1731-84-6Relevant articles and documents
Model of selectivity to methyl pelargonate in hydrocarbomethoxylation of 1-octene in the presence of the Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid catalytic system
Batashev, S. A.,Sevostyanova, N. T.
, p. 1561 - 1568 (2020)
The model of selectivity to methyl pelargonate was developed for the hydrocarbomethoxylation of 1-octene catalyzed by the Pd(PPh3)2Cl2—PPh3—p-toluenesulfonic acid system (378 K). The ratio of the rate of methyl pelargonate formation to the sum of the rates of formation of three isomeric esters (reaction products) was accepted as the differential selectivity of the reaction. The model represents a system of equations relating the differential selectivity of the reaction to the CO pressure and concentrations of methanol, PPh3, and p-toluenesulfonic acid. The model adequately depicts the experimental data in a wide range of 1-octene conversions up to 95.5%. The regularities of a change in the reaction selectivity were substantiated using the hydride multiroute mechanism of hydrocarbomethoxylation of 1-octene.
Synthesis of new diphosphine ligands and their application in pd-catalyzed alkoxycarbonylation reactions
Pews-Davtyan, Anahit,Fang, Xianjie,Jackstell, Ralf,Spannenberg, Anke,Baumann, Wolfgang,Franke, Robert,Beller, Matthias
, p. 1168 - 1174 (2014)
Carbocyclic and N-heterocyclic analogues of the industrially applied ligand bis(di-tert-butylphosphinomethyl)benzene (1) have been synthesized in moderate to very good yields. The new ligands are based on benzene, tetralin, lutidine, pyrazine, quinoxaline, and maleimide backbones. Electronic and steric variations of the phosphorous donor sites were performed. As a benchmark reaction, the palladium-catalyzed methoxycarbonylation of 1-octene has been tested. Ester yields up to 64 and high linear selectivities up to 92 were achieved. So much potential: Carbocyclic and N-heterocyclic analogues of bis(di-tert- butylphosphinomethyl) benzene (1) have been synthesized in moderate to very good yields. The new ligands demonstrated their catalytic potential in palladium-catalyzed methoxycarbonylation of 1-octene.
Ozonolytic transformations of olefinic derivatives of L-menthol and ricinolic acid
Ishmuratov,Yakovleva,Shayakhmetova,Botsman,Nasibullina,Muslukhov,Tolstikov
, p. 631 - 635 (2006)
Ozonolysis and reduction of olefinic derivatives of ricinolic acid and L-menthol were studied using hydroxylamine hydrochloride and sodium trisacetoxyborohydride to reduce the peroxide products.
An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium-Chain Alkenes
Holzapfel, Cedric,Bredenkamp, Tyler
, p. 2598 - 2606 (2015)
The methoxycarbonylation reaction provides a route to the synthesis of esters from medium-chain alkenes that may be used as fuel supplements. However, the known productive catalytic systems are expensive and/or unstable at elevated temperatures. Most of the data available on the methoxycarbonylation of alkenes is derived from ethylene and styrene as substrates. To broaden the scope, we conducted a comparative study of a range of phosphine ligands under comparable conditions for the methoxycarbonylation of 1-octene. The results demonstrate that a number of ligand structural motifs facilitate the process effectually. Furthermore, the critical importance of alkene isomerization and the acid/ligand and Pd/ligand ratios are presented.
Direct Synthesis of an α,ω-Diester from 2,7-Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps
Ostrowski, Karoline A.,Vogelsang, Dennis,Seidensticker, Thomas,Vorholt, Andreas J.
, p. 1840 - 1846 (2016)
A new tandem catalytic process was designed and developed as a tool for the direct conversion of the widely available feedstock 2,7-octadienol into an α,ω-diester. This innovative auto-tandem catalysis is atom efficient and consists of three consecutive palladium-catalysed reactions: ether formation, ether carbonylation and alkoxycarbonylation. By using the design of experiments (DoE) approach, significant parameters were determined and the yield of the desired α,ω-diester was optimised. Model substrates allowed deeper insight into the progress of the reaction to be gained and, as a result, the reaction sequence was uncovered. Furthermore, by simply applying other ligands, a different reaction path was followed, allowing other, new tandem catalytic sequences to be explored and enabling new compounds to be obtained.
Reaction Mechanism of Pd-Catalyzed “CO-Free” Carbonylation Reaction Uncovered by In Situ Spectroscopy: The Formyl Mechanism
Geitner, Robert,Gurinov, Andrei,Huang, Tianbai,Kupfer, Stephan,Gr?fe, Stefanie,Weckhuysen, Bert M.
supporting information, p. 3422 - 3427 (2020/12/15)
“CO-free” carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C?H activation of in situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in situ observed Pd-hydride, Pd-formyl and Pd-acyl species.
Method for enhancing long-chain olefin hydrogen esterification reaction by ionic liquid
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Paragraph 0065-0080, (2021/06/13)
The invention relates to a method for preparing carboxylic ester through long-chain olefin hydrogen esterification reaction. The method is characterized by comprising the following steps: mixing long-chain olefin of which the C number is greater than or equal to 4 with a catalyst, a carbonyl source and alkyl alcohol according to a certain ratio, and carrying out hydrogen esterification reaction in a high-boiling-point solvent such as ester, ketone, ether, amide, aromatic hydrocarbon, sulfone (sulfoxide) or conventional ionic liquid. The first ligand is a bidentate phosphine ligand, and the second ligand is an ionic liquid containing a single-coordination central atom (N, P). The method has the advantages that raw material gas and liquid phases can be in full contact, the catalyst and a high-boiling-point solvent system can be recycled, and rapid separation of the catalyst and a product is achieved. In the conjugated olefin hydrogen esterification reaction, the olefin conversion rate is more than 80%, and the product selectivity is more than 85%; in the monoolefine hydrogen esterification reaction, the olefin conversion rate is greater than 90%, and the product selectivity is greater than 95%.