Evidence for an alkene metathesis reaction during the unimolecular dissociation of (CH3)3COCHCH2*+

Abstract : The unimolecular reaction of the metastable tert-butyl vinyl ether radical cation leads mainly to elimination of ethylene. From metastable ion studies as well as Fourier transform ion cyclotron resonance measurements and by using isotopic labeling, it is proposed that the fragmentation begins with the cleavage of the O-C(butyl) bond. This behavior, which contrasts with that of ionized alkylethers, is the consequence of the presence of a vinyl group that allows the formation of a neutral allylic radical. The key intermediate of the fragmentation is likely to be a [CH2CHOH, (CH3)2CCH2]*+ complex in which a cycloaddition-cycloreversion reaction occurs. This intermediate is the same as that produced by a McLafferty rearrangement in appropriate aldehyde radical cations.
Document type :
Journal articles
Complete list of metadatas

https://hal-polytechnique.archives-ouvertes.fr/hal-00922244
Contributor : Denis Roura <>
Submitted on : Friday, December 27, 2013 - 8:51:46 PM
Last modification on : Wednesday, March 20, 2019 - 12:12:02 PM

Identifiers

Collections

Citation

Guillaume van der Rest, J.P. Denhez, Julia Chamot-Rooke, Philippe Mourgues, Henri Audier. Evidence for an alkene metathesis reaction during the unimolecular dissociation of (CH3)3COCHCH2*+. European Journal of Mass Spectrometry, IM Publications, 2000, 6 (2), pp.113-120. ⟨10.1255/ejms.323⟩. ⟨hal-00922244⟩

Share

Metrics

Record views

102