Benzimidazole derivatives

Abstract

The present invention relates to: compounds of formula (I) wherein the substituents are as defined in claim 1; processes and methods for preparing a compound of formula (I); an agrochemical composition comprising a compound of formula (I) as defined in claim 1; the preparation of these compositions and the use of these compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi. (I).

Description

[0001] This invention relates to benzimidazole derivatives that kill microorganisms, for example, as active ingredients, which have microbial activity, particularly fungicidal activity, and more particularly activity against oomycetes. The invention also relates to: the preparation of these benzimidazole derivatives; intermediates useful in the preparation of these benzimidazole derivatives; the preparation of these intermediates; agricultural chemical compositions comprising at least one of these benzimidazole derivatives; the preparation of these compositions; and the use of these benzimidazole derivatives or compositions in agriculture or horticulture for combating, controlling, or preventing infection of plants, harvested food crops, seeds, or inanimate materials by plant pathogenic microorganisms, particularly fungi, and more particularly oomycetes.

[0002] It has now been unexpectedly discovered that some novel benzimidazole derivatives possess favorable antifungal properties, particularly against oomycetes.

[0003] Therefore, in a first aspect, the present invention provides a compound having formula (I).

[0004] (I)

[0005] Wherein ring W is a 5-8 membered carbon ring, a 5-8 membered heterocyclic ring, a 6-12 membered aromatic ring, or a 5-11 membered heteroaromatic ring, wherein each of the 5-8 membered carbon ring, the 5-8 membered heterocyclic ring, the 6-12 membered aromatic ring, or the 5-11 membered heteroaromatic ring is optionally selected independently from one to four members of R. 1 Substituents of the substituents;

[0006] A 1 It is a carbon atom or a nitrogen atom;

[0007] A 2 It is a carbon atom or a nitrogen atom;

[0008] A 3 Independently is CR 3 Or N, provided that there are no more than four A's. 3 If it is N, then no more than three A's are preferred. 3 If it is N, then no more than two A's are preferred. 3 If it is N, then no more than one A is preferred. 3 It is N, and more preferably five A's. 3 It is CR 3 ;

[0009] A 4 and A 5 Independently selected from CH and N, preferably A 4 and A 5 It's CH, or A. 4 It is CH and A 5 It is N, or A 4It is N and A 5 It is CH, and even more preferably A. 4 It is CH and A 5 It is N;

[0010] R 1 Selected from halogens, hydroxyl groups, amino groups, and 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 group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and CN, wherein 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, C 2-6 alkynyl group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each of the alkylamino carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; and wherein optionally two of the radicals are geminal R. 1 Together with the carbon atoms to which they are attached, they form carbonyl groups;

[0011] R 2 Selected from 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 thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C1-6 Alkoxy, amino, and -NHC(O)C 1-6 Alkyl; preferably R 2 Selected from 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 groups and -NHC(O)C 1-6 Alkyl; and more preferably R 2 Selected from hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Alkoxy;

[0012] R 3 Independently selected from hydrogen and 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, C 1-6 alkyl carbonyl and hydroxyl, wherein 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6Alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl, and C 1-6 Each of the alkyl carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN;

[0013] R 5 Selected from -NHC(O)R 6 Halogen, cyano, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-3 alkylsulfonamide group, C 1-3 Alkylaminocarbonyl, C 3-6 Cycloalkylaminocarbonyl, C 1-3 alkoxyaminocarbonyl, -NHS(O)2C 1-3 Alkyl, and , where R 7 Selected from C 1-3 Alkyl and C 3-6 cycloalkyl; and preferably R 5 Selected from

[0014]

[0015] R 6 Selected from 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 alkoxyamino, and C 1-6 Alkyl C 1-6 alkoxyamino, wherein 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 alkoxyamino, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN; and preferably R. 6 Selected from C 1-6 Alkyl, C 1-6 Alkoxy, C3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl and C 1-6 Alkoxy C 1-6 Alkyl, wherein 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 of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN;

[0016] Or its salts or N-oxides.

[0017] In a preferred embodiment, the present invention provides a compound having formula (I).

[0018] (I)

[0019] Wherein ring W is a 5-8 membered carbon ring, a 5-8 membered heterocyclic ring, a 6-12 membered aromatic ring, or a 5-11 membered heteroaromatic ring, wherein each of the 5-8 membered carbon ring, the 5-8 membered heterocyclic ring, the 6-12 membered aromatic ring, or the 5-11 membered heteroaromatic ring is optionally selected independently from one to four members of R. 1 Substituents of the substituents;

[0020] A 1 It is a carbon atom or a nitrogen atom;

[0021] A 2 It is a carbon atom or a nitrogen atom;

[0022] A 3 Independently is CR 3 Or N, provided that there are no more than four A's. 3 If it is N, then no more than three A's are preferred. 3 If it is N, then no more than two A's are preferred. 3 If it is N, then no more than one A is preferred. 3 It is N, and more preferably five A's. 3 It is CR 3 ;

[0023] A 4 and A 5 Independently selected from CH and N, preferably A 4 and A 5 It's CH, or A. 4 It is CH and A 5 It is N, or A 4 It is N and A 5 It is CH, and even more preferably A.4 It is CH and A 5 It is N;

[0024] R 1 Selected from halogens, hydroxyl groups, amino groups, and 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 group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and CN, wherein 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, C 2-6 alkynyl group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each of the alkylamino carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; and wherein optionally two of the radicals are geminal R. 1 Together with the carbon atoms to which they are attached, they form carbonyl groups;

[0025] R 2 Selected from 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 thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C1-6 Alkyl; preferably R 2 Selected from 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 groups and -NHC(O)C 1-6 Alkyl; and more preferably R 2 Selected from hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Alkoxy;

[0026] R 3 Independently selected from hydrogen and 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, C 1-6 alkyl carbonyl and hydroxyl, wherein 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6alkylaminocarbonyl, and C 1-6 Each of the alkyl carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN;

[0027] R 5 It is -NHC(O)R 6 ;and

[0028] R 6 Selected from 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 alkoxyamino, and C 1-6 Alkyl C 1-6 alkoxyamino, wherein 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 alkoxyamino, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN; and preferably R. 6 Selected from 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 Alkyl, wherein 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 of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN;

[0029] Or its salts or N-oxides.

[0030] In a second aspect, the present invention provides an agricultural chemical composition comprising a compound having formula (I), and more particularly an agricultural chemical composition comprising a fungicide-effective amount of a compound having formula (I). The composition may further comprise at least one compound selected from: additional active ingredients, suitable formulation inert agents, carriers, adjuvants, and any mixtures thereof.

[0031] Compounds having formula (I) can be used to control plant pathogenic microorganisms. Therefore, in order to control plant pathogens, compounds having formula (I) according to the present invention, or compositions comprising compounds having formula (I), can be directly applied to the plant pathogen, the site of the plant pathogen, particularly plants susceptible to plant pathogen attack, or plant propagation material.

[0032] Therefore, in a third aspect, the present invention provides the use of compounds having formula (I) as described herein, or compositions comprising compounds having formula (I), for combating, preventing or controlling plant pathogens.

[0033] In a fourth aspect, the present invention provides a method for combating, preventing, or controlling plant pathogens, the method comprising applying to the plant pathogen, to the site of the plant pathogen, particularly to a plant susceptible to the plant pathogen, or to the plant's propagation material a compound having formula (I) as described herein, or a composition comprising a compound having formula (I). According to this fourth aspect of the invention, the method may exclude methods of treating a human or animal body by surgery or therapy.

[0034] Compounds having formula (I) are particularly effective against, prevent, or control of plant pathogenic fungi, especially oomycetes. Therefore, in a fifth aspect, the present invention provides the use of compounds having formula (I) as described herein, or compositions comprising compounds having formula (I), for controlling plant pathogenic fungi, especially oomycetes.

[0035] In a sixth aspect, the present invention provides a method for combating, preventing, or controlling plant pathogenic diseases such as plant pathogenic fungi, the method comprising applying to said plant pathogenic fungi, or to the site of said plant pathogenic fungi, particularly to plants susceptible to attack by plant pathogenic fungi, especially oomycetes, or to the propagation material of plants a compound having formula (I) as described herein, or a composition comprising a compound having formula (I). According to this sixth aspect of the invention, the method may exclude methods of treating a human or animal body by surgery or therapy.

[0036] When a group is indicated to be substituted with, for example, an alkyl group, this includes those groups that are part of other groups, such as alkyl groups in alkylthio groups.

[0037] Definitions:

[0038] - The term "halogen" or "halogen group" refers to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br) or iodine (iodo or I), preferably fluorine, chlorine or bromine.

[0039] - The term "amino" refers to the -NH2 group.

[0040] - As used herein, the term "alkyl" (in isolation or as part of a chemical group) refers to a straight-chain or branched hydrocarbon, preferably having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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. Alkyl groups having 1 to 4 carbon atoms are preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0041] - The term "alkenyl" (in isolation or as part of a chemical group) refers to a straight-chain or branched hydrocarbon, preferably 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, 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. Alkenyl groups having 2 to 4 carbon atoms are preferred, such as 2-propenyl, 2-butenyl, or 1-methyl-2-propenyl.

[0042] - The term "alkynyl" (in isolation or as part of a chemical group) refers to a straight-chain or branched hydrocarbon, preferably 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, 3-hexynyl, 4-hexynyl The group comprises 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-hexadiynyl. Alynyl groups having 2 to 4 carbon atoms are preferred, such as ethynyl, 2-propynyl, or 2-butynyl-2-propynyl.

[0043] - The term "cycloalkyl" (in isolation or as part of a chemical group) refers to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic hydrocarbon, preferably 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. Cycloalkyl groups having 3, 4, 5, 6, or 7 carbon atoms are preferred, such as cyclopropyl or cyclobutyl.

[0044] - The term "alkoxy" refers to an alkoxy group having the formula -OR a The group, wherein R a It is an alkyl group as generally defined above. Examples of alkoxy groups 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 mentioned above).

[0045] - The term "alkylthioalkyl" refers to a compound with the formula -SR a The group, wherein R a It is an alkyl group as generally defined above.

[0046] - The term "alkylsulfinyl" refers to a group having the formula -S(O)R a The group, wherein R a It is an alkyl group as generally defined above.

[0047] - The term "alkylsulfonyl" refers to a group having the formula -S(O)2R a The group, wherein R a It is an alkyl group as generally defined above.

[0048] - The term "alkyl carbonyl" refers to an alkyl group having the formula R a C(O)- groups, where R a It is an alkyl group as generally defined above.

[0049] - The term "alkoxycarbonyl" refers to a group having the formula R a The group of OC(O)-, where R a It is an alkyl group as generally defined above.

[0050] - The term "alkylamino" refers to an amino group having the formula R a NH- groups, where R a It is an alkyl group as generally defined above.

[0051] - The term "di-alkylamino" refers to a substance having the formula R a R b NH- groups, where R a and R b It is an alkyl group as generally defined above.

[0052] - The term "alkoxyamino" refers to an amino group having the formula R a NH- groups, where R a It is an alkoxy group as generally defined above.

[0053] - The term "alkylaminocarbonyl" refers to an alkylaminocarbonyl group having the formula R a The group of NHC(O)-, wherein R a It is an alkyl group as generally defined above.

[0054] - The term "di-alkylaminocarbonyl" refers to a group having the formula R a R b The group of NC(O)-, wherein R a and R b It is an alkyl group as generally defined above.

[0055] - The term "alkoxyaminocarbonyl" refers to a group having the formula R a The group of NHC(O)-, wherein R a It is an alkoxy group as generally defined above.

[0056] - The term "cycloalkylaminocarbonyl" refers to a group having the formula R a The group of NHC(O)-, wherein R a It is a cycloalkyl group as generally defined above.

[0057] - The term "alkylsulfonamide group" refers to a group having the formula RaS(O)2NH-, where R a It is an alkyl group as generally defined above.

[0058] - Hydroxyl ("hydroxyl" or "hydroxy") represents the -OH group.

[0059] In the context of this invention, the terms “counter,” “prevention,” or “control,” and variations thereof, refer to reducing any undesirable influences, such as pathogenic, and more particularly plant pathogenic, especially fungal infections such as oomycetes, on plants or plant-derived products, and pathogenic damage, to a level that shows improvement.

[0060] As used herein, the term "effective amount" refers to the amount of a compound, its salt, or N-oxide that provides the desired effect when applied in a single or multiple applications.

[0061] The effective amount is readily determined by those skilled in the art using known techniques and by observing results obtained under similar conditions. Many factors are considered in determining the effective amount, including but not limited to: the type of plant or derivative to be applied; the pathogen to be controlled and its life cycle; the specific compound applied; the type of application; and other relevant circumstances.

[0062] Compounds having at least one basic center and having formula (I) can form, for example, acid addition salts with: strong inorganic acids (such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, or hydrohalic acid), strong organic carboxylic acids (such as unsubstituted or, for example, halogenated C1-C4 alkylcarboxylic acids, such as acetic acid, saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, or phthalic acid, such as hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid, or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or, for example, halogenated C1-C4 alkylsulfonic acids or arylsulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid). A compound having at least one acidic group of formula (I) may, for example, form a salt with a base, such as a mineral salt, like an alkali metal or alkaline earth metal salt, such as a sodium salt, potassium salt or magnesium salt; or form a salt with ammonia or an organic amine (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-alkylamines, such as ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxyalkylamines, such as monoethanolamine, diethanolamine or triethanolamine).

[0063] In each case, the compound having formula (I) according to the invention is in a free form, an oxidized form (as an N-oxide), a covalently hydrated form, or a salt form (e.g., an agronomically 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. For example, they are described in the book "Heterocyclic N-oxides" published by A. Albini and S. Pietra in 1991 by CRC Press in Boca Raton. The compound having formula (I) according to the invention also includes hydrates that can form during salt formation.

[0064] The compounds of formula (I) according to the invention also include hydrates that may form during salt formation.

[0065] In another embodiment, a compound of formula (I) according to the invention is provided, wherein four A 3 It is CR 3 And an A 3 It is N.

[0066] In another embodiment, a compound having formula (I) according to the invention is provided, wherein

[0067] yes And preferably four A's 3 It is CR 3 .

[0068] In another embodiment, a compound having formula (I) according to the invention is provided, wherein

[0069] yes And preferably four A's 3 It is CR 3 .

[0070] In another embodiment, a compound of formula (I) according to the invention is provided, wherein five A 3 It is CR 3 .

[0071] In another embodiment, a compound having formula (I) according to the invention is provided, wherein A 1 It is a carbon atom and A 2 It is a nitrogen atom.

[0072] In another embodiment, a compound having formula (I) according to the invention is provided, wherein A 1 It is a carbon atom and A 2It is a carbon atom.

[0073] In another embodiment, a compound having formula (I) according to the invention is provided, wherein A 1 It is a nitrogen atom and A 2 It is a carbon atom.

[0074] In another embodiment, a compound having formula (I) according to the invention is provided, wherein A 1 It is a nitrogen atom and A 2 It is a nitrogen atom.

[0075] In another embodiment, a compound of formula (I) according to the invention is provided, wherein the ring W

[0076] Selected from:

[0077]

[0078] in The symbol represents the attachment point with the benzimidazole group in formula (I), and # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and

[0079] Where R 11 Selected from 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 alkynyl group, wherein 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 by one to three independent substituents selected from the following: halogen, hydroxyl, and CN.

[0080] The ring W can be optionally selected by one to four independently chosen from R as defined in this invention. 1 Substituents are substituted.

[0081] More preferably, around W

[0082] You can choose from:

[0083]

[0084] in The symbol represents the attachment point with the benzimidazole group in formula (I), and # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and where R 11 It is as defined in this invention.

[0085] The ring W can be optionally selected by one to four independently chosen from R as defined in this invention. 1 Substituents are substituted.

[0086] In a particular embodiment, a compound having formula (I) according to the present invention is provided, wherein...

[0087] Ring W is a 5-8 membered heterocyclic ring or a 5-11 membered heteroaromatic ring, wherein each of the 5-8 membered heterocyclic ring or the 5-11 membered heteroaromatic ring is optionally selected from one to four independently selected from R. 1 Substituents of the substituents;

[0088] A 1 It is a carbon atom or a nitrogen atom;

[0089] A 2 It is a carbon atom or a nitrogen atom; and more preferably a ring W. Selected from:

[0090]

[0091] in The symbol represents the attachment point with the benzimidazole group in formula (I), and # represents the attachment point with the group formed by A. 3 The attachment points of the ring formed by the group, wherein the ring W is optionally selected by one to four independently chosen from R as defined in this invention. 1 Substituents are substituted, and R is wherein 11 As defined in this invention;

[0092] A 3 Independently is CR 3 Or N, provided that there are no more than three A's. 3 If it is N, then no more than two A's are preferred. 3 If it is N, then no more than one A is preferred. 3 It is N, and more preferably five A's. 3 It is CR 3 ;

[0093] A 4 It is CH, and A 5 It is N;

[0094] R 1 Selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C3-6 cycloalkyl, C 1-6 alkoxy, and CN, wherein 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 and C 1-6 Each of the alkoxy groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN;

[0095] R 2 Selected from 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 groups and -NHC(O)C 1-6 Alkyl; and preferably R 2 Selected from hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Alkoxy;

[0096] R 3 Independently selected from hydrogen and 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl and hydroxyl, wherein 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 group, C 3-6 cycloalkyl and C 3-6 cycloalkyl-C 1-6 Each of the alkyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; preferably R. 3 Independently selected from hydrogen and C1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, halogen, C 3-6 cycloalkyl and C 3-6 cycloalkyl-C 1-6 Alkyl, wherein 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 3-6 cycloalkyl and C 3-6 cycloalkyl-C 1-6 Each of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogen, hydroxyl, and CN; and more preferably R 3 Independently selected from hydrogen and C 1-6 Alkyl, C 1-6 Alkoxy groups and halogens, wherein the C 1-6 Alkyl and C 1-6 Each of the alkoxy groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN;

[0097] R 5 It is -NHC(O)R 6 ;and

[0098] R 6 Selected from 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 alkoxyamino, and C 1-6 Alkyl C 1-6 alkoxyamino, wherein 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 1-6alkoxyamino, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN; and preferably R. 6 Selected from 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 Alkyl, wherein 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 of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN.

[0099] In another embodiment, the compound according to the invention is selected from:

[0100] N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0101] N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0102] N-[5-[6-[2-(4-fluorophenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0103] N-[5-[6-[1-(4-fluorophenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0104] N-[5-[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0105] N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0106] N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0107] N-[5-[6-[4-(4-fluorophenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0108] N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0109] N-[5-[6-[4-(4-fluorophenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0110] N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate; and

[0111] N-[5-[6-[3-(4-cyano-3-methoxy-phenyl)pyrazin-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate.

[0112] The method according to the invention has the advantageous property of protecting plants from pathogenic (such as plant pathogens), especially fungal (such as oomycetes) attacks or infections that cause plant diseases and damage; particularly in the case of plants, the invention can control, limit or prevent pathogenic damage to plants, plant parts, plant propagation material and / or growing plants.

[0113] The compounds in Tables 1.1 to 1.63 below illustrate specific compounds of the present invention.

[0114] Table 1.1 Compounds having formula (Ia) are provided.

[0115] (Ia)

[0116] Where A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0117] Table Z A 3b A 4 A 5 R 2 R 3 and R 5 Substituent definition:

[0118]

[0119] Table 1.2 Compounds E2.1 to E2.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0120] Table 1.3 Compounds E3.1 to E3.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0121] Table 1.4 Compounds E4.1 to E4.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0122] Table 1.5 Compounds E5.1 to E5.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R5 As defined in Table Z.

[0123] Table 1.6 Compounds E6.1 to E6.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0124] Table 1.7 Compounds E7.1 to E7.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0125] Table 1.8 Compounds E8.1 to E8.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0126] Table 1.9 Compounds E9.1 to E9.644 having formula (Ia) are provided, wherein A 3a It is N, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0127] Table 1.10 Compounds E10.1 to E10.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0128] Table 1.11 Compounds E11.1 to E11.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0129] Table 1.12 Compounds E12.1 to E12.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R3 and R 5 As defined in Table Z.

[0130] Table 1.13 Compounds E13.1 to E13.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0131] Table 1.14 Compounds E14.1 to E14.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0132] Table 1.15 Compounds E15.1 to E15.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0133] Table 1.16 Compounds E16.1 to E16.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0134] Table 1.17 Compounds E17.1 to E17.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0135] Table 1.18 Compounds E18.1 to E18.644 having formula (Ia) are provided, wherein A 3a It is CH, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0136] Table 1.19 Compounds E19.1 to E19.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R2 R 3 and R 5 As defined in Table Z.

[0137] Table 1.20 Compounds E20.1 to E20.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0138] Table 1.21 Compounds E21.1 to E21.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0139] Table 1.22 Compounds E22.1 to E22.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0140] Table 1.23 Compounds E23.1 to E23.644 having formula (Ia) are provided, wherein A 3aIt's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0141] Table 1.24 Compounds E24.1 to E24.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0142] Table 1.25 Compounds E25.1 to E25.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0143] Table 1.26 Compounds E26.1 to E26.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A5 R 2 R 3 and R 5 As defined in Table Z.

[0144] Table 1.27 Compounds E27.1 to E27.644 having formula (Ia) are provided, wherein A 3a It's CF, ring W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0145] Table 1.28 Compounds E28.1 to E28.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0146] Table 1.29 Compounds E29.1 to E29.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0147] Table 1.30Compounds E30.1 to E30.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0148] Table 1.31 Compounds E31.1 to E31.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0149] Table 1.32 Compounds E32.1 to E32.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0150] Table 1.33 Compounds E331 to E33.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A.3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0151] Table 1.34 Compounds E34.1 to E34.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0152] Table 1.35 Compounds E35.1 to E35.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0153] Table 1.36 Compounds E36.1 to E36.644 having formula (Ia) are provided, wherein A 3a It is CCl, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0154] Table 1.37 Compounds E37.1 to E37.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0155] Table 1.38 Compounds E38.1 to E38.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0156] Table 1.39 Compounds E39.1 to E39.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0157] Table 1.40 Compounds E40.1 to E40.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0158] Table 1.41 Compounds E41.1 to E41.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0159] Table 1.42 Compounds E42.1 to E42.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0160] Table 1.43 Compounds E43.1 to E43.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3and R 5 As defined in Table Z.

[0161] Table 1.44 Compounds E44.1 to E44.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0162] Table 1.45 Compounds E45.1 to E45.644 having formula (Ia) are provided, wherein A 3a It is CCH3, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0163] Table 1.46 Compounds E46.1 to E46.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0164] Table 1.47 Compounds E47.1 to E47.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0165] Table 1.48 Compounds E48.1 to E48.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0166] Table 1.49 Compounds E49.1 to E49.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0167] Table 1.50 Compounds E50.1 to E50.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R2 R 3 and R 5 As defined in Table Z.

