The Micro-Scale Synthesis of (117)Sn-enriched Tributyltin Chloride and Its Characterization by GC-ICP-MS and NMR Techniques

Chemosphere. 2014 Jul;107:386-392. doi: 10.1016/j.chemosphere.2014.01.003. Epub 2014 Jan 25.

Abstract

Organotin compounds (OTCs) are among the most toxic substances ever introduced to the environment by man. They are common pollutants in marine ecosystems, but are also present in the terrestrial environment, accumulated mainly in sewage sludge and landfill leachates. In investigations of the degradation and methylation processes of OTC in environmental samples, the use of enriched isotopic tracers represents a powerful analytical tool. Sn-enriched OTC are also necessary in application of the isotope dilution mass spectrometry technique for their accurate quantification. Since Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) are not commercially available as single species, "in house" synthesis of individual butyltin-enriched species is necessary. In the present work, the preparation of the most toxic butyltin, namely TBT, was performed via a simple synthetic path, starting with bromination of metallic Sn, followed by butylation with butyl lithium. The tetrabutyltin (TeBT) formed was transformed to tributyltin chloride (TBTCl) using concentrated hydrochloric acid (HCl). The purity of the synthesized TBT was verified by speciation analysis using the techniques of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) and nuclear magnetic resonance (NMR). The results showed that TBT had a purity of more than 97%. The remaining 3% corresponded to DBT. TBT was quantified by reverse isotope dilution GC-ICP-MS. The synthesis yield was around 60%. The advantage of this procedure over those previously reported lies in its possibility to be applied on a micro-scale (starting with 10mg of metallic Sn). This feature is of crucial importance, since enriched metallic Sn is extremely expensive. The procedure is simple and repeatable, and was successfully applied for the preparation of (117)Sn-enriched TBTCl from (117)Sn-enriched metal.

Keywords: (117)Sn-enriched tributyltin chloride; Characterization; Gas chromatography–inductively coupled plasma mass spectrometry; Micro-scale synthesis; Nuclear magnetic resonance; Tracer in environmental studies.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chemistry Techniques, Synthetic / methods*
  • Drug Stability
  • Environmental Pollutants / analysis
  • Environmental Pollutants / chemical synthesis*
  • Environmental Pollutants / chemistry*
  • Gas Chromatography-Mass Spectrometry*
  • Isotopes
  • Magnetic Resonance Spectroscopy
  • Organotin Compounds / chemistry
  • Reproducibility of Results
  • Tin / chemistry*
  • Trialkyltin Compounds / analysis
  • Trialkyltin Compounds / chemical synthesis*
  • Trialkyltin Compounds / chemistry*

Substances

  • Environmental Pollutants
  • Isotopes
  • Organotin Compounds
  • Trialkyltin Compounds
  • tetrabutyltin
  • tributyltin
  • Tin