Pyrazole amide compound containing uracil as well as preparation method and application of pyrazole amide compound

Abstract

The invention belongs to the technical field of pesticides, and discloses a pyrazole amide compound containing uracil as well as a preparation method and application of the pyrazole amide compound. The pyrazole amide compound containing the uracil or the salt of the pyrazole amide compound as shown in the formula (I) is prepared, the pyrazole amide compound containing the uracil or the salt of the pyrazole amide compound shows excellent pre-emergence and post-emergence weeding effects on various weeds such as barnyard grass, green bristlegrass and chickweed, and the compound D23 disclosed by the patent US5356863A only shows post-emergence weeding activity; the pre-emergence weeding activity is not shown. Besides, the pyrazole amide compound containing uracil or salt thereof provided by the invention has extremely high safety to wheat, rice and corn in pre-emergence soil spraying treatment, and also has relatively high safety to rice and corn in post-emergence stem and leaf spraying treatment; the composition can be processed into various dosage forms such as missible oil, a suspending agent, a dispersible oil suspending agent and the like which meet agricultural production requirements, and the diversity requirements of pesticide preparations are met.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a pyrazole amide compound containing uracil, a preparation method thereof, and an application thereof. Background Art

[0002] Phenyl heterocyclic compounds containing uracil usually have extremely high herbicidal activity. Benzobicyclon, fluthiacet-methyl, flupoxam, and pyrabenzoxim in commercial herbicides all belong to this type of compound. Although this type of compound has the advantages of high activity, low dosage, and safety to mammals, its safety to crops is still not satisfactory, which greatly limits the application scope of uracil herbicides. Developing uracil herbicides with good crop safety is still an urgent problem to be solved in production.

[0003] Patent US5356863A discloses a uracil compound shown in formula (a) and its herbicidal activity, and US20060089262A1 discloses a uracil compound shown in formula (b) and its herbicidal activity.

[0004]

[0005] During the applicant's detailed study on the structure-activity relationship of uracil compounds, it was found that pyrazole amide compounds containing uracil were not disclosed in the above patents, and this type of compound may have herbicidal potential but has not been studied. Summary of the Invention

[0006] In order to discover compounds with high herbicidal activity and good crop safety, the inventors carried out research on pyrazole amide compounds containing uracil and thus completed the present invention. Specifically, the present invention provides the following technical solutions.

[0007] In a first aspect, the present invention provides a pyrazole amide compound containing uracil, and the pyrazole amide compound containing uracil has a structure shown in formula (I):

[0008]

[0009] In formula (I):

[0010] R 1 is selected from one of hydrogen or halogen;

[0011] R 2 is selected from halogen;

[0012] R 3 is selected from one of C1-C4 alkyl;

[0013] R 4 is selected from one of hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl;

[0014] R 5 is selected from one of hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl.

[0015] Furthermore, in the above formula (I):

[0016] R 1 is selected from hydrogen or fluorine;

[0017] R 2 is chlorine;

[0018] R 3 is selected from methyl or ethyl;

[0019] R 4 is selected from one of C1-C4 alkyl or C1-C4 haloalkyl;

[0020] R 5 is selected from one of C1-C4 alkyl or C1-C4 haloalkyl.

[0021] Furthermore, the compounds represented by formula (I) include:

[0022] Compound NO.01: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide;

[0023] Compound NO.02: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;

[0024] Compound NO.03: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide;

[0025] Compound NO.04: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide;

[0026] Compound NO.05: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide;

[0027] Compound NO.06: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide;

[0028] Compound NO.07: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide;

[0029] Compound NO.08: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide;

[0030] Compound NO.09: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;

[0031] Compound NO.10: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide;

[0032] Compound NO.11: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide;

[0033] Compound NO.12: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide;

[0034] Compound NO.13: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide;

[0035] Compound NO.14: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide;

[0036] Compound NO.15: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide;

[0037] Compound NO.16: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;

[0038] Compound NO.17: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide;

[0039] Compound NO.18: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide;

[0040] Compound NO.19: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide;

[0041] Compound NO.20: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide;

[0042] Compound NO.21: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide.

[0043] In a second aspect, the present invention provides a method for preparing the above-mentioned pyrazolecarboxamide compounds containing uracil. Specifically, the compound shown in formula (I) can be prepared by an acylation reaction of compound III and II in a suitable solvent under basic conditions. The synthetic route is shown in Scheme 1. Scheme 1:

[0044]

[0045] Compound Ⅲ is prepared by the reduction reaction of Compound Ⅳ in a suitable solvent, and its synthetic route is shown in Scheme 2, Scheme 2:

[0046]

[0047] Compound Ⅳ is prepared by the nitration reaction of Compound Ⅴ, and its synthetic route is shown in Scheme 3, Scheme 3:

[0048]

[0049] Compound Ⅴ is prepared by the N-methylation reaction of Compound Ⅵ in a basic environment, and its synthetic route is shown in Scheme 4, Scheme 4:

[0050]

[0051] Compound Ⅵ is prepared by the cyclization reaction of Compound Ⅶ and ethyl (N,N-dimethylaminocarbonyl) amino-4,4,4-trifluorobut-2-enoate in acetic acid, and its synthetic route is shown in Scheme 5, Scheme 5:

[0052]

[0053] R 1 ,R 2 ,R 3 ,R 4 and R 5 are defined as described above.

