Insecticidal compounds

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, and their uses as insecticides. ##STR00001##

Claims

1. A compound of formula (I), ##STR00070## 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—, —CH.sub.2—C═N—O— or —CH═C—CH.sub.2—O—; R.sup.1 is hydrogen, formyl, 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, C.sub.1-C.sub.8alkoxycarbonylC.sub.1-C.sub.8alkylaminoC.sub.1-C.sub.8alkyl, phenyl-C.sub.1-C.sub.8alkoxycarbonyl, phenyl-C.sub.1-C.sub.4alkyl or phenyl-C.sub.1-C.sub.4alkyl wherein the phenyl moiety is substituted by one to three R.sup.7, wherein each alkyl or alkoxy group may be optionally substituted with from one to three halogen atoms or with a cyano group; R.sup.2 is hydrogen, halogen, cyano, C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkyl substituted by one to three R.sup.6a, C.sub.1-C.sub.8haloalkyl or C.sub.1-C.sub.8haloalkyl substituted by one to three R.sup.6a, C.sub.3-C.sub.8cycloalkyl or C.sub.3-C.sub.8cycloalkyl substituted by one to three R.sup.6b, C.sub.3-C.sub.8cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl or C.sub.2-C.sub.8alkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8haloalkenyl or C.sub.2-C.sub.8haloalkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, phenyl, phenyl substituted by one to three R.sup.7, phenyl-C.sub.1-C.sub.4alkyl, phenyl-C.sub.1-C.sub.4alkyl wherein the phenyl moiety is substituted by one to three R.sup.7, 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R.sup.7, 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl or 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl wherein the heteroaryl moiety is substituted by one to three R.sup.7, —NH(R.sup.8), —N(R.sup.8)(R.sup.9), —OR.sup.10, —SR.sup.10, —S(O)R.sup.10, —S(O).sub.2R.sup.10, COR.sup.10, COOR.sup.10; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is phenyl or phenyl substituted by one to three R.sup.6b or pyridine or pyridine substituted by one to three R.sup.6b; 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; each 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; each R.sup.6b is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, amino, C.sub.1-C.sub.8alkylamino, di-C.sub.1-C.sub.8alkylamino, hydroxyl, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.8alkoxy or C.sub.1-C.sub.8haloalkoxy; 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, or C.sub.1-C.sub.8haloalkoxy; R.sup.8 and R.sup.9 are independently hydrogen, cyano, C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkyl substituted by one to three R.sup.6a, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, C.sub.1-C.sub.8haloalkoxy substituted by one to three R.sup.6a, C.sub.1-C.sub.8alkoxy substituted by one to three R.sup.6a, C.sub.1-C.sub.8haloalkyl or C.sub.1-C.sub.8haloalkyl substituted by one to three R.sup.6a, C.sub.3-C.sub.8cycloalkyl or C.sub.3-C.sub.8cycloalkyl substituted by one to three R.sup.6b, C.sub.3-C.sub.8cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl or C.sub.2-C.sub.8alkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8haloalkenyl or C.sub.2-C.sub.8haloalkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, phenyl, phenyl substituted by one to three R.sup.7, phenyl-C.sub.1-C.sub.4alkyl, phenyl-C.sub.1-C.sub.4alkyl wherein the phenyl moiety is substituted by one to three R.sup.7, 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R.sup.7, 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl or 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl wherein the heteroaryl moiety is substituted by one to three R.sup.7, or R.sup.8 and R.sup.9 together with the nitrogen atom can be linked through a C.sub.3-C.sub.8alkylene chain, a C.sub.3-C.sub.8alkylene chain substituted by one to three R.sup.6b or a C.sub.3-C.sub.8alkylene chain, where one carbon atom is replaced by O, S, S(O) or SO.sub.2; R.sup.10 is hydrogen, cyano, C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkyl substituted by one to three R.sup.6a, C.sub.1-C.sub.8haloalkyl or C.sub.1-C.sub.8haloalkyl substituted by one to three R.sup.6a, C.sub.3-C.sub.8cycloalkyl or C.sub.3-C.sub.8cycloalkyl substituted by one to three R.sup.6b, C.sub.3-C.sub.5cycloalkyl where one carbon atom is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8alkyl where one carbon atom in the cycloalkyl group is replaced by O, S, S(O) or SO.sub.2, or C.sub.3-C.sub.8cycloalkyl-C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl or C.sub.2-C.sub.8alkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8haloalkenyl or C.sub.2-C.sub.8haloalkenyl substituted by one to three R.sup.6a, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, phenyl, phenyl substituted by one to three R.sup.7, phenyl-C.sub.1-C.sub.4alkyl, phenyl-C.sub.1-C.sub.4alkyl wherein the phenyl moiety is substituted by one to three R.sup.7, 5-6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R.sup.7, 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl or 5-6 membered heteroaryl-C.sub.1-C.sub.4alkyl wherein the heteroaryl moiety is substituted by one to three R.sup.7; and an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide thereof.

