3-N-CYCLOPROPYLMETHYL-2-FLUOROBENZAMIDE COMPOUND, PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

Disclosed are a 3-N-cyclopropylmethyl-2-fluorobenzamide compound, a preparation method therefor and the use thereof. The compound has a structure as represented by the following formula I. This compound can be used for the preparation of an m-diamide compound substituted with a 3-N-cyclopropylmethyl derivative. The m-diamide compound substituted with the 3-N-cyclopropylmethyl derivative, when serving as an insecticide, has the characteristics of a good fast-acting property, needing to use a low amount thereof, and being more beneficial for environmental protection. The 3-N-cyclopropylmethyl-2-fluorobenzamide compound is easy to synthesize and has mild conditions, and when used for preparing a m-diamide compound insecticide substituted with a 3-N-cyclopropylmethyl derivative, same is easy to synthesize and has a low synthesis cost and a high yield.

Claims

1. A 3-N-cyclopropylmethyl-2-fluorobenzamide compound, which has a structure defined by Formula I: ##STR00092## wherein: Q is selected from ##STR00093## wherein represents the connection position of Q; Y is selected from C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6 haloalkoxyl; Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 are identical or different, and each independently selected from any one or a combination of at least two of H, F, Cl, Br, I, CN, NO.sub.2, substituted or unsubstituted 3-10 membered heterocyclic group, 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, or C.sub.1-C.sub.6 haloalkylsulfonyl; R.sub.1 is selected from H, 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 cyclohaloalkyl; R.sub.2 is selected from H or halogen; and W and W′ are each independently selected from O or S.

2. The 3-N-cyclopropylmethyl-2-fluorobenzamide compound according to claim 1, wherein in Formula I, Y is selected from trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, trifluoromethoxyl, or difluoromethoxyl; R.sub.1 is selected from H, methyl, monochloromethyl, monofluoromethyl, cyclopropyl or perfluorocyclopropyl; R.sub.2 is selected from H, Cl or F; Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 are identical or different, and each independently selected from H, F, Cl, Br, I, CN, trifluoromethyl, trifluoromethoxyl, methylsulfonyl or trifluoromethyl sulfonyl.

3. The 3-N-cyclopropylmethyl-2-fluorobenzamide compound according to claim 1, wherein in Formula I, Y is selected from trifluoromethyl, trifluoromethoxyl or difluoromethoxyl; R.sub.1 is selected from H or methyl; R.sub.2 is selected from H; Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 are identical or different, and each independently selected from H, F, Cl, Br, I, CN, trifluoromethyl, trifluoromethoxyl, methylsulfonyl or trifluoromethyl sulfonyl.

4. The 3-N-cyclopropylmethyl-2-fluorobenzamide compound according to claim 1, wherein the 3-N-cyclopropylmethyl-2-fluorobenzamide compound is selected from any one of the compounds below, ##STR00094## ##STR00095## ##STR00096## ##STR00097##

5. A compound, which is an intermediate to prepare the 3-N-cyclopropylmethyl-2-fluorobenzamide compound according to claim 1, wherein the compound has a structure defined by Formula II: ##STR00098## wherein: Y is selected from C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6 haloalkoxyl; R.sub.1 is selected from H, 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 cyclohaloalkyl; R.sub.2 is selected from H or halogen; and W is selected from O or S.

6. The compound according to claim 5, wherein in Formula II, Y is selected from trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, trifluoromethoxyl and difluoromethoxyl; R.sub.1 is selected from H, 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.2 is selected from H, F or Cl; and W is selected from O or S.

7. The compound according to claim 5, wherein in Formula II, Y is selected from trifluoromethyl, trifluoromethoxyl, difluoromethoxyl; R.sub.1 is selected from H or methyl; R.sub.2 is selected from H; and W is selected from 0.

8. The compound according to claim 5, wherein the compound is selected from any one of the compounds below, ##STR00099##

9. A compound, which is an intermediate to prepare the compound according to claim 5, which has a structure defined by Formula III: ##STR00100## wherein: Y is selected from C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6 haloalkoxyl; R.sub.1 is selected from H, F or methoxyl; and W is selected from O or S.

