EP4652157A1 - Procédé de traitement de liquides ioniques à base de sel d'iminium - Google Patents

Procédé de traitement de liquides ioniques à base de sel d'iminium

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Publication number
EP4652157A1
EP4652157A1 EP24702054.8A EP24702054A EP4652157A1 EP 4652157 A1 EP4652157 A1 EP 4652157A1 EP 24702054 A EP24702054 A EP 24702054A EP 4652157 A1 EP4652157 A1 EP 4652157A1
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EP
European Patent Office
Prior art keywords
acid
salt
alcoholate
iminium
adduct
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24702054.8A
Other languages
German (de)
English (en)
Inventor
Willi Kantlehner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technikum Laubholz GmbH TLH
Original Assignee
Technikum Laubholz GmbH TLH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technikum Laubholz GmbH TLH filed Critical Technikum Laubholz GmbH TLH
Publication of EP4652157A1 publication Critical patent/EP4652157A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms

Definitions

  • Iminium salt-based ionic liquids are used in many processes as solvents or reaction media (see e.g. Ionic Liquids for Clean Technology, K. R. Seddon, J. Chem. Tech. Biotechnol. 1997, 68, 351-356; Room Temperature Molten Salts, N. N. Ene, Roum. Chem. Q. Rev. 1993, 1, 333- 351). In these applications, separation of the desired products results in ionic liquids that are contaminated by unreacted reactants, added auxiliaries or reaction products.
  • iminium salt-based ionic liquids available on an industrial scale mostly contain chloride ions as anionic component, with l-butyl-3-methyl-imidazolium chloride (1) produced on an industrial scale by BASF SE being an example.
  • iminium salt-based ionic liquids that contain other, e.g. reactive, strongly nucleophilic anions such as iodide, thiocyanate or cyanide.
  • reactive ionic liquids can basically be prepared from chloride salts of iminium salt-based ionic liquids via reactions known as "anion metathesis".
  • a solution of the salt AX, whose anions X' are to be exchanged, is mixed with the solution of another salt BY, which contains the desired anion Y'.
  • the cation B + of the salt BY is chosen so that the salt BX is insoluble and precipitates.
  • the resulting solution of the desired ionic liquid AY is evaporated and AY is isolated as a residue.
  • a large number of guanidinium salts with different anions have been prepared according to this principle (cf. e.g. W. Kantlehner, J. Mezger, I. Tiritiris, R. Kreß, W. Frey, Z. Naturforsch. 2021, 76b, 133-162).
  • Guanidinium salts with anions that contain organofluorine-containing groups are sparingly soluble in water. If water-soluble guanidinium salts are mixed with aqueous solutions that contain alkali salts with organofluorine-containing anions, such as CFaSChLi, CFaSChNa, C ⁇ SOsNa, or N(CF3SO2N)2Na, the guanidinium salts precipitate (see EP 1363345 A2 or DE 10325051A1). b) Decomposition of acid-labile anions
  • anion exchange can be achieved by alkylating the anion.
  • alkylation can still be achieved with very strong alkylating agents.
  • guanidinium chlorides are converted into guanidinium tetrafluoroborates with triethyloxonium tetrafluoroborate, releasing volatile ethyl chloride and diethyl ether (cf. e.g. W. Kantlehner, J. Mezger, I. Tiritiris, R. Kreß, W. Frey, Z Naturforsch. 2021, 76b, 133-162).
  • the difficulty with the processes described is also that for the conversion to take place, differences in the specific properties of the ionic liquid used as the reactant and the ionic liquid obtained as the product must be present, suitable reagents such as alkylating agents must be available, or complexable or decomposable anions must be present in the ionic liquid used as the reactant.
  • the present invention addresses this need.
  • iminium salt-based ionic liquids in general can be converted to iminium alcoholate adducts, which belong to the class of orthoamides, by adding alcoholates. These adducts can be purified from polar impurities and salts due to their electrically neutral structure.
  • such a treatment has the advantage that at the orthoamide or adduct stage, an acid can be added that has a different anion than the ionic liquid from which the orthoamide or adduct was produced, which in the overall reaction corresponds to an anion exchange (anion metathesis).
  • the present invention relates to a process for treating an ionic liquid based on a substituted or unsubstituted iminium salt (Im + X ), wherein the iminium salt is reacted in a first step i) with an alcoholate to form an electrically neutral iminium alcoholate adduct, in a second step ii) the salt formed from the cation of the alcoholate and the anion X- of the iminium salt is separated and in a third step iii) the electrically neutral iminium alcoholate adduct is reacted with an acid HY to form an iminium salt Im + Y _ , wherein X and Y may be the same or different.
  • the iminium salt which is subjected to the treatment according to the invention is in a preferred embodiment as an imidazolium salt.
  • the iminium salt can also have a cation which is not based on an imidazole ring, such as an N,O-bisalyzed pyrrolidone, R 1 -C(NR 2 2 )2 + , R 1 -C(NR 2 )(SR2) + or a guanidinium cation (C(NR 2 2 )3 + ), where R 2 can be the same or different in the structures shown and denotes a hydrocarbon radical, preferably in the form of an alkyl radical, and where R 1 denotes a hydrocarbon radical, preferably in the form of an alkyl radical.
