Isoxazoline-substituted benzamides and analogues as insecticides

1. A compound of formula (I)

wherein

A 1 , A 2 , A 3 and A 4 are independently of one another C—H, C—R 5 , or nitrogen;

R 1 is hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkylcarbonyl-, C 1 -C 8 alkoxy, C 1 -C 8 alkoxy-C 1 -C 8 alkyl or C 1 -C 8 alkoxycarbonyl-;

R 2 is C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by one to three R 6a , C 1 -C 8 haloalkyl, C 1 -C 8 haloalkyl substituted by one to three R 6a , C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by one to three R 6b , C 3 -C 8 cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkenyl substituted by one to three R 6a , C 2 -C 8 haloalkenyl, C 2 -C 8 haloalkenyl substituted by one to three R 6a , C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, phenyl, phenyl substituted by one to three R 7 , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 , 5-6 membered heteroaryl-C 1 -C 4 alkyl, 5-6 membered heteroaryl-C 1 -C 4 alkyl wherein the heteroaryl moiety is substituted by one to three R 7 , —N(R 8 )(R 9 ), halogen or —OR 10 ;

R 3 is C 1 -C 8 haloalkyl;

R 4 is aryl, aryl substituted by one to three R 7 , heteroaryl or heteroaryl substituted by one to three R 7 ;

R 5 is independently halogen, cyano, nitro, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, or C 1 -C 8 alkoxycarbonyl-, or two R 5 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge;

R 6a is independently cyano, nitro, amino, C 1 -C 8 alkylamino, N,N—C 1 -C 8 dialkylamino, hydroxy, C 1 -C 8 alkoxy, or C 1 -C 8 haloalkoxy;

R 6b is independently halogen, cyano, nitro, oxo, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, amino, C 1 -C 8 alkylamino, N,N—C 1 -C 8 dialkylamino, hydroxyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, phenyl, phenyl substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 ;

R 7 is independently halogen, cyano, nitro, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy;

R 8 and R 9 are independently hydrogen, cyano, cyano-C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by one to three R 6a , C 2 -C 8 alkenyl, C 2 -C 8 alkenyl substituted by one to three R 6a , C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, C 1 -C 8 haloalkoxy substituted by one to three R 6a , C 1 -C 8 alkoxy substituted by one to three R 6a , C 1 -C 8 haloalkyl, C 1 -C 8 haloalkyl substituted by one to three R 6a , C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by one to three R 6b , C 3 -C 8 cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkenyl substituted by one to three R 6a , C 2 -C 8 haloalkenyl, C 2 -C 8 haloalkenyl substituted by one to three R 6a , C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, phenyl, phenyl substituted by one to three R 7 , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 , 5-6 membered heteroaryl-C 1 -C 4 alkyl, 5-6 membered heteroaryl-C 1 -C 4 alkyl wherein the heteroaryl moiety is substituted by one to three R 7 , —S(O)R 10 , —S(O) 2 R 10 , COR 10 , COOR 10 , or R 8 and R 9 together with the nitrogen atom can be linked through a C 3 -C 8 alkylene chain, a C 3 -C 8 alkylene chain substituted by one to three R 6b or a C 3 -C 8 alkylene chain, where one carbon atom is replaced by O, S, S(O) or SO 2 ;

R 10 is hydrogen, cyano-C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by one to three R 6a , C 1 -C 8 haloalkyl, C 1 -C 8 haloalkyl substituted by one to three R 6a , C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by one to three R 6b , C 3 -C 8 cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl-C 1 -C 8 alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO 2 , C 3 -C 8 cycloalkyl-C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkenyl substituted by one to three R 6a , C 2 -C 8 haloalkenyl, C 2 -C 8 haloalkenyl substituted by one to three R 6a , C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, phenyl, phenyl substituted by one to three R 7 , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 , 5-6 membered heteroaryl-C 1 -C 4 alkyl or 5-6 membered heteroaryl-C 1 -C 4 alkyl wherein the heteroaryl moiety is substituted by one to three R 7 ;

n is 1 or 2;

or a tautomer, isomer, enantiomer, salt or N-oxide thereof.

2. The compound according to claim 1 , wherein A 1 is CR 5 and A 2 , A 3 and A 4 are each CH, wherein R 5 is as defined in claim 1 .

3. The compound according to either claim 1 , wherein R 1 is hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkylcarbonyl- or C 1 -C 8 alkoxycarbonyl-.

4. The compound according claim 1 , wherein R 2 is C 1 -C 8 alkyl or C 1 -C 8 alkyl substituted by one to three R 6a , C 1 -C 8 haloalkyl or C 1 -C 8 haloalkyl substituted by one to three R 6a , C 3 -C 8 cycloalkyl or C 3 -C 8 cycloalkyl substituted by one to three R 6b , phenyl, phenyl substituted by one to three R 7 , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 , halogen or —N(R 8 )(R 9 ) wherein R 8 , R 9 , R 6a and R 6b are as defined in claim 1 .

5. The compound according to claim 1 , wherein R 3 is C 1 -C 4 haloalkyl.

6. The compound according to claim 1 , wherein R 4 is phenyl or phenyl substituted by one to three R 7 ; wherein R 7 is independently halogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, or C 1 -C 8 haloalkoxy.

