A benzopentacyclic aromatic ester compound, and a preparation method and use thereof

Abstract

The application provides a benzopentacyclic aromatic ester compound and a preparation method and application thereof, in particular to a compound shown in formula (I) or a pharmaceutically acceptable salt thereof and an application thereof in preparing a fungicide in an agronomic field or a horticultural field, wherein the compound shown in formula (I) shows excellent biological activity on various pathogenic bacteria in the agronomic field or the horticultural field, and excellent effects can be obtained at a lower dose.

Description

Technical Field

[0001] This invention belongs to the field of agronomic or horticultural fungicide technology, specifically relating to an aromatic ester compound containing a benzo[5]-5-membered ring, its preparation method, and its uses. Background Technology

[0002] In agriculture, with the promotion of straw return to the field and no-till technology, the treatment of plant residues in production is insufficient. Many pathogens overwinter and oversummer through plants, resulting in a large number of plant pathogens remaining in the soil. Furthermore, as disease resistance becomes increasingly serious, farmers need to increase pesticide use, but this leads to increased pesticide residues, causing pollution and environmental burden. Therefore, there is a need to develop new pesticide varieties with high effectiveness.

[0003] Patent document WO2016039459 discloses the following aromatic ester compounds CK1 (compound number 82) and CK2 (compound number 291):

[0004]

[0005] Patent document JP2016056100 discloses the following aromatic ester compound CK3 (compound number 105):

[0006]

[0007] Patent document JP2016056117 discloses the following aromatic ester compound CK4 (compound number 49):

[0008]

[0009] However, the bioactivity of the aforementioned compounds still needs further improvement. The inventors conducted in-depth research to discover bactericides with superior performance. Summary of the Invention

[0010] To address the aforementioned technical problems, the present invention provides an aromatic ester compound containing a benzo5-membered ring, as shown in formula (I), or a pharmaceutically acceptable salt thereof.

[0011]

[0012] R1 is selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl, or NR. A R B ;

[0013] R A or R BThey may be the same or different, and are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl or COOC1-C6 alkyl;

[0014] R2 is selected from hydrogen or C1-C6 alkyl;

[0015] Alternatively, R1 and R2 can be connected together to form...

[0016] R3 is selected from hydrogen or C1-C6 alkyl;

[0017] R4 and R5 may be the same or different, and are independently selected from hydrogen, cyano, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy or NHR8;

[0018] R8 is selected from hydrogen or C1-C6 alkyl;

[0019] A is selected from the following groups without substituents: phenyl, pyridinyl, pyrazinyl, pyridinyl, pyrimidinyl, naphthyl, triazinyl, pyrroleyl, thienyl, thiazolyl, isothiazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl or benzo[3-C6]cycloalkyl;

[0020] W is selected from O and S(O). n CH2, C (=O) or NR9;

[0021] n is selected from 0, 1, or 2;

[0022] R9 is selected from hydrogen or C1-C6 alkyl;

[0023] X and Y may be the same or different, and are independently selected from CH2, O, S or Se; wherein X and Y are not both CH2, and when one of X or Y is selected from CH2, the other is selected from Se;

[0024] R6 and R7 may be the same or different, and are independently selected from hydrogen, halogen, hydroxyl, cyano, amino, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy; or R6 and R7 together with the carbon atom attached to them form C=O or C=S.

[0025] The condition is that the compound shown in Formula I is not a

[0026] According to an embodiment of the present invention, R1 is selected from hydrogen, C1-C4 alkyl, or NR A R B ;

[0027] R A Or R BThey may be the same or different, and are independently selected from hydrogen, C1-C4 alkyl, Or COOC1-C4 alkyl;

[0028] R2 is selected from hydrogen or C1-C4 alkyl;

[0029] Alternatively, R1 and R2 can be connected together to form...

[0030] R3 is selected from hydrogen or C1-C4 alkyl;

[0031] R4 and R5 may be the same or different, and are independently selected from hydrogen, cyano, hydroxyl, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy or NHR8;

[0032] R8 is selected from hydrogen or C1-C4 alkyl;

[0033] A is selected from the following groups without substitution: phenyl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, naphthyl, triazinyl, pyrroleyl, thiophenyl, thiazolyl, isothiazolyl, triazolyl, tetrazolyl, oxazolyl, or isoxazolyl;

[0034] W is selected from O, S, CH2, or NR9;

[0035] R9 is selected from hydrogen or C1-C4 alkyl;

[0036] X and Y may be the same or different, and are independently selected from O or S;

[0037] R6 and R7 may be the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, hydroxyl, cyano, amino, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, and C1-C4 haloalkoxy; or, R6 and R7 together with the carbon atom attached to them form a C=O or C=S group.

[0038] According to an embodiment of the present invention, R1 is selected from hydrogen, methyl, ethyl, Amino or NHCOOC(CH3)3;

[0039] According to embodiments of the present invention, R2 and R3 may be the same or different, and are independently selected from hydrogen, methyl or ethyl;

[0040] Alternatively, R1 and R2 can be connected together to form...

[0041] According to embodiments of the present invention, R4 and R5 may be the same or different, and are independently selected from hydrogen, methyl, methoxy or cyano;

[0042] According to embodiments of the present invention, A is selected from unsubstituted phenyl, pyridyl, pyrazinyl, pyridinyl, pyrimidinyl, naphthyl, thiophenyl, or thiazolyl groups; for example, it is selected from the following groups:

[0043] According to an embodiment of the present invention, W is selected from O or S;

[0044] According to an embodiment of the present invention, X and Y may be the same or different, and are independently selected from O or S;

[0045] According to embodiments of the present invention, R6 and R7 may be the same or different, and are independently selected from hydrogen, methyl, methoxy, fluorine, and chlorine; or, R6 and R7 together with the carbon atom attached to them form C=O or C=S.

[0046] According to an embodiment of the present invention, the compound of formula (I) is selected from the following compounds or pharmaceutically acceptable salts thereof.

[0047]

[0048] Table 1.

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] According to an embodiment of the present invention, when R6, R7 and the carbon atom attached to them form C=O, the compound of formula (I) is selected from the following compound (II) or a pharmaceutically acceptable salt thereof.