[0054] Furthermore, in the above preparation method:

[0055] In Scheme 1, the suitable solvent is selected from: tetrahydrofuran, acetonitrile, toluene, xylene, N,N-dimethylformamide, dichloromethane, chloroform, pyridine; the reagent used to adjust the pH to basic conditions is selected from: triethylamine, pyridine, potassium carbonate, sodium hydroxide; the reaction temperature is between ice bath and the boiling point of the solvent, preferably 30-120 °C; the reaction time is 1-12 h, preferably 1-6 h;

[0056] In Scheme 2, the reducing reagent used in the reduction reaction is selected from one of the following: iron powder + hydrochloric acid, iron powder + acetic acid, iron powder + ammonium chloride, zinc powder + ammonium chloride, stannous chloride + hydrochloric acid, hydrogen + palladium on carbon; the solvent is selected from one of the following: methanol, ethanol, acetic acid; the temperature of the reduction reaction is 60 - 120 °C, preferably 60 - 80 °C; the time of the reduction reaction is 2 - 14 h, preferably completed within 4 h;

[0057] In Scheme 3, the nitrating reagent used in the nitration reaction is selected from one or more of the following: concentrated nitric acid, potassium nitrate, iron nitrate, ceric ammonium nitrate, preferably concentrated nitric acid; the solvent used in the nitration reaction is concentrated sulfuric acid; the temperature of the nitration reaction is -10 - 30 °C, preferably -10 - 0 °C; the dosage of the nitrating reagent, relative to the dosage of compound V, is 1 - 1.5 equivalents, preferably 1.05 - 1 equivalent; the time of the nitration reaction is 0.5 - 3 h, preferably completed within 40 min;

[0058] In Scheme 4, the N-methylation reagent used in the N-methylation reaction can be various N-methylation reagents well-known in the art, such as methyl iodide or dimethyl sulfate; the dosage of the N-methylation reagent, relative to the dosage of compound VI, is 1 - 4 equivalents, preferably 2 equivalents; the base used to adjust the pH to alkaline conditions is selected from one or more of the following: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, lithium carbonate, cesium carbonate, sodium hydride, preferably potassium carbonate; the dosage of the base, relative to the dosage of compound VI, is 1.0 - 1.5 equivalents, preferably 1.2 equivalents; the solvent used in the N-methylation reaction is selected from one of the following: N,N-dimethylformamide, tetrahydrofuran, acetone, acetonitrile; the reaction temperature is 0 - 120 °C, preferably the reflux temperature of the solvent; the reaction time is 5 - 48 h, preferably completed within 8 h;

[0059] In Scheme 5: the dosage of ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorocrotonate, relative to compound VII, is 1.0 - 1.5 equivalents, preferably 1.2 equivalents; the temperature of the cyclization reaction is 30 - 150 °C, preferably 80 - 120 °C; the time of the cyclization reaction is 5 - 48 h, preferably completed within 8 h.

[0060] According to the above preparation method, the substitution situations of each group of the synthesized pyrazolamide compounds containing uracil NO.01 - 21 are shown in Table 1.

[0061] Table 1. Structures of Compounds NO.01 - 21

[0062]

[0063]

[0064] Thirdly, the present invention provides the application of the above-mentioned pyrazole amide compounds containing uracil.

[0065] Furthermore, in the above application, the pyrazole amide compounds containing uracil are used for preparing herbicides.

[0066] Furthermore, in the above application, the active ingredient of the herbicide contains the pyrazole amide compounds containing uracil.

[0067] Compared with the prior art, the "pyrazole amide compounds containing uracil, their preparation methods and applications" of the present invention have the following beneficial effects:

[0068] The present invention firstly proposes a class of pyrazole amide compounds containing uracil as shown in formula (I) or their salts, and provides specific preparation methods.

[0069] The present invention proves that when the pyrazole amide compounds containing uracil or their salts are used as components of herbicides, they show excellent pre-emergence and post-emergence herbicidal effects on various weeds such as barnyard grass, green foxtail, chickweed, etc., while the compound D23 disclosed in Patent US5356863A only shows post-emergence herbicidal activity and does not show pre-emergence herbicidal activity.

[0070] More importantly, the compounds as shown in formula (I) disclosed in this patent have extremely high safety for wheat, rice and corn in pre-emergence soil spray treatment, and also have relatively high safety for rice and corn in post-emergence foliar spray treatment, while the compound D23 disclosed in Patent US5356863A causes serious phytotoxicity to wheat, corn and rice in post-emergence foliar spray treatment.

