N-phenylalkyl pyridinecarboxamide compounds and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to N-phenylalkyl pyridinecarboxamide compounds and the use thereof. The compounds are shown as general formula (I), wherein A1, A2, A3, A4 and A5 each independently represent N or CY; M represents O; n is 0 or 1; and R1, R2, R3, R4, X1, X2, X3, X4 and Y each independently represent hydrogen, halogen, nitro, etc. The compounds have excellent control effects on harmful organisms and / or fungi (especially nematodes, fusarium head blight and sclerotinia stem rot).

Description

Pyridinecarboxylic acid phenylalkylamide compounds and their applications Technical Field

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

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides and fungicides, pests and diseases have acquired resistance, making them difficult to control with existing insecticides and fungicides. Furthermore, some known pest control agents are highly toxic, or some damage ecosystems through their long-term residual properties. Despite the existence of numerous known fungicides and nematocides, such as WO2007108483A1, which discloses N-2-(hetero)arylethylformamide derivatives and their use as fungicides and nematocides, there remains a need to develop new pest control agents with low toxicity and low residual properties. Summary of the Invention

[0003] In order to solve the above problems existing in the prior art, the present invention provides a pyridinecarboxylic acid phenylalkylamide compound, which has excellent control effects on harmful organisms and / or fungi (especially nematodes, head mold, and sclerotinia).

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

[0005] A pyridinecarboxylic acid phenylalkylamide compound, its salt and N-oxide:

[0006] wherein A1, A2, A3, A4, and A5 independently represent N or CY;

[0007] M stands for O;

[0008] n is 0 or 1;

[0009] R1, R2, R3, R4, X1, X2, X3, X4, and Y independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, sulfhydryl, carboxyl, sulfonic acid, formyl, haloformyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "alkyl", "alkenyl" or "alkynyl" is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-alkylene-(CO)OH or -O-alkylene-(CO)OR 22 is substituted by at least one group in;

[0010] R 21 Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-alkylene-(CO)OR 22 、-(SO2)R22 、-(SO2)OR 22 、-alkylene-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2;

[0011] R 22 Each independently represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclic group, wherein the "alkyl", "alkenyl" or "alkynyl" is optionally selected from halogen, cyano, trialkylsilyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 is substituted by at least one group in;

[0012] R 23 Each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl;

[0013] R 24 each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl;

[0014] or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group wherein the 1-position is a nitrogen atom;

[0015] R 25 Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, or phenyl substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, phenoxy, or phenoxy substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0016] The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10、-(SO2)R 10 、-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-substituted -OCH2CH2- or -OCH2O-;

[0017] R 10 Each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0018] In a specific embodiment, R1, R2, R3, R4, X1, X2, X3, X4, and Y independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, sulfhydryl, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22, wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C8 alkylene)-(CO)OH or -O-(C1-C8 alkylene)-(CO)OR 22 is substituted by at least one group in;

[0019] R 21 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-(C1-C8 alkylene)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C8 alkylene)-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2;

[0020] R 22Each independently represents a C1-C8 alkyl, a C2-C8 alkenyl, a C2-C8 alkynyl, a C3-C8 cycloalkyl, a C3-C8 cycloalkenyl, an aryl or a heterocyclic group, wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 is substituted by at least one group in;

[0021] R 23 Each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl or heterocyclylC1-C8 alkyl;

[0022] R 24 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylsulfonyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl or C3-C8 cycloalkenylC1-C8 alkyl;

[0023] or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group wherein the 1-position is a nitrogen atom;

[0024] R 25 Each independently represents 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, phenyl, or phenyl substituted by at least one group selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, phenoxy, or phenoxy substituted by at least one group selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, or halo-C1-C8 alkoxy;

[0025] The aforementioned “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-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 unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0026] R 10 Each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

[0027] In a specific embodiment, R1, R2, R3, R4, X1, X2, X3, X4, and Y independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, sulfhydryl, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C6 alkylene)-(CO)OH or -O-(C1-C6 alkylene)-(CO)OR 22 is substituted by at least one group in;

[0028] R 21 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-(C1-C6 alkylene)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C6 alkylene)-(SO2)R 22 、-(CO)N(R24 )2 or -(SO2)N(R 24 )2;

[0029] R 22 Each independently represents a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C6 cycloalkyl, a C3-C6 cycloalkenyl, an aryl or a heterocyclic group, wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally selected from halogen, cyano, tri-C1-C6 alkylsilyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 is substituted by at least one group in;

[0030] R 23 Each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclyl or heterocyclylC1-C6 alkyl;

[0031] R 24 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl or C3-C6 cycloalkenylC1-C6 alkyl;

[0032] or N(R 21 )2、N(R 24 ) 2 independently represent unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl

[0033] R 25Each independently represents 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, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, phenoxy or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0034] The aforementioned “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-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 unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0035] R 10 Each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0036] In one embodiment, A1, A2, A3, A4, and A5 independently represent N or CY, and at most two groups are N.

[0037] In the definition of the compounds represented by the above general formula and in all the following structural formulas, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms can be straight-chain or branched. For example, the compound word "-O-alkylene-(CO)OR 10" " in which the alkylene group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl 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. The term "cycloalkyl" refers to a group consisting of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohex ...

[0038] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0039] If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0040] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein refers to being substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0041] The present invention also encompasses salts or N-oxides of each compound of formula I.

[0042] Those skilled in the art also understand that because salts of compounds exist in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, salts also have the biological utility of the non-salt forms.

[0043] Thus, various salts of the compounds of the invention (and active ingredients used in combination with the active ingredients of the invention) can be used to control invertebrate pests and animal parasites. Agriculturally and / or physiologically acceptable salts include acid addition salts formed with the following inorganic or organic acids, such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid.

[0044] Suitable salts include salts of cations which do not adversely affect the pesticidal and / or parasiticidal action of the compounds of formula I. Suitable cations are therefore particularly alkali metal ions, including sodium, potassium and lithium, alkaline earth metal ions, including calcium and magnesium, and transition metal ions, including manganese, copper, iron, zinc, cobalt, lead, silver, nickel, and ammonium or organoammonium ions, including monoalkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, monoalkenylammonium, dialkenylammonium, trialkenylammonium, monoalkynylammonium, dialkynylammonium, monoalkanolammonium, dialkanolammonium, C5-C6-cycloalkylammonium, piperidinium, morpholinium, pyrrolidinium or benzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

[0045] N-oxides can be prepared by reacting a compound of the invention with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00 / 15615 or C. White, Science, vol 318, p. 783, 2007.

[0046] The present invention also provides a method for preparing pyridinecarboxylic acid phenylalkylamide compounds, salts thereof and N-oxides, comprising the following steps:

[0047] (1) The compound represented by the general formula II is subjected to a condensation reaction with the compound represented by the general formula III to obtain the compound represented by the general formula I. The reaction equation is as follows:

[0048] Alternatively, (2) when n is 0, compound IV and compound V are coupled to produce compound I, and the chemical reaction equation is as follows:

[0049] Wherein, W represents halogen or OH, either Z1 or Z2 represents halogen, and the other represents Substituents A1, A2, A3, M, n, R1, R2, R3, R4, X1, X2, X3 and X4 are as defined above.

[0050] In one embodiment, the reaction of steps (1) and (2) is carried out in the presence of a solvent.

[0051] In another embodiment, a condensing agent and / or a base is added during the reaction of step (1).

[0052] In another embodiment, a catalyst and / or a base is added in step (2).

[0053] In another specific embodiment, the solvent in steps (1) and (2) is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, tetrahydrofuran, ethyl acetate or water.

[0054] In another specific embodiment, the base in steps (1) and (2) is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KHCO3, KF, CsF, KI, NaI, K3PO4, K2HPO4, NaOH, KOH, NaH, KH, etc.) or an organic base (such as DMAP, pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, etc.).

[0055] In another embodiment, the condensing agent in step (1) is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU and HATU.

[0056] In another specific embodiment, the catalyst in step (2) is selected from at least one of Pd(dppf)Cl2, Pd(PPh3)4, PdCl2, Pd(OAc)2, Pd(PPh3)2Cl2, NiCl2(dppf) and PdCl2(dppf)·CH2Cl2 (CAS No.: 95464-05-4).

[0057] In addition, the compound represented by general formula I can also be prepared by referring to the methods shown in WO2015078800A1, WO2007108483A1, etc.

[0058] The present invention also provides an intermediate, as shown in Formula II, III, IV or V.

[0059] The present invention also provides a composition for killing pests and / or fungi (especially nematodes, head blight, and sclerotinia), comprising a biologically effective amount of at least one of the pyridinecarboxylic acid phenylalkylamide compounds, salts thereof, and N-oxides.

[0060] In one embodiment, the composition further comprises a formulation adjuvant.

[0061] In another embodiment, the composition further comprises other active ingredients.

[0062] The present invention also provides a method for controlling harmful organisms and / or fungi (especially nematodes, head blight, and sclerotinia), comprising contacting the harmful organisms and / or fungi or their environment with a biologically effective amount of the pyridinecarboxylic acid phenylalkylamide compound, its salt and N-oxide, or the composition.

[0063] The present invention also provides the use of the pyridinecarboxylic acid phenylalkylamide compound, its salt and N-oxide or the composition in preventing and controlling harmful organisms and / or fungi (especially nematodes, head mold, and sclerotinia).

[0064] The compounds of formula I have been found to be useful for controlling damage caused by pests and / or fungi.

[0065] In one embodiment, the compound of Formula I can be used in agriculture.

[0066] The present invention is therefore furthermore directed to a method for controlling damage and / or yield losses caused by pests and / or fungi, which method comprises applying an effective amount of a compound of formula I to the pests, to the locus of the pests, or to plants susceptible to attack by pests and / or fungi or to plant propagation material.

[0067] The compounds according to the invention can be used for controlling, i.e. limiting or destroying, harmful organisms and / or fungi which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stalks, rhizomes, seeds or roots, and in some cases even on plant organs formed at a later point in time, for protection against these harmful organisms.

[0068] The compounds of formula I according to the invention are preventively and / or therapeutically valuable active ingredients in the field of pest control. Even at low application rates, they can be used to combat pests and / or fungi that are resistant to pesticides. The compounds of formula I have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.

[0069] The compounds according to the invention can act on all or individual developmental stages of normally sensitive and also resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the compounds according to the invention can manifest itself directly, i.e., for example, by the destruction of the pests during molting, which occurs immediately or after a certain period of time, or indirectly, for example, by a reduction in egg laying and / or hatching rates, good activity corresponding to a destruction rate (mortality) of at least 50% to 60%.

[0070] It has now been found that the compounds of formula I according to the invention have (for practical purposes) a very advantageous spectrum of activity for protecting animals and useful plants against attack and damage by nematodes. The present invention therefore also makes available nematicidal compositions comprising the compounds of the invention, such as those of formula I.

[0071] The compounds of formula I are particularly useful for the control of nematodes. In another aspect, the present invention therefore also relates to a method for controlling damage to plants or parts thereof caused by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; cereal cyst nematodes, Heterodera avenae, Heterodera glycines, Heterodera schachtii and Heterodera schachtii. schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Eelonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Mesocriconema species;Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus, and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species, and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; False rootknot nematodes Needle nematodes, Longidorus elongatus, and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species;Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus, and other Trichodorus species; Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes), Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;

[0072] In particular, the nematode species: Meloidogyne, Heterodera, Coelenteroides and Pratylenchus can be controlled by the compounds according to the invention.

[0073] Examples of animal pests are:

[0074] - from the order Acarina, for example,

[0075] Acalitus spp., Acaricalus spp., Aceria spp., Acarina ...

[0076] - from the order Phthirus, for example,

[0077] Haematoptes, Longignatus, Human lice, Pemphigoids, and Psyllids;

[0078] - from the order Coleoptera, e.g.

[0079] Amphimallon majale, Amphimallon majale, Oriental beetle, Amphimallon majale, Astylus atromaculatus, Ataenius spp., Atomaria linearis, Beet flea beetle, Cerotoma spp., Single leaf beetle, Root neck beetle, Green beetle, Curculionidae, Rhinoceros beetle, Rhinoceros beetle, Root firefly beetle, Diloboderus abderus, Eremnus spp., Black sugarcane beetle, Coffee berry borer, Lagria vilosa, Potato beetle, Rice water beetle, Liogenys spp., Maecolaspis spp., Chestnut velvet beetle, American leaf beetle (Megascelis spp.), Melighetes aeneus, Myochrous beetle, armatus, saw-beetle spp., Otiorhynchus spp., horn beetle spp., spotted beetle spp., beetle spp., rape flea beetle spp., Rhyssomatus aubtilis, root beetle spp., scarab beetle, rice weevil spp., wheat moth spp., pseudo-root beetle spp., pointed cryptomonas spp., soybean stem beetle, ground beetle spp., castanea spp., and trophoderm beetle spp.;

[0080] - from the order Diptera, e.g.

[0081] Aedes spp., Anopheles spp., Sorghum fruit fly, Bactrocea oleae, Garden midge, Bradysia spp., Red-headed blowfly, Bactrocera spp., Chrysomelidae spp., Culex spp., Yellow fly, Bactrocera spp., Ground fly, Drosophila melanogaster, Toilet fly, Gastrocera spp., Geomyza tripunctata, Glossina spp., Desmodium spp., Lipid fly, Liriomyza spp., Lucilia spp., Liriomyza spp., Housefly spp., Mylomyia spp., Swedish straw fly, Spring fly, Grass fly spp., Bactrocera spp., Riveria quadrifasciata, Scatella spp., Fungus gnat, Bitefly spp., Tabanus spp., Tapeworm spp., and Crane spp.;

[0082] - from the order Hemiptera, e.g.

[0083] Acanthocoris scabrator, Green stink bug, Alfalfa blind bug, Amblypelta nitida, Bathycoelia thalassina, Soil stink bug, Cockspur, Clavigralla tomentosicollis, Creontiades spp., Cocoa stink bug, Dichelops furcatus, Cotton stink bug, Edessa spp., Euchistus spp., Eurydema pulchrum, Flat shield bug, Brown-winged stink bug, Horcias nobilellus, Rice stink bug, Lygus, Tropical scale, Murgantia histrionic), Neomegalotomus spp., Nesidiocoris tenuis, Green stink bug, Nysius simulans, Oebalus insularis, Skin stink bug, Wall stink bug, Red assassin bug, Cocoa stink bug, Scaptocoris castanea, Black stink bug (Scotinophara spp.), Thyanta spp., Triatomine bug, Cassava web bug (Vatiga illudens);

[0084] - from the order Homoptera, e.g.

[0085] Aphids, Adalges spp., Agallina ensigera, Agonascena targionii, Aleurodicus spp., Aleurocanthus spp., Sugarcane hole whitefly, Aleurothrixus floccosus, Cabbage whitefly (Aleyrodes brassicae), Cotton leafhopper (Amarasca biguttula), Yellow-circled sawfly (Amritodus atkinson), Kidney-shielded scale, Aphididae, Aphid, Scale (Aspidiotus spp.), Eggplant groove aphid, Bactericera cockerelli, Aleurodicus spp., Brachycaudus spp., Cabbage aphid, Cavariella spp., Two-tailed aphid (Cavariella aegopodii) Scop.), Lecanus spp., Brown Scale, Net-seed Grass Leaf Scale, Cicadella spp., Cofana spectra, Cryptomelania spp., Cicadulina spp., Brown Soft Scale, Corn Yellow-winged Leafhopper, Whitefly spp., Citrus Psyllid, Wheat Aphid, Western Aphid, Small Green Leafhopper, Apple Aphid, Grape Leafhopper spp., Wax Clam spp., Glycaspis brimblecombei, Cabbage Aphid, Hyalopterus spp., Super-tumor Aphid species, Lemon Green Leafhopper (Idioscopus clypealis), Jacobiasca lybica, Laodelphax striatum, Ball-hard Scale, Oyster Shield Scale, Lopaphis erysimi, Lyogenys maidis, Longitudinal Aphid, Mahanarva spp., Metcalfa pruinosa), wheat aphid, Myndus crudus, aphid spp., Taiwan leek aphid, black-tailed leafhopper spp., brown planthopper (Nilaparvata spp.), pear green aphid, Odonaspis ruthae, parasitic sugarcane woolly aphid, bayberry whitefly, Caulis psyllid, scutellaria spp., gall aphid spp., corn waxhopper, flat-horned planthopper spp., hopscotch aphid, phylloxera spp., Mosella spp., white-shielded scale spp., mealybug spp., cotton blind bug (Pseudatomoscelis seriatus), psyllid spp., cotton scale (Pulvinaria aethiopica), round-shielded scale spp., Quesada gigas, electric leafhopper (Recilia dorsalis), constrictor aphid spp., black-helmeted scale spp., leafhopper spp., dichotomous aphid spp., wheat aphid (Sitobion spp.)), white-backed planthopper, Spissistilus festinus, Tarophagus proserpina, aphids, whiteflies, Tridiscus sporoboli, Trionymus spp., African psyllids, orange-headed scale, Zygina flammigera, Zyginidia scutellaris;

[0086] - from the order Hymenoptera, e.g.

