Benzimidazole derivatives

Abstract

The present invention relates to compounds of the formula (I) wherein the substituents are as defined in claim 1, to processes and methods for preparing compounds of the formula (I), to agrochemical compositions comprising compounds of the formula (I) as defined in claim 1, and to methods for preparing the same. To the preparation of these compositions and to 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. # imgabs0 #

Description

[0001] The present invention relates to microbicidal benzimidazole derivatives, for example as active ingredients, which have microbicidal activity, especially fungicidal activity, more particularly activity against oomycetes. The invention also relates to the preparation of these benzimidazole derivatives, to intermediates useful in the preparation of these benzimidazole derivatives, to the preparation of these intermediates, to agrochemical compositions comprising at least one of these benzimidazole derivatives, to the preparation of these compositions and to the use of these benzimidazole derivatives or compositions in agriculture or horticulture for combating, controlling or preventing the infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, especially fungi, more especially oomycetes.

[0002] It has now surprisingly been found that certain novel benzimidazole derivatives have advantageous fungicidal properties, especially against oomycetes.

[0003] Accordingly, in a first aspect, the present invention provides a compound of formula (I)

[0004]

[0005] wherein Z is O or S, and preferably Z is O;

[0006] A is CH or N;

[0007] A 1 independently is N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 is N, and more preferably four A 1 are CR 1 ;

[0008] R 1 independently is selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl;

[0009] A 2 independently is CR 2 or N, provided that no more than three A2 is N, preferably no more than two A 2 is N, preferably no more than one A 2 is N, and more preferably four A 2 is CR 2 ;

[0010] R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, where C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 each of the alkyl, alkoxy, alkoxy-C-alkyl, alkoxy-C-alkoxy, alkenyl, alkynyl, cycloalkyl, cycloalkyl-C-alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxycarbonyl, alkylaminocarbonyl, di-alkylaminocarbonyl and alkylcarbonyl groups is optionally substituted by one to three substituents independently selected from: halogen, hydroxy and CN;

[0011] A 3 is independently CR 3 or N;

[0012] R 3 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkylthio, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, amino, C 1-6 Alkylamino, di-C 1-6 -Alkylamino and C 3-6 Cycloalkylamino, wherein C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkylthio, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, amino, C 1-6 Alkylamino, di-C 1-6 -Alkylamino and C 3-6 Each cycloalkylamino group is optionally substituted by one to three substituents independently selected from: halogen, hydroxy, and CN;

[0013] R 4 Selected from C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-4 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, C 1-6 Alkylthio-C 1-6 Alkyl, C 1-6 Alkylsulfinyl-C 1-6 Alkyl, C 1-6 Alkylsulfonyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl-C 1-6 Alkyl, C1-6 alkylaminocarbonyl-C 1-6 alkyl, di-C 1-6 alkylaminocarbonyl-C 1-6 alkyl and CN, wherein C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl and di-C 1-6 alkylaminocarbonyl-C 1-6 each of the alkyl groups is optionally substituted by one to three substituents independently selected from: halogen and CN;

[0014] wherein A 3 and R 4 optionally together form a ring, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring; and

[0015] R 5 is 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 alkoxyC 1-6 alkyl, C 1-6 alkylamino, di-C 1-6 alkylamino and C 1-6 alkylC 1-6 alkoxyamino, wherein each of the groups is optionally substituted by one to three substituents independently selected from: halogen and CN;

[0016] or a salt or N-oxide thereof.

[0017] In a second aspect, the present invention provides an agrochemical composition comprising a compound having formula (I), and more particularly an agrochemical composition comprising a fungicidally effective amount of a compound having formula (I). The composition may further comprise at least one compound selected from the following: additional active ingredients, suitable formulation inert agents, carriers, adjuvants, and any mixtures thereof.

[0018] The compound having formula (I) can be used to control phytopathogenic microorganisms. Thus, in order to control plant pathogens, the compound having formula (I) according to the present invention, or a composition comprising a compound having formula (I), can be applied directly to the plant pathogen, the locus of the plant pathogen, in particular a plant susceptible to attack by the plant pathogen, or to the propagation material of the plant.

[0019] Thus, in a third aspect, the present invention provides the use of a compound having formula (I) as described herein, or a composition comprising a compound having formula (I), for combating, preventing or controlling plant pathogens.

[0020] In a fourth aspect, the present invention provides a method for combating, preventing or controlling plant pathogens, the method comprising applying a compound having formula (I) as described herein, or a composition comprising a compound having formula (I), to the plant pathogen, to the locus of the plant pathogen, in particular to a plant susceptible to attack by the plant pathogen, or to the propagation material of the plant.

[0021] The compound having formula (I) is particularly effective in combating, preventing or controlling phytopathogenic fungi, especially oomycetes. Thus, in a fifth aspect, the present invention provides the use of a compound having formula (I) as described herein, or a composition comprising a compound having formula (I), for controlling phytopathogenic fungi, especially oomycetes.

[0022] In a sixth aspect, the present invention provides a method for combating, preventing or controlling phytopathogenic diseases such as phytopathogenic fungi, the method comprising applying a compound having formula (I) as described herein, or a composition comprising a compound having formula (I), to the phytopathogenic fungi, or to the locus of the phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi, especially oomycetes, or to the propagation material of the plant.

[0023] When a group is indicated as being substituted, for example, by an alkyl group, this includes those groups that are part of another group, such as the alkyl group in an alkylthio group.

[0024] Definition:

[0025] - The term "halogen" refers to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br) or iodine (iodo or I), preferably fluorine, chlorine or bromine.

[0026] - As used herein, the term "alkyl" (alone or as part of a chemical group) denotes a straight-chain or branched-chain 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. Alkyls having 1 to 4 carbon atoms are preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0027] - The term "alkenyl" (used alone or as part of a chemical group) denotes 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. Alkenyls having 2 to 4 carbon atoms are preferred, such as 2-propenyl, 2-butenyl, or 1-methyl-2-propenyl.

[0028] - The term "alkynyl" (alone or as part of a chemical group) refers to a straight-chain or branched-chain 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, 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. Alkynyl groups having 2 to 4 carbon atoms are preferred, such as ethynyl, 2-propynyl, or 2-buten-2-yl.

[0029] - The term "cycloalkyl" (alone 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.

[0030] - The term "alkoxy" refers to a group having the formula -OR a wherein R a 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.

[0031] - The term "alkylthio" refers to a group having the formula -SR a wherein R a is an alkyl group as generally defined above.

[0032] - The term "alkylsulfinyl" refers to a group having the formula -S(O)R a wherein R a is an alkyl group as generally defined above.

[0033] The term "alkylsulfonyl" refers to a group having the formula -S(O)2R a wherein R a is an alkyl group as generally defined above.

[0034] - The term "alkoxycarbonyl" refers to a group having the formula R a OC(O)-, where R a is an alkyl group as generally defined above.

[0035] - The term "alkylaminocarbonyl" refers to a group having the formula R a NHC(O)-, where R a is an alkyl group as generally defined above.

[0036] - Hydroxyl ("hydroxyl" or "hydroxy") represents the -OH group.

[0037] In the context of the present invention, the terms "combat", "prevent" or "control" and their variations refer to reducing any undesired effects, such as pathogenic, more particularly phytopathogenic, especially fungal such as oomycetes, on plants or plant-derived products, the infestation or attack of the pathogen and the pathogenic damage to a level showing improvement.

[0038] As used herein, the term "effective amount" refers to the amount of a compound, its salt or N-oxide which, upon single or multiple administrations, provides the desired effect.

[0039] The effective amount can be readily determined by those skilled in the art using known techniques and by observing the results obtained in similar circumstances. In determining the effective amount, many factors are considered, including but not limited to: the type of plant or plant-derived product to be treated; the pathogen to be controlled and its life cycle; the particular compound to be administered; the type of administration; and other relevant circumstances.

[0040] A compound of formula (I) having at least one basic center can form, for example, acid addition salts with, for example: strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or halogen-substituted C1-C4 alkanoic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or halogen-substituted C1-C4 alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). A compound of formula (I) having at least one acidic group can form salts, for example, with bases, such as mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0041] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form (as N-oxides), in covalent hydrated form, or in salt form (e.g., in an agronomically useful or agrochemically acceptable salt form). N-oxides are the oxidized form of tertiary amines or of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, published in 1991 by CRC Press, Boca Raton. The compounds of formula (I) according to the invention also include the hydrates that may form during salt formation.

[0042] The compounds of formula (I) according to the invention also include the hydrates that may form during salt formation.

[0043] In another embodiment, there is provided a compound of formula (I) according to the invention, wherein four A 1 are CR 1 .

[0044] In another embodiment, there is provided a compound of formula (I) according to the invention, wherein two A 1 are CR 1 and two A 1 are N.

[0045] In another embodiment, there is provided a compound of formula (I) according to the invention, wherein three A 1 are CR 1 and one A 1 is N.

[0046] In another embodiment, there is provided a compound of formula (I) according to the invention, wherein R 1 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl, and preferably R 1 is independently selected from hydrogen and C 1-6 alkyl.

[0047] In another embodiment, there is provided a compound of formula (I) according to the invention, wherein is preferably is and more preferably is

[0048] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, wherein 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 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl group is each optionally substituted with one to three substituents independently selected from: halogen, hydroxy and CN; and preferably R 2 is independently selected from hydrogen, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, wherein C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy group is each optionally substituted with one to three substituents independently selected from: halogen, hydroxy and CN.

[0049] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein R 3 is independently selected from hydrogen, hydroxy, halogen, CN, 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 3-6Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, di-C 1-6 -Alkylamino and C 3-6 Cycloalkylamino, where 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, C 3-6 Cycloalkyl-C 1-6 Alkyl, amino, C 1-6 Alkylamino, di-C 1-6 -Alkylamino and C 3-6 Each of the cycloalkylamino groups is optionally substituted by one to three substituents independently selected from: halogen, hydroxy, and CN. In a preferred embodiment, R 3 can be hydrogen.

[0050] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein four A 2 are CR 2 and A 3 is N.

[0051] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein

[0052] is And preferably, three A 2 are CR 2 and A 3 is CR 3 .

[0053] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein

[0054] is And preferably, three A 2 are CR 2 and A 3 is CR 3 .

[0055] In another embodiment, there is provided a compound of formula (I) according to the present invention, wherein four A 2 are CR 2 and A 3 is CR 3 , and preferably is

[0056] Among them is In a specific embodiment, R 2 as defined in the present invention; preferably R 2 is independently selected from hydrogen, hydroxyl, halogen, CN, 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, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, wherein 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, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 each of the alkylcarbonyl groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxyl and CN; and more preferably R 2 is independently selected from hydrogen, halogen, CN, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, wherein C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 each of the alkoxy groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxyl and CN.

[0057] In another embodiment, there is provided a compound having formula (I) according to the present invention, wherein R 4 is selected from C 1-6 alkyl, C 1-6Alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl and C 1-6 alkoxy, where 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 and C 1-6 Each of the alkoxy groups is optionally substituted by one to three substituents independently selected from the following: halogen and CN; preferably and R 4 selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl and C 1-6 alkoxy, where 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 is optionally substituted by one to three substituents independently selected from the following: halogen and CN; and where A 3 and R 4 together optionally form a ring, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring.

[0058] In another embodiment, there is provided a compound having formula (I) according to the present invention, where A 3 is CR 3 and where R 3 and R 4 together form a ring, preferably a 5- to 8-membered heterocyclic ring, preferably a 6-membered heterocyclic ring, and more preferably one of the rings W1, W2 or W3 as described in the following compounds having formula (I):

[0059]

[0060] The carbon and / or nitrogen atoms forming the ring (W1, W2 or W3) may be substituted by R 3 and R 4 groups as defined in the present invention, and more preferably may be substituted by R3' Group substitution, where R 3' is selected from hydrogen, C 1-6 alkyl and C 3-6 cycloalkyl, where C 1-6 alkyl and C 3-6 each of the cycloalkyl groups is optionally substituted with one to three substituents independently selected from the following: halogen and CN. For example, a compound having the formula (I-W3) can be as follows:

[0061]

[0062] In a preferred embodiment, the compounds having the formulas (I-W1), (I-W2), and (I-W3) can be as described below:

[0063]

[0064] The carbon and / or nitrogen atoms forming the ring (W1, W2, or W3) are substituted by R 3’ groups, where R 3’ is selected from hydrogen, C 1-6 alkyl and C 3-6 cycloalkyl, where C 1-6 alkyl and C 3-6 each of the cycloalkyl groups is optionally substituted with one to three substituents independently selected from the following: halogen and CN. For example, a compound having the formula (I-W3) can be as follows:

[0065]

[0066] In another embodiment, there is provided a compound having the formula (I) according to the present invention, where R 5 is 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, where each of the groups is optionally substituted with one to three substituents independently selected from the following: halogen and CN.

[0067] In a specific embodiment, there is provided a compound having the formula (I) according to the present invention, where

[0068] Z is O;

[0069] A is N;

[0070] Four A 1 are CR 1 where R 1 is independently selected from hydrogen, hydroxyl, halogen, CN, C1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl and C 1-6 alkoxy; and preferably

[0071] is preferably is and more preferably is

[0072] four A 2 is CR 2 ; wherein R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl and C 1-6 alkylsulfonyl, wherein C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl and C 1-6 alkylsulfonyl group is optionally substituted by one to three substituents independently selected from: halogen, hydroxy and CN; and preferably R 2 is independently selected from hydrogen, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, where C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 each of the alkoxy groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxy, and CN;

[0073] A 3 is CR 3 where R 3 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino and C 3-6 cycloalkylamino, where C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino and C 3-6 each of the cycloalkylamino groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxy, and CN; and preferably R 3 is hydrogen;

[0074] R 4 selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl and C 1-6 alkoxy, wherein each of 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 alkoxy groups is optionally substituted by one to three substituents independently selected from the following: halogen and CN; and wherein A 3 and R 4 together optionally form a ring, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring; and

[0075] R 5 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of the said groups is optionally substituted by one to three substituents independently selected from the following: halogen and CN and preferably R 5 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 each of the said groups is optionally substituted by one to three substituents independently selected from the following: halogen and CN.