10. The compound according to claim 9, wherein in Formula III, Y is selected from trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, trifluoromethoxyl, or difluoromethoxyl; and W is selected from O or S.

11. The compound according to claim 9, wherein in Formula III, Y is selected from trifluoromethyl, trifluoromethoxyl, or difluoromethoxyl; and W is selected from O.

12. A process comprising preparing the meta-carboxamido benzamide compound defined by Formula A using the 3-N-cyclopropylmethyl-2-fluorobenzamide compound according to claim 1: ##STR00101## wherein: Q is selected from ##STR00102## wherein represents the connection position of Q; Y is selected from C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6 haloalkoxyl; Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 are identical or different, and each independently selected from any one or a combination of at least two of H, F, Cl, Br, I, CN, NO.sub.2, substituted or unsubstituted 3-10 membered heterocyclic group, 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, or C.sub.1-C.sub.6 haloalkylsulfonyl; R.sub.1 is selected from H, 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 cyclohaloalkyl; R.sub.2 is selected from H or halogen; W and W′ are each independently selected from O or S.

13. The process according to claim 12, wherein the preparation of meta-carboxamido benzamide compound defined by Formula A contains following steps: (1) subjecting a 3-N-cyclopropylmethyl-2-fluorobenzamide compound defined by Formula II to react with a compound defined by Formula B to obtain a compound defined by Formula I, wherein the reaction formula is as follows: ##STR00103## (2) subjecting the compound defined by Formula I to react with a bromination reagent to obtain a compound defined by Formula A, wherein the reaction formula is as follows: ##STR00104## wherein Y, R.sub.1, R.sub.2, W, W′, and Z are defined identically as in claim 12.

Description

DETAILED DESCRIPTION

[0099] Technical solutions of the present application will be further described in the following Examples. Those skilled in the art should understand that the examples herein are only illustrative, and the present application is not limited thereto.

Preparation Example 1

[0100] Preparation of N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (Compound No. 2.1). The preparation method is as follows.

(1) Preparation of N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl)-2-fluoro-3-nitro benzamide

[0101] ##STR00071##

[0102] 2-fluoro-3-nitrobenzoic acid (5.9 g, 31.9 mmol), toluene (60 mL) and thionyl chloride (7.6 g, 63.8 mmol) were added to a reaction flask in sequence. The mixture was heated and refluxed for 2 hours under stirring, and concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. 4-(heptafluoroisopropyl)-2-(trifluoromethyl)aniline (10.0 g, 30.4 mmol) was added to 2-fluoro-3-nitrobenzoyl chloride, and toluene (10 mL) was added to the mixture. The mixture was heated to 120° C., and after 8 hours the reaction mixture was cooled to room temperature, and added with ethyl acetate (100 mL) and H.sub.2O (100 mL) for extraction and layer separating. The organic layer was washed with saturated brine, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (SGC) (eluent: petroleum ether (PE): ethyl acetate (EA)=9:1) to obtain the target compound (14.1 g, yellow solid, 93.4% yield).

[0103] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.74 (s, 1H), 8.35 (t, J=8.5 Hz, 1H), 8.20-8.03 (m, 3H), 7.96 (s, 1H), 7.62 (t, J=8.0 Hz, 1H).

(2) Preparation of 3-amino-2-fluoro-N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl) benzamide

[0104] ##STR00072##

[0105] N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide (5.0 g, 10.1 mmol) was dissolved in EtOH (50 mL), and concentrated hydrochloric acid (1.0 mL) and tin (II) chloride dihydrate (9.1 g, 40.3 mmol) were added in sequence. Then the mixture was heated and refluxed for 2 hours. After the reaction solution was evaporated to dryness, the pH of the mixture was adjusted by 10% sodium hydroxide solution to 12. The reaction mixture was extracted with EA (50 mL). The organic layer was washed with saturated brine and dried over anhydrous sodium sulphate. The mixture was concentrated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=5:1) to obtain 4.3 g (yield 91.5%) of yellow solid.

