Synergistic insecticidal compositions

Abstract

The present invention provides a synergistic insecticidal composition comprising as essential active ingredients a neuronal sodium channel antagonist in combination with one or more compounds selected from the group consisting of pyrethroids, pyrethroid-type compounds, recombinant nucleopolyhedroviruses capable of expressing an insect toxin, organophosphates, carbamates, formamidines, macrocyclic lactones, amidinohydrazones, GABA antagonists and acetylcholine receptor ligands. Also provided are methods for synergistic insect control and crop protection.

What is claimed is:  
     
         1 . A synergistic insecticidal composition comprising a synergistically effective amount of a neuronal sodium channel antagonist in combination with one or more compounds selected from Group A.  
     
     
         2 . The composition according to  claim 1  having a neuronal sodium channel antagonist compound of formula  
       
         
           
           
               
               
           
         
       
       wherein 
 A is CR 4 R 5  or NR 6 ;  
 W is O or S;  
 X, Y, Z, X′, Y′ and Z′ are each independently H; 
 halogen; OH; CN; NO 2 ; C 1 -C 6 alkyl optionally substituted with one or more halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 3 -C 6 cyclo alkyl, C 2 -C 6 alkenyloxy or sulfonyloxy groups;  
 C 1 -C 6 alkoxy optionally substituted with one or more halogen, C 1 -C 3 alkoxy or C 3 -C 6 cycloalkyl groups;  
 C 1 -C 6 alkoxycarbonyl, C 3 -C 6 cycloalkylcarbonyloxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy groups;  
 aminocarbonyloxy optionally substituted with one or more C 1 -C 3 alkyl groups;  
 C 1 -C 6 alkoxycarbonyloxy; C 1 -C 6 alkylsulfonyloxy; C 2 -C 6 alkenyl; or NR 12 R 13 ;  
 
 m, p and q are each independently an integer of 1, 2, 3, 4, or 5;  
 n is an integer of 0, 1 or 2;  
 r is an integer of 1 or 2;  
 t is an integer of 1, 2, 3 or 4;  
 R, R 1 , R 2 , R 3 , R 4  and R 5  are each independently H or C 1 -C 4 alkyl;  
 R 6  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxy carbonyl, C 1 -C 6 alkylthio, or C 1 -C 6 haloalkylthio;  
 R 7  and R 8  are each independently H; halogen;  
 C 1 -C 6 alkyl; C 1 -C 6 alkylcarbonyloxy; or phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 halo alkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy groups;  
 R 9  and R 10  are each independently H, or C 1 -C 4 alkyl;  
 R 11  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, or C 1 -C 6 halo alkoxycarbonyl;  
 R 12  and R 13  are each independently H or C 1 -C 6 alkyl;  
 G is H; C 1 -C 6 alkyl optionally substituted with one or more halogen, C 1 -C 4 alkoxy, C 1 -C 6 haloalkoxy, CN, NO 2 S(O) u R 14 , COR 15 , CO 2 R 16 , phenyl or C 3 -C 6 cycloalkyl groups; 
 C 1 -C 6 alkoxy; C 1 -C 6 haloalkoxy; CN; NO 2 ; S(O) u R 17 ;  
 COR 18 ; CO 2 R 19 ; phenyl optionally substituted with one or more halogen, CN, C 1 -C 3 haloalkyl, or C 1 -C 3 haloalkoxy groups;  
 C 3 -C 6 cycloalkyl; or phenylthio;  
 
 Q is phenyl optionally substituted with one or more halogen, CN, SCN, NO 2 , S(O) u R 20 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, or NR 21 , R 22  groups;  
 u is an integer of 0, 1 or 2;  
 R 14 , R 15 , R 16 , R 18 , R 19 , R 21  and R 22  are each independently H or C 1 -C 6 alkyl;  
 R 17  and R 20  are each independently C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;  
 R 33  is CO 2 R 34 ;  
 R 34  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl or halophenyl; and the dotted line configuration C N represents a double bond or a single bond; or a stereoisomer thereof.  
 
