Pesticidally active heterocyclic derivatives with sulphur containing substituents

1. A compound of formula I

wherein

A represents CH, N or CR; wherein R is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, cyano, nitro or halogen;

X is S, SO or SO 2;

R 1 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, C 1 -C 4 haloalkyl, cyano and C 1 -C 4 alkyl; or R 1 is C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 haloalkyl and C 1 -C 4 alkyl;

or R 1 is C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl or C 2 -C 6 alkynyl;

R 2 a and R 2 b are, independently from each other, hydrogen, halogen, cyano, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxyl, methoxy and cyano; or

R 2 a and R 2 b are, independently from each other, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, O(C 1 -C 4 haloalkyl), or —C(O)C 1 -C 4 haloalkyl; or

R 2 a and R 2 b are, independently from each other, C 3 -C 6 cycloalkyl which can be mono - or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 haloalkyl and C 1 -C 4 alkyl;

R 3 is hydrogen, halogen, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxyC 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl; or

R 3 is C 3 -C 6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and cyano; or

R 3 is phenyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, nitro, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxy, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; or

R 3 is C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl or C 2 -C 6 haloalkynyl; or

R 3 is C 1 -C 6 haloalkylsulfanyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 haloalkoxy, —C(O)C 1 -C 4 haloalkyl, C 1 -C 6 alkylsulfanyl, C 1 -C 6 alkylsulfinyl or C 1 -C 6 alkylsulfonyl; or

R 3 is a five- to six-membered, aromatic, partially saturated or fully saturated ring system linked via a nitrogen atom to the ring which contains the substituent G 3 , said ring system can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, nitro, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl and —C(O)C 1 -C 4 alkyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; and said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where said ring system may not contain more than one oxygen atom and not more than one sulfur atom; or

R 3 is a five-to six membered, aromatic, partially saturated or fully saturated ring system linked via a carbon atom to the ring which contains the substituent G 3 , said ring system can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, nitro, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl and —C(O)C 1 -C 4 alkyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; and said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where said ring system may not contain more than one oxygen atom and not more than one sulfur atom;

R 8 is C 1 -C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen and C 1 -C 2 alkylsulfinyl;

G 1 is NR 4 and G 2 is C(Y);

Y is O or S;

G 3 is N or CR 9;

R 4 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl; or

R 4 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by R 7; or

R 4 is C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl which can be mono- or polysubstituted by R 10 ; or

R 4 is C 1 -C 4 alkyl substituted by cyano, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkoxy,

C 1 -C 4 alkoxyC 1 -C 4 alkoxy, C 3 -C 6 cycloalkyl or by phenyl, which itself can be mono - or polysubstituted by substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, cyano, C 1 -C 4 haloalkyl and C 1 -C 4 alkoxy;

R 4 is C 2 -C 6 alkenyl substituted by R 11 or C 2 -C 6 alkynyl substituted by R 11 ; or

R 4 is C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxy, C 1 -C 6 alkylsulfanyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfanyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 haloalkylsulfinyl or hydroxyl; or

R 4 is a five- to six-membered, aromatic, partially saturated or fully saturated ring system, said ring system can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, nitro, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl and —C(O)C 1 -C 4 alkyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; and said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where said ring system may not contain more than one oxygen atom and not more than one sulfur atom;

R 6 and R 9 , independently from each other, are hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 6 cycloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxyC 1 -C 4 alkyl, or C 1 -C 4 haloalkyl;

R 7 and R 10 , independently from each other, are halogen, nitro, cyano, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 haloalkyl;

R 11 is nitro, cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 haloalkylsulfinyl or phenyl which itself can be mono - or polysubstituted by substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, cyano, C 1 -C 4 haloalkyl and C 1 -C 4 alkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

2. A compound of formula I according to claim 1 represented by the compounds of formula I-1

wherein the substituents X, A, R 1 , R 2 a, R 3 , R 4 and R 8 are as defined under formula I in claim 1 .

3. A compound of formula I-1 according to claim 2 , wherein

A is C—H or N;

R 1 is C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalklyl;

R 2 a is halogen, C 1 -C 4 haloalkyl, cyano or C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C 1 -C 4 alkyl;

R 4 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

R 3 is hydrogen, halogen or C 1 -C 4 haloalkyl;

and X and R 8 are as defined in claim 2 .

4. A compound of formula I-1 according to claim 2 , wherein

A is C—H or N;

R 1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl;

R 2 a is halogen, trifluoromethyl, cyano or cyclopropyl which can be monosubstituted by cyano;

R 3 is hydrogen or trifluoromethyl;

R 4 is methyl or ethyl;

and X and R 8 are as defined in claim 2 .

5. A compound of formula I-1 according to claim 2 , wherein

A is C-H or N;

R 1 is ethyl;

R 2 a is trifluoromethyl;

R 3 is hydrogen or trifluoromethyl;

R 4 is methyl; and

X and R 8 are as defined in claim 2 .

6. A compound of formula I according to claim 1 represented by the compounds of formula (I-1a)

wherein

A is N or CH;

R 1 is C 1 -C 4 alkyl;

R 2 a is C 1 -C 4 haloalkyl;

R 3 is hydrogen, halogen, C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl or C 3 -C 6 cycloalkyl; or

R 3 is phenyl which can be mono- or di-substituted by substituents selected from the group consisting of cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 haloalkyl; or

R 3 is pyrazolyl, which can be mono-substituted by C 1 -C 4 haloalkyl; or

R 3 is pyridinyl which can be mono- or di-substituted by substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and halogen; or

R 3 is pyrimidinyl which can be mono-substituted by C 1 -C 4 alkoxy;

R 4 is C 1 -C 6 alkyl or C 1 -C 6 haloalkyl, preferably 1,1,1-trifluoroethyl;

R 4 is C 1 -C 4 alkyl mono-substituted by cyano, C 1 -C 4 alkylsulfanyl, phenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy C 1 -C 4 alkoxy or C 3 -C 6 cycloalkyl; or

R 4 is C 2 -C 6 alkenyl or C 2 -C 6 allynyl; or

R 4 is C 2 -C 6 alkenyl substituted by phenyl;

R 4 is benzyl which can be mono-substituted by C 1 -C 4 alkoxy;

R 8 is C 1 -C 4 alkyl; preferably methyl; and

X is S or SO 2 .

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

8. A substrate selected from nonwoven and fabric material comprising a composition according to claim 7 .