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The structure of protonated 3-pyridyl-substituted 5-amino-1H-1,2,4-triazoles: an experimental and theoretical study

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Abstract

The molecular and crystal structures and tautomerism of protonated isomeric 3-pyridyl- substituted 5-amino-1H-1,2,4-triazoles were studied within the framework of density function- al theory and by X-ray analysis. According to B3LYP/6-311++G(2d,2p) calculations of six possible tautomeric forms A-F, tautomers A with the N-protonated pyridine moiety are predominant in the gas phase. 5-Amino-4H-1-onium compounds (tautomers D) of higher polarity are next in stability; their relative energies decrease as follows: 3-pyridin-4-yl-, 3-pyridin-3-yl-, and 3-pyridin-2-yl-5-amino-4H-1,2,4-triazol-1-onium cation. A comparison of experimental 13C NMR spectra of tautomers A and D with their NMR spectra calculated by the GIAO method showed that both tautomeric forms can coexist in comparable amounts in DMSO solutions. Tautomers A and D were detected by X-ray analysis in crystals of 5-amino-3-(pyrid- in-2-yl)-1H-1,2,4-triazolium salts.

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References

  1. EP Pat. 2125817 A1.

  2. C. A. Lipinski, J. Med. Chem., 1983, 26, 1.

    Article  CAS  Google Scholar 

  3. X. Ouyang, X. Chen, E. L. Piatnitski, A. S. Kiselyov, H.-Y. He, Y. Mao, V. Pattaropong, Y. Yu, K. H. Kim, J. Kincaid, L. Smith II, W. C. Wong, S. P. Lee, D. L. Milligan, A. Malikzay, J. Fleming, J. Gerlak, D. Deevi, J. F. Doody, H.-H. Chiang, Sh. N. Patel, Y. Wang, R. L. Rolser, P. Kussie, M. Labelle, M. C. Tuma, Bioorg. Med. Chem. Lett., 2005, 15, 5154.

    Article  CAS  Google Scholar 

  4. A. V. Dolzhenko, B. J. Tan, A. V. Dolzhenko, G. N.Ch. Chiu, W. K. Chui, J. Fluorine Chem., 2008, 129, 429.

    Article  CAS  Google Scholar 

  5. M. D. Rainey, M. E. Charlton, R. V. Stanton, M. B. Kastan, Cancer Res., 2008, 68, 7466.

    Article  CAS  Google Scholar 

  6. K. Guo, A. A. Shelat, R. K. Guy, M. B. Kastan, J. Biomol. Screening, 2014, 19, 1.

    Article  CAS  Google Scholar 

  7. L. Mishra, V. J. Ram, D. S. Kushwaha, Transition. Met. Chem., 1989, 14, 384.

    Article  CAS  Google Scholar 

  8. S. Ferrer, R. Ballesteros, A. Sambartolome, M. Gonzalez, G. Alzuet, J. Borras, M. Liu, J. Inorg. Biochem., 2004, 98, 1436.

    Article  CAS  Google Scholar 

  9. A. Castineiras, I. Garcia-Santos, Z. Anorg. Allg. Chem., 2008, 634, 2907.

    Article  CAS  Google Scholar 

  10. V. M. Chernyshev, E. V. Tarasova, A. V. Chernysheva, V. B. Rybakov, Acta Crystallogr., Sect. E: Struct. Rep. Online, 2011, 67, o466.

  11. V. M. Chernyshev, E. V. Tarasova, A. V. Chernysheva, V. A. Taranushich, Russ. J. Appl. Chem. (Engl. Transl.), 2011, 84, 1890 [Zh. Prikl. Khim., 2011, 84, 1804].

    Article  CAS  Google Scholar 

  12. E. Anders, K. Wermann, B. Wiedel, J.-J. Vanden Eynde, Liebigs Ann./Recueil, 1997, 745.

    Google Scholar 

  13. M. Daszkiewicz, M. K. Marchewka, Spectrochim. Acta, Part A, 2012, 95, 204.

    Article  CAS  Google Scholar 

  14. A. D. Becke, J. Chem. Phys., 1993, 98, 1372.

    Article  CAS  Google Scholar 

  15. 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, D. J. Fox, Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford, 2009.

