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.
Directing Selectivity to Aldehydes, Alcohols, or Esters with Diphobane Ligands in Pd-Catalyzed Alkene Carbonylations
Aitipamula, Srinivasulu,Britovsek, George J. P.,Nobbs, James D.,Tay, Dillon W. P.,Van Meurs, Martin
, p. 1914 - 1925 (2021/06/28)
Phenylene-bridged diphobane ligands with different substituents (CF3, H, OMe, (OMe)2, tBu) have been synthesized and applied as ligands in palladium-catalyzed carbonylation reactions of various alkenes. The performance of these ligands in terms of selectivity in hydroformylation versus alkoxycarbonylation has been studied using 1-hexene, 1-octene, and methyl pentenoates as substrates, and the results have been compared with the ethylene-bridged diphobane ligand (BCOPE). Hydroformylation of 1-octene in the protic solvent 2-ethyl hexanol results in a competition between hydroformylation and alkoxycarbonylation, whereby the phenylene-bridged ligands, in particular, the trifluoromethylphenylene-bridged diphobane L1 with an electron-withdrawing substituent, lead to ester products via alkoxycarbonylation, whereas BCOPE gives predominantly alcohol products (n-nonanol and isomers) via reductive hydroformylation. The preference of BCOPE for reductive hydroformylation is also seen in the hydroformylation of 1-hexene in diglyme as the solvent, producing heptanol as the major product, whereas phenylene-bridged ligands show much lower activities in this case. The phenylene-bridged ligands show excellent performance in the methoxycarbonylation of 1-octene to methyl nonanoate, significantly better than BCOPE, the opposite trend seen in hydroformylation activity with these ligands. Studies on the hydroformylation of functionalized alkenes such as 4-methyl pentenoate with phenylene-bridged ligands versus BCOPE showed that also in this case, BCOPE directs product selectivity toward alcohols, while phenylene-bridge diphobane L2 favors aldehyde formation. In addition to ligand effects, product selectivities are also determined by the nature and the amount of the acid cocatalyst used, which can affect substrate and aldehyde hydrogenation as well as double bond isomerization.
PLATINUM COMPLEXES HAVING FERROCENE LIGANDS FOR THE CATALYSIS OF THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
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Paragraph 0053-0057, (2021/10/02)
Platinum complexes having ferrocene ligands for the catalysis of the alkoxycarbonylation of ethylenically unsaturated compounds.
