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WO2007063327A1 - Sels d’hydroxylammonium en tant que liquides ioniques - Google Patents

Sels d’hydroxylammonium en tant que liquides ioniques Download PDF

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WO2007063327A1
WO2007063327A1 PCT/GB2006/004503 GB2006004503W WO2007063327A1 WO 2007063327 A1 WO2007063327 A1 WO 2007063327A1 GB 2006004503 W GB2006004503 W GB 2006004503W WO 2007063327 A1 WO2007063327 A1 WO 2007063327A1
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ionic liquid
liquid according
hydroxylammonium
hydroxylammonium ions
ions
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Adam John Walker
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Bioniqs Ltd
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Bioniqs Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/06—Glycolic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/12—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/077—Ionic Liquids

Definitions

  • This invention relates to ionic liquids, their preparation and their uses.
  • Ionic liquids are compounds which are composed exclusively or predominantly of ions but are in liquid form, generally having a melting point below ambient temperature. They arise from combinations of suitable ions, in which the lattice energy and melting point are abnormally low. This may be achieved through the use of bulky, asymmetrical, charge-delocalised ions, which associate relatively weakly and with a low degree of structural order.
  • Ionic liquids can possess a number of remarkable properties, including negligible vapour pressure, high solubilising power and a broad liquid temperature range, which have rendered them interesting alternatives to conventional liquids in a variety of applications.
  • Ionic liquids may be made up of anions and cations or alternatively may consist of zwitterions which carry both a positive and a negative charge on the same molecule. Most commonly an ionic liquid will comprise an anion and a cation.
  • ionic liquids comprised nitrogen- or phosphorous-based cations, generally substituted with one or more alkyl groups. Examples were based on a nucleus selected from quaternary ammonium cations, pyrrolidinium cations, imidazolium cations, triazolium cations, pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations and triazinium cations. These types of ionic liquids tend to be highly viscous, potentially hazardous and strongly absorbent of UV and visible light. Furthermore, the preparation of these ionic liquids can involve a number of chemical and chromatographic steps that can make the process time consuming, expensive and inefficient.
  • modified ionic liquids were disclosed in which one of the component ions, typically the cation, included a functional group selected from alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl groups.
  • a functional group selected from alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl groups.
  • WO-2005/097731 discloses further ionic liquids which comprise as the cation a primary, secondary or tertiary ammonium ion containing a protonated nitrogen atom.
  • the nitrogen atom can be substituted with one, two or three hydrocarbyl groups, and the hydrocarbyl groups can themselves be substituted, in order to tailor their functionality, with groups such as nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), thiol, alkylthio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen, alkyl optionally interrupted by one or more ether or thioether linkages, alkoxy, alkenyl, hydroxy, carbonyl, carboxyl, boronate, silyl and substituted amino.
  • Such liquids have been found to demonstrate high solvation capabilities, low viscosity and low toxicity, making them useful in a broader
  • the charged nitrogen (or on occasions phosphorous) atom at the nucleus of the cation is bound only to hydrogen and/or carbon atoms.
  • Ionic liquids containing a hydroxyl group -OH on one of the hydrocarbyl side chains have been used, as described in WO-2004/063383, as reaction media for biocatalytic reactions.
  • the enzyme used is a hydrolase, however, such ionic liquids can suffer from the drawback that the hydroxyalkyl function may interfere with or participate in the reaction being catalysed.
  • the present inventors have developed alternative ionic liquids, examples of which can overcome or at least mitigate this drawback, which can have a range of desirable properties and/or which can broaden the range of applications for ionic liquids in particular as solvents and more particularly in biocatalysis.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from hydrogen or hydrocarbyl.
  • the ionic liquid has the formula:
  • n is an integer, for example from 1 to 3, typically 1 or 2, most typically 1, and X is a suitable anion for instance as described below.
  • This liquid is novel over previously known ionic liquids in that it incorporates a direct covalent bond between a charged nitrogen atom and an oxygen atom. It thus incorporates the -OR 4 functionality that has previously only been present as a substituent on hydrocarbyl groups, and the associated benefits in terms of solvation properties, in particular polarity and hydrogen bonding ability. However the oxygen atom is no longer readily esterifiable and is therefore stable for use in biocatalytic reactions involving hydrolases and similarly reactive moieties. Ionic liquids according to the invention can also be biodegradable, especially when the counterion is chosen appropriately (for example the anion may be acetate, propionate, glycolate or lactate).
  • Ionic liquids according to the invention may also have relatively low, often water-like, viscosities, and can thus be more easily processed and handled for instance when used as bulk reaction media.
  • Certain ionic materials of the general formula R 1 R 2 R 3 N + -OR 4 X ⁇ are already known, but exist in solid form at ambient temperature and typically have relatively high melting points. Examples include hydroxylammonium chloride (melting point 155- 159 0 C), hydroxylammonium phosphate (melting point 169-171 0 C), hydroxylammonium sulphate (melting point 17O 0 C), N-methyl hydroxylammonium chloride (melting point 86-88 0 C), N,N-dimethyl hydroxylammonium chloride (melting point 107-109 0 C) and N-methyl methoxylammonium chloride (melting point 112- 115 0 C).
