylethanolammonium octanoate
N-Methylethanolammoniumoctanedioate
N-MethyletlaanolammoniurQ octenoate
N-Methyl N-Methylethano lammonium nonanedioate
N~MethylethanoLammomumnonenoate
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WO 2005/097731 PCT/GB2005/001364
N-Methylemanolammonium decanoate N-Methylemanolammorriuni decanedioate N-Methylemanolarnmonium decenoate N-Memylemanolammonium undecanoate N-Methylethanolammom'um undecanedioate N~Memylemanolammonium undecenoate N-Methylethanolammonium dodecanoate N-Methylethanolammonium dodecanedicarboxylate N-Methylethanolammonium dodecenecarboxylate N-Methylethanolammonium cyclohexanecarboxylate. N-Methylethanolammonium cyclohexenecarboxylate N-Methylethanolammonium phenoxide N-Meth5dethanolammonium benzoate N-Methylethanolammonium benezenedicarboxylate N-Methylethanolammonium benzenetricarboxylate N-Methylethanolammonium 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-Me1iiylethanolaminonium crotonate N-Methylethanolammonium malate N-Methylethanolammonium pyruvate N-Methylethanolammonium succinate
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WO 2005/097731 PCT7GB2005/001364
N -Methyl ethanolanimontum citrate
N-Memylethanolammonium funiarate
N-Memylethatiolanxmoniumphenylacetate
N-Methylethanolammonium oxalate
N-MethylethanolamBiorii\imbis(1iifluoromethylsulphonyl)imide
N-Methylethanolammo mum carb onate
N--Metl"iyk;tliaiiolammomum hydrogen carbonate
N-Methylethanolammonium sulphate
N-Methylethanolammonium hydrogen sulphate
N-Methylethanolammonium phosphate
N-Methylethanolammonium hydrogen phosphate
N-M ethylethanol ammonium dthydro gen phosphate
N-Methylethanolammonium methanesulphonate
N-Methylemanolamiiioniiim.trifluoromethanesulphonate
N -Methylethanolammordum emylenediaminetetraacetate
N-Methyletihanolammonium hexafluorophosphate
N-Methylethanolammoniumtet]:afluoroborate
N-MethylethanLolammoniumtrifluoroacetate
N-Methylethcinolammoniumpentailuoropropanoate
N-Methylethanolamnioniuniheptailuorobu.tanoate
N-Methylethanolanimomumphosphoenolpyruvate
N-Methylethanolamrrj.onium nicotiniamide adenine dinucleotide phosphate
N-Methylethianolanunonium adenosinephosphate
N-Methylethanolammonium adenosine diphosphate
N-Methylethanolammonium adenosine triphosphate
N-Meth5rlethanolanimonium oxyniacate
N-Methylethanolammonium nitrate
N-Methyletbanolai)Qmonium nitrite
N,N-Di(memoxyettiyr)ammonium chloride
N,N-Di(methoxyethyl)ammonium bromide
]Sr,N-Di(methoxyethyl)ammoniurja iodide
50

