Aromatic compounds from furanics

Patent metadata

Field	Value
Publication number	US-10562875-B2
Application number	US-201716079751-A
Country	US
Kind code	B2
Filing date	Feb 27, 2017
Priority date	Feb 26, 2016
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

Described are methods for preparing phenols, benzene carboxylic acids, esters and anhydrides thereof from furanic compounds by reaction with a dienophile, wherein the furanic compounds are reacted with a hydrazine and/or oxime and then reacted with a dienophile.

First claim

The invention claimed is:

1. A method of preparing an optionally substituted compound comprising formula (I):

wherein:
G is OH CHO, or CO 2 H, an ether thereof, an ester thereof, or an anhydride thereof, the method comprising:

(i) reacting a biomass-derived compound comprising formula (II) with a compound comprising formula (III):

wherein:
the compound of formula (II) is optionally substituted at one or more of the 3, 4, or 5 position with a C 1 -C 20 hydrocarbyl or with F, Cl, Br, I, CH 2 F, CH 2 Cl, CH 2 Br, CH 2 I, CN, NO 2 , CHO, CO 2 H or ester thereof, CH 2 NH 2 or secondary, tertiary, or quaternary amine or amide thereof, or CH 2 OH or ester or ether thereof; wherein said C 1 -C 20 hydrocarbyl is optionally substituted is one or more of F, Cl, Br, I, CH 2 F, CH 2 Cl, CH 2 Br, CH 2 I, CN, NO, CHO, CO 2 H or ester thereof, CH 2 NH 2 or secondary, tertiary, or quaternary amine or amide thereof, or CH 2 OH or ester or ether thereof;
X is O and z is 0, or
X is N and z is 1,
R 1 is a C 1 -C 20 hydrocarbyl, optionally substituted with one or more phenyl, F, Cl, Br, I, CH 2 F, CH 2 Cl, CH 2 Br, CH 2 I, CN, NO 2 , CHO, CO 2 H or ester thereof, CH 2 NH 2 or secondary, tertiary, or quaternary amine or amide thereof, or CH 2 OH or ester or ether thereof, and
R 2 is hydrogen or a C 1 -C 20 hydrocarbyl, optionally substituted with one or more phenyl, F, Cl, Br, I, CH 2 F, CH 2 Cl, CH 2 Br, CH 2 I, CN, NO 2 , CHO, CO 2 H or ester thereof, CH 2 NH 2 or secondary, tertiary, quaternary amine or amide thereof, or CH 2 OH or ester or ether thereof,

to give an optionally substituted compound comprising formula (IV):

(ii) reacting the optionally substituted compound comprising formula (IV) with a C 2 -C 12 alkene or C 2 -C 12 alkyne in the presence of a Lewis and/or Brønsted acid catalyst to give an optionally substituted compound comprising formula (V):

(iii) hydrolyzing said optionally substituted compound comprising formula (V) to yield the optionally substituted compound comprising formula (I), wherein G is CHO, and
(iv-a) optionally decarbonylating the product of step (iii) to provide the optionally substituted compound comprising formula (I), wherein G is OH, or
(iv-b) optionally oxidizing the product of step (iii) to yield the optionally substituted compound comprising formula (I), wherein G is CO 2 H, and
(v) optionally converting the optionally substituted compound comprising formula (I), wherein G is OH, CHO, or CO 2 H to the ether, ester, or anhydride thereof.

2. The method according to claim 1 , wherein said optionally substituted compound comprising formula (II) is furfural, furan-2,5-dicarbaldehyde, methoxymethylfurfural, chloromethylfurfural, 5-hydroxymethylfurfural, or a mixture thereof.

3. The method according to claim 1 , wherein the optionally substituted compound comprising formula (I) is a phenol, a hydroxyl benzene tricarboxylic acid, a hydroxyl benzene dicarboxylic acid, a hydroxyl benzene carboxylic acid, a benzene dicarboxylic acid, a benzene tricarboxylic acid, or a benzene tetracarboxylic acid, or an ester, ether or anhydride thereof.