[0055]

[0056] Table 2.

[0057]

[0058]

[0059] According to an embodiment of the present invention, when R6, R7, together with the carbon atom they are attached to, form C=S, the compound of formula (I) is selected from the following compound (III) or a pharmaceutically acceptable salt thereof.

[0060]

[0061] Table 3.

[0062]

[0063] To reduce the length of the specification, exemplary groups and / or compounds of the present invention are described in the form of the above tables.

[0064] The present invention also provides a method for preparing the compound represented by formula (I) as described above or a pharmaceutically acceptable salt thereof, the method comprising: method (1)

[0065]

[0066] The compound shown in formula (V) reacts with the compound shown in formula (IV) to give the compound shown in formula (I);

[0067] Among them, R1, R2, R3, R4, R5, R6, R7, A, W, X, and Y have the definitions described above.

[0068] According to an embodiment of the present invention, the compound represented by formula (V) is prepared by the following method:

[0069]

[0070] 1) The compound shown in formula (VII) reacts with the compound shown in formula (VIII) to give the compound shown in formula (VI);

[0071] 2) The compound shown in formula (VI) undergoes a reduction reaction to give the compound shown in formula (V);

[0072] Among them, R4, R5, R6, R7, A, W, X, and Y have the definitions described above, and L1 is a leaving group, such as a halogen atom (exemplary examples are fluorine, chlorine, bromine, and iodine).

[0073] According to an embodiment of the present invention, when R1 in the compound represented by formula (I) or its pharmaceutically acceptable salt is NR A R B The compound can also be prepared according to the following method (2):

[0074] Method (2)

[0075]

[0076] The compound shown in formula (I-2) reacts with the compound shown in formula (IX) to give the compound shown in formula (I-1);

[0077] Among them, R A R BR1, R2, R3, R4, R5, R6, R7, A, W, X, Y have the definitions described above;

[0078] L2 is selected from leaving groups, such as halogen atoms (exemplary examples are fluorine, chlorine, bromine or iodine).

[0079] According to an embodiment of the present invention, in method (1), compound (IV) reacts with compound (V) in the presence of a condensing agent and a base to prepare compound (I). Preferably, the condensing agent is selected from N,N'-carbonyldiimidazole (CDI), N,N'-dicyclohexylcarbodiimide (DCC), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), etc. The base is selected from organic bases and inorganic bases; for example, it can be selected from one, two, or more of triethylamine, pyridine, DIEA, DMAP, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium hydride, etc. Preferably, the reaction is carried out in a solvent; the solvent can be selected from one, two, or more of toluene, acetonitrile, tetrahydrofuran, etc. Preferably, the reaction temperature is 25°C to 120°C.

[0080] According to an embodiment of the present invention, in step 1), the compound shown in (VII) reacts with the compound shown in formula (VIII) in the presence of a base to prepare compound (VI). Preferably, the base is selected from organic bases and inorganic bases; for example, it is selected from one, two, or more of triethylamine, pyridine, DIEA, DMAP, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium hydride, etc. Preferably, the reaction is carried out in a solvent; the solvent may be selected from one, two, or more of N,N-dimethylformamide, toluene, acetone, acetonitrile, tetrahydrofuran, etc. Preferably, the reaction temperature is 25°C to 150°C.

[0081] According to an embodiment of the present invention, in step 2), compound (VI) is used to prepare compound (V) in the presence of a reducing agent (e.g., sodium borohydride or lithium aluminum hydride). Preferably, the reaction is carried out in a solvent; the solvent may be selected from one, two, or more of benzene, toluene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methanol, ethanol, etc. Preferably, the reaction temperature is -30°C to 25°C.

[0082] According to an embodiment of the present invention, in method (2), compound (I-2) reacts with compound (IX) in the presence of a catalyst and a base to prepare compound (I-1). Preferably, the catalyst is selected from Pd2(dba)3, Pd(OAc)2, (dppf)PdCl2, etc. The base is selected from organic bases and inorganic bases; for example, it can be selected from one, two, or more of triethylamine, pyridine, DIEA, DMAP, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium hydride, etc. Preferably, the reaction is carried out in a solvent; the solvent can be selected from one, two, or more of toluene, xylene, dioxane, tert-amyl alcohol, etc. Preferably, the reaction temperature is 50°C to 130°C.

[0083] According to an embodiment of the present invention, the above reaction can be carried out with reference to the methods described in patent documents WO2014006945 or WO2017126197 or other similar methods.

[0084] The preparation method of the present invention can be adapted to the appropriate reaction conditions and the selection of raw materials in each case. For example, in a one-step reaction, only one substituent can be replaced with another substituent according to the present invention, or multiple substituents can be replaced with other substituents according to the present invention in the same reaction step.

[0085] If the compounds cannot be obtained via the above route, they can be prepared by deriving other compounds of formula (I) or by conventionally changing the synthetic route.

[0086] The reaction mixture is post-processed in a conventional manner, such as by mixing with water, phase separation, and purification of the crude product by chromatography, for example, on alumina or silica gel.

[0087] According to embodiments of the present invention, a pharmaceutically acceptable salt of the compound represented by formula (I) can be prepared by known methods. For example, a pharmaceutically acceptable acid addition salt of the compound represented by formula (I) can be obtained by suitable acid treatment. The preparation method is as follows: the compound represented by formula (I) is reacted with an acid (organic acid, inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, malic acid, or citric acid, etc.) to obtain a pharmaceutically acceptable salt of the compound represented by formula (I). Preferably, the reaction is carried out in a solvent; preferably, the solvent is selected from water, diethyl ether, toluene, etc.

[0088] The above preparation method can obtain a mixture of isomers of the compound shown in formula (I). If pure isomers are required, they can be separated by conventional methods such as crystallization or chromatography.

[0089] According to embodiments of the present invention, the compound represented by formula (I) further includes its isomers, racemates, deuterated compounds, and hydrates.

[0090] Unless otherwise specified, all of the above reactions can be conveniently carried out at atmospheric pressure or at the pressure of the reaction itself.

[0091] The present invention also provides the use of the compound represented by formula (I) above or a pharmaceutically acceptable salt thereof in the preparation of a fungicide for use in the agronomic field (agricultural fungicide) or the horticultural field (horticultural fungicide).

[0092] The present invention also provides the use of at least one of the compounds represented by formula (I) above or a pharmaceutically acceptable salt thereof as a fungicide, said fungicide being used in the agronomic field (agricultural fungicide) or the horticultural field (horticultural fungicide).

[0093] The present invention also provides a composition comprising at least one of the compounds represented by formula (I) above, or a pharmaceutically acceptable salt thereof, as an active ingredient.

[0094] The present invention also provides the use of the composition as a fungicide, which can be used in the fields of agronomy (agricultural fungicide) or horticulture (horticultural fungicide).

[0095] The present invention also provides a method for controlling pathogens (e.g., plant pathogens) or diseases in the fields of agronomy or horticulture, the method comprising applying an effective amount of the compound represented by formula (I) above or a pharmaceutically acceptable salt thereof or at least one of the compositions to the growth medium of the pathogen or disease (e.g., plant pathogens).

[0096] The examples of diseases mentioned below are only used to illustrate the present invention, and are by no means limiting the present invention.

[0097] The compound represented by formula (I) or its pharmaceutically acceptable salt or the composition thereof may be used to control the following diseases or their corresponding pathogens: oomycete diseases, such as downy mildew (downy mildew of cucumber, rapeseed, soybean, beet, sugarcane, tobacco, pea, loofah, winter melon, cantaloupe, cabbage, spinach, radish, grape, and onion), and white rust (white rust of rapeseed). Diseases include white rust of cabbage, damping-off (rapeseed damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cottony rot (pepper cottony rot, loofah cottony rot, winter melon cottony rot), blight (blight of broad bean, cucumber, pumpkin, winter melon, watermelon, cantaloupe, pepper, leek, garlic, cotton blight), and late blight (potato late blight, tomato late blight), etc.Deuteromycete diseases, such as wilt (sweet potato wilt, cotton wilt, sesame wilt, castor bean wilt, tomato wilt, bean wilt, cucumber wilt, loofah wilt, pumpkin wilt, winter melon wilt, watermelon wilt, cantaloupe wilt, pepper wilt, broad bean wilt, rapeseed wilt, soybean wilt), root rot (pepper root rot, eggplant root rot, bean root rot, cucumber root rot, bitter gourd root rot, cotton black root rot, broad bean root rot), damping-off (cotton seedling damping-off, sesame damping-off, pepper damping-off, cucumber damping-off, cabbage damping-off), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry anthracnose). Anthracnose (including diseases such as anthracnose of peppers, eggplants, beans, cucumbers, bitter melons, zucchini, winter melons, watermelons, cantaloupes, and lychees); Verticillium wilt (including cotton, sunflowers, tomatoes, peppers, and eggplants); Black spot (including zucchini, winter melons, and cantaloupes); Gray mold (including cotton boll mold, kenaf gray mold, tomato gray mold, pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, and kiwifruit gray mold); Brown spot (including cotton brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, winter melon brown spot, soybean brown spot, sunflower brown spot, and pea brown spot). Spot disease (broad bean brown spot), black spot (flax false black spot, rapeseed black spot, sesame black spot, sunflower black spot, castor bean black spot, tomato black spot, pepper black spot, eggplant black spot, green bean black spot, cucumber black spot, celery black spot, carrot black rot, carrot black spot, apple black spot, peanut black spot), leaf spot (tomato leaf spot, pepper leaf spot, celery leaf spot), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring spot (soybean ring spot, sesame ring spot, green bean ring spot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (tomato stem base rot, vegetable leaf blight). Bean stem base rot), and others (corn round spot, kenaf waist break, rice blast, chestnut black sheath disease, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon large leaf spot, peanut net spot, tea red leaf spot, pepper white star disease, winter melon leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute stem spot, soybean purple spot, sesame leaf spot, castor bean gray spot, tea brown leaf spot, eggplant brown round star disease, common bean red spot, bitter gourd white spot, watermelon spot, jute blight, sunflower root and stem rot, common bean anthracnose, soybean target spot, eggplant scab leaf spot, cucumber target spot, tomato leaf mold, eggplant leaf mold, broad bean red spot, etc.);Basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, wheat leaf rust, flower rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (corn silk smut, corn smut, sorghum silk smut, sorghum loose smut, sorghum sturdy smut, sorghum pillar smut, chestnut smut, sugarcane smut, bean rust), and others (such as wheat sheath blight, rice sheath blight, etc.); ascomycete diseases, such as powdery mildew (wheat powdery mildew, rapeseed powdery mildew, sesame powdery mildew, etc.). Powdery mildew in sunflowers, beets, eggplants, peas, loofahs, pumpkins, zucchini, winter melons, cantaloupes, grapes, and broad beans; sclerotinia stem rot in flax, rapeseed, soybeans, peanuts, tobacco, peppers, eggplants, beans, peas, cucumbers, bitter melons, winter melons, watermelons, and celery; and black spot in apples and pears.

[0098] According to embodiments of the present invention, the compound represented by formula (I) or its agrochemically acceptable salt or the composition thereof can be used to control the following pathogens or their corresponding diseases:

