Phenamidine compound containing coumarin structure or salt, composition and application thereof

Abstract

The invention belongs to the field of pesticides, and particularly relates to a phenylamidine compound containing a coumarin structure or a pesticide acceptable salt, a composition and application of the phenylamidine compound, the compound has the structure shown in the formula (I), and all groups in the formula are defined in the specification. According to the compound disclosed by the invention, a substituted coumarin structure is introduced on the basis of an amidine structure, and the compound capable of being used as a bactericide is developed and obtained and has very outstanding biological activity and crop safety.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticides, and particularly relates to a benzene amidine compound containing a coumarin structure or a salt thereof, a composition, and use of the compound or the salt thereof as an agricultural fungicide. BACKGROUND

[0002] Natural product coumarin and its analogues are a kind of natural products with good fungicidal activity, and there have been reports on designing coumarin structure and methoxy acrylate fungicide structure together to design such a compound with high biological activity as coumoxystrobin. The outstanding fungicidal activity of aryl amidine compounds is reported in patents CN101636083A and CN116529235A. In order to design a novel compound with obvious fungicidal activity, natural product coumarin is introduced into amidine compounds, and the compounds exhibit outstanding fungicidal activity, and there is no literature report on such structure at present. SUMMARY

[0003] To solve the above problems in the prior art, the present application provides a benzene amidine compound containing a coumarin structure or a salt thereof, a composition, and use thereof. The applicant introduces natural product coumarin structure into amidine compounds, and designs a compound with novel structure and high fungicidal activity, which has very outstanding biological activity and improved crop safety.

[0004] The technical scheme adopted by the present application to achieve the above-mentioned purpose is as follows: a benzene amidine compound containing a coumarin structure or a salt thereof acceptable as a pesticide, which has the following structural formula:

[0005]

[0006] In formula (I),

[0007] R1 is selected from H, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;

[0008] R2 is selected from H, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio or halogenated C1-C6 alkylthio;

[0009] R3 is selected from H, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio or halogenated C1-C6 alkylthio;

[0010] R4 is selected from H, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio or halogenated C1-C6 alkylthio;

[0011] R5is selected from H, halogen, C1-C6alkyl, haloC1-C6alkyl, C1-C6alkoxy, haloC1-C6alkoxy, C1-C6alkylthio or haloC1-C6alkylthio;

[0012] R6is selected from H, C1-C6alkyl;

[0013] R7is selected from H, C1-C6alkyl;

[0014] R8is selected from H, C1-C6alkyl;

[0015] X represents C1-C6alkyl, halogen.

[0016] Further, in formula (I), X represents CH3, C2H5, F, Cl or Br;

[0017] Further, X represents CH3, Cl or Br;

[0018] Still further, X represents CH3or Br.

[0019] Further, in formula (I), R1is selected from H, halogen, C1-C4alkyl, haloC1-C4alkyl;

[0020] R2is selected from H, halogen, C1-C4alkyl, haloC1-C4alkyl, C1-C4alkoxy, haloC1-C4alkoxy, C1-C4alkylthio or haloC1-C4alkylthio;

[0021] R3is selected from H, halogen, C1-C4alkyl, haloC1-C4alkyl, C1-C4alkoxy, haloC1-C4alkoxy, C1-C4alkylthio or haloC1-C4alkylthio;

[0022] Further, R1is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl;

[0023] R2is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl;

[0024] R3is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, t-butyl, iso-butyl, cyclopentyl, cyclohexyl, trifluoromethyl, trifluoroethyl, trifluoromethoxy;

[0025] Still further, R1is selected from H, Cl, methyl, ethyl;

[0026] R2is selected from H, Cl, methyl, ethyl;

[0027] R3is selected from H, Br, methyl, ethyl.

[0028] Further, in formula (I), R4is selected from H, halogen, C1-C4alkyl, haloC1-C4alkyl, C1-C4alkoxy, haloC1-C4alkoxy, C1-C4alkylthio, or haloC1-C4alkylthio;

[0029] R5is selected from H, halogen, C1-C4alkyl, haloC1-C4alkyl, C1-C4alkoxy, haloC1-C4alkoxy, C1-C4alkylthio, or haloC1-C4alkylthio;

[0030] Further, R4is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, t-butyl, iso-butyl, cyclopentyl, cyclohexyl, trifluoromethyl, trifluoroethyl, trifluoromethoxy;

[0031] R5is selected from H, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, t-butyl, iso-butyl, cyclopentyl, cyclohexyl, trifluoromethyl, trifluoroethyl;

[0032] Further, R4is selected from H, methyl, ethyl, n-propyl, trifluoromethyl, trifluoroethyl;

[0033] R5is selected from H, methyl, ethyl, n-propyl, n-butyl.

[0034] Further, in formula (I), R6is selected from H, methyl, ethyl, n-propyl;

[0035] Further, R6is methyl.

[0036] Further, in formula (I), R7is selected from H, C1-C4alkyl;

[0037] R8is selected from H, C1-C4alkyl;

[0038] Further, R7is selected from methyl, ethyl, n-propyl;

[0039] R8is selected from methyl, ethyl, n-propyl;

[0040] Further, R7is selected from methyl, ethyl;

[0041] R8is selected from ethyl, n-propyl;

[0042] Further, R7is methyl;

[0043] R8is ethyl.

