Process for the manufacture of an amino ester

Abstract

Process for the manufacture of an amino ester of formula (I) R.sub.1OC(O)(CH.sub.2).sub.nNH.sub.2 (I) in which n is an integer from 10 to 15 from an unsaturated ester responding to formula (II) R.sub.1OC(O)(CH.sub.2).sub.mCHCHR.sub.2 (II) in which R.sub.1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms; R.sub.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.sub.1OC(O)(CH.sub.2).sub.mCHCH(CH.sub.2).sub.pCN (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).

Claims

1. A method for the manufacture of an ester-nitrile corresponding to formula (III)
R.sub.1OC(O)(CH.sub.2).sub.mCHCH(CH.sub.2).sub.pCN(III) from an unsaturated ester responding to formula (II)
R.sub.1OC(O)(CH.sub.2).sub.mCHCHR.sub.2(II) in which R.sub.1 is either H or a saturated alkyl group containing from 1 to 5 carbon atoms, m is equal to 7, 9, 10 or 11, and p is equal 1, wherein when m is equal to 7, R.sub.2 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; when m is equal to 9, R.sub.2 is a saturated alkyl group containing from 6 to 8 carbon atoms; when m is equal to 10, R.sub.2 is a saturated alkyl group containing 5 carbon atoms; and when m is equal to 11, R.sub.2 is a saturated alkyl group containing 8 carbon atoms; said method comprising submitting the unsaturated ester of formula (II) to a catalytic cross-metathesis reaction with 3-pentenenitrile in order to obtain the ester-nitrile responding to formula (III).

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

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

4. The method according to claim 3, wherein the triglyceride is extracted from a vegetable oil.

5. A method for the manufacture of an amino ester of formula (I)
R.sub.1OC(O)(CH.sub.2).sub.mNH.sub.2(I) in which R.sub.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 1 to an hydrogenation in order to obtain the amino ester of formula (I).

6. The method according to claim 4, 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.

7. 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 5, and manufacturing the polyamide by auto-polycondensing said amino ester.

8. The method according to claim 1, wherein m is equal to 9, 10 or 11.

9. The method according to claim 1, in which m is equal to 7, R1 is a saturated alkyl group containing from 1 to 5 carbon atoms and R2 is a saturated alkyl group containing 8 carbon atoms.

Description

EXAMPLE 1

(1) In a Schlenk tube under argon, 6 mg (0.007 mmol; 0.06 mol %/methyl oleate) of Grubbs 2nd generation catalyst was weighted. Then 4.24 g (11.87 mmol) of distilled methyl oleate and 1.02 g (12.45 mmol) of distilled 3-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h at atmospheric pressure. Reaction mixture was then subjected to analysis. Methyl oleate conversion was 63%, 3-pentenenitrile conversion was 58% and C12 ester-nitrile selectivity was 41% (methyl oleate reference)

EXAMPLE 2

(2) In a Schlenk tube under argon, 102 mg (0.120 mmol; 1 mol %/methyl oleate) of Grubbs 2nd generation catalyst was weighted. Then 4.25 g (11.90 mmol) of distilled methyl oleate and 1.01 g (12.33 mmol) of distilled 3-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h. Reaction mixture was then subjected to analysis Methyl oleate conversion was 76%, 3-pentenenitrile conversion was 80% and C12 ester-nitrile selectivity was 49% (methyl oleate reference)

EXAMPLE 3

(3) In a Schlenk tube under argon, 101 mg (0.119 mmol; 1 mol %/methyl oleate) of Grubbs 2nd generation catalyst and 17.65 g of anhydrous toluene were weighted. Then 4.25 g (11.90 mmol) of distilled methyl oleate and 1.03 g (12.57 mmol) of distilled 3-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h. Reaction mixture was then subjected to analysis. Methyl oleate conversion was 78%, 3-pentenenitrile conversion was 77% and C12 ester-nitrile selectivity was 48% (methyl oleate reference).

EXAMPLE 4

(4) In a Schlenk tube under argon, 101 mg (0.119 mmol; 1 mol %/methyl oleate) of Grubbs 2nd generation catalyst was weighted. Then 4.23 g (11.84 mmol) of distilled methyl oleate and 1.01 g (12.41 mmol) of distilled 2-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h. Reaction mixture was then subjected to analysis. Methyl oleate conversion was 70%, 2-pentenenitrile conversion was 54%, C11 ester-nitrile selectivity was 29% (reference methyl oleate)

EXAMPLE 5

(5) In a Schlenk tube under argon, 102 mg (0.120 mmol; 1 mol %) of Grubbs 2nd generation catalyst and 17.85 g of anhydrous toluene were weighted. Then 4.26 g (11.93 mmol) of distilled methyl oleate and 1.01 g (12.41 mmol) of distilled 2-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h. Methyl oleate conversion was 79%, 2-pentenenitrile conversion was 86% and C11 ester-nitrile selectivity was 41% (reference methyl oleate)

EXAMPLE 6

(6) In a Schlenk tube under argon, 2.12 g (10.58 mmol) of distilled methyl-10-undecenoate was weighted then 4.00 g (42.90 mmol) of distilled 2-pentenenitrile and finally 17.89 g of anhydrous toluene were added. Finally 5 mg (0.008 mmol; 0.07 mol %) of Grubbs 2nd generation catalyst was added. The reaction mixture was stirred 1 h at 100 C. and then subjected to analysis. Methyl-10-undecenoate conversion was 81%, 2-pentenenitrile conversion was 22%, C12 ester-nitrile selectivity was 96% (reference methyl-10-undecenoate).

EXAMPLE 7

(7) In a Schlenk tube under argon, 8 mg (0.012 mmol; 1.2 mol %) of Hoveyda-Grubbs 2nd generation catalyst and 26.5 g of anhydrous dichloromethane were weighted. Then 0.36 g (1.02 mmol) of distilled methyl oleate and 0.19 g (2.34 mmol) of distilled 3-pentenenitrile were added. The reaction mixture was stirred at 40 C. during 4 h. Reaction mixture was then subjected to analysis. Methyl oleate conversion was 87%, 3-pentenenitrile conversion was 63% and C12 ester-nitrile selectivity was 50% (reference methyl oleate).

EXAMPLE 8

(8) In a Schlenk tube under argon, 5 mg (0.008 mmol; 0.07 mol %) of Hoveyda-Grubbs 2nd generation catalyst was weighted. Then 4.2 g (11.8 mmol) of distilled methyl oleate and 1.0 g (12.2 mmol) of distilled 3-pentenenitrile were added. The reaction mixture was stirred at 60 C. during 4 h. Reaction mixture was then subjected to analysis. Methyl oleate conversion was 69%, 3-pentenenitrile conversion was 66% and C12 ester-nitrile selectivity was 50% (reference methyl oleate).