Pyrrole compound and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to a pyrrole compound and the use thereof. The compound is as represented by general formula I: (i), wherein X represents hydrogen, halogen, alkyl, alkenyl, alkynyl, etc.; Y represents hydrogen, halogen, cyano, trialkylsilyl, alkyl, etc.; and Z represents aryl or heterocyclyl. The compound has a good prevention and control effect on harmful organisms and / or fungi (especially nematodes, gibberellic disease, sheath blight and gray mold).

Description

Pyrrole compounds and their applications Technical Field

[0001] The invention belongs to the technical field of pesticides, and particularly relates to a pyrrole compound and application thereof. Background Art

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides and fungicides, pests and diseases have acquired drug resistance, making them difficult to control with existing insecticides and fungicides. Furthermore, some known pest control agents are highly toxic, or some damage ecosystems through their long-term residual properties. Despite the existence of numerous known fungicides, such as CA1286293C, which discloses a phenylcyanopyrrole compound and its use as a fungicide, there remains a need to develop new pest control agents with low toxicity and low residual properties. Summary of the Invention

[0003] In order to solve the above problems existing in the prior art, the present invention provides a pyrrole compound and its application, wherein the compound has excellent control effects on harmful organisms and / or fungi (especially nematodes, ergot, sheath blight, and gray mold).

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

[0005] A pyrrole compound, as shown in general formula I:

[0006] wherein X represents hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclyl, arylalkyl, heterocyclylalkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -alkylene-OR3, -alkylene-SR3, -alkylene-(CO)OR3, -alkylene-(SO2)R3 or -alkylene-N(R3)2;

[0007] Y represents hydrogen, halogen, cyano, trialkylsilyl, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclyl, arylalkyl, heterocyclylalkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -alkylene-OR3, -alkylene-SR3, -alkylene-(CO)OR3, -alkylene-(SO2)R3 or -alkylene-N(R3)2;

[0008] Z represents an aryl group or a heterocyclic group;

[0009] R3 each independently represents hydrogen, an alkyl, alkenyl or alkynyl group which is unsubstituted or substituted by at least one of halogen, alkoxy, alkoxycarbonyl or alkylthio, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group;

[0010] The aforementioned “cycloalkyl” and “cycloalkenyl” are optionally substituted by at least one group selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, or cycloalkylalkyl;

[0011] The aforementioned “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, cycloalkylalkyl, aryl or heterocyclyl which is unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy, -OR 10 , -SR 10 ,-(CO)OR 10 ,-(SO)R 10 , -(SO2)R 10 ,-N(R 10 )2,-alkylene-OR 10 ,-alkylene-SR 10 ,-alkylene-(CO)OR 10 ,-alkylene-(SO)R 10 ,-alkylene-(SO2)R 10 ,-alkylene-N(R 10 )2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with -OCH2CH2- or -OCH2O- which is unsubstituted or substituted with halogen or alkyl;

[0012] R 10 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, cycloalkylalkyl, aryl, heterocyclyl, or aryl or heterocyclyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy;

[0013] The following compounds are excluded:

[0014] In a specific embodiment, X represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, aryl, heterocyclyl, aryl C1-C8 alkyl, heterocyclyl C1-C8 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -(C1-C8 alkylene)-OR3, -(C1-C8 alkylene)-SR3, -(C1-C8 alkylene)-(CO)OR3, -(C1-C8 alkylene)-(SO2)R3 or -(C1-C8 alkylene)-N(R3)2;

[0015] Y represents hydrogen, halogen, cyano, triC1-C8 alkylsilyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, aryl, heterocyclic group, arylC1-C8 alkyl, heterocyclic groupC1-C8 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(C1-C8 alkylene)-OR3, -(C1-C8 alkylene)-SR3, -(C1-C8 alkylene)-(CO)OR3, -(C1-C8 alkylene)-(SO2)R3 or -(C1-C8 alkylene)-N(R3)2;

[0016] R3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl which is unsubstituted or substituted by at least one of halogen, C1-C8 alkoxy, C1-C8 alkoxycarbonyl or C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl or heterocyclic group;

[0017] The aforementioned “C3-C8 cycloalkyl” and “C3-C8 cycloalkenyl” are optionally substituted by at least one group selected from 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, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, or C3-C8 cycloalkylC1-C8 alkyl;

[0018] The aforementioned “heterocyclyl” or “aryl” is optionally 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, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, C3-C8 cycloalkylC1-C8 alkyl, an aryl or heterocyclyl group which is unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy, -OR 10 , -SR 10 ,-(CO)OR 10 ,-(SO)R 10 , -(SO2)R 10 ,-N(R 10 )2,-(C1-C8 alkylene)-OR 10 ,-(C1-C8 alkylene)-SR 10 ,-(C1-C8 alkylene)-(CO)OR 10 ,-(C1-C8 alkylene)-(SO)R 10 ,-(C1-C8 alkylene)-(SO2)R 10 ,-(C1-C8 alkylene)-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with -OCH2CH2- or -OCH2O- which is unsubstituted or substituted with halogen or C1-C8 alkyl;

[0019] R 10 Each of the groups is independently hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, C3-C8 cycloalkylC1-C8 alkyl, aryl, heterocyclic group, or aryl or heterocyclic group substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

[0020] In another embodiment, X represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, aryl, heterocyclyl, aryl-C1-C6 alkyl, heterocyclyl-C1-C6 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -(C1-C6 alkylene)-OR3, -(C1-C6 alkylene)-SR3, -(C1-C6 alkylene)-(CO)OR3, -(C1-C6 alkylene)-(SO2)R3 or -(C1-C6 alkylene)-N(R3)2;

[0021] Y represents hydrogen, halogen, cyano, triC1-C6 alkylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, haloC1-C6 alkyl, haloC2-C6 alkenyl, haloC2-C6 alkynyl, aryl, heterocyclic group, arylC1-C6 alkyl, heterocyclic groupC1-C6 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(C1-C6 alkylene)-OR3, -(C1-C6 alkylene)-SR3, -(C1-C6 alkylene)-(CO)OR3, -(C1-C6 alkylene)-(SO2)R3 or -(C1-C6 alkylene)-N(R3)2;

[0022] R3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-C6 alkoxy, C1-C6 alkoxycarbonyl or C1-C6 alkylthio, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclic group;

[0023] The aforementioned “C3-C6 cycloalkyl” and “C3-C6 cycloalkenyl” are optionally substituted by at least one group selected from 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, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, or C3-C6 cycloalkylC1-C6 alkyl;

[0024] The aforementioned “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, C3-C6 cycloalkylC1-C6 alkyl, aryl or heterocyclyl substituted by 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, -OR 10 , -SR 10 ,-(CO)OR 10 ,-(SO)R 10 , -(SO2)R 10 ,-N(R 10 )2,-(C1-C6 alkylene)-OR 10 ,-(C1-C6 alkylene)-SR 10 ,-(C1-C6 alkylene)-(CO)OR 10 ,-(C1-C6 alkylene)-(SO)R 10 ,-(C1-C6 alkylene)-(SO2)R 10 ,-(C1-C6 alkylene)-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with -OCH2CH2- or -OCH2O- which is unsubstituted or substituted with halogen or C1-C6 alkyl;

[0025] R 10 Each of the groups is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, C3-C6 cycloalkylC1-C6 alkyl, aryl, heterocyclic group, or aryl or heterocyclic group substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0026] In the definitions of the compounds represented by the above general formula and in all the following structural formulas, the technical terms used, whether used alone or in compound terms, represent the following substituents: Alkyl groups having more than two carbon atoms may be straight-chain or branched. For example, in the compound term "-alkylene-(CO)OR3," alkylene may be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. Alkyl groups include, 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; and C6 alkyl-hexyl, such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be at any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein double bonds can be at any position. Halogen is fluorine, chlorine, bromine or iodine.

