Production of aromatic acids and phenolics

Patent metadata

Field	Value
Publication number	US-12528758-B2
Application number	US-202017766615-A
Country	US
Kind code	B2
Filing date	Oct 22, 2020
Priority date	Oct 22, 2019
Publication date	Jan 20, 2026
Grant date	Jan 20, 2026

Abstract

The invention is directed to a process for the preparation of an aromatic acid or a phenolic compound, said process comprising reacting a dienophile and a furanic compound comprising an acetal moiety in a Diels-Alders reaction to obtain an aromatic compound comprising said acetal moiety, followed by hydrolysis and oxidation of said acetal moiety into a hydroxide or carboxylate moiety to form the aromatic acid or phenolic compound, wherein said dienophile is selected from the group consisting of alkylenes, acetylenes, acrylates, maleates, fumarates, maleimides, propiolates, acetylene dicarboxylates, and benzynes and wherein said acetal moiety is bound directly to the 2-position of the furanic compound.

First claim

The invention claimed is:

1 . A method for the preparation of an aromatic acid or a phenolic compound, said method comprising reacting a dienophile and a furanic compound comprising an acetal moiety in a Diels-Alders reaction to obtain an aromatic compound comprising said acetal moiety, followed by hydrolysis and oxidation of said acetal moiety into a hydroxide or carboxylate moiety to form the aromatic acid or phenolic compound, wherein said dienophile is selected from the group consisting of alkylenes, acetylenes, acrylates, maleates, fumarates, maleimides, propiolates, acetylene dicarboxylates, and benzynes and wherein said acetal moiety is bound directly to the 2-position of the furanic compound.

2 . The method according to claim 1 , wherein the furanic compound has a structure according to formula I,

wherein,
R 1 is selected from the group consisting of H, C 1 -C 20 alkyl, —CH(OR 2 )(OR 3 ), CH 2 OH and esters and ethers thereof, CO 2 H and esters thereof, and amides and tertiary amines of CH 2 NH 2 , and optionally polymer supported; and
R 2 and R 3 are independently a C 1 -C 20 hydrocarbyl;
or wherein R 2 and R 3 together form a ring and represent a C 1 -C 20 hydrocarbylene.

3 . The method according to claim 1 , wherein the dienophile has a structure according to formula II,

wherein
R 4 and R 5 are each independently selected from the group consisting of H, C 1 -C 8 hydrocarbyl CO 2 Z wherein Z is H or an optionally halogenated C 1 -C 8 hydrocarbyl or
R 4 and R 5 together form a ring and represent —(CO)X(CO)—, wherein X═O, CH 2 , NH, NMe, NEt, NPr, NBu, NPh, or S; and
wherein represent a double or triple bond.

4 . The method according to claim 1 , wherein the aromatic acid has a structure according to formula IVaa and the phenolic compound has a structure according to formula IVab or esters and ethers thereof;

and wherein R 1 is selected from the group consisting of H, C 1 -C 20 alkyl, —CH(OR 2 )(OR 3 ), CH 2 OH and esters and ethers thereof, CO 2 H and esters thereof, and amides and tertiary amines of CH 2 NH 2, and optionally polymer supported;
R 2 and R 3 are independently a C 1 -C 20 hydrocarbyl; or wherein R 2 and R 3 together form a ring and represent a C 1 -C 20 hydrocarbylene; and
R 4 and R 5 are each independently selected from the group consisting of H, C 1 -C 8 hydrocarbyl, CO 2 Z wherein Z is H or an optionally halogenated C 1 -C 8 hydrocarbyl or
R 4 and R 5 together form a ring and represent —(CO)X(CO)—, wherein X═O, CH 2 , NH, NMe, NEt, NPr, NBu, NPh, or S.

5 . The method according to claim 1 , wherein the aromatic acid has a structure according to formula IVba and the phenolic compound has a structure according to formula IVbb or esters and ethers thereof;

and R 1 is selected from the group consisting of H, C 1 -C 20 alkyl, —CH(OR 2 )(OR 3 ), CH 2 OH and esters and ethers thereof, CO 2 H and esters thereof, and amides and tertiary amines of CH 2 NH 2, and optionally polymer supported;
R 2 and R 3 are independently a C 1 -C 20 hydrocarbyl; or wherein R 2 and R 3 together form a ring and represent a C 1 -C 20 hydrocarbylene; and
R 4 and R 5 are each independently selected from the group consisting of H, C 1 -C 8 hydrocarbyl, CO 2 Z wherein Z is H or an optionally halogenated C 1 -C 8 hydrocarbyl or
R 4 and R 5 together form a ring and represent —(CO)X(CO)—, wherein X═O, CH 2 , NH, NMe, NEt, NPr, NBu, NPh, or S.

