Phenyl-substituted oxadiazole compound and use thereof

Abstract

The present invention relates to the technical field of pesticides, and in particular to a phenyl-substituted oxadiazole compound and a use thereof. The compound is as shown in formula I, wherein P represents O or S; Q represents O or S; X is aryl or heterocyclyl; R1, R2, R3, R4, R5, and R6 each independently represent hydrogen, halogen, alkyl, alkenyl, or the like; and R7 represents hydrogen, alkyl, alkenyl, alkynyl, or the like. The compound has an excellent fungicidal effect.

Description

Phenyl-substituted oxadiazole compounds and their applications Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a phenyl-substituted oxadiazole 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 residues. In this context, despite the existence of numerous known fungicides, such as the oxadiazole compounds disclosed in CN106455572B 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 phenyl-substituted oxadiazole compound and its applications. The compound exhibits excellent bactericidal activity.

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

[0005] A phenyl-substituted oxadiazole compound as shown in Formula I:

[0006] Where P represents O or S;

[0007] Q represents O or S;

[0008] X represents aryl or heterocyclic group;

[0009] R1, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the alkyl, alkenyl, or alkynyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, -S(O) n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2;

[0010] R7 represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or -(CO)R;

[0011] n represents 0, 1, or 2;

[0012] The aforementioned “cycloalkyl”, “heterocyclic” or “aryl” may optionally be 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, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogen-substituted -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-.

[0013] R can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl, or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano, or alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

[0014] In one specific embodiment, R1, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl group is optionally selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, or -S(O). n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2;

[0015] R7 represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, cyano-C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, or -(CO)R;

[0016] The aforementioned “cycloalkyl”, “heterocyclic” or “aryl” may optionally be substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated 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, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogenated -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-.

[0017] R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, 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, 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, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl group is optionally selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, or -S(O). n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2;

[0019] R7 represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, cyano-C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, or -(CO)R;

[0020] The aforementioned “cycloalkyl”, “heterocyclic” or “aryl” may optionally be substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, -OR, -SR, -(CO)R, -(CO)OR, -N(R)2, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogenated -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-.

[0021] R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkoxycarbonyl substituted with at least one group selected from halogen, hydroxyl, C1-C6 alkoxy, cyano, or C1-C6 alkoxycarbonyl, 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.

[0022] 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.

[0023] 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

[0024] 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.

[0025] Furthermore, unless otherwise specified, "replaced by at least one group" as used in this invention means substituted 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 substituted, the substituents can also be substituted at any position, as long as they conform to the rules of chemical bond attachment. For example, a heteroaryl group substituted by one methyl group. Can represent wait.

[0026] 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.

[0027] 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.

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

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

[0030] (1) When P represents O, compound II and compound III undergo a condensation reaction to prepare compound I-1. The chemical reaction equation is as follows:

[0031] Alternatively, (2) when P represents S, compound I-1 undergoes a thioreaction to yield compound I-2, and the chemical reaction equation is as follows:

[0032] Where M represents OH or halogen, and the substituents R1, R2, R3, R4, R5, R6, R7, X and Q are defined as described above.

[0033] In one specific embodiment, the reaction (1) is carried out in the presence of a solvent.

[0034] In another specific embodiment, a condensing agent and / or a base are added during the reaction (1).

[0035] In another specific embodiment, the solvent for the reaction (1) is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, toluene, pyridine, acetonitrile, dichloroethane, dimethyl sulfoxide, 1,4-dioxane, dichloromethane, or ethyl acetate.

[0036] In another specific embodiment, the base in the reaction (1) process 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, N,N-diisopropylethylamine, etc.

[0037] In another specific embodiment, the condensing agent of the reaction (1) is selected from at least one of 4-pyrrolylpyridine (4-PPy), benzotriazol-1-yl-oxytripyrrolylphosphine hexafluorophosphate (Py-BOP), (3H-1,2,3-triazolo[4,5-b]pyridine-3-oxy)tri-1-pyrrolyl hexafluorophosphate (Py-AOP), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), 1-hydroxybenzotriazole (HOBT), 1,3-dicyclohexylcarbodiimide (DCC), O-benzotriazole-tetramethylurea hexafluorophosphate (HBTU), n-butylphosphine anhydride, or 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate (HATU).

[0038] In one specific embodiment, the reaction (2) is carried out in the presence of a solvent and a thioreagent.

[0039] In another specific embodiment, the solvent for the reaction (2) is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dichloroethane dimethyl sulfoxide, 1,4-dioxane, dichloromethane, or ethyl acetate.

[0040] In another specific embodiment, the thioreagent in reaction (2) is selected from at least one of Lawson's reagent, phosphorus pentasulfide, sodium sulfide, hydrogen sulfide, or thiourea.

[0041] The present invention also provides an antifungal composition comprising a biologically effective amount of a compound of formula I.