[0027] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0028] If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0029] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein refers to being substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0030] The compounds of formula I in each case in free form or in salt form, and where appropriate their tautomers, may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule, 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 isomer mixtures and should be understood in this sense in each case above and below, even if no specific stereochemical details are mentioned in each case. The present invention therefore covers all such isomers and tautomers and their mixtures in all proportions, as well as isotopic forms, such as deuterated compounds.

[0031] In another embodiment, Formula I is also understood to include salts or hydrates thereof. Exemplary salts include, but are not limited to, hydrochlorides, hydrobromides, and hydroiodides.

[0032] It will also be understood by those skilled in the art that, unless otherwise indicated, additional substitutions are permissible as long as chemical bonding and strain energy rules are met and the product still exhibits fungicidal activity.

[0033] Another embodiment of the present application is a method for preparing the pyrrole compound, comprising the following steps:

[0034] (1) When Y is hydrogen, the compound represented by the general formula II is reacted with dimethyl (1-diazo-2-oxopropyl)phosphonate to obtain the compound represented by the general formula I-1, and the reaction equation is as follows:

[0035] (2) When Y is not hydrogen, it is prepared by conventional substitution reaction of the compound represented by general formula I-1.

[0036] Or, (3) when X is not hydrogen, By conventional substitution reaction.

[0037] Wherein, X, Y and Z are defined as above.

[0038] In one embodiment, the reaction of step (1) is carried out in the presence of a solvent.

[0039] In another embodiment, a base is added during the reaction of step (1).

[0040] In one embodiment, the solvent of step (1) is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane or ethyl acetate.

[0041] In a specific embodiment, the base in step (1) is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KHCO3, KF, CsF, KI, NaI, K3PO4, K2HPO4, NaOH, KOH, NaH, KH, etc.) or an organic base (such as pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, etc.).

[0042] Another embodiment of the present application is an intermediate, as shown in the aforementioned formula II.

[0043] The present invention also provides a composition for killing pests and / or fungi (especially nematodes, head mold, sheath blight, and gray mold), comprising a biologically effective amount of at least one of the pyrrole compounds.

[0044] In one embodiment, the composition further comprises a formulation adjuvant.

[0045] In another embodiment, the composition further comprises other active ingredients.

[0046] The present invention also provides a method for controlling harmful organisms and / or fungi (especially nematodes, head mold, sheath blight, and gray mold), comprising contacting the harmful organisms and / or fungi or their environment with a biologically effective amount of the pyrrole compound or the composition.

[0047] The present invention also provides use of the pyrrole compound or the composition in preventing and controlling harmful organisms and / or fungi (especially nematodes, head mold, sheath blight, and gray mold).

[0048] The compounds of formula I have been found to be useful for controlling damage caused by pests and / or fungi.

[0049] In one embodiment, the compound of Formula I can be used in agriculture.

[0050] The present invention is therefore furthermore directed to a method for controlling damage and / or yield losses caused by pests and / or fungi, which method comprises applying an effective amount of a compound of formula I to the pests, to the locus of the pests, or to plants susceptible to attack by pests and / or fungi or to plant propagation material.

[0051] The compounds according to the invention can be used for controlling, i.e. limiting or destroying, harmful organisms and / or fungi which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stalks, rhizomes, seeds or roots, and in some cases even on plant organs formed at a later point in time, for protection against these harmful organisms.

[0052] The compounds of formula I according to the invention are preventively and / or therapeutically valuable active ingredients in the field of pest control. Even at low application rates, they can be used to combat pests and / or fungi that are resistant to pesticides. The compounds of formula I have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.

[0053] The compounds according to the invention can act on all or individual developmental stages of normally sensitive and also resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the compounds according to the invention can manifest itself directly, i.e., for example, by the destruction of the pests during molting, which occurs immediately or after a certain period of time, or indirectly, for example, by a reduction in egg laying and / or hatching rates, good activity corresponding to a destruction rate (mortality) of at least 50% to 60%.

[0054] It has now been found that the compounds of formula I according to the invention have (for practical purposes) a very advantageous spectrum of activity for protecting animals and useful plants against attack and damage by nematodes. The present invention therefore also makes available nematicidal compositions comprising the compounds of formula I according to the invention.

[0055] The compounds of formula I are particularly useful for the control of nematodes. In another aspect, the present invention therefore also relates to a method for controlling damage to plants or parts thereof caused by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; cereal cyst nematodes, Heterodera avenae, Heterodera glycines, Heterodera schachtii and Heterodera schachtii. schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Eelonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Mesocriconema species;Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus, and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species, and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; False rootknot nematodes Needle nematodes, Longidorus elongatus, and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species;Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus, and other Trichodorus species; Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes), Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;

[0056] In particular, the nematode species: Meloidogyne, Heterodera, Coelenteroides and Pratylenchus can be controlled by the compounds according to the invention.

[0057] On the other hand, the present invention also relates to a method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, wherein a compound of formula I is applied to a plant, its part or its place as an active ingredient. The significant difference of the compound of formula I according to the present invention is activity, good plant tolerance and environmental safety. They have very useful treatment, prevention and systemic properties and are used to protect a variety of useful plants. The compound of formula I can be used to suppress or destroy the disease that occurs on the plant or plant part (fruit, flower, leaf, stem, tuber, root) of a variety of different useful plants, while also protecting those plant parts that are grown later from phytopathogenic microorganisms. It is also possible to use the compound of formula I as a dressing agent for treating plant propagation materials, particularly seeds (fruit, tuber, grain) and plant cuttings (e.g., rice), for protecting against fungal infection and against phytopathogenic fungi present in the soil.

[0058] Examples of fungi include: the class Deuteromycetes (e.g., Botrytis, Pyrospora, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); the class Basidiomycetes (e.g., Rhizoctonia, Puccinia, Puccinia); the class Ascomycetes (e.g., Venturia and Powdery Mildew, Monocystis, Moniliformis, Uncinaria); the class Oomycetes (e.g., Phytophthora, Pythium, Monoparagus); the class Zygomycetes (e.g., Rhizopus); the family Pucciniaceae, particularly those of the genus Pucciniaceae, such as Puccinia pachyrhizi, which is also known as Asian soybean rust, and those of the family Pucciniaceae, particularly those of the genus Pucciniaceae, such as Puccinia graminis, also known as stem rust or black rust, which is a problem disease in cereals, and Puccinia recondita, also known as brown rust.

[0059] Among the plants and possible diseases of these plants which can be protected by the method according to the invention, mention may be made of:

[0060] - Wheat, for the control of the following seed diseases: Fusarium (Fusarium spp. and Fusarium rosobacterium), black bunt (Tilletia tritici, Tilletia dwarfii, or Tilletia indica), Septoria (Septoria glumae), and loose smut;

[0061] - wheat, for the control of the following diseases of the above-ground parts of the plant: cereal eye spot (Tapesia yallundae, Tapesia acuiformis), take-all (Tapesia taecii), root blight (F. culmorum, F. graminearum), black spot (Rhizoctonia graminearum), powdery mildew (Erysiphe graminis forma specie tritici), rust (Puccinia striatum and Puccinia reclusa), and Septoria diseases (Septoria tritici and Septoria glume);

[0062] - wheat and barley, for the control of bacterial and viral diseases, such as barley yellow mosaic; - barley, for the control of the following seed diseases: net blotch (Pyricularia trichomoniasis, Pyricularia terrestris, and Cochliobolus graminis), loose smut (loose smut), and fusarium (Fusarium nivale and Fusarium roseum);

