Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst

Abstract

In this contribution, a protocol was established for the selective catalytic hydrogenation of nitroarenes to the corresponding N-arylhydroxylamines. The reduction of 1-(4-chlorophenyl)-3-((2-nitrobenzyl)oxy)-1H-pyrazole, an intermediate in the synthesis of the antifungal reagent pyraclostrobin that includes carbon-chlorine bonds, benzyl groups, carbon-carbon double bonds and other structures that are easily reduced, was chosen as the model reaction for catalyst evaluation and condition optimization. Extensive passivant evaluation showed that RANEY®-nickel treated with ammonia/DMSO (1 : 10, v/v) afforded the optimal result, especially with a particle size of 400-500 mesh. To combine the modified catalyst with continuous-flow reaction technology, the reaction was conducted at room temperature, rendering the desired product with a conversion rate of 99.4% and a selectivity of 99.8%. The regeneration of catalytic activity was also studied, and an in-column strategy was developed by pumping the passivate liquid overnight. Finally, the generality of the method was explored, and 7 substrates were developed, most of which showed a good conversion rate and selectivity, indicating that the method has a certain degree of generality.

Scheme 1. General scheme for the catalytic hydrogenation of nitroarene.

Scheme 2. Catalytic hydrogenation for NA-1: the synthesis of a key intermediate for pyraclostrobin.

Fig. 1. FT-IR spectra for different catalysts.

Fig. 2. SEM and TEM spectra for different catalysts: TEM for DA80 (a), DA200 (b), DA400 (c); SEM for DA80 (d), DA200 (e), DA400 (f).

Fig. 3. Kinetic profile of the batch reaction.

Fig. 4. Result for reaction performance and catalyst regeneration.

Scheme 3. Conformed mechanism of catalytic hydrogenation of pyraclostrobin intermediate.

Fig. 5. The setup scheme for the micropacked bed continuous reactor.