[0071] The pyrazole amide compounds containing uracil or their salts provided by the present invention can be processed into various dosage forms such as emulsifiable concentrates, suspensions, dispersible oil suspensions, etc. that meet the requirements of agricultural production, and can be adjusted according to different plots, crops, temperatures, etc. to meet the diversity requirements of pesticide formulations.

[0072] The pyrazole amide compounds containing uracil or their salts provided by the present invention have high safety for crops and can be used for weed control in field crops. In actual use, it can be considered to compound the pyrazole amide compounds containing uracil of the present invention with existing pesticide ingredients, or compound pyrazole amide compounds containing uracil with different chemical structures, in order to achieve the synergistic effect among various ingredients and achieve better weed control effects. Description of the Drawings

[0073] Figure 1 It is the chemical structural formula of the pyrazole amide compounds containing uracil. Detailed Embodiments

[0074] The present invention will be described below in conjunction with embodiments. The technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the scope of protection of the present invention.

[0075] Example 1

[0076] This example describes the preparation of a pyrazole amide compound containing uracil. Specifically, this example describes the preparation of N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., Compound NO.02).

[0077] 1) Preparation of 3-(4-chloro-2-fluorophenyl)-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound VI-01)

[0078] 1.45 g (10 mmol) of 2-fluoro-4-chloroaniline (Compound

[0079] VII-01), 20.0 mL of anhydrous acetic acid, and 3.05 g (12 mmol) of ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorobut-2-enoate were successively added to a 100 mL reaction flask, and the mixture was heated to 120 °C and refluxed with stirring for 4 h. The reaction mixture was cooled to room temperature, diluted with 100 mL of water, and then extracted with ethyl acetate (3 × 50 mL). The organic layer was washed with saturated sodium bicarbonate solution (3 × 50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain Compound VI-01, which was directly used in the next step without purification. The reaction process of this step is shown below.

[0080]

[0081] 2) Preparation of 3-(4-chloro-2-fluorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound V-01)

[0082] Dissolve 3.08 g (10 mmol) of Compound VI-01 in 20 mL of acetone, add 2.76 g (20 mmol) of anhydrous K2CO3 (base) and 1.70 g (12 mmol) of methyl iodide (N-methylation reagent), and reflux at 70 °C for 4.0 h. Cool the reaction solution, concentrate it under reduced pressure to remove acetone, add 20 mL of water, extract with ethyl acetate (3 × 20 mL), wash the organic layer with 1 M hydrochloric acid (3 × 20 mL), dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain 2.31 g of Compound V-01 with a yield of 71.5%. The reaction process of this step is shown below.

[0083]

[0084] 3) Preparation of 3-(4-chloro-2-fluoro-5-nitrophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound IV-01)

[0085] Add 3.22 g (10 mmol) of Compound V-01 and 5.0 mL of concentrated sulfuric acid (solvent) to a 100 mL three-necked flask in sequence, cool to -10 °C, and slowly add dropwise a mixture of 2.0 mL of concentrated sulfuric acid and 68% nitric acid with a volume ratio of = 1:1 (the nitrating reagent is 68% nitric acid, diluted with concentrated sulfuric acid). After stirring in an ice bath for 2.0 h, pour the reaction solution into ice water, continue to stir for 10 min, filter, and dry to obtain 3.27 g of Compound IV-01 with a yield of 89%. Without purification, directly proceed to the next reaction. The reaction process of this step is shown below.

[0086]

[0087] 4) Preparation of 3-(5-amino-4-chloro-2-fluorophenyl)-{1}-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound III-01)

[0088] Add 2.8 g (50 mmol) of iron powder to 15 mL of 5% aqueous acetic acid solution, heat to 80 °C, and then add 10 mL of a solution containing 3.67 g (10 mmol) of Compound IV-01, which is prepared from acetic acid and ethyl acetate with a volume ratio of = 1:1. Stir and react at 80 °C for 3 h, cool, add a mixture of 30 mL of water and ethyl acetate with a volume ratio of = 1:1 to the obtained mixture, and then filter. Extract the filtrate with ethyl acetate, wash the organic phase successively with water and saturated sodium bicarbonate solution, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain 2.52 g of Compound III-01 with a yield of 75%. The reaction process of this step is shown below.

[0089]

[0090] Preparation of N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., Compound No. 02)

[0091] Add 337 mg (1.0 mmol) of Compound III-01, 276 mg (2.0 mmol) of K2CO3 (base), and 10.0 mL of toluene (solvent) successively into a 100 mL reaction flask. After the sample is dissolved, cool it to 0 °C, and slowly add dropwise 2.0 mL of a toluene solution containing 233 mg (1.2 mmol) of 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride (Compound II-02). After the addition is complete, raise the temperature to 110 °C and reflux with stirring for 3.0 h. Cool the reaction mixture, adjust the pH to 2 - 3 with 1.0 M hydrochloric acid, and extract with ethyl acetate (3 × 20 mL). Wash the organic layer with saturated brine (3 × 20 mL), dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain 401 mg of Compound No. 02 with a yield of 81%. The reaction process of this step is shown as follows.

