Process for preparation of organic carboxylic acids

Abstract

A process for the preparation of organic carboxylic acids which comprises converting a formic acid ester expressed by the general formula HCOOR wherein R stands for a chain or cyclic aliphatic hydrocarbon radical which may have an aliphatic unsaturation, an aryl radical, an aralkyl radical or a heterocyclic radical, At an elevated temperature under raised pressure of carbon monixide to an organic carboxylic acid expressed by the general formula RCOOH wherein R is as defined above.

What I claim is: 
     
       1. A process for the preparation of organic carboxylic acids comprising converting a formic acid ester of the formula HCOOR wherein R is an alkyl radical of 1 to 6 carbon atoms, an alkenyl or alkynyl radical of 2 to 6 carbon atoms, or an alicyclic hydrocarbon group of 4 to 10 carbon atoms, into an organic acid of the formula RCOOH wherein R is defined above, at a temperature of from 100° to 350° C. and in the presence of carbon monoxide under a pressure of at least 80 kg/cm 2  gauge wherein the partial pressure of carbon monoxide is at least 50 kg/cm 2  gauge, the conversion being effected .[.either without a catalyst or.]. in the presence of .[.a metal per se belonging to Group VIII or Group IIb or.]. a salt or a nonsalt compound .[.thereof.]. .Iadd.of a Group VIII metal selected from the group consisting of cobalt, nickel and iron or Group IIb metal .Iaddend.acting as a catalyst, said catalyst being present in an amount of 0.2-200 milligram atoms, reckoned as the metal, per mol of the starting formic acid ester, said conversion being effected in a polar organic solvent .Iadd.selected from the group of amides, nitriles, ketones having high boiling points and heterocyclic compounds selected from pyridine and picoline. .Iaddend. .[.2. The process of claim 1 wherein a 
     
     
        catalyst is used..]. 3. The process of claim .[.2.]. .Iadd.1 .Iaddend.wherein the .[.a metal or the.]. .Iadd.catalyst is a .Iaddend.compound .[.thereof is.]. selected from the group consisting of the .[.metals and.]. compounds of cobalt, nickel, iron, .[.rhodium,.]. 
     
     
        mercury and zinc. 4. The process as described in claim .[.2.]. .Iadd.1 .Iaddend.wherein the metal belonging to Group VIII or Group IIb is present 
     
     
        as a salt. 5. The process as described in claim 4 wherein the salt is that 
     
     
        of .[.a.]. .Iadd.said .Iaddend.Group VIII metal. 6. The process as described in claim .[.2.]. .Iadd.1 .Iaddend.wherein the reaction is conducted in the presence of a catalyst containing a metal of .Iadd.said 
     
     
        .Iaddend.Group VIII. 7. The process as described in claim 6 wherein the catalyst is .[.(a) a Group VIII metal per se, (b).]. .Iadd.(a) .Iaddend.an organic acid salt, .[.(c).]. .Iadd.(b) .Iaddend.a beta-diketone or beta-keto acid ester complex, .[.(d).]. .Iadd.(c) .Iaddend.a hydroxide, .[.(e).]. .Iadd.(d) .Iaddend.a carbonate, .[.(f).]. .Iadd.(e) .Iaddend.a bicarbonate, .[.(g).]. .Iadd.(f) .Iaddend.a nitrate, .[.(h).]. .Iadd.(g) .Iaddend.a sulfate, .[.(i).]. .Iadd.(h) .Iaddend.an oxide, .[.(j).]. .Iadd.(i) .Iaddend.a salt of a halogen oxy-acid, .[.(k).]. .Iadd.(j) .Iaddend.a complex of an organic onium compound, .[.(l).]. .Iadd.(k) .Iaddend.a carbonyl compound or .[.(m).]. .Iadd.(l) .Iaddend.a halide of 
     
     
        .[.a.].  .Iadd.said .Iaddend.metal of group VIII. 8. The process as described in claim 6 wherein the catalyst is a combination of (A) .[.(a) a Group VIII metal per se, (b).]. .Iadd.(a) .Iaddend.an organic acid salt, .[.(c).]. .Iadd.(b) .Iaddend.a beta-diketone or beta-keto acid, ester complex, .[.(d).]. .Iadd.(c) .Iaddend.a hydroxide, .[.(e).]. .Iadd.(d) .Iaddend.a carbonate, .[.(f).]. .Iadd.(e) .Iaddend.a bicarbonate, .[.(g).]. .Iadd.(f) .Iaddend.a nitrate, .[.(h).]. .Iadd.(g) .Iaddend.a sulfate, .[.(i).]. .Iadd.(h) .Iaddend.an oxide or .[.(j).]. .Iadd.(i) .Iaddend.a carbonyl compound of .[.a.]. .Iadd.said .Iaddend.metal of Group VIII, and (B) (a') molecular halogen, (b') a hydrohalogenic acid, (c') an alkali metal or alkaline earth metal halide or (d') a halogen oxyacid or 
     
     
        its alkali metal or alkaline earth metal salt. 9. The process as described in claim .[.2.]. .Iadd.1 .Iaddend.wherein the reaction is conducted in the presence of a catalyst containing a metal of Group IIb of the Periodic 
     
