阅读说明：本技术 官能化的双环呋喃及其合成 (Functionalized bicyclic furans and synthesis thereof ) 是由 K·坎德尔 S·T·科恩 M·塞尔希克欧利 C·C·H·阿蒂恩扎 A·A·盖尔乌斯卡 于 2019-02-11 设计创作，主要内容包括：一种5,5’-二-(保护的)-2,2’-双环呋喃：其中每个R<Sup>1</Sup>独立地是未取代的或者取代的5-或者6-元1,3-二氧代-2-基环基团。制造所述双环呋喃的方法包括偶联2-(保护的)-糠醛。使用所述双环呋喃的方法包括脱保护、官能化和/或聚合来形成聚酯。该聚酯可以是可再生的高性能聚酯,其提供了低生产成本、高持续性和优异性能的组合。(A5, 5 '-bis- (protected) -2, 2' -bicyclic furan: wherein each R 1 Independently an unsubstituted or substituted 5-or 6-membered 1, 3-dioxo-2-yl ring group. A method of making the bicyclic furans includes coupling 2- (protected) -furfural. Methods of using the bicyclic furans include deprotection, functionalization, and/or polymerization to form polyesters. The polyester may be a renewable high performance polyester that provides a combination of low production cost, high sustainability, and excellent performance.)

1. A composition of matter comprising a 5, 5 '-di- (protected) -2, 2' -bicyclic furan having formula (F-I):

wherein each R¹Independently a 5-or 6-membered 1, 3-dioxo-2-yl ring group, which may be optionally substituted with one or more substituents.

2. A furan coupling process comprising coupling protected 2-furfural to form 5, 5 '-di- (protected) -2, 2' -bicyclic furan.

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

4. The method of claim 2 or claim 3, wherein the coupling comprises palladation.

5. The method of any one of claims 2-4, further comprising protecting the 2-furfural to form a protected 2-furfural.

6. The method of claim 5, wherein the 2-furfural is protected by reaction with an alkylene glycol to form a 2-furfural alkylene glycol acetal.

7. The method of claim 6, wherein the alkylene glycol contains 2 to 12 carbon atoms.

8. The process of any one of claims 5-7, wherein the protecting is carried out in the presence of a catalyst.

9. The method of any one of claims 2-8, further comprising deprotecting the 5, 5 '-bis (protected) -2, 2' -bicyclic furan to form (2, 2 '-bicyclic furan) -5, 5' -dicarbaldehyde.

10. The method of claim 9, wherein the 5, 5 '-bis (protected) -2, 2' -bicyclic furan comprises 5, 5 '-bis (alkylene glycol acetal) -2, 2' -bicyclic furan.

11. The method of claim 9 or claim 10, wherein the deprotecting comprises contacting 5, 5 '-bis (protected) -2, 2' -bicyclic furan with a catalyst.

12. A process comprising polymerizing 5, 5 '-bis (protected) -2, 2' -bicyclofuran in one or more steps, optionally comprising forming one or more intermediates 5, 5 '-bis- (substituted) -2, 2' -bicyclofuran, to form a polyester comprising (2, 2 '-bicyclofuran) -5, 5' -dicarboxylate building blocks.

13. The method of any one of claims 2-11, further comprising polymerizing 5, 5 '-bis (protected) -2, 2' -bicyclic furan in one or more steps, optionally including forming one or more intermediate 5, 5 '-bis- (substituted) -2, 2' -bicyclic furans, to form a polyester comprising (2, 2 '-bicyclic furan) -5, 5' -dicarboxylate structural units.

14. The method of claim 12 or claim 13, further comprising:

reacting and forming at least one intermediate of said 5, 5 '-bis (protected) -2, 2' -bicyclic furan;

optionally recovering one or more intermediates; and

polymerizing the last of the one or more intermediates.

15. The process of claim 14, including wherein the final intermediate has the following formula (F-III):

wherein each R³Independently hydrogen, hydroxyalkyl, carboxyalkyl, halo, OR 'OR combinations thereof, OR wherein the final intermediate is an anhydride thereof, wherein R' (if present) is hydrogen, hydrocarbyl, hydroxyalkyl, carboxyalkyl, OR combinations thereof.

16. The method of claim 14 or claim 15, further comprising protecting 2-furfural with an alkylene glycol to form 2-furfural alkylene glycol acetal; wherein forming at least one intermediate comprises producing an alkylene glycol; and optionally recycling alkylene glycol from the at least one intermediate formation step to the 2-furfural protection step.

17. The process of any one of claims 14-16, wherein a first of the intermediates comprises (2, 2 '-bicyclic furan) -5, 5' -dicarbaldehyde.

18. The method of claim 17, further comprising converting the (2, 2 '-bicyclofuran) -5, 5' -dicarboxaldehyde to (2, 2 '-bicyclofuran) -5, 5' -dicarboxylic acid or a dialkyl (2, 2 '-bicyclofuran) -5, 5' -dicarboxylate or a combination thereof.

19. The method of claim 18, wherein the converting comprises heating (2, 2 '-bicyclic furan) -5, 5' -dicarbaldehyde in the presence of an oxidizing agent.

20. The method of claim 18, wherein the converting comprises contacting (2, 2 '-bicyclic furan) -5, 5' -dicarbaldehyde in the presence of an oxidizing agent.

21. The process of any one of claims 14-20, wherein the final intermediate 5, 5 '-bis- (substituted) -2, 2' -bicyclic furan has formula (F-IV):

wherein each R⁴Is hydrogen, hydrocarbyl, hydroxyalkyl, carboxyalkyl or a combination thereof, or wherein the final intermediate is an anhydride thereof.

22. The method of claim 21, wherein the 5, 5 '-bis (protected) -2, 2' -bicyclic furan comprises 5, 5 '-bis- (alkylene glycol acetal) -2, 2' -bicyclic furan, and forming the intermediate comprises contacting the 5, 5 '-bis- (alkylene glycol acetal) -2, 2' -bicyclic furan with vanadium (V) oxide and a peroxide.

23. The process of any one of claims 14-22, wherein the 5, 5 'substituent of the final intermediate 2, 2' -bicyclic furan comprises a carboxylic acid group or an ester yielding the equivalent thereof; and

wherein the polymerization comprises contacting the final intermediate with a functionalized compound and forming a polyester, wherein the functionalized compound comprises two or more hydroxyl groups.

24. The method of any one of claims 12-16, wherein the 5, 5 '-bis (protected) -2, 2' -bicyclic furan comprises 5, 5 '-bis- (alkylene glycol acetal) -2, 2' -bicyclic furan, and forming the intermediate comprises contacting the 5, 5 '-bis- (alkylene glycol acetal) -2, 2' -bicyclic furan with a palladium on carbon catalyst in the presence of an oxidizing agent.

25. The method of claim 24, wherein the functionalized compound comprises two or more carboxylic acid groups or an ester yielding an equivalent thereof; the method further comprises contacting a bis (2-hydroxyalkyl) (2, 2 '-bicyclofuran) -5, 5' -dicarboxylate with the functionalized compound.

Examples