Gas-phase Ion-molecule Reactions in Organophosphorus esters

Self-condensation ion–molecule reactions of trimethyl phosphite, triethyl phosphite, dimethyl phosphonate, trimethyl phosphate and 2,2-dichlorovinyl dimethyl phosphate (dichlorvos) were investigated by ion trap mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry. Reaction paths for the main processes observed were elucidated by parent ion selection and for reaction times up to 500 ms. In parallel, high-resolution measurements were performed in order to determine the composition of the principal ions. Among the compounds under examination, trimethyl phosphite and triethyl phosphite mainly give [M Y H]Y and [M Y (RO)2P]Y (R = CH3, C2H5) adduct ions, whereas trimethyl phosphate and dimethyl phosphonate display [2M Y H]Y ions, as the only abundant products, formed by reaction of [MY H]Y and M. 2,2-Dichlorovinyl dimethyl phosphate mostly shows fragmentation processes. The reaction patterns of the compounds examined were related to their different structural features. Gas-phase basicities of the phosphoryl compounds were also determined or re-examined.