Production of xylene derivatives

Patent metadata

Field	Value
Publication number	US-10815245-B2
Application number	US-201616060510-A
Country	US
Kind code	B2
Filing date	Dec 8, 2016
Priority date	Dec 9, 2015
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

The present invention relates to the production of xylene derivatives from furfural and its derivatives. The invention describes new routes for converting furfural and its derivatives into xylene derivatives including novel intermediates.

First claim

The invention claimed is:

1. A process for the preparation of a compound of the Formula (I)

wherein
X and Y are O, or X and Y are S;
R is a C 1-4 alkylene group which may optionally be substituted with one or more R 1 ;
R 1 is a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more functional nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups;
R 2 independently is H, alkyl, alkenyl or aryl; and
R 3 and R 4 independently are H or —CN, provided that at least one of R 3 and R 4 is —CN; and
R 5 is R 2 , —CH 2 OR 2 , —CO 2 R 2 or

the process comprising reacting a compound of the Formula (II)

wherein X, Y, R, R 2 and R 5 are defined as above;
with a compound of the Formula (III) or (III′)

wherein R 3 and R 4 are defined as above.

2. The process according to claim 1 , wherein R is CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH(CH 3 )—CH(CH 3 )— or —CH 2 —C(CH 3 ) 2 —CH 2 —.

3. The process according to claim 1 , wherein R 2 is H.

4. A process for the preparation of a compound of Formula (IV)

wherein
R 2 independently is H, alkyl, alkenyl or aryl;
R 3 and R 4 independently are H or —CN, provided that at least one of R 3 and R 4 is —CN;
R 5 is R 2 , —CH 2 OR 2 , —CO 2 R 2 or

wherein X and Y are O, or X and Y are S;
R is a C 1-4 alkylene group which may optionally be substituted with one or more R 1 ; and
R 1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups;
the process comprising a) dehydration/aromatization of a compound of the Formula (I)

wherein X, Y, R, R 2 , R 3 , R 4 and R 5 are defined as above;
to obtain a compound of the Formula (V)

wherein X, Y, R, R 2 , R 3 , R 4 and R 5 are defined as above;
followed by deprotection of the compound of Formula (V);
or
comprising b) carrying out the dehydration/aromatization and the deprotection of the compound of Formula (I) in a single step.

5. The process according to claim 4 , wherein R is —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH(CH 3 )—CH(CH 3 )— or —CH 2 —C(CH 3 ) 2 —CH 2 —.

6. The process according to claim 4 , wherein R 2 is H.

7. The process according to claim 4 , wherein the compound of Formula (I) is obtained by reacting a compound of the Formula (II)

wherein X and Y are O, or X and Y are S;
R is a C 1-4 alkylene group which may optionally be substituted with one or more R 1 ;
R 1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups;
R 2 independently is H, alkyl, alkenyl or aryl; and
R 5 is R 2 , —CH 2 OR 2 , —CO 2 R 2 or

with a compound of the Formula (III) or (III′)

wherein R 3 and R 4 independently are H or —CN, provided that at least one of R 3 and R 4 is —CN.

8. A compound of the Formula (I)

wherein
X and Y are O, or X and Y are S;
R is a C 1-4 alkylene group which may optionally be substituted with one or more R 1 ;
R 1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups;
R 2 independently is H, alkyl, alkenyl or aryl;
R 3 and R 4 independently are H or —CN, provided that at least one of R 3 and R 4 is —CN; and
R 5 is R 2 , —CH 2 OR 2 , —CO 2 R 2 or

provided that
X and Y are O;
and/or
R is a C 1-4 alkylene group which is substituted with one or more R 1 .

9. The compound according to claim 8 , wherein R is —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH(CH 3 )—CH(CH 3 )— or —CH 2 —C(CH 3 ) 2 —CH 2 —.

10. The compound according to claim 8 , wherein R 2 is H.

11. A method comprising obtaining 3- or 2-cyanobenzaldehyde or 2,3-dicyanobenzaldehyde from a compound of Formula (I) made according to the process of claim 1 and converting the 3- or 2-cyanobenzaldehyde or 2,3-dicyanobenzaldehyde into 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid, respectively.

12. The method according to claim 11 , further comprising converting 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid into isophthalic acid, orthophthalic acid or hemimellitic acid.

13. The method according to claim 11 , further comprising converting 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid into 3-aminomethylbenzoic acid, 2-aminomethylbenzoic acid or 2,3-di(aminomethyl)benzoic acid.

14. The compound according to claim 8 , wherein X and Y are O.

15. The compound according to claim 8 , wherein R is a C 1-4 alkylene group which is substituted with one or more R 1 .

Assignees

• Rhodia Operations
• Centre Nat Rech Scient

Inventors

• Morvan Didier
• Back Olivier
• Wischert Raphaël
• Muller Eric

Classifications

• C07D493/08 Primary

  Bridged systems · CPC title

• C07C211/27

  having amino groups linked to the six-membered aromatic ring by saturated carbon chains · CPC title

• C07C209/48

  by reduction of nitriles · CPC title

• C07D317/30

  Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07B43/04

  of amino groups · CPC title