Processes for the preparation of pesticidal compounds

• US 10,100,033 B2
• Filed: 12/22/2017
• Issued: 10/16/2018
• Est. Priority Date: 12/29/2016
• Status: Active Grant

• Current Assignee: Corteva Agriscience LLC (Corteva, Inc.)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Li, Xiaoyong, Molitor, Erich, Roth, Gary Alan, Ober, Matthias S., Hanley, Patrick, Staton, Tina T.
• Primary Examiner(s): Aulakh, Charanjit
• Application Number:
  US15/853,096
• Publication Number:
  US 20180186766A1
• Time in Patent Office: 298 Days
• Field of Search: 5462754
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: C07D 401/04 directly linked by a ring-member-to-ring-member bond

Abstract

This application relates to efficient and economical synthetic chemical processes for the preparation of pesticidal thioethers and pesticidal sulfoxides. Further, the present application relates to certain novel compounds necessary for their synthesis. It would be advantageous to produce pesticidal thioethers and pesticidal sulfoxides efficiently and in high yield from commercially available starting materials.

Claims

1. A process for preparing a compound of the formula 1

2. The process of claim 1, wherein the copper catalyst in step (a) is copper (I) chloride (CuCl ), copper (II) chloride (CuCl₂), copper (I) bromide (CuBr) or copper (I) iodide (CuI ).

3. The process of claim 1, wherein the ligand in step (a) is selected from the group consisting of triethylenetetramine (TETA), N,N′

-bis(2-hydroxyethyl)ethylenediamine (BHEEA) and 8-hydroxyquinoline.

4. The process of claim 1, wherein the additive is used, and the additive is a dialkylamine, a trialkylamine, a benzonitrile or N,N,N′

N′

-tetramethylethylenedinamine (TMEDA).

5. The process of claim 1, wherein the ligand in step (a) is N,N′

-dimethylethane-1,2-diamine (DMEDA), and the additive is used and the additive is a dialkylamine, a trialkylamine, a benzonitrile or N,N,N′

N′

-tetramethylethylenedinamine (TMEDA).

6. The process of claim 1, wherein the base in step (a) is selected from the group consisting of sodium bicarbonate (NaHCO₃), sodium carbonate (Na₂CO₃), calcium carbonate (CaCO₃), cesium carbonate (Cs₂CO₃), lithium carbonate (Li₂CO₃), potassium carbonate (K₂CO₃), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH), calcium hydroxide (Ca(OH)₂), sodium diphosphate (Na₂HPO₄), potassium phosphate (K₃PO₄), sodium phosphate (Na₃PO₄), sodium methoxide (NaOCH₃) and sodium ethoxide (NaOCH₂CH₃).

7. The process of claim 1, wherein the solvent of step (a) is acetonitrile (CH₃CN), benzonitrile, dioxane, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), 2-methyl tetrahydrofuran, toluene, methanol (MeOH), or ethanol (EtOH).

8. The process of claim 1, wherein the 3-halopyridine is 3-bromopyridine.

9. The process of claim 1, wherein R³ is H.

10. The process of claim 1, wherein R¹ is Cl.

11. A process for preparing a compound of the formula

12. The process of claim 11, wherein the copper catalyst in step (a) is copper (I) chloride (CuCl), copper (II) chloride (CuCl₂), copper (I) bromide (CuBr) or copper (I) iodide (CuI).

13. The process of claim 11, wherein the ligand in step (a) is selected from the group consisting of triethylenetetramine (TETA), N,N′

-bis(2-hydroxyethyl)ethylenediamine (BHEEA) and 8-hydroxyquinoline.

14. The process of claim 11, wherein the additive is used in step (a), and the additive is a dialkylamine, a trialkylamine, a benzonitrile or N,N,N′

N′

-tetramethylethylenedinamine (TMEDA).

15. The process of claim 11, wherein the ligand in step (a) is N,N′

-dimethylethane-1,2-diamine (DMEDA), and the additive is used and the additive is a dialkylamine, a trialkylamine, a benzonitrile or N,N,N′

N′

-tetramethylethylenedinamine (TMEDA).

16. The process of claim 11, wherein the base in step (a) is selected from the group consisting of sodium bicarbonate (NaHCO₃), sodium carbonate (Na₂CO₃), calcium carbonate (CaCO₃), cesium carbonate (Cs₂CO₃), lithium carbonate (Li₂CO₃), potassium carbonate (K₂CO₃), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH), calcium hydroxide (Ca(OH)₂), sodium diphosphate (Na₂HPO₄), potassium phosphate (K₃PO₄), sodium phosphate (Na₃PO₄), sodium methoxide (NaOCH₃) and sodium ethoxide (NaOCH₂CH₃).

17. The process of claim 11, wherein the solvent of step (a) is acetonitrile (CH₃CN), benzonitrile, dioxane, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), 2-methyl tetrahydrofuran, dimethylsulfoxide (DMSO), toluene, methanol (MeOH), or ethanol (EtOH).

18. The process of claim 11, wherein the alkylating agent in step (b) is a C₁-C₆ alkyl group substituted with a leaving group selected from the group consisting of Br, I, a triflate (-OTf), a tosylate (-OTs) and a mesylate (-OMs).

19. The process of claim 11, wherein the base in step (b) is selected from the group consisting of sodium bicarbonate (NaHCO₃), sodium carbonate (NaHCO₃), calcium carbonate (CaCO₃), cesium carbonate (Cs₂CO₃), lithium carbonate (Li₂CO₃), potassium carbonate (K₂CO₃), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH), calcium hydroxide (Ca(OH)₂), sodium hydride (NaH), lithium hydride (LiH), potassium hydride (KH), sodium methoxide (NaOCH₃), sodium ethoxide (NaOCH₂CH₃) and sodium t-butoxide (NaOt-Bu).

20. The process of claim 11, wherein the inorganic acid in step (c) is selected from the group consisting of HF, HCl, HBr, H₂SO₄, H₃PO₄, H₃BO₄, HNO₃ and HClO₄.