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.