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
Article
First Online:
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Accepted:

Abstract

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

Keywords

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

Notes

Acknowledgments

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

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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

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