6290-49-9Relevant articles and documents
Heteropolyacids as efficient catalysts for the synthesis of precursors to ethylene glycol by the liquid-phase carbonylation of dimethoxymethane
Wang, Junpeng,Liu, Jianhua,Song, Heyuan,Chen, Jing
, p. 806 - 808 (2015)
Methyl methoxyacetate (MMAc), a precursor to ethylene glycol (EG), was synthesized successfully via the liquid-phase carbonylation of dimethoxymethane (DMM) catalyzed by heteropolyacids (HPAs). The experiment results showed that H3PW12O40 (PW12) exhibited the best catalytic performance for the carbonylation of DMM, and its high catalytic activity was attributed to the synergistic effect between its superior acidic strength and the high polarity of the solvent.
Cobalt-catalyzed Hydroesterification of Formaldehyde Dialkyl Acetals
Murata, Kazuhisa,Matsuda, Akio,Masuda, Takashi
, p. 2141 - 2142 (1985)
Co2(CO)8-organic amine system was found to be an effective catalyst for the production of alkoxyacetic ester from formaldehyde dialkyl acetals and CO; this is the first example of homogeneous hydroesterification of acetals.
Activity enhancement of Nafion resin: Vapor-phase carbonylation of dimethoxymethane over Nafion-silica composite
Liu, Shiping,Zhu, Wenliang,Shi, Lei,Liu, Hongchao,Liu, Yong,Ni, Youming,Li, Lina,Zhou, Hui,Xu, Shutao,He, Yanli,Liu, Zhongmin
, p. 153 - 159 (2015)
A kind of composite materials consisting of nano-sized Nafion resin homogeneously dispersed in a high-surface silica matrix was prepared by sol-gel method and used as catalysts in the vapor-phase carbonylation reaction of dimethoxymethane for production of methylmethoxy acetate. These composite catalysts showed much higher catalytic activity in comparison with the original pure Nafion resin catalyst. The remarkable improvement of catalytic performance was due to the increased accessibility of acid sites of Nafion resin in the composite catalysts. The contents of Nafion-H resin and silica precursors were found to have a great influence on the structure of the composite, resulting in different catalytic activity during DMM carbonylation reactions. Furthermore, the comparison of the composite catalysts with high-silica H-Y and H-Beta zeolite catalysts demonstrated that the excellent catalytic performance is closely related to the higher acid strength and larger pores of Nafion-silica composite materials.
A boron-doped carbon aerogel-supported Cu catalyst for the selective hydrogenation of dimethyl oxalate
Lu, Xiaodong,Lu, Xiaodong,Wang, Guofu,Yang, Yu,Kong, Xiangpeng,Chen, Jiangang
, p. 3232 - 3240 (2020/03/06)
Carbon aerogels (CA) were applied in the synthesis of Cu/CA catalysts by the impregnation method and the catalysts with boron-doped CA supports were systematically characterized and evaluated in the hydrogenation of dimethyl oxalate (DMO). The Cu/xB-CA catalyst with 25 wt% copper showed 100% DMO conversion and the highest ethylene glycol (EG) or methyl glycolate (MG) selectivity of 70% at 230 °C as well as a lifetime of over 150 h. The characterization results disclosed the reason the performance of the catalysts could be tuned facilely by changing the amount of boron doping, which effectively influenced the interrelation between copper and CA, acidity and alkalinity of catalysts and Cu dispersion. Both the original carbon aerogels and that promoted with little B could provide larger surface areas and high dispersion of the metal. The species, size of copper particles and the ratio of Cu+/(Cu+ + Cu0) could be regulated by boron doping, thus adjusting the type of hydrogenation products.
Excellent prospects in methyl methoxyacetate synthesis with a highly active and reusable sulfonic acid resin catalyst
Chen, Fei,Shi, Lei,Bello, SuleimanSabo,Fan, Jiaqi,Wang, Yan,Zhang, Dongxi,Yao, Jie
, p. 1346 - 1353 (2020/02/04)
Methyl methoxyacetate (MMAc) is a significant chemical product and can be applied as a gasoline and diesel fuel additive. This study aimed to achieve the industrial production of MMAc via dimethoxymethane (DMM) carbonylation. The effects of industrial DMM sources, reaction temperature, water content, pretreatment temperature, reaction pressure and time, the ratio of CO to DMM and recycle times were systematically investigated without any solvent. The conversion of DMM was 99.98% with 50.66% selectivity of MMAc at 393 K, 6.0 MPa reaction pressure, with the ratio of CO to DMM of only 1.97/1. When water was extracted from the DMM reactant, the MMAc selectivity significantly rose to 68.83%. This resin catalyst was reused for more than nineteen times in a slurry phase reactor and continuously performed for 300 h without noticeable loss of activity in a fixed bed reactor, displaying excellent stability. The mixed products were successfully separated by distillation, and 99.18% purity of MMAc was obtained. Therefore, the reported DMM carbonylation to MMAc process has an excellent basis for industrial application.