  • An ionic liquid according to the present invention in contrast, must exist in liquid form, at least under the operating conditions relevant to its intended use.
  • it will be capable of existing in liquid form below 5O 0 C, preferably below 4O 0 C, more preferably below 3O 0 C and ideally at room temperature, which for the present purposes may be defined as from 18 to 25°C, typically about 2O 0 C.
  • the charged nitrogen atom 1ST may be either a primary, a secondary, a tertiary or a quaternary nitrogen; in other words, respectively, either all, two, one or none of R 1 , R 2 and R 3 may be hydrogen.
  • at least one of R 1 , R 2 and R 3 is not hydrogen, especially if R 4 is hydrogen.
  • R 1 , R 2 and R 3 may be hydrogen, and yet more preferred for none of R 1 , R 2 and R 3 to be hydrogen - in other words, the cation is preferably a quaternary ammonium cation.
  • R 4 is selected from hydrogen and unsubstituted alkyl, typically C 1 to C 8 or C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl such as methyl, ethyl or propyl or such as methyl or ethyl, in particular methyl.
  • R 4 is hydrogen
  • R 4 is unsubstituted alkyl as defined above.
  • R 4 is hydrogen.
  • hydrocarbyl may be defined as any group containing carbon and hydrogen, which may also contain one or more heteroatoms such as oxygen, nitrogen, sulphur, phosphorous or halogen.
  • the term embraces saturated, partially saturated and unsaturated groups, whether aromatic or aliphatic, whether straight chain, branched chain, cyclic or any combination thereof.
  • Hydrocarbyl thus includes, but is not limited to, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aralkyl, alkaryl, heterocyclyl, heteroaryl, alkoxy and moieties containing a combination of two or more such groups.
  • a hydrocarbyl group is unsubstituted.
  • it does not contain any heteroatoms.
  • alkyl includes both straight and branched chain alkyl radicals, of any chain length but typically of from 1 to 12 carbon atoms, more suitably from 1 to 10 or from 1 to 8 carbon atoms, preferably from 1 to 6 or from 1 to 4 or from 1 to 3 (for instance 2 or 3) carbon atoms.
  • Suitable examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • cycloalkyl encompasses aliphatic saturated hydrocarbyl ring-containing moieties such as for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • alkenyl includes both straight and branched chain alkenyl radicals, which contain one or more carbon-carbon double bonds. Again they may be of any chain length, typically from 2 to 12 carbon atoms, more suitably from 2 to 10 or from 2 to 8 carbon atoms, yet more preferably from 2 to 6 carbon atoms. Examples include ethylene, n-propyl-1-ene, n-propyl-2-ene and isopropylene.
  • Cycloalkenyl encompasses ring-containing groups where the ring structure incorporates one or more carbon-carbon double bonds.
  • alkynyl includes both straight and branched chain alkynyl radicals, which contain one or more carbon-carbon triple bonds. They may be of any chain length, typically from 2 to 12 carbon atoms, more suitably from 2 to 10 or from 2 to 8 carbon atoms, yet more preferably from 2 to 6 carbon atoms. "Cycloalkynyl” encompasses ring-containing groups where the ring structure incorporates one or more carbon- carbon triple bonds.
  • aryl includes aromatic (and thus at least partially unsaturated) hydrocarbyl groups, which will typically incorporate one or more cyclic structures. Such groups may contain for example from 3 to 12 carbon atoms, preferably from 3 to 10 or from 4 to 8 carbon atoms. They may be fused to one or more saturated or unsaturated rings. A typical example is phenyl. It is to be noted that the term “hydrocarbyl” also embraces radicals which combine both alkyl and aryl moieties, in particular aralkyl and alkaryl groups such as for instance benzyl.
  • heterocyclyl includes a ring system containing one or more heteroatoms selected for example from N, O and S. It may be saturated, unsaturated or partially unsaturated. The ring containing the heteroatom may be fused to one or more other rings, which in turn may be saturated, unsaturated or partially unsaturated and may themselves contain heteroatom(s).
  • a heterocyclyl radical will be a 3 to 10- membered ring system, preferably a 5 to 10-membered system, more preferably a 5- or 6-membered system. It may be or incorporate aromatic moieties.
  • cyclic groups such as cycloalkyl, aryl or heterocyclyl include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzotbiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isooxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine,
  • alkoxy includes both straight chain and branched alkyl radicals, for example of 1 to 12 carbon atoms, preferably of 1 to 8 or 1 to 6 carbon atoms, which contain one or more oxygen atoms or hydroxyl.
  • alkoxy groups include methoxy and ethoxy groups, as well as alcohols (which may be mono-, di- or polyols) such as in particular (CH 2 ) n OH where n is an integer from for example 1 to 8, preferably from 1 to 6 or from 1 to 4.