    Google Scholar 

  16. J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev., 2005, 105, 2999.

    Article  CAS  Google Scholar 

  17. R. Ditchfield, Mol. Phys., 1974, 27, 789.

    Article  CAS  Google Scholar 

  18. F. Blanco, I. Alkorta, J. Elguero, Magn. Reson. Chem., 2007, 45, 797.

    Article  CAS  Google Scholar 

  19. I. Alkorta, J. Elguero, A. Font, J. Galcera, I. Mata, E. Molins, A. Virgili, Tetrahedron, 2014, 70, 2784.

    Article  CAS  Google Scholar 

  20. G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr., 2008, 64, 112.

    Article  CAS  Google Scholar 

  21. V. I. Minkin, A. D. Garnovskii, J. Elguero, Adv. Heterocycl. Chem., 2000, 76, 157.

    Article  CAS  Google Scholar 

  22. A. V. Dolzhenko, G. Pastorin, A. V. Dolzhenko, W.-K. Chui, Tetrahedron Lett., 2009, 50, 2124.

    Article  CAS  Google Scholar 

  23. M. Pagacz-Kostrzewa, R. Bronisz, M. Wierzejewska, Chem. Phys. Lett., 2009, 473, 238.

    Article  CAS  Google Scholar 

  24. V. M. Chernyshev, A. V. Chernysheva, Z. A. Starikova, Heterocycles, 2010, 81, 2291.

    Article  CAS  Google Scholar 

  25. A. V. Astakhov, V. M. Chernyshev, Chem. Heterocycl. Compd. (Engl. Transl.), 2014, 50, 319 [Khim. Geterotsikl. Soedinenii, 2014, 349].

    Article  CAS  Google Scholar 

  26. W. P. Oziminski, Tetrahedron, 2013, 69, 3197.

    Article  CAS  Google Scholar 

  27. T. Lukmanov, S. P. Ivanov, E. M. Khamitov, S. L. Khursan, Comput. Theor. Chem., 2013, 1023, 38.

    Article  CAS  Google Scholar 

  28. R. M. Claramunt, C. López, M. D. Santa María, D. Sanz, J. Elguero, Prog. Nucl. Magn. Reson. Spectrosc., 2006, 49, 169.

    Article  CAS  Google Scholar 

  29. V. M. Chernyshev, A. V. Astakhov, V. V. Ivanov, Z. A. Starikova, Acta Crystallogr., Sect. E: Struct. Rep. Online, 2010, 66, o1644.

  30. A. V. Dolzhenko, G. K. Tan, L. L. Koh, A. V. Dolzhenko, W. K. Chui, Acta Crystallogr., Sect. E: Struct. Rep. Online, 2009, 65, o125.

  31. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.

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Authors and Affiliations

  1. Platov South-Russian State Polytechnic University, 132 ul. Prosveshcheniya, 346428 Novocherkassk, Rostov Region, Russian Federation

    V. M. Chernyshev, A. V. Astakhov, A. V. Chernysheva & E. V. Tarasova

  2. M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991, Moscow, Russian Federation

    V. B. Rybakov

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  1. V. M. Chernyshev
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  2. A. V. Astakhov
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  3. V. B. Rybakov
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  4. A. V. Chernysheva
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  5. E. V. Tarasova
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Correspondence to V. M. Chernyshev.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2591—2598, December, 2014.

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Chernyshev, V.M., Astakhov, A.V., Rybakov, V.B. et al. The structure of protonated 3-pyridyl-substituted 5-amino-1H-1,2,4-triazoles: an experimental and theoretical study. Russ Chem Bull 63, 2591–2598 (2014). https://doi.org/10.1007/s11172-014-0784-3

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  • DOI: https://doi.org/10.1007/s11172-014-0784-3

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