[0087] Arge spp., Arge spp., Argetotermes ...

[0088] - from the order Isoptera, e.g.

[0089] Coptotermes, Corniternes cumulans, Coptotermes, Macrotermes, Macrotermes, Microtermes, Reticulitermes; tropical fire ants

[0090] - from the order Lepidoptera, e.g.

[0091] Long-winged torrefies, brown-banded torrefies, clear-winged torrefies, ground moths, cotton leafworms, Amylois spp., pea moths, yellow torrefies, silver moths (Argyresthia spp.), banded torrefies, yarrow-patterned torrefies, cotton miners, corn borers, powdery moths, peach fruit moths, grass borers, leaf rollers, Chrysoteuchia topiaria, grape fruit moths, leaf rollers, cloud torrefies, pattern torrefies, sheath moths, lepidoptera, Cosmophila flava, grass borers, cabbage borers, apple torrefies, boxwood moths, torrefies, boxwood moths, stem borers, Sudan bollworms, diamond borers, African stem borers, powdery moths, leaf torrefies (Epinotia) spp.), fine-spotted lantern moth, Etiella zinckinella, flower tortoise spp., ring-needle moth, yellow tussock moth spp., root cutter spp., Feltia jaculiferia, Grapholita spp., green budworm moth, Spodoptera spp., cabbage borer, Herpetogramma spp., American white moth, tomato borer, Lasmopalpus lignosellus, spiral leafminer, leafminer spp., grape flower tortoise, Loxostege bifidalis, tussock moth spp., miner spp., leaf miner spp., cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae spp., fall geometre spp., Orniodes indica, European corn borer, super-small tortoise spp., brown tortoise spp., small-eyed tortoise spp., stem borer, Pectinophora gossypiela, coffee leafminer, armyworm, potato moth, cabbage butterfly, Pieris spp., diamondback moth, budworm spp., leaf moth spp., mint leafminer, Richia albicosta, Scirpophaga spp., stem borer, stalkworm, Spodoptera spp., cotton leaf roller, stalkworm, Heteroptera spp., leaf roller, cabbage looper, tomato leafminer, and brood moth spp.;

[0092] - from the order Maophaga, e.g.

[0093] Damalina spp. and Trichodesmosis spp.;

[0094] - from the order Orthoptera, e.g.

[0095] Blatta, Blattella, Mole Cricket, Madeira Cockroach, Locust, American Mole Cricket (Neocurtilla hexadactyla), Periplaneta, Scapteriscus spp., and Desert Locust;

[0096] - from the order Rodentia, for example,

[0097] Booklice;

[0098] - from the order Siphonaptera, e.g.

[0099] Ceratophyllum, Ctenophora and Xenophora;

[0100] - from the order Thysanoptera, for example,

[0101] Calliothrips phaseoli, Flower Thrips spp., Sun Thrips spp., Brown-banded Thrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Banded Thrips spp., Thrips spp.;

[0102] - from the order Thysanura, e.g.

[0103] Silverfish.

[0104] On the other hand, the present invention also relates to a method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, wherein a compound of formula I is applied to a plant, its part or its place as an active ingredient. The significant difference of the compound of formula I according to the present invention is activity, good plant tolerance and environmental safety. They have very useful treatment, prevention and systemic properties and are used to protect a variety of useful plants. The compound of formula I can be used to suppress or destroy the disease that occurs on the plant or plant part (fruit, flower, leaf, stem, tuber, root) of a variety of different useful plants, while also protecting those plant parts that are grown later from phytopathogenic microorganisms. It is also possible to use the compound of formula I as a dressing agent for treating plant propagation materials, particularly seeds (fruit, tuber, grain) and plant cuttings (e.g., rice), for protecting against fungal infection and against phytopathogenic fungi present in the soil.

[0105] Examples of fungi include: the class Deuteromycetes (e.g., Botrytis, Pyrospora, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); the class Basidiomycetes (e.g., Rhizoctonia, Puccinia, Puccinia); the class Ascomycetes (e.g., Venturia and Powdery Mildew, Monocystis, Moniliformis, Uncinaria); the class Oomycetes (e.g., Phytophthora, Pythium, Monoparagus); the class Zygomycetes (e.g., Rhizopus); the family Pucciniaceae, particularly those of the genus Pucciniaceae, such as Puccinia pachyrhizi, which is also known as Asian soybean rust, and those of the family Pucciniaceae, particularly those of the genus Pucciniaceae, such as Puccinia graminis, also known as stem rust or black rust, which is a problem disease in cereals, and Puccinia recondita, also known as brown rust.

[0106] Among the plants and possible diseases of these plants which can be protected by the method according to the invention, mention may be made of:

[0107] - Wheat, for the control of the following seed diseases: Fusarium (Fusarium spp. and Fusarium rosobacterium), black bunt (Tilletia tritici, Tilletia dwarfii, or Tilletia indica), Septoria (Septoria glumae), and loose smut;

[0108] - wheat, for the control of the following diseases of the above-ground parts of the plant: cereal eye spot (Tapesia yallundae, Tapesia acuiformis), take-all (Tapesia taecii), root blight (F. culmorum, F. graminearum), black spot (Rhizoctonia graminearum), powdery mildew (Erysiphe graminis forma specie tritici), rust (Puccinia striatum and Puccinia reclusa), and Septoria diseases (Septoria tritici and Septoria glume);

[0109] - wheat and barley, for the control of bacterial and viral diseases, such as barley yellow mosaic; - barley, for the control of the following seed diseases: net blotch (Pyricularia trichomoniasis, Pyricularia terrestris, and Cochliobolus graminis), loose smut (loose smut), and fusarium (Fusarium nivale and Fusarium roseum);

[0110] - barley, for the control of the following diseases of the above-ground parts of the plant: cereal eye spot (Tapesia yallundae), net blotch (Pyricularia teres and Cochlosporium graminis), powdery mildew (Erysiphe graminis formas pecie hordei), dwarf leaf rust (Puccinia hordei) and leaf spot (Puccinia hordei);

[0111] - Potatoes, for the control of tuber diseases (particularly Aralia solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytophthora infestans) and some viruses (Virus Y);

[0112] - Potatoes, for the control of the following foliar diseases: early blight (Alternaria solani), mildew (Phytophthora infestans);

[0113] - Cotton, for the control of the following diseases in young plants grown from seed: damping-off and blight (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Thalassemia radicifolia);

[0114] - protein-producing plants, such as peas, for controlling the following seed diseases: anthracnose (Psoralea corylifolia, Mycosphaeria pisum), fusarium (Fusarium oxysporum), gray mold (Botrytis cinerea) and mildew (Peronospora pisum);

[0115] - Oilseed rape, for the control of the following seed diseases: Stenotrophomonas brassicae, Alternaria brassicae, and Sclerotinia sclerotiorum;

[0116] - Corn, for the control of various seed diseases (Rhizopus, Penicillium, Trichoderma, Aspergillus, and Gibberella);

[0117] - Flax, for controlling this seed disease: Alternaria linicola;

[0118] - Deep forest trees, for controlling damping-off disease (Fusarium oxysporum, Rhizoctonia solani);

[0119] - Rice, for the control of the following diseases of above-ground parts: blast (Pyricularia oryzae), bordered sheath spot (Rhizoctonia solani);

[0120] - Leguminous plants, for the control of the following diseases on seeds or young plants grown from seeds: damping-off and blight (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium spp.);

[0121] - Leguminous plants, for the control of the following diseases on aerial parts: gray mold (Botrytis spp.), powdery mildew (especially Erysiphe spp., Erysiphe spp. and Pyrophila spp.), Fusarium spp. (Fusarium oxysporum, Fusarium rosporum), leaf spot (Cladosporium spp.), Alternaria leaf spot (Alternaria spp.), anthracnose (Colletotrichum spp.), Septoria leaf spot (Septoria spp.), black spot (Rhizoctonia solani), mildew (for example, Downy mildew of lettuce, Peronospora spp., Pseudocoperonospora spp., Phytophthora spp.);

[0122] - fruit trees, for the control of various diseases of aerial parts: candidiasis (Monilia fructigenae, M. laxa), scab (Viburnum indica), powdery mildew (Monilia albicans); - vines, for the control of the following foliar diseases: in particular gray mold (Botrytis cinerea), powdery mildew (Uncinaria officinalis), black rot (Guignardia biwelli) and mildew (Plasmopara viticola);

[0123] Beetroot for the following diseases of aerial parts: cercospora blight (brown blight of beet), powdery mildew (Erysiphe beticola), leaf spot (Erysiphe beticola).

[0124] The fungicidal compositions according to the invention can also be used to combat fungal diseases that are susceptible to growth on or in wood. The term "wood" refers to all types of wood species, as well as all types of wood intended for construction work, such as solid wood, high-density wood, laminated wood, and plywood. The method for treating wood according to the invention essentially involves contacting with one or more compounds according to the invention or compositions according to the invention; this includes, for example, direct application, spraying, immersion, injection, or any other suitable means.

[0125] When used alone, the compounds of the present invention are effective in controlling nematodes, insects, acarid pests and / or fungal pathogens of growing or harvested agronomic plants. They can also be used in combination with other bioactive agents used in agriculture, for example, one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activators, molluscicides, and pheromones (chemical or biological). Mixing the compounds of the present invention or their compositions in the form of pesticides with other pesticides often results in a wider spectrum of pest control. For example, the compounds of formula I of the present invention can be effectively combined or used in combination with pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cycloalkadienes, formamidines, tin phenolates, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles, and the like.

[0126] By adding, for example, one or more insecticides, acaricides, nematocides and / or fungicidal active agents, the activity of these compositions according to the present invention can be significantly widened, and is suitable for the environment that dominates. The combination of the compound of formula I with other insecticides, acaricides, nematocides and / or fungicidal active agents can also have further, unexpected advantages, which can also be described as synergistic activities in a wider sense. For example, plants can better tolerate, reduce phytotoxicity to it, and harmful organisms or fungi can be controlled at their different developmental stages or better behave during their production (for example, in grinding or mixing processes, in their storage or their use).

[0127] The following list of pesticides together with the compounds that can be used according to the invention is intended to illustrate the possible combinations by way of example.

[0128] The following combination of a compound of formula I with another active compound is preferred (the abbreviation "TX" means "each compound selected from Table 1, Table A of the present invention"):

[0129] An adjuvant selected from the group consisting of petroleum + TX,

[0130] A miticide, which is selected from the group consisting of the following substances: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenylsulfone+TX, abamectin+TX, acetoquinone+TX, acetofenapyr+TX, flumethrin+TX, aldicarb+TX, aldicarb+TX, α-cypermethrin+TX, cypermethrin+TX, sulfamethoxam+TX, aminothioate+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, AVI382+TX, AZ60541+TX, azinphos-m-tetrahydrofuran ... arsenic trioxide+TX, AVI382+TX, AZ60541+TX, azinphos-m-tetrahydrofuran+TX, arsenic trioxide+TX, arsenic trioxide+TX, arsenic trioxide ethyl)+TX, azobenzene+TX, azacyclotin+TX, azothoate+TX, benclorac+TX, benoxafos+TX, benzoximate+TX, benzyl benzoate+TX, bifenazate+TX, bifenthrin+TX, binachlor+TX, bromethrin+TX, bromocyclene+TX, bromophos+TX, ethyl bromophos+TX, bromopropylate+TX, buprofezin+TX, butanone carbendazim+TX, butanone sulfone carbendazim+TX, butanone carbendazim+TX, lime sulfur mixture (calcium polysulfide)+TX, campheechlor+TX, carbanolate+TX, carbaryl+TX, carbofuran+TX, carbothion+TX, CGA50'439+TX, chinomethionat+TX, chlorbenside+TX, chlordimeform+TX, chlordimeform hydrochloride+TX, chlorfenapyr+TX, chlorfenapyr+TX, chlorfenson+TX, chlorfensulphide+TX, chlorfenphos+TX, ethyl ester acaricide Chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorpyrifos + TX, methyl chlorpyrifos + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, clofentezine + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, thiophene + TX,Cyanthoate + TX, Cyflumetofen [400882-07-7] + TX, Cyhalothrin + TX, Cypermethrin + TX, DCPM + TX, DDT + TX, Demephion + TX, Demephion-O + TX, Demephion-S + TX, Demeton + TX, Demeton-Methyl + TX, Demeton-O + TX, Demeton-Methyl-O + TX, Demeton-S + TX, Demeton-Methyl-S + TX, Demeton-S-methylsulphon + TX, Difenothiocarb + TX, Dialifos + TX, Dimethoate Azinphos + TX, dichlorvos + TX, dicliphos + TX, Kailesan + TX, dicrotophos + TX, pendimethalin + TX, dimefox + TX, dimethoate + TX, dinactin + TX, dinex + TX, dinex-diclexine + TX, dinobuton + TX, dinocap + TX, dinocap-4 + TX, dinocap-6 + TX, dinitrate + TX, dinopenton + TX, dinosulfon + TX, dinotefuran rbon)+TX, dioxaphos+TX, diphenyl sulfone+TX, disulfiram+TX, ethophos+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, endosulfan+TX, endothion+TX, EPN+TX, eprinomectin+TX, ethion+TX, ethoate-methyl+TX, etoxazole+TX, etrimfos+TX, fenazaflor+TX, quinazaquin+TX, fenbutatinoxide+TX, fenothiocarb+TX X, cypermethrin + TX, fenpyrad + TX, fenpyroximate + TX, fenson + TX, fentrifanil + TX, cypermethrin + TX, fipronil + TX, fluacrypyrim + TX, fluzolan + TX, flubenzimine + TX, flufenoxuron + TX, flucythrinate + TX, fluenetil + TX, flufenoxuron + TX, flumethrin + TX, fluorbenside + TX,flupyradifurone+TX, fluvalinate+TX, FMC1137+TX, fluvalinate+TX, fluvalinate hydrochloride+TX, formothion+TX, formparanate+TX, γ-HCH+TX, glyodin+TX, halfenprox+TX, heptenophos+TX, hexadecyl cyclopropanecarboxylate+TX, hexathiazolin+TX, iodomethane+TX, isocarbophos+TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate+TX, ivermectin+TX 、jasmolin I+TX、jasmolin II+TX、jodfenphos+TX、lindane+TX、lufenlon+TX、malathion+TX、malonoben+TX、mecarbam+TX、mephosfolan+TX、methylthiophene+TX、methacrifos+TX、methamidophos+TX、methidathion+TX、methoate+TX、methodifosyl+TX、metolcarb+TX、metofenphos+TX、methyl bromide+TX、metolcarb+TX、metolcarb+TX、mexacarbate+TX、milbemycin+TX、milbemycin oxime)+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, NC-184+TX, NC-152+TX, nifluridide+TX, nikkomycin+TX, nitrilacarb+TX, nitrilacarb 1:1 zinc chloride complex+TX, NNI-0101+TX, NNI-0250+TX, oxydemeton-methyl (oxydemeton-methyl)+TX, oxamyl+TX, oxydeprofos+TX, sulfamethoxam ( oxydisulfoton)+TX, pp'-DDT+TX, parathion+TX, permethrin+TX, petroleum+TX, fenthion+TX, fenthion+TX, fenthion+TX, phorate+TX, phosalone+TX, phosfolan+TX, phosmet+TX, phosphamidon+TX, phoxim+TX, methyl pirimiphos+TX, polychloroterpenes+TX, polynactins+TX, prochlorperazine+TX, profenofos+TX, promacyl+TX, propargyl+TX, propetamphos+TX, propoxur+TX,Prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimidifen + TX, pyrimidifen + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, RA-17+TX, rotenone+TX, schradan+TX, sebufos+TX, selamectin+TX, SI-0009+TX, sophamide+TX, spirodiclofen+TX, spiromesiclofen+TX, SSI-121+TX, sulfilam+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, S21-121 +TX, fluvalinate+TX, tebufenpyrad+TX, TEPP+TX, terbucarb+TX, stirofos+TX, tetradifon+TX, tetranactin+TX, tetrasul+TX, thiafenox+TX, thiocarboxime+TX, thiofanox+TX, thiometon-methyl )+TX, chlorpyrifos+TX, thuringiensin+TX, triamiphos+TX, triarathene+TX, triazophos+TX, triazuron+TX, trichlorfon+TX, trifenofos+TX, trinactin+TX, cypermethrin+TX, vaniliprole and YI-5302+TX,

[0131] An algaecide, the algaecide being selected from the group consisting of: 3-benzo[b]thiophen-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide+TX, copper dioctoate+TX, copper sulfate+TX, cybutryne+TX, dichlone+TX, dichlorophen+TX, endoxan+TX, fentin+TX, slaked lime+TX, nabam+TX, quinoclamine+TX, quinonamid+TX, simazine+TX, fentin acetate, and fentin hydroxide+TX.