[0076] In a preferred embodiment, is wherein R 2 is as defined in the present invention; preferably R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, wherein 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, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 each of the alkylcarbonyl groups is optionally substituted with one to three substituents independently selected from: halogen, hydroxy, and CN; preferably, R 2 is independently selected from hydrogen, halogen, CN, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, wherein C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 each of the alkoxy groups is optionally substituted with one to three substituents independently selected from: halogen, hydroxy, and CN, and more preferably, R 2 is independently selected from hydrogen, halogen, CN, and C 1-6 alkoxy, wherein C 1-6 the alkoxy group is optionally substituted with one to three substituents independently selected from: halogen, hydroxy, and CN.

[0077] In a preferred embodiment, is wherein R 2 is as defined in the present invention; preferably R 2 is selected from hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6Alkoxy-C 1-6 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, di-C 1-6 Alkylaminocarbonyl and C 1-6 Alkylcarbonyl, wherein 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, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, di-C 1-6 Alkylaminocarbonyl and C 1-6 Each of the alkylcarbonyl groups is optionally substituted with one to three substituents independently selected from the following: halogen, hydroxy, and CN; more preferably, R 2 Independently selected from halogen, CN, C 1-6 Alkoxy and C 1-6 Alkoxy-C 1-6 Alkyl, wherein C 1-6 Alkoxy and C 1-6 Alkoxy-C 1-6 Each of the alkyl groups is optionally substituted with one to three substituents independently selected from the following: halogen, hydroxy, and CN.

[0078] In another embodiment, the compounds according to the invention are selected from:

[0079] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]-4-(methoxymethyl)-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0080] Methyl N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0081] Methyl N-[5-[4-ethyl-6-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0082] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-4-(methoxymethyl)-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0083] Methyl N-[5-[6-[ethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-(methoxymethyl)-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0084] Methyl N-[5-[4-ethyl-6-[(4-fluoro-3-methoxyphenyl)-(methoxymethyl)carbamoyl]-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0085] Methyl N-[5-[6-[cyanomethyl-(4-fluorophenyl)carbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0086] Methyl N-[5-[6-[cyanomethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0087] Methyl N-[5-[6-[(4-cyano-3-methoxyphenyl)-methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0088] Methyl N-[5-[6-[(4-cyano-3-fluorophenyl)-methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0089] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]-4-methyl-imidazo[4,5-c]pyridin-1-yl]-2-pyridinyl]carbamate;

[0090] Methyl N-[5-[5-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0091] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)-(2-methoxyethyl)carbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate;

[0092] 3-(6-Acetamido-3-pyridinyl)-N-(4-fluoro-3-methoxyphenyl)-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0093] N-(4-Fluoro-3-methoxyphenyl)-N,7-dimethyl-3-[6-(methylcarbamoylamino)-3-pyridyl]benzimidazole-5-carboxamide;

[0094] Ethyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0095] Methyl N-[5-[4-ethyl-6-[(4-fluorophenyl)(methoxymethyl)carbamoyl]-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0096] 3-[6-(Cyclopropanecarbonylamino)-3-pyridyl]-N-(4-fluoro-3-methoxyphenyl)-N,7-dimethylbenzimidazole-5-carboxamide;

[0097] Methyl N-[5-[6-[(2-methoxypyridin-4-yl)methylcarbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0098] Methyl N-[5-[6-(6-fluoro-4-methyl-2,3-dihydroquinoxaline-1-carbonyl)-4-methyl-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0099] Methyl N-[5-[5-[(4-fluorophenyl)methylcarbamoyl]-7-methylimidazo[4,5-b]pyridin-3-yl]-2-pyridyl]carbamate;

[0100] Methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0101] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)(methoxymethyl)carbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridyl]carbamate;

[0102] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]imidazo[4,5-c]pyridin-1-yl]-2-pyridyl]carbamate;

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

[0104] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0105] Methyl N-[5-[6-[(4-fluorophenyl)(methoxymethyl)carbamoyl]-4-(methoxymethyl)-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0106] Methyl N-[5-[6-[(4-fluorophenyl)(2-methoxyethyl)carbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0107] Methyl N-[5-[6-[2-cyanoethyl-(4-fluorophenyl)carbamoyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0108] 3-(6-Acetamido-3-pyridinyl)-N-(4-fluorophenyl)-N,7-dimethyl-1H-benzimidazole-5-carboxamide;

[0109] Methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]-4-(methoxymethyl)-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0110] Methyl N-[5-[2-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-6-methyl-9H-purin-9-yl]-2-pyridinyl]carbamate;

[0111] Methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0112] Methyl N-[5-[6-[ethyl-(4-fluorophenyl)carbamoyl]-4-(methoxymethyl)-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0113] Methyl N-[5-[5-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-7-methyl-imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0114] Methyl N-[5-[5-[(4-fluoro-3-methylphenyl)methylcarbamoyl]-7-methyl-imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0115] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]imidazo[4,5-b]pyridin-1-yl]-2-pyridinyl]carbamate;

[0116] Methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0117] Methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]-4-methylimidazo[4,5-c]pyridin-1-yl]-2-pyridinyl]carbamate;

[0118] Methyl N-[5-[5-[(4-fluoro-3-methylphenyl)methylcarbamoyl]imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0119] Methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]imidazo[4,5-b]pyridin-1-yl]-2-pyridinyl]carbamate;

[0120] Methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]imidazo[4,5-c]pyridin-1-yl]-2-pyridinyl]carbamate;

[0121] Methyl N-[5-[2-[(4-fluorophenyl)methylcarbamoyl]purin-9-yl]-2-pyridinyl]carbamate;

[0122] 3-[6-(Cyclopropanecarbonylamino)-3-pyridinyl]-N-(4-fluorophenyl)-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0123] N-(4-fluorophenyl)-N,7-dimethyl-3-[6-(methylcarbamoylamino)-3-pyridinyl]-1H-benzo[d]imidazole-5-carboxamide;

[0124] N-(4-fluorophenyl)-N,7-dimethyl-3-[6-(1H-pyrazole-5-carbonylamino)-3-pyridinyl]-1H-benzo[d]imidazole-5-carboxamide;

[0125] N-(4-fluoro-3-methoxyphenyl)-N,7-dimethyl-3-[6-(1H-pyrazole-5-carbonylamino)-3-pyridinyl]-1H-benzo[d]imidazole-5-carboxamide;

[0126] N-(4-fluoro-3-methoxyphenyl)-N,7-dimethyl-3-[6-(1H-pyrazole-4-carbonylamino)-3-pyridinyl]-1H-benzo[d]imidazole-5-carboxamide;

[0127] N-(4-Fluorophenyl)-N,7-dimethyl-3-[6-(1H-pyrazole-4-carbonylamino)-3-pyridinyl]benzimidazole-5-carboxamide;

[0128] N-(4-Fluorophenyl)-N,7-dimethyl-3-[6-[(1-methylpyrazole-4-carbonyl)amino]-3-pyridinyl]benzimidazole-5-carboxamide;

[0129] N-(4-Fluoro-3-methoxyphenyl)-N,7-dimethyl-3-[6-[(1-methylpyrazole-4-carbonyl)amino]-3-pyridinyl]benzimidazole-5-carboxamide;

[0130] N-(4-Fluoro-3-methoxyphenyl)-N,7-dimethyl-3-[6-[(2-methylpyrazole-3-carbonyl)amino]-3-pyridinyl]benzimidazole-5-carboxamide;

[0131] N-(4-Fluorophenyl)-N,7-dimethyl-3-[6-[(2-methylpyrazole-3-carbonyl)amino]-3-pyridinyl]benzimidazole-5-carboxamide;

[0132] Ethyl N-[5-[6-[(4-fluorophenyl)methylaminocarbonyl]-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0133] Methyl N-[5-[4-ethyl-6-[(4-fluorophenyl)methylaminocarbonyl]-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0134] Methyl N-[5-[2-[(4-fluorophenyl)methylaminocarbonyl]-6-methyl-9H-purin-9-yl]-2-pyridinyl]carbamate;

[0135] Methyl N-[5-[5-[(4-fluorophenyl)methylaminocarbonyl]imidazo[4,5-b]pyrazin-3-yl]-2-pyridinyl]carbamate;

[0136] Methyl N-[5-[2-[(4-fluoro-3-methylphenyl)methylaminocarbonyl]-9H-purin-9-yl]-2-pyridinyl]carbamate;

[0137] Methyl N-[5-[2-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)-9H-purin-9-yl]-2-pyridinyl]carbamate;

[0138] Methyl N-[5-[5-(6-fluoro-3,4-dihydro-2H-quinoline-1-carbonyl)imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0139] Methyl N-[5-[6-(6-fluoro-3,4-dihydro-2H-quinolin-1-carbonyl)imidazo[4,5-b]pyridin-1-yl]-2-pyridinyl]carbamate;

[0140] Methyl N-[5-[5-[(4-fluorophenyl)methylcarbamoyl]imidazo[4,5-b]pyridin-3-yl]-2-pyridinyl]carbamate;

[0141] Methyl N-[5-[6-[(4-fluoro-3-methylphenyl)methylcarbamoyl]imidazo[4,5-b]pyridin-1-yl]-2-pyridinyl]carbamate;

[0142] Methyl N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-4-methyl-1H-benzimidazol-1-yl]-2-pyridinyl]carbamate;

[0143] Methyl N-[5-[2-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-9H-purin-9-yl]-2-pyridinyl]carbamate;

[0144] Methyl N-[4-[2-[(4-chlorophenyl)methylcarbamoyl]-9H-purin-9-yl]phenyl]carbamate;

[0145] 9-(4-acetamidophenyl)-N-(4-chlorophenyl)-N-methylpurine-2-carboxamide;

[0146] 3-(4-acetamidophenyl)-N-(4-chlorophenyl)-N-methyl-1,2,3-benzotriazole-5-carboxamide;

[0147] Methyl N-[4-[6-[(4-chlorophenyl)methylcarbamoyl]-1H-benzotriazol-1-yl]phenyl]carbamate;

[0148] 1-(4-acetamidophenyl)-N-(4-chlorophenyl)-N-methylimidazo[4,5-c]pyridine-6-carboxamide;

[0149] N-(4-chlorophenyl)-3-[6-[(2-methoxyacetyl)amino]-3-pyridinyl]-N,7-dimethyl-1H-benzimidazole-5-carboxamide;

[0150] N-(4-fluoro-3-methoxyphenyl)-3-[6-[(2-methoxyacetyl)amino]-3-pyridinyl]-N,7-dimethyl-1H-benzimidazole-5-carboxamide

[0151] N-(3,4-Difluorophenyl)-3-[6-[(2-methoxyacetyl)amino]-3-pyridinyl]-N,7-dimethyl-benzimidazole-5-carboxamide;

[0152] 3-[4-(Cyclopropanecarbonylamino)phenyl]-N-(3,4-difluorophenyl)-N,7-dimethyl-benzimidazole-5-carboxamide;

[0153] 3-(6-Acetamido-3-pyridinyl)-N-(4-fluoro-3-methyl-phenyl)-N,7-dimethyl-benzimidazole-5-carboxamide;

[0154] 3-[6-(Cyclopropanecarbonylamino)-3-pyridinyl]-N-(4-fluoro-3-methyl-phenyl)-N,7-dimethyl-benzimidazole-5-carboxamide;

[0155] tert-Butyl N-[4-[6-[(3,4-difluorophenyl)methyl-carbamoyl]benzimidazol-1-yl]phenyl]carbamate;

[0156] 3-[6-(Cyclopropanecarbonylamino)-3-pyridinyl]-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-benzimidazole-5-carboxamide;

[0157] Methyl N-[4-[6-[(4-fluoro-3-methoxy-phenyl)methyl-carbamoyl]-4-methyl-benzimidazol-1-yl]phenyl]carbamate;

[0158] tert-Butyl N-[4-[6-[(3,4-difluorophenyl)methyl-carbamoyl]-4-methyl-benzimidazol-1-yl]phenyl]carbamate;

[0159] Benzyl N-[4-[6-[(3,4-difluorophenyl)methyl-carbamoyl]-4-methyl-benzimidazol-1-yl]phenyl]carbamate;

[0160] Methyl N-[4-[6-[(3,4-difluorophenyl)methyl-carbamoyl]-4-methyl-benzimidazol-1-yl]phenyl]carbamate;

[0161] 3-(4-Acetamidophenyl)-N-(3,4-difluorophenyl)-N,7-dimethyl-benzimidazole-5-carboxamide;

[0162] Benzyl N-[4-[6-[(4-fluoro-3-methoxy-phenyl)methyl-carbamoyl]-4-methyl-benzimidazol-1-yl]phenyl]carbamate;

[0163] tert-Butyl N-[4-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]phenyl]carbamate;

[0164] N-(4-Cyanophenyl)-3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0165] N-(4-Chlorophenyl)-3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0166] N-(4-Fluoro-3-methoxyphenyl)-3-(6-carbamoyl-3-pyridyl)-N-methyl-1H-benzo[d]imidazole-5-carboxamide;

[0167] N-(4-Cyano-3-methoxyphenyl)-3-[6-(cyclopropanecarbonylamino)-3-pyridyl]-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0168] N-(4-Fluoro-3-methoxyphenyl)-3-[6-[(2-methoxyacetyl)amino]-3-pyridyl]-N-methyl-1H-benzo[d]imidazole-5-carboxamide;

[0169] Methyl N-[5-[6-[(4-cyanophenyl)methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridyl]carbamate;

[0170] 3-(6-Acetamido-3-pyridyl)-N-(3,4-difluorophenyl)-N,7-dimethyl-1H-benzo[d]imidazole-5-carboxamide;

[0171] 3-(4-Acetamidophenyl)-N-(4-fluoro-3-methoxyphenyl)-N-methyl-1H-benzo[d]imidazole-5-carboxamide;

[0172] 3-(6-Acetamido-3-pyridyl)-N-(4-fluoro-3-methoxyphenyl)-N-(methoxymethyl)-7-methyl-1H-benzo[d]imidazole-5-carboxamide;

[0173] Methyl N-[5-[6-[(4-chlorophenyl)methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridyl]carbamate;

[0174] Methyl N-[5-[6-[(3,4-difluorophenyl)methylcarbamoyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridyl]carbamate;

[0175] 3-[6-(Cyclopropanecarbonylamino)-3-pyridinyl]-N-(4-fluoro-3-methoxyphenyl)-N-(methoxymethyl)-7-methyl-1H-benzo[d]imidazole-5-carboxamide; and

[0176] Methyl N-[5-[6-[(4-chlorophenyl)methylcarbamothioyl]-4-methyl-1H-benzo[d]imidazol-1-yl]-2-pyridinyl]carbamate.

