A phenoxyacetyl pyrazole compound and its application

Abstract

The present invention discloses a phenoxyacetyl pyrazole compound and its application. The compound is shown as general formula (I): The definitions of each substituent in general formula I are shown in the specification. The compound of general formula I in the present invention has excellent herbicidal activity and can be used for controlling agricultural weeds.

Description

Technical Field

[0001] The present invention belongs to the field of herbicides. Specifically, it is a phenoxyacetylpyrazole compound and its application. Background Art

[0002] Due to the succession and change of weed populations, the emergence and rapid development of resistance to chemical pesticides, the continuous strengthening of people's awareness of ecological environment protection, the increasing understanding of chemical pesticide pollution, the impact of pesticides on non-target organisms, and the increasing attention to the fate of pesticides in the ecological environment. With the gradual reduction of the world's cultivated land area, the continuous growth of the population, and the increasing demand for food, people are forced to rapidly develop agricultural production technologies, improve and perfect farming systems, and continuously invent new and improved herbicidal compounds and compositions.

[0003] The phenoxyacetylpyrazole compound as shown in the present invention has not been disclosed. Summary of the Invention

[0004] The object of the present invention is to provide a phenoxyacetylpyrazole compound with a novel structure and safe for crops and its application.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] A phenoxyacetylpyrazole compound, characterized in that the compound is shown as general formula I:

[0007]

[0008] In the formula:

[0009] R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl or C3-C6 cycloalkyl C1-C3 alkyl;

[0010] R2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl;

[0011] R3 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkylcarbonyl, C1-C6 haloalkylcarbonyl, C1-C6 alkoxycarbonyloxy C1-C6 alkyl, C1-C6 alkylsulfonyl, benzoyl or benzenesulfonyl, and the hydrogen on the benzoyl or benzenesulfonyl may be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0012] R4 is selected from a benzene ring or a pyridine ring, and the hydrogen on the benzene ring or the pyridine ring may be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 halocycloalkyl C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy, C1-C6 haloalkoxy C1-C6 alkyl, C1-C6 haloalkoxy C1-C6 alkoxy, C3-C6 cycloalkyl C1-C3 alkoxy, C3-C6 cycloalkyloxy;

[0013] R5 is selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl;

[0014] R6 is selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl;

[0015] For the preferred compound, in general formula I:

[0016] R1 is selected from C1-C6 alkyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C3 alkyl;

[0017] R2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;

[0018] R3 is selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyloxy C1-C6 alkyl, C1-C6 alkylsulfonyl, benzoyl or benzenesulfonyl, and the hydrogen on the benzoyl or benzenesulfonyl can be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0019] R4 is selected from a benzene ring or a pyridine ring, and the hydrogen on the benzene ring or the pyridine ring can be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy or C3-C6 cycloalkyl C1-C3 alkoxy;

[0020] R5 is selected from hydrogen, C1-C6 alkyl or C3-C6 cycloalkyl;

[0021] R6 is selected from hydrogen, C1-C6 alkyl or C3-C6 cycloalkyl;

[0022] For the further preferably compound, in general formula I:

[0023] R1 is selected from C1-C6 alkyl or C3-C6 cycloalkyl C1-C3 alkyl;

[0024] R2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;

[0025] R3 is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyloxy C1-C6 alkyl or C1-C6 alkylsulfonyl;

[0026] R4 is selected from a benzene ring or a pyridine ring, and the hydrogen on the benzene ring or the pyridine ring can be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl or C1-C6 alkoxy;

[0027] R5 is selected from hydrogen or C1-C6 alkyl;

[0028] R6 is selected from hydrogen or C1-C6 alkyl;

[0029] For the still further preferably compound, in general formula I:

[0030] R1 is selected from C1-C3 alkyl;

[0031] R2 is selected from hydrogen, methyl, difluoromethyl, trifluoromethyl or cyclopropyl;

[0032] R3 is selected from hydrogen, C1-C6 alkyl, C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyloxy C1-C6 alkyl;

[0033] R4 is selected from a benzene ring or a pyridine ring, and the hydrogen on the benzene ring or pyridine ring may be substituted by one or more of the following substituents, and the substituents are selected from halogen, cyano, nitro, methyl or trifluoromethyl;

[0034] R5 is selected from hydrogen or methyl;

[0035] R6 is selected from hydrogen or methyl;

[0036] In the definition of the general formula I compound given above, the definitions of the terms used are as follows:

[0037] Alkyl refers to a straight-chain or branched-chain form, such as groups like methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. Cycloalkyl refers to a form including a cyclic chain, such as groups like cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Alkenyl refers to a straight-chain or branched-chain alkenyl, such as groups like 1-propenyl, 2-propenyl, butenyl, pentenyl and hexenyl, etc. Alkynyl refers to a straight-chain or branched-chain alkynyl, such as groups like 1-propynyl, 2-propynyl, butynyl, pentynyl and hexynyl, etc. Alkoxy refers to a group in which an alkyl is connected to an oxygen atom at the end, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, etc.