[0044] Further, formula (I) is any one of the following structures:

[0045]

[0046] In the above definitions of the structural formulae of the compounds, the professional terms used have the following meanings:

[0047] C1-C6 alkyl: straight chain or branched alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, and the like.

[0048] Halogen or halide: fluorine, chlorine, bromine, iodine.

[0049] Halogenated C1-C6 alkyl: straight chain or branched alkyl group having 1 to 6 carbon atoms, in which the hydrogen atoms of the alkyl group are partially or totally substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and the like.

[0050] C1-C4 alkoxy: straight chain or branched alkyl group having 1 to 6 carbon atoms, bonded to the structure via an oxygen atom, for example, methoxy, ethoxy, and the like.

[0051] Halogenated C1-C4 alkoxy: straight chain or branched alkyl group having 1 to 6 carbon atoms, in which the hydrogen atoms of the alkyl group are partially or totally substituted with halogen, bonded to the structure via an oxygen atom, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, and the like.

[0052] C1-C6 alkylthio: straight chain or branched alkyl group having 1 to 6 carbon atoms, bonded to the structure via a sulfur atom, for example, methylthio, isopropylthio, and the like.

[0053] Halogenated C1-C4 alkylthio: straight chain or branched alkyl group having 1 to 6 carbon atoms, in which the hydrogen atoms of the alkyl group are partially or totally substituted with halogen, bonded to the structure via a sulfur atom, for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, and the like.

[0054] The salt is a pesticide-acceptable salt, which can be a salt of the pyrazoline derivative of the present application and a chemically-acceptable acid, wherein the chemically-acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid, etc.) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, or benzoic acid, etc.); the pesticide-acceptable salt can also be a salt of the pyrazoline derivative of the present application and a chemically-acceptable base, wherein the chemically-acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine, etc.);

[0055] Further, the pesticide-acceptable salt can be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridine salt, or a choline salt.

[0056] The present application also provides the use of at least one of the coumarin-structured phenylamidine compounds or its agriculturally acceptable salt as described above or the fungicidal composition as described above in the control of plant diseases in agriculture and other fields. The compound of formula (I) can be obtained by reacting the intermediate compound of formula (II) with the intermediate compound (III) (in the following listed chemical formulae, the substituents and symbols have the same meaning as defined in the general formula I, unless otherwise defined):

[0057]

[0058] R1, R2, R3, R4, R5, R6, R7, R8, X are defined as described above, and are not repeated here. R9 is selected from C1-C6 alkyl.

[0059] Further, the molar ratio of the compound of formula II to the compound of formula III is 0.5 2:1, for example 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1.

[0060] Further, the solvent is selected from one or more of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane, ethyl acetate, 1,4-dioxane.

[0061] Further, the temperature of the reaction is greater than or equal to 0°C and less than or equal to the boiling point of the selected solvent.

[0062] Further, the time of the reaction is 0.5-24 hours.

[0063] Further, the compound of formula III is prepared by reacting the compound of formula IV with the compound of formula V in the presence or absence of a catalyst to obtain the compound of formula III, as shown in the following reaction formula:

[0064]

[0065] wherein R1, R2, R3, R4, R5, R6, R9, X are defined as described above, and are not repeated here.

[0066] Further, in the preparation of the compound of formula III, no catalyst can be added.

[0067] Further, in the preparation of the compound of formula III, the catalyst is selected from an organic acid or an inorganic acid.

[0068] Further, the organic acid is selected from any one of p-toluenesulfonic acid, benzenesulfonic acid, methylsulfonic acid, trifluoroacetic acid or acetic acid or a combination of two.

[0069] Further, the inorganic acid is selected from any one or a combination of two of zinc chloride, ferric chloride, ammonium chloride, hydrochloric acid, sulfuric acid, and hydrobromic acid.

[0070] Further, in the preparation of the compound of Formula III, the reaction can be carried out without a solvent.

[0071] Further, in the preparation of the compound of Formula III, the reaction can be carried out in a suitable solvent, which is any one or a combination of at least two of dichloromethane, 1,2-dichloroethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, n-butanol, water, N,N dimethylformamide, or dimethyl sulfoxide.

[0072] Further, in the preparation of the compound of Formula III, the reaction temperature is greater than or equal to 25°C and less than or equal to the boiling point of the reaction solvent.

[0073] Further, in the preparation of the compound of Formula III, the reaction time is 0.5-48 hours.

[0074] Further, the compound of Formula IV is prepared by reducing the compound of Formula VI in the presence of a reducing agent to obtain the compound of Formula IV, as shown in the following reaction formula

[0075]

[0076] wherein R1, R2, R3, R4, R5, and R6 are defined as described above, which will not be repeated here.

[0077] Further, in the preparation of the compound of Formula IV, the reducing agent is any one or a combination of at least two of hydrogen gas, hydrazine hydrate, iron powder, zinc powder, stannous chloride, or sodium dithionite.

