AMIDE COMPOUNDS AND PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

Provided are amide compounds and a preparation method therefor and the use thereof. The amide compounds have a structure represented by formula I. The amide compounds of the present invention have high insecticidal activity at a low dosage and have a good fast-acting property. The dosage of the pesticide will be reduced during application due to the good insecticidal activity of the amide compounds at low dosage, which is more conducive to environmental protection and has broad application prospect.

Claims

1. An amide compound of formula I: ##STR00044## wherein, Q is independently Q1, Q2, Q3 or Q4: ##STR00045## Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, and Z.sub.5 are independently of each other H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 halocycloalkyl, 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 H or F; R.sub.2 is 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 halocycloalkyl; R.sub.3 is H or halogen; R.sub.4 is —OCF.sub.2H or —CF.sub.3, in a case when Q is Q1, R.sub.4 is —OCF.sub.2H; and W.sub.1 and W.sub.2 are independently of each other O or S.

2. The amide compound according to claim 1, wherein, Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, and Z.sub.5 are independently of each other H, F, Cl, Br, I, CN, NO.sub.2, methyl, ethyl, n-propyl, i-propyl, c-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, methoxyl, ethoxyl, n-propoxyl, i-propoxyl, t-butoxyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, difluoromethoxyl, trifluoromethoxyl, pentafluoroethoxyl, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; R.sub.2 is H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-pentyl, neopentyl, isopentyl, 4-methyl-2-pentyl, n-hexyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, cyclopropyl, cyclobutyl, cyclopentyl, perfluorocyclopropyl, perfluorocyclobutyl or perfluorocyclopentyl; and R.sub.3 is H, F or Cl.

3. The amide compound according to claim 1, wherein, Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, and Z.sub.5 are independently of each other H, F, Cl, Br, I, CN, NO.sub.2, methyl, trifluoromethyl, difluoromethoxyl, trifluoromethoxyl, methylsulfonyl or trifluoromethylsulfonyl; R.sub.1 is H or F; R.sub.2 is H or methyl; R.sub.3 is H or Cl; and W.sub.1 and W.sub.2 are independently of each other O.

4. The amide compound according to claim 1, wherein the amide compound is selected from any one of the compounds below: ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##

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

6. An intermediate for preparing the amide compound according to claim 1, wherein the intermediate has a structure as shown in formula XIV: ##STR00056## wherein: R.sub.1 is H or F; R.sub.2 is H, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.8 cycloalkyl or C.sub.3-C.sub.8 halocycloalkyl; R.sub.3 is H or halogen; and W.sub.2 are independently of each other O or S.

7. (canceled)

8. An insecticidal composition, characterized in comprising active ingredient(s) and acceptable carrier in agriculture, wherein the active ingredient(s) are the amide compound according to claim 1 or the tautomers, enantiomers, diasteromers or salts thereof.

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

10. A method for controlling insects, characterized in applying an effective amount of the amide compound according to claim 1, or the tautomers, enantiomers, diasteromers or salts thereof, to pests or their habitat.

11. The method for controlling insects according to claim 10 wherein the effective amount is from 7.5 g/ha to 1000 g/ha.

12. A method for controlling insects, characterized in applying an effective amount of the insecticidal composition of claim 8, to pests or their habitat.

Description

DETAILED DESCRIPTION

[0111] Representative Examples of this invention will be described in the following Examples. Those skilled in the art should understand that the examples herein are only illustrative, and this invention is not limited thereto. Unless otherwise stated, compounds were dissolved in DMSO-d.sub.6 and measured by Brucker 400 MHz spectrometer to obtain their .sup.1H NMR spectra, respectively. Chemical shifts were given in ppm relevant to a TMS standard. SGC represents silica gel column chromatography, PE represents petroleum ether, EA represents ethyl acetate in the following examples.

PREPARATION EXAMPLES

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

Step 1: N-(2-bromo-4-(perfluoropropan-2-yl)-6-(difluoromethoxy)phenyl)-2-fluoro-3-nitrobenzamide

[0112] ##STR00024##

[0113] Thionyl chloride (25.7 g, 216.1 mmol) was added to 2-fluoro-3-nitrobenzoic acid (11.1 g, 59.85 mmol) in toluene (30 mL), and the mixture was heated and refluxed for 2 hours. The solvent was removed by distillation to get the coarse product 2-fluoro-3-nitrobenzoyl chloride. To 2-fluoro-3-nitrobenzoyl chloride was added 2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)aniline (20.25 g, 58.85 mmol), N, N-diisopropylethylamine (12.89 g, 99.75 mmol) and N, N-dimethylpyridin-4-amine (2.44 g, 19.95 mmol). The mixture was stirred at 110° C. for 8 hours. TLC showed the reaction was completed. The reaction mixture was diluted with H.sub.2O (100 mL) and extracted with EA (200 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 10.4 g (yield 30.32%) of the target compound.

[0114] .sup.1H NMR: 10.79 (s, 1H), 8.36 (t, J=8.0 Hz, 1H), 8.02 (t, J=8.0 Hz, 1H), 7.93 (s, 1H), 7.62 (t, J=8.0 Hz, 2H), 7.40 (t, J=72 Hz, 1H).

Step 2: Preparation of 3-amino-N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl) phenyl)-2-fluorobenzamide

[0115] ##STR00025##

[0116] To the solution of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(difluoromethoxy)phenyl)-2-fluoro-3-nitrobenzamide (10.4 g, 18.15 mmol) in anhydrous EtOH (50 mL) was added tin(II) chloride dihydrate (16.37 g, 72.58 mmol) and concentrated hydrochloric acid (0.5 mL). Then the mixture was heated and refluxed for 3 hours. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by 10% sodium hydroxide solution to 12. The reaction mixture was extracted with EA (200 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=5:1) to obtain 7.4 g (yield 75.05%) of the target compound as brown oil.

[0117] .sup.1H NMR: 10.20 (s, 1H), 7.89 (s, 1H), 7.53 (s, 1H), 7.32 (t, J=72.0 Hz, 1H), 7.03-6.89 (m, 2H), 6.80 (t, J=6.7 Hz, 1H), 5.39 (s, 2H).

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

[0118] ##STR00026##

[0119] To the solution of 3-amino-N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl) phenyl)-2-fluorobenzamide (3.0 g, 5.53 mmol) in anhydrous 1,2-dichloroethane (30 mL) was added cyclopropanecarbaldehyde (0.37 g, 5.08 mmol) and trifluoroacetic acid (7.78 g, 33.14 mmol). Then the reaction mixture was stirred at room temperature for 10 mins. Sodium triacetoxyborohydride (3.51 g, 16.57 mmol) was added to the mixture. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by saturated sodium bicarbonate aqueous solution to 8. The reaction mixture was extracted with dichloromethane (20 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=10:1) to obtain 2.47 g (yield 75%) of the target compound as yellow oil.

[0120] .sup.1H NMR: 10.01 (s, 1H), 7.66 (s, 1H), 7.30 (s, 1H), 7.09 (t, J=72.0 Hz, 1H), 6.85 (t, J=7.8 Hz, 1H), 6.69 (t, J=7.7 Hz, 1H), 6.56 (t, J=6.2 Hz, 1H), 5.47 (s, 1H), 2.79 (t, J=5.7 Hz, 2H), 0.90-0.80 (m, 1H), 0.24-0.18 (m, 2H), 0.01 (q, J=4.9 Hz, 2H).

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

[0121] ##STR00027##

[0122] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.50 mmol) in anhydrous tetrahydrofuran (5 mL) was added benzoyl chloride (77 mg, 0.55 mmol) and pyridine (79 mg, 1.00 mmol). The mixture was stirred at 80° C. for 4 hours. TLC showed the reaction was completed. The reaction mixture was extracted with EA (40 mL), washed with 2M HCl (5 mL) and saturated sodium bicarbonate aqueous solution (30 mL), dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=8:1) to obtain 0.18 g (yield 52.63%) of the target compound.

