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Evidence for the Amino–Claisen rearrangement occurring in the molecular ions of N ‐allylaniline
Author(s) -
Vandezonneville Alexandra,
Flammang Robert,
Maquestiau Andre,
Kingston Eric,
Bey John H.
Publication year - 1986
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210210610
Subject(s) - ion , dissociation (chemistry) , metastability , chemistry , molecule , claisen rearrangement , collision induced dissociation , mass spectrum , rearrangement reaction , cleavage (geology) , stereochemistry , crystallography , mass spectrometry , tandem mass spectrometry , materials science , organic chemistry , chromatography , fracture (geology) , composite material , catalysis
One of the most intense peaks in the mass spectrum of N ‐allylaniline is at m / z 106 (97%). High resolution analysis and collision‐induced dissociation studies confirm that this peak contains mostly [C 7 H 8 N] + ions having the anilinomethene structure, but also a small contribution is seen from [C 8 H 10 ] + ions which result from the loss of the elements of HCN from molecular ions, following an Amino–Claisen rearrangement. The occurrence of a thermal rearrangement in the sample molecules cannot, however, be completely ruled out. Studies on metastable molecular ions of N ‐allylaniline and collision‐induced dissociation of the m / z 106 ions formed from these show that, in the case of molecular ions with energies closer to threshold, the rearrangement reaction competes much more effectively with the direct cleavage reaction.