ISSN:
0030-493X
Schlagwort(e):
Chemistry
;
Analytical Chemistry and Spectroscopy
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The metastable ion characteristics of N-alkyl-N-methylmethyleneiminium ions (\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H}_2 {\rm C}=\!=\mathop {\rm N}\limits^ + ({\rm CH}_3){\rm R} $\end{document}, R = n-CmH2m + 1, m = 3, 4, 5, 6, 8, 10, 14, 18) are reported and discussed. For R = n-propyl, alkene loss by onium reaction and alkene loss by McLafferty rearrangement occur, whereas for the higher homologues only the latter reaction is observed. As a result of 2H and 13C labelling experiments, the mechanism of alkene loss by γ-H transfer and β-cleavage does not change with increasing chain length and the iminium ions do not isomerize prior to decomposition, neither by H-D scrambling nor by carbon skeleton rearrangement. Whereas the sequence of elementary steps during fragmentation is not affected, the energetics of the reaction change as the chain length increases. Resulting from thermodynamic estimations, the enthalpy of reaction ΔHr, critical energy E0 and reverse critical energy E0r diminish markedly as R increases from n-propyl to n-octadecyl. The knowledge of the reaction energetics including kinetic energy release data allows information about partitioning of excess energy into internal and translational degrees of freedom to be deduced.
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/oms.1210280808
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