[0063] - barley, for the control of the following diseases of the above-ground parts of the plant: cereal eye spot (Tapesia yallundae), net blotch (Pyricularia teres and Cochlosporium graminis), powdery mildew (Erysiphe graminis formas pecie hordei), dwarf leaf rust (Puccinia hordei) and leaf spot (Puccinia hordei);

[0064] - Potatoes, for the control of tuber diseases (particularly Aralia solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytophthora infestans) and some viruses (Virus Y);

[0065] - Potatoes, for the control of the following foliar diseases: early blight (Alternaria solani), mildew (Phytophthora infestans);

[0066] - Cotton, for the control of the following diseases in young plants grown from seed: damping-off and blight (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Thalassemia radicifolia);

[0067] - protein-producing plants, such as peas, for controlling the following seed diseases: anthracnose (Psoralea corylifolia, Mycosphaeria pisum), fusarium (Fusarium oxysporum), gray mold (Botrytis cinerea) and mildew (Peronospora pisum);

[0068] - Oilseed rape, for the control of the following seed diseases: Stenotrophomonas brassicae, Alternaria brassicae, and Sclerotinia sclerotiorum;

[0069] - Corn, for the control of various seed diseases (Rhizopus, Penicillium, Trichoderma, Aspergillus, and Gibberella);

[0070] - Flax, for controlling this seed disease: Alternaria linicola;

[0071] - Deep forest trees, for controlling damping-off disease (Fusarium oxysporum, Rhizoctonia solani);

[0072] - Rice, for the control of the following diseases of above-ground parts: blast (Pyricularia oryzae), bordered sheath spot (Rhizoctonia solani);

[0073] - Leguminous plants, for the control of the following diseases on seeds or young plants grown from seeds: damping-off and blight (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium spp.);

[0074] - Leguminous plants, for the control of the following diseases on aerial parts: gray mold (Botrytis spp.), powdery mildew (especially Erysiphe spp., Erysiphe spp. and Pyrophila spp.), Fusarium spp. (Fusarium oxysporum, Fusarium rosporum), leaf spot (Cladosporium spp.), Alternaria leaf spot (Alternaria spp.), anthracnose (Colletotrichum spp.), Septoria leaf spot (Septoria spp.), black spot (Rhizoctonia solani), mildew (for example, Downy mildew of lettuce, Peronospora spp., Pseudocoperonospora spp., Phytophthora spp.);

[0075] - fruit trees, for the control of various diseases of aerial parts: candidiasis (Monilia fructigenae, M. laxa), scab (Viburnum indica), powdery mildew (Monilia albicans); - vines, for the control of the following foliar diseases: in particular gray mold (Botrytis cinerea), powdery mildew (Uncinaria officinalis), black rot (Guignardia biwelli) and mildew (Plasmopara viticola);

[0076] Beetroot for the following diseases of aerial parts: cercospora blight (brown blight of beet), powdery mildew (Erysiphe beticola), leaf spot (Erysiphe beticola).

[0077] The fungicidal compositions according to the invention can also be used to combat fungal diseases that are susceptible to growth on or in wood. The term "wood" refers to all types of wood species, as well as all types of wood intended for construction work, such as solid wood, high-density wood, laminated wood, and plywood. The method for treating wood according to the invention essentially involves contacting with one or more compounds according to the invention or compositions according to the invention; this includes, for example, direct application, spraying, immersion, injection, or any other suitable means.

[0078] When used alone, the compounds of the present invention are effective in controlling nematodes, insects, acarid pests and / or fungal pathogens of growing or harvested agronomic plants. They can also be used in combination with other bioactive agents used in agriculture, for example, one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activators, molluscicides, and pheromones (chemical or biological). Mixing the compounds of the present invention or their compositions in the form of pesticides with other pesticides often results in a wider spectrum of pest control. For example, the compounds of formula I of the present invention can be effectively combined or used in combination with pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cycloalkadienes, formamidines, tin phenolates, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles, and the like.

[0079] By adding, for example, one or more insecticides, acaricides, nematocides and / or fungicidal active agents, the activity of these compositions according to the present invention can be significantly widened and adapted to prevailing environments. Combinations of compounds of formula I with other insecticides, acaricides, nematocides and / or fungicidal active agents can also have further, unexpected advantages. For example, plants can better tolerate them, reduce phytotoxicity, and harmful organisms or fungi can be controlled at their different developmental stages or behave better during their production (for example, in grinding or mixing processes, in their storage or their use).

[0080] The other fungicides may include: 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxy quinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, QST713), benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Borgundy mixture, boscalid, bromuconazole, bupirimate, calcium sulfur polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium Minitans, copper hydroxide, copper tanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid,Cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammoniumethylenebis-(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, and triphenyltin hydroxide. hydroxide), ferbam, ferimzone, fluazinam, fludioxonil, flumorph,Fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, triethylamine Fosetyl, fosetyl-aluminium, fuberidazole, furaxyl, furametpyr, guazatine, guazatine acetate, sodium tetrasulfide (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate sulfate), imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprethiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate), kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide,mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acid) 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 sulfate), probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb,Proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenyl phenoxide, sodium bicarbonate bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oil, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol imenol, triazoxide, tricyclazole, triridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila,Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate hydrate), 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate, ampropylfos, anilazine, azithiram, barium polysulfide, ferric bromide (Bayer 32394), benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl,benzamorf, 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, cupric hydrazinium sulfate sulfate), cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, E BP), ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, 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 bis(dimethyldithiocarbamate) bis(dimethyldithiocarbamate), octachloroketone (OCH), phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, 5-acetyl-8-hydroxyquinoline (quinacetol); 5-acetyl-8-hydroxyquinoline sulfate (quinacetolsulfate), quinazamid, quinconazole, rabenzazole, salicylanilid e), pyraclostrobin (SSF-109), sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide,Urbacid, zarilamid, and any combination thereof.

[0081] The other nematicides may include: AKD-3088, 1,2-dibromo-3-chloropropane, 1,2-dichloropropane, 1,2-dichloropropane and 1,3-dichloropropene, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, avermectin, acetoprolin, aldicarb, and (aldicarb), aldoxycarb, AZ60541, benclothiaz, benclothiaz, butylpyridaben, cadusafos, carbofuran, carbon disulfide, carbofuran butylsulfonate, chloropicrin, chlorpyrifos, cloethocarb, cytokinins, dazomet, D BCP, DCIP, diamidafos, dichlofenthion, dicliphos, dimethoate, imaquine, imaquine benzoate, eprinomectin, eprinomectin, ethoprophos, ethylene dibromide, fenamiphos, tebufenpyrad, fenpyrad, fosthiazate, fosthietan, furfural, GY-81, heterophos, iodomethane, isamidofos, isazofos, kinetin, mecarphon, mecarphon-methyl, metamifene, metamifene potassium, metamifene sodium, methyl bromide, methyl isothiocyanate, milbemycin oxime oxime), moxidectin, a component of Myrothecium verrucaria, NC-184, oxamyl, phorate, phosphamidon, phosphocarb, sebufos, selamectin, spinosad, terbam, terbufos, tetrachlorothiophene, thiafenox, thionazin, triazophos, triazuron, xylenol, YI-5302 and zeatin, fluensulfone [318290-98-1], and any combination thereof.

[0082] In general, the mass ratio between the two components in any combination of the present invention is independently from one another from 100:1 to 1:100, preferably from 75:1 to 1:75, more preferably from 50:1 to 1.50, especially from 25:1 to 1:25, advantageously from 10:1 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, by mass, and also on the other hand, by molar ratios.

[0083] Examples of methods of application of the compounds and compositions of the present invention, i.e. methods of controlling pests / fungi in agriculture, are spraying, misting, dusting, brushing, seed dressing, broadcasting or pouring - which are selected to suit the intended purpose under the prevailing circumstances.

