Insecticidal compounds

Abstract

The present invention relates to novel triazole derivatives of formula (I) having insecticidal activity, to processes and intermediates for preparing them, to insecticidal, acaricidal, nematicidal or molluscicidal compositions comprising them and to methods of using them to combat and control insect, acarine, nematode or mollusc pests ##STR00001## wherein Y, X.sub.1, X.sub.2 and Q are as defined in claim 1; or salts thereof.

Claims

1. A compound selected from: ##STR00225##

2. A method 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) as defined in claim 1.

3. An insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1 together with an agrochemically acceptable diluent or carrier.

4. A composition according to claim 3 which further comprises one or more additional insecticidal, acaricidal, nematicidal or molluscicidal compounds.

5. A method of protecting useful plants from insects, acarines, nematodes or molluscs, comprising applying to said plants, to the locus thereof, or to plant propagation material thereof, an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1.

6. A method, comprising: reacting a compound of formula (III), ##STR00226## wherein Y is chlorine or bromine, with a base and compound of formula (XIV), ##STR00227## wherein X.sub.2 is cyano and X.sub.1 is hydrogen; R is hydrogen or C.sub.1-C.sub.4 alkyl; R.sub.4 is OH, Cl, F, Br or I; and Q is a group selected from Q1, Q2, Q3, Q4 and Q5, where Q1 is a group of formula (IIa): ##STR00228## where the substituents W1 are independently selected from halogen, cyano, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy, and n1 is 1 or 2, Q2 is a group of formula (IIb): ##STR00229## where W.sub.2 is selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy, Q3 is a group of formula (IIc): ##STR00230## where W.sub.3 is selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy, Q4 is a group of formula (IId): ##STR00231## where W.sub.4 is selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy, and Q5 is a group of formula (IIe) ##STR00232## where W.sub.5 is selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy, to form a compound of formula (I), ##STR00233##

7. A method, comprising: reacting a compound of formula (VII), ##STR00234## wherein Y is chlorine or bromine, with (Ac).sub.2O to form a compound of formula (III), ##STR00235##

8. The compound of claim 1, wherein the compound is: ##STR00236##

9. The compound of claim 1, wherein the compound is: ##STR00237##

10. The compound of claim 1, wherein the compound is: ##STR00238##

11. The compound of claim 1, wherein the compound is: ##STR00239##

12. The compound of claim 1, wherein the compound is: ##STR00240##

Description

PREPARATION EXAMPLES

Example P.1: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-pyridine-4-carboxamide (Entry 2 of the Table B)

Step 1: N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide

(1) ##STR00029##
To a suspension of 11 g 2-fluoro-3-nitro-benzoic acid in 170 ml dichloromethane a drop of N,N-dimethylformamide was added, followed by 5.55 ml oxalyl dichloride. The resulting yellow suspension was stirred at ambient temperature for 5.5 hours. Then the solution was evaporated to give 12.2 g of 2-fluoro-3-nitro-benzoyl chloride. To a solution of 20.7 g 2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline in 200 ml acetonitrile were added 12.2 g 2-fluoro-3-nitro-benzoyl chloride and 0.84 g potassium iodide, and the resulting solution was heated to reflux for 18 hours. Then the solvent was evaporated, the residue dissolved in ethyl acetate and extracted with aqueous sodium bicarbonate. The organic phase was dried over anhydrous sodium sulfate, and the solvent was evaporated. Thus, 29 g of crude N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide was obtained, which was used for step 2 without further purification. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.44 (t, 1H), 8.28 (t, 1H), 8.07 (d, 1H), 7.81 (s, 1H), 7.52 (m, 2H), 6.60 (t, 1H).

Step 2: 3-amino-N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-benzamide

(2) ##STR00030##
To a suspension of 15.07 g N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide and 3.67 g iron powder in 100 ml ethanol and 30 ml water was added 1 ml of concentrated hydrochloric acid. The resulting dark suspension was heated to reflux for 7 hours. The mixture was allowed to cool to ambient temperature, filtered over celite, and the solvent was evaporated. The residue was dissolved in ethyl acetate and washed with brine. The organic phase was separated, dried over anhydrous sodium sulfate and evaporated. The residue was purified by chromatography on silica gel, using heptane/ethyl acetate (9:1 to 1:1) as eluent. Thus, 5.23 g of 3-amino-N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-benzamide was obtained. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.13 (d, 1H), 7.80 (s, 1H), 7.52 (s, 1H), 7.45 (t, 1H), 7.11 (t, 1H), 6.99 (t, 1H), 6.60 (t, 1H), 3.90 (s, broad, 2H).

