Benzoyl pyrazole derivative as well as preparation method and application thereof

Abstract

The invention relates to the technical field of compound synthesis and pesticides, in particular to benzoyl pyrazole derivatives and a preparation method and application thereof, and the benzoyl pyrazole derivatives are benzoyl pyrazole derivatives containing diarylether groups. The derivative has effective pre-emergence and post-emergence herbicidal activity, is good in crop selectivity and can be applied to herbicides; the derivative is simple in structure and preparation process, low in production cost and wide in application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of compound synthesis, and specifically relates to a benzoylpyrazole derivative and a preparation method and application thereof. Background Art

[0002] Weed damage is a long-standing problem in agricultural production around the world. Since weeds compete with crops for nutrients, water, light, space and other resources, they not only lead to reduced crop yields and reduced agricultural product quality, but also cause huge economic losses worldwide every year. The use of chemical herbicides is one of the effective means of controlling weeds. Therefore, the development of new herbicides with broad spectrum, high efficiency and low resistance risk is a necessary condition for achieving sustainable agricultural production and improving crop quality and yield.

[0003] In recent years, small molecules with benzoylpyrazole fragments have been widely used in the fields of medicine, pesticides, materials, etc. In the field of pesticides, benzoylpyrazole compounds show various biological activities, such as antibacterial, antifungal, insecticidal, weeding, etc. At present, benzoylpyrazole compounds have become one of the focuses of attention in the research of herbicide creation. Among them, the herbicides that have been developed and listed, such as pyraclostrobin, pyraclostrobin, pyrazol, benzylpyrazole, and benzylpyrazole all contain benzoylpyrazole structures. This type of herbicide has the advantages of unique mechanism of action, high-efficiency herbicidal activity, good safety and low resistance risk, and is an important herbicide choice in modern agriculture. Therefore, the design of synthetic herbicidal drug small molecules based on benzoylpyrazole units is very consistent with the current trend of new pesticide creation.

[0004] In the prior art, patent CN107674025A discloses a 4-benzoylpyrazole compound and its preparation method and application, which has efficient post-emergence herbicidal activity, but has problems such as crop safety to be improved and high production cost. Although the disclosed compound has certain similarities with the compound of the present invention, the compound represented by the general formula of the present invention is significantly different from the prior art, has a relatively novel structure, and has good herbicidal activity, and the raw materials are easily available, the overall yield is high, and has great application prospects. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a benzoylpyrazole derivative and a preparation method and application thereof.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] A benzoylpyrazole derivative was designed and synthesized, and the general structural formula of the benzoylpyrazole derivative is as follows:

[0008]

[0009] In formula (I):

[0010] X is selected from C or N, R 1 are selected from H, halogen, nitro, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy;

[0011] R 2 are selected from H, halogen, nitro, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy;

[0012] R 3 is a fluorine or chlorine atom; R 4 It is a chlorine atom and a methylsulfone group.

[0013] The benzoylpyrazole derivatives include the following compounds:

[0014] Compound A1: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate;

[0015] Compound A2: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoate;

[0016] Compound A3: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate;

[0017] Compound A4: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-nitro-5-(p-toluenesulfonyloxy)benzoate;

[0018] Compound A5: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chlorophenoxy)-2-nitrobenzoate;

[0019] Compound A6: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate;

[0020] Compound A7: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate;

[0021] Compound A8: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate;

[0022] Compound A9: 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate;

[0023] Compound A10: 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate;

[0024] Compound A11: (4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate;

[0025] Compound A12: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate;

[0026] Compound A13: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate;

[0027] Compound A14: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate;

[0028] Compound A15: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate;

[0029] Compound A16: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate;

[0030] Compound A17: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate;

[0031] Compound A18: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate.

[0032] The present invention also provides a method for preparing a benzoylpyrazole derivative, comprising the following steps:

[0033] (1) Preparation of intermediate 1:

[0034] The polysubstituted phenol / hydroxypyridine was dissolved in DMF, potassium carbonate (1.2 mmol) was added, and the substituted 5-chlorobenzoic acid methyl ester was slowly added under stirring at room temperature. The reaction system was reacted at 120° C. for 8 hours. After the reaction, it was extracted with water and ethyl acetate, concentrated under reduced pressure, dried and subjected to column chromatography to obtain intermediate 1.