WO 2005/097731 PCT/GB2005/001364
N3N-Di(methoxyethyl)ammonium formate N,N-Di(raethoxyeth.yl)ammonium acetate N,N-Di(metlioxyethyl)ammonium propanoate N,N-Di(methoxyethyl)ammoniumpropanedioate N,N-Di(m.ethoxyethyl)ammoniuin butanoate jNf,N-Di(methoxyethyl)amiDonium butenoate N,N-Di(inetb.oxyethyl)amnioniumbutanedioate ]Sf,N-Di(methoxyethyl)ammoniurQ pentanoate 1SI,N-Di(niethoxyetb.yl)amm onium pentanedioate N,N-Di(inethoxyethyl)ammonium pentenoate N,N-Di(methoxyethyl)arnmoiiiiiin hexanoate lNf,N-Di(methoxyetb.yl)ammoniimi hexenoate 2ST,1S[-Di(raethoxyethyl)ammonium heptanoate N,N-Di(methoxyethyl)ammoriitixnheptanedioate N,N-Di(metiioxye&yl)animoidumheptenoate N,N-Di(methoxyethyl)amrQonium octanoate N,N-Di(me1iioxyethyl)ammoiiiumoctanedioate N,N-Di(methoxyethyl)ainmonivun octenoate N,N-Di(methoxyethyl)arnmoiiiiim nonanoate N,N-Di(methoxyethyl)ammoniinnnonanedioate N,N-Di(methoxyethyl)arumoEiium nonenoate N,N-Di(methoxyethyl)ammonium decanoate N,Isf-Di(methoxyetb.yl)amnioriiiimdecanedioate N,N-Di(raetb.oxyethyl)aminomuin decenoate N,N-Di(metibLoxyethyl)anunoiuuin undecanoate N,N-Di(metiioxyet]iyl)arrimoriiumirndecanedioate N?N-Di(methoxyethyl)ainino^iiim undecenoate N,N-Di(methoxyethyl)aminordiini dodecanoate N7N-Di(methoxyethyl)ainjndiiimndodecanedicarboxylate N,N-Di(metb.oxyeth.yl)animoriiiimdodecenecarboxylate N,N-Di(methoxyethyl)aiimioiiiiiincyclob.exaaecarboxylate
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WO 2005/097731 PCT/GB2005/001364
N,N-Di(methoxyethyl)ammonivim cyclohexenecarboxyjate
N,N-Di(methoxyethyl)ammoriiumphenoxide
N,N-Di(tue:tibLOX3'ethyl)axrimotiiiiaibenzoate
N,N-Di(methoxyethyl)ammonium benezenedicarboxylate
N,N-Di(methoxyethyl)aimnoniiunbenzenetricaiboxylate
N,N-Di(methoxyethyl)auunoniumberizenetetracarboxylate
N,N -Di(methoxyethyl)ammoiii'ura chl orobenzoate
N,N-Di(methoxyethyl)axrimoDiiinifluorobenzoate
N,N-Di(methoxyethyl)atomoniuinpeiitaclilorobenzoate
N,N- Di(niethoxyetliyl)arninonium pentafluorobenzoate
N,N-Di(]3iethoxyeth3'l)ammoniimi s;alicylate
N,N-Di(methoxy ethyl) ammonium glycolate
NjN-Di(m.ethoxyethyl)ammoniumlactate
N,N~Di(m.ethoxyethyl)ammoniumpaatotheiiate
N,N-Di(methoxyethyl)ammoniuin tartrate
N,N-Di(methoxyethyl)atnmonium hydrogen tartrate
N,N-Di(meth(3xyethyl)ammoniuni mandelate
N,N-Di(rciethoxyethyl)arrirrioiiiurncrotoriate
N,N-Di(methoxyethyl)ammoniummalate
N,N-Di( nieth.ox>rethyl)ammonium pyruvate
N,N-Di(r)iethoxyeth3d)ainmoniiirn succinate
N,N-Di(methoxyetliyl)ammoEdtirQ citrate
N,N-Di(raethoxye1iiyl)arninoniiirnfltrnarate
N,N-Di(rDethoxyethyl)ammoniTHn phenylacetate
N,N~Di(methoxyettiy])ammonium oxalate
N,N-Di(ine1iioxye1iiyl)ariimordiimb:Ls(1iifluorome1iiylsxilphonyl)im
]sF,N-Di(methoxyethyI)ammoniuinc;3xboBate
N,N-Di(methoxyethyl)ammonium hydrogen carbonate
N,N-Di(methoxyethyl)aromoiiium sulphate
N,N-Di(methoxyethyr)ammoninm hydrogen sulphate
N,N-Di(methoxyethyl)ainrnoniurji phosphate
52

