Processes for the preparation of pesticidal compounds

• US 9,723,839 B2
• Filed: 07/29/2016
• Issued: 08/08/2017
• Est. Priority Date: 10/17/2013
• Status: Active Grant

• Current Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Yang, Qiang, Lorsbach, Beth, Whiteker, Gregory, DeAmicis, Carl, Muhuhi, Joseck M.
• Primary Examiner(s): Morris, Patricia L
• Application Number:
  US15/223,055
• Publication Number:
  US 20160345580A1
• Time in Patent Office: 375 Days
• Field of Search: 5462754
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: C07D 231/38 Nitrogen atoms nitro radicals C07D231/16
• CPC Class Codes: C07D 231/40 Acylated on said nitrogen atom
• CPC Class Codes: C07D 401/04 directly linked by a ring-member-to-ring-member bond

Abstract

The present application provides processes for making pesticidal compounds and compounds useful both as pesticides and in the making of pesticidal compounds.

Claims

1. A process comprising:

(a) halogenating and reducing 4-nitropyrazole

2. The process according to claim 1 wherein R¹ is C₁-C₄ haloalkyl.

3. The process according to claim 1 wherein R¹ is CH₂CH₂CF₃.

4. The process according to claim 1 wherein R¹ is C₁-C₄ alkyl-C₃-C₆ halocycloalkyl.

5. The process according to claim 1 wherein R¹ is CH₂(2,2-difluorocyclopropyl).

6. The process according to claim 1, wherein thioether (4d)

7. The process of claim 1, wherein the base in step (b) is a metal carbonate, a metal hydroxide or a metal phosphate.

8. The process of claim 1, wherein the base in step (b) is a NaHCO₃.

9. The process of claim 1, wherein step (b) is carried out in the presence of a mixture of tetrahydrofuran and water.

10. The process of claim 1, wherein the base in step (c) is a metal carbonate, a metal hydroxide, a metal phosphate or metal hydride.

11. The process of claim 1, wherein the base in step (c) is potassium hydroxide.

12. The process of claim 1, wherein step (c) is carried out in the presence of a polar solvent.

13. The process of claim 1, wherein step (c) is carried out in the presence of methanol.

14. The process of claim 1, wherein the halopyridine in step (d) is 3-bromopyridine.

15. The process of claim 1, wherein the copper salt in step (d) is copper(I) chloride (CuCl), copper(II) chloride (CuCl₂) or copper(I) iodide (CuI).

16. The process of claim 1, wherein the amine in step (d) is N,N′

-dimethylethane-1,2-diamine.

17. The process of claim 1, wherein the base in step (d) is potassium phosphate or potassium carbonate.

18. The process of claim 1, wherein R²—

X² in step (e) is selected from the group consisting of methyl iodide, ethyl bromide, ethyl iodide, propargyl chloride, propargyl bromide, ethyl mesylate, propargyl mesylate, ethyl tosylate, and propargyl tosylate.

19. The process of claim 1, wherein base in step (e) is a metal carbonate, a metal hydroxides, a metal phosphate or metal hydride.

20. The process of claim 1, wherein base in step (e) is cesium carbonate.