Leaving Group Effects in a Series of Electrosprayed CcHhN1 Anthracene Derivatives

  • Maha T. Abutokaikah
  • Giri R. Gnawali
  • Joseph W. Frye
  • Curtis M. Stump
  • John Tschampel
  • Matthew J. Murphy
  • Eli S. Lachance
  • Shanshan Guan
  • Christopher D. Spilling
  • Benjamin J. BythellEmail author
Research Article


We investigate the gas-phase structures and fragmentation pathways of model compounds of anthracene derivatives of the general formula CcHhN1 utilizing tandem mass spectrometry and computational methods. We vary the substituent alkyl chain length, composition, and degree of branching. We find substantial experimental and theoretical differences between the linear and branched congeners in terms of fragmentation thresholds, available pathways, and distribution of products. Our calculations predict that the linear substituents initially isomerize to form lower energy branched isomers prior to loss of the alkyl substituents as alkenes. The rate-determining chemistry underlying these related processes is dominated by the ability to stabilize the alkene loss transition structures. This task is more effectively undertaken by branched substituents. Consequently, analyte lability systematically increased with degree of branching (linear < secondary < tertiary). The resulting anthracen-9-ylmethaniminium ion generated from these alkene loss reactions undergoes rate-limiting proton transfer to enable expulsion of either hydrogen cyanide or CNH. The combination of the differences in primary fragmentation thresholds and degree of radical-based fragmentation processes provide a potential means of distinguishing compounds that contain branched alkyl chain substituents from those with linear ones.


Gas-phase structure Imine Density functional theory CID Petroleum Oil Protonation 



This work was supported by an American Chemical Society Petroleum Research Fund grant (56678-DNI6) and a University of Missouri Research Board Award. Maha T. Abutokaikah thanks the Saudi Arabia Culture Mission for funding part of her graduate work and the University of Missouri St. Louis for a Graduate Fellowship. Calculations were performed at the University of Missouri Science and Technology Rolla, MO.

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© American Society for Mass Spectrometry 2019

Authors and Affiliations

  • Maha T. Abutokaikah
    • 1
  • Giri R. Gnawali
    • 1
  • Joseph W. Frye
    • 1
  • Curtis M. Stump
    • 1
  • John Tschampel
    • 1
  • Matthew J. Murphy
    • 1
  • Eli S. Lachance
    • 1
  • Shanshan Guan
    • 1
  • Christopher D. Spilling
    • 1
  • Benjamin J. Bythell
    • 1
    Email author
  1. 1.Department of Chemistry and BiochemistryUniversity of MissouriSt. LouisUSA

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