BROMINATION METHOD FOR M-DIAMIDE COMPOUNDS

Abstract

The present disclosure provides a bromination method for m-diamide compounds comprising reacting a compound represented by formula I with a brominating reagent in the presence of an oxidant to obtain a brominated product represented by formula II. The method adopts a special design of brominating reagents and reaction conditions to introduce a bromine atom at a specific site of the m-diamide compound, with 87.9 to 99.5% yield of a brominated product obtained by the reaction and higher than 91.8% purity. Therefore, the bromination method has a simple route, mild reaction conditions, high efficiency, and does not require complicated and cumbersome post-treatment processes; furthermore, raw materials used for the bromination reaction are readily available, costs of the brominating reagent are low, and the brominated product finally obtained has high yield and high purity, thus the method is a novel one with a broad application prospect.

Claims

1. A bromination method for m-diamide compounds, wherein the bromination method comprises: reacting a compound represented by formula I with a brominating reagent in the presence of an oxidant to obtain a brominated product represented by formula II, the scheme is as follows: ##STR00014## wherein, Z is selected from any one of the group consisting of hydrogen, halogen, cyano, nitro, C1-C6 linear or branched alkyl, halogenated C1-C6 linear or branched alkyl, C1-C6 linear or branched alkoxyl, halogenated C1-C6 linear or branched alkoxyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C1-C6 alkylsulfinyl, and halogenated C1-C6 alkylsulfinyl; W.sub.1 and W.sub.2 are each independently O or S; R.sub.1 is selected from any one of C1-C6 linear or branched alkyl or ##STR00015##  R.sub.4 is selected from the group consisting of hydrogen, halogen, C1-C6 linear or branched alkyl, halogenated C1-C6 linear or branched alkyl, C3-C8 cycloalkyl, and halogenated C3-C8 cycloalkyl, R.sub.5 is hydrogen or halogen, and the wavy line represents the connecting site of the group; Y is selected from any one of the group consisting of halogen, C1-C6 linear or branched alkyl, halogenated C1-C6 linear or branched alkyl, C1-C6 linear or branched alkoxyl, and halogenated C1-C6 linear or branched alkoxyl; R.sub.2 is hydrogen, halogen or methoxyl; and R.sub.3 is fluoro or trifluoromethyl; wherein the oxidant is selected from any one or a combination of at least two of the group consisting of a metal perchlorate, metal chlorate, metal hypochlorite, and chlorine; and the molar ratio of the oxidant to the compound represented by formula I is from 0.4:1 to 2.0:1.

2. The bromination method according to claim 1, wherein the brominating reagent is selected from the group consisting of metal bromide, ammonium bromide, bromine, and hydrobromic acid; and the molar ratio of the brominating reagent to the compound represented by formula I is from 0.55:1 to 2.0:1.

3. The bromination method according to claim 2, wherein the metal is an alkali metal or an alkaline earth metal.

4. The bromination method according to claim 3, wherein the brominating reagent is sodium bromide, potassium bromide, bromine or hydrobromic acid.

5. (canceled)

6. The bromination method according to claim 1, wherein the metal is an alkali metal or an alkaline earth metal.

7. The bromination method according to claim 6, wherein the oxidant is selected from the group consisting of sodium chlorate, potassium chlorate, sodium hypochlorite, potassium hypochlorite, and chlorine.

8. The bromination method according to claim 1, wherein the reaction is performed in the presence of an alkaline compound; and the molar ratio of the alkaline compound to the compound represented by formula I is from 0.1:1 to 2.0:1.

9. The bromination method according to claim 8, wherein the alkaline compound is selected from any one or a combination of at least two of the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, and ammonia.

10. The bromination method according to claim 9, wherein the metal is an alkali metal or an alkaline earth metal.

11. The bromination method according to claim 10, wherein the alkaline compound is sodium hydroxide or potassium hydroxide.

12. The bromination method according to claim 1, wherein the reaction is performed in the presence of a solvent and; the solvent is selected from any one or a combination of at least two of the group consisting of haloalkane solvents, aromatic hydrocarbon solvents, alcoholic solvents, chain or cyclic ether solvents, and nitrile solvents and; wherein, based on 1 mol of the amount of the compound represented by formula I, the amount of the solvent is 500-5000 g.