Step 3: N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-(ethylamino)-2-fluoro-benzamide

(3) ##STR00031##
To a solution of 2.32 g 3-amino-N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-benzamide, 0.27 ml acetic acid and 0.20 g acetaldehyde in 19.2 ml methanol was added 311 mg sodium cyanoborohydride. The reaction mixture was stirred at ambient temperature for 2 hours. Then the solvent was evaporated and the residue purified by chromatography on silica gel, using ethal acetate/heptane (1:19 to 1:4) as eluent. Thus, 1.98 g of N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-(ethylamino)-2-fluoro-benzamide was obtained. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.12 (d, 1H), 7.79 (s, 1H), 7.50 (s, 1H), 7.34 (t, 1H), 7.15 (t, 1H), 6.90 (t, 1H), 6.60 (t, 1H), 3.98 (s, broad, 1H), 3.23 (q, 2H), 1.32 (t, 3H).

Step 4: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-pyridine-4-carboxamide (Entry 2 of the Table B)

(4) ##STR00032##
To a solution of 0.70 g N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-(ethylamino)-2-fluoro-benzamide in 4.9 ml tetrahydrofuran was added 267 mg of isonicotinoyl chloride hydrochloride. The suspension was heated to 70° C. for 1 hour. Then the reaction mixture was allowed to ambient temperature, and the solvent was evaporated. The residue was purified by chromatography on silica gel, using dichloromethane/methanol (1.5 to 4% methanol) as eluent. Thus, 765 mg N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-pyridine-4-carboxamide was obtained as a solid, mp=186-188° C. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.50 (s, broad, 2H), 8.02 (t, 1H), 7.83 (d, 1H), 7.78 (s, 1H), 7.49 (s, 1H), 7.43 (t, 1H), 7.28 (t, 1H), 7.18 (s, broad, 2H), 6.55 (t, 1H), 4.00 (m, broad, 2H), 1.28 (t, broad, 3H).

Example P.2: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-1-oxido-pyridin-1-ium-4-carboxamide (Entry 11 of the Table B)

(5) ##STR00033##
To a solution of 454 mg N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-pyridine-4-carboxamide in 6.7 ml dichloromethane was added 173 mg 3-chlorobenzenecarboperoxoic acid. The resulting clear solution was stirred at ambient temperature for 18 hours. Then the solvent was evaporated, and the residue purified by chromatography on silica gel, using dichloromethane/methanol (1.5 to 10% methanol) as eluent. Thus, 421 mg N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-fluoro-phenyl]-N-ethyl-1-oxido-pyridin-1-ium-4-carboxamide was obtained as a solid, mp=103-106° C. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.07 (t, 1H), 8.01 (d, 2H), 7.88 (d, 1H), 7.80 (s, 1H), 7.50 (s, 1H), 7.45 (t, 1H), 7.36 (t, 1H), 7.21 (d, 2H), 6.60 (t, 1H), 3.95 (m, broad, 2H), 1.27 (t, 3H).

Example P.3: N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-[(4-cyanobenzoyl)amino]-2-methoxy-benzamide (Entry 14 of the Table B)

Step 1: N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide

(6) ##STR00034##
12.3 g-fluoro-3-nitro-benzoic acid was dissolved in m dichloromethane and a drop of N,N-dimethylformamide was added. Then 6.2 ml oxalyl dichloride was added slowly over 30 min, and the mixture was stirred at ambient temperature for 3.5 hours, then the solvent was evaporated. The residue was dissolved in 70 ml of acetonitrile and added slowly to a solution of 20 g 2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline and of 0.92 g potassium iodide in 150 mL of acetonitrile. The reaction mixture was heated to reflux for 18 hours, allowed to cool to ambient temperature, and the solvent evaporated. The residue was taken up in ethyl acetate and washed with saturated aqueous sodium bicarbonate, the organic phase was separated, dried over anhydrous sodium sulfate and evaporated. Thus, 31.5 g of crude N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide was obtained, which was used for step 2 without further purification. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.43 (t, 1H), 8.28 (t, 1H), 8.10 (d, 1H), 7.67 (s, 1H), 7.50 (m, 2H), 6.60 (t, 1H).

