Pyrrole compound and application thereof

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a pyrrole compound and application thereof. The compound is shown as a general formula I: # imgabs0 #, wherein X represents hydrogen, halogen, alkyl, alkenyl, alkynyl and the like; y represents hydrogen, halogen, cyano, trialkylsilyl, alkyl or the like; z represents an aryl group or a heterocyclic group. The compound has excellent prevention and treatment effects on pests and / or fungi (especially nematode, gibberellic disease, banded sclerotial blight, gray mold and anthracnose).

Description

Technical Field

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

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests and diseases have developed drug resistance, and it has become difficult to control them with the existing insecticides or fungicides. In addition, some of the known pest control agents are highly toxic or, due to their long persistence, damage the ecosystem. In this context, although a large number of fungicides are known, such as CA1286293C discloses a phenylcyanopyrrole compound and its application as a fungicide, there is still a need to develop new pest control agents with low toxicity and low residue. Summary of the Invention

[0003] To solve the above problems existing in the prior art, the present invention provides a pyrrole compound and its application, and the compound has excellent control effects on pests and / or fungi (especially nematodes, head blight, sheath blight, gray mold, anthracnose).

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

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

[0006]

[0007] Wherein, 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;

[0008] 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;

[0009] Z represents aryl or heterocyclic group;

[0010] R3 independently represents hydrogen, an alkyl, alkenyl or alkynyl group which is unsubstituted or substituted by at least one group selected from halogen, alkoxy, alkoxycarbonyl or alkylthio, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group;

[0011] The aforesaid "cycloalkyl group" and "cycloalkenyl group" 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;

[0012] The aforesaid "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, an 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-;

[0013] R 10 independently represents hydrogen, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a halocycloalkyl group, a cycloalkyl group substituted by alkyl, a cycloalkylalkyl group, an aryl group, a heterocyclic group, or an aryl or heterocyclic group substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy;

[0014] And the following compounds are excluded:

[0015]

[0016] 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, 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;

[0017] 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-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;

[0018] 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;

[0019] 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;

[0020] The foregoing "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;

[0021] R 10 are each independently hydrogen, 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, heterocyclic group, or aryl or heterocyclic group 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.

[0022] In another specific 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, heterocyclic group, aryl-C1-C6 alkyl, heterocyclic-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;

[0023] 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-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;

[0024] 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;

[0025] The foregoing "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;

[0026] 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;

[0027] R 10 are each independently hydrogen, 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, heterocyclic group, or aryl or heterocyclic group 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.

[0028] In the definitions of the compounds represented by the above general formula and all the following structural formulas, the technical terms used, whether used alone or in a compound word, represent the following substituents: An alkyl group having more than two carbon atoms can be straight-chain or branched-chain. For example, in the compound word "-alkylene-(CO)OR3", the alkylene can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl - methyl; C2 alkyl - ethyl; C3 alkyl - propyl such as n-propyl or isopropyl; C4 alkyl - butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl - pentyl such as n-pentyl; C6 alkyl - hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, the alkenyl group is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. The alkynyl group is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. The multiple bond can be at any position of each unsaturated group. The cycloalkyl group is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, the cycloalkenyl group is a monocyclic alkenyl group having, for example, three to six carbocyclic members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, where the double bond can be at any position. The halogen is fluorine, chlorine, bromine or iodine.

[0029] Unless otherwise specified, the "aryl" as used in the present invention includes, but is not limited to, phenyl, naphthyl, The "heterocyclic group" not only includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups

[0030]

[0031] etc., but also includes, but is not limited to, heteroaryl, i.e., an aromatic cyclic group containing, for example, 3 to 6 ring atoms and also optionally having a benzo ring fused thereto, and 1 to 4 (e.g., 1, 2, 3 or 4) of the ring atoms being heteroatoms selected from oxygen, nitrogen and sulfur, such as

[0032] If a group is substituted by a group, this shall be understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned. Additionally, the identical or different substitution characters contained in the identical or different substituents are each independently selected and may be the same or different. This also applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude those compounds that are known to those skilled in the art to be chemically unstable under standard conditions.

[0033] Additionally, unless otherwise specified, "substituted by at least one group" as used in the present invention means substituted by, for example, 1, 2, 3, 4, or 5 groups; for a group without a specific connection position indicated (including a heterocyclic group, an aryl group, etc.), it can be connected at any position, including positions connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it conforms to the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group can represent etc.

[0034] In each case, the compound of formula I in free form or salt form, and, where appropriate, its tautomer can exist in the form of one of the possible isomers or as a mixture of these, for example in the form of a pure isomer, such as an enantiomer and / or a diastereoisomer, or as a mixture of isomers, such as a mixture of enantiomers, for example a racemate, a mixture of diastereoisomers or a mixture of racemates, depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configurations, and / or depending on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers and also to all possible mixtures of isomers and should be understood in this sense in each of the following and above cases, even if the stereochemical details are not specifically mentioned in each case. The present invention thus encompasses all such isomers and tautomers and mixtures thereof in all proportions, together with isotopic forms, such as deuterated compounds.

[0035] In another embodiment, formula I is also understood to include their salts or hydrates. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, and hydroiodide.

[0036] Those skilled in the art also understand that, unless otherwise stated, additional substitution is allowed as long as the chemical bond formation and strain energy rules are satisfied and the product still exhibits fungicidal activity.

[0037] Another embodiment of the present application is a method for preparing the pyrrole compound, comprising the following steps:

[0038] (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:

[0039]

[0040] (2) When Y is not hydrogen, it is obtained from the compound shown by General Formula I-1 through a conventional substitution reaction.

[0041] Or, (3) when X is not hydrogen, it is obtained from through a conventional substitution reaction.

[0042] Among them, the definitions of X, Y and Z are as described above.

[0043] In a specific embodiment, the reaction of step (1) is carried out in the presence of a solvent.

[0044] In another specific embodiment, a base is added during the reaction of step (1).

[0045] In a specific embodiment, the solvent in step (1) is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane or ethyl acetate.

[0046] In a specific embodiment, the bases in step (1) are all selected from at least one of inorganic bases (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KHCO3, KF, CsF, KI, NaI, K3PO4, K2HPO4, NaOH, KOH, NaH, KH, etc.) or organic bases (such as pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, etc.).

[0047] Another embodiment of the present application is an intermediate, as shown by the aforementioned Formula II.

[0048] The present invention also provides a pesticidal and / or fungicidal (especially nematodes, Gibberella zeae, Rhizoctonia solani, Botrytis cinerea, Colletotrichum) composition, comprising at least one of the pyrrole compounds in a biologically effective amount.