[0092]

[0093] Example 2

[0094] This example describes the preparation of a pyrazolecarboxamide compound containing uracil. Specifically, this example describes the preparation of N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (i.e., Compound No. 03).

[0095] Steps 1) - 4) are the same as in Example 1.

[0096] Add 337 mg (1.0 mmol) of Compound III-01, 276 mg (2.0 mmol) of K2CO3 (base), and 10.0 mL of toluene (solvent) successively into a 100 mL reaction flask. After the sample is dissolved, cool it to 0 °C, and slowly add dropwise 2.0 mL of a toluene solution containing 254 mg (1.2 mmol) of 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride (Compound II-03). After the addition is complete, raise the temperature to 110 °C and reflux with stirring for 3.0 h. Cool the reaction mixture, adjust the pH to 2 - 3 with 1.0 M hydrochloric acid, and extract with ethyl acetate (3 × 20 mL). Wash the organic layer with saturated brine (3 × 20 mL), dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain 430 mg of Compound No. 03 with a yield of 84%. The reaction process of this step is shown as follows.

[0097]

[0098] Referring to the preparation method of Example 2, the following compounds were prepared:

[0099] Using 1H-pyrazole-4-carbonyl chloride to replace 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide (i.e., Compound NO.01) was prepared;

[0100] Using 1,3-dimethyl-1H-pyrazole-4-carbonyl chloride to replace 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide (Compound NO.04) was prepared;

[0101] Using 3,5-dimethyl-1H-pyrazole-4-carbonyl chloride to replace 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide (Compound NO.05) was prepared;

[0102] Using 3-methyl-1H-pyrazole-4-carbonyl chloride to replace 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide (Compound NO.06) was prepared;

[0103] Using 3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride to replace 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (Compound NO.07) was prepared.

[0104] Example 3

[0105] This example describes the preparation of pyrazolamide compounds containing uracil. Specifically, this example describes the preparation of N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., Compound NO.09).

[0106] 1) Preparation of 3-(2,4-dichlorophenyl)-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound VI-02)

[0107] In a 100 mL reaction flask, 1.61 g (10 mmol) of 2,4-dichloroaniline (Compound VII-02), 20.0 mL of anhydrous acetic acid (solvent), and 3.05 g (12 mmol) of ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorobut-2-enoate were added in sequence. The mixture was heated to 120 °C and stirred under reflux for 4 h. The reaction mixture was cooled to room temperature, diluted with 100 mL of water, and then extracted with ethyl acetate (3 × 50 mL). The organic layer was washed with saturated sodium bicarbonate solution (3 × 50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain Compound VI-02, which was directly used in the next step without purification. The reaction process of this step is shown below.

[0108]

[0109] 2) Preparation of 3-(2,4-dichlorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound V-02)

[0110] Dissolve 3.24 g (10 mmol) of Compound VI-02 in 20 mL of acetone, add 2.76 g (20 mmol) of anhydrous K2CO3 (base) and 1.51 g (12 mmol) of dimethyl sulfate (N-methylating reagent), and reflux at 70 °C for 4.0 h. After cooling the reaction solution, acetone was removed by concentration under reduced pressure, 20 mL of water was added, and then extracted with ethyl acetate (3 × 20 mL). The organic layer was washed with 1 M hydrochloric acid (3 × 20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.87 g of Compound V-02 with a yield of 85.1%. The reaction process of this step is shown below.

[0111]

[0112] 3) Preparation of 3-(2,4-dichloro-5-nitrophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound IV-01)

[0113] In a 100 mL three-necked flask, 3.37 g (10 mmol) of compound V-02 and 5.0 mL of concentrated sulfuric acid (solvent) were added successively. After cooling to -10 °C, a mixture of 2.0 mL of concentrated sulfuric acid and 68% nitric acid with a volume ratio of 1:1 (the nitrating reagent is 68% nitric acid, diluted with concentrated sulfuric acid) was slowly added dropwise. After stirring in an ice bath for 2.0 h, the reaction solution was poured into ice water, and stirring was continued for 10 min. After filtration and drying, 3.25 g of compound IV-02 was obtained with a yield of 85%. Without purification, it was directly subjected to the next reaction. The reaction process of this step is shown below.

[0114]

[0115] 4) Preparation of 3-(5-amino-2,4-dichlorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., compound III-02)

[0116] In 15 mL of 5% aqueous acetic acid solution, 2.8 g (50 mmol) of iron powder was added. After heating to 80 °C, 10 mL of a solution containing 3.83 g (10 mmol) of compound IV-02 was added. The solution was prepared from acetic acid and ethyl acetate with a volume ratio of 1:1. The reaction was stirred at 80 °C for 3 h and then cooled. To the resulting mixture, a mixture of 30 mL of water and ethyl acetate with a volume ratio of 1:1 was added, and then filtration was carried out. The filtrate was extracted with ethyl acetate. The organic phase was washed successively with water and saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.40 g of compound III-02 with a yield of 68%. The reaction process of this step is shown below.

