1499-32-7Relevant academic research and scientific papers
O, O ′-diester methylenediphosphonotetrathioate: Synthesis, characterization, and potential applications
Amir, Aviran,Sayer, Alon H.,Zagalsky, Rostislav,Shimon, Linda J. W.,Fischer, Bilha
, p. 270 - 277 (2013)
A new transformation of methylene-bis(phosphonic dichloride) into tetrathiobisphosphonate derivatives is reported. The reaction of methylene-bis(phosphonic dichloride) with 1,2-ethanedithiol in bromoform in the presence of AlCl3 formed methylene-bis(1,3,2-dithiaphospholane-2- sulfide), which gave rise to O,O′-diester-methylenediphosphonotetrathioate analogues 1a-k upon reaction with phenols and alkyl alcohols in the presence of DBU. Reaction mechanisms are proposed, and all products were characterized by 31P, 13C, and 1H NMR. An X-ray crystal structure was obtained for intermediate 2. The potential of the novel scaffold for selective coordination of metal-ions was examined by coordination of Hg(II) and Pb(II) by 1f, as determined by FT-IR, and chelation of Zn(II), but not Ca(II), by 1b, as determined by 31P/1H NMR. UV-vis measurements of 1g-Ni(II) mixture revealed a 2:1 ligand:metal complex. These derivatives are potential antioxidants, and their ability to inhibit ·OH formation in Fenton reactions was quantified by ESR measurements. Analogue 1g proved to be a most potent antioxidant (IC50 53 μM), inhibiting the Cu(I)-catalyzed Fenton reaction at lower concentrations than GSH, ascorbic acid, and EDTA. Analogue 1c inhibited the Fe(II)-catalyzed Fenton reaction at about the same concentrations as ascorbic acid (IC50 83 vs 93 μM). In summary, the novel compounds, 1a-k, proved to chelate various borderline/soft Lewis acid metal-ions, and may be useful as antioxidants and metal extractors.
Synthesis and evaluation of novel water-soluble ligands for the complexation of metals during the partitioning of actinides
Iqbal, Mudassir,Huskens, Jurriaan,Sypula, Michal,Modolo, Giuseppe,Verboom, Willem
experimental part, p. 2591 - 2600 (2012/01/04)
Different types of water-soluble ligands were synthesized and their capability was evaluated by solvent extraction studies to complex trivalent actinides and suppress their extraction by a strong lipophilic ligand, such as TODGA. The back extraction efficiency of hydrophilic diglycolamide (DGA) derivatives with a varying number of ethylene glycol groups, or containing sodium acetate moieties on the amidic nitrogen shows a decrease in back-extraction efficiency with increasing number of ethylene glycol units on the amidic nitrogen at various pH values of the aqueous phase. Among the PS donating ligands only the ligand with a malonamide backbone exhibits a high reverse extraction efficiency, although, with no selectivity for americium. Within the water-soluble tripodal ligands, i.e. the amide derivatives of nitrilotriacid with N,N-dimethyl and N,N-bis(hydroxyethyl) moieties, the first one shows a pronounced selectivity for Am(iii) over Eu(iii), with a maximum separation factor of 11.1, while the latter one more efficiently complexes the radionuclides in the aqueous phase with a maximum separation factor of 5. Isothermal microcalorimetry experiments of the complexation of Eu(iii) by a selected series of ligands confirm the observed trend in the back extraction properties.
