Insecticidal pyrrolidin-yl-aryl-carboxamides
The invention relates to compounds of formula (I): where A 1 , A 2 , A 3 , A 4 , G 1 , R 1 , R 2 , R 3 and R 4 are as defined in claim 1 ; or a salt or N-oxide thereof. Furthermore, the present invention relates to processes and intermediates for preparing compounds of formula (I), to insecticidal, acaricidal, nematicidal and molluscicidal compositions comprising the compounds of formula (I) and to methods of using the compounds of formula (I) to control insect, acarine, nematode and mollusc pests.
1. A compound of formula (I)
where
A 1 , A 2 , A 3 and A 4 are independently of each other C—H, C—R 5 or nitrogen;
G 1 is oxygen or sulfur;
R 1 is hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy-, C 1 -C 8 alkylcarbonyl-, C 1 -C 8 alkoxycarbonyl- or C 1 -C 8 haloalkoxycarbonyl-;
R 2 is a group of formula (II)
where
L is a single bond or C 1 -C 6 alkylene; and
Y 1 , Y 2 and Y 3 are independently of another CR 8 R 9 , C═O, C═N—OR 10 , N—R 10 , S, SO, SO 2 , S═N—R 10 or SO═N—R 10 , provided that at least one of Y 1 , Y 2 or Y 3 is not CR 8 R 9 , C═O or C═N—OR 10 ;
R 3 is C 1 -C 8 haloalkyl;
R 4 is aryl or aryl substituted by one to five R 7 , or heteroaryl or heteroaryl substituted by one to five R 7 ;
each R 5 is independently halogen, cyano, nitro, C 1 -C 8 alkyl, 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 3 -C 10 cycloalkyl, C 1 -C 8 alkoxy-, C 1 -C 8 haloalkoxy-, C 1 -C 8 alkylthio-, C 1 -C 8 haloalkylthio-, C 1 -C 8 alkylsulfinyl-, C 1 -C 8 haloalkyl-sulfinyl-, C 1 -C 8 alkylsulfonyl- or C 1 -C 8 haloalkylsulfonyl-, or
two R 5 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge;
R 6 is hydrogen, C 1 -C 8 haloalkyl or C 1 -C 8 alkyl;
each R 7 is independently halogen, cyano, nitro, C 1 -C 8 alkyl, 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, hydroxy, C 1 -C 8 alkoxy-, C 1 -C 8 haloalkoxy-, mercapto, C 1 -C 8 alkylthio-, C 1 -C 8 haloalkylthio-, C 1 -C 8 alkylsulfinyl-, C 1 -C 8 haloalkylsulfinyl-, C 1 -C 8 alkylsulfonyl-, C 1 -C 8 haloalkylsulfonyl-, C 1 -C 8 alkylcarbonyl-, C 1 -C 8 alkoxycarbonyl-, aryl or aryl substituted by one to five R 11 , or heterocyclyl or heterocyclyl substituted by one to five R 11 ;
each R 8 and R 9 is independently hydrogen, halogen, C 1 -C 8 alkyl or C 1 -C 8 haloalkyl;
each R 10 is independently hydrogen, cyano, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkylcarbonyl-, C 1 -C 8 haloalkylcarbonyl-, C 1 -C 8 alkoxycarbonyl-, C 1 -C 8 haloalkoxycarbonyl-, C 1 -C 8 alkylsulfonyl-, C 1 -C 8 haloalkylsulfonyl-, aryl-C 1 -C 4 alkylene- or aryl-C 1 -C 4 alkylene- where the aryl moiety is substituted by one to three R 12 , or heteroaryl-C 1 -C 4 alkylene- or heteroaryl-C 1 -C 4 alkylene- where the heteroaryl moiety is substituted by one to three R 12 ;
each R 11 and R 12 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- or C 1 -C 8 alkoxycarbonyl-;
or a salt or N-oxide thereof.
2. A compound according to claim 1 where A 1 is C—R 5 , A 2 is C—H, A 3 is C—H or nitrogen and A 4 is C—H or nitrogen.
3. A compound according to claim 1 where G is oxygen.
4. A compound according to claim 1 where R 1 is hydrogen, methyl, ethyl, methylcarbonyl-, or methoxycarbonyl-.
5. A compound according to claim 1 where R 2 is a group of formula (IIc)
where
R 13 is C 1 -C 8 alkyl,
m is 0, 1, 2, 3, 4, or 5, and
Y 2 is S, SO, SO 2 , S═N—R 10 , SO═N—R 10 or C═N—OR 10 .
