- 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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- Catalytic oxidation of cyclohexane to KA oil by zinc oxide supported manganese 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin
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A series of manganese metalloporphyrins were prepared and tested in cyclohexane oxidation. It has been found that the manganese 5,10,15,20-tetrakis(4-nitrophonyl) porphyrin (Mn-TNPP) presents better catalytic performance. The Mn-TNPP was then immobilized on different supports, and characterized by UV-vis, FT-IR, XRD, TG/DTG and ICP. Among these supported Mn-TNPP catalysts, Mn-TNPP/ZnO exhibits the best selectivity to KA oil and higher turnover number in cyclohexane oxidation. The influence of the reaction conditions and the recycle of the catalysts are discussed. Mn-TNPP/ZnO catalyst presents the average cyclohexane conversion of 7.17%, KA oil selectivity of 91.18%, and the average catalytic turnover number of 6.53 × 104 after six times of recycle under 150 °C and 1.0 MPa.
- Feng, Ze,Xie, Yujia,Hao, Fang,Liu, Pingle,Luo, He'An
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p. 221 - 225
(2015/10/28)
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- Assessment of formation channels of cyclohexyl mono- and dicarboxylates in oxidation of cyclohexane
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Temperature dependences of the rate constants of the esterification reactions of the main carboxylic acids contained in oxidized cyclohexane (adipic, caproic, and formic) by cyclohexanol in a nonpolar medium were determined by solving the inverse kinetic problem.
- Kotel'Nikova,Revkov,Voronina,Perkel
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experimental part
p. 287 - 294
(2009/06/05)
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- Highly efficient and metal-free aerobic hydrocarbons oxidation process by an o-phenanthroline-mediated organocatalytic system
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A highly efficient o-phenanthroline-mediated, metal-free catalytic system has been developed for oxidation of hydrocarbons with dioxygen in the presence of N-hydroxyphthalimide; various hydrocarbons were efficiently and high selectively oxidized, e.g., ethylbenzene to acetophenone in 97% selectivity and 76% conversion, under mild conditions.
- Tong, Xinli,Xu, Jie,Miao, Hong
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p. 1953 - 1957
(2007/10/03)
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- NONCHAIN CONVERSION OF alpha -DIKETONES AND TRANSACYLATION OF CARBOXYLIC-ACID ANHYDRIDES UNDER AUTOXIDATION CONDITIONS.
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The present investigation produced the following conclusion. The oxidation of 8,9-hexadecanedione by peroxylauric acid in benzene solution conforms to the kinetic equation for a second-order reaction. The oxidation is accompanied by transacylation of the caprylic anhydride formed with lauric acid. The anhydrides formed by transcylation take part in the formation of ester products of autoxidation. Lauric acid actively catalyzes the reaction of 8,9-hexadecanedione with peroxylauric acid.
- Perkel',Freidin,Neginskaya,Stolyankova,Ivanova
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p. 1444 - 1449
(2007/10/02)
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