[0123] Compound No. 1: .sup.1H NMR: 10.32 (s, 1H), 7.91 (s, 1H), 7.64-7.50 (m, 4H), 7.33-7.15 (m, 6H), 3.70 (d, J=76.0 Hz, 2H), 1.05-1.03 (m, 1H), 0.41 (d, J=8.0 Hz, 2H), 0.09 (br s, 2H).

Example 2: Preparation of N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-(N-(cyclopropylmethyl)-4-fluorobenzamido)-2-fluorobenzamide (Compound No. 31)

[0124] ##STR00028##

[0125] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3 ((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.50 mmol) in anhydrous tetrahydrofuran (5 mL) was added 4-fluorobenzoyl chloride (87 mg, 0.55 mmol) and pyridine (79 mg, 1.00 mmol). The mixture was stirred at 80° C. for 4 hours. TLC showed the reaction was completed. The reaction mixture was extracted with EA (40 mL), washed with 2M HCl (5 mL) and saturated sodium bicarbonate aqueous solution (30 mL), dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=8:1) to obtain 0.054 g (yield 15.01%) of the target compound.

[0126] Compound No. 31: .sup.1H NMR: 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).

Example 3: Preparation of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide (Compound No. 26)

Step 1: Preparation of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-2-fluoro-3-nitrobenzamide

[0127] ##STR00029##

[0128] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-2-fluoro-3-nitrobenzamide (2.29 g, 4.0 mmol) in anhydrous dimethyl sulfoxide (20 mL) was added sodium borohydride (300 mg, 8.0 mmol). Then the mixture was heated at 60° C. for 4 hours. TLC showed the reaction was finished. The reaction mixture was diluted with H.sub.2O (50 mL) and extracted with EA (50 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=10:1) to obtain 1.10 g (yield 49.55%) of the target compound as yellow oil.

[0129] .sup.1H NMR: 10.83 (s, 1H), 8.82 (s, 1H), 8.52 (d, J=8.0 Hz, 1H), 8.43 (d, J=8.0 Hz, 1H), 7.94 (s, 1H), 7.90 (t, J=8.0 Hz, 1H), 7.59 (s, 1H), 7.38 (t, J=72 Hz, 1H).

Step 2: Preparation of 3-amino-N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-2-fluorobenzamide

[0130] ##STR00030##

[0131] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl) phenyl)-2-fluoro-3-nitrobenzamide (1.1 g, 1.97 mmol) in anhydrous EtOH (20 mL) was added tin(II) chloride dihydrate (1.70 g, 7.90 mmol) and concentrated hydrochloric acid (0.2 mL). Then the mixture was heated and refluxed for 3 hours. TLC showed the reaction was finished. After the solvent was removed by distillation, 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 magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=5:1) to obtain 0.8 g (yield 76.92%) of the target compound as yellow solid.

[0132] .sup.1H NMR: 10.10 (s, 1H), 7.89 (s, 1H), 7.52 (s, 1H), 7.31 (t, J=72 Hz, 1H), 7.19-7.10 (m, 3H), 6.78 (d, J=8.0 Hz, 1H), 5.36 (s, 2H).

Step 3: Preparation of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide

[0133] ##STR00031##

[0134] To the solution of 3-amino-N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-2-fluorobenzamide (0.8 g, 1.52 mmol) in anhydrous 1,2-dichloroethane (20 mL) was added cyclopropanecarbaldehyde (99 mg, 1.37 mmol) and trifluoroacetic acid (1.04 g, 9.12 mmol). Then the reaction mixture was stirred at room temperature for 10 mins. Sodium triacetoxyborohydride (0.96 g, 4.56 mmol) was added to the mixture. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by saturated sodium bicarbonate aqueous solution to 8. The reaction mixture was extracted with dichloromethane (20 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=10:1) to obtain 0.60 g (yield 68.18%) of the target compound as brown oil.

Step 4: Preparation of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl) phenyl)-3-(4-cyano-N-(cyclopropylmethyl)benzamido)-2-fluorobenzamide

[0135] ##STR00032##

[0136] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(1,1,1,3,3,3-hexafluoropropan-2-yl) phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide (0.20 g, 0.34 mmol) in toluene (5 mL) was added 4-cyanobenzoyl chloride (83 mg, 0.52 mmol) and N, N-diisopropylethylamine (66 mg, 0.52 mmol). The mixture was stirred at reflux for 4 hours. The reaction mixture was diluted with H.sub.2O (20 mL) and extracted with EA (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=6:1) to obtain 0.15 g (yield 62.31%) of the target compound as white solid.

[0137] Compound No. 26: .sup.1H NMR: 10.32 (s, 1H), 7.92 (s, 1H), 7.81-7.76 (m, 2H), 7.72 (d, J=8.0 Hz, 2H), 7.54 (s, 1H), 7.51-7.47 (m, 3H), 7.31 (4, J=74.4 Hz, 2H), 3.79 (d, J=6.4 Hz, 2H), 1.07-0.99 (m, 1H), 0.45-0.41 (m, 2H), 0.16 (br s, 2H).

Example 4: Preparation of N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl) phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-6-fluoronicotinamide (Compound No. 106)

Step 1: Preparation of 2-fluoro-3-nitrobenzoyl chloride

[0138] ##STR00033##

[0139] Thionyl chloride (54.00 g, 455.64 mmol) was added to 2-fluoro-3-nitrobenzoic acid (16.87 g, 91.16 mmol) in toluene (200 mL), and the mixture was heated and refluxed for 2 hours. The solvent was removed by distillation to get the coarse product 2-fluoro-3-nitrobenzoyl chloride.

Step 2: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide

[0140] ##STR00034##

[0141] To 2-fluoro-3-nitrobenzoyl chloride was added 2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (31.00 g, 75.97 mmol), N, N-diisopropylethylamine (19.64 g, 151.94 mmol) and N,N-dimethylpyridin-4-amine (3.71 g, 30.39 mmol). The mixture was stirred at 100° C. TLC showed the reaction was completed. The reaction mixture was diluted with H.sub.2O (100 mL) and extracted with EA (100 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=4:1) to obtain 21.82 g (yield 50.00%) of the target compound as yellow oil.

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

[0142] ##STR00035##

[0143] To the solution of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide (21.82 g, 37.94 mmol) in anhydrous EtOH (200 mL) was added tin(II) chloride dihydrate (34.24 g, 151.76 mmol) and concentrated hydrochloric acid (3 mL). Then the mixture was heated and refluxed for 2 hours. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by 10% sodium hydroxide solution to 10. The reaction mixture was extracted with EA (200 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=4:1) to obtain 18.08 g (yield 87.40%) of the target compound as yellow solid.

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

[0144] ##STR00036##

[0145] To the solution of 3-amino-N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (5 g, 9.19 mmol) in 1,2-dichloroethane (20 mL) was added cyclopropanecarbaldehyde (580 mg, 8.27 mmol) and trifluoroacetic acid (6.27 g, 55.02 mmol). Then the reaction mixture was stirred at room temperature for 10 mins. Sodium triacetoxyborohydride (5.83 g, 27.51 mmol) was added to the mixture. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by saturated sodium bicarbonate aqueous solution to 8. The reaction mixture was extracted with dichloromethane (20 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=20:1) to obtain 3.94 g (yield 71.8%) of the target compound as brown oil.

Step 5: Preparation of N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl) carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-6-fluoronicotinamide

[0146] ##STR00037##

[0147] To the solution of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide (300 mg, 0.50 mmol) in toluene (5 mL) was added 6-fluoronicotinoyl chloride (87.86 mg, 0.55 mmol) and N, N-diisopropylethylamine (97.06 mg, 0.75 mmol). The mixture was stirred at 110° C. for 4 hours. TLC showed the reaction was completed. The reaction mixture was diluted with H.sub.2O (10 mL) and extracted with EA (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=4:1) to obtain 145 mg (yield 40.09%) of the target compound as yellow solid.

[0148] Compound No. 106: .sup.1H NMR: 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).

