Tetrazolinone compound and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a tetrazolinone compound and the use thereof. The compound is represented by formula I: wherein A1, A2 and A3 each independently represent N, N-R10 or C-R11, and are not simultaneously C-R11; A4 represents N or C-R12; R1, R2, R3, R4, R6, R7, R8, R9, R11 and R12 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, etc.; and R5 and R10 each independently represent hydrogen, alkyl, alkenyl, alkynyl, etc. The compound has an excellent antimicrobial effect.

Description

A tetrazolinone compound and its application Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a tetrazolinone compound and its applications. Background Technology

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests have acquired resistance, becoming difficult to control with existing pesticides or fungicides. Furthermore, some known pest control agents are highly toxic, or some damage ecosystems through their long-term persistence. In this context, despite the existence of numerous known fungicides, such as WO2013162072A1 which discloses tetrazolinone compounds and their applications as fungicides, there is still a need to develop new pest control agents with low toxicity and low residue. Summary of the Invention

[0003] To address the aforementioned problems in the prior art, this invention provides a tetrazolinone compound and its applications. The compound exhibits excellent bactericidal activity.

[0004] The technical solution adopted in this invention is as follows:

[0005] A tetrazolinone compound as shown in Formula I:

[0006] Where A1, A2, and A3 independently represent N and NR, respectively. 10 or CR 11 And not both are CR 11 ;

[0007] A4 represents N or CR 12 ;

[0008] R1, R2, R3, R4, R6, R7, R8, R9, R 11 R 12 Each of these groups independently represents hydrogen, halogen, alkyl, alkenyl, alkynyl, nitro, cyano, cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). n R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogen, trialkylsilyl, cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) nAn alkyl, alkenyl, or alkynyl group substituted with at least one of the substituents selected from R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2;

[0009] R5, R 10 Each of the following can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or an alkyl, alkenyl, or alkynyl group substituted with at least one of the following substituents: halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, cycloalkyl, heterocyclic, or aryl.

[0010] n is 0, 1, or 2;

[0011] The aforementioned cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R;

[0012] R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl, cycloalkyl, cycloalkenyl, aryl, cyano or alkoxycarbonyl, cycloalkyl, cycloalkenyl, phenyl, or cycloalkyl, cycloalkenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0013] In one specific implementation, represent

[0014] R1, R2, R3, R4, R6, R7, R8, R9, R 11 R 12 Each of these groups independently represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, nitro, cyano, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). nR, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogens, triC1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) n C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted by at least one of R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2;

[0015] R5, R 10 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one substituent selected from halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, C3-C8 cycloalkyl, heterocyclic or aryl;

[0016] The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R;

[0017] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, cyano, or C1-C8 alkoxycarbonyl, or C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, phenyl, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkenyl, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halogenated C1-C8 alkoxy, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or phenyl.

[0018] In another specific embodiment, R1, R2, R3, R4, R6, R7, R8, R9, R11 R 12 Each of these groups independently represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, nitro, cyano, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). n R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogens, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) n C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted by at least one of the substituents R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2;

[0019] R5, R 10 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 ynyl group substituted with at least one of the following: halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, C3-C6 cycloalkyl, heterocyclic or aryl.

[0020] The aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R;

[0021] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, cyano, or C1-C6 alkoxycarbonyl, or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, or C3-C6 cycloalkyl, C3-C6 cycloalkenyl, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkenyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halogenated C1-C6 alkoxy, or C3-C6 cycloalkyl, C3-C6 cycloalkenyl, or phenyl.

[0022] In another specific implementation, represent

[0023] In the definitions of compounds shown in the above general formulas and in all the following structural formulas, the technical terms used, whether alone or in compound terms, represent the following substituents: alkyl groups having more than two carbon atoms can be straight-chain or branched. For example, in the compound term "cycloalkylalkyl," the alkyl group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl, or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, alkenyl groups are, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, ethynyl, propynyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position in each unsaturated group. Cycloalkyl groups are carbocyclic saturated ring systems having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl groups are monocyclic alkenyl groups having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein double bonds can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0024] Unless otherwise specified, the term "aryl" in this invention includes, but is not limited to, phenyl, naphthyl, and... The "heterocyclic group" includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. And, including but not limited to, heteroaryl groups, i.e., aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused with benzo[a] rings, wherein 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms are selected from oxygen, nitrogen, and sulfur, for example

[0025] The terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes instances where said event or situation occurs and instances where said event or situation does not occur. For example, the term "optionally...substituted" means that the specified atom or group is unsubstituted or substituted by one or more substituents. If a group is substituted by a group, this should be understood to mean that the group is substituted by one or more groups, either the same or different, selected from those groups mentioned. Furthermore, the same or different substitution characters contained in the same or different substituents are chosen independently and may be the same or different. This also applies to ring systems formed from different atoms and units. Meanwhile, the scope of the claims excludes compounds that are chemically unstable under standard conditions, as known to those skilled in the art.

