2,5-disubstituted-1,4-diaminobenzenes

Patent metadata

Field	Value
Publication number	US-9522870-B2
Application number	US-201213416904-A
Country	US
Kind code	B2
Filing date	Mar 9, 2012
Priority date	Mar 9, 2012
Publication date	Dec 20, 2016
Grant date	Dec 20, 2016

Abstract

Asymmetrical 2,5-disubstituted-1,4-diaminobenzenes are provided, along with a process for forming both symmetrical and asymmetrical 2,5-disubstituted-1,4-diaminobenzenes.

First claim

What is claimed is:

1. A composition comprising 2,5-disubstituted-1,4-diaminobenzenes wherein at least 90% of the 2,5-disubstituted-1,4-diaminobenzenes are asymmetrical.

2. The composition of claim 1 , wherein the 2,5-disubstituted-1,4-diaminobenzenes comprise 2,5-dinitro-substituted-1,4-diaminobenzenes.

3. The composition of claim 1 wherein the asymmetrical 2,5-disubstituted-1,4-diaminobenzenes are 2,5-dialkylamino-substituted-1,4-diaminobenzenes.

4. The composition of claim 1 wherein the asymmetrical 2,5-disubstituted-1,4-diaminobenzenes have the general formula

where R 1 and R 2 are different, wherein R 1 and R 2 are each selected from the group consisting of R 3 NH—, R 4 R 5 N—, R 6 O—, and R 7 S—, where R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the group consisting of substituted and unsubstituted hydrocarbon groups containing from 1 to 24 carbon atoms, branched aliphatic groups, linear lower aliphatic groups, cyclic aliphatic groups, homocyclic aryl groups, and heterocyclic aryl groups.

5. A process for preparing the composition of claim 1 , the process including:
providing 2,5-difluoro-1,4-dinitrobenzenes;
reacting 2,5-difluoro-1,4-dinitrobenzenes with a first amine or a first alcohol or a first thiol to form a mono-substituted product;
reacting the mono-substituted product with a second amine or a second alcohol or a second thiol, respectively, to form 2,5-disubstituted-1,4-dinitrobenzenes; and
reducing the 2,5-disubstituted-1,4-dinitrobenzenes to form the 2,5-disubstituted-1,4-diaminobenzenes.

6. The process of claim 5 , wherein the first amine and the second amine are the same or different, wherein the first alcohol and the second alcohol are the same or different, and wherein the first thiol and the second thiol are the same or different.

7. The process of claim 6 , wherein the first amine and the second amine are each selected from the group consisting of primary amines and secondary amines.

8. The process of claim 5 , wherein the process of providing 2,5-difluoro-1,4-dinitrobenzenes includes:
reacting 2,5-difluoroanilines with acetic anhydride to form N-(2,5-difluorophenyl)acetamides;
nitrating the N-(2,5-difluorophenyl)acetamides to form N-(2,5-difluoro-4-nitrophenyl)acetamides;
deprotecting the N-(2,5-difluoro-4-nitrophenyl)acetamides to form 2,5-difluoro-4-nitroaniline having an amino group in the 1 position; and
oxidizing the amino group to the corresponding nitro group to form the 5-difluoro-1,4-dinitrobenenes.

9. The process of claim 5 wherein the 2,5-disubstituted-1,4-diaminobenzenes have the general formula

where R 1 and R 2 are the different and R 1 and R 2 are each selected from the group consisting of R 3 NH—, R 4 R 5 N—, R 6 O—, and R 7 S—, where R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the group consisting of substituted and unsubstituted hydrocarbon groups containing from 1 to 24 carbon atoms, branched aliphatic groups, linear lower aliphatic groups, cyclic aliphatic groups, homocyclic aryl groups, and heterocyclic aryl groups.

10. The composition of claim 4 , wherein R 1 and R 2 are each selected from the group consisting of R 3 NH—, R 6 O—, and R 7 S—, where R 3 , R 6 , and R 7 are each independently selected from the group consisting of substituted and unsubstituted hydrocarbon groups containing from 1 to 24 carbon atoms, branched aliphatic groups, linear lower aliphatic groups, cyclic aliphatic groups, and heterocyclic aryl groups.

11. The composition of claim 1 wherein the composition is prepared by:
providing 2,5-difluoro-1,4-dinitrobenzenes;
reacting 2,5-difluoro-1,4-dinitrobenzenes with a first amine to form mono-substituted products;
reacting the mono-substituted product with a second amine to form 2,5-disubstituted-1,4-dinitrobenzenes; and
reducing the 2,5-disubstituted-1,4-dinitrobenzenes to form the 2,5-disubstituted-1,4-diaminobenzenes.

12. The composition of claim 11 , wherein the asymmetrical 2,5-disubstituted-1,4-diaminobenzene has the general formula

where R 1 and R 2 are different, and wherein R 1 and R 2 are each selected from the group consisting of R 3 NH— and R 4 R 5 N—, where R 3 , R 4 , and R 5 are each independently selected from the group consisting of substituted and unsubstituted hydrocarbon groups containing from 1 to 24 carbon atoms, branched aliphatic groups, linear lower aliphatic groups, cyclic aliphatic groups, homocyclic aryl groups, and heterocyclic aryl groups.

Assignees

• Zhou Zhang-Lin
• Lam Si-Ty
• Zhao Lihua
• Hewlett Packard Development Co Lp

Inventors

• Zhou Zhang-Lin
• Lam Si-Ty
• Zhao Lihua

Classifications

• C09B51/00

  Nitro or nitroso dyes · CPC title

• C07C211/50 Primary

  with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• G11B7/246

  containing dyes · CPC title