Process for the reductive amination and selective hydrogenation of substrates containing a selected halogen
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07C-229/00
C07C-209/26
C07C-209/36
C07C-249/04
출원번호
US-0914744
(2014-08-26)
등록번호
US-10167248
(2019-01-01)
우선권정보
EP-13183017 (2013-09-04)
국제출원번호
PCT/EP2014/068083
(2014-08-26)
국제공개번호
WO2015/032653
(2015-03-12)
발명자
/ 주소
Moonen, Kristof
Vandeputte, Bart
Scheldeman, Daan
Dumoleijn, Kim
출원인 / 주소
Taminco BVBA
대리인 / 주소
Carmen, Dennis
인용정보
피인용 횟수 :
0인용 특허 :
8
초록▼
Disclosed is a process for performing a chemical reaction selected from reductive amination and hydrogenation of a first functional group in an organic feed substrate, which feed substrate comprises at least one further functional group containing a halogen atom, wherein the halogen atom is selected
Disclosed is a process for performing a chemical reaction selected from reductive amination and hydrogenation of a first functional group in an organic feed substrate, which feed substrate comprises at least one further functional group containing a halogen atom, wherein the halogen atom is selected from the list consisting of chlorine, bromine, iodine, and combinations thereof, in the presence of hydrogen and a heterogeneous catalyst comprising at least one metal from the list of Pd, Rh, and Ru, together with at least a second metal from the list consisting of Ag, Ni, Co, Sn, Cu and Au. The process is preferably applied for the reductive amination of 2-chloro-benzaldehyde to form 2-chloro-benzyldimethylamine, as an intermediate in the production of agrochemically active compounds and microbiocides of the methoximinophenylglyoxylic ester series. Further disclosed is a composition rich in 2-chloro-benzyldimethylamine, further comprising an amount of 2-chloro-benzyl alcohol and being low in chlorotoluene isomers.
대표청구항▼
1. A process for the reductive amination of a halo-benzaldehyde in the presence of a nitrogen containing compound, wherein the halogen atom is selected from the list consisting of chlorine, bromine, iodine, and combinations thereof, in the presence of hydrogen and a heterogeneous catalyst supported
1. A process for the reductive amination of a halo-benzaldehyde in the presence of a nitrogen containing compound, wherein the halogen atom is selected from the list consisting of chlorine, bromine, iodine, and combinations thereof, in the presence of hydrogen and a heterogeneous catalyst supported on carbon, said heterogenous catalyst comprising at least one first metal comprising palladium, rhodium, or ruthenium, together with at least one second metal comprising silver, nickel, cobalt, tin, copper, or gold. 2. The process according to claim 1, wherein the nitrogen compound is selected from ammonia, a primary amine, a secondary amine, and mixtures thereof. 3. The process according to claim 1, wherein the reductive amination is performed in two steps, in the first step reacting the aldehyde with the nitrogen containing compound, and in the subsequent step introducing hydrogen and the catalyst. 4. The process according to claim 1, wherein the heterogeneous catalyst comprises the first metal at a concentration in the range of 0.1-10.0% by weight, based on the total weight of the catalyst and the second metal at a concentration in the range of 0.05-40% by weight, based on the total weight of the catalyst. 5. The process according to claim 1, further comprising the step of putting the first metal onto the carbon support by precipitation and putting the second metal onto a support by precipitation, at the same time as putting the first metal onto the support or after having put the first metal onto the support. 6. The process according to claim 1, wherein the heterogeneous catalyst has been heat treated prior to its use in the process, at a temperature in the range of 50-500° C. wherein the heat treatment is performed for at least 2 hours. 7. The process according to claim 1, wherein the heterogeneous catalyst comprises the first metal and the second metal in a weight ratio of the second metal relative to the first metal in the range of 0.05:1.0 to 10.0:1.0. 8. The process according to claim 1, wherein the heterogeneous catalyst has a metal area, as measured by carbon monoxide chemisorption of at least 3.0 m2/g. 9. The process according to claim 1, wherein the heterogeneous catalyst has been pre-reduced prior to its use in the process. 10. The process according to claim 1, wherein the reductive amination is performed at a H2 partial pressure in the range of 0.01-250 bar gauge and at a temperature in the range of 0-300° C. 11. The process according to claim 1, wherein the process is performed in continuous mode. 12. The process according to claim 1, wherein the reductive amination is performed in the presence of a solvent. 13. The process according to claim 1, wherein reaction products of said process comprise ortho-chloro-benzyldimethylamine and wherein the process further comprises preparing a Grignard reagent from said ortho-chloro benzyl dimethyl amine, and further subjecting the Grignard reagent to a Grignard reaction. 14. The process according to claim 1, wherein the reaction products comprise ortho-chloro-benzyldimethylamine, further comprising converting said ortho-chloro-benzyldimethylamine to chloromethylphenylglyoxylic ester. 15. The process according to claim 14, wherein said chloromethylphenylglyoxylic ester is converted to a methoximinophenylglyoxylic ester. 16. The process according to claim 1, wherein said halo-benzaldehyde comprises ortho-chlorobenzaldehyde, meta-chlorobenzaldehyde, or para-chlorobenzaldehyde. 17. The process according to claim 1, wherein said amine compound comprises a secondary amine. 18. The process according to claim 1, wherein said heterogeneous catalyst comprises a first metal comprising palladium and a second metal comprising silver, copper, nickel, or cobalt. 19. The process according to claim 1, wherein the halogen atom on said halo-benzaldehyde comprises chlorine, and after conversion of said halo-benzaldehyde, at least 95% of the halo-benzaldehyde retains said chlorine atom. 20. The process of claim 19, wherein at least 98% of the halo-benzaldehyde retains said chlorine atom after conversion. 