초록 ▼

This invention is directed to an improved process for the preparation of N-(phosphonomethyl)glycine (i.e., "glyphosate"), a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine. The process comprises combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen

This invention is directed to an improved process for the preparation of N-(phosphonomethyl)glycine (i.e., "glyphosate"), a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine. The process comprises combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of a noble metal catalyst. The N-substituted N-(phosphonomethyl)glycine reactant has formula (V): wherein R1 and R2 are independently selected from the group consisting of hydrogen, halogen,--PO3R12R13,--SO3R14,--NO2, hydrocarbyl, and substituted hydrocarbyl other than--CO2R15; and R7, R8, R9, R12, R13, R14 and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

대표청구항 ▼

We claim: 1. An oxidation catalyst comprising a noble metal, an electroactive molecular species having an oxidation potential of at least about 0.3 volts vs. SCE and a support comprising a polymer, wherein the noble metal is on the support. 2. The oxidation catalyst of claim 1 wherein the electro

We claim: 1. An oxidation catalyst comprising a noble metal, an electroactive molecular species having an oxidation potential of at least about 0.3 volts vs. SCE and a support comprising a polymer, wherein the noble metal is on the support. 2. The oxidation catalyst of claim 1 wherein the electroactive molecular species is hydrophobic. 3. The oxidation catalyst of claim 1 wherein the electroactive molecular species comprises a compound selected from the group consisting of triphenylmethane; N-hydroxyphthalimide; 2,4,7-trichlorofluorene; N,N'-bis(3-methylphenyl)-N,N'-diphenyl benzidine; tris(4-bromophenyl)amine; 2,2,6,6-tetramethyl piperidine N-oxide; 5,10,15,20-tetraphenyl-21H,23H-porphine iron(III) chloride; 5,10,15,20-tetraphenyl-21H,23H porphine nickel(II); 4,4'-difluorobenzophenone; 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine iron (III) chloride; and phenothiazine. 4. The oxidation catalyst of claim 1 wherein the electroactive molecular species comprises 2,2,6,6-tetramethyl piperidine N-oxide. 5. The oxidation catalyst of claim 1 wherein the electroactive molecular species comprises a triarylamine. 6. The oxidation catalyst of claim 1 wherein the electroactive molecular species comprises N,N'-bis(3-methylphenyl)-N,N-diphenyl benzidine. 7. The oxidation catalyst of claim 1 wherein (a) the catalyst comprises a promoter, and (b) at least about 0.05% by weight of the catalyst consists of the promoter. 8. The oxidation catalyst of claim 7 wherein the promoter comprises a metal selected from the group consisting of aluminum, ruthenium, osmium, indium, gallium, tantalum, tin, and antimony. 9. The oxidation catalyst of claim 1 wherein the support comprises a polymer selected from the group consisting of polyamide, polyimide, polycarbonate, polyurea, and polyester. 10. The oxidation catalyst of claim 1 wherein the support comprises a polymer selected from the group consisting of polyethylene imine, polyaminostyrene, sulfonated polystyrene, polyvinyl pyridine, and a salt of polyacrylic acid. 11. The oxidation catalyst of claim 1 wherein the support comprises polystyrene. 12. The oxidation catalyst of claim 1 wherein the support comprises polystyrene substituted with dimethylamine groups. 13. The oxidation catalyst of claim 1 wherein the support comprises sulfonated polystyrene. 14. The oxidation catalyst of claim 1 wherein the support comprises polyvinyl pyridine. 15. The oxidation catalyst of claim 1 wherein the electroactive molecular species comprises a compound selected from the group consisting of N-hydroxyphthalimide; 2,2,6,6-tetramethyl piperidine N-oxide; N,N'-bis(3-methylphenyl)-N,N'-diphenyl benzidine; and tris(4-bromophenyl)amine. 16. The oxidation catalyst of claim 1 wherein the electroactive molecular species is on the surface of the noble metal. 17. The oxidation catalyst of claim 9 wherein the electroactive molecular species is on the surface of the noble metal, the surface of the support or both. 18. The oxidation catalyst of claim 1 wherein the catalyst comprises a noble metal selected from the group consisting of platinum, palladium, rhodium, iridium, osmium and gold. 19. The oxidation catalyst of claim 1 wherein the catalyst comprises platinum. 20. The oxidation catalyst of claim 1 wherein the support is in the form of cross-linked beads. 21. The oxidation catalyst of claim 20 wherein the cross-linked beads are porous. 