Fluoropicolinoyl fluorides and processes for their preparation

1. A process for the preparation of 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 1,2, 3 or 4;

wherein the sum of m and n is less than or equal to 4;

which comprises fluorinating a compound of Formula A:

wherein R, m and n are as previously defined;

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

2. The process of claim 1 , wherein m is 0.

3. The process of claim 1 , wherein n is 2 or 3.

4. The process of claim 1 , wherein the compound of Formula I is:

wherein R is 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; and

n is 1, 2 or 3.

5. The process of claim 4 , wherein n is 2.

6. The process of claim 1 , wherein the compound of Formula I is:

wherein R is phenyl 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.

7. 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.

8. The process of claim 7 , wherein the catalyst is a crown ether.

9. The process of claim 8 , wherein the crown ether is 18-crown-6.

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

11. The process of claim 10 , wherein the metal fluoride is selected from the group consisting of sodium fluoride, potassium fluoride and cesium fluoride.

12. The process of claim 11 , wherein the metal fluoride is potassium fluoride.

13. The process of claim 1 , which includes a solvent, wherein the solvent is an alkyl nitrile or an alkyl sulfone.

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

15. The process of claim 1 for the preparation of a compound of the formula

wherein

R is fluoro or phenyl 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; and

n is 1 or 2;

which comprises reacting a compound of Formula A:

wherein R and n are as previously defined;

with potassium fluoride in the presence of a crown ether and a solvent.

16. The process of claim 15 , wherein the solvent is acetonitrile or sulfolane.

17. 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 or3; and

n is 0, 1, 2, 3 or 4;

wherein the sum of m and n is between 1 and 4.

18. The compound of claim 17 , wherein m is 0 and n is 1, 2, 3 or 4.

19. The compound of claim 17 of the formula:

20. The compound of claim 17 of the formula:

wherein R is aryl substituted with from 0 to 5 substituents independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy; and

n is 1, 2 or3.

21. The compound of claim 17 , wherein n is 1 or 2.

22. The compound of claim 17 of the formula: