PESTICIDALLY ACTIVE HETEROCYCLIC DERIVATIVES WITH SULPHUR CONTAINING SUBSTITUENTS

Abstract

Compounds 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.

##STR00001##

Claims

1. A compound of formula I, ##STR00114## wherein G.sub.1 is nitrogen or CR.sub.2; G.sub.2 is nitrogen or CR.sub.3; G.sub.3 is nitrogen or CR.sub.4; G.sub.4 is nitrogen or CR.sub.5; G.sub.5 is nitrogen or CR.sub.6, with the proviso that not more than 2 nitrogens as G may follow consecutively; R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6 are, independently from each other, hydrogen, halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4haloalkyl substituted by one or two hydroxy, C.sub.1-C.sub.4haloalkyl substituted by one or two methoxy, C.sub.1-C.sub.4haloalkyl substituted by one or two cyano; or R.sub.2, R.sub.3, R.sub.4, R.sub.5 or R.sub.6, independently from each other, are C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfonyl, O(C.sub.1-C.sub.4haloalkyl), SF.sub.5, phenylcarbonylthio, cyano, mercapto, C.sub.1-C.sub.4alkoxycarbonyl, or —C(O)C.sub.1-C.sub.4haloalkyl; or two adjacent R.sub.i, wherein R.sub.i is selected from R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, taken together may form a fragment —OCH.sub.2O— or —OCF.sub.2O—; Q is a radical selected from the group consisting of formula Q.sub.1 to Q.sub.2: ##STR00115## wherein the arrow denotes the point of attachment to the triazole ring; and wherein X is S, SO or SO.sub.2; each R is, independently from each other, hydrogen, halogen, C.sub.1-C.sub.4haloalkoxy or C.sub.1-C.sub.4haloalkyl; each R.sub.1 is, independently from each other, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl or C.sub.2-C.sub.6alkynyl; and each R.sub.7 is, independently from each other, hydrogen or halogen; and R.sub.8 is hydrogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4haloalkyl; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds; with the exception of 2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsulfanyl-pyridine; 2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-ethylsulfanyl-pyridine; and 2-[5-(4-n-pentylphenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsufonyl-pyridine.

2. A compound of formula I according to claim 1, represented by the compounds of formula I-1 ##STR00116## wherein G.sub.1, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.1 is S, SO or SO.sub.2; Ra.sub.1 is hydrogen, halogen or C.sub.1-C.sub.4haloalkyl; R.sub.11 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; and R.sub.8 is as defined under formula I in claim 1; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds.

3. A compound of formula I-1 according to claim 2, wherein G.sub.1 is N, G.sub.2 is CH, G.sub.3 is CH, G.sub.4 is C(CF.sub.3) and G.sub.5 is CH.

4. A compound of formula I-1 according to claim 2, wherein G.sub.1 is CH, G.sub.2 is N, G.sub.3 is CH, G.sub.4 is C(CF.sub.3) and G.sub.5 is CH.

5. A compound of formula I according to claim 1 represented by the compounds of formula I-2 ##STR00117## wherein G.sub.1, G.sub.2, G.sub.3, G.sub.4, and G.sub.5 are as defined under formula I in claim 1; X.sub.2 is S, SO or SO.sub.2; Ra.sub.2 is hydrogen, halogen or C.sub.1-C.sub.4haloalkyl; R.sub.12 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R.sub.8 is as defined under formula I in claim 1; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds.

6. A compound of formula I-2 according to claim 5, wherein G.sub.1 is N, G.sub.2 is CH, G.sub.3 is CH, G.sub.4 is C(CF.sub.3) and G.sub.5 is CH.

7. A compound of formula I-2 according to claim 5, wherein G.sub.1 is CH, G.sub.2 is N, G.sub.3 is CH, G.sub.4 is C(CF.sub.3) and G.sub.5 is CH.