  • halogen means either F, Cl, Br or I, typically either F, Cl or Br, more typically either F or Cl.
  • a heterocyclic group such as for example a piperidine or piperazine group.
  • nitrogen-containing cyclic groups are preferably aliphatic. In embodiments of the invention, it may however be preferred that none of the groups R 1 to R 3 be joined together in this way.
  • a hydrocarbyl group may be substituted, at any point(s) along its length, with one or more substituents selected for example from nitrogen-containing functional groups (including nitrile, nitro or amino or another basic nitrogen-containing functional group), thiol, alkylthio, sulphonyl, thiocyanate, isothiocyanate, azido, hydrazino, halogen (for instance fluorine, chlorine or bromine, in particular fluorine or chlorine), alkyl optionally interrupted by one or more ether or thioether linkages, alkoxy, alkenyl, hydroxyl, carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl, substituted amino (eg, mono- or di-alkylamino or alkyamido) and hydrocarbyl groups as defined above.
  • nitrogen-containing functional groups including nitrile, nitro or amino or another basic nitrogen-containing functional group
  • thiol alkylthio,
  • substituents for use in this context are selected from the group consisting of alkenyl, hydroxyl, alkoxyl, amino, thio, carbonyl and carboxyl groups. More preferably, substituents are selected from hydroxyl, alkoxyl, carbonyl and amino groups. Most preferably, they are selected from hydroxyl and alkoxyl groups, in particular hydroxyl.
  • R 1 to R 3 may be alkyl (suitably C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl) substituted with one or more (suitably one) hydroxyl groups; in other words, it may be an alkanolyl group such as a C 1 to C 4 or C 1 to C 3 alkanolyl group, for example ethanolyl or propanolyl.
  • R 1 to R 3 may be alkyl (suitably C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl) substituted with one or more (suitably one) alkoxy groups.
  • Suitable alkoxy groups are C 1 to C 4 or C 1 to C 3 alkoxy groups, such as methoxy or ethoxy.
  • Substituents may in particular be selected so as to tailor the ionic liquid to have one or more desired properties, for instance as described in WO-2004/063383. hi particular the liquid may be tailored to mimic one or more properties of water (or indeed of any other solvent which it is intended to replace).
  • functional groups may be included which provide a labile proton, which are capable of hydrogen-bonding and/or which increase polarity.
  • the chain length of the substituents R , R and R will influence the melting point, viscosity and other physicochemical properties of the ionic liquid.
  • R 1 , R 2 and R 3 is an optionally substituted alkyl group, typically a C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl group such as ethyl or propyl or such as methyl or ethyl, preferably an unsubstituted alkyl group.
  • both R and R are optionally substituted alkyl, preferably C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl such as methyl, ethyl or propyl or such as methyl or ethyl, preferably unsubstituted alkyl.
  • R 1 and R 2 may be the same or different, preferably the same.
  • R 3 is then preferably hydrogen.
  • R 4 is also preferably hydrogen, although it may alternatively be alkyl, for example C 1 to C 8 or C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl (suitably unsubstituted) such as octyl, propyl, ethyl or methyl, in particular methyl.
  • R 1 , R 2 and R 3 may be optionally substituted alkyl, preferably C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl such as methyl, ethyl or propyl or such as methyl or ethyl, preferably unsubstituted alkyl.
  • R 1 , R 2 and R 3 may be the same or different, preferably the same.
  • R 4 is preferably hydrogen, although it may alternatively be alkyl, for example C 1 to C 8 or C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl (suitably unsubstituted) such as octyl, propyl, ethyl or methyl, in particular methyl.
  • R 1 , R 2 and R 3 are each independently selected from unsubstituted C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl.
  • R 4 is then suitably H, although it may be alkyl as discussed above.
  • the ionic liquid may be an N,N,N- trimethyl hydroxylammonium salt, an N,N,N-triethyl hydroxylammonium salt, an N,N,N-tripropyl hydroxylammonium salt or an N,N,N-tributyl hydroxylammonium salt.
  • N-methyl-N,N-dialkyl hydroxylammonium salt such as an N- methyl-N,N-diethyl hydroxylammonium salt, an N-methyl-N,N-dipropyl hydroxylammonium salt or an N-methyl-N,N-dibutyl hydroxylammom ' um salt. Most preferably it is an N,N,N-triethyl or N,N,N-tripropyl hydroxylammom ' um salt.
