Methylene ester bridge-containing compound, and preparation method therefor and use thereof as bactericide

Abstract

The present invention relates to a methylene ester bridge-containing compound, and a preparation method therefor and the use thereof as a bactericide. The compound has a structure as shown in formula (I). The compound of the present invention has a broad-spectrum bactericidal activity against a variety of plant fungal diseases, can be used alone or in combination with other agents for the control of a variety of plant fungal diseases, and specifically has excellent control effects on rice sheath blight, cucumber gray mold, wheat Fusarium head blight and Sclerotinia stem rot in oilseed rape.

Description

Methylene ester bridge-containing compounds, methods for preparing the same and fungicide applications TECHNICAL FIELD

[0001] The present application relates to the field of pesticide chemistry, in particular to a methylene ester bridge-containing compound, a method for preparing the same and a fungicide application. BACKGROUND

[0002] Fungal diseases not only affect food security, but also threaten biodiversity. In order to prevent the occurrence of plant diseases and reduce the losses caused by them, a large number of fungistatic and fungicidal active compounds have been reported and applied. Among the existing fungicide varieties, only a small number of them contain ester fungicides, and they are not the main active fragments.

[0003] Developing a methylene ester-containing structure as an active fragment for the prevention and control of plant fungi is a new design concept. In the case of maintaining efficacy, ester bonds are easily hydrolyzed in the plant body, so they often do not cause phytotoxicity. Therefore, it is a technical problem to be solved by the present application to design and develop a high-efficiency, high-activity and low-toxicity fungicide with methylene ester as the skeleton. SUMMARY

[0004] The purpose of the present application is to provide a methylene ester bridge-containing compound, which can be applied as a fungicide in the field of agronomy.

[0005] In the first aspect of the present application, a methylene ester bridge compound, an optical isomer thereof, a cis-trans isomer thereof or a pesticidally acceptable salt thereof is provided, and the compound has a structure as shown in formula (I):

[0006] wherein each A is independently selected from the group consisting of phenyl, -(C1-C8 alkylene)phenyl, -N=CH-phenyl; wherein one or more hydrogen atoms on A are optionally substituted with Ra selected from the group consisting of halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 10 aryl, 4-8 membered heteroaryl, 4-8 membered heterocyclyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C1-C6 thioalkyl;

[0007] each T is independently halogen, hydroxyl, nitro, amino, cyano, or a substituted or unsubstituted group selected from the group consisting of C1-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkoxy, C3-C6 cycloalkoxy, C5-C7 cycloalkenyl, C3-C 10 cycloalkyl, 4-8 membered heterocyclyl, C6-C 10Aryl, 5-8 membered aromatic heterocyclic, -(C1-C8 alkylene)(C6-C 10 aryl), -(C6-C 10 aryl)-O-(C6-C 10 aryl), -(C6-C 10 aryl)-(C6-C 10 aryl), -(C1-C8 alkylene)(5-10 heteroaryl), -OC(=O)(C6-C 10 aryl), -OC (=O)(C6-C 10 Aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C 10 Aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl), -(C1-C8 alkylene)(C3-C6 cycloalkyl), -(C1-C8 alkylene)(4-10 heterocyclic), -(C1-C8 alkylene)NHC(=O)(4-10 heteroaryl);

[0008] W is independently: cyano, substituted or unsubstituted groups selected from the group consisting of C1-C1. 10 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C6-C 10 Aryl, 5-8 membered heteroaryl, 4-8 membered heterocyclic, C3-C 10 Cycloalkyl, -(C1-C8 alkylene)(C3-C 10 cycloalkyl), -(C1-C8 alkylene)(C6-C 10 aryl), -(C1-C8 alkylene)(4-10 heteroaryl), -(C1-C8 alkylene)(4-8 heterocyclic), -O(C1-C 10 Alkyl), -O (C3-C) 10 cycloalkyl), -O (C6-C) 10 aryl), -O (4-10 membered heteroaryl), -O (4-8 membered heterocyclic), -NH (C1-C 10 Alkyl), -NH (C3-C) 10 cycloalkyl), -NH (C6-C 10 Aryl), -NH (4-10 membered heteroaryl), -NH (4-8 membered heterocyclic);

[0009] Unless otherwise specified, substitution means that one or more hydrogen atoms on a group are substituted by a substituent selected from the group consisting of: deuterium, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkyl, and halo-C1-C4 alkoxy.

[0010] In another preferred embodiment, the compound has the structures shown in formulas (IA) and (IB):

[0011] wherein said R1 is selected from the group consisting of halogen, cyano, nitro, hydroxy, substituted or unsubstituted C1-C8 alkyl; each m, n is independently an integer between 0 and 5;

[0012] the remaining substituents are as described above.

[0013] In another preferred embodiment, said A is: -CF3,

[0014] In another preferred embodiment, each T is independently halogen, hydroxy, nitro, amino, cyano, C1-C4 alkyl, haloC1-C4 alkyl, C2-C4 alkenyl, haloC2-C4 alkenyl, C2-C4 alkynyl, haloC2-C4 alkynyl, C2-C4 alkenyloxy, haloC2-C4 alkenyloxy, C2-C4 alkynyloxy, haloC2-C4 alkynyloxy, C1-C4 alkoxy, or substituted or unsubstituted C3-C7 cycloalkyl, 5-8 membered heterocyclyl, phenyl, 5-8 membered aromatic heterocyclyl, biphenyl, naphthyl,

[0015] In another preferred embodiment, each T is independently halogen, hydroxy, nitro, amino, cyano, methyl, ethyl, propyl, isopropyl, ethynyl, propynyl, butynyl, ethoxy, propoxy, isopropoxy, propenyloxy, propynyloxy, fluoroethynyl, bromoethynyl, chloroethynyl, fluoropropynyl, bromopropynyl, chloropropynyl, fluorobutynyl, bromobutynyl, chlorobutynyl, trifluoromethyl, difluoromethyl,

[0016] wherein X is selected from the group consisting of F, Cl, Br, I, CF3, OCF3, OCH3;

[0017] o, p are selected from 0, 1, 2, 3, 4, 5.

[0018] In another preferred embodiment, each W is independently cyano, C1-C4 alkyl, haloC1-C4 alkyl, or substituted or unsubstituted C3-C7 cycloalkyl, phenyl, 5-8 membered aromatic heterocyclyl.

[0019] In another preferred embodiment, each W is independently cyano, -CF3, -CH2CF3, -CH2CH2CF3,

[0020] wherein Y is selected from the group consisting of F, Cl, Br, I;

[0021] q is selected from 0, 1, 2, 3, 4, 5.

