Process for the manufacture of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof

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 (SbHal5), activated by hydrogen fluoride (HF);

• 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) 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 (SbHal5) with hydrogen fluoride (HF) present in excess concentration, to produce as targeted compound bis-1,4-[(4,4′-difluorophenyl)-carbonyl]-phenylene.