Example 5: Preparation of N-(3-((2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl) phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)-6-fluoronicotinamide (Compound No. 118)

[0149] ##STR00038##

[0150] To the solution of N-(2-bromo-6-(difluoromethoxy)-4-(perfluoropropan-2-yl)phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide (0.30 g, 0.50 mmol) in toluene (5 mL) was added 6-fluoronicotinoyl chloride (96 mg, 0.60 mmol) and N, N-diisopropylethylamine (97 mg, 0.75 mmol). The mixture was stirred at reflux for 4 hours. TLC showed the reaction was completed. The reaction mixture was extracted with EA (40 mL), washed with 2M HCl (5 mL), saturated sodium bicarbonate aqueous solution (30 mL), dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=5:1) to obtain 89 mg (yield 25.63%) of the target compound.

[0151] Compound No. 118: .sup.1H NMR: 10.36 (s, 1H), 8.15 (s, 1H), 7.94 (s, 1H), 7.90 (s, 1H), 7.75 (t, J=8.0 Hz, 1H), 7.60 (s, 1H), 7.54 (s, 1H), 7.36 (t, J=8.0 Hz, 1H), 7.32 (t, J=76.0 Hz, 1H), 7.14-7.10 (m, 1H), 3.73 (br s, 2H), 1.06-1.00 (m, 1H), 0.42 (d, J=8.0 Hz, 2H), 0.12 (d, J=20.0 Hz, 2H).

Example 6: Preparation of N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl) phenyl)carbamoyl)-2-fluorophenyl)-2-chloro-N-(1-cyclopropylethyl)isonicotinamide (Compound No. 124)

Step 1: Preparation of meth 13-((1-cyclopropylethyl)amino)-2-fluorobenzoate

[0152] ##STR00039##

[0153] To the solution of methyl 3-amino-2-fluorobenzoate (2.00 g, 11.82 mmol) in 1,2-dichloroethane (65 mL) was added 1-cyclopropylethan-1-one (2.98 g, 35.47 mmol), trifluoroacetic acid (8.08 g, 70.92 mmol) and sodium triacetoxyborohydride (7.51 g, 35.47 mmol) was added to the mixture. The mixture was stirred at 45° C. for 1 hour. TLC showed the reaction was finished. After the solvent was removed by distillation, the pH of the mixture was adjusted by saturated sodium bicarbonate aqueous solution (50 mL) to 8. The reaction mixture was extracted with dichloromethane (80 mL). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. The solvent was evaporated under reduced pressure and the obtained residue was purified by SGC (eluent: PE:EA=10:1) to obtain 2.50 g (yield 89.11%) of the target compound as colorless oil.

Step 2: Preparation of Methyl 3-(2-chloro-N-(1-cyclopropylethyl)isonicotinamido)-2-fluorobenzoate

[0154] ##STR00040##

[0155] Thionyl chloride (4.93 g, 44.25 mmol) was added to 2-chloroisonicotinic acid (1.39 g, 8.85 mmol) in toluene (15 mL), and the mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 2-chloroisonicotinoyl chloride in THF (5 mL) was used for the next step without further purification. To the solution of methyl 3-((1-cyclopropylethyl)amino)-2-fluorobenzoate (2.00 g, 8.43 mmol) in anhydrous THF (80 mL) was added triethylamine (0.90 g, 8.93 mmol) and 2-chloroisonicotinoyl chloride. The mixture was stirred at 80° C. for 6 hours. TLC showed the reaction was finished. The reaction mixture was diluted with H.sub.2O (80 mL) and extracted with EA (100 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=10:1) to obtain 1.93 g (yield 60.89%) of the target compound as yellow solid.

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

[0156] ##STR00041##

[0157] Methyl 3-(N-(1-cyclopropylethyl)-2-chloro isonicotinamido)-2-fluorobenzoate (1.50 g, 3.98 mmol) was dissolved in methanol (15 mL), 10% sodium hydroxide aqueous solution (6.4 mL) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed the reaction was completed. After the solvent was removed by distillation, the coarse product was dissolved in H.sub.2O (30 mL) and extracted with ethyl acetate (50 mL). The pH of the aqueous phase was acidified by the addition of 2M hydrochloric acid to 3 and extracted with ethyl acetate (40 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure to obtain 1.20 g (yield 83.09%) of the target compound.

Step 4: Preparation of N-(3-((2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl) carbamoyl)-2-fluorophenyl)-2-chloro-N-(1-cyclopropylethyl)isonicotinamide

[0158] ##STR00042##

[0159] To the solution of 3-(N-(1-cyclopropylethyl)-2-chloroisonicotinamido)-2-fluorobenzoic acid (0.51 g, 1.40 mmol) in toluene (6 mL) was added thionyl chloride (0.73 g, 7.00 mmol). Then the mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the coarse 3-(2-chloro-N-(1-cyclopropylethyl)isonicotinamido)-2-fluorobenzoyl chloride in THF (3 mL) was used for the next step without further purification. To 2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)aniline (0.52 g, 1.27 mmol) was added N, N-diisopropylethylamine (0.30 g, 2.55 mmol), N,N-dimethylpyridin-4-amine (62.28 mg, 509.76 μmol) and 3-(2-chloro-N-(1-cyclopropylethyl)isonicotinamido)-2-fluorobenzoyl chloride. The mixture was stirred at 110° C. for 2-3 hours. TLC showed the reaction was completed. The reaction mixture was diluted with H.sub.2O (40 mL) and extracted with EA (60 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=4:1) to obtain 0.32 g (yield 33.25%) of the target compound as yellow solid.

[0160] Compound No. 124: .sup.1H NMR: 10.62 (d, J=28.4 Hz, 1H), 8.43 (s, 1H), 8.28 (d, J=4.8 Hz, 1H), 7.96 (s, 1H), 7.81 (dt, J=22.8, 7.1 Hz, 1H), 7.65 (s, 1H), 7.43-7.33 (m, 2H), 7.31-7.20 (m, 1H), 4.06 (br s, 1H), 1.40 (d, J=6.5 Hz, 1H), 1.24 (s, 3H), 0.60 (d, J=7.6 Hz, 2H), 0.41 (d, J=3.6 Hz, 2H) (m, 1H), 0.41 (d, J=8.0 Hz, 2H), 0.09 (br s, 2H).

Example 7: Preparation of N-(3-((2-bromo-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-N-(cyclopropylmethyl)nicotinamide (Compund No. 156)

[0161] ##STR00043##

[0162] To the solution of N-(2-bromo-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)-6-(trifluoromethyl) phenyl)-3-((cyclopropylmethyl)amino)-2-fluorobenzamide (200 mg, 0.34 mmol) in toluene (5 mL) was added nicotinoyl chloride (58 mg, 0.41 mmol) and N, N-diisopropylethylamine (89 mg, 0.69 mmol). The mixture was stirred at 110° C. TLC showed the reaction was completed.

[0163] The reaction mixture was diluted with H.sub.2O (20 mL) and extracted with EA (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue was purified by SGC (eluent: PE:EA=4:1) to obtain 196 mg (yield 82.99%) of the target compound as white solid.

[0164] Compound No. 156: .sup.1H NMR: 10.59 (s, 1H), 8.50-8.39 (m, 3H), 7.96 (s, 1H), 7.79 (s, 1H), 7.80-7.77 (m, 2H), 7.74-7.68 (m, 1H), 7.57-7.47 (m, 2H), 7.29 (dd, J=7.7, 4.8 Hz, 1H), 3.81 (d, J=6.8 Hz, 2H), 1.12-1.00 (m, 1H), 0.48-0.38 (m, 2H), 0.15 (d, J=4.5 Hz, 2H).

[0165] In addition to the compounds described in the examples, compounds in Table 1 can be prepared according to the similar methods as described in examples 1-7. Hereinbelow, Table 3 shows the NMR data of some compounds prepared according to examples 1-7.

