Insecticidal compounds based on N-arylsulfanylmethylcarboxamidearylthiosulfonamides derivatives

1. A compound of formula I

wherein

A 1 is C—R 5b ;

A 2 , A 3 and A 4 are independently of one another C—H;

Y 1 —Y 2 —Y 3 is —C═N—O—, —C═N—S—, —C═N—CH 2 —, —C═CH—O——N—CH 2 —CH 2 — or —C═CH—S;

n is 0, 1 or 2;

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

R 2 is hydrogen, C 1 -C 8 alkyl or C 1 -C 8 alkyl substituted by one to five R 6 , C 2 -C 8 alkenyl or C 2 -C 8 alkenyl substituted by one to five R 6 , C 2 -C 8 alkynyl or C 2 -C 8 alkynyl substituted by one to five R 6 , C 3 -C 10 cycloalkyl or C 3 -C 10 cycloalkyl substituted by one to five R 7 , aryl-C 1 -C 4 alkylene or aryl-C 1 -C 4 alkylene wherein the aryl moiety is substituted by one to five R 8 , heterocyclyl-C 1 -C 4 alkylene or heterocyclyl-C 1 -C 4 alkylene wherein the heterocyclyl moiety is substituted by one to five R 8 , aryl or aryl substituted by one to five R 8 , heterocyclyl or heterocyclyl substituted by one to five R 8 ;

or R 1 and R 2 together with the nitrogen atom to which they are bound form a 4- to 7-membered cycle containing carbon atoms as ring members and optionally containing one oxygen atom or one sulfur atom optionally oxidized as a ring member and wherein the cycle is optionally substituted by 1 to 5 groups independently selected from halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy;

R 3 is C 1 -C 8 haloalkyl;

R 4 is aryl or aryl substituted by one to five R 9 , or heteroaryl or heteroaryl substituted by one to five R 9 ;

R 5b is halogen, 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 or C 3 -C 10 cycloalkyl substituted by one to five R 7 ;

each R 6 is independently halogen, cyano, nitro, hydroxy, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, 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, or C 1 -C 8 haloalkylsulfonyl;

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

each R 8 and R 9 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 10 or heterocyclyl or heterocyclyl substituted by one to five R 10 ;

each R 10 is independently halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;

or a salt or N-oxide thereof.

2. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —C═N—O—.

3. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —C═N—CH 2 —.

4. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —C═CH—O—.

5. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —N—CH 2 —CH 2 —.

6. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —C═N—S—.

7. A compound according to claim 1 , wherein Y 1 —Y 2 —Y 3 is —C═CH—S.

8. A compound according to claim 1 , wherein R 5b is halogen or methyl.

9. A compound according to claim 1 , wherein R 2 is C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by one to five groups independently selected from halogen, cyano, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkenyl substituted by one to five halogen, C 2 -C 4 alkynyl or C 2 -C 4 alkynyl substituted by one to five halogen, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by one to five groups independently selected from halogen, cyano, methyl and halomethyl, phenyl-C 1 -C 2 alkylene or phenyl-C 1 -C 2 alkylene wherein the phenyl moiety is optionally substituted by one to three substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy, pyridyl-C 1 -C 2 alkylene or pyridyl-C 1 -C 2 alkylene wherein the pyridyl moiety is optionally substituted by one to three substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy, thietanyl, oxo-thietanyl, dioxo-thietanyl, oxetanyl, tetrahydrofuranyl, thietanyl-methyl, oxo-thietanyl-methyl, dioxo-thietanyl-methyl, and oxetanyl-methyl.

10. A compound according to claim 1 , wherein R 2 is C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by one to five groups independently selected from halogen, cyano, methoxy and methylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkenyl substituted by one to five halogen, C 2 -C 4 alkynyl or C 2 -C 4 alkynyl substituted by one to five halogen, C 3 -C 4 cycloalkyl or C 3 -C 4 cycloalkyl substituted by one to five groups independently selected from halogen, cyano, methyl and halomethyl, pyridylmethyl or pyridylmethyl wherein the pyridyl moiety is substituted with one to four groups selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy.

11. A compound according to claim 1 , wherein R 1 and R 2 together with the nitrogen atom to which they are bound form a 4- to 7-membered cycle containing carbon atoms as ring members and optionally containing one oxygen atom or one sulfur atom optionally oxidized as a ring member and wherein the cycle is optionally substituted by 1 to 5 groups independently selected from halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy.

12. A compound according to claim 1 , wherein R 3 is chlorodifluoromethyl or trifluoromethyl.

13. A compound according to claim 1 , wherein R 4 is group A1

wherein X is C—R 12 or nitrogen and each R 12 is independently hydrogen, halogen or trihalomethyl, wherein at least two R 12 are not hydrogen.

