EP4025563A1 - Method for purifying 2-(fluoroalkyl or fluoroalkoxy)-4,5-dicyanoimidazoles - Google Patents

Method for purifying 2-(fluoroalkyl or fluoroalkoxy)-4,5-dicyanoimidazoles

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Publication number
EP4025563A1
EP4025563A1 EP20771791.9A EP20771791A EP4025563A1 EP 4025563 A1 EP4025563 A1 EP 4025563A1 EP 20771791 A EP20771791 A EP 20771791A EP 4025563 A1 EP4025563 A1 EP 4025563A1
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EP
European Patent Office
Prior art keywords
compound
formula
iii
temperature
phase
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.)
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EP20771791.9A
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German (de)
French (fr)
Inventor
Rémy Teissier
Grégory Schmidt
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Arkema France SA
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Arkema France SA
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Publication of EP4025563A1 publication Critical patent/EP4025563A1/en
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    • 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
    • C07D233/66—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a process for the purification of imidazole.
  • the present invention also relates to a process for preparing lithium salt of imidazolate.
  • a lithium-ion battery includes at least a negative electrode, a positive electrode, a separator, and an electrolyte.
  • the electrolyte consists of a lithium salt dissolved in a solvent which is generally a mixture of organic carbonates, in order to have a good compromise between viscosity and dielectric constant.
  • lithium hexafluorophosphate LiPF 6
  • LiPF 6 lithium hexafluorophosphate
  • WO 2010/023413 proposes several synthetic routes for the manufacture of these pentacyclic anions, one of which consists of the condensation of diaminomaleonitrile (DAMN) on an acid derivative such as a fluorinated acid anhydride, followed by a proton / lithium exchange. The condensation is carried out in a single step.
  • DAMN diaminomaleonitrile
  • WO 2015/49435 describes the preparation of fluoroalkyl-4,5-dicyanoimidazole salts of purity compatible with applications in batteries or in ionic liquids.
  • the process involves the use of activated carbon to purify the salts of pentacyclic anions.
  • activated carbon is a delicate operation and capable of bringing ions such as Ca 2+ or K + ions into the medium, which can lead to a decrease in performance in the batteries.
  • activated carbons commonly require washing in depth before use, which is restrictive and expensive.
  • at least one recrystallization step is necessary to obtain the desired purity and an acceptable Hazen coloration.
  • the present invention relates to a process for the purification of a compound of the following formula (III): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said process comprising the following steps: a. a step of heating a composition comprising said compound of formula (III) in an organic solvent S3, at a temperature Ti until dissolution of said compound of formula
  • phase P1 comprising said compound of formula (III);
  • phase P2 vs. a step of separating the phases P1 and P2 at the temperature T 2 ; d. a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
  • Rf represents CF 3 , CHF 2 , C 2 F 5 , C 3 F, C 2 F OCF 3 , or CF 2 OCF 3 preferably CF 3 , C 2 F 5 , or C 2 F 4 OCF 3 .
  • the compound of formula (III) is that for which Rf represents CF 3 .
  • the present invention relates to a process for purifying a compound of the following formula (III): wherein Rf is C2F4OCF3 OR a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said process comprising the following steps: a. a step of heating a composition comprising said compound of formula (III) in an organic solvent S3 having a donor number ranging from 0.1 to 10, at a temperature Ti until dissolution of said compound of formula (III); b. a step of cooling to an intermediate temperature T 2 of between 23 ° C and the temperature T1 leading to a two-phase composition comprising:
  • phase P1 comprising said compound of formula (III);
  • phase P2 vs. a step of separating the phases P1 and P2 at the temperature T 2 ; d. a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
  • the organic solvent S3 preferably has a donor number ranging from 0.1 to 10.
  • the donor index of a solvent represents the value -DH, DH being the enthalpy of the interaction (Kcal / mol) between the solvent and the antimony pentachloride (Journal of Solution Chemistry, vol. 13, No. 9 , 1984).
  • the organic solvent S3 is preferably chosen from aromatics or aliphatic or cyclic alkanes, such as, for example, toluene, benzene, xylene, cyclohexane, heptane.
  • the organic solvent S3 is toluene.
  • the temperature Ti is the temperature at which the compound of formula (III) is dissolved in the organic solvent S3.
  • the temperature Ti can be between 40 ° C and the boiling point of the organic solvent S3, preferably between 50 ° C and 120 ° C, advantageously between 60 ° C and 100 ° C.
  • the temperature Ti is advantageously equal to 70 ° C.
  • composition used in step a), comprising the compound of formula (III) and the organic solvent S3, can be obtained by contacting the organic solvent S3 with the compound of formula (III) in solid form.
  • the compound of formula (III) can be in hydrated form, that is to say that the compound of formula (III) can contain a water content of between 1% and 25%, preferably between 5% and 20% and preferably between 10% and 16% by weight relative to the total weight of the compound of formula (III).
  • the mass content of the compound of formula (III) in the composition comprising the organic solvent S3 can range from 1% to 70% by weight, preferably from 5% to 50% by weight, preferably from 8 % to 30% by weight relative to the total weight of said composition.
  • the temperature T 2 is between 23 ° C and the temperature Ti, preferably between 23 ° C and 50 ° C, and advantageously between 30 ° C and 50 ° C.
  • Step b) leads to a two-phase composition comprising:
  • phase P1 comprising said compound of formula (III);
  • Phase P1 is advantageously a liquid phase, it comprises in particular organic solvent S3.
  • Phase P1 preferably comprises more than 30%, preferably more than 35%, and advantageously more than 40% of the compound of formula (III) initially contained in the solution obtained at the end of step a).
  • Phase P1 preferably comprises from 0.5% to 70% by weight, preferably from 1% to 50% by weight, preferably from 5% to 30% by weight of the compound of formula (III) relative to the total weight of said phase P1.
  • Phase P2 can comprise compound of formula (III) in a content strictly less than 45%, preferably less than 35% of the initial content of compound of formula (III) in the solution obtained at the end of stage at).
  • Phase P2 can comprise impurities resulting from the process for preparing the compound of formula (III), such as coloring agents and TFA.
  • phase P2 has a higher density than that of phase P1.
  • Phase P2 can be separated from phase P1, for example by settling followed by purging of the lower phase or by pumping of the upper phase.
  • the purification process according to the invention comprises a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
  • the temperature T 3 can be between 40 ° C and -30 ° C, preferably between 25 ° C and -15 ° C, and even more preferably between 10 ° C and -5 ° C.
  • the temperature T3 is advantageously 0 ° C.
  • the temperature T 3 is advantageously the temperature at which the compound of formula (III) crystallizes from the organic solvent S3.
  • Steps a, b, c, d can be repeated on P2 in order to recover more compound III.
  • the number of repetitions is between 2 and 4, preferably 3.
  • the aforementioned purification process may include an additional step e) of filtering the composition obtained at the end of step d). Filtration advantageously results in a compound of formula (III) in solid form and in a filtrate.
  • the solid is advantageously subjected to an additional drying step, preferably under a stream of nitrogen at 23 ° C or more.
  • the aforementioned purification process advantageously makes it possible to prepare a compound of formula (III) with a good yield and a reduced content of impurities, in particular a reduced content of agents capable of coloring the product, and / or of TFA (trifluoroacetic acid) and / or in amides derived from the compound of formula (III):
  • the purification process advantageously makes it possible to prepare a compound of formula (III) having less coloration.
  • the purification process also advantageously makes it possible to obtain a compound of formula (III) with a good yield and a reduced content of impurities in a smaller number of steps, without the need for costly additional purification steps.
  • the purification process according to the invention can comprise a step a ’), prior to step a), of bringing the compound of formula (III) into contact with the organic solvent S3.
  • the organic solvent S3 is added to the compound of formula (III).
  • step a ′ The compound of formula (III) from step a ′) can be obtained by a process comprising the following steps:
  • step x) step of heating the composition obtained in step x) at a temperature T 6 , preferably between 30 ° C and 80 ° C, advantageously between 40 ° C and 70 ° C;
  • step y step of cooling the composition obtained in step y) until the formation of crystals of compound of formula (III);
  • the compound of formula (III) in step x) can be obtained by any process for preparing a compound of formula (III), optionally subjected to a step of evaporating the reaction solvent.
  • the above-mentioned compound of formula (III) can be obtained by a process comprising: i. a step of reaction of the diaminomaleonitrile of formula (I): with the compound of formula (II) below: in which Y represents a chlorine atom or the OCORf group, to form the salified amide compound of formula (IVa) and / or the corresponding amine (IVb), at a temperature T 4
  • the temperature T which can range from 0 to 80 ° C, preferably from 10 to 50 ° C, more preferably from 20 to 30 ° C, for example about 25 ° C.
  • step (i) lasts from 1 to 12 hours, preferably from 1 to 3 hours, and / or step (ii) lasts from 1 to 12 hours, preferably from 1 to 3 hours .
  • the diaminomaleonitrile of formula (I) and the compound of formula (II) are dissolved in a solvent prior to step (i), the solvent preferably being 1, 4-dioxane.
  • Step (i) is preferably carried out by dissolving the reagents in an S1 solvent.
  • the solvent S1 can be chosen from the group consisting of 1, 4-dioxane, toluene, dimethylformamide, and their mixtures, the solvent S1 preferably being 1, 4-dioxane.
  • the concentration of DAMN of formula (I) in the reaction medium of step (i) is preferably from 0.001 to 2 mol / L, more preferably from 0.1 mol / L to 1 mol / L.
