Quinazine carboxylic ester compound as well as preparation method and application thereof

Abstract

The invention provides a quinolizine carboxylic ester compound which has a novel structure and is shown in a formula (I). The compound has a certain control effect on bacterial germs and diseases in the fields of agriculture and horticulture. The invention also provides a novel application of the compound shown in the formula (V) in preparation of a bactericide. The bactericide is used in the agricultural field (agricultural bactericide) or the horticultural field (horticultural bactericide).

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural fungicides, and specifically relates to a quinolizine carboxylate compound and a preparation method and application thereof. Background Art

[0002] Bacterial diseases are common diseases in my country's agricultural production. Their harmfulness has surpassed that of viruses and has become the second largest pathogen after fungi. Although plant bacterial diseases account for a small proportion of all plant diseases, they are extremely harmful and difficult to prevent and control. Once infected, the planting area may become a lifelong epidemic area. Because of their explosive, epidemic and destructive characteristics, they usually cause serious reductions in plant yields.

[0003] In current agricultural production, the use of chemical agents is still an important means of preventing and controlling bacterial diseases; the most important agent in the prevention and control of bacterial diseases is copper preparations. The long-term use of large amounts of copper preparations will cause damage to the environment. Therefore, there is an urgent need to develop a new type of bacterial control agent. Summary of the invention

[0004] In order to improve the above technical problems, the present invention provides a quinolizine carboxylate compound or a pesticide acceptable salt thereof as shown in the following formula (I):

[0005]

[0006] wherein R1, R2, and R3 are the same or different and are independently selected from H, halogen, C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, hydroxy C1-10 alkyl, C3-10 cycloalkyl, or C3-10 cycloalkyloxy;

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

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

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

[0010] R b Selected from C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, hydroxy C1-10 alkylene.

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

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

[0014] According to the technical solution of the present invention, R a Selected from C1-6 alkylene, C1-6 alkoxy, halogenated C1-6 alkylene, hydroxy C1-6 alkyl.

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

[0016] According to an embodiment of the present invention, R1, R2, and R3 are 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 are 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 halogen.

[0019] According to an embodiment of the present invention, the halogen includes fluorine, chlorine, bromine, and iodine.

[0020] According to an embodiment of the present invention, R4, R5, and R6 are 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 are 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 an embodiment of the present invention, R4 and R5 are the same or different and are independently selected from H, halogen, C1-4 alkyl, C1-4 alkoxy; preferably, R4 and R5 are the same or different and are independently selected from H or halogen.

[0023] According to an embodiment of the present invention, R6 is selected from H, halogen, C1-4 alkoxy, C1-4 alkyl, C1-4 alkoxy; preferably, R6 is selected from C1-4 alkyl, such as methyl, ethyl, propyl, 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, hydroxyl C1-4 alkyl; preferably, R7 is selected from H, halogen, C1-4 alkyl, C1-4 alkoxy; further preferably, R7 is selected from H, halogen, C1-4 alkyl.

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

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

[0027] According to an embodiment of the present invention, it is the following specific compound or its pesticidally acceptable salt:

[0028]

[0029] According to an embodiment of the present invention, the quinolizine carboxylate compound represented by formula (I) is selected from the compound represented by the following formula (II):

[0030]

[0031] The present invention also provides a method for preparing the compound of formula (I) or its pesticide acceptable salt, which comprises the following steps:

[0032] 1) reacting the compound represented by formula (III) with a halogenating agent to obtain a compound represented by formula (IV);

[0033] 2) The compound represented by formula (IV) and HO-R a -OR b Reaction to obtain a compound represented by formula (I);

[0034] The reaction formula is as follows:

[0035]

[0036] Among them, R1, R2, R3, R4, R5, R6, R7, R a , R b Having the definitions as above;

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

[0038] According to an embodiment of the present invention, the halogenating agent is selected from a chlorinating agent, a brominating agent, such as thionyl chloride and the like.

[0039] According to an embodiment of the present invention, the reaction is carried out in a solvent, preferably the solvent is 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 distilled off to precipitate the compound represented by 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 the compounds represented by formula (I) or pesticide-acceptable salts thereof as an active ingredient.

