M-diamide compound and preparation method therefor and use thereof

Abstract

Provided are m-diamide compounds and a preparation method therefor and the use thereof. The m-diamide compounds have a structure represented by formula I. The m-diamide compounds of the present invention can have a high insecticidal activity at a low dose and take effect rapidly, can exert the insecticidal activity one day after application, can achieve a high insecticidal activity within three days, and have a good fast-acting property; moreover, due to the good effect at a low dose, the m-diamide compounds can reduce the damage to plants and human beings caused by excessive drug concentrations, enable less drug residue to be generated during application which is more conducive to environmental protection, and have broad application prospects.

Claims

1. A kind of meta-carboxamido benzamide compounds of formula I: ##STR00024## wherein: Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxyl, C.sub.1-C.sub.6 haloalkoxyl, C.sub.1-C.sub.6 alkylsulfinyl, C.sub.1-C.sub.6 haloalkylsulfinyl, C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 haloalkylsulfonyl; Y.sub.1 is selected from the group consisting of F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6 haloalkoxyl; Y.sub.2 is C.sub.1-C.sub.6haloalkyl; R.sub.1 is selected from the group consisting of H, F or OCH.sub.3; R.sub.2 is selected from the group consisting of F or CF.sub.3; R.sub.3 is selected from the group consisting of H, F, Cl, Br, I, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 halocycloalkyl; R.sub.4 is selected from the group consisting of H or halogen; W.sub.1 and W.sub.2 are independently of each other O or S.

2. A kind of meta-carboxamido benzamide compounds according to claim 1, wherein: R.sub.1 is selected from the group consisting of F or OCH.sub.3; R.sub.2 is F.

3. A kind of meta-carboxamido benzamide compounds according to claim 1, wherein: Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO.sub.2, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, difluoromethoxyl, trifluoromethoxyl, methylsulfinyl, trifluoromethyl sulfinyl, methylsulfonyl or trifluoromethyl sulfonyl; Y.sub.1 is selected from the group consisting of F, Cl, Br, I, CN, NO.sub.2, methyl, i-propyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl or trifluoromethoxyl; Y.sub.2 is selected from the group consisting of trifluoromethyl, pentafluoroethyl or heptafluoroisopropyl; R.sub.1 is selected from the group consisting of F or methoxyl; R.sub.2 is F; R.sub.3 is selected from the group consisting of H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, 1-methylbutyl, 2,2-dimethylpropyl, 2-methylbutyl, 1,3-dimethylbutyl, n-hexyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, cyclopropyl, cyclobutyl, cyclopentyl, perfluorocyclopropyl, perfluoro cyclobutyl or perfluorocyclopentyl; R.sub.4 is selected from the group consisting of H, F or Cl; W.sub.1 and W.sub.2 are independently of each other O.

4. A kind of meta-carboxamido benzamide compounds according to claim 1, wherein the meta-bisamide derivatives are selected from any one of the compounds below, or a combination of at least two thereof: N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(dicyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(cyclopropylmethyl) benzamido)-2-fluorobenzamide; N-(2-bromo-4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(dicyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-chloro-N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-bromo-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-iodo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-bromo-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-bromo-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-bromo-N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-iodobenzamido)-2-fluorobenzamide; N-(2-iodo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-iodobenzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-(methylsulfonyl)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-(trifluoromethoxy)benzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)-4-fluorobenzamido)-2-fluorobenzamide; N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-(1-chlorocyclopropyl)ethyl)-4-cyanobenzamido)-2-fluorobenzamide; or N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)-4-(methylsulfonyl)benzamido)-2-fluorobenzamide.

5. The tautomers, enantiomers, diasteromers or salts of the compounds according to claim 1.

6. An intermediate for preparing compounds according to claim 1, wherein the intermediate is characterized by a structure as shown in formula VIII ##STR00025## wherein: Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxyl, C.sub.1-C.sub.6 haloalkoxyl, C.sub.1-C.sub.6 alkylsulfinyl, C.sub.1-C.sub.6 haloalkylsulfinyl, C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 haloalkylsulfonyl; R.sub.3 is selected from the group consisting of H, F, Cl, Br, I, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 halocycloalkyl; R.sub.4 is selected from the group consisting of H or halogen, W.sub.1 and W.sub.2 are independently of each other O or S.

7. An insecticidal composition, characterized in comprising active ingredient(s) and acceptable carrier in agriculture, wherein the active ingredient(s) are the meta-carboxamido benzamide compounds according to claim 1 or the tautomers, enantiomers, diasteromers or salts thereof.

8. The insecticidal composition according to claim 7, wherein the weight percentage of the active ingredient(s) is 1%-99%.

9. A method for controlling insects, characterized in applying effective concentration of the compounds as defined in claim 1, or the tautomers, enantiomers, diasteromers or salts thereof, to insects or their habitat.

10. The method for controlling insects according to claim 9, wherein the effective concentration is within a range of from 10 g/ha to 1000 g/ha.