  • the molar ratio of compound (I) to compound (II) is preferably from 0.25 to 1.5, more preferably from 0.5 to 1.25.
  • the second step (ii) is carried out at a temperature T 5 which is greater than T.
  • T 5 is greater than T 4 by at least 10 ° C, or by at least 20 ° C, or by at least 30 ° C, or by at least 40 ° C, or by at least 50 ° C, or at least 60 ° C, or at least 70 ° C.
  • the temperature T 5 corresponds to the boiling point of the solvent used.
  • T 5 ranges from 30 to 180 ° C, more particularly from 60 to 150 ° C, more preferably from 75 to 140 ° C, for example around 100 or 101 ° C (which corresponds to the temperature of boiling 1,4-dioxane).
  • the concentration of compound (IVa) and / or (IVb) in the reaction medium during the second step preferably ranges from 0.001 to 2 mol / L, more preferably from 0.05 mol / L to 0.75 mol / L.
  • the second step (ii) is carried out immediately following the first step without intermediate purification and advantageously without any separation step, simply by modifying the temperature of the reaction mixture, by heating.
  • the amide is salified by adding a carboxylic acid which also makes it possible to improve the yield of the second stage by acid catalysis.
  • the acids used are, for example, trifluoroacetic acid, acetic acid or benzoic acid and preferably trifluoroacetic acid.
  • the molar ratio of compound (IVa) and / or (IVb) to the catalyst preferably ranges from 0.5 to 20, more preferably from 1 to 10.
  • the temperature of the reaction T may be constant throughout the first step, and the temperature of the reaction T 5 may be constant throughout the second step, but this is not necessarily the case.
  • the condition that T 5 is greater than T means that the temperature over the whole of the second step is higher than the temperature over the whole of the first step, that is to say again that the minimum temperature reached during the second stage is greater than the maximum temperature reached during the first stage.
  • a transition period may be necessary to go from the first stage to the second stage and to effect the required temperature change.
  • This transition period preferably has a duration of less than 1 hour, for example less than 30 minutes, for example less than 20 minutes, for example less than 10 minutes, for example less than 5 minutes.
  • the above-mentioned steps i) and ii) can be followed by a step of distilling a solvent S1 / water azeotrope, in particular at a temperature ranging from 40 ° C to 90 ° C.
  • the present invention also relates to a process for preparing a lithium imidazolate compound of formula (V): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said method comprising:
  • Rf represents CF 3 , CHF 2 , C2F5, C3F7, C2F4OCF3, or CF2OCF3, preferably CF 3 , C2F5, C2F4OCF3.
  • the present invention relates to a process for preparing a lithium imidazolate compound of formula (V), in which Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms or C2F4OCF3, said process comprising:
  • the compound of formula (V) is that for which Rf represents CF 3 .
  • the lithiated base can be selected from the group consisting of lithium hydride, lithium carbonate, lithium hydroxide, and mixtures thereof.
  • the lithiated base is lithium carbonate.
  • the lithiated base can be in solid form or in the form of an aqueous or organic composition (for example a suspension or a solution).
  • concentration of lithiated base in the aqueous or organic composition preferably ranges from 0.01 to 10 mol / L, more preferably from 0.1 to 5 mol / L.
  • the compound of formula (III) obtained at the end of the purification process as described above can be in solid form, or in solution in an organic solvent.
  • the compound (III) can be at a concentration which preferably ranges from 0.01 to 5 mol / L, more preferably from 0.1 to 3 mol / L in the organic phase.
  • the compound of formula (III) is dissolved in an organic solvent S4, preferably having a donor number ranging from 1 to 70, advantageously from 5 to 65.
  • organic solvent S4 preferably having a donor number ranging from 1 to 70, advantageously from 5 to 65.
  • solvent S4 one can mention in particular esters, nitriles or ethers.
  • the organic solvent S4 is chosen from methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile, dioxane, or tetrahydrofuran, and even more preferably acetonitrile.
  • step 2) comprises adding a composition comprising the compound of formula (III) in an aqueous lithiated base composition.
  • the reaction of step 2) can be carried out at a temperature between 0 ° C and 100 ° C, preferably between 10 ° C and 50 ° C, even more preferably between 20 ° C and 30 ° C.
  • the duration of step 2) can be between 1 h and 72 h, preferably between 3 h and 24 h, even more preferably between 6 h and 18 h.
  • the process may include an additional step of evaporating the water and the solvent, preferably under vacuum.
  • the water is preferably removed by azeotropic distillation.
  • the process can comprise an additional step of recrystallization of the compound of formula (V) in an organic solvent S4 as defined above.
  • the purification process according to the invention advantageously leads to compounds of formula (V), and in particular LiTDI, having a reduced content of impurities, such as by example a reduced or even zero content of amide-LiTDI, of Ca 2+ , K + , TFA-Li, etc., and less coloration.
  • the purification process according to the invention advantageously makes it possible to prepare the compounds of formula (V), and in particular LiTDI, with improved purity without requiring the use of numerous additional purification steps.
  • Such purity advantageously allows the use of compounds of formula (V) in batteries or in ionic liquids.
  • between x and y or “ranging from x to y” is meant an interval in which the limits x and y are included.
  • the temperature “between -20 and 80 ° C” notably includes the values -20 ° C and 80 ° C.
  • the Hazen coloration is measured according to the Hazen standard, for dissolving (I) in a non-absorbent solvent in the Visible range, at a concentration of 1 mol / L, on a Hach Licol 50 spectrophotometer, in cells of 11 mm in diameter.
  • a solution provides a value of less than 10 Hazen, the optical path is increased by using a 50mm cell for more precision.
  • the Hazen values given in the examples are the means of 3 measurements of the same solution.
  • NMR analysis conditions for fluorinated species in F19, H1, C13 NMR are as follows:
  • the NMR spectra and quantifications were carried out on a Bruker AV 400 spectrometer, at 100.62 MHz for C13 and 376.47 MHz for F19, on a 5 mm BBFO + type probe.
  • Sample The samples are dissolved in DMSO-d6 (approximately 30 mg in 0.6 ml).
  • the solvent is D2O due to the insolubility of LiF in DMSO.
  • the relative quantification in F19 NMR is carried out by integration of the signals of the fluorinated species, weighted by the number of fluorine contributing to the signal, a method well known to those skilled in the art.
  • the absolute quantification in F19 NMR is made by metered addition of ⁇ , ⁇ , ⁇ -trifluorotoluene (TFT), Aldrich in the tube containing the compound, and by integration of the signals of the fluorinated species to be assayed in comparison with that of the CF 3 of this internal standard, according to a method well known to those skilled in the art.
  • TFT trifluorotoluene
  • Aldrich Aldrich in the tube containing the compound
  • the limit of quantification of such a species than LiTDI at the frequency of 376.47 MHz and the chosen probe is of the order of about fifty ppm.
  • the temperature of the double wall is adjusted to 100 ° C and the pressure in the reactor is gradually reduced to distill the dioxane / water azeotrope at 70 ° C.
  • Four additions of 10 kg of dioxane are made at this temperature while continuing the distillation.
  • the pressure is adjusted so as to ensure distillation of the solvent at 60 ° C.
  • the medium is concentrated at 60 ° C until a brown oil is obtained.
  • This oil is then taken up in water with a water: oil mass ratio of 1: 1.
  • the whole is stirred and heated to 60 ° C until a homogeneous brown paste is obtained, then cooled.
  • the crystals obtained are then filtered and then resuspended in water at room temperature (23 ° C) and then filtered. This operation is done three times in all.
  • Example 1 The product obtained in Example 1 is taken up in 280 kg of toluene and, with stirring, is brought to 70 ° C for 2 hours. A colored solution is obtained. Cooled to 40 ° C, and two phases are obtained. A very colored heavy phase gradually forms at the bottom of the reactor. This is purged. The light yellow solution is recovered. By cooling to 0 ° C, solid HTDI is recovered. The solid HTDI is recovered by filtration and then washing with toluene at a temperature between 0 ° C and 25 ° C.
  • Example 3 process for preparing LiTDI
  • Example 2 The solid HTDI obtained in Example 2 is dissolved in acetonitrile to obtain a solution of between 40% and 50% by weight of HTDI. At room temperature, this solution is gradually added to a suspension of 5 kg of U 2 CO 3 in 94 kg of acetonitrile while controlling the evolution of CO 2 . The mixture is left under stirring at room temperature (23 ° C.) overnight.
  • the water of reaction is removed by distillation of the water / CH 3 CN azeotrope.
  • the excess lithium carbonate is filtered off and the reaction medium is then concentrated at 70 ° C. under reduced pressure to a LiTDI / CH 3 CN concentration of 30% by weight.
  • the concentrate is cooled to -10 ° C. LiTDI crystallizes. It is filtered, rinsed twice with acetonitrile cooled to -20 ° C. Its purity measured by NMR is 100%.
  • the process advantageously makes it possible to obtain LiTDI with a Hazen coloration of 14 without having to carry out an activated carbon treatment.

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Abstract

The present invention concerns a method for purifying a compound of following formula (III), in which Rf is a fluorinated alkyl group or fluorinated alkoxyl group comprising 1 to 5 carbon atoms, said method comprising the following steps: a) a step of heating a composition comprising the compound of formula (III) in an organic solvent S3, to a temperature T1 until the compound of formula (III) has dissolved; b) a step of cooling to an intermediate temperature T2 between 23°C and temperature T1 resulting in a two-phase composition comprising: - a phase P1 comprising the compound of formula (III); - a phase P2; c) a step of separating phases P1 and P2 at temperature T2; d) a step of cooling phase P1 to a temperature T3 until crystals of the compound of formula (III) are formed.

