Recognition and resolution of isomeric alkyl anilines by mass spectrometry

Abstract

Two MS techniques have been used to recognize and resolve a representative isomeric pair of N-alkyl and ring-alkyl substituted anilines. The first technique (1) uses MS/MS to perform ion/molecule reactions of structurally-diagnostic fragment ions (SDFI) whereas the second (2) uses traveling wave ion mobility spectrometry (TWIMS) of the pair of protonated molecules followed by on-line collision-induced dissociation (CID), that is, MS/TWIMS-CID/MS. Isomeric C7H7N+ ions of m/z 106 (1′ from 4-butylaniline and 2 from N-butylaniline) are formed as abundant fragments by 70 eV EI of the anilines, and found to function as suitable SDFI. Ions 1′ and 2 display nearly identical unimolecular dissociation chemistry, but contrasting bimolecular reactivity with ethyl vinyl ether, isoprene, acrolein, and 2-methyl-1,3-dioxolane. Ion 2 forms adducts to a large extent whereas 1′ is nearly inert towards all reactants tested. The intact protonated anilines are readily resolved and recognized by MS/TWIMS-CID/MS in a SYNAPT mass spectrometer (Waters Corporation, Manchester, UK). The protonated N-butyl aniline (the more compact isomer) displays shorter drift time and higher lability towards CID than its 4-butyl isomer. The general application of SDFI 1′ and 2 and other homologous and analogous ions and MS/TWIMS-CID/MS for absolute recognition and resolution of isomeric families of N-alkyl and ring-alkyl mono-substituted anilines and analogues is discussed.

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Correspondence to Marcos N. Eberlin.

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Published online October 17, 2008

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Benassi, M., Corilo, Y.E., Uria, D. et al. Recognition and resolution of isomeric alkyl anilines by mass spectrometry. J Am Soc Mass Spectrom 20, 269–277 (2009). https://doi.org/10.1016/j.jasms.2008.10.004

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Keywords

  • Aniline
  • Acrolein
  • Dioxolane
  • Travel Wave
  • Substitute Aniline