  • ionic liquids according to the invention may comprise cations selected from the group consisting of N-alkyl hydroxylammonium ions; N,N- dialkyl hydroxylammonium ions (for instance N,N-dimethyl, N-methyl-N-ethyl, N- methyl-N-propyl, N,N-diethyl, N-ethyl-N-propyl, N,N-dipropyl or N,N-dibutyl hydroxylammonium ions, preferably N,N-diethyl or N,N-dipropyl hydroxylammonium ions or N-ethyl-N-methyl hydroxylammonium ions); N,N,N-trialkyl hydroxylammonium ions (for instance N,N,N-trimethyl, N-ethyl-N-methyl-N-propyl, N,N,N-triethyl or N,N,N-tripropyl
  • ionic liquids comprising cations selected from the group consisting of N,N-dialkyl hydroxylammonium ions (especially N,N-diethyl hydroxylammonium ions) and N,N,N-trialkyl hydroxylammonium ions (especially N,N,N-triethyl and N,N,N-tripropyl hydroxylammonium ions).
  • R 1 may be substituted with one or more hydroxyl groups, preferably one. It may for example be an alkanolyl group such as a C 2 to C 6 , preferably a C 2 to C 5 , alkanolyl group, in particular ethanolyl, propanolyl or butanolyl, more particularly ethanolyl or propanolyl, most particularly ethanolyl.
  • alkanolyl group such as a C 2 to C 6 , preferably a C 2 to C 5
  • alkanolyl group in particular ethanolyl, propanolyl or butanolyl, more particularly ethanolyl or propanolyl, most particularly ethanolyl.
  • Such groups may in some cases be substituted with two or more, such as two or three, hydroxyl groups; they may thus contain diol or polyol moieties.
  • R 2 and R 3 are preferably each independently selected from hydrogen and unsubstituted alkyl, such as C 1 to C 6 alkyl, C 1 to C 4 alkyl or C 1 to C 3 alkyl. In some cases at least one of R 2 and R 3 is hydrogen, optionally both.
  • R and R 3 are unsubstituted alkyl, such as C 1 to C 6 alkyl, C 1 to C 4 alkyl or C 1 to C 3 alkyl - here R 2 and R 3 may be the same or different, preferably the same.
  • R4 is then preferably hydrogen, but may alternatively be alkyl, for example C 1 to C 8 or C 1 to C 6 or C 1 to C 4 or C 1 to C 3 alkyl (suitably unsubstituted) such as propyl, ethyl or methyl, in particular methyl.
  • the cation may be an N,N-dialkyl-N-(2-hydroxyethyl) hydroxylammonium ion, such as an N,N-dimethyl-N-(2-hydroxyethyl) hydroxylammoniurn ion, an N,N-diethyl-N-(2-hydroxyethyl) hydroxylammonium ion or an N,N-dipropyl-N-(2-hydroxyethyl) hydroxylammonium ion.
  • N,N-dialkyl-N-(2-hydroxyethyl) hydroxylammonium ion such as an N,N-dimethyl-N-(2-hydroxyethyl) hydroxylammoniurn ion, an N,N-diethyl-N-(2-hydroxyethyl) hydroxylammonium ion or an N,N-dipropyl-N-(2-hydroxyethyl) hydroxylammonium ion.
  • N 9 N- dialkyl-N-(2-hydroxyethyl)-O-alkyl hydroxylammonium ion preferably an N 9 N- dialkyl-N-(2-hydroxyethyl)-O-methyl hydroxylammonium ion such as an N 9 N 9 O- trimethyl-N-(2-hydroxyethyl) hydroxylammonium ion or an N,N-diethyl-N-(2- hydroxyethyl)-O-methyl hydroxylammonium ion
  • R 1 and R 2 may be hydroxyl-substituted as described above.
  • R 1 and R 2 may be the same or different, preferably the same.
  • R 3 is then preferably either hydrogen or unsubstituted alkyl, such as C 1 to C 6 alkyl, C 1 to C 4 alkyl or C 1 to C 3 alkyl. More preferably R 3 is then hydrogen.
  • R 1 , R 2 and R 3 may be hydroxyl-substituted as described above.
  • the three groups may be the same or different; preferably at least two of them are the same; more preferably all three of them are the same.
  • R 1 may be an alkoxyalkyl group, of the formula -R 4 -O-R 5 where R 4 is unsubstituted alkylene, preferably C 2 to C 6 alkylene, more preferably C 2 to C 4 alkylene, such as ethylene or propylene; and R 5 is unsubstituted alkyl, preferably C 1 to C 6 alkyl, more preferably C 1 to C 4 alkyl, such as methyl, ethyl or propyl.
  • R 2 and R 3 are preferably each independently selected from hydrogen and unsubstituted alkyl, such as C 1 to C 6 alkyl, C 1 to C 4 alkyl or C 1 to C 3 alkyl.
  • at least one of R 2 and R 3 is hydrogen, preferably both.
  • R 1 and R 2 may be alkoxyalkyl as described above.
  • R 1 and R 2 may be the same or different, preferably the same.
  • R 3 is then preferably either hydrogen or unsubstituted alkyl, such as C 1 to C 6 alkyl, C 1 to C 4 alkyl or C 1 to C 3 alkyl. More preferably R 3 is then hydrogen.
  • R 1 , R 2 and R 3 may be alkoxyalkyl as described above.
  • the three groups may be the same or different; preferably at least two of them are the same; more preferably all three of them are the same.