[0035] (2) Preparation of intermediate 2:

[0036] Take intermediate 1, sodium hydroxide and 80% methanol solution, mix and stir, continue stirring at room temperature for 6 hours, after the reaction is complete, pour the reaction solution into ice water, then add dilute hydrochloric acid solution under stirring, when the pH of the mixed solution is adjusted to 2-3, solid precipitates; filter to obtain solid, and dry in vacuum to obtain intermediate 2;

[0037] (3) Preparation of intermediate 3:

[0038] Dissolve polysubstituted benzoic acid in dry dichloromethane, then add triethylamine and 2-chloro-1-methylpyridinium iodide (CMPI), continue stirring until the mixture is uniformly mixed, add 1,3-dimethyl-5-pyrazolone and triethylamine at room temperature, and allow the reaction system to react at room temperature for 8-10 hours. After the reaction is complete, wash with saturated sodium bicarbonate solution, dry with anhydrous sodium sulfate, and recrystallize to obtain 1,3-dimethyl-1H-pyrazol-5-yl polysubstituted benzoate, which is intermediate 3;

[0039] (4) Preparation of intermediate 4:

[0040] After the intermediate 3 and 1,4-dioxane are uniformly mixed, stirring is continued; then, trimethylsilyl cyanide and triethylamine are added to the reaction system in sequence at room temperature to react at room temperature. After the reaction is complete, 1,3-dimethyl-5-hydroxy-1H-pyrazole-4-yl polysubstituted benzoyl, namely, intermediate 4, is obtained through extraction, drying and column chromatography steps;

[0041] (5) Preparation of target compound benzoylpyrazole derivatives:

[0042] The intermediate 2 is dissolved in dry dichloromethane, and then triethylamine and 2-chloro-1-methylpyridinium iodide (CMPI) are added, and the mixture is stirred continuously to be evenly mixed, and then the intermediate 4 and triethylamine are added at room temperature, and the reaction system is reacted at room temperature for 8-10 hours. After the reaction is complete, the mixture is washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain a benzoylpyrazole derivative.

[0043] In step (1), the molar ratio of the polysubstituted phenol / hydroxypyridine, substituted 5-chlorobenzoic acid methyl ester and potassium carbonate is: polysubstituted phenol / hydroxypyridine: substituted 5-chlorobenzoic acid methyl ester: potassium carbonate = 1:1.2:1.5; the amount of DMF is controlled by adding 1 mL of DMF per millimole of polysubstituted phenol / hydroxypyridine.

[0044] In step (2), the molar ratio of the intermediate 1 to sodium hydroxide is: intermediate 1: sodium hydroxide = 1:2; the amount of the 80% methanol is controlled by adding 1 mL of 80% ethanol per millimole of the intermediate 1.

[0045] In step (3), the molar ratio of the polysubstituted benzoic acid, 1,3-dimethyl-5-pyrazolone, triethylamine and CMPI is as follows: polysubstituted benzoic acid: 1,3-dimethyl-5-pyrazolone: ​​triethylamine: CMPI = 1: 1.25: 2: 1.25; the amount of dichloromethane is controlled by adding 1 mL of dichloromethane per millimole of polysubstituted benzoic acid.

[0046] In step (4), the molar ratio of the intermediate 3, trimethylsilyl cyanide and triethylamine is: intermediate 3: trimethylsilyl cyanide: triethylamine = 1:1:2; the amount of 1,4-dioxane is controlled by adding 1 mL of 1,4-dioxane per millimole of intermediate 3.

[0047] In step (5), the molar ratio of the intermediate 2, intermediate 4, triethylamine and CMPI is as follows: intermediate 2: intermediate 4: triethylamine: CMPI = 1: 1.25: 2: 1.25; the amount of dichloromethane is controlled by adding 1 mL of dichloromethane per millimole of intermediate 2.

[0048] The preparation route of the benzoylpyrazole derivatives is any one of the following:

[0049]

[0050] Another object of the present invention is to use the benzoylpyrazole derivatives in the preparation of weed control and weed growth enzyme inhibitors.

[0051] Specifically, the weeds are goosegrass, barnyard grass, velvet, amaranth, purslane, foxtail grass, morning glory, zinnia, alfalfa, grain amaranth, crabgrass, clover, Sudan grass, arrowroot, Pea, bluegrass, ryegrass, licorice, dandelion, bitter tongue grass, Chinese milk vetch, hairy vetch, marigold, European rapeseed, shepherd's purse, Bidens pilosa, and Bermuda grass.

