PESTICIDALLY ACTIVE DIAZINE-AMIDE COMPOUNDS

Abstract

Compounds of formula I (1) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

##STR00001##

Claims

1. A compound of the formula I ##STR00226## wherein R.sub.1 is H, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6cyanoalkyl, aminocarbonylC.sub.1-C.sub.6alkyl, hydroxycarbonylC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6nitroalkyl, trimethylsilaneC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkeny, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl-, C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl- wherein the C.sub.3-C.sub.4cycloalkyl group is substituted with 1 or 2 halo atoms, oxetan-3-yl-CH.sub.2-, benzyl or benzyl substituted with halo or C.sub.1-C.sub.6haloalkyl; A.sub.1 is N or C—R.sub.2c; R.sub.2c is H, halogen, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, or C.sub.1-C.sub.3haloalkoxy; R.sub.2a is C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.3-C.sub.6cycloalkyl substituted with one to three substituents independently selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, cyano, and halogen, C.sub.3-C.sub.6cycloalkoxy substituted with one to three substituents independently selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, cyano, and halogen, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.4alkoxy, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.4alkyl substituted with one to five substituents independently selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, cyano, and halogen, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.4alkoxy substituted with one to five substituents independently selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, cyano, and halogen, C.sub.1-C.sub.5cyanoalkyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4haloalkyl sulfonyl, C.sub.1-C.sub.4alkylsulfinyl, or C.sub.1-C.sub.4haloalkylsulfinyl; R.sub.2b is H, halogen, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy, SFS, or CN; R.sub.3 is C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.3haloalkyl; A.sub.2 is CR.sub.4b or N; R.sub.4b is hydrogen, or halogen; R.sub.4a is cyano, or C.sub.1-C.sub.3haloakoxy; R.sub.5a and R.sub.5b are, independently of each other, selected from hydrogen, halogen, CN, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3alkoxy, and C.sub.1-C.sub.3haloalkoxy; or agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.

2. The compound according to claim 1 wherein R.sub.3 is methyl.

3. The compound according to claim 1, wherein A.sub.1 is N.

4. The compound according to claim 1, wherein A.sub.1 is C—R.sub.2c, where R.sub.2c is hydrogen or halogen.

5. The compound according to claim 1, wherein R.sub.1 is hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl or HCH≡CCH.sub.2—.

6. The compound according to claim 1, wherein R.sub.2a is C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.3-C.sub.6cycloalkyl substituted with one to three substituents independently selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, cyano, and halogen, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.4alkyl substituted with one to five substituents independently selected from halogen and C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.5cyanoalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.4haloalkyl sulfonyl or C.sub.1-C.sub.4haloalkylsulfinyl

7. The compound according to claim 1, wherein R.sub.2b is halogen, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy, or CN.

8. The compound according to claim 1, wherein R.sub.4a is cyano, or C.sub.1-C.sub.3fluoroalkoxy.

9. The compound according to claim 1, wherein A.sub.2 is N.

10. The compound according to claim 1, wherein A.sub.2 is CH.

11. The compound according to claim 1, wherein R.sub.5a and R.sub.5b, independent of each other, are selected from hydrogen, halogen, and methyl.

12. A composition comprising the compound according to claim 1, one or more auxiliaries and diluent, and optionally one more other active ingredient.

13. A method of combating and 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 the compound according to claim 1, or of a composition comprising said compound, one or more auxiliaries and diluent, and optionally one more other active ingredient.

14. A plant propagation material, comprising, or treated with or adhered thereto, the compound according to claim 1, or of a composition comprising said compound, one or more auxiliaries and diluent, and optionally one more other active ingredient.

15. A compound of formulae IIaa to IIae ##STR00227## wherein R.sub.1 is H, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6cyanoalkyl, aminocarbonylC.sub.1-C.sub.6alkyl, hydroxycarbonylC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6nitroalkyl, trimethylsilaneC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkeny, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl-, C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl- wherein the C.sub.3-C.sub.4cycloalkyl group is substituted with 1 or 2 halo atoms, oxetan-3-yl-CH.sub.2—, benzyl or benzyl substituted with halo or C.sub.1-C.sub.6haloalkyl; and R.sub.4 is ##STR00228## wherein R.sub.4a is cyano or C.sub.1-C.sub.3haloakoxy, and A.sub.2 is CR.sub.4b or N, wherein R.sub.4b is hydrogen, or halogen.

16. The compound according to claim 4, wherein R2c is hydrogen.

17. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of the compound according to claim 1, or of a composition comprising said compound, one or more auxiliaries and diluent, and optionally one more other active ingredient.