[0049] In a specific embodiment, the composition further includes formulation aids.

[0050] In another specific embodiment, the composition further includes other active ingredients.

[0051] The present invention also provides a method for controlling pests and / or fungi (especially nematodes, Fusarium head blight, sheath blight, gray mold, anthracnose), which comprises bringing the pests and / or fungi or their environment into contact with a biologically effective amount of the pyrrole compound or the composition as described above.

[0052] The present invention also provides the use of the pyrrole compound or the composition as described above in controlling pests and / or fungi (especially nematodes, Fusarium head blight, sheath blight, gray mold, anthracnose).

[0053] It has been found that the compounds of formula I are useful for controlling damage caused by pests and / or fungi.

[0054] In one embodiment, the compounds of formula I can be used in agriculture.

[0055] Therefore, the present invention furthermore relates to a method for controlling damage and / or yield loss caused by pests and / or fungi, which method comprises applying an effective amount of a compound of formula I to the pests, the locus of the pests, or to plants or plant propagation material susceptible to attack by pests and / or fungi.

[0056] These compounds according to the invention can be used to control, i.e. limit or destroy, pests and / or fungi occurring especially on plants, in particular useful plants 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 certain cases still provide protection against these pests even on plant organs formed at a later time point.

[0057] These compounds of formula I according to the invention are active ingredients having preventive and / or therapeutic value in the field of pest control, and even when applied at low application rates, they can be used against pests and / or fungi having biocide resistance. These compounds of formula I have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.

[0058] These compounds according to the invention can act on all or individual developmental stages of normally sensitive as well as resistant animal pests (such as representatives of insects or Acarina). The insecticidal or acaricidal activity of these compounds according to the invention can manifest itself directly, i.e.: for example, the destruction of pests during molting, which occurs immediately or after a period of time; or indirectly, for example, a reduced oviposition and / or hatching rate, and a good activity corresponds to a destruction rate (mortality) of at least 50%-60%.

[0059] It has now been found that the compounds of formula I according to the invention have (for practical purposes) a very advantageous activity spectrum for protecting animals and useful plants against nematode attack and damage. Accordingly, the present invention also makes available nematicidal compositions comprising the compounds of formula I according to the invention.

[0060] These compounds having the formula I are particularly useful for the control of nematodes. Thus, in another aspect, the present invention also relates to a method for controlling damage caused to plants or parts thereof 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; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina species; stem and foliar nematodes, Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus, and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species;Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awlnematodes, 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, Nacobbus species; Needle nematodes, Longidorus elongatus, and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi

[0061] (Pratylenchus penetrans), Pratylenchus curvitatus, Pratylenchus goodeyi

[0062] (Pratylenchus goodeyi) and other Pratylenchus species; burrowing nematodes such as citrus burrowing nematode, 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.

[0063] In particular, these nematode species can be controlled by the compounds of the present invention: Meloidogyne, Heterodera, Rotylenchus and Pratylenchus.

[0064] On the other hand, the present invention also relates to a method for controlling or preventing useful plants from being infested by plant-pathogenic microorganisms, wherein a compound of formula I is applied as an active ingredient to the plants, their parts or their sites. The compounds of formula I according to the present invention are significantly distinguished by their activity, good plant tolerance and environmental safety. They have very useful therapeutic, preventive and systemic properties and are used to protect a variety of useful plants. The compounds of formula I can be used to inhibit or destroy diseases occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of a variety of different useful plants, while also protecting those plant parts that grow later, for example, from plant-pathogenic microorganisms. It is also possible to use the compounds of formula I as a dressing agent for treating plant propagation materials, especially seeds (fruits, tubers, grains) and plant cuttings (such as rice), for protecting against fungal infestation as well as against plant-pathogenic fungi present in the soil.

[0065] Examples of fungi include: Deuteromycetes (e.g., Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); Basidiomycetes (e.g., Rhizoctonia, Puccinia, Uromyces); Ascomycetes (e.g., Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula); Oomycetes (e.g., Phytophthora, Pythium, Plasmopara); Zygomycetes (e.g., Rhizopus); the family Phakopsoraceae, especially those of the genus Phakopsora, such as Phakopsora pachyrhizi, which is also known as Asian soybean rust, and those of the family Pucciniaceae, especially those of the genus Puccinia, such as Puccinia graminis, also known as stem rust or black rust, which is a problem disease in cereal plants, and Puccinia recondita, also known as brown rust.

[0066] Among these plants and the possible diseases among these plants protected by the method according to the present invention, the following can be mentioned:

[0067] - Wheat, for controlling the following seed diseases: Fusarium (Microdochium nivale and Fusarium roseum), bunt (Tilletia caries, Tilletia controversa or Tilletia indica), Septoria diseases (Septoria nodorum) and loose smut;

[0068] - Wheat, for controlling the following diseases of the aerial parts of plants: cereal eyespot (Tapesia yallundae, Tapesia acuiformis), take-all (Gaeumannomyces graminis), root rot (Fusarium culmorum, Fusarium graminearum), black point (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specialis tritici), rust (Puccinia striiformis and Puccinia recondita), and Septoria diseases (Septoria tritici and Septoria nodorum);

[0069] - Wheat and barley, for controlling bacterial and viral diseases, such as barley yellow mosaic virus; - Barley, for controlling the following seed diseases: net blotch (Pyrenophora teres, Pyrenophora graminea, and Cochliobolus sativus), loose smut (Ustilago nuda), and Fusarium (Microdochium nivale and Fusarium roseum);

[0070] - Barley, for controlling the following diseases of the aerial parts of plants: cereal eyespot (Tapesia yallundae), net blotch (Pyrenophora graminea and Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specialis hordei), leaf rust (Puccinia hordei), and leaf blotch (Rhynchosporium secalis);

[0071] - Potato, for controlling tuber diseases (especially Psyllium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytophthora infestans), and certain viruses (virus Y);

[0072] - Potato, for controlling the following foliar diseases: early blight (Alternaria solani), mildew (Phytophthora infestans);

[0073] - Cotton, for controlling the following diseases of young plants grown from seeds: damping-off and phytophthora rot (Rhizoctonia solani, Fusarium oxysporum), and black root rot (Thielaviopsis basicola);

[0074] - Protein-producing plants, such as peas, for controlling the following seed diseases: anthracnose (Colletotrichum pisi, Mycosphaerella pinodes), Fusarium (Fusarium oxysporum), gray mold (Botrytis cinerea), and mildew (Peronospora pisi);

[0075] - Oil-containing plants, such as rapeseed, for controlling the following seed diseases: Phoma lingam, Alternaria brassicicola, and Sclerotinia sclerotiorum;