  • iminium salts that can be treated in the process described here include the following l,3-dialkyl-l,3,4-triazolium salts (4), 2,3,5-trialkyl-l,3-oxazolium salts (5), 2,3,5-trialkyl-l,3,4-oxdiazolium salts (6), 2,3,5-trialkyl-l,3-thiazolium salts (7), 2,3,4-trialkyl-l,3,4-thiadiazolium salts (7), 1,2-dialkyl-pyrimidinium salts (9) and 1,2,3-trialkyl-3,4,5,6-tetrahydro-pyrimidinium salts (10):
  • X and Y are the same (see the following figure using the example of an ionic liquid with an imidazolium cation), ie compound 1 is the same as compound 3a.
  • Such a process is suitably designed as a process for purifying the reacted ionic liquid 1, in which polar and in particular ionic impurities are separated from the iminium alcoholate adduct with the salt in step ii).
  • Impurities to be separated include impurities such as arise in typical applications of ionic liquids, e.g. formate, acetate, butanoate, chloride, bromide, iodide, or tetrafluoroborate.
  • the guanidinium salt 11 has a melting point of 296 °C (cf. W.
  • Kantlehner E. Haug, W. W. Mergen, P. Speh, T. Maier, J. J. Kapasakalidis, H.-J. Brauner, H. Hagen, Synthesis 1983, 13, 904-905
  • the orthoamide derivative 5 is formed as an adduct from the guanidinium salt 11 as a colorless to pale yellow liquid with a boiling point of 73 °C/10 Torr (see W.
  • Kantlehner, W. W. Mergen, Synthesis 1979, 11, 343-344 which is miscible with ether, ethyl acetate, benzene, cyclohexane in any ratio.
  • X and Y are different, ie the compound 1 is, as far as the anion is concerned, different from the compound 3.
  • Such a process is designed as a process for producing an ionic liquid Im + Y' from an ionic liquid Im + X _ , in which the anion Y- is separated from the anion X", which is contained in the starting product.
  • X- is a halide, in particular in the form of chloride, or the anion of a CI or C2 carboxylic acid (ie formate or acetate).
  • X- is particularly preferably chloride.
  • an alcoholic alcoholate solution is used as an "alcoholate source" in step i), it may be expedient to remove excess alcohol after the reaction in order to avoid subsequent solvent mixtures with the alcohol, which may promote less complete separation of the impurities or salts.
  • the alcohol can be separated from the mixture by any method suitable for removal, for example distillation or vacuum treatment.
  • an alcohol can be used as a solvent for the ionic liquid (preferably in the form of methanol or ethanol), for example, and to facilitate separation of the salt in step ii) via filtration.
  • the alcoholate which is added to the substituted or unsubstituted imidazolium salt in step i) according to the process according to the invention is advantageously a C1-C4 alcoholate, with methoxide and ethanolate being particularly preferred.
  • the cation of the alcoholate used can particularly preferably be an alkali metal cation, more preferably in the form of sodium or potassium. Sodium is usually preferred for reasons of cost and availability.
  • the processes according to the first or second embodiment can expediently be further designed such that an aprotic non-polar solvent is added to the mixture in step ii) before the salt formed from the cation of the alcoholate and the anion X- of the iminium salt is separated.
  • an aprotic non-polar solvent is added to the mixture in step ii) before the salt formed from the cation of the alcoholate and the anion X- of the iminium salt is separated.
  • aprotic non-polar solvent the present invention is not subject to any relevant restrictions, ie aliphatic or aromatic hydrocarbons can be used as solvents, where "aliphatic” includes “cycloaliphatic” forms.
  • Suitable aliphatic or aromatic hydrocarbon solvents are, for example, hexane, pentane, cyclohexane, cyclopentane, toluene, benzene or xylene or mixtures of the solvents mentioned.
  • Other suitable solvents are ethers such as diethyl ether or methyl t-butyl ether, or esters such as ethyl acetate or ethyl propionate and nitriles such as acetonitrile.
  • halogenated and especially chlorinated hydrocarbons such as dichloromethane or chloroform.
  • the solvent is not limited to the specific examples mentioned, but it is more important that the iminium alcoholate adduct dissolves in the solvent, while polar impurities are not dissolved and remain as residue.
  • distillation here also includes cases of treatment under reduced pressure in which the solvent is evaporated and then condensed again by appropriate cooling.
  • a carboxylic acid such as a fatty acid
  • HY a carboxylic acid
  • a protic solvent such as alcohol (e.g. as solvent for an alcoholate used) additionally being present.
  • the water can form the main part of the solvent and make up, for example, more than 80% by weight, preferably more than 90% by weight and even more preferably more than 93% by weight of the total amount of solvent in the mixture.
  • the separation of the salt formed from the cation of the alcoholate and the anion of the iminium salt can be carried out in step ii) using any method suitable for the separation of solid or denser residues.
  • the salt is separated by filtration, preferably at ambient temperature (20 to 28°C) or a lower temperature above the deposition temperature of the iminium alcoholate adduct.