[0084] A preferred method of application in agriculture is application to the leaves of the plants (foliar application), it being possible to select the frequency and rate of application in accordance with the risk of infection by the pest / fungus in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action) by applying the compound to the locus of the plants, for example, by applying a liquid composition of the compound to the soil (by drench) or by applying the compound in solid form in the form of granules to the soil (soil application). In the case of rice plants, such granules can be metered into flooded paddies.

[0085] The application rates per hectare are generally 1 g to 2000 g of active ingredient per hectare, in particular 10 g / ha to 1000 g / ha, preferably 10 g / ha to 600 g / ha, such as 50 g / ha to 300 g / ha.

[0086] These compounds of the present invention and composition thereof are also suitable for the protection (for example seed, such as fruit, tuber or grain, or nursery plant) of plant propagation material against the harmful organism of above-mentioned type.This propagation material can be processed with this compound before planting, and for example seed can be processed before sowing.Alternately, this compound can be applied to seed grain (coating), and this is by being immersed in liquid composition by grain or by applying a kind of solid composition layer and realize.When this propagation material is planted in the application site, it is also possible for example to apply these compositions to seed furrow during drilling.These treatment methods for plant propagation material and the plant propagation material therefore processed are other themes of the present invention.Typically, treatment rate will depend on plant and harmful organism / fungus to be controlled, usually between 1 gram to 200 grams of every 100kg seeds, preferably between 5 grams to 150 grams of every 100kg seeds, as between 10 grams to 100 grams of every 100kg seeds.

[0087] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in a preferred embodiment refers to true seeds.

[0088] The present invention also includes seeds coated with or treated with a compound of formula I or containing a compound of formula I. The term "coated with or treated with and / or containing" generally means that in most cases the active ingredient is on the surface of the seed when applied, although a greater or lesser 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 available a plant propagation material having a compound of formula I adhered thereto. In addition, a composition comprising plant propagation material treated with a compound of formula I is thereby available.

[0089] Seed treatment includes all applicable seed treatment techniques known in the art, such as, seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with the compound of formula I can be achieved by any known method and used, such as, before sowing the seeds or during sowing / planting, spraying or by dusting.

[0090] Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar beets or fodder beets; fruit, such as pome, stone or stoneless fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, such as strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oilseed plants, such as rapeseed, mustard, chestnuts, olives, sunflowers, coconuts, castor beans, cocoa or peanuts; cucurbit crops, such as pumpkins, cucumbers or melons; Fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as oranges, lemons, grapevines, or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; plants of the Lauraceae family, such as avocado, Cinnamonium, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantaginaceae, rubber plants, and ornamental plants (e.g., flowers and lawn plants or turf).

[0091] In one embodiment, the plant is selected from the group consisting of cereals, corn, soybeans, rice, sugarcane, vegetables, and oil plants.

[0092] The term "plants" is to be understood as also including plants transformed by the use of recombinant DNA techniques and which are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular Bacillus.

[0093] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available.

[0094] Typically, the compounds of the invention are used in the form of a composition (eg, a formulation) comprising a carrier. The compounds of the present invention and their compositions can be used in different forms, for example, aerosol sprayers, capsule suspensions, cold atomization concentrates, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, capsule granules, fine granules, flowable concentrates for seed treatment, gases (under pressure), gas-generating products, granules, hot atomization concentrates, macrogranules, 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 suspensions (ulv), 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.

[0095] A formulation typically comprises a liquid or solid carrier and optionally one or more conventional formulation adjuvants, which may be solid or liquid adjuvants, 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, binders, and / or tackifiers. The composition may further comprise a fertilizer, micronutrient donor, or other product that influences plant growth, and includes a combination comprising a compound of the invention and one or more other bioactive agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.

[0096] The present invention therefore also makes available a composition comprising a compound according to the invention together with an agronomic carrier and optionally one or more customary formulation auxiliaries.

[0097] These compositions are prepared with methods known per se, for example by grinding, screening and / or squeezing solid compounds of the present invention and in the presence of at least one auxiliary agent, for example by closely mixing and / or grinding the compound of the present invention with one or more auxiliary agents. In the case of solid compounds of the present invention, the grinding / grinding of the compound is in order to ensure a specific particle size. The methods for preparing these compositions and the purposes of these compounds of the present invention for preparing these compositions are also a theme of the present invention.

[0098] Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or capsules in a polymeric mass, these compositions comprising at least one compound according to the invention and the type of composition being chosen to suit the intended purpose and the prevailing circumstances.

[0099] Examples of suitable liquid carriers are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8 to C 12 alkylbenzene moieties, such as xylene mixtures, alkylated naphthalenes or tetralins, 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-methylpyrrolidin-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, non-epoxidized or epoxidized vegetable oils, such as non-epoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oils.

[0100] Examples of solid carriers for example dusts and dispersible powders are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite normally. In order to improve physical properties, it is also possible to add highly dispersed silica or highly dispersed absorbent polymers. Suitable particle adsorptive carriers for granules are porous, such as pumice, gravel, sepiolite or bentonite, and suitable non-absorptive carrier materials are calcite or sand. In addition, a large amount of granulated materials of inorganic or organic natural materials can be used, particularly dolomite or pulverized plant residues.

[0101] Depending on the type of active ingredient to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are to be regarded only as examples; a large number of other surfactants conventionally used in the field of formulations and suitable according to the present invention are described in the relevant literature.

[0102] Suitable nonionic surfactants are, in particular, polyethylene glycol ether derivatives of aliphatic or cycloaliphatic alcohols, polyethylene glycol ether derivatives of saturated or unsaturated fatty acids or polyethylene glycol ether derivatives of alkylphenols, which may contain from about 3 to about 30 glycol ether groups and from about 8 to about 20 carbon atoms in the (cyclo)aliphatic hydrocarbon residue or from about 6 to about 18 carbon atoms in the alkyl portion of the alkylphenol. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkylpolypropylene glycols having from 1 to about 10 carbon atoms in the alkyl chain and from about 20 to about 250 glycol ether groups and from about 10 to about 100 propylene glycol ether groups. Typically, the above compounds contain from 1 to about 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonoxynol, castor oil polyethylene glycol ether, polypropylene glycol / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

[0103] These cationic surfactants are in particular quaternary ammonium salts which generally have at least one alkyl residue (from about 8 to about 22 carbon atoms) as a substituent and (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl residues as further substituents. These salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

[0104] Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are alkali metal salts, alkaline earth metal salts, or (unsubstituted or substituted) ammonium salts of fatty acids having from about 10 to about 22 carbon atoms, such as the sodium or potassium salts of oleic acid or stearic acid, or natural fatty acid mixtures (obtainable, for example, from coconut oil or tall oil); mention should also be made of the fatty acid methyltaurine. However, synthetic surfactants are more commonly used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives, or alkylarylsulfonates. These fatty sulfonates and fatty sulfates are usually alkali metal salts, alkaline earth metal salts, or (substituted or unsubstituted) ammonium salts and usually have alkyl residues having from about 8 to about 22 carbon atoms, alkyl also being understood as an alkyl moiety including acyl residues; examples that may be mentioned are the sodium or calcium salts of ligninsulfonic acid, the sodium or calcium salts of lauryl sulfate, or the sodium or calcium salts of fatty alcohol sulfate mixtures prepared from natural fatty acids. This group also includes sulfates and sulfonates 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 alkylarylsulfonates are sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid / formaldehyde condensates. In addition, suitable phosphates, such as the phosphate esters of p-nonylphenol / (4-14)ethylene oxide adducts, or phospholipids are also possible.