Description

PROCÉDÉ DE PURIFICATION DE 2-(FLUOROALKYL OU FLUOROALKOXY)-4,5-DICYANOIMIDAZOLES 2- (FLUOROALKYL OR FLUOROALKOXY) -4,5-DICYANOIMIDAZOLES PURIFICATION PROCESS
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
La présente invention concerne un procédé de purification d’imidazole. The present invention relates to a process for the purification of imidazole.
La présente invention concerne également un procédé de préparation de sel de lithium d’imidazolate. The present invention also relates to a process for preparing lithium salt of imidazolate.
ARRIERE-PLAN TECHNIQUE TECHNICAL BACKGROUND
Une batterie lithium-ion comprend au moins une électrode négative, une électrode positive, un séparateur et un électrolyte. L’électrolyte est constitué d’un sel de lithium dissous dans un solvant qui est généralement un mélange de carbonates organiques, afin d’avoir un bon compromis entre la viscosité et la constante diélectrique. A lithium-ion battery includes at least a negative electrode, a positive electrode, a separator, and an electrolyte. The electrolyte consists of a lithium salt dissolved in a solvent which is generally a mixture of organic carbonates, in order to have a good compromise between viscosity and dielectric constant.
Parmi les sels les plus utilisés figure l’hexafluorophosphate de lithium (LiPF6), qui possède beaucoup des nombreuses qualités requises mais présente le désavantage de se dégrader sous forme de gaz d’acide fluorhydrique. Cela pose des problèmes de sécurité, notamment dans le contexte de l’utilisation des batteries lithium-ion pour les véhicules particuliers. Among the most widely used salts is lithium hexafluorophosphate (LiPF 6 ), which has many of the many qualities required but has the disadvantage of degrading in the form of hydrofluoric acid gas. This poses safety problems, particularly in the context of the use of lithium-ion batteries for private vehicles.
D’autres sels ont donc été développés pour fournir des électrolytes de batteries Li-ion, et notamment le LiTDI (1-trifluorométhyl-4,5-dicarbonitrile-imidazolate de lithium) et le LiPDI (1-pentafluoroéthyl-4,5-dicarbonitrile-imidazolate de lithium), tel que décrit dans WO 2010/023413. Ces sels présentent l’avantage de posséder moins d’atomes de fluor et de comporter des liaisons fortes carbone-fluor en lieu et place des liaisons plus faibles phosphore- fluor du LiPF6. En outre, ces sels présentent de très bonnes conductivités de l’ordre de 6 mS/cm, une très bonne dissociation entre l’anion imidazolate et le cation lithium. Other salts have therefore been developed to provide electrolytes for Li-ion batteries, and in particular LiTDI (lithium 1-trifluoromethyl-4,5-dicarbonitrile-imidazolate) and LiPDI (1-pentafluoroethyl-4,5-dicarbonitrile lithium imidazolate), as described in WO 2010/023413. These salts have the advantage of having fewer fluorine atoms and of having strong carbon-fluorine bonds instead of the weaker phosphorus-fluorine bonds of LiPF 6 . In addition, these salts exhibit very good conductivities of the order of 6 mS / cm, very good dissociation between the imidazolate anion and the lithium cation.
WO 2010/023413 propose plusieurs voies de synthèse pour la fabrication de ces anions pentacycliques, dont l’une consiste en la condensation du diaminomaléonitrile (DAMN) sur un dérivé d’acide tel qu’un anhydride d’acide fluoré, suivie d’un échange proton/lithium. La condensation est réalisée en une seule étape. WO 2010/023413 proposes several synthetic routes for the manufacture of these pentacyclic anions, one of which consists of the condensation of diaminomaleonitrile (DAMN) on an acid derivative such as a fluorinated acid anhydride, followed by a proton / lithium exchange. The condensation is carried out in a single step.
WO 2015/49435 décrit la préparation de sels de fluoroalkyl-4,5-dicyanoimidazole de pureté compatible avec les applications en batterie ou en liquides ioniques. Le procédé met en oeuvre l’utilisation de charbon actif pour purifier les sels d’anions pentacycliques. Or l’utilisation de charbon actif est une opération délicate et susceptible d’amener dans le milieu des ions tels que des ions Ca2+ou K+qui peuvent conduire à une diminution des performances dans les batteries. De plus, les charbons actifs nécessitent couramment un lavage en profondeur avant leur utilisation, ce qui est contraignant et coûteux. Enfin, au moins une étape de recristallisation est nécessaire pour obtenir la pureté souhaitée et une coloration de Hazen acceptable. WO 2015/49435 describes the preparation of fluoroalkyl-4,5-dicyanoimidazole salts of purity compatible with applications in batteries or in ionic liquids. The process involves the use of activated carbon to purify the salts of pentacyclic anions. However, the use of activated carbon is a delicate operation and capable of bringing ions such as Ca 2+ or K + ions into the medium, which can lead to a decrease in performance in the batteries. In addition, activated carbons commonly require washing in depth before use, which is restrictive and expensive. Finally, at least one recrystallization step is necessary to obtain the desired purity and an acceptable Hazen coloration.
Il existe donc un besoin de fournir un nouveau procédé de préparation de sels d’anions pentacycliques permetttant de remédier au moins en partie à au moins l’un des inconvénients susmentionnés. There is therefore a need to provide a novel process for the preparation of salts of pentacyclic anions which can at least partially overcome at least one of the aforementioned drawbacks.
DESCRIPTION DE L’INVENTION DESCRIPTION OF THE INVENTION
Procédé de purification Purification process
La présence invention concerne un procédé de purification d’un composé de formule (III) suivante : dans laquelle Rf est un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone, ledit procédé comprenant les étapes suivantes : a. une étape de chauffage d’une composition comprenant ledit composé de formule (III) dans un solvant organique S3, à une température Ti jusqu’à dissolution dudit composé de formuleThe present invention relates to a process for the purification of a compound of the following formula (III): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said process comprising the following steps: a. a step of heating a composition comprising said compound of formula (III) in an organic solvent S3, at a temperature Ti until dissolution of said compound of formula
(ni) ; b. une étape de refroidissement à une température intermédiaire T2 comprise entre 23°C et la température Ti conduisant à une composition biphasique comprenant : (ni); b. a step of cooling to an intermediate temperature T 2 of between 23 ° C and the temperature Ti leading to a two-phase composition comprising:
- une phase P1 comprenant ledit composé de formule (III) ; - a phase P1 comprising said compound of formula (III);
- une phase P2; c. une étape de séparation des phases P1 et P2 à la température T2; d. une étape de refroidissement de la phase P1 à une température T3 jusqu’à la formation de cristaux du composé de formule (III). - a phase P2; vs. a step of separating the phases P1 and P2 at the temperature T 2 ; d. a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
Selon un mode de réalisation, Rf représente CF3, CHF2, C2F5, C3F , C2F OCF3, ou CF2OCF3 de préférence CF3, C2F5, ou C2F4OCF3. According to one embodiment, Rf represents CF 3 , CHF 2 , C 2 F 5 , C 3 F, C 2 F OCF 3 , or CF 2 OCF 3 preferably CF 3 , C 2 F 5 , or C 2 F 4 OCF 3 .
De préférence, le composé de formule (III) est celui pour lequel Rf représente CF3. Selon un mode de réalisation, la présente invention concerne un procédé de purification d’un composé de formule (III) suivante : dans laquelle Rf est C2F4OCF3 OU un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone, ledit procédé comprenant les étapes suivantes : a. une étape de chauffage d’une composition comprenant ledit composé de formule (III) dans un solvant organique S3 ayant un nombre donneur allant de 0,1 à 10, à une température Ti jusqu’à dissolution dudit composé de formule (III) ; b. une étape de refroidissement à une température intermédiaire T2 comprise entre 23°C et la température T1 conduisant à une composition biphasique comprenant : Preferably, the compound of formula (III) is that for which Rf represents CF 3 . According to one embodiment, the present invention relates to a process for purifying a compound of the following formula (III): wherein Rf is C2F4OCF3 OR a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said process comprising the following steps: a. a step of heating a composition comprising said compound of formula (III) in an organic solvent S3 having a donor number ranging from 0.1 to 10, at a temperature Ti until dissolution of said compound of formula (III); b. a step of cooling to an intermediate temperature T 2 of between 23 ° C and the temperature T1 leading to a two-phase composition comprising:
- une phase P1 comprenant ledit composé de formule (III) ; - a phase P1 comprising said compound of formula (III);
- une phase P2; c. une étape de séparation des phases P1 et P2 à la température T2; d. une étape de refroidissement de la phase P1 à une température T3 jusqu’à la formation de cristaux du composé de formule (III). - a phase P2; vs. a step of separating the phases P1 and P2 at the temperature T 2 ; d. a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
Etape de chauffage a) Heating step a)
Le solvant organique S3 a de préférence un nombre donneur allant de 0,1 à 10. The organic solvent S3 preferably has a donor number ranging from 0.1 to 10.
L’indice donneur d’un solvant représente la valeur -DH, DH étant l’enthalpie de l’interaction (Kcal/mol) entre le solvant et le pentachlorure d’antimoine (Journal of Solution Chemistry, vol. 13, No. 9, 1984). The donor index of a solvent represents the value -DH, DH being the enthalpy of the interaction (Kcal / mol) between the solvent and the antimony pentachloride (Journal of Solution Chemistry, vol. 13, No. 9 , 1984).
