- Reactivity of a Ruthenium(0) Complex Bearing a Tetradentate Phosphine Ligand: Applications to Catalytic Acrylate Salt Synthesis from Ethylene and CO2
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By using a zerovalent, electron-rich ruthenium complex bearing a tetradentate phosphine ligand, a five-membered ruthenalactone was generated by oxidative cyclization of ethylene and CO2. This ruthenalactone underwent thermal, reversible β-H elimination to afford an acrylato(hydrido)ruthenium(II) complex, which liberated acrylate salt on treatment with a base. The reaction was successfully applied to the first ruthenium-catalyzed synthesis of an acrylate salt from ethylene and CO2. This study demonstrated the feasibility of the electron-rich ruthenium(0) complex as a catalyst in CO2-fixation chemistry.
- Ito, Tatsuyoshi,Takahashi, Kohei,Iwasawa, Nobuharu
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- Electrochemical reactor for sustainable transformation of bio-mass derived allyl alcohol into acrylate and pure hydrogen
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Acrylic acid is widely used in the chemical, polymer, cosmetic and food industries. Typically, it is produced through processes with a high environmental impact. In this paper, we demonstrate the co-production of the potassium acrylate salt and hydrogen gas from allyl alcohol in a liquid flow fed anion exchange membrane electrolysis cell operating at 60 °C and ambient pressure. We compare in electrolysis cell tests, two electrocatalysts Pd/C and Pd-CeO2/C evaluating the activity and selectivity for acrylate production. Electrolysis cell parameters are tuned obtaining a maximum conversion of allyl alcohol of 96% and a selectivity to acrylate of 50% at an operating cell voltage of 1 V. Operating at a lower cell potential (0.7 V) the selectivity for acrylate increases to 74%. Hydrogen gas is produced in the separated cathode compartment at an energy cost of 26 KWh kgH2-1, which is around half when compared to state-of-the-art water electrolyzers. The electrochemical oxidation mechanism of allyl alcohol is also studied and discussed, providing for the first time an insight into the pathways for formation of acrylate with respect to the other principle oxidation products (propionate and 3-hydroxypropionate).
- Bellini, Marco,Di Vico, Benedetto,Innocenti, Massimo,Miller, Hamish Andrew,Oberhauser, Werner,Pagliaro, Maria Vincenza,Vizza, Francesco,Zangari, Giovanni
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- ACRYLATES THROUGH OLEFIN/CARBON DIOXIDE COUPLING
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Methods of producing α,β-unsaturated carboxylic acid salts are described. A method can include reacting an alkene and carbon dioxide with a composition that includes a carboxylation catalyst and an inorganic base in a protic solvent under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid.
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Paragraph 0067
(2019/04/11)
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- CONTINUOUS PROCESS FOR THE CONVERSION OF OLEFINS AND CARBON DIOXIDE TO ACRYLATES VIA SOLUTION PHASE REACTOR
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Disclosed is a continuous process for producing α,β-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an α,β-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.
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Paragraph 0208
(2019/01/04)
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- Process for the preparation of bromo-substituted aromatic esters of α,β-unsaturated acids
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A process for the preparation of bromo-substituted aromatic esters of α, β-unsaturated acids of the formula STR1 wherein n is 1 or 2, x=6'n, and R and R' are hydrogen or alkyl; comprises reacting a salt of α,β-unsaturated acid and an alkali with a bromo-substituted benzyl halide in an inert substantially water-immiscible solvent and in the presence of a phase-transfer catalyst.
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- Process for producing allyl aminothiazole acetate intermediates
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There is described a process for the manufacture of a compound of the formula STR1 wherein R1 is lower alkyl, lower alkanoyl, lower alkenyl or the group --CH2 COOR2 or --C(CH3)2 COOR2 and R2 is a readily cleavable group, by reacting a compound of the formula STR2 wherein R is lower alkyl, with an alkali metal allylate and reacting the resulting compound of the formula STR3 wherein M is an alkali metal atom, with a compound of the formula R1 -X, wherein X is a leaving group. This process can be used to manufacture antimicrobially active mono-β-lactam, cephalosporin and penicillin derivatives.
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