Pyridine amide compound and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a pyridine amide compound and the use thereof. The compound is as represented by formula I, wherein W1 is O or S; R1 is hydrogen, alkyl, alkenyl, alkynyl, etc.; R3, R4 and R5 are each independently hydrogen, halogen, alkyl, etc.; and X1, X2, X3, X 4, X5, Y1, Y2, X3 and Y4 are each independently hydrogen, halogen, alkyl, etc. The compound has a good bactericidal effect.

Description

A pyridine amide compound and its application Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a pyridine amide compound and its application. 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 WO2016109302A1 which discloses pyridine amide 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 pyridine amide compound and its applications. The compound exhibits excellent bactericidal activity.

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

[0005] A pyridine amide compound as shown in Formula I:

[0006] Where W1 is O or S;

[0007] R1 is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl;

[0008] R3, R4, and R5 are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogen, trialkylsilyl, cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n An alkyl, alkenyl, or alkynyl group substituted by at least one of the substituents in R, -O(CO)R, or -O(CO)OR;

[0009] X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, and -S(O), respectively. n R, -N(R)2, -(CO)R, -(CO)N(R)2, or an alkyl, alkenyl or alkynyl group substituted with at least one substituent selected from halogen, cycloalkyl, heterocyclic or aryl groups;

[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, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -(CO)R, -(CO)OR, -N(R)2, -(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 substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano or alkoxycarbonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0013] In one specific embodiment, R1 is hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, or C3-C8 cycloalkyl-C1-C8 alkyl.

[0014] R3, R4, and R5 are, independently, hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogens, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n A C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted with at least one of the substituents R, -O(CO)R or -O(CO)OR;

[0015] X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, and -S(O). n R, -N(R)2, -(CO)R, -(CO)N(R)2, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted with at least one substituent selected from halogen, C3-C8 cycloalkyl, heterocyclic or aryl groups;

[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, -N(R)2, -(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 or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

[0018] In another specific embodiment, R1 is hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl.

[0019] R3, R4, and R5 are, independently, hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogens, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted by at least one of R, -O(CO)R or -O(CO)OR;

[0020] X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, and -S(O), respectively. nR, -N(R)2, -(CO)R, -(CO)N(R)2, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl group substituted with at least one substituent selected from halogen, C3-C6 cycloalkyl, heterocyclic or aryl groups;

[0021] 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, -N(R)2, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R;

[0022] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano or C1-C6 alkoxycarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy.

[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 provides a pyridine amide compound having a chiral center as shown in Formula I':

[0028] Wherein, the substituents R1, R3, R4, R5, X1, X2, X3, X4, X5, Y1, Y2, Y3, Y4 and W1 are defined as described above and *the carbon atom position has at least one (1, 2 or 3) chiral centers (i.e. R3, R4 and / or R5 are not hydrogen);

[0029] Based on the content of stereoisomers having R and S configurations at position 1, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); and / or

[0030] Based on the content of stereoisomers having R and S configurations at position 2, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); and / or

[0031] Based on the content of stereoisomers having R and S configurations at position 3, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S).

[0032] "Stereochemical purity" refers to the percentage of the amount of the stereoisomer relative to the total amount of stereoisomers that generate chiral centers.

[0033] Compounds of Formula I, in their respective free or salt forms, and where appropriate, their tautomers, may exist as one of the possible isomers or as mixtures thereof, for example, as pure isomers, such as enantiomers and / or diastereomers, or as mixtures of isomers, such as mixtures of enantiomers, such as racemic mixtures, diastereomer mixtures, or racemic mixtures, depending on the number of asymmetric carbon atoms present in the molecule, their absolute and relative configurations, and / or on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers and also to all possible mixtures of isomers and should be understood in this sense in each of the above and below, even if stereochemical details are not specifically mentioned in each case. The present invention therefore covers all such isomers and tautomers and mixtures thereof in all proportions, together with isotopic forms, such as deuterated compounds.

[0034] In another embodiment, Formula I is also understood to include their salts or hydrates. Exemplary salts include, but are not limited to, hydrochlorides, hydrobroms, and hydroiodates.

[0035] 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.

[0036] Another embodiment of this application is a method for preparing the pyridine amide compound, comprising the following steps:

[0037] Compound I is prepared by a condensation reaction of compound II and compound III, and the chemical reaction equation is as follows:

[0038] Wherein, L1 represents OH or halogen; the definitions of substituents R1, R3, R4, R5, Y1, Y2, Y3, Y4, X1, X2, X3, X4, X5 and W1 are as described above.

[0039] In one specific embodiment, the reaction is carried out in the presence of a solvent and a base.

[0040] In another specific embodiment, a catalyst is added during the reaction process.

[0041] In one specific embodiment, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, 1,4-dioxane, dichloromethane, or ethyl acetate.

[0042] In one specific embodiment, the base is selected from at least one of inorganic or organic bases, such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, pyrazole, triethylamine, pyridine, or DIEA / DIPEA, etc.

[0043] In one specific embodiment, the catalyst is selected from at least one of DMAP or 4-PPy.

[0044] In addition, another embodiment of this application is a bactericidal composition containing a biologically effective amount of compound of formula I or I' (active ingredient A); preferably, in one embodiment, it further includes a formulation adjuvant; in another embodiment, it further includes other active ingredients.

[0045] In another specific embodiment, the other active ingredient (active ingredient B) is selected from at least one of the following: prothioconazole (CAS No.: 178928-70-6), difenoconazole (CAS No.: 119446-68-3), tebuconazole (CAS No.: 107534-96-3), flutriafol (CAS No.: 133855-98-8), propiconazole (CAS No.: 60207-90-1), hexaconazole (CAS No.: 79983-71-4), chlorfluazuron (CAS No.: 1417782-03-6), cyproconazole (CAS No.: 94361-06-5), cyproconazole (CAS No.: 88671-89-0), and tebuconazole (CAS No.: 836). 57-24-3), triadimefon (CAS No.: 43121-43-3), fenbendazole (CAS No.: 76674-21-0), benzimidazole (CAS No.: 1072957-71-1), fluopyram (CAS No.: 907204-31-3), thifluzamide (CAS No.: 130000-40-7), pyraclostrobin (CAS No.: 881685-58-1), bifenpyroxime (CAS No.: 581809-46-3), pyraclostrobin (CAS No.: 183675-82-3), chlorpyrifos (CAS No.: 902760-40-1), azoxystrobin (CAS No.: 915410-70-7), mancozeb (CAS No.: 57-24-3), triadimefon (CAS No.: 43121-43-3), fenbendazole (CAS No.: 76674-21-0), benzimidazole (CAS No.: 1072957-71-1), fluopyram (CAS No.: 907204-31-3), thiamethoxam (CAS No.: 130000-40-7), pyraclostrobin (CAS No.: 183675-82-3), chlorpyrifos (CAS No.: 902760-40-1), azoxystrobin (CAS No.: 915410-70-7), mancozeb ... : 8018-01-7), Zineb (CAS No.: 12122-67-7), Azoxystrobin (CAS No.: 131860-33-8), Pyraclostrobin (CAS No.: 175013-18-0), Azoxystrobin (CAS No.: 117428-22-5), Azoxystrobin (CAS No.: 143390-89-0), Azoxystrobin (CAS No.: 141517-21-7), Fluopyram (CAS No.: 1228284-64-7), Prochloraz (CAS No.: 67747-09-5), Fluopyram (CAS No.: 658066-35-4), Iprodione (CAS No.: 875915-78-9), Fluazinam (CAS No.: 79622-59-6), iprodione (CAS No.: 36734-19-7), procymidone (CAS No.: 32809-16-8), sclerotinib (CAS No.: 24096-53-5), fluopyram (CAS No.: 861647-84-9), pentachloronitrobenzene (CAS No.: 82-68-8), tricyclazole (CAS No.: 41814-78-2), isoprothiolane (CAS No.: 26087-47-8), isoprothiolane (CAS No.: 50512-35-1), isoprothiolane (CAS No.: 115852-48-7), kasugamycin (CAS No.: 6980-18-3), trifluoperoxynil (CAS No.: 911499-62-2)Allylbenzylthiazide (CAS No.: 27605-76-1), Thiopyram (CAS No.: 3052252-63-5), Ethirimol (CAS No.: 23947-60-6), Benomyl (CAS No.: 220899-03-6), Fluopyram (CAS No.: 864237-81-0), Fludioxonil (CAS No.: 131341-86-1), Carbendazim (CAS No.: 10605- 21-7), pyrimethanil (CAS No.: 53112-28-0), azoxystrobin (CAS No.: 121552-61-2), thiophanate-methyl (CAS No.: 23564-05-8), thiram (CAS No.: 137-26-8), chlorothalonil (CAS No.: 1897-45-6), captan (CAS No.: 133-06-2), or dicyandioxonone (CAS No.: 3347-22-6).