[0038] The general formula compound I of the present invention can be prepared by the following method:

[0039]

[0040] The target compound I is prepared by reacting the general formula II compound with the general formula III compound (commercially available) in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours. The suitable solvents are selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide, etc.

[0041] Adding a suitable base is beneficial to the reaction. The suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.

[0042] X is selected from halogen.

[0043] The preparation method of the compound of general formula II is as follows:

[0044]

[0045] In the above formula, general formula IV reacts in a suitable solvent under the action of a base and a catalyst at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours to obtain the compound of general formula II; the suitable solvent is selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide, etc. The suitable base is selected from sodium carbonate, potassium carbonate or triethylamine, etc. The suitable catalyst is selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, azide quaternary ammonium salt, metal cyanide or DMAP, etc.

[0046] The preparation method of the compound of general formula IV is as follows:

[0047]

[0048] The compound of general formula V and the compound of general formula VI (prepared by the method described in the commercially available or reference EP0240001) react in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 24 hours to obtain the compound of general formula IV. The suitable solvent is selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide, etc.

[0049] Adding a suitable base is beneficial to the reaction. The suitable base is selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.

[0050] The corresponding raw material carboxylic acid of the compound of general formula V (prepared by the method described in reference CN109867624A) reacts with an acyl halide reagent in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours to obtain the compound of general formula V. The acyl halide reagent is selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride, etc. The suitable solvent is selected from dichloromethane, 1,2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid acyl halide reagent, etc.

[0051] The compound of general formula I of the present invention has herbicidal activity and can be used for controlling various weeds in agriculture.

[0052] The present invention also includes a herbicidal composition comprising a compound of general formula I as an active ingredient. The weight percentage content of the active ingredient in the herbicidal composition is 1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.

[0053] The herbicidal composition of the present invention can be applied in various formulations. Usually, the compound of the present invention is dissolved or dispersed in a carrier to prepare a formulation for easier dispersion when used as a herbicide. For example, these chemical formulations can be made into wettable powders or emulsifiable concentrates, etc. Therefore, in these compositions, at least one liquid or solid carrier is added, and usually a suitable surfactant needs to be added.

[0054] The present invention also provides a method for controlling weeds, which includes applying a herbicidally effective amount of the herbicidal composition of the present invention to the surface of the weeds or the place where the weeds grow or their growth medium. A more suitable effective dose is 1 gram to 1000 grams per hectare, and the preferred effective dose is 10 grams to 500 grams per hectare. For certain applications, one or more other herbicides can be added to the herbicidal composition of the present invention, which can produce additional advantages and effects.

[0055] The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators, fertilizers, etc.

[0056] It should be clear that various transformations and modifications can be made within the scope defined by the claims of the present invention.

[0057] Advantages of the present invention:

[0058] Compared with known phenoxyacetylpyrazole compounds, the structure is novel, and the phenoxyacetylpyrazole compounds of the present invention have unexpectedly high herbicidal activity, and also have high herbicidal activity at lower doses. It is not only highly efficient, but also reduces the amount of pesticides used, lowers the cost, and reduces environmental pollution. Detailed implementation mode

[0059] The following examples and bioassay test results can be used to further illustrate the present invention, but do not mean to limit the present invention.

[0060] Synthesis examples

[0061] Example 1. Synthesis of Compound 65

[0062] (1) Synthesis of 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propanoic acid

[0063]

[0064] Add 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propionic acid propargyl ester (5 g, 14.3 mmol) and ethanol (50 mL) into a reaction flask, and dropwise add 10% aqueous sodium hydroxide solution (6 g, 15 mmol). React at room temperature for 2 hours, remove the solvent, add water (50 mL), and adjust the pH to 2-3 with 10% dilute hydrochloric acid under an ice bath. A solid precipitates out. Filter and dry to obtain 4.1 g of a white solid with a yield of 92%.

[0065]

[0066] (2) Synthesis of 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propanoyl chloride

[0067] Add 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propionic acid (4.1 g, 13.2 mmol) and toluene (30 mL) into a reaction flask, and slowly add thionyl chloride (4.7 g, 40 mmol). Heat the mixture under reflux for 4 hours, and evaporate the solvent under reduced pressure to obtain 4.3 g of a yellow oil, which is directly used for the next step.