     
     
         3 . The composition according to  claim 1  having a neuronal sodium channel antagonist compound of formula  
       
         
           
           
               
               
           
         
       
       wherein 
 W is O or S;  
 X″ and Y″ are each independently H; halogen; CN;  
 SCN; C 1 -C 6 alkyl optionally substituted with one or more halogen, NO 2 , CN, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, halophenyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, or C 1 -C 4 alkoxycarbonyl groups; 
 C 2 -C 4 alkenyl; C 2 -C 4 haloalkenyl; C 2 -C 4 alkynyl; C 2 -C 4 haloalkynyl; C 3 -C 6 cycloalkyl; C 3 -C 6 halocycloalkyl; phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl groups;  
 C 1 -C 4 alkylcarbonyl; C 1 -C 4 haloalkylcarbonyl; or NR 28 R 29 ;  
 
 m is an integer of 1, 2, 3, 4 or 5;  
 G′ is phenyl optionally substituted with one or more groups which may be the same or different selected from X″;  
 a 5-membered heteroaromatic ring containing one or two heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said 5-membered heteroaromatic ring being attached via carbon and being optionally substituted with one or more groups which may be the same or different selected from X″; or 
 a 6-membered heteroaromatic ring containing one or two heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said 6-membered heteroaromatic ring being attached via carbon and being optionally substituted with one or more groups which may be the same or different selected from X′;  
 
 Q′ is H; C 1 -C 6 alkyl optionally substituted with one or more halogen, CN, C 1 -C 3 alkoxy, C 6 -C 6 alkoxycarbonyl, or phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylsulfonyl or C 1 -C 4 alkylsulfinyl groups; 
 C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; or phenyl optionally substituted with one to three groups, which may be the same or different, selected from X″;  
 
 R 23 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are each independently H or C 1 -C 4 alkyl; and the dotted line configuration C N represents a double bond or a single bond; or a stereoisomer thereof.  
 
     
     
         4 . The composition according to  claim 2  wherein the neuronal sodium channel antagonist is a compound of formula I or III.  
     
     
         5 . The composition according to  claim 4  wherein the dotted line configuration C N represents a double bond.  
     
     
         6 . The composition according to  claim 5  wherein the compound of formula III is in the S-form.  
     
     
         7 . The composition according to  claim 6  wherein W is O; X is trifluoromethoxy and is in the 4-position; Y is trifluoromethyl and is in the 3-position; Z is CN and is in the 4-position; A is CH 2 ; n is 0; m, p and q are each 1; R and R 1  are each H; Z′ is Cl; R 33  and G are each CO 2 CH 3 ; and Q is p-(trifluoromethoxy)phenyl.  
     
     
         8 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are cypermethrin, cyhalomethrin, cyfluthrin, permethrin, ethofenprox or silafluofen.  
     
     
         9 . The composition according to  claim 7  wherein the one or more compounds selected from Group A is a recombinant nucleopolyhedrovirus capable of expressing insect toxin.  
     
     
         10 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are profenofos, acephate, sulprofos, malathion, diazinon, methyl parathion, or terbufos.  
     
     
         11 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are methonyl, thiodicarb, or fenothiocarb.  
     
     
         12 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are amitraz, chlordimeform, or chlorfenamidine.  
     
     
         13 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are avermectin, emamectin, milbemectin, nemadectin, or moxidectin.  
     
     
         14 . The composition according to  claim 7  wherein the one or more compounds selected from Group A is hydramethylnon.  
     
     
         15 . The composition according to  claim 7  wherein the one or more compounds selected from Group A are fipronil, endosulfon, imidacloprid, acetamiprid, nitenpyram or thiamethoxam.  
     
     
         16 . A method for synergistic insect control which comprises contacting said insect with a synergistically effective amount of a neuronal sodium channel antagonist in combination with one or more compounds selected from Group A.  
     
