The structure and tautomerism of pyrrolotetrazoles have been studied with quantum-chemical methods (HF/6-31G** and DFT B3LYP/ANO-S) in the gas phase. According to the calculations of the total energies of various prototropic forms of these heterocyclic systems (1Н-, 3Н-, 5Н- and 7Н-tautomers), it was shown that for unsubstituted pyrrolotetrazole and its derivatives containing methyl substituents at the carbon atom(s), the most stable form is the 5Н-tautomer where aromaticity of the tetrazole fragment is maintained. On the contrary, for pyrrolotetrazoles with electron-withdrawing substituents (CN or Cl), the most stable form is the 1Н-tautomer, where the pyrrole fragment is aromatic. This effect may be determined by the differences of the relative electron accepting of the heterocyclic half-rings.
Similar content being viewed by others
Notes
Zubarev, V. Yu.; unpublished results; 2002.
References
D'Ischia, M.; Napolitano, A.; Pezzella, A. In Comprehensive Heterocyclic Chemistry III, Katritzky, A. R.; Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K., Eds.; Elsevier: Oxford, 2008, vol. 3, p. 357.
Trofimov, B. A.; Mikhaleva, A. I.; Schmidt, E. Yu.; Sobenina, L. N. Chemistry of Pyrroles, CRC Press (Taylor & Francis Group): New York, 2015.
Ostrovskii, V. A.; Koldobskii, G. I.; Trifonov, R. E. In Comprehensive Heterocyclic Chemistry III, Katritzky, A. R.; Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K., Eds.; Elsevier: Oxford, 2008, vol. 6, p. 257.
Ostrovskii, V. A.; Trifonov, R. E.; Popova, E. A. Russ. Chem. Bull., Int. Ed. 2012, 61, 768. [Izv. Akad. Nauk, Ser. Khim. 2012, 765].
Moderhack, D.; Decker, D. 14th International Congress of Heterocyclic Chemistry, Antwerpen, 1993, Abstracts of Papers, PO 3-211.
Moderhack, D.; Decker, D. Heterocycles 1994, 37, 683.
Moderhack, D.; Decker, D. J. Org. Chem. 1996, 61, 5646.
Moderhack, D.; Decker, D.; Holtmann, B. J. Chem. Soc., Perkin Trans. 1 2001, 720.
Moderhack, D.; Decker, D.; Holtmann, B. J. Chem. Soc., Perkin Trans. 1 2001, 729.
Suzuki, M.; Sato, K. JP Patent 05165172, 29.06.1993; Chem. Abstr. 1994, 120, 148794.
Vidal, L.; Malle, G. WO Patent 9735554, 02.10.1997; Chem. Abstr. 1997, 127, 311358.
Marco-Contelles, J.; Pérez-Mayoral, E.; Ballesteros, P. In Comprehensive Heterocyclic Chemistry III, Katritzky, A. R.; Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K., Eds.; Elsevier: Oxford, 2008, vol. 11, p. 199.
Hilt, G.; Hess, W.; Hengst, C. In Comprehensive Heterocyclic Chemistry III, Katritzky, A. R.; Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K., Eds.; Elsevier: Oxford, 2008, vol. 11, p. 351.
Moderhack, D. Heterocycles 2008, 75, 1.
Dulcere, J.-P.; Tawil, M.; Santelli, M. J. Org. Chem. 1990, 55, 571.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K. J.; Foresman, B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9; Gaussian, Inc.: Pittsburgh, 1998.
Karlström, G.; Lindh, R.; Malmqvist, P.-Å.; Roos, B. O.; Ryde, U.; Veryazov, V.; Widmark, P.-O.; Cossi, M.; Schimmelpfennig, B.; Neogrády, P.; Seijo, L. Comput. Mater. Sci. 2003, 28, 222.
Shchipanov, V. P. Chem. Heterocycl. Compd. 1983, 19, 909. [Khim. Geterotsikl. Soedin. 1983, 1130].
Kizhnyaev, V. N.; Vereshchagin, L. I. Russ. Chem. Rev. 2003, 72, 143. [Usp. Khim. 2003, 72, 159].
Ivashkevich, O. A.; Gaponik, P. N.; Koren, A. O.; Bubel, O. N.; Fronchek, E. V. Int. J. Quantum Chem. 1992, 43, 813.
Trifonov, R. E.; Alkorta, I.; Ostrovskii, V. A.; Elguero, J. J. Mol. Struct.: THEOCHEM 2004, 668, 123.
Pozharskii, A. F. Theoretical Fundamentals of Heterocyclic Chemistry [in Russian]; Khimiya: Moscow, 1985, p. 22.
Pozharskii, A. F. Chem. Heterocycl. Compd. 1985, 21, 717. [Khim. Geterotsikl. Soedin. 1985, 867].
Balaban, A. T.; Oniciu, D. C.; Katritzky, A. R. Chem. Rev. 2004, 104, 2777.
Krygowski, T. M.; Szatylowicz, H.; Stasyuk, O. A.; Dominikowska, J.; Palusiak, M. Chem. Rev. 2014, 114, 6383.
Shcherbakova, I.; Elguero, J.; Katritzky, A. R. In Advances in Heterocyclic Chemistry, Katritzky, A. R., Ed.; Academic Press: New York, 2000, vol. 77, p. 51.
This work was supported by the Russian Science Fund (project 14-50-00069). The authors express their gratitude to A. V. Gaenko for help in the DFT calculations.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Khimiya Geterotsiklicheskikh Soedinenii, 2015, 51(3), 246–249
Rights and permissions
About this article
Cite this article
Zubarev, V.Y., Trifonov, R.E., Ostrovskii, V.A. et al. A theoretical study of annular tautomerism of pyrrolotetrazoles in the gas phase. Chem Heterocycl Comp 51, 246–249 (2015). https://doi.org/10.1007/s10593-015-1692-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10593-015-1692-7