benzimidazole derivatives

Abstract

The present invention relates to a compound of formula (I) (wherein the substituents are as defined in claim 1), a process and method for preparing a compound of formula (I), a pesticide composition comprising the compound of formula (I) as described in claim 1, the preparation of these compositions, and the use of the compound or composition in agriculture or horticulture to control, prevent or control ectoparasitism of plants, harvested food crops, seeds or non-biological materials by plant pathogenic microorganisms, particularly fungi. [Formula 1] JPEG2026524702000232.jpg69161

Description

[Technical Field]

[0001] The present invention relates to microbiocidal benzimidazole derivatives having microbiocidal activity, particularly fungicidal activity, and more particularly activity against oomycetes, for example, as active ingredients. The present invention also relates to the preparation of these benzimidazole derivatives, intermediates useful for the preparation of these benzimidazole derivatives, the preparation of these intermediates, agrochemical compositions comprising at least one benzimidazole derivative, the preparation of these compositions, and the use of benzimidazole derivatives or compositions in agriculture or horticulture to control, control or prevent ectoparasitism of plants, harvested food crops, seeds or abiotic materials by plant pathogenic microorganisms, particularly fungi, and more particularly oomycetes. [Overview of the project] [Means for solving the problem]

[0002] Surprisingly, it has now been discovered that certain novel benzimidazole derivatives possess advantageous fungicidal properties, particularly against eggs.

[0003] Therefore, in the first aspect, the present invention relates to formula (I) [ka] (In the formula, ring W is a 5-8 membered carbon ring, a 5-8 membered hetero ring, a 6-12 membered aromatic ring, or a 5-11 membered hetero aromatic ring, and each of the 5-8 membered carbon ring, 5-8 membered hetero ring, 6-12 membered aromatic ring, or 5-11 membered hetero aromatic ring is R 1 They may be optionally substituted with 1 to 4 substituents independently selected from the original, A 1 However, it is a carbon atom or a nitrogen atom, A 2 However, it is a carbon atom or a nitrogen atom, A 3 However, CR became independent 3 or N, provided there are 4 or fewer A 3 The number of A's is N, and preferably there are three or fewer A's. 3is N, preferably two or fewer A 3 is N, preferably one or fewer A 3 is N, more preferably five A 3 is CR 3 and A 4 and A 5 is independently selected from CH and N, preferably A 4 and A 5 is CH or A 4 is CH and A 5 is N or A 4 is N and A 5 is CH, even more preferably A 4 is CH and A 5 is N R 1 is halogen, hydroxy, amino, C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and CN, selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 [[ID=,80]]alkynyl, C 1-6 alkoxy, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each alkylaminocarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, hydroxyl, and CN, and optionally two geminal R groups. 1 However, they may also form a carbonyl group together with the carbon to which they are bonded. R 2 However, hydrogen, hydroxyl, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups, preferably R 2 However, hydrogen, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxy and -NHC(O)C 1-6 Selected from alkyl, more preferably R 2 However, hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Selected from alkoxy, R 3 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6Alkoxy, halogen, CN, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkylsulfanyl, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, C 1-6 Independently selected from alkylcarbonyl, and hydroxy, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkylsulfanyl, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each of the alkylcarbonyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, hydroxy, and CN, R 5 is -NHC(O)R 6 halogen, cyano, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, C 1-3 Alkylsulfonamide, C 1-3 Alkylaminocarbonyl, C 3-6 Cycloalkylaminocarbonyl, C 1-3 Alkoxyaminocarbonyl, -NHS(O)2C1-3 Alkyl, and [ka] Selected from, R 7 However, C 1-3 Alkyl and C 3-6 Selected from cycloalkyl, preferably R 5 but, [ka] Selected from, R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN, preferably R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6Selected from alkyl groups, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. The present invention provides compounds, or salts or N-oxides thereof.

[0004] In a preferred embodiment, the present invention relates to formula (I) [ka] (In the formula, ring W is a 5-8 membered carbon ring, a 5-8 membered hetero ring, a 6-12 membered aromatic ring, or a 5-11 membered hetero aromatic ring, and each of the 5-8 membered carbon ring, 5-8 membered hetero ring, 6-12 membered aromatic ring, or 5-11 membered hetero aromatic ring is R 1 They may be optionally substituted with 1 to 4 substituents independently selected from the original, A 1 However, it is a carbon atom or a nitrogen atom, A 2 However, it is a carbon atom or a nitrogen atom, A 3 However, CR became independent 3 or N, provided there are 4 or fewer A 3 The number of A's is N, and preferably there are three or fewer A's. 3 is N, preferably two or fewer A 3 is N, preferably one or less A 3 N is more preferably five A 3 CR 3 And, A 4 and A 5 However, it is independently selected from CH and N, preferably A 4 and A 5 Is CH or A 4 CH is, A 5 Is N, or A 4 N is A 5CH is, and furthermore A 4 CH is, A 5 N is, R 1 However, halogen, hydroxy, amino, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Selected from alkylaminocarbonyl and CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each alkylaminocarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, hydroxyl, and CN, and optionally two geminal R groups. 1 However, they may also form a carbonyl group together with the carbon to which they are bonded. R 2 However, hydrogen, hydroxyl, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups, preferably R 2 However, hydrogen, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxy and -NHC(O)C 1-6 Selected from alkyl, more preferably R 2 However, hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Selected from alkoxy, R 3 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, halogen, CN, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, C 1-6Selected independently from alkylcarbonyl and hydroxyl, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkylsulfonyl C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, and C 1-6 Each alkylcarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. R 5 However, -NHC(O)R 6 And, R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN, preferably R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Selected from alkyl groups, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN. The present invention provides compounds, or salts or N-oxides thereof.

[0005] In a second aspect, the present invention provides a pesticide composition comprising a compound of formula (I), more specifically, a pesticide composition comprising a bactericidal and decimaltably effective amount of a compound of formula (I). The composition may further comprise at least one compound selected from additional active ingredients, suitable inert ingredients, carriers, auxiliaries, and any mixtures thereof.

[0006] Compounds of formula (I) can be used to control plant pathogenic microorganisms. Therefore, to control plant pathogens, compounds of formula (I) according to the present invention, or compositions containing compounds of formula (I), can be applied directly to plant pathogens, habitats of plant pathogens, in particular plants susceptible to attack by plant pathogens, or plant reproductive materials.

[0007] Accordingly, in a third aspect, the present invention provides the use of a compound of formula (I) described herein, or a composition comprising a compound of formula (I), for eradicating, preventing, or controlling plant pathogens.

[0008] In a fourth aspect, the present invention provides a method for eradicating, preventing or controlling a plant pathogen, comprising applying a compound of formula (I) described herein or a composition comprising a compound of formula (I) to the plant pathogen, the habitat of the plant pathogen, in particular plants susceptible to damage by the plant pathogen, or plant reproductive material. According to this fourth aspect of the present invention, methods for treating the body of a human or animal by surgery or treatment may be excluded from this method.

[0009] Compounds of formula (I) are particularly effective in eradicating, preventing, or controlling plant pathogenic fungi, especially oomycetes. Accordingly, in a fifth aspect, the present invention provides the use of compounds of formula (I) described herein, or compositions containing compounds of formula (I), for controlling plant pathogenic fungi, especially oomycetes.

[0010] In a sixth aspect, the present invention provides a method for eradicating, preventing, or controlling plant pathogenic diseases such as plant pathogenic fungi, comprising applying a compound of formula (I) described herein or a composition containing a compound of formula (I) to the plant pathogenic fungi or the habitat of the plant pathogenic fungi (particularly plants susceptible to damage from plant pathogenic fungi, particularly oomycetes) or plant reproductive material. According to this sixth aspect of the present invention, methods for treating the body of a human or animal by surgery or treatment may be excluded from this method.

[0011] When it is indicated that a group (e.g., alkyl) is substituted, this includes these groups (e.g., alkyl in alkylthio) which are part of other groups. [Modes for carrying out the invention]

[0012] Definition: - The terms "halogen" or "halo" refer to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br), or iodine (iod or I), preferably fluorine, chlorine, or bromine.

[0013] - The term "amino" refers to the -NH2 group.

[0014] - As used herein, either alone or as part of a chemical group, the term "alkyl" preferably refers to a linear or branched hydrocarbon having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, and 2-ethylbutyl. A alkyl group having 1 to 4 carbon atoms is preferred, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl.

[0015] - The term "alkenyl," either alone or as part of a chemical group, preferably represents a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one double bond, such as vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl- 2-Pentenyl, 4-Methyl-2-Pentenyl, 3-Methyl-3-Pentenyl, 4-Methyl-3-Pentenyl, 1-Methyl-4-Pentenyl, 2-Methyl-4-Pentenyl, 3-Methyl-4-Pentenyl, 4-Methyl-4-Pentenyl, 1,1-Dimethyl-2-Butenyl, 1,1-Dimethyl-3-Butenyl, 1,2-Dimethyl-2-Butenyl, 1,2-Dimethyl-3-Butenyl, 1,3-Dimethyl-2-Butenyl This represents methyl-2-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, and 1-ethyl-2-methyl-2-propenyl. An alkenyl group having 2 to 4 carbon atoms is preferred, for example, 2-propenyl, 2-butenyl, or 1-methyl-2-propenyl.

[0016] - The term "alkynyl," either alone or as part of a chemical group, preferably refers to a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one triple bond, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, and 3-hexynyl. This represents 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl, and 2,5-hexadinyl. Alkynnyls having 2 to 4 carbon atoms are preferred, for example, ethynnyl, 2-propynyl, or 2-butynyl-2-propenyl.

[0017] - The term "cycloalkyl," either alone or as part of a chemical group, preferably refers to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic hydrocarbon having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, or adamantyl. Cycloalkyls having 3, 4, 5, 6, or 7 carbon atoms are preferred, such as cyclopropyl or cyclobutyl.

[0018] - The term "alkoxy" is derived from the formula -OR a It refers to the base of, and in the formula, R aThis refers to an alkyl group as generally defined above. Examples of alkoxys include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy. The term "alkoxyalkyl" refers to an alkyl group substituted with the alkoxy group (as described above).

[0019] - The term "alkylsulfanyl" is derived from the formula -SR a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.

[0020] - The term "alkylsulfinyl" is derived from the formula -S(O)R a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.

[0021] - The term "alkylsulfonyl" is derived from the formula -S(O)2R a It refers to the base of, and in the formula, R a This is an alkyl group as generally defined above.

[0022] - The term "alkylcarbonyl" is derived from the formula R a It refers to the C(O)- group, and in the formula, R a This is an alkyl group as generally defined above.

[0023] - The term "alkoxycarbonyl" is derived from the formula R a It refers to the OC(O)- group, and in the formula, R a This is an alkyl group as generally defined above.

[0024] - The term "alkylamino" is derived from the formula R a It refers to the NH- group, and in the formula, R a This is an alkyl group as generally defined above.

[0025] - The term "dialkylamino" is derived from the formula R a It refers to the NH- group, and in the formula, R aThis is an alkyl group as generally defined above.

[0026] - The term "alkoxyamino" is derived from the formula R a It refers to the NH- group, and in the formula, R a This is an alkoxy group as generally defined above.

[0027] - The term "alkylaminocarbonyl" is derived from the formula R a It refers to the NHC(O)- group, and in the formula, R a This is an alkyl group as generally defined above.

[0028] - The term "dialkylaminocarbonyl" is derived from the formula R a R b It refers to the base of NC(O)-, and in the formula, R a and R b This is an alkyl group as generally defined above.

[0029] - The term "alkoxyaminocarbonyl" is derived from the formula R a It refers to the NHC(O)- group, and in the formula, R a This is an alkoxy group as generally defined above.

[0030] - The term "cycloalkylaminocarbonyl" is derived from the formula R a It refers to the NHC(O)- group, and in the formula, R a This is an alkyl group as generally defined above.

[0031] - The term "alkylsulfonamide" refers to the group of the formula RaS(O)2NH-, where R a This is an alkyl group as generally defined above.

[0032] - Hydroxyl or hydroxy represents the -OH group.

[0033] In relation to the present invention, the terms “to eradicate,” “to prevent,” or “to control,” and their variations thereof, mean reducing pathogenicity, more specifically plant pathogenicity, any undesirable effects such as fungi including oomycetes, exocytosis or attack on plants or plant-derived products, and pathogenic damage, to a level in which improvement is demonstrated.

[0034] As used herein, the term "effective amount" refers to the amount of a compound, its salt, or N-oxide that produces the desired effect through one or more applications.

[0035] The effective dose can be readily determined by those skilled in the art by observing the results obtained using known techniques and under similar circumstances. Several factors, including but not limited to the following, are considered in determining the effective dose: the type of plant or derivative product to which it is applied, the pathogen being controlled and its life cycle, the specific compound to which it is applied, the type of application, and other relevant circumstances.

[0036] Compounds of formula (I) having at least one basic center can form acid addition salts, for example, with strong inorganic acids, such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrite, phosphoric acid, or hydrohalic acid; with strong organic carboxylic acids, such as unsubstituted or halogenated C1-C4 alkane carboxylic acids, such as acetic acid; with saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, or phthalic acid; with hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid, or citric acid; or with organic sulfonic acids, such as unsubstituted or halogenated C1-C4 alkanes or aryl sulfonic acids, such as methane or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can form salts with bases, such as mineral salts, such as alkali metal or alkaline earth metal salts, such as sodium, potassium or magnesium salts, or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono, di or tri lower alkylamines, such as ethyl, diethyl, triethyl or dimethylpropylamine, or mono, di or trihydroxy lower alkylamines, such as mono, di or triethanolamine.

[0037] In each case, the compound of formula (I) according to the present invention exists in free form, oxidized form as an N-oxide, covalently in hydrate form, or in salt form, such as an agrochemically usable or agrochemically acceptable salt form. The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. These are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compound of formula (I) according to the present invention also includes hydrates that may be formed during salt formation.

[0038] The compound of formula (I) according to the present invention also includes a hydrate that may be formed during salt formation.

[0039] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein four A 3 CR 3 And one A 3 This is N.

[0040] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein, [ka] but, [ka] Preferably, four A 3 However, CR 3 That is the case.

[0041] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein, [ka] but, [ka] Preferably, four A 3 However, CR 3 That is the case.

[0042] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein five A 3 However, CR 3 That is the case.

[0043] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein A 1 A is a carbon atom, 2 That is a nitrogen atom.

[0044] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein A 1 A is a carbon atom, 2 It is a carbon atom.

[0045] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein A 1 A is a nitrogen atom, 2 It is a carbon atom.

[0046] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein A 1 A is a nitrogen atom, 2 That is a nitrogen atom.

[0047] In further embodiments, compounds of formula (I) according to the present invention are provided, wherein the ring W [ka] However, the following: [ka] Selected from, During the ceremony, * represents the binding site to the benzimidazole group in formula (I), and # represents A 3 It represents the bonding point to the ring formed by the group, R 11 is hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 Selected from Alkinyl, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 Each alkynyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. Ring W is R as defined in this invention. 1It may be optionally substituted with 1 to 4 substituents selected independently of it.

[0048] More preferably, ring W [ka] The following: [ka] It can be selected from, During the ceremony, * represents the binding site to the benzimidazole group in formula (I), and # represents A 3 R represents the bonding point to the ring formed by the group. 11 However, this is as defined in the present invention. Ring W is R as defined in this invention. 1 It may be optionally substituted with 1 to 4 substituents selected independently of it.

[0049] In certain embodiments, a compound of formula (I) according to the present invention is provided, wherein, Ring W is a 5-8 membered heterocycle or a 5-11 membered heteroaromatic ring, and each of the 5-8 membered heterocycle or 5-11 membered heteroaromatic rings is R 1 They may be optionally substituted with 1 to 4 substituents independently selected from the original, A 1 However, it is a carbon atom or a nitrogen atom, A 2 However, it is a carbon atom or a nitrogen atom, more preferably a ring W [ka] The following: [ka] Selected from, During the ceremony, * represents the binding site to the benzimidazole group in formula (I), and # represents A 3 This represents the bonding point to the ring formed by the group, where the ring W is R as defined in this invention. 1R may be optionally substituted with 1 to 4 substituents independently selected from the above, 11 However, as defined in the present invention, A 3 However, CR became independent 3 or N, provided there are 3 or fewer A 3 is N, preferably two or fewer A 3 is N, preferably one or less A 3 N is more preferably five A 3 CR 3 And, A 4 CH is, A 5 N is, R 1 However, halogen, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Selected from alkoxy and CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, and C 3-6 Cycloalkyl-C 1-4 Alkyl and C 1-6 Each alkoxy group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. R 2 However, hydrogen, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy and -NHC(O)C 1-6 Selected from alkyl groups, preferably R 2 However, hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Selected from alkoxy, R3 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, halogen, CN, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Selected independently from alkyl and hydroxy, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, and C 3-6 Cycloalkyl-C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs, preferably R 3 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, halogen, C 3-6 Cycloalkyl, and C 3-6 Cycloalkyl-C 1-6 Selected independently of alkyl, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C3-6 cycloalkyl, and C 3-6 Cycloalkyl-C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs, more preferably R3 However, hydrogen, C 1-6 Alkyl, C 1-6 Selected independently from alkoxy and halogens, C 1-6 Alkyl and C 1-6 Each alkoxy group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs. R 5 However, -NHC(O)R 6 And, R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN, preferably R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Selected from alkyl groups, C 1-6 Alkyl, C1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Each alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens and CN.

[0050] In further embodiments, the compounds according to the present invention are selected from the following: Methyl N-[5-[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[2-(4-fluorophenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[1-(4-fluorophenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluorophenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluorophenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate; Methyl N-[5-[6-[3-(4-cyano-3-methoxyphenyl)pyrazine-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate.

[0051] The methods according to the present invention have advantageous properties for protecting plants from pathogenic attacks or ectoparasites that cause disease and damage to plants, such as plant pathogenic fungi, particularly oomycetes, and in the case of plants in particular, the present invention can control, limit or prevent pathogenic damage to plants, parts of plants, plant propagation materials and / or grown plants.

[0052] The compounds listed in Tables 1.1 to 1.63 below exemplify specific compounds of the present invention.

[0053] Table 1.1 shows equation (Ia) [ka] We provide a compound of which, in formula A 3a The ring W is N. [ka] but [ka] And in the formula, * represents the bond site to the benzimidazole group in formula (Ia), and # represents A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0054] [Table 1-1]

[0055] [Table 1-2]

[0056] [Table 1-3]

[0057] [Table 1-4]

[0058] [Table 1-5]

[0059] [Table 1-6]

[0060] [Table 1-7]

[0061] [Table 1-8]

[0062] Table 1-9

[0063] Table 1-10

[0064] Table 1-11

[0065] Table 1-12

[0066] Table 1-13

[0067] Table 1-14

[0068] Table 1-15

[0069] Table 1-16

[0070] Table 1-17

[0071] Table 1-18

[0072] [Table 1-19]

[0073] [Table 1-20]

[0074] [Table 1-21]

[0075] [Table 1-22]

[0076] [Table 1-23]

[0077] [Table 1-24]

[0078] [Table 1-25]

[0079] [Table 1-26]

[0080] Table 1.2 provides compounds E2.1 to E2.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0081] Table 1.3 provides compounds E3.1 to E3.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0082] Table 1.4 provides compounds E4.1 to E4.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0083] Table 1.5 provides compounds E5.1 to E5.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0084] Table 1.6 provides compounds E6.1 to E6.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0085] Table 1.7 provides compounds E7.1 to E7.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0086] Table 1.8 provides compounds E8.1 to E8.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0087] Table 1.9 provides compounds E9.1 to E9.644 of formula (Ia), where A 3a The ring W is N. [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0088] Table 1.10 provides compounds E10.1 to E10.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0089] Table 1.11 provides compounds E11.1 to E11.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia),# However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0090] Table 1.12 provides compounds E12.1 to E12.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0091] Table 1.13 provides compounds E13.1 to E13.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3and R 5 However, this is defined in Table Z.

[0092] Table 1.14 provides compounds E14.1 to E14.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0093] Table 1.15 provides compounds E15.1 to E15.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0094] Table 1.16 provides compounds E16.1 to E16.644 of formula (Ia), where A 3ais CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0095] Table 1.17 provides compounds E17.1 to E17.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0096] Table 1.18 provides compounds E18.1 to E18.644 of formula (Ia), where A 3a is CH, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0097] Table 1.19 provides compounds E19.1 to E19.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0098] Table 1.20 provides compounds E20.1 to E20.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0099] Table 1.21 provides compounds E21.1 to E21.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0100] Table 1.22 provides compounds E22.1 to E22.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5However, this is defined in Table Z.

[0101] Table 1.23 provides compounds E23.1 to E23.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0102] Table 1.24 provides compounds E24.1 to E24.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0103] Table 1.25 provides compounds E25.1 to E25.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0104] Table 1.26 provides compounds E26.1 to E26.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0105] Table 1.27 provides compounds E27.1 to E27.644 of formula (Ia), where A 3a CF is ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0106] Table 1.28 provides compounds E28.1 to E28.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0107] Table 1.29 provides compounds E29.1 to E29.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0108] Table 1.30 provides compounds E30.1 to E30.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0109] Table 1.31 provides compounds E31.1 to E31.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0110] Table 1.32 provides compounds E32.1 to E32.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0111] Table 1.33 provides compounds E331 to E33.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0112] Table 1.34 provides compounds E34.1 to E34.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0113] Table 1.35 provides compounds E35.1 to E35.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0114] Table 1.36 provides compounds E36.1 to E36.644 of formula (Ia), where A 3a is CCl, and ring W [ka] but [ka] And in the formula,* represents the bonding point to the benzimidazole group in formula (Ia), # is A 3 represents the bonding point to the ring formed by the A 3b group, and A 4 and A 5 and R 2 and R 3 and R 5 are as defined in Table Z.

[0115] Table 1.37 provides compounds E37.1 to E37.644 of formula (Ia), wherein A 3a is CCH3, and ring W

Chemical formula

Chemical formula

[0117] Table 1.39 provides compounds E39.1 to E39.644 of formula (Ia), wherein A 3a is CCH3 and ring W

Chemical formula

Chemical formula

[0118] Table 1.40 provides compounds E40.1 to E40.644 of formula (Ia), wherein A 3a is CCH3 and ring W

Chemical formula

Chemical formula

[0120] Table 1.42 provides compounds E42.1 to E42.644 of formula (Ia), where A 3a This is CCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0121] Table 1.43 provides compounds E43.1 to E43.644 of formula (Ia), where A 3a This is CCH3, and ring W [ka] is

Chem.

[0122] Table 1.44 provides compounds E44.1 to E44.644 of formula (Ia), wherein A 3a is CCH3, and ring W

Chem.

Chem.

[0123] Table 1.45 provides compounds E45.1 to E45.644 of formula (Ia), wherein A 3a is CCH3, and ring W

Chem.

Chem.

[0124] Table 1.46 provides compounds E46.1 to E46.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0125] Table 1.47 provides compounds E47.1 to E47.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5, R 2 , R 3 and R 5 However, this is defined in Table Z.

[0126] Table 1.48 provides compounds E48.1 to E48.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0127] Table 1.49 provides compounds E49.1 to E49.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0128] Table 1.50 provides compounds E50.1 to E50.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0129] Table 1.51 provides compounds E51.1 to E51.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0130] Table 1.52 provides compounds E52.1 to E52.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0131] Table 1.53 provides compounds E53.1 to E53.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0132] Table 1.54 provides compounds E54.1 to E54.644 of formula (Ia), where A 3a This is CCN, and the ring W [ka] but [ka] And in the formula, *However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0133] Table 1.55 provides compounds E55.1 to E55.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0134] Table 1.56 provides compounds E56.1 to E56.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0135] Table 1.57 provides compounds E57.1 to E57.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0136] Table 1.58 provides compounds E58.1 to E58.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0137] Table 1.59 provides compounds E59.1 to E59.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0138] Table 1.60 provides compounds E60.1 to E60.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0139] Table 1.61 provides compounds E61.1 to E61.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0140] Table 1.62 provides compounds E62.1 to E62.644 of formula (Ia), where A 3a This is COCH3, and ring W [ka] but [ka] And in the formula, * However, this represents the binding site to the benzimidazole group in formula (Ia), # However, A 3 This represents the bonding point to the ring formed by the group, A 3b , A 4 , A 5 , R 2 , R 3 and R 5 However, this is defined in Table Z.

