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Electron‐impact induced fragmentation of alkylthiopyridines. The extent of ring nitrogen involvement
Author(s) -
King Kenneth F.,
Hershenson Fred M.,
Bauer Ludwig,
Bell Charles L.
Publication year - 1969
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570060614
Subject(s) - chemistry , electron ionization , fragmentation (computing) , ring (chemistry) , pyridine , alkyl , nitrogen , mass spectrum , sulfide , nitrogen atom , ion , medicinal chemistry , polyatomic ion , organic chemistry , computer science , ionization , operating system
The fragmentation patterns obtained upon electron impact of 2‐, 3‐, and 4‐alkylthio‐pyridines were examined to determine the extent that the ring nitrogen is involved. The effect of the size of the alkyl group, as well as the ring position of the sulfide on the fragmentation of the methyl‐, ethyl‐, n ‐propyl‐, n ‐butyl‐ and t ‐butylthiopyridines, is discussed. The mass spectrum of 2‐ n ‐octylthiopyridine is also recorded. The molecular ions decomposed with rupture of the bonds α, β, γ, and δ from the hetero‐aromatic ring. The molecular ions also exhibited the loss of alkenes via a number of mechanisms, notably the loss of C n‐1 H 2n from the alkyl group of 2‐alkylthiopyridines by a transition involving the rupture of a C‐C bond γ to the ring and the transfer of a proton on a carbon ϵ to the ring. The role of the pyridine sp 2 nitrogen in this and other fragmentations is discussed. An elimination of HS radical is also observed in a number of these alkylthiopyridines.