[0117]

[0118] 5) Preparation of N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., compound NO.09)

[0119] In a 100 mL reaction flask, 353 mg (1.0 mmol) of compound Ⅲ-02, 276 mg (2.0 mmol) of K2CO3 (base), and 10.0 mL of toluene (solvent) were successively added. After the sample was dissolved, it was cooled to 0 °C, and a toluene solution containing 233 mg (1.2 mmol) of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride (compound Ⅱ-02) was slowly added dropwise. After the addition was complete, the temperature was raised to 110 °C and refluxed with stirring for 3.0 h. The reaction mixture was cooled, and the pH was adjusted to 2 - 3 with 1.0 M hydrochloric acid, and then extracted with ethyl acetate (3 × 20 mL). The organic layer was washed with saturated brine (3 × 20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 435 mg of compound NO.09 with a yield of 85%. The reaction process of this step is shown below.

[0120]

[0121] Referring to the preparation method of Example 3, the following compounds were prepared:

[0122] Using 1H-pyrazole-4-carbonyl chloride to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride, N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide (compound NO.08) was prepared;

[0123] Using 1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride, N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (compound NO.10) was prepared;

[0124] Using 1,3-dimethyl-1H-pyrazole-4-carbonyl chloride to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride, N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide (compound NO.11) was prepared;

[0125] 3,5-Dimethyl-1H-pyrazole-4-carbonyl chloride was used to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide (Compound NO. 12);

[0126] 3-Methyl-1H-pyrazole-4-carbonyl chloride was used to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide (Compound NO. 13);

[0127] 3-(Trifluoromethyl)-1H-pyrazole-4-carbonyl chloride was used to replace 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (Compound NO. 14).

[0128] Example 4

[0129] This example describes the preparation of pyrazole carboxamide compounds containing uracil. Specifically, this example describes the preparation of N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., Compound NO. 16).

[0130] 1) Preparation of 3-(4-chlorophenyl)-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound VI-03)

[0131] 1.27 g (10 mmol) of 4-chloroaniline (Compound VII-03), 20.0 mL of anhydrous acetic acid (solvent), and 3.05 g (12 mmol) of ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorocrotonate were successively added to a 100 mL reaction flask, heated to 120 °C, and refluxed and stirred for 4 h. The reaction mixture was cooled to room temperature, diluted with 100 mL of water, and then extracted with ethyl acetate (3 × 50 mL). The organic layer was washed with saturated sodium bicarbonate solution (3 × 50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain Compound VI-03, which was directly used in the next step without purification. The reaction process of this step is shown as follows.

[0132]

[0133] 2) Preparation of 3-(4-chlorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound V-03)

[0134] Dissolve 2.9 g (10 mmol) of Compound VI-03 in 20 mL of acetone, add 2.76 g (20 mmol) of anhydrous K2CO3 (base) and 1.70 g (12 mmol) of methyl iodide (N-methylating reagent), and reflux at 70 °C for 4.0 h. Cool the reaction solution, concentrate it under reduced pressure to remove acetone, add 20 mL of water, extract with ethyl acetate (3 × 20 mL), wash the organic layer with 1 M hydrochloric acid (3 × 20 mL), dry over anhydrous sodium sulfate, concentrate under reduced pressure, and purify by silica gel column chromatography to obtain 2.25 g of Compound V-03 with a yield of 74.1%. The reaction process of this step is shown as follows.

[0135]

[0136] 3) Preparation of 3-(4-chloro-3-nitrophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound IV-03)

[0137] Add 3.04 g (10 mmol) of Compound V-03 and 5.0 mL of concentrated sulfuric acid (solvent) to a 100 mL three-necked flask in sequence, cool to -10 °C, slowly add dropwise a mixture of 2.0 mL of concentrated sulfuric acid and 68% nitric acid with a volume ratio of 1:1 (the nitrating reagent is 68% nitric acid, diluted with concentrated sulfuric acid). After stirring in an ice bath for 2.0 h, pour the reaction solution into ice water, continue to stir for 10 min, filter by suction and dry to obtain 2.72 g of Compound IV-03 with a yield of 78%. Without purification, directly proceed to the next step of the reaction. The reaction process of this step is shown as follows.

[0138]

[0139] 4) Preparation of 3-(3-amino-4-chlorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (i.e., Compound III-01)

[0140] Add 2.8 g (50 mmol) of iron powder to 15 mL of 5% aqueous acetic acid solution. After heating to 80 °C, add 10 mL of a solution containing 3.49 g (10 mmol) of Compound IV-03. The said solution is prepared from acetic acid and ethyl acetate with a volume ratio of 1:1. Stir and react at 80 °C for 3 h, then cool. Add a mixture of 30 mL of water and ethyl acetate with a volume ratio of 1:1 to the obtained mixture, and then filter. The filtrate is extracted with ethyl acetate. The organic phase is washed successively with water and saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 1.85 g of Compound III-03, with a yield of 59%. The reaction process of this step is shown as follows.

