PIPERIC ACID DERIVATIVE AND APPLICATION THEREOF

Abstract

The present invention belongs to the fields of insecticides and acaricides, and particularly relates to a piperonylic acid derivative and application thereof. The structure is shown in a general formula I, and the definition of each substituent in the formula is described in the description. The compound of the general formula I has excellent insecticidal and acaricidal activity and can be used for controlling various pests and mites.

##STR00001##

Claims

1. A piperonylic acid derivative, characterized in that the structure of the piperonylic acid derivative is shown in a general formula I: ##STR00141## wherein: X.sup.1 is selected from halogens; X.sup.2 is selected from H or halogens; X.sup.3 is selected from halogens or C.sub.1-C.sub.3 haloalkyl; X.sup.4 is selected from H or halogens; R is selected from H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.10 alkenyl, C.sub.1-C.sub.6 alkoxy C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 alkylthio C.sub.1-C.sub.6 alkyl.

2. The piperonylic acid derivative according to claim 1, characterized in that in the general formula I: X.sup.1 is selected from F, Cl or Br; X.sup.2 is selected from H, F, Cl or Br; X.sup.3 is selected from F, Cl, Br, I or halomethyl; X.sup.4 is selected from H, F, Cl or Br.

3. The piperonylic acid derivative according to claim 2, characterized in that in the general formula I: X.sup.1 is selected from F; X.sup.2 is selected from H or F.

4. The piperonylic acid derivative according to claim 2, characterized in that in the general formula I: X.sup.4 is selected from H or F.

5. The piperonylic acid derivative according to claim 2, characterized in that in the general formula I: R is selected from H, C.sub.1-C.sub.6 alkyl or methylthiopropyl.

6. A purpose of the piperonylic acid derivative of claim 1 as an insecticide or an acaricide in field of agriculture, forestry or sanitation.

7. An insecticidal or acaricidal composition, comprising the piperonylic acid derivative of claim 1 as an active component and an acceptable carrier in agriculture, forestry or sanitation, the weight percentage content of the active component in the composition being 1-99%.

8. A method for controlling pests or mites, characterized in that the composition of claim 7 is applied to a pest or a mite, or a growing medium at an effective dose of 10 g to 1000 g per hectare.

Description

DETAILED DESCRIPTION

[0075] The following specific embodiments are used to further illustrate the present invention, but the present invention is not limited to these examples.

SYNTHESIS EMBODIMENTS

Embodiment 1: Preparation of Compound I-42

1) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-nitrobenzamide

[0076] ##STR00122##

[0077] 2-fluoro-3-nitrobenzoic acid (3.71 g, 20.0 mmol), thionyl chloride (16.05 g) and DMF (0.20 g) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 6 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in acetonitrile (40 mL), and then 2-bromo-6-difluoromethoxy-4-heptafluoroisopropylaniline (4.06 g, 10.0 mmol) and potassium iodide (0.42 g) were added. The resulting mixture was heated to 85° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, taking about 12 hours, the reaction solution was cooled to room temperature, filtered to remove insolubles, and decompressed to distill off acetonitrile. Ethyl acetate (30 mL) was added to dissolve the residue. The solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silia gel to obtain 5.32 g of the target compound as a white solid, with 92% yield (calculated based on the 2-bromo-6-difluoromethoxy-4-heptafluoroisopropylaniline).

[0078] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.42 (t, 1H), 8.28 (t, 1H), 8.12 (d, 1H), 7.82 (s, 1H), 7.52-7.50 (m, 2H), 6.60 (t, 1H).

2) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-aminobenzamide

[0079] ##STR00123##

[0080] To a reaction flask N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-nitrobenzamide (2.89 g, 5.0 mmol), dioxane (20 mL) and stannous chloride (4.60 g, 20.0 mmol) were added, and then concentrated hydrochloric acid (4 mL) was slowly added dropwise. The reaction mixture was heated to 60-65° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the mixture was cooled to room temperature, and then poured into ice water (30 mL). Ethyl acetate (50 mL) was added. Sodium hydroxide was slowly added to neutralize to pH=8-9. After the resulting mixture with precipitate was filtered through diatomite, the filter cake was washed with ethyl acetate and the filtrate was layered. The organic phase was dried over anhydrous magnesium sulfate and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.56 g of the target compound as a yellow solid, with 93% yield.

[0081] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.14 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.45 (t, 1H), 7.09 (t, 1H), 7.00 (t, 1H), 6.60 (t, 1H), 3.93 (s, br, 2H).

3) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(methylamino)benzamide

[0082] ##STR00124##

[0083] Concentrated sulfuric acid (3 mL) and N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-aminobenzamide (0.55 g, 1.0 mmol) were added to a reaction flask, and fully stirred for dissolving. Aqueous formaldehyde solution (2 mL) was slowly added dropwise at 30-35° C., and then the temperature was increased to 40° C. to continue the reaction. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and slowly poured into ice water (10 mL), and fully stirred. The solid was precipitated, and filtered, and the filter cake was purified by column chromatography on silica gel to obtain 0.51 g of the target compound as a white solid, with 90% yield.

[0084] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.13 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.35 (t, 1H), 7.17 (t, 1H), 6.89 (t, 1H), 6.60 (t, 1H), 4.14 (s, br, 1H), 2.94 (s, 3H).

4) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-42)

[0085] ##STR00125##

[0086] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The acyl chloride obtained was dissolved in toluene (20 mL), and then N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-methylaminobenzamide (0.50 g, 0.89 mmol) was added. The resulting mixture was heated to 110° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and fully stirred. The solid was gradually precipitated, and filtered. The filter cake was purified by column chromatography on silica gel to obtain 0.57 g of the target compound as a white solid, with 85% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-methylaminobenzamide).

[0087] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.03 (t, 1H), 7.96 (d, 1H), 7.80 (d, 1H), 7.50 (s, 1H), 7.43 (t, 1H), 7.31 (t, 1H), 7.20 (s, 1H), 7.05 (s, br, 1H), 6.89 (d, br, 1H), 6.55 (t, 1H), 3.48 (s, 3H).

Embodiment 2: Preparation of Compound I-41

[0088] ##STR00126##

[0089] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.06 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The acyl chloride obtained was dissolved in toluene (20 mL), and then N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide (0.50 g, 0.9 mmol) was added. The resulting mixture was heated to 110° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and fully stirred. The solid was gradually precipitated, and filtered. The filter cake was purified by column chromatography on silica gel to obtain 0.52 g of the target compound as a white solid, with 78% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide).

[0090] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.60 (t, 1H), 8.07-8.03 (m, 2H), 7.86 (t, 1H), 7.81 (s, 1H), 7.69-7.68 (m, 2H), 7.52 (s, 1H), 7.38 (t, 1H), 7.21 (d, 1H), 6.61 (t, 1H).

Embodiment 3: Preparation of Compound I-43

1) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-ethylaminobenzamide

[0091] ##STR00127##

[0092] N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide (2.20 g, 4.0 mmol), 40% acetaldehyde aqueous solution (0.67 g, 6.0 mmol), acetic acid (0.2 mL) and methanol (20 mL) were added to a reaction flask, and fully stirred for dissolving, and sodium cyanoborohydride (0.39 g, 6.0 mmol) was slowly added pinch by pinch at 25-30° C., and then the reaction mixture was stirred at room temperature to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was decompressed to distill off methanol, and ethyl acetate (30 mL) was added to dissolve. the resulting mixture was washed successively with 4M sodium hydroxide solution and a saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.12 g of the target compound as a white solid, with 91% yield.

[0093] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.13 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.34 (t, 1H), 7.15 (t, 1H), 6.90 (t, 1H), 6.60 (t, 1H), 3.99 (s, br, 1H), 3.25 (q, 2H), 1.33 (t, 3H).

2) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(N-ethyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-43)

[0094] ##STR00128##

[0095] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in tetrahydrofuran (20 mL), and N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-ethylaminobenzamide (0.52 g, 0.9 mmol) was added. The reaction mixture was heated to 70° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and decompressed to distill off tetrahydrofuran, and then ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 0.62 g of the target compound as a white solid, with 90% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-ethylaminobenzamide).

[0096] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.03 (t, 1H), 7.94 (d, 1H), 7.79 (d, 1H), 7.49 (s, 1H), 7.44 (t, 1H), 7.32 (t, 1H), 7.19 (s, 1H), 7.03 (s, br, 1H), 6.87 (s, br, 1H), 6.55 (t, 1H), 3.99-3.93 (m, br, 2H), 1.27 (t, 3H).

Embodiment 4: Preparation of Compound I-46

1) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-n-butylaminobenzamide

[0097] ##STR00129##

[0098] N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide (2.20 g, 4.0 mmol), n-butyraldehyde (0.44 g, 6.0 mmol), acetic acid (0.2 mL) and methanol (20 mL) were added to a reaction flask, and fully stirred for dissolving, and sodium cyanoborohydride (0.39 g, 6.0 mmol) was slowly added pinch by pinch at 25-30° C., and then the reaction mixture was stirred at room temperature to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was decompressed to distill off methanol, and ethyl acetate (30 mL) was added to dissolve. the resulting mixture was washed successively with 4M sodium hydroxide solution and a saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.09 g of the target compound as a white solid, with 86% yield.

[0099] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.13 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.32 (t, 1H), 7.14 (t, 1H), 6.90 (t, 1H), 6.60 (t, 1H), 4.04 (s, br, 1H), 3.19 (t, 2H), 1.70-1.65 (m, 2H), 1.50-1.44 (m, 2H), 0.99 (t, 3H).

2) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(N-n-butyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-46)

[0100] ##STR00130##

[0101] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in tetrahydrofuran (20 mL), and N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-n-butyl aminobenzamide (0.55 g, 0.9 mmol) was added. The reaction mixture was heated to 70° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and decompressed to distill off tetrahydrofuran, and then ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 0.58 g of the target compound as a pale yellow solid, with 81% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-n-butylaminobenzamide).

[0102] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.03 (t, 1H), 7.94 (d, 1H), 7.79 (s, 1H), 7.49 (s, 1H), 7.46 (t, 1H), 7.32 (t, 1H), 7.18 (s, 1H), 7.01 (s, br, 1H), 6.86 (s, br, 1H), 6.55 (t, 1H), 3.88 (t, br, 2H), 1.65-1.62 (m, br, 2H), 1.41-1.38 (m, br, 2H), 0.95 (t, 3H).

Embodiment 5: Preparation of Compound I-50

1) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(cyclopropylmethylamino)benzamide

[0103] ##STR00131##

[0104] N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide (2.20 g, 4.0 mmol), cyclopropanecarboxaldehyde (0.44 g, 6.0 mmol), acetic acid (0.2 mL) and methanol (20 mL) were added to a reaction flask, and fully stirred for dissolving, and sodium cyanoborohydride (0.39 g, 6.0 mmol) was slowly added pinch by pinch at 25-30° C., and then the reaction mixture was stirred at room temperature to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was decompressed to distill off methanol, and ethyl acetate (30 mL) was added to dissolve. the resulting mixture was washed successively with 4M sodium hydroxide solution and a saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.11 g of the target compound as a white solid, with 87% yield.

[0105] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.15 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.33 (t, 1H), 7.13 (t, 1H), 6.88 (t, 1H), 6.60 (t, 1H), 4.21 (s, br, 1H), 3.04 (d, 2H), 1.18-1.12 (m, 1H), 0.63-0.60 (m, 2H), 0.31-0.28 (m, 2H).

2) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(N-cyclopropylmethyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-50)

[0106] ##STR00132##

[0107] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in tetrahydrofuran (20 mL), and N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-cyclopropylmethylamino benzamide (0.54 g, 0.9 mmol) was added. The reaction mixture was heated to 70° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and decompressed to distill off tetrahydrofuran, and then ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 0.57 g of the target compound as a white solid, with 80% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-(cyclopropylmethylamino)benzamide).

[0108] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.04 (t, 1H), 7.95 (d, 1H), 7.79 (s, 1H), 7.52-7.49 (m, 2H), 7.32 (t, 1H), 7.20 (s, 1H), 7.05 (s, br, 1H), 6.87 (s, br, 1H), 6.55 (t, 1H), 3.84-3.73 (m, br, 2H), 1.09 (s, br, 1H), 0.50 (s, br, 2H), 0.14-0.19 (m, br, 2H).

Embodiment 6: Preparation of Compound I-60

1) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(3-methylthiopropylamino)benzamide

[0109] ##STR00133##

[0110] N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-aminobenzamide (2.20 g, 4.0 mmol), 3-methylthiopropanal (0.64 g, 6.0 mmol), acetic acid (0.2 mL) and methanol (20 mL) were added to a reaction flask, and fully stirred for dissolving, and sodium cyanoborohydride (0.39 g, 6.0 mmol) was slowly added pinch by pinch at 25-30° C., and then the reaction mixture was stirred at room temperature to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was decompressed to distill off methanol, and ethyl acetate (30 mL) was added to dissolve. the resulting mixture was washed successively with 4M sodium hydroxide solution and a saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.19 g of the target compound as a white solid, with 85% yield.

[0111] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.13 (d, 1H), 7.79 (s, 1H), 7.51 (s, 1H), 7.34 (t, 1H), 7.15 (t, 1H), 6.93 (t, 1H), 6.60 (t, 1H), 4.19 (s, br, 1H), 3.35 (t, 2H), 2.65 (t, 2H), 2.14 (s, 3H), 2.00-1.95 (m, 2H).

2) Preparation of N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropyl phenyl)-2-fluoro-3-(N-(3-methylthiopropyl)-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-60)

[0112] ##STR00134##

[0113] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in tetrahydrofuran (20 mL), and N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-(3-methylthiopropylamin o)benzamide (0.57 g, 0.9 mmol) was added. The reaction mixture was heated to 70° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and decompressed to distill off tetrahydrofuran, and then ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 0.61 g of the target compound as a white solid, with 82% yield (calculated based on the N-(2-bromo-6-difluoromethoxy-4-heptafluoroisopropylphenyl)-2-fluoro-3-(3-methylthiopropylamin o)benzamide).

[0114] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.03 (t, 1H), 7.92 (d, 1H), 7.79 (d, 1H), 7.52-7.49 (m, 2H), 7.33 (t, 1H), 7.18 (s, 1H), 7.01 (s, br, 1H), 6.86 (s, br, 1H), 6.55 (t, 1H), 3.97 (s, br, 2H), 2.57 (s, br, 2H), 2.08 (s, 3H), 1.97 (s, br, 2H).

Embodiment 7: Preparation of Compound I-81

[0115] ##STR00135##

[0116] 2-fluoro-3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzoic acid (CN109206397) (2.06 g, 6.0 mmol), thionyl chloride (3.60 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 100° C. to react for 4 hours, and decompressed to distill off thionyl chloride and toluene. The obtained acyl chloride was dissolved in acetonitrile (15 mL), and 2-chloro-6-difluoromethoxy-4-heptafluoroisopropylaniline (1.46 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added. The reaction mixture was heated to reflux for 8 hours. The reaction mixture was cooled to room temperature, and ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.21 g of the target compound as a white solid, with 80% yield (calculated based on the 2-chloro-6-difluoromethoxy-4-heptafluoroisopropylaniline).

[0117] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.60 (t, 1H), 8.06-8.01 (m, 2H), 7.87 (t, 1H), 7.69-7.68 (m, 2H), 7.65 (s, 1H), 7.48 (s, 1H), 7.39 (t, 1H), 7.22 (d, 1H), 6.62 (t, 1H).

