Selective Catalytic Hydrogenation of Diethyl Oxalate and Related Esters

Ziebart, Carolin; Jackstell, Ralf; Beller, Matthias

doi:10.1002/cctc.201300209

Cited by 39 publications

(18 citation statements)

References 69 publications

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“…The catalytic activity and stability of Cu-AS-AC, Cu-AM-AC and Cu-AS-AE were investigated in DEO hydrogenation, which proceeded via ethyl glycolate (EGly) to EG, while EG could be dehydrated further to ethanol (Scheme 1). Other products 9 like 2-Butanol may also be generated [32,34]. To compare the catalytic properties of all three catalysts, the effect of reaction temperature, reaction pressure, liquid hourly space velocity (LHSV) and long-term catalytic stability was investigated.…”

Section: Catalytic Activity and Stabilitymentioning

confidence: 99%

Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol

Ding

Popa

Tang

et al. 2017

Applied Catalysis B: Environmental

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Dimethyl Oxalate (DMO) hydrogenation for ethylene glycol (EG) production is problematic due to environmental concerns and safety regulations. Therefore, development of improved methods for diethyl oxalate (DEO) hydrogenation based EG production is desirable. The objective of this research was to develop a cost-effective © 2017. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/ 2 and environmentally benign approach for the synthesis of highly active and stable Cu/SiO 2 catalysts for selective hydrogenation of diethyl oxalate (DEO) to ethylene glycol (EG). Here, ammonium carbonate is used to prepare Cu/SiO 2 catalysts through deposition precipitation instead of the conventional pollution-producing evaporation process associated with the use of ammonia. The Cu/SiO 2 catalysts prepared with the new method achieved 6.9-13.1% higher selectivity and showed better stability. The improved stability and selectivity resulted from increased chemical adsorption of DEO and H 2 due to the high Cu 2 O concertation and Cu + /(Cu 0 +Cu + ) ratio (reduced from ion-exchanged Cu-O-Si units), and reduced carbon deposition on the Cu/SiO 2 catalyst. The Cu 2 O reduced from Cu-O-Si units in the Cu/SiO 2 catalyst prepared bythe new method was more stable than the Cu + species reduced from copper phyllosilicate in the Cu/SiO 2 catalyst prepared by the conventional method. Therefore, the new Cu/SiO 2 catalyst preparation method appears most promising.

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Section: Catalytic Activity and Stabilitymentioning

confidence: 99%

Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol

Ding

Popa

Tang

et al. 2017

Applied Catalysis B: Environmental

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“…As expected, the propiolactam,v alero- lactam,a nd caprolactam derivatives werea ll successfully reduced and produced corresponding amino alcohols 8-10 in almostq uantitative yields, which indicated the feasibility of the protocol. Furthermore, the electronic properties of substituents on the N-phenyl ring hardly showeda ny effect on the reductivetransformation;good to excellent yields were provided (11)(12)(13)(14)(15). Note that the position of the substituent on the Nphenylr ing showed as light impact on the outcomes: ortho-, meta-, and para-methyl substitutes all resulted in good to excellent yields (87, 96, and 99 %f or 11 a, 11 b,a nd 11 c,r espectively).G ratifyingly,t he halide groups were also fully compatible (76-99%, 16-18), and the ring size of lactams showeda slight impact on the yield.…”

Section: Resultsmentioning

confidence: 99%

“…[10][11][12][13] Under mild reaction conditions, ruthenium pincer complex 1 (Ru-MACHO, Scheme 1), ac ommercially available bifunctional catalyst, has exhibited extremelyh igh catalytic activity in the hydrogenation of ketones, amides, and carboxyl esters in the presenceo fasuitable strong base. [14] In contrast, hydride analogue 2 (Ru-MACHO-BH,S cheme 1b) does not require as trong base for activation in similarh ydrogenation reactions,d ue to lack of ac hloride ligand. [15] Given that the NÀH group and RuÀHm oiety of pincerc omplex 1 were all essential for the activation of the challenging amide CÀNb ond, [9a] N-methylatedp incer complexes 3 and 4 were also reported as advantageousc atalysts in the hydrogenationo fc arbon dioxide.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium‐Pincer‐Catalyzed Hydrogenation of Lactams to Amino Alcohols

Chen

Wang

2018

Chemistry An Asian Journal

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By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.

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“…Ding 等 [18b] 研究提出 RuH 与配体 NH 的协同作用是该化合物取得优异加氢活性的关键. 2013 年, Beller 研究组 [19] 进一步考察了该类化合物催化草酸二乙酯(DEO)加氢的反应性能, 结果如表 2 所示. 在 NaOEt/四氢呋喃(THF)溶液中于 100 ℃、6.0 MPa H 2 等条件下反应 20 h, 1 可以催化 DEO 转化为 EG (表 2, Entry 1).…”

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“…在 NaOEt/四氢呋喃(THF)溶液中于 100 ℃、6.0 MPa H 2 等条件下反应 20 h, 1 可以催化 DEO 转化为 EG (表 2, Entry 1). 这一结果与 Gusev 等 [20] Beller 等 [19]…”

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Advances for Ruthenium Catalysts with Metal-Ligand Cooperation for Hydrogenation of Oxalates into Ethylene Glycol

Fang¹,

Duan²,

Zhang³

et al. 2020

Chin. J. Org. Chem.

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Ethylene glycol (EG) is an important fundamental chemical material, which has been widely used in the production of industrial chemicals such as polyester. Catalytic hydrogenation of oxalate into EG is a key step in the "coal-to-EG" industrial route. Design of efficient catalysts for catalyzing the hydrogenation of oxalate esters is a research hotspot. The research progress of ruthenium catalysts with metal-ligand cooperation in the homogeneous catalytic hydrogenation of oxalate esters in the past decade is reviewed. Based on the relationship between the catalyst structures and properties, the catalytic hydrogenation mechanism is discussed, which provides a reference for the further design and development of new catalysts with excellent performance.

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Selective Catalytic Hydrogenation of Diethyl Oxalate and Related Esters

Abstract: Scheme 1.Steps in the hydrogenation of oxalic acid esters.

Cited by 39 publications

References 69 publications

Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol

Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol

Ruthenium‐Pincer‐Catalyzed Hydrogenation of Lactams to Amino Alcohols

Advances for Ruthenium Catalysts with Metal-Ligand Cooperation for Hydrogenation of Oxalates into Ethylene Glycol

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