620-02-0Relevant academic research and scientific papers
Catalytic Conversions in Water: a Novel Carbonylation Reaction Catalysed by Palladium Trisulfonated Triphenylphosphine Complexes
Papadogianakis, Georgios,Maat, Leendert,Sheldon, Roger A.
, p. 2659 - 2660 (1994)
The renewable basic chemical 5-hydroxymethylfurfural (HMF) is selectively carbonylated to the new compound 5-formylfuran-2-acetic acid using a water-soluble palladium complex of trisulfonated triphenylphosphine as the catalyst in an acidic aqueous medium at 70 deg C and 5 bar CO pressure; when hydrogen iodide is the acid component, the reaction follows a different course and HMF is selectively reduced to 5-methylfurfural.
One-pot synthesis of furans from various saccharides using a combination of solid acid and base catalysts
Tuteja, Jaya,Nishimura, Shun,Ebitani, Kohki
, p. 275 - 281 (2012)
One-pot synthesis of furans from various saccharides such as arabinose, rhamnose, and lactose were performed over solid acid and base catalysts. The combination of Amberlyst-15 and hydrotalcite catalysts showed successful activity for corresponding furans formation such as 2-furaldehyde (furfural), 5-hydroxymethyl-2-furaldehyde (HMF), and 5-methyl- 2-furaldehyde (MF) via one-pot synthesis including isomerization and dehydration reactions. Moreover, the acidbase pair catalysts were also found to display excellent activity for the transformation from mixed-sources of sugars to furans. It was indicated that the isomerization of saccharides and successive dehydration in the one-pot synthesis of furans will be a great approach in a biorefinery.
Green catalytic synthesis of 5-methylfurfural by selective hydrogenolysis of 5-hydroxymethylfurfural over size-controlled Pd nanoparticle catalysts
Sun, Guohan,An, Jiahuan,Hu, Hong,Li, Changzhi,Zuo, Songlin,Xia, Haian
, p. 1238 - 1244 (2019)
A green approach for the conversion of 5-(hydroxymethyl)furfural (HMF) to 5-methylfurfural (MF) by using size-controlled palladium catalysts has been developed. Palladium nanoparticles (Pd NPs) with various sizes supported on activated carbon were prepared with polyvinylpyrrolidone (PVP) as the capping agent. The reaction results showed that all the PVP-assisted Pd catalysts achieved high selectivity whilst the hydrogenation ability of Pd NPs could be rationally tuned by varying the mole ratio of Pd/PVP. 2.5% Pd-PVP/C (1:2) presented a satisfactory activity with 80% MF yield and 90% selectivity. The reaction kinetics study showed that the transformation of HMF into MF over bifunctional PVP-assisted Pd NPs underwent an acid-catalyzed esterification followed by a Pd-catalyzed hydrogenolysis procedure. The role of formic acid in the transformation is not only as a hydrogen-donating agent but also as a reactant to form the key intermediate. This work provides a novel and environmentally-friendly method for the selective hydrogenation of bio-based HMF to MF.
Novel pathways to 2,5-Dimethylfuran via biomass-derived 5-(chloromethyl)furfural
Dutta, Saikat,Mascal, Mark
, p. 3028 - 3030 (2014)
2,5-Dimethylfuran (DMF) is one of the most actively pursued biomass-derived chemicals due to the fact that it can serve both as a biofuel and an intermediate for drop-in terephthalate polymers. DMF can be accessed via catalytic hydrogenation of 5-(hydroxymethyl)furfural (HMF), but the difficult accessibility of HMF from cellulosic biomass is a major impediment to the commercial development of such a process. Alternatively, 5-(chloromethyl)furfural (CMF) is freely accessible in high yield directly from raw biomass and is shown here to be efficiently reduced to DMF under mild conditions via simple derivatives (aldimine, acetal).