[0106] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.14 (s, 1H), 8.16-8.03 (m, 2H), 7.93 (s, 1H), 7.07-6.92 (m, 2H), 6.86 (t, J=5.8 Hz, 1H), 5.43 (s, 2H).

(3) Preparation of N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl)-3-((cyclopropyl methyl)amino)-2-fluorobenzamide

[0107] ##STR00073##

[0108] 3-amino-2-fluoro-N-(4-(heptafluoroisopropyl)-2-(trifluoromethyl)phenyl)benzamide (4.0 g, 8.6 mmol) was dissolved in DMF (20 mL), and (bromomethyl)cyclopropane (1.7 g, 12.9 mmol) and potassium carbonate (2.4 g, 17.2 mmol) were added in sequence. Then the mixture was heated to 120° C. The reaction was under TLC monitor until completed, and then the reaction was finished. Ethyl acetate (100 mL) and H.sub.2O (100 mL) were added for extraction and layer separating. The organic layer was taken and washed with saturated brine, and then dried over anhydrous sodium sulphate. The mixture was concentrated under reduced pressure and the obtained residue was purified by SGC (eluent: petroleum ether:ethyl acetate=9:1) to obtain 2.2 g (yield 49.2%) of the target compound as light yellow solid.

[0109] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.18 (s, 1H), 8.12-8.07 (m, 1H), 8.04 (d, J=8.7 Hz, 1H), 7.92 (s, 1H), 7.10 (t, J=7.9 Hz, 1H), 6.94 (t, J=8.2 Hz, 1H), 6.90-6.82 (m, 1H), 5.82-5.72 (m, 1H), 3.03 (t, J=6.2 Hz, 2H), 1.12-1.08 (m, 1H), 0.50-0.42 (m, 2H), 0.24 (q, J=4.4 Hz, 2H).

Preparation Example 2

Preparation of N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl)-3-(N-(1-cyclopropyl ethyl)benzamido)-2-fluorobenzamide

(1) Preparation of N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl)-2-fluoro-3-nitro benzamide

[0110] ##STR00074##

[0111] 2-fluoro-3-nitrobenzoic acid (0.94 g, 5.1 mmol), toluene (10 mL) and thionyl chloride (1.2 g, 10.2 mmol) were added to a reaction flask in sequence. The mixture was heated and refluxed for 2 hours under stirring, and concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. 4-(heptafluoroisopropyl)-2-(difluoromethoxyl)aniline (2.0 g, 4.9 mmol) was added to 2-fluoro-3-nitrobenzoyl chloride, and toluene (5 mL) was added to the mixture. The mixture was heated to 120° C., and after 8 hours the reaction mixture was cooled to room temperature, and added with ethyl acetate (30 mL) and H.sub.2O (30 mL) for extraction and layer separating. The organic layer was washed with saturated brine, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether:ethyl acetate=10:1) to obtain 2.3 g (yellow solid, yield 95.0%) of the target compound.

[0112] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.62 (s, 1H), 8.42-8.30 (m, 2H), 8.13-8.04 (m, 1H), 7.71-7.53 (m, 3H), 7.35 (t, J=72.7 Hz, 1H).

(2) Preparation of 3-amino-2-fluoro-N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl) benzamide

[0113] ##STR00075##

[0114] N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl)-2-fluoro-3-nitrobenzamide (1.6 g, 3.0 mmol) was dissolved in the mixture of EtOH (20 mL) and H.sub.2O (5 mL), and Zn powder (0.98 g, 15.0 mmol) and ammonium chloride (0.8 g, 15.0 mmol) were added in sequence. Then the mixture was heated and refluxed for 5 hours. After the reaction liquid was evaporated to dryness under reduced pressure, the pH of the mixture was adjusted by 10% sodium carbonate solution to 9-10. The reaction mixture was extracted with EA (50 mL). The organic layer was washed with saturated brine and dried over anhydrous sodium sulphate. The mixture was concentrated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=5:1) to obtain 1.31 g (yield 94.2%) of the target compound as yellow solid.

