Skip to main content
SpringerLink
Log in

The first principle computational study for the competitive mechanisms of oxidative aromatization of 2-substituted imidazolines using KMnO4/SiO2

  • Original Paper
  • Published:
Journal of the Iranian Chemical Society Aims and scope Submit manuscript

Abstract

The efficiently oxidized various types of 2-substituted imidazolines to the corresponding imidazoles using potassium permanganate supported on silica gel (KMnO4/SiO2) under mild conditions and at room temperature have been reported before. In this study, the competitive concerted, catalytic stepwise (E 1 cb′ Cat .) and E 1 cb′ mechanisms of the oxidative aromatization process of 2-imidazolines to the corresponding imidazoles using KMnO4/SiO2 have been theoretically investigated by DFT-B3LYP/6-31G** method. The achieved data from this computational study confirmed that the reaction occurs by stepwise E 1 cb′ mechanism on the basis of the anomeric effect.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. P.W. Hochachka, G.N. Somero, Biochemical Adaptation: Mechanisms and Process in Physiological Evolution (Oxford University Press, New York, 2002)

    Google Scholar 

  2. T. Castaño, A. Encinas, C. Pérez, A. Castro, N.E. Campillo, C. Gil, Design, synthesis, and evaluation of potential inhibitors of nitric oxide synthase. Bioorg. Med. Chem. 16(11), 6193–6206 (2008)

    Article  Google Scholar 

  3. R.G. Bogle, G.S. Whitley, S.C. Soo, A.P. Johnstone, P. Vallance, Effect of anti-fungal imidazoles on mRNA levels and enzyme activity of inducible nitric oxide synthase. Br. J. Pharmacol. 111(4), 1257–1261 (1994)

    Article  CAS  Google Scholar 

  4. M.H. Khalid, Y. Tokunaga, A.J. Caputy, E. Walters, Inhibition of tumor growth and prolonged survival of rats with intracranial gliomas following administration of clotrimazole. J. Neurosurg. 103(1), 79–86 (2005)

    Article  CAS  Google Scholar 

  5. M.R. Sunderland, R.H. Cruickshank, S.J. Leighs, The efficacy of antifungal azole and antiprotozoal compounds in protection of wool from keratin-digesting insect larvae. Text. Res. J. 84(9), 924–931 (2014)

    Article  CAS  Google Scholar 

  6. I. Mohammadpoor-Baltork, M.A. Zolfigol, M. Abdollahi-Alibeik, Novel and chemoselective dehydrogenation of 2-substituted imidazolines with potassium permanganate supported on silica gel. Tetrahedron Lett. 45, 8687–8690 (2004)

    Article  CAS  Google Scholar 

  7. M.E. Campos, R. Jimenez, F. Martinez, H. Salgado, Heterocycles 40, 841–849 (1995)

    Article  CAS  Google Scholar 

  8. M.R. Grimmett, Part-3: five-membered rings with one oxygen, sulfur or nitrogen atom: 3.06-pyrroles and their benzo derivatives: (iii) synthesis and applications, in Comprehensive Heterocyclic Chemistry, vol. 4, ed. by K.T. Potts (Pergamon, Oxford, 1984)

  9. J.G. Lambardino, E.H. Wiseman, J. Med. Chem. 17, 1182–1188 (1974)

    Article  Google Scholar 

  10. H.G. Kim, J.K. Lee, J.T. Lee, C.S. Lee, Bull. Korean Chem. Soc. 21, 345–347 (2000)

    CAS  Google Scholar 

  11. G. Levesque, J.-C. Gressier, M. Proust, Synthesis 13, 963–965 (1981)

    Article  Google Scholar 

  12. I. Mohammadpoor-Baltork, M. Abdollahi-Alibeik, Bull. Korean Chem. Soc. 24, 1354–1356 (2003)

    Article  CAS  Google Scholar 

  13. J.H. Clark, Catalysis of Organic Reactions by Supported Inorganic Reagents (VCH, Weinheim, 1994)

    Google Scholar 

  14. D.G. Lee, Oxidizing agents, in Encyclopedia of Reagents for Organic Synthesis, ed. by L.A. Paquette (Wiley: New York, 1995)

  15. J.T.B. Ferreira, W.O. Cruz, P.C. Vieira, M. Yonashiro, J. Org. Chem. 52, 3698–3699 (1987)

    Article  Google Scholar 

  16. R. Jasiński, A new mechanistic insight on β-lactam systems formation from 5-nitroisoxazolidines. RSC Adv. 5, 50070–50072 (2015)

    Article  Google Scholar 

  17. A.B. Kącka, R.A. Jasiński, A density functional theory mechanistic study of thermal decomposition reactions of nitroethyl carboxylates: undermine of “pericyclic” insight. Heteroat. Chem. 27(5), 279–289 (2016)

    Article  Google Scholar 

  18. R. Jasiński, A. Kącka, A polar nature of benzoic acids extrusion from nitroalkyl benzoates: DFT mechanistic study. J. Mol. Mod. 21(3), 59 (2015)

