The Photochemical Dimerization of 4-Nitro-2-Phenylindone. A DFT Study

From Top Italian Scientists Journal
Published
June 3, 2024
Title
The Photochemical Dimerization of 4-Nitro-2-Phenylindone. A DFT Study
Authors
Maurizio D’Auria, Lucia Emanuele, Rocco Racioppi.
DOI
10.62684/EYVJ9669
Keywords
Photochemistry; Indone dimerization; DFT
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Maurizio D'Auria(a), Lucia Emanuele(b), Rocco Racioppi(a).

(a) Dipartimento di Scienze, Università della Basilicata, Via dell’Ateneo Lucano 10, 85100 Potenza, Italy. Email: maurizio.dauria@unibas.it; rocco.racioppi@unibas.it

(b) Department of Arts and Restoration, University of Dubrovnik, Branitelja Dubrovnika 41, 20000 Dubrovnik, Croatia. Email: lemanuel@unidu.hr

Abstract

A DFT study of the photochemical dimerization on 4-nitro-2-phenylindone has been performed. The reaction was performed by Marussia Bakunin in 1911 but the reaction products were not identified. Calculations allow us to know that the reaction occurred through the first excited singlet state. The nature of the first excited singlet state allowed the formation of both head-to-head and head-to-tail dimers. Finally, the main product was the syn-trans head-to-tail dimer, while the other two compounds found by Bakunin in lower yields were the syn-trans head-to-head dimer and the syn-cis head-to-tail dimer. The results described by Bakunin can not be interpreted assuming the reaction occurred through the formation of the excited triplet state.

Declarations

Conflict of Interest

The Authors declare that there is no conflict of interest.

References

  1. Colella, C. (2023). Magistero e scienza, ma non solo, nella lunga e operosa vita di Maria Bakunin, Atti del Simposio “Marussia Bakunin a 150 anni dalla nascita”, Napoli, 2 febbraio 2023, pp. 117-144, doi 10.32092/1108m
  2. Bakunin, M. (1900). Sulla formazione degli indoni in rapporto con le stereoisomerie e su di un nuovo metodo per la preparazione di indoni, anidridi ed eteri. Gazzetta Chimica Italiana, 30(II), 340-364.
  3. Bakunin, M., & Lanis, F. (1911). Reazioni fotochimiche dei nirofenilindoni. Nota I. Gazzetta Chimica Italiana, 41(II), 155-184.
  4. Bassani, D. M. (2004). The dimerization of cinnamic acid derivatives. In CRC Handbook of Oganic Photochemistry and Photobiology, Second Ed., Ed. By Horspool, W., and Lenci, F., CRC Press, Boca Raton, ISBN 0-8493-1348-1, pp. 20-1 – 20-20.
  5. Novak, M., Salemink, C. A., & Khan I. (1984). Biological activity of the alkaloids of Erythroxylum Coca and Erythroxylum Novogranatense. Journal of Ethnopharmacology, 10, 261-274. https://doi.org/10.1016/0378-8741(84)90015-1.
  6. D'Auria, M., Piancatelli, G. & Vantaggi, A. (1990). Photochemical Dimerization in Solution of Methyl 2-Furyl and 2-Thienyl-acrylate and Related Compounds. Journal of Chemical Society Perkin Transactions I, 2999-3002. https://doi.org/10.1039/P19900002999.
  7. D'Auria, M., D'Annibale, A., & Ferri, T. (1992) Photochemical Behaviour of Furylidene Carbonyl Compounds. Tetrahedron, 48, 9323-9336.
    8. https://doi.org/10.1016/S0040-4020(01)85622-2.
  8. D’Auria, M. (1996). Regio- and Stereochemical Control in the Photodimerization of Methyl 3-(2-Furyl)acrylate. Heterocycles, 43, 959-968. https://doi.org/10.3987/COM-95-7367.
  9. D’Auria, M., & Racioppi, R. (1997). Photochemical Dimerization in Solution of Arylacrylonitrile Derivatives. Tetrahedron, 53, 17307-17316. https://doi.org/10.1016/S0040-4020(97)10155-7.
  10. D’Auria, M., & Racioppi, R. (1998). Photochemical Dimerization of Esters of Urocanic Acid. Journal of Photochemistry and Photobiology, A: Chemistry, 112, 145-148. https://doi.org/10.1016/S1010-6030(97)00292-X.
  11. D’Auria, M., Emanuele, L., Mauriello, G., & Racioppi, R. (2000). Photochemical Dimerisation of 2-Vinylfuran and 2-Vinylthiophene Derivatives Bearing Electron-withdrawing Groups. Journal of Photochemistry and Photobiology, A: Chemistry, 134, 147-154. https://doi.org/10.1016/S1010-6030(00)00260-4.
  12. D’Auria, M. (2001). Photochemical Dimerization in Solution of Heterocyclic Substituted Alkenes bearing an Electron Withdrawing Group. Heterocycles, 54, 475-496. https://doi.org/10.3987/REV-00-SR(I)3
  13. D’Auria, M., Emanuele, L., Esposito, V., & Racioppi, R. (2002). The Photochemical Dimerization of 3-heteroaryl-acrylates. Arkivoc, 2002(11), 65-78. https://doi.org/10.3998/ark.5550190.0003.b08
  14. D'Auria, M. (2014). A DFT study of the photochemical dimerization of methyl 3-(2-furyl)acrylate and allyl urocanate. Molecules 19, 20482-20497. https://doi.org/10.3390/molecules191220482.
  15. Gaussian 09, Revision A.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
  16. Epiotis, N. D. (1974). The Theory of Pericyclic Reactions. Angewandte Chemie, International Edition in English, 13, 751-828. https://doi.org/10.1002/anie.197407511.
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