TABLE-US-00003 TABLE 3 Compound No. .sup.1H NMR (DMSO-d.sub.6, δ: ppm) 13 10.33 (s, 1H), 7.91 (s, 1H), 7.80-7.77 (m, 2H), 7.54 (s, 1H), 7.47-7.41 (m, 2H), 7.33 (t, J = 72 Hz, 1H), 7.32-7.21 (m, 5H), 3.78 (d, J = 8 Hz, 2H), 1.07-1.01 (m, 1H), 0.44-0.40 (m, 2H), 0.14-0.11 (m, 2H). 14 10.29 (s, 1H), 7.91 (s, 1H), 7.74-7.66 (m, 3H), 7.57-7.46(m, 4H), 7.33-7.31 (m, 2H), 3.73 (s, 2H), 1.04-1.00 (m, 1H), 0.42 (d, J = 8.0 Hz, 2H), 0.13 (d, J = 16.0 Hz, 2H). 27 10.29 (s, 1H), 7.90 (s, 1H), 7.74-7.50 (m, 7H), 7.33-7.31 (m, 2H), 3.74 (d, J = 16.0 Hz, 2H), 1.05-1.02 (m, 1H), 0.43 (d, J = 8.0 Hz, 2H), 0.14 (d, J = 8.0 Hz, 2H). 28 10.33 (s, 1H), 7.91 (s, 1H), 7.80 (d, J = 12 Hz, 2H), 7.61 (d, J = 8 Hz, 2H), 7.54-7.47 (m, 5H), 7.30 (t, J = 72 Hz, 1H), 3.81 (d, J = 8 Hz, 2H), 1.08-1.02 (m, 1H), 0.46-0.41 (m, 2H), 0.16-0.15 (m,2H). 43 10.33 (s, 1H), 7.91 (s, 1H), 7.80-7.77 (m, 2H), 7.54 (s, 1H), 7.50-7.44 (m, 2H), 7.37-7.34 (m, 2H), 7.32 (t, J = 72 Hz, 1H), 7.07 (t, J = 8 Hz, 2H), 3.78 (d, J = 4 Hz, 2H), 1.06-1.00 (m, 1H), 0.44-0.40 (m, 2H), 0.15-0.11 (m, 2H). 44 10.31 (s, 1H), 7.90 (s, 1H), 7.68-7.48 (m, 3H), 7.33 (t, J = 72.0 Hz, 2H), 7.32 (brs, 6H), 3.69 (d, J = 16.8 Hz, 2H), 1.02 (brs, 1H), 0.41 (d, J = 7.7 Hz, 2H), 0.09 (s, 2H). 55 7.92 (t, J = 7.2 Hz, 2H), 7.71 (d, J = 1.9 Hz, 1H), 7.59-7.35 (m, 2H), 7.23 (s, 2H), 7.18-7.04 (m, 2H), 6.48 (t, J = 73.1 Hz, 1H), 3.70 (s, 2H), 1.16 (s, 9H), 1.04 (d, J = 6.2 Hz, 1H), 0.41 (d, J = 8.0 Hz, 2H), 0.22-0.02 (m, 2H). 61 10.32 (s, 1H), 7.90 (d, J = 1.9 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.69 (d, J = 7.1 Hz, 1H), 7.55 (d, J = 9.0 Hz, 4H), 7.33 (s, 1H), 7.32 (t, J = 72.8 Hz, 1H), 3.79 (s, 1H), 3.70(s, 1H), 3.17 (s, 3H), 1.03 (s, 1H), 0.43 (d, J = 8.1 Hz, 2H), 0.13 (s, 2H). 77 10.29 (s, 1H), 7.90 (s, 1H), 7.62-7.49(m, 3H), 7.50-7.38 (m, 1H), 7.36-7.25 (m, 2H), 7.20-7.08 (m, 1H), 6.98 (t, J = 9.3 Hz, 1H), 3.88-3.76 (m, 1H), 3.65 (dd, J = 13.6, 7.0 Hz, 1H), 1.05-0.99 (m, 1H), 0.44 (d, J = 7.9 Hz, 2H), 0.21-0.06 (m, 2H). 78 10.31 (s, 1H), 7.91 (s, 1H), 7.67-7.48 (m, 4H), 7.38-7.26 (m, 3H), 7.33 (t, J = 72 Hz, 1H), 3.89 (dd, J = 13.8, 7.1 Hz, 1H), 3.57 (dd, J = 13.9, 7.0 Hz, 1H), 1.07-0.98 (m, 1H), 0.46 (d, J = 8.1 Hz, 2H), 0.17 (d, J = 3.7 Hz, 2H). 81 10.32 (s, 1H), 7.90 (s, 1H), 7.67 (t, J = 6.5 Hz, 1H), 7.64-7.47 (m, 1H), 7.32 (brs, 3H), 7.14 (s, 3H), 3.70 (d, J = 38.8 Hz, 2H), 1.02 (brs, 1H), 0.42 (d, J = 7.6 Hz, 2H), 0.11 (brs, 2H). 83 10.33 (s, 1H), 7.90 (s, 1H), 7.68-7.47 (m, 4H), 7.35-7.27 (m, 1H), 7.28-7.07 (m, 3H), 3.8 (dd, J = 13.9, 7.1 Hz, 1H), 3.62 (dd, J = 13.8, 7.2 Hz, 1H), 1.08-0.96 (m, 1H), 0.44 (d, J = 7.9 Hz, 2H), 0.15 (s, 2H). 85 10.34 (s, 1H), 7.91 (s, 1H), 7.73 (t, J = 7.3 Hz, 1H), 7.61 (s, 1H), 7.52 (s, 1H), 7.35 (t, J = 8.0 Hz, 1H), 7.31 (t, J = 72.0 Hz, 1H), 7.23 (s, 2H), 7.00 (s, 2H), 3.69 (s, 2H), 1.00 (brs, 1H), 0.42 (d, J = 7.2 Hz, 2H), 0.09 (s, 2H). 98 10.29 (s, 1H), 7.90 (s, 1H), 7.81 (d, J = 17.9 Hz, 1H), 7.72 (s, 1H), 7.61-7.44 (m, 5H), 7.34 (dd, J = 16.9, 8.0 Hz, 2H), 3.87-3.70 (m, 2H), 1.04 (brs, 1H), 0.51-0.42 (m, 2H), 0.21 (d, J = 33.7 Hz, 2H). 100 10.63 (s, 1H), 8.68-8.32 (m, 3H), 7.95 (s, 1H), 7.85-7.66 (m, 2H), 7.60 (s, 1H), 7.45-7.24 (m, 2H), 3.74 (br s, 2H), 1.03 (br s, 1H), 0.42 (d, J = 7.0 Hz, 2H), 0.10 (br s, 2H). 101 10.60 (s, 1H), 8.56-8.37 (m, 3H), 7.96 (s, 1H), 7.73 (s, 1H), 7.60 (s, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.30-7.12 (m, 2H), 3.74 (d, J = 6.3 Hz, 2H), 1.03 (br s, 1H), 0.43 (d, J = 6.9 Hz, 2H), 0.13 (d, J = 13.2 Hz, 2H). 105 10.63 (s, 1H), 8.42 (s, 1H), 8.30 (s, 1H), 7.95 (s, 1H), 7.79 (t, J = 7.0 Hz, 2H), 7.63 (s, 1H), 7.49-7.36 (m, 2H), 3.75 (d, J = 40.6 Hz, 2H), 1.03 (br s, 1H), 0.42 (d, J = 6.3 Hz, 2H), 0.12 (d, J = 28.2 Hz, 2H). 108 10.56 (s, 1H), 8.42 (s, 1H), 8.21 (d, J = 8.0 Hz, 1H), 7.95 (s, 1H), 7.88 (d, J = 7.2 Hz, 1H), 7.82-7.79 (m, 2H), 7,65-7.63 (m, 1H), 7.39-7.36 (m, 1H), 3.86 (br s, 2H), 1.05 (br s, 1H), 0.47 (d, J = 7.6 Hz, 2H), 0.20-0.18 (m, 2H). 109 10.59 (s, 1H), 8.42 (s, 1H), 7.96 (s, 1H), 7.77-7.68(m, 2H), 7.59 (t, J = 6.4 Hz, 1H), 7.32 (t, J = 7.6 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 3.84 (br s, 1H), 3.65 (br s, 1H), 1.02 (br s, 1H), 0.45 (d, J = 8.0 Hz, 2H), 0.16 (br s, 2H). 110 10.63 (s, 1H), 8.42 (s, 1H), 8.30 (d, J = 4.8 Hz, 1H), 7.96 (s, 1H), 7.79 (t, J = 7.2 Hz, 1H), 7.62-7.61(m, 1H), 7.42-7.36(m, 2H), 7.25 (d, J = 4.0 Hz, 1H), 3.79-3.67(m, 2H), 1.05-1.00(m, 1H), 0.43 (d, J = 7.6 Hz, 2H), 0.13 (d, J = 22.8 Hz, 2H). 111 10.51 (s, 1H), 8.31 (s, 1H), 8.03 (d, J = 5.2 Hz, 1H), 7.85 (s, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.51(t, J = 6.8 Hz, 1H), 7.26(t, J = 8.0 Hz, 1H) 7.10 (s, 1H), 6.99(s, 1H), 3.70-3.55(m, 2H), 0.92(brs, 1H), 0.33 (d, J = 8.0 Hz, 2H), 0.03 (d, J = 22.0 Hz, 2H). 