[0115] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 9.97 (d, J=5.2 Hz, 1H), 8.39 (d, J=8.8 Hz, 1H), 7.64 (dd, J=8.8, 2.0 Hz, 1H), 7.51 (d, J=2.0 Hz, 1H), 7.62 (t, J=72.8 Hz, 1H), 5.45 (s, 2H).

(3) Preparation of N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl)-3-((cyclopropyl methyl)amino)-2-fluorobenzamide

[0116] ##STR00076##

[0117] 3-amino-2-fluoro-N-(4-(heptafluoroisopropyl)-2-(difluoromethoxyl)phenyl)benzamide (4.7 g, 10.0 mmol) was dissolved in DMF (20 mL), and (bromomethyl)cyclopropane (1.62 g, 12.0 mmol) and potassium carbonate (1.7 g, 12.0 mmol) were added in sequence. Then the mixture was heated to 120° C. for reaction. The reaction was under TLC monitor until completed, and then the reaction was finished. Ethyl acetate (100 mL) and H.sub.2O (100 mL) were added for extraction and layer separating. The organic layer was washed with saturated brine, and then dried over anhydrous sodium sulphate. The mixture was concentrated under reduced pressure and the obtained residue was purified by SGC (eluent: petroleum ether:ethyl acetate=10:1) to obtain 2.7 g (yield 51.9%) of the target compound as light yellow solid.

[0118] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 9.76 (d, J=4.8 Hz, 1H), 8.13 (d, J=8.7 Hz, 1H), 7.40-7.37 (m, 1H), 7.28-7.21 (m, 1H), 7.06 (5, J=72.0, 1H), 6.85 (t, J=8.0 Hz, 1H), 6.73-6.60 m, 2H), 5.55-5.42 (m, 1H), 2.82-2.73 (m, 2H), 0.72-0.65 (m, 1H), 0.28-0.18 (m, 2H), 0.05-0.01 (m, 2H).

Preparation Example 3

Preparation of the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide (Compound No. 62 in CN109497062A)

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-fluorobenzamido)-2-fluorobenzamide

[0119] ##STR00077##

[0120] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL), pyridine (69 mg, 0.86 mmol) and 4-fluorobenzoyl chloride (0.11 g, 0.69 mmol) were added to a reaction flask in sequence. The mixture was warmed up to 80° C. for reaction, and after 4 hours the reaction mixture was cooled down to room temperature. The pH of the mixture was adjusted by 2M HCl to 6. EA (100 mL) and H.sub.2O (100 mL) were added for extraction and layer separating. The organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.33 g (yield 89.2%) of the target compound as white solid.

[0121] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.21 (s, 1H), 8.09 (d, J=8.0 Hz, 1H), 7.99 (d, J=8.0 Hz, 1H), 7.92 (s, 1H), 7.61-7.59 (m, 2H), 7.36-7.22 (m, 6H), 3.68 (d, J=52.0 Hz, 2H), 1.02 (brs, 1H), 0.40 (d, J=8.0 Hz, 2H), 0.08 (brs, 2H).

(2) Preparation of N-(2-bromo-4-(heptafluoroisopropyl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide

[0122] ##STR00078##

[0123] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-fluorobenzamido)-2-fluorobenzamide (0.15 g, 0.23 mmol) in DMF (4 mL) was added N-bromosuccinimide (45 mg, 0.26 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O were added to the reaction mixture for extraction and layer separating. The organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.16 g (yield 94.1%) of the target compound as white solid.

[0124] .sup.1H NMR (DMSO-d6, 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).

Preparation Example 4

Preparation of the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-benzamido)-2-fluorobenzamide (Compound No. 4 in CN109497062A)

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-benzamido)-2-fluorobenzamide

[0125] ##STR00079##

[0126] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL), pyridine (69 mg, 0.86 mmol) and benzoyl chloride (97 mg, 0.69 mmol) were added to a reaction flask in sequence. The mixture was warmed up to 80° C. for reaction, and after 4 hours the reaction mixture was cooled down to room temperature. The pH of the mixture was adjusted by 2M HCl to 6, and EA (100 mL) H.sub.2O (100 mL) were added for extraction and layer separating. The organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.34 g (yield 94.4%) of the target compound as white solid.