[0076] - Maize, for controlling various seed diseases: (Rhizopus, Penicillium, Trichoderma, Aspergillus, and Gibberella fujikuroi);

[0077] Flax, for controlling the seed disease: Alternaria linicola;

[0078] Forest trees, for controlling damping-off (Fusarium oxysporum, Rhizoctonia solani);

[0079] Rice, for controlling the following diseases in the above-ground part: blast (Magnaporthe oryzae), bordered sheath spot (Rhizoctonia solani);

[0080] Leguminous plants, for controlling the following diseases in the seeds or young plants grown from the seeds: damping-off and Phytophthora rot (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium spp.);

[0081] Leguminous plants, for controlling the following diseases in the above-ground part: grey mould (Botrytis spp.), powdery mildew (especially Erysiphe cichoracearum, Sphaerotheca fuliginea and Leveillula taurica), Fusarium spp. (Fusarium oxysporum, Fusarium roseum), leaf spot (Cladosporium spp.), Cladosporium leaf spot (Cladosporium spp.), anthracnose (Colletotrichum spp.), Septoria leaf spot (Septoria spp.), black spot (Rhizoctonia solani), mildew (e.g. Bremia lactucae, Peronospora spp., Pseudoperonospora spp., Phytophthora spp.);

[0082] Fruit trees, for controlling various diseases in the above-ground part: Monilia diseases (Monilia fructigenae, M. laxa), scab (Venturia inaequalis), powdery mildew (Podosphaera leucotricha); Vine plants, for controlling the following foliar diseases: especially grey mould (Botrytis cinerea), powdery mildew (Uncinula necator), black rot (Guignardia bidwellii) and mildew (Plasmopara viticola);

[0083] Beetroot, for the following diseases in the above-ground part: cercospora blight (Cercospora beticola), powdery mildew (Erysiphe beticola), leaf spot (Cercospora beticola).

[0084] The fungicidal composition according to the invention can also be used against fungal diseases liable to grow on or inside wood. The term "wood" means all types of wood species, and all types of wood intended for construction work, such as solid wood, high-density wood, laminated wood and plywood. The method according to the invention for treating wood mainly comprises contacting one or more compounds or compositions according to the invention; this includes, for example, direct application, spraying, soaking, injection or any other suitable means.

[0085] When used alone, the compounds of the present invention can effectively control nematodes, insects, acarine pests and / or fungal pathogens of agronomic plants that are growing or have been harvested. They can also be used in combination with other biocides used in agriculture, for example, one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activators, molluscicides and pheromones (chemical or biological). Mixing the compounds or their compositions of the present invention in the form of a biocide with other biocides often results in a broader biocidal spectrum. For example, these compounds of the present invention having the formula I can be effectively combined or used in combination with the following compounds, which are pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cyclodienes, formamidines, phenol tin compounds, chlorinated hydrocarbons, benzoylphenylureas, pyrroles and the like.

[0086] By adding, for example, one or more insecticidal, acaricidal, nematicidal and / or fungicidal active agents, the activity of these compositions according to the present invention can be significantly broadened and is suitable for the prevailing environment. The combination of the compounds having the formula I with other insecticidal, acaricidal, nematicidal and / or fungicidal active agents can also have further, unexpected advantages. For example, better tolerance of the plants to them, reduced phytotoxicity, and pests or fungi can be controlled at their different developmental stages or have better behavior during their production (for example, during grinding or mixing processes, during their storage or during their use).

[0087] Said 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, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Burgundy mixture, boscalid, bromuconazole, bupirimate, calcium 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, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine,

[0088] (diphenylamine), dithianon, dodemorph, dodemorph acetate, dodine, dodine freebase, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatineacetates, tetrathionate (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil,Imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, 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, methyliodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acid), orysastrobin,Oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuryacetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, 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,Sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oil, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, 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,

[0089] (1,3-dichloro-1,1,3,3-tetrafluoroacetone 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-methoxyethylmercuryacetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury)sulfate, bis(tributyltin)oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox,Climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenylsuccinimideN-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), octachloronone (OCH), phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combination thereof.,

[0090] 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-thio-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, avermectin, acetoprole, alanycarb, aldicarb, aldoxycarb, AZ60541, benclothiaz, benomyl, butylpyridaben, cadusafos, carbofuran, carbon disulfide, carbosulfan, chloropicrin, chlorpyrifos, cloethocarb, cytokinins, dazomet, DBCP, DCIP, diamidafos, dichlofenthion, dicliphos, dimethoate, emamectin, emamectin benzoate, emamectin enantate, eprinomectin, ethoprophos, ethylene dibromide, fenamiphos, pyrimidifen, fenpyrad, fosthiazate, fosthietan, furfural, GY-81, heterophos, methyl iodide, isamidofos, isazofos, kinetin, mecarphon, methidathion, metam, metam potassium, metam sodium, methyl bromide, methyl isothiocyanate, milbemycin oxime, moxidectin, Myrothecium verrucaria components, NC-184, methiocarb, 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.

[0091] In general, the mass ratio between two components in any combination of the present invention is independently 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 on the other hand, the molar ratio.

[0092] Examples of methods of applying the compounds and their compositions of the present invention, i.e., methods for controlling pests / fungi in agriculture, such as spraying, atomizing, dusting, brushing, seed dressing, broadcasting or watering - they are selected to be suitable for the intended purpose of the environment at that time.

[0093] A preferred method of application in agriculture is application to the leaves of these plants (foliar application), and it is possible to select the frequency and rate of application to conform to the infestation risk of the pests / fungi under discussion. Alternatively, the active ingredient can reach the plants via the root system (systemic action), which is achieved by applying the compound to the sites of these plants, for example, by applying a liquid composition of the compound to the soil (by soaking) 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 paddy fields.

[0094] The application rate per hectare is generally from 1 g to 2000 g of active ingredient per hectare, especially from 10 g / ha to 1000 g / ha, preferably from 10 g / ha to 600 g / ha, such as from 50 g / ha to 300 g / ha.

[0095] These compounds and their compositions of the present invention are also suitable for protecting plant propagation materials (such as seeds, fruits, tubers or grains, or nursery plants) against pests of the above types. The propagation materials can be treated with the compound before planting, for example, seeds can be treated before sowing. Alternatively, the compound can be applied to the seed grains (coating), which is achieved by dipping the grains into a liquid composition or by applying a layer of a solid composition. When the propagation materials are planted at the application site, it is also possible, for example, to apply these compositions into the seed furrows during drilling. These methods of treating plant propagation materials and thus treated plant propagation materials are additional subjects of the present invention. Typically, the treatment rate will depend on the plants to be controlled and the pests / fungi, usually between 1 g and 200 g per 100 kg of seeds, preferably between 5 g and 150 g per 100 kg of seeds, such as between 10 g and 100 g per 100 kg of seeds.