Embodiment 8: Preparation of Compound I-2

[0118] ##STR00136##

[0119] 2-fluoro-3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzoic acid (CN109206397) (2.14 g, 6.0 mmol), thionyl chloride (3.60 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 100° C. to react for 6 hours, and decompressed to distill off thionyl chloride and toluene. The obtained acyl chloride was dissolved in acetonitrile (15 mL), and 2-difluoromethoxy-4-heptafluoroisopropyl-6-iodoaniline (1.83 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added. The reaction mixture was heated to reflux for 8 hours. The reaction mixture was cooled to room temperature, and ethyl acetate (30 mL) was added to dissolve. The resulting mixture was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.51 g of the target compound as a white solid, with 78% yield (calculated based on the 2-difluoromethoxy-4-heptafluoroisopropyl-6-iodoaniline).

[0120] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.03 (t, 1H), 7.99 (d, 1H), 7.91 (d, 1H), 7.51 (s, 1H), 7.45 (t, 1H), 7.31 (t, 1H), 7.21 (s, 1H), 7.04 (s, br, 1H), 6.89 (d, br, 1H), 6.52 (t, 1H), 3.49 (s, 3H).

Embodiment 9: Preparation of Compound I-62

1) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-nitrobenzamide

[0121] ##STR00137##

[0122] 2-fluoro-3-nitrobenzoic acid (3.74 g, 20.0 mmol), thionyl chloride (16.05 g) and DMF (0.20 g) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 6 hours, and decompressed to distill off thionyl chloride. The obtained acyl chloride was dissolved in acetonitrile (40 mL), and then 2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyaniline (4.29 g, 10.0 mmol) and potassium iodide (0.42 g) were added. The resulting mixture was heated to 85° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, taking about 12 hours, the reaction solution was cooled to room temperature, filtered to remove insolubles, and decompressed to distill off acetonitrile. Ethyl acetate (30 mL) was added to dissolve the residue. The solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution to separate an organic phase. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off organic solvents. The residue was purified by column chromatography on silia gel to obtain 5.35 g of the target compound as a white solid, with 89% yield (calculated based on the 2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyaniline).

[0123] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.44 (t, 1H), 8.29 (t, 1H), 8.08 (d, 1H), 7.89 (s, 1H), 7.60 (s, 1H), 7.53 (t, 1H).

2) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-aminobenzamide

[0124] ##STR00138##

[0125] To a reaction flask N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-nitrobenzamide (2.99 g, 5 mmol), dioxane (20 mL) and stannous chloride (4.60 g, 20.0 mmol) were added, and then concentrated hydrochloric acid (4 mL) was slowly added dropwise. The reaction mixture was heated to 60-65° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the mixture was cooled to room temperature, and then poured into ice water (30 mL). Ethyl acetate (50 mL) was added. Sodium hydroxide was slowly added to neutralize to pH=8-9. After the resulting mixture with precipitate was filtered through diatomite, the filter cake was washed with ethyl acetate and the filtrate was layered. The organic phase was dried over anhydrous magnesium sulfate and decompressed to distill off organic solvents. The residue was purified by column chromatography on silica gel to obtain 2.66 g of the target compound as a yellow solid, with 93% yield.

[0126] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.14 (d, 1H), 7.87 (s, 1H), 7.57 (s, 1H), 7.46 (t, 1H), 7.10 (t, 1H), 7.01 (t, 1H), 3.92 (s, br, 2H).

3) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-methylaminobenzamide

[0127] ##STR00139##

[0128] Concentrated sulfuric acid (3 mL) and N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-aminobenzamide (0.57 g, 1.0 mmol) were added to a reaction flask, and fully stirred for dissolving. Aqueous formaldehyde solution (2 mL) was slowly added dropwise at 30-35° C., and then the temperature was increased to 40° C. to continue the reaction. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and slowly poured into ice water (10 mL), and fully stirred. The solid was precipitated, and filtered, and the filter cake was purified by column chromatography on silica gel to obtain 0.52 g of the target compound as a white solid, with 89% yield.

