PROCESSES TO PRODUCE CERTAIN 2-(PYRIDINE-3-YL)THIAZOLES

• US 20130324737A1
• Filed: 05/30/2013
• Published: 12/05/2013
• Est. Priority Date: 06/04/2012
• Status: Active Grant

• Current Assignee: Corteva Agriscience LLC (Corteva, Inc.)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Ross, Ronald Jr., DeAmicis, Carl, Zhu, Yuanming, Niyaz, Noormohamed M., Arndt, Kim E., West, Scott P., Roth, Gary
• Granted Patent: US 9,108,952 B2
• Time in Patent Office: Days
• US Class Current: 546/270.7
• CPC Class Codes: C07D 213/83 Thioacids; Thioesters; Thioamides; Thioimides
• CPC Class Codes: C07D 417/04 directly linked by a ring-member-to-ring-member bond

Abstract

The invention disclosed in this document is related to the field of processes to produce certain 2-(pyridine-3-yl)thiazoles as intermediates for the synthesis of pesticidal thiazole amides.

Claims

1. A process comprising

2. A process according to claim 1 wherein each R¹ is independently selected from H, F, and Cl.

3. A process according to claim 1 wherein each R¹ is H.

4. A process according to claim 1 wherein R³ is selected from H, (C₁-C₆)alkyl, (C₁-C₆)haloalkyl, and (C₆-C₂₀)aryl.

5. A process according to claim 1 wherein R³ is selected from H, CF₃, CH₂F, CHF₂, CH₃, CH₂CH₃, CH(CH₃)₂, and phenyl.

6. A process according to claim 1 wherein R³ is selected from H and CH₃.

7. A process according to claim 1 wherein R⁴ is (C₁-C₆)alkyl(C₃-C₁₀)cyclohaloalkyl.

8. A process according to claim 1 wherein R⁴ is selected from H, (C₁-C₆)alkyl, (C₁-C₆)alkyl(C₆-C₂₀)aryl, (C₁-C₆)haloalkyl, (C₁-C₆)alkyl(C₃-C₁₀)cycloalkyl, (C₃-C₁₀)cycloalkyl-β

-(C₁-C₆)alkyl, and (C₃-C₁₀)cyclohaloalkyl.

9. A process according to claim 1 wherein R⁴ is selected from H, CH₃, CH₂CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, cyclopropyl, (C₆-C₂₀)aryl, CH₂-phenyl, CH₂-phenyl-OCH₃, CH₂OCH₂-phenyl, CH₂CH₂CH₃, CH₂CH₂F, CH₂CH₂OCH₃, CH₂cyclopropyl, and cyclopropyl-O—

CH₂CH₃.

10. A process according to claim 1 wherein R⁴ is selected from H, CH₃, CH₂CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂CH₂CH₃, cyclopropyl, CH₂cyclopropyl, and CH₂CH═

CH₂, CH₂C≡

CH.

11. A process according to claim 1 wherein step a is conducted in formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water, or a mixture thereof.

12. A process according to claim 1 wherein step a is conducted in methanol.

13. A process according to claim 1 wherein step b compound (III) is cyclized using a dehydrating agent selected from POCl₃, H₂SO₄, SOCl₂, P₂O₅, polyphosphoric acid, p-toluene sulfonic acid, trifluoroacetic anhydride, and a mixture thereof.

14. A process according to claim 1 wherein step b is conducted at a temperature from about 60°

C. to about 120°

C.

15. A process according to claim 1 wherein step b is conducted in acetonitrile.

16. A process according to claim 1, wherein R³ of compound (IV) is H, said process further comprising halogenating said R³ to F, Cl, Br, or I.

17. A process according to claim 16 wherein said halogenating is conducted in a solvent selected from dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, and dimethyl sulfoxide.

18. A process according to claim 17 wherein said solvent is dichloromethane.

19. A process according to any one of claims 16, 17, and 18 wherein said halogenating is conducted at a temperature from about 0°

C. to about ambient.

20. A process according to any one of claims 16, 17, and 18, wherein R³ is Cl.

21. A compound having the following structure