Open AccessProposed mechanisms for the fragmentation of doubly allylic alkenamides (tingle compounds) by low energy collisional activation in a triple quadrupole mass spectrometer
Author(s) -
Richard D. Hiserodt,
B. M. Pope,
Michael Cossette,
Mark L. Dewis
Publication year - 2004
Publication title -
journal of the american society for mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.961
H-Index - 127
eISSN - 1879-1123
pISSN - 1044-0305
DOI - 10.1016/j.jasms.2004.06.009
Subject(s) - chemistry , triple quadrupole mass spectrometer , mass spectrometry , fragmentation (computing) , moiety , allylic rearrangement , ion , triple bond , spectrometer , quadrupole mass analyzer , computational chemistry , double bond , medicinal chemistry , stereochemistry , selected reaction monitoring , organic chemistry , tandem mass spectrometry , physics , chromatography , quantum mechanics , computer science , catalysis , operating system
Tingle compounds are a class of alkenamides with organoleptic properties that include a numbing or a pins and needles effect that is generally perceived on the lips and in the mouth when consumed. They occur in nature in a number of botanical species. Spilanthol and Pellitorine are important examples of tingle compounds. A number of homologs and analogs were synthesized to study the effect of chain length, double bond location, and amide moiety on the tingle effect. This also provided the opportunity to study the behavior of these compounds in the collision cell of a triple quadrupole mass spectrometer. The doubly allylic 2E,6Z-alkenamides, which made up the largest class studied, fragmented in a characteristic way to produce a distonic radical cation and a cyclopropene cation. Mechanisms for the formation of these ions are proposed. The mechanisms are supported by energy-resolved mass spectrometric data, the analysis of deuterated analogs and homologs that are not doubly allylic, and exact mass measurements. Exceptions to the proposed mechanisms are also presented. These data represent the first attempt to apply mechanistic principles to the product ions observed in the MS/MS spectra of these compounds. The authors believe the results of this study will facilitate the identification of these and similar compounds and contribute to the fundamental understanding of the behavior of alkenamides in the collision cell of a triple quadrupole mass spectrometer.