Wasserlösliche Phosphane, III [1]. Wasserlösliche primäre Phosphane mit Ammoniumgruppierungen NR2R' in der Seitenkette -donorfunktionalisierte Amphiphile / Water-Soluble Phosphanes, III [1]. Water-Soluble Primary Phosphanes with Ammonium Groups NR2R' in the Side Chain -Donor-Functionalized Amphiphiles

Abstract

Primary and secondary aminoalkylphosphanes R2N-(CH2)m-PH2 (R2 = Me2, nBu2, C5H10, C4H8O, 2-(1-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1-6) or [R2N-(CH2)m]2PH (7, R2 = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ω̃ -chloroalkylamines R2N-(CH2)m-Cl in the superbasic medium DMSO/KOH (DMSO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4-6 with R'I (R' = Me, CnH2n+1; n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes [R'R2N-(CH2)m-PH2]+I- (11-16f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of 11-16f decreases with increasing chain length (n) of R′ 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HCl affords the water-soluble hydrochlorides [HR2N-(CH2)m-PH2]+Cl- (19-22). The cationic primary phosphanes 11-16f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H2O2 the primary phosphane oxide [Me3N-(CH2)2-P(O)H2]+I- (23) or the phosphonous acid [Me3N-(CH2)2- P(O)(OH)H]+I- (23a) are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4-6 (L) with Fe2(CO)9 at ambient temperature yields stable complexes (CO)4FeL (26-30). Under more rigorous conditions Fe3 clusters (31, 32) with free R2N groups are obtained.