- Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
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The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.
- Yang, Ji,Liu, Jiawang,Ge, Yao,Huang, Weiheng,Ferretti, Francesco,Neumann, Helfried,Jiao, Haijun,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 9527 - 9533
(2021/03/08)
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- Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes
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The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.
- Yang, Ji,Liu, Jiawang,Neumann, Helfried,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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p. 1514 - 1517
(2020/01/08)
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- Assisted Tandem Catalytic Conversion of Acrylates into Adipic Esters
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A ruthenium-catalyzed tail-to-tail dimerization of acrylates followed by hydrogenation results in the synthesis of adipic esters in one pot. An imine-ligated ruthenium complex that has good catalytic reactivity for tail-to-tail dimerization of methyl acrylate can be readily converted to a hydrogenation catalyst resulting in the assisted tandem catalytic conversion of methyl acrylate to methyl adipate.
- Maity, Pradip K.,Tunge, Jon A.
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p. 3419 - 3423
(2018/07/31)
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- Highly efficient and green esterification of carboxylic acids in deep eutectic solvents without any other additives
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A protocol that carboxylic acids esterifies with the quaternary ammonium salt of deep eutectic solvent (DES) is presented, which opens a new access to ester using DES as alkylating agent, solvent, and catalyst. The reaction runs smoothly in DES without any other additives. Substituted cinnamic acids, aromatic acids, and aliphatic acids can be esterified in moderate to good yields. The advantages of this reaction include excellent functional group compatibility and simple reaction procedure.
- Yasmin, Sumera,Sheng, Wen-Bing,Peng, Cai-Yun,Rahman, Atta-ur,Liao, Duan-Fang,Choudhary, M. Iqbal,Wanga, Wei
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supporting information
p. 68 - 75
(2017/12/26)
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- PROCESS FOR DOUBLE CARBONYLATION OF ALLYL ETHERS TO CORRESPONDING DIESTERS
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The invention relates to a process for doubly carbonylating allyl ethers to the corresponding diesters, wherein a linear or branched allyl ether is reacted with a linear or branched alkanol (alcohol) with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI.
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Paragraph 0095; 0103
(2017/07/14)
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- Esterification of dicarboxylic acids with benzyl alcohol under the action of the microwave radiation
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Reaction of dicarboxylic acid with benzyl alcohol under the microwave irradiation proceeds faster as compared to the thermal conditions. The main reaction products are alkyl dicarboxylates, and the monoester and dibenzyl ether are formed as the side products. A proposal about the nature of the nonthermal effect in the reactions stimulated by the microwave irradiation is considered.
- Aver'yanov,Batrakova,Samuilov,Spiridonova,Kochnev,Galibeev,Gnezdilov
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experimental part
p. 1920 - 1923
(2009/02/08)
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- Synergism of microwaves and immobilized enzyme catalysis in synthesis of adipic acid esters in nonaqueous media
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Low-energy microwave irradiation leads to enhancement by a factor of up to 2.63 in comparison with conventional heating in immobilized lipase-catalyzed esterification of adipic acid with various alcohols and this effect is due to the greater frequency of collision, without any change in activation energy of the two modes of heating. Copyright Taylor & Francis, Inc.
- Yadav, Ganapati D.,Lathi, Piyush S.
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p. 1699 - 1705
(2007/10/03)
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- ESTER COMPOUND, PLASTICIZER FOR BIODEGRADABLE ALIPHATIC POLYESTER RESIN, AND BIODEGRADABLE RESIN COMPOSITION
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An ester compound represented by formula (1)R1OOC―(CH2)m―COOR2???( 1 ) wherein R1 and R2 are different from each other and each represents a group of formula (2)―(R3O)nR4???( 2 ) wherein R3 is a C1-6 alkylene group; R4 is a C1-10 straight- or branched-chain alkyl group, a C6-12 aryl group, C7-15 arylalkyl group or a C7-15 alkylaryl group; m is an integer from 0 to 8, and n is an integer from 0 to 6. This compound is suitable as a plasticizer for biodegradable aliphatic polyester resins.
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- Efficient esterification of carboxylic acids with alkyl halides catalyzed by fluoride ions in ionic liquids
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Ionic liquids based on 1,3-dialkylimidazolinium methanesulfonate have been used as efficient reusable reaction media in the esterification of several carboxylic acids with alkyl halides catalyzed by fluoride ions. The method has wide applicability, and it is mild and green; it is useful for the protection of acids, via ester formation, for alkali labile molecules.
- Brinchi,Germani,Savelli
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p. 6583 - 6585
(2007/10/03)
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- SELECTIVE MONOETHERIFICATION AND MONOESTERIFICATION OF DIOLS AND DIACIDS UNDER PHASE-TRANSFER CONDITIONS
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Research on the selectivity of etherification reactions of diols and esterification reactions of diacids by alkyl halides under phase-transfer catalysis has shown that under such conditions, selectivity of monoetherification increases in the order prim sec tert diols, though overall yield of monoether decreases from sec to tert diols.Monoesterification of diacids was accomplished with a high degree of selectivity.Optimal extraction of diols and diacids was found to correspond in general to chain lengths of around 5 carbons.This could mean that the complex formed between the catalyst and the anion to react is stabilized for certain carbon lengths by inner solvation in virtue of its spatial conformation.
- Zerda, Jaime de la,Barak, Gabriela,Sasson, Yoel
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p. 1533 - 1536
(2007/10/02)
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