[0105] Typically, these compositions comprise from 0.1% to 99% (in particular from 0.1% to 95%) of a compound according to the invention and from 1% to 99.9% (in particular from 5% to 99.9%) of at least one solid or liquid carrier, it being possible in principle for 0% to 25% (in particular from 0.1% to 20%) of the composition to be a surfactant (in each case % denotes percentage by weight). However, for commercial purposes, concentrated compositions are generally preferred, the end user in principle using diluted compositions having a significantly lower concentration of active ingredient.

[0106] Examples of suitable formulation types for tank mix compositions are solutions, dilute emulsions, suspensions or mixtures thereof, and dusts.

[0107] As to the nature of the formulations, the methods according to the invention, such as foliage, drench, spraying, atomizing, dusting, spreading, coating or pouring, may be chosen according to the intended purposes and the prevailing circumstances.

[0108] Such tank-mix compositions are generally prepared by diluting one or more pre-mix compositions containing different pesticides and, optionally, additional adjuvants with a solvent (eg, water).

[0109] Suitable carriers and adjuvants can be solid or liquid and are the substances customary in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, extenders, binders or fertilizers.

[0110] Generally, tank-mix formulations for foliar or soil application comprise 0.1% to 20%, especially 0.1% to 15%, of the desired ingredients and 99.9% to 80%, especially 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%, especially 0.1% to 15%, based on the tank-mix formulation.

[0111] Typically, premix formulations for foliar application comprise 0.1% to 99.9%, in particular 1% to 95%, of the desired ingredient and 99.9% to 0.1%, in particular 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), whereby the adjuvants may be a surfactant, in an amount of 0 to 50%, in particular 0.5% to 40%, based on the premix formulation.

[0112] Typically, tank mix formulations for seed treatment applications comprise 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of solid or liquid adjuvants (including, for example, a solvent such as water), where the adjuvant can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank mix formulation.

[0113] Typically, premix formulations for seed treatment applications comprise 0.5% to 99.9%, especially 1% to 95% of the desired ingredients, and 99.5% to 0.1%, especially 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), where the adjuvants can be a surfactant, in an amount of 0 to 50%, especially 0.5% to 40%, based on the tank mix formulation.

[0114] While commercial products are preferably formulated as concentrates (eg, pre-mix compositions (formulations)), end users typically employ diluted formulations (eg, tank mix compositions).

[0115] Preferred seed treatment premix formulations are aqueous suspension concentrates. This formulation can be applied to the seed using conventional processing techniques and machines, such as fluidized bed technology, drum grinding method, static rotation (rotostatic) seed processor and drum applicator. Other methods, such as spouted bed, can also be useful. These seeds can be pre-coated with glue before coating. After coating, these seeds are typically dried and then transferred to a glue coating machine for coating. Such methods are well known in the art.

[0116] Generally, the premix composition of the invention comprises 0.5 to 99.9% by mass, in particular 1 to 95%, advantageously 1 to 50% by mass of the desired ingredients, and 99.5 to 0.1%, in particular 99 to 5% by mass of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the auxiliary agents (or adjuvants) may be a surfactant in an amount of 0 to 50%, in particular 0.5 to 40%, by mass, based on the premix formulation.

[0117] In a preferred embodiment, independent of any other embodiment, the compound of formula I, I', I" or 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. The composition or mixture for protecting plant propagation material may also comprise at least one copolymer from water-soluble and water-dispersible film-forming polymers that improve the attachment of the active ingredient to the treated plant propagation material, the polymers generally having an average molecular weight of at least 10,000 to about 100,000.

[0118] The combinations of the invention (ie, those comprising a compound of the invention and one or more additional biologically active agents) may be administered simultaneously or sequentially.

[0119] In this case, the components of a combination are administered sequentially (i.e., one by one), and the components are administered sequentially within a reasonable period relative to each other to achieve the biological effect, such as within a few hours or days. The order in which the components of the combination are administered, i.e., whether the compound of formula I should be administered first, is not critical for practicing the present invention.

[0120] In the case where the ingredients of the combination are applied simultaneously in the present invention, they may be applied as a composition comprising the combination, in which case (A) the compound of formula I and one or more ingredients of the combination may be obtained from a separate formulation source and mixed together (referred to as a tank mix, ready-to-use, spray broth or slurry), or (B) the compound of formula I and one or more ingredients of the combination may be sourced as separate formulation mixtures (referred to as a premix, i.e., mixture, concentrate or formulated product).

[0121] In one embodiment, independently of other embodiments, a compound according to the invention is administered as a combination. Thus, the present 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 tank mix or premix composition.

[0122] The combinations according to the invention may have advantageous properties, examples of which may be mentioned: favorable behavior during formulation and / or application (e.g. when grinding, sieving, emulsifying, dissolving or dispersing); increased storage stability, improved photostability; more favorable degradability; improved toxicological and / or ecotoxicological behavior; or other advantages with which a person skilled in the art will be familiar. DETAILED DESCRIPTION

[0123] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0124] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0125] Table 1 Compound structures and their 1 H NMR

[0126] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0127] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0128] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0129] 1. Synthesis of Compound 2

[0130] Compound 2-1 (200 mg, 0.80 mmol, 1 eq) was dissolved in 5 ml of methanol, and dimethyl (1-diazo-2-oxopropyl)phosphonate (168 mg, 0.87 mmol, 1.1 eq) and potassium carbonate (221 mg, 1.6 mmol, 2 eq) were added. The atmosphere was purged with nitrogen three times and stirred at room temperature for 2 h. After monitoring the reaction for completion, water and ethyl acetate were added for extraction. The organic phase was washed twice with saturated brine and dried over anhydrous sodium sulfate. The sample was stirred and subjected to normal phase separation (EA / PE = 1 / 3) to obtain 60 mg of compound 2, with a yield of 30%.

[0131] 2. Synthesis of Compound 1

[0132] (1) Compound 1-1 (1.4 g, 1 eq, 6.6 mmol) was dissolved in 30 ml of ether. DIBAL-H (13.2 ml, 2 eq, 13.2 mmol, 1 mol / L in Toluene) was added under ice-bath conditions and reacted for 3 h. The reaction was monitored until the starting material disappeared. The reaction solution was partitioned by adding water, and the organic phase was purified by column chromatography to obtain compound 1-2 (0.6 g, purity 83%, yield 42%) as a white solid.

[0133] (2) Compound 1-2 (300 mg, 1 eq, 1.39 mmol) was dissolved in 10 ml of methanol, and dimethyl (1-diazo-2-oxopropyl)phosphonate (803 mg, 3 eq, 3.41 mmol) and potassium carbonate (578 mg, 3 eq, 3.41 mmol) were added. The reaction was allowed to react at room temperature for 8 h. The reaction was monitored until the starting material disappeared. The reaction solution was dried and the organic phase was purified by column chromatography to obtain compound 1, weighing 65 mg (purity 99%, yield 22%), as a brown oil.

[0134] 3. Synthesis of compound 5

[0135] Compound 2 (60 mg, 0.24 mmol) was dissolved in 5 ml of THF. Sodium hydroxide (12 mg, 0.28 mmol) was added under ice-cooling conditions and the mixture was allowed to react for 30 minutes. Acetyl chloride (38 mg, 0.56 mmol) was added and the mixture was allowed to react at room temperature for 1 hour. LCMS monitored the reaction to be complete. Water was added to quench the reaction. 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 5 (50 mg, 72%).

[0136] 4. Synthesis of Compound 153

[0137] (1) Compound 153-1 (1.0 g, 1.0 eq, 4.5 mmol) was dissolved in 30 ml of ether. DIBAL-H (9.1 ml, 2.0 eq, 9.1 mmol, 1.0 mol / L in Toluene) was added under ice-bath conditions and allowed to react for 3 h. The reaction was monitored until the starting material disappeared. The reaction solution was partitioned by adding water, and the organic phase was purified by column chromatography to obtain compound 153-2 (0.7 g, purity 95%, yield 69%) as a white solid.