[0046] In another specific embodiment, the weight ratio of active ingredients A and B in the composition is 1:12500-50:1, 1:6250-10:1, 1:2500-5:1, 1:1250-1:1, 1:800-1:2, 1:500-1:5, 1:400-1:8, 1:320-1:10, 1:250-1:16, 1:160-1:20, 1:125-1:40, or 1:100-1:50.

[0047] Another embodiment of this application is the use of the compound of formula I or I' or the above-described fungicidal composition in the control of plant pathogenic fungi. This use is for protecting plants from plant pathogenic microorganisms or for treating plants infected by plant pathogenic microorganisms, including applying the compound of formula I or I' or a composition containing said compound to soil, plants, parts of plants, leaves, and / or roots.

[0048] 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.

[0049] Preferably, the compounds of this application are applied in formulation form, said formulation comprising one or more compounds of formula I or 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.

[0050] 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.

[0051] Wettable powders that can be pressed into water-dispersible particles comprise an intimate mixture of one or more compounds of formula I or 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.

[0052] Based on the total weight of the emulsifiable concentrate, the emulsifiable concentrate of compound I or I' can be contained in a suitable liquid at a conventional concentration, for example, from about 1 wt% to about 50 wt%. 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.

[0053] 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.

[0054] 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.

[0055] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of formula I or 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.

[0056] Compounds of Formula I or 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.

[0057] Powders containing compounds of formula I or 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 total weight.

[0058] 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 16 Ethoxylated 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.

[0059] 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.

[0060] The compounds of this application can also be combined with other fungicides to form fungicidal mixtures and 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, bitertanol, 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, mancozeb, mandipropamid, manebMefenoxam, 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, probenazoleProchloraz, 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, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazoleValidamycin, 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, Dinoterbon, Dipyrithione, and other fungicides. Ditalimfos, Dodicin, Drazoxolon, EBP, ESBP, Etaconazole, Ethim, Ethirim, Fenaminosulfonate, Fenapanil, Fenitropan, Fluotrimazole, Furcarbanil, Furconazole, Furconazole-cisFurmecyclox, 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, Sultropen, Tecoram, Thiadifluor, ThiofenThiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trihlamide, urethane, zarilamid, and any combinations thereof.

[0061] 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 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. Common insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, and amiton oxalate. oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, bioopermethrinBistrifluron, Borax, Boric acid, Bromfenvinfos, Bromocyclen, Bromo-DDT, Bromophos, Bromophos-ethyl, Bufencarb, Buprofezin, Butacarb, Butathiofos, Butocarboxim, Butonate, Butoxycarboxim, Cadusafos, Calcium arsenate, Calcium polysulfide, Camphechlor, Carbanolate, Carbaryl, Carbofuran, Carbon disulfide disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride Hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel.Clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate Coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cymethrin Thioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth Earth), diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin,Dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone ( ecdysterone, emamectin, emamectinbenzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate Formate, Ethyl-DDD, 1,2-Dibromoethane, 1,2-Dichloroethane, Ethylene oxide, Etofenprox, Etrimfos, EXD, Famphur, Fenamiphos, Fenazaflor, Fenchlorphos, Fenethacarb, Fenfluthrin, Fenitrothion, Fenobucarb, Fenoxacrim, Fenoxycarb, Fenpirithrin, FenpropathrinFensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride Hydrochloride, Fosmethilan, Fospirate, Fosthietan, Furathiocarb, Furethrin, Gamma-cyhalothrin, Gamma-HCH, Halfenprox, Halofenozide, HCH, HEOD, Heptachlor, Heptenophos, Heterophos, Hexaflumuron, HHDN, Hydamethylnon, Hydrocyanide cyanide), hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I.Jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride Chloride, mesulfenfos, metaflumizone, methicrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, emthoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methyl chloroform Chloroform, methylenechloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycinoxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naledNaphthalene, Nicotine, Nifluridide, Nitenpyram, Nithiazine, Nitrilacarb, Novaluron, Noviflumuron, Omethoate, Oxamyl, Oxdemeton-methyl, Oxdeprofos, Oxdisulfoton, Para-dichlorobenzene, Parathion, Parathion-methyl, Penfluron, Pentachlorophenol ophenol), permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite Arsenite), Potassium thiocyanate, PP'-DDT, Prallethrin, Precocene I, Precocene II, Precocene III, Primidophos, Profenofos, Profluralin, Promacyl, Promecarb, Propaphos, Proetamphos, Proxur, Prothidathion, Prothiofos, Prothoate, Protrifenbute, Pyraclofos, Pyrafluprole, PyrazophosPyrethrin, pyrethrin I, pyrethrin II II), Pyrethrins, Pyridaben, Pyridalyl, Pyridaphenthion, Pyrifluquinazon, Pyrimidifen, Pyrimitate, Pyriprole, Pyriproxyfen, Quassia, Quinalphos, Quinalphos-methyl, Quinothion, Rafoxanide, Resmethrin, Rotenone, Ryania, Sabadilla, Schradan, Selamectin, Silafluofen, Silica Gel, Sodium Arsenite, Sodium Fluoride fluoride), sodium hexafluorosilicate, sodium thiocyanate, sophamide, spintoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfurylfluoride, sulprofos, tau-fluval Inate), tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin,Tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, trisulfanilamide azamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethocarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combination thereof.

[0062] 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 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 with the herbicide, mixed with a herbicide container, or applied sequentially with the herbicide. Common herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor; acifluorfen; aclofen; acrolein; alachlor; allidochlor; alloxydim; and allyl alcohol. Alcohol), pentachloropentanolic acid (alorac), ametridone, ametryn, amibuzin, amicarazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrol, ammonium sulfate Sulfamate, Anilofos, Anisuron, Asulam, Atrazine, Azafenidin, Azimsulfuron, Aziprotryne, Barban, BCPC, Beflubutamid, Benazolin, Bencarbazone, Fluroxypyr (benfluralin), benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzzipram, benzobicyclon, benzofenap, benzofluor, benzoylpropBenzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid acid), cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, ethoxyfen (ch Loreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylinCinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clonazol, clonazol, clonazol, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate sulfate), CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dilamide chlormate), 2,4-D propionic acid (dichlorprop), dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, di Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimexano, Dimidazon, Dinitramine, DinofenateDinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron. Herbicides including ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, and ferrous sulfate. Sulfate), Flamprop, Flamprop-M, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazolate, Flucarbazone, Flucetosulfuron, Fluchloralin, Flufe nacet), flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine,Fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, quizalofop-P (haloxyfop-P), hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indicarb indanofan), indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocillin, isomethiozin, isoruron, nitrogen, Herbicides include: isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactoferrin, lenacil, linuron, methylarsine (MAA), monoammonium methylarsine (MAMA), MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, and mefenoxam. Fenacet), mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, metalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide bromide, methyl isothiocyanate, methyl dymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monouron, morfamquat, MSMA.Naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, octachlorophen, orbencarb, orthylamine o-dichlorobenzene), orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid acid), pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate cyanate), pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor,Propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, promethazine Xan), Prynachlor, Pydanon, Pyraclonil, Pyraflufen, Pyrasulfotole, Pyrazolynate, Pyrazosulfuron, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyriclor, Pyridafol, Pyr idate), pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P ), rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid.Sulglycapin, Swep, TCA, Tebutam, Tebuthiuron, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbuthylazine, Tebuchlor rbutryn), tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, pyrimethanil tioclorim), toramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, trilopyr, tridiphane, trietazine, trifloxysulfuron The following herbicides are listed: trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

[0063] 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 against fungal invasion, with a compound of formula I or I' or the aforementioned fungicidal composition.

