A quinolizine carboxylate compound, a preparation method and use thereof

Abstract

The present application provides a quinolizine carboxylate compound of formula (I) with a novel structure, which has certain control effect on bacterial pathogenic bacteria and diseases in the field of agriculture and horticulture. The present application also provides a new application of a compound of formula (V) in the preparation of a bactericide for the field of agriculture (agricultural bactericide) or the field of horticulture (horticultural bactericide).

Description

Technical Field

[0001] This invention belongs to the field of agricultural fungicide technology, specifically relating to a quinazon carboxylic acid ester compound, its preparation method, and its uses. Background Technology

[0002] Bacterial diseases are common in my country's agricultural production, and their harmfulness has surpassed that of viruses, making them the second largest pathogen after fungi. Although bacterial diseases account for a small proportion of all plant diseases, their damage is extremely serious and difficult to control. Once infected, the planting area may become a lifelong epidemic zone. Due to their characteristics of outbreaks, epidemics, and devastation, they usually cause severe yield reductions.

[0003] In current agricultural production, the use of chemical agents remains an important means of controlling bacterial diseases. The most important agents in the control of bacterial diseases are copper-based agents. However, the long-term use of large quantities of copper-based agents can cause environmental damage. Therefore, there is an urgent need to develop a new type of bacterial control agent. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention provides a quinazon carboxylic acid ester compound or a pesticide-acceptable salt thereof, as shown in formula (I).

[0005]

[0006] Among them, R1, R2, and R3 may be the same or different, and are independently selected from H, halogen, C1-10 alkyl, C1-10 alkoxy, halo-C1-10 alkyl, hydroxy-C1-10 alkyl, C3-10 cycloalkyl, or C3-10 cycloalkyloxy.

[0007] R4, R5, and R6 may be the same or different, and are independently selected from H, halogen, C1-10 alkyl, C1-10 alkoxy, halo-C1-10 alkyl, hydroxy-C1-10 alkyl, C3-10 cycloalkyl, or C3-10 cycloalkyloxy.

[0008] R7 is selected from H, halogens, C1-10 alkoxy groups, C1-10 alkyl groups, and halogenated C1-10 alkyl groups;

[0009] R a Selected from C1-10 alkylene, C1-10 alkoxy, halo-C1-10 alkylene, and hydroxy-C1-10 alkylene;

[0010] R b It is selected from C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, and hydroxy-C1-10 alkylene.

[0011] According to the technical solution of the present invention, R1, R2, and R3 may be the same or different, and are independently selected from H, halogen, C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, hydroxy C1-6 alkyl, C3-8 cycloalkyl, or C3-8 cycloalkyloxy.

[0012] According to the technical solution of the present invention, R4, R5, and R6 may be the same or different, and are independently selected from H, halogen, C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, hydroxy C1-6 alkyl, C3-8 cycloalkyl, or C3-8 cycloalkyloxy.

[0013] According to the technical solution of the present invention, R7 is selected from H, halogen, C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, and hydroxy C1-6 alkyl.

[0014] According to the technical solution of the present invention, R a It is selected from C1-6 alkylene, C1-6 alkoxy, halo-C1-6 alkylene, and hydroxy-C1-6 alkyl.

[0015] According to the technical solution of the present invention, R b It is selected from C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, and hydroxy C1-6 alkyl.

[0016] According to embodiments of the present invention, R1, R2, and R3 may be the same or different, and are independently selected from H, halogen, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, hydroxy C1-4 alkyl, C3-6 cycloalkyl, or C3-6 cycloalkyloxy; preferably, R1, R2, and R3 may be the same or different, and are independently selected from H, halogen, or C1-4 alkyl.

[0017] According to an embodiment of the present invention, R1 and R3 are H.

[0018] According to an embodiment of the present invention, R2 is a halogen.

[0019] According to embodiments of the present invention, halogens include fluorine, chlorine, bromine, and iodine.

[0020] According to embodiments of the present invention, R4, R5, and R6 may be the same or different, and are independently selected from H, halogen, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, hydroxy C1-4 alkyl, C3-6 cycloalkyl, or C3-6 cycloalkyloxy.

