Piperonylic acid derivative and preparation and application thereof

Abstract

The present invention belongs to the fields of insecticides, acaricides and fungicides, and particularly relates to a piperonylic acid derivative, and preparation 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 exhibits excellent insecticidal, acaricidal and fungicidal activity and can be used for controlling various harmful insects, mites or fungus. ##STR00001##

Claims

1. A method for controlling fungus on plants comprising, applying a composition comprising an effective amount of a piperonylic acid derivative of general formula I: ##STR00030## where X.sup.1 and X.sup.2 are F; R is H or methyl; and Y.sup.1 and Y.sup.2 are Br, and an acceptable carrier, where the effective amount includes a weight percentage of the piperonylic acid derivative being 1-99% and where the application to the plant is at a dosage of 10 g to 1000 g per hectare.

Description

DETAILED DESCRIPTION

(1) 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 1-45

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

(3) ##STR00011##

(4) 2-fluoro-3-nitrobenzoic acid (9.72 g, 52.4 mmol), thionyl chloride (40.05 g) and DMF (0.40 g) were added to a reaction flask. The reaction mixture was heated to 80 C. to react for 8 hours, and decompressed to distill off thionyl chloride to obtain acid chloride. 1,3-dimethyl-2-imidazolidinone (160 mL), 2-promo-4-heptafluoroisopropyl-6-trifluoromethylaniline (16.40 g, 40.0 mmol) and potassium iodide (1.68 g) were added, and the resulting mixture was heated to 100 C. to react for 48 hours. The reaction solution was cooled to room temperature, and filtered to remove insolubles. Ethyl acetate (100 mL) was added to dissolve. The resulting 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 silica gel to obtain 2.10 g of the target compound as a white solid, with 9% yield (calculated based on the 2-bromo-4-heptafluoroisopropyl-6-trifitioromethylaniline).

(5) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.47-8.42 (m, 1H), 8.32-8.26 (m, 1H), 8.21 (d, 1H), 8.17 (s, 1H), 7.94 (s, 1H), 7.55-7.49 (m, 1H).

(6) 2) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-3-amino-2-fluorobenzamide

(7) ##STR00012##

(8) To the reaction flask, N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-2-fluoro-3-nitrobenzamide (1.44 g, 2.5 mmol), dioxane (10 mL) and stannous chloride (2.28 g, 10.0 mmol) were added, and then concentrated hydrochloric acid (2 mL) was slowly added dropwise. The reaction mixture WM 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 (15 mL). Ethyl acetate (30 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 1.26 g of the target compound as a yellow solid, with 91% yield.

(9) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.29 (d, 1H), 8.13 (s, 1H), 7.91 (s, 1H), 7.50-7.44 (m, 1H), 7.12-7.07 (m, 1H), 7.04-6.94 (m, 1H), 3.93 (br. s, 2H).

(10) 3) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethyl phenyl)-2-fluoro-3-methylaminobenzamide

(11) ##STR00013##

(12) Concentrated sulfuric acid (3 mL) and N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethyl phenyl)-3-amino-2-fluorobenzamide (0.55 g, 1.0 mmol) were added to the 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 92% yield.

(13) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.28 (d, 1H), 8.13 (s, 1H), 7.90 (s, 1H), 7.40-7.36 (m, 1H), 7.19-7.14 (m, 1H), 6.93-6.88 (m, 1H), 4.13 (br. s, 1H), 2.94 (s, 3H).

(14) 4) Preparation of N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-2-fluoro-3-(N-methyl-2,2-difluoro-1, 3-benzodioxole-5-carboxamido) Benzamide (Compound I-45)

(15) ##STR00014##

(16) 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.02 g), toluene (10 mL) and DMF (1 drop) were added to the reaction flask. The reaction mixture were 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-trifluoromethylphenyl)-2-fluoro-3-methylaminobenzamide (0.51 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 0.57 g of the target compound as a white solid, with 84% yield (calculated based on the N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-2-fluoro-3-methylaminobenzamide).

(17) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.13-8.04 (m, 3H), 7.91 (s, 1H), 7.52-7.47 (m, 1H), 7.37-7.31 (m, 1H), 7.20 (s, 1H), 7.02 (d, 1H), 6.87 (d, 1H), 3.51 (s, 3H).