[0045] The present invention also provides the use of the compound represented by the above formula (I) or its pesticide acceptable salt and composition in the preparation of a fungicide, wherein the fungicide is used in the agricultural field (agricultural fungicide) or the horticultural field (horticultural fungicide).

[0046] The present invention also provides a method for preventing and 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 their pesticide-acceptable salts or the composition to the growth medium of the pathogens or diseases.

[0047] The present invention also provides the use of a compound represented by the following formula (V) or a pesticide-acceptable salt thereof in the preparation of a fungicide, wherein the fungicide is used in the agricultural field (agricultural fungicide) or the horticultural field (horticultural fungicide).

[0048]

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

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

[0051] Pathogens: Euripplinia (e.g., Pathogen of Chinese cabbage soft rot, causing Chinese cabbage soft rot), Pseudomonas syringae (e.g., Angular leaf spot of cucumber, causing angular leaf spot of cucumber), Acidovorax (e.g., cucurbit fruit spot pathogen, e.g., Watermelon fruit spot pathogen, causing cucurbit fruit spot), Dickie's genus (e.g., Dickie's dadanti, causing sweet potato stem rot), Ralstonia (e.g., Ralstonia solanacearum, causing tobacco bacterial wilt), Xanthomonas (e.g., Xanthomonas oryzae, causing rice bacterial blight), Pectobacterium (formerly Erwinia, e.g., Erwinia carrot soft rot, Erwinia potato black shank subspecies; causing soft rot of cruciferous vegetables, e.g., causing potato black shank, etc.);

[0052] Diseases: Cabbage soft rot, cucumber angular spot, melon fruit spot, sweet potato stem rot, tobacco bacterial wilt, rice white leaf blight, potato black shank.

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

[0054] Gram-negative bacteria: Erwinia (causing fire blight of apricot, etc.); Pectobacterium (causing soft rot of cruciferous vegetables, potato black leg, etc.); Dickie's genus (causing sweet potato stem rot, corn bacterial stem rot, rice bacterial basal rot, potato black leg, pear rust, etc.); Pantoea (causing corn bacterial wilt, corn Pantoea leaf spot, red bean bacterial leaf blight, stone fruit tree canker, etc.); Pseudomonas (causing peach canker, pea bacterial Phytophthora, bacterial black spot of crucifer, bacterial leaf spot of tomato, bacterial spot of tomato, bacterial black spot of rape, bacterial angular spot of sesame, bacterial angular spot of cucumber, wildfire of tobacco, bacterial brown spot of corn, bacterial brown spot of corn, bacterial stem blight of broad bean, bacterial spot of soybean, bacterial leaf spot of beet, bacterial pith necrosis of tomato, soft rot of Pseudomonas aeruginosa of ginseng, etc.); Ralstonia (causing various bacterial wilt diseases, etc.); Burkholderia ( The genus Acidovorax (cause bacterial wilt of carnation, onion rot, bacterial ear blight of rice, etc.); the genus Acidovorax (cause fruit spot of melon, brown spot of orchid, brown streak of oat, bacterial leaf spot of konjac, etc.); the genus Xanthomonas (cause bacterial leaf blight of rice, bacterial streak of rice, spot disease of pepper and tomato, scab of pepper and tomato, bacterial black spot of mango, bacterial leaf spot of pepper, bacterial blight of poinsettia, angular spot of cotton, bacterial spot of soybean, black rot of crucifer, wood Potato bacterial wilt, sugarcane gummosis, anthurium bacterial blight, citrus canker, hyacinth yellow rot, peach bacterial punchhole, strawberry angular leaf spot, poplar bacterial canker, etc.); Agrobacterium (causing root cancer in Rosaceae, etc.); Xylem bacteria (causing Pierce's disease in grapes and citrus variegated chlorosis, etc.); Phloemobacter (causing citrus Huanglongbing, etc.); Enterobacter (causing poplar wilt, etc.); Xylophilus (causing bacterial blight in grapes, etc.).