14. A compound according to claim 1 , wherein A 1 is C—R 5b ; A 2 , A 3 and A 4 are C—H; Y 1 —Y 2 —Y 3 is —C═N—O—, —C═N—S—, —C═N—CH 2 —, —C═CH—O—N—CH 2 —CH 2 — or —C═CH—S; R 1 is hydrogen; R 2 is C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by one to five groups independently selected from halogen, cyano, methoxy and methylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkenyl substituted by one to five halogen, C 2 -C 4 alkynyl or C 2 -C 4 alkynyl substituted by one to five halogen, C 3 -C 4 cycloalkyl or C 3 -C 4 cycloalkyl substituted by one to five groups independently selected from halogen, methyl and halomethyl, pyridylmethyl or pyridylmethyl wherein the pyridyl moiety is substituted with one to four groups selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy; or R 1 and R 2 together with the nitrogen atom to which they are bound form a 4- to 7-membered cycle containing carbon atoms as ring members and optionally containing one oxygen atom as a ring member; R 3 is trifluoromethyl; R 4 is group A1

wherein X is C—R 12 and each R 12 is independently hydrogen, halogen or trihalomethyl, wherein at least two R 12 are not hydrogen; R 5b is halogen or methyl.

15. A compound according to claim 14 , wherein A 1 is C—R 5b ; A 2 , A 3 and A 4 are C—H; Y 1 —Y 2 —Y 3 is —C═N—O—, —C═N—S—, —C═N—CH 2 —, —C═CH—O—N—CH 2 —CH 2 — or —C═CH—S; R 1 is hydrogen; R 2 is methyl, ethyl, propyl, butyl, fluoroethyl, fluoropropyl, fluorobutyl, difluoroethyl, difluoropropyl, difluorobutyl, trifluoroethyl, trifluoropropyl, trifluorobutyl, cyclopropyl, cyanocyclopropyl, cyanocyclobutyl, cyclobutyl, 1-methoxy-ethyl, 2-methoxy-ethyl, 1-methoxy-methyl, 1-methylsulfanyl-ethyl-, 1-methylsulfanyl-methylallyl, propargyl, pyridylmethyl; R 3 is trifluoromethyl; R 4 is group A1, wherein X is C—R 12 and each R 12 is independently hydrogen, halogen or trihalomethyl, wherein at least two R 12 are not hydrogen; R 5b is chloro, bromo or methyl.

16. A mixture comprising a compound of formula I* and a compound of formula I**

wherein Y 1 —Y 2 —Y 3 is —C═N—O—, —C═N—S—, —C═N—CH 2 —, —C═CH—O—, —N—CH 2 —CH 2 — or —C═CH—S; and A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , R 3 , R 4 and n are as defined in claim 1 , and wherein the molar proportion of the compound of formula I** compared to the total amount of both the compound of formula I* and I** is greater than 50%.

17. A mixture according to claim 16 , wherein, R 4 is group A1

wherein X is C—R 12 or nitrogen and each R 12 is independently hydrogen, halogen or trihalomethyl, wherein at least two R 12 are not hydrogen;

and wherein the molar proportion of the compound of formula I** compared to the total amount of both the compound of formula I* and I** is greater than 70%.

18. A mixture according to claim 16 , wherein, A 1 is C—R 5b ; A 2 , A 3 and A 4 are C—H; Y 1 —Y 2 —Y 3 is —C═N—O—, —C═N—CH 2 —, —C═CH—O— N—CH 2 —CH 2 — or —C═CH—S; R 1 is hydrogen, R 2 is C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted b one to five groups independently selected from halogen, cyano, methoxy and methylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkenyl substituted b one to five halogen, C 2 -C 4 alkynyl or C 2 -C 4 alkynyl substituted by one to five halogen, C 3 -C 4 cycloalkyl or C 3 -C 4 cycloalkyl substituted by one to five groups independently selected from halogen, methyl and halomethyl, pyridylmethyl or pyridylmethyl wherein the pyridyl moiety is substituted with one to four groups selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy; or R 1 and R 2 together with the nitrogen atom to which they are bound form a 4- to 7-membered cycle containing carbon atoms as ring members and optionally containing one oxygen atom as a ring member; R 3 is trifluoromethyl; R 4 is group A1

wherein X is C—R 12 and each R 12 is independently hydrogen, halogen or trihalomethyl, wherein at least two R 12 are not hydrogen; R 5b is halogen or methyl;

and wherein the molar proportion of the compound of formula I** compared to the total amount of both the compound of formula I* and I** is greater than 70%.

19. 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 and optionally at least one additional compound having biological activity.

20. 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 component B is at least one compound selected from the group consisting of imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazin, 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 and tebufenozide.