[0138] (2) Compound 153-2 (0.7 g, 1.0 eq, 3.1 mmol) was dissolved in 10 ml of methanol, and dimethyl (1-diazo-2-oxopropyl)phosphonate (1.8 g, 3.0 eq, 9.4 mmol) and potassium carbonate (1.3 g, 3.0 eq, 9.4 mmol) were added. The reaction was carried out at room temperature for 8 h. The reaction was monitored until the starting material disappeared. The reaction solution was dried and the organic phase was purified by column chromatography to obtain compound 153 (0.07 g, purity 90%, yield 10%) as a brown solid.

[0139] 5. Synthesis of Compound 154

[0140] (1) 154-1 (3.22 g, 1 eq, 11.32 mmol) was dissolved in 40 ml of methanol, and p-methylphenylsulfonylmethyl isocyanide (2.21 g, 1 eq, 11.32 mmol) and potassium hydroxide (825 mg, 1.3 eq, 14.71 mmol) were added. The reaction was carried out in an ice bath for 2 h. The reaction was monitored until the starting material disappeared. The reaction solution was dried and the organic phase was purified by column chromatography to obtain compound 154-2 (2.24 g, purity 90%, yield 67%) as a white solid.

[0141] (2) Compound 154-2 (2.24 g, 1 eq, 7.6 mmol) was dissolved in 30 ml of ether. DIBAL-H (15.2 ml, 2 eq, 15.2 mmol, 1 mol / L in Toluene) was added under ice-bath conditions and allowed to react for 3 h. The reaction was monitored until the starting material disappeared. The reaction solution was partitioned by adding water, and the organic phase was purified by column chromatography to obtain compound 154-3 (1.36 g, purity 93%, yield 60%) as a white solid.

[0142] (3) Compound 154-3 (500 mg, 1 eq, 1.68 mmol) was dissolved in 10 ml of methanol, and dimethyl (1-diazo-2-oxopropyl)phosphonate (968 mg, 3 eq, 5.04 mmol) and potassium carbonate (696 mg, 3 eq, 5.04 mmol) were added. The reaction was allowed to react at room temperature for 8 h. The reaction was monitored until the starting material disappeared. The reaction solution was dried and the organic phase was purified by column chromatography to obtain compound 154 (60 mg, purity 98%, yield 12%) as a white solid.

[0143] 6. Synthesis of Compound 159

[0144] In a 50 mL single-necked flask, compound 2 (150 mg, 0.61 mmol) was dissolved in 1.5 mL of N,N-dimethylformamide. Tetrabutylammonium iodide (224 mg, 0.61 mmol) was added. Sodium hydroxide (37 mg, 0.91 mmol) was added under ice-cooling and incubated for half an hour. Compound 159-2 (107 mg, 0.91 mmol) was then added and allowed to react at room temperature for 5 hours. LCMS monitored the reaction completion. The reaction solution was quenched with water and extracted 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 / 20) to afford compound 159 (131 mg, 75.35%) as a brown solid.

[0145] 7. Synthesis of Compound 166

[0146] (1) Compound 166-1 (400 mg, 2.17 mmol) was dissolved in 8 mL of carbon tetrachloride at room temperature. AIBN (178.26 mg, 1.09 mmol) and NBS (309.13 mg, 1.74 mmol) were added and the mixture was allowed to react at 80°C for 8 h. LCMS monitoring confirmed the completion of the reaction. The reaction solution was diluted with water and extracted with dichloromethane. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (PE = 100%) to afford compound 166-2 (300 mg, 52.51%) as a light yellow oil.

[0147] (2) Compound 2 (140.9 mg, 0.57 mmol) was dissolved in 5 ml of DMF. NaH (22.8 mg, 0.57 mmol) was added at 0°C and the mixture was allowed to react at room temperature for 30 min. 166-2 (100 mg, 0.38 mmol) was added to the reaction mixture and the mixture was allowed to react at room temperature for 4 h. LCMS monitored the reaction to be complete. The reaction mixture was diluted with water, the aqueous phase was extracted with ethyl acetate, the organic phase was washed with saturated brine, dried, and concentrated, and the residue was purified by column chromatography (EA / PE = 1 / 5) to give compound 166-3 (120 mg, 73.53%) as a white oil.

[0148] 8. Synthesis of Compound 167

[0149] (1) Compound 2 (200 mg, 0.8 mmol) was dissolved in 5 ml of DCM, and Boc2O (265 mg, 1.2 mmol), triethylamine (242 mg, 2.4 mmol), and a catalytic amount of DMAP were added. The reaction was allowed to react at room temperature for 1 hour. LCMS confirmed the completion of the reaction. Water was added to quench the reaction. 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 / 5) to give compound 167-1 (167 mg, 60%).

[0150] (2) Compound 167-1 (167 mg, 0.48 mmol) was dissolved in 5 ml of THF. The mixture was cooled to -78°C and n-butyllithium (0.2 ml, 0.57 mmol) was added dropwise. The mixture was kept warm for 30 minutes. Methyl iodide (341 mg, 2.4 mmol) was added and the mixture was naturally warmed to room temperature for 1 hour. The reaction was completed as monitored by LCMS. Ammonium chloride solution was added to quench the reaction. 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 / 5) to give compound 167 (60 mg, 35%).

[0151] 9. Synthesis of Compound 168

[0152] Compound 2 (100 mg, 0.4 mmol) was dissolved in 5 ml of DMF, and compound 168-1 (114 mg, 0.48 mmol), a catalytic amount of tetrakistriphenylphosphine palladium (20 mg, 0.02 mmol), and a catalytic amount of CuI were added. The mixture was allowed to react overnight at room temperature under a nitrogen atmosphere. LCMS confirmed the reaction was complete. 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 / 2) to afford compound 168 (71 mg, 49%).

[0153] 10. Synthesis of Compound 169

[0154] (1) Substrate 169-1 (1.3 g, 7.4 mmol) was dissolved in toluene in a single-necked flask. Ethyl cyanoacetate (1 g, 8.9 mmol) and potassium acetate (724 mg, 7.4 mmol) were added and reacted at 100°C overnight. After completion of the reaction, the toluene was removed, and the mixture was extracted with ethyl acetate / water. The mixture was purified by silica gel column chromatography to obtain intermediate 169-2 (1.5 g, 5.6 mmol, 75%).

[0155] (2) Substrate 169-2 (1.5 g, 5.6 mmol) was dissolved in methanol in a single-necked flask. Compound 169-3 (1.2 g, 6.2 mmol) and potassium hydroxide (403 mg, 7.3 mmol) were added and reacted at room temperature for 6 h. After completion of the reaction, the methanol was removed by rotary evaporation, and the mixture was extracted with ethyl acetate / water. The mixture was purified by silica gel column chromatography to obtain intermediate 169-4 (1.3 g, 5.2 mmol, 93.4%).

[0156] (3) Substrate 169-4 (1.3 g, 5.2 mmol) was dissolved in diethyl ether in a single-necked flask. DIBAL-H (7.8 mmol) was slowly added at -78°C and allowed to react overnight at room temperature. After the reaction was complete, a small amount of water was added to quench the reaction, the mixture was filtered through celite, and the filter cake was washed twice with ethyl acetate. The solvent was evaporated under reduced pressure to obtain intermediate 169-5 (310 mg, 1.2 mmol, 23.9%).