  • the "deposition temperature” refers to the temperature at which the iminium alcoholate adduct is no longer dissolved, e.g. as a result of crystallization or phase separation.
  • the separation is carried out by decanting the solution of the iminium alcoholate adduct in an aprotic non-polar solvent, optionally after centrifugation to concentrate undissolved components at the bottom of a reaction vessel.
  • the temperature also has a certain significance, which on the one hand should be chosen so that the iminium salt and the iminium alcoholate adduct produced therefrom are in liquid form, but on the other hand the temperature should not be so high that the iminium alcoholate adduct undergoes significant decomposition.
  • the temperature for steps i) and ii) is kept below 120°C, in particular below 100°C and more preferably below 80°C.
  • the anion of the iminium salt used in step i) is preferably a halide and particularly preferably chloride if the process according to the invention produces a product with a Y- other than X-.
  • X- can be present as a halide or chloride.
  • the anion can also be a carboxylate, alkyl sulfate, alkyl or aryl sulfonate.
  • the acid added in step iii) can be any acid in the processes according to both embodiments described above which reacts with the imidazole alcoholate orthoamide to release alcohol (ROH), i.e. it must be a protic acid.
  • Suitable acids of this type include, but are not limited to, hydrochloric acid, hydrobromic acid, hydroiodic acid, Cl-C18 carboxylic acids, i.e. e.g.
  • acetic acid or propionic acid methanesulfonic acid
  • dialkylphosphonic acid in particular in the form of dimethyl or diethylphosphonic acid
  • thiocyanuric acid hydrogen cyanide, cyanic acid, nitric acid, nitrous acid
  • sulfuric acid alkyl sulfuric acid, alkyl or aryl sulfonic acid, HN(SO2CF 3 )2, trifluoroacetic acid and trifluoromethanesulfonic acid.
  • Y- in the above-mentioned compound 3 can also be an adduct of a carboxylic acid and a deprotonated carboxylic acid (in the form R-CO-HOCOR), in which the proton of the carboxylic acid is stabilized by the carboxylate group of the deprotonated carboxylic acid.
  • the acid added in step iii) can be added at a suitable temperature, which can be adjusted depending on the reactivity of the iminium alcoholate adduct and the stability against undesirable decomposition.
  • the acid is added at ambient temperature (20 to 28°C).
  • the acid is added at a reduced temperature, eg, -30°C to 15°C or -20°C to 0°C.
  • the reaction mixture can subsequently be heated to a higher temperature, eg, 45 to 100°C or 60 to 90°C.
  • the iminium salt used in the process according to the invention is an imidazolium salt
  • the imidazolium cation contained in the salt is substituted on the nitrogen atoms (T and 3' positions) and is preferably unsubstituted on the 4' and 5' positions.
  • the carbon atom on the 2' position can be substituted with an aryl radical (e.g. in the form of phenyl) or with NR 2 , where R can be an alkyl or aryl radical and the two Rs can be the same or different.
  • the imidazolium cation of the imidazolium salt is substituted in the 1'- and 3'-position (corresponding to the radicals R 1 and R 3 in the reaction scheme above) or in the 1'-, 2'- and 3'-position (corresponding to the radicals R 1 , R 2 and R 3 in the reaction scheme above) with (Cl-C6)-alkyl groups, where a 2'-position can be substituted not only by alkyl but also by aryl or alkylaryl, and the alkyl group can have an alkyloxy or aryloxy substituent.
  • R 1 and R 3 can be the same or different.
  • the imidazolium cation of the imidazolium salt is selected from the group consisting of l-ethyl-3-methylimidazolium, 1,3-dimethylimidazolium, l-butyl-3-methylimidazolium cation, l-butyl-3-ethylimidazolium, 1,3-diethylimidazolium, l-ethyl-3-isopropylimidazolium, l-allyl-3-methylimidazolium, l-allyl-3-ethylimidazolium, l-allyl-3-isopropylimidazolium, l-allyl-3-butylimidazolium cations.
  • Imidazolium salt is preferably selected from halides, in particular Chloride, bromide or iodide, the carboxylate of a Cl-C18 carboxylic acid, in particular a Cl-C12 carboxylic acid such as acetate, formate, propionate, butanoate or octanoate, a dialkyl phosphate, in particular in the form of dimethyl or diethyl phosphate, dialkyl phosphonate such as dimethyl or diethyl phosphonate, methylsulfonate, thiocyanate, cyanate, nitrate, nitrite, N(SO2CF 3 )2, N(SO2C4F 9 )2 and trifluoromethanesulfonate.
  • halides in particular Chloride, bromide or iodide
  • the carboxylate of a Cl-C18 carboxylic acid in particular a Cl-C12 carboxylic acid such as acetate, formate, propionate
  • step iii) of the process described the alcohol is regenerated from the added acid and the alcoholate bound in the iminium alcoholate adduct, which is usually not desired for further use of the imidazolium salt formed as an ionic liquid. It is therefore preferred if the process according to the invention additionally has a step in which the alcohol is removed from the product formed.
  • suitable processes for this purpose reference can be made to the above information on processes for removing excess alcohol, whereby distillation and/or vacuum treatment can be stated as particularly suitable.
  • a 2-alkylidene imidazole 15 can be formed in equilibrium with the imidazole alcoholate adduct 14 by elimination of alcohol:
  • Such 2-alkylidene-imidazoles are known to often not have high thermal stability, so that isolation of these products is usually only possible with significant losses in yield (see, for example, WO 2007/131498 Al). It is therefore preferred if imidazole-alcoholate adducts from which alcohol can be split off are treated under very mild thermal conditions, e.g. less than 120°C and in particular less than 100°C in steps i) and ii).
  • the processing is carried out under conditions in which the 2-alkylidene imidazole formed accounts for a proportion of the total amount of imidazole alcoholate adduct and 2-alkylidene imidazole of 2 to 80% by weight and more preferably 5 to 30% by weight.
  • the 2-alkylidene imidazole formed accounts for a proportion of the total amount of imidazole alcoholate adduct and 2-alkylidene imidazole of 2 to 80% by weight and more preferably 5 to 30% by weight.
  • no pure 2-alkylidene imidazole is to be isolated in the process described here, but there is no need for this because both imidazole alcoholate adduct and 2-alkylidene imidazole are converted into imidazolium salt by the addition of acid.
  • the process in order to subsequently be able to correctly adjust the required amount of acid to be added and not to introduce excess acid into the system, it may be expedient for the process to additionally comprise a step for determining the amount of acid to be added in step iii) which is required to completely convert the mixture of imidazole-alcoholate adduct of 2-alkylidene-imidazole into imidazolium salt (i.e. a stoichiometric amount based on the molar amount of imidazole units in the mixture).
  • Such adjustment is possible, for example, by determining the imidazole-alcoholate adduct to 2-alkylidene-imidazole ratio by means of ⁇ -NMR or by titration.
  • the present invention relates to an imidazolium salt (Im + Y ) which is obtainable by the process described above, and wherein Y- is selected from the group comprising bromide, iodide, a C3-C18 carboxylic acid, a dialkyl phosphonate, in particular in the form of dimethyl or diethyl phosphonate, a dialkyl phosphate, in particular in the form of dimethyl or diethyl phosphate, methyl sulfonate, thiocyanate, cyanate, nitrate, nitrite, an alkyl sulfate, an alkyl or aryl sulfonate, in particular in the form of the dimethyl or diethyl derivatives, N(SO2CF 3 )2 and trifluoromethanesulfonate.
  • Y- is selected from the group comprising bromide, iodide, a C3-C18 carboxylic acid, a dialkyl phospho
  • Y- is a C3-C18 carboxylic acid (and in particular a CIO to C18 carboxylic acid), it is also possible that Y- is in the form of an adduct of deprotonated carboxylic acid and carboxylic acid, as stated above.
  • Such an imidazolium salt is characterized by a high purity of the anion, which is formed, for example, to at least 90 mol% (based on the total amount of anions in the imidazolium salt), more preferably to at least 95 mol%, even more preferably to at least 98 mol% and even more preferably to at least 99 mol% from the specified anion (e.g. thiocyanate).
  • the process is carried out in such a way that the separation of the salt formed from the cation of the alcoholate and the anion X- of the iminium salt according to step ii) takes place after the addition of an acid HY to form an iminium salt Im + Y _ according to step iii).
  • the ionic liquid can be obtained after precipitation and/or crystallization from the reaction mixture and separation of the dissolved salts formed from the alcoholate and the anion X-.
  • the described process allows ionic liquids to be regenerated in a simple manner, whereby polar impurities or salts that cannot be removed from the ionic liquids by extraction with non-polar solvents are separated.
  • the described process allows the simple and cost-effective production of iminium salts with unusual and commercially unavailable anions, which would otherwise have to be produced using much more complex processes.
  • the filtrate is mixed with 2.88 g (0.02 mol) of octanoic acid in 5 ml of acetonitrile while stirring, and a voluminous, gelatinous precipitate forms when heated. After stirring for about 20 minutes, the precipitate is filtered off with suction. The filtrate is evaporated in a vacuum, giving a voluminous, gelatinous mass, which is heated under reflux with 15 ml of acetonitrile for 15 minutes while stirring, breaking up the gelatinous, clumped mass from time to time. After cooling, the precipitate is filtered off with suction.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de traitement d'un liquide ionique, dans lequel un sel d'iminium, en particulier sous la forme d'un sel d'imidazolium, est mis à réagir avec un alcoolate pour obtenir un adduit iminium-alcoolate, puis le sel formé à partir du cation de l'alcoolate et de l'anion du sel d'iminium est séparé, puis un sel d'iminium est reformé par ajout d'un acide. Du fait de la polarité beaucoup plus faible par rapport au sel d'iminium, l'adduit iminium-alcoolate permet une séparation facile des impuretés polaires ou un échange propre de l'anion du sel d'iminium lorsque l'acide ajouté a un anion différent de celui initialement présent dans le sel d'iminium.
EP24702054.8A 2023-01-20 2024-01-19 Procédé de traitement de liquides ioniques à base de sel d'iminium Pending EP4652157A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102023101455.2A DE102023101455A1 (de) 2023-01-20 2023-01-20 Verfahren zur Behandlung von Iminiumsalz-basierten ionischen Flüssigkeiten
PCT/EP2024/051243 WO2024153790A1 (fr) 2023-01-20 2024-01-19 Procédé de traitement de liquides ioniques à base de sel d'iminium