[0127] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.21 (s, 1H), 8.09 (d, J=8.0 Hz, 1H), 7.99 (d, J=8.0 Hz, 1H), 7.92 (s, 1H), 7.61-7.59 (m, 2H), 7.36-7.22 (m, 6H), 3.68 (d, J=52.0 Hz, 2H), 1.02 (brs, 1H), 0.40 (d, J=8.0 Hz, 2H), 0.08 (brs, 2H).

(2) Preparation of N-(2-bromo-4-(heptafluoroisopropyl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-benzamido)-2-fluorobenzamide

[0128] ##STR00080##

[0129] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-benzamido)-2-fluorobenzamide (0.14 g, 0.22 mmol) in DMF (4 mL) was added N-bromosuccinimide (44 mg, 0.25 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O was added to the reaction mixture for extraction and layer separating, and the organic layer was washed saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.14 g (yield 90.3%) of the target compound as white solid.

[0130] .sup.1H NMR (CDCl.sub.3-d, 400 MHz), 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).

Preparation Example 5

Preparation of the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-chlorobenzamido)-2-fluorobenzamide (Compound No. 41 in CN109497062A)

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-chlorobenzamido)-2-fluorobenzamide

[0131] ##STR00081##

[0132] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL), pyridine (69 mg, 0.86 mmol) and 4-chlorobenzoyl chloride (120 mg, 0.69 mmol) were added to a reaction flask. The mixture was warmed up to 80° C. for reaction, and after 4 hours the reaction mixture was cooled down to room temperature, and the pH of the mixture was adjusted by 2M HCl to 6. 100 mL EA and 100 mL H.sub.2O were added for extraction and layer separating. The organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.36 g (yield 94.2%) of the target compound as white solid.

[0133] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.21 (s, 1H), 8.10 (dd, J=8.6, 2.1 Hz, 1H), 7.99 (d, J=8.6 Hz, 1H), 7.92 (t, J=2.3 Hz, 1H), 7.67-762 (m, 2H), 7.34-7.30 (m, 5H), 3.69 (d, J=23.9 Hz, 2H), 1.02 (brs, 1H), 0.40 (d, J=8.0 Hz, 2H), 0.09 (brs, 2H).

(2) Preparation of N-(2-bromo-4-(heptafluoroisopropyl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-chlorobenzamido)-2-fluorobenzamide

[0134] ##STR00082##

[0135] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-chlorobenzamido)-2-fluorobenzamide (0.17 g, 0.26 mmol) in DMF (4 mL) was added N-bromosuccinimide (50 mg, 0.28 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O were added to the reaction mixture for extraction and layer separating. The organic layer was washed saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.18 g (yield 93.7%) of the target compound as white solid.

[0136] .sup.1H NMR (DMSO-d6, 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).

Preparation Example 6

Preparation the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl) phenyl)-3-(N-(cyclopropylmethyl)-4-bromobenzamido)-2-fluorobenzamide

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-bromobenzamido)-2-fluorobenzamide

[0137] ##STR00083##

[0138] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL), pyridine (69 mg, 0.86 mmol) and 4-bromobenzoyl chloride (152 mg, 0.69 mmol) were added to a reaction flask. The mixture was warmed up to 80° C., after 4 hours the reaction mixture was cooled down to room temperature, and the pH of the mixture was adjusted by 2M HCl to 6. 100 mL EA and 100 mL H.sub.2O were added for extraction and layer separating, and the organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.13 g (yield 32.06%) of the target compound as white solid.

[0139] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.23 (s, 1H), 8.11 (d, J=8.7 Hz, 1H), 8.00 (d, J=8.6 Hz, 1H), 7.93 (s, 1H), 7.70-7.61 (m, 2H), 7.46 (s, 2H), 7.31 (dd, J=19.3, 11.8 Hz, 3H), 3.69 (d, J=15.9 Hz, 2H), 1.02 (brs, 1H), 0.41 (d, J=7.8 Hz, 2H), 0.10 (s, 2H).