112 10.36 (s, 1H), 8.47 (s, 2H), 7.90 (s, 1H), 7.77-7.66 (m, 2H), 7.64-7.48 (m, 3H), 7.32 (m, 2H), 3.86-3.60 (m, 2H), 1.02 (brs, 1H), 0.42 (d, J = 7.7 Hz, 2H), 0.20-0.03 (m, 2H). 113 10.33 (s, 1H), 8.47 (d, J = 3.9 Hz, 2H), 7.91 (s, 1H), 7.69 (t, J = 6.0 Hz, 1H), 7.56 (d, J = 12.9 Hz, 2H), 7.36-7.18 (m, 4H), 3.90-3.59 (m, 2H), 1.03 (brs, 1H), 0.43 (d, J = 7.7 Hz, 2H), 0.13 (s, 2H). 117 10.37 (s, 1H), 8.30(s, 1H), 7.91(s, 1H), 7.80-7.73(m, 2H), 7.65-7.53(m, 2H), 7.45-7.35(m, 2H), 7.32 (t, J = 72.0 Hz, 1H), 3.73 (d, J = 8.0 Hz, 2H), 1.04-1.01(m, 1H), 0.42 (d, J = 8.0 Hz, 2H), 0.13(d, J= 12.0 Hz, 2H). 119 10.36 (s, 1H), 8.31 (d, J = 4.8 Hz, 1H), 7.91 (s, 1H), 7.77 (t, J = 7.8 Hz, 1H), 7.66-7.49 (m, 2H), 7.48-7.31 (m, 2H), 7.32 (t, J = 72.0 Hz, 1H), 7.25 (d, J = 4.8 Hz, 1H), 3.71 (q, J = 13.9, 10.9 Hz, 2H), 1.03 (brs, 1H), 0.44 (d, J = 7.8 Hz, 2H), 0.14 (dd, J = 11.4, 4.2 Hz, 2H). 120 10.22 (s, 1H), 8.01 (d, J = 4.8 Hz, 1H), 7.78 (s, 1H), 7.62 (t, J = 7.2 Hz, 1H), 7.50-7.44 (m, 1H), 7.41 (s, 1H), 7.24-7.20 (m, 1H), 7.32 (t, J = 72.0 Hz, 1H), 7.08 (d, J = 4.8 Hz, 1H), 6.97(br s, 1H), 3.67-3.55 (m, 2H), 1.29 (brs, 1H), 0.31 (d, J = 8.4 Hz, 2H), 0.06-0.04 (m, 2H). 121 10.56 (d, J = 28.9 Hz, 1H), 8.52-8.35 (m, 3H), 7.95 (s, 1H), 7.79 (d, J = 24.4 Hz, 1H), 7.65 (d, J = 30.2 Hz, 2H, 7.37 (t, J = 7.6 Hz, 1H), 7.26 (s, 1H), 4.06 (br s, 1H), 1.41 (br s, 1H), 1.24 (s, 3H), 0.55 (d, J = 47.9 Hz, 2H), 0.35 (d, J = 43.8 Hz, 2H). 122 10.56 (d, J = 29.4 Hz, 1H), 8.44 (d, J = 4.4 Hz, 2H), 8.42 (s, 1H), 7.96 (s, 1H), 7.75 (dt, J = 20.3, 7.2 Hz, 1H), 7.61 (s, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.22 (s, 2H), 4.13-3.99 (m, 1H), 1.40 (d, J = 6.0 Hz, 1H), 1.24 (s, 3H), 0.55 (d, J = 41.6 Hz, 2H), 0.36 (d, J = 47.0 Hz, 2H). 123 10.57 (d, J = 26.5 Hz, 1H), 8.41 (s, 1H), 8.12 (s, 1H), 7.95 (s, 1H), 7.93-7.69 (m, 2H), 7.64 (s, 1H), 7.41 (t, J = 7.7 Hz, 1H), 7.07 (d, J = 6.0 Hz, 1H), 4.06 (br s, 1H), 1.42 (br s, 1H), 1.24 (s, 3H), 0.55 (d, J = 51.6 Hz, 2H), 0.35 (d, J = 37.2 Hz, 2H). 144 10.27 (s, 1H), 8.64 (d, J = 2.2 Hz, 1H), 8.30-8.22 (m, 1H), 7.99-7.84 (m, 2H), 7.63-7.51 (m, 3H), 7.31 (t, J = 72.8 Hz, 1H), 7.25 (t, J = 7.8 Hz, 1H), 3.91 (dd, J = 14.0, 7.0 Hz, 1H), 3.65 (dd, J = 14.1, 7.3 Hz, 1H), 1.06 (s, 1H), 0.45 (d, J = 7.8 Hz, 2H), 0.17 (d, J = 5.0 Hz, 2H). 145 10.26 (s, 1H), 8.22 (s, 1H), 7.91 (d, J = 2.0 Hz, 1H), 7.85-7.70 (m, 2H), 7.54 (s, 2H), 7.51 (s, 1H), 7.33 (t, J = 72 Hz, 1H), 7.24 (t, 7=8.1 Hz, 1H), 3.86 (d, J = 8.4 Hz, 1H), 3.59 (d, J = 6.7 Hz, 1H), 1.12-0.98 (m, 1H), 0.43 (d, J = 7.8 Hz, 2H), 0.15 (d, J = 4.8 Hz, 2H). 146 10.28 (s, 1H), 8.28 (s, 1H), 7.96 (d, J = 8.5 Hz, 1H), 7.91 (s, 1H), 7.70 (d, J = 8.5 Hz, 1H), 7.53 (d, J = 10.6 Hz, 2H), 7.51 (m, 1H), 7.33 (t, J = 72.8 Hz, 1H), 7.25 (t, J = 7.9 Hz, 1H), 3.88 (dd, J = 14.2, 6.9 Hz, 1H), 3.61 (dd, J = 14.1, 7.3 Hz, 1H), 1.05 (s, 1H), 0.44 (d, J = 7.7 Hz, 2H), 0.16 (d, J = 5.1 Hz, 2H). 147 10.29 (s, 1H), 8.35 (s, 1H), 8.14-8.04 (m, 1H), 7.91 (d, J = 2.0 Hz, 1H), 7.63 (d, J = 8.4 Hz, 1H), 7.53 (d, J = 11.0 Hz, 3H), 7.33 (t, J = 72.0 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H), 3.88 (dd, J = 14.1, 7.0 Hz, 1H), 3.60 (dd, J = 14.4, 7.2 Hz, 1H), 1.10-1.00 (m, 1H), 0.43 (d, J = 7.8 Hz, 2H), 0.15 (d, J = 4.7 Hz, 2H). 148 10.27 (s, 1H), 9.02 (d, J = 2.6 Hz, 1H), 8.60 (dd, J = 8.6, 2.6 Hz, 1H), 7.97-7.88 (m, 2H), 7.63-7.52 (m, 3H), 7.32 (t, J = 72.4 Hz, 1H), 7.26 (t, J = 7.8 Hz, 1H), 3.91 (dd, J = 14.0, 7.0 Hz, 1H), 3.66 (dd, J = 13.9, 7.2 Hz, 1H), 1.06 (s, 1H), 0.46 (h, J = 4.3 Hz, 2H), 0.22-0.14 (m, 2H). 149 10.28 (s, 1H), 8.71 (d, J = 2.0 Hz, 1H), 8.35 (dd, J = 8.2, 2.1 Hz, 1H), 7.96-7.88 (m, 1H), 7.84 (d, J = 8.2 Hz, 1H), 7.55 (d, J = 8.2 Hz, 3H), 7.33 (t, J = 72.8 Hz, 1H), 7.26 (t, J = 7.8 Hz, 1H), 3.89 (dd, J = 14.0, 7.0 Hz, 1H), 3.65 (dd, J = 14.1, 7.2 Hz, 1H), 1.03 (dt, J = 13.3, 7.2 Hz, 1H), 0.44 (d, J = 7.9 Hz, 2H), 0.17 (d, J = 5.0 Hz, 2H). 150 10.50 (d, J = 12.5 Hz, 1H), 8.63 (s, 1H), 8.41 (s, 1H), 8.26 (d, J = 7.4 Hz, 1H), 7.95 (s, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.61 (dt, J = 13.2, 6.7 Hz, 2H), 7.30 (t, J = 7.1 Hz, 1H), 3.82 (d, J = 25.2 Hz, 2H), 1.06 (s, 1H), 0.45 (d, J = 7.8 Hz, 2H), 0.19 (s, 2H). 152 10.55 (s, 1H), 8.42 (s, 1H), 8.27 (s, 1H), 7.96 (s, 2H), 7.71 (d, J = 8.4 Hz, 1H), 7.61-7.52 (m, 2H), 7.28 (t, J = 7.6 Hz, 1H), 3.82 (s, 1H), 3.69 (s, 1H), 1.05 (s, 1H), 0.44 (d, J = 7.5 Hz, 2H), 0.16 (s, 2H). 153 10.54 (s, 1H), 8.70 (s, 1H), 8.42 (s, 1H), 8.36 (d, J = 9.7 Hz, 1H), 7.96 (s, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.59 (dt, J = 12.4, 7.0 Hz, 2H), 7.29 (t, J = 7.7 Hz, 1H), 3.78 (d, J = 28.6 Hz, 2H), 1.04 (s, 1H), 0.45 (d, J = 8.0 Hz, 2H), 0.17 (s, 2H). 154 10.53 (s, 1H), 9.04-8.98 (m, 1H), 8.61 (dd, J = 8.6, 2.4 Hz, 1H), 8.42 (s, 1H), 7.95 (s, 2H), 7.61 (dt, J = 22.0, 6.6 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 3.80 (d, J = 43.6 Hz, 2H), 1.05 (s, 1H), 0.46 (d, J = 7.9 Hz, 2H), 0.18 (s, 2H). 