Preparation of imides containing a fluorosulfonyl group

Patent metadata

Field	Value
Publication number	US-10128525-B2
Application number	US-201515304577-A
Country	US
Kind code	B2
Filing date	Apr 1, 2015
Priority date	Apr 18, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

A process for preparing a fluoro compound of formula: R2—(SO2)—NX—(SO2)—F (III) including: (a) a first step for obtaining the chloro compound of formula: R1—(SO2)—NX—(SO2)—Cl; (II) this first step including the reaction of the sulfamide of formula: R0—(SO2)—NH2 (I) with a sulfureous acid and a chlorinating agent; and (b) a second step for obtaining the fluoro compound of formula (III), this second step including the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid in at least one organic solvent; in which: X represents either a hydrogen atom or a monovalent cation M; R1 represents an electron-withdrawing group having a positive Hammett parameter σp; if R1 represents Cl, then R0 represents OH; otherwise, R0 is identical to R1; and if R1 represents Cl, then R2 represents F; otherwise, R2 is identical to R1.

First claim

The invention claimed is:

1. A process for preparing a fluoro compound of formula:
R 2 —(SO 2 )—NX—(SO 2 )—F  (III)

comprising:
(a) a first step for obtaining the chloro compound of formula:
R 1 —(SO 2 )—NX—(SO 2 )—Cl;  (II)

this first step comprising the reaction of the sulfamide of formula:
R 0 —(SO 2 )—NH 2   (I)

with a sulfureous acid and a chlorinating agent; and
(b) a second step for obtaining the fluoro compound of formula (III), this second step comprising the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid in at least one organic solvent;
in which:
X represents either a hydrogen atom or a monovalent cation M;
R 1 represents an electron-withdrawing group having a positive Hammett parameter σ p ;
if R 1 represents Cl, then R 0 represents OH; otherwise, R 0 is identical to R 1 ; and
if R 1 represents Cl, then R 2 represents F; otherwise, R 2 is identical to R 1 .

2. The process as claimed in claim 1 , in which R 1 is chosen from Cl, F, CF 3 , CHF 2 , CH 2 F, C 2 HF 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 3 HF 6 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 3 F 6 OCF 3 , C 2 F 4 OCF 3 , C 2 H 2 F 2 OCF 3 , CF 2 OCF 3 , C 6 F 13 , C 7 F 15 , C 8 F 17 and C 9 F 19 .

3. The process as claimed in claim 1 , in which M represents an alkali metal or alkaline-earth metal cation or a quaternary ammonium cation.

4. The process as claimed in claim 1 , in which the sulfureous acid used in the first step is chosen from chlorosulfonic acid, sulfuric acid, oleum and mixtures thereof.

5. The process as claimed in claim 1 , in which the chlorinating agent used in the first step is chosen from thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphonyl trichloride, phosphoryl trichloride and mixtures thereof.

6. The process as claimed in claim 1 , in which:
a catalyst is used for the reaction of the sulfamide with the sulfureous acid and the chlorinating agent in the first step; and/or
the reaction of the sulfamide with the sulfureous acid and the chlorinating agent in the first step is performed at a temperature of between 30 and 150° C.; and/or
the reaction of the sulfamide with the sulfureous acid and the chlorinating agent in the first step is performed at a pressure of between 1 and 7 bar absolute.

7. The process as claimed in claim 1 , in which:
the mole ratio between the sulfureous acid and the sulfamide used in the first step is between 1 and 5; and/or
the mole ratio between the chlorinating agent and the sulfamide used in the first step is between 1 and 10.

8. The process as claimed in claim 1 , in which the organic solvent in the second step has a donor number of between 1 and 70.

9. The process as claimed in claim 1 , in which the organic solvent in the second step is chosen from esters, nitriles, dinitriles, ethers, diethers, amines and phosphines, and mixtures thereof.