[0168] Table 1.51 Compounds E51.1 to E51.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0169] Table 1.52 Compounds E52.1 to E52.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0170] Table 1.53 Compounds E53.1 to E53.644 having formula (Ia) are provided, wherein A 3a It's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0171] Table 1.54 Compounds E54.1 to E54.644 having formula (Ia) are provided, wherein A 3aIt's CCN, ring W yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0172] Table 1.55 Compounds E55.1 to E55.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0173] Table 1.56 Compounds E56.1 to E56.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0174] Table 1.57 Compounds E57.1 to E57.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0175] Table 1.58 Compounds E58.1 to E58.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0176] Table 1.59 Compounds E59.1 to E59.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0177] Table 1.60 Compounds E60.1 to E60.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0178] Table 1.61Compounds E61.1 to E61.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0179] Table 1.62 Compounds E62.1 to E62.644 having formula (Ia) are provided, wherein A 3a It is COCH3, with a ring of W. yes ,in The symbol represents the attachment point with the benzimidazole group in formula (Ia), and the symbol # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0180] Table 1.63 Compounds E63.1 to E63.644 having formula (Ia) are provided, wherein A 3a It is COCH3, the ring is ring 9, and A 3b A 4 A 5 R 2 R 3 and R 5 As defined in Table Z.

[0181] The compounds according to the invention can have numerous benefits, particularly including favorable levels of bioactivity for protecting plants against fungal diseases or superior properties for use as active ingredients in agrochemicals (e.g., higher bioactivity, favorable activity spectrum, increased safety, improved physicochemical properties, or increased biodegradability). The compounds according to the invention exhibit particularly favorable levels of bioactivity for protecting plants against oomycetes such as Phytophthora, Plasmopara, and Pythium.

[0182] The compound having formula (I) according to the invention can be prepared as shown in schemes 1 to 13 below, wherein (unless otherwise stated) each variable is defined as defined in the invention.

[0183] A compound having formula (I) can be produced by combining a compound having formula (II) with a compound having formula (III) (where either R... 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 The reaction can form C3-C8 cycloalkyl groups 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 a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene. In some cases, the reaction results can be improved by adding boric acid or molecular sieves to the reaction mixture. It should be understood that these transformations are carried out in an air or oxygen atmosphere, as oxygen is required as the final oxidant. In some cases, copper substances can be used in stoichiometric amounts. This transformation is depicted in Scheme 1.

[0184]

[0185] Option 1

[0186] Alternatively, compounds of formula (I) can be prepared by reacting a compound of formula (II) with a compound of formula (IV) (where X is Cl, Br, or I) 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 in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran, or toluene. This transformation is depicted in Scheme 2.

[0187]

[0188] Option 2

[0189] Compounds having formula (IIa) (where A) 1 The carbon atom in formula (II) can be produced by a compound having formula (Va) (where R is carbon atom in formula (II)). 9It is prepared by using a protecting group, such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP). Compounds having the formula (Va) (where R...) are used to prepare compounds... 9 Protecting groups, such as SEM, Boc, or THP, can be obtained from compounds having formula (VI) (where any R) 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 Together they can form C3-C8 cycloalkyl groups, and R 9 The reaction is carried out in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol, or water in the presence of a protecting group (e.g., SEM, Boc, or THP) and a compound having formula (VIIa) (where X is Cl, Br, or I) in the presence of a base such as Cs₂CO₃, K₂CO₃, or NaOtBu and a suitable palladium catalyst such as tetra(triphenylphosphine)palladium, palladium dichloride, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate, or bis(diphenylphosphine)palladium(II) chloride. This transformation is depicted in Scheme 3.

[0190]

[0191] Option 3

[0192] Compounds having formula (VI) (where any R) 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 Together they can form C3-C8 cycloalkyl groups, and R 9 (A protecting group, such as SEM, Boc, or THP) can be used by making a compound having formula (VIII) (where X is Cl, Br, or I, and R) 9 It is a protecting group, such as SEM, Boc or THP) and a compound having formula (IX) (where any R 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 Compounds of formula (IX) can be prepared by reacting a base such as Cs₂CO₃, potassium acetate or NaOtBu and a suitable palladium catalyst such as tetra(triphenylphosphine)palladium, palladium dichloride, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate or bis(diphenylphosphine)palladium(II) chloride in a suitable solvent such as dimethylformamide, dioxane, tetrahydrofuran, ethanol or water. Compounds of formula (IX) are commercially available or can be prepared by those skilled in the art using a procedure described in very detail. Compounds of formula (VIII) (where X is Cl, Br or I, and R...) 9The protecting group (such as SEM, Boc, or THP) can be obtained by protecting the nitrogen of the imidazole ring of a compound having formula (X) (where X is Cl, Br, or I) using a very detailed procedure known to those skilled in the art. The compound having formula (X) is commercially available or can be prepared by those skilled in the art using a very detailed procedure. These transformations are depicted in scheme 4.

[0193]

[0194] Option 4

[0195] Alternatively, compounds having formula (Va) can be exchanged using a metal halide exchange reagent such as butyllithium or ethyl magnesium bromide. A compound having formula (XIa) (where X is H, Cl, Br, or I) can be exchanged with a compound having formula (VIII) (where X is Cl, Br, or I, and R...). 9 It is prepared by reacting a protecting group (such as SEM, Boc, or THP) in a suitable solvent such as tetrahydrofuran, diethyl ether, or dioxane. These transformations are depicted in Scheme 5.

[0196]

[0197] Option 5

[0198] Compounds having formula (XIa) (where X is Cl, Br, or I) can be prepared by reacting a compound having 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 having formula (XIa) (where X is Cl, Br, I, or a trifluoromethanesulfonate group) can be prepared by reacting a compound having formula (XIIIa) with trifluoromethanesulfonic anhydride and optionally a base such as triethylamine or pyridine, or a halogenating agent such as phosphorus trichloride or phosphorus tribromooxide, or by a sequential reaction with phosphorus trichloride and sodium iodide. These transformations are carried out in pure solvents or in suitable solvents such as dichloromethane, toluene, or xylene. These transformations are depicted in Scheme 6.

[0199]

[0200] Option 6

[0201] Compounds having formula (XIIa) and compounds having formula (XIIIa) are commercially available, or those skilled in the art will know that they can be synthesized by known methods. Some methods for synthesizing such heteroaromatic compounds can be found in the following publications: J.A. Joule and K. Mills (2010), Heterocyclic Chemistry, 5th ed., 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 ed., 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 ed., Elsevier. Furthermore, those skilled in the art will recognize that compounds having formula (XIIa) and compounds having formula (XIIIa) can be readily obtained by CC cross-coupling, CN cross-coupling, or by direct CH activation.This section cites a subset of numerous publications describing such transformations: J.-Q. Chen, J.-H. Li, Z.-B. Dong, Adv. SynthCatal. [Advanced Synthesis and Catalysis] 2020, 362, 3311; F. Bellina, R. Rossi, Adv. Synth.Catal. [Advanced Synthesis and Catalysis] 2010, 1223; E. Kang, HT Kim, JM Joo, Org. Biomol.Chem. [Organic and Biomolecular Chemistry] 2020, 18, 6192; Q. Yang, Y. Zhao, D. Ma, Org.Process Res. Dev. [Research and Development of Organic Processes] 2022, 26, 1690; H. Kaddouri, V. Vicente, A. Ouali, F. Ouazzani, M. Taillefer, Angew. Chem. Int. Ed. [Angewandte Chemie International Edition] 2009, 48, 333; JJ Li and GW Gribble (2007) Palladium in Heterocyclic Chemistry, 2nd ed., Elsevier; A. de Meijere, S. Bräse, M. Oestreich (2014) Metal-Catalyzed Cross-Coupling Reactions and More, Vol. 1-3, Wiley-VCH.

[0202] Compounds having formula (IIb) (where A) 2 The carbon atom in formula (II) can be removed by removing a compound having formula (Vb) (where R) 9 It is obtained by protecting the group of SEM, Boc, or THP. Compounds having the formula (Vb) (where R) 9 (SEM, Boc, or THP) can be achieved by mixing a compound having formula (XIVb) (where X is Cl, Br, or I) with a compound having formula (XV) (where any R) 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8The reaction can form C3-C8 cycloalkyl groups by coupling 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 tetra(triphenylphosphine)palladium, palladium dichloride, [1,1-bis(diphenylphosphine)ferrocene]dichloropalladium(II), palladium acetate, or bis(diphenylphosphine)palladium(II) chloride. Compounds having formula (XV) are commercially available or can be prepared by those skilled in the art using a procedure described in very detail. This transformation is depicted in Scheme 7.

[0203]

[0204] Option 7

[0205] Compounds having the formula (XIVb) (where R) 9 If it is a protecting group, such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP), and X is Cl, Br, or I, it can be used to make a compound having the formula (XVIb) (where R) 9 The protective group (such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP), and X being Cl, Br, or I) is reacted with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, or N-iodosuccinimide in a suitable solvent such as DMF, acetonitrile, dichloromethane, or tetrahydrofuran to prepare the product. This transformation is depicted in Scheme 8.

[0206]

[0207] Option 8

[0208] Compounds having formula (IIc) (where A) 1 (The nitrogen atom in formula (II)) can be removed by removing a compound having formula (Vc) (where R) 9 It is obtained by protecting a group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP). Compounds having the formula (Vc) (where R) 9 Protecting groups, such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP), can be used in compounds having the formula (XIVc) (where R... 9 It is a protecting group, such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP), and X is Cl, Br, or I) and a compound having the formula (XV) (where any R) 8Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 Together, they can form C3-C8 cycloalkyl groups, which are obtained by coupling 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, Me3tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhos Pd G3 or tBuBrettPhos Pd G3, in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran or toluene. This transformation is depicted in Scheme 9.

[0209]

[0210] Option 9

[0211] Alternatively, compounds having the formula (Vc) (where R) 9 Protecting groups, such as SEM, Boc, or THP, can be obtained from compounds having formula (VI) (where any R) 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8 Together they can form C3-C8 cycloalkyl groups, and R 9 The reaction is prepared by coupling a protecting group (such as SEM, Boc, or THP) with a compound having formula (XIIc) 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 a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene. In some cases, the reaction results can be improved by adding boric acid or molecular sieves to the reaction mixture. It should be understood that these transformations are carried out under air because oxygen is required as the final oxidant. In some cases, copper substances can be used in stoichiometric amounts. This transformation is depicted in Scheme 10.

[0212]

[0213] Option 10

[0214] Compounds having formula (XVII) (where X is Cl, Br, or I) can be produced by compounds having formula (III) (where any R is Cl, Br, or I). 8 Each of the following is independently hydrogen, C1-C6 alkyl, or two of the R groups. 8The reaction can be prepared by Suzuki cross-coupling of a compound having the formula (XVIII) (where any X is independently Cl, Br, or I) 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 a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran, or toluene. In some cases, the reaction results can be improved by adding boric acid or molecular sieves to the reaction mixture. It should be understood that these transformations are carried out in an air or oxygen atmosphere, as oxygen is required as the final oxidant. In some cases, copper substances can be used in stoichiometric amounts. This transformation is depicted in Scheme 11.

[0215]

[0216] Option 11

[0217] A compound having formula (XVIII) (where X is Cl, Br, or I) can be obtained by combining a compound having formula (XIX) (where X is Cl, Br, or I) with a compound having formula (XX) (where R is Cl, Br, or I). 10 It is prepared by reacting (C1-C6 alkyl) in the presence of an acid such as toluenesulfonylsulfonic acid, sulfuric acid or trifluoroacetic acid, in a suitable solvent such as toluene, methanol, ethanol, acetonitrile or water. This transformation is depicted in Scheme 12.

[0218]

[0219] Option 12

[0220] Compounds having formula (XIX) (where X is Cl, Br, or I) can be prepared by reducing compounds having formula (XXI) (where X is Cl, Br, or I) in the presence of a catalyst such as palladium acetate or palladium in a suitable solvent such as tetrahydrofuran, ethanol, methanol, or water with hydrogen, or in the presence of an acid such as hydrogen chloride, ammonium chloride, or acetic acid with iron or zinc. Compounds having formula (XXI) (where X is Cl, Br, or I) can be prepared by reducing compounds having formula (XXII) (where X is Cl, Br, or I, and where X...) 2 It is prepared by reacting F, Cl, Br or I with a compound having formula (XXIII) and a base such as Cs2CO3, K2CO3, triethylamine, N,N-diethylethylamine or sodium tert-butoxide in a suitable solvent such as tetrahydrofuran, ethanol, methanol, acetonitrile or N,N-dimethylformamide. This transformation is depicted in Scheme 13.

[0221]

[0222] Option 13

[0223] Those skilled in the art will also recognize that compounds having formula (I) can alternatively 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 understand that the synthetic routes describing the preparation of these particular compounds can also be used to synthesize similar compounds having formula (I) of that particular compound, wherein said compounds have the same ring W. Therefore, the routes described in the experimental section should also be considered as general routes for obtaining compounds having formula (I).

[0224] The following compounds having 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-methoxy-phenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazol-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-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 2). These synthetic routes describe the de novo synthesis of compounds having formula (Id) (where ring W is 1,2,4-oxadiazine) and the synthesis of compounds having formula (IId) (where ring W is 1,2,4-oxadiazine). This method can generally be used to obtain similar compounds having formulas (Id) and (IId).

[0225]

[0226] The following compounds having formulas (Ie) and (IIe) 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-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 5). This synthetic route describes the de novo synthesis of compounds having formula (Ie) (where ring W is imidazole) and the synthesis of compounds having formula (IIe) (where ring W is imidazole). These methods can generally be used to obtain similar compounds having formulas (Ie) and (IIe).

[0227]

[0228] The following compounds having formulas (If) and (IIf) 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-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 7). This synthetic route describes the de novo synthesis of compounds having formula (If) (where ring W is a triazole) and the synthesis of compounds having formula (IIf) (where W is a triazole). These methods can generally be used to obtain similar compounds having formulas (If) and (IIf).

[0229]

[0230] The following compounds having formulas (Ig) and (IIg) 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-triazol-3-yl]-4-methyl-benzimidazol-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-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 11). These synthetic routes describe the de novo synthesis of compounds having formula (Ig) (where ring W is a triazole) and the synthesis of compounds having formula (IIg) (where ring W is a triazole). This method can generally be used to obtain similar compounds having formula (Ig) and formula (IIg).

[0231]

[0232] The following compounds having formulas (Ih) and (IIh) 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-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate (compound 1). This synthetic route describes the de novo synthesis of compounds having formula (Ih) (where ring W is a triazole) and the synthesis of compounds having formula (IIh) (where ring W is a triazole). This method can generally be used to obtain similar compounds having formulas (Ih) and (IIh).

[0233]

[0234] Those skilled in the art will understand that some of the above reactions (in which the nitrogen atom of the imidazole (or triazole) ring in the central ring is not substituted) may proceed more efficiently if the imidazole (or triazole) nitrogen atom is masked by a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or 2-tetrahydropyranyl (THP). The protection of the imidazole and triazole rings with SEM, Boc, or THP, and the subsequent deprotection of these groups, are transformations well known to those skilled in the art. Information on these transformations can be found in the literature, including Greene's Protective Groups in Organic Synthesis, 4th Edition, Chapter 7.

[0235] When the term "compound / compounds according to the invention" is used, it refers to compounds according to the present invention.

[0236] Alternatively, compounds according to the invention can be obtained using standard synthetic techniques known to those skilled in the art. Non-exhaustive examples include oxidation, reduction, hydrolysis, coupling, aromatic nucleophilic or electrophilic substitution, nucleophilic substitution, nucleophilic addition, olefination, oxime formation, alkylation, and halogenation.

[0237] The compounds according to the invention can be converted into another compound according to the invention by methods known per se, which is achieved by replacing one or more substituents of the starting compound according to the invention with another or one or more substituents according to the invention in a conventional manner.

[0238] Depending on the reaction conditions and the choice of starting materials appropriate to each situation, it may be possible, for example, to replace only one substituent with another substituent according to the invention in a single reaction step, or to replace multiple substituents with other substituents according to the invention in the same reaction step.

[0239] Salts of the compounds according to the invention can be prepared in ways known per se. Thus, for example, acid addition salts of the compounds according to the invention are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with a base are obtained by treatment with a suitable base or a suitable ion exchanger reagent.

[0240] Salts of compounds according to the invention can be converted into free compounds, acid addition salts (e.g., by treatment with a suitable basic compound or a suitable ion exchanger reagent) and base salts (e.g., by treatment with a suitable acid or a suitable ion exchanger reagent) in conventional ways.

[0241] Salts of compounds according to the invention can be converted in a manner known per se into other salts or acid addition salts of compounds according to the invention, for example, into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) in a suitable solvent with a suitable metal salt of the acid (such as a salt of sodium, barium, or silver, for example, silver acetate), in which the inorganic salt (e.g., silver chloride) formed is insoluble and thus precipitates out from the reaction mixture.

[0242] Depending on the procedure or reaction conditions, compounds according to the invention that have salt-forming properties can be obtained in free form or as salts.

[0243] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configurations, and / or depending on the configuration of the non-aromatic double bonds present in the molecule, the compounds according to the invention and, where appropriate, their tautomers (in each case, in free or salt form) can exist in one of the possible stereoisomers or as mixtures of these, for example, in the form of pure stereoisomers, such as enantiomers and / or diastereomers, or as mixtures of stereoisomers, such as mixtures of enantiomers, such as racemic mixtures, diastereomer mixtures, or racemic mixtures; the invention relates to pure stereoisomers as well as all possible mixtures of stereoisomers, and should be understood in this sense in each case above and below, even when stereochemical details are not explicitly mentioned in each case.

[0244] Mixtures of diastereomers or racemates of the compounds according to the invention, in free or salt form (their acquisition may depend on the selected starting materials and procedures), can be isolated into pure diastereomers or racemates in a known manner, based on the physicochemical differences of these components, for example by stepwise crystallization, distillation and / or chromatography.

[0245] An enantiomer mixture (such as a racemic mixture) that can be obtained in a similar manner can be resolved into optical enantiomers by known methods, for example by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, such as high-performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with a specific immobilized enzyme using suitable microorganisms; by forming an encapsulation compound, such as using a chiral crown ether, in which only one enantiomer is complexed; or by conversion into salts of diastereomers, for example by reacting the racemic mixture of the basic final product with an optically active acid (such as a carboxylic acid, such as camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, such as camphorsulfonic acid), and the diastereomer mixture that can be obtained in this manner can be separated, for example by stepwise crystallization based on their different solubilities, from which the desired enantiomer can be freed by the action of a suitable reagent (such as a basic reagent).

[0246] Pure diastereomers or enantiomers can be obtained according to the invention, not only by separating suitable mixtures of stereoisomers, but also by methods of normally known diastereoselective or enantiomeric synthesis, for example by using starting materials with suitable stereochemistry according to the invention.

[0247] N-oxides can be prepared by reacting the compounds according to the invention with a suitable oxidant (e.g., H2O2 / urea adduct) in the presence of an acid anhydride (e.g., trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem. [Journal of Medicinal Chemistry] 32 (12), 2561-73, 1989 or WO 00 / 15615.

[0248] If the individual components have different biological activities, it is advantageous to isolate or synthesize biologically more effective stereoisomers in each case, such as enantiomers or diastereomers or mixtures of stereoisomers, such as mixtures of enantiomers or mixtures of diastereomers.

[0249] If appropriate, the compounds according to the invention and their tautomers (in each case in free or salt form) can also be obtained as hydrates and / or include other solvents, such as those that can be used to crystallize compounds that are present in solid form.

[0250] The following examples illustrate, but do not limit, the present invention.

[0251] Compounds having formula (I) as defined in this invention can be used in the agricultural sector and related application areas as active ingredients, for example, for controlling plant pathogens, or for controlling putrefactive microorganisms or potentially harmful organisms on non-living materials. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance, and environmental safety. They possess highly useful therapeutic, preventative, and systemic properties and can be used to protect many cultivated plants. Compounds having formula (I) as defined in this invention can be used to inhibit or destroy pathogens present on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various useful plant crops, while also protecting later-growing plant parts from, for example, plant pathogenic microorganisms.

[0252] Compounds having formula (I) as defined in this invention can also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, alters, or prevents fungal growth. The term "fungicide effective amount" means the amount of one or a combination of such compounds that can affect fungal growth. Controlling or altering effects include all deviations from natural development, such as killing, inhibiting, etc., and prevention includes the formation of barriers or other defenses within or on the plant to prevent fungal infection.

[0253] Compounds having formula (I) as defined in this invention can also be used as seed dressings for treating plant propagation materials, such as seeds (if fruits, tubers, or grains), or plant cuttings (e.g., rice), to protect them from fungal infection and to combat plant pathogenic fungi present in the soil. Propagation materials can be treated with compositions comprising compounds having formula (I) as defined in this invention before planting: for example, seed dressing can be applied before sowing. Compounds having formula (I) as defined in this invention can also be applied to grains (coating) by impregnating seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when planting the propagation material, for example, by applying it to the furrows of the seeds during sowing. This invention also relates to such methods of treating plant propagation materials, and to plant propagation materials treated in this way.

[0254] Furthermore, compounds having formula (I) as defined in this invention can be used to control fungi in relevant fields, such as in the protection of industrial materials (including wood and wood-related technical products), in food storage, and in hygiene management.

[0255] In addition, this invention can be used to protect non-living materials (such as wood, wall panels, and coatings) from fungal attack.

[0256] Compounds having formula (I) as defined in this invention and fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They effectively control a broad spectrum of plant diseases, such as leaf pathogens in ornamental plants, turf, vegetables, field crops, cereals, and fruit crops.

