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Porous modified bentonite as efficient and selective catalyst in the synthesis of 1,5-benzodiazepines

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Abstract

The synthesis of 1,5 benzodiazepine using natural and modified Argentinean bentonite (pillared layered clay and porous clay heterostructure) as catalysts through a condensation reaction between o-phenylenediamine (o-PDA) and excess of acetone as reactive and solvent at room temperature is reported. The catalysts were found to be highly active and selective, affording a high yield of the corresponding benzodiazepine. The effects of the modification of the natural bentonite and reaction conditions, such as temperature, time and amount of catalyst were investigated. The catalysts were also successfully employed for the preparation of other derivatives of 1,5-benzodiazepine using substituted o-PDAs and ketones. In all cases, the reactions are highly selective and are completed within 1–3 h. The catalyst showed excellent activity in all cases, showing 86–90% isolated yields of the corresponding derivatives of 1,5-benzodiazepine. The easy work-up procedure and the recyclable catalyst make this methodology attractive for large-scale operations.

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Acknowledgments

We are grateful to Ing. Edgardo Soto, María E. Canafoglia and Diego Peña for their contributions in experimental measurements. Financial support from CONICET, CICPBA, MINCyT-ECOS SUD France and ANPCyT–PICT Projects (2494/06 and 1134/06) is gratefully acknowledged. C. I. Cabello is a member of the research staff of CICPBA, Argentina.

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Authors and Affiliations

  1. Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” (CINDECA), CCT CONICET La Plata, Universidad Nacional de La Plata (UNLP), 47 No 257, 1900, La Plata, Argentina

    Mercedes Muñoz, Gabriel Sathicq, Gustavo Romanelli, Silvina Hernández & Carmen I. Cabello

  2. Centro de Química Inorgánica (CEQUINOR)-CCT CONICET La Plata, Universidad Nacional de La Plata (UNLP), Calles 47 y 115, 1900, La Plata, Argentina

    Irma L. Botto

  3. Unité de Catalyse et chimie du solide (UCCS), UMR-CNRS 8181, Université des Sciences et technologies de Lille, 59655, Villeneuve d’Ascq, Cedex, France

    Mickael Capron

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  1. Mercedes Muñoz
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  2. Gabriel Sathicq
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  3. Gustavo Romanelli
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  4. Silvina Hernández
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  5. Carmen I. Cabello
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Correspondence to Gustavo Romanelli or Carmen I. Cabello.

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Carmen I. Cabello is a Member of CIC-PBA and Facultad de Ingeniería, UNLP.

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Muñoz, M., Sathicq, G., Romanelli, G. et al. Porous modified bentonite as efficient and selective catalyst in the synthesis of 1,5-benzodiazepines. J Porous Mater 20, 65–73 (2013). https://doi.org/10.1007/s10934-012-9575-0

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