Method of synthesising amino acid by metathesis, hydrolysis, then hydrogenation

Patent metadata

Field	Value
Publication number	US-9790168-B2
Application number	US-201414766956-A
Country	US
Kind code	B2
Filing date	Feb 10, 2014
Priority date	Feb 8, 2013
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

A method of synthesising an amino acid from an unsaturated fatty compound I that includes at least the following steps: cross-metathesis with a short unsaturated compound II, one of compounds I or II comprising a nitrile function and the other of these compounds II or I an ester function, so as to obtain and recover at least one monounsaturated nitrile ester NEU; hydrolysis of the NEU in unsaturated acid nitrile NAU; hydrogenation of the NAU to saturated amino acid AA; and then purification of the AA, if applicable, in particular by crystallisation. Also, a polymer obtained by polymerisation using the amino acid synthesised according to the method.

First claim

The invention claimed is:

1. A process for synthesizing an amino acid from an unsaturated fatty compound I of formula:
R 1 —CH═CH—[(CH 2 ) q —CH═CH] p —(CH 2 ) n —R 2 in which:

R 1 is H, an alkyl radical of 1 to 11 carbon atoms, optionally comprising a hydroxyl function, or (CH 2 ) m —R 4
m is an integer in the range from 0 to 11,
n is an integer in the range from 2 to 13,
p is an integer, p being equal to 0, 1 or 2,
q is an integer equal to 0 or 1,
R 2 is COOR 5 or CN,
R 4 is H or R 2
R 5 is an alkyl radical of 1 to 11 carbon atoms or a radical comprising two or three carbon atoms bearing one or two hydroxyl functions, or alternatively a diglyceride or a triglyceride residue in which each fatty acid of said glyceride residue is either saturated or unsaturated,
wherein the process comprises at least the following steps:
cross metathesis with a unsaturated compound II, the unsaturated compound II having a main chain comprising less than 8 carbons, one of the compounds I or II comprising a nitrile function and the other of these compounds II or I an ester function, so as to obtain and recover at least one monounsaturated nitrile ester UNE;
hydrolysis of the UNE into an unsaturated acid nitrile UAN;
hydrogenation of the UAN into a saturated AA; and
optional purification of the AA.

2. The process as claimed in claim 1 , in which compound I is chosen from fatty acid esters or nitriles derived from fatty acids, chosen from: obtusilic acid (cis-4-decenoic acid) and caproleic acid (9-decenoic acid), lauroleic acid (cis-5-dodecenoic acid) and linderic acid (cis-4-dodecenoic acid), myristoleic acid (cis-9-tetradecenoic acid), physeteric acid (cis-5-tetradecenoic acid) and tsuzuic acid (cis-4-tetradecenoic acid), palmitoleic acid (cis-9-hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-oxodecenoic acid), petroselinic acid (cis-6-octadecenoic acid), vaccenic acid (cis-11-octadecenoic acid) and ricinoleic acid (12-hydroxy-cis-9-octadecenoic acid), gadoleic acid (cis-9-eicosenoic acid), gondoic acid (cis-11-eicosenoic acid), cis-5-eicosenoic acid and lesquerolic acid (14-hydroxy-cis-11-eicosenoic acid), cetoleic acid (cis-11-docosenoic acid) and erucic acid (cis-13-docosenoic acid), and also the polyunsaturated acids linoleic acid and linolenic acid.

3. The process as claimed in claim 1 , in which compound I is chosen from:
CH 2 ═CH—(CH 2 ) n —R 2 ,
CH 3 —CH═CH—(CH 2 ) n —R 2 , or
CH 3 —CH 2 —CH═CH—(CH 2 ) n —R 2 .

4. The process as claimed in claim 1 , in which R 2 is COOR 5 , the unsaturated nitrile compound II being chosen from: acrylonitrile, fumaronitrile, 2-butenenitrile, 1-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile and 1-pentenenitrile, and mixtures thereof.

5. The process as claimed in claim 1 , in which R 2 is CN, the unsaturated ester compound II being chosen from the compounds of formula:
R 6 —HC═CH—(CH 2 )n-COOR 7

in which n is 0 or 1; R 6 is CH 3 or H; R 7 is Me, Et or Bu.

