Combined synthesis of a nitrile-ester/acid and of a diester/diacid

Patent metadata

Field	Value
Publication number	US-9567293-B2
Application number	US-201414766951-A
Country	US
Kind code	B2
Filing date	Feb 10, 2014
Priority date	Feb 8, 2013
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

A method for the combined synthesis of a mono-unsaturated nitrile-ester(acid) and of a bi-functional carbonyl compound, wherein it includes a step including the cross metathesis mc1 of an unsaturated fatty acid/ester compound with an unsaturated nitrile compound, in which mc1 is performed with partial conversion such as to obtain and recover, separately, at least the following products: a mono-unsaturated nitrile-ester/acid and a symmetrical compound, diester or diacid respectively including a double bond located in the middle of the molecular chain of compound, and subsequently a step including the oxidation cleavage cp2 of the double bond of compound, such as to form a single type of carbonyl compound having formula R2-(CH2)n-COR′, in which R′ is H or OH, depending on the operating conditions selected for the oxidation cleavage cp2. Also, the production of monomers for the polymer industry.

First claim

The invention claimed is:

1. A process for the conjugate synthesis of a monounsaturated nitrile ester (acid) and of a difunctional carbonyl compound (V), of formula R 2 —(CH 2 ) n —COR′ in which R′ is H or OH, from the same unsaturated fatty compound (I) comprising at least one ester or acid function, respectively, of formula:
R 1 —CH═CH—[(CH 2 ) q —CH═CH] p —(CH 2 ) n —R 2   (I)

in which R 1 is H or an alkyl radical comprising from 1 to 4 carbon atoms, R 2 is an ester or acid function and n, p and q are integers such that 3≦n≦13; 0≦p≦3; 0≦q≦1,
wherein the process comprises:
a step of cross metathesis cm1 of compound (I) with an unsaturated nitrile compound (II) chosen from: acrylonitrile, fumaronitrile, 2-butenenitrile, 1-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile and 1-pentenenitrile, in which cm1 is brought to partial conversion so as to obtain, and to recover separately, at least the following products: a monounsaturated acid (ester)-nitrile (Ill) and a symmetrical compound (IV), respectively a diester or diacid comprising a double bond located in the middle of the molecular chain of compound (IV) of formula R 2 —(CH 2 ) n —HC═CH—(CH 2 ) n —R 2 resulting from the homometathesis of compound (I), and then
a step of oxidative cleavage cl2 of the double bond respectively of the diester or diacid compound (IV), so as to form a single type of carbonyl compound (V) of formula R 2 —(CH 2 ) n —COR′ in which R′ is H or OH, depending on the operating conditions chosen for the oxidative cleavage cl2,
in which the cross metathesis step is performed to a degree of conversion in the range from 30% to 90%.

2. The process as claimed in claim 1 , in which compound (I) is a fatty acid or an ester of an unsaturated fatty acid of plant or animal origin.

3. The process as claimed in claim 1 , wherein the process also comprises a step of hydrogenation of the monounsaturated ester/acid nitrile (III) obtained to form a saturated α,ω-amino ester/acid.

4. The process as claimed in claim 3 , in which compound (I) comprises an unsaturation located in the delta x position relative to the ester or acid group R2, which makes it possible to determine the formula of the saturated ω-amino ester/acid.

5. The process as claimed in claim 1 , wherein the process also comprises, prior to step cm1, at least one of the following reactions: ethenolysis, butenolysis, propenolysis and/or thermal cracking (pyrolysis) of compound (I), so as to obtain a fatty ester/acid of formula:
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 .

6. The process as claimed in claim 1 , in which compound (I) is a fatty ester or acid of formula CH 2 ═CH—(CH 2 ) n —COOR 3 in which R 3 is H or an alkyl radical comprising from 1 to 11 carbon atoms and n is an integer in the range from 3 to 13.

7. The process as claimed in claim 1 , in which the unsaturated nitrile compound (II) used in step cm1 is acrylonitrile.

8. The process as claimed in claim 1 , in which the cross metathesis step is performed to a degree of conversion in the range from 40% to 90%.

9. The process as claimed in claim 1 , in which the cross metathesis step is performed in the presence of a metathesis catalyst of ruthenium-carbene type 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 such as 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.

10. The process as claimed in claim 9 , wherein the catalyst corresponds to the formula:

11. The process as claimed in claim 1 , wherein the process comprises an optional intermediate step of hydrolysis between cm1 and cl2 when compound (IV) is a diester, to give the diacid compound (IV).

12. The process as claimed in claim 1 , in which the oxidative cleavage step is performed using aqueous hydrogen peroxide solution and/or ozone as oxidizing agent.

13. The process as claimed in claim 1 , wherein the oxidative cleavage step is performed under oxidative conditions to give a compound of formula R 2 —(CH 2 ) n —COOH, acid ester or diacid.

14. The process as claimed in claim 13 , wherein the compound of formula R 2 —(CH 2 ) n —COOH is subjected to a hydrolysis to give the diacid when R 2 is an ester function.

15. The process as claimed in any one of the preceding claims, wherein the oxidative cleavage step is performed under reductive conditions to give the ester/acid-aldehyde of formula R 2 —(CH 2 ) n —CHO.

16. The process as claimed in claim 15 , wherein the compound of formula R 2 —(CH 2 ) n —CHO is subjected to an additional reduction to give the ester/acid-alcohol of formula R 2 —(CH 2 ),—CH2OH.

17. A process, wherein the process comprises:
starting with the same unsaturated fatty compound (I) comprising, respectively, at least one ester or acid function, of formula:
R 1 —CH═CH—[(CH 2 ) q —CH═CH] p —(CH 2 ) n —R 2   (I)

in which R 1 is H or an alkyl radical comprising from 1 to 4 carbon atoms, R 2 is an ester or acid function and n, p and q are integers such that 3≦n≦13; 0≦p≦3; 0≦q≦1,
a step of cross metathesis cm1 of compound (I) with an unsaturated nitrile compound (II) chosen from: acrylonitrile, fumaronitrile, 2-butenenitrile, 1-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile and 1-pentenenitrile, in which cm1 is brought to partial conversion so as to obtain, and to recover separately, at least the following products: a monounsaturated acid (ester)-nitrile (Ill) and a symmetrical compound (IV), respectively a diester or diacid comprising a double bond located in the middle of the molecular chain of compound (IV) of formula R 2 —(CH 2 ) n —HC═CH—(CH 2 ) n —R 2 resulting from the homometathesis of compound (I),
in which the cross metathesis step is performed to a degree of conversion in the range from 30% to 90%.

18. The process as claimed in claim 1 , wherein the process also comprises the hydrogenation of at least part of the symmetrical compound (IV) leading to the corresponding saturated compound (IVs) of formula R 2 —(CH 2 ) n —CH 2 —CH 2 —(CH 2 ) n —R 2 .

19. The process as claimed in claim 17 , wherein the process also comprises a step of hydrogenation of the monounsaturated ester/acid nitrile (III) obtained to form a saturated α,ω-amino ester/acid.

20. A process for synthesizing polymer by polymerization using at least one monomer, comprising at least one ω-amino acid, an 107 -amino ester, a diaci

Assignees

• Arkema France

Inventors

• Dubois Jean-Luc
• Couturier Jean-Luc
• Brandhorst Markus

Classifications

• C07C55/18

  Azelaic acid · CPC title

• C07C253/30 Primary

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

• C08F132/06

  having two or more carbon-to-carbon double bonds · CPC title

• C07C227/04

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

• C07C67/475 Primary

  by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules · CPC title