[0064] 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.

[0065] 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.

[0066] 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. Tomato (Alternaria solani) and barley spot disease (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 the compound may not be equally effective or effective against the same species of fungus at similar concentrations.

[0067] 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 ).

[0068] It will be apparent to those skilled in the art to understand the teachings of this document that any range or desired value given herein can be extended or modified without losing the desired effect. Detailed Implementation

[0069] 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.

[0070] 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.

[0071] Table 1. Compound Structures

[0072] Table 2 Compounds1 H NMR values

[0073] Table AC is constructed in the same way as Table 1 above, except that the general formula I is replaced with the general formula I' which has a chiral center at the * position. (The * position contains at least one chiral center). In Table A, the entries under the "Serial Number" column heading are described as 1(1S)-53(1S), 55(1S)-152(1S). For example, 1(1S) corresponds to the compound 1 in Table 1 where the chiral carbon at the * position of the general formula is in the S configuration; in Table B, the entries under the "Serial Number" column heading are described as 1(1S,2S)-48(1S,2S), 50(1S,2S)-53(1S,2S), 55(1S,2S)-152(1S,2S). For example, 1(1S,2S) corresponds to the compound in Table 1 where the chiral carbons at positions 1 and 2 are all in the S configuration; in Table C, the entries under the "Serial Number" column heading are described sequentially as 1(1S,2S,3S)-48(1S,2S,3S), 50(1S,2S,3S)-53(1S,2S,3S), and 55(1S,2S,3S)-152(1S,2S,3S). For example, 1(1S,2S,3S) corresponds to the compound in Table 1 where the chiral carbons at positions 1, 2, and 3 are all in the S configuration.

[0074] 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.

[0075] 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.

[0076] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0077] 1. Synthesis of compound 10 (1S, 2S, 3S)

[0078] (1) Compound 10-2 (829 mg, 4.39 mmol) was dissolved in 10 mL of THF. Triethylamine (888 mg, 8.79 mmol), pentanoyl chloride (529 mg, 4.39 mmol), compound 10-1 (580 mg, 2.93 mmol), and a catalytic amount of DMAP were added sequentially in an ice bath. The reaction was carried out overnight at room temperature. The reaction was monitored by LCMS until complete. The reaction was quenched with saturated ammonium chloride. The reaction solution was concentrated and diluted with ethyl acetate. The organic phase was washed with water and saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 1 / 3) to give compound 10-3 (1020 mg, 94.3%).

[0079] (2) Compound 10-3 (1020 mg, 2.76 mmol) was dissolved in 5 ml DCM, and 10 ml hydrochloric acid-dioxane solution was added. The reaction was carried out for 1 hour. The reaction was monitored by LCMS until it was complete. The reaction solution was evaporated to dryness to obtain crude compound 10-4 (743 mg, 100% yield).

[0080] (3) Compound 10-4 (743 mg, 2.76 mmol) was dissolved in 10 ml of DMF, and triethylamine (558 mg, 5.52 mmol) was added and reacted for 1 hour. Compound 10-5 (466 mg, 2.76 mmol), 4-methylmorpholine (1115 mg, 11 mmol), HOBT (558 mg, 4.14 mmol) and EDCI (791 mg, 4.14 mmol) were added sequentially and reacted overnight at room temperature. The reaction was monitored by LCMS until complete. The reaction solution was concentrated, diluted with ethyl acetate, and the organic phase was washed with water and saturated brine. The solution was dried and concentrated. The residue was purified by column chromatography (EA / PE = 1 / 2) to obtain compound 10-6 (590 mg, 50.8%).

[0081] (4) Compound 10-6 (330 mg, 0.79 mmol) was dissolved in 10 ml of DCM, triethylamine (239 mg, 2.37 mmol) and a catalytic amount of DMAP were added, and then a DCM solution of compound 10-7 (168 mg, 1.19 mmol) was added dropwise. The reaction was carried out for 1 hour, and the reaction was monitored by LCMS to ensure complete reaction. The reaction solution was washed with saturated brine, dried and concentrated. The residue was purified by column chromatography (EA / PE = 3 / 1) to obtain compound 10 (1S, 2S, 3S) (168 mg, 40.7%).

[0082] 2. Synthesis of compound 21 (1S, 2S, 3S)

[0083] Dissolve 21-2 (0.11 g, 1.20 eq) in DCM (5.0 mL), add (COCl)2 (0.27 g, 3.00 eq), add two drops of DMF, react for 1 h, and concentrate the reaction solution. Dissolve 21-1 (0.30 g, 1.00 eq) in DCM (5.0 mL), add triethylamine (0.22 g, 3.00 eq) and DMAP (0.017 g, 0.2 eq), stir for 10 min, dissolve the prepared 2-pyridinecarboxyl chloride in a small amount of DCM, add it to the reaction solution, and react at room temperature for 2 h. Dilute the reaction solution with acetonitrile and monitor with LCMS; the starting material disappears, and the product becomes the main peak. Add water and DCM to the reaction solution, separate the layers, extract the aqueous phase three times with DCM, combine the organic phases, wash the organic phase once with saturated brine, and concentrate. Purified by column chromatography (EA / PE = 1:3) to give 21(1S, 2S, 3S) (white solid, 2.10 g, yield = 57%).

[0084] 3. Synthesis of compound 6 (1S)

[0085] (1) Dissolve 6-2 (1.9 g, 1.50 eq) in 20 mL of tetrahydrofuran. Add potassium tert-butoxide (870 mg, 2.0 eq) under ice bath conditions and stir at room temperature for 40 minutes. Then add 6-1 (0.9 g, 1.0 eq) and stir overnight at room temperature. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The starting material disappears, and the product becomes the main peak. Pour the reaction solution into ice water and extract with ethyl acetate. Wash the organic phase once with saturated sodium chloride solution, dry with anhydrous sodium sulfate, concentrate the organic phase, add silica gel and mix. Purify by column chromatography to obtain 6-3 (white oil, 800 mg, yield = 80%).

[0086] (2) Dissolve 6-3 (800 mg, 1.00 eq) in hydrochloric acid-dioxane solution and stir at room temperature for 1 h. Take the reaction solution, dilute with acetonitrile, and send it to LCMS for monitoring. The starting material disappears, and the product is the main peak. Concentrate the reaction solution under reduced pressure to remove residual solvent, then add silica gel and mix. Purify by column chromatography to obtain 6-4 (white oily substance, 750 mg, yield = 99%).

[0087] (3) Dissolve 6-4 (750 mg, 1.0 eq) in 10 mL of tetrahydrofuran, add methyl magnesium bromide (2.0 mL, 2.0 eq) under ice bath conditions, and stir for 1 h at room temperature. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The starting material disappears, and the product becomes the main peak. Quench the reaction solution with dilute hydrochloric acid, and then extract three times with ethyl acetate. Combine the organic phases, wash the organic phase once with saturated brine, concentrate, and use directly in the next step without purification.