[0177] The method according to the invention has the advantageous property of protecting plants against pathogenic (such as phytopathogenic), in particular fungal (such as oomycetes), attacks or infections which cause diseases and damage to the plants; in particular 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.

[0178] The compounds in Tables 1.1 to 1.132 below illustrate the compounds of the invention.

[0179] Table 1.1 700 compounds E1.1 to E1.700 of formula (Ia) are provided

[0180]

[0181] wherein A is CH, R 2 is H, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are as defined in Table Z.

[0182] Table Z: Definitions of the substituents of A 2a 、A 2b 、R 1 、R 4 and A 6

[0183]

[0184]

[0185]

[0186]

[0187]

[0188] ​

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210] Table 1.2 Seven hundred compounds of formula (Ia), E2.1 to E2.700, are provided, wherein A is CH, R 2 is H, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R4 , A 6 As defined in Table Z.

[0211] Table 1.3 Seven hundred compounds E3.1 to E3.700 of formula (Ia) are provided, where A is CH, R 2 is H, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0212] Table 1.4 Seven hundred compounds E4.1 to E4.700 of formula (Ia) are provided, where A is CH, R 2 is H, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0213] Table 1.5 Seven hundred compounds E5.1 to E5.700 of formula (Ia) are provided, where A is CH, R 2 is H, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0214] Table 1.6 Seven hundred compounds E6.1 to E6.700 of formula (Ia) are provided, where A is CH, R 2 is H, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0215] Table 1.7 Seven hundred compounds E7.1 to E7.700 of formula (Ia) are provided, where A is CH, R 2 is CH3, R5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0216] Table 1.8 There are provided 700 compounds E8.1 to E8.700 having formula (Ia), wherein A is CH, R 2 is CH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0217] Table 1.9 There are provided 700 compounds E9.1 to E9.700 having formula (Ia), wherein A is CH, R 2 is CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0218] Table 1.10 There are provided 700 compounds E10.1 to E10.700 having formula (Ia), wherein A is CH, R 2 is CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0219] Table 1.11 There are provided 700 compounds E11.1 to E11.700 having formula (Ia), wherein A is CH, R 2 is CH3, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0220] Table 1.12 700 compounds of formula (Ia), namely E12.1 to E12.700, are provided, wherein A is CH, R 2 is CH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0221] Table 1.13 700 compounds of formula (Ia), namely E13.1 to E13.700, are provided, wherein A is CH, R 2 is CH2CH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0222] Table 1.14 700 compounds of formula (Ia), namely E14.1 to E14.700, are provided, wherein A is CH, R 2 is CH2CH3, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0223] Table 1.15 700 compounds of formula (Ia), namely E15.1 to E15.700, are provided, wherein A is CH, R 2 is CH2CH3, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0224] Table 1.16 700 compounds of formula (Ia), namely E16.1 to E16.700, are provided, wherein A is CH, R 2 is CH2CH3, R 5 is OCH3, A7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0225] Table 1.17 700 compounds of formula (Ia), E17.1 to E17.700, are provided, where A is CH, R 2 is CH2CH3, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0226] Table 1.18 700 compounds of formula (Ia), E18.1 to E18.700, are provided, where A is CH, R 2 is CH2CH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0227] Table 1.19 700 compounds of formula (Ia), E19.1 to E19.700, are provided, where A is CH, R 2 is F, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0228] Table 1.20 700 compounds of formula (Ia), E20.1 to E20.700, are provided, where A is CH, R 2 is F, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0229] Table 1.21 Seven hundred compounds of formula (Ia), E21.1 to E21.700, are provided, wherein A is CH, R 2 is F, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0230] Table 1.22 Seven hundred compounds of formula (Ia), E22.1 to E22.700, are provided, wherein A is CH, R 2 is F, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0231] Table 1.23 Seven hundred compounds of formula (Ia), E23.1 to E23.700, are provided, wherein A is CH, R 2 is F, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0232] Table 1.24 Seven hundred compounds of formula (Ia), E24.1 to E24.700, are provided, wherein A is CH, R 2 is F, R 5 R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0233] Table 1.25 Seven hundred compounds of formula (Ia), E25.1 to E25.700, are provided, wherein A is CH, R 2 is Cl, R 5 is CH3, A7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0234] Table 1.26 There are provided 700 compounds E26.1 to E26.700 of formula (Ia), wherein A is CH, R 2 R 2 is Cl, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0235] Table 1.27 There are provided 700 compounds E27.1 to E27.700 of formula (Ia), wherein A is CH, R 2 is Cl, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0236] Table 1.28 There are provided 700 compounds E28.1 to E28.700 of formula (Ia), wherein A is CH, R 2 is Cl, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0237] Table 1.29 There are provided 700 compounds E29.1 to E29.700 of formula (Ia), wherein A is CH, R 2 is Cl, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0238] Table 1.30 Seven hundred compounds E30.1 to E30.700 of formula (Ia) are provided, where A is CH, R 2 is Cl, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0239] Table 1.31 Seven hundred compounds E31.1 to E31.700 of formula (Ia) are provided, where A is CH, R 2 is Br, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0240] Table 1.32 Seven hundred compounds E32.1 to E32.700 of formula (Ia) are provided, where A is CH, R 2 is Br, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0241] Table 1.33 Seven hundred compounds E33.1 to E33.700 of formula (Ia) are provided, where A is CH, R 2 is Br, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0242] Table 1.34 Seven hundred compounds E34.1 to E34.700 of formula (Ia) are provided, where A is CH, R 2 is Br, R 5 is OCH3, A 7 is N and A2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0243] Table 1.35 Seven hundred compounds E35.1 to E35.700 of formula (Ia) are provided, wherein A is CH, R 2 is Br, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0244] Table 1.36 Seven hundred compounds E36.1 to E36.700 of formula (Ia) are provided, wherein A is CH, R 2 is Br, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0245] Table 1.37 Seven hundred compounds E37.1 to E37.700 of formula (Ia) are provided, wherein A is CH, R 2 is CN, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0246] Table 1.38 Seven hundred compounds E38.1 to E38.700 of formula (Ia) are provided, wherein A is CH, R 2 is CN, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0247] Table 1.39700 compounds of formula (Ia), namely E39.1 to E39.700, are provided, wherein A is CH, R 2 is CN, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0248] Table 1.40 700 compounds of formula (Ia), namely E40.1 to E40.700, are provided, wherein A is CH, R 2 is CN, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0249] Table 1.41 700 compounds of formula (Ia), namely E41.1 to E41.700, are provided, wherein A is CH, R 2 is CN, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0250] Table 1.42 700 compounds of formula (Ia), namely E42.1 to E42.700, are provided, wherein A is CH, R 2 is CN, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0251] Table 1.43 700 compounds of formula (Ia), namely E43.1 to E43.700, are provided, wherein A is CH, R 2 is OCH3, R 5 is CH3, A 7 is CH and A 2a 、A2b , R 1 , R 4 , A 6 As defined in Table Z.

[0252] Table 1.44 Seven hundred compounds E44.1 to E44.700 of formula (Ia) are provided, where A is CH, R 2 is OCH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0253] Table 1.45 Seven hundred compounds E45.1 to E45.700 of formula (Ia) are provided, where A is CH, R 2 is OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0254] Table 1.46 Seven hundred compounds E46.1 to E46.700 of formula (Ia) are provided, where A is CH, R 2 is OCH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0255] Table 1.47 Seven hundred compounds E47.1 to E47.700 of formula (Ia) are provided, where A is CH, R 2 is OCH3, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0256] Table 1.48700 compounds of formula (Ia), namely E48.1 to E48.700, are provided, wherein A is CH, R 2 is OCH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0257] Table 1.49 700 compounds of formula (Ia), namely E49.1 to E49.700, are provided, wherein A is CH, R 2 is OCH2CH3, R 5 R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0258] Table 1.50 700 compounds of formula (Ia), namely E50.1 to E50.700, are provided, wherein A is CH, R 2 is OCH2CH3, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0259] Table 1.51 700 compounds of formula (Ia), namely E51.1 to E51.700, are provided, wherein A is CH, R 2 is OCH2CH3, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0260] Table 1.52 700 compounds of formula (Ia), namely E52.1 to E52.700, are provided, wherein A is CH, R 2 is OCH2CH3, R 5 is OCH3, A 7is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0261] Table 1.53 Seven hundred compounds E53.1 to E53.700 of formula (Ia) are provided, where A is CH, R 2 is OCH2CH3, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0262] Table 1.54 Seven hundred compounds E54.1 to E54.700 of formula (Ia) are provided, where A is CH, R 2 is OCH2CH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0263] Table 1.55 Seven hundred compounds E55.1 to E55.700 of formula (Ia) are provided, where A is CH, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0264] Table 1.56 Seven hundred compounds E56.1 to E56.700 of formula (Ia) are provided, where A is CH, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0265] Table 1.57 700 compounds of formula (Ia), E57.1 to E57.700, are provided, wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0266] Table 1.58 700 compounds of formula (Ia), E58.1 to E58.700, are provided, wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0267] Table 1.59 700 compounds of formula (Ia), E59.1 to E59.700, are provided, wherein A is CH, R 2 is OCH2CH2OCH3, R 5 R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0268] Table 1.60 700 compounds of formula (Ia), E60.1 to E60.700, are provided, wherein A is CH, R 2 is OCH2CH2OCH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0269] Table 1.61700 compounds of formula (Ia), namely E61.1 to E61.700, are provided, where A is CH, R 2 is OH, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0270] Table 1.62 700 compounds of formula (Ia), namely E62.1 to E62.700, are provided, where A is CH, R 2 is OH, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0271] Table 1.63 700 compounds of formula (Ia), namely E63.1 to E63.700, are provided, where A is CH, R 2 is OH, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0272] Table 1.64 700 compounds of formula (Ia), namely E64.1 to E64.700, are provided, where A is CH, R 2 is OH, R 5 R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0273] Table 1.65 700 compounds of formula (Ia), namely E65.1 to E65.700, are provided, where A is CH, R 2 is OH, R 5 is A 7 is CH and A 2a 、A2b , R 1 , R 4 , A 6 As defined in Table Z.

[0274] Table 1.66 Seven hundred compounds E66.1 to E66.700 of formula (Ia) are provided, wherein A is CH, R 2 is OH, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0275] Table 1.67 Seven hundred compounds E67.1 to E67.700 of formula (Ia) are provided, wherein A is N, R 2 is H, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0276] Table 1.68 Seven hundred compounds E68.1 to E68.700 of formula (Ia) are provided, wherein A is N, R 2 is H, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0277] Table 1.69 Seven hundred compounds E69.1 to E69.700 of formula (Ia) are provided, wherein A is N, R 2 is H, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0278] Table 1.70Seven hundred compounds of formula (Ia), E70.1 to E70.700, are provided, wherein A is N, R 2 is H, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0279] Table 1.71 Seven hundred compounds of formula (Ia), E71.1 to E71.700, are provided, wherein A is N, R 2 is H, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0280] Table 1.72 Seven hundred compounds of formula (Ia), E72.1 to E72.700, are provided, wherein A is N, R 2 is H, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0281] Table 1.73 Seven hundred compounds of formula (Ia), E73.1 to E73.700, are provided, wherein A is N, R 2 is CH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0282] Table 1.74 Seven hundred compounds of formula (Ia), E74.1 to E74.700, are provided, wherein A is N, R 2 is CH3, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R1 , R 4 , A 6 As defined in Table Z.

[0283] Table 1.75 Seven hundred compounds E75.1 to E75.700 of formula (Ia) are provided, wherein A is N, R 2 is CH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0284] Table 1.76 Seven hundred compounds E76.1 to E76.700 of formula (Ia) are provided, wherein A is N, R 2 is CH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0285] Table 1.77 Seven hundred compounds E77.1 to E77.700 of formula (Ia) are provided, wherein A is N, R 2 is CH3, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0286] Table 1.78 Seven hundred compounds E78.1 to E78.700 of formula (Ia) are provided, wherein A is N, R 2 is CH3, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0287] Table 1.79700 compounds of formula (Ia), E79.1 to E79.700, are provided, where A is N, R 2 is CH2CH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0288] Table 1.80 700 compounds of formula (Ia), E80.1 to E80.700, are provided, where A is N, R 2 is CH2CH3, R 5 R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0289] Table 1.81 700 compounds of formula (Ia), E81.1 to E81.700, are provided, where A is N, R 2 is CH2CH3, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0290] Table 1.82 700 compounds of formula (Ia), E82.1 to E82.700, are provided, where A is N, R 2 is CH2CH3, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0291] Table 1.83 700 compounds of formula (Ia), E83.1 to E83.700, are provided, where A is N, R 2 is CH2CH3, R 5 is A 7 is CH and A2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0292] Table 1.84 Seven hundred compounds of formula (Ia), E84.1 to E84.700, are provided, wherein A is N, R 2 is CH2CH3, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0293] Table 1.85 Seven hundred compounds of formula (Ia), E85.1 to E85.700, are provided, wherein A is N, R 2 is F, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0294] Table 1.86 Seven hundred compounds of formula (Ia), E86.1 to E86.700, are provided, wherein A is N, R 2 is F, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0295] Table 1.87 Seven hundred compounds of formula (Ia), E87.1 to E87.700, are provided, wherein A is N, R 2 is F, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0296] Table 1.88700 compounds of formula (Ia), E88.1 to E88.700, are provided, wherein A is N, R 2 is F, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0297] Table 1.89 700 compounds of formula (Ia), E89.1 to E89.700, are provided, wherein A is N, R 2 is F, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0298] Table 1.90 700 compounds of formula (Ia), E90.1 to E90.700, are provided, wherein A is N, R 2 is F, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0299] Table 1.91 700 compounds of formula (Ia), E91.1 to E91.700, are provided, wherein A is N, R 2 is Cl, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0300] Table 1.92 700 compounds of formula (Ia), E92.1 to E92.700, are provided, wherein A is N, R 2 is Cl, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R1 , R 4 , A 6 As defined in Table Z.