11. A method for controlling insects, characterized in applying effective concentration of the composition of claim 7 to insects or their habitat.

12. The method for controlling insects according to claim 9, wherein the effective concentration is within a range of from 25 g/ha to 500 g/ha.

13. A kind of meta-carboxamido benzamide compounds according to claim 3, wherein Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO.sub.2, trifluoromethyl, trifluoromethoxyl, methylsulfonyl or trifluoromethyl sulfonyl.

14. A kind of meta-carboxamido benzamide compounds according to claim 3, wherein Y.sub.1 is selected from the group consisting of Br or I; Y.sub.2 is trifluoromethyl group; R.sub.1 is selected from the group consisting of F or methoxyl; R.sub.2 is F; R.sub.3 is selected from the group consisting of H, methyl or cyclopropyl; R.sub.4 is selected from the group consisting of H or Cl.

15. A kind of meta-carboxamido benzamide compounds according to claim 3, wherein Z is CN.

Description

EXAMPLES

(1) Representative Examples of this invention will be described in the following Examples. Those skilled in the art should understand that the examples herein are only illustrative, and this invention is not limited thereto. SGC represents silica gel column chromatography in the following examples.

Preparation Examples

Example 1: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (Compound No. 4)

Step 1: Preparation of methyl 3-((cyclopropylmethyl)amino)-2-fluorobenzoate

(2) ##STR00007##

(3) To the solution of methyl 3-amino-2-fluorobenzoate (20 g, 118.23 mmol) in anhydrous DMF (200 mL) was added potassium carbonate (21.24 g, 153.70 mmol) and (bromomethyl) cyclopropane (20.75 g, 153.70 mmol). Then the mixture was heated and refluxed for 16 hours. TLC showed the reaction was finished. The reaction mixture was extracted with ethyl acetate (100 mL) and H.sub.2O (200 mL). The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: petroleum ether:ethyl acetate=10:1) to obtain 13 g (yield 49.390%) of the target compound as light yellow liquid.

Step 2: Preparation of methyl 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoate

(4) ##STR00008##

(5) Thionyl chloride (31.99 g, 268.9 mmol) was added to benzoic acid (6.67 g, 53.78 mmol) in toluene (50 mL), and the mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse product benzoyl chloride in THF (30 mL) was used for the next step without further purification. To the solution of methyl 3-((cyclopropylmethyl)amino)-2-fluorobenzoate (10.00 g, 44.82 mmol) in anhydrous THF (100 mL) was added pyridine (4.25 g, 53.78 mmol) and benzoyl chloride. Then the mixture was stirred at room temperature for 4 hours. TLC showed the reaction was completed. To the mixture was added ethyl acetate (50 mL). The organic layer was washed with 2 M hydrochloric acid and saturated brine, and then dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: petroleum ether:ethyl acetate=8:1) to obtain 13 g (yield 88.70%) of the target compound as colorless liquid.

Step 3: Preparation of 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoic acid

(6) ##STR00009##

(7) Methyl 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoate (13.00 g, 40.88 mmol) was dissolved in methanol (100 mL), 10% sodium hydroxide aqueous solution (6.54 g, 163.52 mmol, 65.4 mL) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed the reaction was completed. After the solvent was removed by distillation, the coarse product was dissolved in H.sub.2O (100 mL) and extracted with ethyl acetate (50 mL). The pH of the aqueous phase was acidified by the addition of 2M hydrochloric acid to 7 and extracted with ethyl acetate (100 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure to obtain 12 g (yield 93.82%) of the target compound as colorless liquid, which converts to white solid after standing overnight.

Step 4: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide

(8) ##STR00010##

(9) To the solution of 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoic acid (0.40 g, 1.28 mmol) in toluene (6 mL) was added thionyl chloride (0.75 g, 6.40 mmol). Then the mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse product 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride in THF (3 mL) was used for the next step without further purification, 2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.52 g, 1.28 mmol) was charged to anhydrous THF (4 mL) and cooled to −70° C. under a nitrogen atmosphere, 2.0 M lithium diisopropyl amide hexane solution (0.77 mL, 1.54 mmol) was added dropwise thereto. After 5 min 3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride dissolved in THF (3 mL) was added dropwise thereto and the mixture was stirred at −70° C. for 30 min and at room temperature for another 30 min. TLC showed the reaction was finished. The reaction mixture was diluted with H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 0.25 g (yield 27.84%) of the target compound.

(10) For Compound No. 4: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 8.15 (d, J=2.1 Hz, 1H), 8.03 (br s, 2H), 7.92 (d, J=2.1 Hz, 1H), 7.55 (br s, 1H), 7.35-7.21 (m, 5H), 3.84 (d, J=93.6 Hz, 2H), 1.14 (br s, 1H), 0.59-0.40 (m, 2H), 0.20 (d, J=42.2 Hz, 2H).

