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On the 1,1‐elimination of nitrous acid and the loss of hydroxyl from the molecular ion of the methyl ester of γ‐nitrobutyric acid
Author(s) -
MolenaarLangeveld T. A.,
Nibbering N. M. M.
Publication year - 1974
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.1210090212
Subject(s) - nitrous acid , chemistry , methyl radical , polyatomic ion , ion , methyl group , hydrogen , hydrogen atom , medicinal chemistry , organic chemistry , group (periodic table) , radical
It is shown by D labelling experiments that nitrous acid and hydroxyl, eliminated from the methyl ester of γ‐nitrobutyric acid upon electron‐impact, contain a γ‐hydrogen atom to the extent of ∼ 85% and ∼ 100%, respectively. The loss of nitrous acid is the third case of a highly specific 1,1‐elimination from a molecular ion 1a,1b reported hitherto and arguments are presented for the essential role played by carbomethoxy group in this reaction, i.e. it converts the nitro structure of the molecular ion to its acinitro structure. The results obtained further point to a stepwise character of the McLafferty rearrangement, at least for the present case.