[0257] These fungi and fungal vectors, as well as plant pathogenic bacteria and viruses, that can control diseases include, for example:

[0258] *Pyrtomium umbellatus*, *Alternaria* species, *Hymenopterus* species, *Cyclophorus* species, *Aspergillus* species (including *Aspergillus flavus*, *Aspergillus fumigatus*, *Aspergillus nidus*, *Aspergillus niger*, *Aspergillus terreus*), *Bretschneidera* species (including *A. pullulans*), *Blastomyces dermatitidis*, *Powdery mildew fungus*, *Bremia lactucae*, *Botrytis* species (including *B. dothidea*, *B. obtusa*), *Botrytis* species (including *B. cinerea*), *Candida* species (including *Candida albicans*, *Candida glabrata*, *Candida krusei*, *Candida lusitaniae*, *Candida parapsilosis*, *Candida tropicalis*), *Cephaloascus* *Fragrans*, *Cercosporidium* species, *Cercosporidium* species (including *C. arachidicola*), *Cercosporidium personatum*, *Cladosporium* species, *Cercosporidium*, *Cercosporidium* species, *Anthracnose* species (including *C. musae*), *Cryptococcus neoformans*, *Diaporthe* species, *Didymella* species, *Helicobacter* species, *Cercosporidium* species, *Epidermophyton* species, *Pyrus pyriformis* species, *Erythromycetes* species (including *E. cichoracearum*), *Eutypa*. *Fusarium* genus (including *Fusarium graminearum*, *Fusarium graminearum*, *Fusarium lancifolium*, *Fusarium moniliforme*, *Fusarium gloeodes*, *Fusarium solani*, *Fusarium oxysporum*, *Fusarium oxysporum*, *Fusarium calcinans*), *Gibberella fujikuroi*, *Gloeodes pomigena*, *Gloeosporium musarum*, *Glomerella cingulate*, *Guignardia bidwellii*, *Gymnosporangium juniperi-virginianae*, *Helicobacter*, *Camponotus*, *Histoplasma* (including *Histoplasma capsulatum* (H.)).*Capsulatum*, *Leptographium lindbergi*, *Leveillula taurica*, *Lophodermium seditiosum*, *Microdochium nivale*, *Microsporum*, *Sclerotium*, *Mucor*, *Cyclophorus* (including *Cyclophorus gracilis* and *M. pomi*), *Truncus*, *Picea*, *Paracocyspora*, *Penicillium* (including *Penicillium fingernail* and *Penicillium italicum*), *Mycorrhiza*, *Peronospora* (including *Peronospora cornensis*, *Peronospora philippinensis*, *Peronospora sorghum*), *Peronospora*, *Syngonium glume*, *Laminaria*, *Phellinusigniarus*, *Pholopsis*, *Phomopsis*, *Phomopsis* *Phytophthora*, *Phytophthora* (including pathogenic *Phytophthora*), *Monomothora* (including *Monomothora holsicae*, *P. viticola*), *Lycospora*, *P. leucotricha* (including *P. leucotricha*), *Polymyxa graminis*, *Polymyxa betae*, *Pseudocercosporella herpotrichoides*, *Pseudomonas*, *Peronospora* (including *P. hordei*, *P. recondita*, *P. striiformis*, *P. triticina*), *Sclerotium*, *Sclerotium*, *P. oryzae* (including *P. oryzae*), *Pythium* (including *P. ulcerativeola*), *P. columnaris*, *Rhizomucor*, *Rhizopus* *Pusillus*, *Rhizopus*, *Rhizopus*, *Rhizopus*, *Pyrhodochrocephala* (including *S. nodorum* and *S. leucocephala*), *Schizothyrium pomi*, *Sclerotium* species, *S. sclerotium* species, *S. scabra* species (including *S. nodorum* and *S. scabra*).The fungi causing powdery mildew include: *Sphaerotheca macularis*, *Sphaerotheca fusca* (*Sphaerotheca fuliginea*), *Sporothorix*, *Stagonosporanodorum*, *Stemphylium spp*, *Stereum hirsutum*, *Thanatephorus cucumeris*, *Thielaviopsis basicola*, *Ustilago*, *Trichoderma* (including *Trichoderma harzianum*, *Trichoderma konjac*, and *Trichoderma viride*), *Trichoderma*, *Ustilago*, *Ustilago*, and *Ustilago* (including *Ustilago aubergine*). *Inaequalis*, *Verticillium* species, and *Xanthomonas* species.

[0259] In particular, compounds having formula (I) as defined in this invention and fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens belonging to the Basidiomycetes, Ascomycetes, Oomycetes and / or Deuteromycetes, Blasocladiomycete, Chytridiomycete, Glomeromycete and / or Mucoromycete classes. More particularly, compounds having formula (I) as defined in this invention can be used to control Oomycetes.

[0260] These pathogens may include:

[0261] Oomycetes, including 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 diseases such as those caused by *Pythium aphanidermatum*, *Pythium arrhenomanes*, *Pythium graminicola*, *Pythium irregulare*, and *Pythium forestum*. Diseases caused by *Pythium ultimum* and *Pythium sylvaticum*; diseases caused by *Peronosporale* species such as *Peronospora destructor*, *Peronospora parasitica*, *Plasmopara viticola*, *Plasmopara halstedii*, *Pseudoperonospora cubensis*, *Albugo candida*, *Sclerophthora macrospora*, and *Bremia lactucae*; and others such as *Aphanomyces cochlioides*, *Labyrinthulazosterae*, *Peronosclerospora sorghi*, and *Sclerospora graminicola*.

[0262] Ascomycetes, including diseases such as spot, blight, wilt, or downy mildew and / or rot, such as those caused by: Pleosporales, including Stemphylium solani (garlic white spot fungus), Stagonospora tainanensis (Tainan daffodil spores), Spilocaea oleaginea (olive rot fungus), Setosphaeria turcica (corn large leaf spot fungus), Pyrenochaeta lycoperisici (tomato scab), Pleospora herbarum (leaf lichen spores), Phona destructiva (stem rot fungus), Phaeosphaeria herpotrichoides (wheat leaf dark coccidioides), Phaeococcus gaeumannii (brown cryptococcus), Ophiosphaerella graminicola (grass spores), Ophiobolus graminis (wheat take-all), and Leptosphaeria (cruciferous small coccidioides). The following fungi are listed: maculans, soft rot fungus (Hendersonia creberrima), leaf blight fungus (Helminthosporium triticirepentis), maize large leaf spot fungus (Setosphaeria turcica), soybean endospermum (Drechslera glycines), watermelon vine blight fungus (Didymella bryoniae), olive pea bud blight fungus (Cycloconium oleagineum), multi-headed spore fungus (Corynespora cassiicola), spore fungus (Cochliobolus sativus), dragon fruit black spot fungus (Bipolaris cactivora), apple black spot fungus (Venturia inaequalis), round spore fungus (Pyrenophora teres), oat straw spore fungus (Pyrenophoratritici-repentis), alternata alternata, brassicae alternata, and solanum alternata. *Septoria solani* and *Alternaria tomatophila*; Capnodiales such as *Septoria tritici*, *Septoria nodorum*, and *Septoria spp.*The fungi causing the following diseases are listed: *Cercospora aracidola*, *Cercospora sojina*, *Cercospora zeae-maydis*, *Cercosporella capsellae*, *Cercosporella herpotrichoides*, *Cladosporium carpophilum*, *Cladosporium effusum*, *Passalora fulva*, *Cladosporium oxysporum*, *Dothistroma septosporum*, *Isariopsis clavispora*, *Mycosphaerella graminicola*, *Mycovellosiella koepkeii*, and *Phaeoisariopsis*. * *Pseudocercospora vitis*, *Pseudocercospora*, *Pseudocercospora*, *Pseudocercospora*, *Pseudocercospora*, *Pseudocercospora*, *Pyricularia ... * *Phomopsis viticola*, *Sirococcus clavigignenti-juglandacearum*, and *Tubakia**Dryina* species, *Dicarpella* spp., *Valsa ceratosperma* (the causal agent of apple tree rot); and others, such as *Actinothyrium graminis*, *Ascochyta pisi*, *Aspergillus flavus*, *Aspergillus fumigatus*, *Aspergillus nidulans*, *Asperisporium caricae*, *Blumeriella jaapii* (the causal agent of leaf spot), *Candida* spp., *Capnodium ramosum*, *Cephaloascus* spp., *Cephalosporium gramineum*, *Ceratocystis paradoxa*, and *Chaetomium* species. *Hymenoscyphus pseudoalbidus*, *Coccidioides* spp., *Cylindrosporium padi*, *Diplocarpon malae*, *Drepanopeziza campestris*, *Elsinoe ampelina*, *Epicoccum nigrum*, *Epidermophyton* spp., *Eutypa lata*, *Geotrichum candidum*, *Gibellina cerealis*, *Gloeocercospora sorghi*, *Gloeodes pomigena*, *Gloeosporium perennans*, endophytic fungi of dead wheat (Gloeotinia temulenta), and *Griphospaeria*. Corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina* *graminicola*, *Microdochium nivale*, *Monilinia fructicola*, *Monographella albescens*, *Monosporascus cannonballus*, *Naemacyclus* spp., *Ophiostoma novo-ulmi*, *Paracoccidioides brasiliensis*, *Penicillium expansum*, *Pestalotia rhododendri*, *Petriellidium* spp., *Pezicula* spp., *Phialophora gregata*, *Phyllachora pomigena*, *Phymatotrichumomnivora*, *Physalospora* abdita, tobacco spore shell (Plectosporium tabacum), potato skin spot fungus (Polyscytalum pustulans), alfalfa pseudodisc (Pseudopeziza medicaginis), brassicae sclerotiorum (Pyrenopeziza brassicae), sorghum spore spore (Ramulis porasorghi), Douglas fir leaf spot fungus (Rhabdocline pseudotsugae), barley cloud spot fungus (Rhynchosporium secalis), rice broom broom (Sacrocladium oryzae), species of the genus Scedosporium spp., pome spore spore (Schizothyrium pomi), sclerotinia sclerotiorum, small sclerotinia (Sclerotinia minor); species of the genus Sclerotium spp.), Typhulaishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, SporonemaPowdery mildew, including fungi such as *Phyllidioides*, *Stigminapalmivora*, *Tapesia yallundae*, *Taphrina bullata*, *Thielviopsis basicola*, *Trichoseptoria fructigena*, and *Zygophiala jamaicensis*; and powdery mildew, such as those from the order Erysiphales, including *Blumeria graminis*, *Erysiphe polygoni*, *Uncinula necator*, *Sphaerotheca fuligena*, *Podosphaera leucotricha*, *Podospaera macularis*, *Golovinomyces cichoracearum*, and *Leveillula*. Those caused by *Taurica*, *Microsphaera diffusa*, *Oidiopsis gossypii*, *Phyllactinia guttata*, and *Oidium arachidis*; molds, such as those caused by *Botryosphaeriales* like *Dothiorella aromatica*, *Diplodiaseriata*, *Guignardia bidwellii*, *Botrytis cinerea*, *Botryotinia allii*, *Botryotinia fabae*, *Fusicoccum amygdali*, *Lasiodiplodia theobromae*, *Macrophoma theicola*, *Phyllosticta*, and others. Anthracnose caused by *Colletotrichum gloeosporioides*, *Colletotrichum lagenarium*, and *Colletotrichum cucurbitacearum*.Those caused by *Gastrodia elata*, *Glomerella cingulata*, and *Colletotrichum graminicola*; and those caused by wilt or blight, such as those caused by *Hylocereus* species like *Aperistocene stenoptera*, *Ergotae*, *Fusarium oxysporum*, *Fusarium graminicola*, *Fusarium virguliforme*, *Fusarium oxysporum*, *Fusarium glomerulosa*, *Fusarium oxysporum f.sp.cubense*, *Gerlachia nivale*, *Fusarium fusiforme*, *Fusarium zedoaria*, *Gerlachia* species, *Lysimachia verrucosa*, *Nectria ramulariae*, *Trichoderma viride*, *Trichoderma pulvinata*, and *Verticillium theobromae*.

[0263] Basidiomycetes include diseases such as smut caused by smut fungi like *Ustilaginoidea virens*, *Ustilago nuda*, *Ustilago tritici*, and *Ustilago zeae*, and rust diseases caused by stalk rust fungi such as *Cerotelium fici*, *Chrysomyxa arctostaphyli*, *Coleosporium ipomoeae*, *Hemileia vastatrix*, *Puccinia arachidis*, *Puccinia cacabata*, *Puccinia graminis*, *Puccinia recondita*, *Puccinia sorghi*, *Puccinia hordei*, and *Puccinia striiformis*. f.sp. Hordei), Puccinia striiformisf.sp.Those caused by *Secalis*, *Pucciniastrum coryli*; or those caused by *Ruscidea* species such as *Cronartium ribicola*, *Gymnosporangium juniperi-viginianae*, *Melampsora medusae*, *Phakopsora pachyrhizi*, *Phragmidium mucronatum*, *Physopella ampelosidis*, *Tranzschelia discolor*, and *Uromyces viciae-fabae*; and other rots and diseases, such as those caused by *Cryptococcus* species, *Tea bud rot*, *Marasmiellus inodera*, *Schefflera* species, and *Sphacelotheca*. The fungi causing wheat smut include *Reiliana*, *Typhulaishikariensis*, *Urocystis agropyri*, *Itersonilia perplexans*, *Corticium invisum*, *Laetisaria fuciformis*, *Waitea circinata*, *Rhizoctonia solani*, *Thanetephorus cucurmeris*, *Entyloma dahliae*, *Entylomella microspora*, *Neovossia moliniae*, and *Tilletia caries*.

[0264] Bulbophyllum class, such as Physoderma maydis.

[0265] Mucormycetes, such as *Choanephora cucurbitarum*; species of the genus *Mucor* (*Mucor spp.*); and *Rhizopus spp.*.

[0266] Together with diseases caused by other species and genera closely related to those listed above.

[0267] In addition to their antifungal activity, these compounds and compositions comprising compounds of formula (I) as defined in this invention may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species, as well as certain protozoa.

[0268] Within the scope of this invention, the target crops and / or useful plants to be protected typically include perennial and annual crops, such as berry plants, such as blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, such as barley, corn, millet, oats, rice, rye, sorghum, triticale, and wheat; fiber plants, such as cotton, flax, hemp, jute, and sisal; field crops, such as sugar beets and forage beets, coffee beans, hops, mustard, canola, poppies, sugarcane, sunflowers, tea, and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; and grasses, such as Bermuda grass, bluegrass, benjamin grass, centipede grass, sedge, and black clover. Wheatgrass, St. Augustine grass, and zoysia grass; herbs such as basil, borage, chives, coriander, lavender, angelica, 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; palm trees such as oil palms; ornamental plants such as flowers, shrubs, and trees; other trees such as cacao trees, coconut palms, olive trees, and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melons, okra, onions, peppers, potatoes, squash, rhubarb, spinach, and tomatoes; and grapevines such as grapes.

[0269] Useful plants and / or target crops according to the invention include conventional and genetically enhanced or genetically engineered varieties, such as insect-resistant varieties (e.g., Bt. and VIP varieties), and disease-resistant, herbicide-tolerant varieties (e.g., glyphosate- and glufosinate-resistant corn varieties, commercially available under the trademarks RoundupReady® and LibertyLink®), as well as nematode-tolerant varieties. By way of example, suitable genetically enhanced or genetically engineered crop varieties include Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

[0270] The terms “useful plant” and / or “target crop” should be understood to also include useful plants that have developed tolerance to herbicides (like bromuconazole) or herbicide classes (such as HPPD inhibitors, ALS inhibitors, such as flusulfuron, flusulfuron-methyl, and triflusulfuron-methyl, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthase) inhibitors, or PPO (protoporphyrinogen-oxidase) inhibitors) through conventional breeding or genetic engineering methods. An example of a crop that has developed tolerance to imidazolinones (such as methoxyfenozide) through conventional breeding methods (mutation) is Clearfield® Summer Canola (Canola). Examples of crops that have been genetically engineered to be resistant to herbicides or herbicides include glyphosate-resistant and glufosinate-resistant corn varieties, which are commercially available under the trademarks RoundupReady®, Herculex I®, and LibertyLink®.

[0271] The terms “useful plant” and / or “target crop” should be understood to include those that are naturally or have been conditioned to be resistant to harmful insects. This includes plants transformed using recombinant DNA technology to, for example, synthesize one or more selectively acting toxins, which are known from, for example, toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-parasitic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi. An example of a crop modified to express Bacillus thuringiensis toxins is Btmaize KnockOut® (Syngenta Seeds). An example of a crop including those encoding insecticidal resistance and thus expressing more than one gene for more than one toxin is VipCot. (Syngenta Seeds). Crops or their seed material can also be resistant to multiple types of pests (so-called superimposed transgenic events when produced through genetic modification). For example, plants can express insecticidal proteins while being resistant to herbicides, such as Herculex I. (Dow AgroSciences, Pioneer Hi-Bred International).

[0272] The terms “useful plant” and / or “target crop” should be understood to also include useful plants that have been transformed using recombinant DNA technology to synthesize selectively active resistance substances, such as so-called “pathogenic mechanism-associated proteins” (PRPs, see, for example, EP-A-0 392 225). Examples of such resistance substances and transgenic plants capable of synthesizing such resistance substances are known, for example, from EP-A-0 392 225, WO 95 / 33818, and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described in, for example, the disclosures mentioned above.

[0273] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from *Bacillus cereus* or *Bacillus japonicus*; or insecticidal proteins from *Bacillus thuringiensis*, such as δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from bacterial colonizing nematodes, such as species of *Photorhabdus* spp. or species of *Xenorhabdus* spp., such as *Photorhabdus luminescens* and *Xenorhabdus* nematode pathogens. (nematophilus); toxins produced by animals, such as scorpion venom, spider venom, bee venom, and other insect-specific neurotoxins; toxins produced by fungi, such as streptotoxins; phytohemagglutinins, such as pea lectin, barley lectin, or snowdrop lectin; agglutinins; protease inhibitors, such as trypsin inhibitors, serine inhibitors, potato glycoproteins, cystatin, and papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, maize-RIP, absinthecin, loofah seed toxin, saponin toxin, or scutellarin; steroid metabolic enzymes, such as 3-hydroxysteroid oxidase, decidual steroid-UDP-glycosyltransferase, cholesterol oxidase, decidualin inhibitors, 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.

[0274] Furthermore, in the context of this invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vip) (e.g., Vip1, Vip2, Vip3, or Vip3A) should be understood to obviously also include mixed toxins, truncated toxins, and modified toxins. Mixed toxins are generated through novel recombination of different combinations of domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are substituted. In such amino acid substitutions, it is preferable to insert a non-naturally occurring protease recognition sequence into the toxin, for example, as in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0275] Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0276] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described in, for example, the disclosures mentioned above. CryI type deoxyribonucleic acid and its preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0277] The toxins contained in genetically modified plants make them resistant to harmful insects. These insects can exist in any insect taxonomy, but are particularly common in beetles (Coleoptera), dipterans (Diptera), and moths (Lepidoptera).

[0278] Transgenic plants containing one or more genes encoding resistance to insecticides and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants are: YieldGard® (a corn variety expressing Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing both Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing Cry9C toxin); Herculex I® (a corn variety expressing Cry1Fa2 toxin and the enzyme phosphatidylin N-acetyltransferase (PAT) for acquiring resistance to the herbicide glufosinate); NuCOTN 33B® (a cotton variety expressing Cry1Ac toxin); Bollgard I® (a cotton variety expressing Cry1Ac toxin); Bollgard II® (cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate resistance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0279] Other examples of such genetically modified crops are:

[0280] 1. Bt11 corn, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, Registry No. C / FR / 96 / 05 / 10. A genetically modified corn variety that expresses a truncated Cry1Ab toxin to resist the European corn borer (Ostrinianubilalis and Sesamia nonagrioides). Bt11 corn is also transgenic to express PAT enzymes for tolerance to the herbicide glufosinate.

[0281] 2. Bt176 corn, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. A genetically modified corn variety that expresses the Cry1Ab toxin transgenic to resist the European corn borer (corn borer and mealybug). Bt176 corn is also transgenic to express the PAT enzyme for tolerance to the herbicide glufosinate.

[0282] 3. MIR604 corn, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. A transgenic corn variety resistant to insects by expressing a modified Cry3A toxin. This toxin is modified by inserting a cathepsin-G-protease recognition sequence, Cry3A055. The preparation of this type of transgenic corn plant is described in WO 03 / 018810.

[0283] 4. MON 863 corn, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses Cry3Bb1 toxin and is resistant to certain Coleoptera.

[0284] 5. IPC 531 cotton, from Monsanto Europe, 270-272 Tefallen Boulevard, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0285] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, Registry No. C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F to acquire resistance to certain lepidopteran insects and expressing the PAT protein to acquire tolerance to the herbicide glufosinate.

[0286] 7. NK603 × MON 810 corn, from Monsanto Europe, 270-272 Boulevard de Tverren, B-1150 Brussels, Belgium, Registry No. C / GB / 02 / M3 / 03. Composed of conventionally bred hybrid corn varieties by crossing the genetically modified cultivar NK603 and MON 810. NK603 × MON 810 corn transgenically expresses the protein CP4 EPSPS obtained from Agrobacterium strain CP4, which confers tolerance to the herbicide Roundup® (containing glyphosate), and also expresses the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. Kurstak, which brings tolerance to certain lepidopteran insects, including the European corn borer.

[0287] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds and seedlings, and established vegetation.

[0288] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0289] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds, which can be used for plant propagation, as well as nutrient materials, such as cuttings or tubers (e.g., potatoes). References may include, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant. References may also include germinating plants and young plants that will be transplanted after germination or emergence. These young plants may be protected before transplanting by complete or partial treatment with maceration. Preferably, "plant propagation material" should be understood to mean seeds.

[0290] The pesticides mentioned in this article that use their common names are known, for example, from "The Pesticide Manual", 19th edition, British Crop Protection Council 2021.

[0291] Compounds having formula (I) as defined in this invention can be used in their unmodified form, or preferably, together with adjuvants conventionally used in the field of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coated pastes, directly sprayable or dilutable solutions or suspensions, thin emulsions, wettable powders, soluble powders, dusts, granules, and also capsules (e.g., in polymeric forms). The method of application, such as spraying, atomizing, dusting, spreading, coating, or irrigating, is selected according to the intended purpose and the prevailing environment for the type of composition. The composition may also contain additional adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders or thickeners, and fertilizers, micronutrient donors, or other formulations for achieving specific effects.

[0292] Suitable carriers and / or adjuvants, for example for agricultural uses, can be solid or liquid and are substances useful in formulation techniques, such as natural or recycled minerals, solvents, dispersants, wetting agents, thickeners, binders, or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0293] Suspension concentrates are aqueous formulations in which finely dispersed solid particles of an active compound are suspended. These formulations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as antifoamers and crystal growth inhibitors. When used, these concentrates are diluted in water and are typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0294] Wettable powders are finely dispersed granular formulations that readily disperse in water or other liquid carriers. These granules contain the active ingredient retained in a solid matrix. Typical solid matrices include bleaching clay, kaolin, silica, and other readily wettable organic or inorganic solids. Wettable powders typically contain 5% to 95% of the active ingredient, plus small amounts of wetting agents, dispersants, or emulsifiers.

[0295] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of an active compound and a liquid or solid emulsifier, or may contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0296] Granular formulations consist of both extrudates and coarser granules, and are typically applied undiluted to the area requiring treatment. Typical carriers used in granular formulations include sand, bleaching clay, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic absorbent active compounds or materials that can be coated with active compounds. Granular formulations typically contain 5% to 25% of the active ingredient, which may include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or binders such as dextrin, gums, or synthetic resins.

[0297] Powdered agents are free-flowing mixtures of active ingredients and finely dispersed solids (such as talc, clay, flour, and other organic and inorganic solids that act as dispersants and carriers).

[0298] Microcapsules are typically droplets or particles of active ingredient encapsulated within an inert, porous shell that allows the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets typically ranges from 1 to 50 micrometers. The encapsulated liquid typically constitutes 50% to 95% of the capsule weight and may contain a solvent in addition to the active compound. The encapsulated particles are typically porous particles, with a porous membrane sealing the pores and retaining the active species in liquid form within the pores. The diameter of the particles typically ranges from 1 millimeter to 1 centimeter, and preferably from 1 to 2 millimeters. The particles are formed by extrusion, aggregation, or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and carbon concentrate. Shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthates.

[0299] Other useful formulations for agrochemical 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 sprays can also be used, in which the active ingredient is dispersed in a finely dispersed form due to the evaporation of a low-boiling-point dispersant solvent carrier.