Example 2: Preparation of

N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (Compound No. 23)

Step 1: Preparation of methyl 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoate

(11) ##STR00011##

(12) Thionyl chloride (3.2 g, 26.9 mmol) was added to 4-cyanobenzoic acid (0.80 g, 5.38 mmol) in toluene (6 mL). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse product 4-cyanobenzoyl chloride was dissolved in THF (3 mL) and used for the next step. To the solution of 3-((cyclopropylmethyl)amino)-2-fluorobenzoate (1.0 g, 4.48 mmol) in anhydrous THF (6 mL) was added triethylamine (0.74 g, 5.38 mmol) and 4-cyanobenzoyl chloride THF solution dropwise. The mixture was stirred at room temperature for 4 hours. TLC showed the reaction was completed. The mixture was diluted with H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL) and. The organic layer was washed with saturated brine dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 1.40 g (yield 88.83%) of the target compound.

Step 2: Preparation of 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoic acid

(13) ##STR00012##

(14) Methyl 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoate (1.40 g, 3.96 mmol) was dissolved in methanol (20 mL), 10% sodium hydroxide aqueous solution (0.63 g, 15.86 mmol, 6.3 mL) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed the reaction was completed. After the solvent was removed by distillation, the residue was dissolved in H.sub.2O (20 mL) and extracted with ethyl acetate (10 mL). The organic phase was dropped. The pH of the aqueous phase was acidified to 7 by 2M hydrochloric acid and extracted with ethyl acetate (10 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure to obtain 1.30 g (yield 96.79%) of the target compound as a white solid.

Step 3: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide

(15) ##STR00013##

(16) To 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoic acid (0.75 g, 2.22 mmol) in toluene (6 mL) was added thionyl chloride (1.31 g, 11.10 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse product 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride was dissolved in THF (3 mL) and used for the next step. 2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.90 g, 2.22 mmol) was charged to anhydrous THF (4 mL) and cooled to −70° C. under a nitrogen atmosphere. 2.0 M lithium diisopropyl amide hexane solution (1.30 mL, 2.66 mmol) was added dropwise thereto. After 5 min 3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride THF solution was added dropwise. The mixture was stirred at −70° C. for 30 min and at room temperature for another 30 min. TLC showed the reaction was finished. The reaction mixture was diluted with saturated NH.sub.4Cl solution (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 0.24 g (yield 14.91%) of the target compound.

(17) For Compound No. 23: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 8.14 (d, J=2.0 Hz, 1H), 8.12-7.94 (m, 2H), 7.91 (t, J=1.4 Hz, 1H), 7.58-7.39 (m, 4H), 7.32 (t, J=7.9 Hz, 1H), 3.81 (dd, J=76.0, 18.8 Hz, 2H), 1.11 (br s, 1H), 0.5 (br s, 2H), 0.20 (d, J=36.7 Hz, 2H).

Example 3: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzamide (Compound No. 37)

(18) ##STR00014##

(19) (1) To 3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzoic acid (0.45 g, 1.12 mmol) in toluene (6 mL) was added thionyl chloride (0.67 g, 5.60 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzoyl chloride was dissolved in THF (3 mL) and used for the next step.

(20) (2) 2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.46 g, 1.12 mmol) was charged to anhydrous THF (4 mL) and cooled to −70° C. under a nitrogen atmosphere. 2.0 M lithium diisopropyl amide hexane solution (0.70 mL, 1.42 mmol) was added dropwise thereto. After 5 min 3-(N-(cyclopropylmethyl)-4-(trifluoromethyl)benzamido)-2-fluorobenzoyl chloride THF solution was added dropwise. The mixture was stirred at −70° C. for 30 min and at room temperature for another 30 min. TLC showed the reaction was finished. The reaction mixture was diluted with H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 0.11 g (yield 13.75%) of the target compound.

(21) For Compound No. 37: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 8.21-7.79 (m, 4H), 7.66-7.28 (m, 5H), 3.85 (d, J=104.7 Hz, 2H), 1.12 (br s, 1H), 0.51 (br s, 2H), 0.20 (d, J=42.7 Hz, 1H).

Example 4: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (Compound No. 41)

(22) ##STR00015##

(23) (1) To 3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoic acid (0.60 g, 1.76 mmol) in toluene (6 mL) was added thionyl chloride (1.04 g, 8.80 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride was dissolved in THF (3 mL) and used for the next step.

(24) (2) 2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.72 g, 1.76 mmol) was charged to anhydrous THF (4 mL) and cooled to −70° C. under a nitrogen atmosphere. 2.0 M lithium diisopropyl amide hexane solution (1.05 mL, 2.11 mmol) was added dropwise thereto. After 5 min 3-(4-chloro-N-(cyclopropylmethyl)benzamido)-2-fluorobenzoyl chloride THF solution was added dropwise. The mixture was stirred at −70° C. for 30 min and at room temperature for 30 another min. TLC showed the reaction was finished. The reaction mixture was diluted with H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 0.15 g (yield 11.63%) of the target compound.

