Spectrotitration of ethane-1-hydroxy-1,1-diphosphonic acid (EHDP(tm)) with thorium diaminocyclohexanetetra-acetate.
An automatic spectrotitration procedure for EHDP has been developed. It is applicable to samples containing 50mug or more of EHDP, with a relative standard deviation of 3% if no interfering materials are present. The sensitivity can be extended down to about 5mug, but titration blanks become significant and the standard deviation increases markedly. Thorium diaminocyclohexanetetra-acetate (Th-DCTA) is used as the titrant, to give a ternary species (Th-DCTA)(2)-EHDP. The end-point in the spectrotitration is due to deprotonation of Xylenol Orange indicator when it is incorporated into a weaker ternary species after all the EHDP has reacted. Salts such as NaCl, NaClO(4), Na(2)SO(4) and NaNO(3) interfere if present at concentrations of 0.1-0.5M. The method is much more sensitive to orthophosphate, but this interference can be averted by isolating the EHDP before titration by selectively adsorbing the phosphonate on calcium hydroxyapatite.
Metal chelates of phosphonate-containing ligands
Abstract The polarographic behavior of copper, lead, antimony, and zinc ions in the presence of the title ligand, HEDP, is discussed. In highly alkaline solutions, the reversible wave of copper splits into two components, reversible and irreversible, the first of which is attributed to the reduction of the free cupric ions and the second wave was assigned to the reduction of the copper phosphonate species. The polarograms of zinc and antimony showed the presence of a single irreversible wave. In the case of lead, a quasi-reversible wave is observed. Cobalt and nickel forms inactive phosphonate chelates as inferred from the suppression of the wave heights with increasing of both the concentration of the ligand and the pH of the medium. In the presence of sufficiently excess HEDP buffered to pH 11.8, mixtures of the six elements showed the presence of four reasonably separated waves at half-wave potential values −0.51, −0.83, −1.17, and −1.55 V vs SCE corresponding to the reductions of copper, lead, antimony, and zinc complexes, respectively. The possibility of the individual and simultaneous analysis of these elements in their ternary mixtures with cobalt and nickel is discussed.
Synthesis of 2,4-dideoxy-.beta.-D-erythro-hexopyranosyl nucleosides
The synthesis of 1-(2,4-dideoxy-β-D-erythro-hexopyranosyl)thymine (12) 1 was accomplished using two different synthetic routes. It was obtained starting either from 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose or from tri-O-acetyl-D-glucal. The other modified nucleosides, with either a cytosine, guanine, or adenine moiety, were synthesized using the second reaction scheme. Deoxygenation reactions were accomplished with the (2,4-dichlorophenoxy)thiocarbonyl derivatives generated in situ