[0088] (4) N-tert-Butoxycarbonyl-L-alanine (810 mg, 1.4 eq) was dissolved in 10 mL of tetrahydrofuran. Triethylamine (1.39 g, 4.5 eq) and tert-valeryl chloride (513 mg, 1.4 eq) were added sequentially under ice bath conditions. After stirring for 15 min, crude product 6-5 from the previous step and a catalytic amount of 4-dimethylaminopyridine were added. The reaction solution was then moved to room temperature and stirred for 5 h. The reaction solution was taken, diluted with acetonitrile, and monitored by LCMS. The starting material disappeared, and the product became the main peak. The reaction solution was quenched with saturated ammonium chloride solution, then extracted three times with ethyl acetate. The organic phase was washed once with saturated sodium bicarbonate solution and once with saturated brine. The solution was concentrated and used directly in the next step without further purification.

[0089] (5) Dissolve the crude product 6-6 from the previous step in hydrochloric acid-dioxane solution and stir at room temperature for 2 hours. Take the reaction solution, dilute it with acetonitrile, and monitor it by LCMS. The starting material disappears, and the product becomes the main peak. Rotate the reaction solution to dryness. It can be used directly in the next step without purification.

[0090] (6) Dissolve 10-5 (516 mg, 1.0 eq) in dichloromethane, add benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (1.58 g, 1.0 eq) at room temperature, stir for 30 min, then add a mixed solution of crude product 6-7 from the previous step in dichloromethane and triethylamine (1.23 g, 4.0 eq). Stir at room temperature for 5 h. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The starting material disappears, and the product becomes the main peak. Add the reaction solution directly to silica gel and mix. Purify by column chromatography to obtain 6-8 (pale yellow oil, 500 mg, yield = 34%).

[0091] (7) Dissolve 2-pyridinecarboxylic acid (51 mg, 1.0 eq) in 10 mL of dichloromethane, add oxaloyl chloride (157 mg, 3.0 eq) and 2 drops of N,N-dimethylformamide, stir at room temperature for 30 min, and after the reaction is complete, evaporate the reaction solution to an oily state to prepare the acyl chloride for later use. Dissolve 6-8 (200 mg, 1.0 eq) in 10 mL of dichloromethane, add triethylamine (125 mg, 3.0 eq) and 4-dimethylaminopyridine (10 mg, 0.2 eq) in sequence, and add the prepared acyl chloride solution in dichloromethane dropwise under ice bath, stirring at room temperature for 1 h. Take the reaction solution, dilute with acetonitrile, and monitor by LCMS. The starting material disappears, and the product is the main peak. Evaporate the reaction solution to an oily state, load the sample onto a silica gel column by wet method, and purify by column chromatography to obtain the target compound 6 (1S) (light yellow solid, 130 mg, yield = 53.49%).

[0092] 4. Synthesis of compound 16 (1S, 2S, 3S)

[0093] (1) Dissolve 16-1 (1000 mg, 2.1 mmol, 1 eq), potassium trifluoroborate (431 mg, 3.2 mmol, 1.5 eq), and CsF (816 mg, 5.37 mmol, 2.5 eq) in 10 mL of dioxane and 1 mL of water. After purging three times, add Pd(dppf)Cl2·CH2Cl2 (105 mg, 0.13 mmol, 0.06 eq). After the addition is complete, purge three times and heat to 85 °C overnight. The reaction is then complete. The reaction mixture is concentrated and filtered through a column to obtain product 16-2 (700 mg, Y = 78%).

[0094] (2) Dissolve 2-pyridinecarboxylic acid (59 mg, 0.48 mmol, 1 eq) in 20 mL of dichloromethane, add 1 drop of N,N-dimethylformamide, and add oxaloyl chloride (153 mg, 1.2 mmol, 2.5 eq) dropwise. After the addition is complete, react at room temperature for 0.5 h, and concentrate to prepare acyl chloride for later use. Dissolve 16-2 (200 mg, 0.48 mmol, 1 eq) in 20 mL of dichloromethane, cool to 0 °C, add triethylamine (245 mg, 2.4 mmol, 5 eq), and add the above acyl chloride solution dropwise. After the reaction is complete for 0.5 h, add water, stir and separate the liquids. Mix the organic phase and pass it through a column to obtain product 16(1S, 2S, 3S) (100 mg, Y = 39%).

[0095] 5. Synthesis of compound 18 (1S, 2S, 3S)

[0096] (1) Compound 18-1 (2.5 g, 0.014 mol) and CuI (6.6 g, 0.03 mol) were added to 100 mL of acetonitrile, and isoamyl nitrite (3.5 g, 0.03 mol) was added dropwise. The mixture was heated to 40 °C and stirred until the reaction was complete. The mixture was directly mixed and purified in normal phase to obtain compound 18-2 (1.25 g, 0.004 mol, y = 31%).

[0097] (2) Compound 18-2 (250 mg, 0.86 mmol), trimethylethynylsilane (169 mg, 1.72 mmol) and CuI (0.1 eq) were added to 5 mL of triethylamine. After purging, Pd(PPh3)2Cl2 (0.1 eq) was added and the temperature was raised to 70 °C and stirred until the reaction was complete. The mixture was directly mixed and purified in normal phase to obtain compound 18-3 (220 mg, 0.85 mmol, y = 98%).

[0098] (3) N-tert-butoxycarbonyl-L-alanine (241 mg, 1.28 mmol) was dissolved in 10 mL of tetrahydrofuran. Triethylamine (258 mg, 2.6 mmol) and tert-valeryl chloride (154 mg, 1.28 mmol) were added sequentially under ice bath conditions. The mixture was stirred for 15 min. Then, compound 18-3 (220 mg, 0.85 mmol) and catalytic amount of 4-dimethylaminopyridine were added. The reaction solution was brought to room temperature and stirred until the reaction was complete. The mixture was extracted with water and ethyl acetate and purified in normal phase to obtain compound 18-4 (350 mg, 0.81 mmol, y = 96%).

[0099] (4) Dissolve compound 18-4 (350 mg, 0.81 mmol) in 10 mL of hydrochloric acid-dioxane solution and stir at room temperature until the reaction is complete. After concentration, the crude product of compound 18-5 is obtained and used directly in the next step.

[0100] (5) The crude compound 18-5, compound 10-5 (204 mg, 1.22 mmol) and triethylamine (245 mg, 2.43 mmol) were dissolved in 10 mL of dichloromethane and stirred at room temperature for 0.5 h. Then, benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (632 mg, 1.22 mmol) was added and stirred at room temperature until the reaction was complete. The mixture was extracted with water and dichloromethane and purified in normal phase to obtain compound 18-6 (300 mg, 0.62 mmol, y = 77%).

[0101] (6) Compound 18-6 (300 mg, 0.62 mmol) was dissolved in 5 mL of methanol, and potassium fluoride (144 mg, 2.48 mmol) was added. The mixture was stirred at room temperature until the reaction was complete. After concentration, it was extracted with water and ethyl acetate to obtain compound 18-7 (230 mg, 0.56 mmol, y = 90%).

[0102] (7) Compound 18-7 (230 mg, 0.56 mmol), triethylamine (170 mg, 1.68 mmol) and catalytic amount of 4-dimethylaminopyridine were dissolved in 5 mL of dichloromethane. A dichloromethane solution of compound 2-pyridinecarboxyl chloride (79 mg, 0.56 mmol) was added dropwise under ice bath. The mixture was stirred until the reaction was complete. The mixture was extracted with water and dichloromethane and purified in normal phase to obtain compound 18 (1S, 2S, 3S) (70 mg, 0.14 mmol, y = 24%).

[0103] 6. Synthesis of compound 109 (1S, 2S)

[0104] (1) Compound 109-1 (1 g, 8.47 mmol) was dissolved in 10 mL of tetrahydrofuran, purged with nitrogen, and 4-chlorophenyl magnesium bromide (7.61 g, 35.57 mmol) was slowly added at 0 °C. After the addition was complete, the mixture was allowed to rise naturally to room temperature, and the reaction was completed under controlled conditions. The reaction was then quenched with saturated ammonium chloride, extracted with ethyl acetate, and purified in normal phase to give compound 109-2 (1.33 g, 4.49 mmol, y = 53%).

