Multiple-stage mass spectrometry in structural characterization of organophosphorus compounds

• Published in: Journal of the American Society for Mass Spectrometry 1993-02, Vol.4 (2), p.125-134
• Main Authors: Zeller, Loreen C., Farrell, John T., Kenttämaa, Hilkka I., Kuivalainen, Tuula
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Mass spectrometry; Organic chemistry; Reactivity and mechanisms
• ISSN: 1044-0305; 1879-1123
• DOI: 10.1016/1044-0305(93)85068-9

Multiple-stage mass spectrometry involving consecutive collision-activated dissociation reactions was used to examine the structures of fragment ions commonly formed on electron ionization of organophosphorus esters. The compounds studied include several aryl thiophosphates, some of which are analogs of common pesticides. Energy-resolved collision-activated dissociation experiments allow the dissociation of the molecular ions of these compounds in such a manner that only a few fragment ions dominate the spectrum. An abundant fragment ion of m/z 109, formed from all of the compounds studied, can have at least four different stable structures: (CH 3O) 2PO +, CH 3CH 2OP(O)OH +, CH 2=CHOP(H)(OH) 2 +, and (CH 2O) 2P(H)OH +. The structure of the fragment ion of m/z 109 was found to reflect the phosphorus-containing part of the compounds studied. Another abundant fragment ion obtained for all the aryl esters studied is structurally characteristic of the aromatic moiety of the molecule. This fragment ion is the result of a complex rearrangement involving transfer of an alkylene group to the aromatic ring from the phosphorus-containing part of the molecular ion. The utility of these fragment ions in the structural characterization of unknown organophosphorus esters is discussed.