626-95-9Relevant articles and documents
Partially biobased polymers: The synthesis of polysilylethers via dehydrocoupling catalyzed by an anionic iridium complex
Zhai, Xiao-Yong,Wang, Xiao-Qing,Ding, Yi-Xuan,Zhou, Yong-Gui
, p. 1197 - 1200 (2020)
Partially biobased polysilylethers (PSEs) are synthesized via dehydrocoupling polymerization catalyzed by an anionic iridium complex. Different types (AB type or AA and BB type) of monomers are suitable. Levulinic acid (LA) and succinic acid (SA) have been ranked within the top 10 chemicals derived from biomass. BB type monomers (diols) derived from LA and SA have been applied to the synthesis of PSEs. The polymerization reactions employ an air-stable anionic iridium complex bearing a functional bipyridonate ligand as catalyst. Moderate to high yields of polymers with number-average molecular weights (Mn) up to 4.38 × 104 were obtained. A possible catalytic cycle via an Ir-H species is presented. Based on the results of kinetic experiments, apparent activation energy of polymerization in the temperature range of 0–10 °C is about 38.6 kJ/mol. The PSEs synthesized from AA and BB type monomers possess good thermal stability (T5 = 418 °C to 437 °C) and low glass-transition temperature (Tg = ?49.6 °C).
Transformation of γ-valerolactone into 1,4-pentanediol and 2-methyltetrahydrofuran over Zn-promoted Cu/Al2O3catalysts
Arai, Masahiko,Cheng, Haiyang,Lin, Weiwei,Liu, Ke,Liu, Qiang,Shi, Ruhui,Wang, Zhuangqing,Wu, Peixuan,Zhang, Chao,Zhao, Fengyu,Zhao, Zhenbo
, p. 4412 - 4423 (2020)
The transformation of γ-valerolactone (GVL) into 1,4-pentanediol (1,4-PDO) and 2-methyltetra-hydrofuran (2-MTHF) in the presence of H2, one of the useful biomass conversion and utilization processes, was investigated with monometallic Cu/Al2O3 and bimetallic ZnCu/Al2O3 catalysts. A 10 wt% Cu-loaded monometallic catalyst produced 1,4-PDO and 2-MTHF in comparable quantities at a medium conversion (～50%). When Zn was added in a range of Zn/Cu molar ratios of up to 2, in contrast, the catalysts yielded 1,4-PDO in a high selectivity of about 97% at low and high conversion levels. In addition, the 1,4-PDO selectivity over the ZnCu/Al2O3 catalysts remained almost unchanged during recycled runs. That is, the addition of Zn to Cu/Al2O3 switched the product selectivity and improved the catalyst stability and reusability. Furthermore, the physicochemical properties of the catalysts were characterized by several methods including XRD, TEM, TPR, XPS, FTIR of adsorbed pyridine, and so on. On the basis of those results, the relationships between the catalytic performance (activity, selectivity, and reusability) and the catalyst structural features were discussed.
Manganese-Catalyzed Hydrogenation of Sclareolide to Ambradiol
Zubar, Viktoriia,Lichtenberger, Niels,Schelwies, Mathias,Oeser, Thomas,Hashmi, A. Stephen K.,Schaub, Thomas
, (2021/11/16)
The hydrogenation of (+)-Sclareolide to (?)-ambradiol catalyzed by a manganese pincer complex is reported. The hydrogenation reaction is performed with an air- and moisture-stable manganese catalyst and proceeds under relatively mild reaction conditions at low manganese and base loadings. A range of other esters could be successfully hydrogenated leading to the corresponding alcohols in good to quantitative yields using this easy-to-make catalyst. A scale-up experiment was performed leading to 99.3 % of the isolated yield of (?)-Ambradiol.
Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
supporting information, p. 5665 - 5679 (2021/08/16)
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
Synthesis and characterisation of a range of Fe, Co, Ru and Rh triphos complexes and investigations into the catalytic hydrogenation of levulinic acid
Omoruyi, Uwaila,Page, Samuel J.,Apps, Samantha L.,White, Andrew J.P.,Long, Nicholas J.,Miller, Philip W.
, (2021/01/19)
The coordination chemistry of the N-triphos ligand (NP3Ph, 1b) has been investigated with a range of Fe, Co and Rh precursors and found to form either tridentate or bidentate complexes. Reaction of NP3Ph with [Rh(COD)(CH3CN)2]BF4 resulted in the formation of the tridentate complex [Rh(COD)(κ3-NP3Ph)]BF4 (3) in the solid state, however, in solution a bidentate complex predominates in more polar solvents. Reaction of NP3Ph with Fe carbonyl precursors revealed the formation of the bidentate complexes [Fe(CO)3(κ1,κ2-NP3Ph)Fe(CO)4] (4) and [Fe(CO)3(κ2-NP3Ph)] (5), while reaction with FeBr2 resulted in the paramagnetic bidentate complex [Fe(Br)2(κ2-NP3Ph)] (6). Reaction of NP3Ph with CoCl2 gave a dimeric Co species [(κ2-NP3Ph)CoCl(κ1,κ2-NP3Ph)CoCl3] (7), while Zn powder reduction of NP3Ph Co halides resulted in the formation of the tridentate complexes of the type: [Co(X)(κ3-NP3Ph)]. The related triphos Ru complex, [Ru(CO3)(CO)(κ3-CP3Ph)] (2), has also been isolated and characterised. Preliminary catalytic hydrogenation of levulinic acid (LA) was conducted with 2 and 3. The Ru complex was found to be catalytically active, giving high conversions of LA to form gamma-vvvalerolactone (GVL) and 1,4-pentanediol (1,4-PDO), while 3 was found to be catalytically inactive. In situ catalytic testing with 1b and Fe(BF4)2.6H2O resulted in low conversions of LA while a combination of 1b and Co(BF4)2.6H2O gave high conversions to GVL.
