188-72-7Relevant articles and documents
Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
Baumgartner, María T.,Camargo Solórzano, Patricia,Jimenez, Liliana B.,Puiatti, Marcelo
, p. 21974 - 21985 (2020/07/03)
Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford thebay-substituted perylene. By using AlCl3as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2and N(CH3)2groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38percent yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C-C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.
Facile synthesis of terrylene and its isomer benzoindenoperylene
Avlasevich, Yuri,Kohl, Christopher,Muellen, Klaus
, p. 1053 - 1057 (2007/10/03)
3-(1-Naphthyl)perylene was synthesised by a palladium-catalysed cross-coupling reaction of 3-bromoperylene and 1-naphthaleneboronic acid. Oxidative cyclodehydrogenation of 3-(1-naphthyl)perylene selectively afforded terrylene or its isomer, benzo[4,5]indeno[1,2,3-cd]perylene. The yield of terrylene, an important fluorophore for single molecular spectroscopy, was significantly improved in comparison to literature methods. Benzoindenoperylene has an absorption maximum at 508 nm and shows no fluorescence in contrast to terrylene. The Royal Society of Chemistry 2006.