[0141] Table 1.63 provides compounds E63.1 to E63.644 of formula (Ia), and A 3a COCH3 is, cycle is cycle 9, A 3b , A 4 , A 5 , R 2 , R 3 and R5 However, this is defined in Table Z.

[0142] The compounds according to the present invention may have numerous advantages, including, in particular, advantageous levels of biological activity for protecting plants from fungal diseases, or excellent properties for use as agricultural chemical active ingredients (e.g., higher biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or improved biodegradability). The compounds according to the present invention have particularly advantageous levels of biological activity for protecting plants from oomycetes such as Phytophthora, Plasmopara, and Pythium.

[0143] The compounds of formula (I) according to the present invention can be prepared as shown in the following schemes 1 to 13, where, unless otherwise specified, the definition of each variable site is as defined in the present invention.

[0144] The compound of formula (I) is reacted in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene with a base such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4, or NaOtBu, and a suitable catalyst such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide, or copper(I) bromide, with the compound of formula (II) and formula (III) (wherein any of R 8 However, they are either hydrogen, C1-C6 alkyl, or two R atoms, independently of each other. 8 It can be prepared by reaction with compounds (which can combine to form C3-C8 cycloalkyl groups). In some cases, the reaction results can be improved by adding boric acid or molecular sieves to the reaction mixture. These conversions are understood to be carried out under an air or oxygen atmosphere, as oxygen is required as a terminal oxidizing agent. In some cases, copper species may be used in stoichiometric amounts. This conversion is shown in Scheme 1. [ka] Scheme 1

[0145] Alternatively, the compound of formula (I) can be prepared by the reaction of the compound of formula (II) with the compound of formula (IV) (wherein X is Cl, Br, or I) in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran, or toluene, in the presence of a base such as Cs2CO3, K2CO3, K2HPO4, or NaOtBu, and a suitable palladium catalyst such as XPhos Pd G3, t-BuXPhos Pd G3, Me4tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhos Pd G3, or tBuBrettPhos Pd G3. This transformation is shown in Scheme 2. [ka] Scheme 2

[0146] Formula (IIa) (wherein, A 1 A compound of formula (Va)(where R is the carbon atom in formula (II)) is a compound of formula (Va)(where R is the carbon atom in formula (II)). 9 It can be prepared from compounds of which the protecting group is trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranil (THP). Formula (Va) (wherein R 9 Compounds of formula (VI) (wherein R is a protecting group such as SEM, Boc, or THP) are prepared in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu, and in the presence of a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, palladium dichloride [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate, or bis(diphenylphosphine)palladium(II) chloride, in the presence of formula (VI) (wherein any R 8 However, they are independently of each other: hydrogen, selected from C1-C6 alkyl groups, or two R groups. 8 These can come together to form a C3-C8 cycloalkyl group, R 9It can be prepared by the reaction of a compound of formula (VIIa) (where X is a protecting group such as SEM, Boc, or THP) with a compound of formula (VIIa) (where X is Cl, Br, or I). This transformation is shown in Scheme 3. [ka] Scheme 3

[0147] Equation (VI) (In the equation, any R 8 These are, independently of each other, hydrogen and C 1- Selected from C6 alkyl groups, or two R groups 8 together become C 3- C8 cycloalkyl can be formed, R 9 Compounds of formula (VIII) (wherein X is a protecting group such as SEM, Boc or THP) are defined as follows: 9 A compound of formula (IX) (wherein R is a protecting group such as SEM, Boc, or THP), and 8 Either one of them is independent of hydrogen and C1-C6 alkyl, or two R 8 Together in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, potassium acetate, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, palladium dichloride, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate, or bis(diphenylphosphine)palladium(II) chloride, C 3- It can be prepared by reaction with a compound of the form of C8 cycloalkyl. The compound or formula (IX) is commercially available or can be prepared by those skilled in the art using very well described procedures. Formula (VIII) (wherein X is Cl, Br or I, and R 9Compounds of formula (X) (wherein X is Cl, Br, or I) can be obtained by protecting the nitrogen of the imidazole ring of a compound of formula (X) (wherein X is Cl, Br, or I) using very well-documented procedures known to those skilled in the art. The compound or formula (X) is commercially available or can be prepared by those skilled in the art using very well-documented procedures. These transformations are shown in Scheme 4. [ka] Scheme 4

[0148] Alternatively, the compound of formula (Va) is mixed with the compound of formula (XIa) (wherein X is H, Cl, Br or I) and the compound of formula (VIII) (wherein X is Cl, Br or I) using a metal halogen exchange reagent such as butyllithium or ethylmagnesium bromide in a suitable solvent such as tetrahydrofuran, diethyl ether or dioxane. 9 However, these can be prepared by reaction with compounds containing protecting groups such as SEM, Boc, or THP. These transformations are shown in Scheme 5. [ka] Scheme 5

[0149] Compounds of formula (XIa) (wherein X is Cl, Br, or I) can be prepared by reacting a compound of formula (XIIa) with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, bromine, or iodine, and optionally a base such as lithium diisopropylamine or butyllithium, in a suitable solvent such as DMF, acetonitrile, dichloromethane, tetrahydrofuran, or acetic acid. Alternatively, compounds of formula (Va) (wherein X is Cl, Br, I, or a triflate group) can be prepared by reacting a compound of formula (VIIa) with trifluoromethanesulfonic anhydride and optionally a base such as triethylamine or pyridine, or a halogenating agent such as phosphorus oxychloride or phosphorus oxybromide, or by a sequential reaction with phosphorus oxychloride and sodium iodide. These conversions are carried out in their original form or in a suitable solvent such as dichloromethane, toluene, or xylene. These conversions are shown in Scheme 6. [ka] Scheme 6

[0150] Compounds of formula (XIIa) and (XIIIa) are commercially available or, as those skilled in the art will recognize, can be synthesized by known methods. Several methods for the synthesis of such heteroaromatic compounds can be found in the following publications: J.A. Joule and K. Mills (2010), Heterocyclic Chemistry, Fifth Edition, Wiley-Blackwell; V.J. Ram, A. Sethi, M. Nath, R. Pratap (2019), The Chemistry of Heterocycles Nomenclature and Chemistry of Three to Five Membered Heterocycles, 1st Edition, Elsevier; V.J. Ram, A. Sethi, M. Nath, R. Pratap (2019), The Chemistry of Heterocycles Chemistry of Six to Eight Membered N, O, S, P and Se Heterocycles, 1st Edition, Elsevier. Furthermore, those skilled in the art will recognize that the compounds of formula (XIIa) and formula (XIIIa) can be readily obtained by any of the following: CC cross-coupling, CN cross-coupling, or direct CH activation.A vast subset of literature describing such transformations is referenced herein: J.-Q.Chen, J.-H.Li, Z.-B.Dong, Adv.Synth Catal.2020, 362, 3311; F.Bellina, R.Rossi, Adv.Synth.Catal.2010, 1223; E.Kang, HT.Kim, JMJoo, Org.Biomol.Chem.2020, 18, 6192; Q.Yang, Y.Zhao, D.Ma, Org.Process Res.Dev.2022, 26, 1690; H.Kaddouri, V.Vicente, A.Ouali, F.Ouazzani, M.Taillefer, Angew.Chem.Int.Ed.2009, 48, 333; JJLi and GWGribble (2007), Palladium in Heterocyclic Chemistry, Second Edition, Elsevier; A. de Meijere, S. Braese, M. Oestreich (2014), Metal-Catalyzed Cross-Coupling Reactions and More, Volume 1 to 3, Wiley-VCH.

[0151] Equation (IIb)(A 2 However, the compound of the carbon atom in formula (II) is formula (Vb) (wherein R 9 It can be obtained by removing the protecting group of the compound (where is SEM, Boc, or THP). Formula (Vb) (wherein R 9 The compound of formula (XIVb) (where X is Cl, Br, or I) is mixed with the compound of formula (XV) (where R is any of the R compounds) in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water, in the presence of a base such as Cs2CO3, K2CO3, or NaOtBu, and a suitable palladium catalyst such as tetrakistriphenylphosphine palladium, palladium dichloride, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate, or bis(diphenylphosphine)palladium(II) chloride, and the compound of formula (XIVb) (where X is Cl, Br, or I) 8However, they are independently of each other: hydrogen, selected from C1-C6 alkyl groups, or two R groups. 8 It can be obtained by a coupling reaction with a compound (which can combine to form a C3-C8 cycloalkyl group). The compound or formula (XV) is commercially available or can be prepared by those skilled in the art using very well described procedures. This transformation is shown in Scheme 7. [ka] Scheme 7

[0152] Formula (XIVb) (wherein, R 9 The compound of formula (XVIb) (wherein R is a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP), and X is Cl, Br, or I) is used in a suitable solvent such as DMF, acetonitrile, dichloromethane, or tetrahydrofuran. 9 This can be prepared by reacting a compound with a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranil (THP), where X is Cl, Br, or I, with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, or N-iodosuccinimide. This conversion is shown in Scheme 8. [ka] Scheme 8

[0153] Formula (IIc) (wherein, A 1 Compounds of formula (Vc) (where R is the nitrogen atom in formula (II)) are defined as follows: 9 It can be obtained by removing the protecting group of a compound (where R is a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranil (THP)). Formula (Vc) (wherein R 9Compounds of formula (XIVc) (where R is a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP)) are prepared in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran, or toluene, in the presence of a base such as Cs2CO3, K2CO3, K2HPO4, or NaOtBu, and a suitable palladium catalyst, and in the presence of a suitable palladium catalyst such as XPhos Pd G3, t-BuXPhos Pd G3, Me3tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhos Pd G3, or tBuBrettPhos Pd G3. 9 A compound of formula (XV) (wherein any R is a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranil (THP), and X is Cl, Br, or I), and formula (XV) (wherein any R 8 However, they are independently of each other: hydrogen, selected from C1-C6 alkyl groups, or two R groups. 8 This can be obtained by a coupling reaction with a compound (which can combine to form a C3-C8 cycloalkyl group). This transformation is shown in Scheme 9. [ka] Scheme 9

[0154] Alternatively, equation (Vc) (where R 9 Compounds of formula (VI) (wherein R is a protecting group such as SEM, Boc, or THP) are prepared in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene, in the presence of a base such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4, or NaOtBu, and a suitable catalyst such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide, or copper(I) bromide, in the presence of formula (VI) (wherein any R 8 However, they are independently of each other: hydrogen, selected from C1-C6 alkyl groups, or two R groups. 8These can come together to form a C3-C8 cycloalkyl group, R 9 This can be prepared by coupling a compound of formula (XIIc) with a compound of formula (XIIc) (where is a protecting group such as SEM, Boc, or THP). In some examples, the reaction outcome can be improved by adding boric acid or molecular sieves to the reaction mixture. These conversions are understood to be carried out under air, as oxygen is required as the terminal oxidizing agent. In some cases, copper species may be used in stoichiometric amounts. This conversion is shown in Scheme 10. [ka] Scheme 10

[0155] Compounds of formula (XVII) (wherein X is Cl, Br, or I) are prepared in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene, in the presence of a base such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4, or NaOtBu, and a suitable catalyst such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide, or copper(I) bromide, in the presence of compound (III) (wherein R 8 However, they are independently of each other: hydrogen, selected from C1-C6 alkyl groups, or two R groups. 8 These can be prepared by Suzuki cross-coupling of a compound of formula (XVIII) (wherein X is Cl, Br, or I) with a compound of formula (XVIII). In some cases, the reaction results can be improved by adding boric acid or molecular sieves to the reaction mixture. These conversions are understood to be carried out under an air or oxygen atmosphere, as oxygen is required as the terminal oxidizing agent. In some cases, copper species may be used in stoichiometric amounts. This conversion is shown in Scheme 11. [ka] Scheme 11

[0156] Compounds of formula (XVIII) (wherein X is Cl, Br, or I) are mixed with compounds of formula (XIX) (wherein X is Cl, Br, or I) in a suitable solvent such as toluene, methanol, ethanol, acetonitrile, or water, in the presence of an acid such as tosyl sulfonic acid, sulfuric acid, or trifluoroacetic acid, and compound (XX) (wherein R 10 However, it can be prepared by reaction with a compound (which is C1-C6 alkyl). This transformation is shown in Scheme 12. [ka] Scheme 12

[0157] Compounds of formula (XIX) (wherein X is Cl, Br, or I) can be prepared by reduction of compound (XXI) (wherein X is Cl, Br, or I) with hydrogen in a suitable solvent such as tetrahydrofuran, ethanol, methanol, or water, in the presence of a catalyst such as palladium acetate or palladium, and using iron or zinc in the presence of an acid such as hydrochloric acid, ammonium chloride, or acetic acid. Compounds of formula (XXI) (wherein X is Cl, Br, or I) can be prepared by reduction of compound (XXII) (wherein X is Cl, Br, or I) with hydrogen in a suitable solvent such as tetrahydrofuran, ethanol, methanol, acetonitrile, or N,N-dimethylformamide. 2 However, it can be prepared by the reaction of a compound (which is F, Cl, Br or I) with a compound of formula (XXIII) and a base such as Cs2CO3, K2CO3, triethylamine, N,N-diethylethaneamine or sodium tert-butoxide. This transformation is shown in Scheme 13. [ka] Scheme 13

[0158] Those skilled in the art will also recognize that compounds of formula (I) can be prepared by de novo construction of ring W. Such synthetic routes have been used and are described in the experimental section of this invention. Those skilled in the art will also understand that the synthetic routes describing access to these particular compounds can also be used to synthesize similar compounds of formula (I) of these particular compounds (which have the same ring W). Therefore, these routes described in the experimental section should also be considered general routes for obtaining compounds of formula (I).

[0159] The compounds of the following formulas (Id) and (IId) can be prepared according to the synthetic routes used in Examples 1 and 2. Example 1 describes the preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 6), and Example 2 describes the preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 2). These synthetic routes describe the de novo synthesis of the compound of formula (Id) in which ring W is 1,2,4-oxadiazine, and the synthesis of the compound of formula (IId) in which ring W is 1,2,4-oxadiazine. This method can be commonly used to obtain compounds similar to those of formula (Id) and formula (IId). [ka]

[0160] The compounds of formulas (Ie) and (IIe) below can be prepared according to the synthetic route used in Example 3. Example 3 describes the preparation of methyl N-[5-[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 5). This synthetic route describes the de novo synthesis of the compound of formula (Ie) where ring W is imidazole, and the synthesis of the compound of formula (IIe) where ring W is imidazole. These methods can be commonly used to obtain similar compounds of formulas (Ie) and (IIe). [ka]

[0161] The compounds of formulas (If) and (IIf) below can be prepared according to the synthetic route used in Example 4. Example 4 describes the preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 7). This synthetic route describes the de novo synthesis of the compound of formula (If) where ring W is triazole, and the synthesis of the compound of formula (IIf) where W is triazole. These methods can be commonly used to obtain similar compounds of formulas (If) and (IIf). [ka]

[0162] The compounds of formulas (Ig) and (IIg) below can be prepared according to the synthetic routes used in Examples 5 and 6. Example 5 describes the preparation of methyl N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 9), and Example 6 describes the preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 11). This synthetic route describes the de novo synthesis of the compound of formula (Ig) in which ring W is triazole, and the synthesis of the compound of formula (IIg) in which ring W is triazole. This method can be commonly used to obtain compounds similar to those of formula (Ig) and formula (IIg). [ka]

[0163] The compounds of formulas (Ih) and (IIh) below can be prepared according to the synthetic route used in Example 7. Example 7 describes the preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 1). This synthetic route describes the de novo synthesis of the compound of formula (Ih) where ring W is triazole, and the synthesis of the compound of formula (IIh) where ring W is triazole. This method can be commonly used to obtain similar compounds of formulas (Ih) and (IIh). [ka]

[0164] It will be understood by those skilled in the art that some of the above reactions, in which the central imidazole (or triazole) nitrogen atom is unsubstituted, may function more efficiently if that imidazole (or triazole) nitrogen atom is masked with a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranil (THP). The protection reactions of imidazole and triazole rings with SEM, Boc, or THP, along with the subsequent deprotection of those groups, are transformations well understood by those skilled in the art. Information on these transformations can be found in literature such as Greene's Protective Groups in Organic Synthesis, Fourth Edition, Chapter 7.

[0165] When the term "compound / multiple compounds according to the present invention" is used, it refers to the compound according to the present invention.

[0166] Alternatively, the compounds according to the present invention can be obtained by using standard synthetic techniques known to those skilled in the art. Non-exclusive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, olefination reactions, oxime formation, alkylation, and halogenation reactions.

[0167] Compounds according to the present invention can be converted in a manner known by themselves to other compounds according to the present invention by replacing one or more substituents of the starting compound according to the present invention with other substituents according to the present invention in a conventional manner.

[0168] Depending on the selection of suitable reaction conditions and starting materials in each case, for example, it may be possible to replace only one substituent with another substituent according to the present invention in one reaction step, or to replace multiple substituents with other substituents according to the present invention in the same reaction step.

[0169] Salts of the compounds according to the present invention can be prepared by methods known in themselves. For example, acid addition salts of the compounds according to the present invention can be obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with a base can be obtained by treatment with a suitable base or a suitable ion exchange reagent.

[0170] Salts of the compounds according to the present invention can be converted to the free compound by conventional methods, acid addition salts can be converted, for example, by treatment with a suitable basic compound or a suitable ion exchange reagent, and salts with a base can be converted, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

[0171] Salts of the compounds according to the present invention can be converted to other salts of the compounds according to the present invention, acid addition salts, for example, other acid addition salts, by methods known to the present invention, for example, by treatment of an inorganic acid salt, such as a silver acetate hydrochloride, with a suitable metal salt of the acid, such as a sodium, barium, or silver salt of the acid, in a suitable solvent (for example, an inorganic salt that forms silver chloride is insoluble therein and therefore precipitates from the reaction mixture).

[0172] Depending on the procedure or reaction conditions, the compounds according to the present invention, which have salt-forming properties, can be obtained in free form or in salt form.

[0173] In each case, the compounds according to the present invention, in free form or salt form, and optionally their tautomers, may exist in one form of possible stereoisomers or as mixtures thereof, depending on the number, absolute and relative configuration of chiral carbon atoms present in the molecule and / or the configuration of non-aromatic double bonds present in the molecule, in the form of pure isomers, such as anticellar and / or diastereomers, or as enantiomer mixtures, such as racemic compounds, diastereomer mixtures or racemic compound mixtures; the present invention relates to pure stereoisomers and to all possible stereoisomer mixtures, and in all cases above and below, even when stereochemical details are not specifically described, they should be understood in this sense.

[0174] Depending on the starting materials and procedures selected, the diastereomer mixtures or racemic compounds of the compounds according to the present invention, either in free or salt form, can be separated into pure diastereomers or racemic compounds based on physicochemical differences of the components by known methods, such as fractional crystallization, distillation, and / or chromatography.

[0175] Enantiomer mixtures such as racemates, which can be obtained by similar methods, can be separated into optical counterparts by known methods, for example by recrystallization from an optically active solvent, by chromatography on a chiral adsorbent, for example by high-performance liquid chromatography (HPLC) on acetylcellulose with the help of suitable microorganisms, by cleavage with a specific immobilized enzyme using a chiral crown ether, for example, through the formation of an inclusion compound, so that only one enantiomer is complexed, or by conversion to a diastereomer salt, for example by reacting the racemate, which is a basic final product, with an optically active acid, for example carboxylic acid, such as camphor, tartaric acid, or malic acid, or sulfonic acid, such as camphorsulfonic acid, and the diastereomer mixture thus obtained can be separated, for example by fractional crystallization based on their different solubility to obtain diastereomers (from which the desired enantiomer can be released by the action of a suitable reagent, such as a basic reagent).

[0176] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating a suitable mixture of stereoisomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example, by carrying out the steps according to the present invention using suitable stereochemical starting materials. N-oxides can be prepared by reacting the compounds according to the present invention with a suitable oxidizing agent, such as an H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidation is known from the literature, for example from J.Med.Chem.,32(12),2561-73,1989 or International Publication No. 00 / 15615.

[0177] When individual components have different biological activities, it is advantageous to isolate or synthesize the more biologically effective stereoisomers, such as enantiomers or diastereomers, or stereoisomer mixtures, such as enantiomer mixtures or diastereomer mixtures, in each case.

[0178] The compounds according to the present invention and, optionally, their tautomers may be obtained in free form or salt form, optionally in hydrate form, and / or in other solvents, such as solvents that have been used to crystallize compounds existing in solid form.

[0179] The following examples illustrate, but are not limiting, the present invention.

[0180] The compounds of formula (I) as defined in this invention may be used, for example, as active ingredients for controlling plant pathogens, or as non-living substances for controlling potentially harmful microorganisms or organisms to humans in the agricultural sector and related fields of use. Novel compounds are distinguished by their excellent activity at low doses, the sufficient tolerance exhibited by plants, and their environmental safety. They possess highly useful therapeutic, preventive, and systemic properties and can be used to protect many cultivated plants. The compounds of formula (I) as defined in this invention can also be used to suppress or eradicate pathogens appearing on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting those parts of the plant that will grow later from plant pathogenic microorganisms.

[0181] Compounds of formula (I) as defined in the present invention may also be used as fungicides. As used herein, the term “fungicide” means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidal effective amount” means an amount of a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural occurrence, such as death or delay, and prevention includes the formation of barriers or other defenses in or on plants to prevent fungal infection.

[0182] For protection against fungal infections and plant pathogenic fungi occurring in the soil, the compound of formula (I) as defined in this invention may also be used as a coating agent for treating plant propagation materials, such as seeds, tubers or grains, or plant cuttings (e.g., rice), such as fruits. The propagation material may be treated with a composition containing the compound of formula (I) as defined in this invention before planting: for example, seeds may be coated before sowing. The compound of formula (I) as defined in this invention may also be applied to grains (coated) by impregnating them in a liquid formulation or by coating the seeds with a solid formulation. The composition may also be applied to the planting site when the propagation material is planted, for example, in the sowing furrow during sowing. This invention also relates to such methods for treating plant propagation materials and to plant propagation materials thus treated.

[0183] Furthermore, the compounds of formula (I) as defined in the present invention may be used in related fields, for example, in the protection of industrial materials, including wood and wood-related industrial products, in food storage, and in hygiene management to control fungi.

[0184] In addition, the present invention may also be used to protect non-biological materials, such as sawn timber, wall coverings, and paints, from fungal attacks.

[0185] The compounds of formula (I) as defined in this invention, and fungicidal compositions containing them, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens. They are effective in controlling a wide range of plant diseases, including leaf pathogens of ornamental plants, turfgrasses, vegetables, crops, grains, and fruit crops.

