Abstract
The reactions of O −.2 with alkyl and aryl esters of benzenedicarboxylic acids have been studied under negative-ion chemical ionization (NICI) conditions via a conventional chemical ionization source. Reaction mechanisms have been elucidated by using ion isolation techniques on a Fourier transform ion cyclotron resonance mass spectrometer. In addition, 18O −.2 has been used as the reagent and the products of competitive reactions that involve the mixed esters of benzenedicarboxylic acids have been studied. O −.2 reactions with the alkyl esters of 1,2- and l,3-benzenedicarboxylic acids are attributed to SN2 displacement at the O-alkyl carbon. The spectra of mixed alkyl esters show that O −.2 attack is reduced at sterically hindered alkyl groups. In contrast with the spectra of 1,2- and l,3-benzenedicarboxylic acids, the spectra of 1,4-benzenedicarboxylic acids are dominated by M−. production. Reactions of O −.2 with phenyl benzoates and the aryl esters of benzenedicarboxylic acids proceed via addition-elimination pathways. Experiments with mixed alkyl-aryl benzenedicarboxylic acid esters show that the addition-elimination reaction pathway is preferred over O-alkyl SN2 displacement. The O2/ Ar-NICI mass spectra show features that can be used to distinguish 1,2-, 1,3-, and 1/4-benzenedicarboxylic acid esters. Molecular and fragment ions provide structural information complementary to that generated under electron ionization and chemical ionization conditions.
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Stemmler, E.A., Diener, J.L. & Swift, J.A. Gas-Phase reactions of O −.2 with alkyl and aryl esters of benzenedicarboxylic acids. J Am Soc Mass Spectrom 5, 990–1000 (1994). https://doi.org/10.1016/1044-0305(94)80017-0
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DOI: https://doi.org/10.1016/1044-0305(94)80017-0