(25) For Compound No. 41: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 8.18-7.84 (m, 4H), 7.53 (t, J=7.7 Hz, 1H), 7.37-7.07 (m, 4H), 3.81 (d, J=85.0 Hz, 2H), 1.11 (br s, 1H), 0.49 (br s, 2H), 0.17 (d, J=32.1 Hz, 2H).

Example 5: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide (Compound No. 62)

(26) ##STR00016##

(27) To 3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzoic acid (2.20 g, 6.67 mmol) in toluene (20 mL) was added thionyl chloride (3.97 g, 33.35 mmol l). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzoyl chloride was used for the next step.

(28) 2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (3.26 g, 7.99 mmol), N,N-Diisopropyl-ethylamin (1.72 g, 13.30 mmol) and 4-N,N-dimethylaminopyridine (0.33 g, 2.69 mmol) was added to 3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzoyl chloride. The mixture was heated at 120° C. for 2 hours. The reaction mixture was dissolved in H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=3:1) to obtain 1.80 g (yield 37.5%) of the target compound.

(29) For Compound No. 62: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 10.56 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.70-7.56 (m, 2H), 7.38-7.32 (m, 3H), 7.09 (br s, 2H), 3.69 (br s, 2H), 1.03-1.01 (m, 1H), 0.41-0.39 (m, 2H), 0.08-0.06 (m, 2H).

Example 6: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide (Compound No. 8)

Step 1: Preparation of methyl 3-((1-cyclopropylethyl)amino)-2-fluorobenzoate

(30) To a solution of methyl 3-amino-2-fluorobenzoate (2.00 g, 11.82 mmol) in anhydrous 1,2-dichloroethane (65 mL) was added 1-cyclopropylethan-1-one (2.98 g, 35.47 mmol), trifluoroacetic acid (8.08 g, 70.92 mmol) and sodium triacetoxyborohydride (7.51 g, 35.47 mmol) at room temperature. The mixture was heated at 45° C. for 1 hour. When TLC showed the reaction was finished, the mixture was diluted with saturated NaHCO.sub.3 solution (50 mL) and extracted with dichloromethane (80 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=10:1) to obtain 1.50 g (yield 53.5%) of the target compound as colorless oil.

Step 2: Preparation of methyl 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoate

(31) Thionyl chloride (6.27 g, 52.68 mmol) was added to benzoic acid (1.54 g, 12.64 mmol) in toluene (15 mL). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse benzoyl chloride was dissolved in THF (5 mL) and used for the next step.

(32) To a solution of methyl 3-((1-cyclopropylethyl)amino)-2-fluorobenzoate (2.50 g, 10.54 mmol) in anhydrous THF (15 mL) was added triethylamine (1.60 g, 15.80 mmol) and benzoyl chloride THF solution. The mixture was heated and stirred at 80° C. for 6 hours. TLC showed the reaction was completed. The mixture was diluted with H.sub.2O (50 mL) and extracted with ethyl acetate (60 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=10:1) to obtain 1.03 g (yield 28.6%) of the target compound as a yellow solid.

Step 3: Preparation of 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoic acid

(33) Methyl 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoate (1.00 g, 2.93 mmol) was dissolved in methanol (10 mL). 10% sodium hydroxide aqueous solution (0.46 g, 11.72 mmol, 4.6 mL) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed the reaction was completed. After the solvent was removed by distillation, the residue was dissolved in H.sub.2O (20 mL) and extracted with ethyl acetate (10 mL). The organic phase was dropped. The pH of the aqueous phase was acidified to 3 by the addition of 2M hydrochloric acid. Then the mixture was extracted with ethyl acetate (10 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure to obtain 0.60 g (yield 62.6%) of the target compound.

Step 4: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzamide

(34) To 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoic acid (0.60 g, 1.83 mmol) in toluene (6 mL) was added thionyl chloride (1.09 g, 9.16 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoyl chloride was dissolved in THF (2 mL) and used for the next step.

(35) 2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.75 g, 1.83 mmol) was charged to anhydrous THF (6 mL) and cooled to −70° C. under a nitrogen atmosphere. 2.0 M lithium diisopropyl amide hexane solution (1.10 mL, 2.20 mmol) was added dropwise thereto. After 5 min 3-(N-(1-cyclopropylethyl)benzamido)-2-fluorobenzoyl chloride THF solution was added dropwise. The mixture was stirred at −70° C. for 30 min and at room temperature for another 30 min. When TLC showed the reaction was finished, the reaction mixture was diluted with H.sub.2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=5:1) to obtain 0.23 g (yield 17.5%) of the target compound as a yellow solid.

(36) For Compound No. 8: .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 8.19 (s, 1H), 8.05-7.95 (m, 1H), 7.89 (s, 1H), 7.77-7.73 (m, 1H), 7.56-7.52 (m, 1H), 7.28-7.11 (m, 6H), 4.26-4.23 (m, 1H), 1.63 (br s, 2H), 1.51 (br s, 1H), 0.89-0.40 (m, 5H).

