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Neighboring‐Group Participation in the Gas Phase. Loss of benzaldehyde from [(benzyloxy)methyl]dialkylsilyl‐substituted 1,3‐dithianes
Author(s) -
Fässler Jürg,
Huber Priska,
Bratovanov Svetoslav,
Bigler Laurent,
Bild Norbert,
Bienz Stefan
Publication year - 1995
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19950780719
Subject(s) - chemistry , benzaldehyde , fragmentation (computing) , hydride , intramolecular force , medicinal chemistry , ethanethiol , methyl group , lewis acids and bases , organic chemistry , photochemistry , group (periodic table) , catalysis , hydrogen , computer science , operating system
[(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.