[0078] Further, in the preparation of the compound of Formula IV, the reaction is carried out in the presence of a catalyst, which is preferably any one or a combination of at least two of palladium on carbon, palladium dioxide, Raney nickel, ferric chloride, or basic iron oxide.

[0079] Further, in the preparation of the compound of Formula IV, the reaction solvent is any one or a combination of at least two of dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N,N dimethylformamide, saturated aqueous ammonium chloride, acetic acid, hydrochloric acid, water, or dimethyl sulfoxide.

[0080] Further, in the preparation of the compound of formula IV, the reaction is carried out at a temperature of greater than or equal to 0°C, less than or equal to the boiling point of the reaction solvent, or at the boiling point of the solvent, i.e., under reflux.

[0081] Further, in the preparation of the compound of formula IV, the reaction is carried out for a period of 0.5 to 48 hours.

[0082] Further, the compound of formula VI is prepared by reacting the compound of formula VII with the compound of formula VIII to obtain the compound of formula VI, as shown in the following reaction formula:

[0083]

[0084] wherein L is fluorine or chlorine, and further wherein R1, R2, R3, R4, R5, R6, and X are as defined above, which are not repeated here.

[0085] Further, the molar ratio of the compound of formula VII to the compound of formula VIII is 1:1 to 3.

[0086] Further, in the preparation of the compound of formula VI, the reaction is carried out in the presence of a basic substance, which is an organic base and / or an inorganic base.

[0087] Further, the organic base is any one or a combination of at least two of triethylamine, N,N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, or potassium tert-butoxide.

[0088] Further, the inorganic base is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, or sodium hydride.

[0089] Further, in the preparation of the compound of formula VI, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, 1,2-dichloroethane, acetone, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide.

[0090] Further, in the preparation of the compound of formula VI, the reaction is carried out at a temperature of greater than or equal to 0°C, less than or equal to the boiling point of the reaction solvent, or at the boiling point of the solvent, i.e., under reflux.

[0091] Further, in the preparation of the compound of formula VI, the reaction is carried out for a period of 0.5 to 48 hours.

[0092] In the present application, some of the compounds of formula VII are commercially available reagents, and some of the compounds can be synthesized according to the literature.

[0093] The coumarin derivative has unexpectedly high fungicidal activity and good control effect on plant diseases.

[0094] In the present application, the plant diseases include Oomycetes, Ascomycetes, Basidiomycetes or Deuteromycetes diseases.

[0095] Further, the plant diseases include, but are not limited to, wheat rust, wheat powdery mildew, wheat scab, wheat root rot, wheat sharp eyespot, wheat brown foot rot, wheat leaf blight, cucumber downy mildew, cucumber powdery mildew, melon powdery mildew, bitter gourd powdery mildew, cucumber anthracnose, cucumber fusarium wilt, cucumber downy mildew, cucumber gray mold, grape downy mildew, tomato early blight, tomato late blight, tomato gray mold, rice eyespot, rice blast, watermelon gummy stem blight, peanut scab, peanut black spot, citrus scab, pepper root rot, cotton verticillium wilt, cotton fusarium wilt, rape black stem, rape sclerotinia rot, pear black spot, ginseng rust rot, corn rust, corn curved spore, corn large spot, mango stem rot, apple ring rot, apple spot and leaf fall, apple rot fungus rot, banana leaf spot, soybean rust or potato late blight.

[0096] Further, the plant diseases include cucumber anthracnose, wheat powdery mildew, wheat rust, tomato gray mold, rice blast, apple spot and leaf fall, wheat scab, rice eyespot, cucumber downy mildew.

[0097] In another aspect, the present application provides a fungicide composition, which comprises an active ingredient and a pesticide-acceptable carrier, the active ingredient being the coumarin derivative as described above.

[0098] The fungicide composition of the present application can be used in the fields of agriculture, forestry, health and the like.

[0099] Further, in the fungicide composition, the weight percentage of the active ingredient is 1-99%.

[0100] Further, the pesticide-acceptable carrier comprises a surfactant.

[0101] In the present application, the surfactant is an ionic surfactant or a non-ionic surfactant.

[0102] The surface active agent includes emulsifiers, dispersants or wetting agents. The emulsifiers can be polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amine and commercially available emulsifiers (Nonge 2201B, Nonge 0203B, Nonge 100#, Nonge 500#, Nonge 600#, Nonge 600 2#, Nonge 1601, Nonge 2201, Nonge NP 10, Nonge NP 15, Nonge 507#, Nonge OX 635, Nonge OX 622, Nonge OX 653, Nonge OX 667, Nonge 36#). The dispersants include sodium lignosulfonate, sodium dithionite, calcium lignosulfonate, methyl naphthalene sulfonate formaldehyde condensate and the like. The wetting agents include sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate and the like.

[0103] Further, the pharmaceutically acceptable carrier includes solid carriers and / or liquid carriers. Preferably, the solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; aluminum magnesium silicates such as kaolinite, kaolin, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. The liquid carriers include water and organic solvents, which can also be used as adjuvants or antifreezing additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, dichloromethane and the like; aliphatic hydrocarbons such as petroleum distillates, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butanol, ethylene glycol, glycerol and cyclohexanol and the like; and ethers and esters thereof; and also ketones such as acetone, cyclohexanone and dimethylformamide and N-methyl-pyrrolidone.

