Dimethylthioarsinic anhydride: A standard for arsenic speciation

Dimethylthioarsinic acid (DMTAV) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because of the unavailability of a well characterized standard. The synthesis of DMTAV was accomplished by the reaction of dimethylarsinic acid (DMAV) with hydrogen sulfide. The initial reaction product produced is DMTAV but multiple products over the course of the reaction are also observed. Therefore, a chromatographic separation was developed to monitor the reaction progress via LC–ICP-MS. In this synthesis, conversion of DMAV to DMTAV was not taken to completion to avoid the production of side products. The product was isolated from the starting material by standard organic techniques. Single crystal diffraction demonstrated that solid DMTAV is present in the form of the oxygen-bridged dimethylthioarsinic anhydride. Dissolution of the anhydride in water produces the acid form of DMTAV and the aqueous phase DMTAV provided a characteristic molecular ion of m/z 155 by LC–ESI-MS. The synthesis and isolation of dimethylthioarsinic anhydride provides a stable crystalline standard suitable for identification, toxicological study and exposure assessment of dimethylthioarsinic acid.