[0021] Preferably, R4, R5, and R6 may be the same or different, and are independently selected from H, halogen, C1-4 alkoxy, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, and hydroxy C1-4 alkyl.

[0022] According to embodiments of the present invention, R4 and R5 may be the same or different, and are independently selected from H, halogens, C1-4 alkyl groups, and C1-4 alkoxy groups; preferably, R4 and R5 may be the same or different, and are independently selected from H or halogens.

[0023] According to embodiments of the present invention, R6 is selected from H, halogen, C1-4 alkoxy, C1-4 alkyl, and C1-4 alkoxy; preferably, R6 is selected from C1-4 alkyl, such as methyl, ethyl, propyl, and butyl.

[0024] According to an embodiment of the present invention, R7 is selected from H, halogen, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, and hydroxy C1-4 alkyl; preferably, R7 is selected from H, halogen, C1-4 alkyl, and C1-4 alkoxy; more preferably, R7 is selected from H, halogen, and C1-4 alkyl.

[0025] According to an embodiment of the present invention, R a Selected from C1-6 alkylene, C1-6 alkoxy, and halo-C1-6 alkylene; preferably, R a Selected from C1-4 alkylene groups, such as methylene, ethylene, propylene, and butylene.

[0026] According to an embodiment of the present invention, R b Selected from C1-6 alkylene, C1-6 alkoxy, and halo-C1-6 alkylene; preferably, R b Selected from C1-4 alkyl groups, such as methyl, ethyl, propyl, and butyl.

[0027] According to embodiments of the present invention, it is a specific compound or a pesticide-acceptable salt thereof:

[0028]

[0029] According to an embodiment of the present invention, the quinazon carboxylic acid ester compound represented by formula (I) is selected from the compounds represented by formula (II) below:

[0030]

[0031] This invention also provides a method for preparing compounds of formula (I) above or their pesticide-acceptable salts, the method comprising the following steps:

[0032] 1) The compound shown in formula (III) reacts with a halogenated reagent to give the compound shown in formula (IV);

[0033] 2) The compound shown in formula (IV) and HO-R a -OR b The reaction yields the compound shown in formula (I);

[0034] The reaction formula is as follows:

[0035]

[0036] Among them, R1, R2, R3, R4, R5, R6, R7, R a R b It has the definition described above;

[0037] X is a leaving group, such as a halogen atom, like fluorine, chlorine, bromine, or iodine.

[0038] According to an embodiment of the present invention, the halogenated reagent is selected from chlorinated reagents, brominated reagents, such as thionyl chloride, etc.

[0039] According to an embodiment of the present invention, the reaction is carried out in a solvent, preferably selected from chloroform.

[0040] According to an embodiment of the present invention, the reaction is carried out under reflux conditions.

[0041] According to an embodiment of the present invention, after the reaction is completed, the reacted material is cooled, poured into ice water for cooling, the pH is adjusted to 7-8, and part of the solvent is removed by distillation to precipitate the compound shown in formula (I).

[0042] According to an embodiment of the present invention, the reaction formula is as follows:

[0043]

[0044] The present invention also provides a composition comprising at least one of a compound of formula (I) or a pesticide-acceptable salt thereof as an active ingredient.

[0045] The present invention also provides the use of the compound represented by formula (I) above or its phytochemically acceptable salt and composition in the preparation of fungicides for use in the agricultural field (agricultural fungicides) or the horticultural field (horticultural fungicides).

[0046] The present invention also provides a method for controlling pathogens (such as plant pathogens) or diseases in the agricultural or horticultural fields, the method comprising applying an effective amount of at least one of the compounds represented by formula (I) or a pesticide-acceptable salt thereof, or applying the composition to the growth medium of the pathogen or disease.

[0047] The present invention also provides the use of compounds of formula (V) or their phytochemically acceptable salts in the preparation of fungicides for use in the agricultural field (agricultural fungicides) or the horticultural field (horticultural fungicides).

[0048]

[0049] The present invention also provides a method for controlling pathogens (such as plant pathogens) or diseases in the agricultural or horticultural fields, the method comprising applying an effective amount of at least one of the compounds represented by formula (V) or its phytochemically acceptable salts to the growth medium of the pathogens or diseases.

