INSECTICIDAL COMPOUNDS

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, and their uses as insecticides.

##STR00001##

Claims

1. A compound of formula (I), ##STR00049## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are, independently of one another, C—H, C—R.sup.5 or N; B.sup.1—B.sup.2—B.sup.3—B.sup.4 is —C(R.sup.5aR.sup.5b)—C═N—O—, —CH.sub.2—C═N—CH.sub.2—, —CH.sub.2—C═CH.sub.2—S—, —CH.sub.2—C═N—S—, —CH.sub.2—N—CH.sub.2—CH.sub.2—, —CH.sub.2—C═CH—O—, —CH(OH)—N—CH.sub.2—CH.sub.2—, —C(O)—N—CH.sub.2—CH.sub.2- or —CH═C—CH.sub.2—O—; R.sup.1 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylcarbonyl-, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkoxy-C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxycarbonyl, C.sub.1-C.sub.8alkylcarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxycarbonylsulfanyl, C.sub.1-C.sub.8alkylaminocarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8dialkylaminocarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylaminocarbonylC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8dialkylaminocarbonylC.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkoxycarbonylC.sub.1-C.sub.8alkylaminoC.sub.1-C.sub.8alkyl, wherein each alkyl or alkoxy group may be optionally substituted with from one to three halogen atoms or with a cyano group; or R.sup.1 is selected from —(C.sub.0-C.sub.4alkyl)-C(═O)—C.sub.3-C.sub.6cycloalkyl, —(C.sub.0-C.sub.4alkyl)-O—C(═O)—C.sub.3-C.sub.6cycloalkyl, —(C.sub.0-C.sub.4alkyl)-O—C.sub.3-C.sub.6cycloalkyl, —R.sup.1aOR.sup.1aOR.sup.1b, —R.sup.1aOC(═O)R.sup.1b, —R.sup.1aOC(═O)OR.sup.1b, —R.sup.1aN(R.sup.1c)C(═O)OR.sup.1b, —R.sup.1aOC(═O)N(R.sup.1b)(R.sup.1c), —R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c) and —S—C(═O)OR.sup.1b; R.sup.1a is —(CR.sup.1dR.sup.1e).sub.n; R.sup.1b and R.sup.1c are independently selected from H and C.sub.1-C.sub.4alkyl, wherein each alkyl group is unsubstituted or substituted with one to three halogen atoms or with a cyano group; R.sup.1d and R.sup.1e are independently selected from H and C.sub.1-C.sub.4alkyl; n is selected from 1, 2, 3 and 4; R.sup.2 is cyano, C(S)NH.sub.2 or C(O)NH.sub.2; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is aryl, aryl substituted by one to three R.sup.7, heteroaryl or heteroaryl substituted by one to three R.sup.7; R.sup.5 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8haloalkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, or C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge, a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH(OH)—CH.sub.2—CH.sub.2— bridge, a —C(O)—CH.sub.2—CH.sub.2— bridge or a —N═CH—CH═CH— bridge; R.sup.5a and R.sup.5b are, independently of each other, hydrogen, cyano, halogen, hydroxyl, C.sub.1-C.sub.8alkyl-, C.sub.1-C.sub.8alkyl- substituted by one to five R.sup.6a, C.sub.1-C.sub.8alkylthio-, C.sub.1-C.sub.8haloalkylthio-, C.sub.1-C.sub.8alkylsulfinyl-, C.sub.1-C.sub.8haloalkylsulfinyl-, C.sub.1-C.sub.8alkylsulfonyl-, C.sub.1-C.sub.8haloalkylsulfonyl-, arylthio- or arylthio- wherein the aryl moiety is substituted by one to five R.sup.7, arylsulfinyl- or arylsulfinyl- wherein the aryl moiety is substituted by one to five R.sup.7, arylsulfonyl- or arylsulfonyl- wherein the aryl moiety is substituted by one to five R.sup.7, heterocyclylthio- or heterocyclylthio- wherein the heterocyclyl moiety is substituted by one to five R.sup.7, heterocyclylsulfinyl- or heterocyclylsulfinyl- wherein the heterocyclyl moiety is substituted by one to five R.sup.7, or heterocyclylsulfonyl- or heterocyclylsulfonyl- wherein the heterocyclyl moiety is substituted by one to five R.sup.7, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkenyl, C.sub.1-C.sub.8alkoxy, or C.sub.1-C.sub.8haloalkoxy, provided that at least one of R.sup.5a and R.sup.5b is not hydrogen; R.sup.6 is hydrogen or C.sub.1-C.sub.8alkyl; R.sup.6a is independently halogen, cyano, nitro, amino, hydroxy, oxo, C.sub.1-C.sub.8alkylamino, hydroxyimino, C.sub.1-C.sub.8alkyloxyimino, di-C.sub.1-C.sub.8alkylamino, C.sub.1-C.sub.8alkoxy, acetyloxy, formyloxy, C.sub.1-C.sub.8haloalkoxy, C.sub.1-C.sub.4alkylthio or (C.sub.1-C.sub.4alkyl).sub.0-3silyl; R.sup.7 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy; or an agrochemically acceptable salt, tautomer and N-oxide thereof.

