Potassium fluoride dispersion and process for producing fluorine-containing organic compound using the same

Abstract

A potassium fluoride dispersion essentially consisting of potassium fluoride and an aprotic organic solvent having a boiling point higher than that of methanol, which is obtainable by mixing a mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride with the aprotic organic solvent followed by concentrating the obtained mixture, and a process for producing a fluorine-containing organic compound comprising contacting an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom with the potassium fluoride dispersion.

1 . A potassium fluoride dispersion, which is obtainable by mixing a mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride with the aprotic organic solvent followed by concentrating the obtained mixture to obtain the potassium fluoride dispersion consisting essentially of potassium fluoride and an aprotic organic solvent having a boiling point higher than that of methanol,
 wherein the mixture being a solution wherein potassium fluoride is dissolved perfectly in the methanol,   the potassium fluoride in the dispersion being potassium fluoride wherein a part or all of initial particles, of which particle diameter is 0.1 to 5 μm, are flocculated to form particles having 5 to 25 μm of volumetric average particle diameter, and   the aprotic organic solvent is selected from the group consisting of ether solvents, sulfone, solvents, sulfoxide solvents, amide solvents, nitrile solvents and mixtures thereof.   
     
     
         2 . The potassium fluoride dispersion according to  claim 1 , wherein the mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride is a solution wherein potassium fluoride is dissolved perfectly in methanol. 
     
     
         3 . The potassium fluoride dispersion according to  claim 2 , wherein potassium fluoride in the potassium fluoride dispersion is potassium fluoride wherein a part or all of the initial particles, of which particle diameter is 0.1 to 5 μm, are flocculated to form particles having 5 to 25 μm of volumetric average particle diameter. 
     
     
         4 . A process for producing a potassium fluoride dispersion essentially consisting of potassium fluoride and an aprotic organic solvent having a boiling point higher than that of methanol, which comprises mixing a mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride with the aprotic organic solvent followed by concentrating the obtained mixture. 
     
     
         5 . The method according to  claim 4 , wherein the mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride is a solution wherein potassium fluoride is dissolved perfectly in methanol. 
     
     
         6 . The method according to  claim 4 , wherein the concentration is conducted while adding the mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride into the aprotic organic solvent having a boiling point higher than that of methanol, which is adjusted at a temperature which is the boiling point of methanol or more. 
     
     
         7 . The method according to  claim 4 , wherein the aprotic organic solvent is an aprotic polar solvent. 
     
     
         8 . The method according to  claim 7 , wherein the aprotic polar solvent is a sulfone solvent or a sulfoxide solvent. 
     
     
         9 . The method according to  claim 4 , wherein the mixture containing potassium fluoride and 5 to 50 parts by weight of methanol per 1 part by weight of potassium fluoride is a mixture obtainable by mixing hydrogen fluoride with potassium hydroxide in methanol. 
     
     
         10 . The method according to  claim 9 , wherein hydrogen fluoride is hydrofluoric acid. 
     
     
         11 . The method according to  claim 5 , wherein potassium fluoride in the potassium fluoride dispersion is potassium fluoride wherein a part or all of the initial particles, of which particle diameter is 0.1 to 5 μm, are flocculated to form particles having 5 to 25 μm of volumetric average particle diameter. 
     
     
         12 . A process for producing a fluorine-containing organic compound comprising contacting an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom with the potassium fluoride dispersion according to any one of  claims 1  to  3 . 
     
     
         13 . The process according to  claim 12 , wherein the group capable of being substituted nucleophilically with a fluorine atom is a chlorine atom, a bromine atom, an iodine atom, a nitro group, a sulfo group, an optionally substituted alkylsulfonyloxy group, an optionally substituted arylsulfonyloxy group or an optionally substituted acyloxy group. 
     
     
         14 . The process according to  claim 12 , wherein the organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom is a compound wherein at least one hydrogen atom of an optionally substituted aliphatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom. 
     
     
         15 . The process according to  claim 12 , wherein the organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom is a compound wherein at least one hydrogen atom of an optionally substituted aromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom. 
     
     
         16 . The process according to  claim 12 , wherein the organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom is a compound wherein at least one hydrogen atom of an optionally substituted heteroaromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom. 
     
     
         17 . The process according to  claim 15 , wherein the compound wherein at least one hydrogen atom of an optionally substituted aromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom is tetrachloroterephthalic dichloride, and the fluorine-containing organic compound is tetrafluoroterephthalic difluoride. 
     
     
         18 . The process according to  claim 15 , wherein the compound wherein at least one hydrogen atom of an optionally substituted aromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom is 2,4-dichloronitrobenzene, and the fluorine-containing organic compound is 2,4-difluoronitrobenzene. 
     
     
         19 . The process according to  claim 15 , wherein the compound wherein at least one hydrogen atom of an optionally substituted aromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom is 4-chloronitrobenzene, and the fluorine-containing organic compound is 4-fluoronitrobenzene. 
     
     
         20 . The process according to  claim 16 , wherein the compound wherein at least one hydrogen atom of an optionally substituted heteroaromatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom is 4,5,6-trichloropyrimidine, and the fluorine-containing organic compound is 4,5,6-trifluoropyrimidine. 
     
     
         21 . The process according to  claim 14 , wherein the compound wherein at least one hydrogen atom of an optionally substituted aliphatic hydrocarbon compound is substituted with a group capable of being substituted nucleophilically with a fluorine atom is benzyl bromide, and the fluorine-containing organic compound is benzyl fluoride. 
     
     
         22 - 23 . (canceled) 
     
     
         24 . A method for fluorinating an organic compound comprising contacting an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom with the potassium fluoride dispersion according to any one of  claims 1  to  3 . 
     
     
         25 . A method for fluorinating an organic compound comprising contacting an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom with the potassium fluoride dispersion obtained according to any one of  claims 4  to  11 .