Method for producing halogen-N,N-dimethylbenzylamines

Patent metadata

Field	Value
Publication number	US-10035755-B2
Application number	US-201414772127-A
Country	US
Kind code	B2
Filing date	Mar 4, 2014
Priority date	Mar 6, 2013
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

The invention relates to a method for producing halogen-N,N-dimethylbenzylamines wherein halogen=chlorine or bromine, preferably chloro-N,N-dimethylbenzylamines, preferably ortho-chloro-N,N-dimethylbenzylamine (o-Cl-DMBA), by reductive amination in the absence of sulfur.

First claim

What is claimed is:

1. A method for producing halogen-N,N-dimethylbenzylamines, the method comprising reductive amination of halogenbenzaidehyde with dimethyiamine in the presence of:
hydrogen;
an acid selected from the group consisting of formic acid, acetic acid, and propionic acid; and
at least one catalyst selected from the group consisting of palladium, platinum, ruthenium, nickel, cobalt, nickel-containing catalyst and cobalt-containing catalyst,

wherein the reductive amination is conducted:
at a hydrogen pressure of 5 to 250 bar,
at a temperature of 30-250° C.,
with a molar ratio of the halogenbenzaidehyde to dimethylamine of 1:2-5, and
without the addition of sulfur or further cocatalysts selected from the group consisting of metal oxides or metal mixed oxides, zeolites, metal salts of mineral acids, ammonium salts of mineral acids, metal salts of organic acids, ammonium salts of oroanic acids, acidic ion exchangers, and mixtures thereof.

2. The method as claimed in claim 1 , wherein:
the halogen is chlorine or bromine; and
the reductive amination is done at a temperature of 50 to 150° C. at a hydrogen pressure of 10 to 220 bar.

3. The method as claimed in claim 1 , wherein the catalysts are nickel (Ni) catalysts or cobalt (Co) catalysts produced by leaching out from Ni or Co alloys, Ni or Co on supports selected from the group SiO 2 , Al 2 O 3 , pumice, carbon in the form of skeletal catalysts, elemental Ni(Co) sponge, as Ni oxide, Co oxide, Raney nickel, Raney cobalt.

4. The method as claimed in claim 1 , wherein:
an amount of catalyst used in the reductive amination is 0.1-25% by weight based on the substrate to be hydrogenated; and
an amount of the acid used in the reductive amination is 0.1-10% by weight.

5. The method as claimed in claim 1 , wherein the reductive amination is conducted without solvents.

6. The method as claimed in claim 1 , further comprising conducting the reductive amination in the presence of at least one solvent selected from the group consisting of methanol, ethanol, isopropanol, butanol, toluene, xylene, cyclohexane, isooctane, tetrahydrofuran, dioxane, methyl tert-butyl ester and ethyl acetate.

7. The method as claimed in claim 1 , wherein the molar ratio of the halogenbenzaldehyde to dimethyiamine is 1:1.51-10, and the method comprises conducting the reductive amination at a temperature of 50-150° C., and at an H 2 pressure of 10-220 bar.

8. The method as claimed in claim 1 , wherein:
an amount of catalyst used in the reductive amination is 1.5-12.5% by weight based on the substrate to be hydrogenated; and
an amount of the add used in the reductive amination is 0.5-5% by weight.

9. The method as claimed in claim 1 , wherein the acid is acetic acid.

10. The method as claimed in claim 1 , wherein:
the halogen is chlorine, and the halogenbenzaldehyde is o-chlorobenzaldehyde;
the reductive amination is conducted at a temperature of 50-150° C., and at an H 2 pressure of 10-220 bar;
the at least one catalyst is a Ni or Co catalyst produced by leaching out from Ni or Co alloys, Ni or Co on supports selected from the group SiO 2 , Al 2 O 3 , pumice, carbon in the form of skeletal catalysts, elemental Ni(Co) sponge, as Ni oxide, Co oxide, Raney nickel, Raney cobalt, and an amount of catalyst used in the reductive amination is 1.5-12.5% by weight based on the substrate to be hydrogenated; and
the acid is acetic acid, and an amount of the add used in the reductive amination is 0.5-4% by weight.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Peters Lars
• Schulze Tilling Andreas
• Stirner Wolfgang

Classifications

• C07C211/29

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title

• C07C209/28 Primary

  by reduction with other reducing agents · CPC title

• C07C209/26

  by reduction with hydrogen · CPC title