Oxygen Vacancy Mediated Reactivity of CaO/CuO Composite for the Synthesis of Amino-N-heterocycles

Rajendran, K and Madampadi, R and Shee, S and Subramaniam, R and Khan, TS and Gupta, S and Haider, MA and Jagadeesan, D (2023) Oxygen Vacancy Mediated Reactivity of CaO/CuO Composite for the Synthesis of Amino-N-heterocycles. In: ChemCatChem, 15 (24).

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Abstract

Utilising the oxygen-vacancy-mediated reactivity of CaO/CuO and hydrazine monohydrate in isopropyl alcohol at 353 K, a variety of amino-derivatives of N-heterocycles, including pyridine, indole, quinoline, isoquinoline, and benzothiazole, have been selectively synthesised by reducing their nitro analogues. It is demonstrated that CaO/CuO composite is a reusable, solvent-resilient solid reducing agent that can reduce a variety of nitro-N-heterocyclic substrates. The critical role of the structure of CaO/CuO on the nitro-reduction activity has been studied using spectroscopy and microscopy. DFT simulations indicate the facile formation of oxygen vacancies (EO,vac=�43.4 kJ/mol) on the interface of CaO/CuO surface under reducing environment. The presence of CaO facilitated a stronger interaction of the nitro-substrate on the oxygen vacant CuO (111) surface, resulting into a significantly lower activation energy (Ea=21.9 kJ/mol) for N�O dissociation. The reaction could be scaled up from 1 to 12 mmol of substrate. CaO/CuO is a reusable and a cost-effective alternative to the conventional catalyst (Pd/C, Pt/C). © 2023 Wiley-VCH GmbH.

Item Type:	Journal Article
Publication:	ChemCatChem
Publisher:	John Wiley and Sons Inc
Additional Information:	The copyright for this article belongs to John Wiley and Sons Inc.
Keywords:	Activation energy; Copper oxides; Cost effectiveness; Oxygen vacancies; Substrates, reductions; Amino-N-heterocycle; Benzothiazoles; Hydrazine monohydrate; Isopropyl alcohols; Isoquinolines; N-heterocycles; Nitro reduction; Nitroarenes; Synthesised, Amines
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	01 Mar 2024 05:40
Last Modified:	01 Mar 2024 05:40
URI:	https://eprints.iisc.ac.in/id/eprint/83817

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