[0105] (2) Compound 109-2 (700 mg, 2.36 mmol) was dissolved in 20 mL of dichloromethane, and triethylamine (2.34 g, 23.13 mmol) was added. The mixture was purged with nitrogen, and triethylsilane (2.74 g, 23.6 mmol) was slowly added at 0 °C. After the addition was complete, the mixture was allowed to warm naturally to room temperature, and the reaction was completed under controlled conditions. The mixture was then washed with water, extracted with dichloromethane, and purified in normal phase to obtain compound 109-3 (410 mg, 1.46 mmol, y = 62%).

[0106] (3) Compound 109-3 (410 mg, 1.46 mmol) and N-tert-butoxycarbonyl-L-alanine (304 mg, 1.61 mmol) were dissolved in 10 mL of tetrahydrofuran. Then, triethylamine (442 mg, 4.38 mmol) and 4-dimethylaminopyridine (10 mg, 0.07 mmol) were added sequentially, and tertivalyl chloride (295 mg, 2.19 mmol) was slowly added dropwise under ice bath conditions. After the addition was complete, the reaction was allowed to proceed at room temperature for 2 h until the reaction was completed under controlled conditions. The reaction was then quenched with saturated ammonium chloride aqueous solution, extracted with ethyl acetate, and purified in normal phase to obtain compound 109-4 (620 mg, 1.37 mmol, y = 94%).

[0107] (4) Compound 109-4 (620 mg, 1.37 mmol) was dissolved in 10 mL of dichloromethane, and 3 mL of trifluoroacetic acid was added. The reaction was carried out at room temperature for 2 h to complete. The reaction solution was then directly evaporated to dryness to obtain crude compound 109-5.

[0108] (5) Compound 109-5 (482 mg, 1.37 mmol) and compound 10-5 (255 mg, 1.51 mmol) were dissolved in 10 mL of dichloromethane, and then triethylamine (415 mg, 4.11 mmol) and benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (1.07 g, 2.06 mmol) were added sequentially. The reaction was carried out at room temperature for 2 h under controlled conditions. After post-treatment, the sample was directly mixed with silica gel and purified in normal phase to obtain compound 109-6 (130 mg, 0.26 mmol, y = 19%).

[0109] (6) Compound 109-6 (130 mg, 0.26 mmol) was dissolved in 10 mL of dichloromethane, and then triethylamine (29 mg, 0.29 mmol) and 4-dimethylaminopyridine (2 mg, 0.01 mmol) were added sequentially. 2-pyridinecarboxyl chloride (44 mg, 0.31 mmol) was slowly added dropwise to the reaction solution. The reaction was carried out at room temperature and completed in 0.5 h. After post-treatment, the mixture was washed with water, extracted with dichloromethane, and purified in normal phase to obtain compound 109(1S, 2S) (130 mg, 0.21 mmol, y = 83%).

[0110] 7. Synthesis of compound 117 (1S, 2S, 3S)

[0111] (1) Compound 117-1 (200 mg, 0.83 mmol) was dissolved in 10 mL of methanol in a sealed container, followed by the addition of triethylamine (168 mg, 1.66 mmol) and Pd(dppf)Cl2·CH2Cl2 (34 mg, 0.04 mmol), and CO was introduced. The reaction was carried out at 70 °C for 16 h under controlled conditions. After post-treatment, silica gel was added and the sample was stirred for normal-phase purification to obtain compound 117-2 (170 mg, y = 93%).

[0112] (2) Compound 117-2 (170 mg, 0.77 mmol) and N-tert-butoxycarbonyl-L-alanine (160 mg, 0.85 mmol) were dissolved in 5 mL of tetrahydrofuran. Then, triethylamine (233 mg, 2.31 mmol) and 4-dimethylaminopyridine (5 mg, 0.04 mmol) were added sequentially, and tertivalyl chloride (155 mg, 1.16 mmol) was slowly added dropwise under ice bath conditions. After the addition was complete, the reaction was allowed to proceed at room temperature for 2 h until the reaction was completed under controlled conditions. The reaction was then quenched with saturated ammonium chloride aqueous solution, extracted with ethyl acetate, and purified under normal phase to obtain compound 117-3 (120 mg, 0.31 mmol, y = 40%).

[0113] (3) Compound 117-3 (120 mg, 0.31 mmol) was dissolved in 5 mL of dichloromethane, and 2 mL of trifluoroacetic acid was added. The reaction was carried out at room temperature for 2 h to complete. The reaction solution was then directly evaporated to dryness to obtain crude compound 117-4.

[0114] (4) Compound 117-4 (91 mg, 0.31 mmol) and compound 10-5 (58 mg, 0.34 mmol) were dissolved in 5 mL of dichloromethane, and then triethylamine (94 mg, 0.93 mmol) and benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (242 mg, 0.47 mmol) were added sequentially. The reaction was carried out at room temperature for 2 h to complete. After post-treatment, the sample was directly mixed with silica gel and purified by normal phase to obtain compound 117-5 (115 mg, 0.26 mmol, y = 36%).

[0115] (5) Compound 117-5 (115 mg, 0.26 mmol) was dissolved in 5 mL of dichloromethane, and then triethylamine (29 mg, 0.29 mmol) and 4-dimethylaminopyridine (2 mg, 0.01 mmol) were added sequentially. 2-pyridinecarboxyl chloride (44 mg, 0.31 mmol) was slowly added dropwise to the reaction solution. The reaction was carried out at room temperature and completed in 0.5 h. After post-treatment, the mixture was washed with water, extracted with dichloromethane, and purified in normal phase to obtain compound 117(1S, 2S, 3S) (106 mg, 0.19 mmol, y = 75%).

[0116] 8. Synthesis of compound 121 (1S, 2S, 3S)

[0117] (1) Compounds 117-1 (300 mg, 1.23 mmol), 121-1 (129.66 mg, 1.54 mmol), tetrabutylammonium fluoride (1 M, 1.23 mL), and 1,4-bis(diphenylphosphine)butane (52.62 mg, 0.12 mmol) were placed in a reaction flask containing 8 mL of dimethyl sulfoxide. Pd(PPh3)2Cl2 (43.3 mg, 0.062 mmol) was added, and the mixture was purged with nitrogen three times. The reaction was carried out at 110 °C for 16 hours. The reaction was monitored by LC-MS. The reaction solution was cooled to room temperature. The reaction solution was diluted with water, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The mixture was stirred and dried under normal phase, and then passed through a column to obtain compound 121-2 (210 mg, 84.13%).

[0118] (2) Compound 121-2 (210 mg, 1.038 mmol) was placed in a reaction flask containing 10 mL of tetrahydrofuran. Pivaloyl chloride (187.75 mg, 1.56 mmol), N-tert-butoxycarbonyl-L-alanine (294.62 mg, 1.56 mmol), triethylamine (315.12 mg, 3.11 mmol), and 4-dimethylaminopyridine (25.36 mg, 0.21 mmol) were added in portions at 0 °C. The reaction was carried out at room temperature for 16 hours. The reaction was monitored by LC-MS. The reaction solution was diluted with water, extracted with ethyl acetate, and the organic phase was washed with saturated sodium bicarbonate and dried over anhydrous sodium sulfate. The mixture was evaporated to dryness, stirred, and passed through a normal phase column. After evaporation to dryness, compound 121-3 (400 mg, 99%) was obtained.

[0119] (3) Compound 121-3 (400 mg, 1.071 mmol) and trifluoroacetic acid (1 mL) were placed in a reaction flask containing 4 mL of dichloromethane and reacted at room temperature for two hours. The reaction was monitored by LCMS and the mixture was dried by rotary evaporation to obtain compound 121-4 (260 mg, Yield = 88.80%).