2. A compound of formula (I) 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. A 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, C.sub.1-C.sub.4alkyloxycarbonyl.

4. A 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. A 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. A 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. A 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. A compound of formula (I) according to claim 1, wherein R.sup.3 is C.sub.1-C.sub.4haloalkyl.

9. A compound of formula (I) 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.8alkenyl, 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 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 practiced 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 12.

15. Plant propagation material treated with the pesticidal composition described in claim 12.

16. The compound according to claim 1, provided that if B.sup.1—B.sup.2—B.sup.3—B.sup.4 is —CH.sub.2—C═N—O— then the only meaning of R.sup.5 is that two R.sup.5 on adjacent carbon atoms together form a —CH.sub.2—CH.sub.2—CH.sub.2— bridge, —CH(OH)—CH.sub.2—CH.sub.2— bridge or a —C(O)—CH.sub.2—CH.sub.2— bridge.

17. A compound of formula (Int-VIII), ##STR00071## wherein Z is optionally substituted alkyl or optionally substituted arylalkylene, and A.sup.1, A.sup.2, A.sup.3, A.sup.4, Gi, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and n are as defined for a compound of formula (I) according to claim 1; or a tautomer, enantiomer, salt or N-oxide thereof.

18. A compound of formula (Int-X), ##STR00072## wherein Ti and T.sup.2 are independently CH2 or C═O or CHOH, providing that at least one of T.sup.1 and T.sup.2 is C═O or CHOH and A.sup.1, A.sup.2, A.sup.3, A.sup.4, G.sup.1, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and n are as defined for a compound of formula (I) according to claim 1; or a tautomer, enantiomer, salt or N-oxide thereof.

Description

PREPARATORY EXAMPLES

(1) “Mp” means melting point in ° C. Free radicals represent methyl groups. .sup.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated.

(2) The following LC-MS methods were used to characterize the compounds:

(3) TABLE-US-00012 Method A MS Spectra were recorded on a Mass Spectrometer from Waters (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da). LC Acquity UPLC from Waters: Binary pump, heated column compartment and diode- array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

(4) TABLE-US-00013 Method B MS Spectra were recorded on a Mass Spectrometer from Waters (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 45 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da). LC Acquity UPLC from Waters: Binary pump, heated column compartment and diode- array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

(5) TABLE-US-00014 Method C MS Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) LC Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 um, 30 × 2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH, gradient: 10-100% B in 2.7 min; Flow (ml/min) 0.85

