453-20-3Relevant academic research and scientific papers
Preparation method of hydroxyl oxacycloalkane derivative
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Paragraph 0049-0070, (2021/08/14)
The invention relates to a preparation method of a hydroxyl oxacycloalkane derivative, which comprises the following steps: 1) preparing an initial reaction raw material compound and a catalyst into a raw material solution by using a solvent, and respectively pumping the raw material solution and an oxide material into a continuous flow reactor preheating module from different material conveying equipment for preheating; 2) feeding the material passing through the preheating module into a mixing module, feeding the mixed material into a reaction module, and continuously reacting in the reaction module to obtain a reaction mixture; (3) after the reaction, enabling a reaction mixture to enter a product separation module, and carrying out organic-inorganic separation or solvent removal on reaction liquid at cooling or reaction temperature or raised temperature to obtain a crude product; and refining the crude product to obtain a pure product. According to the method disclosed by the invention, the reaction process can be simplified, the reaction time can be shortened, and the hydroxyl oxacycloalkane derivative can be more efficiently synthesized.
Preparation method of hydroxytetrahydrofuran compound
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Paragraph 0044-0069, (2021/08/19)
The invention discloses a preparation method of a hydroxytetrahydrofuran compound. The method adopts a heterogeneous catalytic reaction step, and is characterized by taking a 3, 4-epoxy tetrahydrofuran compound as a raw material, and carrying out hydrolysis or alcoholysis ring opening, catalytic hydrogenolysis and other catalytic processes to obtain the 3-hydroxytetrahydrofuran compound. The method is green in process, simple to operate, low in catalyst price, relatively simple in separation, efficient and simple to operate, and beneficial to large-scale industrial production of the 3-hydroxytetrahydrofuran compound.
Preparation of Highly Active Monometallic Rhenium Catalysts for Selective Synthesis of 1,4-Butanediol from 1,4-Anhydroerythritol
Wang, Tianmiao,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
, p. 3615 - 3626 (2019/07/15)
1,4-Butanediol can be produced from 1,4-anhydroerythritol through the co-catalysis of monometallic mixed catalysts (ReOx/CeO2+ReOx/C) in the one-pot reduction with H2. The highest yield of 1,4-butanediol was over 80 %, which is similar to the value obtained over ReOx–Au/CeO2+ReOx/C catalysts. Mixed catalysts of CeO2+ReOx/C showed almost the same performance, giving 89 % yield of 1,4-butanediol. The reactivity trends of possible intermediates suggest that the reaction mechanism over ReOx/CeO2+ReOx/C is similar to that over ReOx–Au/CeO2+ReOx/C: deoxydehydration (DODH) of 1,4-anhydroerythritol to 2,5-dihydrofuran over ReOx species on the CeO2 support with the promotion of H2 activation by ReOx/C, isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran catalyzed by ReOx on the C support, hydration of 2,3-dihydrofuran catalyzed by C, and hydrogenation to 1,4-butanediol catalyzed by ReOx/C. The reaction order of conversion of 1,4-anhydroerythritol with respect to H2 pressure is almost zero and this indicates that the rate-determining step is the formation of 2,5-dihydrofuran from the coordinated substrate with reduced Re in the DODH step. The activity of ReOx/CeO2+ReOx/C is higher than that of ReOx–Au/CeO2+ReOx/C, which is probably related to the reducibility of ReOx/C and the mobility of the Re species between the supports. High-valent Re species such as Re7+ on the CeO2 and C supports are mobile in the solvent; however, low-valent Re species, including metallic Re species, have much lower mobility. Metallic Re and cationic low-valent Re species with high reducibility and low mobility can be present on the carbon support as a trigger for H2 activation and promoter of the reduction of Re species on CeO2. The presence of noble metals such as Au can enhance the reducibility through the activation of H2 molecules on the noble metal and the formation of spilt-over hydrogen over noble metal/CeO2, as indicated by H2 temperature-programmed reduction. The higher reducibility of ReOx–Au/CeO2 lowers the DODH activity of ReOx–Au/CeO2+ReOx/C in comparison with ReOx/CeO2+ReOx/C by restricting the movement of Re species from C to CeO2.