[0129] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.12 (d, 1H), 7.86 (s, 1H), 7.57 (s, 1H), 7.37 (t, 1H), 7.18 (t, 1H), 6.90 (t, 1H), 4.14 (s, br, 1H), 2.94 (s, 3H).

4) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzamide (Compound I-62)

[0130] ##STR00140##

[0131] 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.01 g), toluene (10 mL) and DMF (1 drop) were added to a reaction flask. The reaction mixture was heated to 80° C. to react for 4 hours, and decompressed to distill off thionyl chloride. The acyl chloride obtained was dissolved in toluene (20 mL), and then N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-methylaminobenzamide (0.52 g, 0.9 mmol) was added. The resulting mixture was heated to 110° C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature, and fully stirred. The solid was gradually precipitated, and filtered. The filter cake was purified by column chromatography on silica gel to obtain 0.60 g of the target compound as a white solid, with 86% yield (calculated based on the N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyphenyl)-2-fluoro-3-methylaminobenzamide).

[0132] .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): 8.04 (t, 1H), 7.94 (d, br, 1H), 7.87 (s, 1H), 7.56 (s, 1H), 7.46 (t, 1H), 7.32 (t, 1H), 7.20 (s, 1H), 7.03 (s, br, 1H), 6.88 (d, br, 1H), 3.49 (s, 3H).

[0133] At the same time, other compounds shown in the general formula I can also be prepared in the manner described above.

[0134] Determination of Biological Activity

[0135] According to the solubility of test compounds, the compounds are dissolved with acetone or dimethyl sulfoxide, and then diluted with 0.1% Tween 80 solution to form a required concentration of 50 ml test liquid. The content of the acetone or the dimethyl sulfoxide in the total solution is not more than 10%.

Embodiment 10 Determination of Activity Against Armyworm

[0136] The middle leaves of fresh corns were cut into small sections of 3 cm, and dipped into a solution of the required concentration of test compounds for 10 seconds. After dried in shade, the middle leaves were placed in a 9 cm diameter petri dish provided with filter paper. Fourteen regular healthy test insects (third instar) were put into the leaves. Four replicates were set for each treatment. The pure water treatment was set as control check. The treated discs were placed in a chamber of 24° C., 60%-70% relative humidity and day light. After 72 hours, the number of surviving insects was investigated, and the mortality rate was calculated.

[0137] Among some of the testing compounds, compounds I-1, I-2, I-41, I-42, I-43, I-44, I-46, I-47, I-50, I-52, I-57, I-60, I-62, I-81, I-82, I-121 and I-122 showed over 90% mortality rates against armyworm at 10 mg/L.

Embodiment 11 Determination of Activity Against Diamondback Moth

[0138] The leaves of cabbage grown in greenhouse were selected, removed the surface waxy layers, punched into circular leaf discs with a diameter of 2 cm by using a puncher, and dipped into a solution of the required concentration of test compounds for 10 seconds. After dried in shade, the circular leaf discs were placed in a 9 cm diameter petri dish provided with filter paper. Ten regular healthy test insects (second instar) were put into the leaf discs. Four replicates were set for each treatment. The pure water treatment was set as control check. The treated discs were placed in a chamber of 24° C., 60%-70% relative humidity and day light. After 72 hours, the number of surviving insects was investigated, and the mortality rate was calculated.

[0139] Among some of the testing compounds, compounds I-1, I-2, I-41, I-42, I-43, I-44, I-46, I-47, I-50, I-52, I-57, I-60, I-62, I-81, I-82, I-121 and I-122 showed over 90% mortality rates against diamondback moth at 10 mg/L.

