Divergent reactivities of o-haloanilides with CuO nanoparticles in water: a green synthesis of benzoxazoles and o-hydroxyanilides?

RSC Advances Pub Date: 2013-12-18 DOI: 10.1039/C3RA46820H

Abstract

In the present study, three divergent reaction paths emerged when o-haloanilides were subjected to CuO nanoparticles in water. o-Halo (I, Br) phenylbenzamides in the presence of CuO nanoparticles and Cs2CO3 in water at 100 °C provided o-hydroxyphenyl benzamides as the major product. However, a complete change in selectivity was observed in the presence of an organic base/ligand (TMEDA), giving 2-arylbenzoxazole as the exclusive product. The above selectivities were not clearly distinct when the corresponding alkylamides were treated either in the presence or absence of the ligand. A number of o-halophenyl alkylamides provided either exclusively o-dehalogenated products or a mixture of o-dehalogenated and o-hydroxylated products, but none gave 2-alkylbenzoxazoles. In addition to the above selectivities, the use of an environmentally friendly solvent (water) and base, and the recyclability of the catalyst make this procedure a benign alternative to the existing methods for the synthesis of these molecules, viz. o-hydroxybenzamides and o-arylbenzoxazoles.

Graphical abstract: Divergent reactivities of o-haloanilides with CuO nanoparticles in water: a green synthesis of benzoxazoles and o-hydroxyanilides
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