[0300] Suitable agricultural adjuvants and / or carriers useful for formulating the compositions of the present invention among the above-described formulation types are well known to those skilled in the art.

[0301] Suitable liquid carriers include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenyl, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl... Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl diacetate, monoethyl glycerol Ester, glyceryl triacetate, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl lauryl ester, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, poly Ethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin wax, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols (such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is usually the preferred carrier for diluting the concentrate.

[0302] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, chalk, lime, calcium carbonate, bentonite, bleaching clay, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell powder, and lignin.

[0303] A wide range of surfactants are advantageously used in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents typically constitute 0.1% to 15% by weight of the formulation when used. They can be anionic, cationic, nonionic, or polymeric in nature and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; and alkylphenol-epoxide addition products such as nonylphenol-C 18 Ethoxylated compounds; alcohol-epoxide addition products, such as tridecyl alcohol-C 16Ethoxylated compounds; soaps, such as sodium stearate; alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium compounds, such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates.

[0304] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoamers, opacifiers, compatibility agents, masking agents, neutralizers and buffers, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration enhancers, micronutrients, softeners, lubricants, and fixatives.

[0305] Furthermore, other biocidal active ingredients or compositions may be combined with the compositions of the present invention and used in the methods of the present invention, and applied simultaneously or sequentially with the compositions of the present invention. When applied simultaneously, these additional active ingredients may be formulated or mixed together with the compositions of the present invention, for example, in a spray can. These additional biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and / or biological agents.

[0306] Preferably, the following combinations of a compound having Formula I and another active substance in a 1:1 weight ratio are preferred (where the abbreviation "TX" means "a compound selected from the compounds defined in Tables 1.1 to 1.63 and Table A"):

[0307] (7E,9Z)-Dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-Tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-Tetradec-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-Tedec-4-en-1-yl acetate + TX, (E,Z)-Tetradec-4,10-dien-1-yl acetate + TX, (Z)-Dodec-7-en-1-yl acetate + TX, (Z)-Hexadec-11-en-1-yl acetate + TX, (Z)-Hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1-hydroxy-1H-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-(quinoxalo-2-ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, 5-methyl-6-thio-1,3,5-thiadiazin-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, avermectin + TX, miticide quinoline + TX, acetamiprid + TX, acetamiprid + TX, flufenoxuron + TX, acynonapyr + TX, cotton brown leafroller GV + TX, bispyribac-methyl + TX, aflonana + TX, agrobacterium radioduran + TX, AKD-3088 + TX, cotton bollworm + TX, aldicarb + TX, aldicarb + TX, propyrene + pyrethrum + TX, cis-cypermethrin + TX, high-efficiency cypermethrin + TX, alpha-multistriatin + TX, *Amblyseius* species + TX, sulfadiazine + TX, amino acids + TX, cypermethrin + TX, celery cutworm NPV + TX, *Protoceratops spp.* + TX, *Aphidius spp.* +TX, Cotton aphid parasitic wasp + TX, Aphid gall midge + TX, Azoxystrobin + TX, Alfalfa silver-striped noctuid moth NPV + TX, AZ 60541 + TX, Azadirachtin + TX, Triazole tin + TX, Bacillus spp. caterpillar + TX, Bacillus chitinosporus AQ746 (NRRL registry B-21 618) + TX, Bacillus stolonifer + TX, Bacillus spp. Kurstak + TX, Bacillus mycosis fungoides AQ726 (NRRL registry B-21664) + TX, Bacillus pumilus (NRRL registry B-30087) + TX, Bacillus pumilus AQ717 (NRRL registry B-21662) + TX, Bacillus spp. species AQ175 (ATCC registry 55608) + TX, Bacillus species AQ177 (ATCC accession number 55609) + TX, Bacillus species AQ178 (ATCC accession number 53522) + TX, Bacillus spheroidae + TX, Bacillus 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, Unspecified Bacillus subtilis + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) +TX, Bacillus thuringiensis BD#32 (NRRL Registry No. B-21530) + TX, Bacillus thuringiensis + TX, Bacillus thuringiensis subsp. Ayuzawa + TX, Bacillus thuringiensis subsp. Israel + TX, Bacillus thuringiensis subsp. Japan + TX, Bacillus thuringiensis subsp. Kurstak + TX, Bacillus thuringiensis subsp. Tenebrionis + TX, Bacillus thuringiensis subsp. Kurstak BMP 123 + TX, Beauveria bassiana + TX, Beauveria bassiana + TX, Benzyl + TX, Benomyl + TX, Cypermethrin + TX, Benzoate (CAS No.: 2566451-67-8) + TX, Benzoate + TX, Pyrimethanil + TX, β-Cypermethrin + TX, β-Cypermethrin + TX, Vermifentanil + TX, Bifenazate + TX, Bifenthrin + TX, Acaricide + TX, Bio-allethrin + TX, Bio-benzylfuran + TX, Bis(tributyltin)oxide + TX, Bisazir + TX, Diflubenzuron +TX, Flufenoxuron + TX, Breviconin + TX, Broflanilide + TX, Delemulsamide + TX, Bromoacetamide + TX, Bromothion-Ethyl + TX, Bromonitol + TX, Busulfan + TX, Butanol + TX, Butopyronoxyl + TX, Butoxyl (polypropylene glycol) + TX, Butylpyridinium + TX, Thiophanate + TX, Calcium Arsenate + TX, Carbofuran + TX, Carbon Disulfide + TX, Butylcarbofuran + TX, Bataan + 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 No.: 1632218-00-8 + TX, CAS No.: 1808115-49-2 + TX, CAS No.: 1922957-46-7 + TX, CAS No.: 1922957-48-9 + TX, CAS No.: 1956329-03-5 + TX, CAS No.: 1990457-52-7 + TX, CAS No.: 1990457-55-0 + TX, CAS No.: 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.: 2133042-31-4 + 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 No.: 2719848-60-7 +TX, CAS number: RNA (Potato Beetle-Specific Recombinant Double-Strand Interference GS2) + TX, Chlorantraniliprole + TX, Chlordane + TX, Bromnitrothion + TX, Chlorpicrin + TX, Cypermethrin + TX, Chlorpyrifos + TX, Cyclofenac + TX, Chrysoperla carnea + TX, Clenbuterol + TX, Cloethocarb + TX, Thiamethoxam + TX, Codlelure + TX, Codlemone + TX, Copper Arsenite + TX, Copper Dioctanoate + TX, Copper Hydroxide + TX, Copper Sulfate + TX, Cresol + TX, Crufomate + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, benzoylphos + TX, broflanilide + TX, cybenzoxasulfyl (CAS No.: 2128706-04-5) + TX, cybutryne + TX, cyclobutrifluram + TX, pyrethroids + TX, epoxim + TX, codling moth GV + TX, pyridaben + TX, cyetpyrafen + TX, diflubenzuron + TX, lambda-cyhalothrin + TX, cyhalothrin + TX, deltamethrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica (Tomato leafminer) + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, acaricide + TX, chlorpyrifos + TX, dimidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutylsuccinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen +TX, diliphos + TX, dicloomezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif + TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dichlorvos + TX, abamectin + TX, difenoconazole + TX, phosmet + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodecano-8-en-1-yl acetate + TX, dodecano-9-en-1-yl acetate + TX, docosahexadecyl-8,10-dien-1-ylacetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, dextromethorphan + TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon-momfluorothrin + TX, epsilon-benzylfluthrin + TX, Eretmoceruseremicus + TX, cypermethrin + TX, ethion + TX, acetamiprid + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, permethrin + TX, etpyrafen + TX, eugenol + TX, seaweed extract and glycoyl-derived fermentation products + TX, seaweed extract and glycoyl-derived fermentation products containing urea + TX, seaweed extract and fermented plant products + TX, seaweed extract and fermented plant products (containing plant hormones, vitamins, EDTA-chelated copper, zinc and iron) + TX, valproate + TX, fenaminosulf + TX, fenamiphos + TX, quinalfen +TX, pendiflubenzuron + TX, fenitrothion + TX, fenmezoditiaz + TX, sec-butylcarbide + TX, fenthiocarb + TX, fenoxycarb + TX, cypermethrin + TX, fenpyrad + TX, fenpyroximate + TX, fensodium + TX, fentin + TX, fentinacetate + TX, cypermethrin + TX, ferric phosphate + TX, fipronil + TX, fometoquin + TX, flonicamid + TX, pyrimethanil + TX, fluazaindolizine + TX, pyridaben + TX, flufenoxuron + TX, fluchlorfenapyr + TX, fluchlorfenapyr + TX, fluchlordiniliprole + TX, flucitrinate + TX, flufenoxuron + TX, cypermethrin + TX, fluthiamethoxam [318290-98-1] + TX, fluensulfone + TX, pyrimethanil + TX, trifluralin + TX, fipronil + TX, fluhexafon + TX, flupyram + TX, flupyroxystrobin + TX, fluralaner + TX, lambda-cyhalothrin + TX, fluxametamide + TX, formaldehyde + TX, thiazophos + TX, fosthietan + TX, frontalin + TX, furfural + TX, galquin (CAS No.: 2644770-30-7) + TX, γ-cyhalothrin + TX, Gossyplure® (a 1:1 mixture of (Z,E) and (Z,Z) isomers of hexadecyl-7,11-dien-1-ylacetate) + TX, grandlure + TX, cotton weevil pheromone I + TX, cotton weevil pheromone II + TX, cotton weevil pheromone III + TX, cotton weevil pheromone IV + TX, Granulovirus + TX, guadipyr + TX, GY-81 + TX, halfenprox+TX, halofenozide + TX, Harpin + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, NPV of the common bollworm + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, Australian bollworm nucleopolyhedrovirus + TX, Green bollworm nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, quicklime + TX, imidacloprid + TX, imidacloprid + TX, imiprothrin + TX, indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidophos + TX, isazofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS No.: 2892524-05-7) + TX, isothioate + TX, ivermectin + TX, japonilure + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda-cyhalothrin +TX, ledprona (RNA interference agent for potato beetle) + TX, lepimectin + TX, Leptomastix dactylopii (parasitic wasp for citrus scale insect) + TX, lineatin + TX, litlure (sexual pheromone for cutworm) + TX, looplure (sexual pheromone for cutworm) + TX, lotilaner + TX, lufenuron + TX, Macrophorus caliginosus (sexual pheromone for cutworm) + TX, Mamestra brassicae (NPV) + TX, mecarphon + TX, medlure + TX, (3E,5Z)-tetradec-3,5-dienoic acid + TX, metaflumizone +TX, metaldehyde + TX, metam + TX, potassium salt of metam + TX, sodium salt of metam + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, neodecanoamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure +TX, Muscodor albus 620 (NRRL Registry No. 30547) + TX, Muscodorroseus A3-5 (NRRL Registry No. 30548) + TX, Myrothecium verrucaria composition + TX, Nabam + TX, NC-184 + TX, Neem-based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadecyl-2,13-dien-1-yl acetate + TX, octadecyl-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, *Orius* spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, *Paecilomyces fumosoroseus* + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae (microbial insecticide) + TX, P-cymene + TX, penfluron +TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxamicliprole + TX, piperazine + TX, pipeflanilide (CAS No.: 2615135-05-0) + TX, pipeonylbutoxide + TX, pirimicarb + TX, piriphos-ethyl + TX, piriphos-methyl + TX, Plutella xylostella granulovirus + TX, Diamondback moth nucleopolyhedrovirus + TX, Polyhedrovirus + TX, Potassium and molybdenum and EDTA-chelated manganese + TX, Potassium ethyl xanthate + TX, Potassium hydroxyquinoline sulfate + TX, Prallethrin + TX, Probenazole + TX, Profenofos + TX, Profluthrin + TX, Proargite + TX, Proetamphos + TX, Prooxur + TX, Prothiophos + TX, Protrifenbute + TX, Pyflubumide + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridine-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (terpene blend) +TX, QRD 452 (terpene blend) + TX, QRD460 (terpene blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL registration number B-21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenate + TX, sordidin + TX, Spidoxamat + TX, Spinetoram + TX, Spinosad + TX, Spirobudifen + TX, Spirodiclofen + TX, Spiroomesifen + TX, Spiropidion + TX, Spiotetramat + TX, Spodoptera exigua multicapsid nucleopolyhedrosis virus + TX, Spodoptera frugiperda nucleopolyhedrosis virus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, *Steinerne maglaseri* + TX, *Steinernema riobrave* + TX, *Steinernema riobravis* + TX, *Steinernema scapterisci* + TX, *Steinerne maspp.* + TX, *Streptomyces galbus* (NRRL registry number 30232) + TX, *Streptomyces* (NRRL registry number B-30145) +TX, Streptomycin + TX, Streptomycin Sulfate + TX, Strychnine + TX, Sulcatol + TX, Sulfiflumin (CAS No.: 2377084-09-6) + TX, Sulfoxaflor + TX, Tazimcarb + TX, Tebufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tecloftalam + TX, Tefluthrin + TX, Temephos + TX, Tepa + TX, Terbam + TX, Terbufos + TX, Terpene Blend + TX, Tetrachlorantraniliprole + TX, Tetrachlorothiophene + TX, Tetradec-11-en-1-ylacetate + TX, Tetradiphon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetranactin + TX, Tetraniliprole + TX, Theta-cypermethrin + TX, Thiacloprid + TX, Thiafenox + TX, Thiamethoxam + TX, Thiocyram + TX, Thiodicarb + TX, Thiofanox + TX, Thiohempa + TX, Thiomersal + TX, Thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tiapyrachlor (CAS No.: 1255091-74-7) + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene +TX, tralomethrin + TX, transfluthrin + TX, tratahamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tritin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogrammaspp. species + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc-call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium species + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta-Cypermethrin + TX;

[0308] N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methylformamidinium (these compounds can be prepared by the method described in WO2019 / 110427) + TX, (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl ketone (these compounds can be prepared by ... (Prepared by the method described in WO 2017 / 220485) + TX, methyl 2-amino-6-methyl-pyridin-3-carboxylic acid (4-phenoxyphenyl) (this compound can be prepared by the method described in WO 2014 / 006945) + TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl] ketone + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tetadecedec-4-en-1-yl acetate + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicosode-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO 2018 / 153707) +TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazolyl-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared by the method described in WO2017 / 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-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazole-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitrobenzene + TX, 1-hydroxy-1H-pyridin-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazole-5-one + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(1,3-dithiopentane-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl piperate +TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolane-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-dimethylmethyloxy)ethanol + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indane-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indane-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indane-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 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-ethylsulfinyl ethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2,6-dimethyl-1H,5H-[1,4]dithiacino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be derived from WO Prepared by the method described in WO 2011 / 138281) + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]prop-2-ol + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol (this compound can be prepared by the method described in WO 2017 / 029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol (this compound can be prepared by the method described in WO 2017 / 029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolinone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate + TX, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO 2018 / 065414) + TX, 2-cyanothioethyl laurate +TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenten[e]benzimidazole (these compounds can be prepared by the method described in WO2016 / 156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazol-4-carboxynitrile (this compound can be prepared by WO2016 / 156085) + TX, 3 ...4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenten[e]benzimidazole (these compounds can be prepared by the method described in WO2016 / 156085) + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazol-4-carboxynitrile (this compound can be prepared by WO2016 / 156085) + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazol (Prepared by the method described in WO2016 / 156290) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazolium-4-carboxynitrile (this compound can be prepared by the method described in WO2016 / 156290) + TX, 3-bromo-1-chloroprop-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-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazole-5-yl dimethylcarbamate + 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-phenyl-pyridazin-3-carboxynitrile + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazole-3-amine + TX, 4-(quinoxaloline-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile +TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioalkyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thio-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]pyridazine-3-one + TX, 4-chlorophenylphenyl sulfone + TX, 4-methyl(prop-2-ynyl)amino-3,5-dimethylmethylcarbamate + TX, 4-methylnon-5-ol and 4-methylnon-5-one + TX, 5-(1,3-benzodioxane-5-yl)-3-hexylcyclohex-2-enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, 5-amino-1,3,4-thiadiazol-2-thiol zinc salt (2:1) + TX, 5-methyl-6-thio-1,3,5-thiadiazine-3-ylacetic acid + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391) + TX, 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391) + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391) + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiacinro[1,2-c]isothiazolyl-3-carboxynitrile + 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, Aspergillus + TX, Acetaminophen + TX, Aramacin + TX, Aramacin-S-methyl + TX, Acrylonitrile + TX, Cotton Brown Leaf Roller GV + TX, Agrobacterium radiata + TX, Aldicarb + TX, Aldrin + TX, Alpromethazine + TX, Dichlorvos + TX, α-Chlorohydrin + TX, α-Decidin + TX, α-Polycarb + TX, Aluminum Phosphide + TX, Amblyomyces species + TX, Amectotractin + TX, Azoxystrobin + TX, Cypermethrin + TX, Phosphamidon + TX, Methamidophos + TX, Ampicillin + TX, Indoxamyl + TX, Ammonium oxalate + TX, Amitraz + TX, Neonicotinic acid + TX, Celery Earworm NPV + TX, Pterygium wilfordii + TX, pyrimidinol + TX, difenoconazole + TX, fluphenyladenine + TX, anthraquinone + TX, antagonist + TX, short-spurred aphid wasp + TX, cotton aphid parasitic wasp + TX, aphid gall midge + TX, azithion + TX, acaricide + TX, arsenic trioxide + TX, ethyl chlorpyrifos + TX, alfalfa silver-striped moth NPV + TX, azaconazole + TX, methyl pyridinium + TX, azobenzene + TX, azophos + TX, azoxystrobin + TX, pyraclostrobin + TX, Bacillus spheroides + TX, Bacillus thuringiensis δ-endotoxin + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, pyrethroid + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, Beauveria bassiana + TX, benzalkonium chloride + TX, benzoyl peroxide + TX TX, benomyl + TX, benzalkonium chloride + TX, benomyl + TX, benzalkonium chloride + TX, benzoyl permethrin + TX, benzyl benzoate + TX, β-cyhalothrin + TX, β-cypermethrin + TX, cypermethrin + TX, pendimethalin + TX, bio-cypermethrin + TX, bis(2-chloroethyl) ether + TX, bis(tributyltin) oxide + TX, bis(aziridine) methylphosphonic acid sulfide (bisazir) + TX, bismuth subtilis + TX, bifenthrin + TX, bifenthrin + pyraclostrobin + TX, cymoxanil-S + TX, borax + TX, Bordeaux mixture + TX, boscalid + TX, western pine bark beetle pheromone + TX, bromadiolone + TX, bromadiolone + TX, bromadiolone + TX, bromophenylenephos + TX, bromoacetamide + TX, bromoxynil + TX, bromo-DDT + TX, bromothion + TX, bromodimethalin + TX, furazolidone + TX, bromonitrile + TX, methyl parathion + TXTX, Ethylpyrimethanil Sulfonate + TX, Thiazide + TX, Busulfan + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate butyl-3-yne ester + TX, Carbofuran + TX, Terpyrimiphos + TX, Butanone + TX, Butyl ester + TX, DEET + TX, Butoxy(polypropylene glycol) + TX, Butanone sulfonate + TX, Butylpyridinium + TX, Calcium arsenate + TX, Calcium cyanide + TX, Calcium polysulfide + TX, Octochlorbornene + TX, Captan + TX, Captan + TX, Chlorpyrifos + TX, Carbendazim + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Trithion + TX, Carbofuran + TX, Bataan Hydrochloride + TX, CAS No.: 2454319-63-0 + TX, cevadine + TX, chinomethionat + TX, chloralose + TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron +TX, chloroneb + ​​TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, common lacewing + TX, cinerin I + TX, cinerin II + TX, cinerins +TX, cismethrin + TX, cis-resmethrin + TX, clocythrin + TX, closantel + TX, cotyl oleate + TX, apple leafroller pheromone + TX, copper acetylacetonate + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin or jiaxiangjunzhi + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, *Cryptospira mansoni* + TX, CS 708 + TX, cyromazine + TX, cufraneb + ​​TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, codling moth GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, tomato leafminer parasitic wasp + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb + TX, decarbofuran +TX, demephion + TX, O-demephion + TX, S-demephion + TX, demeton-methyl + TX, O-demephion + TX, O-methyldemephion + TX, S-demephion + TX, S-methyldemephion + TX, demeton-S-methylsulfon + TX, diamidofos + TX, chlorfenthion + TX, dibutylphthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichloroquine + TX, dichlorophen + TX, dichlorvos +TX, dichlozoline + TX, didicphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, pea leafminer wasp (Diglyphus isaea) + TX, dilor + TX, dimatif + TX, dimefluthrin + TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimethomorph + TX, dimethrin + TX, dimethyl carbate +TX, dimethylphthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex-diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, diocton + TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, diosulfon + TX, dioterbon + TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos + TX, DNOC + TX, dodecano-8-en-1-yl acetate + TX, dodecano-9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d-tetramethrin + TX, ecdysterone + TX, edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX, enestroburin + TX, (E,E)-enoxastrobin + TX, EPBP + TX, epoxiconazole +TX, eprinomectin + TX, Aphididae + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO2020 / 056090) + TX, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolane-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO 2020 / 056090) + TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate ethyl ester + TX, 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate ethyl ester (this compound can be prepared by the method described in WO 2018 / 158365) + TX, 4-methyloctanoate ethyl ester + TX, ethyl formate + TX, ethylhexane glycol + TX, dibromoethane + TX, dichloroethane + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, feneptamidoquin (CAS No.: 2132414-04-9) + TX, fenethacarb + TX, fenfuram + TX, fenhexamid +TX, fenitrothion + TX, fenopyramid (CAS No.: 2344721-61-3) + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, ethyl fenthion + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, floccoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin+ TX, fluoxytioconazole + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl-aluminium + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, frontalin + TX, furberidazole + TX, furalaxyl + TX, furamettapyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, γ-HCH + TX, glyodine + TX, cotton weevil pheromone + TX, cotton weevil pheromone I + TX, cotton weevil pheromone II + TX, cotton weevil pheromone III + TX, cotton weevil pheromone IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel +TX, Hempa + TX, HEOD + TX, Heptachlor + TX, Heterophos + TX, Heterophos and Heterophosphaeria + TX, Hexaconazole + TX, Hexadecyl cyclopropanecarboxylate + TX, Hexalure + TX, Hexamide + TX, HHDN + TX, Ladybug + TX, Hydralgamyl sulfadiazine + TXTX, quicklime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidophos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram + TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I +TX, Juvenile Hormone II +TX, Juvenile Hormone III +TX, Kadethrin +TX, Kasugamycin +TX, Kasugamycin Hydrochloride Hydrate +TX, Kelevan +TX, Kinetin +TX, Kinoprene +TX, Kresoxim-methyl +TX, Lead Arsenate +TX, Citrus Scale Insect Parasite +TX, Leptophos +TX, Lindane +TX, lineatin + TX, lirimfos + TX, noctuid moth pheromone + TX, white armyworm pheromone + TX, lvbenmixianan + TX, lythidathion + TX, mirid bug + TX, magnesium phosphide + TX, malonoben + TX, cabbage noctuid moth NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + ​​TX, mazidox + TX, m-cumenylmethylcarbamate + TX, mecarbam + TX, mecarphon + TX, Medlure + TX, Mefentrifluconazole + TX, (3E,5Z)-Tetradec-3,5-dienoic acid + TX, Menazon + TX, Mepanipyrim + TX, Meperfluthrin + TX, Mephosfolan + TX, Mepronil + TX, Mercuric oxide + TX, Mercurous chloride + TX, Mesulfen + TX, Mesulfenfos + TX, Metalaxyl + TX, Metam + TX, Metam potassium salt + TX, Metam sodium salt + TX, Yellow-stalked flea + TX, Metarhizium anisopliae + TX, Metarhizium anisopliae Microsporum variant + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methicrifos + TX, mesylate + TX, methasulfocarb + TX, metiotepa + TX, methocarbamate + TX, methoocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor +TX, (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the method described in WO2020 / 193387) + TX, (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared by the method described in WO 2020 / 079111) + TX, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl apholate + TX, methyl bromide + TX, methyleugenol + TX, methyl isothiocyanate + TX, N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012) + TX, N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012) + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, methyl chloroform + TX, dichloromethane + TX, methyl neodecanoamide + TX, metiram + TX, metolcarb + TX, metominostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime oxime) + TX, mipafox + TX, mirex + TX, monocrotophos + TX, morphothion +TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozoline + TX, Varicella vesicatoria composition + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared by the method described in WO2017 / 153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared by the method described in WO2017 / 153380) + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidin + TX, N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidinium + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide +TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidin (this compound can be prepared by the method described in WO 2016 / 202742) + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidin (these compounds can be prepared by the method described in WO2015 / 155075) +TX, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidin (this compound can be prepared by the method described in IPCOM000249876D) + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N-[N-methoxy-C-methyl-carbonimide]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428) + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidin (these compounds can be prepared by the method described in WO2018 / 228896) + TX, sodium mancozeb (nabam) + TX, naphthylphosphide (naftalofos) + TX, dibromophos (naled) + TX, naphthalene + TX, NC-170 + TX, European New Pine Sawfly NPV and Red-headed New Pine Sawfly NPV + TX, nerolidol +TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidin + TX, bis(dimethyldithiocarbamate)nickel + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidin + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide + TX, norbormide + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiophosphate + TX, 2,13-diene-1-yl acetate + TX, 3,13-diene-1-yl acetate + TX, octhilinone + TX, ofuramide + TX, oleic acid + TX, omethoate + TX, orfralure + TX, species of *Symplocos spp.* + TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos+TX, oxydisulfoton + TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces flavus + TX, p-dichlorobenzene + TX, parathion + TX, methyl parathion + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, pH 60-38 + TX, phenamacril + TX, phenkapton + TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, phytoseidocarb + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piperital + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomer isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins + TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, potassium thiocyanate + TX, pp'-DDT + TX, precocene II) + TX, Precozid II + TX, Precozid III + TX, Primidophos + TX, Probenazole + TX, Prochloraz + TX, Proclonol + TX, Procymidone + TX, Profluthrin + TX, Promacyl + TX, Promecarb + TX, Propamocarb + TX, Proiconazole + TX, Propineb + ​​TX, Proxur + TX, Proquinazid + TX, Prothidathion + TX, Prothioconazole + TX, Prothiofos + TX, prothoate + TX, pydiflumetofen + TX, piraclostrobin + TX, pirametostrobin + TX, piraoxystrobin + TX, pirapropoyne + TX, piraziflumid + TX, pirazophos + TX, pirasmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyribencarb + TX, piradachlometyl + TX, piraphenthion + TX, pyridine-4-amine + TX, pirafenox + TX, piramethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia extract + TX, quinalphos + TX, methylquinalphos + TX, quinoclamine +TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, Rmetalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + TX, simazine + TX, simeconazole + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium fluoroacetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenate + TX, sodium selenate + TX, sodium tetrathiocarbonate + TX, sodium thiocyanate + TX, sophamide + TX, banana bulb weevil attractant (sordidin) + TX, spiroxamine + TX, SSI-121 + TX, hairy nematode + TX, small leafroller nematode + TX, noctuid moth nematode + TX, Grignard nematode + TX, Rhabditis nematode + TX, Steinernema riobravis + TX, mole cricket nematode (Steinernema scapterisci) + TX, nematode species + TX, streptomycin + TX, streptomycin sulfate + TX, strychnine + TX, sulcatol + TX, sulcofuron + TX, sulcofuron sodium +TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfoxide + TX, sulfur + TX, sulfonyl fluoride + TX, sulprofos + TX, tar + TX, tau-fluvalinate + TX, tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos + TX, thaba + TX, TEPP + TX, terallethrin + TX, terbam + TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]tert-butyl carbamate + TX, Tetrachloroethane + TX, Tetrachlorothiophene + TX, Tetraconazole + TX, Tetradec-11-en-1-ylacetate + TX, Tetradifon + TX, Tetramethylfluthrin + TX, Tetrasul + TX, Thallium sulfate + TX, Thiabendazole + TX, Thiafenox + TX, Thiapronil + TX, Thiocrofos + TX, Thifluzamide + TX, Thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap +TX, thiosultap-sodium + TX, thiodicarb + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tratamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma species + TX, triclopyricarb + TX, tricyclazole + TX, triridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Western vitiligo + TX, uredepa + TX, validamycin +TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium clavatum + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiamethoxam + TX, zineb + ​​TX, ziram + TX;