[0141]

[0142] 5) Preparation of N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (i.e., Compound NO.16)

[0143] Add 319 mg (1.0 mmol) of Compound III-03, 276 mg (2.0 mmol) of K2CO3 (acid-binding agent), and 10.0 mL of toluene (solvent) successively to a 100 mL reaction flask. After the sample is dissolved, cool to 0 °C, and slowly add dropwise 2.0 mL of a toluene solution containing 233 mg (1.2 mmol) of 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride (Compound II-02). After the addition is complete, raise the temperature to 110 °C and reflux and stir for 3.0 h. Cool the reaction mixture, adjust the pH to 2 - 3 with 1.0 M hydrochloric acid, and extract with ethyl acetate (3 × 20 mL). The organic layer is washed with saturated brine (3 × 20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 376 mg of Compound NO.16, with a yield of 79%. The reaction process of this step is shown as follows.

[0144]

[0145] Referring to the preparation method of Example 4, the following compounds were prepared:

[0146] Using 1H-pyrazole-4-carbonyl chloride to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride, N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide (Compound NO.15) was prepared;

[0147] 1-Methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbonyl chloride was used to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (Compound No. 17).

[0148] 1,3-Dimethyl-1H-pyrazole-4-carbonyl chloride was used to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide (Compound No. 18);

[0149] 3,5-Dimethyl-1H-pyrazole-4-carbonyl chloride was used to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide (Compound No. 19);

[0150] 3-Methyl-1H-pyrazole-4-carbonyl chloride was used to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide (Compound No. 20);

[0151] 3-(Trifluoromethyl)-1H-pyrazole-4-carbonyl chloride was used to replace 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride to prepare N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-lH-pyrazole-4-carboxamide (Compound No. 21).

[0152] Example 5

[0153] This example describes the structural characterization of Compounds No. 1 to No. 21.

[0154] The structural formulas and NMR data of Compounds No. 1 to No. 21 are shown in Table 2.

[0155] Table 2. Structural Formulas and NMR Data of Compounds No. 1 to No. 21

[0156]

[0157]

[0158]

[0159]

[0160] Example 6

[0161] This example describes the formulation types of the pyrazole amide compounds containing uracil for preparing herbicides.

[0162] 1. Emulsifiable concentrate

[0163] By mass percentage, it includes: 10% of the pyrazole amide compound containing uracil, 5% of Agrimer A1-101LC emulsifier, 37% of N-methyl-2-pyrrolidone, and soybean oil to make up to 100%. Mix the above components well in a stirring kettle to obtain an emulsifiable concentrate product with an active ingredient content of 10%.

[0164] 2. Suspension concentrate

[0165] By mass percentage, it includes: 15% of the pyrazole amide compound containing uracil, 3% of ethylene glycol, 5% of nonylphenol polyoxyethylene ether, 10% of sodium lignosulfonate, 1% of sodium carboxymethyl cellulose, 1% of magnesium aluminum silicate, 0.8% of 75% silicone oil emulsion, and water to make up to 100%. Grind the above components well with a sand mill to obtain a suspension concentrate with an active ingredient content of 15%.

[0166] 3. Oil-dispersible suspension concentrate

[0167] By mass percentage, it includes: 15% of the pyrazole amide compound containing uracil, 12% of Rhodia V0 / 02N, 3% of organobentonite, 1% of fumed silica, 2% of citric acid, and methyl oleate to make up to 100%. Grind the above components well with a sand mill to obtain an oil-dispersible suspension concentrate with an active ingredient content of 15%.

[0168] Example 7

[0169] This example describes the pre-emergence herbicidal activity of the pyrazole amide compounds containing uracil as described in formula (I).

[0170] Test weeds: Amaranthus retroflexus (AMA), Stellaria media (STE), Veronica polita (VER), Solanum nigrum (SOL), Abutilon theophrasti (ABU), Setaria viridis (SET), Echinochloa crus-galli (ECH), Digitaria sanguinalis (DIG).

[0171] Test method: Refer to NY / T 1155.3 - 2006 "Pesticide Bioassay Guidelines for Indoor Herbicides - Part 3: Activity Determination Test - Soil Spraying Method" for implementation. The control compounds are selected from compound D23 of patent US5356863A and commercially available flumioxazin. The structural formula of compound D23 is as follows. The test compounds are formulated into 10% emulsifiable concentrate according to the formula described in Example 6. Soil spraying treatment was carried out 1 day after sowing of weeds in each treatment group, and the control effect was investigated 21 days after treatment. The investigation results are shown in Table 3.

[0172]

[0173] According to the damage symptoms and severity of the test weeds, the herbicidal activity of the agents was evaluated according to the following grading criteria.