Le solvant organique S3 est de préférence choisi parmi les aromatiques ou alcanes aliphatiques ou cycliques, tels que par exemple le toluène, le benzène, le xylène, le cyclohexane, l’heptane. De préférence, le solvant organique S3 est le toluène. The organic solvent S3 is preferably chosen from aromatics or aliphatic or cyclic alkanes, such as, for example, toluene, benzene, xylene, cyclohexane, heptane. Preferably, the organic solvent S3 is toluene.
La température Ti est la température à laquelle le composé de formule (III) est dissous dans le solvant organique S3. La température Ti peut être comprise entre 40°C et la température d’ébullition du solvant organique S3, de préférence entre 50°C et 120°C, avantageusement entre 60°C et 100°C. La température Ti est avantageusement égale à 70°C. The temperature Ti is the temperature at which the compound of formula (III) is dissolved in the organic solvent S3. The temperature Ti can be between 40 ° C and the boiling point of the organic solvent S3, preferably between 50 ° C and 120 ° C, advantageously between 60 ° C and 100 ° C. The temperature Ti is advantageously equal to 70 ° C.
La composition utilisée dans l’étape a), comprenant le composé de formule (III) et le solvant organique S3, peut être obtenue par mise en contact du solvant organique S3 avec le composé de formule (III) sous forme solide. The composition used in step a), comprising the compound of formula (III) and the organic solvent S3, can be obtained by contacting the organic solvent S3 with the compound of formula (III) in solid form.
Avant l’étape a), le composé de formule (III) peut se présenter sous forme hydratée c’est-à-dire que le composé de formule (III) peut contenir une teneur en eau comprise entre 1% et 25% de préférence entre 5% et 20% et préférentiellement entre 10% et 16% en poids par rapport au poids total du composé de formule (III). Before step a), the compound of formula (III) can be in hydrated form, that is to say that the compound of formula (III) can contain a water content of between 1% and 25%, preferably between 5% and 20% and preferably between 10% and 16% by weight relative to the total weight of the compound of formula (III).
Avant l’étape a), la teneur massique du composé de formule (III) dans la composition comprenant le solvant organique S3 peut aller de 1% à 70% en poids, de préférence de 5% à 50% en poids, préférentiellement de 8% à 30% en poids par rapport au poids total de ladite composition. Before step a), the mass content of the compound of formula (III) in the composition comprising the organic solvent S3 can range from 1% to 70% by weight, preferably from 5% to 50% by weight, preferably from 8 % to 30% by weight relative to the total weight of said composition.
Etape de refroidissement b) Cooling step b)
La température T2 est comprise entre 23°C et la température Ti, de préférence comprise entre 23°C et 50°C, et avantageusement entre 30°C et 50°C. The temperature T 2 is between 23 ° C and the temperature Ti, preferably between 23 ° C and 50 ° C, and advantageously between 30 ° C and 50 ° C.
L’étape b) conduit à une composition biphasique comprenant : Step b) leads to a two-phase composition comprising:
- une phase P1 comprenant ledit composé de formule (III) ; et - a phase P1 comprising said compound of formula (III); and
- une phase P2. - a phase P2.
La phase P1 est avantageusement une phase liquide, elle comprend notamment du solvant organique S3. Phase P1 is advantageously a liquid phase, it comprises in particular organic solvent S3.
La phase P1 comprend de préférence plus de 30%, de préférence plus de 35%, et avantageusement plus de 40% du composé de formule (III) initialement contenu dans la solution obtenue à l’issue de l’étape a). Phase P1 preferably comprises more than 30%, preferably more than 35%, and advantageously more than 40% of the compound of formula (III) initially contained in the solution obtained at the end of step a).
La phase P1 comprend de préférence de 0,5% à 70% en poids, de préférence de 1% à 50% en poids, préférentiellement de 5% à 30% en poids du composé de formule (III) par rapport au poids total de ladite phase P1. Phase P1 preferably comprises from 0.5% to 70% by weight, preferably from 1% to 50% by weight, preferably from 5% to 30% by weight of the compound of formula (III) relative to the total weight of said phase P1.
La phase P2 peut comprendre du composé de formule (III) en une teneur strictement inférieure à 45%, de préférence inférieure à 35% de la teneur initiale en composé de formule (III) dans la solution obtenue à l’issue de l’étape a). La phase P2 peut comprendre des impuretés issues du procédé de préparation du composé de formule (III), telles que les agents colorants et le TFA. Phase P2 can comprise compound of formula (III) in a content strictly less than 45%, preferably less than 35% of the initial content of compound of formula (III) in the solution obtained at the end of stage at). Phase P2 can comprise impurities resulting from the process for preparing the compound of formula (III), such as coloring agents and TFA.
De préférence, la phase P2 a une densité plus élevée que celle de la phase P1 . Preferably, phase P2 has a higher density than that of phase P1.
La phase P2 peut être séparée de la phase P1 par exemple par décantation suivie d’une purge de la phase inférieure ou d ‘un pompage de la phase supérieure. Phase P2 can be separated from phase P1, for example by settling followed by purging of the lower phase or by pumping of the upper phase.
Etape de refroidissement d) Cooling step d)
Le procédé de purification selon l’invention comprend une étape de refroidissement de la phase P1 à une température T3 jusqu’à la formation de cristaux du composé de formule (III). The purification process according to the invention comprises a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
La température T3 peut être comprise entre 40°C et -30°C, de préférence entre 25°C et -15°C, et encore plus préférentiellement entre 10°C et -5°C. La température T3 est avantageusement 0°C. The temperature T 3 can be between 40 ° C and -30 ° C, preferably between 25 ° C and -15 ° C, and even more preferably between 10 ° C and -5 ° C. The temperature T3 is advantageously 0 ° C.
La température T3 est avantageusement la température à laquelle le composé de formule (III) cristallise dans le solvant organique S3. The temperature T 3 is advantageously the temperature at which the compound of formula (III) crystallizes from the organic solvent S3.
Les étapes a,b,c,d peuvent être répétées sur la P2 afin de récupérer plus de composé III. Le nombre de répétition est compris entre 2 et 4, préférentiellement 3. Steps a, b, c, d can be repeated on P2 in order to recover more compound III. The number of repetitions is between 2 and 4, preferably 3.
Etapes additionnelles Additional steps
Le procédé de purification susmentionné peut comprendre une étape supplémentaire e) de filtration de la composition obtenue à l’issue de l’étape d). La filtration conduit avantageusement à un composé de formule (III) sous forme solide et à un filtrat. The aforementioned purification process may include an additional step e) of filtering the composition obtained at the end of step d). Filtration advantageously results in a compound of formula (III) in solid form and in a filtrate.
Le solide est avantageusement soumis à une étape supplémentaire de séchage, de préférence sous un courant d’azote à 23°C ou plus. The solid is advantageously subjected to an additional drying step, preferably under a stream of nitrogen at 23 ° C or more.
Le procédé de purification susmentionné permet avantageusement de préparer un composé de formule (III) avec un bon rendement et une teneur en impuretés réduite, notamment une teneur réduite en agents susceptibles de colorer le produit, et/ou en TFA (acide trifluoroacétique) et/ou en amides dérivés du composé de formule (III) : The aforementioned purification process advantageously makes it possible to prepare a compound of formula (III) with a good yield and a reduced content of impurities, in particular a reduced content of agents capable of coloring the product, and / or of TFA (trifluoroacetic acid) and / or in amides derived from the compound of formula (III):
Le procédé de purification permet avantageusement de préparer un composé de formule (III) ayant une coloration moindre. Le procédé de purification permet également avantageusement d’obtenir un composé de formule (III) avec un bon rendement et une teneur réduite en impuretés en un nombre d’étapes plus faible, sans nécessité des étapes supplémentaires coûteuses de purification. The purification process advantageously makes it possible to prepare a compound of formula (III) having less coloration. The purification process also advantageously makes it possible to obtain a compound of formula (III) with a good yield and a reduced content of impurities in a smaller number of steps, without the need for costly additional purification steps.
Etapes préalables Preliminary steps
Le procédé de purification selon l’invention peut comprendre une étape a’), préalable à l’étape a), de mise en contact du composé de formule (III) avec le solvant organique S3. De préférence, le solvant organique S3 est ajouté au composé de formule (III). The purification process according to the invention can comprise a step a ’), prior to step a), of bringing the compound of formula (III) into contact with the organic solvent S3. Preferably, the organic solvent S3 is added to the compound of formula (III).
Le composé de formule (III) de l’étape a’) peut être obtenu par un procédé comprenant les étapes suivantes : The compound of formula (III) from step a ′) can be obtained by a process comprising the following steps:
- x) étape de mise en contact d’un composé de formule (III) avec de l’eau, de préférence dans un ratio massique composé de formule (III) : eau allant de 1 : 1 à 1 : 4 avantageusement de 1 : 1 à 1 : 2 ; - x) step of bringing a compound of formula (III) into contact with water, preferably in a mass ratio of compound of formula (III): water ranging from 1: 1 to 1: 4, advantageously from 1: 1 to 1: 2;
- y) étape de chauffage de la composition obtenue à l’étape x) à une température T6, de préférence comprise entre 30°C et 80°C, avantageusement entre 40°C et 70°C ;- y) step of heating the composition obtained in step x) at a temperature T 6 , preferably between 30 ° C and 80 ° C, advantageously between 40 ° C and 70 ° C;
- z) étape de refroidissement de la composition obtenue à l’étape y) jusqu’à la formation de cristaux de composé de formule (III) ; - z) step of cooling the composition obtained in step y) until the formation of crystals of compound of formula (III);
- z’) étape de filtration des cristaux, et éventuellement séchage ; - z ’) stage of filtering the crystals, and optionally drying;
- z”) éventuelle étape de lavage des cristaux avec de l’eau, notamment à 23°C, et éventuellement étape de séchage. - z ") optional step of washing the crystals with water, in particular at 23 ° C, and optionally a drying step.