8. A compound of formula I according to claim 1, represented by the compounds of formula I-3 ##STR00118## wherein A is N or CH; R.sub.10 is phenyl mono- or polysubstituted by substituents independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxycarbonyl or C.sub.1-C.sub.4haloalkyl; or R.sub.10 is phenyl substituted by a fragment —OCF.sub.2O— on two adjacent positions; or R.sub.10 is pyridyl mono- or polysubstituted by substituents independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4haloalkoxy or C.sub.1-C.sub.4haloalkyl; or R.sub.10 is pyridyl substituted by a fragment —OCF.sub.2O— on two adjacent positions; X.sub.3 is S, SO or SO.sub.2; Ra.sub.3 is hydrogen, C.sub.1-C.sub.4haloalkoxy or C.sub.1-C.sub.4haloalkyl; R.sub.13 is C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.8 is hydrogen or C.sub.1-C.sub.4alkyl.

9. A compound of formula I according to claim 1, represented by the compounds of formula I-4 ##STR00119## wherein A is N or CH; R.sub.10′ is a diazine radical selected from the group consisting of formula DA1 to DA5, ##STR00120## wherein the arrow denotes the point of attachment to the triazole ring, and said group R.sub.10′ may be mono- or polysubstituted by substituents independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4haloalkoxy or C.sub.1-C.sub.4haloalkyl; X.sub.4 is S, SO or SO.sub.2; Ra.sub.4 is hydrogen, C.sub.1-C.sub.4haloalkoxy or C.sub.1-C.sub.4haloalkyl; R.sub.14 is C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; and R.sub.8 is hydrogen or C.sub.1-C.sub.4alkyl.

10. A pesticidal composition, which comprises at least one compound of formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case 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 practised 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. Plant propagation material treated in accordance with the method described in claim 12.

14. A compound of formula (X) ##STR00121## wherein Q and R.sub.8 are as defined under formula I in claim 1; and L.sub.G is iodine or bromine.

15. A compound of formula (XII) ##STR00122## wherein Q and R.sub.8 are as defined under formula I in claim 1.

Description

BIOLOGICAL EXAMPLES

Example B1: Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)

Larvicide, Feeding/Residual Contact Activity, Preventive

[0418] Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions.

[0419] After drying, the leaf discs were infested with 5 L1 larvae. The samples were checked for mortality, repellent effect, feeding behaviour, and growth regulation 3 days after treatment (DAT).

[0420] In this test, compounds P1, P2, P4, P5, P7, P10, P12, P15, P16, P20, P21, P22, P24, P33, P46, P48, P56, P59, P60, P61, P62, P63, P64, P65, P66, P68, P69 and P71 showed an activity of over 80% at a concentration of 400 ppm.

Example B2: Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)

(Systemic Activity)

[0421] Test compounds were applied by pipette into 24 well plates and mixed with agar. Lettuce seeds were placed on the agar and the multi well plate is closed by another plate which contains also agar. After 7 days the roots have absorbed the compound and the lettuce has grown into the lid plate. The lettuce leaves were now cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil on a humid gel blotting paper and the plate closed with it. The samples are checked for mortality, repellent effect, feeding behavior, and growth regulation 5 days after infestation.

[0422] In this test, compounds P2, P5, P7, P33, P60, P65, P66 and P68 showed an activity of at least 80% at a concentration of 12.5 ppm.

Example B3: Activity Against Plutella xylostella (Diamond Back Moth)

(Larvicide, Feeding/Residual Contact Activity, Preventive)

[0423] 24-well microtiter plate (MTP) with artificial diet was treated with test solutions by pipetting. After drying, the MTPs were infested with L2 larvae (10-15 per well). After an incubation period of 5 days, samples were checked for larval mortality, antifeedant and growth regulation.

[0424] In this test, compounds P1, P2, P4, P5, P7, P12, P24, P29, P33, P59, P60, P61, P62, P66, P67, P68, P69, P71, P72 and P76 showed an activity of over 80% ata concentration of 400 ppm.

Example B4: Activity Against Diabrotica Balteata (Corn Root Worm)

(Larvae L2 on Maize Sprouts, Feeding/Contact, Preventative)

[0425] Maize sprouts, placed on an agar layer in 24 well micro titer plates were treated with test solutions by spraying. After drying, the MTPs were infested with L2 larvae (6-10 per well). After an incubation period of 5 days, samples were checked for larval mortality and growth regulation.