    Article  Google Scholar 

  19. R. Jasiński, Molecular mechanism of thermal decomposition of fluoronitroazoxy compounds: DFT computational study. J. Fluor. Chem. 160, 29–33 (2014)

    Article  Google Scholar 

  20. A.A. Taherpour, F. Ghasemhezaveh, A. Yari, M.M. Khodaei, N2 elimination thermolysis reactions of 9-(4- and 5-substituted-1,2,3-triazol-1-yl)acridines to produce 1H-pyrido-[4,3,2-kl] derivatives—a theoretical study. Chem. Phys. Lett. 676, 154–168 (2017)

    Article  CAS  Google Scholar 

  21. E. Juaristi, G. Cuevas, Tetrahedron 48, 5019–5087 (1992)

    Article  CAS  Google Scholar 

  22. J.T. Edward, Chem. Ind. Lond. 36, 1102–1104 (1955)

    Google Scholar 

  23. M.A. Zolfigol, M. Kiafar, M. Yarie, A.A. Taherpour, T. Fellowes, A.N. Hancok, A. Yari, J. Mol. Struct. 1137, 674–680 (2017)

    Article  CAS  Google Scholar 

  24. M.A. Zolfigol, M. Safaiee, B. Ebrahimghasri, S. Baghery, S. Alaie, M. Kiafar, A.A. Taherpour, Y. Bayat, A. Asgari, J. Iran. Chem. Soc. 1–14 (2017) (inpress)

  25. M.A. Zolfigol, M. Kiafar, M. Yarie, A.A. Taherpour, M. Saeidi-Rad, RSC Adv. 6, 50100–50111 (2016)

    Article  CAS  Google Scholar 

  26. M. Kiafar, M.A. Zolfigol, M. Yarie, A.A. Taherpour, RSC Adv. 6, 102280–102291 (2016)

    Article  CAS  Google Scholar 

  27. M. Kiafar, M.A. Zolfigol, M. Yarie, A.A. Taherpour, RSC Adv. 6, 107295 (2016)

    Article  CAS  Google Scholar 

  28. Spatran’10-Quantum Mechanics Program: (PC/x86)-1.1.0v4.2011, Wavefunction Inc., USA

  29. E.V. Anslyn, D.A. Dougherty, Modern Physical Organic Chemistry (University Science Books, Sausalito, 2006)

    Google Scholar 

  30. D.L. Pavia, G.M. Lampman, G.S. Kriz, Introduction to Spectroscopy; A Guid for Students of Organic Chemistry, 2nd edn. (Fort Worth Harcourt College Publishers, New York, 2001)

    Google Scholar 

  31. B. Maji, M.K. Barman, Synthesis 49, 3377–3393 (2017)

    Article  CAS  Google Scholar 

  32. N.N. Greenwood, A. Earnshaw, Chemistry of the Elements (Pergamon Press, Oxford, 1984), pp. 1221–1222

    Google Scholar 

  33. A. Carrington, M.C.R. Symons, Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxyanions. J. Chem. Soc. 3373–3380 (1956). doi:10.1039/JR9560003373

  34. D.G. Lee, T. Chen, Reduction of manganate(VI) by mandelic acid and its significance for development of a general mechanism of oxidation of organic compounds by high-valent transition metal oxides. J. Am. Chem. Soc. 115(24), 11231–11236 (1993)

    Article  CAS  Google Scholar 

  35. R.E. Schreiber, H. Cohen, G. Leitus, S.G. Wolf, A. Zhou, L. Que, R. Neumann, Reactivity and O2 formation by Mn(IV)- and Mn(V)-hydroxo species stabilized within a polyfluoroxometalate framework. J. Am. Chem. Soc. 137, 8738–8748 (2015)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors have acknowledged the Theoretical and Computational Research Center of Chemistry Faculty of Razi University-Kermanshah-Iran and Medical Biology Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran.

Author information

Authors and Affiliations

  1. Department of Organic Chemistry, Faculty of Chemistry, Razi University, P.O.Box: 67149-67346, Kermanshah, Iran

    Avat Arman Taherpour, Ako Yari & Fatemeh Ghasemhezaveh

  2. Medical Biology Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran

    Avat Arman Taherpour

  3. Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran

    Mohammad Ali Zolfigol

Authors
  1. Avat Arman Taherpour
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ako Yari
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Fatemeh Ghasemhezaveh
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohammad Ali Zolfigol
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Avat Arman Taherpour.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 861 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Taherpour, A.A., Yari, A., Ghasemhezaveh, F. et al. The first principle computational study for the competitive mechanisms of oxidative aromatization of 2-substituted imidazolines using KMnO4/SiO2 . J IRAN CHEM SOC 14, 2485–2493 (2017). https://doi.org/10.1007/s13738-017-1183-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13738-017-1183-0

Keywords

Search

Navigation