Pesticidally active polycyclic derivatives with sulfur containing substituents
Polycyclic derivatives of formula I wherein the substituents are as defined in claim 1 , and the agrochemically acceptable salts salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se.
1. A method comprising:
reacting a compound of Formula (II),
wherein
Xb 1 is a leaving group, boron derived functional group, or trialkyl tin derivative;
A represents CH, N or the N-oxide;
A 1 is CH, N or the N-oxide;
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
R 1 is C 3 -C 8 cycloalkyl-C 1 -C 4 alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C 1 -C 4 alkyl; or
R 1 is C 2 -C 8 alkenyl, C 2 -C 6 haloalkenyl or C 2 -C 8 alkynyl;
R 2 is halogen, cyano, C 1 -C 8 haloalkyl or C 1 -C 8 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxyl, methoxy and cyano; or
R 2 is 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 is C 3 -C 8 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C 1 -C 4 alkyl;
X 1 is NR 5 , wherein R 5 is hydrogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl; or
X 1 is oxygen or sulfur;
R 3 is hydrogen or C 1 -C 2 -alkyl; and
R 4 is hydrogen, halogen or C 1 -C 3 haloalkyl,
with Yb 1 -Q, Yb 2 -Q, or a Q which contains an appropriate NH functionality,
wherein
Yb 1 is a boron-derived functional group or leaving group;
Yb 2 is a trialkyl tin derivative or leaving group; and
Q is phenyl which 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
Q is a five- to ten-membered monocyclic or fused bicyclic ring system linked via a carbon atom to the ring which contains the group A, said ring system can be aromatic, partially saturated or fully saturated and contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five- to ten-membered ring system can be mono- to polysubstituted by substituents independently 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 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, —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; or
Q 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 group A, said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, with the proviso that said ring system cannot contain more than one oxygen atom and more than one sulfur atom and 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 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, —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;
Q is C 3 -C 6 cycloalkyl, or C 3 -C 6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, CONH 2 , carboxyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl and phenyl, wherein said 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 halo-alkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; or
Q is C 2 -C 6 alkenyl, or C 2 -C 6 alkenyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl and phenyl, wherein said 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
Q is C 2 -C 6 alkynyl, or C 2 -C 6 alkynyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, tri(C 1 -C 4 alkyl)silyl and phenyl, wherein said 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 halo-alkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl; or
Q is C 1 -C 6 alkyl, or C 1 -C 6 alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, tri(C 1 -C 4 alkyl)silyl and phenyl, wherein said 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 halo-alkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl and —C(O)C 1 -C 4 haloalkyl;
to form a compound of formula (I)
wherein R 1 , R 2 , R 3 , R 4 , A, A 1 , X, X 1 , and Q are as defined above;
with the proviso that:
when Xb 1 is a leaving group, Yb 1 is a boron-derived functional group and Yb 2 is a trialkyl tin derivative; and
when X b1 is a boron derived functional group or trialkyl tin derivative, Yb 1 and Yb 2 are leaving groups or the reacting is not with the Q which contains an appropriate NH functionality.
2. The method of claim 1 , wherein the reacting is with Yb 1 -Q.
3. The method of claim 2 , wherein Yb 1 is B(OH) 2 or B(OR b1 ) 2 , wherein R b1 , is a C 1 -C 4 alkyl group or the two groups OR b1 form together with the boron atom a five membered ring.
4. The method of claim 3 , wherein reacting further comprises the presence of a palladium based catalyst, a base, and a solvent.
5. The method of claim 3 , wherein the reacting is a Suzuki Reaction.
6. The method of claim 1 , wherein the reacting is with Yb 2 -Q.
7. The method of claim 6 , wherein Yb 2 is tri-n-butyl tin.
8. The method of claim 7 , wherein the reacting further comprises the presence of a palladium catalyst and inert solvent.
9. The method of claim 7 , wherein the reacting is a Stille Reaction.
10. The method of claim 1 , wherein the reacting is with Q which contains an appropriate NH functionality.
11. The method of claim 10 , wherein the reacting is in the presence of a base.
12. The method of claim 11 , wherein the reacting is in the presence of a copper catalyst and inert solvent.