Process for producing aromatic primary diamines

Patent metadata

Field	Value
Publication number	US-10899726-B2
Application number	US-201515324932-A
Country	US
Kind code	B2
Filing date	Jul 8, 2015
Priority date	Jul 10, 2014
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

A process for the production of aromatic primary amines, by reacting an aromatic dialdehyde with hydrogen and ammonia or an ammonia-liberating compound, in the presence of a hydrogenation catalyst and an amine, wherein the molar ratio of the amine to the aromatic dialdehyde is no less than 1:4 at the start of the reaction.

First claim

The invention claimed is:

1. A process for the production of an aromatic primary diamine, the process comprising reacting an aromatic dialdehyde, wherein the aromatic ring is selected from a group consisting of benzene, pyrene, furan, thiophene, terthiophene, pyrrole, pyridine, terpyridine, pyridine oxide, pyrazine, indole, quinoline, purine, quinazoline, bipyridine, phenanthroline, naphthalene, tetralin, biphenyl, cyclohexylbenzene, indan, anthracene, phenanthrene, fluorene, and azulene, each being optionally substituted with at least one substitution selected from a group consisting of C 1 -C 24 alkyl, amino, hydroxyl, carboxyl, ester, cyano, nitro, halogen, and oxygen; with hydrogen and ammonia or an ammonia-liberating compound selected from the group consisting of urea, uric acid, ammonium salts, symmetrical and unsymmetrical carbamates, carbaminates, semicarbazides, semicarbazoles, and aminium salts and organic/inorganic esters thereof, in the presence of a hydrogenation catalyst and an amine, wherein the molar ratio of the amine to the aromatic dialdehyde is no less than 1:4 at the start of the reaction.

2. The process of claim 1 , wherein the amine is a primary amine or a secondary amine.

3. The process of claim 2 , wherein the amine is a primary amine.

4. The process of claim 3 , wherein the primary amine is selected from a group consisting of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, benzylamine, cyclohexylamine, and ethylene diamine.

5. The process of claim 1 , wherein the amine is a secondary amine selected from the group consisting of dimethylamine, diethylamine, diethanolamine, dicyclohexylamine, diallylamine, piperidine, pyrolidine, morpholine, N-methylbenzylamine, and dibenzylamine.

6. The process of claim 1 , wherein the amine is a tertiary amine selected from a group consisting of trimethylamine, triethylamine, triethanolamine, diisopropylethylamine, tricyclohexylamine, triallylamine, benzyldimethylamine, N-methylmorpholine, and N-methyldibenzylamine.

7. The process of claim 1 , wherein the aromatic dialdehyde has at least one furan ring substituted with two aldehyde groups.

8. The process of claim 1 , wherein the molar ratio of the amine to the aromatic dialdehyde is no less than 1:2 at the start of the reaction.

9. The process of claim 1 , wherein the molar ratio of the amine to the aromatic dialdehyde is no more than 4:1 at the start of the reaction.

10. The process of claim 1 , wherein an ammonia-liberating compound is used.

11. The process of claim 1 , wherein ammonia is used.

12. The process of claim 1 , wherein the molar ratio of the aromatic dialdehyde to the equivalents of ammonia is in the range of 1:2-1:50.

13. The process of claim 1 , wherein the aromatic dialdehyde is fed in a manner to ensure that the molar ratio of amine to the aromatic dialdehyde is no less than 1:4throughout the reaction.

14. The process of claim 1 , wherein the reaction temperature is in a range of 40 to 200° C.

15. The process of claim 1 , wherein the aromatic diamine is 2,5-bis (aminomethyl)furan and the aromatic dialdehyde is 2,5-diformylfuran.

16. The process of claim 4 , wherein the primary amine is selected from a group consisting of methylamine, butylamine, pentylamine, and hexylamine.

17. The process of claim 8 , wherein the molar ratio of the amine to the aromatic dialdehyde is no less than 1:1, at the start of the reaction.

18. The process of claim 9 , wherein the molar ratio of the amine to the aromatic dialdehyde is no more than 3:1 at the start of the reaction.

19. The process of claim 12 , wherein the molar ratio of the aromatic dialdehyde to the equivalents of ammonia is in the range of 1:5-1:20.

20. The process of claim 13 , wherein the aromatic dialdehyde is fed in a manner to ensure that the molar ratio of amine to the aromatic dialdehyde is in a range of 1:4 to 2:1.

Assignees

• Rhodia Operations

Inventors

• Li Peng
• Decampo Floryan

Classifications

• C07D307/52 Primary

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title

• B01J25/02

  Raney nickel · CPC title

• C07C209/26 Primary

  by reduction with hydrogen · CPC title

• C07C211/26

  of an unsaturated carbon skeleton containing at least one six-membered aromatic ring · CPC title