(37) In addition to the compounds described in the examples, other compounds in Table 1 can be prepared according to the similar methods as described in examples 1-6. Herein below, Table 3 shows the NMR data of some compounds prepared according to this invention examples 1-6. The .sup.1H NMR chemical shift values shown therein are based on tetramethylsilane as an internal standard substance unless specified otherwise.

(38) TABLE-US-00003 TABLE 3 Compound No. .sup.1H NMR (CDCl.sub.3, ppm) 22 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.44 (s, 1H), 8.40 (s, 1H), 7.96-7.93 (m, 2H), 7.64-7.58 (m, 1H), 7.34-7.22 (m, 6H), 3.56 (br s, 1H), 1.06-1.03 (m, 1H), 0.84-0.80 (m, 1H), 0.65-0.38 (m, 8H). 24 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.50 (s, 1H), 8.19 (s, 1H), 7.82-7.35 (m, 8H), 3.75 (d, J = 86.5 Hz, 2H), 3.57(s, 3H), 0.87-0.84 (m, 1H), 0.43-0.13 (m, 4H). 26 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.51 (d, J = 27.1 Hz, 1H), 8.54-8.35 (m, 1H), 7.95 (s, 1H), 7.86-7.51 (m, 4H), 7.51-7.20 (m, 3H), 4.03 (q, J = 7.1 Hz, 1H), 1.30-1.19 (m, 3H), 0.93-0.23 (m, 5H). 32 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.45 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.84-7.80 (m, 1H), 7.71-7.61 (m, 3H), 7.45-7.35 (m, 3H), 3.59-3.55 (m, 1H), 1.10 (br s, 1H), 0.85-0.80 (m, 1H), 0.67-0.40(m, 8H). 38 .sup.1H NMR (400 MHz, DMSO-d.sub.6), δ [ppm]: 10.46 (s, 1H), 8.19 (s, 1H), 7.78 (d, J = 25.9 Hz, 3H), 7.56 (d, J = 40.0 Hz, 4H), 7.36 (s, 1H), 3.76 (d, J = 36.8 Hz, 2H), 3.57 (s, 3H), 0.93-0.79 (m, 1H), 0.43 (s, 2H), 0.13 (d, J = 30.4 Hz, 2H). 39 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.44 (d, J = 30.3 Hz, 1H), 8.41 (s, 1H), 7.94 (s, 1H), 7.80-7.73(m, 1H), 7.70-7.27 (m, 6H), 4.09-4.07 (m, 1H), 1.50-1.15 (m, 3H), 0.95-0.19 (m, 5H). 43 400 MHz, DMSO-d.sub.6 δ[ppm]: 10.55 (s, 1H), 8.20 (s, 1H), 7.82 (s, 1H), 7.70-7.59 (m, 2H), 7.32 (br s, 5H), 3.71 (br s, 2H), 3.57 (s, 3H), 1.03 (br s, 1H), 0.42 (br s, 2H), 0.09 (br s, 2H). 44 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.53 (d, J = 25.5 Hz, 1H), 8.46-8.37 (m, 1H), 7.98-7.91 (m, 1H), 7.80-7.55 (m, 2H), 7.32 (d, J = 33.8 Hz, 5H), 4.03 (q, J = 7.1 Hz, 1H), 1.46-1.15 (m, 3H), 0.90-0.18 (m, 5H). 46 400 MHz, CDCl.sub.3-d, δ[ppm]: 8.13 (d, J = 2.0 Hz, 1H), 8.05 (t, J = 7.6 Hz, 1H), 7.90 (s, 1H), 7.54 (t, J = 7.8 Hz, 1H), 7.32 (d, J = 9.7 Hz, 2H), 7.21 (t, J = 6.7 Hz, 3H), 3.81 (d, J = 87.9 Hz, 2H), 1.10 (br s, 1H), 0.50 (br s, 2H), 0.18 (d, J = 35.8 Hz, 2H). 47 400 MHz, CDCl.sub.3-d, δ[ppm]: 8.36 (d, J = 2.1 Hz, 1H), 8.26-7.91 (m, 3H), 7.59 (s, 1H), 7.44-7.29 (m, 3H), 7.23 (br s, 2H), 4.00 (br s, 1H), 3.69 (br s, 1H), 1.14 (br s, 1H), 0.52 (br s, 2H), 0.21 (d, J = 56.0 Hz, 2H). 49 400 MHz, DMSO-d.sub.6 δ[ppm]: 10.54 (s, 1H), 8.20 (s, 1H), 7.82 (s, 1H), 7.70-7.59 (m, 2H), 7.51-7.18 (m, 5H), 3.70 (br s, 2H), 3.57 (s, 3H), 1.02-0.97 (m, 1H), 0.41 (d, J = 8.1 Hz, 2H), 0.17-0.02 (m, 2H). 50 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.53 (d, J = 34.0 Hz, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.76-7.62 (m, 2H), 7.42-7.20 (s, 5H), 4.03-3.97 (m, 1H), 1.39-1.21 (m, 3H), 0.85-0.24 (m, 5H). 52 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.43 (s, 1H), 7.95 (br s, 2H), 7.60-7.54 (m, 4H), 7.26 (br s, 2H), 7.01 (br s, 1H), 3.63 (br s, 2H), 0.93 (br s, 1H), 0.32 (d, J = 8.1 Hz, 2H), 0.04 (br s, 2H). 53 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.61 (s, 1H), 8.50 (d, J = 2.0 Hz, 1H), 7.94 (d, J = 2.1 Hz, 1H), 7.63-7.57 (m, 4H), 7.36(br s, 2H), 7.09 (br s, 1H), 3.69 (br s, 2H), 1.01 (s, 1H), 0.41 (d, J = 8.2 Hz, 2H), 0.08 (br s, 2H). 57 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.59 (s, 1H), 8.42 (d, J = 2.1 Hz, 1H), 7.95 (d, J = 2.1 Hz, 1H), 7.80-7.67 (m, 3H), 7.62-7.52 (m, 3H), 7.35 (s, 1H), 3.75 (s, 2H), 3.16 (s, 3H), 1.03 (s, 1H), 0.53-0.30 (m, 2H), 0.13 (d, J = 16.2 Hz, 2H). 60 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.46 (s, 1H), 8.34 (d, J = 2.1 Hz, 1H), 7.87 (d, J = 2.1 Hz, 1H), 7.65 (t, J = 7.4 Hz, 1H), 7.54 (br s, 1H), 7.36 (br s, 2H), 7.29 (br s, 1H), 7.16 (br s, 2H), 3.62 (br s, 2H), 0.95 (br s, 1H), 0.34 (br s, 2H), 0.07 (s, 2H). 63 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.55 (br s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.72 (d, J = 24.2 Hz, 1H), 7.61 (s, 1H), 7.39-7.26 (m, 3H), 7.05 (s, 2H), 4.02 (br s, 1H), 1.39 (br s, 1H), 1.24 (s, 3H), 0.53 (d, J = 50.9 Hz, 2H), 0.32 (d, J = 44.6 Hz, 2H). 75 400 MHz, DMSO-d.sub.6, δ[ppm]: 8.04 (s, 1H), 7.95 (s, 1H), 7.94-7.63 (m, 2H), 7.42-7.35 (m, 3H), 7.12-6.99 (m, 2H), 5.08-4.78 (m, 1H), 1.48- 1.43 (m, 1H), 1.34-1.08 (m, 6H). 77 400 MHz, DMSO-d.sub.6, δ[ppm]: 10.53 (d, J = 25.6 Hz, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.77 (d, J = 7.6 Hz, 3H), 7.61 (s, 1H), 7.52 (s, 2H), 7.36 (t, J = 7.2 Hz, 1H), 4.06 (br s, 1H), 3.14 (s, 3H), 1.41 (br s, 1H), 1.25 (d, J = 8.5 Hz, 3H), 0.56 (d, J = 33.0 Hz, 2H), 0.35 (d, J = 43.5 Hz, 2H).

