Processes for the preparation of pesticidal compounds

• US 9,550,751 B2
• Filed: 08/03/2015
• Issued: 01/24/2017
• Est. Priority Date: 10/17/2013
• Status: Expired due to Fees

• Current Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Yang, Qiang, Lorsbach, Beth, Ross, Ronald Jr., Gray, Kaitlyn, Zhang, Yu, Roth, Gary
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US14/816,600
• Publication Number:
  US 20150336929A1
• Time in Patent Office: 540 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: C07C 319/18 by addition of thiols to unsaturated compounds
• CPC Class Codes: C07C 319/20 by reactions not involving the formation of sulfide groups
• CPC Class Codes: C07C 321/14 of an acyclic saturated carbon skeleton
• 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 for preparing thioether (1e)

2. The process of claim 1, wherein the halopyridine is 3-iodopyridine or 3-bromopyridine.

3. The process of claim 1, wherein the copper salt is selected from the group consisting of copper(I) chloride, copper(II) chloride, and copper(I) iodide.

4. The process of claim 3, wherein the copper salt is copper(I) chloride.

5. The process of claim 1, wherein the base is potassium carbonate.

6. The process of claim 1, wherein the amine is N,N′

-dimethylethane-1,2-diamine.

7. The process of claim 1, wherein the step of reacting is carried out in a polar solvent.

8. The process of claim 7, wherein the polar solvent is selected from the group consisting of acetonitrile (MeCN), dioxane, and N,N-dimethylformamide.

9. The process of claim 1, wherein the step of reacting is carried out at a temperature between about 50°

C. and about 110°

C.

10. The process of claim 1, wherein R¹ is C₁-C₄ haloalkyl.

11. The process of claim 10, wherein R¹ is —

CH₂CH₂CF₃.

12. The process of claim 1, wherein R¹ is C₁-C₄ alkyl-C₃-C₆ halocycloalkyl.

13. The process of claim 12, wherein R¹ is —

CH₂(2,2-difluorocyclopropyl).

14. A process for preparing pesticidal sulfoxide (1f)

15. The process of claim 14, wherein R¹ is C₁-C₄ haloalkyl.

16. The process of claim 15, wherein R¹ is —

CH₂CH₂CF₃.

17. The process of claim 14, wherein R¹ is C₁-C₄ alkyl-C₃-C₆ halocycloalkyl.

18. The process of claim 17, wherein R¹ is —

CH₂(2,2-difluorocyclopropyl).

19. A process for the preparation of thioether (7b)

20. The process of claim 19, wherein the step of preparing is carried out in the presence of 2,2-dimethoxy-2-phenylacetophenone initiator and long wavelength UV light, in an inert organic solvent.

21. The process of claim 20, wherein the amount of 2,2-dimethoxy-2-phenylacetophenone initiator is from about 1 to about 10 mole percent.

22. The process of claim 21, wherein the amount of 2,2-dimethoxy-2-phenylacetophenone initiator is about 5 mole percent.

23. The process of claim 20, wherein the inert organic solvent is toluene.

24. The process of claim 19, wherein the step of preparing is carried out in the presence of 2,2′

-azobis(4-methoxy-2,4-dimethyl) valeronitrile (V-70) initiator at temperatures of about 0°

C. to about 40°

C. in an inert organic solvent.

25. The process of claim 24, wherein the amount of 2,2′

-azobis(4-methoxy-2,4-dimethyl) valeronitrile (V-70) initiator is from about 1 to about 10 mole percent.

26. The process of claim 25, wherein the amount of 2,2′

-azobis(4-methoxy-2,4-dimethyl) valeronitrile (V-70) initiator is about 5 mole percent.

27. The process of claim 24, wherein the inert organic solvent is selected from the group consisting toluene, ethyl acetate and methanol.

28. The process of claim 19, wherein in the step of acylating, the base is sodium bicarbonate.

29. The process of claim 19, wherein the step of acylating is conducted in a mixture of tetrahydrofuran (THF) and water.