A Study of Hydrogen Rearrangement Reactions in the Molecular Ion of 1,2-Dimethoxyethane by MIKE Spectrometry

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The eliminations of methanol (CH3OH) and formaldehyde (CH2O) molecules from the molecular ion of 1,2-dimethoxyethane have been investigated by using deuterium labelling technique and mass analyzed ion kinetic energy (MIKE) spectra. The MIKE spectra show that the structure of the resultant ion at m/z 58, [M-CH3OH]+., is identical with that of the molecular ion of methyl vinyl ether ([CH3OCH=CH2]+.), and that of the ion at m/z 60, [M-CH2O]+., is an oxonium type ion, [CH3O(H)CH2CH2.)]+. The hydrogen rearrangements associated with these reactions result in thermochemical stabilization in the product systems. The loss of CH3OH molecule is accompanied by a kinetic energy release (T0.5 = 101 meV) larger than that in the elimination of CH2O molecule (T0.5=17 meV). A significant isotope effect is observed in the methanol and formaldehyde losses from deuterated 1,2-dimethoxyethane CH3OCH2CD2OCD3 (2,5-dioxahexane-1,1,1,3,3-d5). These results are discussed along with mechanistic features of both reactions.
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