[0120] (4) Compound 10-5 (199.26 mg, 1.18 mmol) was placed in a reaction flask containing 10 mL of dichloromethane, and benzotriazol-1-yl-oxytripyrrolylphosphine hexafluorophosphate (835.98 mg, 1.61 mmol) was added. The reaction was carried out at room temperature for 0.5 hours. A dichloromethane solution of compound 121-4 (292.78 mg, 1.071 mmol) was added dropwise, followed by triethylamine (325.11 mg, 3.21 mmol). The reaction was carried out at room temperature for 16 hours. The reaction was monitored by LCMS. The reaction solution was diluted with water, extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. The solution was evaporated to dryness, stirred, and passed through a normal phase column. After evaporation to dryness, compound 121-5 (268 mg, Yield = 58.95%) was obtained.

[0121] (5) Compound 2-pyridinecarboxylic acid (268 mg, 0.63 mmol) was dissolved in a reaction flask containing 8 mL of dichloromethane. Oxaloyl chloride (160.27 mg, 1.26 mmol) and N,N-dimethylformamide (4.61 mg, 0.063 mmol) were added, and the mixture was reacted at room temperature for 30 minutes. The reaction was transferred to LCMS with methanol. After the reaction was complete, the solvent was evaporated and the mixture was dried using an oil pump. The prepared acyl chloride was dissolved in 10 mL of dichloromethane and added dropwise at 0 °C to a dichloromethane (10 mL) solution containing compound 121-5 (93.27 mg, 0.76 mmol) and triethylamine (159.71 mg, 1.58 mmol). The reaction was allowed to proceed for 1 h. The reaction solution was diluted with water, extracted with dichloromethane, dried over anhydrous sodium sulfate, and purified by normal phase evaporation to obtain compound 121 (1S, 2S, 3S) (100 mg, Yield = 29.91%).

[0122] 9. Synthesis of compound 122 (1S, 2S, 3S)

[0123] (1) Compound 18-1 (1g, 5.6mmol) and phthalic anhydride (0.83g, 1eq) were dissolved in 15mL of toluene, and triethylamine (2.3mL, 3eq) was added. The mixture was refluxed at 120℃ for 3.5h. The reaction was completed under central control. The mixture was directly mixed and purified to obtain compound 122-1 (1.7g, 98%).

[0124] (2) Compound 122-1 (1.7 g, 5.5 mmol) was dissolved in 30 mL of tetrahydrofuran. After the reaction was carried out in an ice bath, N-tert-butoxycarbonyl-L-alanine (1.56 g, 1.5 eq), triethylamine (1.5 mL, 2 eq), tert-valeryl chloride (1 g, 1.5 eq) and 4-dimethylaminopyridine were added. The reaction was carried out at room temperature for 1 hour. After the reaction was completed, the reaction system was diluted with ethyl acetate, the organic phase was washed with brine, dried with anhydrous sodium sulfate, filtered, concentrated and mixed, and purified in normal phase to obtain compound 122-2 (3.5 g, 87%).

[0125] (3) Compound 122-2 (3.5 g, 7.3 mmol) was dissolved in 30 mL of dichloromethane, and trifluoroacetic acid (1.1 mL, 2 eq) was added. The mixture was stirred at room temperature until the reaction was complete. The reaction system was washed with water, dried and concentrated to obtain crude compound 122-3 (2.5 g, 89%).

[0126] (4) Compound 10-5 (1.45 g, 1.3 eq) and benzotriazol-1-yl-oxytripyrrolylphosphine hexafluorophosphate (4.5 g, 1.3 eq) were dissolved in 60 mL of dichloromethane and reacted for half an hour. Then, a dichloromethane solution of compound 122-3 (2.5 g, 6.6 mmol) and triethylamine (2.7 mL, 3 eq) was added dropwise to the reaction solution, and the reaction was allowed to proceed overnight. After the reaction was completed under central control, the sample was directly mixed and purified in normal phase to obtain compound 122-4 (2 g, 67%).

[0127] (5) Compound 122-4 (2 g, 3.8 mmol) was dissolved in 20 mL of dichloromethane, and 2 mL of hydrazine hydrate solution was added. The mixture was stirred overnight and the reaction was completed under central control. Water was added to separate the contents, and the mixture was extracted with dichloromethane. The organic phase was collected, dried, and concentrated to obtain compound 122-5 (1.45 g, 96%).

[0128] (6) Compound 2-pyridinecarboxylic acid (51 mg, 1.1 eq) was dissolved in 5 mL of dichloromethane, and N,N-dimethylformamide was added as a catalyst. Oxaloyl chloride was added dropwise to prepare acyl chloride for later use. Compound 122-5 (150 mg, 0.37 mmol) and triethylamine (0.2 mL, 3 eq) were dissolved in 5 mL of dichloromethane. The above acyl chloride dichloromethane solution was added dropwise under ice bath. The mixture was stirred at room temperature until the reaction was complete. After washing with water, the mixture was separated. The organic phase was dried with anhydrous sodium sulfate and concentrated. The product 122(1S,2S,3S) (63 mg, 28%) was purified by wet loading.

[0129] 10. Synthesis of compound 124 (1S, 2S, 3S)

[0130] (1) Compound 117-1 (1000 mg, 4.11 mmol, 1 eq.), 4-chloropyrazole (632 mg, 6.17 mmol, 1.5 eq.), 1,10-phenanthroline (370 mg, 2.06 mmol, 0.5 eq.) and cesium carbonate (4020 mg, 12 mmol, 3.0 eq.) were dissolved in 25 mL of N,N-dimethylformamide. Nitrogen gas was introduced three times, CuI (391 mg, 2.06 mmol, 0.5 eq.) was added, and the gas was introduced three more times. The mixture was heated to 120 °C and reacted overnight. After the reaction was completed, the mixture was poured into water, extracted with ethyl acetate, and the organic phase was stirred and passed through a column to obtain compound 124-1 (250 mg, Y = 22%).

[0131] (2) N-tert-butoxycarbonyl-L-alanine (268 mg, 1.42 mmol, 1.5 eq.) was dissolved in 20 mL of tetrahydrofuran and cooled to 0 °C. Triethylamine (267 mg, 2.64 mmol, 2.8 eq.), tert-valeryl chloride (170 mg, 1.42 mmol, 1.5 eq.), 124-1 (250 mg, 0.94 mmol, 1 eq.) and 4-dimethylaminopyridine (23 mg, 0.19 mmol, 0.2 eq.) were added sequentially. After the addition was complete, the mixture was reacted at room temperature overnight. After the reaction was completed, water was added, and the mixture was extracted with ethyl acetate. The organic phase was concentrated, mixed, and filtered through a column to obtain product 124-2 (380 mg, Y = 91%).

[0132] (3) Dissolve 124-2 (380 mg, 0.87 mmol, 1 eq.) in 5 mL of dichloromethane, add 3 mL of trifluoroacetic acid, react at room temperature for 3 h, and after the reaction is complete, concentrate to remove the solvent to obtain crude product 124-3 (yield is 100%).

[0133] (4) Compounds 124-3 (290 mg, 0.86 mmol, 1 eq.), 10-5 (189 mg, 1.12 mmol, 1.3 eq.) and triethylamine (262 mg, 2.59 mmol, 3.0 eq.) were dissolved in 20 mL of dichloromethane and stirred at room temperature for 0.5 h. Benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (629 mg, 1.21 mmol, 1.4 eq.) was added and the reaction was allowed to proceed overnight. After the reaction was completed, the product was concentrated, mixed, and filtered through a column to obtain product 124-4 (410 mg, Y = 97%).