[0186] The fungi and fungal vectors, as well as plant pathogenic bacteria and viruses, that can be controlled for these diseases include, for example, the following: This includes species such as Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. (including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus), Aureobasidium spp. (including A. pullulans), Blastomyces dermatitidis, Blumeria graminis, and Bremia lactucaea. This includes species of the genus Botryosphaeria (including B. lactucae, B. dothidea, and B. obtusa), species of the genus Botrytis (including B. cinerea), species of Candida (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, and C. tropicalis), species of Cephaloascus fragrans, and species of Ceratocystis. Cercospora spp. (including C. arachidicola), Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., and Colletotrichum spp., including C. musae. Cryptococcus neoformans, Diaporthe spp., Didymella spp., Drechslera spp., Elsinoe spp. This includes species of the genus Epidermophyton (spp.), Erwinia amylovora, and Erysiphe species, including E. cichoracearum. Fusarium spp., including Eutypa lata, F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, and Gloeosporium musarum. musarum), Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium sediciosum This includes species such as *Mycosphaerella* (including *M. graminicola*), *Microdochium nivale*, *Microsporum*, *Monilinia*, *Mucor*, *M. graminicola*, and *M. pomi*.), Oncobasidium theobromaeon, Ophiostoma piceae, species of the genus Paracoccidioides spp., species of the genus Penicillium including P. digitatum and P. italicum, species of the genus Petriellidium spp., species of Peronosclerospora including P. maydis, P. philippinensis and P. sorghi, species of Peronospora spp., species of Peronospora, wheat blight fungus (Phaeosphaeria) *Phonophora nodorum*, Phakopsora pachyrhizi, Phellinus igniarus, *Phialophora* spp., *Phoma* spp., *Phomopsis viticola*, *Phytophthora* spp. including *P. infestans*, *Plasmopara* spp. including *P. halstedii*, *P. viticola*, *Pleospora* spp., *Podosphaera* spp. including apple powdery mildew fungus (*P. leucotricha*), *Polymyxa graminis* Pseudomonas graminis), Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis and P. humuli, Pseudopeziza tracheiphila, P. hordei (P.Puccinia spp. (including P. hordei), P. recondita, P. striiformis, P. triticina), Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. (including P. oryzae, the rice blast fungus), Pythium spp. (including P. ultimum), Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arizus This includes species of the genus Rhynchosporium (including *arrhizus*), *Rhynchosporium* spp., *Scedosporium* spp. (including *S. apiospermum* and *S. prolificans*), and *Schizothyrium pomi*. Species of the genera Sclerotinia, Sclerotium, Septoria (including S. nodorum and S. tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix, Stagonospora nodorum, Stemphylium, Stereum hirsutum, and Thanatephorus cucumeris. This includes species such as *Tilletia cucumeris*, *Tilletia basicola*, *Tilletia spp.*, *T. harzianum*, *T. pseudokoningii*, and *T. viride*, as well as species of the genus *Trichoderma*. Species belonging to the genera Trichophyton, Typhula, Uncinula necator, Urocystis, Ustilago, Venturia (including V. inaequalis), Verticillium, and Xanthomonas.

[0187] In particular, compounds of formula (I) as defined in the present invention, and fungicidal compositions containing them, can be used to control plant diseases caused by broad-spectrum fungal plant pathogens in basidiomycetes, ascomycetes, oomycetes and / or deuteromycetes, blasocladiomycetes, chytridiomycetes, glomeromycetes and / or mucoromycetes. More specifically, compounds of formula (I) as defined in the present invention can be used to control oomycetes.

[0188] These pathogens may include the following: Phytophthora diseases, such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, and Phytophthora erythroseptica; and Pythium aphanidermatum and Pythium arenomanes. Pythium diseases, such as those caused by *Pythium arrhenomanes*, *Pythium graminicola*, *Pythium irregulare*, *Pythium sylvaticum*, and *Pythium ultimum*; *Peronospora destructor*, *Peronospora parasitica*, *Plasmopara viticola*, *Plasmopara halstedii*, *Pseudoperonospora cubensis*, *Albugo candida*, and *Sclerophthora macrospora*. Diseases caused by Peronosporales, such as macrospora and Bremia lactucae;Oomycetes, including other species such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi, and Sclerospora graminicola; Ascomycetes, including leaf spot, leaf spot, blast disease or weak spot and / or rot, such as Stemphylium solani, Stagonospora tainanensis, Spirocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, and Helminthosporium triticilepentis. *Tricirepentis*, *Setosphaeria turcica*, *Pyrenophora tritici-repentis*, *Alternaria brassicicola*, *Alternaria solani*, and *Alternaria tomatophila*, *Capsules*, such as *Septoria tritici*, *Septoria glycines*, *Cercospora sojina*, *Cladosporium carpophilum*, and *Cladosporium effusum*. bataticola, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella phiensisGraminicola), Magnaportares, for example Gaeumannomyces graminis, Mignaporthe grisea, Pyricularia oryzae, Diportares viticola, for example Anisogramma anomala, Apiognomonia errabunda, Sirococcus clavigignenti juglandacearum, Valsa ceratosperma, and Actinothyrium graminis, Aspergillus Aspergillus flavus, Capnodium ramosum, Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Eutypa LATA, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi sorghi), Gloeodes pomigena, Gloetinia temulenta, Glyphospheria microdochium nivale, Monilinia fructicola, Monographella albecensalbescens), Monosporascus cannonballus, Naemacyclus spp., Ophioides, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans pomi, Pseudopeziza medaginis, Pyrenopeziza brassicae, Sclerotium spp., Typhula ishikariensis ishikariensis), Seimatosporium mariae, Lepteutypa cupressi, Sphaceloma perseae, powdery mildew, for example, Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaera fuligena, Podosphaera leucotricha, Podosphaera fungi, for example, Botryosphaeriales, for example, Dothiorella aromatica, Diplodia celiata seriata), Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, anthrax, for example, Colletotrichum groeospolioidesgloeosporioides), Colletotrichum lagenarium, Colletotrichum graminicola (Colletotrichum) gossypii, Gromerella singula, and Wilts virguliforme or Bright, e.g., oxysporum. Hypocreales, e.g., Acremonium strictum, Claviceps purpurea, Fusarium culmorum oxysporum, Fusarium graminearum subglutinans, Fusarium cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium species. (spp.), Myrothecium verrucaria The Basidiomycete class includes the following: Ustilaginales, which cause smut disease, such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, and Ustilago zeae; and Puccinia, which cause rust disease, such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, and Puccinia cacabata. Puccinia cacabata), Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. cecalisPucciniales, such as Secalis, Pucciniastrum coryli, or Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor, and Uromyces viciae-fabee. Those caused by Uredinales species such as viciae-fabae; and other rots and diseases, such as Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, and Mycena spp.), Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia molliniae Caused by *Tillets* (*Moliniae*) and *Tillets* caries. Blastocladiomycetes, such as Physoderma maydis. Mucoromycete species, such as Choanephora cucurbitarum, Mucor spp., and Rhizopus arrhizus. Furthermore, diseases caused by other species and genera closely related to those listed above.

[0189] In addition to their fungicidal activity, the compounds of formula (I) as defined in the present invention and compositions containing such compounds may also be active against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies, and other related species, as well as certain protozoa.

[0190] Within the scope of the present invention, target crops and / or useful plants to be protected are typically perennial and annual crops, e.g., berry plants, e.g., blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, e.g., barley, maize (corn), millet, oats, rice, rye, sorghum, rye, and wheat; fiber plants, e.g., cotton, flax, hemp, jute, and sisal; crops, e.g., sugar and fodder beets, coffee, hops, mustard, rapeseed (canola), poppies, sugarcane, sunflowers, tea, and tobacco; fruit trees, e.g., apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; pasture grasses, e.g., Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass , St. Augustine grass and Zoysia grass; herbs, such as basil, borage, chives, coriander, lavender, lavage, mint, oregano, parsley, rosemary, sage, and thyme; legumes, such as kidney beans, lentils, peas, and soybeans; nuts, such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palms, such as oil palms; ornamental plants, such as flowers, shrubs, and trees; other trees, such as cocoa, coconut, olive, and rubber; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, mallow, melon, okra, onions, pepper, potatoes, pumpkins, rhubarb, spinach, and tomatoes; and climbing plants, such as grapes.

[0191] Useful plants and / or target crops according to the present invention include conventional varieties and genetically enhanced or engineered varieties, such as insect-resistant (e.g., Bt. and VIP varieties), disease-resistant, herbicide-resistant (e.g., glyphosate and glufosinate-resistant maize varieties, commercially available under trade names RoundupReady® and LibertyLink®), and nematode-resistant varieties. Examples of appropriately genetically enhanced or engineered varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

[0192] The terms “useful plants” and / or “target crops” should be understood to also include useful plants that have been conferred resistance to herbicides or classifications of herbicides (e.g., HPPD inhibitors, ALS inhibitors, e.g., primisulfuron, prosulfuron, and trifloxysulfuron, EPSPS (5-enol-pyruvir-shikimic acid-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors, or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional breeding methods or genetic manipulation. An example of a crop conferred resistance to imidazolinones, e.g., imazamox, by conventional breeding methods (mutation) is Clearfield® summer rapeseed (canola). Examples of crops in which resistance to herbicides or certain classes of herbicides has been induced through genetic engineering include glyphosate- and glufosinate-resistant maize varieties marketed under trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0193] The terms “useful plants” and / or “target crops” should be understood to include those that are naturally resistant to or conferred resistance to harmful insects. This includes plants transformed by the use of recombinant DNA technology, for example, to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxin, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-symbiotic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi. An example of a crop modified to express Bacillus thuringiensis toxin is Bt maize KnockOut® (Syngenta Seeds). An example of a crop containing multiple genes that express multiple toxins in order to encode insecticide resistance is VipCot® (Syngenta Seeds). Furthermore, crops or their seed materials can exhibit resistance to multiple types of pests (so-called stacked transgenic events, which are produced by genetic modification). For example, plants may have the ability to express insecticidal proteins while simultaneously being herbicide resistant, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0194] The terms “useful plants” and / or “target crops” should be understood to also include useful plants transformed using recombinant DNA technology to enable the synthesis of selectively acting antipathogenic substances, such as so-called “infection-specific proteins” (PRPs, see, e.g., European Patent Application Publication No. 0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from European Patent Application Publication No. 0 392 225, International Publication No. 95 / 33818 and European Patent Application Publication No. 0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications.

[0195] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis such as δ-endotoxins like Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip) such as Vip1, Vip2, Vip3 or Vip3A; or Photorhabdus luminescens, Xenorhabdus nematophilus, etc., such as Photorhabdus spp. or Xenorhabdus Insecticidal proteins of nematode-symbiotic bacteria such as spp.; toxins produced by animals such as scorpion venom, spider venom, large wasp (wasp) venom and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete venom, plant lectins such as pea lectin, barley lectin or snowdrop lectin; aglutinin; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors; lysine, maize-RIP, Examples include ribosomal inactivating proteins (RIPs) such as abrin, rufin, saporin, or briodin; steroid metabolic enzymes such as 3-hydroxysteroid xidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, and HMG-COA-reductase; ion channel blockers such as sodium or calcium channel blockers; juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase, and glucanase.

[0196] Furthermore, it should be understood that in connection with the present invention, there exist δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, as well as explicitly hybrid toxins, cleavage toxins, and modified toxins. Hybrid toxins are recombinantly produced by novel combinations of different domains of these proteins (see, for example, International Publication No. 02 / 15701). Cleavage toxins, such as cleavage 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 substitutions, preferably a protease recognition sequence that is not naturally occurring is inserted into the toxin, for example, in the case of Cry3A055, and a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 03 / 018810).

[0197] Additional examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Application Publication No. 0374753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, European Patent Application Publication No. 0427529, European Patent Application Publication No. 451878, and International Publication No. 03 / 052073.

[0198] The preparation process for such transgenic plants is generally known to those skilled in the art and is described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparations are known, for example, from International Publication No. 95 / 34656, European Patent Application Publication No. 0367474, European Patent Application Publication No. 0401979, and International Publication No. 90 / 13651.

[0199] The toxins contained in transgenic plants confer resistance to harmful insects. Such insects can exist in any of the insect taxa, but are typically found in beetles (Coleoptera), diptera (Diptera), and butterflies (Lepidoptera).

[0200] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include: YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing Cry1Ac toxin); Bollgard Examples include II (registered trademark) (cotton varieties expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (cotton varieties expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (potato varieties expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), and Protecta (registered trademark).

[0201] Further examples of such genetically modified crops include: 1. Bt11 Maize: Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, Registration No. C / FR / 96 / 05 / 10. Genetically modified maize (Zea mays) conferring resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the cleavage-type Cry1Ab toxin. Bt11 maize has also achieved resistance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT. 2. Bt176 Maize: Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, Registration No. C / FR / 96 / 05 / 10. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize has also achieved resistance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT. 3. MIR604 Maize: Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize conferred insect resistance by transgenic expression of modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. Preparation of such transgenic maize plants is described in International Publication No. 03 / 018810. 4. MON 863 Maize: Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects. 5. IPC 531 Cotton: Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, Registration No. C / ES / 96 / 02. 6.1507 Maize, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein Cry1F to acquire resistance to certain Lepidoptera insects and the PAT protein to acquire resistance to the herbicide glufosinate ammonium. 7. NK603 X MON810 Maize: Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, Registration No. C / GB / 02 / M3 / 03. This is a conventional hybrid maize variety resulting from the cross between genetically modified varieties NK603 and MON 810. NK603 X MON 810 maize transgenically expresses the protein CP4 EPSPS, obtained from the Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (which contains glyphosate), and the Cry1Ab toxin, obtained from Bacillus thuringiensis subsp. kurstaki, which provides resistance to certain Lepidoptera, including the European corn borer.

[0202] As used herein, the term “habitat” means cultivated land on which plants grow, or on which seeds of cultivated plants are sown, or on which seeds will be sown in the soil. It includes soil, seeds and seedlings, and established vegetation.

[0203] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0204] The term "plant propagation material" is understood to refer to reproductive parts such as seeds, and vegetative propagation materials such as cuttings or tubers, which can be used for the propagation of plants, such as potatoes. Examples include (strictly speaking) seeds, roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Also, germinated plants and seedlings that will be transplanted after germination or emergence from the soil may be referred to. These seedlings may be protected before transplantation by total or partial treatment by immersion. Preferably, "plant propagation material" is understood to mean seeds. The pesticides referred to herein by their common names are publicly known, for example, from "The Pesticide Manual," 19th Ed., British Crop Protection Council 2021.

[0205] The compounds of formula (I) as defined in the present invention may be used in their unmodified form or, preferably, in combination with auxiliaries conventionally used in the art of formulation. For this purpose, they may be appropriately incorporated in known ways into emulsifiable concentrates, coating pastes, sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, powders for spraying, granules, and also, for example, encapsulations in polymeric substances. As with the type of composition, the method of application, such as spraying, misting, powdering, granulation, coating, or pouring, may be selected according to the intended purpose and the circumstances at the time. The composition may also contain further auxiliaries such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, micronutrient donors, or other formulations for obtaining special effects.

[0206] For example, suitable carriers and / or auxiliaries for agricultural applications may be solids or liquids and are substances useful in compounding techniques, such as natural or recycled inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are described, for example, in International Publication No. 97 / 33890.

[0207] A suspension concentrate is an aqueous formulation in which finely ground solid particles of an active compound are suspended. Such formulations may further contain anti-settling agents and dispersants, wetting agents to enhance activity, and antifoaming agents and crystal growth inhibitors. When used, these concentrates are diluted with water and typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.

[0208] Wettable powders are in the form of finely ground particles that disperse easily in water or other liquid carriers. The particles contain the active ingredient held within a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica, and other easily humidifiable organic or inorganic solids. Wettable powders typically contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersants, or emulsifiers.

[0209] Emulsifying concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of an active compound and a liquid or solid emulsifier, or they may also contain liquid carriers such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and typically applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0210] Granular formulations include both extruded materials and relatively coarse particles and are typically applied undiluted to the area requiring treatment. Typical carriers for granular formulations include sand, fuller's soil, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cob, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or coat active compounds. Granular formulations typically contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or stickers such as dextrin, glue or synthetic resins.

[0211] The powder is a free-flowing mixture of the active ingredient and finely pulverized solids such as talc, clay, powder, and other organic and inorganic solids that act as a dispersant and carrier.

[0212] Microcapsules are typically droplets or granules of an active ingredient encapsulated within an inert, porous shell that allows for the controlled release of the encapsulated material into the surroundings. Encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's mass and may include a solvent in addition to the active compound. Encapsulated granules are generally porous granules having a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form inside the granular pores. Granules are typically 1 millimeter to 1 centimeter in diameter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or they may be naturally occurring. Examples of such materials include vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granular carbon. Examples of shell or membrane materials include natural and synthetic rubber, cellulose-based materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthetes.

[0213] Other useful formulations for agricultural applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalene, xylene, and other organic solvents, in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprayers may also be used, in which the active ingredient is dispersed in a finely pulverized form as a result of evaporation of a low-boiling point dispersible solvent carrier.

[0214] Suitable agricultural additives and / or carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those skilled in the art.

[0215] Examples of liquid carriers that can be used include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, Alpha-pinene, d-Limonene, Ethylene glycol, Ethylene glycol butyl ether, Ethylene glycol methyl ether, γ-Butyrolactone, Glycerol, Glycerol diacetate, Glycerol monoacetate, Glycerol triacetate, Hexadecane, Hexylene glycol, Isoamyl acetate, Isobornyl acetate, Isooctane, Isophorone, Isopropylbenzene, Isopropyl myristate, Lactic acid, Laurylamine, Mesityl oxide, Methoxypropanol, Methyl isoamyl ketone, Methyl isobutyl ketone, Methyl laurate, Methyl octanoate, Methyl oleate, Methylene chloride, m-Xylene, n-Hexane, n-Octylamine, Octadeca Examples include sodium phosphate, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol and other high molecular weight alcohols, ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally a preferred carrier for diluting concentrates.

[0216] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth (kieselguhr), white pigment, diatomaceous earth (diatomaxeous earth), lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

[0217] A wide range of surfactants are advantageously used in both liquid and solid compositions, particularly those designed to be diluted with a carrier before application. When used, these agents typically constitute 0.1% to 15% by mass of the formulation. They may be anionic, cationic, nonionic, or polymeric and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfate salts, e.g., diethanolammonium lauryl sulfate; alkylaryl sulfonate salts, e.g., calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g., nonylphenol-C.sub.18 ethoxylate; tridecyl alcohol-C.sub.16 ethoxylate; soaps, e.g., sodium stearate; alkylnaphthalene sulfonate salts, e.g., sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, e.g., sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, e.g., sorbitol oleate; quaternary amines, e.g., lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, e.g., polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

[0218] Other additives commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light-shielding agents, compatibilizers, chelating agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, mitigating agents, lubricants, and fixing agents.

