Studies on the Formation of N-Methylperfluoroalkylnitrile Cations from Perfluoroacylphenethylamines in Electron Ionisation Mass Spectrometry: Unique Marker Ion Fragments in Methamphetamine Analysis

Abstract

The mass spectra of the perfluoroacyl derivatives of methamphetamine show a unique and characteristic fragment ion identified as the N-methylperfluoroalkylnitrile cation (C nF2 n+1CNCH3)+. This ion appears at various m/z values depending on the nature of the perfluoroacyl species and is generated via rearrangement of the perfluoroacyl immonium fragment formed by loss of the benzyl-radical from the molecular ion. Analogous ions have been described in the mass spectra of other methamphetamine-like side chain substances regardless of the aromatic ring substitution pattern. The scope and limitation of this rearrangement pathway were evaluated in this study by preparing a set of substituted phenethylamines and related compounds of varying structure. The perfluoroacyl moiety leads to the formation of the highest abundance of the N-methyl nitrile cation fragment while hydrocarbon acyl groups do not show the N-methylnitrile cation as a significant peak. The N-methyl group is required for the formation of the N-methyl nitrile cation and higher N-alkyl homologues eliminate the corresponding alkene species from the acyl immonium fragment. The loss of benzaldehyde and acetone from the perfluoroacylimmonium species produces the highest relative abundance of the unique N-methylperfluoroalkylnitrile cation.