[0050] According to embodiments of the present invention, the compound of formula (I) or its phytochemically acceptable salt or the composition or the fungicide, and the compound of formula (V) or its phytochemically acceptable salt or the fungicide, can be used to control the following pathogens or diseases:

[0051] Pathogens: *Eurybacterium* (e.g., *Erwinia spp.*, which causes soft rot of cabbage), *Pseudomonas syringae* (e.g., *Ralstonia solanacearum*, which causes angular leaf spot of cucumber), *Acidophilus* (e.g., *Citrus fulvidracoides*, which causes fruit spot disease in cucurbits), *Digibium* (e.g., *Datidiformes*, which causes stem rot of sweet potato), *Ralstonia* (e.g., *Ralstonia solanacearum*, which causes bacterial wilt of tobacco), *Xanthomonas* (e.g., *Bacillus oryzae*, which causes bacterial blight of rice), *Pectinobacter* (formerly *Erwinia*, e.g., *Erwinia carotenoides*, *Bacillus niger*, *Bacillus niger*, *Bacillus niger*, which causes soft rot in cruciferous vegetables, such as causing black shank of potato).

[0052] Diseases: soft rot of Chinese cabbage, angular leaf spot of cucumber, fruit spot of melons, stem rot of sweet potato, bacterial wilt of tobacco, bacterial leaf blight of rice, black shank of potato.

[0053] According to embodiments of the present invention, the compound represented by formula (I) or its phytochemically acceptable salt or the composition thereof, and the compound represented by formula (V) or its phytochemically acceptable salt thereof, can be used to control the following diseases or their corresponding pathogens:

[0054] 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.).

[0055] 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.).

[0056] 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.

[0057] 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.

[0058] 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 reconstituted 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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 liquid 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 a freshly made granular carrier or by granulation techniques.

[0063] 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 pellets is described in US 4172714, and the preparation of water-dispersible and water-soluble granules is described in US 4144050, US 3920442, and DE 3246493. Tablets are prepared as described in US 5180587, US 5232701, and US 5208030. Films can be prepared by the methods described in GB 2095558 and US 3299566.

[0064] 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.

[0065] 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.

[0066] Beneficial effects

[0067] This invention provides a novel quinazonium carboxylic acid ester compound of formula (I), which has a certain control effect on bacterial pathogens and diseases in agriculture and horticulture.

[0068] The present invention also provides new applications of the compounds represented by formula (V) in the preparation of fungicides for use in the agricultural field (agricultural fungicides) or the horticultural field (horticultural fungicides). Detailed Implementation

[0069] Terminology Definitions and Explanations

[0070] 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.

[0071] In this specification, groups and their substituents may be selected by those skilled in the art to provide stable structural moieties and compounds. When a substituent is described by a conventional chemical formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the structural formula is written from right to left. For example, CH2O is equivalent to OCH2.

[0072] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0073] The term “C1-C10 alkyl” should be understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. For example, “C1-C6 alkyl” means a straight-chain and 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 isomers thereof. 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.

[0074] The above definition of the term "alkyl", such as "C1-C4 alkyl", also applies to other terms containing "C1-C4 alkyl", such as the term "C1-C4 haloalkyl", etc.

[0075] The term "halogenated alkyl" should be understood as a straight-chain or branched alkyl group in which hydrogen atoms are partially or completely replaced by halogen atoms, such as CF3CH2-.

[0076] The term "C3-10 cycloalkyl" should be understood as referring to a saturated monovalent monocyclic, bicyclic, or bridged cycloalkanes having 3 to 10 carbon atoms, preferably "C3-C8 cycloalkyl" or "C3-C6 cycloalkyl". The term "C3-C10 cycloalkyl" should be understood as referring to a saturated monovalent monocyclic, bicyclic, or bridged cycloalkanes having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The C3-C10 cycloalkyl group can be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or a bicyclic hydrocarbon group, such as decahydronaphthalene.