[0099] Gram-negative bacteria: *Erwinia* (causes pear fire blight, etc.); *Pectobacter* (causes soft rot in cruciferous vegetables, black shank in potatoes, etc.); *Digibium* (causes sweet potato stem rot, bacterial stem rot in corn, bacterial basal rot in rice, black shank in potatoes, rust water in pears, etc.); *Panthoxylum* (causes bacterial wilt in corn, panthoxylum leaf spot in corn, bacterial leaf blight in red beans, canker in stone fruits, etc.); *Pseudomonas* (causes canker in peach trees, bacterial canker in peas, etc.). Phytophthora blight, bacterial black spot of cruciferous plants, bacterial leaf spot of tomatoes, bacterial spot of tomatoes, bacterial black spot of rapeseed, bacterial angular leaf spot of sesame, bacterial angular leaf spot of cucumber, wildfire of tobacco, bacterial brown spot of corn, bacterial brown spot of corn, bacterial stem blight of broad beans, bacterial spot of soybeans, bacterial leaf spot of beets, bacterial pith necrosis of tomatoes, soft rot of ginseng (Pseudomonas aeruginosa, etc.); Ralstonia solanaceae (causing various bacterial wilts, etc.); Burkholderia spp. ( This fungus causes bacterial wilt in carnations, onion rot, and bacterial panicle blight in rice; *Acidophilus* species (cause fruit spot in cucurbits, brown spot in orchids, brown streak in oats, and bacterial leaf spot in konjac); *Xanthomonas* species (cause bacterial leaf blight in rice, bacterial leaf streak in rice, leaf spot and scab in peppers and tomatoes, bacterial black spot in mangoes, bacterial leaf spot in peppers, bacterial blight in poinsettias, angular leaf spot in cotton, bacterial spot in soybeans, black rot in cruciferous vegetables, and wood... Bacterial wilt of sweet potato, gummosis of sugarcane, bacterial blight of Anthurium, citrus canker, yellow rot of hyacinth, bacterial shot-hole disease of peach, angular leaf spot of strawberry, bacterial canker of poplar, etc.; Agrobacterium (causing crown gall of Rosaceae plants, etc.); Xylem (causing Pierce's disease of grape and variegated wilt of citrus, etc.); Phloembacterium (causing Huanglongbing of citrus, etc.); Enterobacterium (causing wilt of poplar, etc.); Lignophilic fungi (causing bacterial blight of grape, etc.).

[0100] Gram-positive bacteria: Corynebacterium (causing potato ring rot, tomato bacterial canker, alfalfa bacterial wilt, corn inner wilt, wheat bacterial mosaic, etc.); Streptomyces (causing potato scab, etc.); Bulbacterium (causing bean bacterial wilt, tulip yellow blister spot, bean wilt, etc.); Arthrobacterium (causing American holly leaf blight, etc.); Rhodococcus (causing sweet pea banding, etc.); Bacillus (causing corn Bacillus leaf spot, wheat white leaf streak, etc.); Lassella (causing duckgrass honeydew, etc.).

[0101] According to embodiments of the present invention, the compound represented by formula (I) or its phytochemically acceptable salt or the composition thereof can be used to control the following pathogens or their corresponding diseases: rice blast fungus, rice sheath blight fungus, rice false smut fungus, tomato gray mold fungus, peanut root rot fungus, wheat scab fungus, yellow falcatum fungus, citrus resinosis fungus, potato black scurf fungus, rapeseed sclerotinia sclerotium, false gramineous falcatum fungus, maize verticillium wilt fungus, potato late blight fungus, wheat take-all fungus, and citrus anthracnose fungus.

[0102] To achieve the desired effect, the amount of compound used varies depending on various factors, such as the compound used, the crop being protected, the type of pest, the degree of infection, climatic conditions, the application method, and the formulation used.

[0103] The selection of dosage forms or compositional components described herein should be consistent with the physical properties of the active ingredient, the method of application, and environmental factors such as soil type, humidity, and temperature.

[0104] The dosage forms include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc., which may optionally be thickened into a gel. The dosage forms also include solids such as powders, granules, tablets, pills, films, etc., which may be water-dispersible (“wettable”) or water-soluble. The active ingredient may be microencapsulated and re-formed into a suspension or solid dosage form; alternatively, the entire dosage form of the active ingredient may be encapsulated. Encapsulation can control or delay the release of the active ingredient. Sprayable formulations can be diluted in a suitable medium, with a spray volume of approximately one hundred to several hundred liters per hectare. High-concentration compositions are primarily used as intermediates for further processing.

[0105] Typical solid diluents are described in Watkins et al., *Handbook of Insecticide Dust Diluents and Carriers*, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, *Solvents Guide*, 2nd Ed., Interscience, New York, 1950. McCutcheon's *Detergents and Emulsifiers Annual*, Allured Publ. Corp., Ridgewood, New Jersey, and *Sisely and Wood, Encyclopedia of Surface Active Agents*, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended applications. All formulations may contain small amounts of additives to reduce foaming, prevent clumping, prevent corrosion, inhibit microbial growth, etc., or thickeners to increase viscosity.

[0106] Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinate, alkyl sulfates, alkylbenzene sulfonates, organosilanes, N,N-dialkyl taurate, lignin sulfonates, naphthalene sulfonates with aldehyde condensates, polycarboxylate esters, and polyoxyethylene / polyoxypropylene block copolymers.

[0107] Solid diluents include, for example, clays such as bentonite, montmorillonite, magnesia and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate, sodium bicarbonate, sodium sulfate; liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfone, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa butter, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, dodecyl alcohol and tetrahydrofuran alcohol.

[0108] Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Powders and fine powders can be prepared by mixing or, typically, by grinding in a hammer mill or hydraulic mill. Suspensions are generally prepared by wet milling, for example, by the method described in US 3060084. Granules and pellets are prepared by spraying the active ingredient onto freshly made granular carriers or by granulation techniques. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, 147-48; Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, 8-57; and WO 9113546. The preparation of pills is described in US 4172714; water-dispersible and water-soluble granules are prepared according to methods in US 4144050, US3920442, and DE 3246493; tablets are prepared according to methods in US 5180587, US 5232701, and US5208030. Films can be prepared according to methods in GB2095558 and US 3299566.

[0109] More information on the processing can be found in US 3235361, column 6, line 16 to column 7, line 19, and examples 10-41; US3309192, column 5, line 43 to column 7, line 62, and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; US2891855, column 3, line 66 to column 5, line 17, and examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York 1961, 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

[0110] In this article, for certain applications of the composition, such as in agriculture, one, two or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers may be added to the composition of the present invention, thereby producing additional advantages and effects.

[0111] Terminology Definitions and Explanations

[0112] Unless otherwise defined, all technical terms in this document have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent applications, and publications cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0113] The numerical ranges described in this application specification and claims, when the numerical range can only be "integers", should be understood to include the two endpoints of the range and every integer within the range. For example, "1-5" should be understood to include every integer of 1, 2, 3, 4, and 5.

[0114] In some groups, "-" or The location indicates the connection point.

