Process for the manufacture of an amino ester

Patent metadata

Field	Value
Publication number	US-2016289167-A1
Application number	US-201415037446-A
Country	US
Kind code	A1
Filing date	Nov 18, 2014
Priority date	Nov 18, 2013
Publication date	Oct 6, 2016
Grant date	—

Abstract

Process for the manufacture of an amino ester of formula (I) R 1 —O—C(O)—(CH 2 ) n —NH 2 (I) in which n is an integer from 10 to 15 from an unsaturated ester responding to formula (II) R 1 —O—C(O)—(CH 2 ) m —CH═CH—R 2 (II) in which R 1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms; R 2 is either H or an alkyl group containing from 1 to 10 carbon atoms, either saturated or containing 1 or 2 unsaturations and bearing optionally a hydroxyl, a carboxylic or an ester group, and m is equal to 7, 8, 9, 10 or 11; said process comprising: submitting the unsaturated ester of formula (II) to a catalytic cross-metathesis reaction with a pentenenitrile chosen among 2-pentenenitrile or 3-pentenenitrile in order to obtain a ester-nitrile responding to formula (III) R 1 —O—C(O)—(CH 2 ) m —CH═CH—(CH 2 ) p —CN (III) in which m is equal to 7, 8, 9, 10 or 11 and p is equal to 0 or 1, and submitting the obtained ester-nitrile of formula (III) to an hydrogenation in order to obtain the amino ester of formula (I).

First claim

1 . A process for the manufacture of an amino ester of formula (I)
R 1 —O—C(O)—(CH 2 ) n —NH 2   (I)

in which n is an integer from 10 to 15
from an unsaturated ester corresponding to formula (II)
R 1 —O—C(O)—(CH 2 ) m —CH═CH—R 2   (II)

in which
R 1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms;
R 2 is either H or an alkyl group containing from 1 to 10 carbon atoms, either saturated or containing 1 or 2 unsaturations and bearing optionally a hydroxyl, a carboxylic or an ester group, and
m is equal to 7, 8, 9, 10 or 11;
said process comprising
submitting the unsaturated ester of formula (II) to a catalytic cross-metathesis reaction with 2-pentenenitrile or 3-pentenenitrile in order to obtain a ester-nitrile responding to formula (III)
R 1 —O—C(O)—(CH 2 ) m —CH═CH—(CH 2 ) p —CN  (III)

in which m is equal to 7, 8, 9, 10 or 11 and p is equal to 0 or 1, and
submitting the obtained ester-nitrile of formula (III) to an hydrogenation in order to obtain the amino ester of formula (I).

2 . The process according to claim 1 , wherein the cross-metathesis reaction is carried out by using a ruthenium based homogeneous catalyst.

3 . The process according to claim 1 , wherein
when m is equal to 7, R 2 is either H or an alkyl group containing from 1 to 10 carbon atoms, either saturated or containing 1 or 2 unsaturations and bearing optionally a hydroxyl, a carboxylic or an ester group; when m is equal to 8, R 2 is H; when m is equal to 9, R 2 is a saturated alkyl group containing from 6 to 8 carbon atoms; when m is equal to 10, R 2 is a saturated alkyl group containing 5 carbon atoms; and when m is equal to 11, R 2 is a saturated alkyl group containing 8 carbon atoms.

4 . The process according to claim 1 , wherein the unsaturated ester is an unsaturated ester corresponding to formula (II) in which m is equal to 7, 8 or 11.

5 . The process according to claim 1 , wherein the unsaturated ester is an unsaturated ester corresponding to formula (II) in which m is equal to 7 or 8.

6 . The process according to claim 1 , wherein the unsaturated ester is an unsaturated ester corresponding to formula (II) in which m is equal to 7.

7 . The process according to claim 1 , wherein the unsaturated ester is an unsaturated ester corresponding to formula (II) in which
R1 is a saturated alkyl group containing from 1 to 5 carbon atoms; R 2 is a saturated alkyl group containing 8 carbon atoms, and m is equal to 7.

8 . The process according to claim 1 , comprising only one catalytic cross-metathesis reaction.

9 . The process according to claim 1 , wherein the unsaturated ester of formula (II) is obtained by a reaction other than a catalytic cross-metathesis reaction.

10 . A method for the manufacture of an ester-nitrile corresponding to formula (III)
R 1 —O—C(O)—(CH 2 ) m —CH═CH—(CH 2 ) p —CN  (III)

from an unsaturated ester responding to formula (II)
R 1 —O—C(O)—(CH 2 ) m —CH═CH—R 2   (II)

in which
R 1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms,
R 2 is either H or an alkyl group containing from 1 to 10 carbon atoms, either saturated or containing 1 or 2 unsaturations and bearing optionally a hydroxyl, a carboxylic or an ester group,
m is equal to 7, 8, 9, 10 or 11, and
p is equal to 0 or 1,

said method comprising submitting the unsaturated ester of formula (II) to a catalytic cross-metathesis reaction with 2-pentenenitrile or 3-pentenenitrile in order to obtain the ester-nitrile responding to formula (III).

11 . The method according to claim 10 , wherein the unsaturated ester of formula (II) is obtained by a reaction other than a catalytic cross-metathesis reaction.

12 . The method according to claim 10 , wherein the unsaturated ester of formula (II) is obtained by a transesterification reaction using a triglyceride and an alcohol of formula R 1 OH as reagents, with R 1 as defined, and/or by a hydrolysis reaction using the triglyceride and water as reagents.

13 . The method according to claim 12 , wherein the triglyceride is extracted from a vegetable oil.

14 . A method for the manufacture of an amino ester of formula (I)
R 1 —O—C(O)—(CH 2 ) n —NH 2   (I)

in which R 1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms and n is an integer from 10 to 15,
said method comprising submitting the ester-nitrile of formula (III) manufactured by the method according to claim 10 to an hydrogenation in order to obtain the amino ester of formula (I).

15 . A process for the manufacture of a polyamide, the process comprising
manufacturing an amino ester by the process according to claim 1 , and manufacturing the polyamide by auto-polycondensing said amino ester.

16 . The process according to claim 3 , wherein when m is equal to 7, R2 is an alkyl group containing from 2 to 8 carbon atoms, either saturated or containing 1 or 2 unsaturations and bearing optionally a hydroxyl, a carboxylic or an ester group.

17 . The method according to claim 13 , wherein the vegetable oil is selected from the group consisting of canola, safflower, flaxseed, sunflower, corn, olive, soybean, peanut, cottonseed, palm, castor and coconut oils, and mixtures thereof.

18 . A process for the manufacture of a polyamide, the process comprising
manufacturing an amino ester by the process according to the method according to claim 14 , and manufacturing the polyamide by auto-polycondensing said amino ester.

Assignees

• Rhodia Operations

Inventors

• Marion Philippe
• Morvan Didier

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

• C08G69/44

  Polyester-amides · CPC title