Metal-Free Reduction of Nitrobenzene to Aniline in Subcritical Water

An environmentally friendly approach for the reduction of nitrobenzene to aniline promoted by carbonaceous bio-based materials was successfully achieved under subcritical water conditions. The proposed methodology features a metal-free process, no-hydrogen input as reductor, the use of commercial bio-based carbon materials having low cost and availability, and water as green solvent under subcritical conditions. Using optimized conditions, reduction of nitrobenzene in the presence of commercial NORIT GAC 12-40 or DACARB PC1000 was accomplished at 310 °C for 6 h and quantitatively furnished the target aniline. Treatment of NORIT GAC 12-40 with KOH allowed to decrease charcoal loading (6 g vs 40 g) and increase aniline yields (80% vs 66%). © 2018 American Chemical Society

Microwaves under pressure for the continuous production of quinoline from glycerol

International audienceMicrowave heating is an interesting technology for chemical engineering, since it can provide effective volumetric heating of the reaction medium and reduce energy costs. Many commercially available laboratory-scale microwave reactors have already been used to carry out chemical reactions on a small scale (a few milliliters), and at high temperatures and pressures. Some research has been undertaken to scale-up microwave processes and make them suitable for a larger scale production.Indeed, combining wave propagation through the walls of a reactor with resistance toward high pressure and temperature as well, is not an easy task. For these reasons, this work focuses on the development of a pilot scale microwave apparatus used for the heating of larger reaction volumes under pressure, and under controlled conditions. The specially designed microwave apparatus allows chemical reactions in batch or continuous mode. The applicator operates in single mode enabling a uniform electromagnetic field, and well controlled operating conditions. The main advantage of the setup is the quite large reactor volume that permits either relatively long residence times or relatively high mass flowrates (up to 1 kg/h). The developed microwave apparatus was then used for quinoline synthesis from glycerol via a modified Skraup reaction. The major advantage of our system is the ability to carry out continuous chemical synthesis, at a large pilot scale, and high temperatures (200–220 °C), while ensuring a better control of the pressure (max. 19 bar) through the control of the power absorbed by the reaction medium

Specific formation of isocyanide iron complexes by reaction of primary carbamoyl ferrates with oxalylchloride

cited By 4International audienceReaction of primary carbamoyl ferrates (CO)4Fe[C(O)NHR] - (R=Me, Et, allyl, decyl, cyclohexyl, t-butyl, benzyl, phenyl) with 1/2 equiv. of oxalylchloride affords cis-bis-carbamoyl intermediates: (CO) 4Fe[C(O)NHR]2 which thermally give rise, in good yields, to the mono-isocyanide complexes (CO)4Fe(CNR). The mechanism of the reaction is discussed. Via a similar process, an alkoxycarbamoyl intermediate (CO)4Fe[C(O)NHR](CO2Me) affords Fe(CO)5 and 1,3-dialkylurea. © 2003 Elsevier Science B.V. All rights reserved

Metal-Free Reduction of Nitrobenzene to Aniline in Subcritical Water

An environmentally friendly approach for the reduction of nitrobenzene to aniline promoted by carbonaceous bio-based materials was successfully achieved under subcritical water conditions. The proposed methodology features a metal-free process, no-hydrogen input as reductor, the use of commercial bio-based carbon materials having low cost and availability, and water as green solvent under subcritical conditions. Using optimized conditions, reduction of nitrobenzene in the presence of commercial NORIT GAC 12-40 or DACARB PC1000 was accomplished at 310 °C for 6 h and quantitatively furnished the target aniline. Treatment of NORIT GAC 12-40 with KOH allowed to decrease charcoal loading (6 g vs 40 g) and increase aniline yields (80% vs 66%). © 2018 American Chemical Society