2. The compound according to claim 1, wherein A.sup.1 is C—R.sup.5; A.sup.2 is C—H; A.sup.3 is C—H; and A.sup.4 is C—H, wherein R.sup.5 is halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.8haloalkyl or C.sub.2-C.sub.8alkenyl.

3. The compound of formula (I) according to claim 1, wherein R.sup.2 is halogen, C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.5cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy or di-C.sub.1-C.sub.4alkylamino, C.sub.1-C.sub.4alkylthio or C.sub.1-C.sub.4alkyloxycarbonyl.

4. The compound of formula (I) according to claim 1, wherein R.sup.1 is hydrogen, formyl, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylcarbonyl- or C.sub.1-C.sub.8alkoxycarbonyl-.

5. The compound of formula (I) according to claim 1, wherein R.sup.1 is C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylcarbonyl-, C.sub.3-C.sub.6cycloalkylcarbonyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkoxy-C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxycarbonyl, C.sub.1-C.sub.8alkylcarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxycarbonylsulfanyl, C.sub.1-C.sub.8alkylaminocarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8dialkylaminocarbonyloxyC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkylaminocarbonylC.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8dialkylaminocarbonylC.sub.1-C.sub.8alkyl, or C.sub.1-C.sub.8alkoxycarbonylC.sub.1-C.sub.8alkylaminoC.sub.1-C.sub.8alkyl, wherein each alkyl or alkoxy group may be optionally substituted with from one to three halogen atoms

6. The compound of formula (I) according to claim 4, wherein R.sup.1 is C.sub.1-C.sub.8cyanoalkyl, C.sub.1-C.sub.8alkoxy-C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxycarbonyl or C.sub.1-C.sub.8alkylcarbonyloxyC.sub.1-C.sub.8alkyl.

7. The compound of formula (I) according to claim 6, wherein R.sup.1 is cyanomethyl, methoxymethyl, ethoxymethyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxymethyl, 1-methylethylcarbonyloxymethyl or 1,1-dimethylethylcarbonyloxymethyl.

8. The compound according to claim 1, wherein R.sup.3 is C.sub.1-C.sub.4haloalkyl.

9. The compound according to claim 1, wherein R.sup.4 is phenyl or phenyl substituted by one to three R.sup.6b; R.sup.6b independently is R.sup.6b independently is halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, or C.sub.1-C.sub.4haloalkoxy.

10. The compound according to claim 1, wherein R.sup.5a is halogen, hydroxyl, C.sub.1-C.sub.8alkylthio-, C.sub.1-C.sub.8haloalkylthio-, C.sub.1-C.sub.8alkylsulfinyl-, C.sub.1-C.sub.8haloalkylsulfinyl-, C.sub.1-C.sub.8alkylsulfonyl-, C.sub.1-C.sub.8haloalkylsulfonyl-, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8haloalkenyl; R.sup.5b is halogen or hydrogen.

11. The compound according to claim 1, wherein R.sup.5 is halogen, cyano, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8 alkenyl, C.sub.3-C.sub.8cycloalkyl, or C.sub.1-C.sub.8haloalkyl.

12. 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.

13. A method for controlling pests, which comprises applying a composition according to claim 13 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.

