# US 2014/0194584 A1 · Process for the synthesis of w-Unsaturated nitrile-acid/ester in which two types of cross metathesis are alternated consecutively swing process

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- Number: US 2014/0194584 A1
- Document ID: US20140194584A1
- Status: Published application
- Kind: A1
- Application number: 13/735,366
- Filed: 2013-01-07
- Published: 2014-07-10
- Earliest claimed: 2013-01-07
- Assignees: Arkema France
- Applicants: Arkema France
- Inventors: Jean-Luc Dubois; Jean-Luc Couturier
- Web page: https://patentgrep.com/patent/US20140194584A1

## CPC

- C07C 253/30: by reactions not involving the formation of cyano groups
- C07C 227/04: Formation of amino groups in compounds containing carboxyl groups
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The invention relates to a process for the synthesis of a monounsaturated nitrile-ester (acid) by cross metathesis starting from an unsaturated compound I comprising at least one trivalent nitrile, acid or ester functional group, characterized in that it comprises a stage in which two types of cross metathesis are alternated consecutively: a first type of cross metathesis cm1 with an acrylic compound II chosen from acrylonitrile, acrylic acid or an acrylic ester, one of the compounds I or II comprising a nitrile functional group and the other of these compounds II or I comprising an acid or ester functional group, and a second type of cross metathesis cm2 with a light C2 to C4 alkene compound III, preferably with ethylene. The invention also relates to a process for the synthesis of an α,ω-amino ester (acid) obtained by a process comprising a stage in which the two types of cross metathesis defined above are alternated consecutively, followed by a hydrogenation stage.

## Claims

### Claim 1

A process for the synthesis of a monounsaturated nitrile-ester (acid) by cross metathesis starting from an unsaturated compound I comprising at least one trivalent nitrile, acid or ester functional group, wherein it comprises a stage in which two types of cross metathesis are alternated consecutively:
a first type of cross metathesis (cm1) with an acrylic compound II chosen from acrylonitrile, acrylic acid or an acrylic ester, one of the compounds I or II comprising a nitrile functional group and the other of these compounds II or I comprising an acid or ester functional group, and
a second type of cross metathesis (cm2) with a light C2 to C4 alkene compound III, preferably with ethylene.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein the unsaturated compound I is of formula:
R1—═CH—[(CH2)q—CH═CH]p—(CH2)n—R2
in which:
R1 is H, an alkyl radical having from 1 to 11 carbon atoms, if appropriate comprising a hydroxyl functional group, or a (CH2)m—R4 radical,
m is a whole index within the range from 0 to 11,
n is a whole index within the range from 2 to 13,
p is a whole index equal to 0, 1 or 2,
q is an index equal to 0 or 1,
R2 is COOR5 or CN,
R4 is H or R2,
R5 is chosen from: H, an alkyl radical having from 1 to 11 carbon atoms, a radical comprising two or three carbon atoms carrying one or two hydroxyl functional group(s), or also the residue of a diglyceride or of a triglyceride in which each fatty acid of said glyceride residue is without distinction saturated or unsaturated.

### Claim 3 (depends on 2)

The process as claimed in claim 2, wherein the index p is equal to 0, R1 is equal to H and the cycle of metatheses preferably begins with a cm1 metathesis on the compound I of formula:
CH2═CH—(CH2)n—R2.

### Claim 4 (depends on 2)

The process as claimed in claim 2, wherein the unsaturated compound I is a fatty acid or ester of formula:
CH2═CH—(CH2)n—COOR5,
in which
R5 is H or an alkyl radical having from 1 to 11 carbon atoms.

### Claim 5 (depends on 2)

The process as claimed in claim 2, the unsaturated compound I is a nitrile of formula:
CH2═CH—(CH2)n—CN.

### Claim 6 (depends on 2)

The process as claimed in claim 2, wherein the index p is other than 0 and/or R1 is other than H, and the cycle of metatheses preferably begins with a cm2 metathesis.

### Claim 7 (depends on 4)

The process as claimed in claim 4, wherein the cm1 metathesis reaction is carried out with acrylonitrile and a compound I chosen from 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 and methyl 12-tridecenoate.

### Claim 8 (depends on 5)

The process as claimed in claim 5, wherein the cm1 metathesis reaction is carried out between an acrylic ester (acid) and a compound I chosen from 9-decenenitrile, 10-undecenenitrile, 9-octadecenenitrile or oleonitrile, 9-octadecenedinitrile, eruconitrile or 12-tridecenonitrile.

### Claim 9 (depends on 1)

The process as claimed in claim 1, wherein the cm2 cross metathesis reaction is carried out between a light C2 to C4 alkene III and a compound I chosen from natural oils, triglycerides, polyunsaturated fatty esters and acids, and their mixtures.

### Claim 10 (depends on 1)

The process as claimed in claim 1, wherein it comprises at least the sequence of stages cm1-cm2-cm1 or cm2-cm1-cm2.

### Claim 11 (depends on 1)

The process as claimed in claim 1, wherein the compound I is a triglyceride and the process comprises at least the sequence of stages cm2-cm1, optionally followed by an alcoholysis or hydrolysis stage.

### Claim 12 (depends on 1)

The process as claimed in claim 1, wherein the cross metathesis is carried out in the presence of a ruthenium catalyst chosen from charged or uncharged catalysts of general formula:
(X1)a(X2)bRu(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, preferably chosen from halides, sulfate, carbonate, carboxylates, alkoxides, phenolates, amides, tosylate, hexafluorophosphate, tetrafluoroborate, bis(triflyl)amide, tetraphenylborate and derivatives. 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, 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;
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 general formula: C_(R1)_(R2), for which R1 and R2 are identical or different groups, such as hydrogen or any other functionalized or nonfunctionalized hydrocarbon group of saturated, unsaturated, cyclic, aromatic, branched and/or linear type.

### Claim 13 (depends on 12)

The process as claimed in claim 12, wherein the amount of catalyst present during the metathesis reaction is characterized by a turnover number, equal to the molar ratio, within the range from 5000 to 200 000 and preferably from 10 000 to 50 000.

### Claim 14 (depends on 12)

The process as claimed in claim 12, wherein the cm1 metathesis reaction is carried out in the presence of a catalyst in which L1, L2 and/or L3 is a heterocyclic carbene.

### Claim 15 (depends on 12)

The process as claimed in claim 12, wherein the cm2 metathesis reaction is carried out in the presence of a catalyst in which L1, L2 and L3 are not heterocyclic carbenes.

### Claim 16 (depends on 12)

The process as claimed in claim 12, wherein the cm1 and/or cm2 cross metathesis is carried out in the presence of a ruthenium catalyst corresponding to one of the following formulae:

### Claim 17 (depends on 1)

The process as claimed in claim 1, additionally comprising a stage of hydrogenation of the monounsaturated nitrile-ester (acid) obtained, so that a saturated α,ω-amino ester (acid) is obtained.

### Claim 18 (depends on 17)

The process as claimed in claim 17, wherein the hydrogenation is carried out in the presence of a metathesis catalyst from the preceding stage, this catalyst operating as hydrogenation catalyst.

### Claim 19 (depends on 17)

The process as claimed in claim 17, additionally comprising a stage of synthesis of polyamide by polymerization using the a,w-amino ester (acid) obtained on conclusion of the hydrogenation stage.

### Claim 20 (depends on 1)

A polymer, obtained by polymerization of α,ω-amino ester (acid) synthesized according to the process of claim 1.