Processes for the preparation of heteroaryl carboxylic acids

Patent metadata

Field	Value
Publication number	US-10745376-B2
Application number	US-201716087175-A
Country	US
Kind code	B2
Filing date	Mar 21, 2017
Priority date	Mar 24, 2016
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

Provided herein are processes for the preparation of heteroaryl carboxylic acids.

First claim

What is claimed is:

1. A process for preparing 2-thiophenecarboxylic acid or 3-thiophenecarboxylic acid
the process comprising contacting 2-acetylthiophene or 3-acetylthiophene
with oxygen in the presence of a catalyst component in an oxidation reaction zone comprising a liquid medium, comprising an alkanoic acid,
wherein the catalyst component comprises a first transition metal ion selected from the group consisting of cobalt, copper, manganese, iron, zinc, zirconium, nickel, palladium, cadmium, and mixtures thereof.

2. The process of claim 1 further comprising:
reacting thiophene with acetic anhydride in the presence of a cation ion exchange resin in an acylating reaction zone to produce a product mixture comprising 2-acetylthiophene or 3-acetylthiophene.

3. The process of claim 1 wherein the first transition metal ion is selected from the group consisting of manganese, iron, and copper.

4. The process of claim 3 wherein the first transition metal ion is manganese.

5. The process of claim 1 wherein the catalyst component further comprises a second transition metal ion.

6. The process of claim 5 wherein the second transition metal ion is selected from the group consisting of cobalt, iron, and copper.

7. The process of claim 1 wherein the first transition metal ion is introduced to the liquid medium in a salt form of a halide, a C 2 -C 6 alkanoate, a nitrate, a carbonate, or a combination thereof.

8. The process of claim 1 wherein the process comprises adding a nitrate salt to the liquid medium prior to or during the contacting step to assist with the oxidation reaction.

9. The process of claim 1 wherein the liquid medium comprises a source of halide ions to assist with the oxidation reaction.

10. The process of claim 1 wherein the process further comprises an extraction step in which 2-thiophenecarboxylic acid or 3- thiophenecarboxylic acid is extracted with an extraction liquid medium comprising an organic solvent, and wherein the organic solvent in the extraction step forms an azeotrope with water.

11. The process of claim 1 further comprising chlorinating the thiophene carboxylic acid by reacting a chlorinating agent with the thiophene carboxylic acid dissolved in a chlorination medium comprising an organic solvent to produce thiophene carbonyl chloride.

12. The process of claim 11 further comprising reacting an N-hydroxyamidine of Formula V, or a tautomeric form thereof,

with the thiophene carbonyl chloride, wherein the thiophene carbonyl chloride is 2-thiophenecarbonyl chloride, to produce a 3,5-disubstituted 1,2,4-oxadiazole of Formula IV or a salt thereof:

wherein Ar 1 is selected from the group consisting of phenyl, pyridyl, pyrazyl, oxazolyl, and isoxazolyl, each of which can be optionally independently substituted with one or more substituents selected from the group consisting of halogen, CF 3 , CH 3 , OCF 3 , OCH 3 , CN and C(H)O, and Ar 2 is thienyl.

13. The process of claim 1 wherein the source of oxygen is air.

14. The process of claim 6 wherein the second transition metal ion is cobalt.

15. The process of claim 1 wherein the alkanoic acid is selected from the group consisting of acetic acid and propionic acid.

16. The process of claim 9 wherein the source of halide ions is selected from the group consisting of hydrohalic acids and halide salts.

17. The process of claim 16 wherein the source of halide ions is selected from the group consisting of sodium bromide, sodium chloride, and hydrobromic acid.

18. The process of claim 16 wherein the source of halide ions is a halide salt.

19. The process of claim 18 wherein the halide salt is a calcium salt, a cesium salt, a lithium salt, a sodium salt, or a potassium salt.

Assignees

• Monsanto Technology Llc

Inventors

• Walker Daniel Patrick
• Miller William Harold

Classifications

• B01J27/20

  Carbon compounds · CPC title

• B01J23/75

  Cobalt · CPC title

• C07D413/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• B01J23/74

  Iron group metals · CPC title

• B01J27/25

  Nitrates · CPC title