Although the double Friedel-Crafts acylation of arenes with ethyl chloroglyoxylate is hindered by the strongly deactivating effect of the first-entering glyoxylic substituent, the double reaction is successful with the reactive arene perylene under long reaction times and with concomitant ester hydrolysis. The reaction is regiospecific, giving the 3,9-regioisomer exclusively. This perylenylenediglyoxylic acid is condensed first with o-bromophenylacetic acid and then with α-branched alkylamines to yield the title compounds. Whilst the corresponding tetraalkyl esters only show monotropic mesophases, these diimides show enantiotropic columnar mesophases that can be maintained at room temperature if racemically branched alkyl chains of moderate size are used. A palladium-induced C-C bond migration during the build-up of the arene system leads to an isomeric side product of reduced symmetry that can be isolated by aggregation-controlled chromatographic separation. The HOMO and LUMO energies of the title compounds are considerably higher than those of established perylenetetracarboxdiimides.
Keywords: cyclization; fused-ring systems; liquid crystals; pi interactions; rearrangement.
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