[0096] The term "seed" includes all kinds of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, grains, corms, fruits, tubers, cereals, rhizomes, cuttings, cut shoots and the like and in a preferred embodiment refers to true seeds.

[0097] The invention also encompasses seeds coated or treated with or containing a compound of formula I. The terms "coated with / treated with and / or containing" generally mean that in most cases when applied the active ingredient is on the surface of the seed, although parts of more or less of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the invention makes available a plant propagation material to which a compound of formula I is adhered. In addition, a composition comprising a plant propagation material treated with a compound of formula I is thereby available.

[0098] Seed treatment includes all suitable seed treatment techniques known in the art, such as, seed dressing, seed coating, seed dusting, seed soaking and seed granulation. Application of the compound of formula I for seed treatment can be effected by any known method, such as spraying or by dusting before sowing or during sowing / planting of these seeds.

[0099] Suitable target plants are in particular cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; sugar beet, such as sugar or fodder beet; fruits, such as pomaceous fruits, stone fruits or drupes, such as apple, pear, plum, peach, almond, cherry or berries, such as strawberry, raspberry or blackberry; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa or groundnut; cucurbitaceous plants, such as pumpkin, cucumber or melon; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or sweet pepper; lauraceous plants, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, aubergine, sugar cane, tea, pepper, grapevine, hops, plantain, rubber plants and ornamental plants (such as flowers and turf plants or sods).

[0100] In one embodiment, the plant is selected from cereals, maize, soybean, rice, sugar cane, vegetables and oil plants.

[0101] The term "plant" is to be understood as also including plants transformed by means of recombinant DNA technology which are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, in particular those of the genus Bacillus.

[0102] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available.

[0103] Generally, the compounds of the present invention are used in the form of a composition (e.g., formulation) comprising a carrier. The compounds and compositions of the present invention can be used in different forms, e.g., aerosol spray, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, oil-in-water emulsion, water-in-oil emulsion, capsule granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, large granule, microgranule, oil-dispersible powder, oil-miscible flowable concentrate, oil-miscible liquid, paste, plant rod, powder for dry seed treatment, seed coated with a biocide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ULV) liquid, ultra-low volume suspension (ULV), water-dispersible granule or tablet, water-dispersible powder for slurry treatment, water-soluble granule or tablet, water-soluble powder for seed treatment, and wettable powder.

[0104] A formulation typically comprises a liquid or solid carrier and optionally one or more conventional formulating aids which may be solid or liquid, e.g., non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil or soybean oil), defoamers such as silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactants, binders and / or tackifiers. The composition may further comprise a fertilizer, micronutrient donor or other product affecting plant growth and comprises a combination comprising a compound of the present invention and one or more other bioactive agents such as bactericides, fungicides, nematicides, plant activators, acaricides and insecticides.

[0105] Accordingly, the present invention also makes available a composition comprising a compound of the present invention and an agriculturally economical carrier and optionally one or more conventional formulating aids.

[0106] These compositions are prepared by methods known per se, in the absence of auxiliaries, for example by grinding, sieving and / or extruding the solid compounds of the invention, and in the presence of at least one auxiliary, for example by intimately mixing and / or grinding the compounds of the invention with one or more auxiliaries. In the case of the solid compounds of the invention, the grinding / comminution of the compounds is to ensure a specific particle size. The methods for preparing these compositions and the use of the compounds of the invention for preparing these compositions are also a subject of the invention.

[0107] Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil-dispersible powders, directly sprayable or dilutable solutions, coatable pastes, diluted emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or capsules in polymeric substances, 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.

[0108] Examples of suitable liquid carriers are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the C8 to C 12 alkylbenzene moiety, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic 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 hexylene glycol 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, unepoxidized or epoxidized vegetable oils, such as unepoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil and silicone oils.

[0109] Examples of solid carriers for, for example, dusts and dispersible powders are generally ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly disperse silica or highly disperse absorbent polymers to improve the physical properties. Suitable particulate adsorptive carriers for granules are of the porous type, such as pumice, brick grit, sepiolite or bentonite, and suitable non-adsorptive carrier materials are calcite or sand. In addition, granulated materials of a large number of inorganic or organic natural substances can be used, especially dolomite or comminuted plant residues.

[0110] 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 only to be regarded as examples; a large number of other surfactants which are conventionally used in the field of formulations and are suitable according to the invention are described in the relevant literature.

[0111] 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 polyethylene glycol ether derivatives may contain about 3 to about 30 ethylene glycol ether groups and about 8 to about 20 carbon atoms in the (cyclo)aliphatic hydrocarbon residue or about 6 to about 18 carbon atoms in the alkyl part of the alkylphenol. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopropylene glycol or alkyl polypropylene glycol (having 1 to about 10 carbon atoms in the alkyl chain and having about 20 to about 250 ethylene glycol ether groups and about 10 to about 100 propylene glycol ether groups). Generally, the above compounds contain 1 to about 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonoxynol, polyoxyethylene castor oil, polypropylene glycol / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

[0112] These cationic surfactants are in particular usually quaternary ammonium salts having at least one alkyl residue (about 8 to about 22 C atoms) as a substituent and a (non-halogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl residue as a further substituent. These salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

[0113] Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali metal salts, alkaline earth metal salts or (unsubstituted or substituted) ammonium salts of fatty acids having from about 10 to about 22 C 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 must also be made of fatty acid methyl taurides. However, more commonly used are synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. Generally, these fatty sulfonates and fatty sulfates occur as alkali metal salts, alkaline earth metal salts or (substituted or unsubstituted) ammonium salts and they generally have an alkyl residue having from about 8 to about 22 C atoms, the alkyl also being understood to include the alkyl part of acyl residues; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, the sodium or calcium salts of dodecyl sulfate or the sodium or calcium salts of mixtures of fatty alcohol sulfates prepared from natural fatty acids. This group also includes the sulfate salts and sulfonates of fatty alcohol / ethylene oxide adducts. These sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid residue having from about 8 to about 22 C atoms. Examples of alkylaryl sulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid / formaldehyde condensates. In addition, suitable phosphates (esters), such as the phosphate salts of p-nonylphenol / (4-14) ethylene oxide adducts, or phospholipids, are also possible.

[0114] As a rule, these compositions comprise from 0.1% to 99% (in particular from 0.1% to 95%) of the compounds 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, and in principle it is possible for 0% to 25% (in particular 0.1% to 20%) of the composition to be a surfactant (in each case % denotes % by weight). However, for commercial products, concentrated compositions are generally preferred and the end user in principle uses diluted compositions having a significantly lower concentration of active ingredient.

