METHOD FOR PRODUCING OXYSULPHIDIC AND FLUORINATED DERIVATIVES IN AN IONIC LIQUID MEDIUM

Abstract

The invention relates to a method for producing an oxysulphidic and fluorinated derivative in the form of a salt of formula (II) Ea-SO.sup.Q.sup.+ (II) comprising providing an ionic liquid compound of formula (I) in the liquid state Ea-SOO.sup.Cr (II)Ea representing the fluorine atom or a group having between 1 and 10 carbon atoms selected from fluoroalkyls, perfluoroalkyls and fluoroalkenyls; andQ.sup.+ representing an onium cation, with a sulphur oxide, said ionic liquid compound of formula (I) representing at least 50 wt. % of the initial liquid reactive medium.

Claims

1. A process for the preparation of an oxysulfide and fluorinated derivative in the form of a salt of formula (II):
Ea-SOO.sup.Q.sup.+(II) the process comprising the operation in which an ionic liquid compound of formula (I) in the liquid state:
Ea-COO.sup.Q.sup.+(I) Ea representing a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls; and Q.sup.+ representing an onium cation, is brought together with a sulfur oxide, said ionic liquid compound of formula (I) representing at least 50% by weight of the initial liquid reaction medium.

2. The process as claimed in claim 1, in which the reaction medium is devoid of organic solvent of amide type.

3. The process as claimed in claim 1, in which the onium cation Q.sup.+ is selected from the group consisting of ammonium, phosphonium, pyridinium, pyrazolinium, imidazolium, arsenium, quaternary ammonium and quaternary phosphonium cations.

4. The process as claimed in claim 1, in which the onium cation Q.sup.+ is a quaternary phosphonium cation.

5. The process as claimed in claim 1, in which the cation Q.sup.+ represents a quaternary ammonium cation selected from the group consisting of tetraethylammonium, tetrapropylammonium, tetrabutylammonium, trimethylbenzylammonium, methyltributylammonium and Aliquat 336.

6. The process as claimed in claim 1, in which the cation Q.sup.+ represents a pyridinium cation.

7. The process as claimed in claim 1, for the preparation of a trifluoromethanesulfinic acid onium salt CF .sub.3SOO.sup.Q.sup.+.

8. The process as claimed in claim 7, in which the trifluoromethanesulfinic acid onium salt CF.sub.3SOO.sup.Q.sup.+ is tetrabutylphosphonium trifluoromethanesulfinate CF.sub.3SOOPBu.sub.4.

9. A process for the preparation of a compound in the form of a salt of formula (III):
Ea-SO.sub.3.sup.Q.sup.+(III) Ea representing a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls; and Q.sup.+ representing an onium cation, the process comprising: (i) having available a mixture (M), exhibiting a melting point of less than or equal to 100 C., of an ionic liquid compound of formula Ea-COO.sup.Q.sup.+ (I) and of a compound of formula Ea-SOO.sup.Q.sup.+ (II); and (ii) bringing together said mixture (M) in the liquid state and an oxidizing agent, in order to obtain the compound of formula Ea-SO.sub.3.sup.Q.sup.+ (III), said mixture (M) representing more than 50% by weight of the initial liquid reaction medium.

10. The process as claimed in claim 9, for the preparation of a trifluoromethanesulfonic acid onium salt CF.sub.3SO.sub.3.sup.Q.sup.+.

11. The process as claimed in claim 10, in which the trifluoromethanesulfonic acid onium salt CF.sub.3SO.sub.3.sup.Q.sup.+ is tetrabutylphosphonium trifluoromethanesulfonate CF.sub.3SO.sub.3PBu.sub.4.

12. A process for the preparation of a sulfonimide compound of formula (Ea-SO.sub.2).sub.2NH (IV) or one of its salts (Ea-SO.sub.2).sub.2NMe (IV), Ea representing a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls; and Me representing an alkali metal; the process comprising at least the following stages: (a1) preparation of an oxysulfide and fluorinated derivative of formula Ea-SO.sub.2.sup.Q.sup.+ (II) according to the process described in claim 1; (b1) bromination, chlorination or fluorination of the derivative of formula (II) in order to form a compound of formula (Ea-SO.sub.2)X, with X representing bromine, chlorine or fluorine; (c1) ammonolysis of the compound (Ea-SO.sub.2)X using a tertiary amine NR.sub.3 to give (EaSO.sub.2).sub.2NH.NR.sub.3, with R, which are identical or different, representing a linear or branched alkyl group having from 1 to 20 carbon atoms; (d1) acidification of (EaSO.sub.2).sub.2NH.NR.sub.3 to obtain the sulfonimide compound (Ea-SO.sub.2).sub.2NH (IV); and optionally: (e1) neutralization by an alkali metal Me base of the compound (Ea-SO.sub.2).sub.2NH in order to form the salt of formula (Ea-SO.sub.2).sub.2NMe (IV); and optionally (f1) drying of the salt (Ea-SO.sub.2).sub.2NMe (IV).

13. The process as claimed in claim 12, for the preparation of bis(trifluoromethanesulfonyl)imide (CF.sub.3SO.sub.2).sub.2NH and of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

14. A process for the preparation of a fluorinated derivative of sulfonic acid of formula (V):
Ea-SO.sub.3H (V) Ea representing a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls; the process comprising at least the following stages: preparation according to the process as defined in claim 9 of a derivative of formula Ea-SO.sub.3.sup.Q.sup.+ (III), in which Q.sup.+ represents an onium cation; and acidification of the compound of formula (III) in order to obtain the desired fluorinated derivative of sulfonic acid of formula (V).