[0174] Grading criteria for control effect:

[0175] Grade 1: All dead;

[0176] Grade 2: Equivalent to 0 - 2.5% of the weeds in the blank control area;

[0177] Grade 3: Equivalent to 2.6 - 5% of the weeds in the blank control area;

[0178] Grade 4: Equivalent to 5.1 - 10% of the weeds in the blank control area;

[0179] Grade 5: Equivalent to 10.1 - 15% of the weeds in the blank control area;

[0180] Grade 6: Equivalent to 15.1 - 25% of the weeds in the blank control area;

[0181] Grade 7: Equivalent to 25.1 - 35% of the weeds in the blank control area;

[0182] Grade 8: Equivalent to 35.1 - 67.5% of the weeds in the blank control area;

[0183] Grade 9: Equivalent to 67.6 - 100% of the weeds in the blank control area.

[0184] Table 3. Pre-emergence herbicidal activity of pyrazole amide compounds containing uracil

[0185]

[0186] As can be seen from Table 3, at the application rate of 60 g / ha, some of the tested pyrazole amide compounds containing uracil showed good pre-emergence herbicidal effects on various weeds, while no obvious pre-emergence herbicidal activity was observed for the control compound D23.

[0187] Example 8

[0188] This example describes the post-emergence herbicidal activity of the pyrazole amide compounds containing uracil described by formula (I).

[0189] Tested weeds: Stellaria media (STE), Veronica polita (VER), Solanum nigrum (SOL), Abutilon theophrasti (ABU), Capsella bursa-pastoris (CAP), Echinochloa crus-galli (ECH), Digitaria sanguinalis (DIG).

[0190] Test method: Refer to NY / T 1155.4-2006 "Pesticide Bioassay Guidelines for Laboratory Tests Herbicides Part 4: Activity Determination Tests - Stem and Leaf Spraying Method" for implementation. The control compounds were selected from compound D23 of patent US5356863A and commercially available flumioxazin. The tested compounds were formulated into 10% emulsifiable concentrate according to the formula described in Example 6. Stem and leaf spraying was carried out at the 2-3 leaf stage for gramineous weeds and the 3-4 leaf stage for broad-leaved weeds, and the results were investigated 21 days after treatment. According to the damage symptoms and severity of the tested weeds, the herbicidal activity of the agents was evaluated according to the grading criteria given in Example 7. The investigation results are shown in Table 4.

[0191] Table 4. Post-emergence herbicidal activity of pyrazole amide compounds containing uracil

[0192]

[0193]

[0194] As can be seen from Table 4, at the application rate of 15 g / ha, some of the tested pyrazole amide compounds containing uracil showed good post-emergence herbicidal effects on Stellaria media, Veronica polita, Solanum nigrum, Abutilon theophrasti and Digitaria sanguinalis.

[0195] Example 9

[0196] This example describes the crop safety of the pyrazole amide compounds containing uracil as described in formula (I).

[0197] Test crops: Wheat (Triticum aestivum), rice (Oryza sativa), maize (Zea mays).

[0198] Test method: Refer to NY / T 1965.2 - 2010 "Pesticide - Evaluation Criteria for Crop Safety - Part 2: Test Methods for Determining the Safety of Photosynthetic Inhibiting Herbicides to Crops". The control compound is selected from compound D23 of patent US5356863A. The test compounds are formulated into 10% emulsifiable concentrates according to the formula described in Example 6, and two application rates of 60 g / ha and 90 g / ha are set for application treatment. According to the fresh weight growth inhibition rate of the test crops, the safety of the crops is evaluated, and the evaluation results are shown in Table 5.

[0199] Specific evaluation indicators:

[0200] Inhibition rate of 0: Safe, no phytotoxicity;

[0201] Inhibition rate of 1 - 10%: Slight phytotoxicity;

[0202] Inhibition rate of 11 - 30%: Moderate phytotoxicity;

[0203] Inhibition rate of 31 - 50%: Relatively severe phytotoxicity;

[0204] Inhibition rate > 50%: Severe phytotoxicity.

[0205] Table 5. Evaluation results of the crop safety of pyrazole amide compounds containing uracil

[0206] [[ID= 30]]

[0207] As can be seen from Table 5, when the application rates are 60 and 90 g / ha, pre - emergence soil treatment with compounds NO.02 and NO.03 has good safety for wheat, maize and rice, and post - emergence foliar spray treatment has a slight impact on the growth of rice and maize. Post - emergence foliar spray treatment with the control compound D23 has obvious phytotoxicity to wheat, maize and rice.

[0208] The above - described examples are only a part of the embodiments of the present invention, rather than all embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by relevant deductions and substitutions made by those of ordinary skill in the art under the conditions of the concept of the present invention without creative efforts fall within the scope of protection of the present invention.

Claims

1. A pyrazolamide compound containing uracil, characterized in that, The uracil-containing pyrazolamide compound has the structure shown in formula (I): In formula (I): R 1 selected from one of hydrogen or halogen; R 2 selected from halogens; R 3 selected from one of C1-C4 alkyls; R 4 selected from one of hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl; R 5 Selected from one of hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl.