[0068] (3) Synthesis of Compound 65

[0069]

[0070] Add 1,3-dimethyl-5-hydroxypyrazole (1.5 g, 13.2 mmol), dichloromethane (50 mL), and triethylamine (2 g, 20 mmol) into a reaction flask, and dropwise add the dichloromethane solution (20 mL) of 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propanoyl chloride obtained in the previous step. Stir at room temperature for 2 hours, add triethylamine (2 g, 20 mmol) and acetone cyanohydrin (1 mL), stir overnight at room temperature, add water (80 mL) and stir for half an hour. Adjust the pH of the aqueous phase to 2-3 with 10% dilute hydrochloric acid. A solid precipitates out. Filter and dry to obtain 2.9 g of a yellow solid with a purity of 92% and a yield of 54%.

[0071] Other compounds represented by General Formula I can be obtained by replacing the starting materials according to the method described above. Some compounds of General Formula I are shown in Table 1.

[0072]

[0073] Table 1 Structures and Physical Properties of Some Compounds of General Formula I

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] 1H NMR (600 MHz, CDCl3) data of some compounds are as follows: 1 1H NMR (600 MHz, CDCl3) data of some compounds are as follows:

[0094] Compound 1: 11.49 (brs, 1H), 7.44 (d, 1H), 7.32 (d, 1H), 6.97 (d, 2H), 6.84 - 6.89 (m, 3H), 5.08 (m, 1H), 3.59 (s, 3H), 2.45 (s, 3H), 1.66 (d, 3H).

[0095] Compound 65: 11.73 (brs, 1H), 7.85 (d, 1H), 7.48 (d, 1H), 7.04 (d, 2H), 6.88 (d, 2H), 5.07 (m, 1H), 3.59 (s, 3H), 2.45 (s, 3H), 1.66 (d, 3H).

[0096] Biological assay examples

[0097] Example 2, Determination of Herbicidal Activity

[0098] Seeds of gramineous weeds (Setaria glauca, Echinochloa crusgalli) were sown separately in paper cups with a diameter of 7 cm filled with nutrient soil. After sowing, the soil was covered with a 1-cm layer of soil, compacted, and watered. Then, they were cultured in a greenhouse according to the conventional method. After the weeds reached the 2-3 leaf stage, foliar spray treatment was carried out.

[0099] After the compounds recorded in the above table were dissolved in acetone as the original medicine, the required concentration of the test solution was prepared with 1‰ Tween 80 and standing tap water according to the test requirements. According to the test design dose, spray treatment was carried out on a crawler crop sprayer (designed and produced by Engineer Research Ltd., UK) (spray pressure 1.95 kg / cm 2 , liquid spraying amount 500 L / hm 2 , crawler speed 1.48 km / h). The test was set with 3 replicates. After the test materials were treated, they were placed in the operation hall. After the liquid medicine dried naturally in the shade, they were placed in the greenhouse and managed according to the conventional method. The reaction of the weeds to the medicine was observed and recorded. After treatment, the control effect of the test medicine on the weeds was visually inspected regularly, which was expressed by 0-100%, with "0" representing no control effect and "100%" representing complete killing.

[0100] The test results showed that the compounds of general formula I generally had a high control effect on gramineous weeds. Among some of the tested compounds, for example, Compound 65 had a good control effect on Setaria glauca or Echinochloa crusgalli at an application dose of 600 g a.i. / hm 2 .

[0101] According to the above test method, some compounds of general formula I were selected for the activity test of controlling Setaria glauca, and the results are shown in Table 2.

[0102] Table 2: Activity of Some Compounds of General Formula I against Setaria glauca (post-emergence, control effect %)

[0103]

[0104] According to the above test method, some compounds of general formula I were selected for the activity test of controlling Echinochloa crusgalli, and the results are shown in Table 3.

[0105] Table 3: Activity of Some Compounds of General Formula I against Echinochloa crusgalli (post-emergence, control effect %)

[0106]

[0107] In summary, the phenoxyacetylpyrazole compounds of the present invention have excellent herbicidal activity and also have high herbicidal activity at a low dose, and can be used for controlling various weeds in agriculture.

Claims

1. A phenoxyacetyl pyrazole compound, characterized in that: The compound is represented by general formula I Wherein: R1 is selected from CH3; R2 is selected from CH3; R3 is selected from hydrogen; R4 is selected from R5 is selected from CH3; R6 is selected from hydrogen.

2. Use of the compound of general formula I according to claim 1 for controlling weeds.

3. A herbicidal composition, characterized in that: The herbicidal composition comprises an active substance and an agriculturally acceptable carrier, the active component being the compound of general formula I according to claim 1, and the weight percentage content of the active component in the composition being 1-99%.

4. A method for controlling weeds with the weed control composition according to claim 3, characterized in that: Applying a herbicidally effective dose of the herbicidal composition according to claim 3 to weeds or the growth medium or site of the weeds.

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