[0104] In the preparation of the fungicide composition, the active ingredient can be mixed with the liquid carrier and / or solid carrier, while adding the surface active agent (such as emulsifiers, dispersants, stabilizers, wetting agents), and other adjuvants (such as binders, antifoaming agents, oxidizing agents and the like) can also be added.

[0105] The plant subject to which the fungicide of the present application is applied is not particularly limited; for example, cereals (e.g., rice, barley, wheat, rye, oat, corn, sorghum, etc.), legumes (soybean, mung bean, kidney bean, pea, peanut, etc.), fruit trees / fruits (apple, citrus, pear, grape, peach, Japanese apricot, cherry, walnut, apricot, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, kale, lettuce, onion, green onion, bell pepper, etc.), root vegetables (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial crops (cotton, hemp, paper mulberry, jasmine, rapeseed, sugar beet, ryegrass, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), forage crops (orchard grass, sorghum, timothy, alfalfa, purple alfalfa, etc.), turf grasses (Korean mint, bentgrass, etc.), spice crops (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), and flowers (chrysanthemum, rose, orchid, etc.).

[0106] The present application provides a method for controlling plant diseases, which comprises applying an effective amount of the fungicide composition as described above to the plant diseases or the medium where the plant diseases grow.

[0107] Further, the effective amount is 10-1000 g per hectare.

[0108] The composition of the present application can be applied to the plant diseases or the medium where the plant diseases grow in the form of a formulation. When the compound of general formula I is dissolved or dispersed in a carrier or formulated into a formulation for use as a fungicide, it is more easily dispersed. For example, the chemical formulation can be formulated into various liquid formulations, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules, or capsules.

[0109] For some applications, for example, in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators, or fertilizers, etc. can be added to the fungicide composition of the present application, thereby producing additional advantages and effects.

[0110] Advantages

[0111] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0112] The coumarin derivative with the structure shown in formula I has a significant effect on preventing and treating diseases in agriculture and forestry, and has a good prevention and treatment effect on cucumber anthracnose, wheat powdery mildew, wheat leaf rust and tomato gray mold, and the prevention and treatment effect on cucumber anthracnose is ≥90% when the coumarin derivative concentration is 6.25 ppm; the prevention and treatment effect on rice sheath blight is 100% when the concentration is 100 mg / L; the prevention and treatment effect on wheat powdery mildew is ≥85% when the concentration is 25 ppm; and the preparation method is simple and efficient, easy to scale production, and has a wide application prospect. DETAILED DESCRIPTION

[0113] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0114] Through comprehensive consideration of the economy, diversity and biological activity of the synthesized compounds, some compounds are preferred and listed in the following table. The specific compound structure is shown in Table 1, and the specific compound physical property data is shown in Table 2. The compounds in Tables 1-2 are only for better illustration of the present application, and will not limit the present application, and those skilled in the art should not understand that the scope of the above-mentioned subject matter of the present application is limited to the following compounds.

[0115]

[0116] Table 1: Structure of compound of formula I

[0117]

[0118]

[0119] Table 2 1 H NMR data

[0120]

[0121]

[0122] Methods for preparing the compounds of the present application are illustrated in the Schemes and Examples below. Starting materials can be purchased or prepared by known methods in the literature or as described in detail. Those skilled in the art will appreciate that other synthetic routes can be used to synthesize the compounds of the present application. Although specific starting materials and conditions are depicted in the Schemes below, other suitable starting materials and conditions can be readily substituted. Modifications or variations of the methods disclosed herein can be made by those skilled in the art, such as variations in reaction conditions, including the use of different reagents, to adapt the methods to the preparation of compounds having various isomers, to the preparation of compounds having various substituents, and to the preparation of compounds having various substituent patterns. In addition, the methods described below can be further modified in accordance with the disclosure to prepare other compounds using conventional chemistry methods known to those skilled in the art. For example, appropriate groups can be protected during the course of a reaction.

[0123] Example 1

[0124] Synthesis of Compound 1:

[0125]

[0126] Step 1: Weigh 7-hydroxycoumarin 16.2 g (100 mmol, 1 eq) and 4-bromo-5-fluoro-2-nitrotoluene (23.4 g, 100 mmol, 1 eq) into a 500 ml reaction flask, dissolve in 200 ml DMF, weigh potassium carbonate 27.6 g (200 mmol, 2 eq) into the reaction solution, under magnetic stirring, the reaction system is heated to 80 °C in an oil bath for 2 h, after TLC monitoring the complete disappearance of the starting material, pour the reaction solution into 200 ml water under stirring, precipitate the solid, filter, wash the filter cake with 50 ml water, dry the filter cake, get yellow solid product 7-(2-bromo-5-methyl-4-nitrophenyloxy)-2H-pyran-2-one 33.8 g, yield 89.9%.