[0301] Table 1.93 Seven hundred compounds E93.1 to E93.700 of formula (Ia) are provided, wherein A is N, R 2 is Cl, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0302] Table 1.94 Seven hundred compounds E94.1 to E94.700 of formula (Ia) are provided, wherein A is N, R 2 is Cl, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0303] Table 1.95 Seven hundred compounds E95.1 to E95.700 of formula (Ia) are provided, wherein A is N, R 2 is Cl, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0304] Table 1.96 Seven hundred compounds E96.1 to E96.700 of formula (Ia) are provided, wherein A is N, R 2 is Cl, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0305] Table 1.97700 compounds of formula (Ia), namely E97.1 to E97.700, are provided, wherein A is N, R 2 is Br, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0306] Table 1.98 700 compounds of formula (Ia), namely E98.1 to E98.700, are provided, wherein A is N, R 2 is Br, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0307] Table 1.99 700 compounds of formula (Ia), namely E99.1 to E99.700, are provided, wherein A is N, R 2 is Br, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0308] Table 1.100 700 compounds of formula (Ia), namely E100.1 to E100.700, are provided, wherein A is N, R 2 is Br, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0309] Table 1.101 700 compounds of formula (Ia), namely E101.1 to E101.700, are provided, wherein A is N, R 2 is Br, R 5 is A 7 is CH and A 2a 、A 2b 、R1 , R 4 , A 6 As defined in Table Z.

[0310] Table 1.102 700 compounds E102.1 to E102.700 of formula (Ia) are provided, wherein A is N, R 2 is Br, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0311] Table 1.103 700 compounds E103.1 to E103.700 of formula (Ia) are provided, wherein A is N, R 2 is CN, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0312] Table 1.104 700 compounds E104.1 to E104.700 of formula (Ia) are provided, wherein A is N, R 2 is CN, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0313] Table 1.105 700 compounds E105.1 to E105.700 of formula (Ia) are provided, wherein A is N, R 2 is CN, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0314] Table 1.106700 compounds of formula (Ia), E106.1 to E106.700, are provided, where A is N, R 2 is CN, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0315] Table 1.107 700 compounds of formula (Ia), E107.1 to E107.700, are provided, where A is N, R 2 is CN, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0316] Table 1.108 700 compounds of formula (Ia), E108.1 to E108.700, are provided, where A is N, R 2 is CN, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0317] Table 1.109 700 compounds of formula (Ia), E109.1 to E109.700, are provided, where A is N, R 2 is OCH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0318] Table 1.110 700 compounds of formula (Ia), E110.1 to E110.700, are provided, where A is N, R 2 is OCH3, R 5 is CH3, A 7 is N and A 2a 、A2b , R 1 , R 4 , A 6 As defined in Table Z.

[0319] Table 1.111 Seven hundred compounds E111.1 to E111.700 of formula (Ia) are provided, where A is N, R 2 is OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0320] Table 1.112 Seven hundred compounds E112.1 to E112.700 of formula (Ia) are provided, where A is N, R 2 is OCH3, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0321] Table 1.113 Seven hundred compounds E113.1 to E113.700 of formula (Ia) are provided, where A is N, R 2 is OCH3, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0322] Table 1.114 Seven hundred compounds E114.1 to E114.700 of formula (Ia) are provided, where A is N, R 2 is OCH3, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0323] Table 1.115Seven hundred compounds E115.1 to E115.700 of formula (Ia) are provided, where A is N, R 2 is OCH2CH3, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0324] Table 1.116 Seven hundred compounds E116.1 to E116.700 of formula (Ia) are provided, where A is N, R 2 is OCH2CH3, R 5 is CH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0325] Table 1.117 Seven hundred compounds E117.1 to E117.700 of formula (Ia) are provided, where A is N, R 2 is OCH2CH3, R 5 is OCH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0326] Table 1.118 Seven hundred compounds E118.1 to E118.700 of formula (Ia) are provided, where A is N, R 2 is OCH2CH3, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 as defined in Table Z.

[0327] Table 1.119 Seven hundred compounds E119.1 to E119.700 of formula (Ia) are provided, where A is N, R 2 is OCH2CH3, R 5 is A 7 is CH and A2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0328] Table 1.120 Seven hundred compounds E120.1 to E120.700 of formula (Ia) are provided, wherein A is N, R 2 is OCH2CH3, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0329] Table 1.121 Seven hundred compounds E121.1 to E121.700 of formula (Ia) are provided, wherein A is N, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0330] Table 1.122 Seven hundred compounds E122.1 to E122.700 of formula (Ia) are provided, wherein A is N, R 2 is OCH2CH2OCH3, R 5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0331] Table 1.123 Seven hundred compounds E123.1 to E123.700 of formula (Ia) are provided, wherein A is N, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 As defined in Table Z.

[0332] Table 1.124 700 compounds of formula (Ia), E124.1 to E124.700, are provided, where A is N, R 2 is OCH2CH2OCH3, R 5 is OCH3, A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0333] Table 1.125 700 compounds of formula (Ia), E125.1 to E125.700, are provided, where A is N, R 2 is OCH2CH2OCH3, R 5 is A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0334] Table 1.126 700 compounds of formula (Ia), E126.1 to E126.700, are provided, where A is N, R 2 is OCH2CH2OCH3, R 5 is A 7 is N and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0335] Table 1.127 700 compounds of formula (Ia), E127.1 to E127.700, are provided, where A is N, R 2 is OH, R 5 is CH3, A 7 is CH and A 2a 、A 2b 、R 1 、R 4 、A 6 are defined as in Table Z.

[0336] Table 1.128 700 compounds of formula (Ia), E128.1 to E128.700, are provided, where A is N, R 2 is OH, R5 is CH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0337] Table 1.129 700 compounds of formula (Ia) are provided, E129.1 to E129.700, wherein A is N, R 2 R 2 is OH, R 5 is OCH3, A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0338] Table 1.130 700 compounds of formula (Ia) are provided, E130.1 to E130.700, wherein A is N, R 2 is OH, R 5 is OCH3, A 7 is N and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0339] Table 1.131 700 compounds of formula (Ia) are provided, E131.1 to E131.700, wherein A is N, R 2 is OH, R 5 is A 7 is CH and A 2a , A 2b , R 1 , R 4 , A 6 as defined in Table Z.

[0340] Table 1.132 700 compounds of formula (Ia) are provided, E132.1 to E132.700, wherein A is N, R 2 is OH, R 5 is A 7 is N and A 2a , A 2b , R 1 , R 4 , A6 As defined in Table Z.

[0341] The compounds according to the invention can have a number of advantages, including in particular a favorable level of biological activity for protecting plants against diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety, improved physico-chemical properties, or increased biodegradability). The compounds according to the invention have a particularly favorable level of biological activity for protecting plants against oomycetes such as Phytophthora, Plasmopara, and Pythium.

[0342] The compounds having formula (I) can be prepared as shown in Schemes 1 to 22 below, where (unless otherwise stated) the definition of each variable is as defined in the present invention.

[0343] The compounds having formula (I) can be prepared by reacting a compound having formula (II) with a compound having formula (III), where each R 8 is independently hydrogen, C1-C6 alkyl or two of the Rs 8 together can form a C3-C8 cycloalkyl) 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 outcome can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are carried out under air, as oxygen is required as the final oxidant. In some cases, the copper substance can be used in stoichiometric amounts. This transformation is depicted in Scheme 1.

[0344]

[0345] Alternatively, the compounds having formula (I) can be prepared by reacting a compound having formula (II) with a compound having 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 XPhosPd G3, t-BuXPhos Pd G3, Me4tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhosPd G3 or tBuBrettPhos Pd G3, in a suitable solvent such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran or toluene. This transformation is depicted in Scheme 2.

[0346]

[0347] A compound having the formula (II) wherein Z is O can be prepared by reacting a compound having the formula (V) with a compound having the formula (VI) and a coupling agent such as N,N'-dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and optionally a base such as triethylamine, ethyldiisopropylamine or N-methylmorpholine, in a suitable solvent such as ethyl acetate, dimethylformamide, tetrahydrofuran or dichloromethane. In some cases, the compound having the formula (V) can be used as its analogous lithium salt or sodium salt. This transformation is depicted in Scheme 3.

[0348]

[0349] Alternatively, a compound having the formula (IIa) wherein Z is O can be prepared by reacting a compound having the formula (VII) or its hydrochloride with a compound having the formula (VI) and an optional base such as pyridine, 4-N,N-dimethylaminopyridine, sodium hydroxide, triethylamine, potassium carbonate, in a solvent such as tetrahydrofuran, dioxane, toluene or water. This transformation is depicted in Scheme 4.

[0350]

[0351] The compound having the formula (VII) can be prepared by reacting a compound having the formula (V) with oxalyl chloride, phosgene, thionyl chloride or phosphoryl chloride in a suitable solvent such as toluene, tetrahydrofuran or dichloromethane. In some cases, the compound having the formula (VII) can be isolated as its hydrochloride salt. This transformation is depicted in Scheme 5.

[0352]

[0353] The compound having the formula (V) is commercially available or alternatively can be prepared by saponifying a compound having the formula (VIII) wherein R 9 is C1-C6 alkyl) with a base such as NaOH or LiOH in a suitable solvent such as methanol, ethanol or water, at a temperature between room temperature and reflux. In some cases, the compound having the formula (V) can be isolated as its sodium salt or lithium salt. This transformation is depicted in Scheme 6.

[0354]

[0355] The compound having the formula (VIII) wherein R 9(wherein R is a C1-C6 alkyl) is commercially available, or alternatively can be prepared by reacting a compound of formula (IX) (wherein X is Cl, Br or I) with carbon monoxide and an alcohol R 9 OH (wherein R 9 is a C1-C6 alkyl) in the presence of a catalyst such as PdCl2dppf, and optionally a base such as triethylamine. This transformation is depicted in Scheme 7.

[0356]

[0357] Compounds of formula (IX) (wherein X is Cl, Br or I) are commercially available, or alternatively, compounds of formula (IXa) can be prepared by reacting a compound of formula (X) (wherein X is Cl, Br or I) with a compound of formula (XI) (wherein R 9 is a C1-C6 alkyl) in the presence of an acid such as tosylsulfonic acid, sulfuric acid or trifluoroacetic acid in a suitable solvent such as toluene, methanol, ethanol, acetonitrile or water. This transformation is depicted in Scheme 8.

[0358]

[0360] Compounds of formula (X) (wherein X is Cl, Br or I) are commercially available, or can be prepared by reducing a compound of formula (XII) (wherein X is Cl, Br or I) or a compound of formula (XIII) (wherein X is Cl, Br or I) with hydrogen in the presence of palladium in a suitable solvent such as tetrahydrofuran, ethanol, methanol or water, or by using iron in the presence of an acid such as hydrogen chloride, ammonium chloride or acetic acid. This transformation is depicted in Scheme 9.

[0361]

[0362] Alternatively, compounds of formula (IIa) can be prepared by deprotecting a compound of formula (XIV) (wherein R 10 is a nitrogen protecting group, such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc) or 2-tetrahydropyranyl (THP)). Deprotection conditions are known to those skilled in the art. Compounds of formula (XIV) can be prepared from compounds of formula (XV) (wherein X is Cl, Br or I and R 10is a nitrogen protecting group, such as trimethylsilylethoxymethyl, tert-butoxycarbonyl or 2-tetrahydropyranyl), reacting with an amine of formula (VI) and carbon monoxide in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene] palladium(II) dichloride or bis(benzonitrile)palladium chloride, optionally in the presence of a ligand such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and an optional base such as triethylamine to obtain. A compound of formula (XV) (wherein X is Cl, Br or I and R 10 is a nitrogen protecting group such as trimethylsilylethoxymethyl, tert-butoxycarbonyl or 2-tetrahydropyranyl) can be prepared by protecting the nitrogen group of the imidazole ring of a compound of formula (XI) (wherein X is Cl, Br or I) under conditions known to those skilled in the art. This transformation is depicted in Scheme 10.

[0363]

[0364] Alternatively, a compound of formula (Ia) (wherein Z is O) can be prepared by reacting a compound of formula (XVI) with a compound of formula (VI) and a coupling agent such as N,N'-dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and optionally a base such as triethylamine, ethyldiisopropylamine or N-methylmorpholine, in a suitable solvent such as ethyl acetate, dimethylformamide, tetrahydrofuran or dichloromethane. In some cases, the compound of formula (XVI) can be used as its analogous lithium salt or sodium salt. This transformation is depicted in Scheme 11.

[0365]

[0367] A compound of formula (XVI) can be prepared by saponifying a compound of formula (XVII) (wherein R 9 is C1-C6 alkyl) with a base such as NaOH or LiOH in a suitable solvent such as methanol, ethanol or water at a temperature between room temperature and reflux. In some cases, the compound of formula (XVII) can be isolated as the sodium salt or lithium salt. This transformation is depicted in Scheme 12.

[0368]

[0369] A compound of formula (XVII) (wherein R 9 is C1-C6 alkyl) can be prepared by reacting a compound of formula (XVIII) (wherein X is Cl, Br or I) with carbon monoxide and an alcohol R9 OH (wherein R 9 is a C1-C6 alkyl group) is prepared by reacting in the presence of a catalyst such as PdCl2dppf, and optionally a base such as triethylamine. This transformation is depicted in Scheme 13.

