Method to prepare phenolics from biomass

Patent metadata

Field	Value
Publication number	US-10407376-B2
Application number	US-201615544172-A
Country	US
Kind code	B2
Filing date	Jan 18, 2016
Priority date	Jan 16, 2015
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The present invention is directed to a method for preparing a final phenolic product from biomass comprising the steps of providing a furanic compound obtainable from biomass; reacting the furanic compound with a dienophile to obtain a phenolic compound; reacting the phenolic compound further to obtain the final phenolic product.

First claim

The invention claimed is:

1. A method for preparing a final phenolic product from biomass comprising the steps of:
a) providing a furanic compound obtainable from C4-, C5-, or C6-sugar units from biomass;
b) reacting the furanic compound with a dienophile to obtain a phenolic compound; and
c) reacting the phenolic compound further in a hydrolysis reaction followed by an oxidation reaction, or in a hydrolysis reaction followed by a decarboxylation reaction, or in a hydrolysis reaction followed by a rearrangement reaction, or in a reduction reaction, or in a nucleophilic substitution to obtain the final phenolic product.

2. Method according to claim 1 , wherein the phenolic compound is obtained by ring-opening of a bicyclic adduct that is obtained by reacting the furanic compound with the dienophile.

3. 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 , —COH, —CO 2 H and esters thereof, —CH 2 NH 2 and secondary, tertiary and quaternary amines or amides thereof and —CH 2 OH and esters or ethers thereof, optionally bound to a solid support.

4. Method according to claim 1 , wherein the dienophile is a compound according to formula (II)

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

5. Method according to claim 1 , wherein the step of reacting the furanic compound with the dienophile is catalyzed by a catalyst which is a protic or Lewis acid, optionally supported on a polymer or a heterogeneous support such as silica.

6. Method according to claim 1 , wherein the furanic compound is reacted with the dienophile at a temperature of −60-350° C.

7. Method according to claim 1 , wherein the furanic compound is reacted with the dienophile at a pressure of 0-200 bar.

8. Method according to claim 1 , wherein reacting the phenolic compound is performed in one or more suitable solvents.

9. Method according to claim 2 , wherein the bicyclic adduct, before ring-opening, is reacted in one or more reaction steps selected from the group consisting of hydrolysis, oxidation, reduction, nucleophilic addition, olefination, nitrosation, elimination, condensation, electrophilic substitution, rearrangement, decarboxylation, decarbonylation and combinations thereof.

10. Method according to claim 1 , wherein the final phenolic product is one or more phenolic selected from the group consisting of compounds according to the following formulae:

wherein
R 2 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —SO 2 X, —SO 3 X, —NX 2 , —COX, —COF, —COCl, —COBr, or —COI; and/or
R 3 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —SO 2 X, —SO 3 X, —NX 2 , —COX, —COF, —COCl, —COBr, or —COI; and
R 4 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —SO 2 X, —SO 3 X, —NX 2 , —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.

11. Method according to claim 1 , wherein the final phenolic product is one or more phenolic selected from the group consisting of compounds according to the following formulae:

wherein
R 1 =linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —SO 2 X, —SO 3 X, —NX 2 , —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; and
R 2 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —SO 2 X, —SO 3 X, —NX 2 , —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; and
R 3 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —Cl 3 , —SO 2 X, —SO 3 X, —NX 2 , —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; and
R 4 =—H, linear or branched C 1 -C 8 -alkyl, —CH═CH 2 , —CO 2 X, —C(O)NX 2 , —CH 2 OX, —CH 2 NX 2 , —CHO, —OX, —CN, —NO 2 , —C(O)NX, —C(═NY)X, —CF 3 , —CCl 3 , —CBr 3 , —Cl 3 , —SO 2 X, —SO 3 X, —NX 2 , —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.

12. Method according to claim 1 , wherein the final phenolic product is one or more phenolic selected from the group consisting of phenol, o-alkylphenol, m-alkylphenol, p-alkylphenol, cresol, 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 and p-hydroxybenzamide.

13. A method for preparing a final phenolic product from biomass comprising the steps of:
a) providing a furanic compound obtainable from biomass, wherein the furanic compound is furan;
b) reacting the furanic compound with a dienophile to obtain a phenolic compound; and
c) reacting the phenolic compound further to obtain the final phenolic product.

14. Method according to claim 4 , wherein EWG=—CN, —NO 2 , —CO 2 X, —C(O)NX, —C(═NY)X, CF 3 , CCl 3 , CBr 3 , Cl 3 , —SO 2 X, —SO 3 X, —COH, —COX, —COF, —COCl, —COBr, —COI, and wherein X and Y are independently H, or linear or branched C 1 -C 8 -alkyl, optionally substituted with halogens and optionally polymer-supported.

15. Method according to claim 6 , wherein the furanic compound is reacted with the dienophile at a temperature of −20-250° C.

1

Assignees

• TNO

Inventors

• Crockatt Marc
• Urbanus Jan Harm
• Konst Paul Mathijs
• De Koning Martijn Constantijn

Classifications

• C07C67/317

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups · CPC title

• C07C67/31

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C37/62

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C37/50

  by reactions decreasing the number of carbon atoms (C07C37/04, C07C37/045, C07C37/055, C07C37/08 take precedence) · CPC title