Process for Manufacture of Fluorinated Benzenes and Fluorinated Benzophenones, and Derivatives Thereof

Abstract

The invention relates to a new process for the manufacture or synthesis, respectively, of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof, in particular of fluorobenzenes and derivatives thereof. The present invention particularly pertains to a novel environmentally friendly process for the synthesis of fluorinated benzenes and benzophenones as raw materials for the manufacture of polyaryletherketones (PAEKs).

What is claimed is: 
     
         1 . A process of preparing a compound comprising one or more aromatic rings by Friedel-Crafts reaction, characterized in that an aromatic ring of a starting material compound is reacted with a Friedel-Crafts reagent in the presence of an activated antimony pentahalide catalyst (SbHal 5 ), activated by hydrogen fluoride (HF); wherein a starting material compound is selected from compounds having the formula (I): 
       
         
           
           
               
               
           
         
         wherein 
         Rn independently denotes one or more substituents selected from the group consisting of hydrogen (H), fluorine (F) and chlorine (Cl); and 
         Hal denotes a halogen selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and Iodine (I); 
         wherein the process of preparing the compound by Friedel-Crafts reaction is a continuous process and the continuous process is performed in at least one SiC-microreactor. 
       
     
     
         2 . The process of preparing the compound according to  claim 1 , wherein the compound prepared is fluorinated in a fluorination reaction. 
     
     
         3 . The process of preparing the compound according to  claim 1 , wherein the starting material compound is selected from compounds having the formula (I),
 wherein   Rn independently denotes a single substituent selected from the group consisting of hydrogen (H), fluorine (F), and chlorine (Cl); and   Hal denotes a halogen selected from the group consisting of fluorine (F) and chlorine (Cl).   
     
     
         4 . The process of preparing the compound according to  claim 1 , wherein the starting material compound is selected from the group of compounds consisting of compounds wherein one of Rn, is fluorine (F) or chlorine (Cl), and the others of Rn are hydrogen, and Hal is fluorine (F) or chlorine (Cl). 
     
     
         5 . The process of preparing the compound according to  claim 1 , wherein the Friedel-Crafts reagent is selected from compounds having the formula (II): 
       
         
           
           
               
               
           
         
         wherein 
         R′n independently denotes one or more substituents selected from the group consisting of hydrogen (H), fluorine (F) and chlorine (Cl); and 
         R1 and R2 independently from each other denote a hydrogen, a tri-halogeno methyl group (—CHal 3 ), a halogenocarbonyl group (—(C═O)Hal) or a halogeno methyl group (—CH 2 Hal), and at least one of R1 and R2 is a tri-halogeno methyl group (—CHal 3 ), a halogeno carbonyl group (—(C═O)Hal) or a halogeno methyl group (—CH 2 Hal), and wherein each halogen (Hal) is fluorine (F), chlorine (Cl), bromine (Br) or Iodine (I), or a boronic acid group. 
       
     
     
         6 . The process of preparing the compound according to  claim 5 , wherein the Friedel-Crafts reagent is selected from compounds having the formula (II),
 wherein   R′n independently denotes a single substituents selected from the group consisting of hydrogen (H), fluorine (F), and chlorine (Cl); and   R1 and R2 independently from each other denote a hydrogen, a trichloromethyl group (—CCl 3 ), a carbonyl chloride group (—(C═O)Cl) or a chloromethyl group (—CH 2 Cl), and at least one of R1 and R2 is a trichloromethyl group (—CCl 3 ), a carbonyl chloride group (—(C═O)Cl) or a chloromethyl group (—CH 2 Cl); or a boronic acid group.   
     
     
         7 . The process of preparing the compound according to  claim 5 , wherein the Friedel-Crafts reagent is selected from compounds having the formula (II), wherein R1 and R2 independently from each other denote a hydrogen, a carbonyl chloride group (—(C═O)Cl) or a chloromethyl group (—CH 2 Cl), or a boronic acid group, and at least one of R1 and R2 is a carbonyl chloride group (—(C═O)Cl) or a chloromethyl group (—CH 2 Cl) or a boronic acid group. 
     