[0026] Furthermore, unless otherwise specified, the phrase "replaced by at least one group" in this invention refers to being replaced by, for example, 1, 2, 3, 4, or 5 groups; groups without specific attachment positions (including heterocyclic groups, aryl groups, etc.) can be attached at any position, including positions attached to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it conforms to the rules of chemical bond attachment. For example, a heteroaryl group substituted by one methyl group. Can represent wait.

[0027] The present invention also covers salts or N-oxides of each compound having chemical formula I.

[0028] Those skilled in the art will also understand that, unless otherwise stated, additional substitutions are permitted, provided that the rules of chemical bonding and strain energy are satisfied and the product still exhibits antifungal activity.

[0029] Another embodiment of this application is a method for preparing the tetrazolinone compound, comprising the following steps:

[0030] (1) Compound I is prepared by a substitution reaction between compound II and compound III. The chemical reaction equation is as follows:

[0031] Or (2) Compound I is prepared by coupling reaction of compound IV with compound V or its salt (such as hydrochloride), and the chemical reaction equation is as follows:

[0032] Wherein, W1 and W2 represent halogens; the definitions of substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, and A4 are as described above.

[0033] In one specific embodiment, the reactions in steps (1) and (2) are carried out in the presence of a solvent.

[0034] In another specific embodiment, an alkali is added during the reaction process in step (1).

[0035] In another specific embodiment, a catalyst and / or base are added in step (2).

[0036] In another specific embodiment, the solvent in steps (1) and (2) is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate.

[0037] In another specific embodiment, the base in steps (1) and (2) is selected from at least one of inorganic or organic bases, such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuOK, EtONa, NaOH, KOH, NaOMe, pyrazole, triethylamine, pyridine, N,N-dimethylethylenediamine, DIEA, etc.

[0038] In another specific embodiment, the catalyst in step (2) is selected from at least one of CuI, CuCl, CuBr, Cu2O, Cu(OAc)2 or CuSO4.

[0039] The present invention also provides an intermediate, as shown in Formula II.

[0040] In addition, another embodiment of this application is a bactericidal composition comprising a biologically effective amount of a compound of formula I; preferably, in one embodiment, it further comprises a formulation adjuvant; in another embodiment, it further comprises other active ingredients.

[0041] Another embodiment of this application is the use of the compound of Formula I or the above-described fungicidal composition in the control of plant pathogenic fungi. This use includes protecting plants from plant pathogenic microorganisms or treating plants infected by plant pathogenic microorganisms, wherein the use comprises applying the compound of Formula I or a composition containing said compound to soil, plants, parts of plants, leaves, and / or roots.

[0042] The compounds of this application can be applied as compounds or as formulations containing said compounds using any of the various known techniques. For example, said compounds can be applied to the roots or leaves of plants to control various fungi without compromising the commercial value of the plants. The substances can be applied in any commonly used formulation type, such as as solutions, powders, wetting powders, flowable concentrates, or emulsifiable concentrates.

[0043] Preferably, the compounds of this application are applied in formulation form, said formulation comprising one or more compounds of Formula I and a botanically acceptable carrier. The concentrated formulation may be dispersed in water or other liquids for application, or the formulation may be a dust or granules that can be applied immediately without further processing. The formulation may be prepared according to methods commonly used in the field of agricultural chemistry.

[0044] This application contemplates the use of all media through which the one or more compounds can be formulated for delivery and use as fungicides. Typically, the formulation is applied as an aqueous suspension or emulsion. The suspension or emulsion can be prepared from water-soluble, water-suspendable, or emulsifiable formulations, which are generally referred to as wettable powders when the water-soluble, water-suspendable, or emulsifiable formulation is a solid; or as emulsifiable oils, aqueous suspensions, or suspension concentrates when the water-soluble, water-suspendable, or emulsifiable formulation is a liquid. It is readily understood that any substance capable of incorporating these compounds can be used, provided that the desired use is achieved without significantly impairing the activity of these compounds as antifungal agents.

[0045] Wettable powders that can be pressed into water-dispersible particles comprise a homogeneous mixture (intimate mixture) of one or more compounds of Formula I, an inert carrier, and a surfactant. The concentration of the compound in the wettable powder, by weight of the total wettable powder, can range from about 10 wt% to about 90 wt%, more preferably from about 25 wt% to about 75 wt%. In the preparation of the wettable powder formulation, the compound can be mixed with any finely pulverized solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite, diatomaceous earth, refined silicates, etc. In this operation, the finely pulverized carrier and surfactant are typically blended with and ground with the compound.

[0046] The emulsifiable concentrate of Formula I can be contained in a suitable liquid at a conventional concentration, for example, from about 1 wt% to about 50 wt%, based on the total weight of the emulsifiable concentrate. The compound can be dissolved in an inert support, which is a mixture of a water-miscible solvent or a water-immiscible organic solvent and an emulsifier. The emulsifiable concentrate can be diluted with water and oil to form a spray mixture in the form of an oil-in-water emulsion. Useful organic solvents include the aromatic fractions of petroleum, particularly the high-boiling cycloalkane and alkene fractions, such as heavy aromatic naphtha. Other organic solvents may also be used, such as terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.

[0047] The emulsifiers that can be advantageously used in this application can be readily determined by those skilled in the art and include a variety of nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers, or blends of two or more emulsifiers. Examples of nonionic emulsifiers used to prepare the emulsifiable concentrates include polyalkylene glycol ethers, and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines, or fatty acids with ethylene oxide or propylene oxide, such as ethoxylated alkylphenols and carboxylic acid esters dissolved in polyols or polyoxyethylenes. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts of alkyl aryl sulfonic acids (e.g., calcium salts), oil-soluble salts of sulfated polyglycol ethers, and suitable salts of phosphorylated polyglycol ethers.

[0048] Representative organic liquids that can be used in the preparation of the emulsifiable concentrates of the compounds of this application are aromatic liquids such as xylene and propylbenzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkylamides of various fatty acids, especially dimethylamides and diol derivatives of fatty glycols such as n-butyl ether, ethyl ether or methyl ether of diethylene glycol, methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oils, aromatic solvents, paraffin oils, etc.; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc.; esters of the above vegetable oils; etc. Mixtures of two or more organic liquids can also be used in the preparation of the emulsifiable concentrate. Organic liquids include xylene and propylbenzene fractions, with xylene being the most preferred in some cases. Surfactant dispersants are typically used in liquid formulations, and the amount of the surfactant dispersant is from 0.1 to 20 wt% based on the total weight of the dispersant and one or more compounds. The formulation may also contain other compatible additives, such as plant growth regulators and other bioactive compounds used in agriculture.

[0049] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of formula I dispersed in an aqueous medium, with a concentration of about 1 wt% to about 50 wt% by weight of the total aqueous suspension. The suspension is prepared by finely grinding one or more of the compounds, and vigorously mixing the ground compounds into a medium composed of water and surfactants selected from the same type described above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous medium.

[0050] Compounds of Formula I can also be applied in granular form, particularly for application to soil. By total weight, the granular formulation typically contains about 0.5 wt% to about 10 wt% of the compound dispersed in an inert carrier, which is wholly or mostly composed of coarsely pulverized inert material, such as attapulgite, bentonite, diatomaceous earth, clay, or similar inexpensive materials. The formulation is typically prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier pre-formed to a suitable particle size (ranging from about 0.5 to about 3 mm). The suitable solvent is one in which the compound is substantially or completely soluble. The formulation can also be prepared by forming the carrier, compound, and solvent into a paste or ointment, then crushing and drying to obtain the desired granular particles.

[0051] Powders containing compound I can be prepared by homogenizing one or more of the compounds in powder form with a suitable powdery agricultural carrier, such as kaolin clay, crushed volcanic rock, etc. The powder may suitably contain about 1% to about 10% of the compounds by weight.

