1-Substituted-perylene derivatives by anionic cyclodehydrogenation. Analysis of the reaction mechanism.

BORIONI, JOSÉ L.; BAUMGARTNER, MARÍA T.; MARCELO PUIATTI; JIMENEZ, LILIANA B.

ACS OMEGA

ACS

Lugar: Washington; Año: 2022

2470-1343

Perylene derivatives constitute a promising class of compounds with technological applications mainly due to their optoelectronic properties. One mechanism proposed to synthesize them, starting from binaphthyl derivatives, is  anionic cyclodehydrogenation (under reductive conditions). However, the scope  of this reaction is limited. In the present study, we report a theoretical and experimental analysis of this particular reaction mechanism for its use in the synthesis of 1-substituted perylenes. Different substituents at position 2 of 1,1′- binaphthalene were evaluated: −OCH3, −OSi(CH3)2C(CH3)3, and −N(CH3)2. Based on density functional theory (DFT) calculations on the proposed mechanism, we suggest that the cyclization takes place from binaphthyl dianion  instead of its radical anion. This dianion has an open-shell diradical nature, and this could be the species that was detected by EPR in  previous studies. The O-substituted derivatives could not afford the perylene derivatives since their radical anions fragment and the  necessary binaphthyl dianion could not be formed. On the other hand, 49% of N,N-dimethylperylen-1-amine was obtained starting from the N-substituted 2-binapthyl derivative as a substrate, employing a simpler experimental methodology.