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Formation of an unusual MH − ion in the methane negative‐ion chemical ionization mass spectra of chlorprothixene and aromatic sulfur compounds
Author(s) -
Callery Patrick S.,
Garland William A.,
Fukudat Elaine K.
Publication year - 1989
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210240605
Subject(s) - chemistry , mass spectrum , ion , electron ionization , chemical ionization , methane , reagent , sulfur , hydrogen atom , adduct , radical ion , photochemistry , mass spectrometry , ionization , inorganic chemistry , organic chemistry , chromatography , alkyl
Abstract The methane negative‐ion chemical ionization (NCI) mass spectrum of chlorprothixene shows an unusual MH − ion. This ion can be accounted for by electron capture followed by H˙ transfer from the reagent gas. The most probable site of electron attachment was concluded to be related to the sulfur atom of the thioxanthene ring based on the observation of analogous ions for structurally related compounds, all containing a heterocyclic sulfur. The MH − ion observed with methane as the reagent gas was shifted to MD − when tetradeuteromethane was used in place of methane. The ratio of [M H] − to MH − did not change with emission current suggesting that the process is independent of the radical concentration in the CI plasma. Consistent with this observation is the lack of CH 3 ˙ or C 2 H 5 ˙ adduct ions in the NCI mass spectrum and the fact that gold‐plating the ion source did not decrease the proportion of MH − . Also, this mechanism is consistent with thermochemical considerations of reactions of a phenyl radical with various alkanes and observations of ions formed by methane NCI from model compounds. Therefore, unlike other MH − ions observed in methane NCI mass spectra, the mechanism of formation does not appear to involve a hydrogen radical addition followed by electron capture.