     
         17 . The method according to  claim 16  having a neuronal sodium channel antagonist compound of formula  
       
         
           
           
               
               
           
         
       
       wherein 
 A is CR 4 R 5  or NR 6 ;  
 W is O or S; X, Y, Z, X′, Y′ and Z′ are each independently H; 
 halogen; OH; CN; NO 2 ; C 1 -C 6 alkyl optionally substituted with one or more halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyloxy or sulfonyloxy groups;  
 C 1 -C 6 alkoxy optionally substituted with one or more halogen, C 1 -C 3 alkoxy or C 3 -C 6 cycloalkyl groups;  
 C 1  -C 6 alkoxycarbonyl, C 3 -C 6 cycloalkyl carbonyloxy, phenyl optionally substituted with one or more halogen, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy groups;  
 aminocarbonyloxy optionally substituted with one or more C 1 -C 3 alkyl groups;  
 C 1 -C 6alkoxycarbonyl,oxy; C 1 -C 6 alkylsulfonyloxy; C 2  -C 6 alkenyl; or NR 12 R 13 ;  
 
 m, p and q are each independently an integer of 1, 2, 3, 4, or 5;  
 n is an integer of 0, 1 or 2;  
 r is an integer of 1 or 2;  
 t is an integer of 1, 2, 3 or 4;  
 R, R 1 , R 2 , R 3 , R 4  and R 5  are each independently H or C 1 -C 4 alkyl;  
 R 6  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, or C 1 -C 6 haloalkylthio;  
 R 7  and R 8  are each independently H; halogen; C 1 -C 6 alkyl; C 1 -C 6 alkylcarbonyloxy; or phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy groups;  
 R 9  and R 10  are each independently H, or C 1 -C 4 alkyl;  
 R 11  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, or C 1 -C 6 halo alkoxycarbonyl;  
 R 12  and R 13  are each independently H or C 1 -C 6 alkyl;  
 G is H; C 1 -C 6 alkyl optionally substituted with one or more halogen, C 1 -C 4 alkoxy, C 1 -C 6 haloalkoxy, CN, NO 2 S(O) u R 14 , COR 15 , CO 2 R 16 , phenyl or C 3 -C 6 cycloalkyl groups; 
 C 1 -C 6 alkoxy; C 1 -C 6 haloalkoxy; CN; NO 2 ; S(O) u R 17 ;  
 COR 18 ; CO 2 R 19 ; phenyl optionally substituted with one or more halogen, CN, C 1 -C 3 haloalkyl, or C 1 -C 3 haloalkoxy groups;  
 C 3 -C 6 cycloalkyl; or phenylthio;  
 
 Q is phenyl optionally substituted with one or more halogen, CN, SCN, NO 2 , S(O) u R 20 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, or NR 21 R 22  groups;  
 u is an integer of 0, 1 or 2;  
 R 14 , R 15 , R 16 , R 18 , R 19 , R 21  and R 22  are each independently H or C 1 -C 6 alkyl;  
 R 17  and R 20  are each independently C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;  
 R 33  is CO 2 R 34 ;  
 R 34  is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, phenyl or halophenyl; and the dotted line configuration C N represents a double bond or a single bond; or  
 a stereoisomer thereof.  
 
     
     
         18 . The method according to  claim 16  having a neuronal sodium channel antagonist compound of formula  
       
         
           
           
               
               
           
