Issue 5, 2015
From the journal:

Catalysis Science & Technology

Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP†

Octavian Dumitru Pavel,a   Peter Goodrich,b   Liliana Cristian,ac   Simona M. Coman,a   Vasile I. Pârvulescu*a  and  Christopher Hardacre*b  

* Corresponding authors

a University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, 4-12 Regina Elisabeta Av., Bucharest, Romania
E-mail: vasile.parvulescu@g.unibuc.ro
Fax: +40214100241

b The QUILL Centre/School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast BT9 5AG, Northern Ireland, UK
E-mail: C.Hardacre@qub.ac.uk
Tel: +44 (0)2890974592

c Centre of Organic Chemistry “Costin D. Nenitescu”, Splaiul Independentei 202B, S 6, 71141 Bucharest, Romania

Abstract

The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a “green” route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz–Prater criterion confirmed the absence of any diffusional constraints.

Graphical abstract: Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP

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Article information

DOI
https://doi.org/10.1039/C5CY00011D
Article type
Paper
Submitted
05 Jan 2015
Accepted
22 Feb 2015
First published
23 Feb 2015

Catal. Sci. Technol., 2015,5, 2696-2704

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Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP

O. D. Pavel, P. Goodrich, L. Cristian, S. M. Coman, V. I. Pârvulescu and C. Hardacre, Catal. Sci. Technol., 2015, 5, 2696 DOI: 10.1039/C5CY00011D

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