An improved cobalt-catalysed alkoxycarbonylation of olefins using secondary phosphine oxide promotors

Huang, Wei-Heng; Jackstell, Ralf; Spannenberg, Anke; Beller, Matthias

doi:10.1039/d3cy00066d

Cited by 4 publications

(1 citation statement)

References 34 publications

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“…Pyridine-promoted cobalt carbonyls demonstrated high efficiency in converting butadiene to adipic acid in a pilot-scale process developed by BASF [28,29]. Cobalt carbonyls were also competent catalysts in the alkoxycarbonylation reactions of alkenes [30]. Nevertheless, to the best of our knowledge, few reports have been produced on the Co-catalyzed methoxycarbonylation of acetylene.…”

Section: Introductionmentioning

confidence: 99%

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species

Wang,

Cao,

Zhang

et al. 2024

Molecules

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Reppe carbonylation of acetylene is an atom-economic and non-petroleum approach to synthesize acrylic acid and acrylate esters, which are key intermediates in the textile, leather finishing, and polymer industries. In the present work, a noble metal-free Co@SiO2 catalyst was prepared and evaluated in the methoxycarbonylation reaction of acetylene. It was discovered that pretreatment of the catalyst by different reductants (i.e., C2H2, CO, H2, and syngas) greatly improved the catalytic activity, of which Co/SiO2-H2 demonstrated the best performance under conditions of 160 °C, 0.05 MPa C2H2, 4 MPa CO, and 1 h, affording a production rate of 4.38 gMA+MP gcat−1 h−1 for methyl acrylate (MA) and methyl propionate (MP) and 0.91 gDMS gcat−1 h−1 for dimethyl succinate (DMS), respectively. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectra of CO adsorption (CO-DRIFTS) measurements revealed that an H2 reduction decreased the size of the Co nanoparticles and promoted the formation of hollow architectures, leading to an increase in the metal surface area and CO adsorption on the catalyst. The hot filtration experiment confirmed that Co2(CO)8 was generated in situ during the reaction or at the pre-activation stage, which served as the genuine active species. Our work provides a facile and convenient approach to the in situ synthetization of Co2(CO)8 for a Reppe carbonylation reaction.

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Section: Introductionmentioning

confidence: 99%

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species

Wang,

Cao,

Zhang

et al. 2024

Molecules

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Strong Acid‐Free Homogeneous Catalytic Systems for the Ester Products Synthesis by Alkenes Alkoxycarbonylation: Recent Advances

Sevostyanova,

Batashev

2024

Eur J Org Chem

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Alkoxycarbonylation represents a method for the ester products synthesis from available reagents – unsaturated compounds, alcohols, and CO. The beginning of research on this reaction was laid in W. Reppe’ works in 1953. In early works, halides and carbonyls of Co, Ni, Rh, and Ir were used as catalysts, and alkoxycarbonylation was often complicated by the unsaturated compounds hydroformylation or alcohol carbonylation. In recent decades, in the presence of the most active and selective Pd‐phosphine systems with strong protonic acids, the products are typically only isomeric esters, which corresponds to the creating waste‐free production principles. At present, a large‐capacity synthesis process for methyl methacrylate, dubbed Alpha, is in operation, with the initial stage being ethylene methoxycarbonylation. In light of these developments, there is a growing interest among chemists and technologists in alkenes alkoxycarbonylation. The use of strong protonic acids as co‐catalysts is essential for the formation of active catalytic complexes. However, these acids are highly corrosive and can cause the alkenes isomerisation. This review is devoted to the analysis of acid‐free homogeneous Pd‐, Ru‐, Co‐, and Ni‐catalysts employed in alkenes alkoxycarbonylation over the past 15 years. As a result, polymers, monomers and other valuable linear and branched esters were obtained.

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Molybdenum disulfide promoted co-catalyzed alkoxycarbonylation

Zheng,

Zhou,

Deng

et al. 2024

Journal of Catalysis

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An improved cobalt-catalysed alkoxycarbonylation of olefins using secondary phosphine oxide promotors

Abstract: In general, cobalt-catalysed carbonylations of olefins require high carbon monoxide (CO) pressure and high temperature to proceed efficiently. In contrast, the presence of secondary phosphine oxide (SPO) promotors, allow the...

Cited by 4 publications

References 34 publications

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species

Strong Acid‐Free Homogeneous Catalytic Systems for the Ester Products Synthesis by Alkenes Alkoxycarbonylation: Recent Advances

Molybdenum disulfide promoted co-catalyzed alkoxycarbonylation

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