Process for the preparation of benzene derivatives from furan derivatives

Patent metadata

Field	Value
Publication number	US-9637437-B2
Application number	US-201314435470-A
Country	US
Kind code	B2
Filing date	Oct 22, 2013
Priority date	Oct 22, 2012
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

Benzene derivatives of the formula (I);

wherein R 1 and R 2 , are the same or different and independently are selected from the group consisting of hydrogen, alkyl, aralkyl, —CHO, —CH 2 OR 3 , —CH(OR 4 )(OR 5 ) and —COOR 6 , wherein R 3 , R 4 and R 5 are the same or different and are selected from hydrogen, alkyl, aryl, alkaryl, aralkyl, alkylcarbonyl or arylcarbonyl, or wherein R 4 and R 5 together form an alkylene group and wherein R 6 is selected from hydrogen, alkyl and aryl, are prepared in a process, which comprises:

reacting a furan derivative of formula (II):

wherein R 1 and R 2 have the meanings above, with ethylene under cycloaddition reaction conditions in the presence of an acid solvent to produce the benzene derivative, wherein the acid solvent is a carboxylic acid and is present in a weight ratio acid solvent to furan derivative from 1:1 to 250:1.

First claim

The invention claimed is:

1. A process for the preparation of benzene derivatives of the formula (I);

wherein R 1 and R 2 , are the same or different and independently are selected from the group consisting of hydrogen, alkyl, aralkyl, —CHO, —CH 2 OR 3 , —CH(OR 4 )(OR 5 ) and —COOR 6 , wherein R 3 , R 4 and R 5 are the same or different and are selected from hydrogen, alkyl, aryl, alkaryl, aralkyl, alkylcarbonyl or arylcarbonyl, or wherein R 4 and R 5 together form an alkylene group and wherein R 6 is selected from hydrogen, alkyl and aryl,
which process comprises:
reacting a furan derivative of formula (II):

wherein R 1 and R 2 have the meanings above,
with ethylene under cycloaddition reaction conditions to produce the benzene derivative, wherein the reaction of the furan derivative and ethylene is carried out in the presence of an acid solvent, and the acid solvent is a carboxylic acid and is present in a weight ratio acid solvent to furan derivative from 1:1 to 250:1.

2. The process according to claim 1 , wherein R 1 and R 2 independently comprise 1 to 8 carbon atoms, optionally in addition to one or more oxygen atoms.

3. The process according to claim 1 , wherein at least one of R 1 and R 2 is alkyl, and wherein the alkyl comprises from 1 to 6 carbon atoms.

4. The process according to claim 1 , wherein at least one of R 1 and R 2 is a —COOR 6 group.

5. The process according to claim 1 , wherein R 3 , R 4 , R 5 and R 6 independently comprise from 1 to 7 carbon atoms.

6. The process according to claim 1 , wherein a desiccating agent is present.

7. The process according to claim 6 , wherein the amount of desiccating agent is in the range of from 50 to 1000% wt, based on the amount of furan derivative.

8. The process according to claim 6 , wherein the desiccating agent is an organic desiccating agent.

9. The process according to claim 8 , wherein the organic desiccating agent is a carboxylic acid anhydride.

10. The process according to claim 9 , wherein the number of carbon atoms in the carboxylic acid anhydride ranges from 2 to 18 carbon atoms.

11. The process according to claim 9 , wherein the carboxylic acid anhydride is acetic anhydride, benzoic anhydride or a mixture thereof.

12. The process according to claim 1 , wherein further an additional dehydration catalyst is present.

13. The process according to claim 12 , wherein the additional dehydration catalyst is a Diels Alder catalyst.

14. The process according to claim 12 , wherein the additional dehydration catalyst has been selected from Lewis acids, Brønsted acids, activated carbon, silica, alumina, silica-alumina, zirconia, zeolites and mixtures thereof.

15. The process according to claim 12 , wherein the additional dehydration catalyst comprises carbon, silica, alumina, silica-alumina, zirconia and/or zeolites as support for a catalytically active metal or metal compound.

16. The process according to claim 14 , wherein the additional dehydration catalyst is an organic or inorganic Brønsted acid.

17. The process according to claim 6 , wherein the desiccating agent is a carboxylic acid anhydride and the acid solvent is the carboxylic acid derived from this carboxylic acid anhydride.

18. The process according to claim 12 , wherein the amount of additional dehydration catalyst is at least 0.5% wt.

19. The process according to claim 1 , wherein the acid solvent comprises a carboxylic acid that contains 1 to 16 carbon atoms.

20. The process according to claim 19 , wherein the acid solvent comprises a carboxylic acid that is used as dehydrating agent.

21. The process according to claim 1 , wherein an additional solvent is included in the mixture of furan derivative, ethylene, acid solvent and optionally desiccating agent.

22. The process according to claim 21 , wherein the solvent is selected from the group consisting of water, alcohols, esters, ketones, amides, aldehydes, acids, ethers, aliphatic or aromatic hydrocarbons, ionic liquids and sulphoxides.

23. The process according to claim 1 , wherein the furan derivative of formula (II) is reacted with ethylene at a temperature in the range from 100 to 450° C.

24. The process according to claim 1 , wherein the furan derivative of formula (II) is reacted with ethylene at an ethylene partial pressure of 10 bar to 1000 bar.

25. The process according to claim 1 , wherein the furan derivative of formula (II) is reacted with ethylene for 0.5 to 72 hours.

26. The process according to claim 1 , wherein R 1 and R 2 are the same or different and independently are selected from the group consisting of alkyl, —CHO, —CH 2 OR 3 and —CH(OR 4 )(OR 5 ), wherein R 3 , R 4 and R 5 are the same or different and are selected from hydrogen, alkyl, aryl, alkylcarbonyl or arylcarbonyl, or wherein R 4 and R 5 together form an alkylene group, which process further comprises the steps of:
recovering a para-substituted benzene derivative product of the reaction between the furan derivative of formula (II) and ethylene; and
oxidizing the thus obtained para-substituted benzene derivative product to yield terephthalic acid.

27. The process according to claim 26 , wherein the oxidizing of the para-substituted benzene derivative product is effected by an oxygen-containing gas in the presence of a catalyst comprising cobalt and manganese.

28. The process according to claim 27 , wherein the catalyst further comprises bromine.

29. The process according to claim 26 , wherein the oxidizing is carried out at a temperature of from 60 to 220° C., at a pressure of from 5 to 100 bar and at a residence time of from 0.1 to 48 hours.

30. The process according to claim 3 , wherein the alkyl is methyl or ethyl.

31. The process according to claim 5 , wherein R 3 , R 4 , R 5 and R 6 independently comprise from 1 to 4 carbon atoms.

32. The process according to claim 10 , wherein the number of carbon atoms in the carboxylic acid anhydride ranges from 2 to 8 carbon atoms.

33. The process according to claim 15 , wherein the catalytically active metal or metal compound includes alkali metals, alkaline earth metals, transition metals, noble metals, rare earth metals or mixtures thereof.

34. The process according to claim 19 , wherein the acid solvent comprises a carboxylic acid that contains from 1 to 8 carbon atoms.

Assignees

• Furanix Technologies Bv
• Coca Cola Co

Inventors

• Wang Bing
• Gruter Gerardus Johannes Maria
• Dam Matheus Adrianus
• Kriegel Robert Michael

Classifications

• C07C2521/08

  Silica · CPC title

• C07C2521/18

  Carbon · CPC title

• C07C51/265

  having alkyl side chains which are oxidised to carboxyl groups · CPC title

• C07C51/50

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

• C07C2523/745

  Iron · CPC title