[0370]

[0371] Alternatively, a compound of formula (Ia) (wherein Z is O) can be prepared, can be obtained from a compound of formula (Ia), and can be obtained by reacting a compound of formula (XVIII) (wherein X is Cl, Br or I) with an amine of formula (VI) in the presence of carbon monoxide and in the presence of a catalyst such as [1,1-bis(diphenylphosphino)ferrocene] palladium(II) dichloride or bis(benzonitrile)palladium chloride, optionally in the presence of a ligand such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and an optional base such as triethylamine. This transformation is depicted in Scheme 14.

[0372]

[0373] A compound of formula (XVIII) can be prepared by reacting a compound of formula (IX) with a compound of formula (III) (wherein each R 8 is independently hydrogen, a C1-C6 alkyl group or two of the R 8 together can form a C3-C8 cycloalkyl group) 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 outcome can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are carried out under air as oxygen is required as the final oxidant. In some cases, the copper substance can be used in stoichiometric amounts. This transformation is depicted in Scheme 15.

[0374]

[0375] A compound of formula (XVIIIa) (wherein X is Cl, Br or I) can be prepared by reacting a compound of formula (XIX) (wherein X is Cl, Br or I) with a compound of formula (XI) (wherein R 9 is a C1-C6 alkyl group) in the presence of an acid such as toluenesulfonic acid, sulfuric acid or trifluoroacetic acid, in a suitable solvent such as toluene, methanol, ethanol, acetonitrile or water. This transformation is depicted in Scheme 16.

[0376]

[0377] A compound of formula (XIX) wherein X is Cl, Br or I can be prepared by reducing a compound of formula (XX) wherein X is Cl, Br or I with hydrogen in the presence of palladium in a suitable solvent such as tetrahydrofuran, ethanol, methanol or water, or with iron in the presence of an acid such as hydrogen chloride, ammonium chloride or acetic acid. This transformation is depicted in Scheme 17.

[0378]

[0379] A compound of formula (XX) wherein X is Cl, Br or I can be prepared by reacting a compound of formula (XXI) wherein X is Cl, Br or I and wherein X 2 is F, Cl, Br or I with a compound of formula (XXII) 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 18.

[0380]

[0381] Alternatively, a compound of formula (XVII) wherein R 9 is C1-C6 alkyl can be prepared by reductive cyclization of a compound of formula (XXIII) wherein R 9 is C1-C6 alkyl with a reagent such as formic acid or methanol in the presence of a reducing agent such as Fe(0) or sodium dithionite in a protic solvent such as methanol or propan-2-ol, and finally in the presence of an additive such as ammonium chloride. A compound of formula (XXIII) wherein R 9 is C1-C6 alkyl can be obtained by reacting a compound of formula (XXIV) wherein X 2 is F, Cl, Br or I and R 9 is C1-C6 alkyl with a compound of formula (XXII) 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 19.

[0382]

[0383] Alternatively, a compound having formula (I) can be prepared by acylating a compound having formula (XXV) with an acylating agent having formula (XXVI) (wherein X is Cl or Br) in the presence of a base such as triethylamine or potassium carbonate. The compound having formula (XXV) can be obtained by reacting a compound having formula (II) with a compound having formula (XXVII) (wherein each R 8 is independently of the others hydrogen, C1-C6 alkyl or two of the R 8 together can form a C3-C8 cycloalkyl) 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 outcome can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are carried out under air as oxygen is required as the final oxidant. In some cases, the copper species can be used in stoichiometric amounts.

[0384] This transformation is depicted in Scheme 20.

[0385]

[0386] A compound having formula (Ib) (wherein Z is S) can be prepared by reacting a compound having formula (Ia) (wherein Z is O) with phosphorus pentasulfide or Lawesson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene or dichloromethane.

[0387] This transformation is depicted in Scheme 21.

[0388]

[0389] A compound having formula (IIb) (wherein Z is S) can be prepared by reacting a compound having formula (IIa) (wherein Z is O) with phosphorus pentasulfide or Lawesson's reagent (CAS: 19172-47-5) in a suitable solvent such as toluene, xylene or dichloromethane. This transformation is depicted in Scheme 22.

[0390]

[0391] A compound having formula (III) (wherein each R 8 is independently of the others hydrogen, C1-C6 alkyl or two of the R 8together can form a C3-C8 cycloalkyl) and a compound having the formula (XXVII) wherein any one of R 8 are, independently of one another, hydrogen, C1-C6 alkyl or two of the R 8 together can form a C3-C8 cycloalkyl) are prepared by known methods or are commercially available.

[0392] The compound having the formula (VI) is prepared by known methods or is commercially available.

[0393] The compound having the formula (XI) wherein R 9 is C1-C6 alkyl) is prepared by known methods or is commercially available.

[0394] The compound having the formula (XXI) wherein X is Cl, Br or I and wherein X 2 is F, Cl, Br or I) is prepared by known methods or is commercially available.

[0395] The compound having the formula (XXII) is prepared by known methods or is commercially available.

[0396] Those skilled in the art should understand that the amide coupling reaction between an acid, an amine and a coupling agent described above can also be carried out using the corresponding acyl chloride and amine. The conversion of an acid into its corresponding acyl chloride is well known to those skilled in the art.

[0397] Those skilled in the art should also understand that if the imidazole (or triazole) nitrogen atom is masked by a protecting group such as trimethylsilylethoxymethyl (SEM), tert-butoxycarbonyl (Boc) or 2-tetrahydropyranyl (THP), some of the above reactions in which the imidazole ring (or triazole) nitrogen atom of the central ring is unsubstituted may proceed more efficiently. The reactions for protecting imidazole and triazole rings with SEM, Boc or THP and the subsequent deprotection of these groups are well-known transformations 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.

[0398] When the term “compound / compounds according to the invention” is used, it refers to the compounds according to the invention.

[0399] Alternatively, the compounds according to the invention can be obtained by using standard synthetic techniques known to those skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, olefination reactions, oxime formation, alkylation and halogenation reactions.

[0400] The compounds according to the invention can be converted into another compound according to the invention in a manner 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 other substituents according to the invention in a conventional manner.

[0401] Depending on the reaction conditions suitable for the respective case and the starting materials, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step, or several substituents can be replaced with other substituents according to the invention in the same reaction step.

[0402] The salts of the compounds according to the invention can be prepared in a manner known per se. Thus, for example, the acid addition salts of the compounds according to the invention are obtained by treatment with a suitable acid or a suitable ion-exchange reagent, and the salts with bases are obtained by treatment with a suitable base or a suitable ion-exchange reagent.

[0403] The salts of the compounds according to the invention can be converted into the free compounds, acid addition salts (for example by treatment with a suitable basic compound or a suitable ion-exchange reagent) and salts with bases (for example by treatment with a suitable acid or a suitable ion-exchange reagent) in a customary manner.

[0404] The salts of the compounds according to the invention can be converted into other salts, acid addition salts of the compounds according to the invention, for example into other acid addition salts, for example by treating a salt of an inorganic acid (such as a hydrochloride) with a suitable metal salt of an acid (such as a salt of sodium, barium or silver, for example silver acetate) in a suitable solvent, in which the inorganic salt formed (such as silver chloride) is insoluble and thus precipitates from the reaction mixture.

[0405] Depending on the procedure or reaction conditions, the compounds according to the invention having salt-forming properties can be obtained in free form or in the form of salts.

[0406] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration, 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 form or in salt form) can exist in the form of one of the possible stereoisomers or as a mixture of these, for example in the form of pure stereoisomers, such as enantiomers and / or diastereoisomers, or as a stereoisomer mixture, such as an enantiomer mixture, for example a racemate, a diastereoisomer mixture or a racemate mixture; the invention relates to pure stereoisomers as well as to all possible stereoisomer mixtures, and in each case above and below should be understood in this sense even when the stereochemical details are not explicitly mentioned in each case.

[0407] A mixture of diastereoisomers or a racemate mixture of the compounds according to the invention in free form or in salt form (the obtaining of which can depend on the starting materials and procedures chosen) can be separated in a known manner into the pure diastereoisomers or racemates on the basis of the physicochemical differences of these components, for example by fractional crystallization, distillation and / or chromatography.

[0408] A mixture of enantiomers (such as a racemate) which can be obtained in a similar manner can be resolved into the optical enantiomers by known methods, for example by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, for example high performance liquid chromatography (HPLC) on acetyl cellulose; by cleavage with a suitable microorganism, by means of a specifically immobilized enzyme; by formation of inclusion compounds, for example using a chiral crown ether in which only one enantiomer is complexed; or by conversion into salts of diastereoisomers, for example by reacting the basic end product racemate with an optically active acid (such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid), and separating the mixture of diastereoisomers which can be obtained in this way, for example by fractional crystallization based on their different solubilities, to obtain the diastereoisomers, from which the desired enantiomer can be liberated by the action of a suitable reagent (such as a basic reagent).

[0409] Pure diastereoisomers or enantiomers can be obtained according to the invention not only by separation of suitable stereoisomer mixtures, but also by methods of diastereoselective or enantioselective synthesis which are generally known, for example by carrying out the method according to the invention with starting materials having suitable stereochemistry.

[0410] The N-oxides can be prepared by reacting a compound according to the invention with a suitable oxidizing agent (e.g., H2O2 / urea adduct) in the presence of an acid anhydride (e.g., trifluoroacetic anhydride). Such oxidations are known from the literature, e.g., from J. Med. Chem. [Journal of Medicinal Chemistry] 32(12), 2561 - 73, 1989 or WO 00 / 15615.

[0411] If the individual components have different biological activities, it is advantageous in each case to isolate or synthesize the biologically more active stereoisomers, such as enantiomers or diastereoisomers or mixtures of stereoisomers, such as mixtures of enantiomers or diastereoisomers.

[0412] If appropriate, the compounds according to the invention and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallizing the compounds present in solid form.

[0413] The following examples illustrate but do not limit the invention.

[0414] The invention also provides intermediates which can be used for preparing the compounds according to the invention.

[0415] The following intermediates form another aspect of the invention.

[0416] A compound of formula (XVI)

[0417]

[0418] wherein A is CH or N;

[0419] A 1 independently is N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 is N, and more preferably four A 1 are CR 1 ;

[0420] R 1 independently is selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6Alkylsulfonyl, C 1-6 alkoxy, amino, and NHC(O)C 1-6 alkyl; and

[0421] R 5 is independently 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 alkoxyC 1-6 alkyl, C 1-6 alkylamino, diC 1-6 alkylamino, and C 1-6 alkylC 1-6 alkoxyamino, wherein each of said groups is optionally substituted with one to three substituents independently selected from: halogen and CN;

[0422] or a salt or N-oxide thereof.

[0423] A compound having formula (XVII)

[0424]

[0425] wherein A is CH or N;

[0426] A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, more preferably no more than one A 1 is N, and even more preferably four A 1 are CR 1 ;

[0427] R 1 is independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino, and NHC(O)C 1-6 alkyl;

[0428] R 5 is independently selected from C 1-6 alkyl, C 1-6 alkoxy, C3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylamino, di-C 1-6 Alkylamino and C 1-6 Alkyl C 1-6 Alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; and

[0429] R 9 is C1-C6 alkyl.

[0430] A compound having formula (XVIII)

[0431]

[0432] wherein A is CH or N;

[0433] A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 is N, and more preferably four A 1 are CR 1 ;

[0434] R 1 is independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl;

[0435] R 5 is 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, di-C 1-6Alkylamino and C 1-6 Alkyl C 1-6 Alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; and

[0436] X is Cl, Br or I.

[0437] A compound having formula (XXIII)

[0438]

[0439] wherein A is CH or N;

[0440] A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 is N, and more preferably four A 1 are CR 1 ;

[0441] R 1 is independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl;

[0442] R 5 is 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; and

[0443] R 9 is C1-C6 alkyl.

[0444] A compound having the formula (XXV)

[0445]

[0446] wherein A is CH or N;

[0447] A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ;

[0448] R 1 is independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl;

[0449] A 2 is independently CR 2 or N, provided that no more than three A 2 are N, preferably no more than two A 2 are N, preferably no more than one A 2 are N, and more preferably four A 2 are CR 2 ;

[0450] R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, di-C 1-6 Alkylaminocarbonyl and C 1-6 Alkylcarbonyl, wherein C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkoxy-C 1-6 Alkyl, C 1-6 Alkoxy-C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-6 Alkyl, C 1-6 Alkylthio, C 1-6 Alkylsulfinyl, C 1-6 Alkylsulfonyl, C 1-6 Alkoxycarbonyl, C 1-6 Alkylaminocarbonyl, di-C 1-6 Alkylaminocarbonyl and C 1-6 Each of the alkylcarbonyl groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxy, and CN;

[0451] A 3 is independently CR 3 or N;

[0452] R 3 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, di-C 1-6 -alkylamino and C 3-6 cycloalkylamino, wherein C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino and C 3-6 Each of the cycloalkylamino groups is optionally substituted by one to three substituents independently selected from the following: halogen, hydroxy, and CN;

[0453] R 4 selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl, diC 1-6 alkylaminocarbonyl-C 1-6 alkyl and CN, wherein C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl and di-C 1-6 alkylaminocarbonyl-C 1-6 each of the alkyl groups is optionally substituted by one to three substituents independently selected from: halogen and CN; wherein A 3 and R 4 together optionally form a ring, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring.

[0454] The compounds of formula (I) as defined in the present invention can be used in the agricultural sector and related fields of use as, for example, active ingredients for controlling plant pathogens, or on inanimate materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance and environmental safety. They have very useful therapeutic, prophylactic and systemic properties and can be used to protect many cultivated plants. The compounds of formula (I) as defined in the present invention can be used to inhibit or destroy pathogens that appear on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those later-growing plant parts from, for example, plant pathogenic microorganisms.