[0309] Acinetobacter rumenella + TX, Cladosporium fungi + TX, Cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, AdoxGV (Capex®) + TX, Agrobacterium radiodurans strain K84 (Galltrol-A®) + TX, Alternaria + TX, Alternaria scabiosifolia + TX, Alternaria scavengata (Smolder®) + TX, Powdery mildew (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus species + TX, Budding bryophytes + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotomeal® + TX, Bionatural Blooming Blossoms® + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinus strain AQ746 + TX, Bacillus chitinus strain CM-1 + TX, Bacillus circulans + TX, Bacillus sturdier (BioSafe®, BioNem-WP®) especially strain CNMC1-1582 (e.g., VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus licheniformis strain HB-2 (Biostart™, formerly known as Rhizoboost®) + TX, Bacillus thuringiensis + TX, Bacillus dead seaii + TX, Bacillus megaterium + TX, Bacillus mycosis fungoides strain AQ726 + TX TX, Bacillus lactis (Milky Spore Powder®) + TX, Bacillus pumilus species + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus spheroidae (VectoLex®) + TX, Bacillus spp. species + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus amyloliquefaciens variant strain FZB24 (Taegro®, Rhizopro®) + TX, Bacillus thuringiensis Ayuzawa GC 91 (Agree®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis Israel (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis Kurstak (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis Kurstak BMP 123 (Baritone®) + TX, Bacillus thuringiensis Kurstak HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis Tenebrionid Beetle (Novodor®, BtBooster) + TX, Bacillus thuringiensis XenTari®, DiPel® + TX, Bacterial species (GROWMEND®, GROWSWEET®, Shootup®) + TX, Bacteriophages of Clavipacterus michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol) ES®, Mycotrol O®, BotaniGuard® + TX, Beauveria bassiana (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria species + TX, Botrytis cinerea + TX, Thyroidobacterium soybean (TerraMax®) + TX, Microsporum brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia + TX, Burkholderia gladiolus + TX, Burkholderia species + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida cheese+ TX, Candida unnamed + TX, Candida fructus + TX, Candida glabrata + TX, Candida gigantea + TX, Candida kojima + TX, Candida oleifera strain O + TX, Candida parapsilosis + TX, Candida flocculation + TX, Candida rhodotorulata + TX, Candida erythrospinata + TX, Candida ridis + TX, Candida rosifolia + TX, Candida sacchari + TX, Candida sacchari (Bio-Coat®, Biocure®) + TX, Candida sakei + TX, Candida species + TX, Candida slenderis + TX, Cediclofenac dilatatus + TX, Cellulomonas xanthogenes + TX, Nova-Cide® + TX, Chaetomium globosum + TX, Hemlock violaceum strain PRAA4-1T (Grandevo®) + TX, Cladosporium pulcherrima + TX, Cladosporium + TX, Cladosporium oxysporum + TX, Cladosporium species + TX, Cladosporium microfiliis + TX, EndoFine® + TX, Anthracnose + TX, Cotans WG® + TX, Cotans species + TX, Cryptococcus yields + TX, Cryptococcus terrestris + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laureus + TX, Cryptococcus laurentii + TX, Cryptex® + TX, Cupriavidus campinensis + TX, Codling moth granulovirus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX TX, *Agmonella* + TX, *Hansophila d'Barry* + TX, *Drechslera hawaiinensis* + TX, *Enterobacter cloacae* + TX, *Enterobacteriaceae* + TX, *Vektor®* + TX, *Pseudomonas* + TX, *Pseudomonas nigricans* + TX, *Pseudomonas* species + TX, *Filobasidium floriforme* + TX, *Fusarium argentis* + TX, *Fusarium chlamydosporium* + TX, *Fusaclean®, Biofox C®* + TX, *Fusarium latriniferum* + TX, *Fusarium* species + TX, *Geotrichum candida* + TX, *Primastop®, Prestop®* + TX, *Pink Pseudomonas* + TX, *SoilGard®* species +TX, Soilgard® + TX, Granupom® + TX, Halophilic Bacillus + TX, Halophilic Bacillus serrata + TX, Halophilic Bacillus tergenti + TX, Halomonas species + TX, Halomonas subglacial + TX, Halovoidococcus polymorpha + TX, Hansenula polymorpha spores in grape juice + TX, Helicovex® nucleopolyhedrovirus for bollworm + TX, Gemstar® nucleopolyhedrovirus for corn moth + TX, Isaria fumosorosea (formerly known as Paecilomyces fumosorosea strain, PFR-97®, PreFeRal®) + TX, Isoflavone formononetin (Myconate®) + TX, Klerk yeast + TX, Klerk yeast species + TX, Laginex® + TX, Verticillium lecanii (formerly known as strain KV01 (e.g., Vertalec® of Koppert / Arysta) conidia (Mycotal®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Disparvirus® + TX, Halophilic sea cocci + TX, Mela glomerata + TX, Destruxin WP® + TX, Met52® + TX, Metschnikowia fruticola (Shemer®) + TX, Methyldochia + TX, Microdochium dimerum (Antibot®) + TX TX, *Microsphaeropsis* + TX, *Microsphaeropsis ochracea* + TX, *Muscodor albus* 620 (Muscudor®) + TX, *Muscodor roseus*, especially strain A3-5 (registration number NRRL 30548) + TX, mycorrhizal species (AMykor®, Root Maximizer®) + TX, *Ophiostoma piliferum* strain AARC-0255 (DiTera®, BROS PLUS®) + TX, *Ophiostoma piliferum* strain D97 (Sylvanex®) +TX, *Paecilomyces lilacinus* + TX, *Paecilomyces lilacinus* strain 251 (MeloCon WG®) + TX, *Paecilomyces lilacinus* (Biostat WP®) + TX, *Bacillus polymyxa* + TX, *BlightBan C9-1®* + TX, *Pantheraea* species + TX, *Paecilomyces zawaei*, especially strain Pn1 (from Syngenta / ChemChina's CLARIVA) + TX, *Bacillus pastoris* species (Econem®) + TX, *Penicillium grayi* + TX, *Penicillium barometz* (Jumpstart®, TagTeam®) + TX, *Penicillium short-dense* + TX, *Penicillium commonum* + TX, *Penicillium grayi* + TX, *Penicillium purpureum* + TX, *Penicillium* species + TX, *Penicillium verum* + TX, *Rotstop®* + TX, Phosphate-soothing 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®) + TX, *Pseudomonas putida* + TX, *Pseudomonas*reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella species spp.) + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula ularubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, SARRITOR® + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratiaplymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spod-X®, Spexit® + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoplanus + TX Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces 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®, Tririanum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) +TX, *Trichoderma inhamatum* + TX, *Trichoderma koningii* + TX, *Trichoderma lignorum* + TX, *Trichoderma longibrachiatum* + TX, *Trichoderma polysporum* (Binab T®) + TX, *Trichoderma* species (LC 52) (Sentinel®) + TX, *Trichoderma taxi* + TX, *Trichoderma virens* (formerly known as *Trichoderma virens* GL-21) (SoilGuard®) + TX, *Trichoderma virens* + TX, *Trichodermaviride* + TX, *Trichoderma virens* strain ICC 080 (Remedier®) + TX, *Trichosporonpullulans* + 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 supplemental nutrients (Natural II®) + TX, Various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Burkholderia caudatus + TX, Nematophyte pathogenic bacillus + TX;

[0310] AGNIQUE® MMF + TX, Azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®, e.g., AZATIN XL from Certis, Inc.) + TX, Plant IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, Canola Oil (Lilly Miller Vegol®) + TX, Chestnut (Chenopodium ambrosioides near ambrosioides) (Requiem®) + TX, Chrysanthemum Extract (Crisant®) + TX, Lamiaceae Essential Oil (Botania®) + TX, Azadirachtin Oil Extract (Trilogy®) + TX, Clove-Rosemary-Peppermint and Thyme Oil Extract (Garden Insect Killer®) + TX, Garlic + TX, Betaine (Greenstim®) + TX, Kaolin (Screen®) + TX TX, Lemongrass Oil (GreenMatch®) + TX, Tea Tree Oil Extract (also known as Tea Tree Oil) (Timorex Gold®) + TX, Clove-Peppermint-Garlic Oil and Peppermint Blend (Soil Shot®) + TX, Clove-Rosemary and Peppermint Extract Blend (EF 400®) + TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF 300®) + TX, Neem Oil + TX, Catnip (Nepeta cataria) (Catnip Oil) + TX, Nepeta catarina + TX, Nicotine + TX, Oregano Oil (MossBuster®) + TX, Pedaliaceae Oil (Nematon®) + TX, Pine Oil (Retenol®) + TX, Pyrethrum + TX, Soapbarb (Quillaja saponaria) (NemaQ®) + TX, Polygonum cuspidatum (Regalia®, Sakalia®) + TX, Rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, Soybean oil (Ortho ecosense®) + TX, Brown algae storage dextran (Laminarin®) + TX, Thyme oil + TX;

[0311] (E,Z)-7,9-dodecadien-1-yl acetate + TX, (E,Z,Z)-3,8,11-tetradecanetrienyl acetate + TX, (Z,Z,E)-7,11,13-hexadecanetrienal + TX, 2-methyl-1-butanol + TX, Biolure® + TX, 3M Sprayable Blackheaded Fireworm Pheromone® + TX, Calcium acetate + TX, Check-Mate® + TX, Paramount dispenser-(CM) / Isomate C-Plus® + TX, Entostat powder (extract from palm trees) (Exosex CM®) + TX, Grape leafroller pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Lavender senjoicin + TX, Leafroller pheromone (3M MEC-LR) Sprayable Pheromone® + TX, Snip7 Fly Bait® + TX, 3M oriental fruit moth sprayable pheromone® + TX, Peach tree borer pheromone (Isomate-P®) + TX, Scenturion® + TX, Starbar PremiumFly Bait® + TX, Tomato pinworm pheromone (3M Sprayable pheromone®) + TX;

[0312] Acerophagus papaya + TX, Adalia-System® + TX, Adaline® + TX, Aphidalia® + TX, *Aphidalia fasciata* + TX, ..., *Aphidalia fasciata* + TX, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasciata*, *Aphidalia fasci loecki + TX, Citripar® + TX, Red wax scale + TX, Golden wasp + TX, Woodland flower bug (Anthocoris nemoralis) (Anthocoris-System®) + TX, Apheline®, Aphiline® + TX, Short-winged aphid wasp + TX, Cotton aphid parasitic wasp (Aphipar®) + TX, Aphelinus-System® + TX, Ervipar® + TX, Tobacco aphid parasitic wasp + TX, Peach red aphid parasitic wasp (Aphipar-M®) + TX, Aphidend®, Aphidoline® + TX, Lingnan yellow aphid wasp + TX, Indian and Pakistan yellow aphid wasp + TX, Hassell's long-tailed biting wasp + TX, Ant-shaped rove beetle (Staphyline®) +TX, Bumblebee species +TX, European bumblebee (Beeline®, Tripol®) +TX, European bumblebee (Natupol Beehive®) +TX, Cephalonomia stephanoderis +TX, Black-backed ladybug +TX, Common lacewing (Chrysoline®, Chrysopa®) +TX, Red lacewing +TX, Cirrospilus ingenuus +TX, Four-banded serpent wasp +TX, White-spotted orange wasp +TX, Closterocerus chamaeleon +TX, Closterocerus species +TX, Coccidoxenoides*Perminutus* (Planopar®) + TX, *Perminutus perminutus* + TX, *Perminutus perminutus* + TX, *Perminutus perminutus* + TX, *Perminutus perminutus* + TX, *Perminutus perminutus* + TX, *Perminutus perminutus* (Cryptobug®, Cryptoline®) + TX, *Perminutus perminutus* (Japanese square-headed beetle) + TX, *Perminutus perminutus* (Minusa®, DacDigline®, Minex®) + TX, *Perminutus perminutus* (Delphastus®) + TX, *Perminutus perminutus* (Delphastus pusillus) + TX, *Perminutus perminutus* (Diaparsis jucunda) + TX, *Perminutus perminutus* (Alizarinus) + TX, *Perminutus perminutus* (Diminex®, Miglyphus®, Digline®) + TX, *Perminutus perminutus* species + TX, *E. scutellarioides* + TX, *Encarsia max®, Encarline®, En-Strip®* + TX, *E. gondii* + TX, *E. haeti* + TX, *Syrphidend®* + TX, *Eretmoceris siphonini* + TX, *E. scutellarioides* + TX, *E. scutellarioides* (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, *E. scutellarioides* (Hyperionia) + TX, *E. scutellarioides* (Bemipar®, Eretline m®) + TX, *Eretmocerus siphonini* + TX, *E. four-spotted ladybug* + TX, *Feltiline®* + TX, *Spidend®* + TX, *Alishan leafminer* + TX, *Fopius ceratitivorus* + TX, Wirless Beehome® + TX, Vespop® + TX, Western Stony Mite + TX, Leystilts scabra + TX, Brachycarpus scabra + TX, HarmoBeetle® + TX, NemaShield HB®, Nemaseek®, Terraneem-Nam®, Terraneem®, Largenem®, B-Green®, NemAttack®, Nematop® + TX, Nemasys H®, BioNem H®, Exhibitline hm®, Largenem-M® + TX, Lawn Patrol® +TX, Spotted Ladybug + TX, Aculeifer-System®, Entomite-A® + TX, Hypoline m®, Entomite-M® + TX, Black Gall Wasp + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Tricolor Jumping Wasp + TX, Leptopar® (Orange Scale Parasite) + TX, Longhorn Jumping Wasp + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Forked Leaf Greenfly (Natufly®) + TX, Tea-footed Aphid Parasitoide + TX, Mirid Bug (Mirical-N®, Macroline c®, Miralical®) + TX, Mesoseiulus longipes + TX, Yellow Broad-stalked Jumping Wasp + TX, Metaphycus lounsburyi + TX, Milacewing® + TX, Yellow-winged Flying Wasp + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseuis californicus + TX, Neoseuis cucumber + TX (THRYPEX®), Pseudo-Neoseiu + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Biofly® + TX, Thripor-I®, Oriline i® + TX, Orius laevigatus (Thripor-L®, Oriline l®) + TX, Oriline m® + TX, Thripor-S® + TX, Pauesia juniperorum + TX, ladybug stalk wasp + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, rough-haired phytoseui + TX, Chilean phytoseui (Spidex®, Phytoline p®) + TX, spotted-bellied thorny bug (Podisus®) + TX, parasitic flea fly curvatus + TX, parasitic flea fly obtusus + TX, parasitic flea fly tricuspis + TXTX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaphorus fasciatus + TX, Pseudleptomastix mexicana + TX, Psyllaphorus fasciatus (complex) + TX, Psyllaphorus species + TX, Rhyzobius lophanthae + TX, Australian ladybug + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Ervibank® wheat aphid + TX, Steinernema nematode (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema nematode (NemaShield®, Nemasys F®, BioNem F®, Steinernema-System®, NemAttack®, Nemaplus®, Exhibitline sf®, Scia-rid®, Entenem®) + TX, Nemasys L®, BioNem L®, Exhibitline srb® + TX, BioVector®, BioVektor® + TX, Nematac S® + TX, Nematac species + TX, Guardian Nematodes® + TX, Stethorus® + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Tricholine b® + TX, Tricho-Strip® + TX, Trichogramma fasciatus + TX, Trichogramma microsporum + TX, Trichogramma corn borer + TX, Trichogramma broad-veined + TX TX, Trichogramma short-tubed wasp + TX, Ichthyophthirius multifiliis + TX;

[0313] Abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Collego® + TX, Cueva® + TX, Delta trap (Trapline d®) + TX, Harpin (ProAct®, Ni-HIBIT Gold CST®) + TX, Fatty acids derived from natural byproducts of extra virgin olive oil (FLIPPER®) + TX, Ferromolybdate (Ferramol®) + TX, Funnel trap (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Ferric phosphate (Lilly Miller Worry Free Ferramol) Slug & Snail Bait® + TX, MCP hail trap (Trapline f®) + TX, parasitic insect Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, locust microsporidia (Semaspore Organic Grasshopper Control®) + TX, pheromone net (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, potassium salt of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, spider venom + TX, sticky traps (Trapline YF®, Rebell Amarillo®) + TX, SuffOil-X® + TX, traps (Takitrapline y + b®) + TX TX, Varroa RNA interference agent (vadescana) (CAS No.: 2643947-26-4) + TX;

[0314] Mojave Bacillus strain R3B (accession number NCAIM(P) B001389) (WO 2013 / 034938) from Certis USA LLC + TX, Bacillus pumilus, particularly strain BU F-33, with NRRL accession number 50185 (from BASF's CARTISSA®, EPA accession number 71840-19) + TX, Bacillus subtilis CX-9060 from Certis USA LLC, Bacillus species, particularly strain D747 (available from Kumiai Chemical Industry Co., Ltd. under DOUBLE NICKEL®), with accession number FERM BP-8234, US Patent No. 7,094,592 + TX, Bacillus subtilis strain BU1814 (from BASF's VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA) + TX, Bacillus subtilis variant strain FZB24, with accession number DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA accession number 70127-5)) + TX, Bacillus subtilis, particularly strain QST713 / AQ713 (with NRRL accession number B-21661 and described in US Patent No. 6,060,051, available from Bayer Crop Science LP as SERENADE® OPTI or SERENADE® ASO) + TX, Bacillus polymyxa, particularly strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) + TX, Bacillus species strains, with accession number NRRL B-50972 or accession number NRRL B-67129, WO2016 / 154297 + TX, Pantothenia glutinosa, especially strain E325 (registration number NRRL B-21856) (available from Northwest Agri Products as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX;