[0052] Beneficial effects:

[0053] The present invention is based on the structure of benzoylpyrazoles, and optimizes and derives to create benzoylpyrazole herbicide small molecules with relatively stable physicochemical properties and excellent drugability; such derivatives have significant post-emergence inhibitory effects on barnyard grass, goosegrass, foxtail grass, ramie, Amaranthus retroflexus and purslane.

[0054] The results of the systematic pre-emergence herbicidal activity test showed that at a concentration of 100 μg / mL, compounds A11, A12 and A14 had excellent pre-emergence inhibitory effects on barnyard grass and purslane, and the weeds basically did not grow, with the inhibition rate reaching more than 70%; at a dose of 10 μg / mL, compound A14 still had excellent pre-emergence inhibitory effects on the roots and stems of barnyard grass and purslane; in the post-emergence herbicidal activity test, at a dose of 300 g ai / ha, compounds A8, A11, A12 and A14 had excellent herbicidal activity against barnyard grass, goosegrass, foxtail grass, ramie, Amaranthus retroflexus and purslane, and the weeds basically withered and their growth was severely inhibited, with the inhibition rate reaching 80%; at a dose of 75 ... At a dosage of 1.5 g ai / ha, the inhibition rates of compounds A6, A8, A11, A12, A13 and A14 on velvetleaf, Amaranthus retroflexus and Portulaca oleracea all reached 100%; at a dosage of 37.5 g ai / ha, the herbicidal activity of compound A14 on barnyard grass and Setaria viridis was comparable to that of acifluorfen and benomyl.

[0055] The benzoylpyrazole derivatives designed and synthesized by the invention have simple structures, simple preparation processes, low production costs, high yields, and non-toxic and harmless preparation processes, and have great application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is a preparation route for the benzoylpyrazole derivatives in Examples 1 to 18. DETAILED DESCRIPTION

[0057] The specific embodiments of the present invention are further described in detail below, but the present invention is not limited to these embodiments, and any improvement or substitution based on the basic spirit of the present embodiment still falls within the scope of protection required by the claims of the present invention.

[0058] Example 1: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A1), comprising the following steps:

[0059] (1) Preparation of methyl 3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate:

[0060] Take 2-chloro-4-trifluoromethylphenol (10.00 g, 50.88 mmol), add 150 mL of DMF to dissolve, then add potassium carbonate (10.42 g, 61.05 mmol), slowly add 2-chlorobenzoic acid methyl ester (10.55 g, 76.32 mmol) dropwise at room temperature, and the reaction system reacts at 120° C. for 8 hours. After the reaction is completed, extract with water and ethyl acetate, concentrate under reduced pressure, and obtain 12.32 g of liquid 3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoic acid methyl ester intermediate after drying and column chromatography, with a yield of 73.23%.

[0061] (2) Preparation of 3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoic acid:

[0062] Take methyl 3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (12.32 g, 33.26 mmol), NaOH (2.98 g, 74.51 mmol) and MeOH (80%, 100 mL), mix and stir, and continue stirring at room temperature for 6 hours. After the reaction is complete, pour the reaction solution into ice water, and then add dilute hydrochloric acid solution under stirring. When the pH of the mixed solution is adjusted to 2-3, solid precipitates; after suction filtration and drying in vacuum, 8.35 g of 3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoic acid intermediate is obtained, with a yield of 70.78%.

[0063] (3) Preparation of 1,3-dimethyl-1H-pyrazol-5-yl-2,4-dichlorobenzoate:

[0064] 2,4-Dichlorobenzoic acid (13.23 g, 69.26 mmol) was dissolved in dry dichloromethane and then Et 3 N (7.01 g, 69.26 mmol) and CMPI (21.12 g, 86.58 mmol) were mixed for a period of time, and then 1,3-dimethyl-5-pyrazolone (9.71 g, 86.58 mmol) and Et 3N (7.01 g, 69.26 mmol), the reaction system was allowed to react at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate and recrystallized to obtain 15.21 g of 1,3-dimethyl-1H-pyrazol-5-yl-2,4-dichlorobenzoate intermediate with a yield of 77.02%;

[0065] (4) Preparation of (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone:

[0066] 1,3-dimethyl-1H-pyrazol-5-yl-2,4-dichlorobenzoate (15.21 g, 53.35 mmol) 220 mL was mixed with 1,4-dioxane and stirred for a while. Then, trimethylsilyl cyanide (5.29 g, 53.35 mmol) and Et 3 N (10.80 g, 106.69 mmol), reacted at room temperature for 18 h, and then extracted, dried, and column chromatographed to obtain 1.87 g of (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone intermediate, with a yield of 12.29%;

[0067] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A1):

[0068] 3-(2-Chloro-4-(trifluoromethyl)phenoxy)benzoic acid (350 mg, 1.11 mmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (111.85 mg, 1.11 mmol) and CMPI (352.98 mg, 1.38 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (393.93 mg, 1.38 mmol) and Et 3 N (111.85 mg, 1.11 mmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.41 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate, with a yield of 63.54%;

[0069] Example 2: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoate (i.e., Compound A2), comprising the following steps:

[0070] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0071] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoate (i.e., Compound A2):

[0072] 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoic acid (350 mg, 1.06 mmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (107.10 mg, 1.06 mmol) and CMPI (318.35 mg, 1.32 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (377.22 mg, 1.32 mmol) and Et 3 N (107.10 mg, 1.06 mmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.39 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoate, with a yield of 61.64%.

[0073] Example 3: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A3), comprising the following steps:

[0074] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0075] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A3):

[0076] 2-Chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoic acid (350 mg, 996.86 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (100.88 mg, 996.86 μmol) and CMPI (318.35 mg, 1.25 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (355.29 mg, 1.25 mmol) and Et 3 N (100.88 mg, 996.86 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.33 mg of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate, with a yield of 55.38%;

[0077] Example 4: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-nitro-5-(p-toluenesulfonyloxy)benzoate (i.e., Compound A4), comprising the following steps:

[0078] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0079] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-nitro-5-(p-toluenesulfonyloxy)benzoate (i.e., Compound A4):

[0080] 2-Nitro-5-(p-tolyloxy)benzoic acid (350 mg, 1.28 mmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (129.62 mg, 1.28 mmol) and CMPI (409.06 mg, 1.60 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (456.52 mg, 1.60 mmol) and Et 3N (129.62 mg, 1.28 mmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.30 mg of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-nitro-5-(p-toluenesulfonyloxy)benzoate, with a yield of 39.18%;

[0081] Example 5: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chlorophenoxy)-2-nitrobenzoate (i.e., Compound A5), comprising the following steps:

[0082] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0083] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chlorophenoxy)-2-nitrobenzoate (i.e., Compound A5):

[0084] 5-(4-chlorophenoxy)-2-nitrobenzoic acid (250 mg, 851.33 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (81.18 mg, 851.33 μmol) and CMPI (271.87 mg, 1.06 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (303.42 mg, 1.06 mmol) and Et 3 N (81.18 mg, 851.33 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.32 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chlorophenoxy)-2-nitrobenzoate, with a yield of 62.88%;

[0085] Example 6: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate (i.e., Compound A6), comprising the following steps:

[0086] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0087] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate (Compound A6):

[0088] 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid (250 mg, 761.96 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (77.11 mg, 761.96 μmol) and CMPI (271.57 mg, 952.45 μmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (243.33 mg, 952.45 μmol) and Et 3 N (77.11 mg, 761.96 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.22 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate, with a yield of 48.30%;

[0089] Example 7: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (i.e., Compound A7), comprising the following steps:

[0090] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0091] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (i.e., Compound A7):

[0092] 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoic acid (250 mg, 802.18 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (69.95 mg, 802.18 μmol) and CMPI (256.18 mg, 1.00 mmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (285.90 mg, 1.00 mmol) and Et 3N (69.95 mg, 802.18 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.24 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate, with a yield of 50.05%;

[0093] Example 8: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A8), comprising the following steps:

[0094] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0095] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A8):

[0096] 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic acid (250 mg, 691.26 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (86.15 mg, 691.26 μmol) and CMPI (220.76 mg, 864.08 μmol) were added and stirred continuously to mix well. After a period of time, (2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (246.37 mg, 864.08 μmol) and Et 3 N (86.15 mg, 691.26 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain 0.23 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate, with a yield of 55.66%;

[0097] Example 9: A method for preparing 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (i.e., Compound A9), comprising the following steps:

[0098] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0099] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-fluoro-4-chlorobenzoic acid;

[0100] (5) Preparation of 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (i.e., Compound A9):