Preparation of N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide

(6) ##STR00061##

(7) To a cooled (0-5° C.) solution of N-vinylformamide (13.0 g) in ethyl acetate (366 mL), was added a solution of sodium bicarbonate (77.6 g) in water (183 mL). After 15 min, to this bi-phasic suspension was added a solution of dibromomethanone oxime (40.8 g) in ethyl acetate (50 mL), while maintaining the temperature between 5-10° C. (a slow gas evolution was observed). After completion of the addition, the reaction was further stirred at room temperature (rt) for 3.5 hours. The mixture was then extracted twice between ethyl acetate and water. The combined organic layers were dried (MgSO.sub.4), filtered and evaporated under vacuo to give 32.6 g of a cloudy brown oil, which corresponds to the desired N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide and could be used as such in the next steps. .sup.1H-NMR (CDCl.sub.3, 400 MHz, 6 in ppm): 3.02-3.19 (m, 1H) 3.49-3.66 (m, 1H) 5.86-6.43 (m, 1H) 6.84-7.25 (m, 1H) 8.16-8.31 (m, 1H)

Preparation of tert-butyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)carbamate

(8) ##STR00062##

Method 1: From tert-butyl N-vinylcarbamate

(9) A suspension of tert-butyl N-vinylcarbamate (25.0 g) and potassium carbonate (49.2 g) in tetrahydrofuran (262 mL) was cooled to 0-5° C. To this mixture was then added a solution of dibromomethanone oxime (39.0 g) in tetrahydrofuran (89.0 mL) at 0-5° C. and was stirred for one hour. The reaction mixture was then stirred at rt for 3 hours. The mixture was then extracted twice between ethyl acetate and water. The combined organic layers were dried (MgSO.sub.4), filtered and evaporated under vacuo to give a 46.1 g of a crude compound.

(10) 30 g of this crude were stirred with 50 ml of diethylether for 2 hours. The resulting beige suspension was filtered, washed with 2×20 ml of diethylether and 2×50 ml of pentane then was dried under vacuo to give 26.54 g of a white solid corresponding to the desired tert-butyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)carbamate. .sup.1H-NMR (CDCl.sub.3, 400 MHz, 6 in ppm): 1.47 (s, 9H) 2.95 (dd, J=18, 4.8 Hz, 1H) 3.49 (dd, J=18, 9.7 Hz, 1H) 5.42 (br. s., 1H) 6.15 (br. s., 1H)

Method 2: From N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide

(11) In a round bottom flask, N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide (200 mg) was dissolved in tetrahydrofuran (2 mL) then 4-(dimethylamino)pyridine (DMAP, 190 mg) was added at rt. The reaction mixture was cooled and the mixture was kept between 5° C. and 10° C. then a solution of tert-butoxycarbonyl tert-butyl carbonate (250 mg) in THF (2 mL) was added dropwise over a period of 5 min. The resulting mixture was stirred for 4 hr at rt. Then a solution of NaOH (5.18 mL, 1N) was added at rt and the mixture was then stirred for one hour. The mixture was diluted with ethyl acetate then washed with water and brine. The combined organic phases were dried (MgSO.sub.4), filtered and evaporated under vacuo to give a crude mixture, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 70/30). Thus, 185 mg of tert-butyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)carbamate was obtained. .sup.1H-NMR (DMSO-d6, 400 MHz, δ in ppm): 1.40 (s, 9H) 2.94 (dd, J=17.8, 4.6 Hz, 1H) 3.53 (dd, J=17.8, 9.7 Hz, 1H) 5.91 (td, J=9.6, 4.4 Hz, 1H) 8.29 (d, J=9.6 Hz, 1H)

Preparation of tert-butyl N-(3-methoxy-4,5-dihydroisoxazol-5-yl)carbamate

(12) ##STR00063##

(13) To a suspension of tert-butyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)carbamate (21.3 g) in methanol (256 mL), was added sodium methanolate (30% in methanol, 22 mL) at ambient temperature and the solution was stirred for 24h. Then the mixture was extracted with brine and ethyl acetate, the organic layer was washed with brine, dried over anhydrous sodium sulfate and the solvent evaporated. The residue was suspended in −70 ml of diethylether and stirred for 2 hours. The resulting suspension was filtered and the solid was washed with −25 ml diethylether and then with 3×40 ml of pentane. The solid was dried under vacuo to give 12.18 g of tert-butyl N-(3-methoxy-4,5-dihydroisoxazol-5-yl)carbamate as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.46 (s, 9H) 2.68 (dd, J=17.2, 4.0 Hz, 1H) 3.29 (br dd, J=17.2, 8.8 Hz, 1H) 3.87 (s, 3H) 5.34-5.53 (m, 1H) 5.97-6.17 (m, 1H).

