Elimination of difluorocarbene from the molecular ions of α,α,α-Trifluorocresols with a fluorine atom migration in an ion trap mass spectrometer

Abstract

The elimination of difluorocarbene (CF(2)) from the molecular ions of m-alpha,alpha,alpha-trifluorocresol (MW 162, 1) and p-alpha, alpha, alpha-trifluorocresol (MW 162, 2) upon electron impact have been investigated using a quadrupole ion trap mass spectrometer. This reaction involves a fluorine (F) atom migration from the trifluoromethyl group to the benzene ring. In the case of 1, an F atom migrates via a four-membered ring transition state to give rise to the molecular ion of p-fluorophenol (MW 112, 5) and a small amount of o-fluorophenol (MW 112, 3). On the other hand, in the case of 2, an F atom migrates to the ipso position of the benzene ring via a three-membered ring transition state to give rise to 5(+). These conclusions were confirmed by the comparison of the energy-resolved mass spectra (collision-induced dissociation (CID) spectra versus collision energy) of the m/z 112 ions from 1(+) and 2(+) with those of reference compounds, o-, m- and p-fluorophenol (3-5).