[0022] In another preferred embodiment, the compound is selected from the following table:

[0023] In a second aspect of the present application, there is provided a pesticidal composition comprising:

[0024] comprising: (a) a compound as described in the first aspect of the present application, an optical isomer, a cis-trans isomer thereof, or a pesticidally acceptable salt thereof, or a combination thereof; and

[0025] optionally (b) a pesticidally acceptable carrier and / or excipient.

[0026] In another preferred embodiment, component (a) is present in an amount of 0.001 to 99.99 wt%, preferably 0.01 to 99.9 wt%, more preferably 0.05 to 90 wt%, based on the total weight of the pharmaceutical composition.

[0027] In another preferred embodiment, the pesticide composition further includes a fungicide selected from the group consisting of: cyprodinil, fluazinam, flumorph, dimethomorph, chlorothalonil, sulfadiazine, mesotriazine, thiabendazole, cyclofludioxazone, streptomycin, pyrimethanil, cyclooxygenase, benzyloxygenase, cyprothiophanate-methyl, thiabendazole, cyprothiophanate-methyl, diclofenac, cymoxanil, high-efficiency metalaxyl, high-efficiency benzyloxygenase, carbendazim, furazolidone, mesotriazine, fluopyram, azoxystrobin, oxadiazon, pyraclostrobin, pyraclostrobin, fluopyram, tebuconazole, fenoxystrobin, tebuconazole, azoxystrobin, oxadiazon. Azoxystrobin, fluopyram, high-efficiency imidacloprid, imidacloprid, cyazofamid, imidacloprid, prochloraz, oxadiazon, malathion, isoprothiolane, oxytetracycline, flutriafol, fluquinazole, difenoconazole, tetraflufenazole, tebuconazole, flusilazole, silfluzoxystrobin, triazole, bifenthrin, cyproconazole, high-efficiency tebuconazole, tebuconazole, fenbendazole, hexaconazole, prothioconazole, tebuconazole, cyproconazole, cyproconazole, imidacloprid, tebuconazole; Thiazoles: thiamethoxam, benzylthiocyanate, octothiazoline, carbendazim, dodecyl morpholine, butyl morpholine, tridemorpholine; Pyrroles: seed dressing powder Fludioxonil, fluazinam, pyridaben, cyclopyridamenil, pyridabenoxime, pyrimidinium cyclomethonium, chlorophenazine alcohol, fluphenazine alcohol, pyrimethanil, pyrimethanil hydrazone, pyrimethanil, fluazinam, fenpyraclostrobin, difenoconazole, ethoxyquinoline, propoxyquinoline, phenoxyquinoline, isopropoxynil, ethoxycarb, bensulfuron-methyl, thiophanate-methyl, isopyram, pyraclostrobin, methyl thiophanate, fenpyroximate, kasugamycin, polyoxin, polyoxin, activated ester, indole ester, bromonitol, benzylsulfamethoxam, toluenesulfonamide, spirocyclamide, pyrazosulfuron, sodium dichloroisocyanurate, pendimethalin Tetrachlorophthalide, tricyclazole, allylphenthiazide, benzyl sulfadiazine, chlornitramine, biguanide octylamine, doxycycline, cymoxanil, cymoxanil, streptomycin, metalaxyl, propineb, benzyl sulfadiazine, chlorpyrifos, methyl thiophanate, carbendazim, benomyl, captan, thiophanate-methyl, chlorpyrifos, chlorpyrifos, furazolidone, fluchlorochlorothiazide, vinazolidone, thiram, isoprothiolane, isoprothiolane, chlorothalonil, eugenol, carvacrol, berberine.

[0028] In a third aspect, the present invention provides the use of a compound as described in the first aspect of the present invention, its optical isomer, cis-trans isomer, or a pesticide composition as described in the second aspect of the present invention, for the preparation of a fungicide.

[0029] In another preferred example, the fungicide controls the following diseases: gray mold (tomato gray mold, pepper gray mold, leek gray mold, kiwi gray mold, strawberry gray mold, cucumber gray mold, etc.), cucumber anthracnose, downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, sugar beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, luffa downy mildew, winter melon downy mildew, muskmelon downy mildew), white rust (rape white rust, Chinese cabbage white rust), damping-off (rape damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton damping-off), damping-off (pepper damping-off, luffa damping-off, winter melon damping-off), bacterial blight (bean bacterial blight, cucumber bacterial blight, winter melon bacterial blight, watermelon bacterial blight, muskmelon bacterial blight, pepper bacterial blight, leek bacterial blight, garlic bacterial blight, cotton bacterial blight), late blight (potato late blight, tomato late blight), and the like.Root rot (pepper root rot, eggplant root rot, bean root rot, cucumber root rot, bitter gourd root rot, cotton root rot, broad bean root rot), damping off (cotton seedling damping off, sesame damping off, pepper damping off, cucumber damping off, Chinese cabbage damping off), yellow wilt (cotton yellow wilt, sunflower yellow wilt, tomato yellow wilt, pepper yellow wilt, eggplant yellow wilt), black spot (zucchini black spot, winter melon black spot, melon black spot), brown spot (cotton brown spot, jute brown spot, sugar beet brown spot, peanut brown spot, pepper brown spot, winter melon brown spot, soybean brown spot, sunflower brown spot, pea brown spot, broad bean brown spot), black spot (flax false black spot, rape black spot, sesame black spot, sunflower black spot, castor black spot, tomato black spot, pepper black spot, eggplant black spot, bean black spot, cucumber black spot, celery black spot, carrot black spot, apple black spot, peanut black spot), brown spot (tomato brown spot, pepper brown spot, celery brown spot), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring spot (soybean ring spot, sesame ring spot, bean ring spot), leaf wilt (sesame leaf wilt, sunflower leaf wilt, watermelon leaf wilt, melon leaf wilt), stem base rot (tomato stem base rot, bean stem base rot), and others (corn round spot, rice blast, millet black sheath disease, sugarcane eye spot, cotton boll rot, peanut crown rot, soybean stem rot, peanut net spot, tea red leaf spot, pepper white spot, winter melon leaf spot, bean black rot, bitter gourd white spot, watermelon spot, jute wilt, sunflower root and stem rot, bean carbon rot, eggplant stick leaf spot, cucumber target spot, tomato leaf mildew, eggplant leaf mildew, broad bean red spot) and the like: Basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, wheat leaf rust, peanut rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust, corn rust), smut (corn silk smut, corn smut, sorghum silk smut, sorghum scattered smut, sorghum hard smut, sorghum column smut, millet grain smut, sugarcane smut, bean rust) and others (such as wheat sharp eyespot, rice sharp eyespot and the like) and the like; Ascomycete diseases, such as powdery mildew (wheat powdery mildew, lettuce powdery mildew, sesame powdery mildew, sunflower powdery mildew, sugar beet powdery mildew, eggplant powdery mildew, pea powdery mildew, loofah powdery mildew, pumpkin powdery mildew, zucchini powdery mildew, winter melon powdery mildew, melon powdery mildew, grape powdery mildew, broad bean powdery mildew), sclerotinia disease (rape sclerotinia disease, soybean sclerotinia disease, peanut sclerotinia disease, tobacco sclerotinia disease, pepper sclerotinia disease, eggplant sclerotinia disease), black spot (apple black spot, pear black spot), root tumor (cabbage root tumor, Chinese cabbage root tumor, cauliflower root tumor, mustard root tumor, radish root tumor, turnip root tumor, rape root tumor).