[0134] (5) Dissolve 2-pyridinecarboxylic acid (124 mg, 1 mmol, 1.2 eq.) in 20 mL of dichloromethane, add 2 drops of N,N-dimethylformamide, and add oxaloyl chloride (267 mg, 2.1 mmol, 2.5 eq.). React at room temperature for 0.5 h. After the reaction is complete, concentrate the solution for later use. Dissolve 124-4 (410 mg, 0.84 mmol, 1 eq.) in 20 mL of dichloromethane, cool to 0 °C, and add triethylamine (426 mg, 4.2 mmol, 5.0 eq.) and the above-mentioned prepared solution sequentially. After the addition is complete, react at room temperature for 1 h. After the reaction is complete, add water, separate the liquids, concentrate the organic phase, and load the sample onto a column using a wet method to obtain product 124 (1S, 2S, 3S) (105 mg, Y = 20%).

[0135] 11. Synthesis of compound 132 (1S, 2S, 3S)

[0136] (1) Compound 117-1 (0.5 g, 2.1 mmol) and (tributyltin)methanol (0.99 g, 1.5 eq) were dissolved in 15 mL of dioxane. Under nitrogen protection, the catalyst chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (0.32 g, 0.2 eq) was added. After gas purging, the reaction was carried out overnight at 80 °C. After the reaction was completed under central control, the reaction system was directly stirred by rotary evaporation and purified in normal phase to obtain compound 132-1 (0.39 g, 98%).

[0137] (2) Compound 132-1 (0.39 g, 2 mmol) was dissolved in 15 mL of dichloromethane, and manganese dioxide (1.79 g, 10 eq) was added. The mixture was stirred overnight at room temperature. After the reaction was completed, the reaction system was filtered with diatomaceous earth, dried by rotary evaporation, and purified in normal phase to obtain compound 132-2 (0.39 g, 99%).

[0138] (3) Compound 132-2 (0.39 g, 2 mmol) was dissolved in a mixed solvent of 10 mL tetrahydrofuran and 2 mL water, and hydroxylamine hydrochloride (0.25 g, 1.5 eq) and sodium acetate (0.34 g, 2 eq) were added. The mixture was reacted at room temperature for 3 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, the organic phase was washed with sodium chloride solution, dried and concentrated, and then purified in normal phase to obtain compound 132-3 (0.27 g, 60%).

[0139] (4) Compound 132-3 (0.27 g, 1.2 mmol) was dissolved in 5 mL of tetrahydrofuran. After the mixture was placed in an ice bath, N-tert-butoxycarbonyl-L-alanine (346.27 mg, 1.5 eq), triethylamine (0.4 mL, 2 eq), tert-valeryl chloride (220.67 mg, 1.5 eq) and catalytic amount of 4-dimethylaminopyridine were added. The mixture was reacted at room temperature for 1 hour. After the reaction was completed, the reaction system was diluted with ethyl acetate, the organic phase was washed with brine, dried with anhydrous sodium sulfate, filtered, concentrated and mixed, and purified in normal phase to obtain compound 132-4 (0.42 g, 90%).

[0140] (5) Compound 132-4 (0.42 g, 1.1 mmol) was dissolved in 5 mL of dichloromethane, and trifluoroacetic acid (0.1 mL, 2 eq) was added. The mixture was stirred at room temperature until the reaction was complete. The reaction system was washed with water, dried and concentrated to obtain compound 132-5 (0.3 g, 96%).

[0141] (6) Compound 10-5 (191 mg, 1.1 eq) and benzotriazol-1-yl-oxytripyrrolylphosphine hexafluorophosphate (587.35 mg, 1.1 eq) were dissolved in 10 mL of dichloromethane and reacted for half an hour. Then, a dichloromethane solution of compound 132-5 (0.3 g, 1 mmol) and triethylamine (0.3 mL, 3 eq) was added dropwise to the reaction solution, and the reaction was allowed to proceed overnight. After the reaction was completed under central control, the sample was directly mixed and purified in normal phase to obtain compound 132-6 (0.3 g, 57%).

[0142] (7) 2-Pyridinecarboxylic acid (91 mg, 1.1 eq) was dissolved in 5 mL of dichloromethane, and N,N-dimethylformamide was added as a catalyst. Oxaloyl chloride was added dropwise to prepare acyl chloride for later use. Compound 132-6 (0.3 g, 0.67 mmol) and triethylamine (0.3 mL, 3 eq) were dissolved in 10 mL of dichloromethane. The above acyl chloride solution in dichloromethane was added dropwise under ice bath and stirred at room temperature until the reaction was complete. After washing with water, the mixture was separated. The organic phase was dried with anhydrous sodium sulfate and concentrated. The product 132(1S,2S,3S) (128 mg, 34%) was purified by wet loading.

[0143] Bioactivity evaluation:

[0144] I. Compound bactericidal activity test

[0145] (1) Sterilization potted plant method:

[0146] 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.

[0147] Soybean Asian rust, corn common rust, wheat leaf rust, and rice blast: The experimental targets were selected from *Phakopsora pachyrhizi* Syd., *Puccinia sorghi*, *Puccinia recondita*, and *Magnaporthe oryza*, all cultured in live pots. Spores from the leaves of pathogenic soybeans, corn, wheat, and rice were washed off 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.

[0148] 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 pumpkin leaves, shake off the excess powder, and gently tap the leaves with a glass rod to evenly distribute the 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.

[0149] Sunflower sclerotinia stem rot: Holes are punched in culture dishes covered with mycelium to create 5mm mycelial cakes. These cakes are then inoculated onto sunflower host material. For protective testing, inoculation is performed 24 hours after pesticide treatment. Inoculated material is then transferred to an incubator or artificial climate chamber for incubation in complete darkness.

[0150] Based on the disease incidence in the blank control group (disease level 9), the inoculated leaves were graded. The following grading method was used:

[0151] Level 0: No disease;

[0152] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0153] Grade 3: The lesion area accounts for 6% to 10% of the total leaf area;

[0154] Level 5: The lesion area accounts for 11% to 25% of the total leaf area;

[0155] Level 7: The lesion area accounts for 26% to 50% of the total leaf area;

[0156] Level 9: The lesion area accounts for more than 50% of the total leaf area.

[0157] Based on the survey data, the disease index and prevention and control effects of each treatment were calculated.

[0158] The disease index is calculated according to formula (1), and the result is rounded to two decimal places: X={(∑(Nixi)) / (Nx9)}x100………………………………………(1)

[0159] In the formula: X—disease index; Ni—number of diseased leaves at each level; i—relative level value; N—total number of leaves surveyed.

[0160] The control effect is calculated according to formula (2): P={(CK-PT) / CK}x100…………………………………………(2)

[0161] In the formula: P—prevention and control effect, in percentage (%); CK—disease index of blank control; PT—disease index of drug treatment.

[0162] Table 3. Results of control using representative compounds

[0163] Table 4 Comparison of control results of representative compounds

[0164] Table 5 Comparison of control results of representative compounds

[0165] Note: N represents no data; control compound A: Reference compound B: Reference compound C:

[0166] II. Composition bactericidal activity test

[0167] Experimental diseases: cucumber powdery mildew, cucumber anthracnose, sunflower sclerotinia stem rot, rice blast, Asian soybean rust, and tomato gray mold.

[0168] Dissolve each active component or composition in acetone (the volume ratio of acetone to spray volume is equal to or less than 0.05), dilute with water containing 0.1% Tween 80, and prepare a test solution of the required concentration. Prepare a separate test solution of the composition according to the set ratio. Using a crop sprayer, spray the test solution onto uniform host plants (uninoculated and without other pesticides before application) grown in a greenhouse. Inoculate the plants with the disease 24 hours later. Based on the disease characteristics, inoculate diseased plants requiring temperature and humidity control and place them in a climate chamber for cultivation. After the disease has fully infected the plants, transfer them to a greenhouse for further cultivation. After the control group has fully developed the disease, conduct a disease survey and record the total number of leaves, the number of diseased leaves, and the disease severity.