[0132] An anthelmintic selected from the group consisting of abamectin + TX, clefonate + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, eprinomectin + TX, ivermectin + TX, milbemycin + TX, moxidectin + TX, piperazine + TX, selamectin + TX, spinosad and thiophanate + TX,

[0133] An avicide selected from the group consisting of chloralose + TX, endrin + TX, fenthion + TX, pyridin-4-amine and strychnine + TX,

[0134] A bactericide, the bactericide consisting of a substance selected from the group consisting of 1-hydroxy-1H-pyridine-2-thione+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bronopol+TX, copper dioctanoate+TX, copper hydroxide+TX, cresol+TX, dichlorophen+TX, dispyrithione+TX, dodesine+TX, fenaminosulf+TX, formaldehyde+TX, mercurophen+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, nickel bis(dimethyldithiocarbamate)+TX, nitrapyrin+TX, octhilinone+TX, oxolinic acid+TX, oxytetracycline+TX, potassium hydroxyquinoline sulfate+TX, probenazole+TX, streptomycin+TX, streptomycin sesquisulfate+TX, chlorpheniramine+TX, thiomersal+TX,

[0135] A biological agent, which is selected from the group consisting of the following substances: Adoxophyes orana GV+TX, Agrobacterium radiobacterium+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Autographa californica NPV+TX, Bacillus firmus+TX, Bacillus firmus+TX, Bacillus sphaericus Neide+TX, Bacillus thuringiensis+TX, Bacillus thuringiensis Berliner+TX, Bacillus thuringiensis.I (Bacillus thuringiensis subsp.aizawai)+TX, Bacillus thuringiensis subsp.israelensis, Bacillus thuringiensis subsp.israelensis+TX, Bacillus thuringiensis k.(Bacillus thuringiensis subsp.kurstaki)+TX, Bacillus thuringiensis t.(Bacillus thuringiensis subsp.tenebrionis+TX, Beauveria bassiana+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Cydia pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmoc eruseremicus+TX, Helicoverpa zea+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens)+TX, Leptomastix dactylopii parasitic wasp (Leptomastix dactylopii)+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer nuclear polyhedrosis virus and red-headed pine sawfly (Neodiprion sertifer) NPV+TX.lecontei nuclear polyhedrosis virus+TX, small flower stink bug+TX, Paecilomyces fumosoroseus+TX, Pasteuria penetrans+TX, Pasteuria thornei+TX, Pasteuria nishizawae+TX, Pasteuria ramosa+TX, Phytoseiulus persimilis+TX, Spodopteraexiguamulticapsid multinucleocapsid nuclear polyhedrosis virus+TX, Steinernema bibionis+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.)+TX, Trichogramma+TX, Typhlodromus occidentalis, and Verticillium lecanii+TX.

[0136] A soil disinfectant selected from the group consisting of methyl iodide and methyl bromide + TX,

[0137] A chemical sterilant selected from the group consisting of apholate + TX, bisazir + TX, busulfan + TX, diflubenzuron + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methylapholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, trothamide and urethaneimide + TX,

[0138] An insect pheromone, the insect pheromone is selected from the group consisting of: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol+TX, (E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX, (E,Z)-tetradec-4,10-dien-1-yl acetate+TX, (Z)-dodec-7-en-1-yl acetate+TX, (Z)-hexadec-11-enal+TX, (Z)-hexadec-11-en-1-yl acetate+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate+TX, (Z)-eicos-13-en-10-one+TX, (Z) -Tetradec-7-en-1-al+TX, (Z)-tetradec-9-en-1-ol+TX, (Z)-tetradec-9-en-1-yl acetate+TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate+TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate+TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate+TX, 14-methyloctadec-1-ene+TX, 4-methylnonanal-5-ol and 4-methylnonanal-5-one+TX, α-multistriatin+TX, western pine beetle gathering pheromone (brevicomin)+TX, dodecadienoyl alcohol (codlelu re)+TX, codlemone+TX, cuelure+TX, disparlure+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodec-8+TX, 10-dien-1-yl acetate+TX, dominicalure+TX, ethyl 4-methyloctanoate+TX, eugenol+TX, southern pine beetle gathering pheromone (frontalin)+TX, gossyplure+TX, grandlure+TX, grandlure mixture I+TX, grandlure mixture II+TX, Eugenol mixture III+TX, Eugenol mixture IV+TX, hexalure acetate+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoicacid+TX, methyleugenol+TX, muscalure+TX, octadeca-2,13-dien-1-yl acetate+TX, octadeca-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradecene-11-yl acetate + TX, tert-butyl ketone + TX, tert-butyl ketone A + TX, tert-butyl ketone B1 + TX, tert-butyl ketone B2 + TX, tert-butyl ketone C and trunc-call + TX,

[0139] An insect repellent selected from the group consisting of 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, DEET+TX, dimethylcarbate+TX, ethyl hexanediol+TX, hexylurea+TX, methoquin-butyl+TX, methyl neodecylamide+TX, oxamate, and hydroxybenzoate+TX,

[0140] An insecticide selected from the group consisting of: 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolane)methylcarbamate TX, 2-(4-chloro-3,5-xylyloxy)ethanol+TX, 2-chlorovinyl diethyl phosphate+TX, 2-imidazolidinone+TX, 2-isovalerylindan-1,3-dione+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate+TX, 2-thiocyanatoethyl laurate+TX, 3-bromo-1-chloroprop-1-ene+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+TX, avermectin+TX, acephate+TX, pyridinium chloride Amitraz + TX, domesticaphos + TX, acetofenapyr + TX, flumethrin + TX, acrylonitrile + TX, cotton boll carb + TX, aldicarb + TX, aldisulfone carb + TX, chlorfenapyr + TX, allethrin + TX, aloamicin + TX, cypermethrin + TX, α-cypermethrin + TX, α-ecdysone + TX, aluminum phosphide + TX, thiothion + TX, thioamide + TX, cypermethrin + TX, amimidone + TX, amimidone hydrogen oxalate + TX, amitraz + TX, neonicotinoid + TX, ethylmethidathion + TX, AVI382 + TX, AZ60541 + TX, azadirachtin + TX, methylpyriphos + TX, azinphos-methyl + TX, azinphos-methyl + TX, Bacillus thuringiensis Bacterial δ-endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, bendiocarb + TX, benfuracarb + TX, sulfanilamide + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bifenthrin + TX, bio-allethrin + TX, bio-allethrin S-cyclopentenyl isomer + TX, bioethanomethrin + TX, pyrethrin + TX, bis(2-chloroethyl) ether + TX, bistrifluan + TX, borax + TX, bromethrin + TX, bromophenirone + TX, bromo-DDT + TX,Bromophos + TX, bromophos-ethyl + TX, thiamethoxam + TX, buprofen + TX, thiamethoxam + TX, butathiofos + TX, butanone + TX, butyl phosphonate + TX, butanone sulfonate + TX, butyl pyridaben + TX, cadusafos + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, toxaphene + TX, chlormethoxam + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbon tetrachloride + TX, trithion + TX, butanone + TX, cartap + TX, cartap hydrochloride + TX, sivaldin + TX, bornyl + TX, chlordane + TX, chlorfenapyr + TX, chlordane + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chloroxyphos + TX, chlorfenapyr + TX, Fenpyridamole + TX, chlorpyrifos + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorpyrifos + TX, chlorpyrifos-methyl + TX, chlorpyrifos + TX, chlorfenapyr + TX, chlorpyrifos I + TX, chlorpyrifos II + TX, chlorfenapyr + TX, cis-resmethrin + TX, cis-resmethrin + TX, cypermethrin + TX, cypermethrin + TX, chlorfenapyr + TX, closantel + TX, clothianidin + TX, copper acetylarensite + TX, copper arsenate + TX, copper oleate + TX, coumaphos + TX, cypermethrin + TX, crotamiton + TX, baclofos + TX, clofosinate + TX, ice crystals Stone+TX, CS708+TX, benzonitrile+TX, cypermethrin+TX, carbofuran+TX, cypermethrin+TX, cyfluthrin+TX, cyhalothrin+TX, cypermethrin+TX, cypermethrin+TX, cyproconazole+TX, d-limonene+TX, d-tetramethrin+TX, DAEP+TX, dazomethon+TX, DDT+TX, decarbofuran+TX, deltamethrin+TX, tanafurphos+TX, tanafurphos-O+TX, tanafurphos-S+TX, entafurphos+TX, entafurphos-methyl+TX, entafurphos-O+TX, entafurphos-O-methyl+TX, entafurphos-S+TX, entafurphos-S-methyl+TX, entafurphos- S-methyl sulfone + TX, diafenthiuron + TX, chlorophos + TX, diamidophos + TX, diazinon + TX, isochlorophos + TX, dimethoate + TX, dichlorvos + TX, dicliphos + TX, dicresyl + TX, dicrotophos + TX, dichlorvos + TX, dichlorvos + TX, dichlorvos + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diflubenzuron + TX, diprophylline (dilor) + TX, tetrafluthrin + TX, methylphos + TX, dimethoate + TX, dimethoate + TX, pyrethrin + TX, methylchlorfenapyr + TX, dichlorvos + TX, dimethoate ...Dinotefuran+TX, fenthiocarb+TX, vesiculophos+TX, dioxocarb+TX, dimethoate+TX, dithiophos+TX, dithiophos+TX, DNOC+TX, doramectin+TX, DSP+TX, ecdysone+TX, EI1642+TX, avermectin+TX, avermectin benzoate+TX, EMPC+TX, fenthrin+TX, endosulfan+TX, endophos+TX, endrin+TX, EPBP+TX, EPN+TX, fenvalerate+TX, eprinomectin+TX, esfenvalerate+TX, etaphos+TX, ethiofencarb+TX, ethiophos+TX, ethiprole+TX , methyl thiophanate + TX, ethoxyproline + TX, ethyl formate + TX, ethyl-DDD + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, ethomethrin + TX, ethomethrin + TX, EXD + TX, sulfamethoxam + TX, fenamiphos + TX, anti-mite azole + TX, pyraclostrobin + TX, fenfluramine + TX, fenitrothion + TX, fenthiocarb + TX, fenfluramine + TX, fenfencarb + TX, fenoxacrim + TX, fenoxycarb + TX, cypermethrin + TX, cypermethrin + TX, fenpyrad + TX, fenthion + TX, fenthion + TX, fenthion-ethyl + TX, cypermethrin + TX, fipronil + TX, flonicamid + T X, flubendiamide [272451-65-7] + TX, flucofuron + TX, flucythrin + TX, flucythrin + TX, flufluanid + TX, flufenoxam + TX, flufenoxuron + TX, flucythrin + TX, fluvalinate + TX, FMC1137 + TX, flufenophos + TX, flufenophos + TX, flufenophos hydrochloride + TX, anthiophos + TX, formparanate + TX, butylfenthion + TX, forspiramate + TX, thiabendazole + TX, butylthiophos + TX, furathiocarb + TX, pyrethroid + TX, γ-cyhalothrin + TX, γ-HCH + TX, biguanide salt + TX, biguanide acetate + TX, GY- 81+TX, benzyl azomethin + TX, chlorfenapyr + TX, HCH+TX, HEOD+TX, Feibuda+TX, heptenophos+TX, cypermethrin+TX, hexaflumuron+TX, HHDN+TX, hydrazone+TX, hydrocyanic acid+TX, methoprene+TX, hyquincarb+TX, imidacloprid+TX, imiprofen+TX, indoxacarb+TX, iodomethane+TX, IPSP+TX, chlorfenapyr+TX, carbofuran+TX, isocarbophos+TX, isothrin+TX, isofenol+TX, transplanting spirit+TX, isoprocarb+TX, O-(methoxyaminothiophosphoryl) salicylic acid isopropyl ester+TX, blastifungin+TX, isosulfanthate+TX, oxathiophos+TX, ivermectin+TX,Jasmonate I + TX, Jasmonate II + TX, Iodonate + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Chlorpentyl + TX, Methoprene + TX, λ-Cyhalothrin + TX, Lead Arsenate + TX, Lepidomicil + TX, Parabromophos + TX, Lindan + TX, Lirimfos + TX, Lufenuron + TX, Thiamethoxam + TX, Metamifenta + TX, 3-Isopropylphenyl Methylcarbamate + TX, Magnesium Phosphide + TX, Malathion + TX, Tebuconazole + TX, Azide + TX, Methiophos + TX, Tetramethylphos + TX, Methiophos + TX, Dimethoate + TX, Mercurous Chloride + TX, Mesulfenfos + TX, Metaflumizone + TX, Metamifenta + TX, Metamex Potassium + TX, Metamex Sodium + TX, Acarb + TX, Methamidophos + TX, Methanesulfonyl Fluoride + TX, Methiocarb + TX, Methiocarb + TX, Ethiocarb + TX, Metomycin + TX, Methoprene + TX, Mequindox + TX, Methothrin + TX, Methoxychlor + TX, Methoxybenzoyl + TX, Methyl Bromide + TX, Methyl Isothiocyanate + TX, Methyl Chloroform + TX, Dichloromethane + TX, Metofluthrin + TX, Methiocarb + TX, Methiocarb + TX, Methiocarb + TX, Zikwei + TX, Mimbetin + TX, Milbemycin + TX, Propylamidophos + TX, Mirex + TX, Monocrotophos + TX, Methosulfate + TX, Moxidectin + TX, Naphthylphos + TX, Dibromophos + TX X, naphthalene + TX, NC-170 + TX, NC-184 + TX, nicotine + TX, nicotine sulfate + TX, fluazifop + TX, nitenpyram + TX, nitrilotriazole + TX, pentocyanamide + TX, pentocyanamide 1:1 zinc chloride complex + TX, NNI-0101 + TX, NNI-0250 + TX, nornicotine + TX, flubendiamide + TX, noviflumuron + TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-ylphosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate + TX, O,O, O',O'-Tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, omethoate + TX, oxamyl + TX, sulfone-methyl + TX, isosulfoxon + TX, sulfone-methyl + TX, pp'-DDT + TX, p-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, chlorfenuron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, permethrin + TX, petroleum oils + TX, PH60-38 + TX, fenthion + TX, phenothrin + TX, pyralid + TX, phorate + TX, phosalone + TX, thiophanate + TX, phosmet + TX, parachlorophos + TX, phosphamidon + TX, phosphine + TX, phoxim + TX, phoxim-methyl + TX,pirimetaphos+TX, pirimetaphos+TX, cypermethrin-ethyl+TX, cypermethrin-methyl+TX, polychlorodicyclopentadiene isomers+TX, polychloroterpenes+TX, potassium arsenite+TX, potassium thiocyanate+TX, propylthioate+TX, precocious phos I+TX, precocious phos II+TX, precocious phos III+TX, acetyl pyrimidophos+TX, profenofos+TX, profluthrin+TX, cypermethrin+TX, pyrimidazopyr+TX, fenflurphos+TX, propoxur+TX, propanil+TX, ethiazole+TX, prothiophos+TX, thiophos+TX, protrifenbute+TX, pymetrozine+TX, pyraclostrobin+TX, pyrazophos+TX, pyrazophos-pyrimidophos (p pyrafluprole) + TX, pyrethrin + TX, pyresmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaben + TX, pyridaflufen + TX, pyrimidin + TX, pyrimidin + TX, pyriproxyfen + TX, pyriproxyfen + TX, quassia extract + TX, quinalphos + TX, quinalphos-methyl + TX, quintiofos + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, RU15525 + TX, RU25475 + TX, Niana (r Yania) + TX, ryanodine + TX, sabaveratrol + TX, octamethrin + TX, cadusafos + TX, selamectin + TX, SI-0009 + TX, SI-0205 + TX, SI-0404 + TX, SI-0405 + TX, flutosan + TX, SN72129 + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, threonylthion + TX, spinosad + TX, spiromesifen + TX, spirotetramat + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfluramid + TX, thiamethoxam + TX, sulfonyl fluoride + TX X, thiopromide + TX, tars + TX, τ-fluvalinate + TX, thiamethoxam + TX, TDE + TX, tebufenozide + TX, tebufenpyrad + TX, butylpyrimidophos + TX, tefluthrin + TX, tebufenox + TX, TEPP + TX, cypermethrin + TX, terbam + TX, terbufos + TX, tetrachloroethane + TX, cypermethrin + TX, θ-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thicrofos + TX, cyfluthrin + TX, cyfluthrin hydrogen oxalate + TX, thiodicarb + TX, long-lasting carb + TX, methyl thiosulfate + TX, cyfluthrin + TX,Thiosultap+TX, thiosultap-sodium+TX, thuringin+TX, tolfenpyrad+TX, tralomethrin+TX, transfluthrin+TX, transpermethrin+TX, cypermethrin+TX, triazophos+TX, triazophos+TX, trichlorfon+TX, trichlormetaphos-3+TX, chlorpyrifos+TX, trichlorprop+TX, triflumuron+TX, thiocarb+TX, methoprene+TX, aphidoxime+TX, vaniliprole+TX, veratridine+TX, veratridine+TX, XMC+TX, methoprene+TX, YI-5302+TX, ζ-cypermethrin+TX, zetamethrin+TX, zinc phosphide+TX, zolaprofos, and ZXI8901+TX, cyantraniliprole[7369 94-63-19]+TX, chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX, cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX, spinetoram [187166-40-1+1871 66-15-0]+TX, spirotetramat[203313-25-1]+TX, sulfoxaflor[946578-00-3]+TX, flufiprole[704886-18-0]+TX, chlorfenapyr[915288-13-0]+TX, tetramethylfluthrin[84937-88-2]+TX,