[0030] In another preferred embodiment, the fungicide controls the following diseases: cucumber downy mildew, apple canker, cucumber gray mold, corn rust, soybean rust, rice sheath blight, wheat powdery mildew, wheat scab, rapeseed sclerotinia, rice blast.

[0031] In a fourth aspect, the present application provides a method for controlling plant pathogens, comprising applying to the environment, soil or plant in need of control a compound according to the first aspect of the present application, an optical isomer thereof, a geometrical isomer thereof or a salt thereof acceptable in agriculture, or a pesticide composition according to the second aspect of the present application.

[0032] It should be understood that, within the scope of the present application, each of the technical features described above and each of the technical features described in detail below (e.g., in the examples) can be combined with each other to form new or preferred technical solutions. Due to the limited space, they will not be listed one by one here. DETAILED DESCRIPTION

[0033] The present inventors have made extensive and in-depth research, and through a large number of screening and testing, provided a methylene ester bridged compound, which has multiple antifungal activities, not only has obvious inhibitory effect on rice sheath blight and cucumber gray mold, but also has good inhibitory activity on wheat scab and rapeseed sclerotinia, and is expected to be used as a new pesticide in agricultural production.

[0034] Terminology

[0035] Group definitions

[0036] The term "C1-C8alkyl" refers to a straight-chain or branched alkyl group having 1-8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl or the like.

[0037] The term "C2-C6alkenyl" refers to a straight-chain or branched alkenyl group having 2-6 carbon atoms, such as ethenyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl or the like.

[0038] The term "C2-C6alkynyl" refers to a straight-chain or branched alkynyl group having 2-6 carbon atoms, such as ethynyl, propynyl or the like.

[0039] The term "C3-C6cycloalkyl" refers to a cyclic alkyl group having 3-7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or the like.

[0040] The term "C5-C7cycloalkenyl" refers to cyclic alkenyl groups having 5-7 carbon atoms, having one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, or the like.

[0041] The term "C1-C6alkoxy" refers to straight or branched chain alkoxy groups having 1-6 carbon atoms, such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, t-butyloxy, or the like.

[0042] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to groups substituted with one or more of the above halogens, which can be the same or different, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.

[0043] The term "alkyl" refers to a group derived from an alkane by the removal of a hydrogen atom.

[0044] The term "ring" or "ring system" refers to a carbocyclic or heterocyclic ring.

[0045] The term "heterocyclyl," "heteroaryl" refers to at least one atom which is not carbon in the backbone of the heterocyclic or heteroaromatic ring. Typically, "heterocyclyl," "heteroaryl" contains no more than 4 nitrogens, no more than 2 oxygens, and / or no more than 2 sulfurs. Unless otherwise indicated, a heterocycle can be a saturated, or unsaturated ring. For example, preferred heterocyclyl groups are morpholinyl, piperidinyl, piperazinyl, tetrahydrofuranyl, tetrahydropyrrolyl, tetrahydropyranyl, and the like. For example, preferred heteroaryl groups are thienyl, furanyl, pyrrolyl, pyridyl, thiazolyl, isothiazolyl, pyrazolyl, pyrimidinyl, benzofuranyl, benzopyrrolyl, benzothienyl, indolyl, benzimidazolyl, quinolinyl, pyridazinyl, and the like.

[0046] The term "DMSO" refers to dimethyl sulfoxide.

[0047] The term "DMF" refers to N,N-dimethylformamide.

[0048] The term "DAST" refers to diethylaminosulfur trifluoride.

[0049] The term "DCC" refers to dicyclohexyl carbodiimide.

[0050] The term "DMAP" refers to 4-dimethylaminopyridine.

[0051] The term "THF" refers to tetrahydrofuran.

[0052] Bactericidal activity of the active substances of the present application

[0053] The term "active substance of the present application" or "active compound of the present application" means a compound of the structure according to formula (I) or an optical isomer, a cis-trans isomer thereof, or a pesticidally acceptable salt thereof. The more preferred compounds of the present application have a significant fungicidal activity, a broad fungicidal spectrum and a strong stability.

[0054] The term "pesticidally acceptable salt" means that the anion of the salt is known and acceptable in forming a fungicide which is acceptable in the art. Preferably, the salt is water-soluble. Suitable acid addition salts formed from the compounds of formula (I) include salts of inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts of organic acids, such as carboxylic acids.

[0055] The compounds of the present application are especially effective in controlling rice sheath blight, cucumber gray mold, wheat scab, and cabbage sclerotinia.

[0056] Fungicide composition containing the active substance of the present application

[0057] The active substances of the present application can be prepared into fungicide compositions in a conventional manner. These active compounds can be formulated into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with the active substance, microencapsulations in polymeric substances, coatings for seeds, and formulations for use with combustion devices, such as smoke cartridges, smoke pots and smoke granules, and ULV cold mist and warm mist formulations.

[0058] These formulations can be produced in known manner, e.g. by mixing the active compound with extenders, that is properly fluid or liquid or solid diluents or carriers, and if desired surfactants, i.e. emulsifiers and / or dispersants and / or foam formers. As extender, there can be used, for example, water, organic solvents, suspension fluids, such as paraffin, vegetable oils, or modified oils, or solid diluents, such as high-boiling aliphatic, cyclic and aromatic hydrocarbons, or alcohols or glycols or oils.

[0059] As liquid solvents there come into consideration, for example, aromatic and aliphatic hydrocarbons, such as xylene, toluene or alkylate naphthalenes; chlorinated hydrocarbons, such as chlorobenzenes or dichloromethane; alcohols, such as ethanol or glycol; ketones, such as acetone, methyl-ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less frequently used polar solvents, such as dimethylformamide, dimethyl sulfoxide and water.

[0060] As liquid diluents or carriers there come into consideration liquids which are gaseous at ambient temperature and under atmospheric pressure, such as aerosol propellants, e.g. halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

[0061] Solid carriers can be natural mineral substances, such as kaolins, clays, talc, quartz, attapulgite, montmorillonite, or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina, and silicates. Solid carriers for granules are crushed and fractionated natural rocks such as pumice, dolomite, calcite, and sepiolite, and synthetic granules of inorganic and organic materials such as sawdust, coconut shells, corn cob, and tobacco stems.

[0062] Nonionic and anionic emulsifiers can be used as emulsifiers and / or foam-forming agents. Examples are polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylaryl polyglycol ethers, alkyl sulfates, alkylsulfonates, arylsulfonates, and albumin hydrolysates. Dispersants include lignosulfite waste liquors and methylcellulose.

[0063] Binders can be used in the formulations, such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules, or latices, such as albumin, gelatin, polyvinylpyrrolidone, and polyvinyl acetate.

[0064] Colorants such as inorganic pigments, such as iron oxide, cobalt oxide, and Prussian blue, organic dyes, such as alizarin dyes or metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc can be used.

[0065] The active compounds of the present application can be present in their commercial preparations in the form of a mixture with other active compounds, such as insecticides, bactericides, fungicides, herbicides, growth control agents, etc. Insecticides include, for example, phosphoric acid esters, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as abamectin, etc. Fungicides include, for example, strobilurins, amides, triazoles, etc.

[0066] Furthermore, the active compounds of the present application can be present in their commercial preparations in the form of a mixture with synergists, which are compounds that enhance the action of the active compounds, and also without synergists, since the active compounds themselves are active.

[0067] The formulations generally contain 0.001 to 99.99% by weight, preferably 0.01 to 99.9% by weight, and more preferably 0.05 to 90% by weight, of the active compounds of the present application, based on the total weight of the fungicide composition. The concentration of active compounds in the commercial preparations or application forms can vary within wide limits. The concentration of active compounds in the application forms can vary from 0.0000001 to 100% (g / v), preferably between 0.0001 and 1% (g / v).

[0068] Methods of making the compounds of the present invention

[0069] The compounds of the present application can be prepared by the following methods, however, the conditions of the methods, such as the reactants, solvents, bases, amounts of compounds used, reaction temperatures, reaction times required, etc. are not limited to the following explanations. The compounds of the present application can also be conveniently prepared by optionally combining various synthetic methods described in the present specification or known in the art, which can be easily performed by those skilled in the art to which the present application pertains.

[0070] The present application is further illustrated by the following specific examples. It is to be understood that these examples are merely illustrative of the present application and do not in any way limit the scope of the application. The experimental procedures in the following examples, where no specific conditions are indicated, were generally carried out in accordance with standard conditions, such as those described in Sambrook et al., Molecular Cloning: A Laboratory Manual (New York: Cold Spring Harbor Laboratory Press, 1989), or as recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight.

[0071] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Also, any method and material similar or equivalent to those described herein can be used in the practice of the present application. The description herein of any particular methods and materials is primarily intended to provide examples of the methods and materials useful in connection with the present application.

[0072] Example 1: Preparation of 1-(2,3,5-trichlorophenyl)ethyl 3,3,3-trifluoropropanoate

[0073] Synthesis of intermediate [1-(2,3,5-trichlorophenyl)ethan-1-ol]:

[0074] In a 100 mL three-necked flask, 5 mmol of 2,3,5-trichlorobenzaldehyde was dissolved in 15 mL of anhydrous THF, and replaced with argon gas three times, and 0.5 M / 20 mL of methyl magnesium bromide was added dropwise under ice bath conditions, and after the addition was completed, it was transferred to an oil bath at 60°C for reaction, and TLC was used for monitoring. After the reaction was completed, it was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate (30 mL*3), dried over anhydrous sodium sulfate, distilled under reduced pressure, purified, and subjected to the next step.

[0075] Preparation of target product: compound I-6 [3,3,3-trifluoropropanoic acid 1-(2,3,5-trichlorophenyl)ethyl ester]

[0076] In a 50 mL round-bottom flask, 1 mmol of 1-(2,3,5-trichlorophenyl)ethane-1-ol was dissolved in 10 mL of tetrahydrofuran, followed by the addition of 1.5 mmol of DCC and 0.1 mmol of catalytic DMAP, and then 2 mmol of 3,3,3-trifluoropropionic acid. The mixture was stirred overnight at room temperature, and the reaction was monitored by TLC. After the reaction was complete, the reaction solution was filtered through diatomaceous earth, and 10 mL of water was added. The aqueous phase was extracted with ethyl acetate (30 mL x 3). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated. The crude product was purified by column chromatography to give 1-(2,3,5-trichlorophenyl)ethyl 3,3,3-trifluoropropionate (85% yield, colorless liquid).

[0077] The final test results are as follows: 1 H NMR (400MHz, CDCl3) δ7.44 (d, J = 2.4Hz, 1H), 7.32 (d, J = 2.3Hz, 1H), 6.25 (q, J = 6.5Hz, 1H), 3.26 (q, J = 10.0Hz, 2H), 1.56 (d, J = 6.5Hz, 3H); HRMS (EI) m / z [M] + C 11 H8Cl3F3O2, calculated value: 333.9542, measured value: 333.9547.

[0078] Example 2: Preparation of ethyl 1-(2,3,5-trichlorophenyl)thiazole-4-carboxylate

[0079] The synthesis of the target compound was similar to that in Example 1, except that thiazol-4-carboxylic acid was used instead of 3,3,3-trifluoropropionic acid. (74% yield, white solid).

[0080] The final test results are as follows: 1 H NMR (400MHz, CDCl3) δ8.89(d,J=1.0Hz,1H),8.31(d,J=1.1Hz,1H),7.46(d,J=1.5Hz ,1H),7.42(s,1H),6.42(q,J=6.4Hz,1H),1.68(d,J=6.5Hz,3H).HRMS(EI)m / z[M]+C 12 H8Cl3NO2S, calculated value: 334.9341, measured value: 334.9338.

