Potassium fluoride dispersion solution, and process for production of fluorinated 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 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. 
   
   
       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  claim 1 . 
   
   
       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 : Use of the potassium fluoride dispersion according to  claim 1  for fluorination of an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom. 
   
   
       23 : Use of the potassium fluoride dispersion obtained according to  claim 4  for fluorination of an organic compound having at least one group capable of being substituted nucleophilically with a fluorine atom. 
   
   
       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  claim 1 . 
   
   
       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  claim 4 .