PESTICIDALLY ACTIVE AZETIDINE SULFONES AMIDE ISOXAZOLINE DERIVATIVES

Abstract

Compounds of formula (I), 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 and can be prepared in a manner known per se.

##STR00001##

Claims

1. A compound of formula (I), ##STR00017## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4, independently of one another, are C—H, C—R.sup.5 or nitrogen; wherein not more than two of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are N; R.sup.1 is selected from C.sub.3-C.sub.6cycloalkylcarbonyl, —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) and —R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c); 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.8alkyl, 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 C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8haloakyl; 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 selected from 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 and C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge; and R.sup.7 is independently selected from halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkoxy and C.sub.1-C.sub.8haloalkoxy; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide thereof.

2. The compound according to claim 1, wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently selected from C—H and C—R.sup.5; R.sup.1 is selected from C.sub.3-C.sub.6cycloalkylcarbonyl, —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)NHR.sup.1b, —R.sup.1aOC(═O)N(R.sup.1b)(R.sup.1c), —R.sup.1aC(═O)NHR.sup.1b, —and R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c); 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.8alkyl, 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 C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8haloakyl; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is phenyl which is unsubstituted or substituted by one to three R.sup.7; R.sup.5 is independently selected from 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 and C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge; and R.sup.7 is independently selected from halogen and C.sub.1-C.sub.8haloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide thereof.

3. The compound according to claim 1, wherein A.sup.2, A.sup.3 and A.sup.4 are C—H and A.sup.1 is C—R.sup.5; R.sup.5 is C.sub.1-C.sub.4alkyl.

4. The compound according to claim 1, wherein R.sup.4 is phenyl which is substituted by one to three R.sup.7 and wherein R.sup.7 is halogen or C.sub.1-C.sub.8haloalkyl.

5. The compound according to claim 1, wherein R.sup.4 is selected from 3,5-bis-(trifluoromethyl)-phenyl, 3-chloro-5-trifluoromethyl-phenyl, 3-bromo-5-trifluoromethyl-phenyl, 3,5-dibromo-phenyl, 3,5-dichloro-phenyl, 3,4-dichloro-phenyl, 3-trifluoromethyl-phenyl, 4-bromo-3,5-dichlorophenyl, 3,5-dichloro-4-fluoro-phenyl and 3,4,5-trichloro-phenyl.

6. The compound according to claim 1, wherein R.sup.3 is —CF.sub.3.

7. The compound according to claim 1, wherein R.sup.2 is selected from methyl, ethyl, propyl, isopropyl, CH.sub.2F, CH.sub.2Cl, CH.sub.2Br, CHF.sub.2, CF.sub.3, CH.sub.2CH.sub.2CF.sub.3 and CH.sub.2CF.sub.3.

8. The compound according to claim 1, wherein R.sup.1 is selected from —R.sup.1aOC(═O)OR.sup.1b and —R.sup.1aN(R.sup.c)C(═O)OR.sup.1b; wherein R.sup.1a is —(CR.sup.1dR.sup.1e).sub.n—; R.sup.1b and R.sup.1c are independently selected from C.sub.1-C.sub.8alkyl, 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 1 or 2.

9. A compound of formula (Int-I) ##STR00018## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4, independently of one another, are C—H, C—R.sup.5 or nitrogen; wherein not more than two of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are N: R.sup.1 is selected from C.sub.3-C.sub.6cycloalkylcarbonyl, —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) and —R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c); 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.8alkyl, 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 C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8haloakyl; R.sup.5 is independently selected from 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 and C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge; and R.sup.6 is hydrogen or S(O).sub.2R.sup.2 and X.sup.B is a halogen, or X.sup.B is cyano, formyl, CH═N—OH or acetyl; or a salt or N-oxide thereof.

10. A compound of formula (Int-II) ##STR00019## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4, independently of one another, are C—H, C—R.sup.5 or nitrogen, wherein not more than two of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are N; R.sup.1 is selected from C.sub.3-C.sub.6cycloalkylcarbonyl, —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) and —R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c); 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.8alkyl, 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 C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8haloakyl; R.sup.5 is independently selected from 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 and C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge; R.sup.6 is hydrogen or S(O).sub.2R.sup.2 and X.sup.C is CH.sub.2-halogen, wherein halogen is bromo or chloro, CH═C(R.sup.3)R.sup.4 or CH.sub.2C(OH)(R)R.sup.4; 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.7 is independently selected from halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkoxy and C.sub.1-C.sub.8haloalkoxy; or a salt or N-oxide thereof.