[0081] Example 3: Preparation of 1-(2,3,5-trichlorophenyl)prop-2-yn-1-yl 3,3,3-trifluoropropionate

[0082] The synthesis of the target compound was similar to that in Example 1, except that...

[0083] Ethynyl magnesium bromide was used instead of methyl magnesium bromide in the synthesis of the intermediate; the oil bath reaction was changed to a room temperature reaction.

[0084] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 7.68 (d, J = 2.4 Hz, 1H), 7.54 (d, J = 2.4 Hz, 1H), 6.75 (d, J = 2.2 Hz, 1H), 3.27 (q, J = 9.9 Hz, 2H), 2.76 (d, J = 2.2 Hz, 1H); HRMS (El) m / z [M]+C 12 H6Cl3F3O2, calc: 343.9385, found: 343.9381.

[0085] Example 4: Preparation of 1-(2,3,5-trichlorophenyl)prop-2-yn-1-yl thiazole-4- carboxylate

[0086] The synthesis of the target compound was similar to Example 1, except that

[0087] Ethynyl magnesium bromide was used instead of methyl magnesium bromide in the synthesis of the intermediate; the oil bath reaction was changed to a room temperature reaction.

[0088] Thiazole-4-carboxylic acid was used instead of 3,3,3-trifluoropropionic acid in the second step reaction.

[0089] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 8.87 (d, J = 2.0 Hz, 1H), 8.33 (d, J = 2.0 Hz, 1H), 7.81 (d, J = 2.4 Hz, 1H), 7.53 (d, J = 2.4 Hz, 1H), 6.97 (d, J = 2.2 Hz, 1H), 2.77 (d, J = 2.3 Hz, 1H); HRMS (El) m / z [M]+C 13 H6Cl3NO2S, calc: 344.9185, found: 344.9190.

[0090] Example 5: Preparation of 1-(2,3,5-trichlorophenyl)but-2-yn-1-yl 3,3,3- trifluoropropionate

[0091] The synthesis of the target compound was similar to Example 1, except that

[0092] Propynyl magnesium bromide was used instead of methyl magnesium bromide in the synthesis of the intermediate; the oil bath reaction was changed to a room temperature reaction.

[0093] The final test results are as follows: 1H NMR (400 MHz, CDC13) δ 7.65 (s, 1H), 7.50 (s, 1H), 6.71 (s, 1H), 3.24 (q, J = 10.0 Hz, 2H), 1.93 (s, 3H); HRMS (El) m / z [M]+C 13 H8Cl3F3O2, calculated: 357.9542, found: 357.9546.

[0094] Example 6: Preparation of 1-(2,3,5-trichlorophenyl)but-2-yn-1-yl thiazole-4- carboxylate

[0095] The synthesis of the target compound is similar to Example 1, except that,

[0096] In the synthesis of the intermediate, propynyl magnesium bromide is used instead of methyl magnesium bromide; the oil bath reaction is replaced by a room temperature reaction.

[0097] In the second step reaction, thiazole-4-carboxylic acid is used instead of 3,3,3- trifluoropropionic acid.

[0098] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 8.86 (d, J = 2.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 7.77 (d, J = 2.4 Hz, 1H), 7.49 (d, J = 2.4 Hz, 1H), 6.92 (d, J = 2.1 Hz, 1H), 1.92 (d, J = 2.1 Hz, 3H); HRMS (El) m / z [M]+C 14 H8Cl3NO2S, calculated: 358.9341, found: 358.9347.

[0099] Example 7: Preparation of cyclopropyl(2,3,5-trichlorophenyl)methyl 3,3,3- trifluoropropionate

[0100] The synthesis of the target compound is similar to Example 1, except that,

[0101] In the synthesis of the intermediate, cyclopropyl magnesium bromide is used instead of methyl magnesium bromide; the oil bath reaction is replaced by a room temperature reaction.

[0102] The final test results are as follows: 1H NMR (400 MHz, CDC13) δ 7.53 (dd, J = 2.0, 1.1 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 5.25 (d, J = 1.0 Hz, 1H), 3.43 (q, J = 7.5 Hz, 2H), 2.58 (s, 1H), 1.50 (d, J = 0.9 Hz, 4H); HRMS (El) m / z [M]+C 13 H 10 Cl3F3O2, calculated: 359.9698, found: 359.9694.

[0103] Example 8: Preparation of cyclopropyl(2,3,5-trichlorophenyl)methyl thiazole-4- carboxylate

[0104] The synthesis of the target compound was similar to Example 1, except that

[0105] The intermediate was synthesized using cyclopropylmagnesium bromide instead of methylmagnesium bromide; the oil bath reaction was changed to a room temperature reaction.

[0106] Thiazole-4-carboxylic acid was used instead of 3,3,3-trifluoropropionic acid in the second step reaction.

[0107] The final test results were as follows: 1 H NMR (400 MHz, CDC13) δ 7.53 (dd, J = 2.0, 1.1 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 5.25 (d, J = 1.0 Hz, 1H), 3.43 (q, J = 7.5 Hz, 2H), 2.58 (s, 1H), 1.50 (d, J = 0.9 Hz, 4H); HRMS (El) m / z [M]+C 14 H 10 Cl3NO2S, calculated: 360.9498, found: 360.9495.

[0108] Example 9: Preparation of cyano(2,3,5-trichlorophenyl)methyl 3,3,3- trifluoropropionate

[0109] Synthesis of the intermediate [2-hydroxy-2-(2,3,5-trichlorophenyl)acetonitrile]:

[0110] In a 100 mL three-necked flask, 5 mmol of 2,3,5-trichlorobenzaldehyde was dissolved in 15 mL of anhydrous DMF, 0.05 mmol of potassium carbonate was added, and the gas was replaced three times under argon protection. 6 mmol of TMSCN was added dropwise at room temperature, and the reaction was stirred at room temperature. TLC was used to monitor the reaction. After the reaction was completed, it was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate (30 mL*3), dried over anhydrous sodium sulfate, and distilled under reduced pressure. No purification was needed, and it was directly used in the next step.

[0111] Target compound I-23 [cyano(2,3,5-trichlorophenyl)methyl 3,3,3-trifluoropropionate]

[0112] The synthesis of the target compound was the same as in Example 1.

[0113] The final test results are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.54 (dd, J = 2.0, 1.1 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 6.60 (d, J = 1.0 Hz, 1H), 3.46 (q, J = 10.0 Hz, 2H); HRMS (EI) m / z [M]+C 11 H 15 Cl3F3NO2, calculated: 344.9338, found: 344.9342.