[0042] In one embodiment, the composition further includes a formulation adjuvant.

[0043] In another embodiment, the composition further includes other active ingredients.

[0044] The present invention also provides a method for controlling plant pathogenic fungi, comprising exposing the harmful fungi or their environment to a biologically effective amount of the compound of formula I or the composition thereof.

[0045] The present invention also provides the use of the compound of Formula I or the composition thereof in the control of plant pathogenic fungi.

[0046] Compounds with chemical formula I have been found to control damage caused by plant pathogenic fungi.

[0047] In one embodiment, a compound having chemical formula I can be used in agriculture.

[0048] Therefore, the present invention further relates to a method for controlling damage caused by plant pathogenic fungi, the method comprising applying an effective amount of a compound having chemical formula I to the pest, the site of the pest, or to a plant susceptible to attack by plant pathogenic fungi, or to plant propagation material.

[0049] These compounds according to the invention can be used to control, i.e., limit or destroy, harmful organisms and / or fungi that appear, particularly on plants, especially useful and ornamental plants in agriculture, horticulture and forestry, or on the organs of such plants, such as fruits, flowers, leaves, stems, rhizomes, seeds or roots, and in some cases, even on plant organs formed at later times, providing protection against these harmful organisms.

[0050] The compounds of Formula I according to the present invention are active ingredients with preventive and therapeutic value in the field of pest control. Even when applied in low doses, they can be used to combat fungi resistant to pesticides. These compounds of Formula I have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.

[0051] This invention relates to a method for controlling or preventing pathogenic microbial infection of useful plants, wherein a compound having chemical formula I is applied as an active ingredient to the plant, its parts, or the site thereof. The compounds having chemical formula I according to the invention are distinguished by their activity, good plant tolerance, and environmental safety. They possess highly useful therapeutic, preventative, and systemic properties and are used to protect a wide variety of useful plants. Compounds having chemical formula I can be used to inhibit or destroy diseases occurring on a variety of different useful plants or plant parts (fruits, flowers, leaves, stems, tubers, roots), while also protecting, for example, later-growing plant parts from pathogenic microbial invasion. It is also possible to use compounds having chemical formula I as dressing agents for treating plant propagation material, particularly seeds (fruits, tubers, grains) and plant cuttings (e.g., rice), to protect against fungal infection as well as against pathogenic fungi present in the soil.

[0052] Examples of fungi include: Deuteromycetes (e.g., *Botrytis*, *Pyrrosia*, *Helicobacter*, *Fusarium*, *Syneosporium*, *Cercospora*, and *Cladosporium*); Basidiomycetes (e.g., *Rhizoctonia*, *Pythium*, and *Phyllostachys*); Ascomycetes (e.g., *Acer niger*, *Pythium*, *Candida*, and *Uncaria*); Oomycetes (e.g., *Phytophthora*, *Pythium*, and *Monocotyle*); Zygomycetes (e.g., *Rhizopus*); Sterilophyceae, especially those of the genus *Sterilophys*, such as *Synostachys beanus*, also known as Asian soybean rust; and those of the family Sterilophyceae, especially those of the genus *Sterilophys*, such as *Sterilophys gracilis*, also known as stem rust or black rust, a problematic disease in cereals; and *Sterilophys cryptica*, also known as brown rust.

[0053] These plants, and the possible diseases of these plants protected by the method according to the invention, include:

[0054] - Wheat, for the control of the following seed diseases: Fusarium (Fusarium solani and Fusarium pink), blackhead (Wheat net smut, Wheat dwarf smut or Wheat Indian smut), spore diseases (Synthia spp.) and smut.

[0055] - Wheat, for controlling the following diseases of the aboveground parts of the plant: cereal eye spot (Tapesia yallundae, Tapesia acuiformis), take-all (oat take-all fungus), root blight (Fusarium culmorum, Fusarium graminearum), black spot (Rhizoctonia graminearum), powdery mildew (Erysiphe graminis forma specie tritici), rust (Rhizoctonia gracilis and Rhizoctonia cryptica), and diseases of the genus *Syngonium* (Syngonium leuciscus and Syngonium glomeratum);

[0056] - Wheat and barley are effective in controlling bacterial and viral diseases, such as barley yellow mosaic virus; - Barley is effective in controlling the following seed diseases: net blotch (Cytosporum oryzae, Cytosporum rotundum, and Cytosporum gracilis), loose smut (loose smut), and Fusarium (Fusarium solani and Fusarium oxysporum).

[0057] - Barley is effective in controlling the following diseases of the above-ground parts of the plant: cereal eye spot (Tapesia yallundae), net spot (Erysiphe graminis formas pecie hordei), powdery mildew (Erysiphe graminis formas pecie hordei), dwarf leaf rust (barley stalk rust) and leaf spot (barley cloud spot fungus);

[0058] - Potatoes are effective in controlling tuber diseases (especially potato psoriasis fungus, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mold (pathogenic Phytophthora), and certain viruses (virus Y).

