554-12-1Relevant articles and documents
Polymer producing palladium complexes of unidentate phosphines in the methoxycarbonylation of ethene
Smith, Graeme,Vautravers, Nicolas R.,Cole-Hamilton, David J.
, p. 872 - 877 (2009)
A wide range of unidentate phosphines have been studied as ligands for the palladium-catalysed methoxycarbonylation of ethene in the presence of methanesulfonic acid using methanol as the solvent. At high phosphine to Pd ratios, methyl propanoate is forme
One-pot, three-component synthesis of open-chain, polyfunctional sulfones
Bouchez, Laure,Vogel, Pierre
, p. 225 - 231 (2002)
Silyl enol ethers of esters, ketones, as well as allylstannane and allylsilanes react with sulfur dioxide activated with t-BuMe2SiOSO2CF3 to give silyl sulfinates that can be reacted in the same pot with a variety of electrophiles generating the corresponding polyfunctional sulfones. The silyl sulfinate intermediates are formed via ene-reactions following probably concerted mechanisms.
Synthesis, characterization and catalytic properties of sulfonic acid functionalized magnetic-poly(divinylbenzene-4-vinylpyridine) for esterification of propionic acid with methanol
Kara, Ali,Erdem, Beyhan
, p. 42 - 47 (2011)
The magnetic-poly(divinylbenzene-4-vinylpyridine) [m-poly(DVB-4VP)] microbeads (average diameter: 180-212 μm) were synthesized by copolymerizing of divinylbenzene (DVB) with 4-vinylpyridine (4VP) and by mixing this copolymer with Fe3O4 nanoparticles. The resultant material was characterized by N2 adsorption/desorption, ESR, elemental analysis, scanning electron microscope (SEM) and swelling studies. After functionalized with sulfonic acid, m-poly(DVB-4VP-SO3H) was characterized by FT-IR and TGA analysis. The results showed that both of Fe3O4 and -SO3H are bonded to the polymer successfully. N2 adsorption/desorption isotherms of synthesized samples had the hysteresis behaviour associated with mesoporous materials (pore diameter: 3.73 nm). Sulfonic acid functionalized mesoporous m-poly(DVB-4VP-SO3H) has been demonstrated to have higher reactivity than commercially available solid acid catalysts for the conversion of propionic acid to methyl ester. The apparent activation energy was found to be 38.5 kJ mol-1 for m-poly(DVB-4VP-20%SO3H). The catalyst showed negligible loss of activity after four repetitive cycles.
Sulfonic acid functionalized poly (ethylene glycol dimethacrylate-1-vinyl- 1,2,4-triazole) as an efficient catalyst for the synthesis of methyl propionate
Erdem, Beyhan,Kara, Ali
, p. 219 - 224 (2011)
Sulfonic acid functionalized poly (ethylene glycol dimethacrylate-1-vinyl- 1,2,4-triazole), poly (EGDMA-VTAZ-SO3H) (average diameter 1.0-1.5 mm), was found to be efficient solid acid catalyst for the esterification of methanol and propionic acid under heterogeneous reaction conditions. The pristine polymer, poly (EGDMA-VTAZ), was produced by suspension polymerization and then proton-conducting polymer was obtained by blending of poly (EGDMA-VTAZ) with different percentage of H2SO4 solutions. The protonation of aromatic heterocyclic rings was proved with Fourier-transform infrared spectroscopy (FT-IR). Thermo gravimetric (TG) analysis showed that the catalyst is thermally stable up to 573 K. The surface morphology of the catalyst was characterized by scanning electron microscopy (SEM). Poly (EGDMA-VTAZ-SO3H) beads can be regenerated and reused, so this provides a potential application. It has a rate constant which exceeds that of Amberlyst-15 by a factor of about four at 333 K. As for the reaction equilibrium constant (Ke), which is independent of temperature ranging from 318 to 343 K, was determined to be 3.16. The apparent activation energy was found to be 41.6 kJ mol-1 for poly (EGDMA-VTAZ-SO3H).
Direct Hydroesterification of Ethylene with Methyl Formate with the New System RuCl3-NR4I-NR3: an Example of Catalytic Activation of the CH Bond of Methyl Formate?