[0315] Budding short-stemmed fungi, especially budding spores of strain DSM14940, budding spores of strain DSM14941, or mixtures of budding spores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, Switzerland) + TX; Pseudozyma aphidis (as disclosed by Yissum Research Development Company, Hebrew University of Jerusalem in WO2011 / 151819) + TX; Saccharomyces cerevisiae, especially strains CNCM1-3936, CNCM1-3937, CNCM1-3938 or CNCM1-3939 (WO 2010 / 086790) from Lesaffre et Compagnie, France + TX;

[0316] Agrobacterium radialis strain K84 (e.g., GALLTROL-A® from AgBioChem, California) + TX, Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN™ from the University of Pretoria) + TX, Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL registry number B-50768, WO 2014 / 028521) (STARGUS® from Marrone BioInnovations) + TX, Bacillus amyloliquefaciens strain FZB42, registry number DSM 23117 (available from ABiTEP, Germany under RHIZOVITAL®) + TX, Bacillus amyloliquefaciens, particularly strain D747 (available from Combinatorial Chemicals Industries under Double Nickel™, with registry number FERM) BP-8234 (US Patent No. 7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (from FMC's QUARTZO® (WG) and PRESENCE® (WP)) + TX, Bacillus licheniformis, particularly strain SB3086, with accession number ATCC 55406, WO 2003 / 000051 (available from Novozymes as ECOGUARD® biofungicide and GREEN RELEAF™) + TX, Bacillus methylotrophicus strain BAC-9912 (from the Chinese Academy of Sciences' Institute of Applied Ecology) + TX, Bacillus mycosis fungi, isolate, with accession number B-30890 (available from Certis USA as BMJ TGAI® or WG and LifeGard™) + TX, Bacillus pumilus, particularly strain GB34 (available from Bayer AG, Germany under YieldShield®) + TX, Bacillus pumilus, particularly strain QST2808 (available from Bayer Crop Science, USA under SONATA®, with registration number NRRL B-30087 and described in US Patent No. 6,245,551 (in Chinese) + TX, Bacillus subtilis CX-9060 from Sertis USA + TX, 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 from BASF AG as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA) + TX, Bacillus subtilis strain GB03 (available from Bayer AG, Germany as Kodiak®) + TX, Bacillus subtilis strain MBI 600 (available from BASF AG as SUBTILEX), with registration number NRRL B-50595, US Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (available from Bion-Tech Ltd., Taiwan, under BIOBAC® WP, registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX, Bacillus amyloliquefaciens variant strain FZB24, with registration number DSM10271 (available from Novozymes under TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX, Bacillus subtilis strain Y1336 (available from Bion-Tech Ltd., Taiwan, under BIOBAC® WP, registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX, Epiphytic Bacillus from BASF AG (WO2016 / 020371) + TX, a *Bacillus polymyxa* plant species from BASF (WO 2016 / 020371) + TX, a *Bacillus* species strain with accession number NRRL B-50972 or NRRL B-67129, WO 2016 / 154297 + TX, *Pseudomonas aeruginosa* strain AFS009 with accession number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations) + TX, *Pseudomonas aeruginosa*, particularly strain MA342 (e.g., CEDOMON®, CERALL®, and CEDRESS® from Bioagri and Koppert) + TX, *Pseudomonas fluorescens* strain A506 (e.g., BLIGHTBAN® A506 from NuFarm) + TX, *Pseudomonas proradix* (e.g., PRORADIX® from Sourcon Padena) + TX, *Streptomyces glaucus* strain K61 (also known as *Streptomyces flavus* strain K61) (accession number DSM7206) (from Verdera's MYCOSTOP®, from BioWorks' PREFENCE®, see Crop Protection 2006, 25, 468-475) + TX, *Streptomyces lidystrophy* strain WYEC108 (also known as *Streptomyces lidystrophy* strain WYCD108US) (from Novozymes' ACTINO-IRON® and ACTINOVATE®) + TX;

[0317] Trichoderma viride strain T11 (IMI352941 / CECT20498) + TX, powdery mildew strain AQ10 with registration number CNCM 1-807 (e.g., AQ 10® from IntrachemBio Italia) + TX, powdery mildew, especially strain AQ 10 (e.g., AQ 10® from IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (as a known product from Syngenta / ChemChina's AFLA-GUARD®) + TX, budding short-stemmed fungi, especially budding spores of strain DSM 14941 + TX, budding short-stemmed fungi, especially budding spores of strain DSM14940 + TX, budding short-stemmed fungi, especially strains DSM14940 and DSM A mixture of budding spores of 14941 (e.g., Botector® from Bio-Film, Switzerland) + TX, *Chaetomium cupreum* (registration number CABI 353812) (e.g., BIOKUPRUM™ from AgriLife) + TX, *Chaetomium globosum* (available from Rivale under RIVADIOM®) + TX, *Cladosporium cladosporioides*, strain H39, with registration number CBS122244, US 2010 / 0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, *Scutellaria*, particularly strain CON / M / 91-8 (registration number DSM9660, e.g., Contans® from Bayer CropScience Biosciences) + TX, Cryptococcus flavescens, strain 3C (NRRL Y-50378) + TX, Dactylaria candida, Dilophosphora alopecuri (available from TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available from Natural Plant Protection under FUSACLEAN®) + TX, Alternaria solani (synonym: Alternaria solani) strain J1446 (e.g., Prestop® from Lallemand) + TX,Clonostachys 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 PlantPathol. 2007, 36(2):95-101) + TX, Clonostachys rosea strain ACM941, especially strain 321U from Adjuvants Plus, such as Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea [Efficacy of Pink Broom Fungus strain ACM941 and fungicide seed treatment for controlling root rot complex in field peas], Can Jour Plant Sci 2003, 83(3): 519-524) disclosed the following strains: Metschnikowia fructticola, especially strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii from BASF (DSM 27859, WO2015 / 067800) + TX, Trichoderma strain ICC 012 (also known as Trichoderma harzianum ICC012), with accession number CABI CCIMI 392716 and Trichoderma gamsii (formerly Trichoderma viride) strain ICC 080, with accession number IMI A mixture of 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. or BIODERMA® from Agrobiosol de Mexico, SA de CV) + TX,Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX, Pseudozymaflocculosa strain PF-A22 UL (available from Plant Products Co., California as SPORODEX® L) + TX, Saccharomyces cerevisiae strain LAS117 cell wall (CEREVISANE® from Lesaffre, ROMEO® from BASF) + TX, Saccharomyces cerevisiae strains CNCM 1-3936, CNCM 1-3937, CNCM 1-3938, CNCM 1-3939 (WO 2010 / 086790) from Lesaffre France + TX, Saccharomyces cerevisiae, especially strain LASO2 (from Agro-Levures et al.) Dérivés) + TX, *Simplicillium lanosoniveum* + TX, strain T34 (e.g., T34 from Biocontrol Technologies SL, Spain) or strain ICC 012 from ISEG + TX, strain WRL-076 (NRRL Y-30842), US Patent No. 7,579,183 + TX, *Talaromyces flavus*, strain V117b + TX, *Trichoderma asperelloides* JM41R (registration No. NRRL B-50759) (from BASF's TRICHO PLUS®) + TX, *Trichoderma*, especially strain SKT-1, with registration No. FERM P-16510 (e.g., from Combinatorial Chemicals Industries' ECO-HOPE®) + TX, *Trichoderma*, especially strain kd (e.g., from Andermatt Biocontrol). Biocontrol's T-Gro + TX, Trichoderma viride strain 77B (from Andermart Biocontrol's T77) + TX, Trichoderma viride strain ATCC 20476 (IMI 206040) + TX, Trichoderma viride strain LC52 (e.g., Tenet from Agrim Technologies Limited) + TX, Trichoderma viride strain LU132 (e.g., Sentinel from Agrim Technologies Limited) + TX,Trichoderma viride strains NMI number V08 / 002388 + TX, Trichoderma viride strains NMI number V08 / 002389 + TX, Trichoderma viride strains NMI number V08 / 002390 + TX, Trichoderma viride strain number V08 / 002387 + TX, Trichoderma viride strain SKT-1 (FERMP-16510), Japanese patent application (Kokai) 11-253151 A + TX, Trichoderma viride strain SKT-2 (FERMP-16511), Japanese patent application (Kokai) 11-253151 A + TX, Trichoderma viride strain SKT-3 (FERM P-17021), Japanese patent application (Kokai) 11-253151 A + TX, Trichoderma viride, especially strain SC1 (registration number CBS 122089, WO 2009 / 116106 and US Patent No. 8,431,120 (from Bi-PA) + TX, *Trichoderma viride*, strain CNCM 1-1237 (e.g., Esquive® WP from Agrauxine, France) + TX, *Trichoderma apicaldos* (e.g., TrichoPlus from BASF) + TX, *Trichoderma galmus* (formerly *Trichoderma viride*) + TX, *Trichoderma galmus* (formerly *Trichoderma galmus*) strain ICC 080 (IMI CC 392151 CABI) (available from Agribairso Mexico as BIODERMA®) + TX, *Trichoderma galmus* strain ICC080 (IMI CC 392151 CABI, e.g., BioDerma from Agribairso Mexico) + TX, *Trichoderma harzianum* + TX, *Trichoderma halbus*, with registration number ATCC28012 + TX, *Trichoderma harzianum* + TX, Trichoderma harzianum rifai T39 (e.g., Trichodex® from Makhteshim, USA) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro) + TX, Trichoderma harzianum strain DB 103 (available from Dagutat Biolab as T-GRO® 7456) + 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 from Mycontrol) + TX,Trichoderma strain IMI 206039 (e.g., Binab TF WP from BINAB Bio-Innovation AB, Sweden) + TX, Trichoderma stolonifera with accession number Ts3550 (e.g., Tricovab from CEPLAC, Brazil) + TX, Trichoderma viride (also known as green broom mold) especially strain GL-21 (e.g., SoilGard from Sertis, USA) + TX, Trichoderma viride strain G-41, formerly known as green broom mold (accession number ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, USA) + 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., *Trianum-P* from Corbett) + TX, *Ulocladium oudemansii* strain U3, with accession number NM 99 / 06216 (e.g., *BOTRY-ZEN®* from Botry-Zen Ltd, New Zealand, and *BOTRYSTOP®* from Bywards) + TX, *Verticillium albo-atrum* (formerly *Verticillium dahliae*) strain WCS850, with accession number WCS850, deposited at the Fungal Culture Centre (e.g., *DUTCH TRIG®* from Tree Care Innovations) + TX, *Verticillium chlamydosporium* + TX;

[0318] A mixture of brown azotobacters and Clostridium pasteurellii (available from Agrinos under INVIGORATE®) + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available from FMC under QUARTZO® (WG) and PRESENCE® (WP)) + TX; *Semen Sesamum indicum* stem nodule, particularly strain ZB-SK-5 + TX; *Azospirillum brasiliensis* (e.g., VIGOR® from KALO) + TX; *Azospirillum lipophilicus* (e.g., VERTEX-IF™ from TerraMax) + TX; *Azotobacter spheroidae*, particularly strain H23 + TX; brown azotobacters, particularly strain ATCC 12837 + TX; *Bacillus amyloliquefaciens* BS27 (registration number NRRL B-5015) + TX. TX, Bacillus amyloliquefaciens, especially strain FZB42 (e.g., RHIZOVITAL® from Abitep GmbH, Germany) + TX, Bacillus amyloliquefaciens, especially strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from BiofilmCrop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, WO2017 / 205258) + TX, Bacillus amyloliquefaciens TJ1000 (available from Novozymes as QUIKROOTS®) + TX, Bacillus cereus member EE128 (NRRL No. B-50917) + TX, Bacillus cereus member EE349 (NRRL No. B-50928) + TX, Bacillus cereus, especially strain BP01 (ATCC # PTA-7542, WO2017 / 205258) 55675, such as MEPICHLOR® from Arysta Lifescience (USA) + TX, Bacillus mycosis fungoides BT155 (NRRL No. B-50921) + TX, Bacillus mycosis fungoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycosis fungoides EE118 (NRRL No. B-50918) + TX, Bacillus mycosis fungoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus, especially strain GB34 (e.g., YIELD SHIELD® from Bayer CropScience, Germany) + TX, Bacillus pumilus, especially strain QST2808 (NRRL No. B-30087) + TX, Bacillus sianniae, especially strain KCTC 13613T + TX. TX, Bacillus subtilis, particularly strain AQ30002 (registration number NRRL B-50421 and described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis strain MBI 600 (e.g., SUBTILEX® from BASF AG) + TX, Bacillus subtilis strain rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available from BASF AG as TEQUALIS®) + TX, Bacillus tekirae strain NII-0943 + TX, Bacillus thuringiensis strain BT013A (NRRL No. B-50924), also known as Bacillus thuringiensis 4Q7 + TX, Slow-growing rhizobium of soybean (e.g., OPTIMIZE® from Novozymes) + TX, Delft acidophilus strain RAY209 (e.g., from Brett Young Seeds' BIOBOOST® + TX, Lactobacillus species (e.g., LACTOPLANT® from LactoPAFI) + TX, Meso- and Slow-growing Rhizobia (e.g., NODULATOR from BASF) + TX, Bacillus polymyxa, especially strain AC-1 (e.g., TOPSEED® from Green Biotechnology Ltd.) + TX, Pseudomonas aeruginosa, especially strain PN1 + TX, Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovarviciae (e.g., NODULATOR from BASF) + TX, Rhizobium leguminosarium biovarviciae, especially strain Z25 (CECT 4585) + TX, Serratia marcescens, especially strain SRM (MTCC 8708) + TX TX, *Rhizobium sinense* strain NRG-185-1 from Bayer Crop Science + TX, *Thiobacillus* species (e.g., CROPAID® from Cropaid Ltd, UK) + TX;

[0319] Varicella salina strain AARC-0255 (e.g., DiTera™ from Valent Biosciences) + TX, Penicillium baicalensis strain ATCC 22348 (e.g., JumpStart® from Acceleron BioAg) + TX, Penicillium baicalensis strain ATCC ATCC20851 + TX, Paecilomyces lilacinus (formerly known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g., BioAct from Bayer CropScience Biosciences) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472, e.g., Polyversum from Bioprepraty, Czech Republic) + TX TX, *Rhizopogon amylopogon* (from Agri-Enterprise, formerly Myco-Sol of Helena Chemical Company) + TX, *Rhizopogon fulvigleba* (e.g., from Agri-Enterprise, formerly Myco-Sol of Helena Chemical Company) + TX, *Rhizopogon vulgaris* strain V117b + TX, *Trichoderma echinococcus* strain (from Plant Health Products, South Africa, Eco-T) + TX, *Trichoderma echinococcus* strain kd (e.g., T-Gro from Andermart Biocontrol) + TX, *Trichoderma viride*, especially strain number V08 / 002387 + TX, *Trichoderma viride* strain CNCM 1-1237 (e.g., Esquive® WP from Aglaucus, France) + TX, Trichoderma viride strain LC52 (also known as Trichoderma viride strain LU132, e.g., Sentinel from Agrim Technology Ltd.) + TX, Trichoderma viride strain NMI number V08 / 002388 + TX, Trichoderma viride strain NMI number V08 / 002389 + TX, Trichoderma viride strain NMI number V08 / 002390 + TX, Trichoderma viride strain SC1 (described in WO 2009 / 116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g., from Andermatt Biocontrol or Corbett's Trianum-P) + TX, Trichoderma harzianum strain TSTh20 + TX, Trichoderma viride strain GI-3 + TXTrichoderma viride strain GL-21 (e.g., SoilGard® from Sertis, Inc., USA) + TX; Trichoderma viride strain B35 (Pietr et al., 1993, Zesz.Nauk.AR w Szczecinie161: 125-137) + TX; Verticillium leuciscinum (formerly Verticillium dahliae) strain WCS850 (CBS 276.92, e.g., Dutch Trig from Tree Care Innovations, Inc.) + TX;

[0320] Agrobacterium radialis strain K84 (Galltrol from Ager Biosciences) + TX, Bacillus amyloliquefaciens, especially strain PTS-4838 (e.g., AVEO from Valencia Biosciences) + TX, Bacillus mycosis fungoides isolate J. (e.g., BmJ from Certis USA) + TX, Bacillus spheroidae, especially serotype H5a5b strain 2362 (strain ABTS-1743) (e.g., VECTOLEX® from Valencia Biosciences) + TX, Bacillus thuringiensis Israel strain BMP 144 (e.g., AQUABAC® from Becker Microbial Products IL, Illinois) + TX, Bacillus thuringiensis subsp. niger strain GC-91 + TX, Bacillus thuringiensis subsp. niger, especially serotype H-7 (e.g., FLORBAC® WG from Valencia Biosciences) + TX TX, Bacillus thuringiensis subsp. Ayusawa, especially strain ABTS-1857 (SD-1372, e.g., XENTARI® from Valencia Biosciences) + TX, Bacillus thuringiensis subsp. Israel (serotype H-14) strain AM65-52 (accession number ATCC1276) (e.g., VECTOBAC® from Valencia Biosciences) + TX, Bacillus thuringiensis subsp. Kurstak strain ABTS 351 + TX, Bacillus thuringiensis subsp. Kurstak strain BMP 123 (from Becker Microbial Products, Illinois, and BARITONE from Bayer Crop Science) + TX, Bacillus thuringiensis subsp. Kurstak strain EG 2348 (from Certis, Inc., USA) + TX, Bacillus thuringiensis subsp. Kurstak strain EG 7841 (from CRYMAX, Certis, Inc., USA) + TX, Bacillus thuringiensis Kurstak subspecies strain HD-1 (e.g., DIPEL® ES from Valencia Biosciences, USA) + TX, Bacillus thuringiensis Kurstak subspecies strain PB 54 + TX, Bacillus thuringiensis Kurstak subspecies strain SA 11 (from Certis Biosciences, USA) + TX, Bacillus thuringiensis Kurstak subspecies strain SA 12 (from Certis Biosciences, USA) + TX, Bacillus thuringiensis Tenebrionibacterium subspecies strain NB 176 (SD-5428, e.g., NOVODOR® FC from BioFa DE, Germany) + TX,Bacillus thuringiensis Colmer variant (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis Japanese variant strain Buibui + TX, Bacillus thuringiensis Kurstak variant strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global) + TX, Bacillus laterosporus + TX, Burkholderia species, especially Burkholderia renogeri strain A396 (also known as Burkholderia renogeri strain MBI 305) (registration numbers NRRL B-50319, WO 2011 / 106491 and WO 2013 / 032693, e.g., MBI206 TGAI and ZELTO® from Maronny BioInnovation) + TX, Chromobacterium Subtsugae, especially strains PRAA4-1T (e.g., MBI-203, such as GRANDEVO® from Maronny BioInnovation) + TX, *Scabiei ve6* (from Cobert's MYCOTAL) + TX, *Paenibacillus popilliae* (formerly *Bacillus popilliae*, such as MILKY SPORE POWDER™ or MILKY SPORE GRANULAR™ from St. Gabriel Laboratories) + TX, *Serratia entomophila* (e.g., INVADE® from Wrightson Seeds) + TX, *Serratia muscaria*, especially strain SRM (accession number MTCC 8708) + TX, *Trichoderma echinococcus* (from Novozymes' TRICHODERMAX) + TX, *Wolbachia* ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX;

[0321] Beauveria bassiana strain ATCC 74040 (e.g., NATURALIS® from IntrachemBio Italia) + TX, Beauveria bassiana strain ATP02 (accession number DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (accession number ATCC74250, e.g., BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074, disclosed in WO 2017 / 066094, Pioneer Hi-Bred International) + TX, Metarhizium anisopliae Roberts 15013-1 (deposited under NRRL accession number 67073) + TX TX, Metarhizium anisopliae 23013-3 (deposited under NRRL accession number 67075) +TX, Paecilomyces lilacinus strain 251 (from MELOCON, Ceres, Inc., USA) +TX;

[0322] Granulovirus (GV) + TX for codling moth (Cydia pomonella), nucleopolyhedrovirus (NPV) + TX for cotton bollworm (Helicoverpa armigera), granulovirus (GV) + TX for summer fruit tortrix (Adoxophyes orana), mNPV + TX for beet armyworm (Spodoptera exigua), and mNPV + TX for fall armyworm (Spodoptera frugiperda).

[0323] Burkholderia species, especially Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigasparora species + TX, Glomus species + TX, Laccaria species + TX, LactoBacillus buchneri + TX, Paraglomus species + TX, Pisolithus tinctorus + TX, Pseudomonas species + TX, Rhizobium species, especially Rhizobium trifolium + TX, Rhizopogon species + TX, Scleroderma species + TX, Streptomyces species + TX, and Suillus species. + TX, Agrobacterium spp. + TX, Azorhizobium caulinodans + TX, Azospirillums pp. + TX, Azotobacter spp. + TX, Bradyrhizobium spp. + TX, Gigasparora monosporum + TX;

[0324] Garlic (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Wormwood + TX, Biokeeper WP + TX, Cruciferous extracts, especially rapeseed powder or mustard powder + TX, Cassia nigricans + TX, Bitter orange vine + TX, Chenopodium anthelminticum + TX, Quinoa saponin extracts from quinoa seeds (e.g., Heads Up® (quinoa saponins) from Heads Up plant Protectants, Canada) + TX, Chitin + TX, Dryopteris filix-mas + TX, Horsetail + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from Stockton, STK) + TX TX, naturally occurring blad peptides extracted from lupin seeds (FRACTURE® from FMC) + TX, naturally occurring blad peptides extracted from lupin seeds (PROBLAD® from Sertis Europe) + TX, pyrethroids + TX, Quassia amara + TX, Quercus + TX, soapberry extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX (from Maronni Bio) + TX, Requiem™ insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryanodine / rennetine + TX, comfrey + TX, artemisia + TX, thymol + TX, thymol mixed with geraniol (CEDROZ from Eden Research) + TX, thymol mixed with geraniol and eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, nettle + TX, veratrine + TX, mistletoe + TX;

[0325] Mercuric oxide + TX, octathione + TX, methyl thiophanate + TX;

[0326] MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperine + TX, 2-isovaleryl indan-1,3-dione + TX, 4-(quinoxalo-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxane-5-yl)-3-hexylcyclohex-2-enone + TX, aramaenobenzene + TX, aramaenobenzene-S-methyl + TX, α-bromadiolone + TX, α-chlorool + TX, aluminum phosphide + TX, anthraquinone + TX, antagonist + TX, arsenic trioxide + TX, barium carbonate + TX, chlorpyrifos + TX, dimethomorph + TX, bromadiolone + TX, bromadiolone + TX, bromadiolone + TX, calcium cyanide + TX, chloralose + TX, chlorpyrifos + TX, cholecalciferol + TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, chlorpyrifos + TX, cyprodinil + TX, cyprodinil + TX, pyrimethanil + TX, cyprodinil + TX, diazinon + TX, allyl oxychloride + TX, dicyclopentadiene + TX, cyprodinil + TX, thiamethoxam + TX, phosmet + TX, calciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenchlordine + TX, flufenoxuron + TX, fluoroacetamide + TX, flufenoxuron + TX, flufenoxuron hydrochloride + TX, flufenoxuron + TX, fenchlordine + TX, fenchlordine oxime + TX, cyprodinil + TX, γ-HCH + TX, Biguanide Octyl Salt + TX, Biguanide Octyl Acetate + TX, HCH + TX, Hydrogen Cyanide + TX, Imanin + TX, Iodomethyl + TX, Isoxafen (including isoxadifen-ethyl) + TX, Lindane + TX, Magnesium Phosphide + TX, MB-599 + TX, Mefenpyr (including mefenpyr-diethyl) + TX, Mefensulfonamide + TX, Carbendazim + TX, Methyl Bromomethyl + TX, Nerolidol + TX, Sodium Chloride + TX, Petroleum Oil + TX, Ratphosphide + TX, Phosphine + TX, Phosphate + TX, Warfarin + TX, Piperyl Butyl Ether + TX, Synergistic Aldehyde + TX, Potassium Arsenite + TX, Thiamethoxam + TX, Propyl Isomer + TX, Pyridine-4-amine + TX, rodenticide + TX, Polygonum cuspidatum extract + TX, ribavirin +TX, S421 + TX, onion glycoside + TX, synergistic powder + TX, sesamin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, silane + TX, mixed carbendazim + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiram + TX.

