Fluoropicolinoyl fluorides and processes for their preparation

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.