A derivatization strategy for the detection and identification of volatile trialkylphosphites using liquid chromatography-online solid phase extraction and offline nuclear magnetic resonance spectroscopy

• Volatile and labile trialkylphosphites were converted to stable non-volatile derivatives.
• Derivatives formed in good yields, reasonable timeframe, under mild conditions.
• Strong UV absorbing derivatives were purified by LC–UV–SPE.
• Derivatives identified by LC–UV retention time and NMR spectral signatures.
• The experiments are easy, sensitive, rugged, and repeatable.

We demonstrate herein the application of selective derivatization method that converts volatile and labile trialkylphosphites (TAPs) into virtually non-volatile, thermally stable, and UV absorbing derivatives. After simple sample preparation, purification/enrichment of the derivatives was achieved by using high performance liquid chromatography (HPLC) coupled to on-line post column solid phase extraction (SPE) system. These derivatives were subjected to 31P{1H} NMR and 1D-selTOCSY experiments. Conclusive identification was achieved on the basis of their HPLC retention time and NMR spectral signatures (δH1,δpE1δH1,δpE1, nJH–H, and 3JP–H). This method was tested for the unambiguous identification of a mixture containing low concentrations (∼10 μg mL−1) of trimethylphosphite (TMP), triethylphosphite (TEP), triisopropylphosphite (TIP), and tributylphosphite (TBP) along with a high concentration of irrelevant background chemicals. It offered a high dynamic range and good detection limit and recovery (>75%) without the need for special NMR probe heads or exotic NMR experiments.