Method for preparing phenolics using a catalyst

Patent metadata

Field	Value
Publication number	US-10364203-B2
Application number	US-201616064871-A
Country	US
Kind code	B2
Filing date	Dec 22, 2016
Priority date	Dec 22, 2015
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

The invention is directed to a method for preparing a phenolic compound comprising reacting a furanic compound with a dienophile in the presence of a catalyst comprising yttrium.

First claim

The invention claimed is:

1. Method for preparing a phenolic compound comprising reacting a furanic compound with a dienophile in the presence of a catalyst comprising yttrium.

2. Method according to claim 1 , wherein the catalyst further comprises a ligand.

3. Method according to claim 1 , wherein the catalyst comprises yttrium(III) triflate.

4. Method according to claim 1 , wherein the catalyst is applied on a solid support.

5. Method according to claim 1 wherein the furanic compound is a compound according to formula I

wherein R 1 and R 2 are independently selected from the group consisting of H, linear or branched C 1 -C 8 alkyl, F, Cl, Br, I, —CH 2 F, —CH 2 Cl, —CH 2 Br, —CH 2 I, —CN, —NO 2 , —CHO, —CO 2 H or esters thereof, —CH 2 NH 2 or secondary amines, tertiary amines, quaternary amines or amides thereof, and —CH 2 OH or esters or ethers thereof; and wherein the furanic compound is optionally bound to a solid support.

6. Method according to claim 1 wherein the dienophile is acetylene, optionally substituted with one or more linear or branched C 1 -C 8 alkyl groups, or wherein the dienophile is a compound according to formula (II)

wherein EWG is an electron withdrawing group and R 3 ═H, linear or branched C 1 -C 8 alkyl.

7. Method according to claim 1 , wherein the phenolic compound is one or more phenolic compound selected from the group consisting of compounds according to the following formulae IIIa-IIIh:

8. Method according to claim 1 , wherein reacting the furanic compound with the dienophile is carried out in an apolar, aprotic and/or non-coordinating solvent.

9. Method according to claim 1 , wherein reacting the furanic compound with the dienophile is carried out at a temperature ranging from −60-350° C.

10. Method according to claim 1 , wherein the phenolic compound is reacted further in one or more reaction steps selected from the group consisting of hydrolysis, oxidation, reduction, nucleophilic addition, olefination, rearrangement, decarboxylation, and decarbonylation to obtain a final phenolic product.

11. Method according to claim 10 , wherein the final phenolic product is selected from the group consisting of phenol, o-alkylphenol, m-alkylphenol, p-alkylphenol, cresols, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2,6-dialkylphenol, 2,5-dialkylphenol, 2,4-dialkylphenol, 2,3-dialkylphenol, 3,4-dialkylphenol, 3,5-dialkylphenol, xylenols, 2,3,4-trialkylphenol, 2,3,5-trialkylphenol, 2,3,6-trialkylphenol, 2,4,5-trialkylphenol, 2,4,6-trialkylphenol, 3,4,5-trialkylphenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, o-cyanophenol, m-cyanophenol, p-cyanophenol, catechol, resorcinol, hydroquione, o-halophenol, m-halophenol, p-halophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxybenzyl alcohol, m-hydroxybenzyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl amine, m-hydroxybenzyl amine, p-hydroxybenzyl amine, o-hydroxyacetophenone, m-hydroxyacetophenone, p-hydroxyacetophenone, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzamide, m-hydroxybenzamide, p-hydroxybenzamide and combinations thereof.

12. Method according to claim 2 , wherein the ligand is a sulfonate ligand.

13. Method according to claim 12 , wherein the sulfonate ligand comprises an alkyl group, an aryl group, or an electron-withdrawing group.

14. Method according to claim 13 , wherein the electron-withdrawing group is a halogenated group comprising at least one halogen atom, a perhalogenated group, a perfluoroalkyl, or a trifluoromethyl group.

15. Method according to claim 4 , wherein the solid support comprises a polymeric support, silica, alumina, silica-alumina, or a zeolite.

16. Method according to claim 6 , wherein EWG is I, —CN, —NO 2 , —CO 2 X, —C(O)NX, —C(═NY)X, CF 3 , CCl 3 , CBr 3 , CI 3 , —SO 2 X, —SO 3 X, —COH, —COX, —COF, —COCl, —COBr, or —COI, wherein X and Y are independently H, or linear or branched C 1 -C 8 alkyl, optionally substituted with halogens and optionally polymer-supported.

17. Method according to claim 8 , wherein the solvent is a C 4 -C 12 hydrocarbon, ether, esters, toluene, heptane, or mesitylene.

18. Method according to claim 9 , wherein the temperature ranges from 20-180° C.

Assignees

• TNO

Inventors

• Crockatt Marc
• Könst Paul Mathijs
• Urbanus Jan Harm
• Snelders Dennis Johannes Maria

Classifications

• C07C67/347 Primary

  by addition to unsaturated carbon-to-carbon bonds · CPC title

• C07C39/06

  Alkylated phenols · CPC title

• C07C37/14 Primary

  by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond · CPC title

• B01J2540/225

  comprising perfluoroalkyl groups or moieties · CPC title

• B01J2531/36

  Yttrium · CPC title