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

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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.

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Acknowledgments

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

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Authors and Affiliations

  1. School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK

    Keith Smith, Mansour D. Ajarim & Gamal A. El-Hiti

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  1. Keith Smith
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  2. Mansour D. Ajarim
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  3. Gamal A. El-Hiti
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Correspondence to Keith Smith.

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Smith, K., Ajarim, M.D. & El-Hiti, G.A. Regioselective Nitration of Deactivated Mono-Substituted Benzenes Using Acyl Nitrates Over Reusable Acidic Zeolite Catalysts. Catal Lett 134, 270–278 (2010). https://doi.org/10.1007/s10562-009-0258-7

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  • DOI: https://doi.org/10.1007/s10562-009-0258-7

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