Step 2: N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-3-nitro-benzamide

(7) ##STR00035##
11.1 g of N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-fluoro-3-nitro-benzamide was dissolved in 190 ml methanol and 5.86 g of potassium carbonate was added. The mixture was heated to 50° C. for 3 hours. Then the solvent was evaporated, the residue was extracted with dichloromethane and water and the layers separated. The organic layer was dried over anhydrous sodium sulfate and the solvent evaporated. Thus, 11.04 g of crude N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-3-nitro-benzamide was obtained, which was used for step 3 without further purification. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.12 (s, 1H), 8.38 (d, 1H), 8.05 (d, 1H), 7.65 (s, 1H), 7.45 (s, 1H), 7.43 (t, 1H), 6.61 (t, 1H), 4.14 (s, 3H).

Step 3: 3-amino-N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-benzamide

(8) ##STR00036##
To a solution of 11.04 g N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-3-nitro-benzamide in 200 ml ethanol was added 40 ml of water, followed by 0.77 ml concentrated hydrochloric acid and 2.85 g iron powder. The mixture was heated to reflux for 18 hours, then allowed to cool to ambient temperature, filtered over celite, and the solvent was evaporated. Thus, 10.06 g of 3-amino-N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-benzamide was obtained, which was used for step 4 without further purification. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.46 (s, 1H), 7.62 (s, 1H), 7.50 (d, 1H), 7.45 (s, 1H), 7.10 (t, 1H), 6.97 (d, 1H), 6.61 (t, 1H), 3.98 (s, 3H), 3.93 (s, broad, 2H).

Step 4: N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-[(4-cyanobenzoyl)amino]-2-methoxy-benzamide (Entry 14 of the Table B)

(9) ##STR00037##
To a solution of 123 mg 3-amino-N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-2-methoxy-benzamide in 2.4 ml acetonitrile were added 4 mg of potassium iodide and 48 mg of 4-cyanobenzoyl chloride. The mixture was heated to reflux for 3 hours, then allowed to cool to ambient temperature, and the solvent evaporated. The residue was dissolved in dichloromethane, washed with saturated aqueous sodium sulfite, then with aqueous sodium bicarbonate, then with brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent evaporated. Thus, without any further purification, 132 mg of N-[2-chloro-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-3-[(4-cyanobenzoyl)amino]-2-methoxy-benzamide was obtained as a solid, mp=90-100° C. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.96 (s, 1H), 8.63 (d, 1H), 8.50 (s, 1H), 8.02 (d, 2H), 7.85 (m, 3H), 7.64 (s, 1H), 7.46 (s, 1H), 7.37 (t, 1H), 6.63 (t, 1H), 4.03 (s, 3H).

Example P.4: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-1-oxido-pyridin-1-ium-4-carboxamide (Entry 183 of the Table B)

Step 1: N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]acetamide

(10) ##STR00038##
To a solution of 2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1(trifluoromethyl) ethyl]aniline (1.0 g) in acetic anhydride (5.5 ml) were added a few drops of concentrated sulfuric acid. The resulting solution was heated at 60° C. for 200 minutes. The consumption of the starting aniline was followed by LC-MS analysis of a aliquots of the reaction mixture. The solution was poured on an ice-water mixture and the resulting emulsion was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated under reduced pressure. The crude solid was dissolved in tetrahydrofurane and treated with 30% (w/w) aqueous sodium hydroxide and stirred at 20° C. for 30 minutes. The hydrolysis of the acetimide (side product of the reaction) to the acetamide was followed by LC-MS analysis of aliquots of the reaction mixture. The emulsion was extracted with ethyl acetate and the organic phase was dried over sodium sulfate. After evaporation of the solvent, the crude product was purified by chromatography through silica gel using an eluent gradient (100% heptane to 40% ethyl acetate-60% heptane. After evaporation of the solvent the desired product was obtained. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.75 (s, 1H), 7.46 (s, 1H), 6.90 (s, 1H), 6.54 (t, J=68 Hz, 1H), 2.25 (s, 3H).

