Process for the manufacture of dihalodiphenylsulfones

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.

1 - 13 . (canceled) 
     
     
         14 . 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: 
       
       
         
           
           
               
               
           
         
         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 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. 
     
     
         15 . The process according to  claim 14 , wherein the fluorinated acid is selected from the group consisting of perfluorinated alkane carboxylic acids, perfluorinated alkane sulfonic acids, and mixtures thereof. 
     
     
         16 . The process according to  claim 14 , wherein the fluorinated acid is distilled off after the halobenzene is added to the reaction. 
     
     
         17 . The process according to  claim 14 , wherein the molar ratio of the acid selected from the group consisting of sulfuric acid, arene sulfonic acid, or oleum to the halobenzene is from 0.2 to 5. 
     
     
         18 . The process according to  claim 17 , wherein the molar ratio is from 0.4 to 2. 
     
     
         19 . The process according to  claim 14 , wherein the process further comprises a catalyst selected from the group consisting of boric acid, boronic acid, aluminosilicates, perfluoroalkanesulfonic acid resins, mixed oxides, and mixtures thereof.