CATALYTIC PROCESS FOR PREPARING AN a,ß-ETHYLENICALLY UNSATURATED CARBOXYLIC ACID SALT

Abstract

A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising a) contacting an alkene and carbon dioxide with a carboxylation catalyst, an organic solvent, and an alkoxide having a secondary or tertiary carbon atom directly bound to an [O.sup.−] group, to obtain a crude reaction product comprising the α,β-ethylenically unsaturated carboxylic acid salt and an alcohol by-product which is the conjugate acid of the alkoxide, b) allowing the α,β-ethylenically unsaturated carboxylic acid salt to precipitate out from the crude reaction product; and c) subjecting at least part of the crude reaction product to a mechanical separation step while maintaining the alcohol by-product in liquid form to obtain a solid phase comprising the α,β-ethylenically unsaturated carboxylic acid salt and a liquid phase comprising the carboxylation catalyst, the organic solvent and the alcohol by-product. The process allows for easy separation of the α,β-ethylenically unsaturated carboxylic acid salt by a mechanical separation operation.

Claims

1-16. (canceled)

17. A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising a) contacting an alkene and carbon dioxide with a carboxylation catalyst, N,N-dimethylformamide, and an alkoxide having a secondary or tertiary carbon atom directly bound to an [O.sup.−] group, to obtain a crude reaction product comprising the α,β-ethylenically unsaturated carboxylic acid salt and an alcohol by-product which is the conjugate acid of the alkoxide, b) allowing the α,β-ethylenically unsaturated carboxylic acid salt to precipitate out from the crude reaction product; and c) subjecting at least part of the crude reaction product to a mechanical separation step while maintaining the alcohol by-product in liquid form to obtain a solid phase comprising the α,β-ethylenically unsaturated carboxylic acid salt and a liquid phase comprising the carboxylation catalyst, the N,N-dimethylformamide and the alcohol by-product.

18. The catalytic process according to claim 17, wherein the mechanical separation step c) comprises a filtration step.

19. The catalytic process according to claim 17, additionally comprising d) distilling the alcohol by-product and optionally the N,N-dimethylformamide off from the liquid phase to obtain an alcohol by-product distillate fraction and optionally a N,N-dimethylformamide distillate fraction, and a residue fraction.

20. The catalytic process according to claim 19, additionally comprising recycling at least part of the residue fraction to step a).

21. The catalytic process according to claim 19, additionally comprising e) contacting at least part of the alcohol by-product distillate fraction obtained in step d) with an alkaline material to regenerate an alkoxide.

22. The catalytic process according to claim 21, additionally comprising recycling at least part of the regenerated alkoxide to step a).

23. The catalytic process according to claim 17, additionally comprising f) contacting the solid phase obtained in step c) with a wash liquid to obtain a spent wash liquid and a purified solid phase in which the carboxylic acid salt is enriched.

24. The catalytic process according to claim 23, wherein the wash liquid is selected from alkanes and alcohols.

25. The catalytic process according to claim 24, wherein the wash liquid is the alcohol by-product.

26. The catalytic process according to claim 24, wherein the wash liquid is the N,N-dimethylformamide.

27. The catalytic process according to claim 17, wherein step c) is performed at a temperature in the range of 0 to 150° C.

28. The catalytic process according to claim 17, wherein the alkoxide is a sodium alkoxide, preferably a sodium alkoxide having a tertiary carbon atom directly bound to an [O.sup.−] group.

29. The catalytic process according to claim 17, wherein the alkene is ethene and the α,β-ethylenically unsaturated carboxylic acid salt is sodium acrylate.

30. The catalytic process according to claim 17, wherein the carboxylation catalyst is a nickel or palladium complex which comprises a bidentate P,X ligand in which X is selected from the group consisting of P, N, O, and carbene, and the P and X atoms are separated by a bivalent linker that comprises 2 to 4 bridging atoms.

Description

EXAMPLE 1

[0255] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium tert-butoxide (40.00 mmol, 3.84 g) and DMF (60 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar), ethene (10 bar) and nitrogen (25 bar) at 25° C. (total pressure of 70 bar). After stirring at 145° C. for 16 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via warm filtration at 80° C. under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A quantitative yield of 3.90 g was obtained, corresponding to a TON of 104.

EXAMPLE 2

[0256] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3,7-dimethyloctan-3-olate (40.00 mmol, 7.21 g) and DMF (60 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A yield of 3.00 g (80%) was obtained, corresponding to a TON of 80.

EXAMPLE 3

[0257] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3,7-dimethyloctan-3-olate as a 48% solution in 3,7-dimethyloctan-3-ol (40 mmol, 15.4 g) and DMF (53 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A yield of 2.88 g (77%) was obtained, corresponding to a TON of 77.

EXAMPLE 4

[0258] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3,7-dimethyloctan-3-olate as a 48% solution in 3,7-dimethyloctan-3-ol (40.00 mmol, 15.4 g), 3,7-dimethyloctan-3-ol (20 mL) and DMF (30 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A yield of 3.05 g (81%) was obtained, corresponding to a TON of 81.

EXAMPLE 5

[0259] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3,7-dimethyloctan-3-olate as a 48% solution in 3,7-dimethyloctan-3-ol (40.00 mmol, 15.4 g), 3,7-dimethyloctan-3-ol (20 mL) and DMF (30 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A yield of 2.84 g (76%) was obtained, corresponding to a TON of 76.

EXAMPLE 6

[0260] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3-methylpentan-3-olate (40.00 mmol, 4.97 g) and DMF (60 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A quantitative yield of 3.91 g, was obtained, corresponding to a TON of 104.

EXAMPLE 7

[0261] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3-methylpentan-3-olate (40.00 mmol, 4.97 g) and DMF (60 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A yield of 3.14 g (84%) was obtained, corresponding to a TON of 84.

EXAMPLE 8

[0262] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3,7-dimethyloctan-3-olate as a 51% solution in 3,7-dimethyloctan-3-ol (40.00 mmol, 14.1 g), and DMF (54 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A quantitative yield of 4.28 g was obtained, corresponding to a TON of 114.

EXAMPLE 9

[0263] A 270 mL steel autoclave was charged with Pd(PPh.sub.3).sub.4 (0.400 mmol, 0.463 g), dcpe (0.440 mmol, 0.187 g), sodium 3-ethyl-pentan-3-olate (40.00 mmol, 5.52 g) and DMF (60 mL) using standard Schlenk techniques under an atmosphere of argon. The autoclave was stirred at 500 rpm for 15 min to solubilize the reactants. The autoclave was pressurized with CO.sub.2 (35 bar) and ethene (10 bar) at 25° C. After stirring at 145° C. for 5 h at 750 rpm, the autoclave was cooled to 80° C., the pressure was released and the reaction mixture, i.e. crude reaction product, was transferred into a 100 mL bottle. The residues in the autoclave vessel were recovered with 15 mL of DMF and transferred into the bottle. The product was separated from the reaction mixture via filtration at room temperature under reduced pressure. The obtained sticky solid was washed with 3×25 mL of DMF, followed by 3×25 mL of n-pentane. The solid residue was dried under vacuum to give the product as a white solid. A quantitative yield of 3.92 g was obtained, corresponding to a TON of 104.