Embodiment 12 Determination of Activity Against Western Flower Thrips Nymphs

[0140] Fresh kidney bean leaves cultured in the glasshouse were selected and uniformly sprayed with 1 ml of the test liquid by using a handheld Airbrush. The leaves were dried naturally and placed in a test tube. Fifteen tidy and healthy western flower thrips nymphs were put into the leaves. Three replicates were set for each treatment. The water treatment was set as control check. After the treatment, the treated tube were placed in a chamber of 24° C., 60%-70% relative humidity and day light. After 72 hours, the number of surviving insects was investigated, and the mortality was calculated.

[0141] Part of test compounds: I-1, I-2, I-41, I-42, I-43, I-44, I-46, I-47, I-50, I-52, I-57, I-60, I-62, I-81, I-82, I-121 and I-122 showed over 90% mortality rates against western flower thrips nymphs at a concentration of 600 mg/L.

[0142] According to the above test method, compounds I-41 and I-42 as well as KC.sub.1, KC.sub.2, KC.sub.3, KC.sub.4 and MC were selected for parallel determination of activity against western flower thrips nymphs. See Table 1 for test results.

TABLE-US-00003 TABLE 1 Parallel Determination Results of Activity of Compounds I-41, I-42, KC.sub.1, KC.sub.2, KC.sub.3, KC.sub.4 and MC against Western Flower Thrips Nymphs (Mortality, %) Mortality (%) Compound 100 mg/L 10 mg/L Compound I-41 95 90 Compound I-42 100 91 KC.sub.1 85 15 KC.sub.2 90 59 KC.sub.3 60 33 KC.sub.4 52 37 MC 76 72 Cyantraniliprole 85 25 Spinetoram 100 90

Embodiment 13 Determination of Acaricidal Activity

[0143] The adult spider mites were put into two true leaves of bean plants. After the number of mites was investigated, the solution of certain concentrations of test compounds was sprayed by using a handheld Airbrush. Three replicates were set for each treatment. Then the leaves were maintained in a standard observation room. After 72 hours, the number of surviving mites was investigated, and the mortality rate was calculated. Compounds I-41, KC.sub.3, KC.sub.4 and MC were selected for parallel determination of activity against Tetranychus cinnabarinus adults. See Table 2 for test results.

TABLE-US-00004 TABLE 2 Parallel Determination Results of Activity of Compounds I-41, KC.sub.3, KC.sub.4 and MC against Tetranychus Cinnabarinus Adult (Mortality, %) Mortality (%) Compound 600 mg/L 100 mg/L 10 mg/L Compound I-41 100 100 87 KC.sub.3 0 0 0 KC.sub.4 0 0 0 MC 0 0 0

Embodiment 14 Determination of Tribolium confusum Adults

[0144] The test liquid was prepared in the order from low dose to high dose according to the test design. Then, the liquid of different concentrations was added to feeding bran and uniformly stirred, and dried in the shade. Then, the resulting feeding bran was collected in a paper cup. Fifty Tribolium confusum adults with consistent size were put in the paper cup. Three replicates were set for each treatment. Control check was set. The treated test materials were put in an observation room under controlled conditions. After 72 h, the number of dead and surviving adults was investigated.

[0145] Part of test compounds: I-1, I-2, I-41, I-42, I-43, I-44, I-46, I-47, I-50, I-52, I-57, I-60, I-62, I-81, I-82, I-121 and I-122 showed over 90% mortality rates against Tribolium confusum adults at a concentration of 600 mg/L.

[0146] According to the above test method, compounds I-42 and I-44 as well as KC.sub.2 and KC.sub.3 were selected for parallel determination of activity against Tribolium confusum adults. See Table 3 for test results.

[0147] Table 3: Parallel Determination Result of Activity of Compounds I-42, I-44, KC.sub.2 and KC.sub.3 against

TABLE-US-00005 Tribolium Confusum Adults (Mortality, %) Mortality (%) Compound 20 mg/L 5 mg/L Compound I-42 100 81 Compound I-44 98 83 KC.sub.2 76 70 KC.sub.3 80 69 Cyantraniliprole 5 0