[0141] A molluscicide selected from the group consisting of di(tributyltin) oxide + TX, bromoacetamide + TX, calcium arsenate + TX, cloethocarb + TX, copper acetyl arsenite + TX, copper sulfate + TX, triphenyltin + TX, ferric phosphate + TX, metaldehyde + TX, methiocarb + TX, niclosamide + TX, niclosamide ethanolamine + TX, pentachlorophenol + TX, sodium pentachlorophenoxide + TX, tazimcarb + TX, thiodicarb + TX, tributyltin oxide + TX, trifenmorph + TX, trimethacarb + TX, triphenyltin acetate and triphenyltin hydroxide + TX, pyriprole + TX,

[0142] A nematicide, the nematicide is selected from the group consisting of the following substances: AKD-3088+TX, 1,2-dibromo-3-chloropropane+TX, 1,2-dichloropropane+TX, 1,2-dichloropropane and 1,3-dichloropropylene+TX, 1,3-dichloropropylene+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thio-1,3,5-Thiadiazin-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, avermectin + TX, acetofenapyr + TX, doxorubicin + TX, aldicarb + TX, aldoxycarb + TX, AZ60541 + TX, benclothiaz + TX, benclothiaz + TX, butylpyridaben + TX, cadusafos + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, chloropicrin + TX, chlorpyrifos + TX, cloethocarb + TX, cytokinins + TX, dazomet + TX, DBCP + TX, DCIP + TX, diamidafos + TX, dichlofenthion + TX, dicliphos + TX, dimethoate +TX, imastatin +TX, imastatin benzoate +TX, eprinomectin +TX, eprinomectin +TX, ethoprophos +TX, ethylene dibromide +TX, fenamiphos +TX, tebufenpyrad +TX, fenpyrad +TX, fosthiazate +TX, fosthietan +TX, furfural +TX, GY-81 +TX, heterophos +TX, iodomethane +TX, isamidofos +TX, isazofos +TX, kinetin +TX, mecarphon +TX, mecarphon +TX, metamifene +TX, metamifene potassium +TX, metamifene sodium +TX, methyl bromide +TX, methyl isothiocyanate +TX, milbemycin oxime oxime) + TX, moxidectin + TX, Myrothecium verrucaria component + TX, NC-184 + TX, oxamyl + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, sebufos + TX, selamectin + TX, spinosad + TX, terbam + TX, terbufos + TX, tetrachlorothiophene + TX, thiafenox + TX, thionazin + TX, triazophos + TX, triazuron + TX, xylenol + TX, YI-5302 and zeatin + TX, fluensulfone [318290-98-1] + TX,

[0143] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate and nitrapyrin + TX,

[0144] A plant activator selected from the group consisting of acibenzolar+TX, acibenzolar-S-methyl+TX, probenazole, and Reynoutria sachalinensis extract+TX.

[0145] A rodenticide, the rodenticide is selected from the group consisting of: 2-isovaleryl indane-1,3-dione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, α-chlorohydrin + TX, aluminum phosphide + TX, antoxin + TX, arsenic trioxide + TX, barium carbonate + TX, bifenthionine + TX, brodifacoum + TX, brodifacoum + TX, calcium cyanide + TX, azotobactone + TX, chlorofacitin + TX, vitamin D3 + TX, chlorfenapyr ... Sodium thiazolin + TX, vitamin D2 + TX, fludioxaline + TX, fluoroacetamide + TX, thiazolin + TX, thiazolin hydrochloride + TX, β-HCH + TX, HCH + TX, hydrocyanic acid + TX, iodomethane + TX, lindane + TX, magnesium phosphide + TX, methyl bromide + TX, thiazolin + TX, phosphine + TX, phosphorus + TX, warfarin + TX, potassium arsenite + TX, warfarin + TX, scilla glycoside + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, thallium sulfate + TX, warfarin and zinc phosphide + TX,

[0146] A synergist selected from the group consisting of: 2-(2-butoxyethoxy)ethyl piperonyl ester+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone+TX, farnesol with nerolidol+TX, MB-599+TX, MGK264+TX, piperonyl butoxide+TX, piprotal+TX, propylisomer+TX, S421+TX, sesamex+TX, sesasmolin and sulfoxide+TX,

[0147] An animal repellent selected from the group consisting of anthraquinone + TX, chloralose + TX, copper naphthenate + TX, copper oxychloride + TX, diazinon + TX, dicyclopentadiene + TX, guazatine + TX, guazatine acetate + TX, methiocarb + TX, pyridin-4-amine + TX, salamine + TX, trimethacarb + TX, zinc naphthenate, and ziram + TX.

[0148] A virucide selected from the group consisting of imanin and ribavirin+TX,

[0149] A wound protective agent, selected from the group consisting of mercuric oxide + TX, octhilinone and methyl thiophanate + TX,

[0150] and a biologically active compound selected from the group consisting of: azaconazole (60207-31-0] + TX, bifenthiazolin [70585-36-3] + TX, oxadiazol [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, fluoxepiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexamethylenetetracycline Alcohol [79983-71-4] + TX, imazalil [35554-44-0] + TX, imidazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pyrifenox [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, silfenazole (s imeconazole) [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, fluconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimefon [55219-65-3] + TX, triflumuron [99387-89-0] + TX, trichlorfonazole [131983-72-7] + TX, tricyclamide [12771-68-5] + TX, chlorfenapyr [60168-88-9] + TX, fluchlorapyramide [63284-71-9] + TX, bupirimate [41483-43-6] + TX, mefenamic acid (dimethirimol) [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodecacyclic morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxafil [118134-30-8] + TX, tridecafil [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, pyrimidine [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX,Flunix [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, furamide [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacar b) [62732-91-6] + TX, chloranil [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58-9] + TX, Iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid ( boscalid)[188425-85-6]+TX、Carboxin[5234-68-4]+TX、Furoxanilide[24691-80-3]+TX、Flutolanil[66332-96-5]+TX、Methiopyrad[55814-41-0]+TX、Oxycarboxin[5259-88-1]+TX、Penthiopyrad[183675-82-3]+TX、Thiopyrad[130000-40-7]+TX、Biguanide[108173-90-6]+TX、Dodine[2439-10-3][112-65-2](free bond)+ TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, etherstrobin [149961-52-4] + TX, enestrobin {Proc. BCPC, Int. Congr., Glasgow. 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX methyl etherstrobin [143390-89-0] + TX, oxazolidinone [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, trifloxystrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX,Pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, salamine [137-26-8] + TX, maneb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, difluanid [1085-98-9] + TX, oxazolidinone (f luoroimide) [41205-21-4] + TX, folpet [133-07-3] + TX, toluenesulfonamide [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide (copperhydroxid) [20427-59-2] + TX, copper chloride (copperoxychlorid) [1332-40-7] + TX, copper sulfate (coppersulfat) [7758-98-7] + TX, copper oxide (copperoxid) [1317-39-1] + TX, mancopper (mancopper) [539 88-93-5]+TX, oxine-copper[10380-28-6]+TX, dinocap[131-72-6]+TX, nitrothal-isopropyl[10552-74-6]+TX, kewensan[17109-49-8]+TX, iprobenphos[26087-47-8]+TX, isoprothiol[50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos[13 457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl[135158-54-2]+TX, difop-butyl[101-05-3]+TX, benzthiazolin[413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat[2439-01-2]+TX, chloroneb[2675-77-6]+TX, chlorothalonil[1897-45-6]+TX,Cyfluanid [180409-60-3] + TX, Cymoxanil [57966-95-7] ​​+ TX, Dichloronaphthoquinone [117-80-6] + TX, Diclocymet [139920-32-4] + TX, Diclomezine [62865-36-5] + TX, Dicloran [99-30-9] + TX, Diethofencarb [87130-20-9] + TX, Dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX , dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [ 79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide[106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium[39148-24-8]+TX, hymexazol[10004-44-1]+TX, propineb[140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin n) [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, mefenacet [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX,Pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, pentachloronitrobenzene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiazolin [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triamcinol [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281 )[156052-68-5]+TX, mandipropamid[374726-62-2]+TX, isopyrazam[881685-58-1]+TX, sedaxane[874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (disclosed in WO2007 / 048556)+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4- Carboxylic acid [2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-amide (disclosed in WO2008 / 148570) + TX, 1-[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl]piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone + TX, 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl]piperidin-1-yl]-2 -[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone [1003318-67-9], both disclosed on page 20 of WO2010 / 123791, WO2008 / 013925, WO2008 / 013622 and WO2011 / 051243) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-diphenyl-2-yl)-amide (disclosed in WO2006 / 087343) + TX, and 1-methyl-2-(2,4,5-trichloro-thiophen-3-yl)-ethyl] + TX.

[0151] References in square brackets after the active ingredient, such as [3878-19-1], refer to Chemical Abstracts registration numbers. The mixing partners described above are known. For example, they are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th Edition; Editor: CDS Tom Lin; The British Crop Protection Council] or in the "Compendium of Pesticide Common Names".

[0152] Most of the active ingredients mentioned above are referred to above by the so-called "common name", the related "ISO common name" or, in individual cases, another "common name". If the name is not a "common name", the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "traditional name", "compound name", or "development code" is used, or if neither one of these names nor the "common name" is used, an "alternative name" is used.

[0153] The mass ratio of any two ingredients in each combination is selected to give the desired, for example, synergistic effect. In general, the mass ratio will vary depending on the specific ingredients and how much of the ingredient is present in the combination. In general, the mass ratio between the two ingredients in any combination of the present invention is independently from one another from 100:1 to 1:100, including from 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:2 0, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:45, 64:46, 63:47, 62:48, 61:49, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:4 6、53:47、52:48、51:49、50:50、49:51、48:52、47:53、46:54、45:55、44:56、43:57、42:58、41:59、40:60、39:61、38:62、37:63、36:64、35:65、34:66、33:67、32:68、31:69、30:70、29:71、28: 72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21:79, 20:80, 19:81, 18:82, 17:83, 16:84, 15:85, 14:86, 13:87, 12:88, 11:89, 10:90, 9:91, 8:92, 7:93, 6:94, 5:95, 4:96, 3:97, 2:98 to 1:99. The preferred mass ratio between any two components of the present invention is from 75:1 to 1:75, more preferably 50:1 to 1.50, especially 25:1 to 1:25, advantageously 10:1 means 1:10, such as 5:1 to 1:5, for example 1:3 to 3:1. These mixing ratios are understood to include, on the one hand, mass ratios and, on the other hand, molar ratios.

[0154] Examples of methods of application of the compounds and compositions of the present invention, i.e. methods of controlling pests / fungi in agriculture, are spraying, misting, dusting, brushing, seed dressing, broadcasting or pouring - which are selected to suit the intended purpose under the prevailing circumstances.

[0155] A preferred method of application in agriculture is application to the leaves of the plants (foliar application), it being possible to select the frequency and rate of application in accordance with the risk of infection by the pest / fungus in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action) by applying the compound to the locus of the plants, for example, by applying a liquid composition of the compound to the soil (by drench) or by applying the compound in solid form in the form of granules to the soil (soil application). In the case of rice plants, such granules can be metered into flooded paddies.

[0156] The application rates per hectare are generally 1 g to 2000 g of active ingredient per hectare, in particular 10 g / ha to 1000 g / ha, preferably 10 g / ha to 600 g / ha, such as 50 g / ha to 300 g / ha.

[0157] These compounds of the present invention and composition thereof are also suitable for the protection (for example seed, such as fruit, tuber or grain, or nursery plant) of plant propagation material against the harmful organism of above-mentioned type.This propagation material can be processed with this compound before planting, and for example seed can be processed before sowing.Alternately, this compound can be applied to seed grain (coating), and this is by being immersed in liquid composition by grain or by applying a kind of solid composition layer and realize.When this propagation material is planted in the application site, it is also possible for example to apply these compositions to seed furrow during drilling.These treatment methods for plant propagation material and the plant propagation material therefore processed are other themes of the present invention.Typically, treatment rate will depend on plant and harmful organism / fungus to be controlled, usually between 1 gram to 200 grams of every 100kg seeds, preferably between 5 grams to 150 grams of every 100kg seeds, as between 10 grams to 100 grams of every 100kg seeds.

[0158] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in a preferred embodiment refers to true seeds.

[0159] The present invention also includes seeds coated with or treated with a compound of formula I or containing a compound of formula I. The term "coated with or treated with and / or containing" generally means that in most cases the active ingredient is on the surface of the seed when applied, although a greater or lesser portion of the ingredient may penetrate into the seed material, depending on the method of application. When the seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention makes available a plant propagation material having a compound of formula I adhered thereto. In addition, a composition comprising plant propagation material treated with a compound of formula I is thereby available.

[0160] Seed treatment includes all applicable seed treatment techniques known in the art, such as, seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with the compound of formula I can be achieved by any known method and used, such as, before sowing the seeds or during sowing / planting, spraying or by dusting.

[0161] Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar beets or fodder beets; fruit, such as pome, stone or stoneless fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, such as strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oilseed plants, such as rapeseed, mustard, chestnuts, olives, sunflowers, coconuts, castor beans, cocoa or peanuts; cucurbit crops, such as pumpkins, cucumbers or melons; Fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as oranges, lemons, grapevines, or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; plants of the Lauraceae family, such as avocado, Cinnamonium, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantaginaceae, rubber plants, and ornamental plants (e.g., flowers and lawn plants or turf).

[0162] In one embodiment, the plant is selected from the group consisting of cereals, corn, soybeans, rice, sugarcane, vegetables, and oil plants.

[0163] The term "plants" is to be understood as also including plants transformed by the use of recombinant DNA techniques and which are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular Bacillus.

[0164] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus subtilis or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of nematode symbiotic bacteria, for example Photorhabdus or Xenorhabdus, such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins; plant lectins, such as pea lectin, barley lectin or snowdrop lectin; lectins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, pyrin ... Protease inhibitors, potato storage protein (patatin), cysteine ​​protease inhibitors, papain inhibitors; ribosome inactivating protein (RIP), such as ricin, corn-RIP, abrin, luffa seed toxin, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0165] In the context of the present invention, delta-endotoxins such as Cry1Ab, Cry1Ac, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3 or Vip3A, should be understood to include, but are not limited to, mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by combining different regions of those proteins (see, for example, WO02 / 15701). Truncated toxins such as truncated Cry1Ab are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO03 / 018810).

[0166] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0374753, WO 93 / 07278, WO 95 / 34656, EP-A-0427529, EP-A-451878 and WO 03 / 052073.

[0167] Methods for preparing such transgenic plants are known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0367474, EP-A-0401979 and WO 90 / 13651.

