18091-23-1Relevant academic research and scientific papers
Tunable and selective conversion of 5-HMF to 2,5-furandimethanol and 2,5-dimethylfuran over copper-doped porous metal oxides
Kumalaputri, Angela J.,Bottari, Giovanni,Erne, Petra M.,Heeres, Hero J.,Barta, Katalin
, p. 2266 - 2275 (2014)
Tunable and selective hydrogenation of the platform chemical 5-hydroxymethylfurfural into valuable C6 building blocks and liquid fuel additives is achieved with copper-doped porous metal oxides in ethanol. A new catalyst composition with improved hydrogenation/hydrogenolysis activity is obtained by introducing small amounts of ruthenium dopant into the previously reported Cu0.59Mg2.34Al1.00 structure. At a mild reaction temperature (100 °C), 2,5-furandimethanol is obtained with excellent selectivity up to >99 %. Higher reaction temperatures (220 °C) favor selective deoxygenation to 2,5-dimethylfuran and minor product 2,5-dimethyltetrahydrofuran with a combined yield as high as 81 %. Notably, these high product yields are maintained at a substrate concentration up to 10 wt % and a low catalyst loading. The influence of different alcohol solvents on product selectivity is explored. Furthermore, reaction intermediates formed at different reaction temperatures are identified. The composition of these product mixtures provides mechanistic insight into the nature of the reduction pathways that influence product selectivity. The catalysts are characterized by elemental analysis, TEM, and BET techniques before and after the reaction. Catalyst recycling experiments are conducted in batch and in a continuous-flow setup.
REACTION OF HALOMETHYLFURANS WITH SODIUM DIMETHYL PHOSPHITE AND TRIMETHYL PHOSPHITE
Pevzner, L. M.,Ignat'ev, V. M.,Ionin, B. I.
, p. 1754 - 1763 (2007/10/03)
Phosphorylation of 2- and 3-chloromethylfurans with sodium dimethyl phosphite in a methanol-benzene medium leads to formation of two products, a methoxy derivative and phosphonate, the first being predominant.Using sodium tert-butoxide as a metalating agent in benzene allows as to drive the process to the formation of phosphonates, but the yields are poor.Phase-transfer catalytic systems based on potassium hydroxide and fluoride are ineffective. 2- and 3-Mono and 2,3- and 2,5-bis(bromomethyl)furancarboxylates are phosphorylated with trimethyl phosphite under conditions of the Arbuzov reaction; however, in the presence of an additional acceptor substituent, such as an acetoxymethyl group, dehalogenation occurs.With 2,5-bis(halomethyl)-furan-3-carboxylates the Arbuzov reaction with trimethyl phosphite proceeds stepwise, the halomethyl group in position 5 reacting first, regardless of the halogen nature.The resulting intermediate products are not halomethyl phosphonates, which was proved by independent synthesis of the latter and by studying their chemical properties.