Preparation method of 4-alkoxyacetoacetate compound
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Paragraph 0044-0045; 0048-0049; 0052-0053; 0056-0057; 0060, (2020/04/22)
The invention discloses a preparation method of a 4-alkoxyacetoacetate compound, and the method comprises the following steps: reacting a compound I with a first alkali in a first solvent to obtain anintermediate II; reacting the intermediate II obtained in the step (1) with a second alkali in a second solvent to obtain an intermediate III; reacting the intermediate III obtained in the step (2) in an aqueous solution of acid to obtain a product IV, namely the 4-alkoxyacetoacetate compound, wherein X is chlorine, bromine or iodine; wherein R is a C1-C4 alkyl group and a derivative thereof. Thepreparation method provided by the invention has the advantages of simple steps, mild conditions, environmental friendliness, cheap and easily available raw materials, stable supply and low cost, andcreates favorable conditions for reducing the raw material cost of dolutegravir.
METHOD FOR PREPARING ACETAL CARBONYL COMPOUND
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Paragraph 0065; 0066; 0067; 0068; 0069; 0070; 0071-0073, (2018/08/03)
The present application provides a method for preparing acetal carbonyl compound used as a mediate for producing ethylene glycol, which comprises a step in which a raw material acetal and a raw gas carbon monoxide go through a reactor loaded with a catalyst containing an acidic microporous silicoaluminophosphate molecular sieve, for carrying out a carbonylation reaction. In the method of the present invention, the conversion rate of the raw material acetal is high, and the selectivity of acetal carbonylation is high, and the catalyst life is long, and no additional solvent is needed in the reaction process, and the reaction condition is relatively mild, and the process is continuous, showing the potential for industrial application. Moreover, the product of acetal carbonyl compound can be used for producing ethylene glycol by hydrogenation followed by hydrolysis.
Synergistic Effect of a Boron-Doped Carbon-Nanotube-Supported Cu Catalyst for Selective Hydrogenation of Dimethyl Oxalate to Ethanol
Ai, Peipei,Tan, Minghui,Yamane, Noriyuki,Liu, Guoguo,Fan, Ronggang,Yang, Guohui,Yoneyama, Yoshiharu,Yang, Ruiqin,Tsubaki, Noritatsu
supporting information, p. 8252 - 8261 (2017/06/23)
Heteroatom doping is a promising approach to improve the properties of carbon materials for customized applications. Herein, a series of Cu catalysts supported on boron-doped carbon nanotubes (Cu/xB-CNTs) were prepared for the hydrogenation of dimethyl oxalate (DMO) to ethanol. The structure and chemical properties of boron-doped catalysts were characterized by XRD, TEM, N2O pulse adsorption, CO chemisorption, H2 temperature-programmed reduction, and NH3 temperature-programmed desorption, which revealed that doping boron into CNT supports improved the Cu dispersion, strengthened the interaction of Cu species with the CNT support, introduced more surface acid sites, and increased the surface area of Cu0 and especially Cu+ sites. Consequently, the catalytic activity and stability of the catalysts were greatly enhanced by boron doping. 100 % DMO conversion and 78.1 % ethanol selectivity could be achieved over the Cu/1B-CNTs catalyst, the ethanol selectivity of which was almost 1.7 times higher than that of the catalyst without boron doping. These results suggest that doping CNTs with boron is an efficient approach to improve the catalytic performance of CNT-based catalysts for hydrogenation of DMO. The boron-doped CNT-based catalyst with improved ethanol selectivity and catalytic stability will be helpful in the development of efficient Cu catalysts supported on non-silica materials for selective hydrogenation of DMO to ethanol.
The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
Fortea-Pérez, Francisco R.,Mon, Marta,Ferrando-Soria, Jesús,Boronat, Mercedes,Leyva-Pérez, Antonio,Corma, Avelino,Herrera, Juan Manuel,Osadchii, Dmitrii,Gascon, Jorge,Armentano, Donatella,Pardo, Emilio
, p. 760 - 766 (2017/07/04)
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes.
METHOD FOR PREPARING POLYOXYMETHYLENE DIMETHYL ETHER CARBONYL COMPOUND AND METHYL METHOXYACETATE
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Paragraph 0051; 0053, (2017/01/23)
A method for preparing a polyoxymethylene dimethyl ether carbonyl compound and/or methyl methoxyacetate as intermediates for producing ethylene glycol, which comprises passing a raw material: polyoxymethylene dimethyl ether or methylal together with carbon monoxide and hydrogen gas through a reactor carrying an acidic molecular sieve catalyst, and performing a reaction to prepare a corresponding product under an appropriate condition where no other solvent is added, in which the process of the reaction is a gas-liquid-solid three-phase reaction, the raw material of polyoxymethylene dimethyl ether or methylal has a high conversion rate, each product has a high selectivity, the catalyst has a long service life, additional solvents are not required to be used, and reaction conditions are relatively mild.
