3068-00-6Relevant articles and documents
A new antiangiogenic C24 oxylipin from the soft coral Sinularia numerosa
Yamashita, Takahiro,Nakao, Yoichi,Matsunaga, Shigeki,Oikawa, Tsutomu,Imahara, Yukimitsu,Fusetani, Nobuhiro
, p. 2181 - 2184 (2009)
A new oxylipin, 15-hydroxy-tetracosa-6,9,12,16,18-pentaenoic acid (15-HTPE; 1) was isolated as an inhibitor of tube-formation from the soft coral Sinularia numerosa. Its structure was elucidated by means of spectral analysis and chemical degradation. 15-H
METHOD FOR PRODUCING ALCOHOL
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Paragraph 0104-0106, (2022/02/05)
The present invention provides a method for selectively producing an alcohol by efficiently hydrogenating a lactone. The present invention is a method for producing an alcohol, the method including hydrogenating a substrate lactone represented by Formula (1), in the presence of a catalyst described below, to produce an alcohol that is represented by Formula (2). In the formulae, R represents a divalent hydrocarbon group which may have a hydroxyl group. The catalyst comprises: metal species including M1 and M2; and a support supporting the metal species, and wherein M1 is rhodium, platinum, ruthenium, iridium, or palladium; M2 is tin, vanadium, molybdenum, tungsten, or rhenium; and the support is hydroxyapatite, fluorapatite, hydrotalcite, or ZrO2.
Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent
Chen, Can,Jiang, Junxiang,Li, Guangci,Li, Xuebing,Wang, Da,Wang, Zhong,Yu, Pei
, (2022/01/12)
Catalytic selective hydrogenation of esterified malic acid to produce 1,2,4-butanetriol (1,2,4-BT) using H2 as the reducing reagent suffers from the low 1,2,4-BT selectivity. Here, Ru/SiO2 catalyst was employed for selective hydrogenation of dimethyl malate (DM) to produce 1,2,4-BT, which gave abnormal high DM conversion (100%) and 1,2,4-BT selectivity (92.4%) in aqueous solvent at 363?K, especially, the 1,2,4-BT yield even is higher than the optimal catalyst reported (Ru-Re, 79.8%). The reaction pathways for the DM hydrogenation on Ru/SiO2 were also proposed, suggesting that extremely high 1,2,4-BT selectivity require for the much high hydrogenation rates at low temperatures, where side-reaction transesterification rates are relatively low. The extremely high hydrogenation activity and 1,2,4-BT selectivity on Ru/SiO2 in aqueous solvent at low temperatures arise from that H2O may coordinate to Ru2+ and prevent the reduction of Ru2+ to Ru under high H2 pressure. Ru/SiO2 surface presents abundant Ru2+ in aqueous solvent, can activate H2 through heterolytic cleavage mode to form hydride, which can significantly increase hydrogenation rates of C = O groups at low temperatures. In addition, the activity and 1,2,4-BT selectivity on Ru/SiO2 catalyst only reduced by 2.3% and 2.6%, respectively over a period of 550?h. Graphical Abstract: [Figure not available: see fulltext.]
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.
Method for preparing 1,2,4-butantriol through reduction of hydrosilane
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Paragraph 0017-0029, (2020/10/30)
The invention discloses a method for preparing 1,2,4-butantriol through reduction of hydrosilane. According to the method, dimethyl malate is selectively reduced into 1,2,4-butantriol under the condition that dioxane is used as a solvent by taking polymethylhydrosiloxane as a reducing agent and potassium tert-butoxide as a catalyst, wherein the reducing agent is low in price, the reaction condition is mild, the selectivity of 1,2,4-butantriol is 100%, and the yield reaches 70%.
Method for producing 1,2,4-butanetriol
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Paragraph 0038; 0041-0052; 0054-0063, (2020/01/12)
The invention provides a method for producing 1,2,4-butanetriol. According to the method, a reaction of 2-butene-1,4-diol and hydrogen peroxide is catalyzed by a tungstate and secondary amine to generate 2,3-epoxy-1,4-butanediol; an epoxy reaction solution is treated by using catalase and then the epoxy reaction solution is directly used for a hydrogenation reaction without separation and purification; under action of a Raney nickel catalyst, the hydrogenation reaction is carried out by adopting a feeding method of slowly pressing the epoxy reaction solution into a hydrogenation kettle; and astabilizing agent is added in a rectification process of 1,2,4-butanetriol to inhibit side reactions such as oxidation, intramolecular dehydration and the like. Compared with the prior art, the preparation method of the 1,2,4-butanetriol provided by the invention has the advantages that the raw materials are easy to obtain, the reaction is stable and is easy to control, purity of the obtained product is high, and the method is very suitable for industrial production. According to the production method provided by the invention, the content of the obtained product 1,2,4-butanetriol is more than99.5%, the content of sensitive impurity 3-hydroxytetrahydrofuran is less than 0.05%, and the content of aldehydes and ketones is less than 10 [mu]g/mL.