Embodiment 2: Preparation of Compound 1-2

(18) ##STR00015##

(19) 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (0.21 g, 1.0 mmol), thionyl chloride (1.08 g), toluene (10 and DMF (1 drop) were added to the 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 toluene (20 mL), and then N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethylphenyl)-3-amino-2-fluorobenzamide (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 0.55 g of the target compound as a white solid, with 83% yield (calculated based on the N-(2-bromo-4-heptafluoroisopropyl-6-trifluoromethyl phenyl)-3-amino-2-fluorobenzamide).

(20) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.20 (s, 1H), 7.99 (s, 1H), 7.47 (d, 1H), 7.38 (s, 1H), 6.96-6.80 (m, 4H), 6.71-6.65 (m, 1H).

Embodiment 3: Preparation of Compound I-51

(21) 1) Preparation of N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-2-fluoro-3-nitrobenzamide

(22) ##STR00016##

(23) 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 to obtain acid chloride. Acetonitrile (40 mL), 2,6-dibromo-4-heptafluoroisopropyl aniline (4.23 g, 10.0 mmol) and potassium iodide (0.42 g) were added. The resulting mixture was heated to 100 C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the mixture was cooled to room temperature, taking about 8 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 resulting 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 silica gel to obtain 5.42 g of the target compound as a white solid, with 91% yield (calculated based on the 2,6-dibromo-4-heptafluoroisopropyl aniline).

(24) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.51-8.46 (m, 1H), 8.31-8.27 (m, 1H), 8.16 (d, 1H), 7.91 (s, 2H), 7.55-7.51 (m, 1H).

(25) 2) Preparation of N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-3-amino-2-fluorobenzamide

(26) ##STR00017##

(27) To the reaction flask, N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-2-fluoro-3-nitrobenzamide (1.48 g, 2.5 mmol), dioxane (10 mL) and stannous chloride (2.28 g, 10.0 mmol) were added, and then concentrated hydrochloric acid (2 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 (15 mL). Ethyl acetate (30 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 1.30 g of the target compound as a yellow solid, with 92% yield.

(28) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.28 (d, 1H), 8.13 (s, 1H), 7.90 (s, 1H), 7.49-7.47 (m, 1H), 7.13-7.10 (m, 1H), 7.04-6.99 (m, 1H), 3.94 (br. s, 1H).

(29) 3) Preparation of N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-2-fluoro-3-(methylamino)benzamide

(30) ##STR00018##

(31) Concentrated sulfuric acid (.sup.3 mL) and N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-3-amino-2-fluorobenzamide (0.56 g, 1.0 mmol) were added to the 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 0.54 g of the target compound as a white solid, with 93% yield.

(32) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.20 (d, 1H), 7.87 (s, 2H), 7.43-7.29 (m, 1H), 7.20-7.18 (m, 1H), 6.93-6.88 (m, 1H), 4.91-4.87 (m, 1H), 2.94 (d, 3H).

(33) 4) Preparation of N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxol e-5-carboxamido)benzamide (Compound I-51)

(34) ##STR00019##

(35) 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 the reaction flask. The reaction mixture were 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-(2,6-dibromide-4-heptafluoroisopropylphenyl)-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 melting point of 157-158 V. and 87% yield (calculated based on the N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-2-fluoro-3-methylaminobenzamide).

(36) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.09-8.04 (m, 2H), 7.87 (s, 2H), 7.47-7.43 (m, 1H), 7.34-7.29 (m, 1H), 7.20 (s, 1H), 7.05 (d, 1H), 6.89 (d, 1H), 3.50 (s, 3H),

Embodiment 4: Preparation of Compound 1-8

(37) ##STR00020##

(38) 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 the 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 toluene (20 mL), and then N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-3-amino-2-fluorobenzamide (0.51 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 0.54 g of the target compound as a white solid, with melting point of 176-177 C. and 80% yield (calculated based on the N-(2,6-dibromide-4-heptafluoroisopropylphenyl)-3-amino-2-fluorobenzamide). .sup.11H NMR (300 MHz, CDCl.sub.3, ppm): 8.57-8.52 (m, 1H), 8.17-8.12 (m, 2H), 7.90-7.86 (m, 3H), 7.70-7.68 (m, 2H), 7.39-7.34 (m, 1H), 7.20 (d, 1H).