[0327] Additionally, the compositions of the present invention can be administered in combination with one or more systemically acquired resistance inducers (“SAR” inducers). SAR inducers are known and described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer aramid-benzene-S-methyl.

[0328] Compounds having formula (I) as defined in this invention are typically used in the form of compositions and can be applied simultaneously or sequentially to crop areas or crops to be treated, along with other compounds. These other compounds may, for example, be fertilizers or micronutrient donors or other formulations that influence plant growth. They may also be selective or non-selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these formulations, if desired, along with additional carriers, surfactants, or application-promoting adjuvants commonly used in the field of formulations.

[0329] Compounds having formula (I) as defined in this invention can be used in the form of (fungicide) compositions for controlling or protecting against plant pathogenic microorganisms, which contain at least one compound having formula (I) as defined in this invention or at least one preferred single compound as defined above as an active ingredient (in free form or in the form of an agrochemically available salt), and contain at least one of the above-described adjuvants.

[0330] Therefore, the present invention provides compositions comprising at least one compound having formula (I) as defined in the present invention, an agriculturally acceptable carrier, and optionally an adjuvant, preferably a fungicidal composition. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to comprising a compound having formula (I) as defined in the present invention, the composition may also comprise at least one or more pest-killing compounds, such as additional fungicidal active ingredients.

[0331] Another aspect of the invention relates to a method for controlling or preventing the infection of plants (e.g., useful plants, such as crop plants), their propagation material (e.g., seeds), harvested crops (e.g., harvested food crops), or inanimate materials by plant pathogenic microorganisms or putrefactive microorganisms or potentially harmful organisms (especially fungal organisms), the method comprising applying as an active ingredient a compound having formula (I) as defined in this invention or a preferred single compound as defined above to these plants, parts of these plants or their sites, their propagation material, or any part of these inanimate materials.

[0332] Control or prevention means reducing the infestation of insect or plant pathogenic microorganisms or putrefactive microorganisms or potentially harmful organisms (especially fungal organisms) to a level that has been proven to be improved.

[0333] A preferred method for controlling or preventing crop infection by plant pathogenic microorganisms (especially fungal organisms) is foliar application, which includes applying a compound of formula (I) as defined in this invention, or an agricultural chemical composition containing at least one of said compounds. The frequency and rate of application will depend on the risk of infection by the corresponding pathogen or insect. However, compounds of formula (I) as defined in this invention can also penetrate the plant via the soil through the roots (systemic action) by soaking the plant in a liquid formulation or by applying the compound in solid form, such as in granular form, to the soil (soil application). In rice crops, such granules can be applied to irrigated paddy fields. Compounds of formula (I) as defined in this invention can also be applied to seeds by soaking the seeds or tubers in a liquid formulation of a fungicide or by coating them with a solid formulation (coating).

[0334] Formulations (e.g., compositions containing compounds of formula (I) as defined in this invention, and (if desired) solid or liquid adjuvants or monomers for encapsulating compounds of formula (I) as defined in this invention) can be prepared in a known manner, typically by closely mixing and / or grinding the compound with a compensator (e.g., a solvent, a solid carrier, and optionally a surfactant compound).

[0335] The methods of application of these compositions, i.e., methods for controlling pathogens of the aforementioned types, such as spraying, atomizing, dusting, brushing, coating, broadcasting, or irrigating—selected to suit the intended purpose in general circumstances—and the use of these compositions for controlling pathogens of the aforementioned types are other subjects of the invention. Typical concentration ratios are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm of active ingredient. The application rate per hectare is preferably 1 g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g / ha, and most preferably 10 to 600 g / ha. When used as a seed soaking agent, a convenient dosage is 10 mg to 1 g of active substance / kg of seeds.

[0336] When the combination of the present invention is used to treat seeds, an application rate of 0.001 to 50 g of the compound of formula (I) per kg of seeds, preferably 0.01 to 10 g per kg of seeds, is generally sufficient.

[0337] Appropriately, compositions according to the invention comprising compounds having formula (I) as defined in the invention may be applied preventively (meaning before the development of the disease) or therapeutically (meaning after the development of the disease).

[0338] The compositions of the present invention can be used in any conventional form, for example, as a double-packaged powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspension emulsion (SE), a capsule suspension (CS), water-dispersible particles (WG), emulsifiable particles (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), an oil dispersant (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical grade (TK), a dispersible concentrate (DC), a wettable powder (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0339] Such compositions can be produced in conventional ways, such as by mixing the active ingredient with appropriate formulation inert agents (diluents, solvents, fillers, and optionally other formulation components, such as surfactants, biocides, antifreeze agents, adhesives, thickeners, and compounds that provide auxiliary effects). Conventional sustained-release formulations designed for long-term sustained efficacy can also be used. In particular, formulations intended for application 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, and other compounds that provide auxiliary effects, such as condensations of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0340] Using the combination and diluent of the present invention, the seed dressing formulation is applied to seeds in a suitable seed dressing formulation form, such as an aqueous suspension or dry powder having good adhesion to seeds, in a manner known per se. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as sustained-release capsules or microcapsules.

[0341] Typically, formulations comprise 0.01% to 90% by weight of the active ingredient, 0% to 20% of an agriculturally acceptable surfactant, and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the surfactant being a compound having formula (I) as defined in this invention, together with components (B) and (C), and optionally other active agents (particularly microbicides, preservatives, or the like). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of the active agent. Application forms of the formulation may, for example, contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0342] However, it is preferable to formulate commercial products as concentrates, while end users will typically use diluted formulations. Example

[0343] The following examples illustrate the invention. Some compounds of the present invention differ from known compounds in that they exhibit greater efficacy at lower dosage rates, which can be verified by those skilled in the art using the experimental procedures outlined in the examples.

[0344] Formulation Examples

[0345]

[0346] The active ingredient and excipients are thoroughly mixed and the mixture is thoroughly ground in a suitable grinder to provide a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0347]

[0348] The active ingredients and adjuvants are thoroughly mixed and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0349]

[0350] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0351]

[0352] Ready-to-use powders are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. These powders can also be used in the dry mixing of seeds.

[0353]

[0354] The active ingredient and excipients are mixed and ground, and the mixture is moistened with water. The mixture is then extruded and dried in an air stream.

[0355]

[0356] The finely ground active ingredient is evenly applied to kaolin clay moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0357] Suspension Concentrates

[0358]

[0359] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation material can be treated and protected from microbial contamination by spraying, watering, or immersion.

[0360] Flowable Concentrates for Seed Treatment

[0361]

[0362] Finely ground active ingredients are tightly mixed with excipients to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation material can be treated and protected from microbial contamination by spraying, watering, or immersion.

[0363] Capsule Suspensions for Slow Release

[0364] A mixture of 28 parts of compounds having formula (I) was mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water was added to this emulsion. The mixture was stirred until polymerization was complete.

[0365] The obtained capsule suspension was stabilized by adding 0.25 parts thickener and 3 parts dispersant. This capsule suspension formulation contains 28% active ingredient. The diameter of the media capsules is 8-15 micrometers.

[0366] The resulting formulation is applied to the seeds as an aqueous suspension in a suitable apparatus for this purpose.

[0367] Analytical Methods:

[0368] Throughout this specification, temperatures are given in degrees Celsius (°C) and "mp." indicates melting point. LC / MS refers to liquid chromatography-mass spectrometry, and the apparatus and methods are described below:

[0369] Method A :

[0370] Equipment: Shimadzu LCMS 2020 mass spectrometer; Column: HALO C18 2.7 µm, 3.0 mm × 30 mm; Mobile phase: MeCN (containing 0.05% HCOOH or 0.05% TFA) - water (containing 0.05% HCOOH or 0.05% TFA); Gradient: MeCN from 5% to 95% in 1.4 min, hold for 0.6 min, total run time 2.5 min; Flow rate: 1.8 mL / min; Column temperature: 50°C; Wavelengths: 214 and 254 nm PDA.

[0371] Table A below summarizes the compounds having formula (I):

[0372] - LC / MS data, such as retention time (RT), [M+H] + ,

[0373] - The type of the method, and / or

[0374] - Melting point (mp).

[0375] Table A:

[0376]

[0377] Example 1 : Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro- 1,2,4-oxadiazol-3-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 6) Step A: Preparation of 6-bromo-4-methyl-lH-benzimidazole

[0378] (Compound 6)

[0379] Step B: Preparation of 7-methyl-3H-benzimidazole-5-carbonitrile

[0380]

[0381] 5-Bromo-3-methyl-phenyl-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 a saturated aqueous solution of NaHCO3 and extracted with dichloromethane. The combined organic phases were washed with brine, dried over sodium sulfate, and concentrated to obtain 6-bromo-4-methyl-1H-benzimidazole.

[0382] LC-MS (Method A): Rt 0.81 min, m / z = 211 / 213 [M+H] +

[0383] Step C: Preparation of [ethoxy-(7-methyl-3H-benzimidazol-5-yl)methylidene]ammonium chloride (Intermediate II)

[0384]

[0385] 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)palladium (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 N2 atmosphere and reflux for 4 hours. After cooling to ambient temperature, the mixture was filtered through diatomaceous earth 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 silica gel column chromatography (dichloromethane / MeOH, 10:1 to 8:2) to obtain 7-methyl-3H-benzimidazole-5-carboxynitrile as a yellow solid.

[0386] LC-MS (Method A): Rt 1.02 min, m / z = 158 [M+H] +

[0387] Step D: Preparation of 4-(4-fluoro-3-methoxy-phenyl)-3-(7-methyl-3H- benzimidazol-5-yl)-5,6-dihydro- 1,2,4-oxadiazole

[0388] (Intermediate I1)

[0389] HCl (g) was bubbled through a stirred solution of 7-methyl-3H-benzimidazol-5-carboxynitrile (1.00 g, 6.36 mmol) in EtOH (15.00 mL) for 50 minutes, while maintaining the temperature of the stirred solution between 10°C and 20°C. The mixture was then stirred at room temperature for 16 hours. The mixture was concentrated under reduced pressure, and the crude product was ground together with methyl tert-butyl ether and filtered to provide [ethoxy-(7-methyl-3H-benzimidazol-5-yl)methylene]ammonium chloride (intermediate I1).

[0390] LC-MS (Method A): Rt 0.40 min, m / z = 204 (M-Cl+H) +

[0391] Step E: Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro- 1,2,4-oxadiazol-3-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 6) Example 2: Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro- 1,2,4-oxadiazol-3-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 2)

[0392]

[0393] Under a nitrogen atmosphere, O-[2-(4-fluoro-3-methoxy-aniline-5-yl)methylene]ammonium chloride (intermediate I1, 0.800 g, 3.94 mmol) was added to a solution of [ethoxy-(7-methyl-3H-benzimidazol-5-yl)methylene]ammonium chloride (intermediate I1, 0.800 g, 3.94 mmol) in acetic acid (12.0 mL). The mixture was heated at 80°C for 8 hours. The resulting mixture was then adjusted to pH 7–8 with a saturated aqueous solution of NaHCO3 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 silica gel column chromatography (dichloromethane / MeOH, 100:0 to 93:7) to give 4-(4-fluoro-3-methoxy-phenyl)-3-(7-methyl-3H-benzimidazol-5-yl)-5,6-dihydro-1,2,4-oxadiazine as a yellow solid.

[0394] LC-MS (Method A): Rt 0.80 min, m / z = 341 [M+H] +

[0395] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ = 12.55 (s, 1 H), 8.17 (s, 1 H), 7.34 (s, 1 H), 7.06 (s, 1 H), 6.96 (dd, J = 11.2, 8.6 Hz, 1 H), 6.51 - 6.45 (m, 1H), 6.12 (dd, J = 9.8, 4.8 Hz, 1 H), 4.16 - 4.11 (m, 2 H), 3.85 - 3.81 (m, 2H), 3.65 (s, 3 H), 2.42 (s, 3 H).

[0396] Step A: Preparation of 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazol-5-yl)- 5,6-dihydro- 1,2,4-oxadiazole Step B: Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro- 1,2,4-oxadiazol-3-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 2)

[0397] Copper(I) (1.35 g, 9.40 mmol) was added to a solution of 4-(4-fluoro-3-methoxy-phenyl)-3-(7-methyl-3H-benzimidazol-5-yl)-5,6-dihydro-1,2,4-oxadiazine (0.800 g, 2.35 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-2-pyridyl]carbamate (1.31 g, 4.70 mmol) in MeOH (16.0 mL). The mixture was stirred at room temperature under an O2 atmosphere for 24 hours. The mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 97:3). The purified material was further purified by grinding with acetonitrile to obtain N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a grayish-white solid.

[0398] LC-MS (Method A): Rt 1.10 min, m / z = 491 [M+H] +

[0399] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ = 10.54 (s, 1 H), 8.49 (s, 1 H), 8.41 (d, J = 2.6 Hz, 1 H), 8.04 (d, J = 8.8 Hz, 1 H), 7.81 (dd, J = 8.8, 2.6 Hz, 1H), 7.29 (s, 1 H), 7.16 (s, 1 H), 7.02 - 6.90 (m, 2 H), 6.49 (dt, J = 8.6,3.6 Hz, 1 H), 4.18 - 4.05 (m, 2 H), 3.86 - 3.77 (m, 2 H), 3.74 (s, 3 H), 3.66 (s, 3 H), 2.49 (s, 3 H).

[0400] Example 3: Preparation of methyl N-[5-[6-[l-(4-fluoro-3-methoxy-phenyl)imidazol- 2-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 5) Step A: Preparation of l-(4-fluoro-3-methoxy-phenyl)imidazole

[0401] (Compound 2)

[0402] Step B: Preparation of methyl N-[5-[6-[l-(4-fluoro-3-methoxy-phenyl)imidazol- 2-yl]-4-methyl-benzimidazol- 1 -yl]-2-pyridinyl]carbamate (Compound 5) ​

[0403]

[0404] Under N2, O-[2-(4-fluoroanilino)ethyl]hydroxylamine (0.703 g, 4.13 mmol) was added to a solution of [ethoxy-(7-methyl-3H-benzimidazol-5-yl)methylene]ammonium chloride (intermediate I1, 1.20 g, 4.13 mmol) in acetic acid (15.0 mL). 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 silica gel column chromatography (eluting with MeOH / dichloromethane, 2% to 10%) to give 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazol-5-yl)-5,6-dihydro-1,2,4-oxadiazine as a white solid.

[0405] LC-MS (Method A): Rt 0.76 min, m / z = 311 [M+H] +

[0406] ​ ​

[0407] Copper(I) (0.968 g, 6.77 mmol) was added to a solution of 4-(4-fluorophenyl)-3-(7-methyl-3H-benzimidazol-5-yl)-5,6-dihydro-1,2,4-oxadiazine (0.300 g, 0.64 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-2-pyridyl]carbamate (0.816 g, 2.93 mmol) in MeOH (15.0 mL). The mixture was stirred at room temperature under an O2 atmosphere for 18 hours. The mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 95:5) to obtain N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazine-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a white solid.

[0408] LC-MS (Method A): Rt 0.93 min, m / z = 461 [M+H] +

[0409] 1 H-NMR (400 MHz, DMSO-d 6, ppm) δ = 10.56 (s, 1 H), 8.49 (s, 1 H), 8.41 (d, J = 2.7 Hz, 1 H), 8.04 (d, J = 8.9 Hz, 1 H), 7.86 (dd, J = 8.9, 2.7 Hz, 1H), 7.27 (s, 1 H), 7.12 (s, 1 H), 7.08 - 6.99 (m, 4 H), 4.12 - 4.09 (m, 2 H), 3.80 - 3.78 (m, 2 H), 3.74 (s, 3 H), 2.47 (s, 3 H).

[0410] ​ ​

[0411] (Compound 5)

[0412] ​

[0413]

[0414] At 25°C, imidazole (1.83 g, 26.8 mmol), K₂CO₃ (3.53 g, 25.6 mmol), copper iodide (0.464 g, 2.44 mmol), and pentyl-2,4-dione (0.610 g, 6.10 mmol) were added to a solution of 4-bromo-1-fluoro-2-methoxy-phenylbenzene (5.00 g, 24.4 mmol) in 1-methylpyrrolidone (50.0 mL). The mixture was heated at 120°C for 12 hours. After conversion, the resulting mixture was diluted with water 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 silica gel column chromatography (dichloromethane / MeOH, 100:0 to 96:4) to give 1-(4-fluoro-3-methoxy-phenyl)imidazole as a colorless oil.

[0415] LC-MS (Method A): Rt 0.54 min, m / z = 193 [M+H] +

[0416] Step B: 2-[(6-bromo-4-methyl-benzimidazol-1-yl)methoxy]ethyl-trimethyl-silane (intermediate I2) Preparation

[0417] (Intermediate I2)

[0418] NaH (60.0%, 2.50 g, 62.5 mmol) was slowly added to a solution of 6-bromo-4-methyl-1H-benzimidazole (11.0 g, 52.1 mmol) in anhydrous THF (150 mL) at 0°C under a nitrogen atmosphere. After addition, the solution was stirred at 0°C for 30 minutes. Then, 2-(chloromethoxy)ethyl-trimethylsilane (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 a saturated aqueous solution of NH4Cl 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 silica gel column chromatography (dichloromethane / MeOH, 100:0 to 96:4) to give 2-[(6-bromo-4-methyl-benzimidazol-1-yl)methoxy]ethyl-trimethyl-silane as a brown oil.

[0419] LC-MS (Method A): Rt 0.24 min, m / z = 341 [M+H] +

[0420] Step C: 2-[[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]methyl Preparation of oxyethyl-trimethyl-silane

[0421]

[0422] Under a nitrogen atmosphere at -78°C, n-BuLi (2.5 M, 4.5 mL, 11.2 mmol in hexane) was added dropwise to a solution of 1-(4-fluoro-3-methoxy-phenyl)imidazole (1.80 g, 9.37 mmol) in anhydrous THF (20.0 mL). After addition, the solution was stirred at -78°C for 30 minutes. Then, zinc chloride (2.55 g, 18.7 mmol) in anhydrous THF (20.0 mL) was added dropwise. The solution was stirred at -78°C for 30 minutes. Then, at room temperature under a N2 atmosphere, a solution of 2-[(6-bromo-4-methyl-benzimidazol-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) were added. The reaction was heated at 100°C for 12 hours. The final mixture was quenched with a saturated aqueous NH4Cl solution and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 97:3) to give 2-[[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane as a yellow solid.

[0423] LC-MS (Method A): Rt 0.97 min, m / z = 453 [M+H] +

[0424] Step D: Preparation of 6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-1H-benzimidazole

[0425]

[0426] At room temperature, 2,2,2-trifluoroacetic acid (4.59 g, 40.2 mmol) was added dropwise to a solution of 2-[[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane (1.30 g, 2.01 mmol) in dichloromethane (30 mL). The solution was stirred at room temperature for 4 hours. After completion, the reaction mixture was adjusted to pH 9 with saturated aqueous NaHCO3 solution. The phases were separated, and the organic layer was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 98:2 to 96:4) to give 6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-1H-benzimidazole as a brown solid.

[0427] LC-MS (Method A): Rt 0.77 min, m / z = 323 [M+H] +

[0428] Step E: N-[5-[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazole-1- Preparation of methyl [2-pyridyl]carbamate (compound 5)

[0429] Copper(I) (337 mg, 2.36 mmol) was added to a solution of 6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-1H-benzimidazole (190 mg, 0.589 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)-2-pyridyl]carbamate (246 mg, 0.884 mmol) in MeOH (15.0 mL). The mixture was stirred at room temperature under an O2 atmosphere for 36 hours. The mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 95:5) to give N-[5-[6-[1-(4-fluoro-3-methoxy-phenyl)imidazol-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a grayish-white solid.

[0430] LC-MS (Method A): Rt 0.93 min, m / z = 473 [M+H] +

[0431] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ =10.52 (s, 1 H), 8.51 (s, 1 H), 8.43 (d, J = 2.7 Hz, 1 H), 8.00 (d, J = 8.9 Hz, 1 H), 7.71 (dd, J = 8.9, 2.8 Hz, 1H), 7.47 (d, J = 1.3 Hz, 1 H), 7.33 (s, 1 H), 7.30 - 7.19 (m, 2 H), 7.15 (d,J = 1.3 Hz, 1 H), 7.10 (d, J = 1.6 Hz, 1 H), 6.83 - 6.73 (m, 1 H), 3.75 (d, J= 3.1 Hz, 6H), 2.53 (s, 3H).

[0432] Example 4: N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole Preparation of methyl 1-azolyl]-2-pyridyl]carbamate (compound 7)

[0433] (Compound 7)

[0434] Step A: Preparation of methyl 7-methyl-3H-benzimidazole-5-carboxylate

[0435]

[0436] 6-Bromo-4-methyl-1H-benzimidazole (1.00 g, 4.74 mmol), MeOH (10.0 mL), 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloromethane complex (0.384 g, 0.474 mmol), and N,N-diethylethylamine (1.44 g, 14.2 mmol) were charged into a 25 mL autoclave. The autoclave was then purged with argon, sealed, and pressurized to 2.5 MPa with carbon monoxide. The reaction 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 silica gel column chromatography (petroleum ether / ethyl acetate, 1:1 to 1:2) to obtain methyl 7-methyl-3H-benzimidazole-5-carboxylate as a brown solid.

[0437] LC-MS (Method A): Rt 0.70 min, m / z = 191 [M+H] +

[0438] Step B: Preparation of 7-methyl-3H-benzimidazole-5-carbonylhydrazide (intermediate I3)

[0439] (Intermediate I3)

[0440] 7-Methyl-3H-benzimidazole-5-carboxylate (7.00 g, 36.8 mmol) was added to NH2NH2 . The reaction mixture was stirred in a solution of 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 give 7-methyl-3H-benzimidazole-5-carbonylhydrazide (intermediate I3) as a yellow solid.