         
       
       wherein 
 W is O or S;  
 X″ and Y″ are each independently H; halogen; CN; SCN; C 1 -C 6 alkyl optionally substituted with one or more halogen, NO 2 , CN, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenyl, halophenyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, or C 1 -C 4 alkoxycarbonyl groups;  
 C 2 -C 4 alkenyl; C 2 -C 4 haloalkenyl; C 2 -C 4 alkynyl; C 2 -C 4 haloalkynyl; C 3 -C 6 cycloalkyl; C 3 -C 6 halocycloalkyl; phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl groups; 
 C 1 -C 4 alkylcarbonyl; C 1 -C 4 haloalkylcarbonyl; or NR 28 R 29 ;  
 
 m is an integer of 1, 2, 3, 4 or 5;  
 G′ is phenyl optionally substituted with one or more groups which may be the same or different selected from X″; 
 a 5-membered heteroaromatic ring containing one or two heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said 5-membered heteroaromatic ring being attached via carbon and being optionally substituted with one or more groups which may be the same or different selected from X″; or  
 a 6-membered heteroaromatic ring containing one or two heteroatoms selected from 0 or 1 oxygen, 0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said 6-membered heteroaromatic ring being attached via carbon and being optionally substituted with one or more groups which may be the same or different selected from X″;  
 
 Q′ is H; C 1 -C 6 alkyl optionally substituted with one or more halogen, CN, C 1 -C 3 alkoxy, C 1 -C 6 alkoxycarbonyl, or phenyl optionally substituted with one or more halogen, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylsulfonyl or C 1 -C 4 alkylsulfinyl groups; 
 C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; or phenyl optionally substituted with one to three groups, which may be the same or different, selected from X″;  
 
 R 23 , R 24 , R 25 , R 26 , R 27 , R 28  and R 29  are each independently H or C1-C4alkyl; and the dotted line configuration C N represents a double bond or a single bond; or a stereoisomer thereof.  
 
     
     
         19 . The method according to  claim 17  wherein the neuronal sodium channel antagonist is a compound of formula I or III.  
     
     
         20 . The method according to  claim 19  wherein the dotted line configuration C N represents a double bond.  
     
     
         21 . The method according to  claim 20  wherein the formula III compound is in the S-form.  
     
     
         22 . The method according to  claim 21  wherein W is 0; X is trifluoromethoxy and is in the 4-position; Y is trifluoromethyl and is in the 3-position; Z is CN and is in the 4-position; A is CH 2 ; n is 0; m, p and q are each 1; R and R 1  are each H; Z′ is Cl; R 33  and G are each CO 2 CH 3 ; and Q is p-(trifluoromethoxy)phenyl.  
     
     
         23 . The method according to  claim 19  wherein the one or more compounds selected from Group A are cypermethrin, cyhalomethrin, cyfluthrin, permethrin, ethofenprox or silafluofen.  
     
     
         24 . The method according to  claim 19  wherein the one or more compounds selected from Group A are profenofos, acephate, sulprofos, malathion, diazinon, methyl parathion, or terbufos.  
     
     
         25 . The method according to  claim 19  wherein the one or more compounds selected from Group A are methonyl, thiodicarb, or fenothiocarb.  
     
     
         26 . The method according to  claim 19  wherein the one or more compounds selected from Group A are amitraz, chlordimeform, or chlorfenamidine.  
     
     
         27 . The method according to  claim 19  wherein the one or more compounds selected from Group A are avermectin, emamectin, milbemectin, nemadectin, or moxidectin.  
     
     
         28 . The method according to  claim 19  wherein the one or more compounds selected from Group A is hydramethylnon.  
     
     
         29 . The method according to  claim 19  wherein the one or more compounds selected from Group A are fipronil, endosulfon, imidacloprid, acetamiprid, nitenpyram or thiamethoxam.  
     
     
         30 . The method according to  claim 22  wherein the one or more compounds selected from Group A is hydramethylnon.  
     
     
         31 . The method according to  claim 19  wherein the insect is selected from the group consisting of Blattaria, Isoptera, Diptera, and Hymenoptera.  
     
     
         32 . The method according to  claim 31  wherein the insects are lepidoptera or coleoptera.  
     
     
         33 . A method for protecting a plant from infestation and attack by insects which comprises applying to the foliage or stem of said plant a synergistically effective amount of a composition according to  claim 1.