Wasserlösliche phosphane: II. Ein neuer syntheseweg für wasserlösliche sekundäre und tertiäre phosphane mit sulfonierten aromatischen resten - kristallstruktur von P(p-C6H4-SO3K)3 · KCl · 0.5H2O

Abstract Water soluble tertiary phosphanes 2 , 7 , 10–17 with sulfonated aromatic substituents p - C 6 H 4 -SO 3 K and 2,4-C 6 H 3 (SO 3 K) 2 can be obtained in good yields by nucleophilic aromatic substitution of fluorine in p -F-C 6 H 4 -SO 3 K ( 1 ) or F-C 6 H 3 -2,4-(SO 3 K) 2 ( 5 ) with PH 3 or primary and secondary phosphanes in the superbasic medium dimethyl sulfoxide (DMSO)/KOH(solid). The first water-soluble secondary phosphane HP[C 6 H 3 -2,4-(SO 3 K) 2 ] 2 ( 6 ) having sulfonated aromatic substituents can be obtained if 5 is reacted under similar conditions with PH 3 . Highly sulfonated phosphanes ( 7–9 ) with remarkable solubilities in water are formed upon reaction of 6 with F-C 6 H 5 , n BuBr or C 6 H 5 -CH 2 -Br, respectively, in the superbasic medium. The resulting compounds have been identified by their 1 H, 13 C( 1 H and 31 P( 1 H)NMR spectra. X-Ray structural analysis of P( p - C 6 H 4 -SO 3 K) 3 · KCl · 0.5H 2 O shows C 3 symmetry for the trianion of 2 with the P CP bond angles (103.5(2)°) and PC bond lengths (1.843(4) A) being almost identical to those in Ph 3 P.