[0059] - For potatoes, control the following foliar diseases: early blight (Alternaria alternata), mildew (Phytophthora infestans);

[0060] - Cotton, for controlling the following diseases in young plants that grow from seeds: damping-off and blight (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Rhizoctonia solani);

[0061] - Protein-producing plants, such as peas, are beneficial for controlling the following seed diseases: anthracnose (pea brown spot fungus, pea coccidioidomycetes), Fusarium (Fusarium oxysporum), gray mold (Botrytis cinerea), and mildew (pea downy mildew);

[0062] - Oil-bearing plants, such as rapeseed, are used to control the following seed diseases: Brassica stem bud mold, Alternaria brassicae, and Sclerotinia sclerotiorum;

[0063] - Corn, for controlling a variety of seed diseases: (Rhizopus, Penicillium, Trichoderma, Aspergillus and Fusarium graminearum);

[0064] - Flax, for controlling this seed disease: Alternaria linicola;

[0065] - Forest trees are helpful in controlling damping-off disease (Fusarium oxysporum, Rhizoctonia solani);

[0066] - Rice, used to control the following diseases of the above-ground parts: blast (rice blast) and bordered sheath spot (Rhizoctonia solani);

[0067] - Leguminosae plants, for controlling the following diseases of seeds or young plants growing from seeds: damping-off and blight (Fusarium oxysporum, Fusarium oxysporum, Rhizoctonia solani, Pythium spp.);

[0068] - Leguminosae plants, for controlling the following diseases of the above-ground parts: gray mold (Botrytis cinerea), powdery mildew (especially Asteraceae powdery mildew, Cucurbita powdery mildew, and Pepper powdery mildew), Fusarium (Fusarium oxysporum, Fusarium oxysporum), leaf spot (Cladosporium), Cladosporium leaf spot (Cladosporium), anthracnose (Anthracnose), Phytophthora leaf spot (Phytophthora), black spot (Rhizoctonia solani), and mildew (e.g., lettuce downy mildew, Downy mildew, Pseudomonas, Phytophthora);

[0069] - For fruit trees, it helps control various diseases of the above-ground parts: Candida diseases (Monilia fructigenae, M. laxa), scab (Apple black spot fungus), and powdery mildew (Monilia leucocephala); - For vines, it helps control the following leaf diseases: especially gray mold (Botrytis cinerea), powdery mildew (Botrytis cinephala), black rot (Guignardia bidwellii), and mildew (Botrytis cinephala).

[0070] - Beetroot is susceptible to the following diseases of the above-ground parts: Cercospora blight (beet brown spot fungus), powdery mildew (beet powdery mildew fungus), and leaf spot (beet leaf spot fungus).

[0071] The fungicidal compositions according to the invention can also be used to combat fungal diseases that readily grow on or inside wood. The term "wood" refers to all types of wood species, and all types of wood intended for construction work, such as solid wood, high-density wood, laminated wood, and plywood. Methods for treating wood according to the invention primarily involve contacting one or more of the compounds of the invention or the compositions according to the invention; this includes, for example, direct application, spraying, soaking, injection, or any other suitable means.

[0072] When used alone, the compounds of the present invention are effective in controlling fungal pathogens on growing or harvested plants. They can also be used in combination with other bioactive agents used in agriculture, such as one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activators, molluscicides, and pheromones (chemical or biological). Mixing the compounds of the present invention or combinations thereof in pesticide form with other pesticides generally produces better activity.

[0073] By adding, for example, one or more fungicidal active agents, the activity of these compositions according to the invention can be significantly broadened and adapted to current conditions. Combinations of compounds having Formula I with other fungicidal active agents can also have further, unexpected advantages. For example, better plant tolerance, reduced phytotoxicity, control of harmful fungi at different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during storage, or during use).

[0074] Other fungicides may include: 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, and Bacillus subtilis strain QST713. QST713), benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl compounds, bismerthiazol, bittertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, lime sulfur. Polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, 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 Hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorphFluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, triethylamine Fosetyl, Fosetyl-aluminium, Fuberidazole, Furalaxyl, Furametpyr, 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, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxideMercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofuronamide, oleic acid (fatty acid) Acid), Oxysastrobin, 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), allylbenzazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb,Proquinazid, prothioconazole, piraclostrobin, pirametostrobin, piraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutriasachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate Bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, wood tar, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triad... imenol), triazoloxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophilaThe fungus causing wilt (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, benzalkonium chloride; benzamacril-isobutyl benzamacrilBenzamorf, binapacryl, bis(methylmercury)sulfate, bis(tributyltin)oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, 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, Ditalimfos, Dodicin, Drazoxolon, E. coli BP), ESBP, eticonazole, etem, ethirim, fenaminosulf, fenapanil, finitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, propiconazole (ICIA0858),Isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel di(dimethyldithiocarbamate) Bis(dimethyldithiocarbamate), octachlorophenone (OCH), phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, piracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylamide e), azoxystrobin (SSF-109), sulfadiazine (sultropen), tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trihlamide,Urbacid, Zarilamid, and any combination thereof.