[0101] 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid (250 mg, 761.96 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (77.11 mg, 761.96 μmol) and CMPI (271.87 mg, 952.45 μmol) were added and stirred continuously to mix well. After a period of time, (4-chloro-2-fluorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (303.42 mg, 952.45 μmol) and Et 3 N (77.11 mg, 761.96 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.20 g of 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate, with a yield of 42.87%;

[0102] Example 10: A method for preparing 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (i.e., Compound A10), comprising the following steps:

[0103] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0104] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-fluoro-4-chlorobenzoic acid;

[0105] (5) Preparation of 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (Compound A10):

[0106] 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoic acid (250 mg, 802.18 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et3 N (81.18 mg, 802.18 μmol) and CMPI (256.18 mg, 1.00 mmol) were added and stirred continuously to mix well. After a period of time, (4-chloro-2-fluorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (269.41 mg, 1.00 mmol) and Et 3 N (81.18 mg, 802.18 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.23 g of 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate, with a yield of 46.83%;

[0107] Example 11: A method for preparing (4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A11), comprising the following steps:

[0108] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0109] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-fluoro-4-chlorobenzoic acid;

[0110] (5) Preparation of (4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A11):

[0111] 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic acid (250 mg, 691.26 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (69.05 mg, 691.26 μmol) and CMPI (220.76 mg, 864.08 mmol) were added and stirred continuously to mix well. After a period of time, (4-chloro-2-fluorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (232.15 mg, 864.08 mmol) and Et 3N (69.05 mg, 691.26 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.22 g of (4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate, with a yield of 51.98%;

[0112] Example 12: A method for preparing 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate (i.e., Compound A12), comprising the following steps:

[0113] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0114] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-chloro-4-methylsulfonylbenzoic acid;

[0115] (5) Preparation of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate (Compound A12):

[0116] 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid (250 mg, 761.96 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (77.11 mg, 761.96 μmol) and CMPI (243.33 mg, 952.45 mmol) were added and stirred continuously to mix well. After a period of time, (2-chloro-4-(methylsulfonyl)phenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (313.13 mg, 952.45 mmol) and Et 3 N (77.11 mg, 761.96 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.32 g of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate, with a yield of 68.59%;

[0117] Example 13: A method for preparing 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (i.e., Compound A13), comprising the following steps:

[0118] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0119] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-chloro-4-methylsulfonylbenzoic acid;

[0120] (5) Preparation of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate (i.e., Compound A13):

[0121] 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoic acid (250 mg, 802.18 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (81.18 mg, 802.18 μmol) and CMPI (256.18 mg, 1.00 mmol) were added and stirred continuously to mix well. After a period of time, (2-chloro-4-(methylsulfonyl)phenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (329.66 mg, 1.00 mmol) and Et 3 N (81.18 mg, 802.18 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.35 g of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate, with a yield of 71.26%;

[0122] Example 14: A method for preparing 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A14), comprising the following steps:

[0123] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0124] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-chloro-4-methylsulfonylbenzoic acid;

[0125] (5) Preparation of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate (i.e., Compound A14):

[0126] 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic acid (250 mg, 691.26 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (69.95 mg, 691.26 μmol) and CMPI (220.76 mg, 864.08 μmol) were added and stirred continuously to mix well. After a period of time, ((2-chloro-4-(methylsulfonyl)phenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (284.08 mg, 864.08 μmol) and Et 3 N (69.95 mg, 691.26 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.28 g of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate, with a yield of 66.15%;

[0127] Example 15: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate (i.e., Compound A15), comprising the following steps:

[0128] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0129] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate (i.e., Compound A15):

[0130] 2-Chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoic acid (250 mg, 710.05 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3N (71.85 mg, 710.05 μmol) and CMPI (226.76 mg, 887.56 μmol) were added and stirred continuously to mix well. After a period of time, 2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (253.06 mg, 887.56 μmol) and Et 3 N (71.85 mg, 710.05 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.19 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate, with a yield of 43.70%;

[0131] Example 16: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate (i.e., Compound A16), comprising the following steps:

[0132] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0133] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate (i.e., Compound A16):

[0134] 3-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoic acid (250 mg, 787.03 μmol) was dissolved in 20 mL of dry dichloromethane, followed by addition of Et 3 N (79.64 mg, 787.03 μmol) and CMPI (280.50 mg, 983.79 μmol) were added and stirred continuously to mix well. After a period of time, 2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (251.34 mg, 983.79 μmol) and Et 3N (79.64 mg, 787.03 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.20 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate, with a yield of 41.50%;