[0052] The formulation may additionally contain co-active surfactants to enhance the deposition, wetting, and penetration of the compound onto target crops and microorganisms. These co-active surfactants may optionally be used as a component of the formulation or as a tank mixture. The amount of the co-active surfactant is typically from 0.01 to 1.0 vol% by water spray volume, preferably 0.05 to 0.5 vol%. Suitable co-active surfactants include, but are not limited to, ethoxylated nonylphenol, ethoxylated synthetic alcohols or ethoxylated natural alcohols, sulfosuccinates or sulfosuccinates, ethoxylated organosiloxanes, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylates; benzyl cocoyl dimethyl quaternary ammonium salts; blends of petroleum hydrocarbons, alkyl esters, organic acids, and anionic surfactants; C9-C 11 Alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols (C 12 -C 16Ethoxylated compounds; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl-terminated compounds; nonylphenol ethoxylated compounds + urea ammonium nitrate; emulsified methylated seed oils; tridecyl alcohol (synthetic) ethoxylated compounds (8EO); tallow amine ethoxylated compounds (15EO); PEG (400) dioleate-99. The formulations may also comprise oil-in-water emulsions, such as those disclosed in U.S. Patent Application Serial No. 11 / 495,228, the contents of which are incorporated herein by reference.

[0053] The formulation may optionally include a combination containing other pesticide compounds. These additional pesticide compounds may be fungicides, insecticides, herbicides, nematicides, acaricides, arthropodicides, fungicides, or combinations thereof, which are compatible with the compounds of this application in the chosen application medium and do not antagonize the activity of the compounds of this application. Therefore, in the described embodiments, the other pesticide compounds are used as supplementary toxins for the same or different pesticide uses. The compounds of formula I or I' and pesticide compounds are typically present in combination in a weight ratio of 1:100 to 100:1.

[0054] The compounds of this application can also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of this application are typically applied in combination with other fungicides to control a wider range of undesirable diseases. When applied in combination with other fungicides, the compounds claimed in this application can be formulated together with other fungicides, mixed with other fungicide containers, or applied sequentially with other fungicides. Other fungicides may include: 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, and Bacillus subtilis strain QST713. QST713), benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl compounds, bismerthiazol, bittertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, lime sulfur. Polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans,Copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide oxide), cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion), diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base Freebase), edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph.fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fl uxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, furaidazole, furaxyl, furamepyr, guazatine, guazatine acetates, sodium tetrasulfide (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate sulfate), imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris (albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isothiazine, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozebMandipropamid, Maneb, Mefenoxam, Mepanipyrim, Mepronil, Meptyl-dinocap, Mercuric chloride, Mercuric oxide, Mercurous chloride, Metalaxyl, Metalaxyl-M, Metam, Metam-ammonium, Metam-potassium, Metam-sodium, Metconazole, Methasulfocarb, Methyl iodide, Methyl isothiocyanate isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofuronamide, oleic acid (fatty acid), orysastrobin, oxadixyl, oxine-copper, oxpoconazole Fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuryacetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate.Potassium hydroquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, piraclostrobin, piratostrobin, piraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenol 2-phenyl phenoxide), sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, wood tar oil), tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, triridemorph, trifloxystrobin,Triflumizole, Triforine, Triticonazole, Validamycin, Valifenalate, Valiphenal, Vinclozolin, Zineb, Ziram, Zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.), (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate hydrate), 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate silicate), 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate,Ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury)sulfate, bis(tributyltin)oxide, buthiobate, cadmium calcium copper zinc chromate Sulfate), Carbamorph, Cyanide Acetonide (CECA), Chlobenthiazone, Chloraniformethan, Chlorfenazole, Chlorquinox, Climbazole, Copper Bis(3-phenylsalicylate), Copper Zinc Chromate, Cufraneb, Copper Hydrazine Sulfate Sulfate), Copper chloride (cuprobam), Cycloafuramid, Cypendazole, Cyprofuram, Decafentin, Dichloronaphthoquinone, Dichlozoline, Diclobutrazol, Dimethirimol, Diocton, Dinosulfon, Dibutyl nitrate Noterbon, Dipyrithione, Ditalimfos, Dodicin, Drazoxolon, EBP, ESBP, Etaconazole, Ethylhexidine, Ethirim, Fenaminosulfonate, Fenapanil, Fenitropan, FluotrimazoleFurcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, propiconazole (ICIA0858), isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric acid anhydride anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), octachlorophenone (OCH), phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride Hydrochloride, Pyracarbolid, Pyridinitril, Pyroxychlor, Pyroxyfur, 5-acetyl-8-hydroxyquinoline; 5-acetyl-8-hydroxyquinoline sulfate, Quinazamid, Quinconazole, Rabenzazole, Salicylanilide, SSF-109 (azoxystrobin)Sulforubber, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trihlamide, urethane, zarilamid, and any combination thereof.