[0455] The compounds of formula (I) as defined in the present invention can also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents fungal growth. The term "fungicidally effective amount" means an amount of such a compound or a combination of such compounds that is capable of having an effect on fungal growth. The effects of control or modification include all deviations from natural development, such as killing, arresting, etc., and prevention includes forming a barrier or other defense within or on the plant to prevent fungal infestation.

[0456] The compounds of formula (I) as defined in the present invention can also be used as seed dressings for treating plant propagation materials, such as seeds (e.g., fruits, tubers, or grains), or plant cuttings (e.g., rice), for protecting against fungal infestation and against plant pathogenic fungi present in the soil. The propagation materials can be treated with a composition comprising the compounds of formula (I) as defined in the present invention prior to planting: for example, the seeds can be dressed before sowing. The compounds of formula (I) as defined in the present invention can also be applied to grains (coating) by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site during planting of the propagation materials, such as to the furrow of the seeds during sowing. The present invention also relates to such methods of treating plant propagation materials and to plant propagation materials so treated.

[0457] Furthermore, the compounds of formula (I) as defined in the present 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.

[0458] Furthermore, the present invention can be used to protect inanimate materials (such as wood, wallboards, and coatings) from fungal attack.

[0459] The compounds of formula (I) as defined in the present invention and the fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, such as leaf pathogens of ornamental plants, turf, vegetables, field crops, cereals, and fruit crops.

[0460] These fungi and fungal vectors of the diseases that can be controlled, together with phytopathogenic bacteria and viruses, are for example:

[0461] Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. (including Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus niger, Aspergillus terreus), Aureobasidium spp. (including Aureobasidium pullulans), Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. (including Botryosphaeria dothidea, Botryosphaeria obtusa), Botrytis spp. (including Botrytis cinerea), Candida spp. (including Candida albicans, Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida tropicalis), Cephaloascus fragrans, Ceratocystis spp., Cercospora spp. (including Cercospora arachidicola), Cercosporidium personatum, Cladosporium spp., Claviceps purpurea,

[0462] Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. (including Colletotrichum musae),

[0463] Cryptococcus neoformans, Diaporthe spp, Didymella spp, Exserohilum spp., Elsinoe spp.,

[0464] Epidermophyton spp., Erwinia amylovora, Erysiphe spp. (including Erysiphe cichoracearum),

[0465] Eutypa lata, Fusarium spp. (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium subglutinans, Fusarium solani, Fusarium oxysporum, Fusarium proliferatum), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulata, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Physopella spp., Histoplasma spp. (including Histoplasma capsulatum), Corticium salmonicolor, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. (including Mycosphaerella graminicola, Mycosphaerella pomi), Phaeoacremonium spp., Picea spp., Paracoccidioides spp., Penicillium spp. (including Penicillium digitatum, Penicillium italicum), Myrothecium spp., Peronosclerospora spp. (including Peronosclerospora maydis, Peronosclerospora philippinensis, Peronosclerospora sorghi), Peronospora spp., Septoria nodorum, Phakopsora pachyrhizi, Phellinus igniarius, Sphaeropsis spp., Phomopsis viticola, Phytophthora spp. (including Phytophthora infestans), Plasmopara spp. (including Plasmopara halstedii, Plasmopara viticola), Pleospora spp., Podosphaera spp. (including Podosphaera leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Puccinia spp. (including Puccinia hordei, Puccinia recondita, Puccinia striiformis, Puccinia triticina), Sclerotinia spp., Pyrenophora spp., Pyricularia spp. (including Pyricularia oryzae, P.oryzae)), Pythium spp. (including Pythium ultimum), Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Hyphomycetes spp. (including Scedosporium apiospermum and Scedosporium prolificans), Schizothyrium pomi,

[0466] Species of Sclerotinia, Sclerotium, Septoria spp. (including Septoria nodorum, Septoria tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothrix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp., Trichoderma spp. (including Trichoderma harzianum, Trichoderma pseudokoningii, Trichoderma viride),

[0467] Species of Trichophyton, Typhula, Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. (including Venturia inaequalis), Verticillium spp. and Xanthomonas spp.

[0468] In particular, the compounds of formula (I) as defined in the present invention and the fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in Basidiomycetes, Ascomycetes, Oomycetes and / or Deuteromycetes, Blastocladiomycete, Chytridiomycetes, Glomeromycetes and / or Mucoromycetes. More particularly, the compounds of formula (I) as defined in the present invention can be used to control Oomycetes.

[0469] These pathogens may include:

[0470] 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; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum, and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida, Sclerophthora macrospora, and Bremia lactucae; and others such as Aphanomyces, Labyrinthula zosterae, Peronosclerospora sorghi, and Sclerospora graminicola.

[0471] Ascomycetes, including blotch, spot, blast or blight and / or rot, such as those caused by: Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Cycloconium oleagineum, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila; Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalorafulva), Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, banana black leaf streak pathogen, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, wheat basal rot pathogen, beet leaf spot pathogen, Ramularia collo-cygni; Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae; Diaporthales such as eastern filbert blight pathogen, Apiognomonia errabunda, Cytospora platani, northern soybean stem canker pathogen, Discula destructiva, Gnomonia fructicola, bitter rot of grape pathogen, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma; and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Colletotrichum caricicola, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza brassicaecampestris), Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Grapevine dieback, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, 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, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulisporasorghi), Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew, such as those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis, Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata, and Oidium arachidis; mold, such as those caused by Botryosphaeriaceae such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotiniathose caused by, for example, *Botryosphaeria dothidea*, *Fusicoccum amygdali*, *Lasiodiplodia theobromae*, *Macrophoma theicola*, *Macrophomina phaseolina*, *Phyllosticta cucurbitacearum*; anthracnose, for example, those caused by *Glomerellales* such as *Colletotrichum gloeosporioides*, *Colletotrichum lagenarium*, *Colletotrichum gossypii*, *Glomerella cingulata*, and *Colletotrichum graminicola*; and wilt or blight, for example, those caused by *Hypocreales* such as *Acremonium strictum*, *Claviceps purpurea*, *Fusarium culmorum*, *Fusarium graminearum*, *Fusarium virguliforme*, *Fusarium oxysporum*, *Fusarium subglutinans*, *Fusarium oxysporum f.sp. cubense*, *Gerlachia nivale*, *Gibberella fujikuroi*, *Gibberella zeae*, *Gliocladium species*, *Myrothecium verrucaria*, *Nectria ramulariae*, *Trichoderma viride*, *Trichothecium roseum*, and *Verticillium theobromae*.

[0472] Basidiomycetes, including smuts such as those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts such as those caused by Puccinia such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp.those caused by Secalis, Pucciniastrum coryli; or those caused by rust fungi 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, Exobasidium vexans, Marasmiellus inoderma, Mycena species, Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae, and Tilletia caries.

[0473] Blastocladiomycetes, such as Physoderma maydis.

[0474] Mucoromycetes, such as Choanephora cucurbitarum; Mucor species; Rhizopus arrhizus.

[0475] Together with diseases caused by other species and genera closely related to those listed above.

[0476] In addition to their fungicidal activity, these compounds and compositions comprising compounds of formula (I) as defined in the present invention may also have activity against bacteria such as Erwinia amylovora, Erwinia carotovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies and other related species, as well as certain protozoa.

[0477] Within the scope of the present invention, target crops and / or useful plants to be protected typically include perennial and annual crops such as berry plants, e.g. blackberry, blueberry, cranberry, raspberry and strawberry; cereals, e.g. barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, e.g. cotton, flax, hemp, jute and sisal; field crops, e.g. sugar beet and fodder beet, coffee bean, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, e.g. apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, e.g. bermudagrass, bluegrass, bentgrass, centipede grass, foxtail, ryegrass, St. Augustine grass and zoysiagrass; herbs, such as basil, borage, chive, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes, e.g. kidney bean, lentil, pea and soybean; nuts, e.g. almond, cashew nut, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palm plants, e.g. oil palm; ornamental plants, e.g. flowers, shrubs and trees; other trees, e.g. cacao tree, coconut tree, olive tree and rubber tree; vegetables, e.g. asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, zucchini, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines, e.g. grape.

[0478] Useful plants and / or target crops according to the present invention include conventional as well as genetically enhanced or genetically engineered varieties, such as insect-resistant (e.g. Bt. and VIP varieties) together with disease-resistant, herbicide-tolerant (e.g. glyphosate-resistant and glufosinate-resistant maize varieties, commercially available under the trade names and and nematode-tolerant varieties. By way of example, suitable genetically enhanced or genetically engineered crop varieties include Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

[0479] The terms "useful plant" and / or "target crop" are to be understood as also including useful plants which have been made tolerant to herbicides (such as bromoxynil) or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors such as flupyrsulfuron, flazasulfuron and tritosulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) by conventional breeding methods or genetic engineering methods. Examples of crops which have been made tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutagenesis) are summer rape (canola). Examples of crops which have been made tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties, which are commercially available under the trade names Herculex and respectively.

[0480] The terms "useful plant" and / or "target crop" are to be understood as including those which are naturally or have been made resistant to harmful insects. This includes plants which have been transformed by means of recombinant DNA technology so that they are, for example, capable of synthesizing one or more insecticidal proteins with a selective action, which are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode-parasitic bacteria, and toxins produced by scorpions, arachnids, wasps and fungi. Examples of crops which have been modified to express Bacillus thuringiensis toxins are Bt maize (Syngenta Seeds). Examples of crops which include more than one gene encoding insecticidal resistance and which thus express more than one toxin are (Syngenta Seeds). The crop or its seed material can also be resistant to multiple types of pests (so-called stacked transgenic events when produced by genetic modification). For example, a plant can have the ability to express an insecticidal protein while being tolerant to herbicides, such as Herculex (Dow AgroSciences, Pioneer Hi-Bred International).

[0481] The terms "useful plant" and / or "target crop" are to be understood as also including useful plants which have been transformed by means of recombinant DNA technology such that they are capable of synthesizing selectively active anti-pathogenic substances, such as so-called "pathogenesis-related proteins" (PRPs, see for example EP-A-0 392 225). Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. The methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0482] Toxins which can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of nematode-parasitic bacteria, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycete toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato protease inhibitor, cystatin, papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, maize-RIP, abrin, saporin, soya-bean RIP or bryodin; steroid-metabolizing enzymes, such as 3-hydroxy-steroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-CoA-reductase, ion-channel blockers such as sodium-channel or calcium-channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

[0483] Furthermore, in the context of the present invention, δ-endotoxins (such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (such as Vip1, Vip2, Vip3 or Vip3A) should be understood to clearly also include hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by novel combinations of different 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 replaced. In such amino acid replacements, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence was inserted into the Cry3A toxin (see WO 03 / 018810).

[0484] More examples of such toxins or transgenic 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.

[0485] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0486] The toxins contained in transgenic plants confer on the plants tolerance to harmful insects. Such insects can be present in any insect taxon, but are particularly common among beetles (Coleoptera), dipterous insects (Diptera) and moths (Lepidoptera).

[0487] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (maize variety expressing the Cry1Ab toxin); YieldGard (maize variety expressing the Cry3Bb1 toxin); YieldGard (maize variety expressing the Cry1Ab and Cry3Bb1 toxins); (maize variety expressing the Cry9C toxin); Herculex (Maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate-ammonium); NuCOTN (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac and Cry2Ab toxins); (Cotton variety expressing the Vip3A and Cry1Ab toxins); (Potato variety expressing the Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 European corn borer (CB) trait) and

[0488] Additional examples of such transgenic crops are:

[0489] 1. Bt11 maize, from Syngenta Seeds SAS, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, transgenic expression of truncated Cry1Ab toxin, enabling it to resist the invasion of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt11 maize also transgenically expresses the PAT enzyme to obtain tolerance to the herbicide glufosinate.

[0490] 2. Bt176 maize, from Syngenta Seeds, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, transgenic expression of Cry1Ab toxin, enabling it to resist the invasion of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt176 maize also transgenically expresses the enzyme PAT to obtain tolerance to the herbicide glufosinate.

[0491] 3. MIR604 maize, from Syngenta Seeds, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize with insect resistance by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by inserting a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0492] 4. MON 863 maize, from Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0493] 5. IPC 531 cotton, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0494] 6. 1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B - 1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize that expresses the protein Cry1F to obtain resistance to certain Lepidoptera insects and expresses the PAT protein to obtain tolerance to the herbicide glufosinate.

[0495] 7. NK603×MON 810 maize, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Constituted from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from Agrobacterium sp. strain CP4, which confers tolerance to herbicides (containing glyphosate), and also expresses the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, which confers tolerance to certain Lepidoptera insects (including Ostrinia nubilalis).

[0496] As used herein, the term "site" means the place where a plant grows or on which it grows, or the place where the seeds of a cultivated plant are sown, or the place where seeds are to be placed in the soil. It includes the soil, seeds, and seedlings, along with the established vegetation.

[0497] The term "plant" means all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0498] The term "plant propagation material" shall be understood to denote the reproductive parts of plants, such as seeds, which can be used for the propagation of plants, as well as vegetative material, such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Mention may also be made of germinated plants and young plants which are to be transplanted after germination or after emergence. These young plants can be protected before transplantation by being treated completely or partially by drenching. Preferably, "plant propagation material" shall be understood to denote seeds.

[0499] The pesticides mentioned by their common names in this text are known, for example, from "The Pesticide Manual", 19th edition, British Crop Protection Council 2021.

[0500] The compounds of formula (I) as defined in the present invention can be used in unmodified form or, preferably, together with adjuvants conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules (e.g. in polymeric substances). For the type of composition, the method of application is chosen according to the intended purpose and the circumstances prevailing at the time, such as spraying, atomizing, dusting, broadcasting, spreading or watering. The compositions can also contain further adjuvants, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0501] Suitable carriers and / or adjuvants, for example for agricultural use, can be solid or liquid and are substances useful in the art of formulation, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0502] A suspension concentrate is an aqueous formulation in which fine, solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants and can further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. In use, these concentrates are diluted in water and are generally applied as sprays to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0503] Wettable powders are in the form of finely divided particles that are readily dispersible in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin, silica, and other readily wettable organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus small amounts of wetting agents, dispersing agents, or emulsifying agents.

