Process to prepare 3-methyl-2-nitrobenzoic acid by air oxidation

Patent metadata

Field	Value
Publication number	US-9828328-B2
Application number	US-201515313365-A
Country	US
Kind code	B2
Filing date	May 29, 2015
Priority date	May 29, 2014
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

A method for preparing 3-methyl-2-nitrobenzoic acid is disclosed wherein 1,3-dimethyl-2-nitrobenzene is combined with an oxidation catalyst in the presence of an oxygen source and an initiator, provided that less than 99% of the 1,3-dimethyl-2-nitrobenzene is oxidized.
A method for preparing compounds of Formula 7 and Formula 11 is also disclosed wherein the method is characterized by using 3-methyl-2-nitrobenzoic acid as prepared by the method disclosed above.

wherein R 1 is C 1 -C 7 alkyl, C 3 -C 6 cycloalkyl or C 4 -C 7 alkylcycloalkyl.

First claim

The invention claimed is:

1. A method for preparing a compound of Formula 2

comprising, contacting a compound of Formula 1

with an oxidation catalyst in the presence of an oxygen source and an initiator provided that less than 99% of a compound of Formula 1 is oxidized.

2. The method of claim 1 wherein the oxidation catalyst comprises cobalt(II), cobalt(III), manganese(II), manganese(III), iron(II) or iron(III) salts, or mixtures thereof.

3. The method of claim 2 wherein the oxidation catalyst comprises cobalt(II) acetate tetrahydrate.

4. The method of claim 1 wherein the oxygen source comprises air, a carrier gas enriched with air, a carrier gas enriched with oxygen gas, or oxygen gas.

5. The method of claim 4 wherein the oxygen source comprises air.

6. The method of claim 1 wherein the initiator comprises acetaldehyde, propionaldehyde, metaldehyde, paraldehyde or methylethylketone, or mixtures thereof.

7. The method of claim 6 wherein the initiator comprises acetaldehyde.

8. The method of claim 1 wherein the compound of Formula 1, the oxidation catalyst, the oxygen source and the initiator are contacted in the presence of a suitable solvent.

9. The method of claim 8 wherein the suitable solvent comprises acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, 2-ethylhexanoic acid, acetic anhydride, o-dichlorobenzene or chlorobenzene, or mixtures thereof.

10. The method of claim 9 wherein the suitable solvent comprises acetic acid or a mixture of acetic acid and water.

11. The method of claim 1 wherein the mixture formed by contacting the compound of Formula 1, the oxidation catalyst, the oxygen source and the initiator is heated to a temperature of about 60° C. to about 150° C.

12. The method of claim 11 wherein the mixture is heated to a temperature of about 90° C. to about 115° C.

13. The method of claim 1 wherein the mixture formed by contacting the compound of Formula 1, the oxidation catalyst, the oxygen source and the initiator is pressurized from about 1400 kPa to about 6900 kPa.

14. The method of claim 13 wherein the mixture is pressurized to about 3500 kPa.

15. The method of claim 1 wherein less than 50% of a compound of Formula 1 is oxidized.

16. The method of claim 1 further comprising isolating the compound of Formula 2 by filtering and recycling the filtrate directly in a subsequent oxidation run after combination with additional 1,3-dimethyl-2-nitrobenzene (1) and optional additional oxidation catalyst and solvent.

Assignees

• Du Pont

Inventors

• Jacobson Stephen Ernest
• Dumas Donald J
• Spence Rupert
• Crawford Sarah May
• Surisetty Venkateswara Rao

Classifications

• C07C253/14

  by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups · CPC title

• C07C231/02

  from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines · CPC title

• C07C201/12 Primary

  by reactions not involving the formation of nitro groups · CPC title

• C07C205/57

  having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• C07C255/57

  containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton · CPC title