Method for preparing oxysulphide and fluorinated derivatives by sulphination

Patent metadata

Field	Value
Publication number	US-9873666-B2
Application number	US-201415021419-A
Country	US
Kind code	B2
Filing date	Sep 11, 2014
Priority date	Sep 12, 2013
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

The invention concerns a method for preparing an oxysulphide and fluorinated derivative, said method comprising the reacting, in the presence of an organic solvent, of: i) at least one compound of formula Ea-COOR (I), in which Ea represents the fluorine atom or a group having 1 to 10 carbon atoms chosen from fluoroalkyls, perfluoroalkyls and fluoroalkenyls and R represents hydrogen, a monovalent cation or an alkyl group, and ii) a sulphur oxide, said method being such that the initial molar ratio (sulphur oxide/compound of formula (I)) is less than 0.4 and the concentration of sulphur oxide dissolved in the reaction medium is kept constant for the entire duration of the reaction to a value of between 0.2% and 3% by weight by means of continually adding said sulphur oxide to the reaction medium.

First claim

The invention claimed is:

1. A process for the preparation of an oxysulfide and fluorinated derivative, comprising the reaction, in the presence of an organic solvent, of:
i) at least one compound of formula Ea-COOR (I), wherein Ea represents a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls, and R represents hydrogen, a monovalent cation or an alkyl group, and
ii) a sulfur oxide,

wherein the initial sulfur oxide/compound of formula (I) molar ratio is less than 0.4 and the concentration of dissolved sulfur oxide in the reaction medium is kept constant throughout the duration of the reaction at a value of between 0.2 weight % and 3 weight % by a continuous addition of said sulfur oxide to the reaction medium.

2. The process according to claim 1 , wherein the compound of formula (I) is a salt of a fluorocarboxylic acid in which the R group is a monovalent cation selected from the group consisting of alkali metal cations, quaternary ammonium cations and quaternary phosphonium cations.

3. The process according to claim 2 , wherein R is an alkali metal cation.

4. The process according to claim 1 , wherein the Ea group is selected from the group consisting of a fluorine atom, a CH 2 F— radical, a CHF 2 — radical and a CF 3 — radical.

5. The process according to claim 1 , wherein the sulfur oxide is sulfur dioxide.

6. The process according to claim 1 , wherein the initial sulfur oxide/compound of formula (I) molar ratio is less than 0.2.

7. The process according to claim 1 , wherein the concentration of dissolved sulfur oxide in the reaction medium is monitored in line or in situ by Raman spectrometry, by near infrared spectroscopy or by UV spectroscopy.

8. The process according to claim 1 , wherein the organic solvent is a polar aprotic solvent.

9. The process according to claim 8 , wherein the solvent is N,N-dimethylformamide (DMF), N,N-diethylformamide or N,N-dimethylacetamide.

10. The process according to claim 1 , wherein the concentration of the compound of formula (I) in the organic solvent is between 1 weight % and 40 weight %.

11. The process according to claim 1 , wherein the process is carried out continuously or semicontinuously.

12. The process according to claim 1 , wherein the reaction is carried out at an absolute total pressure between 1 and 20 bar.

13. The process according to claim 1 , wherein the reaction is carried out at a pressure below atmospheric pressure.

14. A process for the preparation of a compound selected from the group consisting of a sulfonimide compound (Ea-SO 2 ) 2 NH, its salts (Ea-SO 2 ) 2 NMe, Me representing an alkali metal, a fluorinated compound having a sulfonic acid functional group —SO 2 OH and exhibiting a formula Ea-SO 2 OH, and an anhydride compound of formula (Ea-SO 2 ) 2 O, wherein Ea represents a fluorine atom or a group having from 1 to 10 carbon atoms selected from the group consisting of fluoroalkyls, perfluoroalkyls and fluoroalkenyls, said process comprising:
preparation of an oxysulfide and fluorinated derivative according to the process of claim 1 ,
using the oxysulfide and fluorinated compound as reactive compound for the synthesis of a sulfonimide compound (Ea-SO 2 ) 2 NH and of its salts (Ea-SO 2 ) 2 NMe, Me representing an alkali metal, of a fluorinated compound having a sulfonic acid functional group —SO 2 OH and exhibiting a formula Ea-SO 2 OH, or of an anhydride compound of formula (Ea-SO 2 ) 2 O.

15. The process according to claim 14 , wherein the salt of a sulfonimide compound of formula (Ea-SO 2 ) 2 NMe is prepared from the oxysulfide and fluorinated derivative the process comprising:
a) the preparation of the oxysulfide and fluorinated derivative;
b) oxidation of the oxysulfide and fluorinated derivative in order to obtain the compound (Ea-SO 2 )X, where X is chlorine or fluorine;
c) ammonolysis of Ea-SO 2 X to give (Ea-SO 2 ) 2 N.HNR″ 3 ;
d) acidification of (Ea-SO 2 ) 2 N.HNR″ 3 to give (Ea-SO 2 ) 2 NH;
e) neutralization, by an alkali metal base, of (Ea-SO 2 ) 2 NH to give (Ea-SO 2 ) 2 NMe; and
f) optionally drying (Ea-SO 2 ) 2 NMe;

wherein R″ represents a linear or branched alkyl group having from 1 to 20 carbon atoms and Me represents an alkali metal.

16. The process according to claim 14 , wherein the fluorinated compound of formula Ea-SO 2 —OH is prepared from the oxysulfide and fluorinated derivative the process comprising:
a) the preparation of the oxysulfide and fluorinated derivative;
b′) the oxidation of the oxysulfide and fluorinated derivative in order to obtain the fluorinated compound of formula Ea-SO 2 —OH.

17. The process according to claim 14 , wherein the anhydride compound of formula (Ea-SO 2 ) 2 O is prepared from the oxysulfide and fluorinated derivative the process comprising:
a) the preparation of the oxysulfide and fluorinated derivative;
b′) the oxidation of the oxysulfide and fluorinated derivative in order to obtain a fluorinated compound of formula Ea-SO 2 —OH;
c′) the anhydrization of the fluorinated compound of formula Ea-SO 2 —OH in order to obtain an anhydride compound of formula (Ea-SO 2 ) 2 O.

Assignees

• Rhodia Operations

Inventors

• Revelant Denis
• Metz François
• Dambrin Valery
• Chauve Marie

Classifications

• B01J31/0227

  being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C309/06

  containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton · CPC title

• C07C303/32 Primary

  of salts of sulfonic acids · CPC title

• C07C303/02

  of sulfonic acids or halides thereof · CPC title