[0115] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0116] As used herein, the term "pharmaceutically acceptable salt" refers to a salt that retains the biological potency of the free acid and free base of the specified compound and has no adverse effects in biological or other respects. The compounds in this application also include pharmaceutically acceptable salts, such as nitrates, hydrochlorides, sulfates, or phosphates. A pharmaceutically acceptable salt is defined as a salt formed by converting a base group in the parent compound into its salt form. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts containing base groups such as amine (amino) groups. The pharmaceutically acceptable salts of this application can be synthesized from the parent compound by reacting a basic group in the parent compound with 1-4 equivalents of an acid in a solvent system.

[0117] The term "C1-C6 alkyl" refers to a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers. In particular, the group is a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, or 4 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, or isomers thereof.

[0118] The above definition of the term "alkyl", such as "C1-C6 alkyl", also applies to other terms containing "C1-C6 alkyl", such as "C1-C6 haloalkyl", "C3-C6 cycloalkyl C1-C6 alkyl", or "COOC1-C6 alkyl", etc.

[0119] The term “C1-C6 alkoxy” means “-O-C1-C6 alkyl”, where “C1-C6 alkyl” has the definition as described above.

[0120] The term “C1-C6 haloalkyl” should be understood as meaning that the 1, 2, 3, 4, 5 or 6 hydrogen atoms on the C1-C6 alkyl group are replaced by halogen atoms (fluorine, chlorine, bromine or iodine), for example CF3CH2-.

[0121] The term “C1-C6 haloalkoxy” means that 1, 2, 3, 4, 5 or 6 hydrogen atoms in “-O-C1-C6 alkyl” are replaced by halogen atoms (fluorine, chlorine, bromine or iodine), wherein “C1-C6 alkyl” has the definition as described above.

[0122] The term "C3-C6 cycloalkyl" refers to a saturated or partially unsaturated monocyclic cyclic hydrocarbon group that may contain 3 to 6 carbon atoms, for example, 3, 4, 5, or 6 carbon atoms. The carbide ring may be a saturated cycloalkyl group or may optionally contain one, two, or more double and / or triple bonds, thereby forming a so-called cycloalkenyl or cycloynyl group. For example, non-limiting examples of monocyclic carbocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and cyclohexadienyl.

[0123] Beneficial effects

[0124] The compounds represented by formula (I) of this invention exhibit excellent activity against a variety of pathogens in agronomy and horticulture. Furthermore, these compounds achieve good control effects at very low doses, and their control effects are superior to existing compounds; therefore, they can be used to prepare fungicides.

[0125] Furthermore, the preparation steps of the compounds of this invention are simple and the yield is high, thus they have good application prospects. Detailed Implementation

[0126] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0127] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0128] The following methods are used for LC-MS analysis:

[0129] Column: Agilent ZORBAX SB-C18 150mm×4.6mm, 5μm (inner diameter);

[0130] Detection wavelength: 254nm;

[0131] Flow rate: 0.8 mL / min;

[0132] Column temperature: 30℃;

[0133] Gradient elution conditions:

[0134] Time (min) Acetonitrile (%) 0.1% formic acid aqueous solution (%) 0.00 50 50 5.00 50 50 15.00 90 10 20.00 90 10

[0135] Synthesis Examples

[0136] Example 1: 4-(benzo[d][1,3]dioxo-5-yloxy)-2-amino-6-methylnicotinic acid benzyl ester (compound 9)

[0137]

[0138] Step 1: Preparation of 4-(benzo[d][1,3]dioxo-5-yloxy)benzaldehyde (intermediate 1)

[0139] At room temperature, 3.72 g (30 mmol) of 4-fluorobenzaldehyde and 4.14 g (30 mmol) of sesamol were dissolved sequentially in 60 mL of N,N-dimethylformamide. 12.44 g (90 mmol) of potassium carbonate was added to the mixture, and the mixture was heated to 110 °C and stirred for 12 h. The mixture was then distilled under reduced pressure, and the residue was extracted with 50 mL of water and ethyl acetate (2 × 30 mL). The combined organic layers were washed with 20 mL of saturated brine and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 5.81 g of the product.

[0140] Step 2: Preparation of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)methanol (intermediate 2)

[0141] At room temperature, 5.0 g (20.6 mmol) of 4-(benzo[d][1,3]dioxo-5-yloxy)benzaldehyde (intermediate 1) was dissolved in methanol (30 mL). 1.56 g (41.2 mmol) of sodium borohydride was added in portions while stirring at 25 °C. The reaction mixture was stirred for 12 h. The reaction mixture was slowly quenched in water (30 mL), filtered, and the filtrate was extracted with ethyl acetate (3 × 30 mL). The combined organic layers were washed with saturated brine (20 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 4.63 g of the product.

[0142] Step 3: Preparation of 4-(benzo[d][1,3]dioxo-5-yloxy)-2-amino-6-methylnicotinic acid benzyl ester (compound 9)

[0143] At room temperature, 0.73 g (3 mmol) of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)methanol (intermediate 2) and 0.55 g (3.6 mmol) of 2-amino-6-methylnicotinic acid (intermediate 3) were dissolved in dichloromethane (20 ml). 0.86 g (4.5 mmol) of EDCI and 0.73 g (6 mmol) of DMAP were added. The reaction mixture was heated to 50 °C and stirred for 3 h. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. Column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) yielded 0.85 g of the product.

[0144] LC / MS[M+H] + =379.12, [M+Na] + =401.10, [M+K] + =417.03. 1 H NMR(400MHz, CDCl3): δ7.94(d,1H),

[0145] 7.43(d,2H),7.14(s,2H),6.96-6.89(m,3H),6.74(s,1H),6.50-6.74(m,2H),6.04(s,2H),5.23(s,2H),2.30(s,3H). 13 CNMR (100MHz, CDCl3) δ166.4,163.4,159.2,157.8,150.4,148.2,143.8,139. 9,130.5,130.1,117.3,112.0,111.6,108.5,102.2,101.9,101.6,65.3,24.3.

[0146] Example 2: 4-(benzo[d][1,3]dioxolane-5-yloxy)-2-amino-6-((tert-butoxycarbonyl)amino)benzyl nicotinate (Compound 34)

[0147]

[0148] 4-(benzo[d][1,3]dioxo-5-yloxy)-2-amino-6-chloronicotinic acid benzyl ester was prepared according to the method in Example 1.

