The Gas-phase Amino-Claisen Rearrangement of Protonated N-Allylaniline

Article abstract of DOI:10.1002/oms.1210230603

Metastable molecular protonated ions of N-allylaniline dissociate with significant losses of ethene and ammonia in the flight path of a mass spectrometer.The structures of the daughter ions formed on the loss of ethene have been elucidated using collision-induced dissociation and it is postulated that two isomeric structures are formed, one corresponding to molecular protonated ions which have undergone an amino-Claisen rearrangement.The relative proportion of this rearranged species is dependent on the exothermicity of the proton-transfer reaction between the sample molecule and the chemical ionization reagent gas ion.It is proposed that the two isomeric parent species differ in the site of protonation.