Dehydration and cyclization of α-, β-dihydroxy carbonyl compounds to 2-substituted furan derivatives

Patent metadata

Field	Value
Publication number	US-11578048-B2
Application number	US-201917046754-A
Country	US
Kind code	B2
Filing date	Apr 4, 2019
Priority date	Apr 13, 2018
Publication date	Feb 14, 2023
Grant date	Feb 14, 2023

Abstract

Processes are disclosed for the synthesis of 2-substituted furan derivatives, such as furan dicarboxylic acid (FDCA), from a starting compound or substrate having a carbonyl functional group (C═O), with hydroxy-substituted carbon atoms at alpha (α) and beta (β) positions, relative to the carbonyl functional group. According a particular embodiment, an α-, β-dihydroxy carboxylate is dehydrated to form a dicarbonyl intermediate by transformation of the α-hydroxy group to a second carbonyl group and removal of the β-hydroxy group. The dicarbonyl intermediate undergoes cyclization and dehydration, to produce the 2-substituted furan derivative. Optionally, a further step of oxidation may be carried out, for example to convert a hydroxymethyl group, as a 5-substituted about the furan ring, to a carboxy group of FDCA.

First claim

What is claimed is:

1. A method for synthesizing a 2-substituted furan derivative, the method comprising:
(a) dehydrating a starting compound comprising an alpha hydroxy group, substituted at an alpha carbon atom with respect to a first carbonyl group, and a beta hydroxy group, substituted at a beta carbon atom with respect to the first carbonyl group, to form a dicarbonyl intermediate by transformation of the alpha hydroxy group to a second carbonyl group and removal of the beta hydroxy group;
(b) cyclizing the dicarbonyl intermediate to produce the 2-substituted furan derivative comprising a 2-substituent of a furan ring including the first carbonyl group,

wherein the method is carried out non-enzymatically, and further wherein the starting compound is a salt of gluconic acid or a salt of glucaric acid.

2. The method of claim 1 , wherein the dehydrating comprises forming water from a combination of the beta hydroxy group and hydrogen of the alpha hydroxy group.

3. The method of claim 1 , wherein step (b) comprises, prior to forming the 2-substituted furan derivative, forming a 2-substituted tetrahydrofuran derivative comprising the 2-substituent and dehydrating the 2-substituted tetrahydrofuran derivative to the 2-substituted furan derivative.

4. The method of claim 1 , wherein the 2-substituted furan derivative is a 2,5-disubstituted furan derivative, having both a 2-substituent and a 5-substitutent about the furan ring of the 2,5-disubstituted furan derivative.

5. The method of claim 4 , wherein the 2,5-disubstituted furan derivative has, as the 5-substituent, a substituent of a delta carbon atom of the starting compound that does not cyclize.

6. The method of claim 5 , wherein the 2,5-disubstituted furan derivative is a corresponding salt of 5-(hydroxymethyl)furan-2-carboxylic acid.

7. The method of claim 6 , further comprising oxidizing at least a portion of the salt of 5-(hydroxymethyl)furan-2-carboxylic acid to provide a corresponding salt of furan-2,5-dicarboxylic acid.

8. The method of claim 7 , wherein the oxidizing is carried out in a same reaction vessel as used for the dehydrating and cyclizing.

9. The method of claim 1 ,
wherein the dehydrating and cyclizing steps are carried out under an inert environment and at a temperature of at least about 30° C.

10. The method of claim 9 , wherein the dehydrating and cyclizing steps are carried out in the presence of a dehydration catalyst comprising a dehydration active metal.

11. The method of claim 10 , wherein the dehydration active metal is tungsten, molybdenum, or vanadium.

12. The method of claim 11 , wherein the tungsten, molybdenum, or vanadium is present in the form of its respective tungstate, molybdate, or vanadate salt.

13. The method of claim 10 , wherein the dehydration catalyst is present in the reaction mixture in an amount from about 0.1 mol-% to about 30 mol-%, based on the α-, β-dihydroxy carbonyl compound.

14. A method of synthesizing furan-2,5-dicarboxylic acid, the method comprising:
(a) dehydrating an α-, β-dihydroxy carboxylate starting material in the form of a salt of gluconic acid or glucaric acid to form a dicarbonyl intermediate from oxidation of the alpha hydroxy group of the starting material to a carbonyl group and removal of the beta hydroxy group of the starting material;
(b) cyclizing the dicarbonyl intermediate by forming a furan ring comprising, as ring members, alpha through delta carbon atoms of the dicarbonyl intermediate, corresponding to alpha through delta carbon atoms with respect to the carboxylate group of the starting compound, to form the corresponding salt of furan-2,5-dicarboxylic acid or the corresponding salt of a precursor of the furan-2,5-dicarboxylic acid;
(c) optionally oxidizing the corresponding salt of the precursor of the furan-2,5-dicarboxylic acid to form the salt of furan-2,5-dicarboxylic acid; and
(d) converting the salt of furan-2,5-dicarboxylic acid from step (b) and step (c) if performed to furan-2,5-dicarboxylic acid, by acidulation;

wherein the method is carried out non-enzymatically.

15. The method of claim 14 , wherein the precursor is 5-(hydroxymethyl)furan-2-carboxylic acid.

16. The method of claim 14 , wherein salts of both gluconic acid and glucaric acid are present as staring materials and are dehydrated and cyclized together.

17. The method of claim 16 , wherein the dehydrating and cyclizing steps are carried out in the presence of a dehydration catalyst comprising a dehydration active metal, and further comprising the step of filtering out the catalyst following the dehydrating and cyclizing steps.

Assignees

• Archer Daniels Midland Co

Inventors

• Brazdil James
• Rogness Donald

Classifications

• C07D307/68 Primary

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title