Nucleophilic Phosphanylation of Fluoroaromatic Compounds with Carboxyl, Carboxymethyl, and Aminomethyl Functionalities − an Efficient Synthetic Route to Amphiphilic Arylphosphanes

Chiral- and multiply-carboxylated phosphanes and phosphanyl derivatives of benzoic and phthalic acids (1−9) are accessible in high yields by nucleophilic phosphanylation of potassium or lithium salts of commercially available fluorobenzoic and 3-fluorophthalic acids with Ph2PH, Ph2PK, PhPLi2 Ph(K)P−(CH2)3−P(K)Ph in superbasic media (DMSO/KOH) or in THF and DME. The hitherto unknown phosphanylphenylacetic acids (10−13) and phosphanylbenzylamines RR′P−C6H4−CH2− NH2 (14−19, R, R′ = H, Me, Ph) with unsubstituted amino groups were also synthesized by this method. The diphenylphosphanyl derivatives 14−16 (R, R′ = Ph) are accessible by an alternative method involving LiAlH4 reduction of the phosphanylbenzonitriles (20−22), which were obtained in high yields by nucleophilic phosphanylation of the corresponding fluoro- or chlorobenzonitriles. The novel bidentate phosphanylbenzonitrile 23 has also been obtained using this synthetic route. All compounds were completely characterized by elemental analysis, NMR spectroscopy, and mass spectrometry.