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J Am Soc Mass Spectrom. 2016 May;27(5):927-39. doi: 10.1007/s13361-016-1357-5. Epub 2016 Feb 25.

Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

Author information

1
Center for Mass Spectrometry, Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Hoboken, NJ, 07030, USA.
2
Center for Mass Spectrometry, Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Hoboken, NJ, 07030, USA. aattygal@stevens.edu.

Abstract

The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

KEYWORDS:

Anilides; CO2 addition; Ion molecule reactions; Negative ion; Nucleophilic addition

PMID:
26914232
DOI:
10.1007/s13361-016-1357-5

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