Fluoropicolinoyl fluorides and processes for their preparation

Patent metadata

Field	Value
Publication number	US-9376388-B2
Application number	US-201514667109-A
Country	US
Kind code	B2
Filing date	Mar 24, 2015
Priority date	Jul 24, 2012
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

Provided herein are fluoropicolinoyl fluorides and processes for their preparation. In some embodiments, provided herein is a process for the preparation of 5-fluoro-6-aryl-picolinoyl fluorides from chloropicolinoyl chlorides.

First claim

What is claimed is:

1. A process for the preparation of a compound of the Formula II:

wherein
R is selected from the group consisting of halo; alkyl; cycloalkyl; alkenyl; alkynyl; alkoxy and aryl substituted with from 0 to 5 substituents independently selected from the group consisting of halo, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy;
R 1 is selected from the group consisting of H; alkyl; cycloalkyl; alkenyl; alkynyl; unsubstituted or substituted C 7 -C 11 arylalkyl; and aryl substituted with from 0 to 5 substituents independently selected from the group consisting of halo, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy;
m is 0, 1, 2 or 3; and
n is 0, 1, 2, 3 or 4;

wherein the sum of m and n is between 1 and 4;
which comprises (a) fluorinating a compound of Formula A:

with a source of fluoride ion to produce a compound of the Formula I:

wherein R is selected from the group consisting of halo; alkyl; cycloalkyl; alkenyl; alkynyl; alkoxy and aryl substituted with from 0 to 5 substituents independently selected from the group consisting of halo, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy;
m is 0, 1, 2 or 3; and
n is 0, 1, 2, 3 or 4;

which further comprises (b) reacting the compound for Formula I with a source of R 1 OH to produce a compound of Formula II.

2. The process of claim 1 wherein R 1 is selected from the group consisting of H; alkyl; cycloalkyl; alkenyl; alkynyl; and aryl substituted with from 0 to 5 substituents independently selected from the group consisting of halo, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy.

3. The process of claim 1 wherein step (b) is performed in the presence of a base.

4. The process of claim 1 , wherein fluorinating a compound of Formula A is performed in the presence of a catalyst, wherein the catalyst is selected from the group consisting of a crown ether, a phosphonium halide, a polyether, a phosphazenium salt, and a tetra-substituted ammonium halide.

5. The process of claim 4 , wherein the catalyst is a crown ether.

6. The process of claim 5 , wherein the crown ether is 18-crown-6.

7. The process of claim 1 , wherein the source of fluoride ion is a metal fluoride.

8. The process of claim 7 , wherein the metal fluoride is selected from the group consisting of sodium fluoride, potassium fluoride and cesium fluoride.

9. The process of claim 8 , wherein the metal fluoride is potassium fluoride.

10. The process of claim 1 , wherein step (a) includes a solvent, wherein the solvent is an alkyl nitrile or an alkyl sulfone.

11. The process of claim 10 , wherein the solvent is acetonitrile or sulfolane.

12. The process of claim 1 , wherein the source of fluoride ion is potassium fluoride, and wherein step (a) is conducted in the presence of a crown ether and a solvent.

13. The process of claim 12 , wherein the solvent is acetonitrile or sulfolane.

14. The process of claim 3 , wherein the base is a trialkylamine base.

15. The process of claim 14 , wherein the trialkylamine base is triethylamine.

Assignees

• Dow Agrosciences Llc

Inventors

• Renga James M
• Cheng Yang
• Muhuhi Joseck M
• Podhorez David E
• Roth Gary A
• West Scott P
• Whiteker Gregory T
• Zhu Yuanming

Classifications

• C07D213/803

  Processes of preparation · CPC title

• C07D213/55 Primary

  Acids; Esters · CPC title

• C07D213/807 Primary

  by oxidation of pyridines or condensed pyridines · CPC title

• A01N43/40

  six-membered rings · CPC title

• C07D213/78 Primary

  Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title