[0426] In this test, compounds P1, P2, P5, P7, P10, P11, P15, P16, P20, P21, P22, P24, P35, P46, P48, P54, P55, P56, P59, P60, P61, P62, P63, P64, P65, P66, P67, P68, P69, P70, P71 and P76 showed an activity of over 80% at a concentration of 400 ppm.

Example B5: Activity Against Myzus persicae (Green Peach Aphid)

(Feeding/Residual Contact Activity, Preventive), Mixed Population

[0427] Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality and special effects (e.g. phytotoxicity). In this test, compounds P1, P2, P7, P8, P15, P16, P19, P20, P22, P24, P30, P33, P34, P46, P48, P53, P55, P58, P59, P60, P61, P62, P66, P68, P69 and P71 showed an activity of over 80% at a concentration of 400 ppm.

Example B6: Activity Against Myzus persicae (Green Peach Aphid)

(Feeding Activity Sachet Test), Mixed Population

[0428] Test compounds were applied by pipette into 24 well plates and mixed with Sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes is placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate is closed with a gel blotting paper and another plastic stencil and then turned upside down. 5 days after infestation the samples were checked on mortality. Application rate: 12.5 ppm.

[0429] In this test, compounds P2, P7, P15, P20, P22, P24, P30 and P33 showed an activity of at least 80% at a concentration of 12.5 ppm.

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

(Systemic/Feeding Activity, Curative), Mixed Population

[0430] Roots of pea seedlings, infested with an aphid population of mixed ages, were placed directly in the test solutions. 6 days after introduction, samples were checked for mortality and special effects on the plant.

[0431] In this test, compounds P2, P6, P7, P8, P14, P34, P35, P55, P58, P60, P66, P68, P69 and P71 showed an activity of at least 80% at a concentration of 24 ppm.

Example B8: Activity Against Thrips tabaci (Onion Thrips)

(Mixed Population, Feeding/Residual Contact Activity, Preventive)

[0432] Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with a thrips population of mixed ages. After an incubation period of 7 days, samples were checked for mortality and special effects (e.g. phytotoxicity).

[0433] In this test, compounds P1, P2, P59, P60, P65, P67, P72 and P76 showed an activity of over 80% at a concentration of 400 ppm.

Example B9: Activity Against Bemisia tabaci (Cotton White Fly)

(Adulticide Contact Activity, Preventative), Adult

[0434] Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with adult white flies. After an incubation period of 7 DAT, samples were checked for mortality and special effects (e.g. phytotoxicity).

[0435] In this test, compounds P1, P2, P7, P8, P48, P49, P58, P59, P60, P61, P68 and P69 showed an activity of over 80% at a concentration of 400 ppm.

Example B10: Activity Against Euschistus heros (Neotropical Brown Stink Bug)

[0436] Soybean leaf 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 were infested with N-2 nymphs. The samples were assessed for mortality 5 days after infestation.

[0437] In this test, compounds P48, P62 and P69 showed an activity of over 80% at a concentration of 400 ppm.

Example B11: Activity Against Frankliniella occidentalis (Western Flower Thrips)

(Mixed Population, Feeding/Contact, Preventative)

[0438] Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with a Frankliniella population of mixed ages. After an incubation period of 7 DAT, samples are checked for mortality and special effects (e.g. phytotoxicity). In this test, compound P42 showed an activity of over 80% at a concentration of 400 ppm.

Example B12: Activity Against Tetranychus urticae (Two-Spotted Spider Mite)

[0439] 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.

[0440] The following compounds resulted in at least 80% mortality at an application rate of 400 ppm: P6, P11, P29 and P57.

Example B13: Activity Against Aedes aegypti (Yellow Fever Mosquito)

[0441] Test solutions, at an application rate of 200 ppm in ethanol, were applied to 12-well tissue culture plates. Once the deposits were dry, five, two to five days old adult female Aedes aegypti were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.

[0442] The following compounds gave at least 80% control of Aedes aegypti after 48 hours: P60 and P62.