Pyrazoline derivatives as insecticidal compounds

Abstract

The present invention relates to compounds of formula I ##STR00001##
wherein P is selected from P1 and P2, or P and R.sup.5 together are P3 ##STR00002##
or P is a heterocycle H, selected from H1 to H9 ##STR00003##
wherein Y.sup.1, Y.sup.2, and Y.sup.3 are independently of each other CH, CR.sup.5, or nitrogen; and G.sup.1, G.sup.2, G.sup.3, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6a, R.sup.6b, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, p, n and k are as defined in the claims. The invention also relates to methods of 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 a compound of formula I.

Claims

1. A compound of formula Int-I ##STR00040## wherein Y.sup.1, Y.sup.2, and Y.sup.3 are independently of each other CH, CR.sup.5, or nitrogen; G.sup.1 is oxygen or sulfur; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is aryl or aryl substituted by one to five R.sup.15, or heteroaryl or heteroaryl substituted by one to five R.sup.15; each R.sup.5 is independently hydrogen, halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkenyl, C.sub.2-C.sub.8haloalkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, C.sub.3-C.sub.10cycloalkyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, 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, or C.sub.1-C.sub.8haloalkylsulfonyl, or two R.sup.5 on adjacent carbon atoms together form a CHCHCHCH bridge or a NCHCHCH bridge; R.sup.6a and R.sup.6b are each independently hydrogen, halogen, cyano, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, or C.sub.3-C.sub.8cycloalkyl, or R.sup.6a and R.sup.6b together with the carbon atom to which they are attached may form a 3 to 6-membered carbocyclic ring; each R.sup.15 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, 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, hydroxy, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, mercapto, 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.8alkylcarbonyl, or C.sub.1-C.sub.8alkoxycarbonyl; and R is hydroxy, C.sub.1-C.sub.15alkoxy or halogen; or a salt or N-oxide thereof; or a compound of formula Int-II ##STR00041## wherein Y.sup.1, Y.sup.2, and Y.sup.3 are independently of each other CH, CR.sup.5, or nitrogen; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is aryl or aryl substituted by one to five R.sup.15, or heteroaryl or heteroaryl substituted by one to five R.sup.15; each R.sup.5 is independently hydrogen, halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.1-C.sub.8alkenyl, C.sub.2-C.sub.8haloalkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, C.sub.3-C.sub.10cycloalkyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, 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, or C.sub.1-C.sub.8haloalkylsulfonyl, or two R.sup.5 on adjacent carbon atoms together form a CHCHCHCH bridge or a NCHCHCH bridge; R.sup.6a and R.sup.6b are each independently hydrogen, halogen, cyano, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, or C.sub.3-C.sub.8cycloalkyl, or R.sup.6a and R.sup.6b together with the carbon atom to which they are attached may form a 3 to 6-membered carbocyclic ring; each R.sup.15 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, 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, hydroxy, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, mercapto, 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.8alkylcarbonyl, or C.sub.1-C.sub.8alkoxycarbonyl; and R.sup.a and R.sup.b are independently selected from hydrogen, C.sub.1-C.sub.8carbonyl, C.sub.1-C.sub.8alkoxycarbonyl, or R.sup.a and R.sup.b together are C(O)(CH.sub.2).sub.rC(O)wherein r is 1 to 4, C(C.sub.1-C.sub.3alkyl)CC(C.sub.1-C.sub.3alkyl)C, or group D ##STR00042## or a salt or N-oxide thereof; or a compound of formula Int-III ##STR00043## wherein Y.sup.1, Y.sup.2, and Y.sup.3 are independently of each other CH, CR.sup.5, or nitrogen; R.sup.3 is C.sub.1-C.sub.8haloalkyl; R.sup.4 is aryl or aryl substituted by one to five R.sup.15, or heteroaryl or heteroaryl substituted by one to five R.sup.15; each R.sup.11 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, 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, hydroxy, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, mercapto, 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.8alkylcarbonyl, or C.sub.1-C.sub.8alkoxycarbonyl; each R.sup.15 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, 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, hydroxy, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, mercapto, 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.8alkylcarbonyl, or C.sub.1-C.sub.8alkoxycarbonyl; n is 1 or 2; and R.sup.a and R.sup.b, are as defined for the compounds of formula Int-II, or a salt or N-oxide thereof.