(39) Other compounds represented by general formula I of this invention can also be prepared according to the methods described above.

FORMULATION EXAMPLES

Example 1: Sample Preparation Method for Emulsifiable Concentrate of Compound 4

(40) TABLE-US-00004 TABLE 4 Formulation of emulsifiable concentrate of compound 4 Content 100% Materials consistency (W/W, %) Remarks Compound 4 5 Active Ingredient Calcium dodecylbenzene 5 Emulsifier sulfonate Polyoxyethylene castor 5 Emulsifier oil Trimethylbenzene 85 Solvent

(41) Preparation method: the amount of each material in Table 4 was weighed. Trimethylbenzene was added into 250 mL three-necked flask followed by addition of compound 4, calcium dodecylbenzene sulfonate and polyoxyethylene castor oil. The mixture was stirred at 40˜50° C. for 1.5 hours and filtered. The emulsion concentrate of 5% compound 4 was obtained.

Example 2: Sample Preparation Method for Wettable Powder of Compound 23

(42) TABLE-US-00005 TABLE 5 Formulation of wettable powder of compound 23 Content 100% Materials consistency (W/W, %) Remarks compound 23 30 Active Ingredient sodium dodecyl sulfate 1.5 Wetting agent sodium lignin sulfonate 6 Dispersant kaolin 62.5 Carrier

(43) Preparation method: the amount of each material in Table 5 was weighed. Compound No. 23, sodium dodecyl sulfate, sodium lignosulfonate and kaolin were mixed evenly and pulverized to an average particle size of 10 microns with a jet mill to obtain wettable powder of 300% compound No. 23.

Examples for Bioactivity Tests

(44) Various kinds of pests were tested with the representative compounds of this invention.