     
         8 . The process of preparing the compound according to  claim 7 , wherein the Friedel-Crafts reagent is selected from the group compounds consisting of chlorobenzoic acid chloride, fluorobenzoic acid chloride, (4-chlorophenyl) boronic acid, benzene-dicarbonyl dichloride and chloromethyl chlorobenzene, and 4-(chloromethyl)-1-chlorobenzene. 
     
     
         9 . The process of preparing the compound according to  claim 1 , wherein
 (i) 2 mole of chlorobenzene as a starting material compound is reacted with 1 mole of tetrachloromethane as a Friedel-Crafts reagent to produce as targeted compound (4,4′-dichlorodiphenyl)-dichloromethane;   (ii) 2 mole fluorobenzene as a starting material compound is reacted with 1 mole of tetrachloromethane as a Friedel-Crafts reagent to produce as targeted compound (4,4′-dichlorodiphenyl)-dichloromethane;   (iii) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of 4-chlorobenzoic acid chloride as a Friedel-Crafts reagent to produce as targeted compound (4,4′-dichloro)-benzophenone;   (iv) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of (4-chlorophenyl) boronic acid as a Friedel-Crafts reagent to produce as targeted compound (4,4′-dichloro)-benzophenone;   (v) 1 mole of fluorobenzene as a starting material compound is reacted with 1 mole of 4-chlorobenzoic acid chloride as a Friedel-Crafts reagent to produce as targeted compound (4-fluoro,4′-chloro)-benzophenone;   (vi) 1 mole of fluorobenzene as a starting material compound is reacted with 1 mole of 4-fluorobenzoic acid chloride as a Friedel-Crafts reagent to produce as targeted compound (4,4′-difluoro)-benzophenone;   (vii) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of 4-chloro-1-(chloromethyl)-benzene as a Friedel-Crafts reagent to produce as targeted compound (4,4′-dichloro)-phenylmethane;   (viii) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of 4-fluoro-1-(chloromethyl)-benzene as a Friedel-Crafts reagent to produce as targeted compound (4-fluoro,4′-chloro)-phenylmethane;   (ix) 1 mole of fluorobenzene as a starting material compound is reacted with 1 mole of 4-chloro-1-(chloromethyl)-benzene as a Friedel-Crafts reagent to produce as targeted compound (4-fluoro,4′-chloro)-phenylmethane;   (x) 1 mole of fluorobenzene as a starting material compound is reacted with 1 mole of 4-fluoro-1-(chloromethyl)-benzene as a Friedel-Crafts reagent to produce as targeted compound (4,4′-difluoro)-phenylmethane;   (xi) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of benzene-1,4-dicarbonyl dichloride as a Friedel-Crafts reagent to produce as targeted compound bis-1,4-[(4,4′-dichlorophenyl)-carbonyl]-phenylene;   (xii) 1 mole of fluorobenzene as a starting material compound is reacted with 1 mole of benzene-1,4-dicarbonyl dichloride as a Friedel-Crafts reagent to produce as targeted compound 1 bis-1,4-[(4,4′-difluorophenyl)-carbonyl]-phenylene.   
     
