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Direct nucleophilic aromatic substitution reactions in the syntheses of anthraquinone derivatives: Chemistry and binding of podands, crown ethers, and a cryptand
Author(s) -
Kim Hyunsook,
Schall Otto F.,
Fang Junping,
Trafton John E.,
Lu Tianbao,
Atwood Jerry L.,
Gokel George W.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050810
Subject(s) - chemistry , cryptand , anthraquinone , nucleophilic substitution , hsab theory , anthraquinones , phenazine , nucleophile , nucleophilic aromatic substitution , substitution reaction , alkylation , medicinal chemistry , chloride , organic chemistry , ion , botany , biology , catalysis
The direct nucleophilic aromatic substitution reactions of anthraquinones have permitted the syntheses of more than 30 novel podands, crown ethers and lariat ethers. Anthraquinones having (ethyleneoxy) n sidearms were obtained by direct displacement of chloride by the anion of CH 3 (OCH 2 CH 2 ) n OH. The ethyleneoxy‐substituted anthraquinones could, in turn, undergo direct replacement by nucleophiles that failed to displace chloride. This approach has been used for the preparation of two‐armed podand derivatives and several novel crown derivatives of anthraquinone. Binding comparisons are presented for several of these new anthraquinones. Direct substitution did not prove successful in the preparation of anthraquinone‐ [2 · 2] ‐cryptand which was obtained by alkylation. The crystal structure of the latter reveals an orientation of ring and anthraquinone appropriate for cation binding, a fact confirmed by cation binding constant measurements.