[0114] Example 10: Preparation of cyano(2,3,5-trichlorophenyl)methyl thiazole-4-carboxylate

[0115] The synthesis of the target compound was similar to that of Example 9, except that

[0116] Thiazole-4-carboxylic acid was used instead of 3,3,3-trifluoropropionic acid in the second step reaction.

[0117] The final test results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.85 (s, 1H), 7.59 (dd, J = 2.0, 0.9 Hz, 1H), 7.52 (d, J = 2.0 Hz, 1H), 7.39 (s, 1H), 6.79 (d, J = 0.9 Hz, 1H); HRMS (EI) m / z [M]+C 14 H 10 Cl3NO2S, calculated: 345.9137, found: 345.9141.

[0118] Example 11: Preparation of cyclobutyl(2,3,5-trichlorophenyl)methyl 3,3,3-trifluoropropionate

[0119] The synthesis of the target compound was similar to Example 1, except that

[0120] The intermediate synthesis used cyclobutyl magnesium bromide instead of methyl magnesium bromide; the oil bath reaction was changed to a room temperature reaction.

[0121] The final test results were as follows: 1 H NMR (400 MHz, CDC13) δ 7.53 (dd, J = 2.0, 0.9 Hz, 1H), 7.50 (d, J = 2.0 Hz, 1H), 5.28 (d, J = 1.1 Hz, 1H), 3.43 (q, J = 7.5 Hz, 2H), 2.40 (s, 1H), 1.72 - 1.23 (m, 6H); HRMS (El) m / z [M]+C 14 H 12 Cl3F3O2, calc. 373.9855, found: 373.9857.

[0122] Example 12: Preparation of cyclobutyl (2,3,5-trichlorophenyl)methyl thiazole-4- carboxylate

[0123] The synthesis of the target compound was similar to Example 1, except that

[0124] The intermediate synthesis used cyclobutyl magnesium bromide instead of methyl magnesium bromide; the oil bath reaction was changed to a room temperature reaction.

[0125] The second step reaction used thiazole-4-carboxylic acid instead of 3,3,3- trifluoropropionic acid.

[0126] The final test results were as follows: 1 H NMR (400 MHz, CDC13) δ 7.53 (dd, J = 2.0, 0.9 Hz, 1H), 7.50 (d, J = 2.0 Hz, 1H), 5.28 (d, J = 1.1 Hz, 1H), 3.43 (q, J = 7.5 Hz, 2H), 2.40 (s, 1H), 1.72 - 1.23 (m, 6H); HRMS (El) m / z [M]+C 15 H 12 Cl3NO2S, calc. 374.9654, found: 374.9650.

[0127] Example 13: Preparation of fluoro(2,3,5-trichlorophenyl)methyl 3,3,3- trifluoropropionate

[0128] In a 100 mL three-necked flask, 5 mmol of 3,3,3-trifluoropropanoic acid was dissolved in 15 mL of anhydrous DCM, and replaced with argon gas for three times, 10 mmol of DAST was added slowly dropwise under ice bath condition, after stirring for 20 min, 15 mmol of 2,3,5-trichlorobenzaldehyde (dissolved in 20 mL of DCM) was added, and the reaction was stirred at room temperature after the dropwise addition was completed. TLC was used for monitoring. After the reaction was completed, the reaction was quenched with saturated aqueous sodium bicarbonate solution, extracted with dichloromethane (30 mL*3), dried over anhydrous sodium sulfate, and distilled under reduced pressure. Column chromatography gave fluoro(2,3,5-trichlorophenyl)methyl 3,3,3-trifluoropropanoate.

[0129] The final test results are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 2.0, 1.0 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 6.45 (d, J = 0.9 Hz, 1H), 3.43 (q, J = 7.5 Hz, 2H); HRMS (EI) m / z [M]+C 10 H5Cl3F4O2, calculated: 337.9291, found: 337.9286.

[0130] Example 14: Preparation of fluoro(2,3,5-trichlorophenyl)methyl thiazole-4- carboxylate

[0131] The synthesis of the target compound is similar to Example 13, except that

[0132] thiazole-4-carboxylic acid is used instead of 3,3,3-trifluoropropanoic acid.

[0133] The final test results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.85 (s, 1H), 7.64 (dd, J = 2.0, 1.1 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.48 (s, 1H), 7.32 (d, J = 1.1 Hz, 1H); HRMS (EI) m / z [M]+C 11 H5Cl3FNO2S, calculated: 338.9091, found: 338.9095.

[0134] Example 15: Preparation of 1-(2,3,5-trichlorophenyl)but-3-yn-2-yl 3,3,3- trifluoropropanoate

[0135] Synthesis of intermediate a [2-(2,3,5-trichlorophenyl)ethan-1-ol]

[0136] In a 100 mL round bottom flask, 20 mmol of 2,3,5-trichlorobenzenacetic acid was dissolved in 40 mL of dry THF and slowly added to a round bottom flask containing a magnetic stir bar with a solution of LiAIH4(24 mmol, 1.2 eq) under ice bath conditions, 0 °C stirred for one hour, upon completion, the reaction mixture was quenched by the addition of cold water until no more hydrogen gas was evolved.

[0137] The reaction mixture was extracted with ether (3 x 20 mL). The combined organic phases were washed with brine (20 mL), dried over anhydrous Na2S04and concentrated in vacuo to obtain intermediate a for the next step without further purification.

[0138] Synthesis of intermediate b [2-(2,3,5-trichlorophenyl)acetaldehyde]

[0139] To intermediate a (20 mmol, 1.0 eq) was added DCM (50 mL) DMP (24 mmol, 1.2 eq). The reaction mixture was stirred at room temperature for 2 hours. Upon completion, the reaction mixture was quenched by the addition of saturated sodium thiosulfate (50 mL) and stirred until the organic phase became clear (about 30 minutes). The organic phase was washed with brine (20 mL), dried over anhydrous Na2S04and concentrated in vacuo to obtain a residue which was subjected to flash column chromatography on silica gel to obtain intermediate b.

[0140] Synthesis of intermediate c [1-(2,3,5-trichlorophenyl)but-3-yn-2-ol]

[0141] Synthesis of intermediate c was similar to example 3, except that 2,3,5- trichlorobenzeneacetaldehyde was used instead of 2,3,5-trichlorobenzaldehyde.

[0142] Target compound I-196 [1-(2,3,5-trichlorophenyl)but-3-yn-2-yl 3,3,3- trifluoropropanoate]

[0143] Synthesis of target compound was similar to example 1, except that,

[0144] 1-(2,3,5-trichlorophenyl)but-3-yn-2-ol instead of 1-(2,3,5-trichlorophenyl)ethan-1-ol.