[0504] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and can consist entirely of the active compound with liquid or solid emulsifying agents, or may also contain liquid carriers 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 usually applied as sprays to the area to be treated. The amount of the active ingredient can range from 0.5% to 95% of the concentrate.

[0505] Granular formulations include both extrudates and coarser granules and are usually applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, ground corn cobs, ground peanut hulls, 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 materials that absorb the active compound or can be coated with the active compound. Granular formulations usually contain 5% to 25% of the active ingredient, which can include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrin, glue, or synthetic resins.

[0506] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clay, flour, and other organic and inorganic solids that serve as dispersants and carriers.

[0507] Microcapsules are typically microdroplets or particles of an active ingredient encapsulated within an inert porous shell that permits the enclosed material to escape into the environment at a controlled rate. The diameter of the encapsulated microdroplets is typically from 1 to 50 microns. The enclosed liquid typically comprises from 50% to 95% by weight of the capsule and may contain solvents in addition to the active compound. The encapsulated particles are usually porous particles in which a porous membrane seals the particle orifice, retaining the active species in liquid form within the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The particles are formed by extrusion, aggregation or spheronization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbonaceous grains. The shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0508] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in a finely divided form due to the evaporation of a low boiling dispersant solvent carrier.

[0509] Suitable agricultural adjuvants and / or carriers useful for formulating the compositions of the present invention in the above formulation types are well known to those skilled in the art.

[0510] Liquid carriers which can be used include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, 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, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isopentanone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin wax, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is usually the preferred carrier for diluting concentrates.

[0511] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

[0512] A wide range of surfactants are advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents typically comprise from 0.1% to 15% by weight of the formulation when in use. They can be anionic, cationic, nonionic or polymeric in nature and can be employed 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; alkylphenol-alkylene oxide adducts such as nonylphenol-C18 ethoxylate; alcohol-alkylene oxide adducts such as tridecanol-C16 ethoxylate; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl esters of sulfosuccinic acid such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines 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.

[0513] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity regulators, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light blockers, compatibility agents, defoaming agents, masking agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavoring agents, spreading agents, penetration aids, micronutrients, emollients, lubricants and fixing agents.

[0514] In addition, further, other biocidal active ingredients or compositions can 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 can be formulated together with the compositions of the present invention or mixed, for example, in a spray tank. These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators and / or biopreparations.

[0515] Preferred combinations of the compound of formula I with another active substance in a weight ratio of 1:1 (where the abbreviation "TX" means "a compound selected from the compounds defined in Tables 1.1 to 1.132 and Table A) are:

[0516] Adjuvants selected from the group consisting of: petroleum (alias) (628) + TX;

[0517] Abamectin + TX, Clofentezine + TX, Acetamiprid + TX, Ethiprole + TX, Fluprothrin + TX, Acynonapyr + TX, Cyprodinil + TX, Afoxolaner + TX, Alanycarb + TX, Allethrin + TX, Alpha - cypermethrin + TX, Alpha - cyhalothrin + TX, Bicyclanil + TX, Aminocarb + TX, Azocyclotin + TX, Bensultap + TX, Tebufenpyrad + TX, Benzpyrimoxan + TX, Beta - cyfluthrin + TX, Beta - cypermethrin + TX, Bifenazate + TX, Bifenthrin + TX, Binapacryl + TX, d - Allethrin + TX, S - Allethrin + TX, Bioallethrin - S - cyclopentenyl isomer + TX, Bistrifluron + TX, Broflanilide + TX, Bromofluorene + TX, Bromophos - ethyl + TX, Buprofezin + TX, Butocarboxim + TX, Cadusafos + TX, Carbaryl + TX, Carbosulfan + TX, Cartap + TX, CAS No.: 1632218 - 00 - 8 + TX, CAS No.: 1808115 - 49 - 2 + TX, CAS No.: 2032403 - 97 - 5 + TX, CAS No.: 2044701 - 44 - 0 + TX, CAS No.: 2128706 - 05 - 6 + TX, CAS No.: 2095470 - 94 - 1 + TX, CAS No.: 2377084 - 09 - 6 + TX, CAS No.: 1445683 - 71 - 5 + TX, CAS No.: 2408220 - 94 - 8 + TX, CAS No.: 2408220 - 91 - 5 + TX, CAS No.: 1365070 - 72 - 9 + TX, CAS No.: 2171099 - 09 - 3 + TX, CAS No.: 2396747 - 83 - 2 + TX, CAS No.: 2133042 - 31 - 4 + TX, CAS No.: 2133042 - 44 - 9 + TX, CAS No.: 1445684 - 82 - 1 + TX, CAS No.: 1445684 - 82 - 1 + TX, CAS No.: 1922957 - 45 - 6 + TX, CAS No.: 1922957 - 46 - 7 + TX, CAS No.: 1922957 - 47 - 8 + TX, CAS No.: 1922957 - 48 - 9 + TX, CAS No.: 2415706 - 16 - 8 + TX, CAS No.: 1594624 - 87 - 9 + TX, CAS No.: 1594637 - 65 - 6 + TX, CAS No.: 1594626 - 19 - 3 + TX, CAS No.: 1990457 - 52 - 7 + TX, CAS No.: 1990457 - 55 - 0 + TX, CAS No.: 1990457 - 57 - 2 + TX, CAS No.: 1990457 - 77 - 6 + TX, CAS No.: 1990457 - 66 - 3 + TX,CAS No.: 1990457-85-6 + TX, CAS No.: 2220132-55-6 + TX, CAS No.: 1255091-74-7 + TX, CAS No.: 2719848-60-7 + TX, CAS No.: 1956329-03-5 + TX, Chlorantraniliprole + TX, Chlordane + TX, Chlorfenapyr + TX, Empenthrin + TX, Chromafenozide + TX, Clenpirin + TX, Cloethocarb + TX, Clothianidin + TX, 2-Chlorophenyl N-methylcarbamate (CPMC) + TX, Cyanofenphos + TX, Cyantraniliprole + TX, Cyclaniliprole + TX, Cyclobutrifluram + TX, Pyrethroid + TX, Etoxazole + TX, Cyenopyrafen or Etpyrafen + TX, Butylflufenpyr + TX, Cyfluthrin + TX, Cyhalodiamide + TX, Cypermethrin + TX, Deltamethrin + TX, Cyproflanilide + TX, Cyromazine + TX, Diflubenzuron + TX, Dimpropyridaz + TX, Dioxabactin + TX, Dinocap + TX, Dinotefuran + TX, EPN + TX, Emamectin (or Emamectin Benzoate) + TX, Esbiothrin + TX, Epsilon-Momfluorothrin + TX, Epsilon-Methobenzfluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethiprole + TX, Etofenprox + TX, Etoxazole + TX, Famphur + TX, Fenazaquin + TX, Flucythrinate + TX, Fenmezoditiaz + TX, Fenitrothion + TX, Fenobucarb + TX, Benfuracarb + TX, Phenoxycarb + TX, Fenpropathrin + TX, Fenpyroximate + TX, Fensulfothion + TX, Fenthion + TX, Fenthion + TX, Fenvalerate + TX, Fipronil + TX, Flometoquin + TX, Flonicamid + TX, Flufenerim + TX, Fluazaindolizine + TX, Flucarbenz + TX, Flufenerim + TX, Flucitrinate + TX, Flucycloxuron + TX, Flucythrinate + TX, Flupyradifurone + TX, Flufenerim + TX, Trifluoromethrin + TX, Butene-fipronil + TX,fluhexafon + TX, tefluthrin + TX, fluopyram + TX, flupentiofenox + TX, flupyradifurone + TX, flupyroxystrobin + TX, flupyrimin + TX, fluralaner + TX, tau-fluvalinate + TX, fluxametamide + TX, fosthiazate + TX, lambda-cyhalothrin + TX, pymetrozine + TX, tebufenozide + TX, pyrimidifen + TX, heptafluthrin + TX, hexythiazox + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloseram + TX, isofenphos + TX, ivermectin + TX, kappa-cypermethane + TX, kappa-hexaflumuron + TX, lambda-cyhalothrin + TX, ledprona + TX, lepimectin + TX, lotilaner + TX, chlorfenapyr + TX, metaflumizone + TX, metaldehyde + TX, metam-sodium + TX, methomyl + TX, methoxyfenozide + TX, metofluthrin + TX, metolcarb + TX, methiocarb + TX, milbemectin + TX, momfluorothrin + TX, niclosamide + TX, nicofluprole + TX; nitenpyram + TX, nithiazine + TX, omethoate + TX, methomyl + TX, oxazosulfyl + TX, parathion-ethyl + TX, permethrin + TX, phenothrin + TX, phosmet + TX, piperonyl butoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, polyhedrosis virus + TX, prallethrin + TX, profenofos + TX, profluthrin + TX, propargite + TX, propaphos + TX, propoxur + TX, prothiofos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyridaben + TX, pyridalyl + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyrimidaben + TX, pyrafluprole + TX, pyriproxyfen + TX, resmethrin + TX, sarolaner + TX, selamectin + TX, silafluofen + TX, spinetoram + TX, spinosad + TX, spirodiclofen + TX, spirotetramat + TX, spirohexamato + TX,spiropidion + TX, spirotetramat + TX, spidoxamat + TX, sulfoxaflor + TX, tebufenozide + TX, pyridaben + TX, tebupirimiphos + TX, tefluthrin + TX, temephos + TX, chlorantraniliprole + TX, tetradiphon + TX, tetramethrin + TX, dimefluthrin + TX, abamectin + TX, flubendiamide + TX, theta - cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiosultap - sodium + TX, thiodicarb + TX, thiofanox + TX, methyldicholorp - thion + TX, cartap - hydrochloride + TX, tigolaner + TX, thiafluamid + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, triazamate + TX, triazophos + TX, trichlorfon + TX, trichloronate + TX, trichlorfon + TX, trifluenfuronate + TX, triflumezopyrim + TX, Tyclopyrazoflor + TX, zeta - cypermethrin + TX, seaweed extract and fermentation products derived from sugar acyls + TX, seaweed extract and fermentation products derived from sugar acyls (containing urea + TX, amino acids + TX, potassium and molybdenum and EDTA - chelated manganese) + TX, seaweed extract and fermented plant products + TX, seaweed extract and fermented plant products (containing phytohormones + TX, vitamins + TX, EDTA - chelated copper + TX, zinc + TX, and iron) + TX, azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL accession number B - 21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B - 21664) + TX, Bacillus pumilus (NRRL accession number B - 30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B - 21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, uncharacterized Bacillus subtilis + 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, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subsp. kurstaki BMP 123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulosis virus + TX, Harpin + TX, Helicoverpa armigera nuclear polyhedrosis virus + TX, Heliothis zea nuclear polyhedrosis virus + TX, Heliothis virescens nuclear polyhedrosis virus + TX, Helicoverpa punctigera nuclear polyhedrosis virus + TX, Metarhizium species + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, neem-based product + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nesiana + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria sp. + TX, p-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces flavidus (NRRL accession number 30232) + TX, Streptomyces species (NRRL accession number B-30145) + TX, terpenoid blend + TX, and Verticillium species + TX;

[0518] An algicide selected from the group consisting of: bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, indoleacetic acid (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) + TX, and triphenyltin hydroxide (IUPAC name) (347) + TX;

[0519] Anthelmintics selected from the group consisting of: avermectin (1) + TX, clophos (1011) + TX, cyclobutafrine + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, and thiophanate (1435) + TX;

[0520] Avicides selected from the group consisting of: chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) + TX, and strychnine (745) + TX;

[0521] Bactericides selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptofen (alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium 8-hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thimerosal (alias) [CCN] + TX;

[0522] Biological agents, selected from the group consisting of: Adoxophyes orana granulovirus (synonym) (12) + TX, Agrobacterium radiobacter (synonym) (13) + TX, Amblyseius spp. (synonym) (19) + TX, Laphygma exigua NPV (synonym) (28) + TX, Anagrus atomus (synonym) (29) + TX, Aphelinus abdominalis (synonym) (33) + TX, Aphidius colemani (synonym) (34) + TX, Aphidoletes aphidimyza (synonym) (35) + TX, Autographa californica NPV (synonym) (38) + TX, Bacillus firmus (synonym) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name)Tenebrionis)(scientific name)(51)+TX, Beauveria bassiana)(alias)(53)+TX, Beauveria brongniartii)(alias)(54)+TX, Chrysoperla carnea)(alias)(151)+TX, Cryptolaemus montrouzieri)(alias)(178)+TX, Cydia pomonella GV)(alias)(191)+TX, Dacnusa sibirica)(alias)(212)+TX, Diglyphus isaea)(alias)(254)+TX, Encarsia formosa)(scientific name)(293)+TX, Eretmocerus eremicus)(alias)(300)+TX, Helicoverpa zea NPV)(alias)(431)+TX, Heterorhabditis bacteriophora and H. megidis)(alias)(433)+TX, Hippodamia convergens)(alias)(442)+TX, Leptomastix dactylopii)(alias)(488)+TX, Macrolophus caliginosus)(alias)(491)+TX, Mamestra brassicae NPV)(alias)(494)+TX, Metaphycus helvolus)(alias)(522)+TX, Metarhizium anisopliae var. acridum)(scientific name)(523)+TX, Metarhizium anisopliae var. anisopliae)(scientific name)(523)+TX, Neodiprion sertifer)NPV and N.lecontei) NPV (alias) (575) + TX, Orius spp. (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimilis (alias) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema sp. (alias) (742) + TX, Steinernema glaseri (alias) (742) + TX, Steinernema riobrave (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema scapterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) + TX and Verticillium lecanii (alias) (848) + TX;.

