METHOD FOR MANUFACTURING BIS(HALOGENO SULFONYL)IMIDE

Abstract

The present invention relates to a new synthetic pathway for manufacturing bis(halogeno sulfonyl)imide, which are useful intermediates in the synthesis of lithium bis(fluorosulfonyl)imide (LiFSI).

Claims

1. A method for manufacturing bis(halogeno sulfonyl)imide of formula (I) or (II): ##STR00007## wherein R is a linear or branched alkyl group comprising from 1 to 10 carbon atoms; and each of X is independently selected from F, Cl and Br; said method comprising: a) providing a sulfuryl halogenide of formula X.sub.aSO.sub.2X.sub.b wherein each of X.sub.a and X.sub.b, identical or different from each other, is selected from F, Cl and Br; b) providing at least one ammonium salt; c) contacting said sulfuryl halogenide and said at least one ammonium salt, to obtain the bis(halogeno sulfonyl)imide of formula (I) or (II).

2. The method according to claim 1, wherein the sulfuryl halogenide is selected from ClSO.sub.2Cl, ClSO.sub.2F and FSO.sub.2F.

3. The method according to claim 1, wherein said at least one ammonium salt complies with formula (III): ##STR00008## wherein R is H or a linear or branched alkyl group comprising from 1 to 10 carbon atoms, and M is selected in the group comprising: F, Cl, carboxylate, sulfate, hydrogen-sulfate, carbonate, hydrogen-carbonate, tetrafluoroborate, hexafluorophosphate.

4. The method according to claim 1, wherein step c) is performed at a temperature from 15 C. to 150 C. and/or under stirring.

5. The method according to claim 1, wherein step c) is performed in the presence of a solvent.

6. The method according to claim 5, wherein said solvent is selected in the group comprising: ethylene carbonate, propylene carbonate, butylene carbonate, -butyrolactone, -valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methyl sulfolane, dimethylsulfoxide, N,N-dimethylformamide, N-methyl oxazolidinone, acetonitrile, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, n-butyl acetate, nitromethane and nitrobenzene.

7. The method according to claim 5, wherein step c) is performed with a molar ratio between the sulfuryl halogenide and said at least one ammonium salt between 100 to 0.1.

8. The method according to claim 1, wherein step c) is performed in the absence of a solvent and/or a temperature between 50 C. and 100 C.

9. The method according to claim 1, wherein the molar ratio between the sulfuryl halogenide and said at least one ammonium salt is between 100 to 0.1.

10. The method according to claim 1, wherein in the bis(halogeno sulfonyl)imide of formula (I) each of X is chlorine [ammonium-CSI] and the method comprises: a*) providing a sulfuryl halogenide of formula ClSO.sub.2Cl; b) providing at least one ammonium salt of formula NH.sub.4.sup.+Cl; c*) contacting said sulfuryl halogenide and said at least one ammonium salt, thus obtaining the ammonium-CSI.

11. The method according to claim 10, said method comprising after step c*), step d) of contacting said ammonium-CSI with at least one fluorinating agent, so as to obtain ammonium-FSI.

12. The method according to claim 11, wherein said at least one fluorinating agent is selected in the group comprising: HF, more preferably anhydrous HF, or X.sub.cF wherein X.sub.c is selected from NH.sub.4, Cs, Li, K.

13. The method according to claim 1, wherein in the bis(halogeno sulfonyl)imide of formula (I) each of X is fluorine [ammonium-FSI] and the method comprises: a **) providing a sulfuryl halogenide of formula ClSO.sub.2Cl; b) providing at least one ammonium salt of formula NH.sub.4.sup.+F; c**) contacting said sulfuryl halogenide and said at least one ammonium salt, thus obtaining the ammonium-FSI.

14. A method for manufacturing lithium bis(fluoro sulfonyl)imide (LiFSI), said method comprising, after step d) as defined in claim 11, step e) of contacting the ammonium-FSI and a compound of formula LiX.sub.d, thus obtaining LiFSI.