  • Particularly preferred ionic liquids according to the invention are those in which the cation is selected from N,N-dialkyl (in particular diethyl) hydroxylammonium ions; N,N,N-trialkyl (in particular trimethyl or more preferably triethyl) hydroxylammonium ions; and N,N-dialkyl-N-alkanolyl hydroxylammonium ions.
  • the counterion in the ionic liquid may be any suitable anion.
  • anion is its ionic weight in order to keep the freezing point of the ionic liquid below the desired temperature and the lattice energy arising from the strength of its interaction with the cation.
  • Suitable anions include halide, halogenated organic or 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 carbon atoms, selected from alkyl and alkyl substituted at any position with alkenyl, alkoxy, alkeneoxy, aryl, arylalkyl, aryloxy, amino, aminoalkyl, thio, thioalkyl, hydroxyl, hydroxyalkyl, carbonyl, oxoalkyl, carboxyl, carboxyalkyl or halogen, including all salts, ethers, esters, pentavalent nitrogen or phosphorus derivatives or stereoisomers thereof.
  • the anion may be selected from bis(trifluoromethylsulphonyl)imide, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, sulphite, hydrogen sulphite, silicate, phosphate, hydrogen phosphate, dihydrogen phosphate, hydrogen phosphite, dihydrogen phosphite, metaphosphate, methanesulphonate, ethanesulphonate, benzenesulphonate, trifluoromethanesulphonate, ethylenediaminetetraacetate, fluoride, chloride, bromide, iodide, hexafluorophosphate, tetrafluoroborate, trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, heptanoate, o
  • the anion may be selected from the group consisting of acetate, propionate, octanoate, glycolate, lactate, oxalate, hydrogen oxalate, palmitate, benzoate, 4-(octyloxy)benzoate, salicylate, sulphate, hydrogen sulphate, thiosulphate, perfluorooctanesulphonate, methanesulphonate, octanesulphonate, trifluoromethanesulphonate, benzenesulphonate, sulphamate, trifluoroacetate, bis(trifluoromethylsulphonyl)imide, hydrogen phosphate, dihydrogen phosphate, hydrogen phosphite, thiocyanate, dicyanimide, phenylphosphonate, phenylphosphinate and bromide.
  • Each of these types of ions may individually represent a preferred embodiment of the present invention.
  • An especially preferred anion is an organic carboxylate, although this may be less suitable where the ionic liquid is to be used as a reaction medium for esterase- catalysed reactions, for instance as described below.
  • the anion is required to include a labile proton then glycolate, tartrate and lactate anions may be preferred; these contain both acid and hydroxyl functional groups.
  • anions include bis(trifluoromethylsulphonyl)imide, sulphamate and organic sulphonates, sulphinates, phosphonates and phosphinates.
  • the anion may be selected from carboxylates (for example acetate, glycolate, propionate or octanoate) and sulphonates (in particular alkyl sulphonates such as methanesulphonate and trifluoromethanesulphonate).
  • carboxylates for example acetate, glycolate, propionate or octanoate
  • sulphonates in particular alkyl sulphonates such as methanesulphonate and trifluoromethanesulphonate.
  • Halides in particular chlorides, may also be suitable anions.
  • An ionic liquid according to the invention may contain cations which are all the same or which are different. It 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.
  • the cation and anion should together be chosen to ensure that the material is liquid at the requisite temperature.
  • Melting point can be affected by factors such as the size of either or both of the ions, their degree of delocalisation of charge and their degree of symmetry, as described above and in the prior art literature relating to ionic liquids.
  • the use of larger, and/or more charge- delocalised ions can for instance help to reduce the ionic liquid's melting point.
  • the invention encompasses an ionic liquid which is composed not of anions and cations but of zwitterions which carry both a positive and a negative charge: in this situation, a single ion will incorporate both the moieties R 1 R 2 R 3 N + -OR 4 and, for instance by appropriate side-chain substitution, an anionic moiety such as X n ⁇ .
  • An ionic liquid according to the invention preferably contains 1 % or less of water, by mass, preferably 1000 ppm or less and more preferably 100 ppm or less. It is thus suitably present in an anhydrous form. It may also be used in the absence of water and other aqueous solvents — for example, it may be used in an anhydrous or substantially anhydrous system which contains 1 % v/v or less, preferably 0.5 % v/v or less, more preferably 0.1 % v/v or less of water.
  • An ionic liquid according to the invention preferably has a freezing point of 4O 0 C or lower, more preferably of 3O 0 C or lower.
  • It preferably has a viscosity of 500 centipoise or less, more preferably 100 centipoise or less, at 25 0 C.
  • Some ionic liquids in accordance with the invention have been found to exhibit a reduction in viscosity with reduced water content. This trend is unusual for ionic liquids, which more typically increase in viscosity as their water content is reduced. Accordingly, a preferred ionic liquid in accordance with the invention exhibits a reduction in viscosity as its water content is lowered, for instance when the water content approaches 100 ppm or less by mass.
