Preparation of 2,5,6-trihydroxy-3-hexenoic acid and 2,5-dihydroxy-3-pentenoic acid and esters thereof from C6 and C5 sugars

Patent metadata

Field	Value
Publication number	US-10315979-B2
Application number	US-201615737395-A
Country	US
Kind code	B2
Filing date	Jun 20, 2016
Priority date	Jun 18, 2015
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

Preparation of 2,5,6-trihydroxy-3-hexenoic acid and 2,5-dihydroxy-3-pentenoic acid and esters thereof from C6 and C5 sugars in the presence of a Lewis Acid material, wherein the yield of the 2,5,6-trihydroxy-3-hexenoic acid or 2,5-dihydroxy-3-pentenoic acid or esters thereof exceeds 15%.

First claim

The invention claimed is:

1. A process for the preparation of 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or esters thereof of the formula
R′—HC═CH—CHOH—COOR  (I)

wherein
R is selected from the group consisting of —H and C 1 -C 8 -alkyl; and
R′ is hydroxymethyl or 1,2-dihydroxyethyl;

the process comprising the steps of:
a. contacting a saccharide composition comprising one or more C6 and/or C5 saccharide units with a Lewis Acid material; and
b. recovering and purifying 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or the esters thereof,
wherein the Lewis Acid material comprises a framework structure and an active metal,
wherein the process results in a yield of 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or esters thereof above 15%,
wherein a concentration of alkali metal ions present in an environment of the Lewis Acid material is kept at a concentration of less than 0.13 mM or at an amount of less than 0.5 wt % of a catalyst composition.

2. The process according to claim 1 , wherein the esters of 2,5,6-trihydroxy-3-hexenoic acid or 2,5-dihydroxy-3-pentenoic acid are 2,5,6-trihydroxy-3-hexenoic acid methyl ester and 2,5-dihydroxy-3-pentenoic acid methyl ester.

3. The process according to claim 1 , wherein the saccharide composition comprises one or more C6 and/or C5 saccharide units selected from the group consisting of sucrose, xylose, mannose, tagatose, galactose, glucose, fructose, arabinose, inulin, amylopectin and sugar syrup.

4. The process according to claim 1 , wherein the saccharide composition contains at least 10% by weight of saccharide units.

5. The process according to claim 1 , wherein the saccharide composition comprises a polar solvent.

6. The process according to claim 5 , wherein the saccharide composition comprises one or more solvents selected from the group consisting methanol, ethanol, DMSO and water.

7. The process according to claim 1 , wherein any alkali metal ion present in the saccharide composition is present in a concentration of less than 0.3 mM.

8. The process according to claim 1 , wherein the concentration of alkali metal ion in the saccharide composition is less than 0.3 mM.

9. The process according to claim 1 , wherein the Lewis acid material contains less than 0.5 wt % of alkali metal ion.

10. The process according to claim 1 , wherein the Lewis Acid material is Sn-BEA.

11. The process according to claim 1 , wherein the Lewis Acid material is Sn-MCM-41.

12. The process according to claim 1 , wherein the saccharide composition is contacted with the Lewis Acid material at a temperature of from 30 to 190° C.

13. The process according to claim 12 , wherein the temperature is from 80 to 170° C.

14. The process according to claim 1 , wherein the saccharide composition is contacted with the Lewis Acid material for a period of at least 10 seconds.

15. The process according to claim 1 , wherein the process is conducted under continuous conditions.

16. The process according to claim 15 , wherein the weight hourly space velocity is between 0.005 and 10 h −1 .

17. The process according to claim 1 , wherein the 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or esters thereof are subjected to a derivatization selected from acylation, silylation, alkylation, hydrolysis, hydrogenation, amidation.

18. The process according to claim 1 , wherein the concentration of alkali metal ions present in the environment of the Lewis Acid material is kept at a concentration of less than 0.13 mM.

19. A process for the preparation of 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or esters thereof of the formula
R′—HC═CH—CHOH—COOR  (I)

wherein
R is selected from the group consisting of —H and C 1 -C 8 -alkyl; and
R′ is hydroxymethyl or 1,2-dihydroxyethyl;

the process comprising the steps of:
c. contacting a saccharide composition comprising one or more C6 and/or C5 saccharide units with a Lewis Acid material; and
d. recovering and purifying 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or the esters thereof,
wherein the Lewis Acid material is a tin catalyst,
wherein the process results in a yield of 2,5,6-trihydroxy-3-hexenoic acid and/or 2,5-dihydroxy-3-pentenoic acid or esters thereof above 15%,

wherein a concentration of alkali metal ions present in an environment of the Lewis Acid material is kept at a concentration of less than 0.13 mM or at an amount of less than 0.5 wt % of a catalyst composition.

Assignees

• Haldor Topsoe As

Inventors

• Taarning Esben
• Sadaba Zubiri Irantzu
• Meier Sebastian

Classifications

• C07C67/39 Primary

  by oxidation of groups which are precursors for the acid moiety of the ester · CPC title

• C07C69/732

  of unsaturated hydroxy carboxylic acids · CPC title

• C07C59/42 Primary

  containing hydroxy or O-metal groups · CPC title

• C07C51/43

  by change of the physical state, e.g. crystallisation · CPC title

• C07C51/50

  Use of additives, e.g. for stabilisation · CPC title