Publications (1)

Publication Number Publication Date
EP4652157A1 true EP4652157A1 (fr) 2025-11-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP24702054.8A Pending EP4652157A1 (fr) 2023-01-20 2024-01-19 Procédé de traitement de liquides ioniques à base de sel d'iminium

Country Status (6)

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EP (1) EP4652157A1 (fr)
KR (1) KR20250133963A (fr)
CN (1) CN120826392A (fr)
DE (1) DE102023101455A1 (fr)
MX (1) MX2025008420A (fr)
WO (1) WO2024153790A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030211389A1 (en) 2002-05-09 2003-11-13 Schlaikjer Carl R. Guanidine derivatives as cations for ambient temperature molten salts in electrochemical power sources
DE10325051A1 (de) 2003-06-02 2004-12-23 Merck Patent Gmbh Ionische Flüssigkeiten mit Guanidinium-Kationen
DE102004003958A1 (de) * 2004-01-26 2005-08-11 Basf Ag Herstellungsmethode für ionische Flüssigkeiten
DE102006023649A1 (de) 2006-05-17 2008-01-03 Philipps-Universität Marburg Hydrophobe ionische Flüssigkeiten

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DE102023101455A1 (de) 2024-07-25
WO2024153790A1 (fr) 2024-07-25
MX2025008420A (es) 2025-12-01
KR20250133963A (ko) 2025-09-09
CN120826392A (zh) 2025-10-21

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