[0168] The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects may be found in any insect taxonomic group, but are particularly commonly found in beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0169] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available.

[0170] Typically, the compounds of the invention are used in the form of a composition (eg, a formulation) comprising a carrier. The compounds of the present invention and their compositions can be used in different forms, for example, aerosol sprayers, capsule suspensions, cold atomization concentrates, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, capsule granules, fine granules, flowable concentrates for seed treatment, gases (under pressure), gas-generating products, granules, hot atomization concentrates, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, pastes, plant sticks, powders for dry seed treatment, seeds coated with pesticides, soluble concentrates, soluble powders, solutions for seed treatment, suspension concentrates (flowable concentrates), ultra-low volume (ulv) liquids, ultra-low volume suspensions (ulv), water-dispersible granules or tablets, water-dispersible powders for slurry treatment, water-soluble granules or tablets, water-soluble powders for seed treatment, and wettable powders.

[0171] A formulation typically comprises a liquid or solid carrier and optionally one or more conventional formulation adjuvants, which may be solid or liquid adjuvants, such as non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil, or soybean oil), defoamers, such as silicone oils, preservatives, clays, inorganic compounds, viscosity modifiers, surfactants, binders, and / or tackifiers. The composition may further comprise a fertilizer, micronutrient donor, or other product that influences plant growth, and includes a combination comprising a compound of the invention and one or more other bioactive agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.

[0172] The present invention therefore also makes available a composition comprising a compound according to the invention together with an agronomic carrier and optionally one or more customary formulation auxiliaries.

[0173] These compositions are prepared with methods known per se, for example by grinding, screening and / or squeezing solid compounds of the present invention and in the presence of at least one auxiliary agent, for example by closely mixing and / or grinding the compound of the present invention with one or more auxiliary agents. In the case of solid compounds of the present invention, the grinding / grinding of the compound is in order to ensure a specific particle size. The methods for preparing these compositions and the purposes of these compounds of the present invention for preparing these compositions are also a theme of the present invention.

[0174] Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or capsules in a polymeric mass, these compositions comprising at least one compound according to the invention and the type of composition being chosen to suit the intended purpose and the prevailing circumstances.

[0175] Examples of suitable liquid carriers are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8 to C 12 alkylbenzene moieties, such as xylene mixtures, alkylated naphthalenes or tetralins, aliphatic or alicyclic hydrocarbons, such as paraffin or cyclohexane, alcohols, such as ethanol, propanol or butanol, ethylene glycol and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or hexanediol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolidin-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, non-epoxidized or epoxidized vegetable oils, such as non-epoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oils.

[0176] Examples of solid carriers for example dusts and dispersible powders are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite normally. In order to improve physical properties, it is also possible to add highly dispersed silica or highly dispersed absorbent polymers. Suitable particle adsorptive carriers for granules are porous, such as pumice, gravel, sepiolite or bentonite, and suitable non-absorptive carrier materials are calcite or sand. In addition, a large amount of granulated materials of inorganic or organic natural materials can be used, particularly dolomite or pulverized plant residues.

[0177] Depending on the type of active ingredient to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are to be regarded only as examples; a large number of other surfactants conventionally used in the field of formulations and suitable according to the present invention are described in the relevant literature.

[0178] Suitable nonionic surfactants are, in particular, polyethylene glycol ether derivatives of aliphatic or cycloaliphatic alcohols, polyethylene glycol ether derivatives of saturated or unsaturated fatty acids or polyethylene glycol ether derivatives of alkylphenols, which may contain from about 3 to about 30 glycol ether groups and from about 8 to about 20 carbon atoms in the (cyclo)aliphatic hydrocarbon residue or from about 6 to about 18 carbon atoms in the alkyl portion of the alkylphenol. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkylpolypropylene glycols having from 1 to about 10 carbon atoms in the alkyl chain and from about 20 to about 250 glycol ether groups and from about 10 to about 100 propylene glycol ether groups. Typically, the above compounds contain from 1 to about 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonoxynol, castor oil polyethylene glycol ether, polypropylene glycol / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

[0179] These cationic surfactants are in particular quaternary ammonium salts which generally have at least one alkyl residue (from about 8 to about 22 carbon atoms) as a substituent and (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl residues as further substituents. These salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

[0180] Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are alkali metal salts, alkaline earth metal salts, or (unsubstituted or substituted) ammonium salts of fatty acids having from about 10 to about 22 carbon atoms, such as the sodium or potassium salts of oleic acid or stearic acid, or natural fatty acid mixtures (obtainable, for example, from coconut oil or tall oil); mention should also be made of the fatty acid methyltaurine. However, synthetic surfactants are more commonly used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives, or alkylarylsulfonates. These fatty sulfonates and fatty sulfates are usually alkali metal salts, alkaline earth metal salts, or (substituted or unsubstituted) ammonium salts and usually have alkyl residues having from about 8 to about 22 carbon atoms, alkyl also being understood as an alkyl moiety including acyl residues; examples that may be mentioned are the sodium or calcium salts of ligninsulfonic acid, the sodium or calcium salts of lauryl sulfate, or the sodium or calcium salts of fatty alcohol sulfate mixtures prepared from natural fatty acids. This group also includes sulfates and sulfonates of fatty alcohol / ethylene oxide adducts. These sulfonated benzimidazole derivatives preferably contain two sulfonyl groups and fatty acid residues of about 8 to about 22 carbon atoms. Examples of alkylarylsulfonates are sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid / formaldehyde condensates. In addition, suitable phosphates, such as the phosphate esters of p-nonylphenol / (4-14)ethylene oxide adducts, or phospholipids are also possible.

[0181] Typically, these compositions comprise from 0.1% to 99% (in particular from 0.1% to 95%) of a compound according to the invention and from 1% to 99.9% (in particular from 5% to 99.9%) of at least one solid or liquid carrier, it being possible in principle for 0% to 25% (in particular from 0.1% to 20%) of the composition to be a surfactant (in each case % denotes percentage by weight). However, for commercial purposes, concentrated compositions are generally preferred, the end user in principle using diluted compositions having a significantly lower concentration of active ingredient.

[0182] Examples of suitable formulation types for tank mix compositions are solutions, dilute emulsions, suspensions or mixtures thereof, and dusts.

[0183] As to the nature of the formulations, the methods according to the invention, such as foliage, drench, spraying, atomizing, dusting, spreading, coating or pouring, may be chosen according to the intended purposes and the prevailing circumstances.

[0184] Such tank-mix compositions are generally prepared by diluting one or more premix compositions containing different pesticides and, optionally, additional adjuvants with a solvent (eg, water).

[0185] Suitable carriers and adjuvants can be solid or liquid and are the substances customary in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, extenders, binders or fertilizers.

[0186] Generally, tank-mix formulations for foliar or soil application comprise 0.1% to 20%, especially 0.1% to 15%, of the desired ingredients and 99.9% to 80%, especially 99.9% to 85%, of solid or liquid adjuvants (including, for example, a solvent such as water), which may be a surfactant in an amount of 0 to 20%, especially 0.1% to 15%, based on the tank-mix formulation.

[0187] Typically, premix formulations for foliar application comprise 0.1% to 99.9%, in particular 1% to 95%, of the desired ingredient and 99.9% to 0.1%, in particular 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), whereby the adjuvants may be a surfactant, in an amount of 0 to 50%, in particular 0.5% to 40%, based on the premix formulation.

[0188] Typically, tank mix formulations for seed treatment applications comprise 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of solid or liquid adjuvants (including, for example, a solvent such as water), where the adjuvant can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank mix formulation.

[0189] Typically, premix formulations for seed treatment applications comprise 0.5% to 99.9%, especially 1% to 95% of the desired ingredients, and 99.5% to 0.1%, especially 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), where the adjuvants can be a surfactant, in an amount of 0 to 50%, especially 0.5% to 40%, based on the tank mix formulation.

[0190] While commercial products are preferably formulated as concentrates (eg, pre-mix compositions (formulations)), end users typically employ diluted formulations (eg, tank mix compositions).

[0191] Preferred seed treatment premix formulations are aqueous suspension concentrates. This formulation can be applied to the seed using conventional processing techniques and machines, such as fluidized bed technology, drum grinding method, static rotation (rotostatic) seed processor and drum applicator. Other methods, such as spouted bed, can also be useful. These seeds can be pre-coated with glue before coating. After coating, these seeds are typically dried and then transferred to a glue coating machine for coating. Such methods are well known in the art.

[0192] Generally, the premix composition of the invention comprises 0.5 to 99.9% by mass, in particular 1 to 95%, advantageously 1 to 50% by mass of the desired ingredients, and 99.5 to 0.1%, in particular 99 to 5% by mass of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the auxiliary agents (or adjuvants) may be a surfactant in an amount of 0 to 50%, in particular 0.5 to 40%, by mass, based on the premix formulation.

[0193] In a preferred embodiment, independent of any other embodiment, the compound of formula I, I', I" or I'" is in the form of a composition for treating (or protecting) plant propagation material, wherein the composition for protecting plant propagation material further comprises a colorant. The composition or mixture for protecting plant propagation material may also comprise at least one copolymer from water-soluble and water-dispersible film-forming polymers that improve the attachment of the active ingredient to the treated plant propagation material, the polymers generally having an average molecular weight of at least 10,000 to about 100,000.

[0194] The combinations of the invention (ie, those comprising a compound of the invention and one or more additional biologically active agents) may be administered simultaneously or sequentially.

[0195] In this case, the components of a combination are administered sequentially (i.e., one by one), and the components are administered sequentially within a reasonable period relative to each other to achieve the biological effect, such as within a few hours or days. The order in which the components of the combination are administered, i.e., whether the compound of formula I should be administered first, is not critical for practicing the present invention.

[0196] In the case where the ingredients of the combination are applied simultaneously in the present invention, they may be applied as a composition comprising the combination, in which case (A) the compound of formula I and one or more ingredients of the combination may be obtained from a separate formulation source and mixed together (referred to as a tank mix, ready-to-use, spray broth or slurry), or (B) the compound of formula I and one or more ingredients of the combination may be sourced as separate formulation mixtures (referred to as a premix, i.e., mixture, concentrate or formulated product).

[0197] In one embodiment, independently of other embodiments, a compound according to the invention is administered as a combination. Thus, the present invention also provides a composition comprising a compound according to the invention as described herein, one or more other bioactive agents and optionally one or more conventional formulation adjuvants; the composition may be in the form of a tank mix or premix composition.

[0198] As an alternative to actual synergistic effects with biological activity, the combinations according to the invention may have unexpectedly advantageous properties which may be desirable as synergistic activities in a broader sense. Examples of such advantageous properties which may be mentioned are: favorable behavior during formulation and / or application (e.g., when grinding, sieving, emulsifying, dissolving or dispersing); increased storage stability, improved photostability; more favorable degradability; improved toxicological and / or ecotoxicological behavior; or other advantages familiar to those skilled in the art.

[0199] The compounds of the invention are preferably used as a nematicide in agriculture.

[0200] The compounds of the present invention may also find application in other areas, such as one or more of the following: protection of stored goods and storage rooms, protection of raw materials (such as wood panels, textiles), floor coverings and buildings, and in hygiene management - especially protection of humans, livestock, and productive livestock against harmful organisms. The present invention thus also makes available pesticidal compositions and methods for such uses. Such compositions for specific uses will need to be modified, and one of ordinary skill will be able to make such compositions available for any specific use.

[0201] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0202] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings from insect attack. The compositions according to the invention can be used, for example, to combat the following pests: beetles, such as the American house beetle, the hairy green tiger beetle, the furniture beetle, the death beetle, Ptilinuspecticornis, Dendrobium pertinex, the fine-toothed fork-tailed beetle, Priobium carpini, the brown powder beetle, the African powder beetle, the southern powder beetle, the flat-stomached beetle, the soft-haired powder beetle, the flat-legged powder beetle, the scale-haired powder beetle, the wood beetle, the wood beetle, the black beetle, the red-bellied oak beetle, the brown heteroptera beetle, the two-spined beetle and the bamboo beetle, and also members of the Hymenoptera, such as the blue-black wood beetle, the giant wood beetle, the Taiga wood beetle and Urocerus augu, and termites such as the yellow-necked wood termite, the hemp-headed sand-mound termite, the Indian and Pakistani structural wood termite, the yellow-limbed Reticulitermes, the Sant's Reticulitermes, the European Reticulitermes, the Das-like termite, the Nevadan termite and the Formosan termite, as well as wingless insects such as silverfish.

[0203] Methods for applying a compound or a combination thereof to stored goods, storage rooms, raw materials (such as wood panels and textiles), floor coverings and buildings, and in hygiene management are known in the art.

[0204] The present invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals (including humans and fish) against infestations and infections caused by helminths, arachnids and arthropod endo- and ectoparasites, which method comprises administering or applying orally, topically or parenterally to the animal an anthelmintic, acaricidal or endo- or ectoparasiticidal amount of a compound of formula I.

[0205] The above method is particularly useful for controlling and preventing infestations and infections caused by helminths, nematodes, mites and endo- and ectoparasites in warm-blooded animals such as cattle, sheep, pigs, camels, deer, horses, poultry, fish, rabbits, goats, mink, fox, chinchillas, dogs and cats, as well as humans.

[0206] In the context of controlling and preventing infestation and infection in warm-blooded animals, the compounds of the present invention are particularly useful for controlling helminths and nematodes. Examples of helminths are members of the class Trematoda, commonly referred to as flukes or flatworms, especially members of the genera Fasciola, Pseudomonas, Homochaetes, Diplochaetes, Ophisthorchis, Fasciola, Echinostoma, and Paragonimus. Nematodes that can be controlled by compounds of formula I include Haemonchus, Osterleghorn, Cooperia, Oesphagastomu, Nematode, Dictyocaulus, Trichuris, Dirofilaria, Ancyclostoma, Ascaris, and similar genera.

[0207] The compounds of the present invention can also control infestations of endoparasitic arthropods, such as the larvae of the skin flies and the gastropod bots. In addition, ectoparasitic infestations of mites and arthropods in warm-blooded animals and fish, including biting lice, sucking lice, botflies, biting flies, muscoid flies, flies, myiasitic fly larvae, gnats, mosquitoes, fleas, mites, ticks, nasal bots, sheep bots, and chiggers, can be controlled, prevented, or eliminated by the compounds of the present invention. Biting lice include members of the order Trichophagus, such as the bovine hair louse, the dog hair louse, and the sheep wool louse (Damilina ovis). Sucking lice include members of the order Pediculus, such as the bovine blood louse, the suicidal blood louse, the bovine jaw louse, and the buffalo blind louse. Biting flies include members of the genus Nigrocera. Ticks include the genera Boophilus, Rhipicephalus, Ixodes, Hyalomma, Amblyomma, and Cercocephalus. The compounds of the present invention may also be used to control mites that are parasitic on warm-blooded mammals and poultry, including mites of the orders Acari and Parasiticus.

[0208] For oral administration to warm-blooded animals, the compounds of the present invention can be formulated into animal feed, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drench medications for animals, gels, tablets, boluses, and capsules. In addition, the compounds of the present invention can also be administered to animals in their drinking water. For oral administration, the selected dosage form should provide the animals with approximately 0.01 mg / kg to 100 g / kg of the compound of the present invention per day.

[0209] Alternatively, the compounds of the present invention can be administered parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection to animals. The compounds of the present invention can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention can be formulated as an implant for subcutaneous administration. In addition, the compounds of the present invention can be administered percutaneously to animals. For parenteral administration, the selected dosage form should provide the animals with a compound of the present invention at a dose of approximately 0.01 mg / kg to 100 mg / kg of animal body weight per day.

[0210] The compounds of the present invention can also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, and pour-on formulations. For topical application, dips and sprays typically contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to 3,000 ppm of the compounds of the present invention. In addition, the compounds of the present invention can be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

[0211] The compounds of the present invention may also be combined or used in conjunction with one or more other parasiticidal compounds (thereby broadening the spectrum of activity), including, but not limited to, anthelmintics such as benzimidazoles, piperazines, levamisole, thiophene pyrimidines, praziquantel, and the like; endectocides such as avermectins, milbemycins, and the like; ectoparasiticides such as arylpyrroles, organophosphates, carbamates, gamma-butyric acid inhibitors including fipronil, pyrethroids, spinosad, imidacloprid, and the like; insect growth regulators such as pyriproxyfen, cypromazine, and the like; and chitin synthase inhibitors such as benzoyl ureas including flufenoxuron.

