2144-41-4Relevant articles and documents
One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol
Hansen, Thomas S.,Barta, Katalin,Anastas, Paul T.,Ford, Peter C.,Riisager, Anders
, p. 2457 - 2461 (2012)
Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hydrogen equivalents needed for the reductive deoxygenation of HMF originate from the solvent itself upon its reforming. Dimethylfuran, dimethyltetrahydrofuran and 2-hexanol were obtained in good yields. At milder reaction temperatures, a combined yield (DMF + DMTHF) of 58% was achieved. Notably, the formation of higher boiling side products and undesired char from HMF is not detected under these reaction conditions.
(OTf)2 as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
Latifi, Elnaz,Marchese, Austin D.,Hulls, Margaret C.W.,Soldatov, Dmitriy V.,Schlaf, Marcel
, p. 4666 - 4679 (2017/10/13)
The complex [Ru(triphos)(CH3CN)3](OTf)2 is an effective catalyst for the hydrogenation of 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium at temperatures between 150 and 200 °C realizing up to 96% combined yields of 2,5-hexanediol and 2,5-dimethyl-tetrahydrofuran with the product distribution being sensitive to the amount of acid co-catalyst (HOTf) present. For the furan, the reaction pathway is through an acid-catalyzed hydrolysis to the dione rather than direct hydrogenation of the ring. The hydrogenation of the dione shows a first order dependence on hydrogen pressure as determined by direct hydrogen uptake rate measurements at temperature and pressure (1.38-6.90 MPa at 150 °C) and is postulated to operate through a heterolytic activation of hydrogen gas by [Ru(H)x(triphos)(Y)y]n+ (Y = solvent, water, counter ion) species formed in situ by loss and hydrogenation of the nitrile ligands. In water the catalyst is deactivated by dimerization to [Ru2(μ-OH)3(triphos)2](OTf).
Cyclization of alkanediols in high-temperature liquid water with high-pressure carbon dioxide
Yamaguchi, Aritomo,Hiyoshi, Norihito,Sato, Osamu,Shirai, Masayuki
experimental part, p. 302 - 305 (2012/07/28)
Dehydration of 1,4-butanediol (1,4-BDO) to tetrahydrofuran (THF), 2R,5R-hexanediol (2R,5R-HDO) to 2,5-dimethyltetrahydrofuran (2,5-DMTHF), and 2,5-dimethyl-2,5-hexanediol (2,5-DM-2,5-HDO) to 2,2,5,5- tetramethyltetrahydrofuran (2,2,5,5-TMTHF) proceeded in high-temperature liquid water at 523 K. The formation rates of cyclic ethers were enhanced by high-pressure carbon dioxide (16.2 MPa). The order of dehydration rates in high-temperature water with carbon dioxide was 2,5-DM-2,5-HDO > 2R,5R-HDO > 1,4-BDO (tertiary > secondary > primary alcohols), which was the same order as the stability of corresponding carbocation species.
