Catalysis Letters

, Volume 134, Issue 3–4, pp 270–278 | Cite as

Regioselective Nitration of Deactivated Mono-Substituted Benzenes Using Acyl Nitrates Over Reusable Acidic Zeolite Catalysts

  • Keith Smith
  • Mansour D. Ajarim
  • Gamal A. El-Hiti


Nitration of benzonitrile was investigated using a nitric acid/acid anhydride/zeolite catalyst system under different reaction conditions. Trifluoroacetic and chloroacetic anhydrides were found to be the most active among the anhydrides tried. Also, zeolites Hβ and Fe3+β (Si/Al = 12.5) were found to be the most active catalysts. For example, nitration of benzonitrile with trifluoroacetyl nitrate under reflux conditions in dichloromethane gave 3- and 4-nitrobenzonitriles in quantitative yield, of which the para-isomer represented 24–28%. The yield of para-isomer was improved to 33% when passivated Hβ was used under similar reaction conditions. This is easily the most para-selective nitration of benzonitrile ever recorded. Also, no ortho-isomer was formed under the conditions tried. The zeolite can be easily recovered, regenerated by heating and reused up to six times to give results similar to those obtained with a fresh sample of the catalyst. The nitration system was applied successfully to a range of deactivated mono-substituted benzenes to give para-isomers in significantly higher proportions than in the corresponding traditional nitration reactions.

Graphical Abstract


Nitration Deactivated mono-substituted benzenes Acyl nitrate Acidic zeolite catalysis Hβ Regioselectivity 



We thank Cardiff University and the Saudi Government for financial support.


