Amino acid preparation method comprising a step of hydroformylation of an unsaturated fatty nitrile

Patent metadata

Field	Value
Publication number	US-10125221-B2
Application number	US-201214362309-A
Country	US
Kind code	B2
Filing date	Dec 3, 2012
Priority date	Dec 1, 2011
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

A process for synthesizing an ω-amino acid compound of formula

HOOC—(CH 2 ) r+2 —CH 2 NH 2 ,

wherein 4≤r≤13 from a monounsaturated fatty nitrile compound of formula

CH 2 ═CH—(CH 2 ) r —CN

the process comprising: 1) a step of hydroformylation of the mono unsaturated fatty nitrile compound by reacting said nitrile with carbon monoxide and di hydrogen 5e-a5 to obtain a nitrile aldehyde compound of formula HOC—(CH2)r+2-CN, then 2) a step of oxidation, in the presence of dioxygen, of the nitrile aldehyde compound to obtain a corresponding nitrile acid compound of formula HOOC—(CH2)r+2-CN, and 3) a step of reduction of the nitrile acid compound to give an w-amino acid of formula

HOOC—(CH 2 ) r+2 —CH 2 NH 2 .

First claim

The invention claimed is:

1. A process for synthesizing an ω-amino acid compound of formula
HOOC—(CH 2 ) r+2 —CH 2 NH 2 ,

wherein r is an integer wherein 4≤r≤13
from a monounsaturated fatty nitrile compound of formula
CH 2 ═CH—(CH 2 ) r —CN

the process comprising:
1) a step of hydroformylation of the monounsaturated fatty nitrile compound by reacting said nitrile with carbon monoxide and dihydrogen to obtain a nitrile aldehyde compound of formula HOC—(CH 2 ) r+2 —CN, then
2) a step of oxidation, in the presence of dioxygen, of the nitrile aldehyde compound to obtain a corresponding nitrile acid compound of formula HOOC—(CH 2 ) r+2 —CN, and
3) a step of reduction of the nitrile acid compound to give an ω-amino acid of formula
HOOC—(CH 2 ) r+2 —CH 2 NH 2 .

2. The process as claimed in claim 1 , wherein the hydroformylation is catalyzed in the presence of a catalyst system comprising:
at least one metal of groups V to XI of the periodic table of elements, selected for its nitrile conversion activity; and
at least one bidentate or monodentate ligand selected for the selectivity of the hydroformylation reaction in favor of the linear aldehyde.

3. The process as claimed in claim 2 , wherein the catalyst system comprises at least one phosphine, one phosphite or one chelating diphosphine selected from the group consisting of PPh 3 , P(OPh) 3 , Dppm, Dppe, Dppb and Xantphos.

4. The process as claimed in claim 2 , wherein the metal of the catalyst system is provided in the form of a precursor comprising said metal and at least one compound selected from the group consisting of acetylacetonates, carbonyl compounds, and mixtures thereof.

5. The process as claimed in claim 2 , wherein the hydroformylation catalyst system comprises rhodium, and/or ruthenium.

6. The process as claimed in claim 2 , wherein the hydroformylation is catalyzed by a catalyst system selected from the group consisting of Rh—PPh 3 , Rh—P(OPh) 3 and Rh-Xantphos, and mixtures thereof.

7. The process as claimed in claim 2 , wherein the [ligand]/[metal] molar ratio is included in the range of from 60:1 to 1:1.

8. The process as claimed in claim 1 , wherein the hydroformylation is carried out in an organic medium.

9. The process as claimed in claim 1 , wherein the hydroformylation is carried out at a temperature included in the range of from 70 to 150° C.

10. The process as claimed in claim 1 , wherein the hydroformylation is carried out for a period of time ranging from 2 to 24 hours.

11. The process as claimed in claim 1 , wherein the hydroformylation is carried out at a partial CO/H 2 pressure included in the range of from 5 to 50 bar and according to a CO:H 2 ratio included in the range of from 1:3 to 3:1.

12. The process as claimed in claim 1 , wherein the [Substrate]/[Metal] ratio is included in the range of from 5000 to 500 000.

13. The process as claimed in claim 1 , wherein the oxidation step is carried out by sparging dioxygen or a dioxygen-containing gas mixture in the product resulting from the hydroformylation, optionally in the presence of the hydroformylation catalyst.

14. The process as claimed in claim 1 , wherein the oxidation step is carried out without the addition of solvent and/or without the addition of dioxygen activation catalyst.

15. The process as claimed in claim 1 , wherein the oxidation step is carried out at a partial dioxygen pressure ranging from 1 bar to 50 bar.

16. The process as claimed in claim 1 , wherein the dioxygen is continuously injected into the reaction medium by bubbling.

17. The process as claimed in claim 1 , wherein a molar ratio of the dioxygen relative to the product resulting from the hydroformylation step is included in the range of from 3:2 to 100:2.

18. The process as claimed in claim 1 , wherein the oxidation is carried out at a temperature included in the range of from 0° C. to 100° C., optionally in 2 consecutive increasing stationary temperature phases.

19. The process as claimed in claim 2 , wherein the hydroformylation step comprises the recycling of the hydroformylation catalyst system, optionally supplemented by a provision of new catalyst and/or ligand during a subsequent hydroformylation cycle.

20. The process as claimed in claim 19 , wherein the recycled catalyst system is obtained by at least partial evaporation of solvent and/or of nitrile-aldehyde and/or of unreacted reagent.

21. The process as claimed in claim 1 , wherein the hydroformylation step results in a selectivity of at least 95% of linear aldehydes.

22. The process as claimed in claim 1 , also comprising a step of catalytic cross metathesis with an alkene selected from the group consisting of ethylene, propylene, but-1-ene and but-2-ene, carried out on a unsaturated fatty nitrile before step 1) R2-CH to produce the monounsaturated fatty nitrile compound of formula CH 2 ═CH—(CH 2 ) r —CN.

Assignees

• Arkema France
• Centre Nat Rech Scient
• Univ Rennes

Inventors

• Dubois Jean-Luc
• Couturier Jean-Luc
• Carpentier Jean-François
• Ternel Jérémy

Classifications

• C07C255/17

  containing cyano groups and doubly-bound oxygen atoms bound to the same acyclic carbon skeleton · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07C253/22

  by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups · CPC title

• C07C227/26

  from compounds containing carboxyl groups by reaction with HCN, or a salt thereof, and amines, or from aminonitriles · CPC title

• C07C255/19

  containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton · CPC title