Es. Eichmann et Js. Brodbelt, EFFECTS OF FUNCTIONAL-GROUP INTERACTIONS ON THE DISSOCIATION REACTIONS OF PROTONATED AMINO-ALCOHOLS, Organic mass spectrometry, 28(6), 1993, pp. 665-671
The dissociation reactions of protonated amino alcohols were examined
in a quadrupole ion trap mass spectrometer. Multi-stage collision-indu
ced dissociation techniques were used to characterize the ions and the
ir fragments and to assist in the determination of the dissociation me
chanisms. In addition, semi-empirical calculations were used to ration
alize the results on the basis of the thermodynamics of the reactions
in question. The reaction of special interest was the double eliminati
on of water and ammonia. For this high-energy process, it is shown tha
t the initial deamination step is the thermodynamically favored one in
most cases. The enthalpies of formation for the various precursor and
product ions and also those for some of the reaction intermediates we
re estimated using molecular modelling and semi-empirical calculation
methods. The values obtained indicated that the minimum endothermicity
of the sequential deamination-dehydration reaction ranges from 209 to
460 kJ mol-1 for the compounds studied here. Moreover, protonation at
the amine site was found to be energetically favored by 38-192 kJ mol
-1 over protonation at the hydroxyl site.