[0219] In addition, other biocides or compositions may be combined with the composition of the present invention and used in the method of the present invention, either simultaneously with or sequentially with the composition of the present invention. When applied simultaneously, these further active ingredients may be compounded together with the composition of the present invention or mixed, for example, in a spray tank. These further biocides may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and / or biological formulations. The following combinations of the compound of formula I with another active substance in a 1:1 weight ratio are preferred (the abbreviation "TX" means "one compound selected from the compounds defined in Tables 1.1 to 1.63 and Table A"): (7E,9Z)-Dodeca-7,9-diene-1-ylacetate+TX, (9Z,11E)-Tetradeca-9,11-diene-1-ylacetate+TX, (9Z,12E)-Tetradeca-9,12-diene-1-ylacetate+TX, (E)-6-methylhepta-2-en-4-ol+TX, (E)-Deca-5-en-1-ylacetate and (E)-Deca-5-en-1-ol+TX, (E)-Trideca-4-en-1-ylacetate+TX, (E,Z)-Tetradeca-4,10-diene-1-ylacetate+TX, (Z)-Dodeca-7-en-1-ylacetate+TX, (Z)-Hexadeca-11-en-1-ylacetate+TX, (Z)-Hexadeca- 11-Enal + TX, (Z)-Hexadeca-13-en-11-in-1-yl acetate + TX, (Z)-Icosa-13-en-10-one + TX, (Z)-Tetradeca-7-en-1-al + TX, (Z)-Tetradeca-9-en-1-ol + TX, (Z)-Tetradeca-9-en-1-yl acetate + TX, 1,2-Dibromo-3-chloropropane + TX, 1,2-Dichloropropane + TX, 1,2-Dichloropropane and 1,3-Dichloropropene + TX, 1,3-Dichloropropene + TX, 14-Methyloctadecene-1-ene + TX, 1-H-pyridine-2-thione + TX, 2-(Octylthio)ethanol + TX, 2-Chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinosyl + TX, acetamiprid + TX, acetoprol + TX, acrinatrin + TX, aquinonapyr + TX, Adoxophyes oranaGV+TX, Afidopiropen+TX, Afoxolaner+TX, Agrobacterium radioactive bacteria+TX, AKD-3088+TX, Aranicarb+TX, Aldicarb+TX, Aldocicarb+TX, Allethrin+TX, Alpha-cypermethrin+TX, Alphamethrin+TX, Alpha-multistriatin+TX, Amblyseius spp.+TX, Amidoflumet+TX, Amino acids+TX, Aminocarb+TX, Anaprapha falcifera NPV+TX, Anagurus atomus+TX, Aphelinus abdominalis+TX, Aphidoletes Bacillus aizawai + TX, Aphidrotes aphidimiza + TX, Aphoret + TX, Autographa californica NPV + TX, AZ 60541 + TX, Azadirachtin + TX, Azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL accession number B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus Bacillus pumilus (NRRL accession number 30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sphaericus Neide + TX, Bacillus satillusBacillus subtilis) AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus subtilis (unspecified) + TX, Bacillus thuringiensis (Bacillus Bacillus thuringiensis)AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. aizawai + TX, Bacillus thuringiensis subsp. israelensis + TX, Bacillus thuringiensis subsp. japonensis + TX, Bacillus thuringiensis subsp. krustaki subsp.kurstaki)+TX, Bacillus thuringiensis subsp.tenebrionis+TX, Bacillus thuringiensis subspec.kurstaki BMP123+TX, Beauveria bassiana+TX, Beauveria bronniabrongniartii) + TX, bencrotiaz + TX, benomyl + TX, bensultap + TX, benciofurmin (CAS number: 2566451-67-8) + TX, benzoximate + TX, benzpyrimoxane + TX, betacyfluthrin + TX, betacypermethrin + TX, betoxazine + TX, bifenazate + TX, bifenthrin + TX, binapacril + TX, bioarethrin + TX, biorethmethrin + TX, bis(tributyltin) oxide + TX, bisazil + TX, bistriflu Ron+TX, Bisflufen+TX, Brevicomin+TX, Brofranilide+TX, Broflutrinate+TX, Bromoacetamide+TX, Bromophos-ethyl+TX, Bronopol+TX, Busulfan+TX, Butocarboxim+TX, Butopyronoxyl+TX, Butoxy(Polypropylene Glycol)+TX, Butylpyridaben+TX, Cadsaphos+TX, Calcium Arsenate+TX, Carbaryl+TX, Carbofuran+TX, Carbon Disulfide+TX, Carbosulfan+TX, Cartape+TX, CAS No.: 1594624-87-9+TX, CAS No.:1922957-47-8+TX, CAS No.:1255091-74-7+TX, CAS No.:1365070-72-9+TX, CAS No.:1445683-71-5+TX, CAS No.:1445684-82-1+TX, CAS No.:158062-71-6+TX, CAS No.:1594626-19-3+TX, CAS No.:1594637-65-6+TX CAS Number: 1632218-00-8+TX, CAS Number: 1808115-49-2+TX, CAS Number: 1922957-46-7+TX, CAS Number: 1922957-48-9+TX, CAS Number: 1956329-03-5+TX, CAS Number: 1990457-52-7+TX, CAS Number: 1990457-55-0+TX, CAS Number: 1990457- 57-2+TX, CAS No.:1990457-66-3+TX, CAS No.:1990457-77-6+TX, CAS No.:1990457-85-6+TX, CAS No.:2032403-97-5+TX, CAS No.:2044701-44-0+TX, CAS No.:2095470-94-1+TX, CAS No.:2128706-05-6+TX, CAS No.:2 133042-31-4+TX, CAS No.: 2133042-44-9+TX, CAS No.: 2171099-09-3+TX, CAS No.: 2220132-55-6+TX, CAS No.: 2396747-83-2+TX, CAS No.: 2408220-91-5+TX, CAS No.: 2408220-94-8+TX, CAS No.: 2415706-16-8+TX CAS number: 2719848-60-7+TX, CAS number: RNA (Leptinotarsa ​​decemlineata-specific recombinant double-strand interference GS2)+TX, Chlorantraniliprole+TX, Chlordan+TX, Chlorfenapyr+TX, Chloropicrin+TX, Chloroprallethrin+TX, Chlorpyrifos+TX, Chromafenozide+TX, Chrysopera carnea+TX, Clempyrin+TX, Chloetocarb+TX, Clothianidin+TX, Codorrelua+TX, Codormon+TX, Copper acetoarsenate+TX, Copper dioctanoate+TX, Copper hydroxide+TX, Copper sulfate + TX, Cresol + TX, Culfomate + TX, Cryptraemus montorzieri + TX, Curelure + TX, Cyanophenphos + TX, Cyantraniliprole + TX, Cibenzoxasulfyl (CAS number: 2128706-04-5) + TX, Sibutrin + TX, Cycloprotril + TX, Cyclotril + TX, Cyclotriium + TX, Cyclotriium + TX, Cycloxapride + TX, Cydia pomonera (Cydia Pomonella GV+TX, cyenopyrafen+TX, cyetopyrafen+TX, cyflumetofen+TX, cyfluthrin+TX, cyhalodimide+TX, cyclohalothrin+TX, cypermethrin+TX, cyphenothrin+TX, cyprofuranilide+TX, cyromazine+TX, cytokinin+TX, Dacnusa sibiricaSibirica+TX), Dazomet+TX, DBCP+TX, DCIP+TX, Deltamethrin+TX, Diafenthiuron+TX, Dialiphos+TX, Diamidaphos+TX, Dibrom+TX, Dibutyl Adipate+TX, Dibutyl Phthalate+TX, Dibutyl Succinate+TX, Diclofenthion+TX, Dichlorophene+TX, Dichlorophene+TX, Dicliphos+TX, Dichloromezothiaz+TX, Diethyltoluamide+TX, Diflubenzuron+TX, Di Griffus Isaea + TX, Dimatif + TX, Dimethoate + TX, Dimethyl carbonate + TX, Dimethyl phthalate + TX, Zinpropyridaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Dipirithione + TX, D-Limonene + TX, Dodeca-8-dien-1-yl acetate + TX, Dodeca-9-dien-1-yl acetate + TX, Dodeca-8,10-dien-1-yl acetate + TX, Dodicine + TX, Domi Nicala+TX, Doramectin+TX, Emamectin+TX, Emamectin Benzoate+TX, Empenthrin+TX, Encalcia Formosa+TX, Endrin+TX, Eprinomectin+TX, Epsilon-Monfluorothrin+TX, Epsilon-Metofluthrin+TX, Eretomocerus Elemicus+TX, Esfenvalerate+TX, Ethion+TX, Ethiprole+TX, Etoprophos+TX, Ethyl 4-Methyloctanoate+TX, Ethyl Xanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etopyrafen + TX, eugenol + TX, seaweed extract and fermentation product derived from melasma + TX, seaweed extract and fermentation product derived from melasma containing urea + TX, seaweed and fermentation product extract + TX, seaweed extract and fermentation product containing plant hormones, vitamins, EDTA-chelated copper, zinc and iron + TX, fenfluthrin + TX, fenitrothion + TX, Fenmezodithiaz+TX, Phenobucarb+TX, Phenothiocarb+TX, Phenoxycarb+TX, Fenpropathrin+TX, Fenpyrad+TX, Fenpyroximate+TX, Fensulfothione+TX, Fenthion+TX, Fentin+TX, Fentin acetate+TX, Fenvalerate+TX, Ferric phosphate+TX, Fipronil+TX, Flomethoquin+TX, Flonicamide+TX, Fluacrypyrim+TX, Fluazindolidine+TX, Fluazuron+TX, Flubendiamide+TX, Flube Ndimin + TX, Fluchlordiniliprole + TX, Flucitrinate + TX, Flucycloxlon + TX, Flucitrinate + TX, Fluensulfone [318290-98-1] + TX, Fluensulfone + TX, Fluphenelim + TX, Flufenprox + TX, Flufiprole + TX, Fluhexaphon + TX, Flumetrin + TX, Fluopyram + TX, Flupyradiflon + TX, Flupyrimin + TX, Flupyroxystrobin + TX, Flulaner + TX, Fluvalinate + TX, Fluxamethamide + T X, formaldehyde + TX, fostiazate + TX, fostiethane + TX, furfural + TX, galquin (CAS number: 2644770-30-7) + TX, gamma-cyhalothrin + TX, gosiplurele (1:1 mixture of (Z,E) and (Z,Z) isomers of hexadeca-7,11-diene-1-yl acetate) + TX, Grandluer + TX, Grandluer I + TX, Grandluer II + TX, Grandluer III + TX, Grandluer IV + TX, granulovirus + TX, gua Dipil+TX, GY-81+TX, Halfenprox+TX, Halofenozide+TX, Harpin+TX, Helicobacter almigera nucleotide polysludge virus+TX, Helicobacter zea NPV+TX, Helicobacter zea nucleotide polysludge virus+TX, Heliotis punctigera nucleotide polysludge virus+TX, Heliotis virescens nucleotide polysludge virus+TX, Hemel+TX, Hempa+TX, Heptaflutrin+TX, Heterorhabditis bacteriophora and H. megidis (H.megidis)+TX, Hexalurea+TX, Hexamide+TX, Hexythiazox+TX, Hippodamia Convergence+TX, Hydramethylnon+TX, Hydralgafen+TX, Hypodamia Convergence+TX, Hydralgafen+TX, Hydrated Lime+TX, Imisiaphos+TX, Imidacloprid+TX, Imiprothrin+TX, Indazapiroxamet+TX, Indoxacarb+TX, Iodomethane+TX, Iprodione+TX, Ipsdienol+TX, Ipsenol+TX, Isamidophos + TX, Isazofos + TX, Isocycloceram + TX, Isoflualanum (CAS number: 2892524-05-7) + TX, Isothioate + TX, Ivermectin + TX, Japonylle + TX, Kappa-bifenthrin + TX, Kappa-tefluthrin + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Kinetin + TX, Lambda-cyhalothrin + TX, Redoprona + TX, Lepimectin + TX, Leptomastix dactylopii dactylopiii+TX), linetin+TX, Litlure+TX, Looplure+TX, rotylanate+TX, lufenuron+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, mecarphone+TX, medolua+TX, megatomoic acid+TX, metaflumizone+TX, metaldehyde+TX, metam+TX, metam-potassium+TX, metam-sodium+TX, Metaphycus herborus+TX, Metarhizium anisopliae var. acridam+TX, Metarhizium anisopliae var. anisopliae+TX, Metarhizium species (spp.)+TX, Metepa+TX, Methiocarb+TX, Methiotepa+TX, Methomyl+TX, Methquin-butyl+TX, Methoxyphenozide+TX, Methyl aphorate+TX, Methyl bromide+TX, Methyl eugenol+TX, Isothiocyanate+TX, Methylneodecanamide+TX, . Metofluthrin + TX, Metolcarb + TX, Mexacarbonate + TX, Milbemectin + TX, Milbemycin oxime + TX, Monfluorothrin + TX, Morzide + TX, Moxidectin + TX, Mascarea + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Myrotesium perulcaria composition + TX, Nabam + TX, NC-184 + TX, Neem wood-based products + TX, Neodiprion Sursif Sertifer) NPV and N. Lecontei NPV + TX, Nickel bis(dimethyldithiocarbamate) + TX, Niclosamide + TX, Niclosamide + TX, Niclosamide-olamine + TX, Nicofluprole + Tx, Nitenpyram + Tx, Nichiazine + Tx, Nitrapyrine + Tx, Octadeca-2,13-diene-1-ylacetate + Tx, Octadeca-3,13-diene-1-ylacetate + Tx, Octylinone + Tx, Omethoate + Tx, Orfural + Tx, Orius spp.) + Tx, orictalal + Tx, ostramon + Tx, oxamate + Tx, oxamyl + Tx, oxazosulfyl + Tx, oxolinic acid + Tx, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus (PaecilomycesPlutella lilacinus + TX, Parathion-ethyl + TX, Pasteuria nisizaue + TX, Pasteuria penetranthus + TX, Pasteuria ramosa + TX, Pasteuria thornyi + TX, Pasteuria ousage + TX, p-cymene + TX, Penflurone + TX, Pentachlorophenol + TX, Permethrin + TX, Phenothrin + TX, Folate + TX, Phosphamidone + TX, Phosphocarb + TX, Phytoseurus persimilis + TX, Picalidin + TX, Pioxaniliprol + TX, Piperazine + TX, Piperfuranilide (CAS number: 2615135-05-0) + TX, Piperonyl butoxide + TX, Pyrimicarb + TX, Pyrimiphos-ethyl + TX, Pyrimiphos-methyl + TX, Plutella xylostella granusGranulosis virus + TX, Plutella xylostella nucleopolyhedovirus + TX, Polycythemia virus + TX, Potassium and molybdenum and EDTA chelated manganese + TX, Potassium ethylxanthate + TX, Potassium hydroxyquinoline sulfate + TX, Prarethrin + TX, Probenazole + TX, Profenofos + TX, Profluthrin + TX, Propargit + TX, Propatanfos + TX, Propoxar + TX, Prothiofos + TX, Protrefenbute + TX, Piflubmid + TX, Pymetrozine + TX, Piraclofos + TX, Pirafluprole + TX, Pyretram + TX, Pyridaben + TX, Pyridaryl + TX, Pyridine-4-amine + TX, Pyrifluquinazon + TX, Pyrimidifen + TX, Pyriminostrobin + TX, Pyriprole [394730-71-3] + TX, Pyriprole + TX, Pi Reproxyfen + TX, QRD420 (terpenoid blend) + TX, QRD452 (terpenoid blend) + TX, QRD460 (terpenoid blend) + TX, Kylia jasaponaria + TX, Quinoclamine + TX, Quinonamide + TX, Resmethrin + TX, Rhodococcus globularus AQ719 (NRRL accession number B-21663) + TX, Salaraner + TX, S-Biorethrin + TX, Cebufo Spodoptera exigua (Spodoptera) exigua) Polycapsid Polyhedrosis Virus + TX, Spodoptera frugiperda Polyhedrosis Virus + TX, Steinernema bionis + TX, Steinernema carpocapsea + TX, Steinernema feltiae + TX, Steinernema grasseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterissii + TX, Steinernema speciesspp.)+TX, Streptomyces garbus (NRRL accession number 30232)+TX, Streptomyces sp. (NRRL accession number B-30145)+TX, Streptomycin+TX, Streptomycin sesquisulfate+TX, Strychnin+TX, Sulcatol+TX, Sulfiflumin (CAS number: 2377084-09-6)+TX, Sulfoxaflor+TX, Tadzymkab+TX, Tebufenozide+TX, Tebufenpyrad+TX, Tebupirimiphos+TX, Tecrophthalam + TX, Tefluthrin + TX, Temephos + TX, Tepa + TX, Terbam + TX, Terbuphos + TX, Terpenoid Blend + TX, Tetrachlorantraniliprole + TX, Tetrachlorothiophene + TX, Tetradeca-11-en-1-yl acetate + TX, Tetradiphon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetractin + TX, Tetraniliprole + TX, Theta-cypermethrin + TX, Thiacloprid + TX, Thiafenox + TX, Thiamethoxam + TX, Thiocyclam + TX, Thiodicarb + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX , Thiometon + TX, Thionadin + TX, Thiophanate + TX, Thiosultap + TX, Thiotepa + TX, Thiapyrachlor (CAS number: 1255091-74-7) + TX, Tigolana + TX, Thiolantraniliprole + TX, Thioxazafen + TX, Tolfenpyrad + TX, Toxafen + TX, Tralomethrin + TX, Transfluthrin + TX, Tretamine + TX, Triazamate + TX, Triazophos + TX, Triazurone + TX, Tributyltin oxide + TX, Trichlorfon + TX, Trichloronate + TX, Trichlorfon + TX, Trichlorfon + TX, Trichlorfon + TX, Trichogramma species (Trichogramma (spp.) + TX, Triphenmorph + TX, Trifluenfronate + TX, Triflumezopyrim + TX, Trimedlua + TX, Trimedlua A + TX, Trimedlua B1 + TX, Trimedlua B2 + TX, Trimedlua C + TX, Trimetacarb + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Trunc-call + TX, Cyclopyrazoflor + TX, Tyclodromer occidentalis + TX, Uredepa + TX, Verticillium lecanii + TX, Verticillium lium spp. + TX, Xylenol + TX, YI-5302 + TX, Zeatin + TX, Zeta-cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these (These compounds can be prepared from the method described in International Publication No. 2019 / 110427) + TX, (3',4',5'-trifluorobiphenyl-2-yl)-amide + TX, (3-methylisoxazole-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone (These compounds can be prepared from the method described in International Publication No. 2017 / 220485) + TX, (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared by the method described in International Publication No. 2014 / 006945) + TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9-diene-1-ylacetate + TX, (9Z,11E)-tetradeca-9,11-diene-1-ylacetate + TX, (9Z,12E)-tetradeca-9,12-diene-1-ylacetate + TX, (E)-6-methylhepta-2-en-4-ol + TX, (E)-deca-5-en-1-ylacetate and (E)-deca-5-en-1-ol + TX, (E)-trideca-4-en-1-ylacetate + TX, (E,Z)-tetradeca-4,10-diene-1-ylacetate + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-Trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-Dodeca-7-en-1-ylacetate + TX, (Z)-Hexadeca-11-en-1-ylacetate + TX, (Z)-Hexadeca-11-enal + TX, (Z)-Hexadeca-13-en-11-in-1-ylacetate + TX, (Z)-Icosa-13-en-10-one + TX, (Z)-Tetradeca-7-en-1-al + TX, (Z)-Tetradeca-9-en-1-ol + TX, (Z)-Tetradeca-9-en-1-ylacetate + TX, (Z,2 E)-5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide (this compound can be prepared by the method described in International Publication No. 2018 / 153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1-yl]acetyl]-4-piperidyl]thiazole-4-yl]-4, 5-Dihydroisoxazole-5-yl]-3-chlorophenyl]methanesulfonate + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin (Zin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridine-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (these compounds can be prepared from the method described in International Publication No. 2017 / 025510) + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane and 1,3-Dichloropropene + TX, 1,3-Dichloropropene + TX, 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4-chlorophenyl)pyrazole-3-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazole-5-one + TX, 10-Diene-1-ylacetate + TX, 14-Methyloctadeca-1-ene + TX, 1-Bromo-2-chloroethane + TX, 1-Dichloro-1-nitro Tan + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazole-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + T X, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate + TX, 2-(2-butoxyethoxy)ethylpiperonylate + TX, 2-(2-butoxyethoxy)ethylthiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-(difluoromethyl (3R)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in International Publication No. 2014 / 095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-Dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadizaol-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenyl Benzosulfonate + TX, 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron (this compound can be prepared by the method described in International Publication No. 2011 / 138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound can be prepared from the method described in International Publication No. 2017 / 029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound can be prepared from the method described in International Publication No. 2017 / 029179) (Preparable) + TX, 2-chlorovinyldiethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(propa-2-inyl)aminophenylmethylcarbamate + TX, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl] Cetoamide (this compound can be prepared by the method described in International Publication No. 2018 / 065414) + TX, 2-thiocyanatoethyl laurate + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by the method described in International Publication No. 2016 / 156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-Dimethylisoquinoline-1-yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene-1,1-dioxide + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in International Publication No. 2016 / 156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitride (this compound can be prepared by the method described in International Publication No. 2016 / 156290) + TX, 3-bromo-1-chloropropa-1-ene + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid + TX, 3-ethyl-1-methoxy-1-[[ 4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro -6-fluorophenyl)-2,5-dimethylpyrazole-3-amine + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazole-1-yl)-3,3-dimethylisoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridine-3-yl) Isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-Triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, 4-chlorophenylphenylsulfone + TX, 4-methyl(propane-2-inyl )amino-3,5-xylylmethylcarbamate + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2-thiadiazole All zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (preparable from the method described in International Publication No. 2020 / 109391) + TX, 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl] -5-methylpyridazine-4-carboxamide (preparable by the method described in International Publication No. 2020 / 109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (preparable by the method described in International Publication No. 2020 / 109391) + TX, 6-Ethyl-5,7-Dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitriel + TX, 6-Isopentenylaminopurine + TX, 8-Fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-Fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-Hydroxyquinoline sulfate + TX, Acethione + TX, Acetoprole + TX, Acibenzolar + TX, Acibenzolar-S-methyl + TX, Acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter Radiobacter) + TX, Aldoxicarb + TX, Aldrin + TX, Allosamidin + TX, Alixicarb + TX, Alpha-chlorohydrin + TX, Alpha-ecdysone + TX, Alpha-multistriatin + TX, Aluminum phosphide + TX, Amblyseius spp. + TX, Amectotractin + TX, Ametoctrazine + TX, Amidothione + TX, Amidothioate + TX, Aminocarb + TX, Aminopyriphen + TX, Amisulbrom + TX, Amiton + TX, Amiton oxalate + TX, Amitraz + TX, Anabacin + TX, Anagrapha falcifera NPV + TX, Anagras atoms atomus)+TX, ancimidor+TX, anilazine+TX, anisifuruprin+TX, anthraquinone+TX, anto+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Aphidoletes aphidimyza+TX, aphorate+TX, aramit+TX, arsenous+TX, atidathion+TX, Autographa californicaBacillus californica NPV+TX, Azaconazole+TX, Azamethiphos+TX, Azobenzene+TX, Azothoate+TX, Azoxystrobin+TX, Bacillus sphaericus Neide+TX, Bacillus thuringiensis Delta Endotoxin+TX, Barium Carbonate+TX, Barium Hexafluoridosilicate+TX, Polybarium Sulfide+TX, Bartholin+TX, Bayer 22 / 190+TX, Bayer 22408+TX, Beauveria blongniartii (brongniartii)+TX, Benalaxyl+TX, Bencrotiaz+TX, Benomyl+TX, Benoxaphos+TX, Bentiavaricarb+TX, Benzothiostrobin+TX, Benzovindiflupir+TX, Benzyl benzoate+TX, Beta-cyfluthrin+TX, Beta-cypermethrin+TX, Bethoxazine+TX, Bioethanomethrin+TX, Biopermethrin+TX, Bis(2-chloroethyl) ether+TX, Bis(tributyltin) oxide+TX X, Bisazil+TX, Bisthiosemi+TX, Vitertanol+TX, Bixafen+TX, Blastisidine-S+TX, Borax+TX, Bordeaux mixture+TX, Boscalid+TX, Brevicomin+TX, Brodifacom+TX, Brofenvalerate+TX, Bromadiolon+TX, Bromethaline+TX, Bromfenbinphos+TX, Bromoacetamide+TX, Bromocyclene+TX, Bromo-DDT+TX, Bromophos+TX, Bromopropylate+TX, Bromuconazole + TX, Bronopol + TX, Bufencarb + TX, Bupirimate + TX, Buprofezin + TX, Busulfan + TX, Buta-3-inyl N-[6-[[(Z)-[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, Butacarb + TX, Butathiophos + TX, Butocarboxim + TX, Butonate + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium arsenate + TX, Calcium cyanide + TX, Calcium polysulfide + TX, Canfechlor + TX, Captafo Electrolyte + TX, Captan + TX, Carbanolate + TX, Carbendazim + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Carbophenothione + TX, Carboxine + TX, Cartabhydrochloride + TX, CAS number: 2454319-63-0 + TX, Sebadin + TX, Quinomethionat + TX, Chloralose + TX, Chlorbenside + TX, Chlorbiculin + TX, Chlordan + TX, Chlordecone + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetol + TX, Chlorf Xenson + TX, Chlorfensilide + TX, Chlorbenzyl acid + TX, Chloroform + TX, Chloroinconazide + TX, Chloromebform + TX, Chloromethirone + TX, Chloroneb + ​​TX, Chlorophacinone + TX, Chloropicrin + TX, Chloropropylate + TX, Chlorthalonil + TX, Chlorfoxime + TX, Chlorprazophos + TX, Chlorthiophos + TX, Clozolinate + TX, Cholecalciferol + TX, Chrysopera carnea + TX, Synerin I + TX, Synerin II + TX Synerin + TX, cismethrin + TX, cis-resmethrin + TX, crocitrin + TX, closantel + TX, codlelure + TX, codolmon + TX, copper acetarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumocrol + TX, coumufuryl + TX, coumaphos + TX, coumatetralyl + TX, spider methoxystrobin (jiaxiangjunzhi) + TX,Cumithoate + TX, spideroxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, clotoxyphos + TX, clufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS708 + TX, Curelure + TX, cufraneb + ​​TX, cyanophenphos + TX, cyanophos + TX, cyanophos + TX, cyanophos + TX, cyanophos + TX, cyanthoate + TX, cyazofamide + TX, sibutrin + TX, cicrethrin + TX, cyclobutriflurum + TX, Cydia pomonella GV + TX, cyflufenaamide + TX, simiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinin + TX, Dacnusa sibirica Sibirica+TX, DAEP+TX, Dazomet+TX, DCIP+TX, DCPM+TX, DDT+TX, Debacarb+TX, Decarbofuran+TX, Demefion+TX, Demefion-O+TX, Demefion-S+TX, Demeton-Methyl+TX, Demeton-O+TX, Demeton-O-Methyl+TX, Demeton-S+TX, Demeton-S-Methyl+TX, Demeton-S-Methylsulfone+TX, Diamidaphos+TX, Dibutyl Adipate+TX, Dibutyl Phthalate+TX, Dibutyl Succinate+TX, Dicapton+TX, Dichlorobunthiazox+TX, Diclofenthion+ TX, Diclofluanide + TX, Dichloron + TX, Dichlorofen + TX, Dichlorvos + TX, Diclozoline + TX, Dicrifos + TX, Diclosimet + TX, Diclomedin + TX, Dichloran + TX, Diclesil + TX, Dicyclanil + TX, Dicyclopentadiene + TX, Dierdrin + TX, Dienochlor + TX, Dietofencarb + TX, Diethyl 5-methylpyrazole 3-yl phosphate + TX, Diethyltoluamide + TX, Difenacum + TX, Difenoconazole + TX, Difethiaron + TX, Diflovidazine + TX, Diglyphus isae isaea)+TX, Dirol+TX, Dimatif+TX, Dimefluthrin+TX, Dimefluthrin+TX, Dimefox+TX, Dimethane+TX, Dimethylimol+TX, Dimethomorph+TX, Dimethrin+TX,Dimethyl carbonate + TX, Dimethyl phthalate + TX, Dimethylvinphos + TX, Dimethilane + TX, Dimoxystrobin + TX, Dynex + TX, Dynex-dicrexin + TX, Diniconazole + TX, Dinocap 4 + TX, Dinocap 6 + TX, Dinoctone + TX, Dinopenton + TX, Dinoprop + TX, Dinosam + TX, Dinoseb + TX, Dinosulfone + TX, Dinotervon + TX, Diophenolane + TX, Dioxabenzophos + TX, Dioxathion + TX, Difacinone + TX, Diphenylsulfone + TX, Dipimethitron + TX, Dipirithione + TX, Disparlure + TX, Disulfiram + TX, Dithian N+TX, Diticlophos+TX, DNOC+TX, Dodeca-8-en-1-ylacetate+TX, Dodeca-9-en-1-ylacetate+TX, Dodeca-8+TX, Dodemorph+TX, Dodicin+TX, Dodyne+TX, Dodyne+TX, Dofenapine+TX, Dominicalure+TX, Doramectin+TX, DSP+TX, d-tetramethrin+TX, Ecdysterone+TX, Edifenphos+TX, EI 1642+TX, EMPC+TX, Encalcia formosa+TX, Endotal+TX, Endothione+TX, Enestrobrin+TX, Enoxastrobin+TX, EPBP+TX, Epoxyconazole+TX, Eprinomectin+TX, Eretomoceras elemicus+TX, Ergocalciferol+TX, Etaphos+TX, Etaboxam+TX, Ethiofencarb+TX, Ethyrimol+TX, Ethoatemethyl+TX, Ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoropropene-1-inoxy]phen [nyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in International Publication No. 2020 / 056090) + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]pyrazole-3-carboxylate (which can be prepared by the method described in International Publication No. 2020 / 056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared by the method described in International Publication No. 2018 / 158365) + TX, ethyl 4-methyloctanoate + TX,Ethyl formate + TX, ethyl hexanediol + TX, dibrominated ethylene + TX, dichloroethylene + TX, ethylene oxide + TX, etridiazole + TX, etrimphos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol and nerolidol + TX, phenamidone + TX, phenaminosulf + TX, phenaminestrobin + TX, phenalimol + TX, phenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fe Chlorphos + TX, Feneptamidoquin (CAS No.: 213241-04-9) + TX, Phenetacarb + TX, Fenflam + TX, Fenhexamide + TX, Fenitrothion + TX, Fenopyramide (CAS No.: 2344721-61-3) + TX, Phenothicarb + TX, Phenoxacrim + TX, Phenoxanil + TX, Fenpiclonil + TX, Fenpicoxamide + TX, Fenpyritrin + TX, Fenpropidine + TX, Fenpropimorph + TX, Fenpyrad + TX, Fenpyra Zamine + TX, Fenpyroximate + TX, Fenson + TX, Fensulfothione + TX, Fenthion + TX, Fenthion-ethyl + TX, Fentin + TX, Fentriphanil + TX, Ferbam + TX, Ferimzon + TX, Ferric phosphate + TX, Furocumafen + TX, Floryl picoxamide + TX, Fluazinam + TX, Fluventeram + TX, Flubenzimine + TX, Flucoflon + TX, Flucycloxlon + TX, Fludioxonil + TX, Fluentyl + TX, Fluphenoxadia Zam+TX, Fluphenoxystrobin+TX, Fluindapir+TX, Flumethylsulfolimu+TX, Flumorph+TX, Fluopicolide+TX, Fluopimomid+TX, Fluopyram+TX, Fluorolebenside+TX, Fluoroacetamide+TX, Fluorimide+TX, Fluoxapiproline+TX, Fluoxastrobin+TX, Fluoxythioconazole+TX, Flupropazine+TX, Flupropazine hydrochloride+TX, Fluquinconazole+TX, Flusilazole+TX, Flusulfamide+TX, Fluthianil + TX, Flutolanil + TX, Flutriafoll + TX, Fluxapiroxad + TX, FMC 1137+TX, Forpet+TX, Formaldehyde+TX, Formethane acid+TX, Formethane hydrochloride+TX, Formparanic acid+TX, Fosetyl-aluminum+TX, Fosmethilan+TX, Phosspire+TX, Phostiethane+TX, Frontalin+TX, Fuberidazole+TX, Flaralaxyl+TX, Flamethopyr+TX, Flathiocarb+TX, Fretolin+TX, Furfural+TX, Gamma-HCH+TX, Gliodin+TX, Grandlua+TX, Grandlua I+TX, Grandlua II+TX, Grandlua III+TX, Grandlua IV+TX, Guazatine+TX, Guazatine Acetate+TX, Halfenprox+TX, HCH+TX, Hemel+TX, Hempa+TX, HEOD+TX, Heptachlor+TX, Heterophos+TX, Heterorabditis bacteriophora and H. megidis+TX, Hexaconazole+TX, Hexadecylcyclopropane carboxylate+TX, Hexamide+TX, HHDN+TX, Hypodamia Convergent+TX, Hydralgafen+TX, Hydrated Lime+TX, Hydrogen Cyanide+TX, Himexazine+ TX, Himexaline + TX, Himandin + Imibenconazole + TX, Iminoctadine + TX, Impilfluxam + TX, Ipconazole + TX, Ipfentrifluconazole + TX, Iflufenoquin + TX, Iprobenphos + TX, Iprodione + TX, Iprovalicarb + TX, Ipsdienol + TX, Ipsenol + TX, IPSP + TX, Isamidophos + TX, Isazofos + TX, Isobenzane + TX, Isocarbophos + TX, Isodrine + TX, Isofenphos + TX, Isofetamide + TX, Isoflusipla Mu + TX, Isolan + TX, Isoprothiolan + TX, Isopyrazam + TX, Isothianil + TX, Isoxathion + TX, Japonylase + TX, Jasmolin I + TX, Jasmolin II + TX, Iodophenphos + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Cadetrin + TX, Kasugamycin + TX, Kasugamycin Hydrochloride Hydrate + TX, Kelevan + TX, Kinetin + TX, Quinoprene + TX, Kresoxim Methyl + TX, Lead Arsenate + TX, Leptomastix Dactylopiidactylopii)+TX, leptophos+TX, lindan+TX, linetin+TX, lilimphos+TX, Litlure+TX, Looplure+TX, lvbenmixianan+TX, lythidathion+TX, Macrolophus caliginosus+TX, magnesium phosphide+TX, maronoben+TX, Mamestra brassicae brassicae) NPV+TX, mancozeb+TX, mandestrobin+TX, maneb+TX, mazidox+TX, m-cumenyl methylcarbamate+TX, mecarbam+TX, mecarfon+TX, medolua+TX, mefentrifluconazole+TX, megatomoic acid+TX, menazone+TX, mepanipyrim+TX, meperfluthrin+TX, mephosphorane+TX, mepronil+TX, mercury oxide+TX, mercury chloride+TX, mesulfen+TX, mesulfenphos+TX, metalaxyl+TX, metam+TX, metam-potassium+TX, metam-sodium+TX, metaphycus herborus+TX, metalhizium anisopliae var. acridam+TX, metalhizium anisopliae var.) Anisoplie + TX, Metaril picoxamide + TX, Metconazole + TX, Metepa + TX, Methacryphos + TX, Methanesulfonyl fluoride + TX, Metasulfocarb + TX, Methiotepa + TX, Metoclotophos + TX, Methoprene + TX, Methquine-butyl + TX, Methotrin + TX, Methoxychlor + TX, Methyl(Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxypropa-2-enoate + TX, Methyl(Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxypropa-2-enoate (These compounds may be prepared from the methods described in International Publication No. 2020 / 193387) + TX, Methyl(Z)-2-[5-(3-isopropylpyrazo [Il-1-yl)-2-methylphenoxy]-3-methoxyprop-2-enoate + TX, Methyl(Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazole-1-yl)phenoxy]prop-2-enoate + TX, Methyl(Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazole-2-yl)phenoxy]prop-2-enoate + TX, Methyl(Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazole [1-yl]phenoxy]prop-2-enoate (these compounds can be prepared from the methods described in International Publication No. 2020 / 079111) + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazole-2-yl]phenoxy]prop-2-enoate + TX, methyl aphorate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6-difluoro Ro-4-isopropylphenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate (These compounds can be prepared from the method described in International Publication No. 2020 / 097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate (These compounds can be prepared from the method described in International Publication No. 2020 / 097012) + TX, methyl N-[[5-[4-(2,4-Dimethylphenyl)triazole-2-yl]-2-methylphenyl]methyl]carbamate + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-buto-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds can be prepared from the method described in International Publication No. 2017 / 153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-buto-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds can be prepared from the method described in International Publication No. 2017 / 153380) (obtained) + TX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-1,2,4- Riazole-3-amine (These compounds can be prepared from the methods described in International Publications 2017 / 055473, 2017 / 055469, 2017 / 093348 and 2017 / 118689) + TX, N-[(1R)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1 -methylpropyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxa Mid + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamide (this compound can be prepared from the method described in International Publication No. 2016 / 202742) + TX, N'-[4-(4,5-dichlorothiazole-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformazine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine (these compounds can be prepared from the methods described in International Publication No. 2015 / 155075) + TX, N'-[5-bromo -2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from the method described in IPCOM000249876D) + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N -Methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide (these compounds can be prepared from the methods described in International Publication No. 2018 / 202428) + TX, N'-[4-(1-cyclopropyl-2,2,2-triph Luoro-1-hydroxy-ethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methyl-formazine (these compounds can be prepared from the methods described in International Publication No. 2018 / 228896) + TX, Nabam + TX, Naphthalophos + TX, Nared + TX, Naphthalene + TX, NC-170 + TX, Neodiprion Certifel NPV and N. Reconte NPV + TX, Nerolidol + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formazine + TX, Nickel bis(dimethyldithiocarbamate) + TX, Niclosamide-olamine + TX, Nicotin + TX, Nicotin sulfate + TX, Niflulidide + TX, Nikcomycin derivatives + TX, N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, Nichiazine + TX, Nitrapyrine + TX, Nitrilacarb + TX, Nitrilacarb 1:1 Zinc chloride complex + TX, Nitrotal-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzenecarbothioamide + TX, norbolmid + TX, Nualimol + TX, O,O,O',O'-tetrapropyldithiopyrophosphate + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-Diene-1-yl acetate + TX, Octylinone + TX, Oflas + TX, Oleic acid + TX, Omethoate + TX, Orflurua + TX, Orius spp. + TX, Oryctalure + TX, Orysastrobin + TX, Ostramon + TX, Oxadixyl + TX, Oxamate + TX, Oxatiapiproline + TX, Oxine-copper + TX, Oxolinic acid + TX, Oxocarboxyne + TX, Oxideprophos + TX, Oxydisulfon + TX, Oxytetracycline + TX, Paclobutrazol + TX, Paecilomyces humosoroseus Fumosoroseus) + TX, Paradichlorobenzene + TX, Parathion + TX, Parathion-methyl + TX, Pefurazoate + TX, Penconazole + TX, Pencyclon + TX, Penflufen + TX, Penflulon + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, Penthiopyrad + TX, Permethrin + TX, PH60~38 + TX, Phenamacryl + TX, Phenakapton + TX, Fosacetim + TX, Phosalon + TX, Phosdiphen + TX, Phosphoran + TX, Phosglycine + TX, Phosniclor + TX, Phosphamidone + TX, Phosphine + TX, Phosphate + TX, Phoxime-methyl + TX, Phthalide + TX, Phytoseiulus persimilis + TX, Picarbutrazox + TX, Picalidine + TX, Picoxystrobin + TX, Pindone + TX, Piperazine + TX, Piperonyl butoxide + TX, Piprotal + TX, Pyrimethaphos + TX, Polychlorodicyclopentadiene isomer + TX, Polychloroterpene + TX, Polynactin + TX, Polyoxin + TX, Potassium arsenate + TX, Potassium ethylxanoate + TX, Hydroxyquinoline sulfate + TX X, potassium thiocyanate + TX, pp'-DX + TX, potassium prosenoate + TX, procymidone + TX, profluthrin + TX, promacil + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + ​​TX, propoxul + TX, propyl isomer + TX, proquinazide + TX, protidathion + TX, prothioconazole + TX, prothiophos + TX, protoate + TX, pidflumetofen + TX, Pyraclostrobin+TX, Pyramethostrobin+TX, Pyraoxystrobin+TX, Pyrapropoin+TX, Pyraziflumid+TX, Pyrazophos+TX, Pyrethmetrin+TX, Pyrethrin I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyribencarb+TX, Pyridaclomethyl+TX, Pyridafenthion+TX, Pyridine-4-amine+TX, Pyriphenox+TX, Pyrimethanil+TX, Pyrimitate+TX, Pyrimorph+ TX, Pyrinulone+TX, Pyriophenone+TX, Pyrisoxazole+TX, Pyrroquilon+TX, Quassia+TX, Quinalphos+TX, Quinalphos-methyl+TX, Quinoclamine+TX, Quinofumelin+TX, Quinonamide+TX, Quinothion+TX, Quinoxyfen+TX, Quinthiophos+TX, Quintozene+TX, 1492+TX, Lafoxanide+TX, Resmethrin+TX, Reynoutria sachalinensis extract+TX, Ribavirin+TX, Rimetalaxyl+TX, Rotenone+TX, Lianya+TX, Lianodine+TX, S421+TX, Sabajira+TX, Shuradan+TX, Siriloside+TX, Seboctilamine+TX, Sebuphos+TX, Sedaxane+TX, Selamectin+TX,Sesamex+TX, Sesamolin+TX, 0009+TX, Siglure+TX, Simazine+TX, Simeconazole+TX, Sodium Arsenite+TX, Sodium Cyanide+TX, Sodium Fluoride+TX, Sodium Fluoroacetate+TX, Sodium Hexafluorosilicate+TX, Pentachlorophenoxide+TX, Sodium Selenate+TX, Sodium Tetrathiocarbonate+TX, Sodium Thiocyanate+TX, Solzidine+TX, Spiroxamine+TX, 121+TX, Steinernema viviornis+TX, Steinernema carpo Capsaea + TX, Stainernema ferritiae + TX, Stainernema gracili + TX, Stainernema riobreve + TX, Stainernema riobravis + TX, Stainernema scapteris + TX, Stainernema species + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Strychnine + TX, Sulcatol + TX, Sulcoflon + TX, Sulcoflon-sodium + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfoxide + TX, Sulfur + TX, Sulfuryl fluoride + TX , Sulprophos + TX, Tar oil + TX, Tau-fluvalinate + TX, Tadimucarb + TX, TDE + TX, Tebuconazole + TX, Tebufloxin + TX, Tebupyrimphos + TX, Tecrophthalam + TX, Temephos + TX, Tepa + TX, TEPP + TX, Terarethrin + TX, Terbam + TX, tert-butyl N-[6-[[[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, Tetrachloroethane + TX, Tetrachlorothiophene + TX, Tetraconazole + TX, Tetradeca-11-en-1-yl acetate + TX, Tetraphon + TX, Tiflusamide + TX, Thiocarboxim + TX, Thiocyclam + TX, Thiocyclam hydrogen oxalate + TX, Thiodiazole copper + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX, Thiometon + TX, Thionadin + TX, Thiophanate + TX, Thiophanate-methyl + TX, Thioquinox + TX, Thiosultap + TX, Thiosultap-sodium + TX, Thiotepa + TX, Thyramine + TX, Thuringensin + TX, Thiazinyl + TX,Tolchlorophos-methyl+TX, Tolprocarb+TX, Trilfluanide+TX, Tralomethrin+TX, Transpermethrin+TX, Tretamine+TX, Triadimephone+TX, Triadimenol+TX, Triamiphos+TX, Triatene+TX, Triazamate+TX, Triazophos+TX, Triazooxide+TX, Triazolone+TX, Tributyltinoxide+TX, Trichlormetaphos-3+TX, Trichloronato+TX, Tricogramma species (Trichogramma spp.)+TX, Triclopyricarb+TX, Tricyclazole+TX, Tridemorph+TX, Triphenmorph+TX, Triphenophos+TX, Trifloxystrobin+TX, Triflumizole+TX, Triforin+TX, Trimedluar+TX, Trimedluar A+TX, Trimedluar B1+TX, Trimedluar B2+TX, Trimetacarb+TX, Trinactin+TX, Trinexapac+TX, Triphenyltin acetate+TX, Triphenyltin hydroxide+TX, Triplene+TX, Triticonazole+TX, Trunc-call+TX, Tyclodromeus occidentalis+TX, Urea + TX, validamixalate + TX, vaniliprole + TX, veratrine + TX, veratrine + TX, berbutin + TX, verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenol + TX, zeatin + TX, zetametrine + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, thiazole zinc + TX, zineb + ​​TX, ziram + TX; Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia (Alternaria cassia)+TX, Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX, Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882 (Aflaguard®)+TX, Aspergillus spp.)+TX, Aureobasidium pullulans+TX, Azospirillum (MicroAZ(registered trademark), TAZO B(registered trademark))+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal(registered trademark))+TX, Azotobacter cysts (Bionatural Blooming Blossoms(registered trademark))+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus chitinosporus (Bacillus Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®), especially strain CNMC 1-1582 (e.g., VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart®, formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillus marismortzii (Bacillus marismortui)+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacillus pumilus spp.)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®)+TX, Bacillus sphaericus (VectoLex®)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®)+TX, Bacillus subtilis strain QST 714(JAZZ(R))+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens.amyloliquefaciens) strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry 1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis crustaki (Bacillus thuringiensis kurstaki)(Javelin(registered trademark), Deliver(registered trademark), CryMax(registered trademark), Bondide(registered trademark), Scutella WP(registered trademark), Turilav WP(registered trademark), Astuto(registered trademark), Dipel WP(registered trademark), Biobit(registered trademark), Foray(registered trademark))+TX, . Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis variety Aizawai var.aizawai)(XenTari(registered trademark), DiPel(registered trademark))+TX, Bacteria spp.(GROWMEND(registered trademark), GROWSWEET(registered trademark), Shootup(registered trademark))+TX, Clavipacter michiganensis bacteriophage(AgriPhage(registered trademark), Bakflor(registered trademark))+TX, Beauveria bassiana(Beaugenic(registered trademark), Brocaril WP(registered trademark))+TX, Beauveria bassiana GHA(Mycotrol ES(registered trademark), Mycotrol O(registered trademark), BotaniGuard(registered trademark))+TX, Beauveria brongniartii(Engerlingspilz(registered trademark), Schweizer Beauveria (registered trademark), Melocont (registered trademark)) + TX, Beauveria genus (Beauveria spp.))+TX, Botrytis cineria+TX, Bradyrhizobium japonicum (TerraMax®)+TX, Brevibacillus brevis+TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX, Candida famata (Candida Candida famata) + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida salmon (Candida sake) + TX, Candida spp.)+TX, Candida tenius+TX, Cedecea davisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporium chlorocephalum+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum oxysporum)+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, . Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.)+TX, Cryptococcus albidus (YIELDPLUS(registered trademark))+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex(registered trademark))+TX, Cupriavidus campinensis+TX, Codlinga granulosis virus (Cydia pomonella granulovirus) (CYD-X(registered trademark), Madex(registered trademark), Madex(registered trademark)Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp.)+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean®, Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®, Prestop®)+TX, Gliocladium roseum roseum)+TX, Gliocladium spp. (SoilGard®)+TX, Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.)+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nuclear polyhedra virus (Helicovex®)+TX, Helicoverpa zea nuclear polyhedra virus (Gemstar®)+TX, Isaria fumosorosea (formerly known as Paecilomyces fumosoroseus strain, PFR-97®, PreFeRal®)+TX, isoflavone formononetin (Myconate®)+TX, Kloeckera apiculata apiculata)+TX, Kloeckera spp.)+TX, Lagenidium giganteum (Laginex®)+TX, Lecanicillium lecanii strain KV01 (formerly known as Verticillium lecanii) (Mycotal®) conidia (e.g., Vertalec® from Koppert / Arysta)+TX, greenhouse whitefly (Lecanicillium longisporum) (Vertiblast®)+TX, Lecanicillium muscarium (Vertikil®)+TX, gypsy moth (Lymantria dispar) nuclear polyhedron virus (Disparvirus®)+TX, Marinococcus halophilus+TX, Meira geuraconigii geulakonigii)+TX, Metarhizium anisopliae (Destruxin WP(registered trademark))+TX, Metarhizium anisopliae (Met52(registered trademark))+TX, Metschnikowia fruticola (Shemer(registered trademark))+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot(registered trademark))+TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus albus)620(Muscudor(registered trademark))+TX, Muscodor roseus, especially strain A3-5 (acceptance number NRRL 30548)+TX, Mycorrhizae spp.)(AMykor(registered trademark), Root Maximizer(registered trademark))+TX, Mulberry dark spot disease fungus (Myrothecium verrucaria) strain AARC-0255 (DiTera(registered trademark), BROS PLUS(registered trademark))+TX, Ophiostoma piliferum strain D97 (Sylvanex(registered trademark))+TX, Paecilomyces farinosus+TX, Paecilomyces lilacinus strain 251 (MeloCon WG(registered trademark))+TX, Paecilomyces linacinus (Biostat WP(registered trademark))+TX, Paenibacillus polymixa polymyxa)+TX, Pantoea agglomerans (BlightBan C9-1(registered trademark))+TX, Pantoea spp.+TX, Pasteuria nishizawae, especially strain Pn1 (CLARIVA from Syngenta / ChemChina);+TX, Pasteuria spp. (Econem(registered trademark))+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart(registered trademark), TagTeam(registered trademark))+TX, Penicillium brevicompactum+TX, Penicillium phlequentans (Penicillium Penicillium frequentans) + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.)+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, Phosphollytic bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX, Pichia guilliermondii+TX, Pichia membranaefaciens+TX, . Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudomonas fluorescens strain A506 (BlightBan A506(registered trademark))+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae (Bio-Save(registered trademark))+TX, Pseudomonas viridiflava+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L(registered trademark))+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior(registered trademark))+TX, Pythium paleocandrum ((Pythium paroecandrum)+TX, Pythium oligandrum (Polygandron®, Polyversum®)+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.)+TX, Rhizobia (Dormal®, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Rhodotorula spp.)+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor (SARRITOR®)+TX, Sclerotinia minor+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.)+TX, Sordaria fimicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®)+TX, Spodoptera littoralis nuclear polyhedrosis virus (Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces glyceoplanus (Streptomyces griseoplanus)+TX, Streptomyces griseoviridis (Mycostop®)+TX, Streptomyces hygroscopicus+TX, Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.)+TX, Trichoderma asperellum (T34 Biocontrol®)+TX, Trichoderma atroviride (Plantmate®)+TX, Trichoderma gamsii (Tenet®)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G®)+TX, Trichoderma harzianum (Trichoderma harzianum)T-39(Trichodex(registered trademark))+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum(Binab T(registered trademark))+TX, Trichoderma genus (Trichoderma spp.)LC 52 (Sentinel (registered trademark)) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) (SoilGuard (registered trademark)) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier (registered trademark)) + TX, Trichosporon pullulans + TX, . Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and auxiliary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes(registered trademark))+TX, Verticillium chlamydosporium+TX, Vip3Aa20(VIPtera(registered trademark))+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae(Camperico(registered trademark))+TX, Xenorhabdfus bovienii+TX, Xenorhabdus nematophilus+TX; AGNIQUE® MMF + TX, Azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®, e.g., AZATIN XL from Certis, USA) + TX, Botanical Insect Growth Regulators (Botanical IGRs) (Neemazad®, Neemix®) + TX, BugOil® + TX, Rapeseed Oil (Lilly Miller Vegol®) + TX, American Antwort (Chenopodium ambrosioides near ambrosioides) (Requiem®) + TX, Chrysanthemum Extract (Crisant®) + TX, Lamiaceae Essential Oil (Botania®) + TX, Neem Oil Extract (Trilogy®) + TX, Clove, Rosemary, Peppermint and Thyme Oil Extract (Garden insect Killer® + TX, Garlic + TX, Glycine Betaine (Greenstim®) + TX, Kaolin (Screen®) + TX, Lemongrass Oil (GreenMatch®) + TX, Tea Tree (Melaleuca alternifolia) Extract (also known as Tea Tree Oil) (Timorex Gold®) + TX, Clove Peppermint Garlic Oil and Mint Mixture (Soil Shot®) + TX, Clove Rosemary and Peppermint Extract Mixture (EF 400®) + TX, Rosemary Sesame Peppermint Thyme and Cinnamon Extract Mixture (EF 300®) + TX, Neem Oil + TX, Catnip (Nepeta cataria) (Catnip Oil) + TX, Catnip (Nepeta Catarina) + TX, Nicotine + TX, Oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, Pine oil (Retenol®) + TX, Pyrethrum + TX, Soap tree (Quillaja saponaria) (NemaQ®) + TX, Japanese knotweed (Reynoutria)sachalinensis (Regalia®, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, brown algae storage glucan (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadiene-1-yl acetate + TX, (E,Z,Z)-3,8,11-Tetradecatrienylate + TX, (Z,Z,E)-7,11,13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, Blackheaded Fireworm Pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium Acetate + TX, Check-Mate® + TX, Codlinga Pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, Entostat Powder (Exosex CM®) (Extract from palm trees) + TX, Grapeberry Moss Pheromone (3M MEC-GBM Sprayable Pheromone(registered trademark))+TX, Lavanzuryl senecioate+TX, Leafroller pheromone (3M MEC-LR Sprayable Pheromone(registered trademark))+TX, Muskamon (Snip7 Fly Bait(registered trademark))+TX, Pear fruit moth pheromone (3M oriental fruit moth sprayable pheromone(registered trademark))+TX, Clearwing moth larva (Peachtree Borer) pheromone (Isomate-P(registered trademark))+TX, Scenturion(registered trademark)+TX, Starbar Premium Fly Bait(registered trademark))+TX, Tomato pinworm pheromone (3M Sprayable pheromone(registered trademark))+TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris cucumeris) (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralisAphidius nemoralis (Anthocoris-System(registered trademark))+TX, Aphelinus abdominalis (Apheline(registered trademark), Aphiline(registered trademark))+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar(registered trademark))+TX, Aphidius ervi (Aphelinus-System(registered trademark))+TX, Aphidius ervi (Ervipar(registered trademark))+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M(registered trademark))+TX, Aphidoletes aphidiminiza aphidimyza) (Aphidend(registered trademark), Aphidoline(registered trademark)) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline(registered trademark)) + TX, Bombus spp. + TX, Bombus terrestris (Beeline(registered trademark), Tripol(registered trademark)) + TX, Bombus terrestris (Natupol Beehive(registered trademark)) + TX, Cephalonomia stephanoderis stephanoderis)+TX, Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®, Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilus ingenusingenuus)+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar(registered trademark))+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae)+TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®)+TX, Delphastus catalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jukunda jucunda)+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea (Diminex(registered trademark)), Miglyphus (registered trademark), Digline (registered trademark)) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max (registered trademark), Encarline (registered trademark), En-Strip (registered trademark)) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend (registered trademark)) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Desert parasitic wasp (Eretmocerus eremicus) (Enermix(registered trademark), Ercal(registered trademark), Eretline e(registered trademark), Bemimix(registered trademark)) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar(registered trademark), Eretline m(registered trademark)) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Feltiline(registered trademark)) + TX, Feltiella acarisuga (Spidend(registered trademark)) + TX, Fopius arisanus + TX, Fopius serratibolus (Fopius ceratitivorus) + TX, formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus osidentalisoccidentalis)+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®, Terranem®, Larvanem®, B-Green®, NemAttack®, Nematop®)+TX, Heterorhabditis megidis (Nemasys H®, BioNem H®, Exhibitline) hm(registered trademark), Larvanem-M(registered trademark))+TX, Heterorhabditis spp. (Lawn Patrol(registered trademark))+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System(registered trademark), Entomite-A(registered trademark))+TX, Hypoaspis miles (Hypoline m(registered trademark), Entomite-M(registered trademark))+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis abnormis)+TX, Leptomastix dactylopii (Leptopar(registered trademark))+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis olegmaeoregmae)+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N®, Macroline c®, Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax lapotorelus raptorellus) and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I®, Oriline) i(registered trademark))+TX, Orius laevigatus (Thripor-L(registered trademark), Oriline l(registered trademark))+TX, Orius majusculus (Oriline m(registered trademark))+TX, Orius laevigatus (Thripor-L(registered trademark), Oriline l(registered trademark))+TX, Oriusstrigicollis)(Thripor-S(registered trademark))+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita(Nemaslug(registered trademark))+TX, Phymastichus coffea+TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus)+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.)