Example 1 Indoor Bioactivity Test Against Mythimna separata

(45) The leaf dip method was used to assay the insecticidal activity of compounds to strains of Mythimna sepatata. Cut above ground part of fresh maize seedlings, about 10 cm. Dip the maize seedlings into the solution prepared with compound of this invention for 10 seconds and dry them in a cool environment. Then cut the dry maize seedlings into 3˜5 cm leaf sections and put 3 leaf sections into each petri dish. Put ten of 4th-instar larvae of Mythimna separatas into each dish, which was repeated by 3 times. Then the dishes were placed in an illumination incubator and incubated at 25° C. in the dark. Symptoms were investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

(46) The insecticidal activity of some compounds of this invention against Mythimna separate is ≥90% (mortality of Mythimna separata) at 1 ppm on the 3rd day after treatment. The compounds are 4, 8, 22, 23, 26, 37, 38, 39, 41, 44, 47, 52, 57, 60, 62 and 75.

Example 2 Indoor Bioactivity Test Against Spodoptera exigua Hiibner

(47) The leaf dip method was used to assay the insecticidal activity of compounds to strains of Spodoptera exigua Hiibner. Dip the leaf disc into the solution prepared with compound of this invention for 10 seconds, and dry them in a cool environment. Then place them in Petri dish with 4 discs per dish. Put the filter paper into the Petri dish to moisturize it. Put 10 of Spodoptera exigua Hiibners into each dish, which was repeated by 3 times. The dishes were placed in an illumination incubator and incubated at 25° C. with 14 hL: 10 hD illumination. The number of Spodoptera exigua Hiibner death was investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

(48) The insecticidal activity of some compounds of this invention against Spodoptera exigua Hiibner is as follows:

(49) The insecticidal activity of compounds 53, 60, and 75 is ≥90% (mortality of Spodoptera exigua Hiibner) at 10 ppm on the 3rd day after treatment.

(50) The insecticidal activity of compounds 4, 23, 37, 41, 46, 47, 57 and 62 is 90% (mortality of Spodoptera exigua Hiibner) at 1 ppm on the 3rd day after treatment.

Example 3 Indoor Bioactivity Test Against Plutella xylostella

(51) The leaf dip method was used to assay the insecticidal activity of compounds to strains of Plutella xylostella. Dip the leaf disc into the solution prepared with compound of this invention for 10 seconds, and dry them in a cool environment. Then place them in Petri dish with 4 discs per dish. Put the filter paper into the Petri dish to moisturize it. Put 10 of Plutella xylostella into each dish, which was repeated by 3 times. The dishes were placed in an illumination incubator and incubated at 25° C. with 14 hL: 10 hD illumination. The number of Plutella xylostella death was investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

(52) The insecticidal activity of some compounds of this invention against Plutella xylostella is as follows:

(53) The insecticidal activity of compounds 37, 39, 57, 60, 63 and 75 is ≥90% (mortality of Plutella xylostella) at 1 ppm on the 3rd day after treatment.

(54) The insecticidal activity of compounds 4, 8, 23, 26, 41 and 62 is ≥90% (mortality of Plutella xylostella) at 0.4 ppm on the 3rd day after treatment.

(55) According to the above method, compound 4 and KC1 were selected and parallelly tested against Plutella xylostella to compare their insecticidal activity. The results are shown in Table 6

(56) TABLE-US-00006 TABLE 6 The mortality of compound 4 and KC1 against Plutella xylostella Mortality (%) Compound name Structure dose 1 d 2 d 3 d Compound 4 0.04 ppm 30 80 100 KC1 (broflanilide) 0.04 ppm  0 56.67  90

(57) Table 6 shows that Compound 4 of this invention has better quick-acting effect than KC1 at a low dose. The mortality of Plutella xylostella is 30% on the 1st day and 80% on the 2nd day after treatment. It has efficient insecticidal activity.

Example 4 Indoor Bioactivity Test Against Spodoptera litura

(58) The leaf dip method was used to assay the insecticidal activity of compounds to strains of Spodoptera litura. Dip the leaf disc into the solution prepared with compound of this invention for 10 seconds, and dry them in a cool environment. Then place them in Petri dish with 4 discs per dish. Put the filter paper into the Petri dish to moisturize it. Put 10 of Spodoptera litura into each dish, which was repeated by 3 times. The dishes were placed in an illumination incubator and incubated at 25° C. with 14 hL: 10 hD illumination. The number of Spodoptera litura death was investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

(59) The insecticidal activity of some compounds of this invention against Spodoptera litura is as follows:

(60) The insecticidal activity of compounds 4, 52, 53, 57, 75 is ≥90% (mortality of Spodoptera litura) at 10 ppm on the 3rd day after treatment.

(61) The insecticidal activity of compounds 23, 37, 41, 47, 60, 62 is ≥90% (mortality of Spodoptera litura) at 0.4 ppm on the 3rd day after treatment.

(62) According to the above method, compound 4, 23 and KC1 were selected and parallelly tested against Spodoptera litura to compare the insecticidal activity. The results are shown in Table 7.