[0212] The parasiticidal compositions of the present invention comprise a parasiticidally effective amount of a compound of the present invention or a combination thereof in admixture with one or more physiologically acceptable inert solid or liquid carriers known in veterinary practice for oral, transdermal, and topical administration. Such compositions may further include various additives, such as stabilizers, defoamers, viscosity regulators, binders, and tackifiers, and while commercial products will preferably be formulated as concentrates, the end user will generally use diluted formulations.

[0213] The compositions according to the invention can also be used for the preparation of compositions for the therapeutic or preventive treatment of fungal diseases in humans and animals, such as, for example, mycoses, dermatoses, tinea versicolor and candidiasis or diseases caused by Aspergillus species, such as Aspergillus fumigatus.

[0214] In one embodiment, independent of any other embodiment, the compound of formula I is an anthelmintic compound.

[0215] In one embodiment, independent of any other embodiment, the compound of formula I is a pesticidal compound, preferably a nematicidal compound. DETAILED DESCRIPTION

[0216] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0217] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0218] Table 1 Compound structures and their 1 H NMR values

[0219] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0220] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0221] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0222] 1. Synthesis of compound 4

[0223] 4-1 (150 mg, 1 eq) was dissolved in 30 ml of DCM, and then 3-trifluoromethylpyridine-2-carboxylic acid (110 mg, 1.1 eq), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (324 mg, 3 eq) and 4-dimethylaminopyridine (21 mg, 0.3 eq) were added in sequence. The reaction was stirred at room temperature for 3 h. After the mid-control reaction was completed, the reaction solution was concentrated and purified by normal phase to obtain 4 (100 mg, 40%).

[0224] 2. Synthesis of compound 5

[0225] (1) Lithium aluminum tetrahydride (87 mg, 4 eq) was dissolved in tetrahydrofuran solution, and then aluminum chloride (305 mg, 4 eq) was slowly added thereto, followed by compound 5-1 (200 mg, 1 eq). The reaction solution was placed at 70°C for 1-2 hours, and the reaction was completed by mid-control. The reaction solution was filtered, and the filtrate was adjusted to alkalinity with saturated sodium bicarbonate solution, and then extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 5-2 (150 mg, purity 90%, yield 74%).

[0226] (2) Compound 5-2 (150 mg, 1 eq) was dissolved in dichloromethane solution, and then 2-(trifluoromethyl)nicotinic acid (98 mg, 1.2 eq) and 4-dimethylaminopyridine (10 mg, 0.2 eq) were added, and finally 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (162 mg, 2 eq) was added. The mixture was stirred at room temperature for 2 h, and the reaction was completed by mid-control. Water was added to the reaction solution for quenching, and then the mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated to obtain compound 5 (65 mg, 29%).

[0227] 3. Synthesis of Compound 6

[0228] (1) 6-1 (3 g, 1 eq) was dissolved in 100 ml of DCM, and then 3-trifluoromethylpyridine-2-carboxylic acid (2.5 g, 1.1 eq), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (7.4 g, 3 eq) and 4-dimethylaminopyridine (0.47 g, 0.3 eq) were added in sequence. The reaction was stirred at room temperature for 3 h. After the intermediate control reaction was completed, the reaction solution was concentrated and purified by normal phase to obtain 6-2 (2.2 g, 42%).

[0229] (2) 6-2 (110 mg, 1 eq) was dissolved in a mixed solution of 10 mL of dioxane and 1 mL of water at room temperature, and then p-methylphenylboronic acid (44 mg, 1.2 eq), cesium fluoride (123 mg, 3 eq) and Pd(dppf)Cl2 (6 mg, 0.03 eq) were added in sequence. After the addition was completed, nitrogen was protected, and the temperature was raised to 100°C and stirred overnight. After the intermediate control reaction was completed, the temperature was lowered to room temperature, the insoluble matter was filtered off with celite, and the filtrate was concentrated and purified by normal phase to obtain 6 (63 mg, 16%).

[0230] 4. Synthesis of Compound 8

[0231] (1) 6-2 (1 g, 1 eq) was dissolved in a mixed solution of 100 mL of dioxane and 10 mL of water at room temperature, and then pinacol diboron (1.3 g, 2 eq), potassium acetate (0.7 g, 3 eq) and Pd(dppf)Cl2 (60 mg, 0.03 eq) were added in sequence. After the addition was completed, nitrogen was protected and the temperature was raised to 100 ° C. and stirred overnight. After the intermediate control reaction was completed, the temperature was lowered to room temperature, the insoluble matter was filtered off with celite, and the filtrate was concentrated and purified by normal phase to obtain 8-1 (600 mg, 54%).

[0232] (2) 8-1 (200 mg, 1 eq) was dissolved in a mixed solution of 20 mL of dioxane and 2 mL of water at room temperature, and then 2-bromo-5-chloropyridine (85 mg, 1 eq), cesium fluoride (200 mg, 3 eq) and Pd(dppf)Cl2 (11 mg, 0.03 eq) were added in sequence. After the addition was completed, nitrogen was protected, and the temperature was raised to 100 ° C. and stirred overnight. After the intermediate control reaction was completed, the temperature was lowered to room temperature, the insoluble matter was filtered off with celite, and the filtrate was concentrated and purified by normal phase to obtain 8 (100 mg, 52%).

[0233] 5. Synthesis of Compound 49

[0234] Compound 49-1 (100 mg, 1 eq) was dissolved in 10 mL of dichloromethane. 1 eq of 3-trifluoromethylpyridine-2-carboxylic acid, 1.5 eq of EDCI, and 0.1 eq of DMAP were added sequentially. The mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was extracted with dilute hydrochloric acid and EA. The organic phase was washed with saturated brine and dried to obtain the crude product. The crude product was purified by normal phase column chromatography to obtain 66 mg of 49-1 as a white solid, in a 41% yield.

[0235] 6. Synthesis of Compound 62

[0236] (1) 62-1 (1.5 g, 9 mmol, 1.0 eq), 2-chloro-5-hydroxypyridine (1.8 g, 1.5 eq), and K2CO3 (4 g, 3 eq) were added sequentially to 30 ml of DMF, and the reaction mixture was stirred at 80°C for 3 hours. LCMS analysis showed that the starting material was almost completely consumed, with a major new peak generated. Water (20 ml) was added to the reaction mixture, which was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 ml x 3), concentrated, and the crude product was separated by column chromatography to obtain 62-2 (2.4 g, 95% yield) as a white solid.

[0237] (2) 62-2 (2 g, 7 mmol, 1 eq) was added to 20 ml of CH3OH, and sodium borohydride (0.3 g, 1.1 eq) was then slowly added to the reaction mixture at 0°C. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. LCMS analysis indicated that the reaction of the starting material was essentially complete. Water (20 ml) was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine (20 ml*3), and the organic phase was concentrated to obtain 62-3 (2 g, 98% yield) as a yellow solid.

[0238] (3) 62-3 (2 g, 7 mmol, 1.0 eq) was added to 20 mL of DCM, and then thionyl chloride (1.5 g, 1.5 eq) was added to the reaction mixture at 0°C. After the addition was complete, the reaction mixture was stirred at 40°C for 1 hour. LCMS analysis showed that the reaction was essentially complete. The crude product was directly purified by column chromatography to obtain 62-4 (2 g, 94% yield) as a white solid.

[0239] (4) 62-4 (2 g, 7 mmol, 1.0 eq), TMSCN (2.0 g, 2 eq), and potassium carbonate (3.0 g, 3 eq) were added to 50 mL of ACN in sequence. The reaction mixture was then incubated at 80°C for 12 h. LCMS analysis revealed the disappearance of the starting material and the main peak was the product. The crude product was directly purified by column chromatography to afford 62-5 (1.5 g, 77% yield) as a yellow solid.

[0240] (5) Lithium aluminum tetrahydride (0.4 g, 2.0 eq) was added to 10 ml of THF at 0°C. Aluminum trichloride (1.3 g, 2 eq) was added to the reaction solution at 0°C. After 1 hour, 62-5 (1.5 g, 1.0 eq) was added. The reaction solution was then allowed to react at room temperature for 6 hours. LCMS analysis indicated that the reaction of the raw materials was essentially complete, with the main peak being the product. Aqueous sodium hydroxide solution (20 ml) was added to the reaction solution, which was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 ml*3). The organic phase was concentrated to obtain a white crude product 62-6 (1.2 g, 81% yield) (white solid).

[0241] (6) 62-6 (100 mg, 1 eq) was dissolved in 10 mL of dichloromethane, and 3-trifluoromethylpyridine-2-carboxylic acid (80 mg, 1 eq), EDCI (200 mg, 3 eq), and DMAP (12 mg, 0.3 eq) were added in sequence. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain 62 (80 mg, 49%, white solid).

[0242] 7. Synthesis of Compound 110

[0243] (1) 140 mg of 110-1 was dissolved in 20 ml of DCM, and o-trifluoromethylpyridine benzoic acid (1 eq), EDCI (1.5), and DMAP (0.1 eq) were added. The mixture was reacted at room temperature for 2 h. After the intermediate control reaction was completed, the DCM was dried and the mixture was washed with EA and dilute hydrochloric acid and saturated brine. The organic phase was mixed and passed through a normal phase column to obtain a yellow oil 110 (140 mg, yield 58%).

[0244] 8. Synthesis of Compound 126

[0245] (1) Compound 126-1 (2.5 g, 1 eq), pinacol diboronate (3.7 g, 1.2 eq), potassium acetate (4.5 g, 3 eq) and Pd(dppf)Cl2 (451 mg, 0.05 eq) were dissolved in a mixed solution of 20 ml of dioxane and 2 mL of water. The solution was flushed with nitrogen three times and then heated to 100°C and stirred overnight. After the reaction was completed, the sample was mixed and passed through a normal phase column to obtain compound 126-2 (1 g, 68%).

[0246] (2) Compound 126-2 (1 g, 1 eq), 2-chloro-5-trifluoromethylpyrimidine (0.8 g, 1.2 eq), potassium carbonate (1.5 g, 3 eq) and Pd(dppf)Cl2 (149 mg, 0.05 eq) were dissolved in a mixed solution of 20 mL of dioxane and 2 mL of water. The solution was replaced with nitrogen three times and then heated to 100°C and stirred overnight. After the reaction was completed, the sample was mixed and passed through a normal phase column to obtain compound 126-3 (700 mg, 65%).

[0247] (3) Compound 126-3 (700 mg, 1 eq) was dissolved in methanol, and excess Raney nickel and aqueous ammonia were added under ice-cooling, and hydrogen was purged. After the reaction was completed, the mixture was filtered and dried to obtain compound 126-4 (500 mg, 70%).

[0248] (4) Compound 126-4 (502 mg, 1 eq) was dissolved in 20 mL of dichloromethane. 3-Bromo-2-pyridinecarboxylic acid (340 mg, 1 eq), EDCI (350 mg, 2 eq) and DMAP (20 mg, 0.1 eq) were added in sequence under ice bath conditions. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid, dried and concentrated, and purified by normal phase chromatography to obtain 126 (496 mg, 61%).

[0249] 9. Synthesis of Compound 127

[0250] (1) Compound 126 (500 mg, 1 eq) was dissolved in dichloromethane and then added dropwise with boron tribromide (1.3 g, 5 eq) under ice-cooling and stirred at room temperature. After the reaction was completed, water was added to quench the reaction, and then ethyl acetate was added to extract the mixture. The organic phase was collected and purified by column chromatography to obtain 127 (80 mg, 16%).

[0251] 10. Synthesis of Compound 142

[0252] (1) Compound 142-1 (20 g, 1 eq), pinacol diboronate (17 g, 1.2 eq), potassium acetate (17.6 g, 3 eq) and Pd(dppf)Cl2 (1.2 g, 0.05 eq) were dissolved in a mixed solution of 100 mL of dioxane and 10 mL of water. The mixture was flushed with nitrogen three times and then heated to 100°C and stirred overnight. The reaction was completed and the mixture was filtered through a normal phase column to obtain compound 142-2 (21 g, 92%).

[0253] (2) Compound 142-2 (16 g, 1 eq), 2-chloro-5-trifluoromethylpyrimidine (9 g, 1.2 eq), potassium carbonate (17 g, 3 eq) and Pd(dppf)Cl2 (1.6 g, 0.05 eq) were dissolved in a mixed solution of 100 mL of dioxane and 10 mL of water. After purging with nitrogen three times, the temperature was raised to 80°C and stirred overnight. The reaction was completed and the mixture was passed through a normal phase column to obtain compound 142-3 (15.6 g, 92%).

[0254] (3) Compound 142-3 (1 g, 1 eq) was dissolved in dichloromethane, and a hydrochloric acid 1,4-dioxane solution was added. After the reaction was completed, the solvent was dried to obtain compound 142-4 (0.8 g, 99% yield).

[0255] (4) Compound 142-4 (502 mg, 1 eq) was dissolved in 20 mL of dichloromethane. 3-Bromo-2-pyridinecarboxylic acid (340 mg, 1 eq), EDCI (350 mg, 2 eq) and DMAP (20 mg, 0.1 eq) were added in sequence under ice bath conditions. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid, dried and concentrated, and the sample was purified by normal phase to obtain 142 (496 mg, 61% yield).

[0256] 11. Synthesis of Compound 136

[0257] (1) Compound 142-3 (4 g, 1 eq) was dissolved in a mixed solution of EtOH / H2O = 5 / 1, iron powder (2.7 g, 5 eq) and ammonium chloride (2.6 g, 5 eq) were added, and the temperature was raised to 80°C. After the intermediate control reaction was completed, the filtrate was filtered, silica gel powder was added, and the mixture was purified by normal phase column to obtain compound 136-1 (3 g, 81% yield).

[0258] (2) Compound 136-1 (3 g, 1 eq) was dissolved in acetonitrile, and sodium nitrite (1.05 g, 2 eq) and cuprous bromide (2.25 g, 2 eq) were added and reacted at 80°C. After the intermediate control reaction, silica gel powder was added and purified by normal phase column chromatography to obtain 136-2 (2.1 g, 60% yield).

[0259] (3) Compound 136-2 (0.2 g, 1 eq) was dissolved in 5 mL of dichloromethane, and 3 equivalents of hydrochloric acid 1,4-dioxane solution was added. After the reaction was completed, the solvent was dried to obtain compound 136-3 (0.2 g, 99% yield).

[0260] (4) Compound 136-3 (502 mg, 1 eq) was dissolved in 20 mL of dichloromethane. 3-Bromo-2-pyridinecarboxylic acid (340 mg, 1 eq), EDCI (350 mg, 2 eq) and DMAP (20 mg, 0.1 eq) were added in sequence under ice bath conditions. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid, dried and concentrated, and the sample was purified by normal phase to obtain 136 (496 mg, 61% yield).

[0261] 12. Synthesis of Compound 141

[0262] (1) Under ice-bath conditions, triphosgene (1.5 g, 5.23 mmol) was dissolved in 15 mL of toluene solution. Compound 136-1 (1.0 g, 2.62 mmol) was then slowly added, followed by DIPEA (0.34 g, 2.62 mmol). After addition, stirring was continued overnight. After completion of the reaction as monitored by LCMS, the reaction solution was filtered, and the residue was rinsed twice with toluene. The filtrate was extracted with water and ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 141-1 (0.85 g, 79%, light yellow solid).

[0263] (2) Compound 141-1 (0.85 g, 2.08 mmol) was dissolved in 15 mL of DMF, followed by the addition of trimethylsilyl azide (0.72 g, 6.24 mmol). After the addition, the atmosphere was purged with nitrogen three times and the mixture was stirred at 100°C overnight. After completion of the reaction as monitored by LCMS, the reaction solution was cooled to room temperature, extracted with water and ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification (PE / EA = 8 / 1) to afford compound 141-2 (0.35 g, 7%, yellow oil).

[0264] (3) Compound 141-2 (0.35 g, 0.77 mmol) was dissolved in 10 mL of hydrochloric acid-1,4-dioxane solution and then allowed to react at room temperature for 2 h. After the reaction was complete as monitored by LCMS, the reaction solution was concentrated to obtain crude compound 141-3 (0.25 g, 92%, yellow oil).

[0265] (4) Compound 141-3 (120 mg, 0.34 mmol) was dissolved in 10 mL of dichloromethane solution, and then 3-bromo-2-pyridinecarboxylic acid (83 mg, 0.41 mmol) and DMAP (10 mg, 0.07 mmol) were added, and finally EDCI (129 mg, 0.68 mmol) was added. The mixture was stirred at room temperature for 2 h, and the reaction was completed at the intermediate control. Water was added to the reaction solution for quenching, and then extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification (PE / EA = 1 / 1) to obtain compound 141 (82 mg, 45%, white solid).