[0055] Furthermore, the compounds described in this application can be combined with other insecticides, including insecticides, nematicides, acaricides, arthropod icides, fungicides, or combinations thereof, wherein the other insecticides are compatible with the compounds of this application in the chosen application medium and do not antagonize the activity of the compounds of this application to form insecticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of this application can be applied in combination with one or more other insecticides to control a wider range of undesirable pests. When applied in combination with other insecticides, the compounds claimed in this application can be formulated together with other insecticides, mixed with other insecticide canisters, or applied sequentially with other insecticides.

[0056] Furthermore, the compounds described in this application can be combined with herbicides that are compatible with and do not antagonize the activity of the compounds in the chosen application medium to form insecticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of this application are typically applied in combination with one or more herbicides to control a wider range of undesirable plants. When applied in combination with a herbicide, the claimed compounds can be formulated together with the herbicide, mixed with a herbicide container, or applied sequentially with the herbicide.

[0057] Another embodiment of this application is a method for preventing and controlling harmful fungi. It involves treating fungi, or materials, plants, soil, or seeds to be protected from fungal invasion, with a compound of Formula I or the above-described fungicidal composition.

[0058] The compounds have been found to have significant antifungal activity, particularly for agricultural applications. Many of these compounds are especially effective for agricultural crops and horticultural plants.

[0059] Those skilled in the art will understand that the efficacy of the compound against the aforementioned fungi establishes the compound's general utility as a fungicide.

[0060] The compound exhibits broad-spectrum activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, the following disease initiators: wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), apple scab (Venturia inaequalis), grape powdery mildew (Uncinula necator), barley scald (Rhynchosporium secalis), rice blast (Pyricularia oryzae), and soybean rust. Soybean rust (Phakopsorapachyrhizi), wheat glume blotch (Leptosphaerianodorum), wheat powdery mildew (Blumeria graminis f.sp.tritici), barley powdery mildew (Blumeria graminis f.sp.hordei), cucurbit powdery mildew (Erysiphe cichoracearum), cucurbit anthracnose (Colletotrichum lagenarium), beet leaf spot (Cercospora beticola), tomato early blight. Early blight of tomato (Alternaria solani) and spot blotch of barley (Cochliobolus sativus)The exact amount of active ingredient applied depends not only on the specific active ingredient applied but also on the desired action, the species and growth stage of the fungus being controlled, and the plant part or other product that will come into contact with the compound. Therefore, all compounds and formulations containing said compounds may not be equally effective or ineffective against the same species of fungus at similar concentrations.

[0061] The compound is applied to plants in a disease-inhibiting and botany-acceptable amount. The term "disease-inhibiting and botany-acceptable amount" refers to the amount of a compound that kills or inhibits plant diseases (to which control is desired) but is not obviously toxic to the plant. This amount is typically from about 0.1 to about 1000 ppm (parts per million), preferably 1 to 500 ppm. The exact concentration of the desired compound varies depending on the fungal disease being controlled, the type of formulation used, the method of application, the specific plant species, climatic conditions, etc. Suitable application rates are typically from about 0.10 to about 4 pounds per acre (about 0.01 to 0.45 grams per square meter, g / m²). 2 Within the range of ).

[0062] It will be apparent to those skilled in the art that any range or desired value given herein can be extended or modified without losing the desired effect. Detailed Implementation

[0063] The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way. The scope of protection of this invention is defined by the claims.

[0064] Given the economic efficiency and diversity of the compounds, we preferentially synthesized a number of compounds, some of which are listed in Table 1 below. Specific compound structures and corresponding compound information are shown in Tables 1-2. The compounds in Table 1 are only for better illustration of the present invention and do not limit the invention. Those skilled in the art should not interpret this as limiting the scope of the above-mentioned subject matter of the invention to the following compounds.