     
         10 . The process of preparing the compound according to  claim 1 , wherein
 A) characterized in that the targeted compound is (4,4′-difluoro)-benzophenone, and further characterized in that
 (i) in a first step, 2 mole of chlorobenzene as a starting material_compound is reacted with 1 mole of tetrachloromethane as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as in situ as intermediate compound (4,4′-dichlorodiphenyl)-dichloromethane, and 
 in a second step, the intermediate compound (4,4′-dichlorodiphenyl)-dichloromethane is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound (4,4′-difluoro)-benzophenone, 
 or 
 (ii) in a first step, 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of 4-chlorobenzoic acid chloride as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as in situ as intermediate compound (4,4′-dichloro)-benzophenone, and 
 in a second step, the intermediate compound 4,4′-dichloro)-benzophenone is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound (4,4′-difluoro)-benzophenone, 
 or 
 (iii) in a first step, 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of (4-chlorophenyl) boronic acid as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as in situ as intermediate compound (4,4′-dichloro)-benzophenone, and 
 in a second step, the intermediate compound 4,4′-dichloro)-benzophenone is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound (4,4′-difluoro)-benzophenone, 
   or   B) characterized in that the targeted compound is (4,4′-difluoro)-phenylmethane, or the targeted compound is (4,4′-difluoro)-benzophenone derived from the said (4,4′-difluoro)-phenylmethane,   and further characterized in that
 (iv) in a first step 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of 4-chloro-1-(chloromethyl)-benzene as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as in situ as intermediate compound (4,4′-dichloro)-phenylmethane, and 
 in a second step, the intermediate compound (4,4′-dichloro)-phenylmethane is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound (4,4′-difluoro)-phenylmethane, 
   wherein the (4,4′-difluoro)-phenylmethane obtained in the second step is further reacted to yield as the targeted compound is (4,4′-difluoro)-benzophenone;
 (v) in a first step chlorobenzene is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as in situ as intermediate compound fluorobenzene, and 
 in a second step, the 1 mole of the intermediate compound fluorobenzene is reacted with 1 mole of tetrachloromethane as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as targeted compound (4,4′-difluoro)-phenylmethane, 
   wherein the (4,4′-difluoro)-phenylmethane obtained in the second step is further reacted to yield as the targeted compound is (4,4′-difluoro)-benzophenone;   C) characterized in that the targeted compound is bis-1,4-[(4,4′-difluorophenyl)-carbonyl]-phenylene,   and further characterized in that
 (vi) 1 mole of chlorobenzene as a starting material compound is reacted with 1 mole of benzene-1,4-dicarbonyl dichloride as a Friedel-Crafts reagent, in the presence of an antimony pentahalide catalyst (SbHal 5 ) activated by hydrogen fluoride (HF) present in low concentration, to produce as in situ as intermediate compound bis-1,4-[(4,4′-dichlorophenyl)-carbonyl]-phenylene, and 
 in a second step, the intermediate compound bis-1,4-[(4,4′-dichlorophenyl)-carbonyl]-phenylene is reacted in the presence of an antimony pentahalide catalyst (SbHal 5 ) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound bis-1,4-[(4,4′-difluorophenyl)-carbonyl]-phenylene. 
   
     
     
         11 . The process of preparing the compound by Friedel-Crafts reaction according to  claim 2 , characterized in that the fluorination reaction is a continuous process. 
     
     
         12 . The process of preparing the compound according to  claim 11 , wherein the fluorination reaction is a continuous process in at least one SiC-microreactor under one or more of the following conditions:
 flow rate: of from about 10 ml/h up to about 400 l/h;   temperature: of from about 30° C. up to about 150° C.;   pressure: of from about 4 bar up to about 50 bar;   residence time: of from about 1 minute, up to about 60 minutes.   
     
     
         13 . The process of preparing a compound according to  claim 2 , wherein the catalyst is a fluorination catalyst wherein the fluorination catalyst is selected from the group consisting of Sb fluorination catalysts providing the active species H 2 F + SbF 6   − . 
     
     
         14 . The process of preparing the compound according to  claim 13 , wherein the catalyst is antimony pentafluoride (SbF 5 ) activated by HF which forms the active species H 2 F + SbF 6   − . 
     
     
         15 . The process of preparing a compound according to  claim 1 , wherein the process comprises a step (b3) purifying and/or isolating the targeted compound obtained in a process of preparing a compound as defined in  claim 1 , to yield the said purified and/or isolated compound. 
     
     
         16 . The process according to  claim 15 , wherein the step (b3) the purifying and/or isolating of the targeted compound comprises or consists of a phase separation method. 
     
     
         17 . The process according to  claim 3 , wherein Hal denotes chlorine (Cl). 
     
     
         18 . The process according to  claim 4 , wherein the starting material compound is selected from the group of compounds consisting of the compounds chlorobenzene, dichlorobenzene, fluorobenzene, and difluorobenzene.