Step 2: N-[3-[acetyl-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide

(11) ##STR00039##
To a solution of N-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]acetamide (0.76 g) in 1,2-dichloroethane (5.1 ml), at 0° C., was added triethylamine (0.60 g), followed by 0.52 g of 2-methoxy-3-[methyl(pyridine-4-carbonyl)amino]benzoyl chloride (prepared from 2-methoxy-3-[methyl(pyridine-4-carbonyl)amino]benzoic acid, oxalyl chloride and a catalytic amount of dimethylformamide in 1,2-dichloroethane). The reaction was complete after stirring of the suspension for 15 hours at ° C. (LC-MS analysis). The reaction mixture was then evaporated, the residue dissolved in ethyl acetate and this solution washed with an aqueous solution of sodium hydrogencarbonate. The organic phase was dried over sodium sulfate, evaporated and the residue was chromatographed on silica gel using a gradient from 1% methyl alcohol in dichloromethane to 10% methyl alcohol in dichloromethane. The desired compound was isolated as a solid showing a melting point of 78-81° C.

Step 3: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide (Entry 182 of the Table B)

(12) ##STR00040##
To a solution of N-[3-[acetyl-[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide (0.278 g) in tetrahydrofurane (1.7 g) was added aqueous sodium hydroxide (1 M, 1.55 ml) and the resulting emulsion was stirred for 1.5 hour at 20° C. The conversion was followed by LC-MS analysis. The reaction mixture was partitioned between water and ethyl acetate. The organic phase was dried over sodium sulfate and evaporated to yield the desired compound as a solid melting at 73-77° C. It was used without further purification in the next step.

Step 4: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-1-oxido-pyridin-1-ium-4-carboxamide (Entry 183 of the Table B)

(13) ##STR00041##
A solution of N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide (0.145 g) in dichloromethane (1.70 g) was treated with 0.052 g of 75% meta-chloroperbenzoic acid. After hours stirring at 20° C., full conversion was observed by LC-MS and TLC analyses. The reaction mixture was concentrated and submitted to column chromatography over silica gel, using a gradient from 100 methyl alcohol in dichloromethane to 7% methyl alcohol in dichloromethane. .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.72 (br.s, 1H), 8.08 (dd, 1H), 7.96 (br. ds, 2H), 7.76 (s, 1H), 7.56 (dd, 1H), 7.45 (s, 1H), 7.40 (t, 1H), 7.20 (br. d, 2H), 6.60 (t, J=72 Hz, 1H), 3.89 (s, 3H), 3.56 (s, 3H).

(14) The compounds in tables B were prepared in the same or a similar way as described above:

