Oxygen exchange during the reaction of POCl3 and waterFaculty of Science - Papers (Archive)
AbstractTo investigate O exchange during the reaction of POCl3 and water, natural abundance POCl3 was reacted with water highly enriched in 18O, and the resulting H3PO4 was isolated as KH2PO4. This reaction was conducted with and without tetrahydrofuran (THF) as a solvent, and was controlled in THF and violent in its absence. Approximately 5 x 10-4M aqueous solutions of the KH2PO4 were analyzed using electrospray ionization mass spectrometry, to estimate the proportions of the mass-clumped 16,17,18O isotope analogues of [H2PO4] -. During analysis, ~29% of [H2PO4] - dehydrated to [PO3]-, for which the proportions of the O isotope analogues were also measured. These proportions were compared with those predicted for O exchange at either four or three positions on the P atom of POCl3. The data strongly support O exchange at all four positions, whether or not THF was used to moderate conditions during the reaction. This result clears the way for safe, predictable synthesis of heavy-O labelled orthophosphate from POCl3 and 18O enriched water for evaluation as an environmental and biochemical tracer. Copyright CSIRO 2011.
Citation InformationRobert Graham Clark, Robert John Morrison, Andrew Thomas, Rebeca Alvarez, et al.. "Oxygen exchange during the reaction of POCl3 and water" (2011) p. 1360 - 1365
Available at: http://works.bepress.com/robert_clark/20/