157 10.58 (s, 1H), 8.46 (s, 1H), 8.43 (s, 1H), 7.96 (s, 1H), 7.79 (d, J = 8.1 Hz, 2H), 7.53 (dt, J = 15.1, 7.5 Hz, 2H), 7.25 (s, 2H), 3.78 (s, 2H), 1.04 (dd, J = 12.7, 6.1 Hz, 1H), 0.44 (d, J = 7.0 Hz, 2H), 0.15 (s, 2H). 161 10.58 (s, 1H), 8.43 (s, 1H), 8.13 (s, 1H), 7.97 (s, 1H), 7.90 (t, J = 8.7 Hz, 1H), 7.81 (d, J = 7.4 Hz, 1H), 7.75 (s, 1H), 7.55 (dt, J = 15.4, 8.0 Hz, 2H), 7.10 (d, J = 10.7 Hz, 1H), 3.82 (d, J = 7.0 Hz, 2H), 1.10-0.97 (m, 1H), 0.49-0.40 (m, 2H), 0.15 (d, J = 4.5 Hz, 2H). 164 10.34 (s, 1H), 8.44 (d, J = 2.7 Hz, 2H), 7.91 (s, 1H), 7.81 (d, J = 12.9 Hz, 2H), 7.71 (d, J = 7.8 Hz, 1H), 7.54 (s, 1H), 7.52-7.45 (m, 2H), 7.32 (t, J = 76.0 Hz, 1H), 7.34-7.25 (m, 1H), 3.80 (d, 7= 7.0 Hz, 2H), 1.08-1.03 (m, 1H), 0.43 (d, J = 18.1 Hz, 2H), 0.14 (d, J = 4.6 Hz, 2H). 165 10.34 (s, 1H), 8.46 (s, 2H), 7.91 (s, 1H), 7.82 (d, J = 9.3 Hz, 2H), 7.57-7.45 (m, 3H), 7.31 (t, J = 72 Hz, 1H), 7.25 (s, 2H), 3.78 (s, 2H), 1.02 (brs, 1H), 0.43 (d, J = 7.1 Hz, 2H), 0.14 (s, 2H). 168 10.34 (s, 1H), 8.28 (s, 1H), 7.91 (s, 1H), 7.83 (d, J = 9.0 Hz, 2H), 7.77 (d, J = 7.9 Hz, 1H), 7.54 (d, J = 6.7 Hz, 2H), 7.50 (d, J = 6.8 Hz, 1H), 7.42 (d, J = 8.2 Hz, 1H), 7.31 (t, J = 72.0 Hz, 1H), 3.80 (d, J = 6.9 Hz, 2H), 1.11-0.97 (m, 1H), 0.48-0.39 (m, 2H), 0.14 (d, J = 4.5 Hz, 2H). 169 10.34 (s, 1H), 8.14 (s, 1H), 7.91 (s, 2H), 7.82 (d, J = 8.9 Hz, 2H), 7.53 (d, J = 7.9 Hz, 2H), 7.50 (d, J = 6.8 Hz, 1H), 7.31 (t, J = 72.0 Hz, 1H), 7.09 (dd, J = 8.5, 2.2 Hz, 1H), 3.81 (d, J = 7.0 Hz, 2H), 1.04 (brs, 1H), 0.43 (d, J = 9.5 Hz, 2H), 0.14 (d, J = 4.8 Hz, 2H). 170 10.35 (s, 1H), 8.28 (br s, 1H), 7.92 (br s, 1H), 7.90-7.81 (m, 2H), 7.60-7.49 (m, 4H), 7.43 (s, 1H), 7.32 (t, J = 72.0 Hz, 1H), 7.28 (s, 1H), 3.77 (s, 2H), 1.09-0.98 (m, 1H), 0.44 (d, J = 7.3 Hz, 2H), 0.15 (s, 2H). 173 10.34 (s, 1H), 8.32 (dd, J = 4.7, 1.3 Hz, 1H), 7.91 (td, J = 6.8, 5.7, 1.6 Hz, 2H), 7.54 (td, J = 9.8, 9.2, 3.3 Hz, 2H), 7.50-7.43 (m, 1H), 7.34 (t, J = 72.7 Hz, 1H), 7.33-7.30 (m, 1H), 7.21 (d, J = 7.8 Hz, 1H), 4.10 (dd, J = 14.2, 7.1 Hz, 1H), 3.45 (s, 1H), 1.02 (tq, J = 12.4, 7.4, 6.1 Hz, 1H), 0.52-0.42 (m, 2H), 0.21 (d, J = 19.6 Hz, 2H). 174 10.62 (s, 1H), 8.42 (s, 1H), 8.32 (dd, J = 4.7, 1.2 Hz, 1H), 7.96 (s, 1H), 7.88 (dd, J = 8.2, 1.2 Hz, 1H), 7.56 (d, J = 6.3 Hz, 1H), 7.51-7.46 (m, 1H), 7.37-7.28 (m, 1H), 7.22 (t, J = 7.8 Hz, 1H), 4.06 (d, J = 15.6 Hz, 1H), 3.48 (d, J = 13.3 Hz, 1H), 1.03 (d, J = 6.2 Hz, 1H), 0.48 (d, J = 8.0 Hz, 2H), 0.21 (d, J = 14.1 Hz, 2H). 175 10.64 (s, 1H), 8.43 (s, 2H), 8.25 (d, J = 2.0 Hz, 1H), 7.96 (s, 1H), 7.62-7.48 (m, 2H), 7.27 (t, J = 7.8 Hz, 1H), 4.00 (s, 1H), 3.57 (s, 1H), 1.02 (s, 1H), 0.48 (d, J = 7.9 Hz, 2H), 0.21 (s, 2H). 176 10.29 (s, 1H), 8.34-8.21 (m, 1H), 7.96 (dd, J = 8.3, 2.4 Hz, 1H), 7.91 (d, J = 2.0 Hz, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.55 (d, J = 9.4 Hz, 1H), 7.51 (d, J = 3.4 Hz, 1H), 7.33 (t, J = 73.6 Hz, 1H), 7.29-7.20 (m, 1H), 3.88 (dd, J = 13.9, 6.5 Hz, 1H), 3.61 (dd, J = 14.5, 7.3 Hz, 1H), 1.04 (q, J = 6.5, 5.3 Hz, 1H), 0.44 (d, J = 7.8 Hz, 2H), 0.16 (d, J = 5.0 Hz, 2H). 177 10.32 (s, 1H), 7.90 (d, J = 1.9 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.69 (d, J =7.1 Hz, 1H), 7.55 (d, J = 9.0 Hz, 4H), 7.33 (s, 1H), 7.32 (t, J = 72.8 Hz, 1H), 3.79 (s, 1H), 3.70(s, 1H), 3.17 (s, 3H), 1.03 (s, 1H), 0.43 (d, J = 8.1 Hz, 2H), 0.13 (s, 2H). 178 8.08 (d, J = 13.6 Hz, 1H), 8.02 (s, 1H), 7.88-7.75 (m, 1H), 7.68 (dd, J = 7.7, 2.1 Hz, 1H), 7.50 (d, J = 1.9 Hz, 1H), 7.48-7.41 (m, 1H), 7.22 (t, J = 7.9 Hz, 1H), 6.83 (dd, J = 8.2, 2.9 Hz, 1H), 6.58 (t, J = 73.0 Hz, 1H), 3.90 (dd, J = 14.0, 7.3 Hz, 1H), 3.73 (dd, J = 13.3, 7.1 Hz, 2H), 1.13 (dt, J = 7.6, 4.2 Hz, 1H), 0.52 (dd, J = 8.0, 3.3 Hz, 2H), 0.22 (d, J = 5.0 Hz, 2H). 179 10.55 (s, 1H), 8.42 (s, 1H), 8.01-7.94 (m, 2H), 7.58 (dd, J = 12.7, 6.7 Hz, 3H), 7.29 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 7.7 Hz, 1H), 3.80 (s, 1H), 3.65 (dd, J = 12.8, 5.8 Hz, 1H), 1.04 (s, 1H), 0.44 (d, J = 7.4 Hz, 2H), 0.16 (s, 2H). 180 10.28 (s, 1H), 7.91 (s, 1H), 7.70-7.65 (m, 1H), 7.63-7.57 (m, 1H), 7.54 (s, 1H), 7.50 (s, 0H), 7.43 (s, 1H), 7.32 (s, 2H), 7.20 (s, 1H), 7.14 (s, 0H), 3.72 (d, J =J = 22.3 Hz, 2H), 2.38 (s, 3H), 1.02 (s, 1H), 0.43 (d, J = 6.6 Hz, 2H), 0.14 (s, 2H). 181 10.30 (s, 1H), 7.91 (s, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.68-7.52 (m, 5H), 7.50 (s, 0H), 7.31 (d, J = 4.9 Hz, 1H), 7.14 (s, 0H), 3.82 (dd, J = 13.8, 7.3 Hz, 1H), 3.70 (dd, J = 14.0, 7.0 Hz, 1H), 1.06-0.97 (m, 1H), 0.45 (d, J = 8.0 Hz, 2H), 0.16 (dd, J = 8.6, 4.7 Hz, 2H). 182 10.28 (s, 1H), 7.93-7.87 (m, 2H), 7.65 (d, J = 10.4 Hz, 2H), 7.55 (d, J = 6.9 Hz, 2H), 7.51 (s, 0H), 7.47 (d, J = 7.9 Hz, 1H), 7.33 (s, 0H), 7.28 (d, J = 9.4 Hz, 2H), 7.14 (s, 0H), 3.90-3.81 (m, 1H), 3.70-3.60 (m, 1H), 2.34 (s, 3H), 1.07-1.00 (m, 1H), 0.46 (d, J = 8.0 Hz, 2H), 0.18 (s, 2H).