  1. 1.
    Olah GA, Malhotra R, Narang SC (1989) Nitration: methods and mechanisms. VCH, New YorkGoogle Scholar
  2. 2.
    Schofield K (1980) Aromatic nitration. Cambridge University Press, CambridgeGoogle Scholar
  3. 3.
    Taylor R (1990) Electrophilic aromatic substitution. Wiley, ChichesterGoogle Scholar
  4. 4.
    Ingold CK (1969) Structure and mechanism in organic chemistry. Bell, LondonGoogle Scholar
  5. 5.
    de la Mare PB, Ridd JH (1959) Aromatic substitution: nitration and halogenation. Butterworths, LondonGoogle Scholar
  6. 6.
    Gigante B, Prazeres A, Marcelo-Curto M, Cornelis A, Laszlo P (1995) J Org Chem 60:3445CrossRefGoogle Scholar
  7. 7.
    Carvalheiro B, Laszlo P, Cornelis A, Marcelo-Curto M (1994) PCT Inc Appl WO 94/19310Google Scholar
  8. 8.
    Smith K, Musson A, DeBoos GA (1998) J Org Chem 63:8448CrossRefGoogle Scholar
  9. 9.
    Smith K, Musson A, DeBoos GA (1996) Chem Commun 469Google Scholar
  10. 10.
    Smith K, Almeer S, Black SJ (2000) Chem Commun 1571Google Scholar
  11. 11.
    Smith K, Almeer S, Peters C (2001) Chem Commun 2748Google Scholar
  12. 12.
    Smith K, Almeer S, Black SJ, Peters C (2002) J Mater Chem 12:3285CrossRefGoogle Scholar
  13. 13.
    Smith K, Ajarim MD, El-Hiti GA (2009) Topics Catal 52:1696CrossRefGoogle Scholar
  14. 14.
    Kalbasi RJ, Ghiaci M, Massah AR (2009) Appl Catal A 353:1CrossRefGoogle Scholar
  15. 15.
    Kuba MG, Prins R, Pirngruber GD (2007) Appl Catal A 333:24CrossRefGoogle Scholar
  16. 16.
    Kuba MG, Prins R, Pirngruber GD (2007) Appl Catal A 333:78CrossRefGoogle Scholar
  17. 17.
    Peng X, Suzuki H, Lu C (2001) Tetrahedron Lett 42:4357CrossRefGoogle Scholar
  18. 18.
    Hajipour AR, Ruoho AE (2005) Tetrahedron Lett 46:8307CrossRefGoogle Scholar
  19. 19.
    Suzuki H, Murashima T (1994) J Chem Soc Perkin Trans 1:903CrossRefGoogle Scholar
  20. 20.
    Bak RR, Smallridge AJ (2001) Tetrahedron Lett 42:6767CrossRefGoogle Scholar
  21. 21.
    Almog J, Klein A, Sokol A, Sasson Y, Sonenfeld D, Tamiri T (2006) Tetrahedron Lett 47:8651CrossRefGoogle Scholar
  22. 22.
    Oxley JC, Smith JL, Moran JS, Canino JN, Almog J (2008) Tetrahedron Lett 49:4449CrossRefGoogle Scholar
  23. 23.
    Dove MFA, Manz B, Montgomery J, Pattenden G, Wood SA (1998) J Chem Soc Perkin Trans 1:1589CrossRefGoogle Scholar
  24. 24.
    Yuan Y, Nie J, Zhang Z, Wang S (2005) Appl Catal A Gen 295:170CrossRefGoogle Scholar
  25. 25.
    Clark JH (2002) Acc Chem Res 35:791CrossRefGoogle Scholar
  26. 26.
    Clark JH (ed) (1994) Catalysis of organic reactions using supported inorganic reagents. VCH, New YorkGoogle Scholar
  27. 27.
    Delaude L, Laszlo P, Smith K (1993) Acc Chem Res 26:607CrossRefGoogle Scholar
  28. 28.
    Smith K (1992) In: Yoshida Z, Ohshiro Y (eds) New aspects of organic synthesis II. Kadonsha, Tokyo and VCH, Weinheim, p 43Google Scholar
  29. 29.
    Butters M (1992) In: Smith K (ed) Solid supports and catalysts in organic synthesis. Ellis Harwood, Chichester, p 130Google Scholar
  30. 30.
    Smith K (1991) In: Scaros MG, Prunier ML (eds) Catalysis of organic reactions. Marcel Dekker, New York, p 91Google Scholar
  31. 31.
    Smith K, El-Hiti GA (2004) Curr Org Synth 1:253CrossRefGoogle Scholar
  32. 32.
    Smith K, El-Hiti GA (2006) Curr Org Chem 10:1603CrossRefGoogle Scholar
  33. 33.
    Smith K, Roberts SD, El-Hiti GA (2003) Org Biomol Chem 1:1552CrossRefGoogle Scholar
  34. 34.
    Smith K, El-Hiti GA, Jayne AJ, Butters M (2003) Org Biomol Chem 1:1560CrossRefGoogle Scholar
  35. 35.
    Smith K, El-Hiti GA, Jayne AJ, Butters M (2003) Org Biomol Chem 1:2321CrossRefGoogle Scholar
  36. 36.
    Smith K, Ewart GM, El-Hiti GA, Randles KR (2004) Org Biomol Chem 2:3150CrossRefGoogle Scholar
  37. 37.
    Smith K, El-Hiti GA, Hammond MEW, Bahzad D, Li Z, Siquet C (2000) J Chem Soc Perkin Trans 1:2745CrossRefGoogle Scholar
  38. 38.
    Smith K, Butters M, Paget WE, Goubet D, Fromentin E, Nay B (1999) Green Chem 1:83CrossRefGoogle Scholar
  39. 39.
    Smith K, Gibbins T, Millar RW, Claridge RP (2000) J Chem Soc Perkin Trans 1:2753CrossRefGoogle Scholar
  40. 40.
    Vogel AI (1989) Vogel’s textbook of practical organic chemistry, 5th edn. Longman, HarlowGoogle Scholar
  41. 41.
    Barker SD, Norris RK, Randles D (1981) Aust J Chem 34:1875Google Scholar
  42. 42.
    Moodie RB (1982) Organic reaction mechanisms 231Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Keith Smith
    • 1
  • Mansour D. Ajarim
    • 1
  • Gamal A. El-Hiti
    • 1
  1. 1.School of ChemistryCardiff UniversityCardiffUK

Personalised recommendations