[0157] (4) Substrate 169-5 (310 mg, 1.2 mmol) was dissolved in methanol in a single-necked flask. Dimethyl (1-diazo-2-oxopropyl)phosphonate (494 mg, 2.4 mmol) and potassium carbonate (355 mg, 2.4 mmol) were added and reacted overnight under nitrogen. After completion of the reaction, the methanol was removed by rotary evaporation, and the mixture was extracted with ethyl acetate / water. The mixture was purified by silica gel column chromatography to yield 169 (60 mg, 0.24 mmol, 20%).

[0158] Biological activity evaluation (sterilization plate method):

[0159] The agent was dissolved in acetone and diluted with sterile water, with different concentrations set according to its activity. Under aseptic conditions, pre-melted sterile culture medium was quantitatively added to a sterile Erlenmeyer flask according to the test treatment. The drug solution was pipetted in order from low to high concentration and added to each of the above Erlenmeyer flasks, shaking thoroughly. Equal amounts were then poured into three 6 cm diameter Petri dishes to create drug-containing plates of the corresponding concentrations. A blank control was used as a control, with three replicates for each treatment. The cultured pathogen was sterilely punched using a 3 mm diameter sterile punch to cut a bacterial cake from the edge of a colony. This cake was inoculated with an inoculator, mycelial side up, onto the center of the drug-containing plate. The plate was covered and incubated at 25°C. After four days, the growth of the pathogen hyphae was assessed by comparing the growth of the blank control Petri dishes. The colony diameter was measured in millimeters (mm) using a caliper. Each colony was measured vertically twice using the cross-section method, and the average value was calculated. According to the survey results, the mycelial growth inhibition rate of each treatment concentration on the target bacteria was calculated according to formula (1) (2), and the unit is percentage (%).

[0160] D=D1-D2…………………………………………(1)

[0161] Where: D is the diameter of colony growth; D1 is the diameter of colony; D2 is the diameter of bacterial cake.

[0162] Where: I——hyphae growth inhibition rate; D0——blank control colony growth diameter; D t ——The growth diameter of the colony after treatment with chemicals.

[0163] Table 2 Representative test results of fungicide inhibition of pathogenic fungal hyphae growth by plate method

[0164] Biological activity evaluation (sterilization pot method):

[0165] The agent was dissolved in dimethyl sulfoxide and diluted to varying concentrations with a 0.1% Tween 80 solution. The solution was evenly sprayed onto the leaf surface until completely wet. Allowed to air-dry, the solution was then used. A blank control was established with no agent. Three controls were established for each agent.

[0166] Inoculation of tomato gray mold, wheat scab, and cucumber anthracnose: Protective tests were performed 24 hours after treatment. In a culture dish already covered with spores, culture medium was added, and spores on the surface were gently scraped off. After filtering through 4 layers of gauze, a concentration of 5×10 6 ~6×10 6 The inoculated material is then placed in an incubator or artificial climate chamber for incubation without light.

[0167] Rice Sheath Blight Inoculation: Protective tests are performed 24 hours after treatment. A culture dish filled with mycelium is perforated to create a 5mm cake, which is then inoculated onto the host material. The inoculated material is then transferred to an incubator or artificial climate chamber for incubation without light.

[0168] According to the disease situation of the blank control (when the disease reaches level 9), the inoculated leaves are graded. The following grading method is used:

[0169] Level 0: no disease;

[0170] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0171] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0172] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0173] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0174] Level 9: The area of ​​lesions accounts for more than 50% of the entire leaf area.

[0175] Based on the survey data, the disease index and prevention and control effect of each treatment were calculated.

[0176] The disease index is calculated according to formula (1), and the result is rounded to two decimal places:

[0177] X={(∑(Ni xi)) / (N x 9)}x 100

[0178] In the formula: X is the disease index; Ni is the number of diseased leaves at each level; i is the relative level value; N is the total number of leaves surveyed.

[0179] The control effect is calculated according to the formula:

[0180] In the formula: P is the control effect, the unit is percentage (%); CK is the disease index of blank control; PT is the disease index of drug treatment.

[0181] Table 3 Representative test results of fungicide inhibition of pathogenic fungal mycelial growth by pot culture method

[0182] Note: N stands for no data.

[0183] Biological activity evaluation (nematode 96-well plate assay):

[0184] (1) Preparation of test agents

[0185] Accurately weigh the test drug, dissolve it in DMSO to prepare a stock solution, and dilute it into different concentration gradient solutions.

[0186] (2) Target nematode isolation

[0187] Southern root-knot nematode: When egg masses emerge from root nodes, use tweezers under a dissecting microscope to remove the egg masses from the nodes and place them in clean water. Soak them in a 0.25% sodium hypochlorite solution for approximately 1 minute. After sieving through a 500-mesh sieve, place them in a 90mm Petri dish containing an appropriate amount of tap water. Place the dish in a sieving device and incubate in a 28°C incubator for 3 days. Second-instar larvae will hatch from the egg masses. Observe the nematode suspension under a microscope and dilute it to approximately 1000 nematodes / mL for later use.

[0188] Mixed-stage pine wood nematodes, mixed-stage rice stem nematodes, and mixed-stage sweet potato stem nematodes: Scoop out the PDA culture medium containing nematodes and invert it onto a petri dish covered with mycelium. Rinse the nematodes off the lid with sterile water. Transfer the nematode suspension to a new petri dish covered with Botrytis cinerea mycelium, using 1 mL of nematode suspension per dish. Incubate in a dark incubator at 25°C. Once the mycelium has been completely consumed by the nematodes, transfer the suspension back to PDA with Botrytis cinerea mycelium for propagation. Store the cultured nematodes at 4°C. Propagate the suspension every 7-10 days, using at least 10 dishes at a time. Prepare a petri dish where all the Botrytis cinerea has been consumed. Rinse the nematodes off the lid with sterile water. Observe the nematode suspension under a microscope and dilute to approximately 1000 nematodes / mL for later use.

[0189] (3) Chemical treatment

[0190] Add 100 μL each of the prepared test agent and nematode suspension to a 96-well culture plate, cover to prevent evaporation, and place in a 28°C incubator. Set up a water control and a test agent control; if a solvent is used, also set up a solvent control.

[0191] (4) Cultivation and observation

[0192] The nematodes treated with the drug were cultured under normal conditions, and the mortality of the nematodes was measured at 48 hours and 72 hours: mortality (%) = (number of dead worms / number of test worms) * 100. Representative test results are shown in Table 4.

[0193] Table 4 Nematode test results

[0194] Note: N stands for no data.

[0195] At the same time, after many tests, it was found that many of the compounds and compositions described in the present invention have good control activity against different types of nematodes, etc., and have the characteristics of broad spectrum, high efficiency, strong systemic activity, etc., and can effectively control harmful organisms and / or fungi. For example, they also have good control activity against different types of fungi such as Ascomycetes, Basidiomycetes, Deuteromycetes, Oomycetes, etc., and have certain commercial value.