15. The process as claimed in claim 14, for the preparation of trifluoromethanesulfonic acid CF.sub.350.sub.3H.

16. A process for the preparation of an anhydride compound of formula (VI):
(Ea-SO.sub.2).sub.2O (VI) Ea representing a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls; the process comprising at least the following stages: preparation according to the process as defined according to claim 14 of a fluorinated derivative of sulfonic acid of formula Ea-SO.sub.3H; and anhydrization of the derivative of formula Ea-SO.sub.3H in order to obtain said desired anhydride compound of formula (VI).

17. The process as claimed in claim 16, for the preparation of trifluoromethanesulfonic anhydride (CF.sub.3SO.sub.2).sub.2O.

18. The process as claimed in claim 3, in which the onium cation Q.sup.+ is selected from the group consisting of tetraalkylphosphonium and tetraalkylammonium cations, the alkyl groups of which, which are identical or different, represent a linear or branched alkyl chain having from 4 to 12 carbon atoms, and tetraarylphosphonium and tetraarylammonium cations, the aryl groups of which, which are identical or different, represent a phenyl or naphthyl group.

19. The process as claimed in claim 4, in which the onium cation Q.sup.+ is tetrabutylphosphonium (PBu.sub.4) cation.

20. The process according to claim 9, wherein the mixture (M) exhibits a melting point of less than or equal to 40 C.

Description

EXAMPLES

[0190] The degree of conversion of a reactant corresponds to the ratio of the molar amount of reactant consumed (converted) during a reaction to the initial amount of reactant.

[0191] The product yield from a reactant corresponds to the ratio of the molar amount of product formed to the molar amount of initial reactant.

[0192] The weight balance corresponds to the ratio of the total weight of material recovered to the total weight of material charged.

[0193] 1. Preparation of TFAPBu.sub.4 (CF.sub.3CO.sub.2PBu.sub.4)

[0194] The following are introduced into a 0.25 l glass reactor: [0195] TFAK (CF.sub.3COOK): 43.8 g (0.3 mol) [0196] PBu.sub.4Cl: 86.7 g (0.3 mol) [0197] H.sub.2O: 110 g The reaction mass is brought to 50 C. with stirring for 20 hours. After cooling and halting the stirring, the medium separates on settling into two liquid phases, which are separated and analyzed; the upper phase is essentially composed of CF.sub.3CO.sub.2PBu.sub.4 and of water (7% by weight).

[0198] The reaction for the formation of TFAPBu.sub.4 can be represented as follows:

##STR00004##

[0199] 2. Sulfination of TFAPBu.sub.4 to Give TFSPBu.sub.4 (CF.sub.3SO.sub.2PBu.sub.4)

[0200] The following are introduced into a 0.1 ml autoclave which has been washed and dried beforehand: [0201] TFAPBu.sub.4: 49.2 g, i.e. 0.12 mol (dried beforehand by azeotropic distillation), [0202] SO.sub.2: 7.76 g, i.e. SO.sub.2/TFAPBu.sub.4 103 mol %.

[0203] The reactor is subsequently closed and heated with stirring at 142 C. for 4 h.

[0204] After returning to ambient temperature (20-22 C.), the reactor is degassed and its contents are transferred into a 0.1 l glass vessel; the resulting reaction medium exists in the form of a dark brown solution.

[0205] The reaction for the sulfination of TFAPBu.sub.4 to give TFSPBu.sub.4 can be represented as follows:

##STR00005##

[0206] The analysis by .sup.19F NMR of the reaction mass gives the following results: [0207] Weight balance: 94% [0208] Conversion of the TFAPBu.sub.4: 61% [0209] Yield of TFSPBu.sub.4: 38%

[0210] 3. Oxidation of the Triflinate CF.sub.3SO.sub.2PBu.sub.4 (TFSPBu.sub.4) to Give the Triflate CF.sub.3SO.sub.3PBu.sub.4 (TAPBu.sub.4)

[0211] The crude reaction product from the preceding stage 2 (45 g) is charged to a 0.1 l three-necked round-bottomed flask and brought to 80 C.; the aqueous hydrogen peroxide (30% aqueous solution: 6 g) is run, over 3 hours, onto the reaction medium maintained 80 C.

[0212] After the aqueous hydrogen peroxide has been run onto the reaction medium, the latter is maintained at 80 C. for 2 hours.

[0213] After returning to ambient temperature (20-22 C.), the resulting reaction medium exists in the form of a light brown solution.

[0214] The reaction for the oxidation of the triflinate to give the triflate can be represented as follows:

##STR00006##

[0215] The analysis by .sup.19F NMR of the reaction mass gives the following results: [0216] Weight balance: 100% [0217] Conversion of the TFSPBu.sub.4: 100% [0218] Yield of TAPBu.sub.4: 97%

[0219] NB: conversion of the residual TFAPBu.sub.4: 0%

[0220] 4. Acidification/Distillation

[0221] The following are introduced into a 50 ml glass reactor: [0222] preceding crude reaction product: 50 g [0223] 20% oleum: 122 g

[0224] The medium is gradually brought to 160 C. with stirring under gradual vacuum (final pressure: 5 mbar) and the condensates are collected and analyzed to give the following results: [0225] Degree of recovery of the TFA (CF.sub.3COOH): 65% [0226] Degree of recovery of the TA (CF.sub.3SO.sub.3H): 50%