(15) TABLE-US-00003 TABLE B [M + H] [M − H] Entry STRUCTURE RT (min) (measured) (measured) Method MP ° C. 1 200-204 2 186-188 3 192-196 4 78-82 5 1.88 672.27 UPLC1 121-124 6 1.94 684.3 UPLC1 121-126 7 119-124 8 220-999 9 0 1.97 712.31 UPLC1 85-90 10 2.12 700.03 UPLC2 86-89 11 103-106 12 112-116 13 1.15 626, 628 SQD13 14 1.93 640.32 UPLC1  90-100 15 1.06 604, 606 ZCQ13 16 1.08 616, 618 ZCQ13 17 2.12 656.07 UPLC2  95-100 18 105-110 19 0 183-184 20  95-100 21 1.98 679.96 UPLC1 22 1.95 692.25 UPLC1 23 2.02 661.28 UPLC1 24 2.10 699.24 UPLC1 25 1.99 726.22 UPCL1 26 2.11 731.26 UPLC1 27 2.10 733.27 UPLC1 28 2.08 715.27 UPLC1 29 0 2.06 731.27 UPLC1 30 2.09 677.28 UPLC1 31 1.95 647.27 UPLC1 32 1.97 665.26 UPLC1 33 2.10 677.28 UPLC1 34 1.99 715.28 UPLC1 35 2.05 673.32 UPLC1 36 2.01 699.23 UPLC1 37 2.04 693.27 UPLC1 38 2.01 683.26 UPLC1 39 0 1.99 704.3 UPLC1 40 2.03 683.26 UPLC1 41 2.08 673.31 UPLC1 42 2.11 733.27 UPLC1 43 2.06 691.31 UPLC1 44 2.19 711.26 UPLC1 45 1.99 621.29 UPLC1 46 1.98 617.32 UPLC1 47 2.04 738.27 UPLC1 48 1.94 637.27 UPLC1 49 0 1.92 648.31 UPLC1 50 2.15 743.31 UPLC1 51 1.99 617.31 UPLC1 52 2.14 745.29 UPLC1 53 1.98 635.32 UPLC1 54 2.13 727.29 UPLC1 55 2.07 655.27 UPLC1 56 2.13 743.29 UPLC1 57 1.96 682.29 UPLC1 58 2.13 689.31 UPLC1 59 00 2.00 695.29 UPLC1 60 01 2.08 687.32 UPLC1 61 02 2.01 677.29 UPLC1 62 03 2.07 689.31 UPLC1 63 04 2.04 727.3 UPLC1 64 05 2.05 671.31 UPLC1 65 06 2.04 687.31 UPLC1 66 07 2.07 711.26 UPLC1 67 08 2.07 633.32 UPLC1 68 09 1.92 603.3 UPLC1 69 0 2.10 695.28 UPLC1 70 1.94 621.3 UPLC1 71 2.12 695.29 UPLC1 72 1.97 671.31 UPLC1 73 2.20 745.3 UPLC1 74 1.98 655.27 UPLC1 75 2.09 633.32 UPLC1 76 1.98 639.29 UPLC1 77 2.04 629.34 UPLC1 78 2.00 639.29 UPLC1 79 0 2.04 649.29 UPLC1 80 2.09 689.31 UPLC1 81 1.98 660.32 UPLC1 82 2.07 629.34 UPLC1 83 1.99 665.27 UPLC1 84 2.05 647.34 UPLC1 85 2.19 667.29 UPLC1 86 2.03 694.3 UPLC1 87 2.13 699.33 UPLC1 88 2.13 701.34 UPLC1 89 0 2.12 683.33 UPLC1 90 2.12 699.34 UPLC1 91 2.12 645.35 UPLC1 92 1.99 615.32 UPLC1 93 2.01 633.32 UPLC1 94 2.03 683.34 UPLC1 95 2.06 667.29 UPLC1 96 2.09 651.33 UPLC1 97 2.11 651.33 UPLC1 98 2.19 701.33 UPLC1 99 0 78-81 100 85-88 101 186-188 102 73-77 103 2.16 720.02 UPLC2 104 2.05 726.97 UPLC2 105 2.29 743.04 UPLC2 106 2.07 759.01 UPLC2 107 1.95 705.04 UPLC2 108 1.98 711 UPLC2 109 0 1.98 711 UPLC2 110 2.07 761 UPLC2 111 1.95 649.02 UPLC2 112 2.00 665.01 UPLC2 113 2.17 676.07 UPLC2 114 2.23 645.06 UPLC2 115 2.04 683.01 UPLC2 116 2.25 710.03 UPLC2 117 2.29 699.08 UPLC2 118 2.06 715.07 UPLC2 119 0 1.95 631.01 UPLC2 120 1.96 649.02 UPLC2 121 2.04 699.05 UPLC2 122 2.02 6.83 UPLC2 123 1.98 667.03 UPLC2 124 2.29 717.06 UPLC2 125 1.96 693.02 UPLC2 126 2.01 689.01 UPLC2 127 1.97 675.33 UPLC2 128 1.99 693.32 UPLC2 129 0 2.04 705.3 UPLC1 130 2.09 701.33 UPLC1 131 2.09 721.27 UPLC1 132 2.11 UPLC1 133 2.09 719.32 UPLC1 134 2.13 739.26 UPLC1 135 2.09 766.26 UPLC1 136 2.16 771.3 UPLC1 137 2.04 717.31 UPLC1 138 2.04 687.3 UPLC1 139 0 2.05 705.28 UPLC1 140 2.13 755.3 UPLC1 141 2.12 739.27 UPLC1 142 2.07 723.29 UPLC1 143 2.07 723.28 UPLC1 144 2.15 773.29 UPLC1 145 2.04 661.33 UPLC1 146 2.08 657.35 UPLC1 147 2.09 677.01 UPLC1 148 2.26 688.34 UPLC1 149 0 2.09 657.35 UPLC1 150 2.09 675.36 UPLC1 151 2.12 695.32 UPLC1 152 2.08 722.3 UPLC1 153 2.16 727.35 UPLC1 154 2.03 673.36 UPLC1 155 2.03 643.33 UPLC1 156 2.04 661.34 UPLC1 157 2.12 711.43 UPLC1 158 2.11 695.31 UPLC1 159 00 2.06 679.33 UPLC1 160 01 2.06 679.33 UPLC1 161 02 2.14 729.35 UPLC1 162 03 2.02 732.29 UPLC1 163 04 2.16 773.29 UPLC1 164 05 1.15 661 UPLC2 Short 165 06 1.14 679.06 UPLC2 Short 166 07 1.10 709 UPLC2 Short 167 08 1.10 689 UPLC2 Short 168 09 1.11 7.07 UPLC2 Short 169 0 1.24 754 UPLC2 Short 170 1.14 761 UPLC2 Short 171 1.12 743 UPLC2 Short 172 1.12 727 UPLC2 Short 173 1.09 645 UPLC2 Short 174 1.10 663 UPLC2 Short 175 1.14 717 UPLC2 Short 176 1.06 661 UPLC2 Short 177 1.08 667 UPLC2 Short 178 1.30 755 UPLC2 Short 179 0 1.17 727 UPLC2 Short 180 1.17 729.05 UPLC2 Short 181 1.30 711.1 UPLC2 Short 182 73-77 183 1.00 690 ZCQ13
LC-MS Method: ZCQ13
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter: Ionization method: Electrospray Polarity: positive and negative ions Capillary: 3.00 kV Cone: 30 V Extractor: 2.00 V Source Temperature: 150° C., Desolvation Temperature: 350C Cone Gas Flow: 50 L/Hr Desolvation Gas Flow: 400 L/Hr Mass range: 100 to 900 Da
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=H2O+5% MeOH+0.05% HCOOH B=Acetonitril+0.05% HCOOH