Le composé de formule (III) de l’étape x) peut être obtenu par tout procédé de préparation d’un composé de formule (III), éventuellement soumis à une étape d’évaporation du solvant réactionnel. The compound of formula (III) in step x) can be obtained by any process for preparing a compound of formula (III), optionally subjected to a step of evaporating the reaction solvent.
Synthèse du composé de formule Synthesis of the compound of formula
Le composé de formule (III) susmentionné peut être obtenu par un procédé comprenant : i. une étape de réaction du diaminomaléonitrile de formule (I): avec le composé de formule (II) suivante : dans laquelle Y représente un atome de chlore ou le groupement OCORf, pour former le composé amide salifié de formule (IVa) et/ou l’amine correspondante (IVb), à une température T4 The above-mentioned compound of formula (III) can be obtained by a process comprising: i. a step of reaction of the diaminomaleonitrile of formula (I): with the compound of formula (II) below: in which Y represents a chlorine atom or the OCORf group, to form the salified amide compound of formula (IVa) and / or the corresponding amine (IVb), at a temperature T 4
(IVa) (IVb) ii. la déshydratation du composé amide salifié de formule (IVa) et/ou l’amine correspondante de formule (IVb) pour former le composé imidazole de formule (III), à une température T5 supérieure à T4. (IVa) (IVb) ii. dehydration of the salified amide compound of formula (IVa) and / or the corresponding amine of formula (IVb) to form the imidazole compound of formula (III), at a temperature T 5 greater than T 4 .
La température T qui peut aller de 0 à 80°C, de préférence de 10 à 50°C, plus préférentiellement de 20 à 30°C, par exemple environ 25°C. The temperature T which can range from 0 to 80 ° C, preferably from 10 to 50 ° C, more preferably from 20 to 30 ° C, for example about 25 ° C.
Selon un mode de réalisation, l’étape (i) dure de 1 à 12 heures, de préférence de 1 à 3 heures, et / ou l’étape (ii) dure de 1 à 12 heures, de préférence de 1 à 3 heures. According to one embodiment, step (i) lasts from 1 to 12 hours, preferably from 1 to 3 hours, and / or step (ii) lasts from 1 to 12 hours, preferably from 1 to 3 hours .
Selon un mode de réalisation, le diaminomaléonitrile de formule (I) et le composé de formule (II) sont dissous dans un solvant préalablement à l’étape (i), le solvant étant de préférence le 1 ,4-dioxane. According to one embodiment, the diaminomaleonitrile of formula (I) and the compound of formula (II) are dissolved in a solvent prior to step (i), the solvent preferably being 1, 4-dioxane.
L’étape (i) est de préférence effectuée en dissolvant les réactifs dans un solvant S1 .Step (i) is preferably carried out by dissolving the reagents in an S1 solvent.
Le solvant S1 peut être choisi dans le groupe constitué du 1 ,4-dioxane, du toluène, du diméthylformamide, et de leurs mélanges, le solvant S1 étant de préférence le 1 ,4-dioxane. The solvent S1 can be chosen from the group consisting of 1, 4-dioxane, toluene, dimethylformamide, and their mixtures, the solvent S1 preferably being 1, 4-dioxane.
La concentration du DAMN de formule (I) dans le milieu réactionnel de l’étape (i) est de préférence de 0,001 à 2 mol/L, plus préférentiellement de 0,1 mol/L à 1 mol/L. Le rapport molaire du composé (I) sur le composé (II) est de préférence de 0,25 à 1 ,5, plus préférentiellement de 0,5 à 1 ,25. La deuxième étape (ii) est effectuée à une température T5 qui est supérieure à T . De préférence, T5 est supérieure à T4 d’au moins 10°C, ou d’au moins 20°C, ou d’au moins 30°C, ou d’au moins 40°C, ou d’au moins 50°C, ou d’au moins 60°C, ou d’au moins 70°C. The concentration of DAMN of formula (I) in the reaction medium of step (i) is preferably from 0.001 to 2 mol / L, more preferably from 0.1 mol / L to 1 mol / L. The molar ratio of compound (I) to compound (II) is preferably from 0.25 to 1.5, more preferably from 0.5 to 1.25. The second step (ii) is carried out at a temperature T 5 which is greater than T. Preferably, T 5 is greater than T 4 by at least 10 ° C, or by at least 20 ° C, or by at least 30 ° C, or by at least 40 ° C, or by at least 50 ° C, or at least 60 ° C, or at least 70 ° C.
Selon un mode de réalisation particulier, la température T5 correspond à la température d’ébullition du solvant utilisé. According to a particular embodiment, the temperature T 5 corresponds to the boiling point of the solvent used.
De préférence, T5 va de 30 à 180°C, plus particulièrement de 60 à 150°C, plus préférentiellement de 75 à 140°C, par exemple d’environ 100 ou 101 °C (ce qui correspond à la température d’ébullition du 1 ,4-dioxane). Preferably, T 5 ranges from 30 to 180 ° C, more particularly from 60 to 150 ° C, more preferably from 75 to 140 ° C, for example around 100 or 101 ° C (which corresponds to the temperature of boiling 1,4-dioxane).
La concentration du composé (IVa) et/ou (IVb) dans le milieu réactionnel lors de la deuxième étape va de préférence de 0,001 à 2 mol/L, plus préférentiellement de 0,05 mol/L à 0,75 mol/L. The concentration of compound (IVa) and / or (IVb) in the reaction medium during the second step preferably ranges from 0.001 to 2 mol / L, more preferably from 0.05 mol / L to 0.75 mol / L.
De préférence, la deuxième étape (ii) est effectuée immédiatement à la suite de la première étape sans purification intermédiaire et avantageusement sans aucune étape de séparation, simplement en modifiant la température du mélange réactionnel, par chauffage. Preferably, the second step (ii) is carried out immediately following the first step without intermediate purification and advantageously without any separation step, simply by modifying the temperature of the reaction mixture, by heating.
Dans le cas où Y = Cl, l’amide est salifié par ajout d’un acide carboxylique qui permet également d’améliorer le rendement de la deuxième étape par catalyse acide. Les acides utilisés sont par exemple de l’acide trifluoroacétique, de l’acide acétique ou de l’acide benzoïque et de préférence de l’acide trifluoroacétique. In the case where Y = Cl, the amide is salified by adding a carboxylic acid which also makes it possible to improve the yield of the second stage by acid catalysis. The acids used are, for example, trifluoroacetic acid, acetic acid or benzoic acid and preferably trifluoroacetic acid.
Le rapport molaire du composé (IVa) et/ou (IVb) sur le catalyseur va de préférence de 0,5 à 20, plus préférentiellement de 1 à 10. The molar ratio of compound (IVa) and / or (IVb) to the catalyst preferably ranges from 0.5 to 20, more preferably from 1 to 10.
La température de la réaction T peut être constante tout au long de la première étape, et la température de la réaction T5 peut être constante tout au long de la deuxième étape, mais ce n’est pas nécessairement le cas. On peut par exemple prévoir une température croissante tout au long de la réaction, ou tout au long de la première étape seulement. Dans de tels cas, la condition selon laquelle T5 est supérieure à T signifie que la température sur l’ensemble de la deuxième étape est supérieure à la température sur l’ensemble de la première étape, c’est- à-dire encore que la température minimale atteinte lors de la deuxième étape est supérieure à la température maximale atteinte lors de la première étape. The temperature of the reaction T may be constant throughout the first step, and the temperature of the reaction T 5 may be constant throughout the second step, but this is not necessarily the case. For example, it is possible to provide for an increasing temperature throughout the reaction, or throughout the first step only. In such cases, the condition that T 5 is greater than T means that the temperature over the whole of the second step is higher than the temperature over the whole of the first step, that is to say again that the minimum temperature reached during the second stage is greater than the maximum temperature reached during the first stage.
Une période de transition peut être nécessaire pour passer de la première étape à la deuxième étape et pour opérer le changement de température requis. Cette période de transition présente de préférence une durée inférieure à 1 heure, par exemple inférieure à 30 minutes, par exemple inférieure à 20 minutes, par exemple inférieure à 10 minutes, par exemple inférieure à 5 minutes. Les étapes i) et ii) susmentionnées peuvent être suivies par une étape de distillation d’un azéotrope solvant S1/eau, en particulier à une température allant de 40°C à 90°C. A transition period may be necessary to go from the first stage to the second stage and to effect the required temperature change. This transition period preferably has a duration of less than 1 hour, for example less than 30 minutes, for example less than 20 minutes, for example less than 10 minutes, for example less than 5 minutes. The above-mentioned steps i) and ii) can be followed by a step of distilling a solvent S1 / water azeotrope, in particular at a temperature ranging from 40 ° C to 90 ° C.
