Processes for the preparation of pesticidal compounds

• US 9,029,554 B1
• Filed: 10/17/2014
• Issued: 05/12/2015
• 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., Zhang, Yu, Roth, Gary, Gray, Kaitlyn
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US14/517,333
• Publication Number:
  US 20150112073A1
• Time in Patent Office: 207 Days
• Field of Search: None
• US Class Current: 546/275.4
• 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 the preparation of 3-chloro-N-ethyl-1H-pyrazol-4-amine (7a) useful in the preparation of pesticidal thioethers (7b), (1e) and pesticidal sulfoxides (1f),

2. The process according to claim 1, wherein the reducing agent is a hydride source.

3. The process according to claim 1, wherein the reducing agent is sodium borohydride.

4. The process according to claim 1, wherein the acid is a Lewis acid.

5. The process according to claim 1, wherein the acid is borontrifluoride etherate.

6. A process for the preparation of thioether (7b) useful as pesticides and in the preparation of pesticidal sulfoxides (1f),

7. The process according to claim 6, wherein R¹ is C₁-C₄ haloalkyl.

8. The process according to claim 6, wherein R¹ is CH₂CH₂CF₃.

9. The process according to claim 6, wherein R¹ is C₁-C₄ alkyl-C₃-C₆ halocycloalkyl.

10. The process according to claim 6, wherein R¹ is CH₂(2,2-difluorocyclopropyl).

11. A compound 3-chloro-N-ethyl-1H-pyrazol-4-amine (7a)

12. A compound N-(3-chloro-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound 4.7):

13. A process comprising:

(a) halogenating and reducing 4-nitropyrazole

14. A process according to claim 13 wherein R¹ is C₁-C₄ haloalkyl.

15. A process according to claim 13 wherein R¹ is CH₂CH₂CF₃.

16. A process according to claim 13 wherein R¹ is C₁-C₄ alkyl-C₃-C₆ halocycloalkyl.

17. A process according to claim 13 wherein R¹ is CH₂(2,2-difluorocyclopropyl).

18. A process according to claim 6 or 13, in which the acyl chloride having the formula C1C(O)CH₂CH₂SR¹ wherein R¹ is CH₂CH₂CF₃ is prepared by the chlorination of

19. A process according to claim 6 or 13, in which the acyl chloride having the formula C1C(O)CH₂CH₂SR¹ wherein R¹ is CH₂CH₂CF₃ is prepared by the chlorination of