(14) Using a similar procedure, using tert-butyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)carbamate and sodium ethoxide, the compound tert-butyl N-(3-ethoxy-4,5-dihydroisoxazol-5-yl)carbamate could be prepared. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.35 (t, J=6.9 Hz, 3H) 1.46 (s, 9H) 2.67 (dd, J=17.1, 4.2 Hz, 1H) 3.29 (dd, J=17.1, 8.9 Hz, 1H) 4.21 (q, J=7.1 Hz, 2H) 5.29-5.54 (m, 1H) 5.92-6.16 (m, 1H)

(15) Using a similar procedure, using N-(3-bromo-4,5-dihydroisoxazol-5-yl)acetamide and sodium methoxide, the compound N-(3-methoxy-4,5-dihydroisoxazol-5-yl)acetamide could be prepared. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 2.02 (s, 3H) 2.74 (dd, J=17.2, 3.7 Hz, 1H) 3.34 (dd, J=17.2, 8.8 Hz, 1H) 3.88 (s, 3H) 6.26 (td, J=8.6, 4.0 Hz, 1H) 6.34-6.58 (m, 1H)

Preparation of benzyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-carbamate

(16) ##STR00064##

(17) To a cold mixture of N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide (0.567 g) in tetrahydrofuran (16 ml), kept between 5° C. to 10° C., sodium hydride (60% in mineral oil, 0.074 g) was added and the reaction mixture was stirred for additional 20 min at ambient temperature. To this mixture was then added benzyl chloroformate (0.5 g) and the reaction was stirred for 2 days at r.t. Then some additional sodium hydride (60% in mineral oil, 0.075 g) and benzyl chloroformate (0.5 g) were added at 0° C. and the mixture was stirred for another 20 min. To this mixture was then added a saturated solution of NH.sub.4Cl (20 ml). Then EtOAc (30 ml) was added and the water phase was extracted with EtOAc (2×30 ml). The combined organic phases were dried (MgSO.sub.4), filtered and evaporated under vacuo to give a crude mixture, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 50/50). Thus 507 mg of benzyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-carbamate was obtained. .sup.1H-NMR (CDCl.sub.3, 400 MHz, 6 in ppm): 3.26-3.52 (m, 2H) 5.25-5.41 (m, 2H) 6.70-6.81 (m, 1H) 7.32-7.49 (m, 5H) 9.21 (s, 1H)

Preparation of N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-acetamide

(18) ##STR00065##

(19) To a mixture of N-(3-bromo-4,5-dihydroisoxazol-5-yl)formamide (1 g) in tetrahydrofuran (25 ml), was added DMAP at ambient temperature then reaction mixture was cooled and the mixture was kept between 5° C. and 10° C. To this mixture, acetic anhydride (0.55 ml) was added dropwise over a period of 5 min and the resulting mixture was stirred at ambient temperature for 20 hours. Then EtOAc and water were added and the water phase was extracted with EtOAc. The combined organic phases were dried over anhydrous magnesium sulfate, filtered and evaporated under vacuo to give a solid (950 mg), which contained N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-acetamide, that could be used as such in the next step. .sup.1H-NMR (CDCl.sub.3, 400 MHz, 6 in ppm): 2.47 (s, 3H) 3.26-3.40 (m, 1H) 3.40-3.54 (m, 1H) 6.66-6.88 (m, 1H) 9.09 (s, 1H)