2. The compound of claim 1, wherein the compound has the formula Int-I.

3. The compound of claim 2, wherein R.sup.3 is trifluoromethyl.

4. The compound of claim 2, wherein R.sup.4 is aryl substituted by one to three R.sup.15, wherein R.sup.15 is halogen or C.sub.1-C.sub.8haloalkyl.

5. The compound of claim 2, wherein R.sup.5 is halogen, cyano, C.sub.1-C.sub.8alkyl, or C.sub.1-C.sub.8haloalkyl.

6. The compound of claim 2, wherein Y.sup.1, Y.sup.2, and Y.sup.3 are CH.

7. The compound of claim 1, wherein the compound has the formula Int-II.

8. The compound of claim 7, wherein R.sup.3 is trifluoromethyl.

9. The compound of claim 7, wherein R.sup.4 is aryl substituted by one to three R.sup.15, wherein R.sup.15 is halogen or C.sub.1-C.sub.8haloalkyl.

10. The compound of claim 7, wherein R.sup.5 is halogen, cyano, C.sub.1-C.sub.8alkyl, or C.sub.1-C.sub.8haloalkyl.

11. The compound of claim 7, wherein Y.sup.1, Y.sup.2, and Y.sup.3 are CH.

12. The compound of claim 1, wherein the compound has the formula Int-III.

13. The compound of claim 12, wherein R.sup.3 is trifluoromethyl.

14. The compound of claim 12, wherein R.sup.4 is aryl substituted by one to three R.sup.15, wherein R.sup.15 is halogen or C.sub.1-C.sub.8haloalkyl.

15. The compound of claim 12, wherein R.sup.5 is halogen, cyano, C.sub.1-C.sub.8alkyl, or C.sub.1-C.sub.8haloalkyl.

16. The compound of claim 12, wherein Y.sup.1, Y.sup.2, and Y.sup.3 are CH.

Description

EXAMPLE 1

4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (A1)

(1) ##STR00029##

Step A: 2-(3,5-dichlorophenyl)-, 1,1-trifluoro-3-nitro-propan-2-ol

(2) ##STR00030##
A mixture of 1-(3,5-dichlorophenyl)-2,2,2-trifluoro-ethanone (12.1 g, 50 mmol), CH.sub.3NO.sub.2 (9.15 g, 150 mmol) and piperidine (0.85 g, 10 mmol) was stirred at 90 C. for 16 h. Then, the reaction mixture was poured into diluted hydrochloric acid and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give 2-(3,5-dichlorophenyl)-1,1,1-trifluoro-3-nitro-propan-2-ol (9.09 g, 60%). .sup.1H NMR (300 MHz, DMSO-d.sub.6): 5.13 (d, J=13.5 Hz, 1H), 5.82 (d, J=13.5 Hz, 1H), 7.70-7.71 (m, 1H), 7.7 5 (s, 2H), 8.12 (s, 1H); .sup.19F NMR (282 MHz, DMSO-d.sub.6): 72.4 s, 3F).

Step B: 1, 3-dichloro-5-[(Z)-2-nitro-1-(trifluoromethyl)vinyl]benzene

(3) ##STR00031##

(4) To a solution of 2-(3,5-dichlorophenyl)-1,1,1-trifluoro-3-nitro-propan-2-ol (3.04 g, 10 mmol) in 100 mL of toluene at 0 C. was added SOCl.sub.2 (5.95 g, 50 mmol) and then pyridine (1.58 g, 20 mmol). The mixture was then slowly warmed to room temperature. After stirring for another 3 h, the mixture was filtered. The filtrate was poured into diluter hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to give 1,3-dichloro-5-[(Z)-2-nitro-1-(trifluoromethyl)vinyl]benzene (1.71 g, 60% yield). .sup.1H NMR (300 MHz, DMSO-d.sub.6): 7.59 (s, 2H), 7.82-7.84 (m, 1H), 8.42-8.43 (m, 1H); .sup.19F NMR (282 MHz, DMSO-d.sub.6): 60.3 (s, 3F).

