Processes for the preparation of pesticidal compounds

• US 9,260,396 B2
• Filed: 05/21/2015
• Issued: 02/16/2016
• 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, Whiteker, Greg, DeAmicis, Carl, Gray, Kaitlyn, Zhang, Yu, Muhuhi, Joseck M.
• Primary Examiner(s): Morris, Patricia L
• Application Number:
  US14/718,621
• Publication Number:
  US 20150252004A1
• Time in Patent Office: 271 Days
• Field of Search: 546/275.4
• US Class Current: 1/1
• 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
• CPC Class Codes: C07D 401/14 containing three or more hetero rings

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. A The process according to claim 1, wherein R¹ is CH₂CH₂CF₃, and the activated carbonyl thioether X¹C(═

O)C₁-C₄-alkyl-S—

R¹, wherein X¹ is selected from Cl, OC(═

O)C₁-C₄ alkyl, or a group that forms an activated carboxylic acid, is prepared from

3. A The process according to claim 1, wherein R¹ is CH₂CH₂CF₃ and the activated carbonyl thioether X¹C(═

O)C₁-C₄-alkyl-S—

R¹ wherein X¹ is selected from Cl, OC(═

O)C₁-C₄ alkyl, or a group that forms an activated carboxylic acid is prepared from

4. A The process according to claim 1, wherein thioether (3c)

5. The process of claim 1, wherein the halogenating and reducing is conducted in a polar protic solvent.

6. The process of claim 5, wherein the polar protic solvent is methanol or ethanol.

7. The process of claim 1, wherein the triethylsilane is used in an amount of about 2.5 equivalents to about 3.5 equivalents.

8. The process of claim 1, wherein R¹ is CH₂CH₂CF₃ or CH₂(2,2-difluorocyclopropyl).

9. The process of claim 1, wherein X¹ is Cl or OC(═

O)C₁-C₄ alkyl.

10. The process of claim 1, wherein step (b) is carried out in the presence of a base.

11. The process of claim 10, wherein the base is sodium bicarbonate.

12. The process of claim 1, wherein step (b) is carried out at a temperature of from about −

10°

C. to about 40°

C.

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

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

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

-dimethylethane-1,2-diamine.

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

17. The process of claim 16, wherein the polar solvent is acetonitrile, dioxane, or N,N-dimethylformamide.

18. The process of claim 1, wherein step (c) is carried out at a temperature of from about 50°

C. and about 110°

C.

19. The process of claim 1, wherein X² is halo, mesylate, or tosylate.

20. The process of claim 1, wherein the base in step (d) is selected from the group consisting of a metal carbonate, a metal hydroxide, a metal phosphate, and a metal hydride.