(20) N-(3-bromo-4,5-dihydroisoxazol-5-yl)acetamide could also be isolated from the same reaction however by performing a basic work up (sodium hydroxide solution). .sup.1H-NMR (CDCl.sub.3, 400 MHz, Q in ppm): 2.03 (s, 3H) 2.93-3.10 (m, 1H) 3.46-3.62 (m, 1H) 6.34 (td, J=9.2, 4.0 Hz, 1H) 6.40-6.60 (m, 1H)

Preparation of benzyl N-(3-methoxy-4,5-dihydroisoxazol-5-yl)carbamate

Step 1: Preparation of Benzyl N-formyl-N-vinyl-carbamate

(21) ##STR00066##

(22) To the cold suspension of sodium hydride (60% in mineral oil, 1.98 g) in tetrahydrofuran (110 mL) was added dropwise N-vinylformamide (1.7 g) and the mixture was stirred for 10 min at 0° C. To this reaction mixture was then added benzyl chloroformate (4 g) portion wise. The reaction mixture was stirred at r.t. for 7 h. To this mixture was then added a saturated solution of NH.sub.4Cl (50 ml). Then the water phase was extracted with EtOAc (2×50 ml). The combined organic phases were dried (Na.sub.2SO.sub.4), filtered and evaporated under vacuo to give a crude mixture, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 50/50). Thus 2 g of benzyl N-formyl-N-vinyl-carbamate was obtained. .sup.1H-NMR (CDCl.sub.3, 400 MHz, δ in ppm): 5.13 (d, J=9.5 Hz, 1H) 5.35 (s, 2H) 5.71 (d, J=16.1 Hz, 1H) 6.62 (dd, J=16.1, 9.5 Hz, 1H) 7.31-7.45 (m, 5H) 9.33 (s, 1H).

Step 2: Preparation of Benzyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-carbamate

(23) ##STR00067##

(24) To a solution of benzyl N-formyl-N-vinyl-carbamate (1.2 g) dissolved in ethyl acetate (29 ml), was added a solution of saturated sodium hydrogencarbonate (29 ml) and solid sodium hydrogencarbonate (2.53 g). To this reaction mixture, dibromomethanone oxime (2.42 g) was added and the reaction was stirred for 18 h. To this mixture was then added a saturated solution of NH.sub.4Cl (30 ml). Then the water phase was extracted with EtOAc (3×50 ml). The combined organic phases were dried (MgSO.sub.4), filtered and evaporated under vacuo to give a crude mixture, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 50/50). Thus, 1.39 g of benzyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-carbamate was obtained. .sup.1H-NMR (CDCl.sub.3, 400 MHz, δ in ppm): 3.25-3.49 (m, 2H) 5.23-5.40 (m, 2H) 6.76 (dd, J=11.0, 5.5 Hz, 1H) 7.32-7.48 (m, 5H) 9.21 (s, 1H)

Step 3: Preparation of benzyl N-(3-methoxy-4,5-dihydroisoxazol-5-yl)carbamate

(25) ##STR00068##

(26) To a solution of benzyl N-(3-bromo-4,5-dihydroisoxazol-5-yl)-N-formyl-carbamate 1.67 g in methanol (51 ml) was added at rt, Cs.sub.2CO.sub.3 (1.68 g) and the reaction mixture was stirred at r.t. for 18h.

(27) To the obtained mixture was added EtOAc (30 ml) then organic phase was washed with Brine (2×30 ml). The combined organic phases were dried (Na.sub.2SO.sub.4), filtered and evaporated under vacuo to give a crude mixture, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 50/50). Thus, 0.377 g of benzyl N-(3-methoxy-4,5-dihydroisoxazol-5-yl)carbamate was obtained. .sup.1H-NMR (CDCl.sub.3, 400 MHz, δ in ppm): 2.73 (d, J=14 Hz, 1H) 3.24-3.42 (m, 1H) 3.88 (s, 3H) 5.04-5.27 (m, 2H) 5.64 (br. s., 1H) 6.09 (br. s., 1H) 7.29-7.44 (m, 5H).

