Advertisement

Journal of Molecular Modeling

, Volume 19, Issue 9, pp 3529–3535 | Cite as

A comparative study of the aromaticity of pyrrole, furan, thiophene, and their aza-derivatives

  • Kalbinur Najmidin
  • Ablikim KerimEmail author
  • Paruza Abdirishit
  • Horigul Kalam
  • Tursungul Tawar
Original Paper
First Online:

Abstract

The relative aromaticity of pyrrole, furan, thiophene, and their aza-derivatives has been examined using TRE (topological resonance energy), MRE (magnetic resonance energy), ring current (RC), and ring current diamagnetic susceptibility (χG) methods. The results obtained were compared with results obtained by others who used the energetic method ASE (aromatic stabilization energy), the geometric method HOMA (harmonic oscillator model of aromaticity), and the magnetic method NICS(1) (nucleus-independent chemical shift). The impact of nitrogen atoms on the aromaticity of the aza-derivatives of pyrrole, furan, and thiophene is discussed. An excellent correlation was found between the energetic (TRE, MRE) and magnetic (RC and χG) criteria of aromaticity for all compounds. It was expected that inclusion of a heteroatom would decrease the aromaticity relative to the cyclopentadienyl anion. Our results show that the type of the first heteroatom, which donates two electrons to the system, as well as the number of nitrogen atoms and their positions in the molecule have a strong effect on aromaticity. In general, aromaticity is enhanced when the nitrogen atom is adjacent to the first heteroatom. The magnitude of aromaticity is related closely with the uniformity of distribution of π-electrons in the molecule.

Keywords

Aromaticity Azoles Diatropicity Resonance energy NICS(1) 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

This work was supported financially by the Natural Science Foundation of China (No. 21262037), and by the Urumqi Science and Technology Project (No. H101133001) of the Xinjiang Uyghur Autonomous Region, China.

