Mass spectral fragmentation pathways of propranolol related beta-fluorinated amines studied by electrospray and electron impact ionization

Rapid Commun Mass Spectrom. 1999;13(16):1671-9. doi: 10.1002/(SICI)1097-0231(19990830)13:16<1671::AID-RCM696>3.0.CO;2-V.


Propranolol, its 1"-mono-, di-, and trifluorinated analogs, and other related compounds were analyzed under electrospray ionization ion trap collision-induced dissociation (ESI-CID) and electron impact (EI) conditions. Interesting trends were observed in the fragment ions formed in both cases. Under ESI conditions, the abundances of product ions easily explained by protonation on the amine nitrogen decreased relative to the abundances of those formed from the ether-protonated species as the number of fluorines increased from zero to three. Under EI conditions, the distribution of fragment ions was shifted away from those arising from a nitrogen-centered cation radical and toward those arising from an ether oxygen-centered cation radical. The changes observed in apparent molecular sites of protonation and of ion radical formation in the mass spectra are consistent with the electron-withdrawing effects of the sequentially added fluorines. These effects are correlated with changes in solution phase pK( a)'s of the fluorinated amines.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Adrenergic beta-Antagonists / chemistry*
  • Animals
  • Fluorine Compounds
  • Humans
  • Mass Spectrometry / methods
  • Propranolol / analogs & derivatives*
  • Propranolol / chemistry*


  • Adrenergic beta-Antagonists
  • Fluorine Compounds
  • Propranolol