Processes for the preparation of pesticidal compounds

Abstract

The present application provides processes for making pesticidal compounds and compounds useful both as pesticides and in the making of pesticidal compounds.

1 . A process comprising reacting 3-hydrazinopyridine dihydrochloride with glyoxylic acid to yield (E)-2-(2-(pyridin-3-yl)hydrazono)acetic acid (6a) 
       
         
           
           
               
               
           
         
       
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . A process comprising acylating 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d) with acetic anhydride, in the presence of a base, to yield N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl) acetamide (1c) 
       
         
           
           
               
               
           
         
       
     
     
         5 . A process comprising condensing 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d) with acetaldehyde and reducing to yield 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (1d) 
       
         
           
           
               
               
           
         
       
     
     
         6 . A process comprising 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) 
       
         
           
           
               
               
           
         
       
     
     
         7 . A process comprising oxidizing methyl 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carboxylate (6c) with diammonium cerium (IV) nitrate (CAN) to yield methyl 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylate (6d) 
       
         
           
           
               
               
           
         
       
     
     
         8 . A process comprising saponifying methyl 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylate (6d) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (6e) 
       
         
           
           
               
               
           
         
       
     
     
         9 . A process comprising hydrolyzing methyl 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylate (6d) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (6e) 
       
         
           
           
               
               
           
         
       
     
     
         10 . A process comprising decarboxylating 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (6e), in the presence of copper (II) oxide, to yield 3-(3-chloro-1H-pyrazol-1-yl) pyridine (5b) 
       
         
           
           
               
               
           
         
       
     
     
         11 .- 15 . (canceled) 
     
     
         16 . A compound 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carbonitrile (6b) 
       
         
           
           
               
               
           
         
       
     
     
         17 . A compound methyl 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carboxylate (6c) 
       
         
           
           
               
               
           
         
       
     
     
         18 . A compound methyl 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylate (6d) 
       
         
           
           
               
               
           
         
       
     
     
         19 . A compound 3-chloro-1-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (6e) 
       
         
           
           
               
               
           
         
       
     
     
         20 .- 23 . (canceled) 
     
     
         24 . A compound ethyl 5-oxo-2-(pyridin-3-yl)pyrazolidine-3-carboxylate (Compound 18.6) 
       
         
           
           
               
               
           
         
       
     
     
         25 . A compound ethyl 3-chloro-1-(pyridin-3-yl)-4,5-dihydro-1H-pyrazole-5-carboxylate (Compound 19.6)