[0115] Examples of formulation types suitable for tank mix compositions are solutions, dilute emulsions, suspensions or mixtures thereof, and dusts.

[0116] For the nature of these formulations, the methods according to the invention, such as leaf, drench, spray, atomize, dust, broadcast, coat or pour, can be selected according to the intended purpose and the prevailing environment.

[0117] Such tank mix formulations are generally prepared by diluting a pre-mix composition containing different pesticidal agents and optionally further adjuvants with a solvent (for example water).

[0118] Suitable carriers and adjuvants can be solid or liquid and are substances commonly used in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, thickeners, fillers, binders, or fertilizers.

[0119] Generally, tank-mix formulations for foliar or soil application comprise from 0.1% to 20%, especially from 0.1% to 15%, of the desired ingredient, and from 99.9% to 80%, especially from 99.9% to 85%, of solid or liquid auxiliaries (including, for example, a solvent such as water), and these auxiliaries can be a surfactant, the amount of which, based on the tank mixture formulation, is from 0 to 20%, especially from 0.1% to 15%.

[0120] Typically, premix formulations for foliar application comprise from 0.1% to 99.9%, especially from 1% to 95%, of the desired ingredient, and from 99.9% to 0.1%, especially from 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), where these adjuvants can be a surfactant, the amount of which, based on the premix formulation, is from 0 to 50%, especially from 0.5% to 40%.

[0121] Generally, tank-mix formulations for seed treatment application comprise from 0.25% to 80%, especially from 1% to 75%, of the desired ingredient, and from 99.75% to 20%, especially from 99% to 25%, of solid or liquid auxiliaries (including, for example, a solvent such as water), where these auxiliaries can be a surfactant, the amount of which, based on the tank mixture formulation, is from 0 to 40%, especially from 0.5% to 30%.

[0122] Typically, premix formulations for seed treatment application comprise from 0.5% to 99.9%, especially from 1% to 95%, of the desired ingredient, and from 99.5% to 0.1%, especially from 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), where these adjuvants can be a surfactant, the amount of which, based on the tank mixture formulation, is from 0 to 50%, especially from 0.5% to 40%.

[0123] Commercial products are preferably formulated as concentrates (e.g., premix compositions (formulations)), and the end user typically uses diluted formulations (e.g., tank mix compositions).

[0124] Preferred seed treatment premix formulations are aqueous suspension concentrates. The formulations can be applied to seeds using conventional treatment techniques and machinery such as fluidized bed technology, drum grinding methods, rotostatic seed processors, and drum applicators. Other methods such as spouted beds can also be useful. The seeds can be pre-gummed before coating. After coating, the seeds are typically dried and then transferred to a gumming machine for gumming. Such methods are well known in the art.

[0125] Generally, the premix compositions of the invention comprise from 0.5% to 99.9% by mass, in particular from 1% to 95%, advantageously from 1% to 50% of the desired ingredient, and from 99.5% to 0.1% by mass, in particular from 99% to 5% of a solid or liquid adjuvant (including for example a solvent such as water), where these auxiliaries (or adjuvants) can be a surfactant, the amount thereof being from 0 to 50% by mass, in particular from 0.5% to 40% based on the premix formulation.

[0126] In a preferred embodiment, independently of any other embodiment, the compound having the formula I, I', I" or I'" is in the form of a composition for treating (or protecting) plant propagation material, where the composition for protecting plant propagation material further comprises a colorant. This composition or mixture for protecting plant propagation material can also comprise at least one copolymer from water-soluble and water-dispersible film-forming polymers, these film-forming polymers improving the attachment of the active ingredient to the treated plant propagation material, the polymer generally having an average molecular weight of at least 10,000 to about 100,000.

[0127] The combinations of the invention (i.e., those comprising the compounds of the invention and one or more other bioactive agents) can be applied simultaneously or sequentially.

[0128] In this case, the components of a combination are applied sequentially (i.e., one by one), the components being applied sequentially within a mutually reasonable period to achieve biological performance, such as within a few hours or days. The order of application of the components in the combination, i.e., whether the compound having the formula I should be applied first, is not critical for carrying out the invention.

[0129] In this case, in the present invention, these combined ingredients are administered simultaneously, and they can be administered as a composition containing the combination. In this case, (A) the compound having the chemical formula I and one or more ingredients in the combination can be obtained from a separate formulation source and mixed together (referred to as tank mixing, ready-to-use, spray broth or slurry), or (B) the compound having the chemical formula I and one or more ingredients in the combination can be used as a source of a separate formulation mixture (referred to as a premix, mixture, concentrate or formulated product).

[0130] In one embodiment, independent of other embodiments, a compound according to the present invention is administered as a combination. Accordingly, the present invention also provides a composition comprising a compound according to the present invention as described herein, one or more other bioactive agents and optionally one or more conventional formulation aids; the composition can be in the form of a tank mix or premix composition.

[0131] These combinations of the present invention can have advantageous properties. Examples of such advantageous properties that can be mentioned are: advantageous behavior during formulation and / or administration (e.g., when grinding, sieving, emulsifying, dissolving or dispersing); increased storage stability, improved light stability; more favorable degradability; improved toxicological and / or ecotoxicological behavior; or other advantages familiar to those of ordinary skill in the art. Detailed Description

[0132] The following examples are used to illustrate the present invention and should not be regarded as limiting the present invention in any way. The scope of the claims for which the present invention is protected is defined by the claims.

[0133] In view of the economy and diversity of the compounds, we preferably synthesized some compounds. Among the many compounds synthesized, some are listed in Table 1 below. The specific compound structures and the corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present invention, but do not limit the present invention. For those skilled in the art, this should not be construed as the scope of the above subject matter of the present invention being limited to the following compounds.

[0134] Table 1 Compound Structures and Their 1 H NMR

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152] Several detailed methods for preparing the compounds of the present invention are illustrated 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 illustrated in detail. Those skilled in the art should understand that the compounds of the present invention can also be synthesized using other synthetic routes. Although 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 various isomers of the compounds resulting from such modifications or variations of the preparation methods of the present invention are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction, etc.

[0153] The method examples provided below are used to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are determined to further illustrate the present invention and do not limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the following table can be purchased commercially or can be easily prepared by those of ordinary skill in the art.

[0154] Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be elaborated here.

