Production of Primary Amines by Reductive Amination of Biomass‐Derived Aldehydes/Ketones

Abstract

Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO , which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for production of ethanolamine, a large-market nitrogen-containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO -containing multivalence Ru association species worked as a bifunctional catalyst, with RuO as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation.

Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors

“…[347] The amination of (biobased) acids (e. g., succinic acid, itaconic acid, LA or 3-HPA) can produce pyrrolidones that are widely used for the synthesis of polymers, dyes, surfactants, pharmaceuticals and agrochemicals. [348][349][350] These gas-liquid reductive aminations may benefit from operation in microreactors by overcoming gas-liquid mass transfer limitations and having well-regulated temperature distribution for an intensified and more selective product formation. [348][349][350] These gas-liquid reductive aminations may benefit from operation in microreactors by overcoming gas-liquid mass transfer limitations and having well-regulated temperature distribution for an intensified and more selective product formation.…”

Selectivity Control in Catalytic Reductive Amination of Furfural to Furfurylamine on Supported Catalysts

“…achieved a 98 % yield of FAM over a Ru/Nb 2 O 3 catalyst by starting from the secondary imine as the reaction substrate, a technique that will discussed at length in this work. Ru/ZrO 2 was used in amination of a variety of aldehydes and ketones derived from biomass by Liang et al., who achieved >90 % yields of several different primary amines with this ruthenium catalyst (though FAM was not the target molecule) . The group also achieved a 6–7 % yield of ethylenediamine from glycolaldehyde using the same Ru/ZrO 2 catalyst, which is an achievement because primary amine production (and especially primary diamines) is significantly more challenging from alcohols than from aldehydes or ketones, as most often the mechanism requires an initial dehydrogenation of the alcohol to the aldehyde/ketone before aldehyde/ketone reductive amination takes place .…”

Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis

“…The alarming predictions of the rapid depletion of fossil‐fuel resources have inspired researchers to develop alternative technologies that exploit renewable energy sources . Many studies have focused on the conversion of lignocellulosic biomass and triglycerides into various platforms of value‐added chemicals . Industrially, triglycerides in oils and fats have been used as feedstocks for the synthesis of fatty amines, amides, nitriles, and alcohols, which in turn are used for the production of surfactants, polymers, and other useful commodity chemicals …”