[0441] LC-MS (Method A): Rt 0.25 min, m / z = 190 [M+H] +

[0442] Step C: Preparation of 2-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole

[0443]

[0444] Diethoxymethoxyethane (0.210 mL, 1.26 mmol) and ammonium hydrochloride (0.0169 g, 0.315 mmol) were added to a solution of 7-methyl-3H-benzimidazol-5-carbazide (intermediate I3, 0.200 g, 1.05 mmol) in anhydrous EtOH (10.0 mL). 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 to 90:10) to obtain 2-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole as a yellow solid.

[0445] LC-MS (Method A): Rt 0.57 min, m / z = 201 [M+H] +

[0446] Step D: 6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole preparation

[0447]

[0448] 4-fluoro-3-methoxy-aniline (818 mg, 5.79 mmol) was added to a stirred solution of 2-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole (580 mg, 2.90 mmol) in acetic acid (15.00 mL). The reaction was then stirred at 115°C for 5 hours. The reaction mixture was concentrated under reduced pressure and diluted with ethyl acetate (80 mL). The combined organic phases were washed with saturated sodium bicarbonate, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 98:2 to 90:10) to give 6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazol as a light brown solid.

[0449] LC-MS (Method A): Rt 0.89 min, m / z = 324 [M+H] +

[0450] Step E: N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole Preparation of methyl 1-[-1-yl]-2-pyridyl]carbamate

[0451] Copper(I) (0.761 g, 5.32 mmol) was added to a solution of 6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (0.430 g, 1.33 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)-2-pyridyl]carbamate (0.740 g, 2.66 mmol) in MeOH (10.00 mL). The mixture was stirred at room temperature under an O2 atmosphere for 16 hours and then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 95:5), and then further purified by grinding with n-hexane to obtain N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a grayish-white powder.

[0452] LC-MS (Method A): Rt 1.03 min, m / z = 474 [M+H] +

[0453] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ = 10.54 (s, 1 H), 8.83 (s, 1 H), 8.58(s, 1 H), 8.46 (d, J = 2.4 Hz, 1 H), 8.01 (d, J = 8.9 Hz, 1 H), 7.76 (dd, J =8.9, 2.7 Hz, 1 H), 7.43 (dd, J = 7.6, 2.4 Hz, 1 H), 7.37 (s, 1 H), 7.30 (dd,J = 11.1, 8.6 Hz, 1 H), 7.23 (s, 1 H), 6.98 - 6.82 (m, 1 H), 3.75 (s, 3 H), 3.74 (s, 3 H), 2.56 (s, 3 H).

[0454] Example 5: N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-phenyl] Preparation of methyl imidazole-1-yl]-2-pyridyl]carbamate (compound 9)

[0455]

[0456] Step A: Preparation of 2-methyl-5-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole (intermediate I4)

[0457] (Intermediate I4)

[0458] At room temperature, trimethyl orthoacetate (1.43 g, 11.8 mmol) and NH4Cl (0.127 g, 2.37 mmol) were added to a stirred solution of 7-methyl-3H-benzimidazol-5-carbazide (intermediate I3, 1.50 g, 7.89 mmol) in anhydrous EtOH (60.0 mL). The reaction mixture was stirred at 80°C for 2 hours. The mixture was then concentrated under reduced pressure, and the residue was diluted with water and filtered. The solid was washed with water to give 2-methyl-5-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole (intermediate I4) as a brown solid.

[0459] LC-MS (Method A): Rt 0.66 min, m / z = 215 [M+H] +

[0460] Step B: 6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzo[] Preparation of imidazole

[0461]

[0462] Add 4-fluoro-3-methylaniline (0.701 g, 5.60 mmol) to a solution of 2-methyl-5-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole (intermediate I4, 600 mg, 2.80 mmol) in AcOH (7.00 mL). Stir the mixture at 115°C for 3 hours. Quench the reaction with a saturated aqueous solution of Na₂CO₃, and extract the mixture with dichloromethane. Wash the combined layers with saturated NaCl, dry over sodium sulfate, and concentrate under reduced pressure. Purify the crude residue by rapid chromatography (dichloromethane / MeOH, 95:5) to obtain 6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole as a yellow solid.

[0463] LC-MS (Method A): Rt 0.80 min, m / z = 322 [M+H] +

[0464] Step C: N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-phenyl] Preparation of methyl imidazole-1-yl]-2-pyridyl]carbamate (compound 9)

[0465] Copper(I) (0.980 g, 6.85 mmol) was added to a solution of 6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (550 mg, 1.71 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)-2-pyridyl]carbamate (0.714 g, 2.57 mmol) in MeOH (7.00 mL). The mixture was stirred at 25°C under an O2 atmosphere for 16 hours. The reaction mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 95:5), and then further purified by grinding in n-hexane to obtain N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a white solid.

[0466] LC-MS (Method A): Rt 0.92 min, m / z = 473 [M+H] +

[0467] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ = 10.56 (s, 1 H), 8.54 (s, 1 H), 8.37 (d, J = 2.6 Hz, 1 H), 8.01 (d, J = 8.9 Hz, 1 H), 7.61 (dd, J = 8.9, 2.7 Hz, 1H), 7.50 (s, 1 H), 7.49-7.47 (m, 1 H), 7.25 (dd, J = 7.9, 4.6 Hz, 2 H), 6.90 (s, 1 H), 3.75 (s, 3 H), 2.56 (s, 3 H), 2.24 (s, 3 H), 2.22 (s, 3 H).

[0468] Example 6: N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl- Preparation of methyl benzimidazol-1-yl]-2-pyridyl]carbamate (compound 11)

[0469] (Compound 11)

[0470] Step A: 6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzene Preparation of imidazole

[0471]

[0472] 4-fluoro-3-methoxy-aniline (0.198 g, 1.40 mmol) was added to a stirred solution of 2-methyl-5-(7-methyl-3H-benzimidazol-5-yl)-1,3,4-oxadiazole (intermediate I4, 0.200 g, 0.934 mmol) in acetic acid (5 mL). The reaction 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 silica gel column chromatography (dichloromethane / MeOH, 98:2 to 90:10) to give 6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole as a light brown solid.

[0473] LC-MS (Method A): Rt 0.82 min, m / z = 338 [M+H] +

[0474] Step B: N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl- Preparation of methyl benzimidazol-1-yl]-2-pyridyl]carbamate (compound 11)

[0475] Copper(I) (0.0933 g, 0.652 mmol) was added to a solution of 6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (0.110 g, 0.326 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)-2-pyridyl]carbamate (136 mg, 0.489 mmol) in MeOH (4.00 mL). The mixture was stirred at room temperature under an O2 atmosphere for 16 hours. The reaction mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 95:5) to give N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate.

[0476] LC-MS (Method A): Rt 1.03 min, m / z = 488 [M+H] +

[0477] 1 H-NMR (400 MHz, DMSO-d 6, ppm) δ = 10.54 (s, 1 H), 8.55 (s, 1 H), 8.43 (d, J = 2.7 Hz, 1 H), 8.02 (d, J = 8.7 Hz, 1 H), 7.69 (dd, J = 8.9, 2.7 Hz, 1H), 7.48-7.37 (m, 2 H), 7.35-7.26 (m, 1 H), 7.10 (s, 1 H), 6.98-6.96 (m, 1H), 3.76 (s, 3 H), 3.75 (s, 3 H), 2.55 (s, 3 H), 2.24 (s, 3 H).

[0478] Example 7: N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole] Preparation of methyl 1-[azol-1-yl]-2-pyridyl]carbamate (compound 1)

[0479] (Compound 1)

[0480] Step A: Preparation of 1-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazole

[0481]

[0482] A mixture of (4-fluoro-3-methoxy-phenyl)hydrazine hydrochloride (CAS 327021-81-8, 1.70 g, 8.83 mmol) in formamide (9.0 mL) was heated at 120°C under a nitrogen atmosphere for 16 hours. The resulting mixture was then diluted with water 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 silica gel column chromatography (petroleum ether / ethyl acetate, 100:0 to 55:45) to give 1-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazole as an off-white solid.

[0483] LC-MS (Method A): Rt 0.99 min, m / z = 194 [M+H] +

[0484] Step B: 2-[[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole- Preparation of 1-yl]methoxy]ethyl-trimethyl-silane

[0485]

[0486] Under a nitrogen atmosphere at -78°C, n-BuLi (2.5 M, 3.0 mL, 7.45 mmol in hexane) was added dropwise to a solution of 1-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazole (1.20 g, 6.21 mmol) in anhydrous THF (20.0 mL). After addition, the solution was stirred at -78°C for 30 minutes. Then, zinc dichloride (1.69 g, 12.4 mmol) in anhydrous THF (20.0 mL) was added dropwise. After addition, the solution was stirred at -78°C for 30 minutes. Then, 2-[(6-bromo-4-methyl-benzimidazol-1-yl)methoxy]ethyl-trimethyl-silane (intermediate I2, 2.12 g, 6.21 mmol) and Pd(PPh3)4 (0.718 g, 0.621 mmol) were added to toluene (20.0 mL) at room temperature under a nitrogen atmosphere. The reaction was heated at 100°C for 12 hours. The reaction was then quenched with a saturated aqueous solution of NH4Cl and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 98:2) to give 2-[[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane as a yellow solid.

[0487] LC-MS (Method A): Rt 1.77 min, m / z = 454 [M+H] +

[0488] Step C: 6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole preparation

[0489]

[0490] A mixture of 2-[[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole-1-yl]methoxy]ethyl-trimethyl-silane (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 ~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 silica gel column chromatography (dichloromethane / MeOH, 100:0 to 90:10) to give 6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole as a brown solid.

[0491] LC-MS (Method A): Rt 0.85 min, m / z = 324 [M+H] +

[0492] Step D: N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazole Preparation of methyl 1-[azol-1-yl]-2-pyridyl]carbamate (compound 1)

[0493] N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)-2-pyridyl]carbamate (0.387 g, 1.39 mmol) and copper(I) oxide (0.531 g, 3.71 mmol) were added to a solution of 6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-1H-benzimidazole (0.300 g, 0.928 mmol) in anhydrous MeOH (8.0 mL). The mixture was stirred at room temperature under an O2 atmosphere for 24 hours. The mixture was then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure. The crude residue was purified by silica gel column chromatography (dichloromethane / MeOH, 100:0 to 97:3), and then further purified by grinding with acetonitrile to obtain N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a grayish-white solid.

[0494] LC-MS (Method A): Rt 1.11 min, m / z = 474 [M+H] +

[0495] 1 H-NMR (400 MHz, DMSO-d 6, ppm) δ = 10.54 (s, 1 H), 8.60 (s, 1 H), 8.46 (d, J = 2.4 Hz, 1 H), 8.22 (s, 1 H), 8.01 (d, J = 8.8 Hz, 1 H), 7.79 (dd, =8.8, 2.6 Hz, 1 H), 7.38 (d, J = 7.8 Hz, 2 H), 7.33 - 7.25 (m, 2 H), 6.91 (dt,J = 8.4, 3.4 Hz, 1 H), 3.75 (d, J = 5.6 Hz, 6 H), 2.56 (s, 3 H).

[0496] Example 8: N-[5-[6-[3-(4-cyano-3-methoxy-phenyl)pyrazin-2-yl]-4-methyl-benzimidazole-1- Methyl [2-pyridyl]carbamate (compound 12)

[0497] (Compound 12)

[0498] Step A: Preparation of 6-bromo-4-methyl-1H-benzimidazole

[0499]

[0500] 5-Bromo-3-methyl-phenyl-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 a saturated aqueous solution of NaHCO3 and extracted with dichloromethane. The combined organic phases were washed with brine, dried over sodium sulfate, and concentrated to obtain 6-bromo-4-methyl-1H-benzimidazole.

[0501] LC-MS (Method A): Rt 0.81 min, m / z = 211 / 213 [M+H] +

[0502] Step B: 5-(6-bromo-4-methyl-benzimidazol-1-yl)pyridin-2-amine

[0503]

[0504] A mixture of 6-bromo-4-methyl-1H-benzimidazole (1.00 g, 4.74 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)pyridine-2-amine (0.84 g, 7.12 mmol), copper(II) acetate (1.32 g, 7.12 mmol), boric acid (0.59 g, 9.5 mmol), and N,N-diisopropylethylamine (1.6 mL, 9.5 mmol) was added to acetonitrile, purged with air, and then 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 resulting crude material was purified by column chromatography (1%–20% methanol in ethyl acetate) to obtain 5-(6-bromo-4-methyl-benzimidazole-1-yl)pyridine-2-amine as a brown solid.

[0505] LC-MS (Method A): Rt 1.12 min, m / z = 303 / 305 [M+H] +

[0506] Step C: Methyl N-[5-(6-bromo-4-methyl-benzimidazol-1-yl)-2-pyridyl]carbamate

[0507]

[0508] Methyl chloroformate (0.19 g, 1.98 mmol) was added to a mixture of 5-(6-bromo-4-methyl-benzimidazol-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 warmed 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 N-[5-(6-bromo-4-methyl-benzimidazol-1-yl)-2-pyridyl]carbamate was used as is in the next step.

[0509] LC-MS (Method A): Rt 1.98 min, m / z = 361 / 363 [M+H] + .

[0510] Step D: 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazol-5-yl]boronic acid

[0511]

[0512] Toluene was added to a mixture of N-[5-(6-bromo-4-methyl-benzimidazol-1-yl)-2-pyridyl]carbamate (0.13 g, 0.60 mmol), bis(pinacolyl)diboron (0.30 g, 1.90 mmol), potassium acetate (0.176 g, 1.786 mmol), and bis(diphenylphosphine)ferrocene]palladium(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 diatomaceous earth mat, and the mother liquor was concentrated to give 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazol-5-yl]boronic acid as a brown solid. The crude material was used as is in the next step.

[0513] LC-MS (Method A): Rt 2.04 min, m / z = 325 (MH)+

[0514] Step E: 4-(3-bromopyrazin-2-yl)-2-methoxybenzyl nitrile

[0515]

[0516] A mixture of (4-cyano-3-methoxy-phenyl)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 rapid chromatography (1%–100% ethyl acetate in cyclohexane) to give 4-(3-bromopyrazine-2-yl)-2-methoxybenzyl nitrile as a white solid.

[0517] LC-MS (Method A): Rt 0.15 min, m / z = 290 / 292 [M+H] +

[0518] Step F: N-[5-[6-[3-(4-cyano-3-methoxy-phenyl)pyrazin-2-yl]-4-methyl-benzimidazole-1- Methyl carbamate [2-pyridyl]carbamate

[0519]

[0520] The mixture of 3-[6-(methoxycarbonylamino)-3-pyridyl]-7-methyl-benzimidazol-5-yl]boronic acid (0.06 g, 16.952 mmol), 4-(3-bromopyrazin-2-yl)-2-methoxybenzyl nitrile (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, ethyl acetate was added, and the organic layer was washed with water, dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by rapid chromatography (1%-10% methanol in ethyl acetate) to give N-[5-[6-[3-(4-cyano-3-methoxy-phenyl)pyrazin-2-yl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamate as a grayish-white solid.

[0521] LC-MS (Method A): Rt 1.05 min, m / z = 492 [M+H] +

[0522] 1 H-NMR (400 MHz, DMSO-d 6 , ppm) δ = 8.58 (dd, J = 8.6, 2.3 Hz, 2H),8.23 - 8.01 (m, 4H), 7.58 (d, J = 8.0 Hz, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.34(s, 1H), 7.29 (s, 1H), 7.24 (s, 1H), 6.97 (d, J = 8.0 Hz, 1H), 3.86 (s, 3H), 3.83 (s, 3H), 2.67 (s, 3H).

[0523] Biological examples:

[0524] The antifungal activity of the compounds of this invention has been tested as follows:

[0525] Preventive treatment for late blight caused by Phytophthora infestans / tomato / leaf disc.

[0526] Tomato leaf discs were placed on water agar in a multi-well plate (24-well size) and sprayed with a prepared test compound diluted in water. One day after application, the leaf discs were inoculated with a suspension of fungal spores. The inoculated leaf discs were incubated in a climate chamber at 16°C and 75% rh under a light scheme of 24 h darkness followed by 12 h light / 12 h darkness, and the activity of the compound was assessed as the percentage of disease control compared to untreated leaf discs when an appropriate level of disease damage was observed (5–7 days after application).

[0527] When compared with an untreated control exhibiting extensive disease development under the same conditions, the following compounds provided at least 80% control of pathogenic *Phytophthora* at 200 ppm:

[0528] 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11.

[0529] Preventive measures against grapevines infected with monopodial fungus / grape / leaf disc (late blight).

[0530] Grapevine leaf discs were placed on water agar in a multi-well plate (24-well specification) and sprayed with a prepared test compound diluted in water. One day after application, the leaf discs were inoculated with a suspension of fungal spores. The inoculated leaf discs were incubated in a climate chamber at 19°C and 80% rh under a 12-h light / 12-h dark light scheme, and the activity of the compound was assessed as the percentage of disease control compared to untreated leaf discs when an appropriate level of disease damage was observed (6–8 days after application).

[0531] When compared with an untreated control exhibiting extensive disease development under the same conditions, the following compounds provided at least 80% control of grape downy mildew at 200 ppm:

[0532] 2, 3, 4, 5, 6, 7, 8, 9, 10, 11.

[0533] Pythium ultimum / Liquid culture (for damping-off disease in seedlings)

[0534] Mycelial fragments and oospores from freshly cultured fungal liquid cultures were directly mixed into nutrient broth (PDB (potato glucose broth)). After placing a solution of the test compound (DMSO) in a microtiter plate (96-well size), the nutrient broth containing the fungal mycelium / spore mixture was added. The test plate was incubated at 24°C, and growth inhibition was determined by photometric assay 2–3 days after application.

[0535] When compared with an untreated control exhibiting extensive disease development under the same conditions, the following compounds provided at least 80% control of *Pythium oxysporum* at 20 ppm:

[0536] 2, 5, 6, 7, 8, 9, 10, 11.

Claims

1. A compound having formula (I) (I) Wherein ring W is a 5-8 membered carbon ring, a 5-8 membered heterocyclic ring, a 6-12 membered aromatic ring, or a 5-11 membered heteroaromatic ring, wherein each of the 5-8 membered carbon ring, the 5-8 membered heterocyclic ring, the 6-12 membered aromatic ring, or the 5-11 membered heteroaromatic ring is optionally selected independently from one to four members of R. 1 Substituents of the substituents; A 1 It is a carbon atom or a nitrogen atom; A 2 It is a carbon atom or a nitrogen atom; A 3 Independently, it is CR 3 Or N, provided that there are no more than four A's. 3 If it is N, then no more than three A's are preferred. 3 If it is N, then no more than two A's are preferred. 3 If it is N, then no more than one A is preferred. 3 It is N, and more preferably five A's. 3 It is CR 3 ; A 4 and A 5 Independently selected from CH and N; R 1 Selected from halogens, hydroxyl groups, amino groups, and 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 group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and CN, wherein 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, C 2-6 alkynyl group, C 1-6 Alkoxy, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl and diC 1-6 Each of the alkylamino carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; and wherein optionally two of the radicals are geminal R. 1 Together with the carbon atoms to which they are attached, they form carbonyl groups; R 2 Selected from 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 thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 Alkoxy, amino, and -NHC(O)C 1-6 alkyl; R 3 Independently selected from hydrogen and 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, diC 1-6 Alkylaminocarbonyl, C 1-6 alkyl carbonyl and hydroxyl, wherein 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl, C 1-6 Alkyl thioalkyl, 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 alkyl carbonyl groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; R 5 It is -NHC(O)R 6 ;and R 6 Selected from 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 alkoxyamino, and C 1-6 Alkyl C 1-6 alkoxyamino, wherein 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 alkoxyamino, and C 1-6 Alkyl C 1-6 Each of the alkoxyamino groups may optionally be substituted by one to three independent substituents selected from the following: halogens and CN; Or its salts or N-oxides.

2. The compound according to claim 1, wherein, Four A's 3 It is CR 3 And an A 3 It is N.

3. The compound according to claim 1 or 2, wherein, yes And preferably four A's 3 It is CR 3 .

4. The compound according to claim 1 or 2, wherein, yes And preferably four A's 3 It is CR 3 .

5. The compound according to claim 1, wherein, Five A's 3 It is CR 3 .

6. The compound according to any one of the preceding claims, wherein, A 4 and A 5 It's CH, or A. 4 It is CH and A 5 It is N, or A 4 It is N and A 5 It is CH.

7. The compound according to any one of the preceding claims, wherein, A 1 It is a carbon atom and A 2 It is a nitrogen atom.

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

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

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

11. The compound according to any one of claims 1 to 6, wherein, Ring W Selected from: in The symbol represents the attachment point with the benzimidazole group in formula (I), and # represents the attachment point with the group formed by A. 3 The attachment point of the ring formed by the group. Where R 11 Selected from 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 alkynyl group, wherein 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 optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN, and The ring W can be arbitrarily selected from one to four independent elements chosen from R. 1 Substituents are substituted.

12. The compound according to claim 11, wherein, Ring W Selected from: in The symbol represents the attachment site with the benzimidazole group in formula (I), and # represents the attachment site with the group composed of A. 3 The attachment point of the ring formed by the group, and where R 11 Selected from 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 alkynyl group, wherein 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 by one to three independent substituents selected from the following: halogen, hydroxyl, and CN.

13. The compound according to any one of the preceding claims, wherein, Ring W is a 5-8 membered heterocyclic ring or a 5-11 membered heteroaromatic ring, wherein each of the 5-8 membered heterocyclic ring or the 5-11 membered heteroaromatic ring is optionally selected from one to four independently selected from R. 1 Substituents of the substituents; A 1 It is a carbon atom or a nitrogen atom; A 2 It is a carbon atom or a nitrogen atom; A 3 Independently, it is CR 3 Or N, provided that there are no more than three A's. 3 It is N; preferably five A's. 3 It is CR 3 ; A 4 It is CH, and A 5 It is N; R 1 Selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy, and CN, wherein 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 and C 1-6 Each of the alkoxy groups may optionally be substituted by one to three independent substituents selected from the following: halogen, hydroxyl, and CN; R 2 Selected from 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 groups and -NHC(O)C 1-6 Alkyl; and more preferably R 2 Selected from hydrogen, CN, C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl and C 1-6 Alkoxy; R 3 Independently selected from hydrogen and 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 group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 Alkyl and hydroxyl, wherein 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 group, C 3-6 cycloalkyl and C 3-6 cycloalkyl-C 1-6 Each of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogen, hydroxyl, and CN; R 5 It is -NHC(O)R 6 ;and R 6 Selected from 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 Alkyl, wherein 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 of the alkyl groups may optionally be substituted by one to three substituents independently selected from the following: halogens and CN.

14. A composition comprising an effective amount of the compound as defined 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 the following: additional active ingredients, suitable formulation inert agents, carriers, adjuvants, and any mixtures thereof.

16. A method for combating, preventing or controlling plant pathogenic diseases, the method comprising applying to a plant pathogen, a site of a plant pathogen, a plant susceptible to attack by a plant pathogen, or plant propagation material thereof a fungicide effective amount of a compound according to any one of claims 1 to 13, or a composition comprising a compound according to any one of claims 1 to 13, or a composition according to claim 14 or 15.

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