[0149] 1.99 g (5.0 mmol) of 4-(benzo[d][1,3]dioxo-5-yloxy)-2-amino-6-chloronicotinic acid benzyl ester was dissolved in 1,4-dioxane (10 mL), and 1.17 g (10.0 mmol) of tert-butyl carbamate, 0.46 g (0.5 mmol) of tris(dibenzylacetone)dipalladium, 0.49 g (0.85 mmol) of Xantphos, and 2.44 g (7.5 mmol) of cesium carbonate were added. The reaction mixture was heated to 120 °C and stirred for 15 h. The mixture was distilled under reduced pressure, and 50 mL of water was added to the residue. Extraction was performed with ethyl acetate (2 × 30 mL). The organic layers were combined, washed with saturated brine (20 mL), and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 1.29 g of the product.

[0150] LC / MS[M+H] + =480.17, [M+Na] + =502.13, [M+K] + =518.09. 1 H NMR (400MHz, CDCl3): δ9.79 (s, 1H),

[0151] 7.97(d,1H),7.35-7.36(m,3H),7.15(s,2H),6.92-7.00(m,4H),6.70(s,1H),6.05(s,2H),5.23(s,2H),1.49(s,9H). 13 C NMR (100MHz, CDCl3) δ166.1,160.4,157.2,155.7,152.3,149.3,148.2,145.8,139.9,129 .5,128.4,128.1,121.6,121.3,115.3,112.6,104.6,101.5,99.2,97.9,79.6,65.6,28.4.

[0152] Example 3: (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)(methoxy)-2-amino-6-methylnicotinic acid methyl ester (Compound 50)

[0153]

[0154] Step 1: Preparation of 5-(p-Tolyloxy)benzo[d][1,3]dioxane (Intermediate 1)

[0155] At room temperature, 3.30 g (30 mmol) of 4-fluorotoluene and 4.14 g (30 mmol) of sesamol were dissolved sequentially in 60 mL of N,N-dimethylformamide. 12.44 g (90 mmol) of potassium carbonate was added to the mixture, and the mixture was heated to 110 °C and stirred for 12 h. The mixture was then distilled under reduced pressure, and the residue was extracted with 50 mL of water and ethyl acetate (2 × 30 mL). The combined organic layers were washed with 20 mL of saturated brine and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 6.23 g of the product.

[0156] Step 2: Preparation of 5-(4-(dibromomethyl)phenoxy)benzo[d][1,3]dioxane (intermediate 2)

[0157] At room temperature, 6.00 g (26.3 mmol) of 5-(p-tolyloxy)benzo[d][1,3]dioxane (intermediate 1) was dissolved in carbon tetrachloride (30 mL). 9.36 g (52.6 mmol) of NBS was added with stirring at 25 °C. After the reaction mixture was heated to 80 °C, 0.65 g (3.9 mmol) of AIBN was added in multiple portions and stirred for 6 h. The mixture was distilled under reduced pressure, and 50 mL of water was added to the residue. Extraction was performed with dichloromethane (2 × 30 mL). The combined organic layers were washed with 20 mL of saturated brine and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) yielded 5.08 g of the product.

[0158] Step 3: Preparation of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)methanediol (intermediate 3)

[0159] At room temperature, 5.00 g (13.0 mmol) of 5-(4-(dibromomethyl)phenoxy)benzo[d][1,3]dioxane (intermediate 2) was dissolved in a mixed solution (dioxane / water = 1 / 2, v / v) (30 mL). 5.39 g (39.0 mmol) of potassium carbonate was added with stirring at 25 °C. The reaction mixture was heated to 100 °C and stirred for 4 h. 50 mL of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (2 × 30 mL). The organic layers were combined, washed with 20 mL of saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 2.81 g of the product.

[0160] Step 4: Preparation of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)(hydroxy)-2-amino-6-methylnicotinic acid methyl ester (intermediate 5)

[0161] At room temperature, 2.60 g (10 mmol) of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)methanediol (intermediate 3) and 1.83 g (12 mmol) of 2-amino-6-methylnicotinic acid (intermediate 4) were dissolved in dichloromethane (30 ml). 2.88 g (15 mmol) of EDCI and 2.44 g (20 mmol) of DMAP were added. The reaction mixture was heated to 50 °C and stirred for 3 h. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. Column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) yielded 2.48 g of the product.

[0162] Step 5: Preparation of (4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)(methoxy)-2-amino-6-methylnicotinic acid methyl ester (compound 50)

[0163] At room temperature, 1.97 g (5 mmol) of methyl 4-(benzo[d][1,3]dioxo-5-yloxy)phenyl)(hydroxy)-2-amino-6-methylnicotinic acid ester (intermediate 5) was dissolved in DMF (30 mL), cooled to 0 °C, and 0.15 g (6 mmol) of NaH was added. The mixture was then heated to 25 °C and stirred for 0.5 h. The mixture was cooled again to 0 °C, and 0.71 g (5 mmol) of iodomethane was added. The mixture was then heated to 25 °C and stirred for 1 h. 30 mL of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate (2 × 30 mL). The organic layers were combined, washed with 20 mL of saturated brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and column chromatography (eluent: a mixture of ethyl acetate and petroleum ether (1:3)) was performed to give 1.14 g of the product.

[0164] LC / MS[M+H] + =409.13, [M+Na] + =431.07, [M+K] +=447.10. 1 H NMR(400MHz, CDCl3): δ7.90(d,1H),

[0165] 7.75(s,1H),7.36-7.39(m,4H),7.15(s,2H),6.92-7.00(m,2H),6.56-6.61(m,2H),6.06(s,2H),3.30(s,3H),2.41(d,3H). 13 C NMR (100MHz, CDCl3) δ 166.3, 158.4, 157.8, 156.2, 149.9, 148.5, 145.6, 137.2, 134.4, 126.5, 125.1, 121.0, 120.8, 116.3, 114.1, 111.0, 107.5, 105.2, 101.7, 72.2, 55.9, 23.3. Other compounds of the present invention were synthesized by the method described above.

