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The unorthodox loss of propyl from the molecular ions of methoxycyclohexane
Author(s) -
MolenaarLangeveld Tineke A.,
Nibbering Nico M. M.
Publication year - 1983
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.1210181005
Subject(s) - chemistry , cleavage (geology) , ion , metastability , deuterium , polyatomic ion , hydrogen , hydrogen bond , bond cleavage , ionization , kinetics , photochemistry , stereochemistry , molecule , atomic physics , organic chemistry , materials science , catalysis , physics , quantum mechanics , fracture (geology) , composite material
It is shown by field ionization kinetics, D and 13 C labelling and metastable ion studies that the loss of a propyl radical from the molecular ion of methoxycyclohexane occurs via two routes. At a molecular ion lifetime of <10 −10 s propyl is eliminated in the ‘classic’ way, i.e. by successive cleavage of the C(1)C(2) bond, 1,5‐H shift from C(6) to C(2) and cleavage of the C(4)C(5) bond. At 10 −10 s the other pathway for propyl loss starts to take place, which is initiated by a hydrogen shift from position 3 or 5 to the methoxy group. This leads in a series of steps to the formation of the 3‐methoxyhexene‐1 ion, which eventually eliminates a propyl radical. In some of the steps specific hydrogen‐deuterium exchange processes have been observed.