+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (Nematac C®, Millennium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®)+TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F (registered trademark), Steinernema-System (registered trademark), NemAttack (registered trademark), Nemaplus (registered trademark), Exhibitline sf (registered trademark), Scia-rid (registered trademark), Entonem (registered trademark)) + TX, Steinernema kraussei (Nemasys L (registered trademark), BioNem L (registered trademark), Exhibitline srb (registered trademark)) + TX, Steinernema riobrave (BioVector (registered trademark), BioVektor (registered trademark)) + TX, Steinernema scapterisci (Nematac S (registered trademark)) + TX, Steinernema spp. (genus Steinernema) + TX, Steinernematid spp. (genus Steinernematid))(Guardian Nematodes(registered trademark))+TX, Stethorus punctillum(Stethorus(registered trademark))+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae(Tricholine b(registered trademark))+TX, Trichogramma brassicae(Tricho-Strip(registered trademark))+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma * ostriniae* + TX, * Trichogramma platneri* + TX, * Trichogramma pretiosum* + TX, * Xanthopimpla stemmator*; Abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper octanoate (Cueva®) + TX, Delta trap (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®, Ni-HIBIT Gold CST®) + TX, Fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER®) + TX, Ferric phosphate (Ferramol®) + TX, Funnel trap (Trapline y(registered trademark))+TX, Gallex(registered trademark)+TX, Grower's Secret(registered trademark)+TX, Homo-brassonolide+TX, Iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait(registered trademark))+TX, MCP hail trap (Trapline f(registered trademark))+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X(registered trademark))+TX, Nosema locustae (Semaspore Organic Grasshopper Control(registered trademark))+TX, Pheromone trap (Thripline ams(registered trademark)) + TX, potassium bicarbonate (MilStop(registered trademark)) + TX, potassium iodide + potassium thiocyanate (Enzicur(registered trademark)) + TX, potassium salt of fatty acid (Sanova(registered trademark)) + TX, potassium silicate solution (Sil-Matrix(registered trademark)) + TX, spider venom + TX, sticky trap (Trapline YF(registered trademark), RebellAmarillo(registered trademark)+TX, SuffOil-X(registered trademark)+TX, Trap (Takitrapline y+b(registered trademark))+TX, Badescana (CAS number: 2643947-26-4)+TX; Bacillus mojavensis strain R3B (acceptance number NCAIM(P)B001389) (International Publication No. 2013 / 034938) + TX manufactured by Certis USA LLC; Bacillus pumilus, in particular strain BU F-33 (CARTISSA® manufactured by BASF, EPA registration number 71840-19) with NRRL acceptance number 50185 + TX; Bacillus subtilis CX-9060 + TX manufactured by Certis USA LLC; Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® manufactured by Kumiai Chemical Industry Co., Ltd.), with acceptance number FERM BP-8234, U.S. Patent No. 7,094,592 + TX; Bacillus subtilis Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) +TX, with strain BU1814 (VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA manufactured by BASF SE, acceptance number DSM 10271), Bacillus subtilis, particularly strain QST713 / AQ713 (NRRL acceptance number B-21661, described in U.S. Patent No. 6,060,051, Bayer CropScience) Paenibacillus polymyxa, particularly strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) +TX, with acceptance number NRRL B-50972 or acceptance number NRRL B-67129, is a member of the genus Paenibacillus.) strain, International Publication No. 2016 / 154297 + TX, Pantoea agglomerans, in particular strain E325 (acceptance number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL® FD BIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, particularly spores of strain DSM14940, spores of strain DSM14941, or mixtures of spores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (disclosed in International Publication No. 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae from Lesaffre et Compagnie, FR cerevisiae), particularly strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (International Publication No. 2010 / 086790) + TX; Agrobacterium radiobacter strain K84 (e.g., GALLTROL-A® from AgBioChem, CA) + TX, Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN® from University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL acceptance number B-50768, International Publication No. 2014 / 028521) (STARGUS® from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, acceptance number DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens, especially strain D747 (acceptance number FERM BP-8234, available as Double Nickel® from Kumiai Chemical Industry Co., Ltd., U.S. 7,094,(Specification No. 592) +TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) manufactured by FMC Corporation) +TX, Bacillus licheniformis having acceptance number ATCC 55406, in particular strain SB3086, International Publication No. 2003 / 000051 (available as ECOGUARD® Biofungicide and GREEN RELEAF® manufactured by Novozymes) +TX, Bacillus methylotrophicus strain BAC-9912 (Chinese Academy of Sciences' Institute of Applied Bacillus mycoides (manufactured by Ecology) +TX, acceptance number B-30890, isolate (available as BMJ TGAI® or WG and LifeGard® from Certis USA LLC) +TX, Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) +TX, Bacillus pumilus, in particular strain QST2808 (with acceptance number NRRL B-30087, described in U.S. Patent No. 6,245,551, Bayer CropScience LP,(Available as SONATA® from the US) +TX, Bacillus subtilis CX-9060 +TX from Certis USA LLC, Bacillus subtilis IAB / BS03 (AVIV® from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) +TX, Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) +TX, Bacillus subtilis strain BU1814 (Available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) +TX, Bacillus subtilis strain GB03 (Available as Kodiak® from Bayer AG, DE) +TX, Bacillus subtilis with acceptance number NRRL B-50595 Bacillus subtilis) strain MBI 600 (available as SUBTILEX from BASF SE), U.S. Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (registered in Taiwan as a biological fungicide and mycicide under registration numbers 4764, 5454, 5096 and 5277, available as BIOBAC® WP from Bion-Tech, Taiwan) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis (subtilis) Y1336 (Registered in Taiwan as a biological fungicide and mycicide under registration numbers 4764, 5454, 5096 and 5277, Bion-Tech,Available as BIOBAC(registered trademark)WP from Taiwan +TX, Paenibacillus epiphyticus (International Publication No. 2016 / 020371) from BASF SE +TX, Paenibacillus polymyxa ssp. plantarum (International Publication No. 2016 / 020371) from BASF SE +TX, Paenibacillus sp. strains with acceptance number NRRL B-50972 or acceptance number NRRL B-67129, Pseudomonas chlororaffis (International Publication No. 2016 / 154297 +TX) with acceptance number NRRL B-50897 Chloraphis strain AFS009, International Publication No. 2017 / 019448 (e.g., AgBiome Innovations,US-made HOWLER (trademark) and ZIO (registered trademark) + TX, Pseudomonas chlororaphis, especially strain MA342 (e.g., CEDOMON (registered trademark), CERALL (registered trademark), and CEDRESS (registered trademark) from Bioagri and Koppert) + TX, fluorescent bacterium (Pseudomonas fluorescens) strain A506 (e.g., BLIGHTBAN (registered trademark) A506 from NuFarm) + TX, Pseudomonas proradix (e.g., PRORADIX (registered trademark) from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (acceptance number DSM) 7206) (MYCOSTOP® manufactured by Verdera, PREFENCE® manufactured by BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® manufactured by Novozymes) + TX; Trichoderma atroviride strain T11 (IMI352941 / CECT20498) + TX, Ampelomyces quisqualis strain AQ10 (e.g., AQ 10® from IntrachemBio Italia) + TX with acceptance number CNCM 1-807, Ampelomyces quisqualis, especially strain AQ 10 (e.g., AQ 10® from IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (product known as AFLA-GUARD® from Syngenta / ChemChina) + TX, Aureobasidium pullulans, especially strain DSM Spores of 14941 + TX, Aureobasidium pullulans, especially spores of strain DSM14940 + TX, Aureobasidium pullulans, especially a mixture of spores of strains DSM14940 and DSM 14941 (e.g., bio-ferm,Botector® (registered trademark) from CH + TX, Chaetomium cupreum (acceptance number CABI 353812) (e.g., BIOKUPRUM® from AgriLife) + TX, Chaetomium globosum (available as RIVADIOM® from Rivale) + TX, Cladosporium cladosporioides, strain H39, U.S. Patent Application Publication No. 2010 / 0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, particularly strain CON / M / 91-8 (acceptance number DSM9660, e.g., Bayer CropScience Biologics) Contans(registered trademark) +TX from GmbH, Cryptococcus flavescens, strain 3C (NRRL Y-50378), +TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS(registered trademark)), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN(registered trademark) from Natural Plant Protection) +TX, Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulata) f. catenulate)) strain J1446 (e.g., Prestop (registered trademark) from Lallemand) + TX, Gliocladium roseum (also known as Clonostachys rosea f. rosea) strain IK726 (Jensen DF,(et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain 'IK726', Australasian Plant Pathol. 2007, 36(2):95-101) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea), particularly strain 321U from Adjuvants Plus, strain ACM941 disclosed in Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83(3): 519-524) + TX, Metschnikowia fructicola, particularly strain NRRL Y-30752+TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, International Publication No. 2015 / 067800)+TX from BASF SE, Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012) with acceptance number CABI CC IMI 392716, and Trichoderma gamsii (formerly T. viride) strain ICC 080 (e.g., from Isagro USA, Inc. under the BIO-TAM® trademark or Agrobiosol de Mexico,SAde CV's BIODERMA (registered trademark) mixture + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP (registered trademark) C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L from Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell wall (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 from Lesaffre et Compagnie, FR (International Publication No. 2010 / 086790) + TX, Saccharomyces cerevisiae *Trichoderma cerevisiae*, especially strain LASO2 (from Agro-Levures et Derives) +TX, Simplicillium lanosoniveum +TX, strain T34 (e.g., T34 Biocontrol by Biocontrol Technologies SL,ES) or strain ICC 012 from Isagro +TX, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183 +TX, Talaromyces flavus, strain V117b +TX, Trichoderma asperelloides JM41R (acceptance number NRRL B-50759) (TRICHO PLUS® registered trademark from BASF SE) +TX, Trichoderma asperelum Trichoderma asperellum, in particular strain SKT-1, acceptance number FERM P-16510 (e.g., ECO-HOPE® from Kumiai Chemical Industry) + TX, Trichoderma asperellum, in particular strain kd (e.g., T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (AndermattBiocontrol's T77)+TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040)+TX, Trichoderma atroviride strain LC52 (e.g., Tenet by Agrimm Technologies Limited)+TX, Trichoderma atroviride strain LU132 (e.g., Sentinel by Agrimm Technologies Limited)+TX, Trichoderma atroviride strain NMI number V08 / 002388+TX, Trichoderma atroviride strain NMI number V08 / 002389+TX, Trichoderma atroviride (Trichoderma Trichoderma atroviride strain NMI number V08 / 002390+TX, Trichoderma atroviride strain number V08 / 002387+TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), Japanese Patent Publication No. 11-253151+TX, Trichoderma atroviride strain SKT-2 (FERMP-16511), Japanese Patent Publication No. 11-253151+TX, Trichoderma atroviride strain SKT-3 (FERMP-17021), Japanese Patent Publication No. 11-253151+TX, Trichoderma atroviride Trichoderma atroviride), particularly strain SC1 (acceptance number CBS 122089, International Publication No. 2009 / 116106 and U.S. Patent No. 8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g., Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertilfertile) (e.g., BASF product TrichoPlus) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, SADE CV) + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g., BioDerma by AGROBIOSOL DE MEXICO, SADE CV) + TX, Trichoderma harmatum + TX, acceptance number ATCC Trichoderma harmatum +TX, Trichoderma harzianum +TX, Trichoderma harzianum rifai T39 (e.g., Trichodex® from Makhteshim, US) +TX, Trichoderma harzianum strain Cepa Simb T5 (from Simbiose Agro) +TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 from Dagutat Biolab) +TX, Trichoderma harzianum strain ITEM 908 (e.g., Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g., Root-Pro by Mycontrol) + TX, Trichoderma polysporumTrichoderma stromaticum (e.g., Trichoderma polysporum) strain IMI 206039 (e.g., Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX, acceptance number Ts3550 (e.g., Trichoderma virens (also known as Gliocladium virens)), particularly strain GL-21 (e.g., SoilGard by Certis, US) + TX, Trichoderma virens strain G-41 (formerly known as Gliocladium virens) (acceptance number ATCC 20906) (e.g., ROOTSHIELD® PLUS from BioWorks, US) WP and TURFSHIELD(registered trademark) PLUS WP)+TX, Trichoderma viride, especially strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie 161:125-137)+TX, Trichoderma viride strain TV1 (e.g., Koppert's Trianum-P)+TX, Ulocladium oudemansii strain U3 (accession number NM 99 / 06216) (e.g., Botry-Zen Ltd, BOTRY-ZEN(registered trademark) of New Zealand and BOTRYSTOP(registered trademark) of BioWorks+TX, Inc.)+TX, Verticillium arbo atrum deposited with the Central Bureau for Fungi Cultures Verticillium albo-atrum) (formerly known as V. dahliae) strain WCS850 (accession number WCS850) (e.g., DUTCH TRIG® registered trademark of Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; A mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, especially strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX, Azospirillum lipoferum lipoferum) (e.g., VERTEX-IF(trademark) manufactured by TerraMax, Inc.) + TX, Azotobacter chroococcum, especially strain H23 + TX, Azotobacter vinelandii, especially strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (acceptance number NRRL B-5015) + TX, Bacillus amyloliquefaciens, especially strain FZB42 (e.g., ABiTEP,RHIZOVITAL® (manufactured by DE) + TX, Bacillus amyloliquefaciens, especially strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® (manufactured by Biofilm Crop Protection)) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, International Publication No. 2017 / 205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® (manufactured by Novozymes)) + TX, Bacillus cereus Bacillus cereus family member EE128 (NRRL number B-50917) + TX, Bacillus cereus family member EE349 (NRRL number B-50928) + TX, Bacillus cereus, especially strain BP01 (ATCC 55675, e.g., MEPICHLOR® manufactured by Arysta Lifescience, US) + TX, Bacillus mycoides BT155 (NRRL number B-50921) + TX, Bacillus mycoides BT46-3 (NRRL number B-50922) + TX, Bacillus mycoides EE118 (NRRL number B-50918) + TX, Bacillus mycoides mycoides)EE141 (NRRL number B-50916)+TX, Bacillus pumilus, especially strain GB34 (e.g., Bayer Crop Science,DE-made YIELD SHIELD (registered trademark), +TX, Bacillus pumilus, especially strain QST2808 (acceptance number NRRL number B-30087) +TX, Bacillus siamensis, especially strain KCTC 13613T +TX, Bacillus subtilis, especially strain AQ30002 (acceptance number NRRL number B-50421, described in US Patent Application No. 13 / 330,576) +TX, Bacillus subtilis, In particular, strain AQ30004 (NRRL number B-50455, described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis, in particular strain MBI 600 (e.g., SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis, in particular strain NII-0943 + TX, Bacillus thuringiensis, also known as Bacillus thuringiensis 4Q7 + TX Bradyrhizobium japonicum (e.g., Novozymes' OPTIMIZE®) + TX, Delftia acidovorans, especially strain RAY209 (e.g., Brett Young Seeds' BIOBOOST®) + TX, Lactobacillus sp. (e.g., LactoPAFI's LACTOPLANT®) + TX, Mesorhizobium cicer (e.g., BASF SE's NODULATOR) + TX, Paenibacillus polymyxa, especially strain AC-1 (e.g., Green Biotech Company Ltd.)TOPSEED® (manufactured by Sourcon Padena) +TX, Pseudomonas aeruginosa, especially strain PN1 +TX, Pseudomonas proradix (e.g., PRORADIX® manufactured by Sourcon Padena) +TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR manufactured by BASF SE) +TX, Rhizobium leguminosarum, especially bv. viciae strain Z25 (acceptance number CECT 4585) +TX, Serratia marcescens, especially strain SRM (acceptance number MTCC 8708) +TX, Sinorhizobium meliloti) strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX; Thiobacillus sp. (e.g., CROPAID® from Cropaid Ltd UK) + TX; Mulberry dark spot disease fungus (Myrothecium verrucaria) strain AARC-0255 (e.g., DiTera® from Valent Biosciences) + TX, Penicillium bilaii strain ATCC 22348 (e.g., JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (formerly known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g., BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligodendrum Pythium oligandrum strain DV74+TX, Pythium oligandrum strain M1 (ATCC 38472, e.g., Polyversum manufactured by Bioprepraty, CZ)+TX, Rhizopogon amylopogon (Myco-Sol manufactured by Agri-Enterprise, LLC, formerly Helena Chemical Company)+TX, Rhizopogon fulvigleba (Myco-Sol manufactured by Agri-Enterprise, LLC, formerly Helena Chemical Company)+TX, Talaromyces flavus strain V117b+TX, Trichoderma asperellum strain (Plant Health Products,Eco-T)+TX from ZA, Trichoderma asperellum strain kd (e.g., T-Gro from Andermatt Biocontrol)+TX, Trichoderma atroviride, particularly strain number V08 / 002387+TX, Trichoderma atroviride strain CNCM 1-1237 (e.g., Esquive® WP from Agrauxine, FR)+TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g., Sentinel from Agrimm Technologies Limited)+TX, Trichoderma atroviride Trichoderma atroviride strain number NMI number V08 / 002388+TX, Trichoderma atroviride strain number NMI number V08 / 002389+TX, Trichoderma atroviride strain number NMI number V08 / 002390+TX, Trichoderma atroviride strain SC1 (described in International Publication No. 2009 / 116106)+TX, Trichoderma harzianum strain 1295-22+TX, Trichoderma harzianum strain ITEM 908+TX, Trichoderma harzianum strain T-22 (e.g., Andermatt Biocontrol or Koppert's Trianum-P)+TX, Trichoderma harzianum strain TSTh20, +TX, Trichoderma virens strain GI-3+TX, Trichoderma virens strain GL-21 (e.g., Certis,SoilGard® (USA-made) +TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie 161:125-137) +TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g., Dutch Trig from Tree Care Innovations) +TX; Agrobacterium radiobacter strain K84 (Galltrol, manufactured by AgBiochem Inc.), +TX; Bacillus amyloliquefaciens, especially strain PTS-4838 (e.g., AVEO, manufactured by Valent Biosciences, US), +TX; Bacillus mycoides, isolate J. (e.g., BmJ, manufactured by Certis USA LLC), +TX; Bacillus sphaericus, especially serotype H5a5b strain 2362 (strain ABTS-1743) (e.g., VECTOLEX®, manufactured by Valent BioSciences, US), +TX; Bacillus thuringiensis israelensis strain BMP 144 (e.g., AQUABAC® from Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, especially serotype H-7 (e.g., FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, especially strain ABTS-1857 (SD-1372, e.g., XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. islaerensis Bacillus thuringiensis subsp. israelensis) (serotype H-14) strain AM65-52 (acceptance number ATCC 1276) (e.g., VECTOBAC® manufactured by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp.Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (BARITONE from Becker Microbial Products, IL and Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (for example, Valent BioSciences, US-made DIPEL(registered trademark) ES)+TX, Bacillus thuringiensis subsp. kurstaki strain PB 54+TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (Certis, US-made JAVELIN)+TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (Certis, US-made THURICIDE)+TX, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, for example, BioFa NOVODOR(registered trademark)FC)+TX manufactured by DE, Bacillus thuringiensis var. Colmeri (for example, TIANBAOBTC manufactured by Changzhou Jianghai Chemical Factory)+TX, Bacillus thuringiensis var. japonensis(japonensis) strain Buibui + TX, Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp., especially Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (acceptance number NRRL B-50319, international publications 2011 / 106491 and 2013 / 032693, e.g., Marrone Bio) MBI206 TGAI and ZELTO(registered trademark) from Marrone Bio Innovations, +TX, Chromobacterium subtsugae, especially strain PRAA4-1T (e.g., MBI-203, e.g., GRANDEVO(registered trademark) from Marrone Bio Innovations) +TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) +TX, Paenibacillus popilliae (formerly known as Bacillus popilliae, e.g., St.MILKY SPORE POWDER (trademark) or MILKY SPORE GRANULAR (trademark) manufactured by Gabriel Laboratories + TX; Serratia entomophila (e.g., INVADE (registered trademark) manufactured by Wrightson Seeds) + TX; Serratia marcescens, especially strain SRM (acceptance number MTCC 8708) + TX; Trichoderma asperellum (TRICHODERMAX manufactured by Novozymes) + TX; Wolbachia pipientis ZAP strain (e.g., ZAP MALES (registered trademark) manufactured by MosquitoMate) + TX; Beauveria bassiana strain ATCC 74040 (e.g., NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (acceptance number DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (acceptance number ATCC74250, e.g., BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL acceptance number 67074, disclosed in International Publication No. 2017 / 066094, Pioneer Hi-Bred) International) +TX, Metarhizium robertsii 15013-1 (deposited under NRRL acceptance number 67073) +TX, Metarhizium robertsii 23013-3 (deposited under NRRL acceptance number 67075) +TX, Paecilomyces lilacinus strain 251 (MELOCON, Certis, US) +TX; Cydia pomonella (Codlinga) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrositis virus (NPV) + TX, Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX; Burkholderia spp., especially Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, Lactobacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp., especially Rhizobium trifolii + TX, Rhizopogon spp.)+TX, Scleroderma spp.+TX, Streptomyces spp.+TX, Suillus spp.+TX, Agrobacterium spp.+TX, Azorhizobium caulinodans+TX, Azospirillum spp.+TX, Azotobacter spp.+TX, Bradyrhizobium spp.+TX, Gigaspora monosporum+TX; Allium sativum (NEMGUARD by Eco-Spray, BRALIC by ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae plant extracts, especially rapeseed powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract derived from quinoa seeds (e.g., Heads Up plant Protectants,Heads Up® (Saponins of Quinoa) + TX (manufactured by CA), Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD, manufactured by STK) + TX, Natural Blad polypeptide extracted from lupine seeds (FRACTURE®, manufactured by FMC) + TX, Natural Blad polypeptide extracted from lupine seeds (PROBLAD®, manufactured by Certis EU) + TX, Pyrethrin + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35, manufactured by BASF) + TX, REGALIA, manufactured by Marrone Bio MAXX)+TX, Requiem® insecticide+TX, Japanese knotweed (Reynoutria sachalinensis) extract (REGALLIA+TX, liania / lianodine+TX, comfrey (Symphytum officinale)+TX, tansy (Tanacetum vulgare)+TX, thymol+TX, thymol mixed with geraniol (CEDROZ, manufactured by Eden Research)+TX, thymol mixed with geraniol and eugenol (MEVALONE, manufactured by Eden Research)+TX, Triact 70+TX, TriCon+TX, nasturtium (Tropaeulum majus)+TX, stinging nettle (Urtica dioica)+TX, veratrin+TX, mistletoe (Viscum album)+TX; Mercury oxide + TX, octylinone + TX, thiophanate-methyl + TX; MGK 264+TX, 2-(2-butoxyethoxy)ethylpiperonylate+TX, 2-isovalerylindan-1,3-dione+TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, α-bromadiolone+TX, α-chlorohydrin+TX, aluminum phosphide+TX, anthraquinone+TX, antz+TX, arsenic trioxide+TX, barium carbonate+TX, benoxacor Lu+TX, Bisthiosemi+TX, Brodifacum+TX, Bromadiolon+TX, Bromethalin+TX, Calcium cyanide+TX, Chloralose+TX, Chlorophacinone+TX, Cholecalciferol+TX, Chloquintoset (including Chloquintoset-Mexyl)+TX, Copper naphthenate+TX, Copper oxychloride+TX, Coumacrol+TX, Coumafuryl+TX, Coumatetralyl+TX, Crimidine+TX, Cyprosulfamide+TX, Diazinon+TX, Dichlormid+TX, Dicyclopentadiene+TX, Diphenacum+TX, Dife Thiaron + TX, Difacinone + TX, Ergocalciferol + TX, Farnesol + TX, Farnesol and Nerolidol + TX, Fenchlorazole (including fenchlorazole-ethyl) + TX, Fenchlorim + TX, Furocumafen + TX, Fluoroacetamide + TX, Flupropazine + TX, Flupropazine hydrochloride + TX, Fluxofenim + TX, Frillazole + TX, γ-HCH + TX, Guazatine + TX, Guazatine acetate + TX, HCH + TX, Hydrogen cyanide + TX, Imanin + TX, Iodomethane + TX, Isoxadife N (containing isoxadiphen-ethyl) + TX, Lindan + TX, Magnesium phosphide + TX, MB-599 + TX, Mefenypr (containing mefenypr-diethyl) + TX, Metocamifen + TX, Methiocarb + TX, Methyl bromide + TX, Nerolidol + TX, Norbolmid + TX, Petroleum + TX, Fosacetim + TX, Phosphine + TX, Phosphate + TX, Phosphate + TX, Pindone + TX, Piperonyl butoxide + TX, Piprotal + TX, Potassium arsenite + TX, Probenazole + TX, Propyl isomer + TX, Pyridine-4-amine + TX, Pyrynulone + TX,Japanese knotweed (Reynoutria sachalinensis) extract + TX, ribavirin + TX, S421 + TX, siriloside + TX, sesamex + TX, sesamolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thyram + TX, trimetacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, thyram + TX.