Claims

1. A pyrrole compound as shown in general formula I: Among them, X represents hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclic group, arylalkyl, heterocyclic alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -alkylene-OR3, -alkylene-SR3, -alkylene-(CO)OR3, -alkylene-(SO2)R3 or -alkylene-N(R3)2; Y represents hydrogen, halogen, cyano, trialkylsilyl, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclic group, arylalkyl, heterocyclic alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -alkylene-OR3, -alkylene-SR3, -alkylene-(CO)OR3, -alkylene-(SO2)R3 or -alkylene-N(R3)2; Z represents aryl or heterocyclic group; R3 each independently represents hydrogen, alkyl, alkenyl or alkynyl which is unsubstituted or substituted by at least one group selected from halogen, alkoxy, alkoxycarbonyl or alkylthio, cycloalkyl, cycloalkenyl, aryl or heterocyclic group; The foregoing "cycloalkyl" and "cycloalkenyl" are optionally substituted by at least one group selected from halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl or cycloalkylalkyl; The foregoing "heterocyclic group" or "aryl group" is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, cycloalkylalkyl, aryl or heterocyclic group which is unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO)R 10 , -(SO2)R 10 , -N(R 10 )2, -alkylene-OR 10 , -alkylene-SR 10 , -alkylene-(CO)OR 10 , -alkylene-(SO)R 10 , -alkylene-(SO2)R 10 , -alkylene-N(R 10 )2 or -O-alkylene-(CO)OR 10 ; or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen- or alkyl-substituted -OCH2CH2- or -OCH2O-; R 10 each independently is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted with alkyl, cycloalkylalkyl, aryl, heterocyclic group, or aryl or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy; and excluding the following compounds:

2. The pyrrole compound according to claim 1, wherein X represents hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo C1-C8 alkyl, halo C2-C8 alkenyl, halo C2-C8 alkynyl, aryl, heterocyclic group, aryl C1-C8 alkyl, heterocyclic C1-C8 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -(C1-C8 alkylene)-OR3, -(C1-C8 alkylene)-SR3, -(C1-C8 alkylene)-(CO)OR3, -(C1-C8 alkylene)-(SO2)R3 or -(C1-C8 alkylene)-N(R3)2; Y represents hydrogen, halogen, cyano, tri-C1-C8 alkylsilyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, aryl, heterocyclic group, aryl-C1-C8 alkyl, heterocyclic group-C1-C8 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(C1-C8 alkylene)-OR3, -(C1-C8 alkylene)-SR3, -(C1-C8 alkylene)-(CO)OR3, -(C1-C8 alkylene)-(SO2)R3 or -(C1-C8 alkylene)-N(R3)2; R3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl which is unsubstituted or substituted by at least one group selected from halogen, C1-C8 alkoxy, C1-C8 alkoxycarbonyl or C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl or heterocyclic group; The aforementioned "C3-C8 cycloalkyl" and "C3-C8 cycloalkenyl" are optionally substituted by at least one group selected from 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, halo-C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl or C3-C8 cycloalkyl-C1-C8 alkyl; The aforementioned "heterocyclic group" 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, halo C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl, aryl or heterocyclic group which is unsubstituted or substituted by 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, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO)R 10 , -(SO2)R 10 , -N(R 10 )2, -(C1-C8 alkylene)-OR 10 , -(C1-C8 alkylene)-SR 10 , -(C1-C8 alkylene)-(CO)OR 10 , -(C1-C8 alkylene)-(SO)R 10 , -(C1-C8 alkylene)-(SO2)R 10 , -(C1-C8 alkylene)-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 ; or two adjacent carbon atoms on the ring form a fused ring with -OCH2CH2- or -OCH2O- which is unsubstituted or substituted by halogen or C1-C8 alkyl; R 10 are each independently hydrogen, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a halogenated C1-C8 alkyl group, a halogenated C2-C8 alkenyl group, a halogenated C2-C8 alkynyl group, a halogenated C3-C8 cycloalkyl group, a C3-C8 cycloalkyl group substituted with a C1-C8 alkyl group, a C3-C8 cycloalkyl C1-C8 alkyl group, an aryl group, a heterocyclic group, or an aryl group or a heterocyclic group substituted with at least one group selected from the group consisting of a halogen, a cyano group, a nitro group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylthio group, a C1-C8 alkylsulfonyl group, a C1-C8 alkoxy group, or a halogenated C1-C8 alkoxy group.

3. The pyrrole compound according to claim 1 or 2, wherein X represents hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, aryl, heterocyclic group, aryl-C1-C6 alkyl, heterocyclic group-C1-C6 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(CO)N(R3)2, -(C1-C6 alkylene)-OR3, -(C1-C6 alkylene)-SR3, -(C1-C6 alkylene)-(CO)OR3, -(C1-C6 alkylene)-(SO2)R3 or -(C1-C6 alkylene)-N(R3)2; Y represents hydrogen, halogen, cyano, tri-C1-C6 alkylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, aryl, heterocyclic group, aryl-C1-C6 alkyl, heterocyclic group-C1-C6 alkyl, -OR3, -SR3, -(CO)R3, -(CO)OR3, -(SO2)R3, -N(R3)2, -(C1-C6 alkylene)-OR3, -(C1-C6 alkylene)-SR3, -(C1-C6 alkylene)-(CO)OR3, -(C1-C6 alkylene)-(SO2)R3 or -(C1-C6 alkylene)-N(R3)2; R3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-C6 alkoxy, C1-C6 alkoxycarbonyl or C1-C6 alkylthio, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclic group; The aforementioned "C3-C6 cycloalkyl" and "C3-C6 cycloalkenyl" are optionally substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl or C3-C6 cycloalkyl-C1-C6 alkyl; The foregoing "heterocyclic group" 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, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, halo-C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl or heterocyclic group which is unsubstituted or substituted by 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, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO)R 10 , -(SO2)R 10 , -N(R 10 )2, -(C1-C6 alkylene)-OR 10 , -(C1-C6 alkylene)-SR 10 , -(C1-C6 alkylene)-(CO)OR 10 , -(C1-C6 alkylene)-(SO)R 10 , -(C1-C6 alkylene)-(SO2)R 10 , -(C1-C6 alkylene)-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 ; or two adjacent carbon atoms on the ring form a fused ring with -OCH2CH2- or -OCH2O- which is unsubstituted or substituted by halogen or C1-C6 alkyl; R 10 each independently is hydrogen, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a halogenated C1-C6 alkyl group, a halogenated C2-C6 alkenyl group, a halogenated C2-C6 alkynyl group, a halogenated C3-C6 cycloalkyl group, a C3-C6 cycloalkyl group substituted with a C1-C6 alkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, an aryl group, a heterocyclic group, or an aryl group or a heterocyclic group substituted with at least one group selected from the group consisting of a halogen, a cyano group, a nitro group, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfonyl group, a C1-C6 alkoxy group, or a halogenated C1-C6 alkoxy group; Preferably, the compound is selected from any one of Table 1 in the specification.

4. The method for preparing the pyrrole compound according to any one of claims 1-3, comprising the following steps: (1) When Y is hydrogen, the compound shown by General Formula II is reacted with dimethyl (1-diazo-2-oxopropyl)phosphonate to obtain the compound shown by General Formula I-1, and the reaction equation is as follows: (2) When Y is not hydrogen, it is prepared by a substitution reaction of the compound represented by the general formula I-1; Or, (3) when X is not hydrogen, from Prepared by a substitution reaction; Wherein, the definitions of X, Y and Z are as shown in any one of claims 1-3; Preferably, the reaction in step (1) is carried out in the presence of a solvent; more preferably, a base is added during the reaction in step (1); further preferably, the solvent in step (1) is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane or ethyl acetate, and / or the base in step (1) is selected from at least one of inorganic bases or organic bases.

5. An intermediate, as shown in formula II of claim 4.

6. A composition for killing pests and / or fungi (especially nematodes, Fusarium head blight, sheath blight, gray mold), characterized in that, Comprising at least one of the pyrrole compounds according to any one of claims 1-3 in a biologically effective amount; preferably, it further comprises formulation adjuvants; more preferably, it further comprises other active ingredients.

7. A method for controlling pests and / or fungi (especially nematodes, Fusarium head blight, sheath blight, gray mold), characterized in that, Including contacting the pest and / or fungus or its environment with a biologically effective amount of the pyrrole compound according to any one of claims 1-3 or the composition according to claim 6.

8. The use of the pyrrole compound according to any one of claims 1-3 or the composition according to claim 6 in controlling pests and / or fungi (especially nematodes, scab, sheath blight, gray mold).

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