7. The compound according to claim 1 , wherein A 1 is CR 5 and A 2 , A 3 and A 4 are each CH; R 1 is hydrogen, methyl, ethyl, methylcarbonyl-, or methoxycarbonyl; R 2 is C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by one to three R 6a , C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 1 -C 8 haloalkyl, di-C 1 -C 8 alkylamino, C 1 -C 4 alkylamino, fluoro, aryl, aryl substituted by one to three R 6b , 5-6 membered heteroaryl or 5-6 membered heteroaryl substituted by one to three R 6b ; R 3 is C 1 -C 4 haloalkyl; R 4 is aryl or aryl substituted by one to three R 6b ; and n is 2; wherein R 5 is halogen or C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 haloalkyl, or C 2 -C 8 alkenyl; R 6a is independently cyano, halogen, nitro, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy; and R 6b is independently halogen, cyano, nitro, C 1 -C 4 alkyl, or C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, or C 1 -C 4 haloalkoxy.

8. The compound according to claim 1 , wherein A 1 is CR 5 and A 2 , A 3 and A 4 are each CH; R 1 is hydrogen; R 2 is C 1 -C 4 alkyl, C 1 -C 4 alkyl substituted by one to three R 6a , C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl, C 1 -C 4 haloalkyl, di-C 1 -C 4 alkylamino, C 1 -C 4 alkylamino, fluoro, 1-3 halo-substituted phenyl, or 5-6 membered heteroaryl; R 3 is chlorodifluoromethyl or trifluoromethyl; R 4 is 3,5-bis-(trifluoromethyl)-phenyl, 3-chloro-5-trifluoromethyl-phenyl, 3-bromo-5-trifluoromethyl-phenyl, 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3-trifluoromethyl-phenyl, 4-bromo-3,5-dichlorophenyl, 3,5-dichloro-4-fluoro phenyl or 3,4,5-trichloro-phenyl; and n is 2; wherein R 5 is bromo, chloro, fluoro, cyano, nitro, methyl, ethyl, trifluoromethyl, cyclopropyl, or vinyl; R 6a is independently fluoro, cyano, nitro, methoxy, difluoromethoxy or trifluoromethoxy; and R 6b is independently bromo, chloro, fluoro, cyano, nitro methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy.

9. A compound of formula (I) according to claim 1 represented by the compounds of formula (Ib)

wherein

R a is hydrogen, halogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, or C 1 -C 8 haloalkoxy;

R b is hydrogen, halogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, or C 1 -C 8 haloalkoxy;

R c is hydrogen, halogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, or C 1 -C 8 haloalkoxy;

R 5 is halogen, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl;

R d is S(O) 2 —R 2 ;

R 2 is C 1 -C 8 alkyl or C 1 -C 8 alkyl substituted by one to three R 6a , C 1 -C 8 haloalkyl or C 1 -C 8 haloalkyl substituted by one to three R 6a , C 3 -C 8 cycloalkyl or C 3 -C 8 cycloalkyl substituted by one to three R 6b , phenyl, phenyl substituted by one to three R 7 , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 , —N(R 8 )(R 9 ), C 1 -C 4 alkylamino, fluoro;

R 5 is independently halogen, cyano, nitro, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 haloalkyl, C 2 -C 8 alkenyl;

R 6a is independently C 1 -C 8 alkoxy, or C 1 -C 8 haloalkoxy;

R 6b is independently oxo, amino, C 1 -C 8 alkylamino, N,N—C 1 -C 8 dialkylamino, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, phenyl, phenyl substituted by one to three R 7 , 5-6 membered heteroaryl or 5-6 membered heteroaryl substituted by one to three R 7 ;

R 7 is independently halogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, or C 1 -C 8 haloalkoxy;

R 8 and R 9 are independently hydrogen, cyano-C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by one to three R 6a , C 2 -C 8 alkenyl or C 2 -C 8 alkenyl substituted by one to three R 6a , phenyl-C 1 -C 4 alkyl, phenyl-C 1 -C 4 alkyl wherein the phenyl moiety is substituted by one to three R 7 , —S(O) 2 R 10 ;

R 10 is hydrogen, cyano-C 1 -C 8 alkyl, C 1 -C 8 alkyl or C 1 -C 8 alkyl substituted by one to three R 6a , phenyl, phenyl substituted by one to three R 7 , 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R 7 .

10. A compound of formula (Int-I)

wherein A 1 , A 2 , A 3 , A 4 , R 1 and R 2 , are as defined for a compound of formula (I) according to claim 1 and X B is a leaving group, or X B is cyano, formyl, CH═N—OH or acetyl; or a tautomer, isomer, enantiomer, salt or N-oxide thereof; or

a compound of formula (Int-II)

wherein A 1 , A 2 , A 3 , A 4 , R 1 and R 2 , are as defined for a compound of formula (I) according to any one of claims 1 to 9 and X C is CH 2 -halogen, CH═C(R 3 )R 4 , or CH 2 C(OH)(R 3 )R 4 wherein R 3 and R 4 are as defined for a compound of formula (I) according to claim 1 ; or a tautomer, isomer, enantiomer, salt or N-oxide thereof; or

a compound of formula (Int-III)

wherein R 1 and R 2 , are as defined for a compound of formula (I) according to claim 1 ; or a tautomer, isomer, enantiomer, salt or N-oxide thereof.

11. A method of combating and/or controlling an invertebrate animal pest which comprises applying to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest a pesticidally effective amount of a compound of formula (I) as defined in claim 1 .

12. A pesticidal composition, which comprises at least one compound of formula (I) according to claim 1 or where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient.

13. A method for controlling pests, which comprises applying a composition according to claim 12 to the pests or their environment with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

14. A method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 12 .

15. Plant propagation material treated with the pesticidal composition described in claim 12 .