Process for the preparation of a benzene compound

Patent metadata

Field	Value
Publication number	US-10266546-B2
Application number	US-201515536708-A
Country	US
Kind code	B2
Filing date	Dec 18, 2015
Priority date	Dec 19, 2014
Publication date	Apr 23, 2019
Grant date	Apr 23, 2019

Abstract

A benzene compound is prepared by reacting a furan compound to produce an unsaturated bicyclic ether having an unsaturated carbon-carbon bond; hydrogenating the unsaturated carbon-carbon bond in the unsaturated bicyclic ether to produce a saturated bicyclic ether; and dehydrating and aromatizing the saturated bicyclic ether to produce the benzene compound.

First claim

The invention claimed is:

1. A process for the preparation of a benzene compound which comprises
(i) reacting a furan compound of formula (I):

wherein R 1 and R 2 are the same or different and independently selected from the group consisting of hydrogen, alkyl, aralkyl, —CHO, —CH 2 OR 3 , —CH(OR 4 )(OR 5 ), —COOR 6 , wherein R 3 , R 4 and R 5 are the same or different and are independently selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl, alkylcarbonyl and arylcarbonyl, or wherein R 4 and R 5 together form an alkylene group, and wherein R 6 is selected from the group consisting of hydrogen, alkyl and aryl,
with an olefin of the formula (II)
R 7 —CH═CH—R 8   (II),

wherein R 7 and R 8 are the same or different and are independently selected from the group consisting of hydrogen, sulfonate, —CN, —CHO, and —COOR 9 , wherein R 9 is selected from the group consisting of hydrogen, and an alkyl group, or R 7 and R 8 together form a —C(O)—O—(O)C— group or a —C(O)—NR 10 —C(O)— group, wherein R 10 represents hydrogen, an aliphatic or an aromatic group, to produce an unsaturated bicyclic ether having an unsaturated carbon-carbon bond;
(ii) hydrogenating the unsaturated carbon-carbon bond in the unsaturated bicyclic ether to produce a saturated bicyclic ether; and
(iii) dehydrating and aromatizing the saturated bicyclic ether to produce the benzene compound.

2. The process according to claim 1 , wherein R 1 and R 2 are the same or different and independently selected from the group consisting of hydrogen, alkyl, aralkyl, —CHO, —CH 2 OR 3 , wherein R 3 is selected from the group consisting of hydrogen and alkyl.

3. The process according to claim 2 , wherein R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms.

4. The process according to claim 1 , wherein R 7 and R 8 are the same or different and are independently selected from the group consisting of hydrogen, —CHO and —COOR 9 , wherein R 9 is selected from the group consisting of hydrogen, and an alkyl group having 1 to 4 carbon atoms, or R 7 and R 8 together form a —C(O)—O—(O)C— group.

5. The process according to claim 4 , wherein R 7 and R 8 together form a —C(O)—O—(O)C— group.

6. The process according to claim 1 , wherein the furan compound of formula (I) is reacted with the olefin of formula (II) at a temperature in the range of 0 to 150° C.

7. The process according to claim 1 , wherein the furan compound of formula (I) is reacted with the olefin of formula (II) in the presence of a Diels-Alder catalyst.

8. The process according to claim 7 , wherein the Diels-Alder catalyst is a Lewis acid.

9. The process according to claim 1 , wherein the molar ratio between the amount of furan derivative of formula (I) to the amount of olefin of formula (II) ranges from 0.1:1 to 10:1.

10. The process according to claim 1 , wherein the unsaturated carbon-carbon bond in the unsaturated bicyclic ether is hydrogenated using gaseous hydrogen in the presence of a hydrogenation catalyst.

11. The process according to claim 10 , wherein the hydrogenation catalyst comprises one or more metals or metal compounds selected from the metals in the Groups 8 to 10 of the Periodic Table of Elements on a carrier.

12. The process according to claim 11 , wherein the one or more metals is selected from Pt, Pd, Ru, Rh, Ni and mixtures thereof.

13. The process according to claim 11 , wherein the carrier is selected from been selected from alumina, silica, titania, zirconia, silica-alumina and carbon.

14. The process according to claim 1 , wherein the unsaturated carbon-carbon bond in the unsaturated bicyclic ether is hydrogenated in the presence of a solvent.

15. The process according to claim 14 , wherein the solvent is selected from the group consisting of hydrocarbons, alcohols, esters, ketones, amides, aldehydes, ethers, ionic liquids and sulphoxides.

16. The process according to claim 15 , wherein the solvent is selected from the group consisting of saturated hydrocarbons and cyclic ethers.

17. The process according to claim 1 , wherein the unsaturated bicyclic ether is hydrogenated at a temperature of 0 to 150° C.

18. The process according to claim 1 , wherein the unsaturated bicyclic ether is hydrogenated at a pressure of 1 to 125 bar.

19. The process according to claim 1 , wherein the saturated bicyclic ether is dehydrated and aromatized in the presence of a catalyst.

20. The process according to claim 19 , wherein the catalyst is an acidic catalyst.

21. The process according to claim 20 , wherein the acidic catalyst is a solid catalyst selected from zeolites, ion exchange resins, sulfonated activated carbon and combinations thereof.

22. The process according to claim 21 , wherein the acidic catalyst is a zeolite.

23. The process according to claim 22 , wherein the zeolite is selected from the group consisting of zeolite Y, zeolite X, zeolite beta, mordenite and mixtures thereof.

24. The process according to claim 22 , wherein the zeolite has a silica/alumina molar ratio in the range of 1 to 200.

25. The process according to claim 1 , wherein the saturated bicyclic ether is dehydrated and aromatized at a temperature of 100 to 350° C.

26. The process according to claim 1 , wherein the saturated bicyclic ether is dehydrated and aromatized in the presence of a solvent.

27. The process according to claim 26 , wherein the solvent is selected from the group consisting of hydrocarbons, alcohols, esters, ketones, amides, aldehydes, ethers, ionic liquids and sulphoxides.

28. The process according to claim 27 , wherein the solvent is toluene, xylene or a mixture thereof.

29. The process according to claim 1 , wherein the saturated bicyclic ether is dehydrated and aromatized at a pressure ranging from 0.5 to 50 bar.

30. The process according to claim 1 , wherein the saturated bicyclic ether is dehydrated and aromatized in a batch or continuous reactor wherein the residence time is from 0.1 to 48 hours.

31. The process according to claim 1 , wherein the benzene compound produced by the dehydration and aromatization of the saturated bicyclic ether, is oxidized.

32. The process according to claim 31 , wherein the oxidation is effected by an oxygen-containing gas in the presence of a catalyst comprising cobalt and manganese or by potassium permanganate or nitric acid.

33. The process according to claim 32 , wherein the catalyst comprises cobalt and manganese, and further comprises bromine.

34. The process according to claim 31 , wherein the oxidation 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.

Assignees

• Avantium Knowledge Centre Bv
• Stichting Wageningen Res

Inventors

• Van Der Waal Jan Cornelis
• De Jong Edserd
• Van Haveren Jacco
• Thiyagarajan Shanmugam

Classifications

• C07D493/04

  Ortho-condensed systems · CPC title

• C07D307/89

  with two oxygen atoms directly attached in positions 1 and 3 · CPC title

• C07D493/18 Primary

  Bridged systems · CPC title

• C07D307/88

  with one oxygen atom directly attached in position 1 or 3 · CPC title

• C07C51/31

  of cyclic compounds with ring-splitting · CPC title