4,4'-Difluorobenzophenone → Phthalonitrile

Participants

Reaction Steps

To a 100 ml, 3-necked flask equipped with a thermometer and a Dean-Stark trap was added 5.0 gm (22.9 mmol) of 4,4'-difluorobenzophenone, 11.56 gm (34.4 mmol) of bisphenol A6F, and 80 ml of N-methyl pyrrolidinone (NMP). After flushing the mixture for 30 minutes with dry nitrogen, 7.6 gm (55.1 mmol) of pulverized anhydrous potassium carbonate was added with stirring. The reaction mixture was stirred at 100° C. for 1 hour. Toluene was added to the Dean-Stark trap and to the reaction vessel (4 ml). The reaction mixture was refluxed at 175°-180° C. for 12 hours. Water which formed as a by-product was removed by azeotropic distillation. The reaction temperature was reduced to 160° C. and the toluene was sweep out of the reaction vessel by removing the glass stopper from the 3-necked flash. When the temperature reached 180° C., it was assumed that the toluene had been removed. Upon cooling to room temperature, 3.97 gm (22.9 mmol) of 4-nitrophthalonitrile was added. The temperature of the mixture was increased to 100° C. and held at this temperature for 4 hours. FTIR spectroscopy showed the absence of hydroxy and nitro bands. The room temperature mixture was then poured into 400 ml of water with stirring. The solid precipitate was collected by suction filtration, washed exhaustively with water, and dried to afford 9.1 gm of oligomeric phthalonitrile monomer.

Provenance & Evidence