Embodiment 5: Preparation of Compound 1-5

(39) 1) Preparation of Methyl-3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzoate (compound II-1)

(40) ##STR00021##

(41) 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (4.08 g, 20 mmol), thionyl chloride (21.40 g) and DMF (0.10 g) were added to the reaction flask. The reaction mixture was refluxed for 6 hours, and decompressed to distill off thionyl chloride to obtain acyl chloride. Toluene (30 mL) and methyl-3-amino-2-fluorobenzoate (3.42 g, 20 mmol) were added. The resulting mixture was refluxed for 3 hours, and cooled to room temperature. The solid was precipitated and filtered. The filter cake was purified by column chromatography on silica gel to obtain 5.89 g of the target compound as a white solid, with melting point of 130-131 C. and 82% yield (calculated based on the methyl-3-amino-2-fluorobenzoate).

(42) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 10.15 (s, 1H), 7.93-7.87 (m, 3H), 7.74-7.69 (m, 1H), 7.41 (d, 1H), 7.34-7.28 (m, 1H), 3.89 (s, 3H).

(43) 2) Preparation of 3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzoic Acid (Compound II-7)

(44) ##STR00022##

(45) Sodium hydroxide (0.62 g, 15 mmol), water (10 mL) and methanol (10 mL) were added to the reaction flask. After the sodium hydroxide was dissolved, methyl-3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzoate (3.57 g, 10 mmol) was added. The reaction mixture was heated to 60-65 C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature. Ethyl acetate (5 mL) was added. The resulting reaction solution was extracted and layered. The aqueous phase was stirred and also adjusted to pH=2-3 with 1N hydrochloric acid. The solid was precipitated, and filtered. The filter cake was dried to obtain 3.13 g of the target compound as a white solid, with melting point of 266-267 C. and 91% yield.

(46) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 13.18 (br. s, 1H), 10.21 (s, 1H), 7.95-7.90 (m, 2H), 7.84-7.80 (m, 1H), 7.74-7.69 (m, 1H), 7.51 (d, 1H), 7.31-7.26 (m, 1H).

(47) 3) Preparation of N-(2-bromo-6-iodo-4-perfluoroisopropylphenyl)-3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzamide (Compound 1-5)

(48) ##STR00023##

(49) 3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzoic acid (2.06 g, 6.0 mmol), thionyl chloride (3.60 g), toluene (10 mL) and DMF (1 drop) were added to the reaction flask. The reaction mixture was heated to 100 C. to react for 4 hours, and decompressed to distill off thionyl chloride and toluene to obtain acyl chloride (compound II-9) as a white solid (melting point of 155-156 C.). Acetonitrile (15 mL), 2-bromo-6-iodo-4-perfluoroisopropyl aniline (1.88 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added. The resulting mixture was refluxed to react for 8 hours and cooled to room temperature. Ethyl acetate (30 mL) was added. The resulting solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off solvents. The residue was purified by column chromatography on silica gel to obtain 2.58 g of the target compound as a white solid, with 81% yield (calculated based on the 2-bronco-6-iodo-4-perfluoroisopropyl aniline).

(50) Compound II-9: .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.80-8.75 (m, 1H), 8.05 (br. s, 1H), 7.90-7.85 (m, 1H), 7.66-7.64 (m, 2H), 7.39-7.33 (m, 1H), 7.20 (d, 1H),

(51) Compound I-5: .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.62-8.57 (m, 8.12-8.05 (m, 3H), 7.96-7.91 (m, 2H), 7.70-7.68 (m, 2H), 7.42-7.36 (m, 1H), 7.21 (d, 1H).

Embodiment 6: Preparation of Compound 1-48

(52) 1) Preparation of Methyl-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzoate (compound II-12)

(53) ##STR00024##

(54) 2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (4.08 g, 20 mmol), thionyl chloride (21.40 g) and DMF (0.10 g) were added to the reaction flask. The reaction mixture was refluxed for 6 hours, and decompressed to distill off thionyl chloride to obtain acyl chloride. Toluene (30 mL) and methyl-2-fluoro-3-methylaminobenzoate (3.70 g, 2.0 mmol) were added. The resulting mixture was refluxed for 3 hours, and cooled to room temperature. The solid was precipitated and filtered. The filter cake was purified by column chromatography on silica gel to obtain 5.90 g of the target compound as a white solid, with 79% yield (calculated based on the methyl-2-fluoro-3-methylaminobenzoate).