[0135] Example 17: A method for preparing 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A17), comprising the following steps:

[0136] Steps (1)-(2): refer to steps (1)-(2) of Example 1;

[0137] Steps (3)-(4): refer to steps (3)-(4) of Example 1, except that 2,4-dichlorobenzoic acid is replaced with 2-chloro-4-methylsulfonylbenzoic acid;

[0138] (5) Preparation of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A17):

[0139] 3-(2-Chloro-4-(trifluoromethyl)phenoxy)benzoic acid (250 mg, 789.49 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (79.89 mg, 789.49 μmol) and CMPI (252.13 mg, 986.86 μmol) were added and stirred continuously to mix well. After a period of time, ((2-chloro-4-(methylsulfonyl)phenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (324.45 mg, 986.86 μmol) and Et 3 N (79.89 mg, 789.49 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.25 g of 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate, with a yield of 51.72%;

[0140] Example 18: A method for preparing 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A18), comprising the following steps:

[0141] Steps (1)-(4): refer to steps (1)-(4) of Example 1;

[0142] (5) Preparation of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate (i.e., Compound A18):

[0143] 3-(2-Chloro-4-(trifluoromethyl)phenoxy)benzoic acid (250 mg, 789.49 μmol) was dissolved in 20 mL of dry dichloromethane, followed by the addition of Et 3 N (79.89 mg, 789.49 μmol) and CMPI (252.13 mg, 986.86 μmol) were added and stirred continuously to mix well. After a period of time, 2,4-dichlorophenyl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone (281.38 mg, 986.86 μmol) and Et 3 N (79.89 mg, 789.49 μmol), and reacted at room temperature for 8-10 hours. After the reaction was complete, it was washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.22 g of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate, with a yield of 45.51%;

[0144] The structural formula and molecular formula of the target compound prepared in the above examples are shown in Table 1, and its physicochemical properties and spectral information are shown in Table 1;

[0145] Table 1 Molecular formula and structural formula of the target compounds obtained in Examples 1-18

[0146]

[0147]

[0148]

[0149] Table 2 Spectral data of target compounds obtained in Examples 1-18

[0150]

[0151]

[0152]

[0153]

[0154] Pre-emergence activity test of target compounds:

[0155] This test uses the culture dish method, with a variety of weeds as the test objects. The seeds are sterilized with 75% ethanol before the test and accelerated to germinate in a constant temperature incubator until they turn white. The germinated seeds are placed in a 12-well plate with 2 layers of filter paper on the plate, with 4-6 seeds in each well. 1mL of the target compound solution with a concentration of 100 and 10μg / mL is taken and immersed in the wells, respectively, with water as the blank control, and trifluorfenapyr and benzathine as the positive control. After the treatment, the culture dish is placed in an artificial climate incubator, with a relative humidity of 75%, and automatic circulation under 16h of light (28℃) and 8h of darkness (25℃). After 5 days of cultivation, the length of the stems and roots of the weed seeds is measured with a ruler and the inhibition rate is calculated. Each experiment has three parallel groups, and each experiment is repeated three times.

[0156] Table 4 Pre-emergence herbicidal activity of target compounds of Examples 1-18 at 100 and 10 μg / mL

[0157]

[0158] Post-emergence activity test of target compounds:

[0159] This test adopts the spray method, with various weeds as the test objects. The weed seeds are evenly spread in 8x 8cm plastic pots filled with two-thirds organic substrate soil and grown in a greenhouse. When both grass weeds and broadleaf weeds grow to the two- to three-leaf stage, they can be used for testing. Dissolve the compound in 100μLDMF and dilute it with 0.1% Tween-80 to a dose of 37.5–300g ai / ha. Trifluorfen and benzathine are used as positive controls and target compounds for drug spraying on all weeds. After the treated weeds are placed in the greenhouse for 15 days, their herbicidal activity is evaluated by visual inspection against the CK group, and repeated three times.