[0155] 1. Synthesis of Compound 2

[0156] Dissolve Compound 2-1 (200 mg, 0.80 mmol, 1 eq) in 5 ml of methanol, add dimethyl (1-diazo-2-oxopropyl)phosphonate (168 mg, 0.87 mmol, 1.1 eq), and potassium carbonate (221 mg, 1.6 mmol, 2 eq). Replace the air with nitrogen three times and stir at room temperature for 2 h. Monitor the completion of the reaction, add water and ethyl acetate for extraction and liquid separation. Wash the organic phase twice with saturated brine and then dry it with anhydrous sodium sulfate. Mix the sample and perform normal-phase separation (EA / PE = 1 / 3) to obtain 60 mg of Compound 2 with a yield of 30%.

[0157]

[0158] 2. Synthesis of Compound 1

[0159] (1) Dissolve Compound 1-1 (1.4 g, 1 eq, 6.6 mmol) in 30 ml of diethyl ether, add DIBAL-H (13.2 ml, 2 eq, 13.2 mmol, 1 mol / L in Toluene) under ice bath conditions and react for 3 h. Monitor the reaction until the starting material disappears. Add water to the reaction solution for liquid separation, and purify the organic phase by column chromatography to obtain Compound 1-2 (0.6 g, purity 83%, yield 42%), a white solid.

[0160]

[0161] (2) Dissolve Compound 1-2 (300 mg, 1 eq, 1.39 mmol) in 10 ml of methanol, add dimethyl (1-diazo-2-oxopropyl)phosphonate (803 mg, 3 eq, 3.41 mmol) and potassium carbonate (578 mg, 3 eq, 3.41 mmol), and react at room temperature for 8 h. Monitor the reaction until the starting material disappears. Concentrate the reaction solution by rotary evaporation, mix the sample, and purify the organic phase by column chromatography to obtain 65 mg of Compound 1 (purity 99%, yield 22%), a brown oil.

[0162]

[0163] 3. Synthesis of Compound 5

[0164] Compound 2 (60 mg, 0.24 mmol) was dissolved in 5 ml of THF. Under ice bath conditions, sodium hydride (12 mg, 0.28 mmol) was added and the reaction was carried out for 30 minutes. Then acetyl chloride (38 mg, 0.56 mmol) was added and the reaction was carried out at room temperature for 1 hour. The reaction was monitored by LCMS until completion. The reaction was quenched by adding water. The reaction solution was concentrated, diluted with ethyl acetate, and 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 obtain compound 5 (50 mg, 72%).

[0165]

[0166] 4. Synthesis of Compound 153

[0167] (1) Compound 153-1 (1.0 g, 1.0 eq, 4.5 mmol) was dissolved in 30 ml of ether. Under ice bath conditions, DIBAL-H (9.1 ml, 2.0 eq, 9.1 mmol, 1.0 mol / L in Toluene) was added and the reaction was carried out for 3 h. The reaction was monitored until the starting material disappeared. The reaction solution was separated by adding water, and the organic phase was purified by column chromatography to obtain compound 153-2 (0.7 g, purity 95%, yield 69%), a white solid.

[0168]

[0169] (2) Compound 153-2 (0.7 g, 1.0 eq, 3.1 mmol) was dissolved in 10 ml of methanol. 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, and the reaction was carried out at room temperature for 8 h. The reaction was monitored until the starting material disappeared. The reaction solution was evaporated to dryness and mixed with the sample. The organic phase was purified by column chromatography to obtain compound 153 (0.07 g, purity 90%, yield 10%), a brown solid.

[0170]

[0171] 5. Synthesis of Compound 154

[0172] (1) 154-1 (3.22 g, 1 eq, 11.32 mmol) was dissolved in 40 ml of methanol. p-Toluenesulfonylmethyl isocyanide (2.21 g, 1 eq, 11.32 mmol) and potassium hydroxide (825 mg, 1.3 eq, 14.71 mmol) were added, and the reaction was carried out under ice bath for 2 h. The reaction was monitored until the starting material disappeared. The reaction solution was evaporated to dryness and mixed with the sample. The organic phase was purified by column chromatography to obtain compound 154-2 (2.24 g, purity 90%, yield 67%), a white solid.

[0173]

[0174] (2) Dissolve compound 154-2 (2.24 g, 1 eq, 7.6 mmol) in 30 ml of diethyl ether. Under ice-bath conditions, add DIBAL-H (15.2 ml, 2 eq, 15.2 mmol, 1 mol / L in Toluene) and react for 3 h. Monitor the reaction until the starting material disappears. Add water to the reaction solution and separate the layers. The organic phase is purified by column chromatography to obtain compound 154-3 (1.36 g, purity 93%, yield 60%), a white solid.

[0175]

[0176] (3) Dissolve compound 154-3 (500 mg, 1 eq, 1.68 mmol) in 10 ml of methanol. Add dimethyl (1-diazo-2-oxopropyl)phosphonate (968 mg, 3 eq, 5.04 mmol) and potassium carbonate (696 mg, 3 eq, 5.04 mmol). React at room temperature for 8 h. Monitor the reaction until the starting material disappears. Concentrate the reaction solution by rotary evaporation and mix the sample. The organic phase is purified by column chromatography to obtain compound 154 (60 mg, purity 98%, yield 12%), a white solid.

[0177]

[0178] 6. Synthesis of compound 159

[0179] In a 50 mL single-necked flask, dissolve compound 2 (150 mg, 0.61 mmol) in 1.5 ml of N,N-dimethylformamide. Add tetrabutylammonium iodide (224 mg, 0.61 mmol). Under ice-bath conditions, add sodium hydride (37 mg, 0.91 mmol) and keep warm for half an hour. Then add compound 159-2 (107 mg, 0.91 mmol) and react at room temperature for 5 h. Monitor the reaction completely by LCMS. Quench the reaction solution with water and extract with ethyl acetate. Wash the organic phase with water and saturated brine, dry and concentrate. The residue is purified by column chromatography (EA / PE = 1 / 20) to obtain compound 159 (131 mg, 75.35%), a brown solid.

[0180]

[0181] 7. Synthesis of compound 166

[0182] (1) At room temperature, dissolve compound 166-1 (400 mg, 2.17 mmol) in 8 mL of carbon tetrachloride, add AIBN (178.26 mg, 1.09 mmol) and NBS (309.13 mg, 1.74 mmol), and react at 80 °C for 8 h. Monitor the reaction by LCMS until completion. Dilute the reaction solution with water, extract the reaction with dichloromethane, wash the organic phase with saturated brine, dry and concentrate. Purify the residue by column chromatography (PE = 100%) to obtain compound 166-2 (300 mg, 52.51%), a pale yellow oil.

