Pesticidally active heterocyclic derivatives with sulfur containing substituents

1. A compound of formula I

wherein

A is CH or N;

X is S, SO or SO 2 ;

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

R 7 and R 8 are, independently from each other, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 cyanoalkyl, C 1 -C 4 alkoxyC 1 -C 4 alkyl, pyridyl or phenyl, wherein said pyridyl or phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, 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 and —C(O)C 1 -C 4 haloalkyl; or

R 7 and R 8 , together with the sulfur atom to which they are attached, form a four- to six-membered, saturated ring system, said ring system can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkyl; and said ring system may contain one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;

n is 0 or 1;

Q is a radical selected from the group consisting of formula Q 1 to Q 3

wherein the arrow denotes the point of attachment to the ring incorporating the radical A;

and wherein

X 1 is O, S or NR 3 , wherein R 3 is C 1 -C 4 alkyl;

R 2 is halogen, C 1 -C 6 haloalkyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl or C 1 -C 6 haloalkoxy;

G 1 is N or CH;

G 2 and G 3 are, independently from each other, N or CH; and

agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.

2. The compound of claim 1 ,

wherein

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

3. The compound of claim 1 ,

wherein

Q is Q 1 ; and

R 2 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

4. The compound of claim 1 ,

wherein

Q is Q 1 ;

X 1 is NR 3 , and R 3 is methyl;

X is SO 2 ;

R 1 is ethyl;

A is CH or N;

R 2 is C 1 -C 6 haloalkyl;

G 1 is N or CH;

n is 0 or 1; and

R 7 and R 8 are, independently from each other, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or phenyl monosubstituted by C 1 -C 4 alkyl, or

R 7 and R 8 , together with the sulfur atom to which they are attached, form a four- to six-membered, saturated ring system which can contain one oxygen atom.

5. The compound of claim 1 ,

wherein

Q is Q 2 ; and

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

6. The compound of claim 1 ,

wherein

Q is Q 2 ;

X is SO 2 ;

R 1 is ethyl;

A is CH or N;

R 2 is C 1 -C 6 haloalkyl;

G 3 is N or CH;

n is 0 or 1; and

R 7 and R 8 are, independently from each other, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or phenyl monosubstituted by C 1 -C 4 alkyl; or

R 7 and R 8 , together with the sulfur atom to which they are attached, form a four- to six-membered, saturated ring system, and said ring system can contain one oxygen atom.

7. The compound of claim 1 ,

wherein

X is SO 2 ;

R 1 is ethyl;

A is CH or N;

n is 0 or 1;

R 7 and R 8 are, independently from each other, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or phenyl monosubstituted by C 1 -C 4 alkyl; or

R 7 and R 8 , together with the sulfur atom to which they are attached, form a four- to six-membered, saturated ring system, and said ring system can contain one oxygen atom; and

Q is a radical selected from the group consisting of formula Q 1a , Q 1b , Q 2a and Q 3a

wherein the arrow denotes the point of attachment to the ring incorporating the radical A;

and

R 2 is C 1 -C 6 haloalkyl.

8. The compound of claim 1 ,

wherein

Q is Q 3 ; and

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

9. The compound of claim 1 ,

wherein

Q is Q 2 ;

X is SO 2 ;

R 1 is ethyl;

A is CH or N;

R 2 is C 1 -C 6 haloalkyl;

G 2 is CH;

G 3 is N or CH;

n is 0 or 1; and

R 7 and R 8 are, independently from each other, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or phenyl which phenyl is monosubstituted by C 1 -C 4 alkyl; or

R 7 and R 8 , together with the sulfur atom to which they are attached, form a four- to six-membered, saturated ring system, and said ring system can contain one oxygen atom.

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

11. A method for controlling pests, which comprises applying a composition according to claim 10 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 practiced on the human or animal body.

12. 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 10 .

13. A process for the preparation of a compound of formula (XI-A)

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl; comprising

a. reacting a compound of formula 14

wherein Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 14 together form a group —O—(CH 2 ) m —O—, wherein m is 2, 3 or 4; with a compound of formula 15

wherein Rf is C 1 -C 6 haloalkyl; and

Y 2 is C 1 -C 6 alkoxy, chloro, fluoro or C 1 -C 6 dialkylamino;

in the presence of a base to produce a compound of formula 16

or a salt thereof; or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 16 together form a group —O—(CH 2 ) m —O—, wherein m is 2, 3 or 4; and

b. reacting a compound of formula 16

or a salt thereof;

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 16 together form a group —O—(CH 2 ) m —O—, wherein m is 2, 3 or 4;

with ammonia, or a salt thereof; to produce a compound of formula 17

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 17 together form a group —O—(CH 2 ) m —O—, in which m is 2, 3 or 4; and

c. reacting a compound of formula 17

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 17 together form a group —O—(CH 2 ) m —O—, in which m is 2, 3 or 4;

with an ammonium salt; in the presence of an acid to produce a compound of formula 10

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl; and

d. reacting a compound of formula 10

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl; with a halogenating agent;

to produce a compound of formula 11

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl; and Hal is a halogen; and

e. reacting a compound of formula 11

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Hal is a halogen; with methylamine, or a salt thereof;

to produce the compound of formula (XI-A)

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl.

14. A process for the preparation of a compound of formula 10 according to claim 13 comprising

b1. reacting a compound of formula 16

or a salt thereof;

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 16 together form a group —O—(CH 2 ) m —O—, wherein m is 2, 3 or 4; with ammonia, or a salt thereof; to produce a reaction mixture comprising a compound of formula 17

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 17 together form a group —O—(CH 2 ) m —O—, wherein m is 2, 3 or 4; and

b2. reacting said mixture directly with an ammonium salt;

in the presence of an acid to produce the compound of formula 10

or a salt thereof; wherein Rf is C 1 -C 6 haloalkyl.

15. A compound of the formula 17

or tautomers and E/Z isomers thereof; wherein Rf is C 1 -C 6 haloalkyl; and

Y 1 is independently halogen or C 1 -C 4 -alkoxy; or

the two radicals Y 1 in a compound of formula 17 together form a group —O—(CH 2 ) m —O—, in which m is 2, 3 or 4.

16. The compound of claim 15 , wherein

wherein Rf is CF 3 .

17. The compound of claim 16 , wherein the compound is

18. A compound, wherein the compound is selected from the group consisting of

19. The compound of claim 18 , wherein the compound is selected from the group consisting of

20. The compound of claim 18 , wherein the compound is selected from the group consisting of

21. The compound of claim 18 , wherein the compound is selected from the group consisting of

22. The compound of claim 18 , wherein the compound is selected from the group consisting of