4. The method according to claim 1 , wherein step (ii) is performed using ethylene.

5. The method according to claim 4 , wherein the optionally substituted compound comprising formula (II) is 5-hydroxymethylfurfural, 5-methoxymethylfurfural, 5-chloromethylfurfural or 2,5-furandicarboxaldehyde, and the optionally substituted compound comprising formula (I) is terephthalic acid.

6. The method according to claim 5 , wherein step (ii) further comprises a catalyst that is a Brønsted acid and/or a Lewis acid supported on a solid material.

7. The method according to claim 5 , wherein the optionally substituted compound comprising formula (II) is furfural and the optionally substituted compound comprising formula (I) is phenol or an ester thereof.

8. The method according to claim 1 , wherein step (ii) performed using C 2 -C 12 alkyne.

9. The method according to claim 8 , wherein the optionally substituted compound comprising formula (III) is a hydroxylamine, wherein X is O.

10. The method according to claim 9 , wherein step (ii) is performed using a propiolate and the optionally substituted compound comprising formula (II) is 2,5-furandicarboxaldehyde, furfural, 5-hydroxymethylfurfural, 5-methoxymethylfurfural, 5-chloromethylfurfural, or a combination thereof.

11. The method according to claim 1 , wherein step (ii) is performed using acrylic acid or an acrylate ester.

12. The method according to claim 1 , further comprising hydrolyzing and oxidizing the optionally substituted compound comprising formula (V) to an optionally substituted ester comprising formula (Ia):

wherein, R 7 is a heteroatom-containing C 1 -C 20 hydrocarbyl group that is optionally substituted with one or more phenyl, F, Cl, Br, I, CH 2 F, CH 2 Cl, CH 2 Br, CH 2 I, CN, NO, CHO, CO 2 H or ester thereof, CH 2 NH 2 or secondary, tertiary, quaternary amine or amide thereof, or CH 2 OH or ester or ether thereof.

13. The method according to claim 1 , wherein the optionally substituted compound comprising formula (III) is provided on a heterogeneous solid support, and the method further comprises recovering the optionally substituted compound comprising formula (III) by separating solid material comprising the optionally substituted compound comprising formula (III) from a liquid phase comprising an optionally substituted aromatic compound comprising formula (I).

14. The method according to claim 1 , wherein the optionally substituted compound comprising formula (II) is an effluent from a reactor for the (catalytic) dehydration of carbohydrates, wherein the effluent comprises water or an organic solvent.

15. The method according to claim 1 , wherein step (ii) is performed using maleic anhydride and the optionally substituted compound comprising formula (V) is converted into the optionally substituted compound comprising formula (I) in a single step comprising hydrolysis step (iii) and oxidation step (iv-b).

16. A method of preparing an aromatic compound, comprising:
activating a furanic compound in an effluent from a catalytic dehydration of carbohydrates using a solid-supported hydrazine compound, solid-supported hydroxylamine compound, or a combination thereof, wherein the activating is performed in the absence of reducing the furanic compound, and
reacting the activated furanic compound with a C 2 -C 12 alkene or C 2 -C 12 alkyne in the presence of a Lewis and/or Brønsted acid catalyst.

17. The method according to claim 1 , wherein step (ii) is performed using ethylene, and the compound comprising formula (I) is phenol, benzoic acid, a benzoic acid ester, or a benzoic acid ether.

18. The method according to claim 6 , wherein the solid support is a heterogeneous support.

19. The method according to claim 1 , wherein R 1 , R 2 , or both R 1 and R 2 are substituted with phenyl, F, CI, Br, I, CH 2 F, CH 2 CI, CH 2 Br, CH 2

Assignees

• TNO
• Nederlandse Organisaite Voor Toegepast Natuurwetenschappelijk Onderzoek Tno

Inventors

• Crockatt Marc
• Urbanus Jan Harm

Classifications

• C07C45/516

  involving transformation of nitrogen-containing compounds to >C = O groups · CPC title

• C07C51/27

  with oxides of nitrogen or nitrogen-containing mineral acids · CPC title

• C07C251/86

  having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C249/16

  of hydrazones · CPC title

• C07C47/54

  Benzaldehyde · CPC title