[0127] Step 2: Weigh 7-(2-bromo-5-methyl-4-nitrophenyloxy)-2H-pyran-2-one 30.08 g (80 mmol, 1 eq), iron powder 22.4 g (400 mmol, 5 eq), ammonium chloride 21.4 g (400 mmol, 5 eq) into a 500 ml reaction flask, add 200 ml ethanol, 50 ml water, heat the reaction system to 80 °C, keep the temperature for 4 h, TLC monitoring the complete reaction of the starting material, filter through a filter funnel with a layer of diatomite, filter the reaction solution while hot, wash the filter cake with 50 ml ethanol, distill the filtrate under reduced pressure, after distilling off the ethanol, extract with 200 ml ethyl acetate, wash the organic phase with water (100*2), saturated NaCl aqueous solution, dry the organic phase with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, get the product crude, purify by column chromatography, get yellow solid product 7-(4-amino-2-bromo-5-methylphenyloxy)-2H-pyran-2-one 19.3 g, yield 69.9%.

[0128] Step three: 7-(4-amino-2-bromo-5-methylphenyloxy)-2H-pyran-2-one 17.2 g (50 mmol) was dissolved in 50 ml of trioxane, the reaction was heated to 120 °C, and the reaction was kept for 2 h. TLC was used to monitor the complete reaction of the starting material. The reaction was distilled under reduced pressure. After the trioxane was distilled off, the reaction was cooled to room temperature and was ready for use.

[0129] Step four:

[0130] The reaction product was dissolved in 50 ml of dichloromethane. N-ethylmethylamine 4.4 g (75 mmol, 1.5 eq) was slowly added dropwise at room temperature. The reaction was stirred at room temperature overnight. The product was obtained by liquid chromatography-mass spectrometry. The product was obtained as a yellow solid by column chromatography. The yield of N'-[5-bromo-2-methyl-4-((2-oxo-2H-chromen-7-yl)oxy)phenyl]-N- methylmethanimidamide 16.5 g was 79.5% for two steps.

[0131] Example 2

[0132] Synthesis of compound 2:

[0133]

[0134] Step one: 3,3-diethoxypropionic acid ethyl ester 20 mmol (3.8 g, 1 eq) and 2- methylresorcinol 2.73 g (22 mmol, 1.1 eq) were weighed into a 100 ml reaction bottle. The reaction was heated to 120 °C and was kept for 15 min. The reaction was clear. The reaction was cooled to 0 °C. Concentrated sulfuric acid 44 mmol (2.4 ml, 2.2 eq) and trifluoroacetic acid 44 mmol (3.3 ml, 2.2 eq) were slowly added dropwise. After the addition was complete, the reaction was stirred at room temperature for 0.5 h. The reaction was precipitated as a solid. The reaction was slowly poured into ice water while stirring. The precipitated solid was filtered and dried to obtain a white solid, 7-hydroxy-8-methyl-2H-pyran-2-one 3.3 g, with a yield of 93.8%.

[0135] Step two: 7-hydroxy-8-methyl-2H-pyran-2-one 1.76 g (10 mmol, 1 eq) and 4-bromo-5- fluoro-2-nitrotoluene (2.34 g, 10 mmol, 1 eq) were weighed into a 50 ml reaction bottle. The reaction was dissolved in 20 ml of DMF. Potassium carbonate 2.76 g (20 mmol, 2 eq) was weighed into the reaction. The reaction was stirred under magnetic stirring. The reaction was heated to 80 °C in an oil bath for 2 h. After the starting material was completely consumed, as monitored by TLC, the reaction was poured into 20 ml of water while stirring. The solid was precipitated. The solid was filtered. The filter cake was washed with 5 ml of water. The filter cake was dried to obtain a yellow solid, 7-(2-bromo-5-methyl-4-nitrophenyloxy)-8-methyl-2H-pyran-2-one 3.12 g, with a yield of 80%.

[0136] Step three: Weigh 7-(2-bromo-5-methyl-4-nitro-phenoxy)-8-methyl-2H-pyran-2-one 3.12 g (8 mmol, 1 eq), iron powder 2.24 g (40 mmol, 5 eq), ammonium chloride 2.14 g (40 mmol, 5 eq) into a 50 ml flask, add ethanol 20 ml, water 5 ml, heat the reaction system to 80 °C, keep the temperature for 4 h, TLC monitor the complete reaction of raw materials, filter the reaction solution through a funnel filled with diatomite, filter the cake with 10 ml of ethanol, filter the filtrate under reduced pressure, after distilling off the ethanol, extract with 50 ml of ethyl acetate, wash the organic phase with water (20*2), saturated NaCl aqueous solution, dry the organic phase with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, obtain the crude product, purify by column chromatography, obtain yellow solid 7-(4-amino-2-bromo-5-methyl-phenoxy)-8-methyl-2H-pyran-2-one 2.02 g, yield 70.1%.

[0137] Step four: Weigh 7-(4-amino-2-bromo-5-methyl-phenoxy)-8-methyl-2H-pyran-2-one 1.8 g (5 mmol) into 10 ml of triethyl orthoformate, heat the reaction solution to 120 °C, keep the temperature for 2 h, TLC monitor the complete reaction of raw materials, distill the reaction solution under reduced pressure, after distilling off the triethyl orthoformate, cool to room temperature for standby.