[0075] In general, in any combination of the present invention, the mass ratio between the two components is independently from 100:1 to 1:100, with preferred mass ratios from 75:1 to 1:75, more preferably from 50:1 to 1.50, especially from 25:1 to 1:25, advantageously 10:1 refers to 1:10, such as from 5:1 to 1:5, for example from 1:3 to 3:1. These mixing ratios are understood to include, on the one hand, a mass ratio, and on the other hand, a molar ratio.

[0076] Examples of methods of applying the compounds and compositions thereof used in this invention, namely methods for controlling harmful microorganisms in agriculture, such as spraying, atomizing, dusting, brushing, seed dressing, broadcasting, or irrigating - are selected to suit the intended objectives of the situation at the time.

[0077] In agriculture, a preferred method of application is to the leaves of these plants (foliar application), with the frequency and rate of application chosen to match the risk of infection by the pests / fungi discussed. Alternatively, the active ingredient can reach the plant via the root system (systemic absorption), achieved by applying the compound to the site of the plant, for example, by applying a liquid composition of the compound to the soil (through saturation) or by applying the compound in solid form as granules to the soil (soil application). In the case of rice plants, such granules can be metered and added to flooded paddy fields.

[0078] The application rate per hectare is generally 1g to 2000g of active ingredient per hectare, especially 10g / ha to 1000g / ha, preferably 10g / ha to 600g / ha, such as 50g / ha to 300g / ha.

[0079] These compounds and compositions thereof of the present invention are also suitable for the protection of plant propagation material (e.g., seeds, fruits, tubers, or grains, or nursery plants) against the aforementioned types of pests. The propagation material can be treated with the compound before planting; for example, seeds can be treated before sowing. Alternatively, the compound can be applied to the seed grains (coating), which is achieved by immersing the grains in a liquid composition or by applying a layer of solid composition. When the propagation material is planted at the application site, these compositions may also be applied, for example, during row sowing. These methods of treating plant propagation material and the treated plant propagation material are further subjects of the present invention. Typically, the treatment rate will depend on the plant to be controlled and the harmful microorganisms, generally between 1 gram and 200 grams per 100 kg of seeds, preferably between 5 grams and 150 grams per 100 kg of seeds, such as between 10 grams and 100 grams per 100 kg of seeds.

[0080] The term seed includes all kinds of seeds and plant propagules, including but not limited to true seeds, seed tubers, suckers, grains, bulbs, fruits, tubers, cereals, rhizomes, cuttings, cut branches and the like, and in a preferred embodiment refers to true seeds.

[0081] The present invention also includes seeds coated or treated with or containing a compound having Formula I. The term "coated with or treated with and / or containing" generally indicates that, in most cases, the active ingredient is on the surface of the seed when applied, although a portion of the ingredient may penetrate into the seed material, depending on the method of application. When the seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention makes it possible to obtain a plant propagation material having a compound having Formula I adhered thereto. Furthermore, a composition comprising plant propagation material treated with a compound having Formula I is thus obtained.

[0082] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, and seed granulation. The application of a compound having chemical formula I can be achieved by any known method, such as spraying or dusting before or during sowing / planting of these seeds.

[0083] Suitable target plants include cereals such as wheat, barley, rye, oats, rice, corn, or sorghum; beets such as sugar beets or fodder beets; fruits such as pome fruits, drupes, or seedless fruits such as apples, pears, plums, peaches, almonds, cherries, or berries such as strawberries, raspberries, or blackberries; legumes such as beans, lentils, peas, or soybeans; oilseed crops such as rapeseed, mustard, chestnuts, olives, sunflowers, coconuts, castor beans, cocoa, or peanuts; and cucurbit crops such as pumpkins, cucumbers, or melons. Fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as oranges, lemons, grapes, or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; Lauraceae plants, such as avocados, camphor (Cinnamonium), or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantains, rubber plants, and ornamental plants (such as flowers and lawn plants or turf).

[0084] In one embodiment, the plant is selected from cereals, corn, soybeans, rice, sugarcane, vegetables, and oilseed plants.

[0085] The term "plant" should be understood to also include plants transformed using recombinant DNA technology that are capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those of the genus Bacillus.