[0160] Table 4 Post-emergence herbicidal activity of target compounds of Examples 1-18

[0161]

[0162]

[0163] Crop safety assessment of target compounds:

[0164] This test adopts the spray method, with a variety of weeds as the test objects. The weed seeds are evenly spread in 8x 8cm plastic pots filled with two-thirds organic matrix soil and grown in a greenhouse. When both grass weeds and broadleaf weeds grow to the two- to three-leaf stage, they can be used for testing. Dissolve the compound in 100μLDMF and dilute it to a dose of 150ga.i. / ha with 0.1% Tween-80. All weeds are sprayed with trifluorfen and benzathine as positive controls and target compounds. After the treated weeds are placed in the greenhouse for 30 days, their herbicidal activity is evaluated by visual inspection against the CK group, and repeated three times.

[0165] Table 5 Crop safety of target compounds of Examples 8, 12, and 14 at a dosage of 150 g ai / ha

[0166]

[0167] As can be seen from Table 3, at a concentration of 100 μg / mL, compounds A10, A11, A12 and A14 had excellent pre-emergence inhibitory effects on barnyardgrass and purslane, and the weeds basically did not grow. The inhibition rates were all above 70%, which were better than the positive controls of benomyl and trifluorfen. At a dosage of 10 μg / mL, compound A14 still had excellent pre-emergence inhibitory effects on the roots and stems of barnyardgrass and purslane, which was better than the positive controls of benomyl and trifluorfen.

[0168] It can be seen from Table 4 that at a dosage of 300 g ai / ha, compounds A8, A11, A12 and A14 have excellent herbicidal activity against barnyard grass, goosegrass, foxtail grass, velvet, Amaranthus retroflexus and purslane, the weeds are basically withered, and their growth is severely inhibited, with inhibition rates reaching 80%, which is better than the positive controls of acifluorfen and benomyl; at a dosage of 75 g ai / ha, the inhibition rates of compounds A6, A8, A11, A12, A13 and A14 against Amaranthus retroflexus and purslane all reach 100%; at a dosage of 37.5 g ai. / ha, the herbicidal activity of compound A14 against barnyard grass and foxtail grass is comparable to that of acifluorfen and benomyl.

[0169] As can be seen from Table 5, compounds A8, A12 and A14 all showed better crop safety than acifluorfen and benomyl for crops such as rice, corn, wheat, peanuts, soybeans and cotton, among which compounds A12 and A14 showed crop safety of no more than 20% for their broad-leaf crops peanuts and cotton.

[0170] In summary, this series of benzoylpyrazole derivatives have excellent herbicidal inhibitory activity. Therefore, this series of compounds can be used as new pre-emergence and post-emergence herbicides, and new selective herbicides are further developed so that they can be applied to more farmlands.

[0171] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A benzoylpyrazole derivative, characterized in that: The general structural formula of the derivative is as follows: In formula (I): X is selected from C or N, R 1 are respectively selected from H, halogen, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy; R 2 are respectively selected from H, halogen, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy; R 3 is a fluorine or chlorine atom; R 4 It is a chlorine atom and a methyl sulfone group.

2. The benzoylpyrazole derivative according to claim 1, characterized in that: Includes the following compounds: Compound A1: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-3-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate; Compound A2: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-methylbenzoate; Compound A3: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate; Compound A4: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-nitro-5-(p-toluenesulfonyloxy)benzoate; Compound A5: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chlorophenoxy)-2-nitrobenzoate; Compound A6: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate; Compound A7: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate; Compound A8: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate; Compound A9: 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate; Compound A10: 4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate; Compound A11: (4-(4-chloro-2-fluorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate; Compound A12: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate; Compound A13: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl 5-(4-chloro-2-fluorophenoxy)-2-nitrobenzoate; Compound A14: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate; Compound A15: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-2-chloro-5-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate; Compound A16: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)benzoate; Compound A17: 4-(2-chloro-4-(methylsulfonyl)benzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate; Compound A18: 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl-4-(2-chloro-4-(trifluoromethyl)phenoxy)benzoate.