Preparation of 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-N-(3-ethoxy-4,5-dihydroisoxazol-5-yl)-2-methyl-benzamide (Compound A01)

(28) ##STR00069##

(29) To a solution of N-(3-ethoxy-4,5-dihydroisoxazol-5-yl)formamide (121 mg) and dry toluene (382 μL), under argon was added triethylamine (0.09 mL). The solution was heated to 100° C. for 30 min then a solution of 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl-benzoyl chloride (208 mg) in dry toluene (1 mL) was added at this temperature. The reaction was stirred under argon at this temperature for 18h. The reaction mixture was cooled to room temperature and then was slowly quenched with 1N NaOH until the solution has a basic pH. The solution was extracted with ethyl acetate. The organic phases were washed with water followed by brine, dried over Na.sub.2SO.sub.4, filtered and evaporated under vacuo to give a yellow oil, which was then purified by using a Rf Combiflash apparatus, using silica gel and eluted with cyclohexane/EtOAc (100/0 to 60/40). Thus, a mixture of the desired product and acetic acid were obtained. It was further diluted with ethyl acetate and washed with Na.sub.2CO.sub.3. Then the organic phase was washed with water followed by brine, dried over Na.sub.2SO.sub.4, filtered and evaporated under vacuo to give a 57 mg of 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-N-(3-ethoxy-4,5-dihydroisoxazol-5-yl)-2-methyl-benzamide (compound A01). .sup.1H-NMR (CDCl.sub.3, 400 MHz, δ in ppm): 1.37 (t, 3H) 2.49 (s, 3H) 2.86 (dd, 1H) 3.45 (dd, 1H) 3.87 (d, 1H) 4.15-4.31 (m, 3H) 6.32-6.51 (m, 1H) 6.58-6.79 (m, 1H) 7.31 (s, 2H) 7.37-7.47 (m, 2H) 7.51-7.63 (m, 2H).

(30) Similarly, 4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-N-(3-ethoxy-4,5-dihydroisoxazol-5-yl)-2-methyl-benzamide (compound A02) could be prepared. .sup.1H-NMR (CDCl.sub.3, 400 MHz, δ in ppm): .sup.1H NMR (400 MHz, Solvent) 6 ppm 7.34-7.45 (m, 2H) 7.24-7.33 (m, 2H) 6.45-6.58 (m, 1H) 6.34-6.45 (m, 3H) 4.23 (q, 2H) 4.09 (d, 1H) 3.79 (d, 1H) 3.52-3.66 (m, 1H) 3.28-3.52 (m, 2H) 2.75-2.92 (m, 2H) 2.51 (s, 3H) 1.37 (t, 3H).

Biological Examples

(31) These Examples illustrate the pesticidal/insecticidal properties of compounds of formula (I).

(32) Tests were performed as follows:

(33) Diabrotica balteata (Corn Root Worm)

(34) 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.

(35) 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: A01, A02.

(36) Euschistus heros (Neotropical Brown Stink Bug)

(37) 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.

(38) 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: A01, A02.

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

(40) 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.

(41) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A01.

(42) Plutella xylostella (Diamond Back Moth): Feeding/Contact Activity

(43) 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 5 days after infestation.

(44) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A01, A02.

(45) Spodoptera littoralis (Egyptian Cotton Leaf Worm)

(46) 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.

(47) The following compounds resulted in at least 80% control at an application rate of 200 ppm: A01, A02.

(48) Tetranychus urticae (Two-Spotted Spider Mite): Feeding/Contact Activity

(49) 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.

(50) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A01, A02.

(51) Thrips tabaci (Onion thrips) Feeding/Contact Activity

(52) 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.

(53) The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A01, A02.