A strategy of ketalization for the catalytic selective dehydration of biomass-based polyols over H-beta zeolite
Che, Penghua,Lu, Fang,Si, Xiaoqin,Ma, Hong,Nie, Xin,Xu, Jie
supporting information, p. 634 - 640 (2018/02/14)
Biomass contains plentiful hydroxyl groups that lead to an oxygen-rich structure compared to petroleum-based chemicals. Dehydration is the most energy-efficient technique to remove oxygen; however, multiple similar vicinal hydroxyl groups in sugar alcohols impose significant challenges for their selective dehydration. Here, we present a novel strategy to control the etherification site in sugar alcohols by the ketalization of the vicinal-diol group for the highly selective formation of tetrahydrofuran derivatives. A ketone firstly reacts with terminal vicinal hydroxyl groups to form the 1,3-dioxolane structure. This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate intramolecular etherification. As a better leaving group than water, the ketone can also promote intramolecular etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with the H-beta zeolite catalyst under mild reaction conditions. This strategy opens up new opportunities for the efficient upgrading of biomass via the modification or protection of hydroxyl groups.
One-pot catalytic selective synthesis of 1,4-butanediol from 1,4-anhydroerythritol and hydrogen
Wang, Tianmiao,Liu, Sibao,Tamura, Masazumi,Nakagawa, Yoshinao,Hiyoshi, Norihito,Tomishige, Keiichi
supporting information, p. 2547 - 2557 (2018/06/18)
A physical mixture of ReOx-Au/CeO2 and carbon-supported rhenium catalysts effectively converted 1,4-anhydroerythritol to 1,4-butanediol with H2 as a reductant. The combination of these two catalysts in a one-pot reaction dramatically increased the selectivity of 1,4-butanediol as well as the conversion of 1,4-anhydroerythritol. The yield of 1,4-butanediol reached ～90%, which is the highest yield from erythritol and 1,4-anhydroerythritol so far, furthermore, at a relatively low reaction temperature of 413 K. This reaction involves the ReOx-Au/CeO2-catalyzed deoxydehydration of 1,4-anhydroerythritol to 2,5-dihydrofuran and ReOx/C-catalyzed successive isomerization, hydration and reduction reactions of 2,5-dihydrofuran.
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.
A pharmaceutical intermediates (S)-3 - hydroxy tetrahydrofuran preparation method (by machine translation)
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Paragraph 0040, (2017/08/31)
The invention provides a pharmaceutical intermediate (S)- 3 - hydroxy tetrahydrofuran preparation method. The method other than racemic 1, 2, 4 - butanetriol as raw materials synthesis of racemic 3 - hydroxy tetrahydrofuran, then esterification of racemic tetrahydrofuran-yl - 3 - fatty acid ester. By lipase hydrolysis in the racemic mixture of (R)- tetrahydrofuran-based - 3 - fatty acid ester after, in in the hydrolysis product under the condition of separating, using the mitsunobu reaction will be hydrolyzed to obtain the of (R)- 3 - hydroxy tetrahydrofuran is converted into (S)- tetrahydrofuran-based - 3 - carboxylic acid ester, finally under alkaline condition all of the tetrahydrofuran ester hydrolyzed to obtain the final product (S)- 3 - hydroxy tetrahydrofuran. (by machine translation)
SYNTHESIS OF R-GLUCOSIDES, SUGAR ALCOHOLS, REDUCED SUGAR ALCOHOLS, AND FURAN DERIVATIVES OF REDUCED SUGAR ALCOHOLS
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Paragraph 0077, (2017/05/31)
Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.
Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters
Li, Yuehui,Topf, Christoph,Cui, Xinjiang,Junge, Kathrin,Beller, Matthias
supporting information, p. 5196 - 5200 (2015/04/27)
Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. An assist from Al: A bifunctional catalyst system consisting of a Ru/phosphine complex and aluminum triflate allows selective hydrogenation of esters to ethers. A variety of lactones were reduced to the desired products in good yields. The catalyst further provides a general method for the reduction of linear esters and reductive etherification of carboxylic acids with alcohols.
METHOD FOR PRODUCING 3-HYDROXYTETRAHYDROFURAN AND METHOD FOR PRODUCING 1, 3-BUTANE DIOL
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, (2015/11/18)
An object of the present invention is to provide a method for producing 3-hydroxytetrahydrofuran that can be used as a raw material for 1,3-butane diol, using as a raw material a compound that can be derived from biomass. The present invention relates to a method for producing 3-hydroxytetrahydrofuran including a step of reacting 1,4-anhydroerythritol and hydrogen to produce 3-hydroxytetrahydrofuran. In the production method, the step of reacting 1,4-anhydroerythritol and hydrogen is preferably allowed to proceed in the presence of a catalyst comprising a carrier and at least one oxide selected from the group consisting of an oxide of a Group 6 element and an oxide of a Group 7 element, the oxide being supported on the carrier.
