Skip to main content
SpringerLink
Log in

Quantum chemical studies of azoles 2. Thermodynamic stability of neutral molecules and intermediates formed during electrophilic substitution of 1,2- and 1,3-azoles

  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

The thermodynamic stability of 1,2- and 1,3-azole molecules, as well as of cationic and bipolar (carbenoid) intermediates in the gas phase and in aqueous solution formed by electrophilic substitution (proton as a model electrophile) was compared based on the analysis of quantum chemical calculations performed at the DFT/B3LYP/6-31G(D) level of theory with zero-point energy corrections. The differences in the chemical behavior of the isomeric 1,2- and 1,3-azole pairs, viz., pyrazole—imidazole, isoxazole—oxazole, and isothiazole—thiazole, were considered.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. L. I. Belenkii, I. D. Nesterov, N. D. Chuvylkin, Chem.-Heterocycl. Compd. (Engl. Transl.), 2013, 49, 1611 [Khim.-Geterotsikl. Soedin., 2013, 1739].

    Google Scholar 

  2. L. I. Belen’kii, N. D. Chuvylkin, Chem. Heterocycl. Compd.-(Engl. Transl.), 1996, 32, 1319 [Khim. Geterotsikl. Soedin., 1996, 1535].

    Google Scholar 

  3. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrewski, J. A. Mont-gomery, Jr., R. E. Stratmann, J. C. Burrant, S. S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. S. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Menucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochters-ki, G. A. Peterson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malik, A. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomp-erts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe,. V. Gill, B. Johnson, W. Heng, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Revision A. 5, Gaussian Inc., Pittsburgh (PA), 1998.

    Google Scholar 

  4. L. I. Belen’kii, T. G. Kim, I. A. Suslov, N. D. Chuvylkin, Russ. Chem. Bull. (Ind. Ed.), 2005, 54, 853 [Izv. Akad. Nauk, Ser. Khim., 2005, 837].

    Article  Google Scholar 

  5. L. I. Belen’kii, N. D. Chuvylkin, I. D. Nesterov, Chem. Heterocycl. Compd. (Engl. Transl.), 2012, 48, 241 [Khim. Geterotsikl. Soedin., 2012, 256].

    Google Scholar 

  6. N. D. Chuvylkin, I. D. Nesterov, L. I. Belenkii, Russ. Chem. Bull. (Engl. Transl.), 2007, 56, 1481 [Izv. Akad. Nauk, Ser. Khim., 2007, 1425].

    Article  CAS  Google Scholar 

  7. F. Freeman, D. J. Lau, A. R. Patel, P. R. Pavia, J. D. Willey, J. Phys. Chem. A, 2008, 112, 8775.

    Article  CAS  Google Scholar 

  8. A. J. Arduengo III, H. V. Rasina Dias, R. L. Harlow, M. Kline, J. Am. Chem. Soc., 1992, 114, 5530.

    Article  CAS  Google Scholar 

  9. A. J. Arduengo III, H. V. Rasina Dias, D. A. Dixon, R. L. Harlow, T. F. Koetze, J. Am. Chem. Soc., 1994, 116, 6812.

    Article  CAS  Google Scholar 

  10. A. J. Arduengo III, H. R. Goerlich, W. J. Marshall, J. Liebigs Ann. Chem., 1997, 365.

    Google Scholar 

  11. W. A. Herrmann, Angew. Chem., Int. Ed., 2002, 41, 1290.

    Article  CAS  Google Scholar 

  12. F. E. Hah, M. C. Jahke, Angew. Chem., Int. Ed., 2008, 47, 3122.

    Article  Google Scholar 

  13. N. I. Korotkikh, V. Sh. Saberov, N. V. Glinyanaya, K. A. Marichev, A. V. Kiselev, A. V. Knishevitskii, G. F. Raenko, O. P. Shvaika, Chem. Heterocycl. Compd. (Engl. Transl.), 2013, 49, 19 [Khim. Geterotsikl. Soedin., 2013, 25].

    Article  CAS  Google Scholar 

  14. A. Schmidt, A. Dreger, Curr. Org. Chem., 2011, 15, 2897.

    Article  CAS  Google Scholar 

  15. J. Wolf, W. Böhlmann, M. Findeisen, T. Gelbrch, H.-J. Hoff-mann, B. Schulze, Angew. Chem., Int. Ed., 2007, 46, 3118.

    Article  CAS  Google Scholar 

  16. A. DeHope, V. Lavaleo, B. Donnadieu, W. W. Schneller, G. Bertrand, Angew. Chem., Int. Ed., 2007, 46, 6922.

    Article  CAS  Google Scholar 

  17. J. Wolf, W. Bõhlmann, M. Findeisen, T. Gelbrch, H.-J. Hoff-mann, B. Schulze, Angew. Chem., Int. Ed., 2007, 46, 6926.

    Article  CAS  Google Scholar 

  18. F. M. Stoyanovich, in Novye napravleniya khimii tiofena [New Directions in Chemistry of Thiophene], Ed. Ya. L. Goldfarb, Nauka, Moscow, 1976, p. 96 (in Russian).