[0138] Step five: Dissolve the above reaction product in 10 ml of dichloromethane, slowly add N-ethylmethylamine 0.44 g (7.5 mmol, 1.5 eq) dropwise at room temperature, stir the reaction solution at room temperature overnight, liquid chromatography-mass spectrometry detection obtains the product, distill the crude product under reduced pressure, purify by column chromatography to obtain 1.72 g of yellow solid product, two-step yield 80.2%.

[0139] Example 3

[0140] Synthesis of compound 3:

[0141]

[0142] Step one: 3,3-diethoxypropionic acid ethyl ester 20 mmol (3.8 g, 1 eq) and 4-methylresorcinol 2.73 g (22 mmol, 1.1 eq) were weighed into a 100 ml reaction flask, and the temperature was raised to 120 °C, and the reaction was maintained for 15 min. The reaction solution was clear, and the solution was cooled to 0 °C. A mixture of concentrated sulfuric acid 44 mmol (2.4 ml, 2.2 eq) and trifluoroacetic acid 44 mmol (3.3 ml, 2.2 eq) was added dropwise. After the addition was complete, the reaction was maintained at room temperature for 0.5 h. The reaction solution precipitated a solid, and the reaction solution was slowly poured into ice water while stirring. The precipitated solid was filtered, and the white solid 7-hydroxy-6-methyl-2H-pyran-2-one 3.2 g was obtained after drying, with a yield of 90.9%.

[0143] Step two: 7-hydroxy-6-methyl-2H-pyran-2-one 1.76 g (10 mmol, 1 eq) and 4-bromo-5-fluoro-2-nitrotoluene (2.34 g, 10 mmol, 1 eq) were weighed into a 50 ml reaction flask, and 20 ml of DMF was added to dissolve the solution. Potassium carbonate 2.76 g (20 mmol, 2 eq) was weighed into the reaction solution. The reaction system was heated to 80 °C in an oil bath for 2 h while stirring. After the starting material was completely consumed, as monitored by TLC, the reaction solution was poured into 20 ml of water while stirring, and a solid was precipitated. The solid was filtered, and the filter cake was washed with 5 ml of water. The filter cake was dried to obtain a yellow solid 7-(2-bromo-5-methyl-4-nitrophenoxy)-6-methyl-2H-pyran-2-one 3.3 g, with a yield of 84.6%.

[0144] Step three: 7-(2-bromo-5-methyl-4-nitrophenoxy)-6-methyl-2H-pyran-2-one 3.1 g (8 mmol, 1 eq), iron powder 2.24 g (40 mmol, 5 eq), and ammonium chloride 2.14 g (40 mmol, 5 eq) were weighed into a 50 ml reaction flask. Ethanol 20 ml and water 5 ml were added. The reaction system was heated to 80 °C, and the reaction was maintained for 4 h. After the starting material was completely consumed, as monitored by TLC, a layer of diatomite was placed on the filter funnel, and the reaction solution was filtered while hot. The filter cake was washed with 10 ml of ethanol. The filtrate was distilled under reduced pressure. After the ethanol was distilled off, the product was extracted with ethyl acetate. The organic phase was washed with water (20*2) and saturated NaCl aqueous solution. The organic phase was dried with anhydrous sodium sulfate. The filtrate was distilled under reduced pressure. The crude product was purified by column chromatography to obtain a yellow solid 7-(4-amino-2-bromo-5-methylphenoxy)-6-methyl-2H-pyran-2-one 2.15 g, with a yield of 74.6%.

[0145] Step four: 7-(4-amino-2-bromo-5-methylphenoxy)-6-methyl-2H-pyran-2-one 1.8 g (5 mmol) was dissolved in 10 ml of triethyl orthoformate, the reaction was heated to 120 °C, and the reaction was maintained for 2 h. TLC was used to monitor the complete reaction of the starting material. The reaction was distilled under reduced pressure. After the triethyl orthoformate was distilled off, the reaction was cooled to room temperature and was ready for use.

[0146] Step five: The reaction product obtained in the previous step was dissolved in 10 ml of dichloromethane. N-ethylmethylamine 0.44 g (7.5 mmol, 1.5 eq) was added slowly dropwise at room temperature. The reaction was stirred at room temperature overnight. The product was obtained by liquid chromatography-mass spectrometry. The crude product was obtained by distillation under reduced pressure. The product was purified by column chromatography to obtain 1.5 g of a yellow solid. The yield of the two steps was 69.9%.

[0147] Example 4

[0148] Synthesis of compound 7:

[0149]

[0150] Step one: 7-hydroxy-4-trifluoromethylcoumarin 2.3 g (10 mmol, 1 eq) and 4-bromo-5-fluoro-2-nitrotoluene (2.34 g, 10 mmol, 1 eq) were dissolved in 20 ml of DMF. Potassium carbonate 2.76 g (20 mmol, 2 eq) was weighed into the reaction. The reaction was stirred magnetically and was heated to 80 °C in an oil bath for 2 h. After the complete disappearance of the starting material was monitored by TLC, the reaction was poured into 20 ml of water while stirring. The solid was filtered, washed with 10 ml of water, and dried to obtain 7-(2-bromo-5-methyl-4-nitrophenyloxy)-4- (trifluoromethyl)-2H-chromen-2-one as a yellow solid. The yield was 85.6%.