[0086] The compounds of the present invention are typically used in the form of a composition comprising a carrier (e.g., a formulation). The compounds and compositions thereof of the present invention can be used in various forms, such as aerosol sprayers, capsule suspensions, cold atomized concentrates, pulverizable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, capsule granules, fine granules, flowable concentrates for seed treatment, gases (under pressure), gas-producing products, granules, thermal atomized concentrates, large granules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, pastes, plant sticks, powders for dry seed treatment, seeds coated with pesticides, soluble concentrates, soluble powders, solutions for seed treatment, suspension concentrates (flowable concentrates), ultra-low volume (ULV) liquids, ultra-low volume (ULV) suspensions, water-dispersible granules or tablets, water-dispersible powders for slurry treatment, water-soluble granules or tablets, water-soluble powders for seed treatment, and wettable powders.

[0087] A formulation typically includes a liquid or solid carrier and optionally one or more commonly used formulation aids, which may be solid or liquid, such as non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil, or soybean oil), defoamers, such as silicone oils, preservatives, clays, inorganic compounds, viscosity modifiers, surfactants, adhesives, and / or thickeners. The composition may further include a fertilizer, micronutrient donor, or other product affecting plant growth, and may include a combination comprising the compounds of the present invention and one or more other bioactive agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.

[0088] Therefore, the present invention also includes a composition comprising a compound of the present invention, an agriculturally economical carrier, and optionally one or more commonly used formulation aids.

[0089] These compositions are prepared by methods known per se, either without additives, such as by grinding, sieving, and / or pressing the solid compounds of the invention, or with at least one additive, such as by tightly mixing and / or grinding the compounds of the invention together with one or more additives. In the case of the solid compounds of the invention, the grinding / crushing of the compound is to ensure a specific particle size. Methods for preparing these compositions and the use of the compounds of the invention for preparing these compositions are also a subject of this invention.

[0090] Examples of compositions used in agriculture include emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, direct sprayable or dilutable solutions, coatable pastes, diluted emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules, or capsules in polymeric substances. These compositions comprise at least one compound according to the invention, and the type of composition is selected to suit the intended purpose and the prevailing environment.

[0091] Examples of suitable liquid carriers are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8 to C9. 12 Alkylbenzene moieties, such as xylene mixtures, alkylated naphthalene or tetrahydronaphthalene, aliphatic or alicyclic hydrocarbons, such as paraffin or cyclohexane, alcohols such as ethanol, propanol or butanol, ethylene glycol and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or hexanediol monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methylpyrrolidone-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils such as unepoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oil.

[0092] Examples of solid carriers used for products such as dusts and dispersible powders are typically ground natural minerals such as calcite, talc, kaolin, montmorillonite, or attapulgite. To improve physical properties, it is also possible to add highly dispersed silica or highly dispersed absorbent polymers. Suitable particulate absorbent carriers for granules are porous, such as pumice, gravel, sepiolite, or bentonite, while suitable non-absorbent carrier materials are calcite or sand. Furthermore, a wide variety of granulated inorganic or organic natural materials can be used, particularly dolomite or pulverized plant residues.

[0093] Depending on the type of active ingredient to be formulated, suitable surfactants are nonionic, cationic, and / or anionic surfactants or mixtures of surfactants that possess good emulsifying, dispersing, and wetting properties. The surfactants mentioned below are merely examples; a large number of other surfactants commonly used in formulations and suitable for use according to the present invention are described in the relevant literature.

[0094] Suitable nonionic surfactants are, in particular, polyethylene glycol ether derivatives of aliphatic or alicyclic alcohols, polyethylene glycol ether derivatives of saturated or unsaturated fatty acids, or polyethylene glycol ether derivatives of alkylphenols, which may contain about 3 to about 30 glycol ether groups and about 8 to about 20 carbon atoms in the (cyclic)aliphatic hydrocarbon residues, or about 6 to about 18 carbon atoms in the alkyl moiety of alkylphenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol, or alkylpolypropylene glycol (having 1 to about 10 carbon atoms in the alkyl chain and about 20 to about 250 glycol ether groups and about 10 to about 100 propylene glycol ether groups). Typically, each propylene glycol unit of the above compounds contains 1 to about 5 glycol units. Examples that may be mentioned include nonylbenzene alcohol ether, castor oil polyethylene glycol ether, polypropylene glycol / polyethylene oxide adduct, tributylphenoxy polyethylene glycol, polyethylene glycol, or octylphenoxy polyethylene glycol. More suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

[0095] These cationic surfactants are typically quaternary ammonium salts having at least one alkyl residue (about 8 to about 22 C atoms) as a substituent and (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl residues as other substituents. These salts are preferably in the form of halides, methyl sulfates, or ethyl sulfates. Examples include stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

