Polyfluoroarenes. Part XI. Reactions of tetrafluorophthalonitrile with nucleophilic reagents

Dimethylformamide, sodium 1-naphtholate, aniline, N-methylaniline, and ammonia readily effect nucleophilic displacement of fluoride ion from the 4-position in tetrafluorophthalonitrile to give high yields of monosubstituted products. Diethylphosphine, sodium benzenethiolate, lithium chloride, and lithium bromide give mainly 4,5-di- and 3,4,5,6-tetra-substituted products under the conditions described. The reaction with lithium chloride has also been applied to tetrafluorohydroquinone, and gives tetrachlorohydroquinone in high yield. Tetrafluorophthalonitrile reacts with arylamines and with polynuclear aromatic hydrocarbons in solvents of low polarity to give stable, crystalline molecular complexes.