Procédé de préparation d’imidazolate de lithium Process for preparing lithium imidazolate
La présente invention concerne également un procédé de préparation d’un composé imidazolate de lithium de formule (V) : dans laquelle Rf est un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone, ledit procédé comprenant : The present invention also relates to a process for preparing a lithium imidazolate compound of formula (V): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said method comprising:
1 ) la purification du composé de formule (III) selon le procédé tel que décrit précédemment ; et 1) the purification of the compound of formula (III) according to the process as described above; and
- 2) la réaction du composé de formule (III) avec une base lithiée. - 2) reaction of the compound of formula (III) with a lithiated base.
Selon un mode de réalisation, Rf représente CF3, CHF2, C2F5, C3F7, C2F4OCF3, ou CF2OCF3 de préférence CF3, C2F5, C2F4OCF3. According to one embodiment, Rf represents CF 3 , CHF 2 , C2F5, C3F7, C2F4OCF3, or CF2OCF3, preferably CF 3 , C2F5, C2F4OCF3.
Selon un mode de réalisation, la présente invention concerne un procédé de préparation d’un composé imidazolate de lithium de formule (V), dans laquelle Rf est un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone ou C2F4OCF3, ledit procédé comprenant : According to one embodiment, the present invention relates to a process for preparing a lithium imidazolate compound of formula (V), in which Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms or C2F4OCF3, said process comprising:
1 ) la purification du composé de formule (III) selon le procédé tel que décrit précédemment ; et 1) the purification of the compound of formula (III) according to the process as described above; and
- 2) la réaction du composé de formule (III) avec une base lithiée. - 2) reaction of the compound of formula (III) with a lithiated base.
De préférence, le composé de formule (V) est celui pour lequel Rf représente CF3. La base lithiée peut être choisie dans le groupe constitué de l’hydrure de lithium, du carbonate de lithium, de l’hydroxyde de lithium, et de leurs mélanges. De préférence, la base lithiée est le carbonate de lithium. Preferably, the compound of formula (V) is that for which Rf represents CF 3 . The lithiated base can be selected from the group consisting of lithium hydride, lithium carbonate, lithium hydroxide, and mixtures thereof. Preferably, the lithiated base is lithium carbonate.
La base lithiée peut se présenter sous forme solide soit sous forme d’une composition aqueuse ou organique (par exemple suspension ou une solution). La concentration en base lithiée dans la composition aqueuse ou organique va de préférence de 0,01 à 10 mol/L, plus préférentiellement de 0,1 à 5 mol/L. The lithiated base can be in solid form or in the form of an aqueous or organic composition (for example a suspension or a solution). The concentration of lithiated base in the aqueous or organic composition preferably ranges from 0.01 to 10 mol / L, more preferably from 0.1 to 5 mol / L.
Le composé de formule (III) obtenu à l’issue du procédé de purification tel que décrit ci-dessus peut être sous forme solide, ou en solution dans un solvant organique. Le composé (III) peut être à une concentration qui va de préférence de 0,01 à 5 mol/L, plus préférentiellement de 0,1 à 3 mol/L en phase organique. The compound of formula (III) obtained at the end of the purification process as described above can be in solid form, or in solution in an organic solvent. The compound (III) can be at a concentration which preferably ranges from 0.01 to 5 mol / L, more preferably from 0.1 to 3 mol / L in the organic phase.
De préférence, préalablement à l’étape 2), le composé de formule (III) est dissous dans un solvant organique S4, ayant de préférence un nombre donneur allant de 1 à 70, avantageusement de 5 à 65. Comme solvant S4, on peut citer notamment les esters, les nitriles, ou les éthers. Avantageusement, le solvant organique S4 est choisi parmi l’acétate de méthyle, l’acétate d’éthyle, l’acétate de butyle, l’acétonitrile, le propionitrile, l’isobutyronitrile, le glutaronitrile, le dioxane, ou le tétrahydrofurane, et encore plus avantageusement l’acétonitrile. Preferably, prior to step 2), the compound of formula (III) is dissolved in an organic solvent S4, preferably having a donor number ranging from 1 to 70, advantageously from 5 to 65. As solvent S4, one can mention in particular esters, nitriles or ethers. Advantageously, the organic solvent S4 is chosen from methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile, dioxane, or tetrahydrofuran, and even more preferably acetonitrile.
De préférence, l’étape 2) comprend l’ajout d’une composition comprenant le composé de formule (III) dans composition aqueuse de base lithiée. Preferably, step 2) comprises adding a composition comprising the compound of formula (III) in an aqueous lithiated base composition.
La réaction de l’étape 2) peut être réalisée à une température comprise entre 0°C et 100°C, de préférence entre 10°C et 50°C, encore plus préférentiellement entre 20°C et 30°C. The reaction of step 2) can be carried out at a temperature between 0 ° C and 100 ° C, preferably between 10 ° C and 50 ° C, even more preferably between 20 ° C and 30 ° C.
La durée de l’étape 2) peut être comprise entre 1 h et 72h, de préférence entre 3h et 24h, encore plus préférentiellement entre 6h et 18h. The duration of step 2) can be between 1 h and 72 h, preferably between 3 h and 24 h, even more preferably between 6 h and 18 h.
Le procédé peut comprendre une étape supplémentaire d’évaporation de l’eau et du solvant, de préférence sous vide. Dans le cas où il y a un solvant organique, l’eau est préférentiellement éliminée par distillation azéotropique. The process may include an additional step of evaporating the water and the solvent, preferably under vacuum. In the case where there is an organic solvent, the water is preferably removed by azeotropic distillation.
Le procédé peut comprendre une étape supplémentaire de recristallisation du composé de formule (V) dans un solvant organique S4 tel que défini ci-dessus. The process can comprise an additional step of recrystallization of the compound of formula (V) in an organic solvent S4 as defined above.
L’utilisation du procédé de purification selon l’invention permet avantageusement de préparer les composés de formule (V), et notamment le LiTDI, avec un rendement amélioré, et notamment avec un nombre d’étapes réduit. The use of the purification process according to the invention advantageously makes it possible to prepare the compounds of formula (V), and in particular LiTDI, with an improved yield, and in particular with a reduced number of steps.
Le procédé de purification selon l’invention conduit avantageusement à des composés de formule (V), et notamment le LiTDI, ayant une teneur réduite en impuretés, telles que par exemple une teneur réduite voire nulle en amide-LiTDI, en Ca2+, K+, TFA-Li..., et une coloration moindre. The purification process according to the invention advantageously leads to compounds of formula (V), and in particular LiTDI, having a reduced content of impurities, such as by example a reduced or even zero content of amide-LiTDI, of Ca 2+ , K + , TFA-Li, etc., and less coloration.
Le procédé de purification selon l’invention permet avantageusement de préparer les composés de formule (V), et notamment le LiTDI, avec une pureté améliorée sans nécessiter l’emploi de nombreuses étapes de purification additionnelles. Une telle pureté permet avantageusement l’utilisation des composés de formule (V) dans les batteries ou dans les liquides ioniques. The purification process according to the invention advantageously makes it possible to prepare the compounds of formula (V), and in particular LiTDI, with improved purity without requiring the use of numerous additional purification steps. Such purity advantageously allows the use of compounds of formula (V) in batteries or in ionic liquids.
Dans le cadre de l’invention, par « compris entre x et y », ou « allant de x à y », on entend un intervalle dans lequel les bornes x et y sont incluses. Par exemple, la température «comprise entre -20 et 80°C » inclus notamment les valeurs -20°C et 80°C. In the context of the invention, by "between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the temperature “between -20 and 80 ° C” notably includes the values -20 ° C and 80 ° C.
La présente invention est illustrée par l’exemple suivant, auquel elle n’est cependant pas limitée. The present invention is illustrated by the following example, to which it is, however, not limited.
EXEMPLES EXAMPLES
La coloration Hazen est mesurée selon la norme Hazen, pour une mise en solution de (I) dans un solvant non absorbant dans le domaine du Visible, à une concentration de 1 mole/L, sur un spectrophotomètre Hach Licol 50, en cellule de 11 mm de diamètre. Lorsqu’une solution fournit une valeur inférieure à 10 Hazen, le trajet optique est augmenté par l’emploi d’une cuve de 50 mm pour plus de précision. Les valeurs Hazen portées dans les exemples sont les moyennes de 3 mesures d’une même solution. The Hazen coloration is measured according to the Hazen standard, for dissolving (I) in a non-absorbent solvent in the Visible range, at a concentration of 1 mol / L, on a Hach Licol 50 spectrophotometer, in cells of 11 mm in diameter. When a solution provides a value of less than 10 Hazen, the optical path is increased by using a 50mm cell for more precision. The Hazen values given in the examples are the means of 3 measurements of the same solution.
Pour les exemples, les conditions d’analyse RMN des espèces fluorées en RMN F19, H1 , C13 sont les suivantes : For the examples, the NMR analysis conditions for fluorinated species in F19, H1, C13 NMR are as follows:
Equipement : Les spectres et quantifications RMN ont été effectués sur un spectromètre Bruker AV 400, à 100,62 MHz pour C13 et 376,47 MHz pour F19, sur une sonde de 5 mm de type BBFO+. Equipment: The NMR spectra and quantifications were carried out on a Bruker AV 400 spectrometer, at 100.62 MHz for C13 and 376.47 MHz for F19, on a 5 mm BBFO + type probe.
