Esters of 5-hydroxymethylfurfural and methods for their preparation

• US 8,940,914 B2
• Filed: 07/20/2012
• Issued: 01/27/2015
• Est. Priority Date: 02/07/2006
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Benecke, Herman P., King, Jerry L. II, Kawczak, Alex Walter, Zehnder, Donald W. II, Hirschl, Erica E.
• Primary Examiner(s): Vajda, Kristin
• Assistant Examiner(s): Rodriguez-Garcia, Valerie
• Application Number:
  US13/554,525
• Publication Number:
  US 20130190516A1
• Time in Patent Office: 921 Days
• Field of Search: 549/473, 549/488
• US Class Current: 549/473
• CPC Class Codes: C07D 307/46 Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
• CPC Class Codes: C07D 307/54 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Abstract

Disclosed are compositions and methods for the production of mono-esters and di-esters from the reaction of HMF and a reactant selected from a diacid or a diacid derivative; typical reactants are PAN, phthaloyl dichloride, dimethyl phthalate, maleic acid, and maleic anhydride or mono-esters that can be prepared from HMF and MAN.

Claims

1. A method for di-ester synthesis comprising:

mixing 5-(hydroxymethyl)-2-furfuraldehyde and dimethyl phthalate with a suitable catalyst; and

heating at about 80°

C. to about 110°

C. while stirring for about 2 to about 4 hours.

2. A method for di-ester synthesis comprising:

melting 5-(hydroxymethyl)-2-furfuraldehyde;

adding phthalic anhydride and an optional esterification catalyst to the molten 5-(hydroxymethyl)-2-furfuraldehyde while stirring; and

reacting the mixture while stirring for about 16 to about 30 hours at a temperature between about 110°

C. to about 140°

C.

3. A method for di-ester synthesis comprising;

mixing a mono-ester reaction product of 5-(hydroxymethyl)-2-furfuraldehyde and phthalic anhydride with a molar equivalent of a coupling reagent;

adding 5-(hydroxymethyl)-2-furfuraldehyde to the mixture;

cooling the mixture to between about −

10°

C. to about 10°

C.; and

reacting the cooled mixture for about 10 to 18 hours at the reduced temperature.

4. The method according to claim 3 wherein the coupling agent is CDI, BOP, PYBOP, or dicyclohexylcarbodiimide.

5. A method for producing a mono-ester and/or a di-ester comprising:

a. contacting 5-(hydroxymethyl)-2-furfuraldehyde with a second reactant selected from maleic anhydride, maleic acid, fumaric acid, dimethylfumarate, phthalic anhydride, phthalic acid, phthalic acid diester, phthalic diacid chloride, isophthalic acid, isophthalic di-ester, isophthalic diacid chloride, terephthalic acid, terephthalic di-ester, terephthalic di-ester, or mixtures thereof in a reaction vessel; and

b. reacting the contacting reactants to obtain the mono-ester and/or di-ester product.

6. The method according to claim 5, wherein the reaction involves a mole ratio of 5-(hydroxymethyl)-2-furfuraldehyde:

maleic anhydride or 5-(hydroxymethyl)-2-furfuraldehyde;

phthalic anhydride of 1;

1 to 1;

2 to obtain increased monoester product.

7. The method according to claim 6, wherein the reaction is at temperatures at which the reactants melt up to about 120°

C.

8. The method according to claim 5, wherein 5-(hydroxymethyl)-2-furfuraldehyde and the second reactant are melted, wherein mono-ester product yield is increased versus di-ester product yield.

9. The method according to claim 5, wherein 5-(hydroxymethyl)-2-furfuraldehyde is added to either phthalic anhydride or maleic anhydride to obtain increased mono-ester product.

10. The method according to claim 5, wherein the mole ratio of 5-(hydroxymethyl)-2-furfuraldehyde:

maleic anhydride is greater than about 2;

1, wherein di-ester product yield is increased versus mono-ester product yield.

11. The method according to claim 7, wherein an optional catalyst and/or an optional water scavenger are used.

12. A method for producing an ester of 5-hydroxymethylfurfural comprising:

a. mixing 5-(hydroxymethyl)-2-furfuraldehyde and phthalic anhydride; and

b. reacting at a temperature between about 75°

C. and about 150°

C. to obtain the product.

13. The method according to claim 12, wherein the reaction is in the presence of a catalyst.

14. The method according to claim 12, wherein a mono-ester is obtained.

15. The method according to claim 12, wherein a di-ester is obtained.

16. The method according to claim 12, wherein a mixture of a mono-ester and a di-ester is obtained.

17. The method according to claim 12, further comprising:

c. separating the product from the reactant mixture.

18. The method according to claim 12, wherein the reaction is carried out in the presence of an inert gas to exclude air from the reaction.

19. The method according to claim 13 wherein the catalyst is selected from pyridine;

(dimethylamino)pyridine;

organic titanates;

dibutyltin dilaurate;

dibutyltin oxide;

tin(II) chloride;

magnesium ethoxide;

carbodiimides;

molecular sieves;

basic or acidic ion exchange resins;

toluene-sulfonic acid;

sulfuric acid;

HCl;

aluminum chloride;

boron trifluoride;

boron trifluoride diethyletherate;

clay;

lanthanide complexes;

or cation radicals.

20. A method for producing a di-ester comprising:

reacting 5-(hydroxymethyl)-2-furfuraldehyde and dimethyl phthalate at an elevated temperature in the presence of a catalyst,

wherein the ratio of 5-(hydroxymethyl)-2-furfuraldehyde;

dimethyl phthalate is about 2;

1 to about 5;

1.

21. The method according to claim 20, wherein the temperature is above about 60°

C.