Department of Organic Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, 91-403 Lodz, Poland.
Biological and Chemical Research Center, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland.
Molecules. 2022 Jun 19;27(12):3930. doi: 10.3390/molecules27123930.
In this paper, we describe the lithiation of -benzylpyrene-1-carboxamide with RLi-TMEDA. We found that the reaction outcome strongly depends on the electrophile used in the quenching step. The electrophile can be introduced at either the benzylic position or at the C-2 position in the pyrene nucleus. Furthermore, when H was used as the quencher, the product of the intramolecular carbolithiation of the pyrene K-region was formed. Dehydrogenation of the obtained compound with DDQ allowed the synthesis of a novel nitrogen polycyclic compound with an aza-benzo[c,d]pyrene (azaolympicene) skeleton. Attempts to extend the reaction scope to the amides substituted in the phenyl ring and gave an unexpected result. The reaction of both compounds with BuLi gave 1-valerylpyrene () in good yield. Photophysical properties, including absorption spectra, emission spectra and quantum yields of the emission of selected products, were studied and discussed.
本文描述了 -苯甲基-1-烟酰胺与 RLi-TMEDA 的锂化反应。我们发现，反应结果强烈依赖于猝灭步骤中使用的亲电试剂。亲电试剂可以引入苄基位置或芘核的 C-2 位置。此外，当 H 用作猝灭剂时，形成了芘 K-区域的分子内卡罗锂化产物。用 DDQ 对所得化合物进行脱氢反应，可合成具有 aza-苯并[c,d]芘（azaolympicene）骨架的新型氮多环化合物。尝试将反应范围扩展到苯基取代的酰胺和，得到了意想不到的结果。两种化合物与 BuLi 的反应均以良好的产率得到 1-戊酰基芘（）。研究并讨论了所选产物的光物理性质，包括吸收光谱、发射光谱和发射量子产率。