(2) Preparation of N-(2-bromo-4-(heptafluoroisopropyl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-bromobenzamido)-2-fluorobenzamide

[0140] ##STR00084##

[0141] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-bromobenzamido)-2-fluorobenzamide (0.13 g, 0.18 mmol) in DMF (4 mL) was added N-bromosuccinimide (36 mg, 0.20 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O were added to the reaction mixture for extraction and layer separating, and the organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 56 mg (yield 38.73%) of the target compound as white solid

[0142] .sup.1H NMR (CDCl.sub.3-d, 400 MHz), δ[ppm]: 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).

Preparation Example 7

Preparation of the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-trifluoromethylbenzamido)-2-fluorobenzamide (Compound No. 37 in CN109497062A)

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-trifluoromethylbenzamido)-2-fluorobenzamide

[0143] ##STR00085##

[0144] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL) pyridine (69 mg, 0.86 mmol) and 4-trifluoromethylbenzoyl chloride (144 mg, 0.69 mmol) were added to a reaction flask in sequence. The mixture was warmed up to 80° C., and after 4 hours the reaction mixture was cooled down to room temperature, and the pH of the mixture was adjusted by 2M HCl to 6. 100 mL EA and 100 mL H.sub.2O were added for extraction and layer separating. The organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.38 g (yield 95.0%) of the target compound as colourless liquid.

[0145] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.16 (s, 1H), 8.12 (dd, J=16.7, 8.3 Hz, 1H), 7.98 (d, J=8.6 Hz, 1H), 7.94-7.86 (m, 2H), 7.73-7.46 (m, 5H), 7.33 (s, 1H), 3.75 (brs, 2H), 1.04 (brs, 1H), 0.42 (d, J=7.2 Hz, 2H), 0.13 (s, 2H).

(2) Preparation of N-(2-bromo-4-(heptafluoroisopropyl)-6-(trifluoromethyl)phenyl)-3-(N-(cyclopropylmethyl)-4-trifluoromethylbenzamido)-2-fluorobenzamide

[0146] ##STR00086##

[0147] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-trifluoromethylbenzamido)-2-fluorobenzamide (0.14 g, 0.20 mmol) in DMF (4 mL) was added N-bromosuccinimide (39 mg, 0.22 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O were added to the reaction mixture for extraction and layer separating, and the organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 140 mg (yield 90.9%) of the target compound as white solid.

[0148] .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).

Preparation Example 8

Preparation of the insecticidal compound N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-cyanobenzamido)-2-fluorobenzamide (Compound No. 32 in CN109497062A)

(1) Preparation of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-cyanobenzamido)-2-fluorobenzamide

[0149] ##STR00087##

[0150] N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.58 mmol), tetrahydrofuran (5 mL), pyridine (69 mg, 0.86 mmol) and 4-cyanobenzoyl chloride (114 mg, 0.69 mmol) were added to a reaction flask in sequence. The mixture was warmed up to 80° C., and after 4 hours the reaction mixture was cooled down to room temperature, and the pH of the mixture was adjusted by 2M HCl to 6. 100 mL EA and 100 mL H.sub.2O were added for extraction and layer separating, and the organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.35 g (yield 92.8%) of the target compound as white solid.

[0151] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.20 (s, 1H), 8.13-8.07 (m, 1H), 8.02-7.92 (m, 2H), 7.80-7.57 (m, 4H), 7.52-7.44 (m, 2H), 7.34-7.29 (m, 1H), 3.73 (s, 2H), 1.03 (brs, 1H), 0.42 (d, J=7.1 Hz, 2H), 0.12 (brs, 2H).

(2) Preparation of N-(2-bromo-6-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclo propylmethyl)-4-cyanobenzamido)-2-fluorobenzamide

[0152] ##STR00088##

[0153] To a solution of N-(2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-cyanobenzamido)-2-fluorobenzamide (0.16 g, 0.25 mmol) in DMF (4 mL) was added N-bromosuccinimide (48 mg, 0.27 mmol) and stirred at room temperature for 4 h. 20 mL EA and 20 mL H.sub.2O were added to the reaction mixture for extraction and layer separating, and the organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 170 mg (yield 93.4%) of the target compound as white solid.

