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Synlett
DOI: 10.1055/a-2547-8910
letter
14th EuCheMS Organic Division Young Investigator Workshop

Mechanochemically Driven Radical Nitration of Electron-Rich ortho and para Di- and Trialkoxyarenes Using Iron(III) Nitrate

Samuel Andrejčák‡
,
Peter Dudᚇ
,
Michal Májek  ∗
This work was funded by the European Union, NextGenerationEU through the Recovery and Resilience Plan for Slovakia (Project No. 09I01-03-V04-00018) and by the European Research Council (ERC), CAPELE (101078608). The views and opinions expressed herein are those of the authors only and do not necessarily reflect those of the European Union or the European Research Council. Neither the European Union nor the granting authority can be held responsible for them.
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Abstract

This study introduces a sustainable mechanochemical approach for the nitration of electron-rich ortho and para di- and trialkoxyarenes using iron(III) nitrate nonahydrate (Fe(NO3)3·9H2O) as a source of nitro radicals. Conventional nitration methods require harsh conditions and hazardous reagents, limiting their application. Herein, mechanochemical activation offers a rapid and efficient alternative with minimal solvent and a reduced reaction time. Screening identified Fe(NO3)3 as the most effective nitrating agent, with successful application with a variety of ortho and para di- and trialkoxyarenes while maintaining high regioselectivity. The scalability and environmental benefits of the method underscore its potential in organic synthesis, advancing a practical, green protocol for radical aromatic nitration.

Key words

radicals - mechanochemistry - nitration - arenes - nitryl radical - iron(III) nitrate - liquid-assisted grinding

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2547-8910.
  • Supporting Information


Publication History

Received: 15 December 2024

Accepted after revision: 27 February 2025

Accepted Manuscript online:
27 February 2025

Article published online:
09 April 2025

© 2025. Thieme. All rights reserved

Georg Thieme Verlag KG
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