[0220] In addition, the compositions of the present invention may be administered together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known, for example, described in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0221] The compounds of formula (I) as defined in the present invention are typically used in the form of compositions and can be applied simultaneously with or consecutively to a crop or plant to be treated with further compounds. These further compounds may be, for example, fertilizers or trace element donors, or other preparations that affect plant growth. They may also be selective or non-selective herbicides, and insecticides, fungicides, bactericidal agents, nematicides, molluskicides, or mixtures of these preparations, and may optionally include further carriers, surfactants, or application enhancers commonly used in the art of formulations.

[0222] The compounds of formula (I) as defined in the present invention can be used in the form of a (fungicidal) composition for the control or protection of plant pathogenic microorganisms, comprising, as an active ingredient, at least one compound of formula (I) as defined in the present invention, or at least one preferred individual compound as defined above in free form or in agrochemically usable salt form, and at least one of the above-mentioned auxiliary agents.

[0223] Accordingly, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in the present invention, an agriculturally acceptable carrier, and optionally an auxiliary agent. The agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may, in addition to the compound of formula (I) as defined in the present invention, comprise at least one or more pesticide compounds, such as additional fungicidal active ingredients.

[0224] Further aspects of the present invention relate to methods for controlling or preventing ectoparasitism by plant pathogenic or putrefactive microorganisms or organisms, particularly fungi, that may be harmful to humans, of plants, for example, useful plants, for example, crop plants, their reproductive materials, for example, seeds, harvested crops, for example, harvested food crops, or non-biological materials, the methods comprising the application of a compound of formula (I) as defined in the present invention, or any of the preferred individual compounds as defined above as active ingredients for plants, to plants, to parts of plants or their habitats, to their reproductive materials, or to any part of non-biological materials.

[0225] Control or prevention means reducing ectopic parasitism by insects, plant pathogenic or putrefactive microorganisms, or organisms potentially harmful to humans, particularly fungi, to a level where improvement is demonstrated.

[0226] A preferred method for controlling or preventing ectoparasitism of crop plants by plant pathogenic microorganisms, particularly fungi, is foliar application, which includes the application of a compound of formula (I) as defined in the present invention, or a pesticide composition containing at least one of the said compounds. The frequency and amount of application will depend on the risk of ectoparasitism by the corresponding pathogen or insect. However, the compound of formula (I) as defined in the present invention can also be introduced into plants through the soil via the roots (osmotic action) by drenching the plant habitat with a liquid formulation or by applying the compound in solid form, such as granular form, to the soil (soil application). In rice crops, such granular material can be applied to flooded paddy fields. The compound of formula (I) as defined in the present invention can also be applied to seeds (coating) by either impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

[0227] A composition containing, for example, a compound of formula (I) as defined in the present invention, and, if desired, a solid or liquid additive or a monomer for encapsulating the compound of formula (I) as defined in the present invention, can be prepared by known methods, typically by closely mixing and / or grinding the compound with an extender, such as a solvent, a solid carrier, and optionally a surfactant.

[0228] Methods of application for the composition, i.e., methods for controlling the above-mentioned types of pathogens, such as spraying, misting, dusting, brushing, coating, diffusion, or pouring (these should be selected according to the intended purpose of the general situation), and the use of the composition for controlling the above-mentioned types of pathogens are also subjects of the present invention. Typical concentration ratios are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of the active ingredient. The application rate per hectare is preferably 1 g to 2000 g of the active ingredient per hectare, more preferably 10 to 1000 g / ha, and most preferably 10 to 600 g / ha. When used as a seed drenching agent, a convenient dosage is 10 mg to 1 g of the active substance per 1 kg of seeds.

[0229] When the combination of the present invention is used for seed treatment, an amount of 0.001 to 50 g of the compound of formula (I) per 1 kg of seed, preferably 0.01 to 10 g per 1 kg of seed, is generally considered sufficient.

[0230] Preferably, a composition comprising a compound of formula (I) according to the present invention as defined herein is applied either preventively (meaning before the onset of disease) or therapeutically (meaning after the onset of disease).

[0231] The compositions of the present invention may be any of the conventional forms, for example, two-component systems, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment fluid concentrate (FS), seed treatment solution (LS), seed treatment water-dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspension emulsion (SE), capsule suspension (CS), water-dispersible granules (WG), emulsifying granules It can be employed in the form of granules (EG), water-in-oil (EO) emulsions, oil-in-water (EW) emulsions, microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), industrial concentrates (TK), dispersible concentrates (DC), wettable powders (WP), or any technically feasible formulation combined with agriculturally acceptable adjuvants.

[0232] Such compositions can be produced by conventional methods, for example, by mixing an active ingredient with a suitable formulation deactivator (diluent, solvent, filler, and optionally other formulation components such as surfactants, biocides, antifreezes, spreading agents, thickeners, and compounds that provide auxiliary effects). Conventional sustained-release formulations may also be employed when sustained effectiveness over a long period is desired. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain surfactants, such as wetting agents and dispersants, as well as other compounds that provide auxiliary effects, such as formaldehyde and condensation products of naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0233] The seed coating formulation is applied to seeds in a manner known to the present invention, utilizing the combination and diluent of the present invention in a preferred seed coating formulation form, such as an aqueous suspension or a dry powder form having good adhesion to seeds. Such seed coating formulations are known in the art. The seed coating formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, such as slow-release capsules or microcapsules.

[0234] Generally, the formulations contain 0.01 to 90% by weight of an activator, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of solid or liquid formulation inerts and auxiliary agents, together with components (B) and (C), at least one compound of formula (I) as defined in the present invention, and optionally other activators, particularly microbiotacitists or preservatives. The concentrated form of the composition generally contains about 2 to 80%, preferably about 5 to 70% by weight of the activator. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of the activator. Commercial products are preferably formulated as concentrates, but end users will typically use diluted formulations.

[0235] Commercial products are preferably formulated as a concentrate, but end users typically use a diluted formulation. [Examples]

[0236] The following examples are helpful in illustrating the present invention. Certain compounds of the present invention can be distinguished from known compounds by their greater potency at lower doses, which can be verified by those skilled in the art using the experimental procedures outlined in the examples.

[0237] Formulation example

[0238] [Table 2]

[0239] By thoroughly mixing the active ingredient with an auxiliary agent and thoroughly grinding the mixture in a suitable pulverizer, a wettable powder can be obtained that can be diluted with water to form a suspension of the desired concentration.

[0240] [Table 3]

[0241] By thoroughly mixing the active ingredient with an auxiliary agent and then grinding the mixture thoroughly in a suitable mill, a powder can be obtained that can be used directly for seed treatment.

[0242] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0243] Emulsions of any required dilution suitable for plant protection can be obtained from this concentrate by dilution with water.

[0244] [Table 4]

[0245] Ready-to-use powders are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for drying and coating seeds.

[0246] Extruded granules Active ingredient [compound of formula (I)] 15% Sodium lignin sulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0247] The active ingredient is mixed with an auxiliary agent and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an airflow.

[0248] Coated granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0249] The finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, a dust-free coated granule is obtained.

[0250] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium lignin sulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0251] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such dilutions, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.

[0252] Fluid concentrate for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer Butanol PO / EO 2% Tristyrenephenol 2% with 10-20 moles of EO 1,2-Benzisothiazolin-3-one (20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0253] The finely ground active ingredient is tightly mixed with an auxiliary agent to obtain a suspension concentrate. By diluting this with water, a suspension of the desired dilution can be obtained. Using such dilutions, not only growing plants but also plant propagation materials can be treated by spraying, pouring, or immersion to protect them from microbial ectoparasitism.

[0254] Sustained-release capsule suspension Mix 28 parts of the compound combination of formula (I) with 2 parts of aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). Emulsify this mixture in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer, and 51.6 parts of water until the desired particle size is reached. Add a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water to this emulsion. Stir the mixture until the polymerization reaction is complete.

[0255] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The medium-sized capsules have a diameter of 8 to 15 microns. The resulting formulation is applied to seeds as an aqueous suspension using an apparatus suitable for the purpose.

[0256] Analysis method: Throughout this specification, temperatures are expressed in degrees Celsius (°C), and "mp" indicates the melting point. LC / MS stands for liquid chromatography-mass spectrometry, and the apparatus and method are described below. Method A: Instrument: Shimadzu LCMS 2020 mass spectrometer; Column: HALO C18 2.7 μm, 3.0 mm × 30 mm; Mobile phase: MeCN (containing either 0.05% HCOOH or 0.05% TFA) - Water (containing either 0.05% HCOOH or 0.05% TFA); Gradient: 5% to 95% MeCN over 1.4 min, hold for 0.6 min, total run time 2.5 min; Flow rate: 1.8 mL / min; Column temperature: 50°C; Wavelength: 214 and 254 nm PDA.

[0257] Table A below summarizes the compounds of formula (I): - LC / MS data, e.g., retention time (RT), [M+H] + etc. - Type of method, and / or - Melting point (mp).

[0258] [Table 5-1]

[0259] [Table 5-2]

[0260] Example 1: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 6) [ka] (Compound 6)

[0261] Step A: Preparation of 6-bromo-4-methyl-1H-benzimidazole [ka] 5-Bromo-3-methylbenzene-1,2-diamine (1.00 g, 4.97 mmol) was added to formic acid (4.58 g, 99.5 mmol) at room temperature. The solution was stirred at 80°C for 1 hour. The reaction mixture was concentrated to dryness, and the resulting mixture was diluted with water. The solution was adjusted to pH 9 with saturated NaHCO3 aqueous solution and extracted with dichloromethane. The combined organic phases were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 6-bromo-4-methyl-1H-benzimidazole. LC-MS (Method A): Rt0.81 min, m / z=211 / 213[M+H] +

[0262] Step B: Preparation of 7-methyl-3H-benzimidazole-5-carbonitrile [ka] A mixture of 6-bromo-4-methyl-1H-benzimidazole (5.00 g, 23.7 mmol), zinc dicyanide (5.56 g, 47.4 mmol), tris(dibenzylideneacetone)dipalladium (2.17 g, 2.37 mmol), and 1,1'-bis(diphenylphosphino)ferrocene (2.63 g, 4.74 mmol) in N,N'-dimethylformamide (50.0 mL) was heated under reflux for 4 hours in an atmosphere of N2. After cooling to ambient temperature, the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 10:1-8:2) on silica gel to obtain 7-methyl-3H-benzimidazole-5-carbonitrile as a yellow solid. LC-MS (Method A): Rt1.02 min, m / z=158[M+H] +

[0263] Step C: Preparation of [ethoxy-(7-methyl-3H-benzimidazole-5-yl)methylene]ammonium chloride (intermediate I1) [ka] (Intermediate I1) To a stirred solution of 7-methyl-3H-benzimidazole-5-carbonitride (1.00 g, 6.36 mmol) in EtOH (15.00 mL), HCl (g) was added and foamed for 50 minutes while maintaining the temperature of the stirred solution between 10 and 20°C. The mixture was then stirred at room temperature for 16 hours. The mixture was concentrated under reduced pressure, the crude product was triturated with methyl tert-butyl ether, and filtered to obtain [ethoxy-(7-methyl-3H-benzimidazole-5-yl)methylene]ammonium chloride (intermediate I1). LC-MS (method A): Rt0.40 min, m / z=204 (M-Cl+H) +

[0264] Step D: Preparation of 4-(4-fluoro-3-methoxyphenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine [ka] To a solution of [ethoxy-(7-methyl-3H-benzimidazole-5-yl)methylene]ammonium chloride (intermediate I1, 0.800 g, 3.94 mmol) in acetic acid (12.0 mL), O-[2-(4-fluoro-3-methoxyanilino)ethyl]hydroxylamine (1.02 g, 5.12 mmol) was added under a N2 atmosphere. The mixture was heated at 80°C for 8 hours. The resulting mixture was then adjusted to pH 7-8 with saturated NaHCO3 aqueous solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 100:0~93:7) on silica gel to obtain 4-(4-fluoro-3-methoxyphenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine as a yellow solid. LC-MS (Method A): Rt0.80 min, m / z=341[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=12.55(s,1H),8.17(s,1H),7.34(s,1H),7.06(s,1H),6.96(dd,J=11.2,8.6Hz,1H),6.51-6.4 5(m,1H),6.12(dd,J=9.8,4.8Hz,1H),4.16-4.11(m,2H),3.85-3.81(m,2H),3.65(s,3H),2.42(s,3H).

[0265] Step E: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 6) To a solution of 4-(4-fluoro-3-methoxyphenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine (0.800 g, 2.35 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (1.31 g, 4.70 mmol) in MeOH (16.0 mL), copper(I) oxide (1.35 g, 9.40 mmol) was added. The mixture was stirred at room temperature under an O2 atmosphere for 24 hours. The mixture was then filtered through Celite. The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 100:0~97:3) on silica gel. The purified material was further purified by trituration with acetonitrile to obtain methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as an off-white solid. LC-MS (method A): Rt1.10 min, m / z=491[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.54(s,1H),8.49(s,1H),8.41(d,J=2.6Hz,1H),8.04(d,J=8.8Hz,1H),7.81(dd,J=8.8,2.6Hz,1H),7.29(s,1H),7.16(s ,1H),7.02-6.90(m,2H),6.49(dt,J=8.6,3.6Hz,1H),4.18-4.05(m,2H),3.86-3.77(m,2H),3.74(s,3H),3.66(s,3H),2.49(s,3H).

[0266] Example 2: Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (Compound 2) [ka] (Compound 2)

[0267] Step A: Preparation of 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine [ka] To a solution of [ethoxy-(7-methyl-3H-benzimidazole-5-yl)methylene]ammonium chloride (intermediate I1, 1.20 g, 4.13 mmol) in acetic acid (15.0 mL), O-[2-(4-fluoroanilino)ethyl]hydroxylamine (0.703 g, 4.13 mmol) was added under N2 conditions. The mixture was heated at 90°C for 16 hours. The resulting mixture was then adjusted to pH 7-8 with saturated NaHCO3 solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluting at MeOH / dichloromethane, 2%-10%) to obtain 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine as a white solid. LC-MS (Method A): Rt0.76 min, m / z=311[M+H] +

[0268] Step B: Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 2) To a solution of 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazole-5-yl)-5,6-dihydro-1,2,4-oxadiazine (0.300 g, 0.64 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.816 g, 2.93 mmol) in MeOH (15.0 mL), copper(I) oxide (0.968 g, 6.77 mmol) was added. The mixture was stirred at room temperature under an O2 atmosphere for 18 hours. The mixture was then filtered through Celite. The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 100:0~95:5) on silica gel to obtain methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as a white solid. LC-MS (Method A): Rt0.93 min, m / z=461[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.56(s,1H),8.49(s,1H),8.41(d,J=2.7Hz,1H),8.04(d,J=8.9Hz,1H),7.86(dd,J=8.9,2.7Hz,1H), 7.27(s,1H),7.12(s,1H),7.08-6.99(m,4H),4.12-4.09(m,2H),3.80-3.78(m,2H),3.74(s,3H),2.47(s,3H).

[0269] Example 3: Preparation of methyl N-[5-[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 5) [ka] (Compound 5)

[0270] Step A: Preparation of 1-(4-fluoro-3-methoxyphenyl)imidazole [ka] To a solution of 4-bromo-1-fluoro-2-methoxybenzene (5.00 g, 24.4 mmol) in 1-methylpyrrolidine-2-one (50.0 mL), imidazole (1.83 g, 26.8 mmol), K2CO3 (3.53 g, 25.6 mmol), copper iodide (0.464 g, 2.44 mmol), and pentane-2,4-dione (0.610 g, 6.10 mmol) were added at 25°C. The mixture was heated at 120°C for 12 hours. After the conversion was complete, the resulting mixture was diluted with water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (dichloromethane / MeOH, 100:0~96:4) to obtain 1-(4-fluoro-3-methoxyphenyl)imidazole as a colorless oil. LC-MS (Method A): Rt0.54 min, m / z=193[M+H] +

[0271] Step B: Preparation of 2-[(6-bromo-4-methyl-benzimidazole-1-yl)methoxy]ethyl-trimethyl-silane (intermediate I2) [ka] (Intermediate I2) To a solution of 6-bromo-4-methyl-1H-benzimidazole (11.0 g, 52.1 mmol) in dry THF (150 mL), NaH (60.0%, 2.50 g, 62.5 mmol) was slowly added at 0°C under an N2 atmosphere. After the addition, the solution was stirred at 0°C for 30 minutes. Then, 2-(chloromethoxy)ethyl-trimethyl-silane (10.4 g, 62.5 mmol) was added dropwise. The resulting solution was slowly warmed to room temperature and stirred for 2 hours. The final mixture was quenched with saturated NH4Cl aqueous solution and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 100:0~96:4) on silica gel to obtain 2-[(6-bromo-4-methyl-benzimidazole-1-yl)methoxy]ethyl-trimethyl-silane as a brown oil. LC-MS (Method A): Rt0.24 min, m / z=341[M+H] +

[0272] Step C: Preparation of 2-[[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethyl-silane [ka] To a solution of 1-(4-fluoro-3-methoxyphenyl)imidazole (1.80 g, 9.37 mmol) in dry THF (20.0 mL), n-BuLi (2.5 M in hexane, 4.5 mL, 11.2 mmol) was added dropwise at -78°C under an N2 atmosphere. After addition, the solution was stirred at -78°C for 30 minutes. Next, zinc chloride (2.55 g, 18.7 mmol) in dry THF (20.0 mL) was added dropwise at -78°C under an N2 atmosphere. The solution was stirred at -78°C for 30 minutes. Next, a solution of 2-[(6-bromo-4-methyl-benzimidazole-1-yl)methoxy]ethyl-trimethyl-silane (intermediate I2, 3.20 g, 9.37 mmol) in toluene (20.0 mL) and Pd(PPh3)4 (1.08 g, 0.937 mmol) was added at room temperature under an N2 atmosphere. The reaction mixture was heated at 100 °C for 12 hours. The final mixture was quenched with saturated aqueous NH4Cl solution and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (dichloromethane / MeOH, 100:0~97:3) on silica gel to obtain 2-[[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethylsilane as a yellow solid. LC-MS (Method A): Rt0.97 min, m / z=453[M+H] +

[0273] Step D: Preparation of 6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-1H-benzimidazole [ka] To a solution of 2-[[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethyl-silane (1.30 g, 2.01 mmol) in dichloromethane (30 mL), 2,2,2-trifluoroacetic acid (4.59 g, 40.2 mmol) was added dropwise at room temperature. The solution was stirred at room temperature for 4 hours. After completion, the reaction mixture was adjusted to pH 9 with saturated NaHCO3 aqueous solution. The phases were separated, and the organic layer was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 98:2~96:4) on silica gel to obtain 6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-1H-benzimidazole as a brown solid. LC-MS (Method A): Rt0.77 min, m / z=323[M+H] +

[0274] Step E: Preparation of methyl N-[5-[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 5) To a solution of 6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-1H-benzimidazole (190 mg, 0.589 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (246 mg, 0.884 mmol) in MeOH (15.0 mL), copper(I) oxide (337 mg, 2.36 mmol) was added. The mixture was stirred at room temperature under an O2 atmosphere for 36 hours. The mixture was then filtered through Celite. The filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 100:0~95:5) on silica gel to obtain methyl N-[5-[6-[1-(4-fluoro-3-methoxyphenyl)imidazole-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as an off-white solid. LC-MS (Method A): Rt0.93 min, m / z=473[M+H]+ 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ =10.52(s,1H),8.51(s,1H),8.43(d,J=2.7Hz,1H),8.00(d,J=8.9Hz,1H),7.71(dd,J=8.9,2.8Hz,1H),7.47(d,J=1.3Hz,1H),7.3 3(s,1H),7.30-7.19(m,2H),7.15(d,J=1.3Hz,1H),7.10(d,J=1.6Hz,1H),6.83-6.73(m,1H),3.75(d,J=3.1Hz,6H),2.53(s,3H).