  • an ionic liquid according to the invention may be trimethyl hydroxylammonium hydroxide, triethyl hydroxylammonium hydroxide or methyldiethyl hydroxylammonium iodide. It may be preferred for the anion of the ionic liquid not to be hydroxide. It may be preferred for the anion not to be a halide, in particular iodide.
  • An ionic liquid according to the invention may be synthesised using known techniques. It may for instance be prepared by (a) reducing a nitro-compound of the formula:
  • R 3 is preferably hydrogen, so that the hydroxylamine product of step (a) is reacted with an acid HX.
  • Suitable readily available starting materials include nitromethane, nitroethane and nitrobenzene.
  • a suitable reducing agent for step (a) may be samarium (II) iodide; a suitable solvent may be a mixture of THF (tetrahydrofuran) and methanol.
  • an ionic liquid according to the invention may be prepared by reacting the appropriate hydroxylamine of the formula:
  • R 3 is hydrocarbyl it should be chosen to react selectively at the nitrogen atom rather than at the oxygen of the -OR 4 group.
  • Suitable readily available starting materials for this synthesis include for example (di)methyl hydroxylamine, (di)ethyl hydroxylamine and methylethyl hydroxylamine. In cases where there are two alkyl substituents, one of them may be joined to the oxygen rather than to the nitrogen atom.
  • Suitable acid starting materials for this reaction are those of formula H-X, where X is as defined above, for example hydrochloric acid, acetic and other carboxylic acids, methanesulphonic acid and bis(trifluoromethylsulphonyl)imidic acid.
  • Substituents included in the side chains of the groups R 1 , R 2 , R 3 and/or R 4 may be present prior to carrying out the above described syntheses, or may be added after the basic oxoammonium compound has been prepared.
  • a further alternative method for the preparation of compounds according to the invention of general formula R 1 R 2 R 3 N + -OH X " involves the neutralisation of an appropriate tertiary amine N-oxide of the general formula R 1 R 2 R 3 N-O with an acid HX, whereby the oxygen atom is protonated leading to the desired product in one step.
  • Suitable candidate amine oxides for this process include N,N,N-trimethylamine N-oxide, N,N,N-triethylamine N-oxide, N,N,N-tripropylamine N-oxide, N,N,N-tributylamine N-oxide, N,N-dimethylethanolamine N-oxide and N,N,N-triethanolarnine N-oxide.
  • Appropriate acids include trifluoromethanesulphonic acid, methanseulphonic acid and bis(trifluoromethylsulphonyl)imidic acid. In general the amine N-oxide and acid should be combined in stoichiometric ratios.
  • the tertiary amine N-oxide starting material may for example be prepared by reacting a tertiary amine (for example trimethylamine, triethylamine, tripropylamine, N 5 N- dimethylethanolamine or N,N,N-triethanolamine) with hydrogen peroxide.
  • a tertiary amine for example trimethylamine, triethylamine, tripropylamine, N 5 N- dimethylethanolamine or N,N,N-triethanolamine
  • the hydrogen peroxide may be used in the form of an aqueous solution, and is preferably present in excess. Following formation of the desired amine N-oxide, excess water and peroxide may be removed from the reaction mixture in vacuo.
  • a yet further alternative method for preparing ionic liquids according to the invention involves metathesis, as described in Example 11 below.
  • the preparation methods described above are preferably carried out in anhydrous or substantially anhydrous conditions. Solvents, excess starting materials and other undesired components may be removed in any suitable manner, for instance in vacuo, by freeze drying or by molecular sieve.
  • a second aspect of the present invention provides a method for preparing an ionic liquid according to the first aspect, involving for example one of the synthetic routes described above.
  • An ionic liquid according to the invention may have many possible uses, including as a solvent or suspending fluid (ie, generally as a liquid carrier) for one or more substances and/or for a chemical or biochemical reaction. It may thus be used as a liquid in its own right, often in the absence of any other solvents and preferably in the absence of water (in other words, it may be used under anhydrous or substantially anhydrous conditions, as described above).
  • a solvent or suspending fluid ie, generally as a liquid carrier
  • reaction medium typically a solvent
  • any reaction which requires a polar, protic and/or hydrogen-bonding solvent, in particular an enzyme-catalysed reaction.
  • hydrolases since it can provide a hydrogen-bonding liquid environment without risk of esterification of the important oxygen-containing functional group.
  • the invention can be of value in other situations where it would be inappropriate, undesirable or difficult to incorporate a hydrogen-bonding functional group onto another part of an ionic liquid, for instance onto a side chain as proposed for the ionic liquids disclosed in WO-2004/063383.
  • Ionic liquids as reaction media for biological and/or chemical reactions can have a number of advantages over the use of more traditional solvents, in particular aqueous solvents.
