Processes for the preparation of pesticidal compounds

• US 9,102,654 B2
• Filed: 10/17/2014
• Issued: 08/11/2015
• 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, Roth, Gary, Niyaz, Noormohamed M., Nissen, Jeffrey, Ross, Ronald Jr., Whiteker, Gregory T., DeAmicis, Carl, Gray, Kaitlyn, Zhang, Yu
• Primary Examiner(s): Morris, Patricia L
• Application Number:
  US14/517,587
• Publication Number:
  US 20150112077A1
• Time in Patent Office: 298 Days
• Field of Search: 546/275.4
• US Class Current: 1/1
• CPC Class Codes: A01N 43/40 six-membered rings
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: C07D 213/77 Hydrazine radicals
• 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 comprising:

(a) reacting 3-hydrazinopyridine dihydrochloride with glyoxylic acid to yield (E)-2-(2-(pyridin-3-yl)hydrazono)acetic acid (6a)

2. A process according to claim 1 wherein 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b) is produced by the process comprising

(a) reacting (E)-2-(2-(pyridin-3-yl)hydrazono)acetic acid (6a) with methyl acrylate, in the presence of a chlorine source, a base, and a sub-stoichiometric amount of water, to yield methyl 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carboxylate (6c)

3. A The process according to claim 1 wherein 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b) is produced by the process comprising

(a) reacting (E)-2-(2-(pyridin-3-yl)hydrazono)acetic acid (6a) with methyl acrylate, in the presence of a chlorine source, an inorganic base, and a sub-stoichiometric amount of water, to yield methyl 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carboxylate (6c)

4. The process according to claim 1, wherein R¹ is CH₂CH₂CF₃ and the suitable activated carboxylic acid, carboxylic acid anhydride, or acid chloride of a carboxylic acid is prepared from

5. The process according to claim 1, wherein R¹ is CH₂CH₂CF₃ and the suitable activated carboxylic acid, carboxylic acid anhydride, or acid chloride of a carboxylic acid is prepared from

6. The process according to claim 1 wherein 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-amine (1d)

7. A The process according to claim 1 wherein 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b),