期刊
ACS OMEGA
卷 7, 期 25, 页码 21860-21867出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsomega.2c02017
关键词
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资金
- Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET)
- Secretaria de Ciencia y Tecnologia, Universidad Nacional de Cordoba (SECyT)
- Agencia Nacional de Promocion Cientifica y Tecnica (ANPCyT)
In this study, the specific reaction mechanism for the synthesis of 1-substituted perylenes was analyzed theoretically and experimentally. The anionic cyclodehydrogenation was found to take place from the binaphthyl dianion, and the O-substituted derivatives were unable to produce the required dianion.
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)(2)C(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.
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