CO Activation Using Nitrogen-Doped Carbon Nanotubes for Reductive Carbonylation of Nitroaromatics to Benzimidazolinone and Phenyl Urea.

Abstract

Carbonylation of nitroaromatics with CO is extensively investigated with efficient but precious group 8-10 metal-based catalysts for the productions of both industrially and academically important chemicals such as isocyanates, formamides, carbamates, ureas and several types of heterocyclic compounds. Herein, we report that rationally designed nitrogen-doped carbon nanotubes (N-CNTs) exhibit catalytic activity toward CO activation for carbonylation of nitroaromatics to benzimidazolinones and ureas. Under the optimal conditions, N-CNT-promoted intramolecular carbonylation of 2-nitroaniline (1a) with CO leads to formation of 1,3-dihydro-2H-benzo[d]imidazol-2-one in 90% yield. Moreover, an intermolecular carbonylation of nitrobenzene and aniline with CO in the presence of the N-CNT gives 70% yield of N,N'-diphenylurea. The N-CNT is also applicable to various benzimidazolinones and phenyl ureas; moreover, it can be readily reused at least 9 times for the carbonylation. The theoretical investigation based on density functional theory calculations indicates that the graphitic N of the N-CNT plays a crucial step in the 1a reduction with CO. The correlation between the structural defect and catalytic performance of the N-CNT reveals an enhanced catalytic activity of the N-CNT with its increased structural defects. This research thus represents a major breakthrough in CO activation for nitroaromatic carbonylation with environmental-friendly, low-cost, and carbon-based catalysts as a potential alternative to expensive and scarce noble-metal-based catalysts.