13. The bromination method according to claim 12, wherein, the haloalkane solvent is selected from any one or a combination of at least two of the group consisting of dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; wherein, the aromatic hydrocarbon solvent is selected from any one or a combination of at least two of the group consisting of benzene, toluene, and xylene; wherein, the alcoholic solvent is selected from any one or a combination of at least two of the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol; wherein, the chain or cyclic ether solvent is selected from any one or a combination of at least two of the group consisting of diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; and wherein, the nitrile solvent is selected from any one or a combination of at least two of the group consisting of acetonitrile, propionitrile, and butyronitrile.

14. The bromination method according to claim 1, wherein Z is selected from any one of the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, fluorinated C1-C4 linear or branched alkyl, fluorinated C1-C4 linear or branched alkoxyl, C1-C4 alkylsulfonyl, and fluorinated C1-C4 alkylsulfonyl; wherein, both of W.sub.1 and W.sub.2 are 0; wherein, R.sub.1 is selected from any one of the group consisting of C1-C4 linear or branched alkyl and ##STR00016## wherein R.sub.4 is selected from the group consisting of hydrogen, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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, and perfluorocyclopentyl, and wherein R.sub.5 is hydrogen, fluorine or chlorine, and the wavy line represents the connecting site of the group; wherein, Y is selected from any one of the group consisting of halogen, C1-C4 linear or branched alkyl, fluorinated C1-C4 linear or branched alkyl, C1-C4 linear or branched alkoxyl, and fluorinated C1-C4 linear or branched alkoxyl; wherein, R.sub.2 is fluorine; and wherein, R.sub.3 is fluorine.

15. The bromination method according to claim 14, wherein, Z is selected from any one of the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, difluoromethoxyl, trifluoromethoxyl, methanesulfonyl, and trifluoromethanesulfonyl; wherein R.sub.1 is methyl, cyclopropylmethyl or 1-cyclopropylethyl; and wherein, Y is trifluoromethyl.

16. The bromination method according to claim 1, wherein the temperature of the reaction is 0-150° C. and; wherein, the reaction time is 0.5-8 hours.

17. The bromination method according to claim 1, wherein the oxidant is added through a pipe or by dropwise addition.

18. The bromination method according to claim 1, wherein the bromination method further comprises post-treatment steps; wherein, the post-treatment steps include organic phase separation, washing, solvent removal and drying.

19. The bromination method according to claim 18, wherein a sodium sulfite solution is used in the washing step; and a concentration of the sodium sulfite solution is 5-20% by weight.

20. The bromination method according to claim 1, wherein the bromination method is carried out by: mixing a compound represented by formula I with a solvent, adding the brominating reagent and an alkaline compound, dropwise adding or charging an oxidant through a pipe at 0-150° C., and then letting the reaction run at 0-150° C. for 0.5-8 hours; and after the reaction is completed, the organic phase is separated, washed with a sodium sulfite solution, evaporated and dried to obtain the brominated product represented by formula II.

Description

DETAILED DESCRIPTION

[0065] The technical solutions of the present disclosure will be further described below by way of specific embodiments. It will be apparent to those skilled in the art that the embodiments are merely illustrations of the present disclosure and should not be construed as specific limitations to the present disclosure.

[0066] The experimental materials used in the following examples of the present disclosure include compounds represented by formula I, brominating reagents, oxidants, alkaline compounds and solvents. The compound represented by formula I can be commercially available, or can be prepared according to the related technics, for example, prepared according to CN104245665A. The brominating reagents, oxidants, alkaline compounds and solvents can all be commercially available.

[0067] Exemplarily, the compound represented by formula I used in Example 3 is 2-fluoro-3-(N-methylbenzamido)-N-[2-(trifluoromethyl)-4-(heptafluoroisopropyl)phenyl)benzamide, i.e., in formula I, Z is hydrogen, W.sub.1 and W.sub.2 are 0, R.sub.1 is methyl, Y is trifluoromethyl, R.sub.2 and R.sub.3 are fluoro.