2. The pyrazolamide compound containing uracil according to claim 1, wherein In formula (I): R 1 is selected from hydrogen or fluorine; R 2 is chlorine; R 3 selected from methyl or ethyl; R 4 selected from one of C1-C4 alkyl or C1-C4 haloalkyl; R 5 Selected from one of C1-C4 alkyl or C1-C4 haloalkyl.

3. The pyrazolamide compound containing uracil according to claim 1, wherein The compounds shown in formula (I) include: Compound NO.01: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide; Compound NO.02: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide; Compound NO.03: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide; Compound NO.04: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide; Compound NO.05: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide; Compound NO.06: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide; Compound NO.07: N-{(2-chloro-4-fluoro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide; Compound NO.08: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide; Compound NO.09: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide; Compound NO.10: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide; Compound No. 11: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide; Compound No. 12: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide; Compound No. 13: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide; Compound No. 14: N-{(2,4-dichloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide; Compound No. 15: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1H-pyrazole-4-carboxamide; Compound No. 16: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide; Compound No. 17: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide; Compound No. 18: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-1,3-dimethyl-1H-pyrazole-4-carboxamide; Compound No. 19: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3,5-dimethyl-1H-pyrazole-4-carboxamide; Compound No. 20: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-methyl-1H-pyrazole-4-carboxamide; Compound No. 21: N-{(2-chloro-5-[(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)]phenyl)}-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide.

4. The preparation method of the uracil-containing pyrazolamide compound according to claim 1, characterized in that, The compound shown in formula (I) can be prepared by the acylation reaction of compound III and II in a suitable solvent under basic conditions. The synthetic route is shown in Scheme 1. Scheme 1: The compound III is prepared by the reduction reaction of compound IV in a suitable solvent. The synthetic route is shown in Scheme 2. Scheme 2: The compound IV is prepared by the nitration reaction of compound V. The synthetic route is shown in Scheme 3. Scheme 3: The compound V is prepared by the N-methylation reaction of compound VI in a basic environment. The synthetic route is shown in Scheme 4. Scheme 4: The compound VI is prepared by the cyclization reaction of compound VII and ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorocrotonate in acetic acid. The synthetic route is shown in Scheme 5. Scheme 5: R 1 ,R 2 ,R 3 ,R 4 and R 5 are defined as described in claim 1.

5. The preparation method according to claim 4, wherein: In Scheme 1, the suitable solvent is selected from one of the following: tetrahydrofuran, acetonitrile, toluene, xylene, N,N-dimethylformamide, dichloromethane, chloroform, pyridine; the reagent for adjusting the pH to basic conditions is selected from one of the following: triethylamine, pyridine, potassium carbonate, sodium hydroxide; the reaction temperature is between ice bath temperature and the boiling point of the solvent; the reaction time is 1 to 12 h; In Scheme 2, the reducing reagent used in the reduction reaction is selected from one of the following: iron powder + hydrochloric acid, iron powder + acetic acid, iron powder + ammonium chloride, zinc powder + ammonium chloride, stannous chloride + hydrochloric acid, hydrogen + palladium on carbon; the solvent is selected from one of the following: methanol, ethanol, acetic acid; the reduction reaction temperature is 60 to 120 °C; the reduction reaction time is 2 to 14 h; In Scheme 3, the nitrating reagent used in the nitration reaction is selected from one or more of the following: concentrated nitric acid, potassium nitrate, iron nitrate, ceric ammonium nitrate; the solvent used in the nitration reaction is concentrated sulfuric acid; the nitration reaction temperature is -10 to 30 °C; the dosage of the nitrating reagent, relative to the dosage of compound V, is 1 to 1.5 equivalents; the nitration reaction time is 0.5 to 3 h; In Scheme 4, the N-methylation reagent used in the N-methylation reaction is selected from: methyl iodide or dimethyl sulfate; the dosage of the N-methylation reagent, relative to the dosage of compound VI, is 1 to 4 equivalents; the base for adjusting the pH to basic conditions is selected from one or more of the following: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, lithium carbonate, cesium carbonate, sodium hydride; the dosage of the base, relative to the dosage of compound VI, is 1.0 to 1.5 equivalents; the solvent used in the N-methylation reaction is selected from one of the following: N,N-dimethylformamide, tetrahydrofuran, acetone, acetonitrile; the reaction temperature is 0 to 120 °C; the reaction time is 5 to 48 h; In Scheme 5: the dosage of ethyl (N,N-dimethylaminocarbonyl)amino-4,4,4-trifluorocrotonate, relative to compound VII, is 1.0 to 1.5 equivalents; the cyclization reaction temperature is 30 to 150 °C; the cyclization reaction time is 5 to 48 h.

6. Use of the pyrazolamide compound containing uracil according to claim 1.

7. The application according to claim 6, characterized in that, The pyrazolamide compound containing uracil is used for preparing herbicides.

8. According to the use described in claim 7, the active ingredient of the herbicide contains the pyrazolamide compound containing uracil according to claim 1.

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