[0183]

[0184] (2) Dissolve compound 2 (140.9 mg, 0.57 mmol) in 5 ml of DMF, add NaH (22.8 mg, 0.57 mmol) at 0 °C, and react at room temperature for 30 min; add 166-2 (100 mg, 0.38 mmol) to the reaction solution and react at room temperature for 4 h. Monitor the reaction by LCMS until completion. Dilute the reaction solution with water, extract the aqueous phase with ethyl acetate, wash the organic phase with saturated brine, dry and concentrate. Purify the residue by column chromatography (EA / PE = 1 / 5) to obtain compound 166-3 (120 mg, 73.53%), a white oil.

[0185]

[0186] 8. Synthesis of Compound 167

[0187] (1) Dissolve compound 2 (200 mg, 0.8 mmol) in 5 ml of DCM, add Boc2O (265 mg, 1.2 mmol), triethylamine (242 mg, 2.4 mmol) and a catalytic amount of DMAP, and react at room temperature for 1 h. Monitor the reaction by LCMS until completion, quench the reaction with water, concentrate the reaction solution, dilute with ethyl acetate, wash the organic phase with water and saturated brine, dry and concentrate. Purify the residue by column chromatography (EA / PE = 1 / 5) to obtain compound 167-1 (167 mg, 60%).

[0188]

[0189] (2) Dissolve compound 167-1 (167 mg, 0.48 mmol) in 5 ml of THF, cool to -78 °C, dropwise add n-butyllithium (0.2 ml, 0.57 mmol), keep the temperature for reaction for 30 minutes, add methyl iodide (341 mg, 2.4 mmol), and let it warm up to room temperature for reaction for 1 hour. Monitor the reaction by LCMS until completion, add ammonium chloride solution to quench the reaction, concentrate the reaction solution, dilute it with ethyl acetate, wash the organic phase with water and saturated brine, dry and concentrate, and purify the residue by column chromatography (EA / PE = 1 / 5) to obtain compound 167 (60 mg, 35%).

[0190]

[0191] 9. Synthesis of compound 168

[0192] Dissolve compound 2 (100 mg, 0.4 mmol) in 5 ml of DMF, add compound 168-1 (114 mg, 0.48 mmol), catalytic amounts of tetrakis(triphenylphosphine)palladium (20 mg, 0.02 mmol) and CuI, and react at room temperature overnight under a nitrogen atmosphere. Monitor the reaction by LCMS until completion, concentrate the reaction solution, dilute it with ethyl acetate, wash the organic phase with water and saturated brine, dry and concentrate, and purify the residue by column chromatography (EA / PE = 1 / 2) to obtain compound 168 (71 mg, 49%).

[0193]

[0194] 10. Synthesis of compound 169

[0195] (1) Dissolve substrate 169-1 (1.3 g, 7.4 mmol) in toluene in a single-necked flask, add ethyl cyanoacetate (1 g, 8.9 mmol) and potassium acetate (724 mg, 7.4 mmol), and react at 100 °C overnight. After the reaction is completed, remove toluene by rotary evaporation, extract with ethyl acetate / water, and purify by silica gel column chromatography to obtain intermediate 169-2 (1.5 g, 5.6 mmol, 75%).

[0196]

[0197] (2) Dissolve substrate 169-2 (1.5 g, 5.6 mmol) in methanol in a single-necked flask, add compound 169-3 (1.2 g, 6.2 mmol) and potassium hydroxide (403 mg, 7.3 mmol), and react at room temperature for 6 h. After the reaction is completed, remove methanol by rotary evaporation, extract with ethyl acetate / water, and purify by silica gel column chromatography to obtain intermediate 169-4 (1.3 g, 5.2 mmol, 93.4%).

[0198]

[0199] (3) Dissolve substrate 169-4 (1.3 g, 5.2 mmol) in diethyl ether in a single-necked flask. At -78 °C, slowly add DIBAL-H (7.8 mmol) and react at room temperature overnight. After completion of the reaction, quench with a small amount of water, filter through diatomaceous earth, and wash the filter cake twice with ethyl acetate. Evaporate the solvent under reduced pressure to obtain intermediate 169-5 (310 mg, 1.2 mmol, 23.9%).

[0200]

[0201] (4) Dissolve substrate 169-5 (310 mg, 1.2 mmol) in methanol in a single-necked flask. Add dimethyl (1-diazo-2-oxopropyl)phosphonate (494 mg, 2.4 mmol) and potassium carbonate (355 mg, 2.4 mmol), and react under nitrogen protection overnight. After completion of the reaction, evaporate methanol, extract with ethyl acetate / water, and purify by silica gel column chromatography to obtain 169 (60 mg, 0.24 mmol, 20%).

[0202]

[0203] Biological activity evaluation (sterilization petri dish method):

[0204] Dissolve the medicament in acetone and dilute it with sterile water, and set different mass concentrations according to its activity. Under aseptic operation conditions, quantitatively add the pre-melted sterilized medium into a sterile conical flask according to the test treatment. Quantitatively pipette the medicament solution from low concentration to high concentration and add it into the above conical flask respectively, and shake well. Then pour an equal amount into 3 petri dishes with a diameter of 6 cm to make medicament-containing plates with corresponding concentrations. Set a treatment without the medicament as a blank control, with 3 replicates for each treatment. For the cultured pathogenic bacteria, under aseptic conditions, use a sterile punch with a diameter of 3 mm to cut a mycelial disc from the edge of the colony, and inoculate the mycelial disc in the center of the medicament-containing plate with the mycelial side facing up, cover the lid, and culture in an incubator at 25 °C. After 4 days, investigate the growth of the pathogenic bacteria mycelia according to the growth of the bacteria in the blank control petri dish. Measure the colony diameter with a caliper, with the unit of millimeter (mm). Measure the diameter of each colony vertically once with the cross method, and take the average value. According to the investigation results, calculate the mycelial growth inhibition rate of each treatment concentration on the tested target bacteria according to formulas (1) and (2), with the unit of percentage (%).

[0205] D = D1 - D2 ………………………………………… (1)

[0206] In the formula: D - the increased diameter of the colony; D1 - the diameter of the colony; D2 - the diameter of the mycelial disc.

[0207]

[0208] In the formula: I——inhibition rate of hypha growth; D0——colony growth diameter of blank control; D t ——colony growth diameter of medicament treatment.

[0209] Table 2 Representative test results of fungicides inhibiting the mycelial growth of pathogenic fungi determined by petri dish method

[0210]

[0211] Bioactivity evaluation (sterilization pot method):

[0212] The medicament is dissolved in dimethyl sulfoxide and then diluted to different concentrations with 0.1% Tween 80 aqueous solution. The liquid medicine is evenly sprayed on the leaf surface until it is completely wetted, and then left to dry naturally for later use. A treatment without medicament is set as the blank control. Three replicates are set for each medicament.

