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Synthesis of 1,5-benzodiazepine from 1,2-phenylenediamine and acetone in the presence of catalytic systems based on montmorillonite: effect of the surface acidity

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Abstract

The effect of the surface acidity of catalytic systems based on montmorillonite (Mt) on the formation of 1,5-benzodiazepine from 1,2-phenylenediamine and acetone was investigated. Two strategies were used for designing the acid sites in the framework of a Mt. The Brønsted type catalysts were prepared by clay modification, changing the nature of the treating acid (0.25 M solutions of HNO3, H2SO4, HOAc and HCl) or the concentration of the solution (0.125–3.0 M HNO3). The Lewis type catalysts were prepared by the pillaring method using bulky Al-hydroxypolycations (OH−/Al3+ = 2.4 mol/mol) and mixed Al, Fe-polycations (OH−/(Al3+ + Fe3+) = 2.4 mol/mol, Al3+/Fe3+ = 12/1 mol/mol), followed by calcination at 500 °C in air. The acidity of the catalysts, i.e., the type and amount of acid sites, was found to play a critical role in the cyclocondensation and dictated the performance of the catalysts. Acid-activated Mt materials gave high yield of 1,5-benzodiazepine in a shorter reaction time compared to Al- and Fe, Al-pillared Mts.

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Acknowledgements

This work was conducted within the framework of the Budget Project AAAA-A17-117041710082-8 for Boreskov Institute of Catalysis. AG also thanks Santander Bank for funding through the Research Intensification Program.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis SB RAS, Prospekt Akad. Lavrentieva 5, 630090, Novosibirsk, Russian Federation

    Maria N. Timofeeva, Ekaterina A. Petrova, Elena A. Mel’gunova & Valentina N. Panchenko

  2. Novosibirsk State Technical University, Prospekt K. Marksa 20, 630092, Novosibirsk, Russian Federation

    Maria N. Timofeeva, Ekaterina A. Petrova & Valentina N. Panchenko

  3. Departamento de Química Aplicada, Universidad Pública de Navarra, 31006, Pamplona, Spain

    Antonio Gil

  4. Departamento de Química Inorgánica, Universidad de Salamanca, Salamanca, Spain

    Miguel A. Vicente

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  1. Maria N. Timofeeva
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  2. Ekaterina A. Petrova
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  3. Elena A. Mel’gunova
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  6. Valentina N. Panchenko
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Correspondence to Maria N. Timofeeva.

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Timofeeva, M.N., Petrova, E.A., Mel’gunova, E.A. et al. Synthesis of 1,5-benzodiazepine from 1,2-phenylenediamine and acetone in the presence of catalytic systems based on montmorillonite: effect of the surface acidity. Reac Kinet Mech Cat 127, 41–52 (2019). https://doi.org/10.1007/s11144-018-1454-5

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  • DOI: https://doi.org/10.1007/s11144-018-1454-5

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