(16) TABLE-US-00004 Time A% B% Flow (ml/min) 0.00 90 10 0.85 1.20 0 100.0 0.85 1.50 0 100.0 0.85
LC-MS Method: SQD13
SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter: Ionization method: Electrospray Polarity: positive and negative ions Capillary: 3.00 kV Cone: 30V Extractor: 2.00 V Source Temperature: 150° C., Desolvation Temperature: 350° C. Cone Gas Flow: 50 L/Hr Desolvation Gas Flow: 650 L/Hr Mass range: 100 to 900 Da
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=H2O+5% MeOH+0.05% HCOOH B=Acetonitril+0.05% HCOOH

(17) TABLE-US-00005 Time A% B% Flow (ml/min) 0.00 90 10 0.85 1.20 0 100.0 0.85 1.50 0 100.0 0.85
LC-MS Method: UPLC1
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (° C.) 150,
Desolvation Temperature (° C.) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da
DAD Wavelength range (nm): 210 to 400
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water/Methanol 9:1, 0.1% formic acid and Solvent B: Acetonitrile, 0.1% formic acid)

(18) TABLE-US-00006 Time Flow rate (minutes) A (%) B (%) (ml/min) 0 100 0 0.75 2.5 0 100 0.75 2.8 0 100 0.75 3.0 100 0 0.75
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60° C.

(19) LC-MS Method: UPLC2

(20) ZQ2000 Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

(21) Ionisation method: Electrospray

(22) Polarity: positive ions

(23) Capillary (kV) 3.5, Cone (V) 60.00, Extractor (V) 3.00, Source Temperature (° C.) 150,

(24) Desolvation Temperature (° C.) 350, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 800

(25) Mass range: 140 to 800 Da

(26) DAD Wavelength range (nm): 210 to 400

(27) Method Waters ACQUITY UPLC with the following HPLC gradient conditions

(28) (Solvent A: Water/Methanol 9:1, 0.1% formic acid and Solvent B: Acetonitrile, 0.1% formic acid)

(29) TABLE-US-00007 Time Flow rate (minutes) A (%) B (%) (ml/min) 0 100 0 0.75 2.5 0 100 0.75 2.8 0 100 0.75 3.0 100 0 0.75
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60° C.

(30) LC-MS Method: UPLC2 Short

(31) ZQ2000 Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

(32) Ionisation method: Electrospray

(33) Polarity: positive ions

(34) Capillary (kV) 3.5, Cone (V) 60.00, Extractor (V) 3.00, Source Temperature (° C.) 150,

(35) Desolvation Temperature (° C.) 350, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 800

(36) Mass range: 140 to 800 Da

(37) DAD Wavelength range (nm): 210 to 400

(38) Method Waters ACQUITY UPLC with the following HPLC gradient conditions

(39) (Solvent A: Water/Methanol 9:1, 0.1% formic acid and Solvent B: Acetonitrile, 0.1% formic acid)

(40) TABLE-US-00008 Time Flow rate (minutes) A (%) B (%) (ml/min) 0 80 20 1 0.1 75 25 1 0.2 70 30 0.75 1.2 0 100 0.75 1.4 0 100 0.75 1.45 80 20 0.75
Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60° C.