[0096] Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surfactant compounds. Examples of suitable soaps are alkali metal salts, alkaline earth metal salts, or (unsubstituted or substituted) ammonium salts of fatty acids having about 10 to about 22 carbon atoms, such as sodium or potassium salts of oleic acid or stearic acid or mixtures of natural fatty acids (obtainable from, for example, coconut oil or tall oil); fatty acid methyl taurine must also be mentioned. However, synthetic surfactants are more commonly used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives, or alkyl aryl sulfonates. Typically, these fatty sulfonates and fatty sulfates are alkali metal salts, alkaline earth metal salts, or (substituted or unsubstituted) ammonium salts and they generally have alkyl residues having about 8 to about 22 carbon atoms, alkyl also understood to include an alkyl moiety comprising an acyl residue; examples that may be mentioned are sodium or calcium salts of lignin sulfonate, sodium or calcium salts of dodecyl sulfate, or sodium or calcium salts of mixtures of fatty alcohol sulfates prepared from natural fatty acids. This group also includes sulfate and sulfonate salts of fatty alcohol / ethylene oxide adducts. These sulfonated benzimidazole derivatives preferably contain two sulfonyl groups and fatty acid residues of about 8 to about 22 carbon atoms. Examples of alkylaryl sulfonates are sodium, calcium, or triethanolamine salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or naphthalenesulfonic acid / formaldehyde condensates. Additionally, suitable phosphates (esters), such as phosphate salts of p-nonylphenol / (4-14)ethylene oxide adducts, or phospholipids, are also possible.

[0097] Typically, these compositions contain 0.1% to 99% (particularly 0.1% to 95%) of the compound according to the invention and 1% to 99.9% (particularly 5% to 99.9%) of at least one solid or liquid carrier. It is also possible, in principle, that 0% to 25% (particularly 0.1% to 20%) of the composition is a surfactant (in each case, % represents a weight percentage). However, for commercial purposes, concentrated compositions are generally preferred, and end users, in principle, use diluted compositions with significantly lower concentrations of the active ingredient.

[0098] Examples of formulation types suitable for barrel mixing compositions include solutions, diluted emulsions, suspensions or mixtures thereof, and dust.

[0099] Regarding the properties of these preparations, the methods of the present invention, such as leafing, wetting, spraying, atomizing, dusting, spreading, coating, or dumping, can be selected according to the intended purpose and the dominant environment.

[0100] This tank-mix formulation composition is generally prepared by diluting one or more premixed compositions containing different biocides and optionally additional adjuvants with a solvent (e.g., water).

[0101] Suitable carriers and adjuvants can be solid or liquid and are substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersants, wetting agents, thickeners, fillers, adhesives or fertilizers.

[0102] In general, tank-mixed formulations for foliar or soil application comprise 0.1% to 20%, particularly 0.1% to 15%, of the desired active ingredient, and 99.9% to 80%, particularly 99.9% to 85%, of solid or liquid adjuvants (including, for example, a solvent such as water), which may be a surfactant, in an amount of 0% to 20%, particularly 0.1% to 15%, based on the tank-mixed formulation.

[0103] Typically, premixed formulations for foliar application comprise 0.1% to 99.9%, particularly 1% to 95%, of the desired ingredient, and 99.9% to 0.1%, particularly 99% to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), wherein such adjuvants may be a surfactant, and the amount of which is 0% to 50%, particularly 0.5% to 40%, based on the premixed formulation.

[0104] Typically, tank-mixed formulations for seed treatment application comprise 0.25% to 80%, particularly 1% to 75%, of the desired ingredient, and 99.75% to 20%, particularly 99% to 25%, of solid or liquid adjuvants (including, for example, a solvent such as water), wherein these adjuvants may be a surfactant, and the amount based on the tank-mixed formulation is 0% to 40%, particularly 0.5% to 30%.

[0105] Typically, premixed formulations for seed treatment application comprise 0.5% to 99.9%, particularly 1% to 95%, of the desired ingredient, and 99.5% to 0.1%, particularly 99% to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), wherein such adjuvants may be a surfactant, and the amount of which is 0% to 50%, particularly 0.5% to 40%, based on the tank mixture formulation.

[0106] Commercial products are preferably formulated as concentrates (e.g., premixed compositions (formulations)), while end users typically use diluted formulations (e.g., tank-mixed compositions).

[0107] Preferred seed treatment premixes are aqueous suspension concentrates. These premixes can be applied to seeds using conventional processing techniques and machinery, such as fluidized bed technology, drum milling methods, rotostatic seed processors, and rotary drum applicators. Other methods, such as spray beds, can also be useful. The seeds can be pre-coated before coating. After coating, the seeds are typically dried and then transferred to a coating machine for further coating. Such methods are well known in the art.

[0108] In general, the premixed compositions of the present invention comprise 0.5% to 99.9%, particularly 1% to 95%, advantageously 1% to 50% by weight of the desired ingredient, and 99.5% to 0.1%, particularly 99% to 5% by weight of a solid or liquid adjuvant (including, for example, a solvent, such as water), wherein these adjuvants (or adjuvants) may be a surfactant, the amount of which is 0% to 50%, particularly 0.5% to 40% by weight based on the premixed formulation.