[0055] Gram-positive bacteria: Corynebacterium (causing potato ring rot, bacterial canker of tomatoes, bacterial wilt of alfalfa, internal wilt of corn, bacterial mosaic of wheat, etc.); Streptomyces (causing potato scab, etc.); Brevibacterium (causing bacterial wilt of beans, yellow blister of tulip, bean wilt, etc.); Arthrobacter (causing American holly leaf blight, etc.); Rhodococcus (causing sweet pea banding, etc.); Bacillus (causing Bacillus leaf spot of corn, white leaf streak of wheat, etc.); Russell's bacillus (causing duckgrass honey ear disease, etc.).

[0056] To obtain the desired effect, the amount of compound used will vary depending on factors such as the compound used, the crop to be protected, the type of pest, the degree of infestation, climatic conditions, the method of application, and the formulation employed.

[0057] The selection of ingredients for the dosage forms or compositions described herein should be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture and temperature.

[0058] The dosage forms include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc., which may be optionally thickened into colloids. The dosage forms also include solids such as dusts, powders, granules, tablets, pills, films, etc., which may be water-dispersible (wettable) or water-soluble. The active ingredient can be microencapsulated and then made into a suspension or solid dosage form; in addition, the entire dosage form of the active ingredient can also be encapsulated. Encapsulation can control or delay the release of the active ingredient. Sprayable dosage forms can be diluted in an appropriate medium, and the spray volume used is about one hundred to several hundred liters per hectare. High-concentration compositions are mainly 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. Surfactants and recommended applications are listed in 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. All formulations may contain small amounts of additives to reduce foaming, prevent caking, prevent corrosion, prevent microbial growth, etc., or thickeners to increase viscosity.

[0060] The surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfonated succinates, alkyl sulfates, alkylbenzene sulfonates, organosilanes, N,N-dialkyl taurates, lignin sulfonates, condensates of naphthalene sulfonates with aldehydes, polycarboxylates and polyoxyethylene / polyoxypropylene block copolymers.

[0061] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silicon dioxide, 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, dodecanol and tetrahydrofuranol.

[0062] Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Dusts and fine powders can be prepared by mixing or grinding, usually in a hammer mill or liquid mill. Suspensions are generally prepared by wet grinding, for example as described in US 3060084. Granules and pills are prepared by spraying the active substance onto a freshly prepared 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, water dispersible and water soluble granules are prepared by the methods described in US 4144050, US 3920442 and DE 3246493, and tablets are prepared by the methods described in US 5180587, US 5232701 and US 5208030. Films can be prepared by the methods described in GB 2095558 and US 3299566.

[0064] For more information on processing, see U.S. Pat. No. 3,235,361, at col. 6, line 16 to col. 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, at col. 5, line 43 to col. 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, at col. 3, line 66 to col. 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] Herein, for certain applications of the composition, such as in agriculture, one, two or more other fungicides, insecticides, miticides, 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] The present invention provides a quinolizine carboxylate compound represented by formula (I) with a novel structure, and the compound has a certain control effect on bacterial pathogens and diseases in the fields of agriculture and horticulture.

[0068] The present invention also provides a new application of the compound represented by formula (V) in the preparation of a fungicide, wherein the fungicide is used in the agricultural field (agricultural fungicide) or the horticultural field (horticultural fungicide). DETAILED DESCRIPTION

[0069] Definitions and explanations of terms

[0070] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of the claims pertains. Unless otherwise indicated, all patents, patent applications, and publications cited herein are incorporated herein by reference in their entirety. If there are multiple definitions of a term herein, the definition in this chapter shall prevail.

[0071] In this specification, groups and substituents thereof may be selected by those skilled in the art to provide stable moieties and compounds. When substituents are described by conventional chemical formulas written from left to right, the substituents also include chemically equivalent substituents that would result from writing the formula 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" is understood to mean a straight or branched saturated monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. For example, "C1-C6 alkyl" means a straight or branched alkyl radical 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, etc. or isomers thereof. In particular, the group has a straight or branched saturated monovalent hydrocarbon group of 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", is also applicable to other terms containing "C1-C4 alkyl", such as the term "C1-C4 haloalkyl", etc.

[0075] The term "haloalkyl" is understood to mean a straight-chain or branched alkyl group in which some or all of the hydrogen atoms are replaced by halogen atoms, such as CF3CH2-.