21. The process according to claim 1, wherein said halo-benzaldehyde comprises ortho-chlorobenzaldehyde, said amine compound comprises a secondary amine, and said heterogeneous catalyst comprises a first metal comprising palladium and a second metal comprising silver, copper, nickel, or cobalt. 22. The process according to claim 1, wherein the process generates a reaction product composition comprising 2-chloro-benzyl-dimethylamine. 23. The process of claim 22, wherein the process generates at least 98.5 wt. % 2-chloro-benzyl-dimethylamine based on the weight of the reaction product composition, not including, if present, water, methanol and dimethylamine. 24. The process of claim 23, wherein the process generates at least 99.1 wt. % 2-chloro-benzyl-dimethylamine. 25. The process of claim 22, wherein the reaction products do not contain more than 0.04 wt. % 2-chloro-dichloromethyl benzene, not more than 1.0 wt. % 2-chloro-benzyl alcohol, not more than 0.20 wt. % 2-chloro-benzaldehyde, and not more than 0.40 wt. % benzyl dimethyl amine, each based on the weight of the reaction product composition, not including, if present, water, methanol and dimethylamine. 26. The process of claim 25, wherein the amount of benzyl dimethyl amine is not more than 0.20 wt. %. 27. The process of claim 1, wherein the carbon support comprises activated carbon. 28. The process of claim 4, wherein the carbon support comprises activated carbon. 29. The process of claim 12, wherein the carbon support comprises activated carbon. 30. The process of claim 18, wherein the carbon support comprises activated carbon. 31. The process of claim 19, wherein the carbon support comprises activated carbon. 32. The process of claim 25, wherein the carbon support comprises activated carbon. 33. The process according to claim 6, wherein the heat treatment is performed for at least 3 hours. 34. A process for the reductive amination of a halo-benzaldehyde in the presence of a nitrogen containing compound at a halo-benzaldehyde conversion of at least 73.2% and a selectivity to a halo-benzylamine of at least 81.3%, wherein the halogen atom is selected from the list consisting of chlorine, bromine, iodine, and combinations thereof, in the presence of hydrogen and a heterogeneous catalyst supported on carbon comprising at least one first metal comprising palladium, rhodium, or ruthenium, together with at least one second metal comprising silver, nickel, cobalt, tin, copper, or gold. 35. The process according to claim 34, wherein the nitrogen compound comprises a secondary amine. 36. The process according to claim 34, wherein the heterogeneous catalyst comprises the first metal at a concentration in the range of 0.1-10.0% by weight, based on the total weight of the catalyst and the second metal at a concentration in the range of 0.05-40% by weight, based on the total weight of the catalyst, and the catalyst has a metal area, as measured by carbon monoxide chemisorption of at least 0.5 m2/g. 37. The process according to claim 34, wherein the heterogeneous catalyst has been heat treated, preferably at a temperature in the range of 50-500° C., the heat treatment being performed for at least 2 hours. 38. The process according to claim 34, wherein the reductive amination is performed at a H2 partial pressure in the range of 0.01-250 bar gauge and at a temperature in the range of 0-300° C. 39. The process according to claim 34, wherein the process is performed in continuous mode. 40. The process according to claim 34, wherein the reductive amination is performed in the presence of a solvent. 41. The process according to claim 34, wherein reaction products of said process comprise ortho-chloro-benzyldimethylamine and wherein the process further comprises preparing a Grignard reagent from said ortho-chloro benzyl dimethyl amine, and further subjecting the Grignard reagent to a Grignard reaction. 42. The process according to claim 34, wherein said heterogeneous catalyst comprises a first metal comprising palladium and a second metal comprising silver, copper, nickel, or cobalt. 43. The process according to claim 34, wherein the halogen atom on said halo-benzaldehyde comprises chlorine, and after conversion of said halo-benzaldehyde, at least 95% of the halo-benzaldehyde retains said chlorine atom. 44. The process of claim 30, wherein at least 98 wt.% of the halo-benzaldehyde retains said chlorine atom after conversion. 45. The process according to claim 34, wherein said halo-benzaldehyde comprises ortho-chlorobenzaldehyde, said amine compound comprises a secondary amine, and said heterogeneous catalyst comprises a first metal comprising palladium and a second metal comprising copper, nickel, or cobalt. 46. The process of claim 34, wherein the process generates at least 98.5 wt.% 2-chloro-benzyl-dimethylamine based on the weight of the reaction product composition, not including, if present, water, solvent and dimethylamine. 47. The process of claim 46, wherein the process generates at least 99.1 wt.% 2-chloro-benzyl-dimethylamine. 48. The process of claim 34, wherein said halo-benzaldehyde comprises ortho-chlorobenzaldehyde, said amine compound comprises a dimethyl amine, and reaction products of the process do not contain more than 0.04 wt.% 2-chloro-dichloromethyl benzene, not more than 1.0 wt.% 2-chloro-benzyl alcohol, not more than 0.20 wt.% 2-chloro-benzaldehyde, and not more than 0.40 wt.% benzyl dimethyl amine, each based on the weight of the reaction product composition, not including, if present, water, solvent and dimethylamine. 49. The process of claim 48, wherein the amount of benzyl dimethyl amine is not more than 0.20 wt.%. 50. The process according to claim 34, wherein the conversion is at least 75% and the selectivity is at least 96.4%. 51. The process according to claim 34, wherein the conversion is at least 95.6% and the selectivity is at least 96.2%. 52. The process according to claim 34, wherein the conversion is at least 98.3% and the selectivity is at least 96.2%. 53. The process according to claim 34, wherein the conversion is at least 80.6% and the selectivity is at least 97.9%. 54. The process according to claim 34, wherein the conversion is at least 99.9% and the selectivity is at least 98.25%.
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이 특허에 인용된 특허 (8)
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