Advertisement

Chemistry of Heterocyclic Compounds

, Volume 44, Issue 12, pp 1472–1482 | Cite as

Quantum-chemical investigation of certain physicochemical properties of C-nitro-1,2,3-triazole and N-alkyl-4(5)-nitro-1,2,3-triazoles

  • O. A. Ivashkevich
  • Vadim E. Matulis
  • P. N. Gaponik
  • G. T. Sukhanov
  • J. V. Filippova
  • A. G. Sukhanova
Article

Quantum-chemical calculations have been carried out on molecular electrostatic potentials, proton affinity in the gas phase, gas phase basicity, and pK BH+ values in aqueous solution for C-nitro- and N-alkyl-4(5)-nitro-1,2,3-triazoles, and the relative stability of the isomeric N-alkyl-4(5)-nitrotriazoles (alkyl = Me, Et, i-Pr, t-Bu) in the gas phase and in aqueous solution. For all the studied substances in the gas phase the 2H-tautomer and the N(2)-isomers were considerably more stable than the corresponding N(1) compounds, and the 3H-tautomer and N(3)-isomer were the least stable. In aqueous solution 1- and 3-isomers had close values of energies, but in the case of C-nitro-1,2,3-triazole the 1H form became even more stable than the 2H-form. It was established which ring nitrogen atoms of 1,2,3-triazoles are protonated in the gas phase and in solution. The obtained data correlate well with the results of experimental investigations on the alkylation of 1,2,3-triazoles in acidic and basic media and of the experimental investigation on the alkylation of C-nitro-1,2,3-triazoles with diethyl sulfate carried out in the present work.

Keywords

4(5)-nitro-1,2,3-triazoles alkylation quantum-chemical calculations B3LYP method basicity 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    V. P. Krivopalov and O. P. Shkurko, Usp. Khim., 74, 369 (2005).Google Scholar
  2. 2.
    L. I. Vereshchagin, N. I. Kuznetsova, L. P. Kirillova, G. T. Sukhanov, and V. V. Shcherbakov, Khim. Geterotsikl. Soedin., 932 (1986). [Chem. Heterocycl. Comp., 22, 745 (1986)].Google Scholar
  3. 3.
    V. Jimenez and J. B. Alderete, Theochem, 775, 1 (2006).CrossRefGoogle Scholar
  4. 4.
    M. Begtrup, C. J. Nielsen, L. Nygaard, S. Samdal, C. E. Sogren, and G. O. Sorensen, Acta Chem. Scand. A42, 500 (1988).CrossRefGoogle Scholar
  5. 5.
    P. Politzer, M. E. Grice, and J. M. Seminario, Int. J. Quant. Chem., 61, 389 (1997).CrossRefGoogle Scholar
  6. 6.
    J.-L. M. Abbound, C. Foces-Foces, R. Notario, R. E. Trifonov, A. P. Volovodenko, V. A. Ostrovskii, I. Alkorta, and J. Elguero, Eur. J. Org. Chem., 3013 (2001).Google Scholar
  7. 7.
    W. P. Oziminski, J. Cz. Dobrowolski, and A. P. Mazurek, J. Mol. Struct., 651–653, 697 (2003).CrossRefGoogle Scholar
  8. 8.
    L. Birkofer and P. Wegner, Chem. Ber., 100, 3485 (1967).CrossRefGoogle Scholar
  9. 9.
    P. Ykman, G. L’abbe, and G. Smets, Tetrahedron Lett., 5225 (1970).Google Scholar
  10. 10.
    E. P. L. Hunter and S. G. Lias, J. Phys. Chem. Ref. Data, 27, 413 (1998).CrossRefGoogle Scholar
  11. 11.
    J. Catalan, J.-L. M. Abbound, and J. Elguero, Adv. Heterocycl. Chem., 41, 187 (1987).CrossRefGoogle Scholar
  12. 12.
    R. E. Trifonov, V. A. Ostrovskii, L. I. Vereshchagin, M. B. Shcherbinin, N. P. Shirokova, and A. O. Koren', Zh. Org. Khim., 31, 928 (1995).Google Scholar
  13. 13.
    R. E. Trifonov, M. B. Shcherbinin, and V. A. Ostrovskii, Zh. Org. Khim., 33, 1116 (1997).Google Scholar
  14. 14.
    Vad. E. Matulis, Thesis for Candidate of Chemical Sciences, Minsk (2005).Google Scholar
  15. 15.
    O. Koren, J. Heterocycl. Chem., 39, 1111 (2002).CrossRefGoogle Scholar
  16. 16.
    M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, J. T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Revision B.03, Gaussian Inc., Pittsburgh, PA (2003).Google Scholar
  17. 17.
    A. D. Becke, J. Chem. Phys., 98, 5648 (1993).CrossRefGoogle Scholar
  18. 18.
    P. N. Gaponik, S. V. Voitekhovich, A. S. Lyakhov, Vadim E. Matulis, O. A. Ivashkevich, M. Quesada, and J. Reedijk, Inorg. Chim. Acta, 358, 2549 (2005).CrossRefGoogle Scholar
  19. 19.
    P. N. Gaponik, M. M. Degtyarik, A. S. Lyakhov, Vadim E. Matulis, O. A. Ivashkevich, M. Quesada, and J. Reedijk, Inorg. Chim. Acta, 358, 3949 (2005).CrossRefGoogle Scholar
  20. 20.
    Vadim E. Matulis, A. S. Lyakhov, P. N. Gaponik, S. A. Voitekhovich, and O. A. Ivashkevich, J. Mol. Struct., 649, 309 (2003).CrossRefGoogle Scholar
  21. 21.
    F. Eckert and A. Klamt, AIChE J., 48, 369 (2002).CrossRefGoogle Scholar
  22. 22.
    O. A. Ivashkevich, P. N. Gaponik, Vit. E. Matulis, and Vad. E. Matulis, Zh. Obshch. Khim., 73, 296 (2003).Google Scholar
  23. 23.
    M. W. Wong, R. Leung-Toung, and C. Wentrup, J. Am. Chem. Soc., 115, 2465 (1993).CrossRefGoogle Scholar
  24. 24.
    A. P. Mazurek and N. Sadlej-Sosnowska, Chem. Phys. Lett., 330, 212 (2000).CrossRefGoogle Scholar
  25. 25.
    L. V. Gurvich, G. A. Khachkuruzov, V. A. Medvedev, I. V. Veits, G. A. Bergman, V. S. Yungman, N. P. Rtishcheva, L. F. Kuratova, G. N. Yurkov, A. A. Kane, B. F. Yudin, B. I. Brounshtein, V. F. Baibuz, V. A. Kvlividze, E. A. Prozorovskii, and B. A. Vorob'ev, Thermodynamic Properties of Individual Substances [in Russian], Akad. Nauk SSSR, Moscow (1962).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2008

Authors and Affiliations

  • O. A. Ivashkevich
    • 1
  • Vadim E. Matulis
    • 1
  • P. N. Gaponik
    • 1
  • G. T. Sukhanov
    • 2
  • J. V. Filippova
    • 2
  • A. G. Sukhanova
    • 2
  1. 1.Research Institute of Physical and Chemical ProblemsBelarusian State UniversityMinskBelarus
  2. 2.Institute for Problems of Chemical and Energetic TechnologiesSiberian Branch of the Russian Academy of SciencesBiyskRussia

Personalised recommendations