[0145] The final test results were as follows: 1H NMR (400 MHz, CDC13) δ 7.52 (d, J = 1.8 Hz, 1H), 7.38 (dt, J = 2.0, 1.0 Hz, 1H), 5.17 (s, 1H), 3.56 (q, J = 10.0 Hz, 2H), 3.29 (s, 1H), 3.24 - 2.98 (m, 2H); HRMS (El) m / z [M]+C 10 H5Cl3F3O2, calc. 357.9542, found: 357.9546.

[0146] Example 16: Preparation of 1-(2,3,5-trichlorophenyl)but-3-yn-2-yl thiazole-4- carboxylate

[0147] The synthesis of the target compound was similar to Example 15, except that,

[0148] Thiazole-4-carboxylic acid was used instead of 3,3,3-trifluoropropionic acid in the last step reaction.

[0149] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 8.85 (s, 1H), 7.52 (d, J = 1.8 Hz, 1H), 7.39 (s, 1H), 7.37 - 7.35 (m, 1H), 5.15 (s, 1H), 3.45 (d, J = 1.0 Hz, 2H), 3.28 (s, 1H); HRMS (El) m / z [M]+C 14 H8Cl3NO2S, calc. 358.9341, found: 358.9346.

[0150] Example 17: Preparation of 1-(3,5-dichloro-2-methylphenyl)prop-2-yn-1-yl 3,3,3- trifluoropropionate

[0151] Synthesis of intermediate a [3,5-dichloro-2-methylbenzaldehyde]

[0152] In a 100 mL three-necked flask, to a solution of 10 mmol of 2,3,5-trichlorobenzaldehyde in tetrahydrofuran was added dropwise 20 mmol of n-butyllithium (n-hexane solution) slowly at -78 °C under the protection of nitrogen, the reaction was stirred at -78 °C for one hour, then 15 mmol of DMF was added dropwise to the mixed solution, and the reaction was continued for one hour. After the reaction was completed, the reaction was quenched with saturated ammonium chloride solution, and the reaction mixture was extracted with ethyl acetate (3 x 20 mL). The combined organic phase was dried over anhydrous sodium sulfate and concentrated in vacuum to obtain the intermediate for the next step without further purification.

[0153] The synthesis of intermediate b [1-(3,5-dichloro-2-methylphenyl)prop-2-yn-1-ol] was similar to Example 1, except that

[0154] Ethynylmagnesium bromide was used instead of methylmagnesium bromide; the oil bath reaction was changed to room temperature reaction.

[0155] Compound I-214 [1-(2,3,5-trichlorophenyl)but-3-yn-2-yl 3,3,3-trifluoropropanoate]

[0156] The synthesis of the target compound was similar to Example 1, except that,

[0157] 1-(3,5-dichloro-2-methylphenyl)prop-2-yn-1-ol was used instead of 1-(2,3,5-trichlorophenyl)ethan-1-ol.

[0158] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 7.48 (d, J = 2.0 Hz, 1H), 7.26 (dd, J = 2.0, 1.1 Hz, 1H), 7.19 (d, J = 0.9 Hz, 1H), 3.46 q, J = 10.0 Hz, 2H), 3.14 (s, 1H), 2.53 (s, 2H); HRMS (EI) m / z [M]+C 13 H9Cl2F3O2, calc. 323.9932, found: 323.9936.

[0159] Example 18: Preparation of 1-(3,5-dichloro-2-methylphenyl)prop-2-yn-1-yl thiazole-4-carboxylate

[0160] The synthesis of the target compound was similar to Example 19, except that,

[0161] Thiazole-4-carboxylic acid was used instead of 3,3,3-trifluoropropanoic acid in the last step reaction.

[0162] The final test results are as follows: 1 H NMR (400 MHz, CDC13) δ 8.85 (s, 1H), 7.52 (s, 1H), 7.41 (d, J = 2.0 Hz, 1H), 7.29 (s, 0H), 6.72 (d, J = 0.9 Hz, 1H), 3.04 (s, 1H), 2.53 (s, 3H); HRMS (EI) m / z [M]+C 14 H9Cl2NO2S, calc. 324.9731, found: 324.9735.

[0163] Using the synthetic methods of Examples 1-18 or analogous organic reactions, other compounds in Table 1 were synthesized.

[0164] Example 19: Biological activity test of the compounds of the present application

[0165] (1) Activation of four test plant pathogenic fungi

[0166] R.S. (Rhizoctonia solani); B.C. (Botrytis cinerea); F.g. (Fusarium Gibberella); S.S. (Sclerotinia sclerotiorum).

[0167] The slant culture of Rhizoctonia solani was picked up with a needle and inoculated into a PDA plate using the streaking method. The plate was activated in an incubator at (28±1) °C for 48 h.

[0168] The slant culture of Botrytis cinerea was picked up with a needle and inoculated into a PDA plate using the streaking method. The plate was activated in an incubator at (25±1) °C for 72 h.

[0169] The slant culture of Fusarium Gibberella was picked up with a needle and inoculated into a PDA plate using the streaking method. The plate was activated in an incubator at (25±1) °C for 96 h.

[0170] The slant culture of Sclerotinia sclerotiorum was picked up with a needle and inoculated into a PDA plate using the streaking method. The plate was activated in an incubator at (28±1) °C for 48 h.

[0171] (2) Determination of antibacterial activity by mycelial growth rate method

[0172] 1 mg of the compound was dissolved in 1 mL of dimethyl sulfoxide (DMSO) to prepare a 1000 mg / L original drug mother liquor. 0.5 mL of the drug-containing DMSO solution and 0.5 mL of 0.1% Tween 80 aqueous solution were added to 49 mL of PDA medium, the mother liquor was diluted 100 times, and the final concentration was 10 mg / L. The blank control was 0.5 mL of DMSO + 0.5 mL of 0.1% Tween 80 aqueous solution. The drug-containing PDA medium was shaken and poured into three sterile culture dishes with a diameter of 9 cm. After the PDA solidified, the fungus to be tested was selected, a puncher was used to make a fungus cake with a diameter of 5 mm, which was then inoculated into the drug-containing medium. The culture dish was sealed to isolate bacterial contamination, labeled and placed in a light incubator at a specific temperature for culture. The culture was incubated for 48-96 h.

[0173] The diameter of the colony growth was measured by the cross method and the inhibition rate was calculated by the following formula:

[0174] The results of the antibacterial activity of the compound of formula (I) against four plant fungi at 10 mg / L are shown in Table 1.