Echantillonnaqe : Les échantillons sont dissous dans DMSO-d6 (environ 30 mg dans 0,6 ml). Dans le cas de la détection de fluorures ou d’ajout de LiF servant à vérifier la présence indésirable de fluorures, le solvant est D2O en raison de l’insolubilité de LiF dans le DMSO.Sample: The samples are dissolved in DMSO-d6 (approximately 30 mg in 0.6 ml). In the case of the detection of fluorides or the addition of LiF to check for the unwanted presence of fluorides, the solvent is D2O due to the insolubility of LiF in DMSO.
Quantification : La quantification relative en RMN F19 est faite par intégration des signaux des espèces fluorées, pondérés du nombre de fluor contribuant au signal, méthode bien connue de l’homme de l’art. La quantification absolue en RMN F19 est faite par ajout dosé d’a,a,oc- trifluorotoluène (TFT), Aldrich dans le tube contenant le composé, et par intégration des signaux des espèces fluorées à doser en comparaison de celle des CF3 de cet étalon interne, selon méthode bien connue de l’homme de l’art. La limite de quantification d’une espèce telle que LiTDI à la fréquence de 376,47 MHz et la sonde choisie est de l’ordre d’une cinquantaine de ppm. Quantification: The relative quantification in F19 NMR is carried out by integration of the signals of the fluorinated species, weighted by the number of fluorine contributing to the signal, a method well known to those skilled in the art. The absolute quantification in F19 NMR is made by metered addition of α, α, α-trifluorotoluene (TFT), Aldrich in the tube containing the compound, and by integration of the signals of the fluorinated species to be assayed in comparison with that of the CF 3 of this internal standard, according to a method well known to those skilled in the art. The limit of quantification of such a species than LiTDI at the frequency of 376.47 MHz and the chosen probe is of the order of about fifty ppm.
Exemple 1 procédé de préparation de HTDI Example 1 method for preparing HTDI
Dans un réacteur vitrifié de 100 litres muni d’un réfrigérant, d’une pompe d’introduction de réactif et d’une prise de température, on introduit 20 kg DAMN (diaminomaléonitrile), de pureté 98% dans 60kg de 1 ,4-dioxane à température ambiante (23°C). La suspension est mise sous agitation tandis qu’on introduit 40,4kg d’anhydride trifluoroacétique (TFAA) de pureté 99% au moyen de la pompe ; la vitesse d’introduction du TFAA est réglée pour que le milieu réactionnel reste à une température inférieure à 30°C (température de paroi du réacteur vers 12°C). La suspension se transforme rapidement en une solution colorée brune. Lorsque la totalité de l’anhydride trifluoroacétique est introduite, on laisse le milieu sous agitation durant 15 minutes puis on augmente la température du milieu réactionnel jusqu’au reflux du dioxane (105°C) (Température de paroi du réacteur : 130°C max) que l’on maintient pour que toute cette opération dure 30 minutes de reflux. 20 kg DAMN (diaminomaleonitrile), 98% purity, in 60 kg of 1, 4- are introduced into a vitrified 100-liter reactor fitted with a condenser, a reagent introduction pump and a temperature measurement. dioxane at room temperature (23 ° C). The suspension is stirred while 40.4 kg of trifluoroacetic anhydride (TFAA) of 99% purity is introduced by means of the pump; the rate of introduction of the TFAA is adjusted so that the reaction medium remains at a temperature below 30 ° C (reactor wall temperature around 12 ° C). The suspension quickly turns into a brown colored solution. When all of the trifluoroacetic anhydride is introduced, the medium is left under stirring for 15 minutes then the temperature of the reaction medium is increased until the dioxane refluxes (105 ° C) (Reactor wall temperature: 130 ° C max ) which is maintained so that this entire operation lasts 30 minutes of reflux.
Puis on règle la température de la double paroi à 100°C et on diminue peu à peu la pression dans le réacteur pour distiller l’azéotrope dioxane/eau à 70°C. Quatre ajouts de 10kg de dioxane sont réalisés à cette température en poursuivant la distillation. On règle la pression de façon à assurer la distillation du solvant à 60°C. On concentre à 60°C le milieu jusqu’à l’obtention d’une huile brune. Cette huile est alors reprise à l’eau avec un ratio massique eau : huile de 1 :1. L’ensemble est mis sous agitation et chauffé à 60°C jusqu’à l’obtention d’une pâte brune homogène, puis refroidi. Les cristaux obtenus sont alors filtrés puis remis en suspension dans de l’eau à température ambiante (23°C) puis filtrés. Cette opération est faite trois fois en tout. Then the temperature of the double wall is adjusted to 100 ° C and the pressure in the reactor is gradually reduced to distill the dioxane / water azeotrope at 70 ° C. Four additions of 10 kg of dioxane are made at this temperature while continuing the distillation. The pressure is adjusted so as to ensure distillation of the solvent at 60 ° C. The medium is concentrated at 60 ° C until a brown oil is obtained. This oil is then taken up in water with a water: oil mass ratio of 1: 1. The whole is stirred and heated to 60 ° C until a homogeneous brown paste is obtained, then cooled. The crystals obtained are then filtered and then resuspended in water at room temperature (23 ° C) and then filtered. This operation is done three times in all.
Le solide est partiellement séché pendant une nuit à température ambiante (23°C) sous un flux d’azote. On obtient 33,7kg de cristaux bruns de HTDI. The solid is partially dried overnight at room temperature (23 ° C) under a stream of nitrogen. 33.7 kg of brown crystals of HTDI are obtained.
Exemple 2 : purification de HTDI Example 2: purification of HTDI
Le produit obtenu à l’exemple 1 est repris par 280kg de toluène et sous agitation est porté à 70°C pendant 2 heures. On obtient une solution colorée. On refroidit à 40°C, et obtient deux phases. Une phase lourde très colorée se forme peu à peu en fond de réacteur. Celle-ci est purgée. On récupère la solution jaune légère. Par refroidissement à 0°C, on récupère de l’HTDI solide. On récupère le HTDI solide par filtration puis lavage par du toluène à une température compris entre 0°C et 25°C. The product obtained in Example 1 is taken up in 280 kg of toluene and, with stirring, is brought to 70 ° C for 2 hours. A colored solution is obtained. Cooled to 40 ° C, and two phases are obtained. A very colored heavy phase gradually forms at the bottom of the reactor. This is purged. The light yellow solution is recovered. By cooling to 0 ° C, solid HTDI is recovered. The solid HTDI is recovered by filtration and then washing with toluene at a temperature between 0 ° C and 25 ° C.
La phase inférieure colorée est traitée deux fois par du toluène selon le même principe. Exemple 3 : procédé de préparation de LiTDI The colored lower phase is treated twice with toluene according to the same principle. Example 3: process for preparing LiTDI
L’HTDI solide obtenu à l’exemple 2 est dissous dans l’acétonitrile pour obtenir une solution entre 40% et 50% poids en HTDI. A température ambiante, on ajoute peu à peu cette solution à une suspension de 5kg de U2CO3 dans 94kg d’acétonitrile en contrôlant le dégagement de CO2. On laisse sous agitation à température ambiante (23°C) pendant une nuit. The solid HTDI obtained in Example 2 is dissolved in acetonitrile to obtain a solution of between 40% and 50% by weight of HTDI. At room temperature, this solution is gradually added to a suspension of 5 kg of U 2 CO 3 in 94 kg of acetonitrile while controlling the evolution of CO 2 . The mixture is left under stirring at room temperature (23 ° C.) overnight.
On élimine l’eau de réaction par distillation de l’azéotrope eau/CH3CN. On filtre le carbonate de lithium en excès puis on concentre le milieu réactionnel à 70°C sous pression réduite jusqu’à la concentration LiTDI/ CH3CN de 30% poids. The water of reaction is removed by distillation of the water / CH 3 CN azeotrope. The excess lithium carbonate is filtered off and the reaction medium is then concentrated at 70 ° C. under reduced pressure to a LiTDI / CH 3 CN concentration of 30% by weight.
On refroidit le concentrât à -10°C. Le LiTDI cristallise. Il est filtré, rincé deux fois par de l’acétonitrile refroidi à -20°C. Sa pureté mesurée en RMN est 100%. The concentrate is cooled to -10 ° C. LiTDI crystallizes. It is filtered, rinsed twice with acetonitrile cooled to -20 ° C. Its purity measured by NMR is 100%.
Il est ensuite séché d’abord sous un courant d’azote puis sous vide à 75°C. En chromatographie ionique la teneur en lithium est mesurée à 3.63%. La couleur Hazen est de 14. Le rendement global par rapport au DAMN est de 43% soit 14,7kg de LiTDI. It is then dried first under a stream of nitrogen and then under vacuum at 75 ° C. In ion chromatography, the lithium content is measured at 3.63%. The Hazen color is 14. The overall yield relative to the DAMN is 43%, ie 14.7 kg of LiTDI.
Le procédé permet avantageusement d’obtenir du LiTDI avec une coloration de Hazen de 14 sans avoir à mettre en oeuvre un traitement au charbon actif. The process advantageously makes it possible to obtain LiTDI with a Hazen coloration of 14 without having to carry out an activated carbon treatment.

