TY  - JOUR
AB  - A novel fragmentation reaction accompanied by the unidirectional migration of three hydrogen atoms has been found in the radical cations of -arylpropanols with electron-donating substituents in the para position. This triple hydrogen (3H) rearrangement reaction is the dominant fragmentation channel of the long-lived molecular ions of trans-2-(4-dimethylaminobenzyl)-l-indanol, 2, but it occurs also in simpler -arylpropanol ions. Deuterium labelling of 2 reveals that the three hydrogen atoms originate with extraordinarily high specificity from the C(l), C(2) and O positions of the alcohol moiety. Cis- and 3-substituted isomers do not undergo this reaction. Along with the 3H rearrangement reaction a unidirectional double hydrogen (2H) rearrangement reaction takes place independently and with less specificity in the trans-2-(4-X-benzyl)-l-indanol ions 1+· and 2+·. No hydrogen exchange occurs during the 3H and 2H rearrangement reactions. Mechanistic alternatives of these unusual fragmentation reactions are discussed; the experimental evidence strongly favours pathways via several intermediate ion-neutral complexes.
DA  - 1988
DO  - 10.1002/oms.1210230904
LA  - eng
IS  - 9
M2  - 643
PY  - 1988
SN  - 0030-493X
SP  - 643-653
T2  - Organic Mass Spectrometry
TI  - Unidirectional triple and double hydrogen rearrangement reactions in the radical cations of gamma-arylalkanols
UR  - https://nbn-resolving.org/urn:nbn:de:0070-pub-17742106
Y2  - 2024-11-22T03:55:05
ER  -