6 . The method according to claim 4 , wherein the aromatic acid or the phenolic compound is such that R 1 is selected from the group consisting of H, C 1 -C 20 alkyl, CH 2 O— alkyl; and R 4 and R 5 are each independently H or CO 2 H.

7 . The method according to claim 1 , wherein said method further comprises preparing the furanic compound comprising an acetal moiety by reacting a corresponding furfural compound with an alcohol or diol under dehydrating conditions.

8 . The method according to claim 1 , wherein reacting the dienophile with the furanic compound is catalyzed by a Lewis and/or Brønsted acid.

9 . The method according to claim 1 , wherein the hydrolysis and oxidation are carried out in two separate steps.

10 . The method according to claim 1 , wherein reacting the dienophile and the furanic compound in a Diels-Alders reaction to obtain the aromatic compound comprises the formation and optionally isolation of an intermediate cycloadduct according to formula V and ring-opening and aromatizing said intermediate to form said aromatic compound,

wherein R 1 is selected from the group consisting of H, C 1 -C 20 alkyl, —CH(OR 2 )(OR 3 ), CH 2 OH and esters and ethers thereof, CO 2 H and esters thereof, and amides and tertiary amines of CH 2 NH 2, and optionally polymer supported;
R 2 and R 3 are independently a C 1 -C 20 hydrocarbyl; or wherein R 2 and R 3 together form a ring and represent a C 1 -C 20 hydrocarbylene; and
R 4 and R 5 are each independently selected from the group consisting of H, C 1 -C 8 hydrocarbyl, CO 2 Z wherein Z is H or an optionally halogenated C 1 -C 8 hydrocarbyl or
R 4 and R 5 together form a ring and represent —(CO)X(CO)—, wherein X═O, CH 2 , NH, NMe, NEt, NPr, NBu, NPh, or S; and represents a double or single bond.

11 . The method according to claim 1 , wherein said hydrolysis of the aromatic compound results in the formation and optionally isolation of an intermediate aldehyde.

12 . The method according to claim 2 , wherein the furanic compound has a structure according to formula I,

wherein,
R 1 H, methyl or CH 2 O—(C 1 -C 20 alkyl); and
R 2 and R 3 are C 1 -C 12 hydrocarbon.

13 . The method according to claim 12 , wherein R 2 and R 3 are benzyl, methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, pentyl, hexyl or octyl.

14 . The method according to claim 2 , wherein R 2 and R 3 together form a ring and represent a C 1 -C 20 hydrocarbylene, selected from the group consisting of —(CH 2 ) 2 —, —(CH(C 1 -C 10 alkyl)CH 2 —, —(CH 2 ) 3 —, —(C(CH 3 ) 2 ) 2 —, —(C(CH 3 ) 2 CH 2 C(CH 3 ) 2 )— and 1,2-phenylene.

15 . The method according to claim 3 , wherein one of R 4 and R 5 is H.

16 . The method according to claim 3 , wherein R 4 and R 5 together form a ring and represent (CO)O(CO)—, —(CO)NMe(CO)—, —(CO)NEt(CO)— or —(CO)NPr(CO)—.

17 . The method according to claim 3 , wherein represents a double bond.

18 . The method according to claim 6 , wherein R 1 is H, methyl or CH 2 O—(C 1 -C 20 alkyl).

19 . The method according to claim 7 , wherein said alcohol has a structure according to R 2 OH and/or R 3 OH wherein R 2 OH and/or R 3 OH are independently a C 1 -C 20 hydrocarbyl and said diol is selected from the group consisting of a C 1 -C 20 hydrocarbylenediol.

Assignees

• TNO

Inventors

• Crockatt Marc

Classifications

• C07C37/0555

  being esterified hydroxy groups · CPC title

• C07C37/56

  by replacing a carboxyl or aldehyde group by a hydroxy group · CPC title

• C07C45/59

  in five-membered rings (from ozonides C07C45/40) · CPC title

• C07C45/52

  by dehydration and rearrangement involving two hydroxy groups in the same molecule · CPC title

• C07C51/265 Primary

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