  • Ionic liquids generally have the 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 generally do not elicit solvolysis phenomena and most can stabilise short-lived reactive intermediates. There are no pH effects in the liquids and there is practically zero vapour pressure over much of their liquid range. Ionic liquids can also exhibit excellent electrical and thermal conductivity whilst being non-flammable, recyclable and generally of low toxicity.
  • An ionic liquid according to the invention may be used as a solvent for numerous materials, including many which are poorly soluble in conventional molecular solvents, for example biopolymers (such as proteins and polysaccharides), natural products (such as terpenes, alkaloids and oils) and minerals. In particular it may be used as a solvent for chitin and/or other aminopolysaccharides.
  • biopolymers such as proteins and polysaccharides
  • natural products such as terpenes, alkaloids and oils
  • minerals such as chitin and/or other aminopolysaccharides.
  • Chitin for example has proved difficult to dissolve in the past and is effectively insoluble in most conventional solvents unless previously covalently modified by a chemical transformation such as deacetylation; it has now been found to dissolve to appreciable concentrations (> 10 g/1) in the ionic liquid N,N-diethyl hydroxylammonium bis(trifluoromethylsulphonyl)imide.
  • a third aspect of the present invention accordingly provides the use of an ionic liquid according to the first aspect, as a liquid carrier (preferably a solvent) for a solute such as those mentioned above.
  • a liquid carrier preferably a solvent
  • Such use may embrace use as an extraction medium, a reaction medium, a chromatographic medium, a cleaning agent or a storage or transportation medium.
  • this aspect of the invention encompasses use of the ionic liquid as a reaction medium for a chemical or biochemical reaction, preferably a catalysed reaction, more preferably a biocatalysed (ie, enzyme-catalysed) reaction.
  • the ionic liquid is preferably used as a solvent for one or more of the reagents and/or for the catalyst and/or for the reaction product.
  • a fourth aspect provides a composition
  • a composition comprising an ionic liquid in accordance with the first aspect of the invention, in combination with an enzyme and optionally also a substrate for the enzyme.
  • Such a composition may be of use in carrying out an enzyme-catalysed reaction; it may therefore also contain one or more chemical or biochemical reactants.
  • the enzyme may or may not require a cofactor. It may for example be a hydrolase (such as a lipase, esterase, nuclease or cellulase), oxidoreductase, isomerase, synthetase, transferase, ligase, lyase, aldolase or carboxylase.
  • a hydrolase such as a lipase, esterase, nuclease or cellulase
  • oxidoreductase isomerase
  • synthetase transferase
  • ligase transferase
  • lyase aldolase or carboxylase.
  • an ionic liquid according to the present invention may be used in a wide variety of applications not necessarily limited to use as a reaction medium.
  • Other examples of possible uses include as a matrix in matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry; as a solvent for a solvent extraction process (eg, to remove components from an immiscible liquid or solid or from biomass); as a carrier for use in chromatography, including gas chromatography; as a hydraulic fluid or lubricant; as a coolant or heat exchange medium; as a cleaning agent; as a wetting agent; as a biocide; as a preservative or fixative; and uses in liquefaction, nuclear fuel reprocessing, fuel cells, electrochemical applications, pervaporation, drug delivery, adhesives and sensors.
  • MALDI matrix in matrix-assisted laser desorption/ionisation
  • Ionic liquids according to the present invention include for example the following, which may be prepared by methods such as those of Examples 1 to 11 below:
  • viscosities were measured using an ANDTM SVlO vibrational viscometer and refractive indices using a Mettler Toledo RefractoTM 30 portable refractometer. Densities were measured simply by determining the mass of a measured volume of the liquid.
  • N,N-diethyl hydroxylamine (90 g) and acetic acid (60.05 g) were reacted together using the generic method described above. After solvent removal, the resulting pale yellow liquid was frozen in liquid nitrogen, transferred to a lyophilizer and dried in vacuo for 48 hours.
  • the melting point of the product was found to be less than -20 0 C. It was miscible in all proportions with water, dimethylsulphoxide, acetonitrile, ethyl acetate, tetrahydrofuran, chloroform and toluene. Its viscosity at 25 0 C was 12 centipoise, its refractive index 1.414.
  • Example 1 was repeated using N,N-diethyl hydroxylamine (90 g) and glycolic acid (77 g).
  • Example 3 preparation of diethyl hydroxylammonium trifluoromethanesulphonate
  • Example 1 was repeated using N,N-diethyl hydroxylamine (90 g) and trifluoromethanesulphonic acid (151 g).
  • Example 1 was repeated using N,N-diethyl hydroxylamine and bis(trifluoromethylsulphonyl)imidic acid.
  • trimethylamine N-oxide dihydrate was prepared by reacting trimethylamine with hydrogen peroxide (3 % aqueous solution), using a 10 % excess of the peroxide. This reaction mixture was left stirring overnight. The product trimethylamine N-oxide dihydrate was then added as a solid to an equimolar amount of bis(trifluoromethylsulphonyl)imidic acid in the form of a 75 % w/w aqueous solution. The reaction was kept cool using an ice bath and by slow addition of the acid. At the conclusion of this neutralisation reaction, the water was removed by freeze drying to yield the product directly.