[0109] In a preferred embodiment, independent of any other embodiment, a compound having chemical formula I is in the form of a composition for treating (or protecting) plant propagation material, wherein the composition for protecting plant propagation material further comprises a colorant. Such a composition or mixture for protecting plant propagation material may also comprise at least one copolymer of a water-soluble and water-dispersible film-forming polymer that improves the adhesion of the active ingredient to the treated plant propagation material, the polymer having an average molecular weight of at least 10,000 to about 100,000.

[0110] The combination of the present invention (i.e., including the compounds of the present invention and one or more other bioactive agents) can be applied simultaneously or sequentially.

[0111] In this case, a combination of components is applied sequentially (i.e., one by one), within a mutually reasonable period, to achieve biological performance, such as within hours or days. The order of application of these components in the combination, i.e., whether the compound having chemical formula I should be applied first, is not critical to the implementation of this invention.

[0112] In this case, the components of these combinations are applied simultaneously in the present invention, and they can be applied as a composition containing the combination, wherein (A) the compound having chemical formula I and one or more components of the combination can be obtained from a separate formulation source and mixed together (referred to as a barrel mix, ready-to-use, spray broth, or slurry), or (B) the compound having chemical formula I and one or more components of the combination can be obtained as a separate formulation mixture source (referred to as a premix, i.e., mixture, concentrate, or formulation product).

[0113] In one embodiment, independent of other embodiments, a compound according to the invention is applied as a combination. Therefore, the invention also provides a composition comprising a compound according to the invention as described herein, one or more other bioactive agents, and optionally one or more conventional formulation adjuvants; the composition may be in the form of a barrel-mixed or premixed composition.

[0114] These combinations of the present invention can have advantageous properties, examples of which may be mentioned are: advantageous behavior during formulation and / or application (e.g., when grinding, screening, emulsifying, dissolving, or dispersing); increased storage stability; improved photostability; more advantageous degradability; improved toxicological and / or ecotoxicological behavior; or other advantages familiar to those skilled in the art. Detailed Implementation

[0115] 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.

[0116] 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. The specific compound structures and corresponding compound information are shown in Table 1. 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.

[0117] Table 1. Compound Structures

[0118] 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.

[0119] 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.

[0120] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0121] 1. Synthesis of Compound 1

[0122] Compound 1-1 (220 mg, 1.16 mmol) was dissolved in 10 mL of N,N-dimethylformamide, followed by the addition of compound 1-2 (300 mg, 1.16 mmol), N,N-diisopropylethylamine (449 mg, 3.47 mmol), and 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate (660 mg, 1.73 mmol). The mixture was stirred at room temperature for 1 hour. The reaction was monitored by LCMS until complete. The mixture was extracted with water and ethyl acetate, dried over an empty container, and purified by column chromatography to give compound 1 (50 mg, 95% purity, 10.0% yield).

[0123] Bioactivity evaluation (bactericidal activity test - pot method):

[0124] The pesticide was prepared by dissolving dimethyl sulfoxide and diluting it with a 0.1% Tween 80 aqueous solution to different concentrations. The solution was sprayed evenly onto the leaf surface until completely wetted, and then allowed to air dry naturally before use. A blank control (treatment without pesticide) was included. Three controls were set up for each pesticide.

[0125] Asian rust of soybean: The experimental target was Phakopsora pachyrhizi Syd., cultured in live pots. Spores from soybean leaves were collected by washing them with a 0.1% Tween 80 aqueous solution and prepared into a suspension (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.

[0126] Common rust of maize: The experimental target was *Puccinia sorghi*, a fungus cultured in live potted plants. Spores were collected from maize leaves using a 0.1% Tween 80 aqueous solution and prepared into a suspension (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.

[0127] Cucumber downy mildew: The experimental target was *Pseudoperonospora cubensis* cultured in live potted plants. Spores were collected from the surface of selected cucumber leaves by washing with a 0.1% Tween 80 aqueous solution and prepared into a suspension (concentration 5 x 10⁻⁶ spores per ml). 4 -1x10 5 (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.

[0128] Rice sheath blight: Protective testing was conducted 24 hours after pesticide treatment. Holes were punched in culture dishes covered with mycelium to create 5mm mycelial discs, which were then inoculated onto the host material. The inoculated material was then transferred to an incubator or artificial climate chamber for incubation in complete darkness.

[0129] Based on the disease incidence in the blank control group (disease level 9), the inoculated leaves were graded. The following grading method was used:

[0130] Level 0: No disease;

[0131] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0132] Grade 3: The lesion area accounts for 6% to 10% of the total leaf area;

[0133] Level 5: The lesion area accounts for 11% to 25% of the total leaf area;

[0134] Level 7: The lesion area accounts for 26% to 50% of the total leaf area;

[0135] Level 9: The lesion area accounts for more than 50% of the total leaf area.

