Pd Nanoparticles and Mixture of CO2/CO/O2 Applied in the Carbonylation of Aniline

CO2 is a compound of high stability which proves useful in some organic syntheses as a solvent or component decreasing explosivity of gases. It is also a good carbonylating agent for aliphatic amines although not for aromatic ones, the latter being carbonylated with phosgene or, as in our previous works, with CO/O2 in the presence of Pd(II) complexes. In this work we have used the mixture of CO/O2 and CO2 for carbonylation of aniline to N,N’-diphenylurea. After optimization of the reaction conditions (56% of CO2 in CO2/CO mixture) we studied the activity of three kinds of pre-catalysts: (a) Pd(II) complexes, (b) Pdblack, and (c) palladium nanoparticles (PdNPs) in the presence of derivatives of pyridine (XnPy). The highest conversion of aniline (with selectivity towards N,N-diphenylurea ca. 90%) was observed for PdNPs. The results show that catalytic cycle involves Pd(0) stabilized by pyridine ligand as active species. Basing on this observation, we put the hypothesis that application of PdNPs instead of Pd(II) complex can eciently reduce the reaction time.