Legrand, Christophe,Castanet, Yves,Mortreux, Andre,Petit, Francis
, p. 1173 - 1174 (1994)
Upon using the simple RuCl3-NR4I-NR3 catalytic combination and dimethylformamide as solvent, an exceptionally reactive system is obtained for direct hydroesterification of ethylene with methyl formate (turnover frequency up to 2000 h-1) in the absence of carbon monoxide.
Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts
Khokarale, Santosh G.,García-Suárez, Eduardo J.,Fehrmann, Rasmus,Riisager, Anders
, p. 1824 - 1829 (2017)
Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction p
Zwitterion enhanced performance in palladium-phosphine catalyzed ethylene methoxycarbonylation
Khokarale,García-Suárez,Xiong,Mentzel,Fehrmann,Riisager
, p. 73 - 75 (2014)
Zwitterions were used for the first time as promoters in ethylene methoxycarbonylation for the production of methyl propionate. They were found to improve the catalytic performance of the Pd-phosphine system. The presence of zwitterions could contribute to stabilize transition states and active catalytic Pd intermediates. The beneficial effect of the zwitterions was found to be most pronounced, when low amount of a strong acid (MeSO3H) was used with respect to palladium (below 2 equiv.). Under these conditions, phosphine ligand alkylation and reaction vessel corrosion are also anticipated to be less severe.
Ethene hydromethoxycarbonylation catalyzed by cis-[Pd(SO 4)(PPh3)2]/H2SO4/PPh 3
Cavinato, Gianni,Facchetti, Sarah,Toniolo, Luigi
, p. 180 - 185 (2010)
The neutral precursor cis-[Pd(SO4)(PPh3)2] turns into an active catalyst for the hydromethoxycarbonylation of ethene when used in combination with H2SO4 and PPh3. The influence of the following operating conditions on the catalytic activity have been studied: (i) H2SO4/Pd ratio; (ii) PPh3/Pd ratio; (iii) total pressure with CO/ethene = 1/1; (iv) pressure of one gas at constant pressure of the other; (v) H2O concentration; (vi) temperature. At 100 °C a TOF = 2168 h-1 has been achieved when the catalytic system is used in the ratios Pd/H2SO4/P = 1/107/18 (mol/mol), under 6 bar (CO/E = 1/1), H2O concentration 0.16% in MeOH by weight. After catalysis and upon addition of LiCl, trans-[Pd(COEt)Cl(PPh3)2], which is related to the Pd-H catalytic cycle, has been isolated. Cis-[Pd(SO 4)(PPh3)2] in CD2Cl2/MeOH reacts with CO to give a PdCOOMe complex (related to the carbomethoxy mechanism ), which neither inserts ethene, nor gives methyl propanoate (MP). In the presence of H2O and H2SO4 the carbomethoxy complex is unstable giving a Pd-H complex, which yields catalysis to MP in the presence of CO and ethene. The Pd-H and Pd-COOMe catalytic cycles are discussed on the basis of the influence of the operating conditions on the TOF and of NMR evidences.
Acid-Promoter-Free Ethylene Methoxycarbonylation over Ru-Clusters/Ceria: The Catalysis of Interfacial Lewis Acid-Base Pair
An, Jinghua,Wang, Yehong,Lu, Jianmin,Zhang, Jian,Zhang, Zhixin,Xu, Shutao,Liu, Xiaoyan,Zhang, Tao,Gocyla, Martin,Heggen, Marc,Dunin-Borkowski, Rafal E.,Fornasiero, Paolo,Wang, Feng
, p. 4172 - 4181 (2018)
The interface of metal-oxide plays pivotal roles in catalytic reactions, but its catalytic function is still not clear. In this study, we report the high activity of nanostructured Ru/ceria (Ru-clusters/ceria) in the ethylene methoxycarbonylation (EMC) re
Borate esters as alternative acid promoters in the palladium-catalyzed methoxycarbonylation of ethylene
Ferreira, Alta C.,Crous, Renier,Bennie, Linette,Meij, Anna M. M.,Blann, Kevin,Bezuidenhoudt, Barend C. B.,Young, Desmond A.,Green, Mike J.,Roodt, Andreas
, p. 2273 - 2275 (2007)
(Chemical Equation Presented) Out with convention! The use of borosalicylic acid, derived from boric and salicylic acids, as the acid promoter in the methoxycarbonylation of ethylene to give methyl propionate has been investigated (see scheme). Not only w