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

[0077] The term "acceptable salt in pesticide science" refers to a salt that retains the biological efficacy of the free acid and free alkali of a given compound, and has no adverse effects in biology or other aspects, and can be obtained by converting the acidic group in the parent compound into the form of a salt. Acceptable salt in pesticide science includes, but is not limited to, inorganic or organic alkali salts of acidic groups such as carboxyl. The acceptable salt in pesticide science described in the present application can be synthesized by the parent compound, i.e., the acidic group in the parent compound reacts with 1-4 equivalents of alkali in a solvent system to form alkali metal (such as sodium, potassium) salts, alkaline earth metal (such as calcium, magnesium) salts, transition metal (such as zinc) salts, ammonium salts, amine (such as diethanolamine, triethanolamine, octylamine, dioctylmethylamine, morpholine) salts, preferably sodium salts, potassium salts, calcium salts, zinc salts or ammonium salts formed by the parent compound.

[0078] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations 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 included in the scope that the present invention is intended to protect.

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

[0080] Example 1 Preparation of Compound of Formula II

[0081]

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

[0083] The hydrogen spectrum and carbon spectrum data of the compound of formula (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: dilute the agent with an appropriate amount of dimethyl sulfoxide to a series of concentrations. Under sterile operating conditions, dispense equal amounts of NB culture solution into test tubes, quantitatively draw the solution from low concentration to high concentration, add it to the above test tubes, shake well, and then add equal amounts of bacterial suspension in the logarithmic growth phase, and repeat 4 times for each treatment. After mixing, place it in a 25℃ shaking incubator in the dark, measure the OD value in the logarithmic growth phase, and calculate its inhibition rate.

[0087]

[0088]

[0089] Example 3 In vivo protective activity assay

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

[0091] The compound to be tested was dissolved in a small amount of dimethyl sulfoxide and then diluted to the test concentration with 0.1% Tween 80. The pathogenic bacteria cultured to the stable growth phase were mixed evenly with the quantitative compound solution.

[0092] The germinated melon seeds, tobacco seeds and potato seeds were soaked in a mixture of bacterial solution and compound for half an hour, and then the seeds were sown in earthworm soil culture cups and placed in a greenhouse for moisturizing culture. The prevention efficacy was investigated after the control group was fully infected.

[0093]

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

[0095] Dissolve the compound to be tested with a small amount of solvent N,N-dimethylformamide and dilute with water to the required concentration. Spray the compound solution on the surface of the plant test material. After the surface solution is air-dried in a cool place, spray the pathogenic bacteria cultured to the stable growth period on the surface of the plant test material, and then place the plant test material in a greenhouse for moisturizing culture. Usually, the culture is about ten days, and after the control is fully infected, the prevention effect is investigated.

[0096]

[0097] 3.3 Targeting potato blackleg pathogen

[0098] Dissolve the test compound with a small amount of dimethyl sulfoxide and dilute with water to the required concentration. Irrigate the test potatoes with the designed concentration of the drug, 200 mL per plant, and keep the dosage of each potato consistent (including the control treatment). Inoculate the black leg pathogen on the second day after the application. According to the results of the disease investigation.

[0099]

[0100] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A quinolizine carboxylate compound or a pesticide-acceptable salt thereof as shown in the following formula (I): in, R1, R2, and R3 are the same or different and are independently selected from H, halogen, C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, hydroxy C1-10 alkyl, C3-10 cycloalkyl, or C3-10 cycloalkyloxy; R4, R5, and R6 are the same or different and are independently selected from H, halogen, C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, hydroxy C1-10 alkyl, C3-10 cycloalkyl, or C3-10 cycloalkyloxy; R7 is selected from H, halogen, C1-10 alkoxy, C1-10 alkyl, halogenated C1-10 alkyl; R a Selected from C1-10 alkylene, C1-10 alkoxy, halogenated C1-10 alkylene, hydroxy C1-10 alkylene; R b Selected from C1-10 alkyl, C1-10 alkoxy, halogenated C1-10 alkyl, hydroxy C1-10 alkylene.