6. The process as claimed in claim 1 , in which the cross metathesis step uses at least one ruthenium-carbene catalyst chosen from the charged or uncharged catalysts of general formula:
(X 1 ) a (X 2 ) b Ru(carbene C) (L 1 ) c (L 2 ) d (L 3 ) e
in which:
a, b, c, d and e are integers, which may be identical or different, with a and b equal to 0, 1 or 2; c, d and e equal to 0, 1, 2, 3 or 4;
X 1 and X 2 , which may be identical or different, each represent a charged or uncharged and monochelating or polychelating ligand; by way of example, mention may be made of halides, sulfate, carbonate, carboxylates, alkoxides, phenoxides, amides, tosylate, hexafluorophosphate, tetrafluoroborate, bis(triflyl)amide, an alkyl, tetraphenylborate and derivatives; X 1 or X 2 can be bonded to L 1 or L 2 or to the carbene C so as to form a bidentate or chelate ligand on the ruthenium; and
L 1 , L 2 and L 3 , which may be identical or different, are electron-donating ligands, such as phosphine, phosphite, phosphonite, phosphinite, arsine, stilbene, an olefin or an aromatic compound, a carbonyl compound, an ether, an alcohol, an amine, a pyridine or derivative, an imine, a thioether, or a heterocyclic carbene; L 1 , L 2 or L 3 can be bonded to the carbene C so as to form a bidentate or chelate ligand, or a tridentate ligand.

7. The process as claimed in claim 1 , wherein the process includes the use of a catalyst of formula:

8. The process as claimed in claim 1 , wherein the metathesis step is performed in liquid medium at a temperature in the range from 20 to 160° C. and at a pressure in the range from 1 to 30 bar.

9. The process as claimed in claim 1 , wherein the metathesis is performed in the presence of a solvent.

10. The process as claimed in claim 1 , in which the hydrolysis step comprises at least one of the following processes:
low-temperature hydrolysis in the presence of sodium hydroxide, by saponification;
medium-temperature hydrolysis in solvent medium and under acidic catalysis;
high-temperature hydrolysis under pressure;
enzymatic hydrolysis,
and mixtures thereof.

11. The process as claimed in claim 1 , in which the hydrogenation step is performed in the presence of at least one metal catalyst chosen from ruthenium, rhodium, palladium and platinum supported on a silicon carbide support.

12. The process as claimed in claim 1 , in which the hydrogenation temperature is in the range from 10 to 300° C. and the pressure is in the range from 1 bar to 300 bar.

13. The process as claimed in claim 1 , in which the hydrogenation step is performed in the presence of a solvent comprising a mixture of a lower alcohol and water.

14. The process as claimed in claim 1 , in which the hydrogenation is performed in the presence of a noble metal catalyst and of a chemical substance bearing a polydentate ligand.

15. The process as claimed in claim 1 , in which the purification comprises at least one step of recrystallization of the product derived from the hydrogenation in an aqueous solution containing a lower aliphatic alcohol and ammonia.

16. The process as claimed in claim 1 , in which the purification comprises at least two successive crystallization steps:
(A) a step in which crude AA crystals are isolated, after dissolution of the hydrogenation product in an aqueous solution containing a lower aliphatic alcohol and an aqueous solution containing ammonia, in a first crystallization device maintained at a temperature in the range from 0 to 30° C., and
(B) a step in which pure AA crystals are isolated, after redissolution of the crude AA crystals obtained in step A in an aqueous solution containing a lower aliphatic alcohol and ammonia in a second crystallization device maintained at a temperature in the range from 30 to 60° C.

17. The process as claimed in claim 1 , also comprising a step of polyamide synthesis by polymerization using the amino acid.

Assignees

• Arkema France

Inventors

• Dubois Jean-Luc
• Couturier Jean-Luc

Classifications

• C07C253/30

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

• C08G69/10

  Alpha-amino-carboxylic acids {(polysuccinimides C08G73/1092)} · CPC title

• C07C229/08

  the nitrogen atom of the amino group being further bound to hydrogen atoms · CPC title

• C07C227/04 Primary

  Formation of amino groups in compounds containing carboxyl groups · CPC title

• C07C253/16

  by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups · CPC title