[0166] Other compounds represented by general formula I of this invention can also be prepared according to the methods described above.

FORMULATION EXAMPLES

Formulation Example 1

[0167] In the embodiment, compound 1 of the invention is used as a representative compound to prepare a formulation. The details are as follows:

[0168] 30 parts (by weight, the other ingredients of this example and formulation examples below are all by weight) of compound 1, 15 parts of polyoxyethylene styrylphenyl ether, 10 parts of phosphite and 45 parts of xylene are evenly mixed to obtain the 30% emulsion of compound 1.

Formulation Example 2

[0169] In the present embodiment, compound 27 of the invention is used as a representative compound to prepare a formulation. The details are as follows:

20 parts of compound 27, 2 parts of sodium dodecyl sulfate, 2 parts of dialkylsulphonate succinate, 1 part of sodium salt of 0-naphthalenesulfonate formaldehyde condensate and 75 parts of diatomite were evenly stirred and mixed to obtain 20% wettable powder of compound 27.

Formulation Example 3

[0170] In the embodiment, compound 43 of the invention is used as a representative compound to prepare a formulation. The details are as follows:

[0171] 30 parts of compound 43 of the invention, 10 parts of ethylene glycol, 6 parts of nonylphenol polyethylene glycol ether, 10 parts of sodium lignosulfonate, 10 parts of carboxymethyl cellulose and 1 part of silicone oil aqueous solution, 33 parts of water were evenly stirred and mixed to obtain 30% suspending agent of compound 43.

Examples for Bioactivity Tests

[0172] Various kinds of pests were tested with the compounds of this invention. Unless otherwise specified, the preparation method of samples and definition of the mortality rate of the insects in the embodiments and this invention are as follows: the preparation method of samples is to weigh 10 mg of the compound and dissolve it in 1 mL DMF to prepare 10,000 ppm mother liquid, which is diluted to necessary concentration by 0.05% Tween-80 water, respectively. The mortality rate is the mortality rate of pests under the test concentration, whose calculating formula is: mortality rate (%)=Number of dead pests/total pests*100

Example 1 of Biological Test: Insecticidal Activity Test Against Mythimna separata

[0173] The leaf dip method was used to assay the insecticidal activity. Cut above ground part of fresh maize seedlings (about 10 cm). Dip the maize seedlings into the solution prepared with compound of this invention for 10 seconds and dry them in a cool environment. Then cut the dry maize seedlings into 3-5 cm leaf sections and put 3 leaf sections into each petri dish. Put ten of 3th-instar larvae of Mythimna separatas into each dish, which was repeated by 3 times. Then the dishes were placed in an illumination incubator and incubated with 14 hL: 10 hD illumination at 25° C. Symptoms were investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

[0174] The insecticidal activity of compounds 55, 144, 145, 146, 147, 148, 149, 150, 152, 153, 154, 173, 174, 175, 176, 177, 178 and 179 of this invention is ≥90% (mortality of Mythimna separate) at 1 ppm on the 3rd day after treatment.