[0065] Table 1. Compound Structures

[0066] Table 2 Compounds 1 H NMR values

[0067] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be commercially available or prepared by methods known in the literature or as detailed in the description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Such variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are all included within the scope of the present invention. Furthermore, the preparation methods described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction process, etc.

[0068] The following method examples are provided to further illustrate the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further explain the invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown below are either commercially available or can be easily prepared by those skilled in the art.

[0069] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0070] 1. Synthesis of Compound 1

[0071] (1) Compound 1-1 (0.3 g, 1.64 mmol) was dissolved in 5 mL of acetonitrile solution, and then cuprous iodide (0.62 g, 3.28 mmol) and tert-butyl nitrite (0.33 g, 3.28 mmol) were added. The reaction solution was allowed to react overnight at room temperature, and the reaction was monitored by LCMS until complete. The reaction solution was quenched in water, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE = 100%) to give compound 1-2 (0.21 g, 44%, white solid).

[0072] (2) Compound 1-2 (0.21 g, 0.71 mmol) was dissolved in 5 mL of dimethyl sulfoxide solution, and then 5-hydroxypyrazole (72 mg, 0.86 mmol), cuprous iodide (135 mg, 0.71 mmol), and cesium carbonate (694 mg, 2.13 mmol) were added. Finally, N,N-dimethylethylenediamine (31 mg, 0.36 mmol) was added. The reaction solution was placed under nitrogen protection and reacted overnight at 110 °C. After the reaction was monitored by LCMS until complete, dilute hydrochloric acid was added to the reaction solution for quenching, followed by extraction three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 1-3 (50 mg, 28%, yellow oil).

[0073] (3) Compounds 1-3 (50 mg, 0.2 mmol) were dissolved in 5 mL of acetonitrile solution, and then compounds 1-4 (56 mg, 0.2 mmol) and potassium carbonate (83 mg, 0.6 mmol) were added. The reaction was carried out at 80 °C for 2 hours, and the reaction was monitored by LCMS until complete. The reaction solution was quenched with water and then extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE / EA = 5 / 2) to give compound 1 (68 mg, 76%, yellow solid).

[0074] 2. Synthesis of Compound 34

[0075] Compound 34-1 (80 mg, 0.31 mmol) was dissolved in 5 mL of dimethyl sulfoxide solution. Then, compound 34-2 (88 mg, 0.31 mmol), cuprous iodide (60 mg, 0.31 mmol), and cesium carbonate (303 mg, 0.93 mmol) were added, followed by N,N-dimethylethylenediamine (15 mg, 0.16 mmol). The reaction mixture was placed under nitrogen protection and reacted overnight at 110 °C. After the reaction was monitored by LCMS until complete, the reaction mixture was quenched with water, then extracted three times with ethyl acetate. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE / EA = 1 / 1) to give compound 34 (95 mg, 74%, yellow solid).

[0076] 3. Synthesis of compounds 73, 77, 78 and 79

[0077] (1) At room temperature, compound 78-1 (500 mg, 1.52 mmol) was dissolved in 5 mL of N,N-dimethylformamide under nitrogen protection. Compound 34-2 (440 mg, 1.52 mmol), cuprous iodide (60 mg, 0.30 mmol), and N,N'-dimethylethylenediamine (54 mg, 0.60 mmol) were added sequentially, and the mixture was stirred at 120 °C for 12 hours. After the reaction was completed, ethyl acetate was added, and the mixture was washed three times with water. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by normal phase mixing to obtain compound 78 (700 mg, 94%).

[0078] (2) At room temperature, compound 78 (700 mg, 1.44 mmol) was dissolved in 5 mL of dichloromethane, and 1 mL of 1,4-dioxane hydrochloride solution (4.0 mmol, 4 M in dioxane) was added. The mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was directly evaporated to obtain compound 77 (400 mg, 69%).

[0079] (3) At 0 °C, compound 77 (400 mg, 0.99 mmol) was dissolved in 5 mL of acetonitrile under nitrogen protection. Sodium hydroxide (60 mg, 1.49 mmol, 60% in oil) was added and stirred for 1 hour. Dibromodifluoromethane (313 mg, 1.49 mmol) and zinc powder (10 mg, 0.15 mmol) were added. After the addition was complete, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with ice water. The mixture was diluted with ethyl acetate, washed three times with water, washed with saturated brine, dried over anhydrous sodium sulfate, and purified by rotary evaporation to obtain a mixture of compounds 79-1 and 73-1 (350 mg, 66%).

