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Journal of Analytical Chemistry

, Volume 73, Issue 12, pp 1162–1176 | Cite as

Characterization of Dialkyl Phosphites by Gas Chromatography–Mass Spectrometry

  • I. G. ZenkevichEmail author
  • V. E. Nosova
ARTICLES

Abstract

The homologous series of dialkyl phosphonates (CnH2n + 1O)2PH=O] (2 ≤ n ≤ 9) (dialkyl phosphites is their commonly used trivial name) was characterized by electron ionization mass spectra and retention indices (RIs) on an RTX-5 standard nonpolar stationary phase. It was established that, in the presence of even one chiral center in the alkyl fragments (for example, in sec-alkanol esters), dialkyl phosphonates were detected in the form of several chromatographic signals due to diastereomers with differences in the retention indices from 4 to 21. The four-coordinated phosphorus atom is the second chiral center. The homologous increments of the retention indices of di-n-alkyl phosphonates (iRI ± sRI = 29 ± 9) and esters having one (–4 ± 10) and two (–61 ± 14) branching points in the carbon skeletons of alkyl fragments were evaluated. These values, which were calculated based on data for a limited number of homologues, make it possible to characterize any compounds from the test series. It was found that the relationship М ≈ 0.14(RI – iRI) + y makes it possible to uniquely determine the molecular weights of analytes according to chromatographic data under the condition of rounding the results to the nearest value of M comparable with y = 12 to the modulus 14 [М ≡ 12(mod14)].

Keywords:

dialkyl phosphonates identification mass spectra gas-chromatographic retention indices homologous increments of retention indices 

Notes

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Copyright information

© Pleiades Publishing, Inc. 2018

Authors and Affiliations

  1. 1.Institute of Chemistry, St. Petersburg State UniversitySt. PetersburgRussia

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