Fluoropicolinoyl fluorides and processes for their preparation

• US 9,376,388 B2
• Filed: 03/24/2015
• Issued: 06/28/2016
• Est. Priority Date: 07/24/2012
• Status: Active Grant

• Current Assignee: Corteva Agriscience LLC (Corteva, Inc.)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Renga, James M., Cheng, Yang, Muhuhi, Joseck M., Podhorez, David E., Roth, Gary A., West, Scott P., Whiteker, Gregory T., Zhu, Yuanming
• Primary Examiner(s): NORTHINGTON DAVI, ZINNA
• Application Number:
  US14/667,109
• Publication Number:
  US 20150191428A1
• Time in Patent Office: 462 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07D 213/55 Acids; Esters
• CPC Class Codes: C07D 213/78 Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 213/803 Processes of preparation
• CPC Class Codes: C07D 213/807 by oxidation of pyridines or condensed pyridines

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.

Claims

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

2. The process of claim 1 wherein R¹ 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, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ 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.