[0175] The insecticidal activity of compounds 105, 110 and 117 of this invention is ≥90% (mortality of Mythimna separate) at 0.1 ppm on the 3rd day after treatment.

[0176] The insecticidal activity of compounds 1, 31, 106, 111, 118 and 120 of this invention is ≥90% (mortality of Mythimna separate) at 0.04 ppm on the 3rd day after treatment.

[0177] According to the above method, compound 31 and KC1 were selected and parallelly tested against Mythimna separate to compare their insecticidal activity. The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Mortality of compound 31 and KC1 against Mythimna separate Mortality (%) Compound concentration 1 d 2 d 3 d 31 0.01 ppm 13.33 63.33 70.00 KC1 0.01 ppm 6.67 16.67 20.00

Example 2 of Biological Test: Insecticidal Activity Test Against Spodoptera litura

[0178] The leaf dip method was used to assay the insecticidal activity. Healthy and pesticide-untreated cabbage leaves was selected to prepare 1 cm of leaf discs by diameter. Dip the leaf discs into the solution prepared with compound of this invention for 10 seconds and dry them in a cool 30 environment. Then place them in 24-well plate with 3 discs per pore. Put 10 of Spodoptera litura into each pore, which was repeated by 3 times. The 24-well plate was placed in an illumination incubator and incubated with 14 hL: 10 hD illumination at 25° C. The dead number of Spodoptera litura was investigated on the 3rd day after treatment, and the mortality was calculated.

[0179] The insecticidal activity of some compounds of this invention against Spodoptera litura is as follows:

[0180] The insecticidal activity of compounds 1, 14, 27, 31, 44, 77, 83, 85, 106, 118, 119, 120 is ≥90% (mortality of Spodoptera litura) at 0.4 ppm on the 3rd day after treatment.

[0181] According to the above method, compound 118 and KC4 were selected and parallelly tested against Spodoptera litura to compare the insecticidal activity. The results are shown in Table 5.

TABLE-US-00005 TABLE 5 Mortality of compound 118 and KC1 against Spodoptera litura Mortality (%, 3 d) compound 0.1 ppm 0.04 ppm 118 95.83 66.67 KC4 75.0 8.83

Example 3 of Biological Test: Insecticidal Activity Test Against Chilo suppressalis

[0182] The rice was cultivated in a plastic pot with a diameter of 9 cm and a height of 10 cm. When the rice grew to 25 cm, the aerial part of robust and consistent rice seedlings was selectively cut. Their leaves were removed and their stems of about 8 cm were kept for use. Pour the solution prepared with compound of this invention into the Petri dish (about 40 mL) and dip the rice stems into the solution for 10 seconds. Take rice stems out and dry them in a cool environment. Put a wet cotton ball at the bottom of finger-like glass tube and 5 rice stems in each tube. Put 10 of 3rd-instar larvae of Chilo suppressa into each tube, which was repeated by 3 times. Seal the tubes with black cotton cloth and tighten them with rubber band. The tubes were placed in a illumination incubator at 28° C. and incubated in the dark (incubated without light). The dead number of Chilo suppressalis was investigated 3 days after treatment. The mortality was calculated.

[0183] The insecticidal activity of some compounds of this invention against Chilo suppressalis is as follows:

[0184] The insecticidal activity of compounds 110 and 124 is ≥90% (mortality of Chilo suppressalis) at 2 ppm on the 3rd day after treatment.

[0185] The insecticidal activity of compounds 1, 14, 27, 31, 44, 85, 106, 118 and 119 is ≥90% (mortality of Chilo suppressalis) at 1 ppm on the 3rd day after treatment.

[0186] According to the above method, compounds 1, 31 and KC3 were selected and parallelly tested against Chilo suppressalis. The results are shown in Table 6.

TABLE-US-00006 TABLE 6 Mortality of compounds 1,31 and KC3 against Chilo suppressalis Mortality (%, 3 d) compounds 2 ppm 1 ppm 0.5 ppm  1 100 96.67 76.67 31 100 100 83.33 KC3 96.67 80.00 20.00

Example 4 of Biological Test: Insecticidal Activity Test Against Aphis craccivora

[0187] Cut a single leaf of broad bean with stem and insert it into a glass jar filled with water (capacity of 20 ml). Five adult Aphis craccivoras were seeded onto each leaf, and covered with plastic cups with holes. The adult aphids were removed after 24 hours. Before the experiment, the base number was investigated and the single leaf with more than 15 nymphs aphids was selected for the experiment. Dip leaf of broad bean with nymphs aphids into the solution of test compound 10s, take out and dry them in a cool environment, 3 parallel repeats. Place the glass jars on the shelf of observation room and covered with plastic cups with holes. 20-25° C. with 14 hL: 10 hD illumination. The number of Aphis craccivora death and alive was investigated on the 3rd day after treatment, and the mortality was calculated.

[0188] The insecticidal activity of compounds 14, 27, 31, 44, 83, 101, 110, 111, 113, 118 and 120 is ≥90% (mortality of Aphis craccivora) at 40 ppm on the 3rd day after treatment.

[0189] According to the above method, compounds 101 and KC4 were selected and parallelly tested against Aphis craccivora to compare the insecticidal activity. The results are shown in Table 7.

TABLE-US-00007 TABLE 7 Mortality of compounds 101 and KC4 against Aphis craccivora Mortality (%, 3 d) compound 40 ppm 10 ppm 1 ppm 101 100.00 83.26 39.11 KC4 65.23 47.15 0

Example 5 of Biological Test: Insecticidal Activity Test Against Spodoptera frugiperda

[0190] The leaf dip method was used to assay the insecticidal activity. Cut above ground part of fresh maize seedlings (about 10 cm). Dip the maize seedlings into the solution prepared with compound of this invention for 10 seconds and dry them in a cool environment. Then cut the dry maize seedlings into 3-5 cm leaf sections and put 3 leaf sections into each petri dish. Put ten of 3th-instar larvae of Spodoptera frugiperda into each dish, which was repeated by 3 times. Then the dishes were placed in an illumination incubator and incubated with 14 hL: 10 hD illumination at 25° C. Symptoms were investigated on the 1st, 2nd and 3rd day after treatment, and the mortality was calculated.

[0191] The insecticidal activity of compounds 1, 14, 27, 31, 44, 77, 81, 83, 85, 105, 106, 111, 118, 119, 120 and 181 is ≥90% (mortality of Spodoptera frugiperda) at 1 ppm on the 3rd day after treatment.

[0192] According to the above method, some compounds of this invention, KC2 and KC3 were selected and parallelly tested against Spodoptera frugiperda to compare the insecticidal activity. The results are shown in Table 8. PGP-2 T

TABLE-US-00008 TABLE 8 Mortality of compounds of the invention, KC2 and KC3 against Spodoptera frugiperda Mortality (%) compound concentration 1 d 2 d 3 d 14 0.1 ppm 29.17 79.17 95.83 44 0.1 ppm 37.50 62.50 91.67 31 0.1 ppm 100 100 100 106 0.1 ppm 41.67 62.50 95.83 118 0.1 ppm 29.17 66.67 91.67 119 0.1 ppm 54.17 79.17 91.67 120 0.1 ppm 58.33 100 100 KC2 0.1 ppm 0 8.33 20.83 KC3 0.1 ppm 0 0 4.17

[0193] The applicant states that the amide compounds of this invention, the preparation methods and applications thereof can be illustrated by the above examples, but this invention is not limited thereto, i.e., which does not mean that the implementation of this invention must rely on the above examples. Those skilled in the art should understand that any improvement to this invention, equivalent replacement of the raw materials for preparing the compounds of this invention, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the scope of protection and disclosure of this invention.