Claims

REVENDICATIONS
1 . Procédé de purification d’un composé de formule (III) suivante : dans laquelle Rf est un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone, ledit procédé comprenant les étapes suivantes : a. une étape de chauffage d’une composition comprenant ledit composé de formule (III) dans un solvant organique S3, à une température Ti jusqu’à dissolution dudit composé de formule (III) ; b. une étape de refroidissement à une température intermédiaire T2 comprise entre 23°C et la température Ti conduisant à une composition biphasique comprenant : 1. Process for the purification of a compound of the following formula (III): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said process comprising the following steps: a. a step of heating a composition comprising said compound of formula (III) in an organic solvent S3, at a temperature Ti until said compound of formula (III) is dissolved; b. a step of cooling to an intermediate temperature T 2 of between 23 ° C and the temperature Ti leading to a two-phase composition comprising:
- une phase P1 comprenant ledit composé de formule (III) ; - a phase P1 comprising said compound of formula (III);
- une phase P2; c. une étape de séparation des phases P1 et P2 à la température T2; d. une étape de refroidissement de la phase P1 à une température T3 jusqu’à la formation de cristaux du composé de formule (III). - a phase P2; vs. a step of separating the phases P1 and P2 at the temperature T 2 ; d. a step of cooling phase P1 to a temperature T 3 until the formation of crystals of the compound of formula (III).
2. Procédé selon la revendication 1 , caractérisé en ce que Rf représente CF3, CHF2, C2F5, C3F , C2F OCF3, OU CF2OCF3, de préférence CF3, C2F5, ou C2F4OCF3. 2. Method according to claim 1, characterized in that Rf represents CF 3 , CHF 2 , C 2 F 5 , C 3 F, C 2 F OCF 3 , OR CF 2 OCF 3, preferably CF 3 , C 2 F 5 , or C 2 F 4 OCF 3 .
3. Procédé selon l’une quelconque des revendications 1 ou 2, caractérisé en ce que Rf représente CF3. 3. Method according to any one of claims 1 or 2, characterized in that Rf represents CF 3 .
4. Procédé selon l’une quelconque des revendications 1 à 3, caractérisé en ce que le solvant organique S3 a de préférence un nombre donneur allant de 0,1 à 10. 4. Method according to any one of claims 1 to 3, characterized in that the organic solvent S3 preferably has a donor number ranging from 0.1 to 10.
5. Procédé selon l’une quelconque des revendications 1 à 4, caractérisé en ce que le solvant organique S3 est choisi parmi les aromatiques ou alcanes aliphatiques ou cycliques, tels que par exemple le toluène, le benzène, le xylène, le cyclohexane, l’heptane. 5. Method according to any one of claims 1 to 4, characterized in that the organic solvent S3 is chosen from aromatics or aliphatic alkanes or cyclic, such as for example toluene, benzene, xylene, cyclohexane, heptane.
6. Procédé selon l’une quelconque des revendications 1 à 5, caractérisé en ce que la température Ti est comprise entre 40°C et la température d’ébullition du solvant organique S3, de préférence entre 50°C et 120°C, avantageusement entre 60°C et 100°C. 6. Method according to any one of claims 1 to 5, characterized in that the temperature Ti is between 40 ° C and the boiling point of the organic solvent S3, preferably between 50 ° C and 120 ° C, advantageously between 60 ° C and 100 ° C.
7. Procédé selon l’une quelconque des revendications 1 à 6, caractérisé en ce qu’avant l’étape a), le composé de formule (III) contient une teneur en eau comprise entre 1% et 25% de préférence entre 5% et 20% et préférentiellement entre 10% et 16% en poids par rapport au poids total du composé de formule (III). 7. Method according to any one of claims 1 to 6, characterized in that before step a), the compound of formula (III) contains a water content of between 1% and 25%, preferably between 5%. and 20% and preferably between 10% and 16% by weight relative to the total weight of the compound of formula (III).
8. Procédé selon l’une quelconque des revendications 1 à 7, caractérisé en ce que la température T2 est comprise entre 23°C et 50°C, et avantageusement entre 30°C et 50°C. 8. Method according to any one of claims 1 to 7, characterized in that the temperature T 2 is between 23 ° C and 50 ° C, and advantageously between 30 ° C and 50 ° C.
9. Procédé selon l’une quelconque des revendications 1 à 8, caractérisé en ce que la phase P1 comprend plus de 30%, de préférence plus de 35%, et avantageusement plus de 40% du composé de formule (III) initialement contenu dans la solution obtenue à l’issue de l’étape a). 9. Method according to any one of claims 1 to 8, characterized in that phase P1 comprises more than 30%, preferably more than 35%, and advantageously more than 40% of the compound of formula (III) initially contained in the solution obtained at the end of step a).
10. Procédé selon l’une quelconque des revendications 1 à 9, caractérisé en ce que la phase P1 comprend de 0,5% à 70% en poids, de préférence de 1% à 50% en poids, préférentiellement de 5% à 30% en poids par rapport au poids total de ladite phase P1. 10. Method according to any one of claims 1 to 9, characterized in that phase P1 comprises from 0.5% to 70% by weight, preferably from 1% to 50% by weight, preferably from 5% to 30. % by weight relative to the total weight of said phase P1.
11. Procédé selon l’une quelconque des revendications 1 à 10, caractérisé en ce que la température T3 est comprise entre 40°C et -30°C, de préférence entre 25°C et - 15°C, et encore plus préférentiellement entre 10°C et -5°C. 11. Method according to any one of claims 1 to 10, characterized in that the temperature T 3 is between 40 ° C and -30 ° C, preferably between 25 ° C and - 15 ° C, and even more preferably between 10 ° C and -5 ° C.
12. Procédé selon l’une quelconque des revendications 1 à 11 , caractérisé en ce qu’il comprend une étape supplémentaire e) de filtration de la composition obtenue à l’issue de l’étape d). 12. Method according to any one of claims 1 to 11, characterized in that it comprises an additional step e) of filtering the composition obtained at the end of step d).
13. Procédé selon l’une quelconque des revendications 1 à 12, caractérisé en ce qu’il comprend une étape a’), préalable à l’étape a), de mise en contact du composé de formule (III) avec le solvant organique S3. 13. Method according to any one of claims 1 to 12, characterized in that it comprises a step a ′), prior to step a), of bringing the compound of formula (III) into contact with the organic solvent. S3.
14. Procédé selon l’une quelconque des revendications 1 à 13, caractérisé en ce que le composé de formule (III) de l’étape a’) est obtenu par un procédé comprenant les étapes suivantes : 14. Method according to any one of claims 1 to 13, characterized in that the compound of formula (III) from step a ’) is obtained by a process comprising the following steps:
- x) étape de mise en contact d’un composé de formule (III) avec de l’eau, de préférence dans un ratio massique composé de formule (III) : eau allant de 1 : 1 à 1 : 4 avantageusement de 1 : 1 à 1 : 2 ; - x) step of bringing a compound of formula (III) into contact with water, preferably in a mass ratio of compound of formula (III): water ranging from 1: 1 to 1: 4, advantageously from 1: 1 to 1: 2;
- y) étape de chauffage de la composition obtenue à l’étape x) à une température T6, de préférence comprise entre 30°C et 80°C, avantageusement entre 40°C et 70°C ;- y) step of heating the composition obtained in step x) at a temperature T 6 , preferably between 30 ° C and 80 ° C, advantageously between 40 ° C and 70 ° C;
- z) étape de refroidissement de la composition obtenue à l’étape y) jusqu’à la formation de cristaux de composé de formule (III) ; - z) step of cooling the composition obtained in step y) until the formation of crystals of compound of formula (III);
- z’) étape de filtration des cristaux, et éventuellement séchage ; - z ’) stage of filtering the crystals, and optionally drying;
- z”) éventuelle étape de lavage des cristaux avec de l’eau, notamment à 23°C, et éventuellement étape de séchage. - z ") optional step of washing the crystals with water, in particular at 23 ° C, and possibly a drying step.
15. Procédé de préparation d’un composé imidazolate de lithium de formule (V) : dans laquelle Rf est un groupement alkyle fluoré ou alkoxyle fluoré comprenant de 1 à 5 atomes de carbone, ledit procédé comprenant : 15. Process for preparing a lithium imidazolate compound of formula (V): wherein Rf is a fluorinated alkyl or fluorinated alkoxyl group comprising from 1 to 5 carbon atoms, said method comprising:
- 1) la purification du composé de formule (III) selon le procédé tel que décrit selon l’une quelconque des revendications 1 à 14 ; et - 1) the purification of the compound of formula (III) according to the process as described according to any one of claims 1 to 14; and
- 2) la réaction du composé de formule (III) avec une base lithiée. - 2) reaction of the compound of formula (III) with a lithiated base.
16. Procédé selon la revendication 15, caractérisé en ce que la base lithiée est choisie dans le groupe constitué de l’hydrure de lithium, du carbonate de lithium, de l’hydroxyde de lithium, et de leurs mélanges. 16. The method of claim 15, characterized in that the lithiated base is selected from the group consisting of lithium hydride, lithium carbonate, lithium hydroxide, and mixtures thereof.
17. Procédé selon l’une quelconque des revendications 15 ou 16, caractérisé en ce que, préalablement à l’étape 2), le composé de formule (III) est dissous dans un solvant organique S4, ayant de préférence un nombre donneur allant de 1 à 70, avantageusement de 5 à 65. 17. Method according to any one of claims 15 or 16, characterized in that, prior to step 2), the compound of formula (III) is dissolved in an organic solvent S4, preferably having a donor number ranging from 1 to 70, preferably 5 to 65.
EP20771791.9A 2019-09-06 2020-09-04 Method for purifying 2-(fluoroalkyl or fluoroalkoxy)-4,5-dicyanoimidazoles Pending EP4025563A1 (en)

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