(55) .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 7.86-7.80 (m, 1H), 7.26-7.22 (m, 1H), 7.14-7.09 (m, 2H), 7.03 (d, 1H), 6.85 (d, 1H), 3.94 (s, 3H), 3.42 (s, 3H).

(56) 2) Preparation of 2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido)benzoic Acid (Compound II-18)

(57) ##STR00025##

(58) Sodium hydroxide (0.62 g, 15 mmol), water (10 mL) and methanol (10 mL) were added to the reaction flask. After the sodium hydroxide was dissolved, methyl-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido) benzoate (3.71 g, 10 mmol) was added. The reaction mixture was heated to 60-65 C. to react. After the reaction was complete by Thin-Layer Chromatography monitoring, the reaction mixture was cooled to room temperature. Ethyl acetate (5 mL) was added. The resulting reaction solution was extracted and layered. The aqueous phase was stirred and also adjusted to pH=2-3 with 1N hydrochloric acid. The solid was precipitated, and filtered. The filter cake was dried to obtain 3.15 g of the target compound as a white solid, with 88% yield.

(59) 1H NMR (300 MHz, CDCl.sub.3, ppm): 13.09 (br. s, 1H), 7.86-7.83 (m, 1H), 7.76-7.71 (m, 2H), 7.59-7.55 (m, 1H), 7.39 (d, 1H), 7.21-7.16 (m, 1H), 3.32 (s, 3H).

(60) 3) Preparation of N-(2-bromo-6-iodo-4-perfluoroisopropylphenyl)-2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido)benzamide (compound I-48)

(61) ##STR00026##

(62) 2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido)benzoic acid (2.14 g, 6.0 mmol), phosphorus tribromide (0.42 g) and toluene (10 mL) were added to the reaction flask. The reaction mixture was heated to 100 C. to react for 4 hours, and decompressed to distill off toluene to obtain acyl bromide (compound II-21) as a yellow oil. Acetonitrile (15 mL), 2-bromo-6-iodo-4-perfluoroisopropylaniline (1.88 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added. The resulting mixture was refluxed to react for 8 hours, and cooled to room temperature. Ethyl acetate (30 mL) was added. The reaction solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off solvents. The residue was purified by column chromatography on silica gel to obtain 2.64 g of the target compound as a white solid, with melting point of 185-186 C. and 81% yield (calculated based on the 2-bromo-6-iodo-4-perfluoroisopropylaniline).

(63) Compound 1-48: .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.10-8.03 (m, 3H), 7.89 (s, 1H), 7.49-7.44 (m, 1H), 7.35-7.30 (m, 1H), 7.20 (s, 1H), 7.05 (d, 1H), 6.88 (d, 1H), 3.50 (s, 3H).

Embodiment 7: Preparation of Compound 1-8

(64) ##STR00027##

(65) 3-(2,2-difluoro-1,3-benzodioxole-5-carboxamido)-2-fluorobenzoic Acid (2.06 g, 6.0 mmol), p-nitrobenzenesulfonyl chloride (1.33 g, 6.0 mmol), acetonitrile (25 mL) and triethylamine (0.67 g, 6.6 mmol) were added to the reaction flask. The reaction mixture was refluxed to react for 4 hours. 2,6-dibromide-4-heptafluoroisopropylaniline (1.69 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added, and the resulting mixture was continuously refluxed to react for 24 hours, and cooled to room temperature. Ethyl acetate (30 mL) was added. The reaction solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off solvents. The residue was purified by column chromatography on silica gel to obtain 1.82 g of the target compound as a white solid, with melting point of 176-177 C. and 60% yield (calculated based on the 2,6-dibromide-4-heptafluoroisopropylaniline).

Embodiment 8: Preparation of Compound I-44

(66) ##STR00028##

(67) 2-fluoro-3-(N-methyl-2,2-difluoro-1,3-benzodioxole-5-carboxamido)benzoic acid (2.14 g, 6.0 mmol), thionyl chloride (3.60 g) and toluene (10 mL) were added to the reaction flask. The reaction mixture was heated to 100 C. to react for 6 hours, and decompressed to distill off thionyl chloride and toluene to obtain acyl chloride (compound II-20) as a yellow oil. Acetonitrile (15 mL), 2,6-diiodo-4-heptafluoroisopropylaniline (2.07 g, 4.0 mmol) and potassium iodide (0.17 g, 1.0 mmol) were added. The resulting mixture was refluxed to react for 8 hours, and cooled to room temperature. Ethyl acetate (30 mL) was added. The reaction solution was washed successively with a saturated aqueous sodium bicarbonate solution and saturated salt solution. The organic phase was dried over anhydrous magnesium sulfate, filtered and decompressed to distill off solvents. The residue was purified by column chromatography on silica gel to obtain 2.70 g of the target compound as a white solid, with 78% yield (calculated based on the 2,6-diiodo-4-heptafluoroisopropylaniline).

