Process for preparing saturated amino acids or saturated amino esters comprising a metathesis step

Patent metadata

Field	Value
Publication number	US-9096490-B2
Application number	US-201113696712-A
Country	US
Kind code	B2
Filing date	May 9, 2011
Priority date	May 7, 2010
Publication date	Aug 4, 2015
Grant date	Aug 4, 2015

Abstract

The subject matter of the invention is a process for synthesizing a saturated long-chain α,ω-amino ester (acid) obtained in a first step by cross-metathesis between an acrylic first compound and a monounsaturated second compound comprising at least one nitrile, acid or ester trivalent function, one of these compounds comprising a nitrile function and the other an acid or ester function, in the presence of a ruthenium carbene metathesis catalyst, and in a second step by hydrogenation of the monounsaturated nitrile ester (acid) obtained in the presence of the metathesis catalyst of the preceding stop, acting as a hydrogenation catalyst.

First claim

The invention claimed is:

1. A process for the synthesis of a saturated long-chain α,ω-amino ester (acid) comprising from 6 to 17 carbon atoms, comprising, first, a cross metathesis reaction between a first acrylic compound, that is acrylonitrile, acrylic acid or an acrylic ester, and a second monounsaturated compound comprising at least one nitrile, acid or ester trivalent functional group, one of these compounds comprising a nitrile functional group and the other an acid or ester functional group, in the presence of a ruthenium carbenes metathesis catalyst, and, second, hydrogenation of monounsaturated nitrile-ester (acid) obtained in the presence of the metathesis catalyst from the cross metathesis reaction acting as hydrogenation catalyst.

2. The process as claimed in claim 1 , wherein the metathesis is carried out according to the following reaction scheme:

with
R 1 ═H or (CH 2 ) m —R 4 ,
R 2 ═COOR 5 or CN,
R 3 ═COOR 5 or CN,
R 4 ═H or R 2 ,
R 5 =alkyl radical of 1 to 4 carbon atoms,
n=2 to 13, m=4 to 11, and
R 2 is different from R 3 .

3. The process as claimed in claim 1 , wherein the cross metathesis reaction with acrylonitrile is carried out with 9-decenoic acid, methyl 9-decenoate, 10-undecenoic acid, methyl 10-undecenoate, oleic acid, methyl oleate, 9-octadecenedioic acid, methyl 9-octadecenedioate, erucic acid, methyl erucate, 12-tridecenoic acid or methyl 12-tridecenoate.

4. The process as claimed in claim 1 , wherein the cross metathesis reaction of the acrylic ester (acid) is carried out with 9-decenenitrile, 10-undecenenitrile, 9-octadecenenitrile or oleonitrile, 9-octadecenedinitrile, eruconitrile or 12-tridecenonitrile.

5. The process as claimed in claim 1 , wherein the metathesis reaction is carried out at a reaction temperature of between 20 and 120° C. and under a pressure of between 1 and 30 bar.

6. The process as claimed in claim 1 , wherein the metathesis reaction is carried out in the presence of a charged or uncharged ruthenium catalyst of formula:
(X1) a (X2) b Ru(carbene C)(L1) c (L2) d (L3) e
in which:
a, b, c, d and e are identical or different integers, with a and b equal to 0, 1 or 2; c, d and e equal to 0, 1, 2, 3 or 4;
X1 and X2, which are identical or different, each represent a charged or uncharged and monochelating or polychelating ligand, X1 or X2 can be bonded to Y1 or Y2 (L1 or L2) or to the (carbene C) so as to form a bidentate or chelate ligand on the ruthenium; and
L1, L2 and L3, which are identical or different, are electron-donating ligands,

it being possible for L1, L2 or L3 to be bonded to the (carbene C) so as to form a bidentate or chelate ligand, or a tridentate ligand, the (carbene C) being represented by the formula:
C_(R1)_(R2), for which R1 and R2 are identical or different and are hydrogen or any other saturated or unsaturated and cyclic, branched or linear hydrocarbonyl group or aromatic hydrocarbonyl group.

7. The process as claimed in claim 6 , wherein the metathesis catalyst corresponds to either of the formulae (A) and (B) below:

8. The process as claimed in claim 1 , wherein the hydrogenation reaction is carried out on the reaction mixture resulting from the metathesis and in the presence of the residual metathesis catalyst acting as hydrogenation catalyst, under hydrogen pressure and in the presence of a base.

9. The process as claimed in claim 1 , wherein the hydrogenation reaction is carried out at a pressure of 5 and 100 bar, and at a temperature of between 50 and 150° C.

10. The process as claimed in claim 1 , wherein the hydrogenation reaction is carried out in the presence of a sodium hydroxide, potassium hydroxide, potassium tert-butoxide or ammonia base, at a content of 10 to 80 mol % with respect to the unsaturated nitrile-ester substrate.

11. The process as claimed in claim 1 , wherein the hydrogenation reaction is carried out in the presence of the degraded metathesis catalyst resulting from the first stage supplemented by a conventional hydrogenation catalyst.

12. The process according to claim 6 , wherein X1 and X2 are each independently halides, sulfate, carbonate, carboxylates, alkoxides, phenolates, amides, tosylate, hexafluorophosphate, tetrafluoroborate, bis(triflyl)amide, or tetraphenylborate.

13. The process according to claim 6 , wherein L1, L2 and L3 are each independently phosphine, phosphite, phosphonite, phosphinite, arsine, stilbene, an olefin, an aromatic compound, a carbonyl compound, an ether, an alcohol, an amine, a pyridine, an imine, a thioether or a heterocyclic carbine.

Assignees

• Couturier Jean Luc
• Dubois Jean Luc
• Miao Xiaowei
• Fischmeister Cedric
• Bruneau Christian
• Dixneuf Pierre
• Arkema France
• Univ Rennes
• Centre Nat Rech Scient

Inventors

• Couturier Jean Luc
• Dubois Jean Luc
• Miao Xiaowei
• Fischmeister Cedric
• Bruneau Christian
• Dixneuf Pierre

Classifications

• C07C253/30

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

• C07C227/04 Primary

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

• C07C229/08

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

• C11C3/12

  by hydrogenation · CPC title

• B01J31/1658

  immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins · CPC title