Synthesis of C1-Symmetric Bulky Redoxi-Active Iminoketones and Diimines of the Pyrene and Aceanthrylene Series

The reactions of oxialyl chloride with pyrene, 2,7-di-tert-butylpyrene, anthracene and 4,7-di-tert-butyl-1,2-dihydroacenaphthylene give the corresponding diketones: cyclopent[cd]pyrene-3,4-dione, 2,7-di-tert-butylcyclopenta[cd]pyrene-3,4-dione, aceanthrylene-1,2-dione, 1,2-diketo-3,8-di-tert-butylpyracene. The diketones react with 2,6-diisopropylaniline to form a series of the corresponding imines. It was shown that 1,2-diketo-3,8-di-tert-butylpyracene does not produce condensation products with 2,6-diisopropylaniline. The effect of the imine substituents on the electronic structure and UV spectra of the aceanthrylene derivatives was studied with by DFT and TD DFT. Structure of 1,2-diketo-3,8-di-tert-butylpyracene, as well as (E)-2-(2,6-diisopropylphenylimino)aceanthrylen-1(2H)-one and 3,4-bis[2,6-diisopropylphenylimino]aceanthrylene was characterized by single crystal X-ray diffraction.