Selective hydrogenation of nitro groups of halonitro aromatic compounds

1. A process for manufacturing a catalyst for hydrogenating nitro groups, comprising:

dispersing an organometallic complex on a solid support to form an intermediate supported catalyst, wherein the organometallic complex corresponds to formula I

wherein,

R 1 -R 6 comprise, independent of one another, one or more of an R, OR, OC(═O)R, or halide, wherein R stands for an alkyl, an aryl, or a hydrogen;

Y 1 -Y 4 are independently an O or an S atom; and

M is a metal atom.

activating the intermediate supported catalyst by reducing the metal atoms; and

wherein prior to and during activation, the organometallic complexes are not exposed to oxygen at a temperature greater than about 100° C.

2. A process as in claim 1 , wherein during use and prior to use, the catalyst is not exposed to oxygen at a temperature greater than about 100° C.

3. A method as in claim 1 , wherein the catalyst is dispersed on the support using a solvent.

4. A process as in claim 1 , wherein M is selected from the group consisting of platinum group metals.

5. A process as in claim 1 , wherein M is selected from the group consisting of palladium, platinum, ruthenium, rhodium, and combinations thereof.

6. A process as in claim 1 , wherein the solid support comprises hydroxyl groups on the surface thereof that bond to at least a portion of the organic ligands of the organometallic complex.

7. A process as in claim 6 , wherein the solid support comprises carbon.

8. A process as in claim 1 , wherein each of R 1 -R 4 is a CH 3 group and R 5 and R 6 are each a hydrogen.

9. A process as in claim 1 , wherein R 1 -R 4 are independently a methyl, benzene, or substituted benzene group.

10. A process as in claim 1 , wherein R 1 -R 4 each comprise at least one carbon atom.

11. A process as in claim 1 , wherein R 5 and R 6 are independently a hydrogen, methyl, isopropyl, tert-butyl, benzene, substituted benzene, Cl, or Br group.

12. A supported catalyst manufactured according to the process of claim 1 .

13. A process for manufacturing an haloamino aromatic compound comprising hydrogenating at least one nitro group of a halonitro aromatic compound in the presence of the catalyst of claim 12 .

14. A process as in claim 13 , wherein the halonitro aromatic compound has the formula

wherein for the halonitro aromatic compound

R 1 signifies hydrogen, C 1 -C 12 -alkyl, C 1 -C 12 -halogen-alkyl, C 6 -C 16 -halogen-aryl, C 3 -C 6 -halogen-heteroaryl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halogen-C 1 -C 4 -alkylphenyl, halogen-C 1 -C 4 -alkoxyphenyl, C 1 -C 12 -hydroxyalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl substituted by C 1 -C 4 -alkyl, C 6 -C 16 -aryl, C 7 -C 16 -aralkyl, C 3 -C 6 -heterocycloalkyl, C 3 -C 16 -heteroaryl, C 4 -C 16 -heteroaralkyl, SO 3 H, SO 2 R 2 , SO 2 N(R 2 ) 2, or a group-Y 1 R 2 ;

Y 1 signifies NR 2 , oxygen or sulfur;

R 2 signifies hydrogen, C 1 -C 12 -alkyl, C 1 -C 12 -halogen-alkyl, C 6 -C 16 -halogen-aryl, C 3 -C 16 -halogen heteroaryl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halogen-C 1 -C 4 -alkylphenyl, halogen-C 1 -C 4 -alkoxyphenyl, C 1 -C 12 -hydroxyalkyl, C 3 -C 8 -cycloalkyl, C 6 C 16 -aryl, C 7 -C 16 -aralkyl, C 3 -C 6 -hetercycloalkyl, C 3 -C 16 -heteroaryl, or C 4 -C 16 -heteroaralkyl;

X signifies fluorine, chlorine, bromine, or iodine; and

r,s, and t, independent of one another, signify a number 1, 2, or 3, whereby r+s+t is less than or equal to six.

15. A process for manufacturing an amino aromatic compound, comprising:

hydrogenating at least one nitro group of a nitro aromatic compound in the presence of a catalyst, the catalyst comprising a molecule with a structure according to formula (I)

wherein,

R 1 -R 6 comprise, independent of one another, one or more of an R, OR, OC(═O)R, or halide, wherein R stands for an alkyl, an aryl, or a hydrogen;

Y 1 -Y 4 are independently an O or an S atom; and

M is a metal atom.

16. A process as in claim 15 , wherein M is selected from the group consisting of palladium, platinum, ruthenium, and rhodium.

17. A process as in claim 15 , wherein each of R 1 -R 4 is a CH 3 group.

18. A process as in claim 17 , wherein each of R 5 and R 6 is an H group.

19. A process as in claim 15 , wherein the catalyst is supported on a solid support.

20. A process as in claim 15 , wherein the solid support comprises hydroxyl groups on the surface thereof.

21. A process as in claim 15 , wherein the halonitro aromatic compound has the formula:

wherein, for the halonitro aromatic compound

R 1 signifies hydrogen, C 1 -C 12 -alkyl, C 1 -C 12 -halogen-alkyl, C 6 -C 16 -halogen-aryl, C 3 -C 6 -halogen-heteroaryl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halogen-C 1 -C 4 -alkylphenyl, halogen-C 1 -C 4 -alkoxyphenyl, C 1 -C 12 -hydroxyalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl substituted by C 1 -C 4 -alkyl, C 6 -C 16 -aryl, C 7 -C 16 -aralkyl, C 3 -C 6 -heterocycloalkyl, C 3 -C 16 -heteroaryl, C 4 -C 16 -heteroaralkyl, SO 3 H, SO 2 R 2 , SO 2 N(R 2 ) 2 , or a group-Y 1 R 2 ;

Y 1 signifies NR 2 , oxygen, or sulfur;

R 2 signifies hydrogen, C 1 -C 12 -alkyl, C 1 -C 12 -halogen-alkyl, C 6 -C 16 -halogen-aryl, C 3 -C 16 -halogen heteroaryl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halogen-C 1 -C 4 -alkylphenyl, halogen-C 1 -C 4 -alkoxyphenyl, C 1 -C 12 -hydroxyalkyl, C 3 -C 8 -cycloalkyl, C 6 -C 16 -aryl, C 7 -C 16 -aralkyl, C 3 -C 6 -hetercycloalkyl, C 3 -C 16 -heteroaryl, C 4 -C 16 -heteroaralkyl;

X signifies fluorine, chlorine, bromine or iodine; and

r,s, and t, independently of one another, signify a number 1, 2 or 3, whereby r+s+t is less than or equal to six.