[0077] The term "pesticide-acceptable salt" refers to a salt that retains the bioactivity of the free acid and free base of a specified compound and has no adverse effects on biology or otherwise, which can be obtained by converting the acidic group in the parent compound into a salt form. Pesticide-acceptable salts include, but are not limited to, inorganic or organic base salts with acidic groups such as carboxyl groups. The pesticide-acceptable salts described in this application can be synthesized from a parent compound by reacting the acidic group in the parent compound with 1-4 equivalents of a base in a solvent system to form alkali metal (e.g., sodium, potassium) salts, alkaline earth metal (e.g., calcium, magnesium) salts, transition metal (e.g., zinc) salts, ammonium salts, amine (e.g., diethanolamine, triethanolamine, octylamine, dioctylmethylamine, morpholine) salts, preferably sodium, potassium, calcium, zinc, or ammonium salts formed from the parent compound.

[0078] 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.

[0079] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0080] Example 1: Preparation of Compound II

[0081]

[0082] In a reaction flask, add 26.1 g (0.1 mol) of the compound shown in formula (V), add 260 g of chloroform, heat to reflux at 66-70 degrees Celsius, add 12.5 g (0.105 mol) of thionyl chloride dropwise. After the addition is complete, reflux at 66-72 degrees Celsius, add 8.0 g of ethylene glycol monomethyl ether (HOCH2CH2OCH3). After the addition is complete, continue reflux for 2 hours, cool to below 30 degrees Celsius, pour the contents of the flask into 500 g of ice water (acidic pH), slowly add potassium carbonate to adjust the pH to 7-8, heat and distill to remove most of the chloroform, and the compound shown in formula (II) precipitates out. Cool to room temperature, filter, and obtain 26.3 g of product with a melting point of 144.9 degrees Celsius.

[0083] Hydrogen and carbon spectral data of compound (II):

[0084] H-NMR (DMSO-d6, 300MHz): δ = 9.07 (s, 1H), 7.85 (d, J = 7.8Hz, 1H), 7.76 (d, J = 7.8Hz, 1H), 5.03-4.81 (m, 3H), 3. 95-3.84(m,2H),3.48(s,3H),3.35-3.01(m,2H),2.38-2.08(m,2H),1.46(d,J=6.6Hz,3H); MS[m / z]: 320[M+1] + .

[0085] Example 2: In vitro activity test

[0086] The test method is as follows: The reagent was diluted with an appropriate amount of dimethyl sulfoxide to a series of concentrations. Under aseptic conditions, NB culture medium was aliquoted into test tubes in equal volumes. Quantitative amounts of the reagent were added sequentially from low to high concentration to the respective test tubes, and the mixture was thoroughly shaken. Then, equal volumes of bacterial suspension in the logarithmic growth phase were added to each treatment, with each treatment repeated four times. After mixing, the tubes were incubated in the dark at 25°C with shaking. The OD value was measured during the logarithmic growth phase, and the inhibition rate was calculated.

[0087]

[0088]

[0089] Example 3: In vivo protective activity assay

[0090] 3.1 Targeting watermelon fruit spot disease, sweet potato stem rot, and tobacco bacterial wilt

[0091] Dissolve the test compound in a small amount of dimethyl sulfoxide, then dilute to the test concentration with 0.1% Tween 80. Mix the pathogenic bacteria cultured to the stable growth phase with the quantitative compound solution thoroughly.

[0092] Pre-germinated melon seeds, tobacco seeds, and potato seeds were soaked in a mixture of bacterial solution and compound for half an hour. The seeds were then sown in earthworm culture cups and placed in a greenhouse for moist cultivation. After the control group developed sufficient disease, the efficacy of the control was investigated.

[0093]

[0094] 3.2 Targeting bacterial angular leaf spot in cucurbits, bacterial leaf blight in rice, and soft rot in cabbage

[0095] The test compound was dissolved in a small amount of N,N-dimethylformamide and diluted with water to the required concentration. The aqueous solution was sprayed onto the surface of the plant material. After the surface solution was air-dried in a cool, shaded place, a suspension of pathogenic bacteria cultured to a stable growth phase was sprayed onto the surface of the plant material. The plant material was then placed in a greenhouse for humidified culture. Typically, the culture lasted about ten days, and after the control group had fully developed disease, the control efficacy was assessed.

