Rationale
Homologous series of alkyl esters of phosphorus‐containing acids, namely, dialkyl phosphonates (synonym: dialkyl phosphites) and trialkyl phosphites, were characterized by electron ionization (EI) mass spectra and gas chromatographic retention indices (GC RI) on semi‐standard non‐polar stationary phases. It is confirmed that GC/MS characterization of any sets of homologues should not be restricted to independent registration of these analytical parameters. Their joint processing in the form of so‐called homologous increments of GC RIs means, firstly, a novel way of evaluating the chromatographic polarity of analytes and, secondly, a new algorithm for the prediction of their molecular weights if no peaks of molecular ions are registered in the mass spectra.
Methods
A standard GC/MS technique, including determination of GC RIs on semi‐standard nonpolar stationary phases in temperature‐programmed regime and electron ionization (EI) mass spectra was used.
Results
A total of 31 dialkyl phosphonate homologues and 37 trialkyl phosphite homologues were characterized by EI mass spectra and GC RIs for the first time. Joint processing of these analytical parameters allows the calculation of so‐called homologous increments of GC RIs, which are useful parameters for evaluating the chromatographic polarity of analytes and predicting their molecular weights.
Conclusions
GC/MS characterization of any sets of homologues should not be restricted to independent registration of the mass spectra and chromatographic retention parameters. Their joint processing in the form of so‐called homologous increments of GC retention indices means, firstly, a novel way of evaluating the chromatographic polarity of analytes and, secondly, a new algorithm for predicting their molecular weights.