[0080] (4) At room temperature, a mixture of compounds 73-1 and 79-1 (150 mg, 0.28 mmol) was dissolved in 5 mL of 1,2-dichloroethane under nitrogen protection. Silver tetrafluoroborate (110 mg, 0.56 mmol) was added, and the mixture was stirred at 90 °C for 1 hour. After the reaction was completed, water was added, and the mixture was extracted three times with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by normal phase mixing to obtain 79 (34 mg, 22%) and 73 (32 mg, 21%).

[0081] Bioactivity evaluation (bactericidal activity test - pot method):

[0082] The agent was dissolved in dimethyl sulfoxide and diluted with 0.1% Tween 80 aqueous solution to different concentrations. Each concentration treatment was repeated three times. The experiment included a solvent control without the agent and a water treatment as blank controls. The solution was sprayed evenly onto the leaf surface until completely wetted, and then allowed to air dry before use.

[0083] Asian rust of soybean and blast of rice: The experimental targets were Phakopsora pachyrhizi Syd. and Magnaporthe oryza, both cultured in live pots. Spores were collected from the surface of soybean and rice leaves, respectively, using a 0.1% Tween 80 aqueous solution and prepared into suspensions (concentration 4 x 10⁻⁶ spores per ml). 5 1 x 10 6 (1 spore), store at 4℃ for later use. Spray the fresh spore suspension onto the leaf surface. For the protective test, inoculate 24 hours after treatment. After inoculation, place in dark conditions with relative humidity above 90% and temperature around 25℃ for disease development. After 24 hours, alternate between light and dark for 12 hours each.

[0084] Cucumber powdery mildew: The experimental target should be cucurbit monothecia [Sphaerotheca cucurbitae (Jacz.) ZYZhao] cultured on live potted plants or detached leaves. Remove diseased and spore-producing cucumber leaves, shake off the excess powder, and gently tap the leaves with a glass rod to evenly distribute the cucumber powdery mildew spores onto the test material. For protective experiments, inoculation should be performed 24 hours after pesticide treatment. After inoculation, the plants should be placed at approximately 25°C and cultured under alternating light and dark conditions for 12 hours each.

[0085] Sunflower sclerotinia stem rot: Puncture holes in petri dishes covered with mycelium to create 5mm mycelial cakes. Inoculate these cakes onto the tomato host material. For protective testing, inoculation should be performed 24 hours after treatment. Inoculated materials should then be transferred to an incubator or artificial climate chamber for incubation in complete darkness.

[0086] Based on the disease incidence in the blank control group (disease level 9), the inoculated leaves were graded. The following grading method was used:

[0087] Level 0: No disease;

[0088] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0089] Grade 3: The lesion area accounts for 6% to 10% of the total leaf area;

[0090] Level 5: The lesion area accounts for 11% to 25% of the total leaf area;

[0091] Level 7: The lesion area accounts for 26% to 50% of the total leaf area;

[0092] Level 9: The lesion area accounts for more than 50% of the total leaf area.

[0093] Based on the survey data, the disease index and prevention and control effects of each treatment were calculated.

[0094] The disease index is calculated according to formula (1), and the result is rounded to two decimal places: X={(∑(Ni xi)) / (N x 9)}x100………………………………………(1)

[0095] In the formula: X—disease index; Ni—number of diseased leaves at each level; i—relative level value; N—total number of leaves surveyed.

[0096] The control effect is calculated according to formula (2): P={(CK-PT) / CK}x100…………………………………………(2)

[0097] In the formula: P—prevention and control effect, in percentage (%); CK—disease index of blank control; PT—disease index of drug treatment.

[0098] Table 3. Control results of representative compounds (applied by stereoscopic sprayer)

[0099] Table 4 Comparison of control results of representative compounds (applied by mobile spray tower)

[0100] Note: N represents no data; control compound A: Reference compound B:

[0101] Furthermore, numerous tests have revealed that the compounds and their compositions described in this invention exhibit good control activity against various fungi, including those belonging to the Ascomycetes, Basidiomycetes, Deuteromycetes, and Oomycetes, and thus possess certain commercial value.