[0275] Example 4: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 7) [ka] (Compound 7)

[0276] Step A: Preparation of methyl 7-methyl-3H-benzimidazole-5-carboxylate [ka] A 25 mL autoclave reactor was packed with 6-bromo-4-methyl-1H-benzimidazole (1.00 g, 4.74 mmol), MeOH (10.0 mL), 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.384 g, 0.474 mmol), and N,N-diethylethaneamine (1.44 g, 14.2 mmol). The autoclave was then flushed with argon, sealed, and pressurized to 2.5 MPa with carbon monoxide. The reaction mixture was stirred at 100 °C for 9 hours. The vessel was then cooled to room temperature and the pressure was released. The reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by column chromatography on silica gel (petroleum ether / ethyl acetate, 1:1-1:2) to obtain methyl 7-methyl-3H-benzimidazole-5-carboxylate as a brown solid. LC-MS (Method A): Rt0.70 min, m / z=191[M+H] +

[0277] Step B: Preparation of 7-methyl-3H-benzimidazole-5-carbohydrazide (intermediate I3) [ka] (Intermediate I3) Methyl 7-methyl-3H-benzimidazole-5-carboxylate (7.00 g, 36.8 mmol) was added to a stirred solution of NH2NH2.H2O / EtOH (70.0 mL, 2:5). The reaction mixture was stirred at 85°C for 16 hours. The reaction mixture was then cooled to room temperature. The precipitate was collected by filtration and dried under reduced pressure to obtain 7-methyl-3H-benzimidazole-5-carbohydrazide (intermediate I3) as a yellow solid. LC-MS (method A): Rt0.25 min, m / z=190[M+H] +

[0278] Step C: Preparation of 2-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole [ka] To a solution of 7-methyl-3H-benzimidazole-5-carbohydrazide (intermediate I3, 0.200 g, 1.05 mmol) in dry EtOH (10.0 mL), diethoxymethoxyethane (0.210 mL, 1.26 mmol) and ammonia hydrochloride (0.0169 g, 0.315 mmol) were added. The mixture was refluxed at 80°C for 3 hours and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0~90:10) to obtain 2-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole as a yellow solid. LC-MS (method A): Rt0.57 min, m / z=201[M+H] +

[0279] Step D: Preparation of 6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole [ka] 4-fluoro-3-methoxyaniline (818 mg, 5.79 mmol) was added to a stirred solution of 2-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole (580 mg, 2.90 mmol) in acetic acid (15.00 mL). The reaction mixture was then stirred at 115 °C for 5 hours. The reaction mixture was concentrated under reduced pressure and then diluted with ethyl acetate (80 mL). The combined organic phase was washed with saturated sodium bicarbonate, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (dichloromethane / MeOH, 98:2~90:10) to obtain 6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-1H-benzimidazole as a light brown solid. LC-MS (Method A): Rt0.89 min, m / z=324[M+H] +

[0280] Step E: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate To a solution of 6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimizole (0.430 g, 1.33 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.740 g, 2.66 mmol) in MeOH (10.00 mL), copper(I) chloride (0.761 g, 5.32 mmol) was added. The mixture was stirred at room temperature under an O2 atmosphere for 16 hours, and then filtered through Celite. The filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 100:0~95:5) on silica gel, and then further purified by trituration with n-hexane to obtain methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as an off-white powder. LC-MS (Method A): Rt1.03 min, m / z=474[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.54(s,1H),8.83(s,1H),8.58(s,1H),8.46(d,J=2.4Hz,1H),8.01(d,J=8.9Hz,1H),7.76(dd,J=8.9,2.7Hz,1H),7.43(dd, J=7.6,2.4Hz,1H),7.37(s,1H),7.30(dd,J=11.1,8.6Hz,1H),7.23(s,1H),6.98-6.82(m,1H),3.75(s,3H),3.74(s,3H),2.56(s,3H).

[0281] Example 5: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 9) [ka]

[0282] Step A: Preparation of 2-methyl-5-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole (intermediate I4) [ka] (Intermediate I4) To a stirred solution of 7-methyl-3H-benzimidazole-5-carbohydrazide (intermediate I3, 1.50 g, 7.89 mmol) in dry EtOH (60.0 mL), trimethyl orthoacetate (1.43 g, 11.8 mmol) and NH4Cl (0.127 g, 2.37 mmol) were added at room temperature. The reaction mixture was stirred at 80°C for 2 hours. The mixture was then concentrated under reduced pressure, the residue was diluted with water, and then filtered off. The solid was washed with water to obtain 2-methyl-5-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole (intermediate I4) as a brown solid. LC-MS (Method A): Rt0.66 min, m / z=215[M+H] +

[0283] Step B: Preparation of 6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole [ka] To a solution of 2-methyl-5-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole (intermediate I4, 600 mg, 2.80 mmol) in AcOH (7.00 mL), 4-fluoro-3-methyl-aniline (0.701 g, 5.60 mmol) was added. The mixture was stirred at 115°C for 3 hours. The reaction product was then quenched with saturated Na2CO3 aqueous solution, and the mixture was extracted with dichloromethane. The combined layers were washed with saturated NaCl, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by flash chromatography column (dichloromethane / MeOH, 95:5) to obtain 6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-1H-benzimidazole as a yellow solid. LC-MS (method A): Rt0.80 min, m / z=322[M+H] +

[0284] Step C: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 9) To a solution of 6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (550 mg, 1.71 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.714 g, 2.57 mmol) in MeOH (7.00 mL), copper(I) oxide (0.980 g, 6.85 mmol) was added. The mixture was stirred at 25°C for 16 hours under an O2 atmosphere. The reaction mixture was then filtered through Celite. The filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 95:5) on silica gel, and then further purified by trituration in n-hexane to obtain methyl N-[5-[6-[4-(4-fluoro-3-methylphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as a white solid. LC-MS (Method A): Rt0.92 min, m / z=473[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.56(s,1H),8.54(s,1H),8.37(d,J=2.6Hz,1H),8.01(d,J=8.9Hz,1H),7.61(dd,J=8.9,2.7Hz,1H),7.50(s, 1H),7.49-7.47(m,1H),7.25(dd,J=7.9,4.6Hz,2H),6.90(s,1H),3.75(s,3H),2.56(s,3H),2.24(s,3H),2.22(s,3H).

[0285] Example 6: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 11) [ka] (Compound 11)

[0286] Step A: Preparation of 6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole [ka] 4-fluoro-3-methoxyaniline (0.198 g, 1.40 mmol) was added to a stirred solution of 2-methyl-5-(7-methyl-3H-benzimidazole-5-yl)-1,3,4-oxadiazole (intermediate I4, 0.200 g, 0.934 mmol) in acetic acid (5 mL). The reaction mixture was then stirred at 115 °C for 5 hours. After the reaction was complete, the resulting mixture was concentrated under reduced pressure, and the crude residue was diluted with dichloromethane. The organic phase was washed with saturated sodium bicarbonate, dried over sodium sulfate, and concentrated. The residue was purified by column chromatography on silica gel (dichloromethane / MeOH, 98:2~90:10) to obtain 6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-1H-benzimidazole as a light brown solid. LC-MS (Method A): Rt0.82 min, m / z=338[M+H] +

[0287] Step B: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 11) To a solution of 6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-1H-benzimidazole (0.110 g, 0.326 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (136 mg, 0.489 mmol) in MeOH (4.00 mL), copper(I) oxide (0.0933 g, 0.652 mmol) was added. The mixture was stirred at room temperature under an O2 atmosphere for 16 hours. The reaction mixture was then filtered through Celite. The filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 100:0~95:5) on silica gel to obtain methyl N-[5-[6-[4-(4-fluoro-3-methoxyphenyl)-5-methyl-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate. LC-MS (Method A): Rt1.03 min, m / z=488[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.54(s,1H),8.55(s,1H),8.43(d,J=2.7Hz,1H),8.02(d,J=8.7Hz,1H),7.69(dd,J=8.9,2.7Hz,1H),7.48- 7.37(m,2H),7.35-7.26(m,1H),7.10(s,1H),6.98-6.96(m,1H),3.76(s,3H),3.75(s,3H),2.55(s,3H),2.24(s,3H).

[0288] Example 7: Preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 1) [ka] (Compound 1)

[0289] Step A: Preparation of 1-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole [ka] A mixture of (4-fluoro-3-methoxyphenyl)hydrazine hydrochloride (CAS327021-81-8, 1.70 g, 8.83 mmol) in formamide (9.0 mL) was heated at 120°C for 16 hours under an N2 atmosphere. The resulting mixture was then diluted with water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (petroleum ether / ethyl acetate, 100:0~55:45) to obtain 1-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole as an off-white solid. LC-MS (Method A): Rt0.99 min, m / z=194[M+H] +

[0290] Step B: Preparation of 2-[[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethylsilane [ka] To a solution of 1-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole (1.20 g, 6.21 mmol) in dry THF (20.0 mL), n-BuLi (2.5 M in hexane, 3.0 mL, 7.45 mmol) was added dropwise at -78°C under an N2 atmosphere. After addition, the solution was stirred at -78°C for 30 minutes. Next, zinc dichloride (1.69 g, 12.4 mmol) in dry THF (20.0 mL) was added dropwise at -78°C under an N2 atmosphere. After addition, the solution was stirred at -78°C for 30 minutes. Next, toluene (20.0 mL) and 2-[(6-bromo-4-methyl-benzimidazole-1-yl)methoxy]ethyl-trimethyl-silane (intermediate I2, 2.12 g, 6.21 mmol) in Pd(PPh3)4 (0.718 g, 0.621 mmol) were added at room temperature under an N2 atmosphere. The reaction mixture was heated at 100 °C for 12 hours. The reaction mixture was then quenched with saturated NH4Cl aqueous solution and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0~98:2) to obtain 2-[[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethylsilane as a yellow solid. LC-MS (Method A): Rt1.77 min, m / z=454[M+H] +

[0291] Step C: Preparation of 6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole [ka] A mixture of 2-[[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethylsilane (2.50 g, 5.51 mmol) in trifluoroacetic acid / dichloromethane (12.0 mL, 1:5) was stirred at room temperature for 12 hours. The reaction mixture was adjusted to pH approximately 7 with saturated aqueous NaHCO3 solution. The resulting mixture was then diluted with water and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (dichloromethane / MeOH, 100:0~90:10) to obtain 6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-1H-benzimidal as a brown solid. LC-MS (method A): Rt0.85 min, m / z=324[M+H] +

[0292] Step D: Preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 1) To a solution of 6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (0.300 g, 0.928 mmol) in dry MeOH (8.0 mL), methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (0.387 g, 1.39 mmol) and copper(I) oxide (0.531 g, 3.71 mmol) were added. The mixture was stirred at room temperature under an O2 atmosphere for 24 hours. The mixture was then filtered on Celite. The filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography (dichloromethane / MeOH, 100:0~97:3) on silica gel, and further purified by trituration with acetonitrile to obtain methyl N-[5-[6-[2-(4-fluoro-3-methoxyphenyl)-1,2,4-triazole-3-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as an off-white solid. LC-MS (Method A): Rt1.11 min, m / z=474[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=10.54(s,1H),8.60(s,1H),8.46(d,J=2.4Hz,1H),8.22(s,1H),8.01(d,J=8.8Hz,1H),7.79(dd,=8.8,2.6 Hz,1H),7.38(d,J=7.8Hz,2H),7.33-7.25(m,2H),6.91(dt,J=8.4,3.4Hz,1H),3.75(d,J=5.6Hz,6H),2.56(s,3H).

[0293] Example 8: Methyl N-[5-[6-[3-(4-cyano-3-methoxyphenyl)pyrazine-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate (compound 12) [ka] (Compound 12)

[0294] Step A: Preparation of 6-bromo-4-methyl-1H-benzimidazole [ka] 5-Bromo-3-methylbenzene-1,2-diamine (1.00 g, 4.97 mmol) was added to formic acid (4.58 g, 99.5 mmol) at room temperature. The solution was stirred at 80°C for 1 hour. The reaction mixture was concentrated to dryness, and the resulting mixture was diluted with water. The solution was adjusted to pH 9 with saturated NaHCO3 aqueous solution and extracted with dichloromethane. The combined organic phases were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 6-bromo-4-methyl-1H-benzimidazole. LC-MS (Method A): Rt0.81 min, m / z=211 / 213[M+H] +

[0295] Step B: 5-(6-bromo-4-methylbenzimidazole-1-yl)pyridine-2-amine [ka] A mixture of bromo-3-methylbenzene-1,2-diamine (1.00 g, 4.97 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-amine (0.84 g, 7.12 mmol), copper(II) acetate (1.3 g, 7.12 mmol), boric acid (5.9 g, 9.5 mmol), and N,N-diisopropylethylamine (1.6 mL, 9.5 mmol) added to acetonitrile was purged with air and stirred at room temperature for 24 hours. The reaction mixture was then concentrated, ethyl acetate was added, and the mixture was filtered. The resulting mother liquor was washed with water, dried over sodium sulfate, and concentrated. The obtained crude material was purified by column chromatography (1-20% methanol in ethyl acetate) to obtain 5-(6-bromo-4-methylbenzimidazole-1-yl)pyridine-2-amine as a brown solid. LC-MS (method A): Rt1.12 min, m / z=303 / 305[M+H] +

[0296] Step C: Methyl N-[5-(6-bromo-4-methyl-benzimidazole-1-yl)-2-pyridyl]carbamate [ka] Methyl chloroformate (0.19 g, 1.98 mmol) was added to a mixture of 5-(6-bromo-4-methyl-benzimidazole-1-yl)pyridin-2-amine (0.4 g, 1.32 mmol), (dimethylamino)pyridine (0.016 g, 0.13 mmol), and pyridine (0.22 mL, 2.64 mmol) in dichloromethane cooled to 0°C. The reaction mixture was heated and stirred at room temperature for 16 hours. The reaction mixture was then concentrated, ethyl acetate was added, the organic layer was washed with water and brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude material was obtained as a brown solid, and methyl N-[5-(6-bromo-4-methyl-benzimidazole-1-yl)-2-pyridyl]carbamate was used directly in the next step. LC-MS (method A): Rt1.98 min, m / z=361 / 363[M+H] +

[0297] Step D: 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazole-5-yl]boronic acid [ka] Toluene was added to a mixture of methyl N-[5-(6-bromo-4-methyl-benzimidazole-1-yl)-2-pyridyl]carbamate (0.13 g, 0.60 mmol), bis(pinacolato)diborone (0.30 g, 1.90 mmol), potassium acetate (0.176 g, 1.786 mmol), and bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (0.05 g, 0.06 mmol). The reaction mixture was degassed with nitrogen and stirred at 80°C for 16 hours. The reaction mixture was then cooled, filtered through a Celite pad, and the mother liquor was concentrated to obtain 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazole-5-yl]boronic acid as a brown solid. The crude material was used directly in the next step. LC-MS (Method A): Rt2.04 min, m / z=325(MH)+

[0298] Step E: 4-(3-bromopyrazine-2-yl)-2-methoxy-benzonitrile [ka] A mixture of (4-cyano-3-methoxyphenyl)boronic acid (3.0 g, 16.95 mmol), 2,3-dibromopyrazine (8.0 g, 33.90 mmol), potassium carbonate (7.0 g, 50.87 mmol), and tetrakis(triphenylphosphine)palladium(0) (2.0 g, 1.70 mmol) in a mixture of 4-dioxane (10.0 mL) and water (2.5 mL) was degassed with nitrogen and then stirred at 80°C for 16 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, and purified by flash chromatography (1-100% ethyl acetate in cyclohexane) to obtain 4-(3-bromopyrazine-2-yl)-2-methoxybenzonitrile as a white solid. LC-MS (method A): Rt0.15 min, m / z=290 / 292[M+H] +

[0299] Step F: Methyl N-[5-[6-[3-(4-cyano-3-methoxyphenyl)pyrazine-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate [ka] A mixture of 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazole-5-yl]boronic acid (0.06 g, 16.952 mmol), 4-(3-bromopyrazine-2-yl)-2-methoxy-benzonitrile (56.0 mg, 0.19 mmol), potassium carbonate (49 mg, 0.35 mmol), and tetrakis(triphenylphosphine)palladium (0) (20.4 mg, 0.0175 mmol) in 4-dioxane (2.0 mL) and water (0.1 mL) was degassed with nitrogen and then stirred at 80°C for 16 hours. The reaction mixture was then cooled, concentrated under reduced pressure, sodium acetate was added, the organic layer was washed with water, dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by flash chromatography (1-10% methanol in ethyl acetate) to obtain methyl N-[5-[6-[3-(4-cyano-3-methoxyphenyl)pyrazine-2-yl]-4-methyl-benzimidazole-1-yl]-2-pyridyl]carbamate as an off-white solid. LC-MS (Method A): Rt1.05 min, m / z=492[M+H] + 1 H-NMR (400MHz, DMSO-d 6 ,ppm)δ=8.58(dd,J=8.6,2.3Hz,2H),8.23-8.01(m,4H),7.58(d,J=8.0Hz,1H),7.36(d,J=8.0Hz,1H), 7.34(s,1H),7.29(s,1H),7.24(s,1H),6.97(d,J=8.0Hz,1H),3.86(s,3H),3.83(s,3H),2.67(s,3H).

[0300] Biological examples: The fungicidal activity of the compound of the present invention was tested as follows.

[0301] Phytophthora infestans / Tomato / Leaf blight preventative (leaf blight) Tomato leaf fragments are placed on agar plates in a multi-well plate (24-well type), and the test compound diluted with water is sprayed onto them. One day after application, a suspension of fungal spores is inoculated onto the leaf fragments. The inoculated leaf fragments are incubated in a climate cabinet at 16°C and 75% rh under a light environment of 24 hours in darkness followed by 12 hours of light / 12 hours of darkness. The activity of the compound is evaluated as the disease control rate compared to untreated leaf fragments when an appropriate level of disease appears on untreated test leaf fragments (5-7 days after application).

[0302] The following compounds, at 200 ppm, provided at least 80% control of Phytophthora infestans, compared to untreated controls under identical conditions, when exhibiting widespread disease development: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11.

[0303] Plasmopara viticola / Grape / Leaf blight preventative (leaf blight) Grapevine leaflets are placed on agar plates in a multi-well plate (24-well type), and the test compound diluted with water is sprayed onto them. One day after application, a fungal spore suspension is inoculated onto the leaflets. The inoculated leaflets are incubated in a climate cabinet at 19°C and 80% rh under a 12-hour light / 12-hour darkness environment. The activity of the compound is evaluated as the disease control rate compared to untreated leaflets when an appropriate level of disease appears on untreated check leaflets (6-8 days after application).

[0304] The following compounds, at 200 ppm, resulted in at least 80% control of Plasmopara viticola, which exhibited widespread disease development, compared to untreated controls under the same conditions: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11.

[0305] Pythium ultimum / Liquid culture (Seedling blight) Newly grown fungal mycelial fragments and oospores from liquid culture are directly mixed into a nutrient medium (PDB potato dextrose medium). After placing a (DMSO) solution of the test compound into a microtiter plate (96-well type), the nutrient medium containing the fungal mycelium / spore mixture is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 2-3 days after application.

[0306] The following compounds, at 20 ppm, provided at least 80% control of Pythium ultimum, compared to an untreated control under the same conditions that exhibited widespread disease: 2, 5, 6, 7, 8, 9, 10, 11.

Claims

1. Equation (I) 【Chemistry 1】 (wherein the formula, ring W is a 5-8 membered carbon ring, a 5-8 membered hetero ring, a 6-12 membered aromatic ring, or a 5-11 membered heteroaromatic ring, and each of the 5-8 membered carbon ring, the 5-8 membered hetero ring, the 6-12 membered aromatic ring, or the 5-11 membered heteroaromatic ring is R 1 It may be optionally substituted with 1 to 4 substituents independently selected from the above, A 1 However, it is a carbon atom or a nitrogen atom, A 2 However, it is a carbon atom or a nitrogen atom, A 3 is independently CR 3 or N, provided that four or fewer A 3 are N, preferably three or fewer A 3 are N, preferably two or fewer A 3 are N, preferably one or fewer A 3 are N, more preferably five A 3 are CR 3 and A 4 and A 5 However, it is selected independently of CH or N, R 1 However, halogen, hydroxy, amino, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Selected from alkylaminocarbonyl and CN, the C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Alkoxy, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each alkylaminocarbonyl group may be optionally substituted with 1 to 3 substituents independently selected from halogens, hydroxyls, and CNs, and optionally two geminal R groups. 1 However, they may also form a carbonyl group together with the carbon to which they are bonded. R 2 However, hydrogen, hydroxyl, halogen, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkyl sulfanyl, C 1-6 Alkyl sulfinyl, C 1-6 Alkyl sulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 Selected from alkyl groups, R 3 is independently selected from hydrogen, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, halogen, CN, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 [[ID=,30]]alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl, C 1-6 alkylcarbonyl, and hydroxy, and each of the C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylsulfanyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C<00000,93>alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl, and C 1-6 each of the alkylcarbonyl groups may be optionally substituted with one to three substituents independently selected from halogen, hydroxy, and CN, R 5 is -NHC(O)R 6 and R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos and C 1-6 Alkyl C 1-6 Selected from alkoxyaminos, the C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, diC 1-6 Alkylamino, C 1-6 Alkoxyaminos and C 1-6 Alkyl C 1-6 Each alkoxyamino group may be optionally substituted with one to three substituents independently selected from halogens and CNs. A compound thereof, or its salt or N-oxide.

2. The four A's 3 CR 3 And one A 3 The compound according to claim 1, wherein is N. 【Request Item 3】 【Chemistry 2】 but, 【Transformation 3】 Preferably, the four A 3 CR 3 The compound according to claim 1 or 2. 【Request Item 4】 【Chemistry 4】 but, 【Transformation 5】 Preferably, the four A 3 CR 3 The compound according to claim 1 or 2.

5. The five A's mentioned above 3 However, CR 3 The compound according to claim 1.

6. A 4 and A 5 Is CH or A 4 CH is A 5 Whether it is N or A 4 N is A 5 The compound according to any one of claims 1 to 5, wherein is CH.

7. A 1 However, it is a carbon atom, A 2 The compound according to any one of claims 1 to 6, wherein the atom is a nitrogen atom.

8. A 1 However, it is a carbon atom, A 2 The compound according to any one of claims 1 to 6, wherein the compound is a carbon atom.

9. A 1 However, it is a nitrogen atom, A 2 The compound according to any one of claims 1 to 6, wherein the compound is a carbon atom.

10. A 1 However, it is a nitrogen atom, A 2 The compound according to any one of claims 1 to 6, wherein the atom is a nitrogen atom.

11. Ring W 【Transformation 6】 However, the following: 【Transformation 7】 Selected from, During the ceremony, * represents the binding site to the benzimidazole group in formula (I), and # represents the A 3 It represents the bonding point to the ring formed by the group, R 11 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 Selected from alkynyl, the C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 Each of the alkynyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs. Ring W is R 1 They may be optionally substituted with 1 to 4 substituents independently selected from the above. The compound according to any one of claims 1 to 6.

12. Ring W 【Transformation 8】 However, the following: 【Chemistry 9】 Selected from, During the ceremony, * represents the binding site to the benzimidazole group in formula (I), and # represents the A 3 R represents the bonding point to the ring formed by the group. 11 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 Selected from alkynyl, the C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl and C 2-6 The compound according to claim 11, wherein each of the alkynyl groups may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs.

13. Ring W is a 5-8 membered heterocyclic ring or a 5-11 membered heteroaromatic ring, and each of the 5-8 membered heterocyclic ring or the 5-11 membered heteroaromatic ring is R 1 It may be optionally substituted with 1 to 4 substituents independently selected from the above, A 1 However, it is a carbon atom or a nitrogen atom, A 2 However, it is a carbon atom or a nitrogen atom, A 3 However, CR became independent 3 or N, provided there are three or fewer A's. 3 is N, preferably the five A 3 CR 3 And, A 4 CH is A 5 N is, R 1 However, halogen, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Selected from alkoxy and CN, the C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, and C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Each alkoxy group may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs. R 2 However, hydrogen, halogens, CN, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 1-6 Alkoxy and -NHC(O)C 1-6 Selected from alkyl, more preferably R 2 However, hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Selected from alkoxy, R 3 However, hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, halogen, CN, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Independently selected from alkyl and hydroxy, the C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, and C 3-6 Cycloalkyl-C 1-6 Each alkyl group may be optionally substituted with one to three substituents independently selected from halogens, hydroxyls, and CNs. R 5 However, -NHC(O)R 6 And, R 6 However, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Selected from alkyl, the C 1-6 Alkyl, C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Each alkyl group may be optionally substituted with one to three substituents independently selected from halogens and CNs. The compound according to any one of claims 1 to 12.

14. A composition comprising a fungicidal amount of the compound described in any one of claims 1 to 13.

15. The composition according to claim 14, wherein the composition further comprises at least one compound selected from additional active ingredients, suitable inactive ingredients, carriers, auxiliaries, and any mixture thereof.

16. A method for eradicating, preventing, or controlling plant pathogenic diseases, comprising applying a fungicidal amount to a plant pathogen, a habitat of a plant pathogen, a plant susceptible to damage by a plant pathogen, or a plant reproductive material thereof, of the compound described in any one of claims 1 to 13, or a composition containing the compound described in any one of claims 1 to 13, or the composition described in claim 14 or 15.

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