14. 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 13.

15. A plant propagation material treated with the pesticidal composition of claim 12.

Description

PREPARATORY EXAMPLES

[0273] “Mp” means melting point in ° C. Free radicals represent methyl groups. .sup.1H and .sup.19F NMR measurements were recorded on Brucker 400 MHz or 300 MHz spectrometers, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated.

[0274] The compounds from this application were prepared using standard coupling conditions with BOP—Cl as a coupling agent, following the generic reaction scheme below:

##STR00043##

[0275] The following LC-MS method was used to characterize the compounds:

TABLE-US-00003 Method A Waters Aquity UPLC-MS using a Sample Organizer with Sample Manager FTN, H-class QSM, Column Manager, 2× Column Manager Aux, photodiode array, ELSD and SQD 2 equipped with a Waters HSS T3 C18 column (column length 30 mm, internal diameter of column 2.1 mm, particle size 1.8 micron). The analysis was conducted using a two minute run time, according to the following gradient table: Time (mins) Solvent A (%) Solvent B (%) Flow (ml/mn) 0 95 5 0.7 1.75 0 100 0.7 1.76 0 100 0.7 2 0 5 0.7 2.01 95 5 0.7 2.11 95 5 0.7 Solvent A: H.sub.2O with 0.05% trifluoroacetic acid (TFA) Solvent B: CH.sub.3CN with 0.05% trifluoroacetic acid (TFA)

TABLE-US-00004 TABLE A1 (analytic data of the compounds of Table A): Compound RT LC-MS number IUPAC name STRUCTURE (min) [M + H] Method A1 N-[(1- cyanocyclopropyl)methy]- 4-[(5S)-5-(3,5- dichlorophenyl)-5- (trifluoromethyl)-4H- isothiazol-3-yl]-2-methyl- benzamide [00044] 1.65 512.3 A A2 N-[(1- cyanocyclopropyl)methyl]- 4-[2-(3,5-dichlorophenyl)- 2-(trifluoromethyl)-3H- furan-4-yl]-2-methyl- benzamide [00045] 1.63 495.4 A A3 4-[(4S,5R)-4-chloro-5- (3,5-dichlorophenyl)-5- (trifluoromethyl)-4H- isoxazol-3-yl]-N-[(1- cyanocyclopropyl)methyl]- 2-methyl-benzamide [00046] 1.64 530.3 A A4 N-[(1- cyanocyclopropyl)methyl]- 4-[3-(3,5-dichloro-4- fluorophenyl)-3- (trifluoromethyl)-2,4- dihydropyrrol-5-yl]-2- methyl-benzamide [00047] 1.42 512.4 A A5 N-[(1- cyanocyclopropyl)methyl]- 2-methyl-4-[3-(3,4,5- trichlorophenyl)-3- (trifluoromethyl)-2,4- dihydropyrrol-5- yl]benzamide [00048] 1.49 528.3 A

Biological Examples

[0276] These Examples illustrate the pesticidal/insecticidal properties of compounds of formula (I).

[0277] Tests were performed as follows:

Example B1

[0278] Diabrotica balteata (Corn Root Worm)

[0279] 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.

[0280] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: A1, A2, A3, A4, A5

Example B2

[0281] Euschistus heros(Neotropical Brown Stink Bug)

[0282] 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.

[0283] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: A1, A2, A3, A4, A5

Example B3

Myzus persicae (Green Peach Aphid). Intrinsic Activity

[0284] 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.

[0285] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: A1, A2, A3, A4, A5

Example B4

[0286] Plutella xylostella (Diamond Back Moth)

[0287] 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 (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

[0288] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: A1, A2, A3, A4, A5

Example B5

Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0289] 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.

[0290] The following compounds resulted in at least 80% control at an application rate of 200 ppm: A1, A2, A3, A4, A5

Example B6

[0291] Tetranychus urticae (Two-Spotted Spider Mite):Feeding/Contact Activity

[0292] 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.

[0293] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A1, A2, A3, A4, A5

Example B7

[0294] Thrips tabaci (Onion Thrips) Feeding/Contact Activity

[0295] Sunflower leaf discs were placed on 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 a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation.

[0296] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A1, A2, A3, A4, A5