Step C: 1,3-dichloro-5-[2,2,2-trifluoro-1,1-bis(nitromethyl)ethyl]benzene

(5) ##STR00032##
Freshly prepared EtONa in EtOH (8 mL, 1 mol/L) was added to a solution of CH.sub.3NO.sub.2 (6.1 g, 100 mmol) in 40 mL of EtOH at room temperature. Then a solution of 1,3-dichloro-5-[(Z)-2-nitro-1-(trifluoromethyl)vinyl]benzene (5.7 g, 20 mmol) in 50 mL of EtOH was slowly added to the mixture. After the addition, the mixture was stirred for another 1 h and poured into diluted hydrochloric acid. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give 1,3-dichloro-5-[2,2,2-trifluoro-1,1-bis(nitromethyl)ethyl]benzene (2.07 g, 30% yield). .sup.1H NMR (300 MHz, DMSO-d.sub.6): 5.69 (d, J=15.0 Hz, 2H), 5.88 (d, J=15.0 Hz, 2H), 7.77 (s, 1H), 7.86 (s, 2H); .sup.19F NMR(282 MHz, DMSO-d.sub.6): 64.5 (s, 3F).

Step D: 4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-1,5-dihydropyrazole

(6) ##STR00033##

(7) A mixture of 1,3-dichloro-5-[2,2,2-trifluoro-1,1-bis(nitromethyl)ethyl]benzene (2.77 g, 8 mmol), Zn powder (5.52 g, 80 mmol) and AcOH (4.8 g, 80 mmol) in 20 mL of MeOH was refluxed for 1 h. Then a saturated NaHCO.sub.3 solution was added to the reaction mixture until the pH value reached 7. Then, ethyl acetate (100 mL) was added to the mixture. The resulting mixture was filtered and organic layer was separated. The aqueous layer was extracted with ethyl acetate twice. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to give 4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-1,5-dihydropyrazole (246 mg, 10% yield). .sup.1H NMR (300 MHz, CDCl.sub.3): 3.75 (d, J=10.5, 1H), 3.98 (d, J=10.5, 1H), 7.01 (s, 1H), 7.24 (s, 2H), 7.38 (s, 1H); .sup.19F NMR(282 MHz, CDCl.sub.3): 69.5 (s, 3F); Mp: 96-98 C.

Step E: tert-butyl 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoate

(8) ##STR00034##
In a high-pressure vial, we introduce successively rac-2,2-bis(diphenylphosphino)-1,1-binaphthyl (0.002 mmol), tert-butyl 4-bromo-2-methyl-benzoate (0.03 mmol), sodium tert-butoxide (0.04 mmol), tris(dibenzylideneacetone) dipalladium (0.0007 mmol), 4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-1,5-dihydropyrazole (8 mg, 0.03 mmol) and toluene (0.3 mL). After degassing by bubbling argon through the deep red solution for 15 min with stirring, the mixture was heated at 80 C. for 12 h.

(9) After purification by column chromatography, using cyclohexane and EtOAc (0 to 20%), the tert-butyl 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoate was isolated in 70% yield as a clear yellow oil. .sup.1HNMR (CDCl.sub.3, 400 MHz): 1.52 (s, 9H), 2.50 (s, 3H), 4.05 (d, 1H), 4.30 (d, 1H), 6.97 (s, 1H), 6.81 (m, 2H), 7.20 (s, 2H), 7.36 (m, 1H), 7.80 (d, 1H). .sup.19FNMR (CDCl.sub.3, 376 MHz): 70.8.

Step F: 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoic acid

(10) ##STR00035##

(11) To a cooled solution (0 to 5 C.) of tert-butyl 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoate (5 mg, 0.011 mmol) in dichloromethane (0.1 mol/L) was added trifluoroacetic acid (0.064 mmol). The resulting mixture was stirred for 6 h with the temperature maintained at 5 C. after which the volatile components were removed under reduced pressure. The resulting crude 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoic acid (6 mg, 100% yield) was isolated as a yellow gum and used as such in the next step.