[0151] Step two: 7-(2-bromo-5-methyl-4-nitrophenyloxy)-4-(trifluoromethyl)-2H-chromen-2-one 3.5 g (8 mmol, 1 eq), iron powder 2.24 g (40 mmol, 5 eq), and ammonium chloride 2.14 g (40 mmol, 5 eq) were weighed into a 500 ml reaction flask. Ethanol 20 ml and water 5 ml were added. The reaction was heated to 80 °C and was maintained for 4 h. The complete reaction of the starting material was monitored by TLC. The reaction was filtered through a funnel lined with diatomaceous earth while hot. The filter cake was washed with 10 ml of ethanol. The filtrate was distilled under reduced pressure. After the ethanol was distilled off, the product was extracted with 50 ml of ethyl acetate. The organic phase was washed with water (20*2), saturated NaCl aqueous solution, and dried over anhydrous sodium sulfate. The filtrate was distilled under reduced pressure to obtain the crude product. The product was purified by column chromatography to obtain 7-(4-amino-2-bromo-5-methylphenoxy)-4-(trifluoromethyl)-2H-pyran-2-one as a yellow solid. The yield was 75.5%.

[0152] Step 3: 7-(4-amino-2-bromo-5-methylphenoxy)-4-(trifluoromethyl)-2H- pyran-2-one 2.1 g (5 mmol) was dissolved in 10 ml of triethyl orthoformate, the reaction solution was heated to 120 °C, and the reaction was allowed to proceed for 2 h. TLC was used to monitor the complete reaction of the starting material. After the triethyl orthoformate was distilled off under reduced pressure, the reaction solution was cooled to room temperature and used as is.

[0153] Step 4: The reaction product from Step 3 was dissolved in 10 ml of dichloromethane, and N-ethylmethylamine 0.44 g (7.5 mmol, 1.5 eq) was added dropwise at room temperature. The reaction solution was stirred at room temperature overnight. LC-MS was used to monitor the production of the product. The product was obtained as a yellow solid after column chromatography. The yield of N'-{5-bromo-2-methyl-4-[2-oxo-4-(trifluoromethyl)-2H-chromen-7-yloxy]phenyl}-N- ethyl-N-methylformimidamide was 1.8 g, and the two-step yield was 74.5%.

[0154] Example 5

[0155] Preparation of Formulations:

[0156] 1. Soluble liquid: 10-50% of the compound of formula (I) and 5-20% of a wetting agent are dissolved in water and / or a water-soluble solvent to make up 100% to obtain the product.

[0157] 2. Emulsifiable concentrate: 10-70% of the compound of formula (I) and 5-10% of an emulsifying agent are dissolved in a water-insoluble organic solvent to make up 100% to obtain the product.

[0158] 3. Aqueous emulsion: 5-40% of the compound of formula (I) and 1-10% of an emulsifying agent are dissolved in 20-40% of a water-insoluble organic solvent. The mixture is introduced into water to make up 100% with the help of an emulsifying machine to form a homogeneous emulsion to obtain the product.

[0159] 4. Suspension concentrate: 10-60% of the compound of formula (I) is ground in a stirred ball mill with the addition of 2-10% of a dispersing agent and 1-5% of a wetting agent, 0.1-2% of a thickening agent, and water to make up 100% to obtain the product.

[0160] 5. Water dispersible granules: 20-80% of the compound of formula (I) is ground with the addition of a dispersing agent and a wetting agent to make up 100%, and it is made into water dispersible granules with the help of industrial production equipment to obtain the product.

[0161] The above are all weight percentages.

[0162] Example 6

[0163] Bioassay: Fusarium pseudograminearum

[0164] The test compound was dissolved in N,N-dimethylformamide and diluted with water containing 0.1% Tween-80 to the desired concentration. The mycelial growth rate method was used to determine the mycelial growth inhibition effect of the agent on Fusarium pseudograminearum. A 5mm diameter disc was punched from the edge of a colony that had been subcultured for 4 days, and the disc was inoculated onto a PDA plate containing the agent, with 3 replicates per treatment. All the culture dishes were incubated in a sterile incubator at 25°C. When the control mycelium grew to two-thirds the diameter of the culture dish, the diameters of the control and treated colonies were measured using the cross method, and the mycelial growth inhibition rate was calculated.

[0165] The effect classification of the specific agent treatment is as follows:

[0166] 50% or less is E;

[0167] 50%-70% is D;

[0168] 70%-80% is C;

[0169] 80%-90% is B;

[0170] 90%-100% is A.

[0171] The structure of the control compound is shown below:

[0172] CK1:

[0173] CK2:

[0174] The control effect is shown in Table 3.

