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2‐Azacycl[3.2.2] azine. Polyhalogenation and nucleophilic displacement reactions
Author(s) -
Fuenles Omar,
Paudler William W.
Publication year - 1975
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.5570120522
Subject(s) - chemistry , azine , sodium methoxide , phosphorus pentachloride , nucleophile , acetic anhydride , medicinal chemistry , butyllithium , derivative (finance) , organic chemistry , acetic acid , catalysis , financial economics , economics
1,4‐Dibromo‐2‐azacycl[3.2.2] azine (2) when treated with methanolic sodium methoxide affords the I‐methoxy‐4‐bromo derivative (3). Perchloro‐2‐azacycl[3.2.2]azine (7) was prepared and treated with methanolic sodium methoxide to yield the 5‐methoxy (8) and 5,7‐dimethoxy (9) derivatives as major products, depending upon reaction conditions. Catalytic removal of the chlorine substituents of compounds 8 and 9 afforded the 5‐methoxy (10) and 5,7‐dimethoxy (11) derivatives. Treatment of compound 2 with butyllithium affords the I‐butyl derivative (5) of 2‐azacycl[3.2.2]azine, while treatment with zinc in acetic acid yields 4‐bromo‐2‐azacycl[3.2.2]azine (6). 4‐Formyl‐2‐azacycl[3.2.2]azine (12) when treated with phosphorus pentachloride affords the 1,3‐dichloro‐4‐formyl derivative 13. Possible rationals for the nucleophilic displacement are given.