3. The method for preparing a benzoylpyrazole derivative according to any one of claims 1 to 2, characterized in that: The steps include: (1) Preparation of intermediate 1: The polysubstituted phenol / hydroxypyridine was dissolved in DMF, potassium carbonate was added, and the substituted 5-chlorobenzoic acid methyl ester was slowly added under stirring at room temperature. The reaction system was reacted at 120°C for 8 hours. After the reaction, it was extracted with water and ethyl acetate, concentrated under reduced pressure, dried and subjected to column chromatography to obtain intermediate 1. (2) Preparation of intermediate 2: Take intermediate 1, sodium hydroxide and 80% methanol solution, mix and stir, continue stirring at room temperature for 6 hours, after the reaction is complete, pour the reaction solution into ice water, then add dilute hydrochloric acid solution under stirring, when the pH of the mixed solution is adjusted to 2-3, solid precipitates; filter to obtain solid, and dry in vacuum to obtain intermediate 2; (3) Preparation of intermediate 3: Dissolve polysubstituted benzoic acid in dry dichloromethane, then add triethylamine and CMPI, continue stirring until the mixture is uniformly mixed, add 1,3-dimethyl-5-pyrazolone and triethylamine at room temperature, and allow the reaction system to react at room temperature for 8-10 hours. After the reaction is complete, wash with saturated sodium bicarbonate solution, dry with anhydrous sodium sulfate, and recrystallize to obtain 1,3-dimethyl-1H-pyrazol-5-yl polysubstituted benzoate, which is intermediate 3; (4) Preparation of intermediate 4: After the intermediate 3 and 1,4-dioxane are uniformly mixed, stirring is continued; then, trimethylsilyl cyanide and triethylamine are added to the reaction system in sequence at room temperature to react at room temperature. After the reaction is complete, 1,3-dimethyl-5-hydroxy-1H-pyrazole-4-yl polysubstituted benzoyl, namely, intermediate 4, is obtained through extraction, drying and column chromatography steps; (5) Preparation of target compound benzoylpyrazole derivatives: The intermediate 2 is dissolved in dry dichloromethane, and then triethylamine and CMPI are added. After continuous stirring to make the mixture evenly mixed, the intermediate 4 and triethylamine are added at room temperature, and the reaction system is allowed to react at room temperature for 8-10 hours. After the reaction is complete, the mixture is washed with a saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and purified by column chromatography to finally obtain a benzoylpyrazole derivative.

4. The method for preparing the benzoylpyrazole derivatives according to claim 3, characterized in that: In step (1), the molar ratio of the polysubstituted phenol / hydroxypyridine, substituted 5-chlorobenzoic acid methyl ester and potassium carbonate is as follows: polysubstituted phenol / hydroxypyridine: substituted 5-chlorobenzoic acid methyl ester: potassium carbonate = 1:1.2:1.5; the amount of DMF is controlled by adding 1 mL of DMF per millimole of polysubstituted phenol / hydroxypyridine; in step (2), the molar ratio of the intermediate 1 and sodium hydroxide is as follows: intermediate 1: sodium hydroxide = 1:2; the amount of 80% methanol is controlled by adding 1 mL of 80% ethanol per millimole of intermediate 1; in step (3), the molar ratio of the polysubstituted benzoic acid, 1,3-dimethyl-5-pyrazolone, triethylamine and CMPI is as follows: polysubstituted benzoic acid: 1,3-dimethyl-5-pyrazolone: Triethylamine:CMPI=1:1.25:2:1.25; the amount of dichloromethane is controlled by adding 1 mL of dichloromethane per mmol of polysubstituted benzoic acid; in step (4), the amounts of intermediate 3, trimethylsilyl cyanide and triethylamine are calculated in molar ratio as follows: intermediate 3:trimethylsilyl cyanide:triethylamine=1:1:2; the amount of 1,4-dioxane is controlled by adding 1 mL of 1,4-dioxane per mmol of intermediate 3.

5. The method for preparing the benzoylpyrazole derivatives according to claim 3, characterized in that: In step (5), the molar ratio of the intermediate 2, intermediate 4, triethylamine and CMPI is as follows: intermediate 2: intermediate 4: triethylamine: CMPI = 1: 1.25: 2: 1.25; the amount of dichloromethane is controlled by adding 1 mL of dichloromethane per millimole of intermediate 2.

6. Use of the benzoylpyrazole derivatives as claimed in claim 1 in the preparation of weed killer and weed growth enzyme inhibitors.

7. The use according to claim 6, characterized in that The weeds are goosegrass, barnyard grass, ramie, amaranth, purslane, foxtail grass, morning glory, zinnia, alfalfa, grain amaranth, crabgrass, clover, Sudan grass, arrowroot, etc. Pea, bluegrass, ryegrass, licorice, dandelion, bitter tongue grass, Chinese milk vetch, hairy vetch, marigold, European rapeseed, shepherd's purse, Bidens pilosa, and Bermuda grass.

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