Reductive activation of arenes, XVIII. Cyanophenylation of aromatic nitrites by terephthalonitrile dianion: Is the charge-transfer complex a key intermediate? Научная публикация
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European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690 |
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| Вых. Данные | Год: 2005, Том: 2005, Номер: 12, Страницы: 2558-2565 Страниц : DOI: 10.1002/ejoc.200400851 | ||||
| Ключевые слова | biaryls; cyanides; electron transfer; reaction mechanisms; reactive intermediates | ||||
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Реферат:
The interaction of terephthalonitrile (1) dianion (1(2-)) with benzonitrile (2) or m-tolunitrile (3) provides 4,4'-dicyanobiphenyl (4) or 4,4'-dicyano-2-methylbiphenyl (5), respectively. This result shows that dianion 12- serves as a reagent for p-cyanophenylation of aromatic nitriles. Based on experimental data, such as the chemical trapping of the 4,4'-dicyanobiphenyl precursor 4-cyano-1-(p-cyanophenyl)cyclohexa-2,5-dienyl anion (7) and the failure to obtain biphenyl 4 through the interaction of independently generated radical anions (RAs) 1(-) and 2(-), as well as on the results of quantum-chemical calculations, a mechanism is suggested that includes a charge-transfer complex (CTC) between 1(2-) and the aromatic nitrile as the key intermediate. The formation of this CTC is followed either by an intracomplex electron transfer (ET) and recombination of terephthalonitrile and aromatic nitrile RAs within an unequilibrated RA pair, or by synchronous ET and bonding of the ipso-carbon atom of terephthalonitrile with the p-carbon atom of the aromatic nitrile. The synthetic significance of p-cyanophenylation of arenecarbonitriles by dianion 1(2-) is illustrated by the high yield of biphenyl product 4 (approx. 90%) as well as by the possibility of a one-pot synthesis of 4-butyl-4'-cyanobiphenyl and 4-butyl-4'-cyano-2-methylbiphenyl by successive treatment of dianion 1(2-) with nitrile 2 or 3 and butyl bromide. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).
Библиографическая ссылка:
Panteleeva E.
, Shchegoleva L.
, Vysotsky V.
, Pokrovsky L.
, Shteingarts V.
Reductive activation of arenes, XVIII. Cyanophenylation of aromatic nitrites by terephthalonitrile dianion: Is the charge-transfer complex a key intermediate?
European Journal of Organic Chemistry. 2005. V.2005. N12. P.2558-2565. DOI: 10.1002/ejoc.200400851 WOS Scopus РИНЦ OpenAlex
Reductive activation of arenes, XVIII. Cyanophenylation of aromatic nitrites by terephthalonitrile dianion: Is the charge-transfer complex a key intermediate?
European Journal of Organic Chemistry. 2005. V.2005. N12. P.2558-2565. DOI: 10.1002/ejoc.200400851 WOS Scopus РИНЦ OpenAlex
Даты:
| Опубликована в печати: | 1 июн. 2005 г. |
Идентификаторы БД:
| Web of science: | WOS:000229947200014 |
| Scopus: | 2-s2.0-20744455827 |
| РИНЦ: | 13479662 |
| OpenAlex: | W2077993828 |