[0166] Table 4. Structural characterization data of exemplary compounds of formula (I)

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185] Formulation Examples

[0186] In the following examples, all percentages are by weight, and all dosage forms were prepared using conventional methods.

[0187] Example 4:

[0188] This embodiment uses the compound obtained in the above embodiment to prepare a wettable powder, specifically using the following raw material composition ratio:

[0189] Compound 1 60.0%, dodecylphenol polyethoxyethylene glycol ether 4.0%, sodium lignosulfonate 5.0%, sodium aluminosilicate 6.0%, montmorillonite (calcined) 25.0%.

[0190] Example 5:

[0191] This embodiment uses the compound obtained in the above embodiment to prepare granules, specifically using the following raw material composition ratio:

[0192] Compound 2 10.0%, other components are sodium dodecyl sulfate 2%, calcium lignosulfonate 6%, potassium chloride 10%, polydimethylsiloxane 1%, and soluble starch to make up to 100%.

[0193] Example 6:

[0194] This embodiment uses the compound obtained in the above embodiment to prepare extruded pellets, specifically using the following raw material composition ratio:

[0195] Compound 3 25.0%, anhydrous calcium sulfate 10.0%, crude lignosulfonate calcium 5.0%, sodium alkylnaphthalene sulfonate 1.0%, calcium / magnesium bentonite 59.0%.

[0196] Example 7:

[0197] This embodiment uses the compound obtained in the above embodiment to prepare an emulsifiable concentrate, specifically using the following raw material composition ratio:

[0198] Compound 4 25.0%, Solvent 150 60%, PEG400 5%, Rhodacal 70 / B 3%, Rhodameen RAM / 77%.

[0199] Example 8:

[0200] This embodiment uses the compound obtained in the above embodiment to prepare an aqueous suspension, specifically using the following raw material composition ratio:

[0201] Compound 9 30.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5%, water to 100.0%.

[0202] Bioactivity assay

[0203] The compounds of this invention exhibit excellent inhibitory activity against a variety of pathogens in agronomy and horticulture.

[0204] Example 9:

[0205] 1. Bactericidal activity assay

[0206] This invention conducted in vitro antifungal activity tests on the compounds against various fungal diseases of plants. The results of the fungicidal activity determination are shown below.

[0207] The testing method is as follows: The sample of the compound to be tested is dissolved in a suitable solvent (such as acetone, methanol, DMSO, etc., selected according to its solubility in the sample) to prepare a test solution of the required concentration. In a cleanroom environment, the test solution is added to the culture medium, mixed thoroughly, and poured into a 9cm petri dish. Pathogen mycelia are then inoculated into the center of the culture medium. The treated culture plate is placed in a constant temperature incubator for cultivation. After 3 days of cultivation, an investigation is conducted. During the investigation, the germination or growth of pathogenic vegetative cells is visually observed, and the antibacterial activity of the compound (expressed as "inhibition rate") is evaluated based on the germination or growth of the blank and solvent control.

[0208] The inhibition rate is calculated as follows: Mycelial growth inhibition rate (inhibition rate) (%) = [(Control colony diameter - Mycelial cake diameter) - (Treatment colony diameter - Mycelial cake diameter)] / (Control colony diameter - Mycelial cake diameter) × 100. Wherein, the control colony refers to the colony after solvent treatment. The mycelial cake diameter is 7 mm.

[0209] (1) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against rice blast fungus are as follows:

[0210] Compounds exhibiting inhibition rates of over 80% against rice blast fungus at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 5 3, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0211] Compounds exhibiting inhibition rates of over 80% against rice blast fungus at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, and 53. 54, 55, 56, 57, 58, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0212] (2) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against rice sheath blight pathogen are as follows:

[0213] Compounds exhibiting inhibition rates exceeding 80% against *Rhizoctonia solani* at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0214] Compounds exhibiting inhibition rates of over 80% against *Rhizoctonia solani* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 45, 46, 47, 48, 52, 53, 54, 5 5, 56, 57, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0215] (3) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against rice false smut are as follows:

[0216] Compounds exhibiting inhibition rates of over 80% against rice false smut at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 5 3, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0217] Compounds exhibiting inhibition rates of over 80% against rice false smut at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 5. 0, 51, 52, 53, 54, 55, 56, 57, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 102, 103, 104, 105, 106, 107, 108, 109.

[0218] (4) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against tomato gray mold are as follows:

[0219] Compounds that exhibited inhibition rates of over 80% against *Botrytis cinerea*, the causal agent of tomato gray mold, at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0220] Compounds that exhibited inhibition rates of over 80% against *Botrytis cinerea*, the causal agent of tomato gray mold, at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50. 51, 52, 55, 56, 57, 62, 63, 64, 65, 66, 67, 68, 69, 70, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0221] (5) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against peanut root rot pathogen are as follows:

[0222] The compounds that exhibited inhibition rates of over 80% against peanut root rot pathogens at a dosage of 10 ppm are: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0223] Compounds exhibiting inhibition rates of over 80% against peanut root rot pathogens at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 16, 17, 18, 19, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, and 50. 51, 52, 53, 54, 55, 56, 57, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 108, 109.

[0224] (6) The results of the in vitro antibacterial activity (expressed as inhibition rate) of some compounds against Fusarium graminearum are as follows:

[0225] Compounds exhibiting inhibition rates of over 80% against Fusarium graminearum at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0226] Compounds that exhibited inhibition rates of over 80% against Fusarium graminearum at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, and 48. 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 106, 107, 108, 109.

[0227] (7) The results of the in vitro antibacterial activity (expressed as inhibition rate) of some compounds against Fusarium oxysporum are as follows:

[0228] The compounds that exhibited inhibition rates of over 80% against *Fusarium oxysporum* at a dose of 10 ppm are: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0229] Compounds exhibiting inhibition rates of over 80% against *Fusarium oxysporum* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 45, 46, 47, 48, 49, 50, and 51. 52, 53, 54, 55, 56, 57, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 100, 101, 102, 103, 104, 105, 106, 109.

[0230] (8) The results of the in vitro antibacterial activity (expressed as inhibition rate) of some compounds against citrus resin pathogens are as follows:

[0231] Compounds exhibiting inhibition rates of over 80% against citrus resin pathogens at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0232] Compounds exhibiting inhibition rates of over 80% against citrus resin pathogens at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 44, 45, 46, 47, 51, 52, 53, and 54. 55, 56, 57, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 108, 109.

