Open Access1-Substituted Perylene Derivatives by Anionic Cyclodehydrogenation: Analysis of the Reaction Mechanism
Author(s) -
José Luis Borioni,
María T. Baumgartner,
Marcelo Puiatti,
Liliana Jiménez
Publication year - 2022
Publication title -
acs omega
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.779
H-Index - 40
ISSN - 2470-1343
DOI - 10.1021/acsomega.2c02017
Subject(s) - perylene , diradical , chemistry , derivative (finance) , conjugated system , density functional theory , amine gas treating , radical ion , reaction mechanism , computational chemistry , ion , combinatorial chemistry , photochemistry , medicinal chemistry , molecule , organic chemistry , catalysis , polymer , singlet state , physics , nuclear physics , financial economics , economics , excited state
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: -OCH 3 , -OSi(CH 3 ) 2 C(CH 3 ) 3 , and -N(CH 3 ) 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.