[0175] Table 2. Antimicrobial activity of the compound of formula (I)

[0176] All documents referred to in the present application are incorporated herein by reference as if each individual document were incorporated by reference. Furthermore, it is to be understood that various modifications and changes can be devised by those skilled in the art which will embody the principles of the present application and the foregoing is intended to be taken as a broad description of the present application.

Claims

1. A methylene ester bridged compound, and its optical isomer, cis-trans isomer or a pesticidally acceptable salt thereof, characterized by, The compound has a structure as shown in formula (I): Wherein, A is independently selected from the group consisting of: phenyl, -(C1-C8 alkylene)phenyl, -N=CH-phenyl; wherein one or more hydrogen atoms on A are optionally substituted by Ra, wherein Ra is selected from the group consisting of: halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C8 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C6-C 10 Aryl, 4-8 membered heteroaryl, 4-8 membered heterocyclic, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C1-C6 thioalkyl; T is independently: halogen, hydroxyl, nitro, amino, cyano, or a substituted or unsubstituted group selected from the group consisting of: C1-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenoxy, C2-C6 alkynoxy, C1-C6 alkoxy, C3-C6 cycloalkoxy, C5-C7 cycloalkenyl, C3-C 10 Cycloalkyl, 4-8 membered heterocyclic, C6-C 10 Aryl, 5-8 membered aromatic heterocyclic, -(C1-C8 alkylene)(C6-C 10 aryl), -(C6-C 10 aryl)-O-(C6-C 10 aryl), -(C6-C 10 aryl)-(C6-C 10 aryl), -(C1-C8 alkylene)(5-10 heteroaryl), -OC(=O)(C6-C 10 aryl), -OC (=O)(C6-C 10 Aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C 10 Aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl), -(C1-C8 alkylene)(C3-C6 cycloalkyl), -(C1-C8 alkylene)(4-10 heterocyclic), -(C1-C8 alkylene)NHC(=O)(4-10 heteroaryl); W is independently: cyano, substituted or unsubstituted groups selected from the group consisting of C1-C1. 10 Alkyl, C2-C6 alkenyl, C2-C6 ynyl, C6-C 10 Aryl, 5-8 membered heteroaryl, 4-8 membered heterocyclic, C3-C 10 Cycloalkyl, -(C1-C8 alkylene)(C3-C 10 cycloalkyl), -(C1-C8 alkylene)(C6-C 10 aryl), -(C1-C8 alkylene)(4-10 heteroaryl), -(C1-C8 alkylene)(4-8 heterocyclic), -O(C1-C 10 Alkyl), -O (C3-C) 10 cycloalkyl), -O (C6-C) 10 aryl), -O (4-10 membered heteroaryl), -O (4-8 membered heterocyclic), -NH (C1-C 10 Alkyl), -NH (C3-C) 10 cycloalkyl), -NH (C6-C 10 Aryl), -NH (4-10 membered heteroaryl), -NH (4-8 membered heterocyclic); Unless specifically indicated, the substituents are one or more hydrogen atoms on a group replaced by a substituent selected from the group consisting of deuterium, halogen, cyano, nitro, C1-C4alkyl, C1-C4alkoxy, halogenated C1-C4alkyl, halogenated C1-C4alkoxy.

2. The compound of claim 1, wherein The compounds have the structure of formula (I-A) and formula (I-B): wherein R1is selected from the group consisting of halogen, cyano, nitro, hydroxy, substituted or unsubstituted C1-C8alkyl; m, n are each independently an integer between 0 and 5; the remaining substituents are as described in claim 1.

3. The compound of claim 1, wherein each said T is independently halogen, hydroxy, nitro, amino, cyano, C1-C4alkyl, haloC1-C4alkyl, C2-C4alkenyl, haloC2-C4alkenyl, C2-C4alkynyl, haloC2-C4alkynyl, C2-C4alkenyloxy, haloC2-C4alkenyloxy, C2-C4alkynyloxy, haloC2-C4alkynyloxy, C1-C4alkoxy, or a substituted or unsubstituted group of the following group: C3-C7cycloalkyl, 5-6 membered heterocyclyl, phenyl, 5-6 membered aromatic heterocyclyl, biphenyl, naphthyl, 4. The compound of claim 1, wherein each said T is independently: halogen, hydroxy, nitro, amino, cyano, methyl, ethyl, propyl, isopropyl, ethynyl, propynyl, butynyl, ethoxy, propoxy, isopropoxy, propenyloxy, propynyloxy, fluoroethynyl, bromoethynyl, chloroethynyl, fluoropropynyl, bromopropynyl, chloropropynyl, fluorobutynyl, bromobutynyl, chlorobutynyl, trifluoromethyl, difluoromethyl, wherein X is selected from the group consisting of: F, Cl, Br, I, CF3, OCF3, OCH3; o, p are selected from 0, 1, 2, 3, 4, 5.

5. The compound of claim 1, wherein each W is independently cyano, C1-C4alkyl, halogenated C1-C4alkyl, or substituted or unsubstituted C3-C7cycloalkyl, phenyl, 5-8 membered heteroaryl.

6. The compound of claim 1, wherein each said W is independently: cyano, -CF3, -CH2CF3, -CH2CH2CF3, wherein Y is selected from the group consisting of: F, Cl, Br, I; q is selected from 0, 1, 2, 3, 4, 5.

7. The compound of claim 1, wherein The compounds are selected from the following table:

8. A pesticidal composition, characterized by, comprising: (a) a compound according to any one of claims 1-7, an optical isomer, a cis-trans isomer thereof, or a pesticidally acceptable salt thereof, or a combination thereof; and optionally (b) a pesticidally acceptable carrier and / or excipient.

9. The use of a compound according to any one of claims 1 to 7, an optical isomer, a geometrical isomer or a salt thereof which is acceptable in agriculture, or a pesticide composition according to claim 8, characterized in that, for the preparation of a fungicide.

10. A method for controlling plant pathogenic fungi, characterized by, comprising applying to the environment, soil, or plant in need of control a compound according to any one of claims 1-7, an optical isomer, a cis-trans isomer thereof, or a pesticidally acceptable salt thereof, or a pesticidal composition according to claim 8. for the preparation of a fungicide. comprising applying to the environment, soil, or plant in need of control a compound according to any one of claims 1-7, an optical isomer, a cis-trans isomer thereof, or a pesticidally acceptable salt thereof, or a pesticidal composition according to claim 8.

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