[0068] Its preparation method is as follows:

[0069] 0.8 g (20 mmol) of powdered sodium hydroxide and 0.93 g (3.3 mmol) of iron (II) sulfate heptahydrate were stirred in an ice bath until the mixture color became black; as soon as the color became black, 5 g of N, N-dimethylformamide, 1 g (2.4 mmol) of 2-fluoro-3-(N-methylbenzamido)-N-[2-(trifluoromethyl)phenyl]benzamide and 1 g (3.4 mmol) of heptafluoroisopropyl iodide in 5 g of N, N-dimethylformamide were added. The resulting mixture was stirred at room temperature for 3 hours, filtered through celite and washed with 50 mL of ethyl acetate. The filtrate was extracted with 40 g of water; the organic phase was dried with magnesium sulfate, filtered and evaporated. The residue was purified by silica gel column chromatography to obtain 0.89 g of a white solid in yield 63%.

[0070] The compounds of formula I used in Examples 1-10 of the present disclosure can all be prepared by the above method. The corresponding raw materials are all commercially available. For brevity, they will not be described in details in the present disclosure.

[0071] In the following examples of the present disclosure, the purity of the brominated product was measured through external standard method by using high-performance organic phase chromatography (HPLC, LC-20AT, Shimadzu Corporation, Japan), and the yield is in mass.

Example 1

[0072] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00004##

[0073] Specifically, it includes the following steps:

[0074] To a 1000 mL three-necked flask, 64.2 g (0.1 mol) of 3-(4-fluoro-N-cyclopropylmethylbenzamido)-2-fluoro-N-[4-(perfluoropropane-2-yl)-2-(trifluoromethyl)phenyl]benzamide, 200 g of carbon tetrachloride, 24.3 g (0.12 mol) of 40% hydrobromic acid, 7.1 g (0.17 mol) of sodium hydroxide, and 30 g of water were added. 149.1 g of 10% sodium hypochlorite solution was added dropwise at 60° C. and the resultant mixture was stirred at 60° C. for 1.5 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 72.7 g of solid brominated product in purity 98.0% and yield 98.8%.

[0075] Characterization data: LC/MS [M+1]: m/z=722;

[0076] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.56 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.70-7.56 (m, 2H), 7.38-7.32 (m, 3H), 7.09 (br s, 2H), 3.69 (br s, 2H), 1.03-1.01 (m, 1H), 0.41-0.39 (m, 2H), 0.08-0.06 (m, 2H).

Example 2

[0077] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00005##

[0078] Specifically, it includes the following steps:

[0079] To a 1000 mL three-necked flask, 66.3 g (0.1 mol) of 3-[4-cyano-N-(1-cyclopropylethyl)benzamido]-2-fluoro-N-[4-(perfluoropropane-2-yl)-2-(trifluoromethyl)phenyl]benzamide, 130 g of diethyl ether, 11.3 g (0.11 mol) of sodium bromide, and 30 g of water were added. 111.7 g of 10% sodium hypochlorite solution was added dropwise at 35° C. and the resultant mixture was stirred at 35° C. for 2 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 71.9 g of solid brominated product in purity 97.1% and yield 94.1%.

[0080] Characterization data: LC/MS [M+1]: m/z=743;

[0081] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.51 (d, J=27.1 Hz, 1H), 8.54-8.35 (m, 1H), 7.95 (s, 1H), 7.86-7.51 (m, 4H), 7.51-7.20 (m, 3H), 4.03 (q, J=7.1 Hz, 1H), 1.30-1.19 (m, 3H), 0.93-0.23 (m, 5H).

Example 3

[0082] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00006##

[0083] Specifically, it includes the following steps:

[0084] To a 1000 mL three-necked flask, 58.4 g (0.1 mol) of 2-fluoro-3-(N-methylbenzamido)-N-[2-(trifluoromethyl)-4-(heptafluoroisopropyl) phenyl]benzamide, 60 g of dichloromethane, 15.5 g (0.15 mol) of sodium bromide, 4.2 g (0.1 mol) of sodium hydroxide, and 40 g of water were added. 21.3 g of 20% sodium chlorate solution was added dropwise at 40° C. and the resultant mixture was stirred at 40° C. for 2 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 67.1 g of solid brominated product in purity 98.3% and yield 99.5%.

[0085] Characterization data: LC/MS [M+1]: m/z=664;

[0086] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.51 (s, 1H), 8.36 (s, 1H), 7.94 (s, 1H), 7.61-7.55 (m, 2H), 7.34-7.22 (m, 6H), 3.17 (s, 3H).

