Synthesis and mass spectrometry of heterocyclic organophosohorus compounds

Abstract

To investigate the synthesis of heterocyclic organophosphorus compounds and their mass spectra, trichloromethylphosphonyl dichloride was prepared by Aluminum Chloride method which was known as Kinnear-Perren reaction. 2-Trichloromethyl-1,3,2-dioxaphospholane, diazaphospholane, oxazaphospholane, oxathiaphospholane, and dioxaphosphorinane derivatives were synthesized by the stepwise esterification of trichloromethylphosphonyl dichloride with 1,2-, 1,3-, 2,3-diols, aminoethanols, 2-mercaptoethanol, and ethylene diamine. The heterocyclic compounds were obtained in the solution of $Et_3N$ as the hydrochloric acid trapping agent. The structures of synthesized products were characterized by their IR, $^1H$ NMR, mass spectra, and elemental analysis. Important spectral data for the series of phospholane and phosphorinane derivatives, Ⅰ-ⅩⅥ, are collected in Tables. The electron-impact (EI) mass spectra of a series of five-and six-membered cyclic compounds have been examined, and the principal fragmentation pathways described. The molecular ions are generally of low abundance in all the compounds. Ions corresponding to the five-membered cyclic groups, which occur by cleavage of the P-C bond, are usually high abundance, producing the base peaks in most the spectra containing P-N and P-S bonds. The EI decompositions of the dioxaphospholanes, which produce four-membered phosphonium ions due to loss of oxygen from five-membered phosphonium ions, and the dioxaphosphorinanes were compared with those of the other heterocyclic molecules.