6. A compound according to claim 1 where R 2 is thietan-3-yl-, 1-oxo-thietan-3-yl-, or 1,1-dioxo-thietan-3-yl-.
7. A compound according to claim 1 where R 3 is chlorodifluoromethyl or trifluoromethyl.
8. A compound according to claim 1 where R 4 is phenyl or phenyl substituted by one to five R 7 .
9. A compound according to claim 1 wherein
A 1 , A 2 , A 3 and A 4 are independently of each other C—H or C—R 5 ;
G 1 is oxygen;
R 1 is hydrogen, methyl or ethyl;
R 2 is a group of formula (IIb)
where
L is a single bond, methylene, ethylene or propylene;
one of Y 1 and Y 2 is S, SO, SO 2 , S═N—R 10 , SO═N—R 10 or C═N—OR 10 and the other is CH 2 ;
R 3 is chlorodifluoromethyl or trifluoromethyl;
R 4 is 3-chloro-5-trifluoromethyl-phenyl-, 3,5-dichloro-phenyl-, 3,5-bis-(trifluoromethyl)-phenyl-, 3,5-dichloro-4-fluoro-phenyl-, 3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-;
each R 5 is independently bromo, chloro, fluoro, methyl, trifluoromethyl or vinyl, or two R 5 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge;
each R 10 is independently methyl, 2,2,2-trifluoro-ethyl or hydrogen;
R 13 is hydrogen or C 1 -C 8 alkyl.
10. A compound according to claim 1 wherein
A 1 , A 2 , A 3 and A 4 are independently of each other C—H or C—R 5 ;
G 1 is oxygen;
R 1 is hydrogen;
R 2 is a group of formula (IIc)
where
m is 0, 1, 2, 3, 4, or 5, and
Y 2 is S, SO, SO 2 , or C═N—OR 10 ;
R 3 is chlorodifluoromethyl or trifluoromethyl;
R 4 is 3-chloro-5-trifluoromethyl-phenyl-, 3,5-dichloro-phenyl-, 3,5-bis-(trifluoromethyl)-phenyl-, 3,5-dichloro-4-fluoro-phenyl-, 3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-;
each R 5 is independently bromo, chloro, fluoro, methyl, trifluoromethyl or vinyl, or two R 5 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge;
each R 10 is independently methyl, 2,2,2-trifluoro-ethyl or hydrogen;
R 13 is methyl.
11. A compound of formula (Int-III)
wherein A 1 , A 2 , A 3 , A 4 , G 1 , L, R 1 , R 3 , R 4 , R 6 , Y 1 , Y 2 and Y 3 are as defined for a compound of formula (I) in claim 1 ; or
a compound of formula (Int-IV);
wherein A 1 , A 2 , A 3 , A 4 , G 1 , L, R 1 , R 6 , R 3 , R 4 , R 6 , Y 1 , Y 2 and Y 3 are as defined for a compound of formula (I) in claim 1 ; or
a compound of formula (Int-V)
wherein A 1 , A 2 , A 3 , A 4 , G 1 , L, R 1 , R 3 , R 4 , R 6 , Y 1 , Y 2 and Y 3 are as defined for a compound of formula (I) in claim 1 ; or
a compound of formula (Int-VI)
wherein A 1 , A 2 , A 3 , A 4 , R 1 and R 2 are as defined for a compound of formula (I) in claim 1 , R 1 ′, R 2′ and R 3 ′ are each independently optionally substituted alkyl or optionally substituted phenyl, R 4 ′ is optionally substituted phenyl or optionally substituted alkyl; or
a compound of formula (Int-VII)
wherein A 1 , A 2 , A 3 , A 4 , R 1 and R 2 are as defined for a compound of formula (I) in claim 1 , R 1 ′, R 2′ and R 3 ′ are each independently optionally substituted alkyl or optionally substituted phenyl.
12. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1 .
13. An insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1 .
14. An insecticidal, acaricidal, nematicidal or molluscicidal composition according to claim 13 comprising an additional compound having biological activity.
15. A method of treatment of insect pests in or on animals, comprising administering an effective amount of a compound as defined in claim 1 , or a composition comprising said compound, to an animal.
16. A compound according to claim 1 , or a composition comprising said compound, for use in treatment of insect pests in or on animals.
17. A combination product comprising a pesticidally effective amount of a component A and a pesticidally effective amount of component B, wherein component A is a compound of formula (I) as defined in claim 1 , and compound B is imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazine, thiamethoxam, pyriprole, deltamethrin, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, selamectin, carprofen, metaflumizone, moxidectin, methoprene (including S-methoprene), clorsulon, pyrantel, amitraz, triclabendazole, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, nemadectin, albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, tetramisole, levamisole, pyrantel pamoate, oxantel, morantel, triclabendazole, epsiprantel, fipronil, lufenuron, ecdysone or tebufenozide.