[0233] (9) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against *Potato black scurvy* are as follows:

[0234] Compounds that exhibited inhibition rates of over 80% against *Potato black scurvy* at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0235] Compounds exhibiting inhibition rates of over 80% against *Potato black scurvy* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 49, 50, 51, 52, 53, 54, 5 5, 57, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0236] (10) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against Sclerotinia sclerotiorum var. sclerotiorum (the causal agent of rapeseed rot) are as follows:

[0237] Compounds exhibiting inhibition rates of over 80% against *Sclerotinia sclerotinia* causal agent of rapeseed at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50. 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 67, 68, 69, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0238] Compounds that exhibited inhibition rates of over 80% against *Sclerotinia sclerotinia* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, and 49. 50, 51, 52, 53, 54, 55, 56, 57, 60, 61, 64, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0239] (11) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against Fusarium oxysporum are as follows:

[0240] The compounds that exhibited inhibition rates of over 80% against *Fusarium oxysporum* at a dose of 10 ppm are: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0241] Compounds exhibiting inhibition rates of over 80% against *Fusarium oxysporum* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, and 52. 53, 54, 55, 56, 57, 61, 62, 63, 64, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 104, 105, 106, 107, 108, 109.

[0242] (12) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against *Verticillium tumefaciens* are as follows:

[0243] Compounds exhibiting inhibition rates of over 80% against *Verticillium tumefaciens* at a dose of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0244] Compounds that exhibited inhibition rates of over 80% against *Verticillium tumefaciens* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 47, 48, 49, 50, 51, 52, and 53. 54, 55, 56, 57, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107.

[0245] (13) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against *Phytophthora indica* are as follows:

[0246] Compounds exhibiting inhibition rates of over 80% against *Phytophthora blight* at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0247] Compounds exhibiting inhibition rates of over 80% against *Phytophthora indusiata* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 39, 40, 41, 42, 43, 44, 45, 46, 47, and 48. , 49, 50, 51, 52, 53, 54, 55, 56, 57, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103.

[0248] (14) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against wheat take-all pathogen are as follows:

[0249] Compounds that exhibited inhibition rates of over 80% against *Tricholoma matsudana* at a dosage of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0250] Compounds exhibiting inhibition rates of over 80% against *Tricholoma matsudana* at a dosage of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 5. 0, 51, 52, 53, 54, 55, 56, 57, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 104, 105, 106, 107, 108, 109.

[0251] (15) The results of the in vitro antibacterial activity (expressed as inhibition rate) of the compound against *Hydrocotyle citrus* are as follows:

[0252] Compounds exhibiting inhibition rates of over 80% against *Hydrocotyledon tomentosa* at a dose of 10 ppm include: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109.

[0253] Compounds exhibiting inhibition rates of over 80% against *Anthracnose citrus* at a dose of 1 ppm include: 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 47, and 4. 8, 49, 50, 51, 56, 57, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 104, 108, 109.

[0254] 2. Test results of exemplary embodiment compounds and control reagents

[0255] This embodiment included an activity comparison test between the exemplary compound and the control compound (control compounds CK1 and CK2 are compounds numbered 82 and 291 in patent document WO2016039459, compound CK3 is compound numbered 105 in patent document JP2016056100, and compound CK4 is compound numbered 49 in patent document JP2016056117; all control compounds were prepared according to the methods reported in the literature). The inhibition rate test results against different pathogens are shown in the table below.

[0256] The test conditions for the comparative experiment were as follows: the inhibition rate was tested according to the above-mentioned test method.

[0257]

[0258]

[0259] Table 5. Inhibition rate (%) test results against different pathogens

[0260]

[0261] In addition to the compounds listed in the table above, the compounds of other exemplary embodiments of the present invention exhibit superior pathogen control activity compared to the control compounds. Therefore, the compounds of formula (I) of the present invention demonstrate excellent activity against a variety of pathogens in the agricultural field.

[0262] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Aromatic esters containing a benzo5-membered ring, or pharmaceutically acceptable salts thereof, as shown in formula (I), (II), or (III) below. （I） (II) (III) 。 2. A method for preparing an aromatic ester compound containing a benzo5-membered ring as shown in claim 1, or a pharmaceutically acceptable salt thereof, wherein, The preparation method includes: Method (1) The compound shown in formula (V) reacts with the compound shown in formula (IV) to give the compound shown in formula (I); Wherein, R1, R2, R3, R4, R5, R6, R7, A, W, X, and Y have the definitions described in claim 1.

3. Use of the aromatic ester compound containing a benzo[a] five-membered ring as described in claim 1, or a pharmaceutically acceptable salt thereof, in the preparation of a bactericide.

4. The use according to claim 3, wherein, The fungicide is used in the fields of agronomy or horticulture.

5. A composition comprising at least one of the benzo[a] pentaneous aromatic ester compound of claim 1 or a pharmaceutically acceptable salt thereof as an active ingredient.

6. Use of the composition of claim 5 as a fungicide, in the fields of agronomy or horticulture.

7. A method for preventing and controlling pathogens or diseases in the fields of agronomy or horticulture, wherein, The method comprises applying an effective amount of the aromatic ester compound containing a benzo[a] five-membered ring as claimed in claim 1, or a pharmaceutically acceptable salt thereof, or at least one of the compositions of claim 5, to the growth medium of pathogens or diseases.

8. The method according to claim 7, wherein, The aromatic ester compound containing a benzo[5] five-membered ring as described in claim 1, or a pharmaceutically acceptable salt thereof, or the composition as described in claim 5, is used to control the following pathogens or their corresponding diseases: rice blast fungus, rice sheath blight fungus, rice false smut fungus, tomato gray mold fungus, peanut root rot fungus, wheat scab fungus, yellow falcatum fungus, citrus resinosis fungus, potato black scurf fungus, rapeseed sclerotinia sclerotium, false grain falcatum fungus, maize verticillium causal agent, potato late blight fungus, wheat take-all fungus, and citrus anthracnose fungus.

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