[0154] .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).

Preparation Example 9

Preparation of the insecticidal compound N-(2-bromo-6-(difluoromethoxyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide

(1) Preparation of N-(2-(difluoromethoxyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropyl methyl)-4-fluorobenzamido)-2-fluorobenzamide

[0155] ##STR00089##

[0156] N-(2-(difluoromethoxyl)-4-(heptafluoroisopropyl)phenyl)-3((cyclopropylmethyl)amino)-2-fluorobenzamide (0.52 g, 1.0 mmol), tetrahydrofuran (5 mL), pyridine (0.12 g, 1.5 mmol) and 4-fluorobenzoyl chloride (0.18 mg, 1.1 mmol) were added to a reaction flask in sequence. The mixture was warmed up to 80° C., and after 2 hours the reaction mixture was cooled down to room temperature, and the pH of the mixture was adjusted by 2M HCl to 6. 100 mL EA and 100 mL H.sub.2O were added for extraction and layer separating, and the organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.58 g (yield 90.5%) of the target compound as white solid.

[0157] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 9.88 (s, 1H), 8.17 (d, J=8.7 Hz, 1H), 7.61-7.40 (m, 4H), 7.36-6.88 (m, 6H), 3.72-3.43 (m, 2H), 0.99-0.87 (m, 1H), 0.42-0.24 (m, 2H), 0.002 (s, 2H).

(2) Preparation of N-(2-bromo-6-(difluoromethoxyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide

[0158] ##STR00090##

[0159] To a solution of N-(2-(difluoromethoxyl)-4-(heptafluoroisopropyl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide (0.65 g, 1.0 mmol) in DMF (10 mL) was added N-bromosuccinimide (196 mg, 1.1 mmol) and stirred at room temperature for 5 h. 30 mL EA and 30 mL H.sub.2O were added to the reaction mixture for reaction and layer separating, the organic layer was washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.67 g (yield 93.1%) of the target compound as white solid.

[0160] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.32 (s, 1H), 7.90 (s, 1H), 7.67-7.51 (m, 4H), 7.38-7.33 (m, 3H), 7.15-7.09 (m, 2H), 3.70 (d, J=20.0 Hz, 2H), 1.06-1.01 (m, 1H), 0.41 (d, J=8.0 Hz, 2H), 0.09 (br s, 2H).

Preparation Example 10

Preparation of the insecticidal compound N-(3-((2-bromo-4-(heptafluoroisopropyl)-6-(trifluoro methyl)phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-6-fluoronicotinamide

[0161] ##STR00091##

[0162] To a solution of N-(3-(2-(trifluoromethyl)4-(heptafluoroisopropyl)-phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-6-fluoronicotinamide (0.65 g, 1.0 mmol) in DMF (10 mL) was added N-bromosuccinimide (196 mg, 1.1 mmol) and stirred at room temperature for 5 h. 30 mL EA and 30 mL H.sub.2O were added for extraction and layer separating, and the organic layer was taken and washed with saturated sodium chloride aqueous solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.65 g (yield 90.0%) of the target compound as white solid.

[0163] .sup.1H NMR (DMSO-d6, 400 MHz), δ[ppm]: 10.62 (s, 1H), 8.42 (s, 1H), 8.15 (s, 1H), 7.95 (s, 2H), 7.78 (t, J=7.1 Hz, 1H), 7.62 (s, 1H), 7.39 (t, J=7.8 Hz, 1H), 7.12 (s, 1H), 3.74 (d, J=45.7 Hz, 2H), 1.03 (br s, 1H), 0.42 (d, J=6.4 Hz, 2H), 0.11 (d, J=27.7 Hz, 2H).

[0164] The applicant states that the 3-N-cyclopropylmethyl-2-fluorobenzamide compounds of this application, the preparation methods and applications thereof can be illustrated by the above examples, but this application is not limited thereto, i.e., which does not mean that the implementation of this application must rely on the above examples. Those skilled in the art should understand that any improvement to this application, equivalent replacement of the raw materials for preparing the compounds of this application, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the scope of protection and disclosure of this application.