References

  1. 1.
    Minkin VI, Glukhovtsev MN, Simkin BY (1994) Aromaticity and antiaromaticity. Wiley, New YorkGoogle Scholar
  2. 2.
    Aihara J (1976) J Am Chem Soc 98:2750–2758CrossRefGoogle Scholar
  3. 3.
    Gutman I, Milun M, Trinajstic N (1977) J Am Chem Soc 99:1692–1704CrossRefGoogle Scholar
  4. 4.
    Kruszewski J, Krygowski TM (1972) Tetrahedron Lett 13:3839–3842CrossRefGoogle Scholar
  5. 5.
    Krygowski TM (1993) J Chem Inf Comput Sci 33:70–78CrossRefGoogle Scholar
  6. 6.
    Chen ZF, Wannere CS, Corminboeuf C, Puchta R, Schleyer PvR (2005) Chem Rev 105:3842–3888CrossRefGoogle Scholar
  7. 7.
    Gomes JANF, Mallion RB (2001) Chem Rev 101:1349–1383CrossRefGoogle Scholar
  8. 8.
    Islas R, Heine T, Merino G (2012) Acc Chem Res 45:215–228CrossRefGoogle Scholar
  9. 9.
    Lazzeretti P (2000) Prog Nucl Magn Reson Spectrosc 36:1–88CrossRefGoogle Scholar
  10. 10.
    Poater J, Duran M, Sola M, Silvi B (2005) Chem Rev 105:3911–3947CrossRefGoogle Scholar
  11. 11.
    Merino G, Vela A, Heine T (2005) Chem Rev 105:3812–3841CrossRefGoogle Scholar
  12. 12.
    Arkin R, Kerim A (2012) Chem Phys Lett 546:144–149CrossRefGoogle Scholar
  13. 13.
    Aihara J (2003) Bull Chem Soc Jpn 76:103–105CrossRefGoogle Scholar
  14. 14.
    Poater J, Garcia-Cruz I, Illas F, Sola M (2004) Phys Chem Chem Phys 6:314–318CrossRefGoogle Scholar
  15. 15.
    Stanger A (2009) Chem Commun 15:1939–1947CrossRefGoogle Scholar
  16. 16.
    Omelchenko IV, Shishkin OV, Gorb L, Leszczynski J, Fiase S, Bultinck P (2011) Phys Chem Chem Phys 13:20536–20548CrossRefGoogle Scholar
  17. 17.
    Islas R, Martinez-Guajardo G, Jimenez-Halla JOC, Sola M, Merino G (2010) J Chem Theory Comput 6:1131–1135CrossRefGoogle Scholar
  18. 18.
    Feixas F, Matito E, Poater J, Sola M (2008) J Comput Chem 29:1543–1554CrossRefGoogle Scholar
  19. 19.
    Schleyer PvR, Maerker C, Dransfeld A, Jiao HJ, van Eikema Hommes NJR (1996) J Am Chem Soc 118:6317–6318CrossRefGoogle Scholar
  20. 20.
    Lu X, Chen ZF (2005) Chem Rev 105:3643–3696CrossRefGoogle Scholar
  21. 21.
    Castro AC, Osorio E, Jimenez-Halla JOC, Matito E, Tiznado W, Gabriel Merino G (2010) J Chem Theory Comput 6:2701–2705CrossRefGoogle Scholar
  22. 22.
    Fallah-Bagher-Shaidaei H, Wannere CS, Corminboeuf C, Puchta R, Schleyer PvR (2006) Org Lett 8:863–866CrossRefGoogle Scholar
  23. 23.
    Corminboeuf C, Heine T, Seifert G, Schleyer PvR, Weber J (2004) Phys Chem Chem Phys 6:273–276CrossRefGoogle Scholar
  24. 24.
    Ramsden AC (2010) Tetrahedron 66:2695–2699CrossRefGoogle Scholar
  25. 25.
    Krygowski TM, Oziminski WP, Ramsden AC (2011) J Mol Model 17:1427–1433CrossRefGoogle Scholar
  26. 26.
    Hehre WJ, McIver RT, Pople JA, Schleyer PvR (1974) J Am Chem Soc 96:7162–7163CrossRefGoogle Scholar
  27. 27.
    Radom L (1974) J Chem Soc Chem Commun 1974:403–404Google Scholar
  28. 28.
    George P, Trachtman M, Brett AM, Bock CW (1977) J Chem Soc Perkin Trans 2:1036–1047Google Scholar
  29. 29.
    Aihara J, Kanno H, Ishida T (2007) J Phys Chem A 111:8873–8876CrossRefGoogle Scholar
  30. 30.
    Aihara J (2006) J Am Chem Soc 128:2873–2879CrossRefGoogle Scholar
  31. 31.
    Aihara J (1981) Bull Chem Soc Jpn 54:1245–1246CrossRefGoogle Scholar
  32. 32.
    Aihara J, Horikawa T (1983) Bull Chem Soc Jpn 56:1853CrossRefGoogle Scholar
  33. 33.
    Aihara J (1985) J Am Chem Soc 107:298–302CrossRefGoogle Scholar
  34. 34.
    Aihara J (1979) J Am Chem Soc 101:5913–5917CrossRefGoogle Scholar
  35. 35.
    Aihara J, Horikawa T (1983) Chem Phys Lett 95:561–563CrossRefGoogle Scholar
  36. 36.
    Aihara J, Ishida T (2010) J Phys Chem A 114:1093–1097CrossRefGoogle Scholar
  37. 37.
    Van-Catledge FA (1980) J Org Chem 45:4801–4802CrossRefGoogle Scholar
  38. 38.
    Alonso M, Herradon B (2007) Chem Eur J 13:3913–3923CrossRefGoogle Scholar
  39. 39.
    Cioslowski J, Matito E, Sola M (2007) J Phys Chem A 111:6521–6525CrossRefGoogle Scholar
  40. 40.
    Giambiagi M, de Giambiagi MS, dos Santos CD, de Figueiredo AP (2000) Phys Chem Chem Phys 2:3381–3392CrossRefGoogle Scholar
  41. 41.
    Cyranski MK, PvR S, Krygowski TM, Jiao HJ (2003) Tetrahedron 59:1657–1665CrossRefGoogle Scholar
  42. 42.
    Cordell FR, Boggs JE (1981) J Mol Struct (THEOCHEM) 85:163–178CrossRefGoogle Scholar
  43. 43.
    Islas R, Chamorro E, Robles J, Heine T, Santos JC, Merino G (2007) Struct Chem 18:833–839CrossRefGoogle Scholar
  44. 44.
    Martinez-Guajardo G, Gomez-Sandoval Z, Jana DF, Calaminici P, Corminboeuf C, Merino G (2011) Phys Chem Chem Phys 13:20615–20619CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Kalbinur Najmidin
    • 1
  • Ablikim Kerim
    • 1
    Email author
  • Paruza Abdirishit
    • 1
  • Horigul Kalam
    • 1
  • Tursungul Tawar
    • 1
  1. 1.Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, School of Chemistry and Chemical EngineeringXinjiang UniversityUrumqiChina

Personalised recommendations

Cite article

Buy options