10. The process as claimed in claim 1 , in which:
the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid of the second step is performed at a temperature of between 0° C. and the boiling point of the organic solvent, preferably between 5° C. and the boiling point of the organic solvent; and/or
the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid of the second step is performed at a pressure of between 0 and 16 bar absolute.

11. The process as claimed in claim 1 , in which the chloro compound of formula (II) is dissolved in the organic solvent prior to the second reaction step.

12. The process as claimed in claim 1 , in which:
the mass ratio between the chloro compound of formula (II) and the organic solvent used in the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid of the second step is between 0.001 and 10; and/or
the mole ratio between the chloro compound of formula (II) and hydrofluoric acid used in the reaction of the chloro compound of formula (II) with anhydrous hydrofluoric acid of the second step is between 0.01 and 0.5.

13. The process as claimed in claim 1 , in which the reaction of the sulfamide with the sulfureous acid and the chlorinating agent of the first step provides the chloro compound of formula:
R 1 —(SO 2 )—NH—(SO 2 )—Cl;  (IIa)

the first step also comprising the reaction of the chloro compound of formula (IIa) with a base, for obtaining the chloro compound of formula:
R 1 —(SO 2 )—NM-(SO 2 )—Cl  (IIb)

in which M represents a monovalent cation.

14. The process as claimed in claim 13 , in which said base is chosen from alkali metal carbonates, alkaline-earth metal carbonates, alkali metal hydroxides, alkaline-earth metal hydroxides, tertiary amines in a polar organic solvent, and mixtures thereof.

15. The process as claimed in claim 1 , comprising, after the second step:
(c) a third step of neutralization of the compound of formula (III).

16. The process as claimed in claim 15 , in which the fluoro compound of formula (III) obtained in the second step is a compound of formula:
R 2 —(SO 2 )—NH—(SO 2 )—F  (IIIa)

and in which the third step of neutralization allows the compound of formula ( 111 a ) to be converted into a compound of formula:
R 2 —(SO 2 )—NM-(SO 2 )—F  (IIIb)

in which M represents a monovalent cation.

17. The process as claimed in claim 1 , comprising, after the second step or, where appropriate, the third step, a final step of cation exchange.

18. The process as claimed in claim 1 , for obtaining LiN(SO 2 F) 2 , LiN(SO 2 CF 3 )(SO 2 F), LiN(SO 2 C 2 F 5 )(SO 2 F), LiN(SO 2 CF 2 OCF 3 )(SO 2 F), LiN(SO 2 C 3 HF 6 )(SO 2 F), LiN(SO 2 C 4 F 9 )(SO 2 F), LiN(SO 2 C 5 F 11 )(SO 2 F), LiN(SO 2 C 6 F 13 )(SO 2 F), LiN(SO 2 C 7 F 15 )(SO 2 F), LiN(SO 2 C 8 F 17 )(SO 2 F) or LiN(SO 2 C 9 F 19 )(SO 2 F).

19. A process for manufacturing an electrolyte, comprising the preparation of an imide salt of formula (IIIb) R 2 —(SO 2 )—NM-(SO 2 )—F, in which M represents a monovalent cation and R 2 represents an electron-withdrawing group having a positive Hammett parameter σ p , via the process of claim 1 , and dissolution thereof in a solvent, said imide salt preferably being a lithium, sodium or potassium salt.

20. A process for manufacturing a battery or a battery cell, comprising the manufacture of an electrolyte as claimed in claim 19 and the insertion of this electrolyte between an anode and a cathode.

Assignees

• Arkema France

Inventors

• Schmidt Gregory
• Audureau Sophie

Classifications

• H01M10/52

  Removing gases inside the secondary cell, e.g. by absorption (vent plugs or other mechanical arrangements for facilitating escape of gases H01M50/30) · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• C07F1/02

  Lithium compounds · CPC title

• C07C303/40

  by reactions not involving the formation of sulfonamide groups · CPC title