Dehydration of carbohydrates to 2-furaldehydes in ionic liquids by catalysis with ion exchange resins
Heguaburu, Viviana,Franco, Jaime,Reina, Luis,Tabarez, Carlos,Moyna, Guillermo,Moyna, Patrick
, p. 88 - 91 (2012)
The dehydration of several sugars, including pentoses, hexoses, di, tri, and polysaccharides, in ionic liquids with acidic ion-exchange resins as heterogeneous catalysts was investigated. Good 2-furaldehydes recovery yields, reaching 92% in some cases, were achieved when Dowex 50W ion-exchange resins and 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) were used. Our results show that this aproach could represent a promising route towards the cost-efficient production of 2-furaldehydes from carbohydrate-based feedstocks.
Characteristic flavor formation of thermally processed N-(1-deoxy-α-D-ribulos-1-yl)-glycine: Decisive role of additional amino acids and promotional effect of glyoxal
Zhan, Huan,Cui, Heping,Yu, Junhe,Hayat, Khizar,Wu, Xian,Zhang, Xiaoming,Ho, Chi-Tang
, (2021/09/28)
The role of amino acids and α-dicarbonyls in the flavor formation of Amadori rearrangement product (ARP) during thermal processing was investigated. Comparisons of the volatile compounds and their concentrations when N-(1-deoxy-α-D-ribulos-1-yl)-glycine r
Homogeneous CuCl2/TMEDA/TEMPO-Catalyzed chemoselective base- and halogen- free aerobic oxidation of primary alcohols in mild conditions
Alves, Otávio A. L.,Chagas, Rafael C. R.,Princival, Jefferson L.,Ribeiro, RogérioT.,Silva, Emmanuel D.,Villar, José A. F. P.
, (2021/08/03)
This article describes the developing of a base- and halogen- free homogeneous system aiming to chemoselectively oxidize allyl, furyl, aryl and heteroaryl primary alcohols. The current easy-to-handle aerobic system uses few amounts of CuCl2/TMEDA/TEMPO system under mild reaction conditions to produce aldehydes in high yields. Moreover, the CuCl2/TMEDA cyclic voltammetry was measured for the first time, disclosing that TMEDA as ligand substantially affects the redox potential (E1/2) of the couple E1/2Cu2+/Cu+ to E1/2Cu2+/Cu+-TMEDA by 454 mV in the redox system.
Direct Synthesis of 5-Methylfurfural from d-Fructose by Iodide-Mediated Transfer Hydrogenation
Xu, Jianwang,Miao, Xinge,Liu, Lei,Wang, Yantao,Yang, Weiran
, p. 5311 - 5319 (2021/11/01)
Herein, a robust catalytic system was developed for the green synthesis of 5-methylfurfural (5-MF) by iodide-mediated transfer hydrogenation. Around 50 % of 5-MF was yielded from d-fructose within 7.5 min using NaI as the catalyst and formic acid as both the hydrogen source and co-catalyst. The catalytic system was used for six consecutive cycles without any decrease in the yield. Various starch and raw biomass could be used as promising starting materials for 5-MF synthesis with moderate yields, and the productivity of 5-MF from corn starch reached 103 mmol gcat?1 h?1, which is comparable with the best result from l-rhamnose. Moreover, the co-production of 5-MF and furfural from raw biomass makes this methodology more competitive than other routes.
Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information, p. 8108 - 8115 (2021/10/29)
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
Green synthesis of heterogeneous copper-alumina catalyst for selective hydrogenation of pure and biomass-derived 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan
Hu, Yulin,Rao, Kasanneni Tirumala Venkateswara,Xu, Chunbao Charles,Yuan, Zhongsun,Zhang, Yongsheng
, (2020/11/26)
In this work novel copper-alumina catalysts were prepared through a solvent-free solid-state grinding method ― a low cost and green catalyst preparation method for selective hydrogenation of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(hydroxymethyl)furan (BHMF). Under the optimized reaction conditions (3 MPa H2, 130 °C, 1 h), >99 % 5-HMF conversion and 93 % BHMF yield were obtained by using a 20CA (20 mol%Cu-Al2O3) catalyst. The catalyst characterization results could reveal that the high catalytic activity and selectivity could be attributed to the presence of both metallic and electrophilic copper (Cu°/Cu2+) species and the uniformly distributed copper nanoparticles. Furthermore, an integrated catalytic process was demonstrated for the first time for direct conversion of mono, di, and polysaccharides into the corresponding BHMF, obtained overall BHMF yield in the range of 25 %–48 %.
