Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

Abstract

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni 0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Recent advances in bio‐based epoxy resins and bio‐based epoxy curing agents

“…Furanyl building blocks are primarily derived from polysaccharides and sugars and have been used for preparing not only epoxy resins but also amine hardeners. Several furan‐based amines have been prepared and investigated including the basic diamine 2,5‐bis(aminomethyl) furan (Figure 10) . In this preparation, the corresponding aldoxime and nitrile resist reduction, often causing low yields .…”

“…Several furan‐based amines have been prepared and investigated including the basic diamine 2,5‐bis(aminomethyl) furan (Figure 10) . In this preparation, the corresponding aldoxime and nitrile resist reduction, often causing low yields . Additionally, Hu et al .…”

Diamines for Polymer Materials via Direct Amination of Lipid‐ and Lignocellulose‐based Alcohols with NH3

“…Accesst ol ong-chain a,w-diamines for polyamides still requirem ulti-stepp rocedures. [34,[36][37][38][39] Alcohols and alcohol derivatives (ketones, aldehydes) are easily accessible already from biomass and can be exploited in the synthesis of amines via the direct amination of alcohols with NH 3 .T he reactionf ollowst he so-called "Hydrogen Shuttling" or "Borrowing Hydrogen" methodology withw ater as the only by-product (Scheme 2). [1,35] Also in case of 5-HMF derived amines, no direct catalytic, atom-efficient routes are currently availablea nd still rely on multi-step routes producing significant amounts of waste.…”

“…[1,35] Also in case of 5-HMF derived amines, no direct catalytic, atom-efficient routes are currently availablea nd still rely on multi-step routes producing significant amounts of waste. [34,[36][37][38][39] Alcohols and alcohol derivatives (ketones, aldehydes) are easily accessible already from biomass and can be exploited in the synthesis of amines via the direct amination of alcohols with NH 3 .T he reactionf ollowst he so-called "Hydrogen Shuttling" or "Borrowing Hydrogen" methodology withw ater as the only by-product (Scheme 2). [40][41][42] To date, severals ystems have been developed that efficientlyc onvert primary and secondary alcohols to primary amines.…”

Feasibility of unsaturated fatty acid feedstocks as green alternatives in bio‐oil refinery

“…For example, there are the following reactions: hydroamination of olefin acid (I); diamine formation from amidation and hydrogenation of olefin acid (J), and amidation and hydrogenation of amino acids (K). Diisocyanate formation is illustrated (L); however, this reaction needs to develop an eco‐friendly reaction process that does not use phosgene …”