[0096]

[0097] 3.3 Targeting potato blackleg fungus

[0098] The test compound was dissolved in a small amount of dimethyl sulfoxide and then diluted with water to the required concentration. The experimental potatoes were drenched at the designed concentration, with 200 mL per plant, ensuring consistent dosage per plant (including the control treatment). Blackleg fungus was inoculated on the second day after application. Disease incidence was assessed based on the results.

[0099]

[0100] 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. A quinazon carboxylic acid ester compound of formula (I) or a pesticide-acceptable salt thereof, in, R1, R2, and R3 may be the same or different, and are independently selected from H and halogens; R4, R5, and R6 may be the same or different, and are independently selected from H, halogens, and C1-4 alkyl groups; R7 is selected from H and halogens; R a Selected from C1-4 alkylene oxides and halo-C1-4 alkylene oxides; R b Selected from C1-4 alkyl and halogenated C1-4 alkyl.

2. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, R1 and R3 are hydrogen (H); R2 is a halogen.

3. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, R4 and R5 may be the same or different, and are independently selected from H or halogens.

4. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, R6 is selected from H, halogens, and C1-4 alkoxy groups.

5. The compound according to claim 4 or a pesticide-acceptable salt thereof, characterized in that, R6 is selected from C1-4 alkyl groups.

6. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, R a Selected from C1-4 alkylene groups.

7. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, R b Selected from C1-4 alkyl groups.

8. The compound according to claim 1 or a pesticide-acceptable salt thereof, characterized in that, The quinazon carboxylic acid esters represented by formula (I) are selected from the compounds represented by formula (II) below:

9. A method for preparing the compound of formula (I) according to any one of claims 1-8 or a pesticide-acceptable salt thereof, the method comprising the following steps: 1) The compound shown in formula (III) reacts with a halogenated reagent to give the compound shown in formula (IV); 2) The compound shown in formula (IV) and HO-R a -OR b The reaction yields the compound shown in formula (I); The reaction formula is as follows: Among them, R1, R2, R3, R4, R5, R6, R7, R a R b It has the definition as described in any one of claims 1-8; X is a leaving group.

10. The preparation method according to claim 9, characterized in that, The halogenated reagent is selected from chlorinated reagents and brominated reagents; And / or, the reaction is carried out in a solvent; And / or, the reaction is carried out under reflux conditions; And / or, after the reaction is complete, cool the reacted material, pour it into ice water to cool, adjust the pH to 7-8, distill to remove part of the solvent, and precipitate the compound shown in formula (I).

11. The preparation method according to claim 10, characterized in that, The solvent is chloroform.

12. A composition comprising at least one of the compounds of formula (I) as claimed in any one of claims 1-8 or a pesticide-acceptable salt thereof as an active ingredient.

13. The use of the compound of formula (I) according to any one of claims 1-8 or a pesticide-acceptable salt thereof, or the composition of claim 12, in the preparation of a fungicide for use in agriculture or horticulture.

14. A method for controlling pathogens or diseases in the agricultural or horticultural field, the method comprising applying at least one of the compounds of formula (I) as described in any one of claims 1-8 or a pesticide-acceptable salt thereof, or applying the composition of claim 12, to the growth medium of the pathogen or disease.

15. The use of a compound of formula (V) or a pesticide-acceptable salt thereof in the preparation of a fungicide for use in agriculture or horticulture; The fungicide is used to prevent and control the following diseases: cucumber angular leaf spot, cucurbit fruit spot, sweet potato stem rot, tobacco bacterial wilt, and rice bacterial leaf blight; 16. A method for controlling pathogens or diseases in the agricultural or horticultural field, the method comprising applying an effective amount of at least one of the compounds of formula (V) of claim 15 or a pesticide-acceptable salt thereof to the growth medium of the pathogen or disease; The pathogens or diseases mentioned are selected from: cucumber angular leaf spot, cucurbit fruit spot, sweet potato stem rot, tobacco bacterial wilt, and rice bacterial leaf blight.

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