Highly active and selective catalysts for the production of methyl propanoate via the methoxycarbonylation of ethene

Clegg, William; Elsegood, Mark R. J.; Eastham, Graham R.; Tooze, Robert P.; Wang, Xiao Lan; Whiston, Keith

doi:10.1039/a905521e

Cited by 239 publications

(185 citation statements)

References 4 publications

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“…107 The ligand, once complexed to palladium has shown very high activity towards the methoxycarbonylation of ethylene with turnover numbers >100,000. 106 As outlined by the authors, the obtained methyl propanoate was suggested to be a possible intermediate for the synthesis of methyl methacrylate. Indeed, the catalytic system patented by the Lucite company is nowadays used in the "Alpha Process" for the production of methyl propanoate leading to the synthesis of methyl methacrylate.…”

Section: The Alkoxycarbonylation Of Simple Alkenesmentioning

confidence: 99%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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Dimethyl 1,19-nonadecanedioate is produced from the methoxycarbonylation of commercial olive, rapeseed or sunflower oils in the presence of a catalyst derived from [Pd 2 (dba) 3 ], bis(ditertiarybutylphosphinomethyl)benzene (BDTBPMB) and methanesulphonic acid (MSA). The diester is then hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-(diphenylphosphinemethyl)ethane (triphos). 1,19-Nonadecadienoic acid is hydrogenated to short chain oligoesters, which can themselves be hydrogenated to 1,19-nonadecanol by hydrogenation in the presence of water.

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Section: The Alkoxycarbonylation Of Simple Alkenesmentioning

confidence: 99%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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“…C 3 -bridged diphenylphosphine of the type reported on the title, or other diaryl analogues, for example with ortho-methoxy substituents on the phenyl rings, are highly active in the copolymerization process [17], whereas bulkier diphosphines such as t-BuP(CH 2 ) 3 PBu-t or 1,2-bis[(di-tertbutyl)phosphinomethyl]benzene are very active and selective in promoting the methoxycarbonylation to MP [8][9][10][11]17]. That steric bulk plays a role of paramount importance in controlling the selectivity of the reaction is also well illustrated by the results obtained using cationic Pd(II) complexes of 1,1 0 -bis(dialkylphosphino) ferrocene ligand, as when alkyl = methyl the catalyst is very active in promoting high molecular weight PK, whereas when alkyl = ethyl lower molecular weight PK are obtained, and when alkyl = i-propyl the products are MP and DEK [18].…”

Section: Introductionmentioning

confidence: 99%

“…Monocarbonylated products form through the so called ''hydride'' mechanism, which involves the insertion of the olefin into a Pd-H bond with formation of a Pd-alkyl bond, followed by the insertion of CO into the Pd-alkyl intermediate with formation of a Pd-acyl species, which undergoes alcoholysis or hydrolysis to the ester or the acid with reformation of the Pd-H species starting the catalytic cycle [8][9][10][11]. DEK forms when the insertion of a second molecule of ethene into the Pd-acyl bond occurs with formation of a Pd-alkylacyl intermediate, followed by protonolysis [12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

Cavinato

Vavasori

Toniolo

et al. 2005

Inorganica Chimica Acta

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The title complex has been synthesized by first reacting dppp with Pd(AcO) 2 in acetone and then with NaHSO 4 in water. It has been characterized by IR, NMR and X-ray diffraction studies. The 31 P NMR spectrum in DMSO shows a singlet at 16.62 ppm indicating that the two P atoms are equivalent and that the sulfate anion is weakly coordinating. The X-ray structure shows that the Pd atom is surrounded in an almost regular square planar environment by the two P atoms and by two O atoms of the sulfate anion and that the neutral complex is accompanied by a water molecule of crystallization. The Pd-P distances (2.217(1) and 2.233(1)) and the P-Pd-P angle (90.78(3)°) are close to those found in other complexes where the chelating diphosphine is the same. Also the Pd-O distances and the O-Pd-O bond angle are comparable to those of other relevant chelating ligands.In MeOH, the title complex, in combination with H 2 SO 4 , catalyses the CO-ethene copolymerization. The productivity reaches a maximum upon increasing the H 2 SO 4 /Pd ratio up to ca. 470 (7650 g of polyketone/g Pd h at 90°C and 45 atm, CO/ethene 1/1). The viscosity of the polyketone passes through a maximum of 0.95 dL/g in m-cresol when the above ratio is ca. 100. It has been proposed that acid promotes the copolymerization process by destabilizing the b-and c-chelates intermediates involved in chain growing process, thus favoring the insertion of the monomers. At relatively high acid concentration the lowering of productivity and viscosity suggests that the sulfate anion competes with the monomers for the coordination to the metal center.In H 2 O-CH 3 COOH as a solvent the productivity strongly depends on the H 2 O/CH 3 COOH ratio, as it passes through a maximum of 12 000 g polymer/g Pd h in the presence of ca. 60% of H 2 O. The productivity is significantly lower than that found when the acetate and chloride analogues are used (27 000 g polyketone/g Pd AE h). Thus, it is likely that the sulfate anion assists significantly the copolymerization process even though the concentration of CH 3 COOH/CH 3 COO À is much preponderant.

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“…Even higher performance to MP was obtained by using the C 4 -bridged ligand dtbpx (99.98% selectivity, TOF = 50,000 h −1 under the same conditions; dtbpx = 1,2-bis[(di-t-butyl)phosphinomethyl]benzene) [23]. The sharp change in selectivity from PK to MP was explained on the basis of steric bulk considerations.…”

Section: Introductionmentioning

confidence: 99%

CO–ethene copolymerisation catalysed by [PdCl2(PPh3)2]/PPh3/HCl in MeOH

Cavinato

Vavasori²,

Amadio³

et al. 2007

Journal of Molecular Catalysis A: Chemical

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The system [PdCl 2 (PPh 3 ) 2 ]/PPh 3 /HCl catalyses the carbonylation of ethene in MeOH as a solvent to give methyl propanoate (MP) or a polyketone (PK).The influence of temperature, Pd/P, CO/ethene and Pd/HCl ratios, and concentration of H 2 O on the catalytic activity has been studied. The catalytic system is active only in the presence of HCl and is stable when P/Pd is ≥6/1 up to 110• C. At 100• C, with Pd/P/HCl = 1/6/1600 (HCl initially added), under 6.0 MPa total pressure, the main product is MP at 1.0 MPa of ethene, whereas is PK when the pressure of the olefin is higher than 4.0 MPa.Water, which forms in the solvent, because of the reaction of MeOH with HCl, has a minor effect. The PK product presents a 2.5-4/1 ratio between the keto and ester end groups. The proposed catalytic cycle takes into account the results.

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Highly active and selective catalysts for the production of methyl propanoate via the methoxycarbonylation of ethene

Cited by 239 publications

References 4 publications

Polymer precursors from catalytic reactions of natural oils

Polymer precursors from catalytic reactions of natural oils

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

CO–ethene copolymerisation catalysed by [PdCl2(PPh3)2]/PPh3/HCl in MeOH

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