Process for the manufacture of dihalodiphenylsulfones

Patent metadata

Field	Value
Publication number	US-9394248-B2
Application number	US-201214111929-A
Country	US
Kind code	B2
Filing date	Apr 12, 2012
Priority date	Apr 18, 2011
Publication date	Jul 19, 2016
Grant date	Jul 19, 2016

Abstract

A process for the preparation of dihalodiphenylsulfones_such as 4,4′-dichlorodiphenyl sulfone or 4,4′-bis-(4-chlorophenylsulfonyl)biphenyl with high regioselectivity, at low temperature and in the absence of toxic reagents by reacting together at least one acid, at least one fluorinated anhydride and at least one halobenzene. The invented process is particularly suited for the manufacture of 4,4′-dichlorodiphenyl sulfone.

First claim

The invention claimed is:

1. A process for making molecule of the formula (M):
X—[Ar 1 —SO 2 —Ar 2 ]—[Ar 3 ] n —[Ar 1 —SO 2 —Ar 2 ] m —X  (M)

wherein:
n and m are independently 0, 1, 2, 3 or 4;
X is a halogen selected from F, Cl, Br, I;
Ar 1 , Ar 2 are equal or different from each other and are aromatic moieties of the formula:

Ar 3 is selected from the group consisting of:

and
each Ri is independently selected from the group consisting of: hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
by reacting together at least one acid selected from the group consisting of sulfuric acid, arene sulfonic acid or oleum, at least one fluorinated anhydride; at least one halobenzene; at least one fluorinated acid and, optionally, an aromatic compound; wherein the process is carried out in the presence of a catalyst selected from the group consisting of boric acid, boronic acid, aluminosilicates, perfluoroalkanasulfonic acid resins, mixed oxides, and mixtures thereof, and in the absence of any solvent or in the presence of a solvent selected from the group consisting of: alkanes, chloroalkenes, chloroalkanes, halobenzenes and carbon disulfide.

2. The process according to claim 1 , wherein the fluorinated anhydride is selected from the group consisting of phosphoric, sulfonic and carboxylic anhydrides.

3. The process according to claim 2 , wherein the fluorinated anhydride is a carboxylic anhydride.

4. The process according to claim 3 , wherein the carboxylic anhydride is trifluoromethanesulfonic acid anhydride or trifluoroacetic anhydride.

5. The process according to claim 1 , wherein the molecule of the formula (M) is a dichlorodiphenyl sulfone.

6. The process according to claim 1 , wherein the process is carried out in the absence of any solvent.

7. The process according to claim 1 , wherein the solvent is selected from the group consisting of dichloromethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, carbon disulfide, trichloroethylene, hexane, cyclohexane, heptane, and petroleum ether.

8. The process according to claim 1 , wherein the process comprises the following steps:
(a) the at least one acid selected from the group consisting of sulfuric acid, arene sulfonic acid or oleum, the at least one fluorinated anhydride, an optional fluorinated acid, and the catalyst are added to a reaction medium at a temperature T 1 ;
(b) the reaction medium is maintained at a temperature T 2 ;
(c) the at least one halobenzene is added to the reaction medium while the reaction medium is maintained at a temperature T 2 ;
(d) the reaction medium is maintained at a temperature T 3 ;
(e) the molecule of the formula (M) is isolated from the reaction medium.

9. The process according to claim 1 , wherein it is done in one pot.

10. The process according to claim 1 , wherein the process is carried out at a temperature that does not exceed 140° C.

11. The process of claim 1 , wherein the aromatic compound is selected from benzene, biphenyl, terphenyl, fluorene, naphthalene, and anthracene.

12. The process of claim 1 , wherein the molecule of formula (M) is made by reacting together the at least one acid, the at least one fluorinated anhydride; the at least one halobenzene, and wherein n=0, and m=0.

13. The process of claim 12 , wherein the at least one acid is sulfuric acid, the at least one fluorinated anhydride is trifluororacetic anhydride, the at least one halobenzene is monochlorobenzene, and the molecule of formula (M) is 4,4′-dichlorodiphenyl sulfone.

14. The process of claim 1 , wherein the molecule of formula (M) is made by reacting together the at least one acid, the at least one fluorinated anhydride; the at least one halobenzene, and an aromatic compound selected from benzene, biphenyl, terphenyl, fluorene, naphthalene, and anthracene, and wherein n≠0.

15. The process of claim 14 , wherein the at least one acid is sulfuric acid, the at least one fluorinated anhydride is trifluororacetic anhydride, the at least one halobenzene is monochlorobenzene, the aromatic compound is biphenyl, and the molecule of formula (M) is 4,4″-bis-(4-chlorophenylsulfonyl)biphenyl.

16. A process for making a molecule of the formula (M):
X—[Ar 1 —SO 2 —Ar 2 ]—[Ar 3 ] n —[Ar 1 —SO 2 —Ar 2 ] m —X  (M)

wherein:
n and m are independently 0, 1, 2, 3 or 4;
X is a halogen selected from F, Cl, Br, I;
Ar 1 , Ar 2 are equal or different from each other and are aromatic moieties of the formula:

Ar 3 is selected from the group consisting of:

and
each Ri is independently selected from the group consisting of: hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; by reacting together at least one acid selected from the group consisting of sulfuric acid, arene sulfonic acid or oleum, at least one fluorinated anhydride; at least one halobenzene; at least one fluorinated acid a catalyst selected from the group consisting of boricacid, boronic acid, aluminosilicates, perfluoroalkanesulfonic acid resins, mixed oxides, and mixtures thereof; and, optionally, an aromatic compound; wherein the process is carried out in the absence of any solvent or in the presence of a solvent selected from the group consisting of: alkanes, chloroalkenes, chloroalkanes, halobenzenes and carbon disulfide, and the at least one fluorinated acid is added to the reaction.

17. The process according to claim 1 , wherein the aluminosilicates are selected from the group consisting of acid-treated clays, zeolites, and mixtures thereof.

18. The process according to claim 17 , wherein the aluminosilicates are montmorillonite K 10 and analogs, H-beta zeolite with a SiO2/al2O3 ratio of ≦40, and mixtures thereof.

19. The process according to claim 16 , wherein the fluorinated acid is selected from the group consisting of perfluorinated alkane carboxylic acids, perfluorinated alkane sulfonic acids, and mixtures thereof.

20. The process according to claim 16 , wherein the fluorinated acid is distilled off after the halobenzene is added to the reaction.

21. The process according to claim 16 , wherein the molar ratio of the acid selected from the group sulfuric acid, arene sulfonic acid, or oleum to the halobenzene is from 0.2 to 5.

22. The process according to claim 21 , wherein the molar ratio is from 0.4 to 2.

Assignees

• Louis Chantal
• Solvay Specialty Polymers Usa

Inventors

• Louis Chantal

Classifications

• C07C315/00 Primary

  Preparation of sulfones; Preparation of sulfoxides · CPC title

• C07C317/14

  having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C315/04 Primary

  by reactions not involving the formation of sulfone or sulfoxide groups · CPC title

• C07C305/22

  having oxygen atoms of sulfate groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C305/06

  Hydrogenosulfates · CPC title