Synthesis of phenyl arsenic analytical standards related to contaminated well water in Kamisu, Ibaraki, Japan

Abstract

To facilitate, by the provision of internal standards, the liquid chromatographic and mass spectrometric analysis of diphenylarsinic acid in well water and other samples related to an incident of environmental contamination in Kamisu, Ibaraki, Japan, syntheses of the analogous perdeuterated and mono-meta-and di-meta-methylated acids were undertaken. The acids were synthesized by cleavage of the triarylarsines by sodium in liquid ammonia. The triarylarsines were made from the reaction of arsenous chloride and sodium with the appropriate aryl-bromo compound. Properties of the compounds are given.

Complexes of diphenylarsinic acid and phenylarsonic acid with thiols: a 1H and 13C NMR study

“…The discovery 1 of high concentrations of diphenylarsinic acid (DPAA, Fig. 1) in well water used for drinking in the town of Kamisu in Ibaraki Prefecture, Japan, together with its reported high toxicity, 2 led us to study the reactions, monitored by NMR spectroscopy, of the compound with cellular thiols, in particular glutathione.…”

Chiral arsinic acid esters revealed by proton NMR spectroscopy

“…Although the environmental pollutant methylphenylarsinic acid (1) lacks any potentially diastereotopic group to reveal chiral arsenic after it has been esterified (or otherwise derivatised), it will exhibit analogous stereochemistry to that described here for ethylphenylarsinic acid (2). The toxicological consequences of this for cellular toxicity are currently unclear.…”

“…1 Probably it had been formed by microbial methylation of phenylarsonic acid that had found its way into the environment through wastes from the manufacture of chemical warfare agents more than 60 years ago. 2,3 When such unsymmetrically substituted arsinic acids, containing pentavalent arsenic, are reduced and bound by sulfur ligands, the resulting trivalent arsenic is chiral; configuration about the arsenic atom is tetrahedral and the lone-pair constitutes the fourth arm of the tetrahedron. 4 We have used NMR spectrocopy to investigate the stereochemical properties of such reduced and derivatised unsymmetrically subsituted arsinic acids.…”

Transformation of diphenylarsinic acid and related compounds in groundwater: production of thiol-containing arsenicals

“…1) was carried out. Research activities have included the development of analytical techniques, [2] monitoring of the concentrations of DPAA and its transformation products in human urine and groundwater, [3,4] studies of the absorption and metabolism of DPAA by plants, [5,6] studies of the toxicodynamics of DPAA in experimental animals [7,8] and studies aimed at elucidating the mechanism of DPAA's toxicity. [9] During recent measurements using liquid chromatographyinductively coupled plasma-mass spectrometry (LC-ICP-MS) of DPAA and related arsenicals in groundwater samples, we detected unknown arsenic species that appeared to be derived from DPAA.…”