Example 4

[0087] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00007##

[0088] Specifically, it includes the following steps:

[0089] To a 1000 mL three-necked flask, 62.5 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-(cyclopropylmethyl)-benzamido]-2-fluorobenzamide, 250 g of toluene, 15.5 g (0.15 mol) of sodium bromide, 4.2 g (0.1 mol) of sodium hydroxide, and 40 g of water were added. 121.5 g of 10% sodium hypochlorite solution was added dropwise at 90° C. and the resultant mixture was stirred at 90° C. for 1 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 69.4 g of solid brominated product in purity 92.1% and yield 90.9%.

[0090] Characterization data: LC/MS [M+1]: m/z=704;

[0091] .sup.1H-NMR (CDCl.sub.3-d, 400 MHz): δ 8.15 (d, J=2.1 Hz, 1H), 8.03 (br s, 2H), 7.92 (d, J=2.1 Hz, 1H), 7.55 (br s, 1H), 7.35-7.21 (m, 5H), 3.84 (d, J=93.6 Hz, 2H), 1.14 (br s, 1H), 0.59-0.40 (m, 2H), 0.20 (d, J=42.2 Hz, 2H).

Example 5

[0092] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00008##

[0093] Specifically, it includes the following steps:

[0094] To a 1000 mL three-necked flask, 65.9 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-(cyclopropylmethyl)-chlorobenzamido]-2-fluorobenzamide, 350 g of acetonitrile, 8.8 g (0.055 mol) of bromine, 4.2 g (0.1 mol) of sodium hydroxide, and 40 g of water were added. 110.8 g of 10% sodium hypochlorite solution was added dropwise at 35° C. and the resultant mixture was stirred at 35° C. for 1.5 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 69.8 g of solid brominated product in purity 93.0% and yield 87.9%.

[0095] Characterization data: LC/MS [M+1]: m/z=739;

[0096] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 8.18-7.84 (m, 4H), 7.53 (t, J=7.7 Hz, 1H), 7.37-7.07 (m, 4H), 3.81 (d, J=85.0 Hz, 2H), 1.11 (br s, 1H), 0.49 (br s, 2H), 0.17 (d, J=32.1 Hz, 2H).

Example 6

[0097] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00009##

[0098] Specifically, it includes the following steps:

[0099] To a 1000 mL three-necked flask, 70.3 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-(cyclopropylmethyl)-bromobenzamido]-2-fluorobenzamide, 400 g of 1,2-dichloroethane, 15.5 g (0.15 mol) of sodium bromide, 8.4 g (0.2 mol) of sodium hydroxide, and 40 g of water were added. 7.8 g (0.11 mol) of chlorine gas was charged at 60° C. and the resultant mixture was stirred at 60° C. for 1 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 78.0 g of solid brominated product in purity 92.8% and yield 92.6%.

[0100] Characterization data: LC/MS [M+1]: m/z=783;

[0101] .sup.1H-NMR (CDCl.sub.3-d, 400 MHz): δ 8.13 (d, J=2.0 Hz, 1H), 8.05 (t, J=7.6 Hz, 1H), 7.90 (s, 1H), 7.54 (t, J=7.8 Hz, 1H), 7.32 (d, J=9.7 Hz, 2H), 7.21 (t, J=6.7 Hz, 3H), 3.81 (d, J=87.9 Hz, 2H), 1.10 (br s, 1H), 0.50 (br s, 2H), 0.18 (d, J=35.8 Hz, 2H).

Example 7

[0102] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00010##

[0103] Specifically, it includes the following steps:

[0104] To a 1000 mL three-necked flask, 69.2 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-(cyclopropylmethyl)-4-trifluoromethylbenzamido]-2-fluorobenzamide, 450 g of chloroform, 17.9 g (0.15 mol) of potassium bromide, 3.3 g (0.05 mol) of potassium hydroxide, and 40 g of water were added. 73.5 g of 20% potassium chlorate solution was added dropwise at 60° C. and the resultant mixture was stirred at 60° C. for 1 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and then dried to obtain 78.8 g of solid brominated product in purity 91.8% and yield 93.8%.

[0105] Characterization data: LC/MS [M+1]: m/z=772;

[0106] .sup.1H-NMR (CDCl.sub.3-d, 400 MHz): δ 8.21-7.79 (m, 4H), 7.66-7.28 (m, 5H), 3.85 (d, J=104.7 Hz, 2H), 1.12 (br s, 1H), 0.51 (br s, 2H), 0.20 (d, J=42.7 Hz, 1H).