    Google Scholar 

  19. Y. Wang, H. Li, S. Han, J. Chem. Phys., 2005, 174501.

    Google Scholar 

  20. M. Buehl, A. Chaumont, R. Schurhammer, G. Wipf, J. Phys. Chem. B, 2005, 109, 18591.

    Article  CAS  Google Scholar 

  21. E. R. Talaty, S. Raja, V. J. Storhaug, A. Doelle, W. R. Carp-er, J. Phys. Chem. B, 2004, 108, 13177.

    Article  CAS  Google Scholar 

  22. N. E. Heimer, R. E. Del Sesto, Z. Meng, J. S. Wilkes, W. R. Carper, J. Mol. Liq., 2006, 124, 84. Cited from Comprehen-sive Heterocyclic Chemistry III, Eds A. R. Katritzky, C. A. Ramsden, E. F. V. Scriven, R. J. K. Taylor, Elsevier, Oxford, 2008, v. 4, p. 149.

    Article  CAS  Google Scholar 

  23. H. Chen, D. R. Justes, R. G. Cooks, Org. Lett., 2005, 7, 3949.

    Article  CAS  Google Scholar 

  24. V. A. Ostrovskii, G. V. Erusalimskii, M. B. Shcherbina, Russ. J. Org. Chem. (Engl. Transl.), 1993, 29, 1073 [Zh. Org. Khim., 1993, 29, 1297].

    Google Scholar 

  25. R. B. Woodward, R. A. Olofson, J. Am. Chem. Soc.,1961, 83, 1007.

    Article  CAS  Google Scholar 

  26. L. I. Belenkii, Chem. Heterocycl. Compd. (Engl. Transl.), 1986, 22, 587 [Khim. Geterotsikl. Soedin., 1986, 749].

    Article  Google Scholar 

  27. A. Albert, Heterocyclic Chemistry. An Introduction, The Athlone Press, University of London, 1959, 424 pp.

    Google Scholar 

  28. M. W. Austin, J. R. Blackborow, J. H. Ridd, B. V. Smith, J. Chem. Soc., 1965, 1051.

    Google Scholar 

  29. I. I. Grandberg, S. V. Tabak, N. I. Bobrova, A. N. Kost, L. G. Vasina, Chem. Heterocycl. Compd. (Engl. Transl.), 1965, 1, 271 [Khim. Geterotsikl. Soedin., 1965, 407].

    Article  Google Scholar 

  30. L. I. Belenkii, V. S. Bogdanov, I. A. Abronin, G. P. Gromova, M. A. Cheskis, R. Z. Zakharyan, Chem. Scripta, 1985, 25, 266.

    CAS  Google Scholar 

  31. L. I. Belenkii, M. A. Cheskis, Chem. Heterocycl. Compd. (Engl. Transl.), 1984, 20, 713 [Khim. Geterotsikl. Soedin., 1984, 881].

    Article  Google Scholar 

  32. L. I. Belenkii, G. P. Gromova, M. A. Cheskis, Ya. L. Goldfarb, Chem. Scripta, 1985, 25, 295.

    CAS  Google Scholar 

  33. M. A. Khan, B. M. Lynch, Y.-Y. Hung, Canad. J. Chem., 1963, 41, 1540.

    Article  CAS  Google Scholar 

  34. B. M. Lynch, Y.-Y. Hung, Canad. J. Chem., 1964, 42, 1605.

    Article  CAS  Google Scholar 

  35. M. R. Grimmett, S. R. Hartshorn, K. Schofield, J. B. Weston, J. Chem. Soc., Perkin Trans. 2, 1972, 1654.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    L. I. Belen´kii, I. D. Nesterov & N. D. Chuvylkin

Authors
  1. L. I. Belen´kii
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. D. Nesterov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. N. D. Chuvylkin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to L. I. Belen´kii.

Additional information

For Part 1, see Ref. 1.

Dedicated to Academician of the Russian Academy of Sciences Yu. N. Bubnov on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2236–2242, October, 2014.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Belen´kii, L.I., Nesterov, I.D. & Chuvylkin, N.D. Quantum chemical studies of azoles 2. Thermodynamic stability of neutral molecules and intermediates formed during electrophilic substitution of 1,2- and 1,3-azoles. Russ Chem Bull 63, 2236–2242 (2014). https://doi.org/10.1007/s11172-014-0728-y

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11172-014-0728-y

Key words

Search

Navigation