Step G: 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (A1)

(12) ##STR00036##
To a solution of 4-[(4S)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoic acid (0.011 mmol) in CH.sub.2Cl.sub.2 (0.4 mL) at rt was added sequentially a catalytic amount of dimethylformamide, and oxalic chloride (0.05 mL). After stirring at rt for 3.5 h, the mixture was evaporated under reduced pressure. The resulting crude 4-[(4S)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoyl chloride (0.0046 g, 0.011 mmol, 100% Yield) was isolated as a brown oil. To a solution of [2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]ammonium; 2,2,2-trifluoroacetate (0.097 mmol, 16 mg) in CH.sub.2Cl.sub.2 (0.8 mL) at 0-5 C. was added Et.sub.3N (0.12 mL) followed by a solution of the 4-[(4S)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzoyl chloride (0.0046 g, 0.011 mmol) in CH.sub.2Cl.sub.2 (0.6 mL). After stirring for 2 h at rt, the mixture was purified directly by reverse phase column chromatography, which provided the desired 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide as a white solid (2 mg).

(13) LCMS (method A): RT 1.92 min, [MH].sup.+555/557; .sup.1HNMR (CDCl.sub.3, 400 MHz): 2.52 (s, 3H), 3.97 (q, 2H), 4.13 (d, 1H), 4.18 (s, 2H), 4.38 (d, 1H), 6.55 (s, 1H), 6.94 (d, 1H), 6.95 (s, 1H), 7.03 (bs, 1H), 7.06 (s, 1H), 7.31 (m, 2H), 7.43 (s, 1H), 7.45 (d, 1H).

(14) .sup.19FNMR (CDCl.sub.3, 376 MHz):70.8 (3F),72.5 (3F).

EXAMPLE 2

N-cyclopropyl-4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-YL]-2-methyl-benzamide (A2)

(15) ##STR00037##

(16) A mixture of 4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-1,5-dihydropyrazole (200 mg, 0.72 mmol), 4-bromo-N-cyclopropyl-2-methyl-benzamide (213 mg, 0.84 mmol), Pd(OAc).sub.2 (16 mg, 0.07 mmol), Cs.sub.2CO.sub.3 (938 mg, 2.88 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (84 mg, 0.14 mmol) in 40 mL of toluene was stirred at 80 C. for 3 h under nitrogen protection. Then the reaction mixture was poured into water and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give N-cyclopropyl-4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-benzamide (75 mg, 22% yield). .sup.1H NMR (300 MHz, DMSO-d.sub.6): 0.48-0.50 (m, 2H), 0.61-0.64 (m, 2H), 2.33 (s, 3H), 2.75-2.78 (m, 1H), 4.42 (s, 2H), 6.90-6.92 (m, 2H), 7.24 (d, J=9.0 Hz, 1H), 7.72-7.74 (m, 3H), 7.85 (s, 1H), 8.06 (d, J=3.9 Hz, 1H); .sup.19F NMR (282 MHz, CDCl.sub.3): 66.9 (s, 3F); ESI-MS: 456 [M+H].sup.+, 478 [M+Na].sup.+; Mp: 85-88 C.

EXAMPLE 3

4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-N-(2,2,2-trifluoroethyl)benzamide (A3)

(17) ##STR00038##

(18) Undernitrogen, 4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-4,5-dihydro-1H-pyrazole (example 1 step D, 150 mg, 0.55 mmol), 4-bromo-2-methyl-N-(2,2,2-trifluoroethyl)benzamide (187 mg, 0.63 mmol), Pd(OAc).sub.2 (12 mg, 0.05 mmol), cesium carbonate (704 mg, 2.16 mmol) and 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (71 mg, 0.15 mmol) were dissolved in 30 ml of toluene. After the addition, the mixture was stirred at 80 C. for 3 h. Then, it was poured into water and extracted with ethyl acetate three times. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to provide 4-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3H-pyrazol-2-yl]-2-methyl-N-(2,2,2-trifluoroethyl)benzamide (140 mg, 52% yield). .sup.1H NMR (300 Mz, CDCl.sub.3): 2.49 (s, 3H), 4.06-4.11 (m, 3H), 4.34-4.38 (d, 1H), 5.97 (t, 1H), 6.90-6.92 (d, 2H), 7.04 (s, 1H), 7.28 (s, 2H), 7.38-7.42 (m, 2H); .sup.19F NMR (300 Mz, DMSO-d.sub.6): 72.23-72.17 (t, 3F), 70.67 (s, 3F); ESI-MS(+): 520 [M+Na].sup.+, M.p. 60-62 C.

(19) The following compounds were prepared following a similar methods to that described in Examples 1 to 3.

