Insecticidal pyrimidinyl aryl hyrdrazones

1. A process for the preparation of a compound of formula (I)

wherein

X 1 and Y 1 independently represent H, halogen, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 1 -C 6 halothioalkyl, or C 1 -C 6 haloalkyl substituted with a substituent selected from the group consisting of hydroxy and C 1 -C 6 acyloxy, with the proviso that at least one of X 1 or Y 1 is not H;

X 2 and Y 2 independently represent H, halogen, CN, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 1 -C 6 halothioalkyl, 1-pyrrolidinyl, 1-piperidinyl, or C 1 -C 6 haloalkyl substituted with a substituent selected from the group consisting of hydroxy and C 1 -C 6 acyloxy, with the proviso that at least one of X 2 or Y 2 is not H;

Z represents CH or N;

L represents H, halogen or C 1 -C 3 -haloalkyl;

Q represents H, halogen, OR 3 , C 1 -C 3 -haloalkyl, SR 3 or NR 4 R 5 ;

R 1 and R 2 independently represents H or CH 3 ;

R 3 represents C 1 -C 4 alkyl which may be unsubstituted or substituted with from one to the maximum number of chloro or fluoro substituents;

R 4 represents H or C 1 -C 4 alkyl;

R 5 represents C 1 -C 4 alkyl which may be unsubstituted or substituted with from one to the maximum number of chloro or fluoro substituents, or with a substituent selected from the group consisting of C 1 -C 4 alkoxy, C 1 -C 4 alkylamino and a pyridin-3-yl substituted in the 6-position of the pyridine ring with halogen, C 1 -C 4 alkoxy or C 1 -C 4 halo alkyl or;

which comprises:

(a) contacting a 2,4,6-trichloropyrimidine (A) or a 2,4,6-trifluoropyrimidine (B)

wherein L is as previously defined

with an aryl amine of formula (C)

wherein X 1 , Y 1 and Z are as previously defined

in a polar aprotic solvent in the presence of base to provide 2-arylamino-4,6-dichloropyrimidines of formula (D) and 4-arylamino-2,6-dichloropyrimidines of formula (E) or 2-arylamino-4,6-difluoropyrimidines of formula (F) and 4-arylamino-2,6-difluoropyrimidines of formula (G), respectively,

wherein L, X 1 , Y 1

 and Z are as previously defined;

(b) contacting 2-arylamino-4,6-dichloropyrimidines of formula (D) or 2-arylamino-4,6-diflloropyrimidines of formula (F) with a nucleophile Q in a polar aprotic solvent in the presence of base to provide 2-arylamino-6-chloropyrimidines of formula (H) or 2-arylamino-6-fluoropyrimidines of formula (J), respectively,

and

wherein X 1 , Y 1 , Q, L and Z are as previously defined

or contacting 4-arylamino-2,6-dihalopyrimidine of formula (E) or (G) with a nucleophile Q in a polar aprotic solvent in the presence of base to provide 4-arylamino-6-halopyrimidines of formula (K) and 4-arylamino-2-halopyrimidines of formula (L)

wherein X 1 , Y 1 , Q, L and Z are as previously defined;

(c) contacting 2-arylamino-6-chlorophyrimidines of formula (H) or 2arylamino-6-fluoropyrimidines of formula (J) with a hydrazine of the formula R 2 NHNH 2 in a polar aprotic solvent to provide the compounds of formula (M)

wherein X 1 , Y 1 , Q, L, R 2 , and Z are as previously defined,

or contacting 4-arylamino-6-halopyrimidines of formula (K) with a hydrazine of the formula RNHNH 2 in a polar aprotic solvent to provide the compounds of formula (N)

wherein X 1 , Y 1 , Q, L, R 2 , and Z are as previously defined,

or contacting 4-arylamino-2-halopyrimidines of formula (L) with a hydrazine of the formula RNHNH 2 in a polar aprotic solvent to provide the compounds of formula (O)

wherein X 1 , Y 1 , Q, L, R 2 , and Z are as previously defined; and

(d) contacting the compounds of formula (N), (M) and (O), individually, with an aryl aldehyde of the formula (VIII)

wherein X 2 , Y 2 and Z are as previously defined

in a polar aprotic solvent to provide the compound of formula (I).