[0266] 13. Synthesis of Compound 143

[0267] (1) Raw material 143-1 (20 g, 83 mmol) was dissolved in 1,4-dioxane. Potassium acetate (24.4 g, 249 mmol), Pd(dppf)Cl2 (2 g, 2.49 mmol), and diboronic acid pinacol ester (31 g, 124 mmol) were added with stirring. The mixture was purged and heated to 100°C under a N2 atmosphere. The mixture was stirred overnight. After the intermediate reaction, the reaction solution was directly mixed and purified (PE / EA = 3:1). The fraction was then spin-dried to obtain compound 143-2 (white solid, 20 g, 83%).

[0268] (2) Compound 143-2 (1 g, 3 mmol) was dissolved in a 1,4-dioxane:water solution (10:1). The mixture was placed in an ice bath and stirred. Potassium carbonate (1.47 g, 9 mmol), Pd(dppf)Cl2 (85 mg, 0.09 mmol), and 2-chloro-5-trifluoromethylpyrimidine (570 mg, 2.7 mmol) were added sequentially. The mixture was purged and heated to 100°C under a N2 atmosphere. The mixture was stirred overnight. After the reaction was completed, the mixture was dried and purified by mixing with PE / EA (5:1). The fraction was dried to give compound 143-3 as a red solid (810 mg, 73%).

[0269] (3) Compound 143-3 (810 mg, 2.62 mmol) was dissolved in methanol, and Raney nickel (wet weight 1 g) and aqueous ammonia (25%, 1 mL) were added. The mixture was stirred overnight under a hydrogen atmosphere. After the reaction was completed, the mixture was filtered through celite, and the filtrate was dried to obtain compound 143-4 (200 mg, yellow solid, 25%).

[0270] (4) Compound 143-4 (100 mg, 0.32 mmol) was dissolved in dichloromethane, and 3-(difluoromethyl)pyridine-2-carboxylic acid (55 mg, 0.32 mmol) and triethylamine (97 mg, 0.96 mmol) were added with stirring. Finally, HATU (182 mg, 0.48 mmol) was added. The reaction was allowed to proceed for 1 h, and the reaction was completed at the intermediate control. The mixture was spin-dried and purified to obtain product 143 (68 mg, 48%).

[0271] 14. Synthesis of Compound 146

[0272] (1) Compound 136-2 (0.1 g, 1 eq), triphenylphosphine (10 mg, 0.2 eq), cyclopropylboronic acid (29 mg, 1.2 eq), palladium acetate (5 mg, 0.1 eq) and potassium phosphate (163 mg, 3 eq) were dissolved in a mixed solution of 10 mL of toluene and 1 mL of water. After purging with nitrogen three times, the temperature was raised to 100°C and stirred overnight. The reaction was completed and the mixture was filtered through a normal phase column to obtain compound 146-1 (60 mg, 76% yield).

[0273] (2) The raw material 146-1 (0.2 g, 1 eq) was dissolved in dichloromethane, and a hydrochloric acid 1,4-dioxane solution was added. After the reaction was completed, the solvent was dried to obtain compound 146-2 (0.2 g, 99% yield).

[0274] (3) Compound 146-2 (500 mg, 1 eq) was dissolved in 20 mL of dichloromethane. 3-Bromo-2-pyridinecarboxylic acid (327 mg, 1 eq), EDCI (350 mg, 2 eq) and DMAP (20 mg, 0.1 eq) were added in sequence under ice bath conditions. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain 146 (496 mg, 62% yield).

[0275] 15. Synthesis of Compound 148

[0276] (1) Compound 136-2 was dissolved in toluene, and 2 equivalents of a tin reagent and 0.05 equivalents of Pd(PPh3)4 were added. The atmosphere was replaced with nitrogen, and the mixture was stirred at 110°C overnight. After the reaction was complete as monitored by LCMS, the filtrate was dried and purified by normal phase purification to obtain product 148-1, which was used directly in the next reaction.

[0277] (2) Compound 148-1 was dissolved in 5 equivalents of dioxane hydrochloride and stirred at room temperature for 2 hours. After the reaction was complete as monitored by LCMS, the filtrate was dried to obtain product 148-2, which was used crude for the next reaction.

[0278] (3) Compound 148-2 was dissolved in 5 mL of dichloromethane, and 1.2 equivalents of 3-bromo-2-pyridinecarboxylic acid and 0.2 equivalents of DMAP were added. 1.5 equivalents of EDCI was added with stirring, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction as monitored by LCMS, the mixture was dried and purified by normal phase purification to yield 148 (50 mg, 16%).

[0279] 16. Synthesis of Compound 149

[0280] Compound 126 (500 mg, 1 eq) was dissolved in DMF, and sodium difluorochloroacetate (500 mg, 3 eq) and cesium carbonate (1 g, 3 eq) were added, and the temperature was raised to 120°C. After the intermediate control reaction was completed, saturated brine was added for extraction, and the organic phase was dried and purified by column chromatography to obtain compound 149 (0.64 g, 70% yield).

[0281] 17. Synthesis of Compound 150

[0282] (1) Compound 150-1 (1 g, 3.83 mmol), 2-chloro-5-(methylthio)pyrimidine (406 mg, 2.55 mmol), potassium carbonate (1.05 g, 7.55 mmol) and Pd(dppf)Cl2 (170 mg, 0.25 mmol) were dissolved in 50 ml of dioxane / 5 ml of water, replaced with nitrogen three times, heated to 100 ° C and stirred overnight. After the intermediate control reaction was completed, the reaction was cooled and filtered. The filtrate was spin-dried and purified by normal phase column to obtain compound 150-2 (800 mg, 81%).

[0283] (2) Lithium aluminum tetrahydride (311 mg, 8.43 mmol) was dissolved in 50 mL of tetrahydrofuran solution, cooled to 0°C, and aluminum trichloride (1.12 g, 8.43 mmol) was slowly added. After stirring for 5 min, compound 150-2 (700 mg, 2.81 mmol) was added and allowed to react overnight. The reaction was complete after liquid chromatography-mass spectrometry. The product was quenched with water, filtered through a pad of celite, and the filtrate was added with water and extracted with ethyl acetate. After two extractions, the organic phases were combined and washed three times with saturated brine. The dried organic phase was spin-dried and subjected to column chromatography to obtain oily compound 150-3 (800 mg, 100%).

[0284] (3) Compound 150-3 (800 mg, 3.04 mmol) was dissolved in 20 ml of DCM. o-Trifluoromethylpyridinebenzoic acid (608 mg, 3.04 mmol), triethylamine (921 mg, 9.12 mmol), and 1.2 equivalents of HATU (1.73 g, 4.56 mmol) were added sequentially. The mixture was stirred at room temperature for 1 hour. After the intermediate reaction was completed, the mixture was extracted with dilute hydrochloric acid and ethyl acetate. The organic phase was washed with saturated brine and dried to obtain the crude product. The crude product was purified by normal phase column chromatography to obtain 150 (556 mg, 41%) as a light yellow oil.

[0285] 18. Synthesis of Compound 151

[0286] (1) Compound 150 (200 mg, 0.45 mmol) was dissolved in 20 mL of DCM, and m-chloroperbenzoic acid (200 mg, 0.98 mmol) was added under ice-cooling. After the addition was complete, the mixture was stirred at room temperature overnight. After the intermediate control reaction was completed, the reaction solution was concentrated and purified by normal phase to obtain compound 151 (180 mg, 84%).

[0287] 19. Synthesis of Compound 153

[0288] (1) Compound 150-1 (600 mg, 1.0 eq), 2-chloro-5-cyclopropylpyrimidine (425 mg, 1.2 eq), potassium carbonate (952 mg, 3.0 eq), and Pd(dppf)Cl2 (5 mol%) were added to a 1,4-dioxane / H2O solution and stirred at 80°C for 2 h under nitrogen. After completion of the reaction as monitored by LCMS, the mixture was extracted with ethyl acetate (30 mL × 3). The combined organic phases were washed with H2O (10 mL × 2), dried, concentrated, and purified by column chromatography to afford compound 153-1 (560 mg, 96%).

[0289] (2) 153-1 (460 mg, 1.0 eq) was added to methanol (10 mL), and 1 mL of Raney nickel and 3 drops of ammonia were added dropwise. H2 was then introduced and stirred at room temperature. After the reaction was complete as monitored by LCMS, the mixture was filtered and the filtrate was concentrated to give crude product 153-2, which was used directly in the next step without purification.

[0290] (3) The crude product 153-2 from the previous step was dissolved in DCM, and 3-bromopyridine-2-carboxylic acid (1.0 eq), HATU (1.5 eq), and TEA (3.0 eq) were added. The reaction mixture was stirred at room temperature overnight. After completion of the reaction as monitored by LCMS, the reaction solution was washed with 1 M HCl (10 mL × 3). The organic phase was dried, concentrated, and purified by column chromatography to afford 153 (233 mg, 29%).

[0291] 20. Synthesis of Compound 166

[0292] (1) Compound 166-1 (5.0 g, 26.3 mmol) was dissolved in 50 mL of DMF solution, followed by the addition of 5-chloro-2-fluoropyridine (4.15 g, 31.56 mmol) and anhydrous potassium carbonate (10.8 g, 78.9 mmol). The reaction solution was stirred at 120°C overnight. LCMS monitored the reaction to completion. The reaction solution was extracted with water and ethyl acetate, and the organic phases were combined, washed several times with saturated brine, and dried over anhydrous sodium sulfate. The mixture was then concentrated and purified by normal phase purification (PE / EA = 7 / 1) to afford compound 166-2 (5.5 g, 69%, yellow oil).

[0293] (2) Compound 166-2 (5.5 g, 18.23 mmol) was dissolved in 50 mL of methanol in an ice bath. Solid sodium borohydride (0.83 g, 21.88 mmol) was then slowly added. After stirring for 2 h, the reaction was complete as monitored by LCMS. The reaction solution was concentrated and then extracted with water and ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford crude compound 166-3 (4.8 g, 87%, white solid).

[0294] (3) Compound 166-3 (4.8 g, 15.81 mmol) was dissolved in 50 mL of dichloromethane, and thionyl chloride (3.76 g, 31.61 mmol) was added dropwise, followed by two drops of DMF as a catalyst. The reaction solution was allowed to react at 40°C for 2 h. After completion of the reaction as monitored by LCMS, the reaction solution was concentrated and sampled, and purified by normal phase purification (PE / EA = 9 / 1) to afford compound 166-4 (4.5 g, 88%, light yellow oil).

[0295] (4) Compound 166-4 (4.5 g, 13.97 mmol) was dissolved in 50 mL of acetonitrile, and trimethylsilyl cyanide (1.66 g, 16.76 mmol) and anhydrous potassium carbonate (5.78 g, 41.91 mmol) were added. The reaction solution was allowed to react overnight at 80°C, and the reaction was complete as monitored by LCMS. The reaction solution was concentrated, and then extracted three times with water and ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification (PE / EA = 6 / 1) to obtain compound 166-5 (4.0 g, 91%, yellow oil).

[0296] (5) Under ice bath conditions, lithium aluminum tetrahydride solid (0.48 g, 12.79 mmol) was dissolved in 20 mL of tetrahydrofuran solution, and then anhydrous aluminum chloride (1.7 g, 12.79 mmol) was slowly added thereto. Finally, compound 13-5 (2.0 g, 6.4 mmol) was dissolved in tetrahydrofuran and added dropwise to the reaction solution. The reaction solution was placed in an ice bath and reacted for 1.5 h. LCMS monitored the reaction to be complete. The reaction solution was filtered, and the filtrate was adjusted to alkalinity with saturated sodium bicarbonate solution, and then extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 166-6 (1.5 g, 74%, white solid).

[0297] (6) Compound 166-6 (150 mg, 0.47 mmol) was dissolved in 10 mL of dichloromethane solution, and then 3-trifluoromethylpyridine-2-carboxylic acid (108 mg, 0.57 mmol), DMAP (12 mg, 0.1 mmol), and finally EDCI (180 mg, 0.94 mmol) were added. The mixture was stirred at room temperature for 2 h, and the reaction was completed at the intermediate control. Water was added to the reaction solution for quenching, and then extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification (PE / EA = 4 / 1) to obtain compound 16 (90 mg, 37%, white solid).

[0298] 21. Synthesis of Compound 170

[0299] (1) Compound 170-1 (5.0 g, 1.00 eq) was added to 100 mL of DMF, followed by the addition of p-trifluoromethylphenol (5.7 g, 1.00 eq) and potassium carbonate (14.5 g, 3.00 eq). The system was heated to 100°C and reacted for 4 h. The system was cooled to room temperature, and saturated brine and ethyl acetate were added for separation and extraction. The organic phase was washed three times with saturated brine, dried, concentrated, and purified by normal phase chromatography to obtain compound 170-2 (6.0 g, 60%).

[0300] (2) Compound 170-2 (6.0 g, 1.00 eq) was dissolved in 30 mL of methanol, and sodium borohydride (1.6 g, 2.00 eq) was slowly added at 0°C for 2 h. The system was quenched with water, concentrated, and extracted with water and ethyl acetate. The organic phase was dried and concentrated to obtain a crude product of compound 170-3 (6.0 g, crude product).

[0301] (3) Compound 170-3 (6.0 g, 1.00 eq) was dissolved in 20 mL of dichloromethane, and thionyl chloride (7.4 g, 3.00 eq) was slowly added dropwise at room temperature until stable, then the temperature was raised to 40°C and the reaction was carried out for 2 h. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain compound 170-4 (3.0 g, 46%).

[0302] (4) Compound 170-4 (3.0 g, 1.00 eq) was dissolved in 30 mL of acetonitrile, and potassium carbonate (6.8 g, 5.00 eq) was added. The atmosphere was purged with nitrogen three times at room temperature, and trimethylsilyl cyanide (2.9 g, 2.00 eq) was added. The temperature was raised to 80°C, and the reaction was allowed to proceed overnight. The system was cooled to room temperature, filtered through celite, and the organic phase was dried, concentrated, and purified by normal phase chromatography to obtain compound 170-5 (2.0 g, 68%).

[0303] (5) Lithium aluminum tetrahydride (1.0 g, 4.00 eq) was slowly added to tetrahydrofuran under an ice bath, followed by the slow addition of aluminum trichloride (4.0 g, 4.00 eq) and the reaction was continued for 0.5 h. Compound 170-5 (2.0 g, 1.00 eq) was dissolved in 10 mL of tetrahydrofuran and slowly added dropwise to the above system for 1 h. The system was quenched with water, filtered through celite, and extracted with water and ethyl acetate. The organic phase was dried and concentrated to afford crude compound 170-6 (2.0 g, crude product).

[0304] (6) Compound 170-6 (300 mg, 1.00 eq) was dissolved in 10 mL of dichloromethane, and o-trifluoromethylpyridinebenzoic acid (191.5 mg, 1.00 eq), triethylamine (304 mg, 3.00 eq) and HATU (762 mg, 2.00 eq) were added in sequence. The mixture was stirred at room temperature for 1-2 h, extracted with water and dichloromethane, and the organic phase was washed three times with dilute hydrochloric acid. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain compound 170 (58.0 mg, 12%).

[0305] 22. Synthesis of Compound 173

[0306] (1) Compound 173-1 (3.0 g, 18 mmol), 3-chloro-4-hydroxybenzotrifluoride (5.5 g, 18 mmol), and K2CO3 (7.8 g, 57 mmol) were added sequentially to 30 mL of DMF, and the reaction mixture was stirred at 80°C for 3 hours. LCMS analysis showed that the starting material was almost completely consumed, with the formation of a major new peak. Water (20 mL) was added to the reaction mixture, which was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 mL x 3). The organic phase was concentrated, and the crude product was separated by column chromatography to obtain 173-2 (3.2 g, 63%) as a white solid.

[0307] (2) Compound 173-2 (3.2 g, 9.5 mmol) was added to 20 ml of CH3OH, and sodium borohydride (0.4 g, 10 mmol) was then slowly added to the reaction mixture at 0°C. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. LCMS analysis indicated that the reaction was essentially complete. Water (20 ml) was added to the reaction mixture, which was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 ml x 3). The organic phase was concentrated to obtain 173-3 (3 g, 94%) as a yellow solid.

