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

✍ Scribed by Martin Hingst; Michael Tepper; Othmar Stelzer

• Book ID: 102657708
• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 654 KB
• Volume: 1998
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199801)1998:1<73::aid-ejic73>3.0.co;2-m

✦ Synopsis

Chiral-and multiply-carboxylated phosphanes and phospha-method. The diphenylphosphanyl derivatives 14Ϫ16 (R, RЈ = Ph) are accessible by an alternative method involving LiAlH 4 nyl derivatives of benzoic and phthalic acids (1Ϫ9) are accessible in high yields by nucleophilic phosphanylation of potas-reduction of the phosphanylbenzonitriles (20Ϫ22), which were obtained in high yields by nucleophilic phosphanyla-sium or lithium salts of commercially available fluorobenzoic and 3-fluorophthalic acids with Ph 2 PH, Ph 2 PK, PhPLi 2 , tion of the corresponding fluoro-or chlorobenzonitriles. The novel bidentate phosphanylbenzonitrile 23 has also been ob-Ph(K)PϪ(CH 2 ) 3 ϪP(K)Ph in superbasic media (DMSO/KOH) or in THF and DME. The hitherto unknown phosphanylphe-tained using this synthetic route. All compounds were completely characterized by elemental analysis, NMR spectros-nylacetic acids (10Ϫ13) and phosphanylbenzylamines RRЈPϪC 6 H 4 ϪCH 2 ϪNH 2 (14Ϫ19, R, RЈ = H, Me, Ph) with un-copy, and mass spectrometry. substituted amino groups were also synthesized by this [᭛] Part VIII: Ref. . conditions.