  • Example 5 could be repeated, firstly using triethylamine and hydrogen peroxide to generate triethylamine N-oxide, and then by reacting the N-oxide with glycolic acid. The product would be N,N,N-triethyl hydroxylammonium glycolate.
  • Example 7 preparation of N,N,N-triethyl hydroxylammonium chloride
  • Example 5 was repeated, firstly using triethylamine and hydrogen peroxide to generate triethylamine N-oxide, and then by reacting the N-oxide with hydrochloric acid. This latter reaction yielded a colourless liquid product, N,N,N-triethyl hydroxylammonium chloride.
  • Example 5 was repeated, firstly using triethylamine and hydrogen peroxide to generate triethylamine N-oxide, and then by reacting the N-oxide with methanesulphonic acid.
  • Example 5 was repeated, firstly using triethylamine and hydrogen peroxide to generate triethylamine N-oxide, and then by reacting the N-oxide with bis(trifluoromethylsulphonyl)imidic acid.
  • the product, N,N,N-triethyl hydroxylammonium bis(trifluoromethylsulphonyl)imide was a colourless liquid. Its viscosity was 49 centipoise, its refractive index 1.403 and its density 1.45 g/cm 3 .
  • Example 5 illustrates the preparation of a hydroxyl-substituted hydroxylammonium salt according to the invention, in which R 1 is ethanolyl.
  • a similar procedure could be used to prepare other hydroxyl- or alkoxyl-substituted ionic liquids according to the invention.
  • Example 5 was repeated, firstly using N,N-dimethylethanolamine and hydrogen peroxide to generate N,N-dimethylethanolamine N-oxide, and then by reacting
  • This example illustrates the use of metathesis as a route to preparation of a desired hydroxylammonium ionic liquid.
  • N,N,N-triethyl hydroxylammonium chloride (prepared from triethylamine N-oxide and gaseous hydrogen chloride) was dissolved in acetone and 1 molar equivalent of sodium acetate was added. The reaction was stirred at room temperature for 12 hours, after which the precipitated sodium chloride was removed by filtration. Residual chloride was removed by passing the solution down an activated alumina column, after which the acetone was removed in vacuo to yield the product as a pale yellow liquid in 78 % yield.
  • Example 12 use in biocatalvsis
  • An ionic liquid in accordance with the invention may be used as a solvent in a biocatalytic reaction, for example the chymotrypsin-catalysed transesterification of 1- propanol and D-phenylalanine acetyl ester.
  • the ionic liquid may be used as an alternative to the usual solvents, with retention of enzyme activity. It provides a stable reaction medium with significant advantages over conventional solvents, in particular higher achievable substrate concentrations, increased biomolecular stability and eco- compatibility. Compared to conventional ionic liquids, those in accordance with the invention can offer higher levels of enzyme activity without risk of the solvent participating in the reaction.

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Abstract

L’invention concerne un liquide ionique contenant des cations de formule : R1R2R3N+-OR4 dans laquelle R1, R2, R3 et R4 sont chacun choisis indépendamment parmi l’hydrogène et un hydrocarbyle, ledit liquide ionique contenant 1 % en masse ou moins d’eau. De tels liquides ioniques peuvent être utilisés notamment en tant que solvants pour biocatalyse.
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US7888412B2 (en) 2004-03-26 2011-02-15 Board Of Trustees Of The University Of Alabama Polymer dissolution and blend formation in ionic liquids
CN103539742A (zh) * 2013-10-15 2014-01-29 河北工业大学 一种离子液体型羟胺盐的制备方法
US8784691B2 (en) 2009-07-24 2014-07-22 Board Of Trustees Of The University Of Alabama Conductive composites prepared using ionic liquids
US8883193B2 (en) 2005-06-29 2014-11-11 The University Of Alabama Cellulosic biocomposites as molecular scaffolds for nano-architectures
US9096743B2 (en) 2009-06-01 2015-08-04 The Board Of Trustees Of The University Of Alabama Process for forming films, fibers, and beads from chitinous biomass
US9278134B2 (en) 2008-12-29 2016-03-08 The Board Of Trustees Of The University Of Alabama Dual functioning ionic liquids and salts thereof
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US10731126B2 (en) 2015-05-29 2020-08-04 Merck Patent Gmbh Deep eutectic solvents and/or ionic liquids in cell culture media
US10927191B2 (en) 2017-01-06 2021-02-23 The Board Of Trustees Of The University Of Alabama Coagulation of chitin from ionic liquid solutions using kosmotropic salts
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US11766835B2 (en) 2016-03-25 2023-09-26 Natural Fiber Welding, Inc. Methods, processes, and apparatuses for producing welded substrates
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US9394375B2 (en) 2011-03-25 2016-07-19 Board Of Trustees Of The University Of Alabama Compositions containing recyclable ionic liquids for use in biomass processing
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