(68) Compound I-44: .sup.1H NMR (300 MHz, CDCl.sub.3, ppm): 8.08-8.03 (m, 2H), 7.86 (s, 2H), 7.45-7.41 (m, 1H), 7.33-7,28 (m, 1H), 7.20 (s, 1H), 7.05 (d, 1H), 6.90 (d, 1H), 3.50 (s, 3H).

(69) At the same time, other compounds shown in the general formula I can also be prepared in the methods described above.

(70) Determination of Biological Activity

(71) Embodiment 9 Determination of Insecticidal Activity

(72) According to the solubility of test compounds, the compounds are dissolved in acetone or dimethyl sulfoxide, and then diluted with 0.1% aqueous solution of Tween 80 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%.

(73) Embodiment 9.1 Determination of Activity Against Armyworm

(74) 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 is 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.

(75) Among some of the testing compounds, compounds I-2, I-5, I-8, I-44, I-45, I-48 and I-51 showed over 90% mortality rates against armyworm at 0.3 mg/L.

(76) According to the above test method, compounds I-8 and I-51 and known compounds KC.sub.1 (compound 160 in US2014206727A1) and KC.sub.3 (compound 3-14 in U.S. Pat. No. 8,853,440B2) were selected for parallel determination of activity against armyworm. See Table 1 for test results.

(77) TABLE-US-00005 TABLE 1 Parallel Determination Results of Activity of Compounds I-8, I-51, KC.sub.1 and KC.sub.3 against Armyworm (Mortality rate, %) Mortality rate (%) Compound 0.3 mg/L 0.1 mg/L Compound I-8 100 100 Compound I-51 100 85.7 KC.sub.1 0 0 KC.sub.3 64.3 28.6

Embodiment 9.2 Determination of Activity Against Diamondback Moth

(78) 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.

(79) Among some of the testing compounds, compounds I-2, I-5, I-8, I-44, I-45, I-48 and I-51 showed over 90% mortality rates against diamondback moth at 1 mg/L.

Embodiment 9.3 Determination of Activity Against Beet Armyworm

(80) The cabbage leaves were punched into circular leaf discs with a diameter of 1 cm by using a puncher. A certain concentration of test compound was sprayed on both sides of each leaf disc at a spray volume of 0.5 ml by a handheld Airbrush. After the leaf discs were dried in shade, 12 test insects (third instar) were put into the leaf discs. Three 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 96 hours, the number of surviving insects was investigated, and the mortality rate was calculated. See Table 2 for parallel determination results of activity of compounds 1-8 and KC.sub.2 (compound 3-1 in U.S. Pat. No. 8,853,440B2) against beet armyworm.

(81) TABLE-US-00006 TABLE 2 Parallel Determination Results of Activity of Compounds I-8 and KC.sub.2 against Beet Armyworm (Mortality rate, %) Mortality rate (%) Compound 1 mg/L 0.2 mg/L Compound I-8 91.7 83.3 KC.sub.2 83.3 66.7

Embodiment 9.4 Determination of Activity Against Green Peach Aphid

(82) A layer of filter paper was covered on the bottom of the 6 cm diameter petri dish. To the petri dish, a proper amount of tap water was added dropwise for moisture retention. Cabbage leaves, on which 15-30 aphids exist, with a suitable size (about 3 cm in diameter) were cut from the cabbage plants breeding peach aphids. After winged aphids and the aphids on the front surface of the leaves were removed, the leaves were placed in the petri dish in a manner of backing on to the petri dish, and sprayed with a handheld Airbrush, with a pressure of 10 psi (about 0.7 kg/cm.sup.2) and a spray volume of 0.5 ml, Three replicates were set for each treatment. After treatment, the cabbage leaves were placed in a standard observation room. After 48 hours, the number of surviving aphids was investigated, and the mortality rate was calculated.

(83) Among some of the testing compounds, compounds I-8 and I-51 showed over 80% mortality rates against green peach aphid at 10 mg/L.