[0213] Inoculation of Botrytis cinerea of tomato, Gibberella zeae of wheat, and Colletotrichum orbiculare of cucumber: For the protective test, inoculation is carried out 24 h after the medicament treatment. In a petri dish filled with spores, add culture solution, gently scrape the surface spores, and filter them through four layers of gauze to prepare a spore suspension with a concentration of 5×10 6 ~6×10 6 per mL, and then spray it on the host test materials with a sprayer. The inoculated test materials are transferred to an incubator or artificial climate chamber for culture without light.

[0214] Inoculation of Rhizoctonia solani of rice: For the protective test, inoculation is carried out 24 h after the medicament treatment. Punch holes in the petri dish filled with mycelia to make 5-mm mycelial cakes, and inoculate the mycelial cakes on the host test materials. The inoculated test materials are transferred to an incubator or artificial climate chamber for culture without light.

[0215] According to the disease incidence of the blank control (when the disease reaches grade 9), the inoculated leaves are investigated by grading. The following grading method is adopted:

[0216] Grade 0: Disease-free;

[0217] Grade 1: The diseased area accounts for less than 5% of the whole leaf area;

[0218] Grade 3: The diseased area accounts for 6% - 10% of the whole leaf area;

[0219] Grade 5: The diseased area accounts for 11% - 25% of the whole leaf area;

[0220] Grade 7: The diseased area accounts for 26% - 50% of the whole leaf area;

[0221] Grade 9: The diseased area accounts for more than 50% of the whole leaf area.

[0222] Based on the survey data, the disease index and prevention and control effect of each treatment were calculated.

[0223] The disease index is calculated according to formula (1), and the result is rounded to two decimal places:

[0224] X={(∑(Ni xi)) / (N x 9)}x 100

[0225] 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.

[0226] The control effect is calculated according to the formula:

[0227]

[0228] 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.

[0229] Table 3 Representative test results of fungicides inhibiting the growth of pathogenic fungi hyphae by pot culture method

[0230]

[0231] Note: N stands for no data.

[0232] Biological activity evaluation (nematode 96-well plate bioassay):

[0233] (1) Preparation of test agents

[0234] Accurately weigh the test agent, dissolve it in DMSO to prepare a stock solution, and dilute it into different concentration gradient solutions.

[0235] (2) Target nematode isolation

[0236] Southern root-knot nematode: When egg masses grow on the root nodes, use tweezers to pick out the egg masses in the root nodes under a dissecting microscope and place them in clean water. Soak them in a 0.25% sodium hypochlorite aqueous solution for about 1 minute, wash and sieve them with a 500-mesh sieve, place them in a 90mm culture dish containing an appropriate amount of tap water, put them in a sieving device, and culture them in a 28°C incubator for 3 days. The egg masses will hatch into second-instar larvae. Observe the concentration of the nematode suspension under a microscope and dilute it to a nematode suspension of about 1,000 nematodes / mL for later use.

[0237] Mixed-stage pine wood nematodes, mixed-stage rice white-tip nematodes, and mixed-stage sweet potato stem nematodes: Dig out the PDA medium with nematodes, invert it on a Petri dish covered with mycelium, wash the nematodes on the lid of the Petri dish with sterile water, transfer the nematode solution to a new Petri dish of Botrytis cinerea mycelium, with 1 mL of nematode solution in each Petri dish. Incubate in a dark incubator at 25 °C. When the mycelium is completely consumed by the nematodes, transfer them again to the Botrytis cinerea mycelium on PDA for propagation. The cultured nematodes are stored at 4 °C. Transfer and propagate every 7 - 10 days. Use at least 10 Petri dishes each time. Prepare Petri dishes where the Botrytis cinerea has been completely eaten, rinse the nematodes on the lid of the Petri dish with sterile water, observe the concentration of the nematode suspension under a microscope, and dilute it to a nematode suspension of about 1000 nematodes / mL for standby.

[0238] (3) Chemical treatment

[0239] Add 100 μL each of the prepared test chemical and nematode suspension to a 96-well culture plate, cover to prevent evaporation, and place in an incubator at 28 °C. Set up a blank control with clear water, a chemical control; if a solvent is used, set up a solvent control as well.

[0240] (4) Incubation and observation

[0241] Incubate the nematodes after chemical treatment under normal conditions, and detect the nematode mortality at 48 h and 72 h: Mortality (%) = (number of dead nematodes / number of test nematodes) * 100. Representative test results are shown in Table 4.

[0242] Table 4 Results of nematocide tests

[0243]

[0244] Note: N represents no data.

[0245] Meanwhile, through a lot of tests, it is found that many of the compounds and their compositions described in the present invention have good control activities against different types of nematodes, etc., and have characteristics such as broad-spectrum, high-efficiency, and strong systemic absorption. They can effectively control pests and / or fungi. For example, they also have good control activities against different types of fungi such as Ascomycetes, Basidiomycetes, Deuteromycetes, and Oomycetes, 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 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; The foregoing "heterocyclic group" or "aryl group" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted with alkyl, cycloalkylalkyl, aryl or heterocyclic group which is unsubstituted or substituted with 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 the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy; And the following compounds are excluded:

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 foregoing "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 is independently hydrogen, 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 with C1-C8 alkyl, C3-C8 cycloalkyl C1-C8 alkyl, aryl, heterocyclic group, or aryl or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo C1-C8 alkoxy.

3. The 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, tris(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-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 foregoing "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 aforementioned "heterocyclic group" or "aryl group" is optionally substituted with 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 with C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl, aryl or heterocyclic group which is unsubstituted or substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo C1-C6 alkoxy, -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; R 10 each independently is hydrogen, 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 with C1-C6 alkyl, C3-C6 cycloalkyl C1-C6 alkyl, aryl, heterocyclic group, or aryl or heterocyclic group substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1 in the specification.

4. The preparation method of the pyrrole compound according to any one of claims 1-3, comprising the following steps: (1) When Y is hydrogen, reacting the compound represented by general formula II with dimethyl (1-diazo-2-oxopropyl)phosphonate to obtain the compound represented 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 general formula I-1; Alternatively, (3) when X is not hydrogen, it is 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 of step (1) is carried out in the presence of a solvent; more preferably, a base is added during the reaction of 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, anthracnose), 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, further comprising formulation adjuvants; more preferably, further comprising other active ingredients.

7. A method for controlling pests and / or fungi (especially nematodes, Fusarium head blight, sheath blight, gray mold, anthracnose), 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. 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, Fusarium head blight, sheath blight, gray mold, anthracnose).

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