15. The method according to claim 14, wherein said compound of formula LiX.sub.d is selected from the group consisting of LiCl, LiF, Li.sub.2CO.sub.3, LiOH, LIOH.Math.H.sub.2O, Li.sub.2SO.sub.4, Li.sub.n(RCO.sub.2).sub.n, Li.sub.2SiO.sub.3, Li.sub.2B.sub.4O.sub.7 and mixtures thereof.

16. The method according to claim 14, wherein step e) is performed in the presence of at least one solvent and LiFSI is obtained as liquid composition comprising from 1 to 70 wt. % of LiFSI based on the total weight of said liquid composition.

17. A method for manufacturing lithium bis(fluoro sulfonyl)imide (LiFSI), said method comprising, after step c**) as defined in claim 13, step e) of contacting the ammonium-FSI and a compound of formula LiX.sub.d, thus obtaining LiFSI.

18. The method according to claim 17, wherein said compound of formula LiX.sub.d is selected from the group consisting of LiCl, LiF, Li.sub.2CO.sub.3, LiOH, LiOH.Math.H.sub.2O, Li.sub.2SO.sub.4, Li.sub.n(RCO.sub.2).sub.n, Li.sub.2SiO.sub.3, Li.sub.2B.sub.4O.sub.7 and mixtures thereof.

19. The method according to claim 17, wherein step e) is performed in the presence of at least one solvent and LiFSI is obtained as liquid composition comprising from 1 to 70 wt. % of LiFSI based on the total weight of said liquid composition.

Description

EXAMPLES

Materials

[0097] Sulfuryl chloride, acetonitrile and ammonium chloride were purchased and used as such. [0098] SO.sub.2Cl.sub.2: Sigma Aldrich (product code #157767, batch #STBK3652) [0099] NH.sub.4Cl: Alfa Alesar (product code #12361, batch #Y28E029)

Methods

[0100] .sup.15N-NMR analysis was performed using Insensitive Nuclear Enhancement by Polarization Transfer (INEPT) as a signal enhancement method.

Example 1 (Neat Conditions)

[0101] In an oven-dried 25 mL round bottom flask containing a PTFE-coated magnetic stirrer, ammonium chloride (1.6 g, 30 mmol, 0.3 equiv.) was added portionwise to neat sulfuryl chloride (8.08 mL, 100 mmol, 1 equiv.) under stirring, at 0 C. The flask was equipped with a reflux condenser and the reaction mixture was stirred at reflux for 24 hours. The reaction mixture was then cooled down to room temperature, filtered and concentrated under reduced pressure to give an orange solid.

[0102] Trituration in acetonitrile finally afforded the pure product as a white solid.

[0103] Yield was 44% (1.54 g, 6.6 mmol) and the characteristic peaks were found with .sup.1H-NMR and .sup.15N-NMR analysis.

Example 2 (with Acetonitrile as the Solvent)

[0104] Following the procedure disclosed in Example 1 above, an excess of sulfuryl chloride was reacted with ammonium chloride, but in the presence of acetonitrile as the solvent.

[0105] The reaction medium was filtered to remove ammonium chloride, and a mixture was obtained, which was analyzed via .sup.1H-NMR.

[0106] This compound was further analyzed by .sup.1H-NMR and .sup.15N-NMR. No peak was detected for HCSI or other side products.

Example 3 (Neat Conditions)

[0107] Following the same procedure disclosed in Example 1 above, SO.sub.2Cl.sub.2 kept at its boiling point was reacted with a sub-stoichiometric amount of NH.sub.4Cl.

[0108] After 1 hour at 69 C., the reaction medium started to solidify and at the end of 24 hours reaction, a mixture of ammonium-CSI and unreacted solid NH.sub.4Cl was recovered.

[0109] Ammonium-CSI was obtained at a yield of 48%. The product was analyzed and characterized by .sup.1H-NMR and .sup.15N-NMR.