Formation of an unusual MH− ion in the methane negative-ion chemical ionization mass spectra of chlorprothixene and aromatic sulfur compounds

✍ Scribed by Patrick S. Callery; William A. Garland; Elaine K. Fukudat

• Publisher: John Wiley and Sons
• Year: 1989
• Tongue: English
• Weight: 487 KB
• Volume: 24
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210240605

✦ Synopsis

The methane negative-ion chemical ionization (NCI) mass spectrum of chlorprothixene shows an unusual MHion. 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 MHion obsewed with methane as the reagent gas was shifted to MDwhen tetradeuteromethane was used in place of methane. The ratio of [M -HI-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,' or C,H,' 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 obsewations of ions formed by methane NCI from model compounds. Therefore, unlike other MH-ions obsewed in methane NCI mass spectra, the mechanism of formation does not appear to involve a hydrogen radical addition followed by electron capture.