Catalytic Reductive Amination of Aromatic Aldehydes on Co-Containing Composites

Abstract

The performance of a series of cobalt-based composites in catalytic amination of aromatic aldehydes by amines in the presence of hydrogen as well as hydrogenation of quinoline was studied. The composites were prepared by pyrolysis of CoII acetate, organic precursor (imidazole, 1,10-phenantroline, 1,2-diaminobenzene or melamine) deposited on aerosil (SiO2). These composites contained nanoparticles of metallic Co together with N-doped carboneous particles. Quantitative yields of the target amine in a reaction of p-methoxybenzaldehyde with n-butylamine were obtained at p(H2) = 150 bar, T = 150 °C for all composites. It was found that amination of p-methoxybenzaldehyde with n-butylamine and benzylamine at p(H2) = 100 bar, T = 100 °C led to the formation of the corresponding amines with the yields of 72–96%. In the case of diisopropylamine, amination did not occur, and p-methoxybenzyl alcohol was the sole or the major reaction product. Reaction of p-chlorobenzaldehyde with n-butylamine on the Co-containing composites at p(H2) = 100 bar, T = 100 °C resulted in the formation of N-butyl-N-p-chlorobenzylamine in 60–89% yields. Among the considered materials, the composite prepared by decomposition of CoII complex with 1,2-diaminobenzene on aerosil showed the highest yields of the target products and the best selectivity in all studied reactions.

Advances and Challenges in Development of Transition Metal Catalysts for Heterogeneous Hydrogenation of Organic Compounds

“…These composites and one new analogue, prepared by pyrolysis of Co 2 + complex with imidazole, deposited on aerosil appeared to be efficient catalysts of amination of p-methoxybenzaldehyde with n-butylamine or benzylamine under pressure of H 2 . [105] No amination occurred at p(H 2 ) = 50 bar and T = 100 °C (Co loading 2 mol %), while complete conversion of aldehyde to amine was achieved at p(H 2 ) = 150 bar and T = 150 °C (Co loading 5 mol %). Typical reaction conditions were p(H 2 ) = 100 bar and T = 100 °C, Co loading 3 mol % under 4 h. The set of the products, included the desired amine, Schiff base (the product of reaction of the starting aldehyde and amine prior to hydrogenation) and pmethoxybenzilic alcohol (the product of aldehyde reduction, Figure 11).…”

“…Amines prepared by amination of aromatic aldehydes in the presence of Co-containing composites. [105] Figure 12. Reaction of furfural hydrogenation and acetal formation in the presence of Ni-containing composites.…”

“…These composites and one new analogue, prepared by pyrolysis of Co 2+ complex with imidazole, deposited on aerosil appeared to be efficient catalysts of amination of p ‐methoxybenzaldehyde with n ‐butylamine or benzylamine under pressure of H 2 [105] . No amination occurred at p(H 2 )=50 bar and T=100 °C (Co loading 2 mol %), while complete conversion of aldehyde to amine was achieved at p(H 2 )=150 bar and T=150 °C (Co loading 5 mol %).…”

“… Amines prepared by amination of aromatic aldehydes in the presence of Co‐containing composites [105] …”