22. The oxidation catalyst of claim 20 wherein the cross-linked beads have a surface area of at least about 10 m2/g. 23. The oxidation catalyst of claim 1 wherein the polymer is capable of being protonated by an acidic noble metal compound. 24. An oxidation catalyst comprising a noble metal and an electroactive molecular species comprising a compound selected from the group consisting of triphenylmethane; N-hydroxyphthalimide; 2,4,7-trichlorofluorene; N,N'-bis (3-methylphenyl)-N,N'-diphenyl benzidine; tris (4-bromophenyl)amine; 2,2,6, 6-tetramethyl piperidine N-oxide; 4,4'-difluorobenzophenone; 5,10, 15,20-tetrakis (pentafluorophenyl)-21H,23H-porphine iron (III) chloride; and phenothiazine. 25. The oxidation catalyst of claim 24 wherein the electroactive molecular species comprises 2,2,6, 6-tetramethyl piperidine N-oxide. 26. The oxidation catalyst of claim 24 wherein the electroactive molecular species comprises a triarylamine. 27. The oxidation catalyst of claim 24 wherein the electroactive molecular species comprises N,N'-bis (3-methylphenyl)-N,N'-diphenyl benzidine. 28. The oxidation catalyst of claim 24 wherein (a) the catalyst comprises a promoter, and (b) at least about 0.05% by weight of the catalyst consists of the promoter. 29. The oxidation catalyst of claim 28 wherein the promoter comprises a metal selected from the group consisting of aluminum, ruthenium, osmium, indium, gallium, tantalum, tin, and antimony. 30. The oxidation catalyst of claim 24 wherein the catalyst comprises a support comprising a material selected from the group consisting of carbon, alumina, silica, titania, zirconia, siloxane, and barium sulfate and wherein the noble metal is on the support. 31. The oxidation catalyst of claim 30 wherein the support comprises a material selected from the group consisting of alumina, silica, titania, zirconia, siloxane, and barium sulfate. 32. The oxidation catalyst of claim 30 wherein the support comprises a material selected from the group consisting of silica, titania, and barium sulfate. 33. The oxidation catalyst of claim 30 wherein the support comprises graphitic carbon. 34. The oxidation catalyst of claim 24 wherein the catalyst comprises a support comprising a polymer and the noble metal is on the support. 35. The oxidation catalyst of claim 34 wherein the support comprises a polymer selected from the group consisting of polyamide, polyimide, polycarbonate, polyurea, and polyester. 36. The oxidation catalyst of claim 34 wherein the support comprises a polymer selected from the group consisting of polyethylene imine, polyaminostyrene, sulfonated polystyrene, polyvinyl pyridine, and a salt of polyacrylic acid. 37. The oxidation catalyst of claim 34 wherein the support comprises polystyrene. 38. The oxidation catalyst of claim 34 wherein the support comprises polystyrene substituted with dimethylamine groups. 39. The oxidation catalyst of claim 34 wherein the support comprises sulfonated polystyrene. 40. The oxidation catalyst of claim 34 wherein the support comprises polyvinyl pyridine. 41. The oxidation catalyst of claim 34 wherein the support is in the form of cross-linked beads. 42. The oxidation catalyst of claim 41 wherein the cross-linked beads are porous. 43. The oxidation catalyst of claim 41 wherein the cross-linked beads have a surface area of at least about 10 m2/g. 44. The oxidation catalyst of claim 34 wherein the polymer is capable of being protonated by an acidic noble metal compound. 45. The oxidation catalyst of claim 24 wherein the electroactive molecular species comprises a compound selected from the group consisting of N-hydroxyphthalimide; 2,2,6,6-tetramethyl piperidine N-oxide; N,N'-bis (3-methylphenyl)-N,N'-diphenyl benzidine; and tris (4-bromophenyl) amine. 46. The oxidation catalyst of claim 24 wherein the electroactive molecular species is on the surface of the noble metal. 47. The oxidation catalyst of claim 34 wherein the electroactive molecular species is on the surface of the noble metal, the surface of the support or both. 48. The oxidation catalyst of claim 24 wherein the catalyst comprises a noble metal selected from the group consisting of platinum, palladium, rhodium, iridium, osmium and gold. 49. The oxidation catalyst of claim 24 wherein the catalyst comprises platinum. 50. An oxidation catalyst comprising a noble metal, an electroactive molecular species having an oxidation potential of at least about 0.3 volts vs. SCE and a support comprising a material selected from the group consisting of alumina, silica, titania, zirconia, siloxane, and barium sulfate and wherein the noble metal is on the support.