Participation of halogen atoms in hydrogen transfer between remote positions in gas-phase ionized isomeric haloresorcinols
✍ Scribed by Adrian Weisz; Denis Andrzejewski; Asher Mandelbaum
- Publisher
- John Wiley and Sons
- Year
- 1992
- Tongue
- English
- Weight
- 393 KB
- Volume
- 27
- Category
- Article
- ISSN
- 1076-5174
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✦ Synopsis
Mono, di-and trihaloresorcinols substituted by a halogen atom at position 2 exhibit a highly specific elimination of H,O on electron impact ionization and under conditions of collisionally induced dissociation (CID). The high isomer specificity suggests the intermediacy of a hydrogen transfer from one of the hydroxy groups to the adjacent halogen atom. A subsequent hydrogen migration to the other hydroxy group readily explains the facile elimination of H,O from the M" ions of these particular isomers. An analogous three-step hydrogen transfer has not been observed in 2,3-dihalo-1,4-hydroquinones. 4-Bromo-and 4iodoresorcinol undergo elimination of the halogen atom followed by a very fast loss of CO under CID conditions, affording IM -Hall + ions of low abundance and highly abundant [ M -Hal -CO] + ions. The elimination of CO is suppressed in the isomeric 5-haloresorcinols, resulting in very highly abundant [ M -Hal] + ions. This behavior suggests that a 'hidden hydrogen transfer' accompanies the elimination of the halogen atom from the molecular ions of 4-haloresorcinols.