Embodiment 9.5 Determination of Activity Against Rice Leaf Folder in Field Trial

(84) A certain concentration of test compounds was sprayed on the leaf surfaces in the peak of the hatching period of the rice leaf folders, with a spray volume of 450 L per hectare. The area of a rice plot was 32 square meters. Three replicates were set for each treatment. After 15 days, the number of surviving rice leaf folders was investigated, and the mortality rate was calculated. See Table 3 for parallel determination results of activity of compounds I-8 and KC.sub.2 against rice leaf folder.

(85) TABLE-US-00007 TABLE 3 Parallel Determination Results of Activity of Compounds I-8 and KC.sub.2 against Rice Leaf Folder in Field Trial (Mortality rate, %) Mortality rate (%) Compound 45 g/ha 30 g/ha Compound I-8 85 83 KC.sub.2 82 79

Embodiment 10 Determination of Acaricidal Activity

(86) According to the solubility of test compounds, the compounds are dissolved in acetone or dimethyl sulfoxide, and then diluted with 0.1% aqueous solution of Tween 80 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%.

(87) 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 observed, and the mortality rate was calculated.

(88) The control compounds C.sub.1 and C.sub.2 (structural formulas are as follows) were non-list compounds included in the scope disclosed by the patent AU2004315003B2. See Table 4 for parallel determination results of activity of compounds I-8, KC.sub.1, KC.sub.2, KC.sub.3, C.sub.1 and C.sub.2 against adult spider mite.

(89) ##STR00029##

(90) TABLE-US-00008 TABLE 4 Parallel Determination Results of Activity of Compounds I-8, KC.sub.1, KC.sub.2, KC.sub.3, C.sub.1 and C.sub.2 against Adult Spider Mite (Mortality rate, %) Mortality rate (%) Compound 600 mg/L 100 mg/L 10 mg/L Compound I-8 100 100 93.3 KC.sub.1 0 0 0 KC.sub.2 0 0 0 KC.sub.3 0 0 0 C.sub.1 0 0 0 C.sub.2 0 0 0

Embodiment 11 Determination of Activity Against Houseflylarva

(91) Third instar housefly larvae were tested by a feed poisoning method. 1000 mg/L, of acetone solution of the test compounds was diluted into a required concentration of test liquid by using a certain concentration of milk powder emulsion according to a test design dose. The test liquid was uniformly added to a 6 cm diameter petri dish provided with filter paper by using a pipette, with 1 ml per dish. The third instar housefly larvae were put into the petri dish. Three replicates were set for each treatment. Then the petri dishes were maintained in a standard observation room. After 72 hours, the number of surviving housefly larvae was investigated, and the mortality rate was calculated. See Table 5 for parallel determination results of activity of compounds I-51 and KC.sub.2 against housefly larva.

(92) TABLE-US-00009 TABLE 5 Parallel Determination Results of Activity of Compounds I-51 and KC.sub.2 against Housefly Larva (Mortality rate, %) Mortality rate (%) Compound 10 mg/L 3 mg/L 1 mg/L Compound I-51 100 90.5 75 KC.sub.2 100 69.6 50

Embodiment 12 Determination of Fungicidal Activity

(93) According to the solubility of test compounds, the compounds are dissolved in acetone, methanol or N,N-Dimethylformamide, and then diluted with 0.1% aqueous solution of Tween 80 to form a required concentration of 50 ml test liquid. The content of the acetone, methanol or N,N-Dimethylformamide in the total solution is not more than 5%.

(94) Cucumber seedlings that grew consistently at two-leaf state were selected, and sprayed with a certain concentration of test compounds. After 24 hours from treatment, the cucumber seedlings were inoculated with cucumber downy mildew spore suspension, and then put into an artificial climate chamber for culture. After infested by diseases, the cucumber seedlings were transferred into a greenhouse for normal culture. After 5 days, the control effect was investigated by a visual method according to the incidence of the control check. The control effect was recorded with 100%-0.100% represented no infection, and 0 represented the infection degree of treatment was equivalent to that of the control check.

(95) Among some of the testing compounds, compounds I-8 and I-51 showed over 90% control effects against cucumber downy mildew at 400 mg/L.

(96) The other compounds shown in the general formula I and obtained by the synthetic method described in the present invention also have the above corresponding characteristics, and achieve unexpected effects.