11. A compound of formula (Int-III) ##STR00020## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4, independently of one another, are C—H, C—R.sup.5 or nitrogen, wherein not more than two of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are N; R.sup.1 is selected from C.sub.3-C.sub.6cycloalkylcarbonyl, —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) and —R.sup.1aC(═O)N(R.sup.1b)(R.sup.1c); 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.8alkyl, 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.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 selected from 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 and C.sub.1-C.sub.8alkoxycarbonyl-, or two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge and R.sup.7 is independently selected from halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkoxy and C.sub.1-C.sub.8haloalkoxy; and R.sup.6 is hydrogen; or a salt or N-oxide thereof.

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 and at least one auxiliary.

13. A method for controlling pests, which comprises applying a composition according to claim 12 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 seeds from the attack by pests, which comprises treating the seeds or the site, where the seeds are planted, with a composition according to claim 12.

15. The compound according to claim 3 wherein R.sup.5 is methyl.

Description

PREPARATORY EXAMPLES

[0371] The following Examples illustrate, but do not limit, the invention.

[0372] The 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, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm, 0.4 ppm, 0.2 ppm, 0.1 ppm or even at lower concentrations.

[0373] “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 relative to a TMS standard. Spectra measured in deuterated solvents as indicated (br means that the following signal pattern is broad e.g. br s is a broad singlet; s=singlet; d=doublet; m=multiplet).

Example 1: Preparation of [[4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-benzoyl]-[1-(difluoromethylsulfonyl)azetidin-3-yl]amino]methyl methyl carbonate (Compound A2)

[0374] ##STR00015##

[0375] To a solution of 4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[1-(difluoromethylsulfonyl)azetidin-3-yl]-2-methyl-benzamide (1000 mg) in tetrahydrofuran (8.23 mL) was added chloromethyl methylcarbonate (1.062 g) at −40° C., under argonatmosphere. The reaction mixture was stirred for 30 min and then a potassium tert-butoxide solution in tetrahydrofuran (2.48 mL, 1M) was added at −40° C. and the mixture was stirred for 90 min, then it was warmed to room temperature and stirred for 4 hours. To the obtained mixture was added water and the water phase was separated and extracted with ethyl acetate. The organic phases were combined, dried over sodium sulfate, filtered and evaporated under reduced pressure. The obtained crude was purified by chromatography over silica gel with ethyl acetate-cyclohexane mixture as an eluent (gradient from 0:1 to 1:1), then a reverse phase chromatography to give [[4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-benzoyl]-[1-(difluoromethylsulfonyl)azetidin-3-yl]amino]methyl methyl carbonate (38 mg) as foam. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.53-7.64 (m, 4H) 7.25-7.32 (m, 1H) 6.04-6.44 (m, 1H) 5.24 (m, 2H) 4.92 (m, 1H) 4.38-4.59 (m, 4H) 4.05-4.18 (m, 1H) 3.78 (s, 3H) 3.69 (d, 1H) 2.35 (s, 3H). 19F NMR (377 MHz, CHLOROFORM-d) δ ppm−79.46 (s, 3F)−113.44 (s, 1F)−121.09 (s, 2F).

[0376] The other compounds were prepared in a similar manner as Example 1.

TABLE-US-00014 TABLE A Compounds of formula AA (AA) [00016] Compound number R1 R2 A1 —CH2N(CH3)C(O)OCH3 CHF2 A2 —CH2OC(O)OCH3 CHF2

TABLE-US-00015 TABLE A-DATA NMR data of Compounds of formula AA as described in Table A: Com- pound Number 1H NMR 19F NMR A1 1H NMR (400 MHz, CDCl3) δ ppm 19F NMR (376 MHz, 7.55-7.63 (m, 4 H) 7.29-7.41 (m, 1 H) CDCl3) δ ppm-79.53 6.03-6.45 (m, 1 H) 4.27-5.00 (m, 6 H) (s, 3 F)-113.38 (s, 1 F)- 4.01-4.16 (m, 1 H) 3.66-3.81 (m, 4 H) 121.07 (s, 2 F) 2.51-3.20 (m, 3 H) 2.39 (br s, 3 H) A2 1H NMR (400 MHz, CDCl3) δ ppm 19F NMR (376 MHz, 7.53-7.64 (m, 4 H) 7.25-7.32 (m, 1 H) CDCl3) δ ppm-79.46 6.04-6.44 (m, 1 H) 5.24 (m, 2 H) 4.92 (s, 3 F)-113.44 (s, 1 F)- (m, 1 H) 4.38-4.59 (m, 4 H) 4.05-4.18 121.09 (s, 2 F) (m, 1 H) 3.78 (s, 3 H) 3.69 (d, 1 H) 2.35 (s, 3 H)

Biological Examples

[0377] These Examples illustrate the pesticidal/insecticidal properties of compounds of formula (Ia).

[0378] Tests were performed as follows:

[0379] Euschistus heros(Neotropical Brown Stink Bug)

[0380] 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.

[0381] 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

[0382] Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0383] 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.

[0384] The following compounds resulted in at least 80% control at an application rate of 200 ppm: A1, A2