(63) TABLE-US-00007 TABLE 7 The mortality of compound 4, 23 and KC1 on Spodoptera litura Mortality (%) Compound name Structure Dose 1 d 2 d 3 d Compound 4   1 ppm 0.4 ppm 73.33 20.00 73.33 26.67 73.33 26.67 Compound 23 0   1 ppm 0.4 ppm 93.33 40.00 100.00 46.67 100.00  60.00 KC1 (broflanilide)   1 ppm 0.4 ppm 26.67  0.00 33.33  0.00 33.33  0.00

(64) The results of Table 7 show that the compounds of this invention have better quick-acting properties and higher insecticidal activity than KC1 at a low dose.

Example 5 Indoor Bioactivity Test Against Chilo suppressalis

(65) The leaf dip method was used to assay the insecticidal activity of compounds to strains of Chilo suppressalis. The rice was cultivated in a plastic pot with a diameter of 9 cm and a height of 10 cm. When the rice grew about 25 cm, the aerial part of robust and consistent rice seedlings were selectively cut. Their leaves were removed and their stems of about 8 cm were kept for use. Pour the solution prepared with compound of this invention into the Petri dish (about 40 mL) and immerse the rice stems into the solution for 10 seconds. Take rice stems out and dry them in a cool environment. Put a wet cotton ball at the bottom of finger-like glass tube and 5 rice stems in each tube. Put 10 of 3rd-instar larvae of Chilo suppressa into each tube, which was repeated by 3 times. Seal the tubes with black cotton cloth and tighten them with rubber band. The tubes were placed in a illumination incubator at 28° C. and incubated in the dark. The number of alive Chilo suppressalis and the total number were investigated 3 days after treatment. The mortality was calculated.

(66) The insecticidal activity of some compounds of this invention against Chilo suppressalis is as follows:

(67) Compounds 39, 47, 50, 52 and 53 have a good insecticidal effect at 10 ppm on the 3rd day after treatment, and the mortality t is ≥90% (mortality of Chilo suppressalis).

(68) Compounds 4, 23, 26, 37, 41, 46 and 62 have a good insecticidal effect at 5 ppm on the 3rd day after treatment, and the mortality is ≥90% (mortality of Chilo suppressalis).

(69) According to the above method, Compound 23 and KC2 were selected and parallelly tested against Chilo suppressalis. The results are shown in Table 8.

(70) TABLE-US-00008 TABLE 8 The mortality of compound 23 and KC2 on Chilo suppressalis Mortality (%, 3d) Compound name Structure 5 ppm 2 ppm 1 ppm 0.4 ppm Compound 23 100 100 93.33 53.33 KC2 93.33 86.67 53.33 0

(71) The results of Table 8 show that the compound of this invention has a better insecticidal effect than KC2 at a lower dose.

Example 6 Biological Activity of Compounds on Soybean Thrips (in Greenhouse)

(72) Experimental Date: 2018 Aug. 6˜2018 Aug. 12

(73) Test system: naturally occurring thrips population on soybeans planted in greenhouse. The basic number of active thripses were more than 100 thripses per trifoliate leaf. Under the same conditions, the sensitivity of the thrips population to Spinetoram (dose: 50 mg/L) is 96.55% mortality on the 6th day after treatment.

(74) The size of the plot: 10 m.sup.2, no repetition.

(75) Test formulation: each compound was made into 5% SL (compound 5%+emulsifier 5%+solvent to make up 100%).

(76) Method: Foliar spray.

(77) {circle around (1)} Spraying time: both adult and larva thripses were in the active period. The number of spray: 1 time.

(78) {circle around (2)} Standard for water usage: when dose was in mg/kg, the upper leaves were wet and water began to drop therefrom.

(79) {circle around (3)} Survey standard: count three single leaves as one leaf. Three leaves were randomly selected and investigated for the number of adult and larva thripses on them.

(80) {circle around (4)} Survey time and number: surveys were carried out 2 days and 6 days after spray, irrespectively. 2 surveys were conducted.

(81) Results and Analysis: the field activity results of Compound 4 against soybean thrips are shown in Table 9.

(82) TABLE-US-00009 TABLE 9 Field activity of compound 4 against soybean thrips (June of 2018, Qingpu, Shanghai) 1 d 6 d Compound dose No. of No. of name ppm thrips Mortality % thrips) Mortality % Compound 4 50 6 97.73 6 94.83 10 20 92.42 2 98.28 Spinetoram 50 16 93.94 4 96.55 Blank control — 264 0.00 116 0.00

(83) The applicant states that the meta-carboxamido benzamide compounds of this invention, the preparation methods and applications thereof can be illustrated by the above mentioned examples, but this invention is not limited thereto, i.e., which does not mean that the implementation of this invention must rely on the above examples. Those skilled in the art should understand that any improvement to this invention, equivalent replacement of the raw materials for preparing the compounds of this invention, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the scope of protection and disclosure of this invention.