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Neighboring-Group participation in the gas phase. Loss of benzaldehyde from [(benzyloxy)methyl]dialkylsilyl-substituted 1,3-dithianes


Fässler, Jürg; Huber, Priska; Bratovanov, Svetoslav; Bigler, Laurent; Bild, Norbert; Bienz, Stefan (2004). Neighboring-Group participation in the gas phase. Loss of benzaldehyde from [(benzyloxy)methyl]dialkylsilyl-substituted 1,3-dithianes. Helvetica Chimica Acta, 78(7):1855-1862.

Abstract

[(Benzyloxy)methyl]dialkylsilyl-substituted 1,3-dithianes show in CI-MS an abundant loss of benzaldehyde from the [M + H]+ quasi-molecular ion. The fragmentation is explained with an intramolecular redox process, where a hydride is proposed to be transferred from the benzyl position to a neighboring thionium ion. This would form a particle that could readily lose benzaldehyde as a neutral fragment. The CI-MS results provide an explanation for the unusual instability of (benzyloxy)methyl-substituted silanes towards acids. In fact, the formation of benzaldehyde was established in the decomposition of a (benzyloxy)methyl-substituted acylsilane in the presence of Lewis or Brønsted acids and ethanethiol. The CI-MS study, therefore, represents a useful method to recognize unusual reactions that are – or might be – important in solution.

Abstract

[(Benzyloxy)methyl]dialkylsilyl-substituted 1,3-dithianes show in CI-MS an abundant loss of benzaldehyde from the [M + H]+ quasi-molecular ion. The fragmentation is explained with an intramolecular redox process, where a hydride is proposed to be transferred from the benzyl position to a neighboring thionium ion. This would form a particle that could readily lose benzaldehyde as a neutral fragment. The CI-MS results provide an explanation for the unusual instability of (benzyloxy)methyl-substituted silanes towards acids. In fact, the formation of benzaldehyde was established in the decomposition of a (benzyloxy)methyl-substituted acylsilane in the presence of Lewis or Brønsted acids and ethanethiol. The CI-MS study, therefore, represents a useful method to recognize unusual reactions that are – or might be – important in solution.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2004
Deposited On:24 Aug 2017 15:57
Last Modified:24 Aug 2017 15:57
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:0018-019X
Publisher DOI:https://doi.org/10.1002/hlca.19950780719

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