[0175] Table 3

[0176]

[0177]

[0178] Example 7

[0179] Bioassay: Blumeria graminis

[0180] The test compound was dissolved in N, N-dimethylformamide and diluted with water containing 0.1% Tween-80 to the desired concentration. The screening was performed by using the method of pot bioassay. The test compound was sprayed on the wheat leaves at the stage of one leaf and one heart by using a spray tower, and 3 replicates were performed each time. After spraying, the wheat leaves were placed in the room for natural drying. 24 hours after the treatment of the test compound, the spores of wheat powdery mildew were evenly scattered on the treated wheat leaves. 10 days after the inoculation of the spores, the investigation was performed when the disease of the control was stable.

[0181] The classification of the control effect after the treatment of the specific test compound is as follows:

[0182] 50% or less is E;

[0183] 50%-70% is D;

[0184] 70%-80% is C;

[0185] 80%-90% is B;

[0186] 90%-100% is A.

[0187] The structures of the control compounds are shown as follows:

[0188] CK1: CK2: The control effect is shown in Table 4.

[0189] Table 4

[0190]

[0191]

[0192] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable the ordinary skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the essence of the present application should be covered within the protection scope of the present application.

Claims

1. A benzalkonium compound containing a coumarin structure, or a salt thereof acceptable as a pesticide, having the following structural formula: In formula (Ⅰ), R1 is selected from H, halogens, C1-C6 alkyl groups, and halo-C1-C6 alkyl groups; R2 is selected from H, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio. R3 is selected from H, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio. R4 is selected from H, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio. R5 is selected from H, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio. R6 is selected from H, C1-C6 alkyl groups; R7 is selected from H and C1-C6 alkyl groups; R8 is selected from H and C1-C6 alkyl groups; X represents C1-C6 alkyl or halogen.

2. The benzoamidine compound containing a coumarin structure as described in claim 1, or its pesticide-acceptable salt, is characterized in that... In formula (I), X represents CH3, C2H5, F, Cl, or Br; Preferably, X represents CH3, Cl, or Br; In a more preferred embodiment, X represents CH3 or Br.

3. The benzoamidine compound containing a coumarin structure as described in claim 2, or its pesticide-acceptable salt, is characterized in that... In formula (I), R1 is selected from H, halogen, C1-C4 alkyl, and halo-C1-C4 alkyl; R2 is selected from H, halogen, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio. R3 is selected from H, halogen, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio. Preferably, R1 is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, and n-butyl; R2 is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, and n-butyl; R3 is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, tert-butyl, isobutyl, cyclopentane, cyclohexyl, trifluoromethyl, trifluoroethyl, and trifluoromethoxy. In a further preferred embodiment, R1 is selected from H, Cl, methyl, and ethyl; R2 is selected from H, Cl, methyl, and ethyl; R3 is selected from H, Br, methyl, and ethyl.

4. The benzoamidine compound containing a coumarin structure as described in claim 1, or its pesticide-acceptable salt, is characterized in that... In formula (I), R4 is selected from H, halogen, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio. R5 is selected from H, halogen, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio. Preferably, R4 is selected from H, F, Cl, Br, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, tert-butyl, isobutyl, cyclopentane, cyclohexyl, trifluoromethyl, trifluoroethyl, and trifluoromethoxy. R5 is selected from H, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, tert-butyl, isobutyl, cyclopentane, cyclohexyl, trifluoromethyl, and trifluoroethyl. Preferably, R4 is selected from H, methyl, ethyl, n-propyl, trifluoromethyl, and trifluoroethyl; R5 is selected from H, methyl, ethyl, n-propyl, and n-butyl.

5. The benzoamidine compound containing a coumarin structure as described in claim 1, or its pesticide-acceptable salt, is characterized in that... In formula (I), R6 is selected from H, methyl, ethyl, and n-propyl; Preferably, R6 is methyl.

6. The benzoamidine compound containing a coumarin structure as described in claim 1, or its pesticide-acceptable salt, is characterized in that... In formula (I), R7 is selected from H and C1-C4 alkyl groups; R8 is selected from H and C1-C4 alkyl groups; Preferably, R7 is selected from methyl, ethyl, and n-propyl; R8 is selected from methyl, ethyl, and n-propyl; In a further preferred embodiment, R7 is selected from methyl or ethyl; R8 is selected from ethyl or n-propyl; In a further preferred configuration, R7 is methyl; R8 is an ethyl group.

7. The benzoamidine compound containing a coumarin structure as described in any one of claims 1-6, or its pesticide-acceptable salt, characterized in that, Equation (I) has any of the following structures:

8. A bactericidal composition, characterized in that, It includes at least one of the benzoamidine compounds containing a coumarin structure as described in any one of claims 1-7, or a salt thereof that is acceptable as a pesticide; preferably, it also includes a formulation carrier or formulation adjuvant.

9. A method for preventing and controlling plant diseases, characterized in that, This includes applying an effective amount of at least one of the benzoamidine compounds containing a coumarin structure as described in any one of claims 1-7, or a salt of the compound that is acceptable as a pesticide, or the fungicidal composition as described in claim 8, to plant diseases or their growing media.

10. The use of at least one of the benzoamidine compounds containing a coumarin structure as described in any one of claims 1-8, or a salt thereof acceptable as a pesticide, or the fungicidal composition as described in claim 8, in the control of plant diseases in agriculture and other fields.

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