Process for preparing esters of α-hydroxy methionine from sugars

Patent metadata

Field	Value
Publication number	US-10280136-B2
Application number	US-201816133100-A
Country	US
Kind code	B2
Filing date	Sep 17, 2018
Priority date	Nov 28, 2014
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

A continuous flow process for the preparation of one or more esters of lactic acid and 2-hydroxy-3-butenoic acid or α-hydroxy methionine analogs from a sugar in the presence of a solid Lewis acid catalyst and a solvent comprising an organic solvent and water. The invention provides a stabilized Lewis acid catalyst for use in a continuous reaction process, where the water is present in an amount of up to or equal to 10 vol. % of the organic solvent.

First claim

What is claimed is:

1. A continuous flow process for the preparation of an α-hydroxy methionine analogue from a sugar selected from one or more of the group consisting of glucose, fructose, mannose, sucrose, xylose, erythrose, erythrulose, threose and glycolaldehyde, in the presence of a compound comprising sulphur, solid Lewis acid catalyst and a solvent comprising an organic solvent and water, wherein the water is present in an amount of up to or equal to 10 vol. % of the organic solvent, and wherein the solid Lewis acid catalyst has a framework structure, which is selected from the group consisting of BEA, MFI, FAU, MOR, FER, MWW, MCM-41 and SBA-15.

2. The process according to claim 1 , wherein the compound comprising sulfur is selected from the group consisting of C 1 -C 5 alkyl thiol, C 1 -C 5 alkyl thiol salts, dimethylmercaptan and dimethyl disulfide.

3. The process according to claim 1 , wherein the vol. % of water present in the organic solvent is from 0.25 to 10 vol. %.

4. A process according to claim 1 , wherein the solid Lewis acid catalyst is calcined after 450 hours.

5. A process according to claim 1 , wherein the solid Lewis acid comprises an active metal selected from one or more of the group consisting of Sn, Ti, Pb, Zr, Ge and Hf.

6. A process according to claim 1 , wherein the solid Lewis acid catalyst is selected from the group consisting of Sn-BEA, Sn-MFI, Sn-FAU, Sn-MOR, Sn-MWW, Sn-MCM-41 and Sn-SBA-15.

7. A process according to claim 1 , wherein the solid Lewis acid catalyst comprises Sn and the loss of Sn from the solid Lewis acid catalyst is less than or equal to 0.11% of the initial amount of Sn per hour on stream.

8. A process according to claim 1 , wherein the solid Lewis acid catalyst comprises Sn and the loss of Sn from the solid Lewis acid catalyst is less than 8% of the initial amount of Sn after 50 hours on stream.

9. A process according to claim 1 , wherein the yield of α-hydroxy methionine analogue ester is greater than 20% after 10 hours on stream.

10. A process according to claim 1 , wherein an alkaline earth metal or alkali metal ion is present in the process.

11. A process according to claim 1 , wherein the solvent is selected from one or more of the group consisting of methanol, ethanol, 1-propanol, 1-butanol and isopropanol.

12. A process according to claim 1 , wherein the temperature of the process is from 140° C. to 200° C.

13. A process according to claim 1 , wherein at least a fraction of the water is introduced to the solvent by mixing the organic solvent with an aqueous sugar solution.

14. A process according to claim 1 , wherein the aqueous sugar solution is a sugar syrup with a sugar dry matter content of 30% or higher.

15. A continuous flow process for the preparation of an alpha-hydroxy methionine analogue from a sugar selected from one or more of the group consisting of glucose, fructose, mannose, sucrose, xylose, erythrose, erythrulose, threose and glycolaldehyde, in the presence of a compound comprising Sulphur, a solid Lewis acid catalyst and a solvent comprising an organic solvent and water, wherein the vol. % of water present in the organic solvent is from 0.25 to 10 vol. % and at least a fraction of the water is introduced to the solvent by mixing the organic solvent with an aqueous sugar solution, and wherein the solid Lewis acid catalyst is Sn-BEA.

16. A process according to claim 15 , wherein the alpha-hydroxy methionine analogue is 2-hydroxy-4-(methylthio)butanoic acid.

17. A process according to claim 15 , wherein the alpha-hydroxy methionine analogue is selected from the group consisting of 2-hydroxy-4-(methylthio)butanoic acid methyl ester, 2-hydroxy-4-(methylthio)butanoic acid ethyl ester, 2-hydroxy-4-(methylthio)butanoic acid propyl ester, 2-hydroxy-4-(methylthio)butanoic acid butyl ester, 2-hydroxy-4-(methylthio)butanoic acid isopropyl ester, 2-hydroxy-4-(methylthio)butanoic acid pentyl ester, 2-hydroxy-4-(methylthio)butanoic acid hexyl ester, and 2-hydroxy-4-(methylthio)butanoic acid heptyl ester, 2-hydroxy-4-(methylthio)butanoic acid octyl ester and 2-hydroxy-4-(methylthio)butanoic acid 2-ethylhexyl ester.

Assignees

• Haldor Topsoe As

Inventors

• Sadaba Zubiri Irantzu
• Taarning Esben

Classifications

• C07C67/475

  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

• C07C319/18 Primary

  by addition of thiols to unsaturated compounds · CPC title

• C07C69/68

  Lactic acid esters · CPC title

• C07C67/44

  by oxidation-reduction of aldehydes, e.g. Tishchenko reaction · CPC title

• C07C69/732

  of unsaturated hydroxy carboxylic acids · CPC title