2. The compound according to claim 1 or its pesticide acceptable salt, characterized in that: R1, R2, and R3 are 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; Preferably, R4, R5, and R6 are 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; Preferably, R7 is selected from H, halogen, C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, hydroxy C1-6 alkyl; Preferably, R a Selected from C1-6 alkylene, C1-6 alkoxy, halogenated C1-6 alkylene, hydroxy C1-6 alkyl; Preferably, R b Selected from C1-6 alkyl, C1-6 alkoxy, halogenated C1-6 alkyl, hydroxy C1-6 alkyl.

3. The compound according to claim 1 or 2 or a pesticide acceptable salt thereof, characterized in that: R1, R2, R3 are 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, R3 are the same or different and are independently selected from H, halogen or C1-4 alkyl; Preferably, R1 and R3 are H; preferably, R2 is halogen; Preferably, R4, R5, and R6 are 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, R4, R5, and R6 are the same or different and are independently selected from H, halogen, C1-4 alkoxy, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, hydroxy C1-4 alkyl; Preferably, R4 and R5 are the same or different and are independently selected from H, halogen, C1-4 alkyl, C1-4 alkoxy; Preferably, R4 and R5 are the same or different and are independently selected from H or halogen; Preferably, R6 is selected from H, halogen, C1-4 alkoxy, C1-4 alkyl, C1-4 alkoxy; Preferably, R6 is selected from C1-4 alkyl; Preferably, R7 is selected from H, halogen, C1-4 alkyl, C1-4 alkoxy, halogenated C1-4 alkyl, hydroxyl C1-4 alkyl; preferably, R7 is selected from H, halogen, C1-4 alkyl, C1-4 alkoxy; further preferably, R7 is selected from H, halogen, C1-4 alkyl. Preferably, R a is selected from C1-6 alkylene, C1-6 alkoxy, halogenated C1-6 alkylene; preferably, R a Selected from C1-4 alkylene; Preferably, R b is selected from C1-6 alkylene, C1-6 alkoxy, halogenated C1-6 alkylene; preferably, R b Selected from C1-4 alkyl, such as methyl, ethyl, propyl, butyl; Preferably, the quinolizine carboxylate compound represented by formula (I) is selected from the compound represented by the following formula (II):

4. A method for preparing a compound of formula (I) or a pesticide acceptable salt thereof according to any one of claims 1 to 3, comprising the following steps: 1) reacting the compound represented by formula (III) with a halogenating agent to obtain a compound represented by formula (IV); 2) The compound represented by formula (IV) and HO-R a -OR b Reaction to obtain a compound represented by formula (I); The reaction formula is as follows: Among them, R1, R2, R3, R4, R5, R6, R7, R a , R b Having the definition of any one of claims 1 to 3; X is a leaving group.

5. The preparation method according to claim 4, characterized in that: The halogenating agent is selected from a chlorinating agent and a brominating agent; Preferably, the reaction is carried out in a solvent; preferably the solvent is selected from chloroform; Preferably, the reaction is carried out under reflux conditions; Preferably, 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 distilled off to precipitate the compound represented by formula (I).

6. A composition comprising as an active ingredient at least one of the compounds represented by formula (I) according to any one of claims 1 to 3 or their pesticidally acceptable salts.

7. Use of the compound represented by formula (I) according to any one of claims 1 to 3 or its pesticide acceptable salt, and the composition according to claim 6 in the preparation of a fungicide, wherein the fungicide is used in the agricultural field (agricultural fungicide) or the horticultural field (horticultural fungicide).

8. A method for preventing and 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 of formula (I) or their pesticide-acceptable salts as described in any one of claims 1 to 3 or the composition as described in claim 6 to a growth medium of the pathogens or diseases.

9. Use of a compound represented by the following formula (V) or a pesticide-acceptable salt thereof in the preparation of a fungicide, wherein the fungicide is used in the agricultural field (agricultural fungicide) or the horticultural field (horticultural fungicide); 10. A method for preventing and controlling pathogens or diseases in the agricultural or horticultural fields, the method comprising applying an effective amount of at least one of the compounds of formula (V) or pesticide-acceptable salts thereof according to claim 9 to a growth medium of the pathogens or diseases.

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