Example 8

[0107] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00011##

[0108] Specifically, it includes the following steps:

[0109] To a 1000 mL three-necked flask, 60.2 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-methyl-4-fluorobenzamido]-2-fluorobenzamide, 500 g of tert-butanol, 23.8 g (0.2 mol) of potassium bromide, 6.6 g (0.1 mol) of potassium hydroxide, and 50 g of water were added. 181.5 g of 10% potassium hypochlorite solution was added dropwise at 60° C. and the resultant mixture was stirred at 60° C. for 1.5 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 66.8 g of solid brominated product in purity 93.3% and yield 91.5%.

[0110] Characterization data: LC/MS [M+1]: m/z=682;

[0111] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.63 (s, 1H), 8.42 (s, 1H), 7.96 (s, 1H), 7.70-7.66 (m, 1H), 7.58 (br s, 1H), 7.39-7.30 (m, 3H), 7.08 (br s, 1H), 3.19 (s, 3H).

Example 9

[0112] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00012##

[0113] Specifically, it includes the following steps:

[0114] To a 1000 mL three-necked flask, 70.8 g (0.1 mol) of N-[2-trifluoromethyl-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-phenyl]-3-[N-(cyclopropylmethyl)-4-trifluoromethoxylbenzamido]-2-fluorobenzamide, 200 g of toluene, 13.1 g (0.11 mol) of potassium bromide, 0.66 g (0.01 mol) of potassium hydroxide, and 40 g of water were added. 147.5 g of 10% potassium hypochlorite solution was added dropwise at 90° C., and the resultant mixture was stirred at 90° C. for 1 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 75.6 g of solid brominated product in purity 92.6% and yield 88.9%.

[0115] Characterization data: LC/MS [M+1]: m/z=788;

[0116] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.46 (s, 1H), 8.34 (d, J=2.1 Hz, 1H), 7.87 (d, J=2.1 Hz, 1H), 7.65 (t, J=7.4 Hz, 1H), 7.54 (br s, 1H), 7.36 (br s, 2H), 7.29 (br s, 1H), 7.16 (br s, 2H), 3.62 (br s, 2H), 0.95 (br s, 1H), 0.34 (br s, 2H), 0.07 (s, 2H).

Example 10

[0117] A bromination method for m-diamide compounds is provided in this example, the scheme is as follows:

##STR00013##

[0118] Specifically, it includes the following steps:

[0119] To a 1000 mL three-necked flask, 70.3 g (0.1 mol) of 2-fluoro-3-[N-cyclopropylmethyl-4-(methanesulfonyl) benzamido]-N-[2-trifluoromethyl-4-(perfluoropropane-2-yl)phenyl]benzamide, 150 g of 1,2-dichloroethane, 28.4 g (0.14 mol) of 40% hydrobromic acid, 8.4 g (0.2 mol) of sodium hydroxide, and 40 g of water were added. 111.8 g of 10% sodium hypochlorite solution was added dropwise at 70° C. and the resultant mixture was stirred at 70° C. for 1.5 h. After the reaction was completed, the organic phase was separated, washed with 100 g of 10% sodium sulfite solution, evaporated and dried to obtain 75.8 g of solid brominated product in purity 93.0% and yield 90.3%.

[0120] Characterization data: LC/MS [M+1]: m/z=783;

[0121] .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): δ 10.59 (s, 1H), 8.42 (d, J=2.1 Hz, 1H), 7.95 (d, J=2.1 Hz, 1H), 7.80-7.67 (m, 3H), 7.62-7.52 (m, 3H), 7.35 (s, 1H), 3.75 (s, 2H), 3.16 (s, 3H), 1.03 (s, 1H), 0.53-0.30 (m, 2H), 0.13 (d, J=16.2 Hz, 2H).

[0122] Applicant has stated that although the bromination methods for m-diamide compounds have been described by the above examples in the present disclosure, the present disclosure is not limited thereto, that is to say, it is not meant that the present disclosure has to be implemented depending on the above process methods. It will be apparent to those skilled in the art that any improvements made to the present disclosure, equivalent replacements and addition of adjuvant ingredients to the raw materials of the products of the present disclosure, and selections of the specific implementations, etc., all fall within the protection scope and the disclosed scope of the present disclosure.