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.
Ruthenium complex immobilized on supported ionic-liquid-phase (SILP) for alkoxycarbonylation of olefins with CO2
Xia, Shi-Ping,Ding, Guang-Rong,Zhang, Rui,Han, Li-Jun,Xu, Bao-Hua,Zhang, Suo-Jiang
, p. 3073 - 3080 (2021/05/05)
In this study, the heterogeneously catalyzed alkoxycarbonylation of olefins with CO2based on a supported ionic-liquid-phase (SILP) strategy is reported for the first time. An [Ru]@SILP catalyst was accessed by immobilization of ruthenium complex on a SILP, wherein imidazolium chloride was chemically integrated at the surface or in the channels of the silica gel support. An active Ru site was generated through reacting Ru3(CO)12with the decorated imidazolium chloride in a proper microenvironment. Different IL films, by varying the functionality of the side chain at the imidazolium cation, were found to strongly affect the porosity, active Ru sites, and CO2adsorption capacity of [Ru]@SILP, thereby considerably influencing its catalytic performance. The optimized [Ru]@SILP-A-2 displayed enhanced catalytic performance and prominent substrate selectivity compared to an independent homogeneous system under identical conditions. These findings provide the basis for a novel design concept for achieving both efficient and stable catalysts in the coupling of CO2with olefins.
Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins
Akiri, Saphan O.,Ojwach, Stephen O.
, (2021/09/09)
Reactions of ligands (E)-N′-(2,6-diisopropylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L1), (E)-N′-(2,6-diisopropylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L2), (E)-N′-(2,6-dimethylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L3), (E)-N′-(2,6-dimethylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L4), and (E)-N-(6-methylpyridin-2-yl)-N′-phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para-tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.