BIOLOGICAL EXAMPLES

(41) These Examples illustrate the insecticidal and acaricidal properties of the compounds of formula (I). The tests were performed as follows: Diabrotica balteata (Corn root worm): 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 MTP's were infested with L2 larvae (6-10 per well). After an incubation period of 5 days, samples were checked for larval mortality. The following compound gave at least 80% control of Diabrotica balteata: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 33, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 66, 68, 69, 70, 71, 74, 76, 77, 78, 79, 80, 81, 82, 83, 84, 86, 87, 89, 90, 91, 92, 93, 94, 95, 99, 100, 101, 102, 103, 104, 105, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 138, 139, 140, 141, 142, 143, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 162, 163, 183. Myzus persicae (Green peach aphid): 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 an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality. The following compounds gave at least 80% control of Myzus persicae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 35, 36, 37, 38, 39, 40, 41, 43, 45, 47, 48, 49, 50, 51, 52, 53, 54, 56, 57, 59, 60, 61, 63, 64, 66, 68, 69, 70, 71, 73, 76, 78, 79, 81, 82, 83, 84, 86, 89, 92, 93, 94, 95, 96, 97, 99, 100, 101, 102, 103, 105, 108, 109, 111, 112, 119, 120, 122, 123, 125, 127, 128, 131, 132, 135, 138, 139, 140, 141, 142, 143, 147, 149, 155, 156, 158, 159, 162. Myzus persicae (Green peach aphid): Test compounds were applied by pipette into 24 well plates and mixed with Sucrose solution. Application rate: 12.5 ppm. 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. The following compounds gave at least 80% control of Myzus persicae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 33, 36, 38, 39, 40, 41, 44, 45, 47, 49, 50, 51, 53, 54, 56, 57, 59, 60, 61, 62, 64, 66, 68, 70, 74, 76, 78, 81, 83, 84, 86, 89, 93, 99, 100, 101, 102, 103, 104, 105, 108, 109, 110, 111, 113, 114, 115, 116, 117, 119, 120, 122, 123, 125, 126, 127, 128, 135, 138, 139, 141, 152, 155, 156, 158, 159, 160, 162, 183. Plutella xylostella (Diamond back moth): 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 MTP's were infested with L2 larvae (7-12 per well). After an incubation period of 6 days, samples were checked for larval mortality. The following compound gave at least 80% control of Plutella xylostella: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 66, 68, 69, 70, 71, 72, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 99, 100, 101, 102, 103, 104, 105, 108, 109, 110, 111, 112, 113, 114, 115, 117, 118, 119, 120, 121, 122, 123, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 149, 150, 151, 152, 154, 155, 156, 157, 158, 159, 160, 162, 163. Spodoptera littoralis (Egyptian cotton leafworm): 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 3 days after treatment (DAT). The following compound gave at least 80% control of Spodoptera littoralis: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 149, 150, 151, 152, 154, 155, 156, 157, 158, 159, 160, 162. Tetranychus urticae (Two-spotted spider mite): 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. The following compounds gave at least 80% control of Tetranychus urticae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 35, 36, 37, 38, 39, 40, 43, 46, 47, 48, 49, 50, 51, 53, 54, 57, 60, 61, 62, 64, 66, 68, 70, 71, 74, 76, 77, 78, 79, 81, 83, 84, 86, 87, 89, 92, 93, 94, 95, 97, 99, 100, 101, 102, 103, 108, 109, 112, 119, 120, 122, 127, 128, 129, 133, 135, 139, 141, 152, 154, 156, 158, 162. Thrips tabaci (Onion thrips): 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 an aphid 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: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 63, 64, 66, 68, 69, 70, 71, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 86, 87, 88, 89, 90, 92, 93, 94, 95, 97, 99, 100, 101, 102, 103, 104, 105, 108, 109, 110, 111, 112, 114, 115, 116, 117, 119, 120, 121, 122, 123, 125, 126, 127, 128, 129, 131, 132, 133, 134, 135, 138, 139, 140, 141, 142, 143, 144, 145, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 162, 163.