WO 2005/097731 PCT/GB2005/001364
N,N-Di(methoxyethyl)ammonium hydrogen phosphate
N,N-Di(methoxyethyl)ammbnium dihydrogen phosphate
N,N-Di(methoxyethyl)ammoniuriiniethanesiilphonate
N,N-Di(methoxyetiiyl)anmioniiimtiifluoromethaiiesulphoria.te
N,N-Di(methoxyetliyl)ammoiiiume1iiylenediarQiiietetraacetate
N,N-Di(methox}rethyl)ammoniumhexafluorophosphate
N,N-Di(methoxyethyl)ammoniumtetrailuoroborate
N,N-Di(methoxyethyl)aininoniumtrifluoroacetate
N,N-Di(methoxyethyl)ammoniumpentafluoropropanoate
N,N-Di (rnethoxyethyl)ammonium heptafluorobutanoate
N,N-Di(methoxyethyl)amm oniurn phosphoenolpyruvate
N,N-Di(methoxyethyl)aminonitxm nicotinamide adenine dinucleotide phosphate
N,N-Di(methoxyethyl)ammordumadenosinephosphate
N,N-Di(methoxyethyl)ammonium adenosine diphosphate
N,N-Di(methox}rethyl)amrQoniiiin adenosine triphosphate
N,N-Di(methoxyethyl)ammoniuin oxyniacate
N5N-Di(raethoxyefhyl)amm0niinn nitrate
N;N-Di(methoxyethyl)ammoiiitun nitritel-(3-Hydroxypropyl)putrescinium chloride
l-(3-Hydrox}'propyl)putrescinium bromide
1 -(3-Hyo!roxypropyl)putrescimirm iodide
1 -(3 -Hydroxypropyl)putrescinium formate
l-(3-Hydroxypropyl)putrescinium acetate
1 -(3 -Hydi-ox)'propyl)putrescinium propanoate
1 -(3-Hydroxypropyl)putrescinium propanedioate
1 -(3-Hydroxypropyl)putrescinium butanoate
1 -(3-Hydroxypropyl)putrescinium butenoate
1 -(3-Hydroxypropyl)putrescinimn butanedioate
1 -(3-Hydroxypropyl)putrescinium pentanoate
1 -(3-Hydrox3'propyl)putrescinium pentanedioate
1 -(3-Hydroxypropyl)putrescinium pentenoate
1 -(3-Hydroxypropyl)putresciniiim hexanoate
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WO 2005/097731 PCT/GB2005/001364
1 -i3-Hydroxypropyl)puti-escinium hexenoate
1 -(3-Hydroxypropyl)putrescinium heptanoate
1 -{3 -Hydroxypropyl)putrescinium heptanedioate
l-(3-Hydroxypropyl)putresciniumheptenoate
l-(3-Hydroxypropyl)putrescinium octanoate
1 -(3-Hydroxypropyl)putrescinium octanedioate
l-(3-Hydroxypropyl)putrescinium octenoate
l-(3 -Hydroxypropyl)putrescinium nonanoate
1 - (3 -Hydroxypropyl)putrescinium nonanedioate
1 - (3 -Hydroxypropyl)putrescinium nonenoate
1 -(3 -Hydroxypropyl)putrescinium decanoate
1 -(3 -Hydroxypropyl)putrescinium decanedioate
1 -(3 -Hydroxypropyl)putrescinium decenoate
1 -(3 -Hydroxypropyl)putrescinium undecanoate
1 -(3-Hydioxy;propyr)putresciiiium undecanedioate
1 -(3-Hydi'oxypropyl)putrescinium undecenoate
1 -(3 -Hyd]'oxypropyl)putrescinium dodecanoate
1 -(3 -Hydiroxypropyl)putresciDium dodecaaedicarboxylate
1 -(3-Hydiroxypropyl)putresciDium dodecenecarboxylate
1 -(3-Hydroxypropyl)putresciiiiuiii cyclohexanecarboxylate
1 -(3-Hydroxypropyl)putresciiiium. cyclohexenecarboxylate
1 -(3-Hydroxypropyl)putresciniuni phenoxide
] -(3-Hydroxypropyl)putrescinium benzoate
1 -(3-Hydroxypropyl)putxescinium benezenedicarboxylate
1 -(3-Hydroxypropyl)putrescinium benzenetricarboxylate
1 -(3 -Hydroxypropy l)putrescinitim benzenetetracarboxy] ate
1 -(3-Hydroxypropyl)putrescinium cHorobenzoate
l-(3-HydroxypTopyl)putrescinium fluorobenzoate
1 -(3 -Hyclxoxypropyl)putresckii"um pentachlorobenzoate
1 -(3 -Hyclxoxypropyl)putresciniiim pentafluorobenzoate
1 -(3 -Hydroxypropyl)putrescinium salicylate
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WO 2005/097731 PCT/GB2005/001364
1 -(3 -Hydroxypropyl)putresciniuni glycolate
1 -(3 -Hydrox)'propyl)putresciniimi lactate
1 -(3 -HydroxypropyDputrescinium paiitotlienate
l-(3-Hydxoxypropyl)putxescinium tartrate
1-(3-Hydroxypropyl)putresciniurn hydrogen tartrate
1 -(3-HydroxypropyDputrescinium mandelate
1 -(3 -HydroxypropyDputrescinium crotonate
l-(3-Hydroxypropyl)putrescinium malate
1-(3-Hydroxypropyl)putrescinium pyruvate
1 -(3 -HydroxypropyDputrescinium succinate
1 -(3-HydroxypropyDputrescinium citrate
1-(3-HydroxypropyDputrescinium fumarate
1 -(3 -HydroxypropyDputrescinium phenylacetate
l-(3-HydroxypropyDputrescinium oxalate
1 -(3-HydroxypropyDputrescinium bis(trifluoromethylsulphonyDimide
l-(3-HydroxypropyDputrescmium methanesulphonate
1 -(3-HydroxypropyDputrescinium trifluoromethanesulplionate
1 -(3-HydroxypropyDputrescimum hexafluorophosphate
1 -(3-HydroxypropyDputrescinium tetrafluoroborate
1 -(3 -HydroxypropyDputrescinium trifluoroacetate
1 -(3-HydroxypropyDputrescinium penta£Iuoropropanoate1 -(3 -HydroxypropyDputrescinium heptafluorobutanoate ;¦
1 -(3 -HydroxypropyDputrescinium phosphoenolpyruvate
l-(3-HyaoxypropyDputresciniumnicotinamide adenine dinucleotide phosphate
1 -(3-HydroxypropyDputrescinium adenosinephosphate
1-(3-HydroxypropyDputrescinium adenosine diphosphate
l-(3-HydroxypropyDputrescinium adenosine triphosphate
1 -(3 -HydroxypropyDputrescinium carbonate
1-(3-HydroxypropyDputrescinium hydrogen carbonate
l-(3-HydroxypropyDputrescinium sulphate
1-(3-HydroxypropyDputrescinium hydrogen sulphate
55