[0136] Based on the survey data, the disease index and prevention and control effects of each treatment were calculated.

[0137] The disease index is calculated according to formula (1), and the result is rounded to two decimal places: X={(∑(Ni xi)) / (N x 9)}x 100………………………………………(1)

[0138] In the formula: X—disease index; Ni—number of diseased leaves at each level; i—relative level value; N—total number of leaves surveyed.

[0139] The prevention and control effect is calculated according to formula (2): P={(CK-PT) / CK}x 100………………………………………(2)

[0140] In the formula: P—prevention and control effect, in percentage (%); CK—disease index of blank control; PT—disease index of drug treatment.

[0141] Table 2. Results of control using representative compounds (mobile spray tower)

[0142] Table 3. Control Results of Representative Compounds (Vertical Sprayer)

[0143] Note: N represents no data; control compound A:

[0144] 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 phenyl-substituted oxadiazole compound as shown in Formula I: in, P represents O or S; Q represents O or S; X represents aryl or heterocyclic group; R1, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the alkyl, alkenyl, or alkynyl group is optionally selected from halogen, cyano, nitro, cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, -S(O) n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2; R7 represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or -(CO)R; n represents 0, 1, or 2; The aforementioned "cycloalkyl", "heterocyclic" or "aryl" may optionally be substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR, -SR, -(CO)R, -(CO)OR, -N(R)2, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogen-substituted -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-. R can independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkyl, alkenyl, or alkynyl substituted with at least one group selected from halogen, hydroxyl, alkoxy, cyano, or alkoxycarbonyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

2. The phenyl-substituted oxadiazole compound according to claim 1, characterized in that, R1, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl group is optionally selected from halogen, cyano, nitro, C3-C8 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, or -S(O). n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2; R7 represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, cyano-C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, or -(CO)R; The aforementioned "cycloalkyl", "heterocyclic" or "aryl" may optionally be substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated 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, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogenated -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-. R independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, phenyl, 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, 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 phenyl-substituted oxadiazole compound according to claim 1, characterized in that, R1, R2, R3, R4, R5, and R6 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, and -S(O), respectively. n R, -(CO)R, or -(CO)N(R)2, wherein the C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl group is optionally selected from halogen, cyano, nitro, C3-C6 cycloalkyl, aryl, heterocyclic, -OR, -SR, -N(R)2, -O(CO)R, -O(CO)OR, or -S(O). n It is substituted with at least one of the groups R, -(CO)R or -(CO)N(R)2; R7 represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, cyano-C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, or -(CO)R; The aforementioned "cycloalkyl", "heterocyclic" or "aryl" may optionally be substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, -OR, -SR, -(CO)R, -(CO)OR, -N(R)2, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R, or form a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogenated -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2CH2-, -OCH2O- or -SCH2S-. R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, phenyl, 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, 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 the compounds in Table 1 of the specification.

4. A method for preparing a phenyl-substituted oxadiazole compound according to any one of claims 1-3, comprising the following steps: (1) When P represents O, compound II and compound III undergo a condensation reaction to prepare compound I-1. The chemical reaction equation is as follows: Alternatively, (2) when P represents S, compound I-1 undergoes a thioreaction to yield compound I-2, and the chemical reaction equation is as follows: in, M represents OH or halogen, and the substituents R1, R2, R3, R4, R5, R6, R7, X, and Q are defined as described in any one of claims 1-3.

5. The method for preparing the phenyl-substituted oxadiazole compound according to claim 4, characterized in that, The reaction (1) is carried out in the presence of a solvent; preferably, a condensing agent and / or a base are added during the reaction; more preferably, the solvent is selected from at least one of DMF, DMA, toluene, pyridine, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, or ethyl acetate; the base is selected from at least one of inorganic or organic bases; and / or the condensing agent is selected from at least one of 4-PPy, Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU, n-butylphosphine anhydride, or HATU; The reaction (2) is carried out in the presence of a solvent and a thioreagent; preferably, the solvent is selected from at least one of DMF, DMA, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane or ethyl acetate; and / or the thioreagent is selected from at least one of Lawson's reagent, phosphorus pentasulfide, sodium sulfide, hydrogen sulfide or thiourea.

6. A bactericidal composition, characterized in that, It contains at least one of the phenyl-substituted oxadiazole compounds according to any one of claims 1-3 in a biologically effective amount; preferably, it further includes a formulation adjuvant; more preferably, it further includes other active ingredients.

7. Use of the phenyl-substituted oxadiazole compound as described in any one of claims 1-3, or the fungicidal composition as described in claim 6, in the control of plant pathogenic fungi.

8. 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 phenyl-substituted oxadiazole compound as described in any one of claims 1-3, or a fungicidal composition as described in claim 6.

Images