18. A method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of the compound according to claim 1, or of a composition comprising said compound, one or more auxiliaries and diluent, and optionally one more other active ingredient.

19. The plant propagation material according to claim 14, wherein said plant propagation material is a seed.

20. The compound according to claim 15, wherein R.sub.1 is hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl or HCH≡CCH.sub.2—.

21. The compound according to claim 15, wherein R.sub.4a is cyano, or C.sub.1-C.sub.3fluoroalkoxy.

22. The compound according to claim 15, wherein and A.sub.2 is CH.

Description

BIOLOGICAL EXAMPLES

[0819] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, δ ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Example B1: Diabrotica balteata (Corn Root Worm)

[0820] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.

[0821] The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P6, P7, P8, P9, P13, P16, P19, P22, P23, P24, P25, P27, P28, P29, P32, P33, P34, P36, P37, P38, P40, P41, P42, P43, P44, P46, P47, P48, P49, P50

Example B2: Euschistus heros (Neotropical Brown Stink Bug)

[0822] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

[0823] The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P28, P29, P32, P34, P36, P40, P47, P48, P49

Example B3: Frankliniella occidentalis (Western Flower Thrips): Feeding/Contact Activity

[0824] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.

[0825] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P44, P48

Example B4: Chilo suppressalis (Striped Rice Stemborer)

[0826] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

[0827] The following compounds resulted in at least 80% control in at least one of the three categories (mortality, anti-feedant or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P22, P23, P24, P25, P26, P27, P28, P29, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P42, P43, P44, P45, P46, P47, P48, P49, P50

Example B5: Plutella xylostella (Diamond Back Moth)

[0828] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.

[0829] The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P22, P23, P24, P25, P26, P27, P28, P29, P30, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P42, P43, P44, P45, P46, P47, P48, P49, P50

Example B6: Myzus persicae (Green Peach Aphid): Feeding/Contact Activity

[0830] Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.

[0831] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 49

Example B7: Myzus persicae (Green Peach Aphid): Systemic Activity

[0832] Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10′000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.

Example B8: Myzus persicae (Green Peach Aphid): Intrinsic Activity

[0833] Test compounds prepared from 10′000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.

[0834] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P2, P9, P32, P34, P37, P40, P44, P47, P48, P49

Example B9: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0835] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

[0836] The following compounds resulted in at least 80% control in at least one of the three categories (mortality, anti-feedant or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P22, P23, P24, P25, P26, P28, P29, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P42, P43, P44, P46, P47, P48, P49, P50

Example B10: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0837] Test compounds were applied by pipette from 10′000 ppm DMSO stock solutions into 24-well plates and mixed with agar. Lettuce seeds were placed onto the agar and the multi well plate was closed by another plate which contained also agar. After 7 days the compound was absorbed by the roots and the lettuce grew into the lid plate. The lettuce leaves were then cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil onto a humid gel blotting paper and the lid plate was closed with it. The samples were assessed for mortality, anti-feedant effect and growth inhibition in comparison to untreated samples 6 days after infestation.

[0838] The following compounds gave an effect of at least 80% control in at least one of the three categories (mortality, anti-feeding, or growth inhibition) at a test rate of 12.5 ppm: P32, P34, P36, P40

Example B11: Tetranychus urticae (Two-Spotted Spider Mite)

[0839] Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation.

[0840] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P22

Example B12: Myzus persicae (Green Peach Aphid)

[0841] Test compounds prepared from 10′000 ppm DMSO stock solutions were applied by a liquid handling robot into 96-well microtiter plates and mixed with a sucrose solution. Parafilm was stretched over the 96-well microtiter plate and a plastic stencil with 96 holes was placed onto the plate. Aphids were sieved into the wells directly onto the Parafilm. The infested plates were closed with a gel blotting card and a second plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.

[0842] The following compounds resulted in at least 80% mortality at an application rate of 50 ppm: P25, P32, P34, P36, P40

Example B13: Plutella xylostella (Diamondback Moth)

[0843] 96-well microtiter plates containing artificial diet were treated with aqueous test solutions, prepared from 10′000 ppm DMSO stock solutions, by a liquid handling robot. After drying, eggs (˜30 per well) were infested onto a netted lid which was suspended above the diet. The eggs hatch and L1 larvae move down to the diet. The samples were assessed for mortality 9 days after infestation.

[0844] The following compounds gave an effect of at least 80% mortality at an application rate of 500 ppm: P19, P20, P22, P23, P24, P25, P26, P27, P28, P29, P31, P32, P33, P34, P36, P37, P38, P39, P40, P41