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Complementary Synthetic Approaches to Elongated Polycyclic Arenes with Regioisomeric Carboxylic Substitution Patterns
Author(s) -
Bock Harald,
Carré Pauline,
Hillard Elizabeth A.,
Durola Fabien
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403339
Subject(s) - chemistry , anthracene , moiety , saponification , substituent , diimide , photochemistry , carboxylic acid , bifunctional , medicinal chemistry , stereochemistry , perylene , organic chemistry , molecule , catalysis
The reaction of 1,5‐dibromoanthracene with butyllithium and diethyloxalate followed by saponification gives anthrylene‐1,5‐diglyoxylic acid as a bifunctional reactant. Its double condensation with 2‐bromophenylacetic acid, followed by double cyclization, leads to a bright‐orange near‐linear dinaphtho‐anthracene‐tetracarboxdiimide with substituents on the naphthalene moieties. An analogous condensation‐cyclization sequence of 2,5‐dibromophenylene‐1,4‐diacetic acid with 1‐naphthylglyoxylic acid leads to an isomeric red diimide substituted on the anthracene nucleus. The striking difference in band gaps shows that diimide substitution on the central moiety of diareno[ a , h ]anthracenes is particularly efficient in inducing long‐wavelength absorption. The substitution dependence of the band gap is found to be mainly caused by a variation of the reduction potentials with substituent position, whereas the oxidation potentials are largely substitution‐independent.