[0169] Disease classification method:

[0170] Grade 0: The entire plant is disease-free;

[0171] Grade 1: Lesions cover less than 5% of the total leaf area;

[0172] Grade 3: Lesions cover 6-10% of the entire leaf area;

[0173] Grade 5: Lesions cover 11-20% of the entire leaf area;

[0174] Grade 7: Lesions cover 21-50% of the entire leaf area;

[0175] Level 9: The lesion area covers more than 50% of the entire leaf area.

[0176] The observed efficacy (C) of the active ingredient or composition obs The following formulas are commonly used for pesticide efficacy evaluation (corrected control efficacy calculation formula): Disease index = ∑(number of diseased leaves at each level × relative level value) / (total number of surveys × 9) × 100 Observation efficacy (%) = (control disease index - treatment disease index) / control disease index × 100

[0177] An efficacy of "0" indicates that the infection level of the treated crop is the same as that of the untreated control crop; an efficacy of "100" indicates that the treated crop is not infected.

[0178] The intended potency of the composition (C) exp The effect was determined using the Abbott method (see Liu Xuemin et al., Synergistic Effect of Mixed Fungicides, Pesticide Science and Management, 2002, 23(5), 12-15). exp =X + Y – XY / 100

[0179] In the formula, X: the efficacy of active component A at a concentration of a;

[0180] Y: The efficacy of active component B at a concentration of b.

[0181] The synergistic effect of the composition was observed using efficacy (C). obs ) and expected effectiveness (C exp The ratio (synergistic ratio) is used for evaluation. When the ratio (synergistic ratio) > 1, the composition exhibits a synergistic effect; when the ratio (synergistic ratio) = 1, the composition exhibits an additive effect; when the ratio (synergistic ratio) < 1, the composition exhibits an antagonistic effect.

[0182] The results of the synergistic effect evaluation of the composition are shown in Table 6-11.

[0183] Table 6. Evaluation of the synergistic effect of the composition on Asian soybean rust.

[0184] Table 7. Evaluation of the synergistic effect of the composition on sunflower sclerotinia stem rot.

[0185] Table 8. Evaluation of the synergistic effect of the composition on rice blast disease.

[0186] Table 9. Evaluation of the synergistic effect of the composition on cucumber powdery mildew.

[0187] Table 10 Evaluation of the synergistic effect of the composition on tomato gray mold.

[0188] Table 11 Evaluation of the synergistic effect of the composition on cucumber anthracnose

[0189] 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 pyridine amide compound as shown in Formula I: in, W1 is either O or S; R1 is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, or cycloalkylalkyl; R3, R4, and R5 are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogen, trialkylsilyl, cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n An alkyl, alkenyl, or alkynyl group substituted by at least one of the substituents in R, -O(CO)R, or -O(CO)OR; X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, and -S(O), respectively. n R, -N(R)2, -(CO)R, -(CO)N(R)2, or an alkyl, alkenyl or alkynyl group substituted with at least one substituent selected from halogen, cycloalkyl, heterocyclic or aryl groups; 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, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -(CO)R, -(CO)OR, -N(R)2, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano or alkoxycarbonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. The pyridine amide compound according to claim 1, characterized in that, R1 is hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl; R3, R4, and R5 are, independently, hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogens, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n A C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted with at least one of the substituents R, -O(CO)R or -O(CO)OR; X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, and -S(O). n R, -N(R)2, -(CO)R, -(CO)N(R)2, or a C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl group substituted with at least one substituent selected from halogen, C3-C8 cycloalkyl, heterocyclic or aryl groups; 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, -N(R)2, -(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 or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C8 alkoxy, cyano or C1-C8 alkoxycarbonyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy.

3. The pyridine amide compound according to claim 1 or 2, characterized in that, R1 is hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl-C1-C6 alkyl. R3, R4, and R5 are, independently, hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -O(CO)R, and -S(O), respectively. n R, -N(R)2, or selected from halogens, triC1-C6 alkylsilyl, C3-C6 cycloalkyl, heterocyclic, aryl, -O(CO)R, -N(R)2, -OR, -S(O) n C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl substituted by at least one of R, -O(CO)R or -O(CO)OR; X1, X2, X3, X4, X5, Y1, Y2, X3, and Y4 are, independently, hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, and -S(O), respectively. n R, -N(R)2, -(CO)R, -(CO)N(R)2, or a C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl group substituted with at least one substituent selected from halogen, C3-C6 cycloalkyl, heterocyclic or aryl groups; 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, -N(R)2, -(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 or C2-C6 alkynyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano or C1-C6 alkoxycarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1 and AC in the specification.

4. A pyridine amide compound having a chiral center as shown in Formula I': in, The substituents R1, R3, R4, R5, X1, X2, X3, X4, X5, Y1, Y2, Y3, Y4, and W1 are defined as described in any one of claims 1-3, and *at least one chiral center is present at the carbon atom position; Based on the content of stereoisomers having R and S configurations at position 1, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); and / or Based on the content of stereoisomers having R and S configurations at position 2, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S); and / or Based on the content of stereoisomers having R and S configurations at position 3, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S).

5. A method for preparing the pyridine amide compound according to any one of claims 1-4, comprising the following steps: Compound I is prepared by a condensation reaction of compound II and compound III, and the chemical reaction equation is as follows: in, L1 represents OH or halogen; the substituents R1, R3, R4, R5, Y1, Y2, Y3, Y4, X1, X2, X3, X4, X5 and W1 are defined as described in any one of claims 1-4; Preferably, the reaction is carried out in the presence of a solvent and a base; more preferably, a catalyst is added during the reaction; even more preferably, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, 1,4-dioxane, dichloromethane or ethyl acetate, the base is selected from at least one of inorganic base or organic base, and / or the catalyst is selected from at least one of DMAP or 4-PPy.

6. A bactericidal composition, characterized in that, It contains at least one of the pyridine amide compounds according to any one of claims 1-4 in a biologically effective amount; preferably, it further includes a formulation adjuvant; more preferably, it further includes other active ingredients.

7. The bactericidal composition according to claim 6, characterized in that, The other active ingredients are selected from at least one of the following compounds: prothioconazole, difenoconazole, tebuconazole, flutriafol, propiconazole, hexaconazole, chlorfluazuron, cyproconazole, cyazofamid, tebuconazole, triadimefon, fenbendazole, benzovindiflubenzuron, fluopyram, thifluzamide, pyraclostrobin, bifenthiophanate-methyl, pyraclostrobin, chlorpyrifos, azoxystrobin, mancozeb, zineb, pyraclostrobin, pyraclostrobin, azoxystrobin, pyraclostrobin, azoxystrobin Azoxystrobin, fluopyram, imazalil, fluopyram, isoprothiolane, fluazinam, iprodione, sclerotinia, fluazinam, pentachloronitrobenzene, tricyclazole, isoprothiolane, isoprothiolane, isoprothiolane, kasugamycin, triflumethoprim, thiamethoxam, allylpyridinium, ethirimol, benomyl, fluopyram, fluoxastrobin, carbendazim, pyrimethanil, pyrimethanil, thiophanate-methyl, thiram, chlorothalonil, captan, or dicyandioxonone.

8. The bactericidal composition according to claim 7, characterized in that, The weight ratio of the pyridine amide compound to other active ingredients is 1:12500-50:1, 1:6250-10:1, 1:2500-5:1, 1:1250-1:1, 1:800-1:2, 1:500-1:5, 1:400-1:8, 1:320-1:10, 1:250-1:16, 1:160-1:20, 1:125-1:40, or 1:100-1:

50.

9. Use of the pyridine amide compound as described in any one of claims 1-4, or the fungicidal composition as described in any one of claims 6-8, in the control of plant pathogenic fungi.

10. 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 pyridine amide compound as described in any one of claims 1-4, or a fungicidal composition as described in any one of claims 6-8.

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