6569-82-0Relevant academic research and scientific papers
Water-Soluble Phosphanes, III. Water-Soluble Primary Phosphanes with Ammonium Groups NR2R' in the Side Chain - Donor-Functionalized Amphiphiles
Brauer, David J.,Fischer, Joerg,Kucken, Stefan,Langhans, Klaus P.,Stelzer, Othmar,Weferling, Norbert
, p. 1511 - 1524 (2007/10/02)
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 2PH (7, R2 = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ω-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, CnH(2n+1); n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes (+)I(-) (11-16f) with quaternary ammonium groups in the alkyl 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 (+)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 (+)I(-) (23) or the phosphonous acid (+)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. - Keywords: Aminoalkylphosphanes, Protonation, Water Solubility, Complexes, Clusters