[0308] (3) Compound 173-3 (3 g, 9.0 mmol) was added to 20 mL of DCM, and then thionyl chloride (1.5 g, 9.0 mmol) was added to the reaction mixture at 0°C. After the addition was complete, the reaction mixture was stirred at 40°C for 1 hour. LCMS analysis showed that the reaction was essentially complete. The crude product was directly purified by column chromatography to obtain 173-4 (3 g, 99%) as a white solid.

[0309] (4) Compound 173-4 (1 g, 2.8 mmol), TMSCN (1.0 g, 5.6 mmol), and potassium carbonate (3.0 g, 9.3 mmol) were added sequentially to 50 mL of ACN. The reaction mixture was then incubated at 80°C for 12 hours. LCMS analysis revealed the disappearance of the starting material and the main peak was the product. The crude product was directly purified by column chromatography to afford 173-5 (0.8 g, 98%) as a yellow solid.

[0310] (5) Lithium aluminum tetrahydride (0.12 g, 2.8 mmol) was added to 10 ml of THF at 0°C. Aluminum trichloride (0.38 g, 2.8 mmol) was added to the reaction solution at 0°C. After 1 hour, compound 173-5 (0.5 g, 1.4 mmol) was added. The reaction solution was then reacted at 60°C for 6 hours. LCMS analysis indicated that the reaction of the raw materials was essentially complete, with the main peak being the product. Aqueous sodium hydroxide solution (20 ml) was added to the reaction solution, which was then extracted with ethyl acetate. The organic phase was washed with saturated brine (20 ml x 3). The organic phase was concentrated to obtain crude white solid 173-6 (0.15 g, 30%).

[0311] (6) Compound 173-6 (150 mg, 0.42 mmol) was dissolved in 10 mL of dichloromethane. Under ice bath conditions, o-trifluoromethylpyridine benzoic acid (97 mg, 0.51 mmol), triethylamine (127 mg, 1.2 mmol) and HATU (327 mg, 0.51 mmol) were added in sequence. The mixture was stirred at room temperature for 1 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain compound 173 (60 mg, 27%) as a white solid.

[0312] Biological activity evaluation (nematode 96-well plate assay):

[0313] (1) Preparation of test agents

[0314] Accurately weigh the test drug, dissolve it in DMSO to prepare a stock solution, and dilute it into different concentration gradient solutions.

[0315] (2) Target nematode isolation

[0316] Southern root-knot nematode: When egg masses emerge from root nodes, use tweezers under a dissecting microscope to remove the egg masses from the nodes and place them in clean water. Soak them in a 0.25% sodium hypochlorite solution for approximately 1 minute. After sieving through a 500-mesh sieve, place them in a 90mm Petri dish containing an appropriate amount of tap water. Place the dish in a sieving device and incubate in a 28°C incubator for 3 days. Second-instar larvae will hatch from the egg masses. Observe the nematode suspension under a microscope and dilute it to approximately 1000 nematodes / mL for later use.

[0317] Mixed-stage pine wood nematodes and mixed-stage sweet potato stem nematodes: Dig out the PDA culture medium containing nematodes and invert it onto a petri dish covered with mycelium. Rinse the nematodes off the lid with sterile water. Transfer the nematode suspension to a new petri dish covered with Botrytis cinerea mycelium, using 1 mL of nematode suspension per dish. Incubate in a dark incubator at 25°C. Once the mycelium has been completely consumed by the nematodes, transfer the suspension back to PDA with Botrytis cinerea mycelium for propagation. Store the cultured nematodes at 4°C. Transfer and propagate every 7-10 days. Use at least 10 petri dishes at a time. Prepare a petri dish where all the Botrytis cinerea has been consumed. Rinse the nematodes off the lid with sterile water. Observe the nematode suspension under a microscope and dilute to approximately 1000 nematodes / mL for later use.

[0318] (3) Chemical treatment

[0319] Add 100 μL each of the prepared test agent and nematode suspension to a 96-well culture plate, cover to prevent evaporation, and place in a 28°C incubator. Set up a water control and a test agent control; if a solvent is used, also set up a solvent control.

[0320] (4) Cultivation and observation

[0321] The nematodes treated with the drug were cultured under normal conditions, and the mortality rate of the nematodes was measured after 48 hours and 72 hours: mortality rate (%) = (number of dead worms / number of test worms) * 100. Representative test results are shown in Table 2.

[0322] Table 2 Nematode test results

[0323] Note: N stands for no data; Reference compound A: Biological activity evaluation (sterilization plate method):

[0324] The drug was dissolved in acetone and diluted with sterile water. Two concentration series (5 and 1 ppm) were established based on the drug's activity, with a final acetone content of 200 μL / 150 mL. Under aseptic conditions, pre-thawed sterile culture medium was quantitatively added to sterile Erlenmeyer flasks according to the test treatment. The drug solution was pipetted sequentially, from low to high concentration, and added to each of the flasks, shaking thoroughly. Equal amounts were then poured into three 6-cm diameter Petri dishes to create drug-containing plates of the corresponding concentrations. A blank control was established for the treatment without the drug, with three replicates per treatment. A sterile, 3-mm diameter sterile punch was used to cut a bacterial cake from the edge of a colony. This cake was inoculated with an inoculator, mycelial side up, onto the center of the drug-containing plate. The plate was then covered and incubated at 25°C. Mycelial growth of the pathogen was then assessed based on the growth of the blank control Petri dishes. Colony diameters were measured with a caliper in millimeters (mm). The diameter of each colony was measured vertically once using the cross method, and the average value was taken. Based on the survey results, the mycelial growth inhibition rate of each treatment concentration on the target bacteria was calculated according to formula (1) (2), and the unit is percentage (%). The representative test results are shown in Table 3. D = D1-D2………………………………………………(1)

[0325] Where: D is the diameter of colony growth; D1 is the diameter of colony; D2 is the diameter of bacterial cake.

[0326] Where: I——hyphae growth inhibition rate; D0——blank control colony growth diameter; D t ——The growth diameter of the colony after treatment with chemicals.

[0327] Table 3 Results of the test on the inhibition of pathogenic fungal mycelial growth by the plate method (4DAA) Note: N stands for no data.

[0328] At the same time, after many tests, it was found that many of the compounds and compositions described in the present invention have good control activity against different types of nematodes, etc., and have the characteristics of broad spectrum, high efficiency, strong systemic activity, etc., and can effectively control harmful organisms and / or fungi. For example, they also have good control activity against different types of fungi such as Ascomycetes, Basidiomycetes, Deuteromycetes, Oomycetes, etc., and have certain commercial value.

Claims

1. A pyridinecarboxylic acid phenylalkylamide compound, its salt and N-oxide: Among them, A1, A2, A3, A4, and A5 each independently represent N or CY; M represents O; n is 0 or 1; R1, R2, R3, R4, X1, X2, X3, X4, and Y each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxy, mercapto, carboxy, sulfo, formyl, halocarbonyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -PO(OR 22 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -Si(R 22 )3, -O(CO)R 22 , -O-(SO2)R 22 , -S(CO)R 22 , -(SO2)OR 22 , -O(CO)OR 22 , -(CO)(CO)OR 22 , -(CO)OR 22 , -O-N=C(R 23 )2, -CR 23 =N-OH or -CR 23 =N-O-R 22 , wherein the "alkyl", "alkenyl" or "alkynyl" is optionally selected from halogen, nitro, cyano, hydroxy, mercapto, carboxy, cycloalkyl, cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -O(CO)H, -O(CO)R 22 , -O-(SO2)R 22 , -(CO)OR 22 , -O(CO)OR 22 ,-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-alkylene-(CO)OH or -O-alkylene-(CO)OR 22 and is substituted by at least one group selected from the group consisting of; R 21 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 22 , -(CO)R 22 , -(CO)OR 22 , -alkylene-(CO)OR 22 , -(SO2)R 22 , -(SO2)OR 22 , -alkylene-(SO2)R 22 , -(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclic group, wherein said "alkyl", "alkenyl" or "alkynyl" is optionally substituted with at least one group selected from halogen, cyano, trialkylsilyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 25 , -SR 25 , -O(CO)R 25 , -(CO)R 25 , -(CO)OR 25 or -O(CO)OR 25 ; R 23 each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclic group or heterocyclic group alkyl; R 24 each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl; or N(R 21 )2, N(R 24 )2 each independently represents a heterocyclic group having a nitrogen atom at the 1-position; R 25 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, phenoxy, or phenoxy substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxy or haloalkoxy; The foregoing "cycloalkyl", "cycloalkenyl", "heterocyclic group" or "aryl" 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, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO2)R 10 , -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-substituted -OCH2CH2- or -OCH2O-; R 10 each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

2. The pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to claim 1, wherein R1, R2, R3, R4, X1, X2, X3, X4, and Y each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxy, mercapto, carboxy, sulfo, formyl, halocarbonyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -PO(OR 22 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -Si(R 22 )3, -O(CO)R 22 , -O-(SO2)R 22 , -S(CO)R 22 , -(SO2)OR 22 , -O(CO)OR 22 , -(CO)(CO)OR 22 , -(CO)OR 22 , -O-N=C(R 23 )2, -CR 23 =N-OH or -CR 23 =N-O-R 22 , wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally selected from halogen, nitro, cyano, hydroxy, mercapto, carboxy, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -O(CO)H, -O(CO)R 22 , -O-(SO2)R 22 , -(CO)OR 22 , -O(CO)OR 22 , -Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C8 alkylene)-(CO)OH or -O-(C1-C8 alkylene)-(CO)OR 22 and is substituted by at least one group selected from the group consisting of; R 21 each independently represents hydrogen, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, an aryl group, a heterocyclic group, -OR 22 , -(CO)R 22 , -(CO)OR 22 , -(C1-C8 alkylene)-(CO)OR 22 , -(SO2)R 22 , -(SO2)OR 22 , -(C1-C8 alkylene)-(SO2)R 22 , -(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 each independently represents a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, an aryl group or a heterocyclic group, wherein the "C1-C8 alkyl group", "C2-C8 alkenyl group" or "C2-C8 alkynyl group" is optionally selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 or -O(CO)OR 25 and is substituted by at least one group selected from the group consisting of; R 23 each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxy C1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, aryl, aryl C1-C8 alkyl, heterocyclic group or heterocyclic group C1-C8 alkyl; R 24 each independently represents hydrogen, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C1-C8 alkoxy group, a C1-C8 alkylsulfonyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkyl C1-C8 alkyl group, a C3-C8 cycloalkenyl group or a C3-C8 cycloalkenyl C1-C8 alkyl group; or N(R 21 )2, N(R 24 )2 each independently represents a heterocyclic group having a nitrogen atom at the 1-position; R 25 each independently represents hydrogen, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a halogenated C1-C8 alkyl group, a halogenated C2-C8 alkenyl group, a halogenated C2-C8 alkynyl group, a phenyl group or a phenyl group substituted by at least one group selected from the following: halogen, cyano, nitro, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C1-C8 alkoxy group, a halogenated C1-C8 alkoxy group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylthio group, a C1-C8 alkylsulfonyl group, a phenoxy group, or a phenoxy group substituted by at least one group selected from halogen, cyano, nitro, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C1-C8 alkoxy group or a halogenated C1-C8 alkoxy group; The foregoing "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclic group" or "aryl" 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, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO2)R 10 , -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 unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 each independently represents hydrogen, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a phenyl group, or a phenyl group substituted with at least one group selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halogenated C1-C8 alkoxy.

3. The pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to claim 1 or 2, wherein R1, R2, R3, R4, X1, X2, X3, X4, and Y each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxy, mercapto, carboxy, sulfo, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -PO(OR 22 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -Si(R 22 )3, -O(CO)R 22 , -O-(SO2)R 22 , -S(CO)R 22 , -(SO2)OR 22 , -O(CO)OR 22 , -(CO)(CO)OR 22 , -(CO)OR 22 , -O-N=C(R 23 )2, -CR 23 =N-OH or -CR 23 =N-O-R 22 , wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally selected from halogen, nitro, cyano, hydroxy, mercapto, carboxy, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic group, aryl, -N(R 21 )2, -(CO)N(R 21 )2, -O(CO)N(R 21 )2, -O(CS)N(R 21 )2, -(SO2)N(R 21 )2, -O(SO2)N(R 21 )2, -OR 22 , -(CO)R 22 , -SR 22 , -(SO)R 22 , -(SO2)R 22 , -O(CO)H, -O(CO)R 22 , -O-(SO2)R 22 , -(CO)OR 22 , -O(CO)OR 22 , -Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C6 alkylene)-(CO)OH or -O-(C1-C6 alkylene)-(CO)OR 22 and is substituted by at least one group selected from the group consisting of; R 21 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 22 , -(CO)R 22 , -(CO)OR 22 , -(C1-C6 alkylene)-(CO)OR 22 , -(SO2)R 22 , -(SO2)OR 22 , -(C1-C6 alkylene)-(SO2)R 22 , -(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclic group, wherein said "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted with at least one group selected from halogen, cyano, tri-C1-C6 alkylsilyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 25 , -SR 25 , -O(CO)R 25 , -(CO)R 25 , -(CO)OR 25 or -O(CO)OR 25 ; R 23 each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclic group or heterocyclic group-C1-C6 alkyl; R 24 each independently represents hydrogen, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C1-C6 alkylsulfonyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C3-C6 cycloalkenyl group or a C3-C6 cycloalkenyl C1-C6 alkyl group; Or N(R 21 )2, N(R 24 )2 each independently represents unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl R 25 each independently represents hydrogen, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a halo-C1-C6 alkyl group, a halo-C2-C6 alkenyl group, a halo-C2-C6 alkynyl group, a phenyl group or a phenyl group substituted with at least one group selected from the following: halogen, cyano, nitro, a C1-C6 alkyl group, a halo-C1-C6 alkyl group, a C1-C6 alkoxy group, a halo-C1-C6 alkoxy group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfonyl group, a phenoxy group, or a phenoxy group substituted with at least one group selected from halogen, cyano, nitro, a C1-C6 alkyl group, a halo-C1-C6 alkyl group, a C1-C6 alkoxy group or a halo-C1-C6 alkoxy group; The foregoing "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclic group" or "aryl" 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, -OR 10 , -SR 10 , -(CO)OR 10 , -(SO2)R 10 , -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 unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 each independently represents hydrogen, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a phenyl group, or a phenyl group substituted with at least one group selected from the group consisting of halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halogenated C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1 in the specification.

4. A method for preparing a pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to any one of claims 1-3, comprising the following steps: (1) Condensing the compound represented by general formula II with the compound represented by general formula III to obtain The compound shown by General Formula I has the following reaction equation: Alternatively, (2) when n is 0, Compound I is prepared by coupling Compound IV and Compound V, and the chemical reaction equation is as follows: wherein, W represents a halogen or OH, any one of Z1 and Z2 represents a halogen, and the other represents The definitions of substituents A1, A2, A3, A4, A5, M, n, R1, R2, R3, R4, X1, X2, X3, and X4 are as described in any one of claims 1-3.

5. The method for preparing a pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to claim 1 or 2, wherein The reactions in steps (1) and (2) are carried out in the presence of a solvent; Preferably, a condensing agent and / or a base are added during the reaction in step (1), or a catalyst and / or a base are added in step (2); More preferably, the solvents in steps (1) and (2) are selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, tetrahydrofuran, ethyl acetate, or water; the bases in steps (1) and (2) are selected from at least one of inorganic bases or organic bases, the condensing agent in step (1) is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU, or HATU, and the catalyst in step (2) is selected from at least one of Pd(dppf)Cl2, Pd(PPh3)4, PdCl2, Pd(OAc)2, Pd(PPh3)2Cl2, and NiCl2(dppf).

6. A composition for killing pests and / or fungi (especially nematodes, scab, sclerotinia), characterized in that, Comprising at least one of the pyridinecarboxylic acid phenylalkylamide compounds, its salts, and N-oxides according to any one of claims 1-3 in a biologically effective amount; preferably, formulation adjuvants are further included; more preferably, other active ingredients are further included.

7. A method for controlling pests and / or fungi (especially nematodes, scab, sclerotinia), characterized in that, Including contacting the pest and / or fungus or its environment with a biologically effective amount of the pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to any one of claims 1-3 or the composition according to claim 6.

8. Use of the pyridinecarboxylic acid phenylalkylamide compound, its salt, and N-oxide according to any one of claims 1-3 or the composition according to claim 6 in controlling pests and / or fungi (especially nematodes, scab, and sclerotinia).

9. An intermediate, as shown in formula II, III, IV, or V of claim 4.

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