     
        Table. 10. The process as described in claim 9 wherein the catalyst is .[.(a) Group IIb metal per se, (b).]. .Iadd.(a) .Iaddend.an organic acid salt, .[.(c).]. .Iadd.(b) .Iaddend.a beta-diketone or beta-keto acid ester complex, .[.(d).]. .Iadd.(c) .Iaddend.a hydroxide, .[.(e).]. .Iadd.(d) .Iaddend.a carbonate, .[.(f).]. .Iadd.(e) .Iaddend.a bicarbonate, .[.(g).]. .Iadd.(f) .Iaddend.a nitrate, .[.(h).]. .Iadd.(g) .Iaddend.a sulfate, .[.(i).]. .Iadd.(h) .Iaddend.an oxide, .[.(j).]. .Iadd.(i) .Iaddend.a salt of a halogen oxy-acid, .[.(k).]. .Iadd.(j) .Iaddend.a complex of an organic onium compound of .[.(l).]. .Iadd.(k) .Iaddend.a 
     
     
        halide of a metal of Group IIb. 11. The process as described in claim 9 wherein the catalyst is a combination of (A) .[.(a) a group IIb metal per se, (b).]. .Iadd.(a) .Iaddend.an organic acid salt, .[.(c).]. .Iadd.(b) .Iaddend.a beta-diketone or beta-keto acid ester complex, .[.(d).]. .Iadd.(c) .Iaddend.a hydroxide, .[.(e).]. .Iadd.(d) .Iaddend.a carbonate, .[.(f).]. .Iadd.(e) .Iaddend.a bicarbonate, .[.(g).]. .Iadd.(f) .Iaddend.a nitrate, .[.(h).]. .Iadd.(g) .Iaddend.a sulfate or .[.(i).]. .Iadd.(h) .Iaddend.an oxide of a metal of Group IIb and (B) (a') a molecular halogen, (b') a hydrohalogenic acid, (c') an alkali metal or alkaline earth metal halide or (d') a halogen oxyacid or its alkali metal or alkaline metal salt.  .[.12. The process as described in claim 2 wherein the organic polar solvent is selected from the group consisting of amides, 
     
     
        amines, nitriles and ketones..]. 13. The process as described in claim 4 wherein the salt is either that of cobalt or mercury. .Iadd.14. The process of claim 1, wherein the organic solvent is one of high polarity and capable of dissolving the catalyst. .Iaddend.  .Iadd.15. The process as in claim 1, wherein the solvent is employed in an amount of 0.2-10 mols per mol of the starting formic acid ester. .Iaddend.  .Iadd.16. The process according to claim 1, wherein the solvent is an amide. .Iaddend. .Iadd.17. The process according to claim 16, wherein the acyl group of the amide corresponds to the acyl group of the objective organic carboxylic acid. .Iaddend.  .Iadd.18. The process according to claim 16, wherein the amide is selected from the group consisting of acetamide, N-methylacetamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, formamide, N-methylformamide and N,N-dimethylformamide. .Iaddend. .Iadd.19. The process of claim 18, wherein the amide is acetamide. .Iaddend. .Iadd.20. The process of claim 18, wherein the amide is N-methylacetamide. .Iaddend.  .Iadd.21. The process of claim 18, wherein the amide is N,N-dimethylacetamlde. .Iaddend.  .Iadd.22. The process of claim 18, wherein the amide is N,N-dimethylpropionamide, .Iaddend. .Iadd.23. The process of claim 16, wherein the amide is a cyclic amide. .Iaddend.  .Iadd.24. The process according to claim 23, wherein the cyclic amide is selected from the group consisting of α-pyrrolidone, N-methylpyrrolidone, α-piperidone and N-methylpiperidone. .Iaddend. .Iadd.25. The process of claim 1, wherein the solvent is a nitrile selected from the group consisting of acetonitrile and propionitrile. .Iaddend.  .Iadd.26. The process of claim 1, wherein the solvent is acetephenone. .Iaddend.