Chlorodifluoromethane → Chloro Fluoro Triazolin-3-one

Participants

Reaction Conditions

Reaction Steps

To a one liter resin flask equipped with a cold finger, mechanical stirrer, gas inlet tube, and a thermometer was added 333 mL of tetraglyme, followed by 50.0 grams (0.220 mole--1.0 equiv.) of 4,5-dihydro-1-(4-chloro-2-fluorophenyl)-3-methyl-5-oxo-1H-1,2,4-triazole (% wt/vol. triazole to solvent--15%). Under a nitrogen atmosphere and with stirring the mixture was warmed to 185° C., and 11.4 grams (0.082 mole--0.373 equiv.) of anhydrous potassium carbonate was added in one portion. To this was then added 7.1 grams (0.082 mole--0.373 equiv.) of gaseous chlorodifluoromethane below the surface of the reaction mixture. Upon completion of the addition the reaction mixture was stirred for about 10 minutes. The sequence of potassium carbonate and chlorodifluoromethane addition was then repeated three additional times for a total addition of 1.5 molar equivalents each of potassium carbonate and chlorodifluoromethane. Upon completion of the fourth set of additions the reaction mixture was held at 185° C. for about 15 minutes. After this time GC analysis of the reaction mixture indicated 100% conversion of the triazole starting material. After the reaction mixture was cooled to ambient temperature, the salt by-products were removed by filtration, and the filtrate was slowly poured into 1200 mL of water. The resultant slurry was stirred, and the solid was collected by filtration, washed with four 100 mL portions of water, and dried to a constant weight, yielding 57.3 grams of 90.6% pure 4-difluoromethyl-4,5-dihydro-1-(4-chloro-2-fluorophenyl)-3-methyl-5-oxo-1H-1,2,4-triazole (86.3% yield). GC analysis of the product indicated the presence of about 2.9% O-isomer by-product.

Provenance & Evidence