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Cation radicals. XXVIII. Isolation and some reactions of dibenzodioxin cation radical perchlorate
Author(s) -
Shine Henry J.,
Shade Lewis R.
Publication year - 1974
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570110206
Subject(s) - chemistry , perchlorate , radical , nucleophile , inorganic chemistry , sulfite , medicinal chemistry , pyridinium , nucleophilic substitution , pyridine , lithium perchlorate , bromide , sodium perchlorate , photochemistry , organic chemistry , ion , electrochemistry , catalysis , electrode
Preparation and isolation of dibenzodioxin cation radical perchlorate ( 2 ) by oxidation of dibenzodioxin in ethyl acetate‐lithium perchlorate at a platinum anode has been achieved. Reasonably pure 2 in amounts of 150–200 mg. were obtained reliably and reproducibly. Reaction of 2 with both nitrite and nitrate ions gave 2‐nitrodibenzodioxin ( 3 ). Reaction of 2 with pyridine gave N ‐(2‐dibenzodioxinyl)pyridinium perchlorate ( 4 ). Reaction with water gave, as anticipated, the stoichiometric amount of dibenzodioxin. Reaction with ammonia, propylamine, t ‐butylamine, and cyanide ion also gave dibenzodioxin with no evidence that nucleophilic substitution had occurred. It is believed that the formation of 3 and 4 represent the first examples of nucleophilic substitution into dibenzodioxin via its cation radical.