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Abstract
Electron ionisation mass spectra of N-methylimidazolidin-4-one organocatalysts were studied by experimental and theoretical means. The molecular ions mostly undergo alpha cleavages of exocyclic substituents that leave the five-membered ring intact. The type of substituent strongly dominates the appearance of the spectra. Fragmentation cascades are corroborated by metastable ion mass spectra. Quantum Chemistry Electron Ionisation Mass Spectra calculations correlate reasonably well with the experimental electron ionisation spectra and reveal mechanistic details of fragmentation pathways. The drawbacks and benefits of such calculations are discussed. Copyright © 2017 John Wiley & Sons, Ltd.
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