WO 2005/097731 PCT7GB2005/001364
I -(3-Hydroxypropyl)putrescimum. phosphate l-(3-Hydroxypropyl)putrescinium hydrogen phosphate l-(3-Hydroxypropyl)putrescinium dihydrogen phosphate 1 -(3-Hydroxypropyl)pufrescmiurn nitrate 1 -(3-Hydroxypropyl)putresciaium 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 nitrogen-containing compound of the formula (11)
NRR'R" (II)
in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), ttuol, alkythio, sulphonyl, thiocyanate, isotbiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, ali:oxy, alkenyl, hydroxy, carbonyl (including aldehyde or ketone), cacrboxyl, boronate, silyl and substituted amino (e.g. mono- or di-alkylamino-, or afkyamido); 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.
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WO 2005/097731 PCT/GB2005/001364
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 en2yrne-catalysed reactions, a solvent for organic
synthesis, a matrix in matrix-assisted 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 nitrogen-containuag
cation of the formula (I)
N'HRR'R" (1)
in which R is a hydrocarbyl group optionally substituted with by one or more substituents selected from nitro gen-containing functional groups (including nitrile, nitro or amino or another basic rntrogen-conta.in.ing 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 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.
31. A method for carrying out an enzyme-catalysed reaction comprising
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WO 2005/097731 PCT/GB2005/001364
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.
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.

Documents:

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Patent Number

269875

Indian Patent Application Number

3208/KOLNP/2006

PG Journal Number

47/2015

Publication Date

20-Nov-2015

Grant Date

13-Nov-2015

Date of Filing

03-Nov-2006

Name of Patentee

INNOVIA FILMS LIMITED

Applicant Address

STATION ROAD, WIGTON CUMBRIA CA7 9BG , THE UNITED KINGDOM

Inventors:

#	Inventor's Name	Inventor's Address
1	WALKER, ADAM, JOHN	Great Britain,1 Long Row, Welby, Grantham, Lincolnshire NG32 3LZ,

PCT International Classification Number

C07C215/40

PCT International Application Number

PCT/GB2005/001364

PCT International Filing date

2005-04-07

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0407908.3	2004-04-07	U.K.