Functionalized bifuran and synthesis thereof

Patent metadata

Field	Value
Publication number	US-11926605-B2
Application number	US-201916978496-A
Country	US
Kind code	B2
Filing date	Feb 11, 2019
Priority date	Mar 21, 2018
Publication date	Mar 12, 2024
Grant date	Mar 12, 2024

Abstract

A 5,5′-Di-(protected)-2,2′-bifuran:

wherein each R 1 is independently an unsubstituted or substituted 5- or 6-member 1,3-dioxo-2-yl ring radical. Processes for making the bifuran include coupling 2-(protected)-furfural. Processes for using the bifuran include deprotection, functionalization, and/or polymerization to form a polyester. The polyester can be a renewable, high-performing polyester offering a combination of low cost of production, high sustainability, and excellent performance.

First claim

The invention claimed is:

1. A furan coupling process comprising coupling a protected 2-furaldehyde to form a 5,5′-di-(protected)-2,2′-bifuran.

2. The process of claim 1 , wherein the coupling comprises oxidative addition, metalation, and reductive elimination, optionally in the presence of an oxidant and/or a catalyst.

3. The process of claim 1 , wherein the coupling comprises palladation.

4. The process of claim 1 , further comprising protecting 2-furaldehyde to form the protected 2-furaldehyde.

5. The process of claim 4 , wherein the 2-furaldehyde is protected by reacting with an alkylene diol to form a 2-furfural alkylene diol acetal.

6. The process of claim 5 , wherein the alkylene diol comprises from 2 to 12 carbon atoms.

7. The process of claim 4 , wherein the protection is in the presence of a catalyst.

8. The process of claim 1 , further comprising deprotecting the 5,5′-di(protected)-2,2′-bifuran to form (2,2′-bifuran)-5,5′-dicarbaldehyde.

9. The process of claim 8 , wherein the 5,5′-di(protected)-2,2′-bifuran comprises 5,5′-di(alkylene diol acetal)-2,2′-bifuran.

10. The process of claim 8 , wherein the deprotecting comprises contacting the 5,5′-di(protected)-2,2′-bifuran with catalyst.

11. The process of claim 1 , further polymerizing a 5,5′-di(protected)-2,2′-bifuran in one or more steps, optionally including formation of one or more intermediate 5,5′-di-(substituted)-2,2′-bifurans, to form a polyester comprising (2,2′-bifuran)-5,5′-dicarboxylate structural units.

12. The process of claim 1 , further comprising polymerizing the 5,5′-di(protected)-2,2′-bifuran in one or more steps, optionally including formation of one or more intermediate 5,5′-di-(substituted)-2,2′-bifurans, to form a polyester comprising (2,2′-bifuran)-5,5′-dicarboxylate structural units.

13. The process of claim 11 , further comprising:
reacting the 5,5′-di(protected)-2,2′-bifuran and forming at least one intermediate;
optionally recovering the intermediate(s); and
polymerizing an ultimate one of the intermediate(s).

14. The process of claim 13 , wherein the ultimate intermediate has the following Formula (F-III):

wherein each R 3 is independently hydrogen, hydroxyalkyl, carboxyalkyl, halide, OR′, or a combination thereof, or
wherein the ultimate intermediate is an anhydride thereof, where R′ (if present) is hydrogen, hydrocarbyl, hydroxyalkyl, carboxyalkyl, or a combination thereof.

15. The process of claim 13 , further comprising protecting 2-furaldehyde with an alkylene diol to form a 2-furfural alkylene diol acetal; wherein forming the at least one intermediate comprises producing alkylene diol; and optionally recycling the alkylene diol from the at least one intermediate formation step to the 2-furaldehyde protection step.

16. The process of claim 13 , wherein a first one of the intermediates comprises (2,2′-bifuran)-5,5′-dicarbaldehyde.

17. The process of claim 16 , further comprising converting the (2,2′-bifuran)-5,5′-dicarbaldehyde to (2,2′-bifuran)-5,5′-dicarboxylic acid or dialkyl (2,2′-bifuran)-5,5′-dicarboxylate, or a combination thereof.

18. The process of claim 17 , wherein the conversion comprises heating the (2,2′-bifuran)-5,5′-dicarbaldehyde in the presence of an oxidant.

19. The process of claim 17 , wherein the conversion comprises contacting the (2,2′-bifuran)-5,5′-dicarbaldehyde in the presence of an oxidant.

20. The process of claim 13 , comprising wherein the ultimate intermediate 5,5′-di-(substituted)-2,2′-bifuran has the Formula (F-IV):

wherein each R 4 is hydrogen, hydrocarbyl, hydroxyalkyl, carboxyalkyl, or a combination thereof, or wherein the ultimate intermediate is an anhydride thereof.

21. The process of claim 20 , wherein the 5,5′-di(protected)-2,2′-bifuran comprises 5,5′-di-(alkylene diol acetal)-2,2′-bifuran, and formation of the intermediate comprises contacting the 5,5′-di-(alkylene diol acetal)-2,2′-bifuran with vanadium (V) oxide and peroxide.

22. The process of claim 13 , wherein the 5,5′ substituents of the ultimate intermediate 2,2′-bifuran comprise carboxylic acid groups or ester producing equivalents thereof; and
wherein the polymerization comprises contacting the ultimate intermediate with the functionalized compound and forming the polyester, wherein the functionalized compound comprises two or more hydroxyl groups.

23. The process of claim 11 , wherein the 5,5′-di(protected)-2,2′-bifuran comprises 5,5′-di-(alkylene diol acetal)-2,2′-bifuran, and formation of the intermediate comprises contacting the 5,5′-di-(alkylene diol acetal)-2,2′-bifuran with palladium on carbon catalyst in the presence of an oxidant.

24. The process of claim 23 , wherein the functionalized compound comprises two or more carboxylic acid groups or ester producing equivalents thereof; the process further comprising contacting the bis(2-hydroxyalkyl) (2,2′-bifuran)-5,5′-dicarboxylate, with the functionalized compound.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kandel Kapil
• Cohn Stephen T
• Salciccioli Michael
• Atienza Crisita Carmen H
• Galuska Alan A

Classifications

• C07D307/36 Primary

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms · CPC title

• C07D307/54

  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 · CPC title

• C08G63/185 Primary

  containing two or more aromatic rings · CPC title

• C07D407/14

  containing three or more hetero rings · CPC title

• Y02E50/10

  Biofuels, e.g. bio-diesel · CPC title