(20) TABLE-US-00006 TABLE A Compounds of formal I- Comp LC/MS LC RT M.P. No. R4 R2 method (min) m/z (obsd) ( C.) A4 3,5- (4R)-2-ethyl-3-oxo- A 1.14 529 [M + H].sup.+ 153-155 dichlorophenyl- isoxazolidin-4-yl- A5 3,5- 1-oxothietan-3-yl- A 1.06 504 [M +H].sup.+ 100-103 dichlorophenyl- A6 3,5- 1,1-dioxothietan-3-yl- A 1.11 518 [M + H].sup.+ 100-105 dichlorophenyl- A7 3,5- (E)-methoxyiminomethyl- B 16.76 495 [M + Na].sup.+ 58-60 dichlorophenyl- A8 3,4,5- 2-oxo-2-(2,2,2- B 16.77 589 [M + H].sup.+ 88-90 trichlorophenyl- trifluoroethylamino)ethyl- A9 3,4,5- (E)-methoxyiminomethyl- B 18.20 529 [M + Na].sup.+ 100-102 trichlorophenyl- A10 3,5-dichloro-4- 2-oxo-2-(2,2,2- B 16.09 595 [M + Na].sup.+ 156-158 fluorophenyl- trifluoroethylamino)ethyl- A11 3,4,5- 2,2,2-trifluoroethyl- B 17.76 530 [M H].sup. 72-74 trichlorophenyl- A12 3,5-dichloro-4- (E)-methoxyiminomethyl- B 16.88 489 [M H].sup. 97-99 fluorophenyl- A13 3,4,5- cyclobutyl- B 17.71 504 [M + H].sup.+ 81-83 trichlorophenyl- A14 3,5-dichloro-4- cyclobutyl- B 16.54 488 [M + H].sup.+ 75-77 fluorophenyl- A15 3,5-dichloro-4- 2,2,2-trifluoroethyl- B 16.50 516 [M + H].sup.+ 56-58 fluorophenyl- A16 3,5- cyclobutyl- B 16.45 470 [M + H].sup.+ 74-76 dichlorophenyl-
Biological Examples
Spodoptera littoralis (Egyptian Cotton Leafworm):

(21) Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with 5 L1 larvae. The samples were checked for mortality, feeding behavior, and growth regulation 3 days after treatment (DAT). Control of Spodoptera littoralis by a test sample is noted when at least one of mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

(22) The following compound gave at least 80% control of Spodoptera littoralis: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16

(23) Heliothis virescens (Tobacco Budworm):

(24) Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation. Control of Heliothis virescens by a test sample is noted when at least one of egg mortality, larval mortality and growth inhibition is higher than the untreated sample.

(25) The following compound gave at least 80% control of Heliothis virescens: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16

(26) Plutella xylostella (Diamond Back Moth):

(27) 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying, the MTPs were infested with L2 larvae (7-12 per well). After an incubation period of 6 days, samples were checked for larval mortality and growth regulation. Control of Plutella xyllostella by a test sample is noted when at least one of mortality and growth inhibition is higher than the untreated sample.
The following compound gave at least 80% control of Plutella xylostella: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16
Diabrotica balteata (Corn Rootworm):
A 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. 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. Control of Diabrotica balteata by a test sample is noted when at least one of larval mortality and growth inhibition is higher than the untreated sample.
The following compound gave at least 80% control of Diabrotica balteata: A1, A2, A3, A4, A5, A6, A7, A16
Diabrotica balteata, (Corn Rootworm)

(28) Maize sprouts, placed on an agar layer in 24-well microtiter plates were sprayed at an application rate of 200 ppm. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition 4 days after infestation. Control of Diabrotica balteata by a test sample is noted when at least one of mortality and growth inhibition is higher than the untreated sample.

(29) The following compound gave at least 80% control of Diabrotica balteata: A8, A9, A10, A11, A12, A13, A14, A15

(30) Thrips tabaci (Onion Thrips):

(31) Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. 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.
The following compounds gave at least 80% control of Thrips tabaci: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16
Tetranychus urticae (Two-Spotted Spider Mite):

(32) Bean leaf discs on agar in 24-well microtiter plates were sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality. Control of Tetranychus urticae by a test sample is noted when at least one of egg mortality, larval mortality, and adult mortality is higher than the untreated sample.

(33) The following compound gave at least 80% control of Tetranychus urticae: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16