Participation of halogen atoms in hydrogen transfer between remote positions in gas‐phase ionized isomeric haloresorcinols

Abstract Mono, di‐ and trihaloresorcinols substituted by a halogen atom at position 2 exhibit a highly specific elimination of H 2 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 2 O from the M +· ions of these particular isomers. An analogous three‐step hydrogen transfer has not been observed in 2,3‐dihalo‐l,4‐hydroquinones. 4‐Bromo‐ and 4‐icdoresorcinol undergo elimination of the halogen atom followed by a very fast loss of CO under CID conditions, affording [M − Hal] + 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.