Method for preparing 1, 2, 4-butantriol through catalytic hydrogenation
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Paragraph 0016-0028, (2020/05/30)
The invention discloses a method for preparing 1, 2, 4-butantriol by catalytic hydrogenation, and the method comprises the following steps: (1) uniformly mixing dimethyl malate and n-propylamine in acertain proportion, reacting at the condensation reflux temperature of the n-propylamine, and cooling to room temperature; removing volatile components through vacuum evaporation; recrystallizing, purifying and the like to obtain corresponding malate diamide; and (2) uniformly mixing the corresponding malate diamide obtained in the step (1) and tetrahydrofuran, carrying out a hydrogenation reaction with hydrogen in the presence of a catalyst at a reaction temperature of 120-200 DEG C under an initial reaction pressure of 5-10 MPa for 10-14 h, and collecting the target product 1, 2, 4-butantriol in the reaction product. The method provided by the invention has the advantages of low cost, mild conditions, simple processing and no pollution to the environment, the reaction yield can reach 85%or above, and the method is easy for industrial implementation.
One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol hydrogenolysis over a tungsten-modified platinum on silica catalyst
Asano, Takehiro,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
supporting information, p. 2375 - 2380 (2020/05/14)
Chemical production of 1,3-butanediol from biomass-derived compounds was first reported by 1,4-anhydroerythritol hydrogenolysis over a Pt-WOx/SiO2 catalyst. The reaction proceeded by ring opening hydrogenolysis of 1,4-anhydroerythritol followed by selective removal of secondary OH groups in 1,2,3-butanetriol, and an overall 1,3-butanediol yield up to 54% was then obtained. The performance of the Pt-WOx/SiO2 catalyst for 1,4-anhydroerythritol hydrogenolysis was closely correlated with that for glycerol hydrogenolysis to 1,3-propanediol. The optimized Pt-WOx/SiO2 (Pt: 4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3-propanediol.
Biosynthesis of 1,4-butanediol from erythritol using whole-cell catalysis
Dai, Lu,Tai, Cui,Shen, Yaling,Guo, Yali,Tao, Fei
, p. 1 - 5 (2018/04/26)
1,4-Butanediol (BDO) biosynthesis from renewable resources is of increasing interest because of global energy and environmental problems. We have previously demonstrated the production of BDO from erythritol by whole-cell catalysis. Here, the effects of several variables on BDO production were investigated, including cell density, temperature, substrate concentration and pH. It was found that the maximum BDO production was obtained at cell density (OD600) of 30. Low temperature and weak alkaline environment were beneficial for the biotransformation. Regarding substrate concentration, 80?g/L of erythritol was found to be optimum for the bioconversion. Under the optimal conditions, the highest concentration of BDO reached 34.5?mg/L, resulting in 5.8-fold increment after optimization. These results will provide useful guidance for enhancing the bioconversion of erythritol to BDO.
Selective C?O Hydrogenolysis of Erythritol over Supported Rh-ReOx Catalysts in the Aqueous Phase
Said, Achraf,Da Silva Perez, Denilson,Perret, Noémie,Pinel, Catherine,Besson, Michèle
, p. 2768 - 2783 (2017/07/28)
Bimetallic Rh-ReOx (Re/Rh molar ratio 0.4–0.5) catalysts supported on TiO2 and ZrO2 were prepared by the successive impregnation of dried and calcined unreduced supported Rh catalysts. Their catalytic performances were evaluated in the hydrogenolysis of erythritol to butanetriols (BTO) and butanediols (BDO) in aqueous solution at 150–240 °C under 30–120 bar H2. The activity depended on the nature of the support, and the highest selectivity to BTO and BDO at 80 % conversion was 37 and 29 %, respectively, in the presence of 3.7 wt %Rh-3.5 wt %ReOx/ZrO2 at 200 °C under 120 bar. The characterization of the catalysts by CO chemisorption, TEM with energy-dispersive X-ray spectroscopy, thermogravimetric analysis with MS, and X-ray photoelectron spectroscopy suggests a different distribution and reducibility of Re species over the supported Rh nanoparticles, which depends on the support.