Claims

1. A tetrazolinone compound as shown in Formula I: in, A1, A2, and A3 independently represent N and NR, respectively. 10 or CR 11 And not both are CR 11 ; A4 represents N or CR 12 ; R1, R2, R3, R4, R6, R7, R8, R9, R 11 R 12 Each of these groups independently represents hydrogen, halogen, alkyl, alkenyl, alkynyl, nitro, cyano, cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). n R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogen, trialkylsilyl, cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) n An alkyl, alkenyl, or alkynyl group substituted with at least one of the substituents selected from R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2; R5, R 10 Each of the following can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or an alkyl, alkenyl, or alkynyl group substituted with at least one of the following substituents: halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, cycloalkyl, heterocyclic, or aryl. n is 0, 1, or 2; The aforementioned cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl, cycloalkyl, cycloalkenyl, aryl, cyano or alkoxycarbonyl, cycloalkyl, cycloalkenyl, phenyl, or cycloalkyl, cycloalkenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. The tetrazolinone compound according to claim 1, characterized in that, represent R1, R2, R3, R4, R6, R7, R8, R9, R 11 R 12 Each of these groups independently represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, nitro, cyano, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). n R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogens, triC1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) n C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted by at least one of R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2; R5, R 10 Each of these can independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl substituted with at least one substituent selected from halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, C3-C8 cycloalkyl, heterocyclic or aryl; The aforementioned C3-C8 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, cyano, or C1-C8 alkoxycarbonyl, or C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, phenyl, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkenyl, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halogenated C1-C8 alkoxy, or C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or phenyl.

3. The tetrazolinone compound according to claim 1 or 2, characterized in that, R1, R2, R3, R4, R6, R7, R8, R9, R 11 R 12 Each of these groups independently represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, nitro, cyano, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, -(CO)R, -(CO)OR, and -S(O). n R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2, -(SO2)N(R)2, or selected from halogens, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, aryl, -OR, -O(CO)R, -(CO)R, -(CO)OR, -S(O) n C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted by at least one of the substituents R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)N(R)2 or -(SO2)N(R)2; R5, R 10 Each of these can independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 ynyl group substituted with at least one of the following: halogen, -OR, -SO2R, -N(R)2, -NR(OR), -NR(SO2R), -(CO)R, C3-C6 cycloalkyl, heterocyclic or aryl. The aforementioned C3-C6 cycloalkyl, heterocyclic, or aryl group is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, cyano or C1-C6 alkoxycarbonyl, or C1-C6 alkyl, C2-C6 alkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, or C3-C6 cycloalkyl, C3-C6 cycloalkenyl, phenyl, or C3-C6 cycloalkyl, C3-C6 cycloalkenyl, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkenyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy, or C3-C6 cycloalkyl, C3-C6 cycloalkenyl or phenyl. Preferably, the compound is selected from any one of the compounds in Table 1 of the specification.

4. A method for preparing a tetrazolinone compound according to any one of claims 1-3, comprising the following steps: (1) Compound I is prepared by a substitution reaction between compound II and compound III. The chemical reaction equation is as follows: Or (2) Compound I is prepared by coupling reaction of compound IV with compound V or its salt, and the chemical reaction equation is as follows: in, W1 and W2 represent halogens; the substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, A1, A2, A3, and A4 are defined as described in any one of claims 1-3; Preferably, the reactions in steps (1) and (2) are carried out in the presence of a solvent; more preferably, an alkali is added during the reaction in step (1), and a catalyst and / or an alkali is added in step (2); even more preferably, the solvent in steps (1) and (2) is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, tetrahydrofuran, or ethyl acetate, the alkali in steps (1) and (2) is selected from at least one of inorganic or organic alkali, and / or the catalyst in step (2) is selected from at least one of CuI, CuCl, CuBr, Cu2O, Cu(OAc)2, or CuSO4.

5. A bactericidal composition, characterized in that, The compound comprises at least one of the tetrazolinone compounds according to any one of claims 1-3 in a biologically effective amount; preferably, it further comprises a formulation adjuvant; more preferably, it further comprises other active ingredients.

6. The use of the tetrazolinone compound as described in any one of claims 1-3, or the fungicidal composition as described in claim 5, in the control of plant pathogenic fungi.

7. A method for controlling harmful fungi, comprising treating fungi or materials, plants, soil or seeds to be protected against fungal invasion with an effective amount of a tetrazolinone compound as described in any one of claims 1-3, or a fungicidal composition as described in claim 5.

8. An intermediate as described in Formula II of claim 4.

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