[0523] Soil disinfectant, which is selected from the group consisting of: methyl iodide (IUPAC name) (542) + TX and methyl bromide (537) + TX;

[0524] Chemical sterilants, which are selected from the group consisting of: apholate [CCN]+TX, bisazir (alias) [CCN]+TX, busulfan (alias) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alias) [CCN]+TX, hexamethylmelamine (hemel) [CCN]+TX, hexaethylphosphoramide (hempa) [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methylapholate [CCN]+TX, morzid [CCN]+TX, penfluron (alias) [CCN]+TX, tepa [CCN]+TX, thiohempa (alias) [CCN]+TX, thiotepa (alias) [CCN]+TX, triethylenemelamine (alias) [CCN]+TX, and urethaneimine (alias) [CCN]+TX;

[0525] An insect pheromone selected from the group consisting of: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-heneicos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-Methyloctadec-1-ene (IUPAC name) (545) + TX, 4-Methylnonan-5-ol and 4-Methylnonan-5-one (IUPAC name) (544) + TX, α-Multistriatin (alias) [CCN] + TX, Western pine beetle aggregation pheromone (brevicomin) (alias) [CCN] + TX, Dodecadienol (codlelure) (alias) [CCN] + TX, Codlemone (alias) (167) + TX, Cuelure (alias) (179) + TX, Epoxynonadecane (disparlure) (277) + TX, Dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, Dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, Dominicalure (alias) [CCN] + TX, Ethyl 4-methyl octanoate (IUPAC name) (317) + TX, Eugenol (alias) [CCN] + TX, Southern pine beetle aggregation pheromone (frontalin) (alias) [CCN] + TX,, 1:1 mixture of (Z,E) and (Z,Z) isomers of [[ID=]], hexalure [CCN] + TX, ipsdienol (alias) [CCN] + TX, ipsenol (alias) [CCN] + TX, japonilure (alias) (481) + TX, lineatin (alias) [CCN] + TX, litlure (alias) [CCN] + TX, looplure (alias) [CCN] + TX, medlure [CCN] + TX, (3E,5Z)-tetradeca-3,5-dienoic acid (megatomoic acid) (alias) [CCN] + TX, methyleugenol (alias) (540) + TX, muscalure (563) + TX, octadec-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, octadec-3,13-dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol (alias) [CCN] + TX, tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, Mediterranean fruit fly attractant (839) + TX, Mediterranean fruit fly attractant A (alias) (839) + TX, Mediterranean fruit fly attractant B1 (alias) (839) + TX, Mediterranean fruit fly attractant B2 (alias) (839) + TX, Mediterranean fruit fly attractant C (alias) (839) TX and trunc-call (alias) [CCN] + TX;

[0526] Insect repellents selected from the group consisting of: 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, N,N-diethyl-meta-toluamide [CCN]+TX, dimethylcarbate [CCN]+TX, dimethyl phthalate [CCN]+TX, 2-ethylhexan-1,3-diol (1137)+TX, hexuron [CCN]+TX, methoquin-butyl (1276)+TX, methyl neodecanoamide [CCN]+TX, oxamate [CCN]+TX, and picaridin [CCN]+TX;

[0527] Molluscicides selected from the group consisting of: bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, aldicarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, triphenyltin (347)+TX, iron(III) phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-ethanolamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenate (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347)+TX, triphenyltin hydroxide (IUPAC name) (347)+TX, and pyriprole [394730-71-3]+TX;

[0528] Nematicides selected from the group consisting of: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, dimefox (999) + TX, cyclaniliprole + TX, cytokinin (alias) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alias) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alias) [CCN] + TX, GY-81 (research code) (423) + TX, fenthion [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl demeton (1258) + TX,Metham(519)+TX, Metham Potassium Salt (alias)(519)+TX, Metham Sodium Salt(519)+TX, Methyl Bromide(537)+TX, Methyl Isothiocyanate(543)+TX, Milbemycin(alias)[CCN]+TX, Moxidectin(alias)[CCN]+TX, Myrothecium verrucaria Composition(alias)(565)+TX, NC-184(Compound Code)+TX, Oxamyl(602)+TX, Phorate(636)+TX, Phosfolan(639)+TX, Phosphocarb[CCN]+TX, Nemacur(alias)+TX, Selamectin(alias)[CCN]+TX, Spinosad(737)+TX, BPMC(alias)+TX, Terbufos(773)+TX, 2,3,5,6-Tetrachloro-1H-thiophene(IUPAC / Chemical Abstracts Name)(1422)+TX, Thiafenox(alias)+TX, Thionazin(1434)+TX, Triazophos(820)+TX, Triazuron(alias)+TX, Xylenol[CCN]+TX, YI-5302(Compound Code)+TX, Zeatin(alias)(210)+TX, Fluensulfone[318290-98-1]+TX, and Fluopyram+TX;;

[0529] Nitrification inhibitors selected from the group consisting of potassium ethyl xanthate[CCN]+TX and nitrapyrin(580)+TX;

[0530] Plant activators selected from the group consisting of acibenzolar(6)+TX, acibenzolar-S-methyl(6)+TX, probenazole(658)+TX and Reynoutria sachalinensis extract(alias)(720)+TX;

[0531] Rodenticide, the rodenticide is selected from the group consisting of: 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chloroalcohol [CCN] + TX, aluminum phosphide (640) + TX, alpha-naphthylthiourea (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bishydroxycoumarin (912) + TX, bromadiolone (89) + TX, brodifacoum (including α-brodifacoum) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alias) (850) + TX, chlororophacinone (1004) + TX, coumatetralyl (1005) + TX, coumatetralone (175) + TX, coumatil (1009) + TX, difenacoum (246) + TX, thiafentanil (249) + TX, diphacinone (273) + TX, calciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, fluridone (1183) + TX, fluridone hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, pindone (1318) + TX, phosdrin (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pival (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) + TX, and zinc phosphide (640) + TX;

[0532] Synergists, selected from the group consisting of: 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (324) + TX, MB-599 (research code) (498) + TX, MGK 264 (research code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propylisomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) + TX and sulfoxide (1406) + TX;

[0533] Animal repellents, selected from the group consisting of: anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, silafluofen (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] + TX and ziram (856) + TX;

[0534] Virucides, selected from the group consisting of: imarox (alias) [CCN] and ribavirin (alias) [CCN] + TX;

[0535] Wound protectants, selected from the group consisting of: mercury oxide (512) + TX, octhilinone (590) + TX and thiophanate-methyl (802) + TX;

[0536] Bioactive substances selected from the following: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorodiphenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, cythioate + TX, fenthion + TX, oxydemeton-methyl + TX, amitraz + TX, chlorbenside + TX, arsenic trioxide + TX, azobenzene + TX, azinphos + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brodifacoum + TX, bromocylen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbaryl + TX, carbophenothion + TX, chinomethionat + TX, chinomethionat-diclexine + TX, dicofol-4 + TX, dicofol-6 + TX, dicofol-o + TX, dinitropentaerythritol + TX, dinitrooctyl phenyl ether + TX, dinitrobutyl phenyl ether + TX, dichlorvos + TX, dichlofenthion + TX, dienochlor + TX, dimefox + TX, dinocap + TX, dinocap-diclexine + TX, dithianon-4 + TX, dithianon-6 + TX, dithianon-o + TX, ethephon + TX, ethylmercuric chloride + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, dioxathion + TX, eprinomectin + TX, ethion + TX, etrimfos + TX, fenazaquin + TX, fenbutatin oxide + TX, fenothiocarb + TX, pyridaben + TX, tebufenpyrad + TX, amisulbrom + TX, chlorfenson + TX, fentrifanil + TX, flufenzin + TX, flucycloxuron + TX, flubenzimine + TX, flubenzimine + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, γ-HCH + TX, guazatine + TX, bifenazate + TX, hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX,Jasmolin I + TX, Jasmolin II + TX, Iodofenphos + TX, Lindane + TX, Propargite + TX, Oxamyl + TX, Disulfoton + TX, Methiocarb + TX, Methacrifos + TX, Methyl bromide + TX, MTMC + TX, Carbaryl + TX, Milbemycin + TX, Propetamphos + TX, Monocrotophos + TX, Phenthoate + TX, Moxidectin + TX, Naled + TX, 4-Chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Flucythrinate + TX, Nikkomycin + TX, Permethrin + TX, Permethrin 1:1 zinc chloride complex + TX, Omethoate + TX, Isoxathion + TX, Aldoxycarb + TX, pp'-DDT + TX, Parathion + TX, Permethrin + TX, Fensulfothion + TX, Phosalone + TX, Phosfolan + TX, Phosmet + TX, Polychloroterpenes + TX, Polynactins + TX, Proclonol + TX, Pyridaphenthion + TX, Propoxur + TX, Ethoprophos + TX, Prothiofos + TX, Pyrethrin I + TX, Pyrethrin II + TX, Pyrethrin + TX, Pyridaphenthione + TX, Pyrimithion + TX, Quinalphos + TX, Quintiofos + TX, R-1492 + TX, Glyodin + TX, Rotenone + TX, Schradan + TX, Nemacur + TX, Selamectin + TX, Sulfotep + TX, Sulprofos + TX, SSI-121 + TX, Sulfenuron + TX, Flufenerim + TX, Sulfotepp + TX, Sulfur + TX, Flufenzine + TX, Tau-fluvalinate + TX, TEPP + TX, Tsumacide + TX, Tetradifon + TX, Binapacryl + TX, Thiafenox + TX, Bendiocarb + TX, Thiofanox + TX, Metasystox + TX, Chlorobenzilate + TX, Bacillus thuringiensis + TX, Triamiphos + TX, Triazuron + TX, Trichlorfon + TX, Streptomycin + TX, Formetanate + TX, Vaniliprole + TX, Bethoxazin + TX, Copper dioctoate + TX, Copper sulfate + TX, Cybutryne + TX, Dichlone + TX, Dichlorophen + TX, Indole-3-acetic acid + TX, Triphenyltin + TX, Calcium hydroxide + TX, Sodium thiosulfate + TX, Algicide + TX, Quinonamid + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Cythioate + TX, Piperazine + TX, Thiophanate + TX, Chloralose + TX, Fenthion + TX, 4-Aminopyridine + TX, Strychnine + TX, 1-Hydroxy-1H-pyridine-2-thione + TX, 4-(Quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-Hydroxyquinoline sulfate + TX, Bronopol + TX, Copper hydroxide + TX,Cresol + TX, dipyrithione + TX, dodixin + TX, sodium sulfamethoxam + TX, formaldehyde + TX, mercurygafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhiothione + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown-banded tornado GV + TX, Agrobacterium radiobacterium + TX, Amblyseius spp. + TX, celery armyworm NPV + TX, Anagrus atomus + TX, short-spur aphid wasp + TX, cotton aphid parasitic wasp (Aphidius colemani) + TX, aphid midge (Aphidoletes aphidimyza+TX, Spodoptera alfalfa NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Codling moth GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens)+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage armyworm NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV+TX, Pseudomonas species+TX, Paecilomyces fumosorum+TX, Phytoseiulus persimilis+TX,Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema species + TX, Trichogramma species + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, sterigmatocystin, diflubenzuron, tepa, thiohempa, thiotepa, trimetrexate, urethane imine, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-heneicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-plicacetin, western pine beetle aggregation pheromone, dodecadienol, codlemone, cue lure, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate + TX, domy lure + TX, ethyl 4-methylcaprylate + TX, eugenol + TX, southern pine beetle aggregation pheromone + TX, luresene mixture + TX, luresene mixture I + TX, luresene mixture II + TX, luresene mixture III + TX, luresene mixture IV + TX, hexalure + TX, ipsdienol + TX, picrodendrol + TX, chafer sex pheromone + TX, trimethyldioxatricyclononane + TX, noctuid sex pheromone + TX, pink bollworm sex pheromone + TX, lure ester + TX, (3E,5Z)-tetradeca-3,5-dienoic acid (megatomoic acid) + TX, insect lure + TX, insectene + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, hecaconbi + TX, coconut rhinoceros beetle aggregation pheromone + TX, felekang + TX, insect lure ring + TX, banana weevil attractant + TX, mycetoctonus lure alcohol + TX, tetradec-11-en-1-yl acetate + TX, Mediterranean fruit fly attractant + TX, Mediterranean fruit fly attractant A + TX, Mediterranean fruit fly attractant B1 + TX, Mediterranean fruit fly attractant B2 + TX, Mediterranean fruit fly attractant C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, dibutyl phthalate + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl phthalate + TX, ethylhexylglycerin + TX, hexuron + TX, mequindox + TX, methyl neodecanoamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovalerylindane-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-cyanothioethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX,5,5-Dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, Acephate + TX, Acrylonitrile + TX, Aldrin + TX, Avermectin + TX, Benfuracarb + TX, α-Ecdysone + TX, Aluminum phosphide + TX, Bassa + TX, Neonicotinoids + TX, Ethyl methidathion + TX, Methyl pirimiphos + TX, Bacillus thuringiensis δ-endotoxin + TX, Barium hexafluorosilicate + TX, Barium polysulfide + TX, Resmethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-Fluvalinate + TX, β-Cypermethrin + TX, Transfluthrin + TX, Bioallethrin + TX, Bis(2-chloroethyl) ether + TX, Borax + TX, Bromfenvinfos + TX, Bromo-DDT + TX, BPMC + TX, Butacarb + TX, Terbam + TX, Butonate + TX, Calcium arsenate + TX, Calcium cyanide + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Cartap hydrochloride + TX, Cevadine + TX, Endosulfan sulfate + TX, Chlordane + TX, Kepone + TX, Chloroform + TX, Chloropicrin + TX, Cyanofenphos + TX, Chlorprazophos + TX, Cis-resmethrin + TX, Cismethrin + TX, Cypermethrin + TX, Cupric acetoarsenite + TX, Cupric arsenate + TX, Cupric oleate + TX, Chlorfenvinphos + TX, Cryolite + TX, CS 708 + TX, Cyanofenphos + TX, Cyanophos + TX, Cycloprothrin + TX, Cythioate + TX, d-Tetramethrin + TX, DAEP + TX, Dazomet + TX, Desmethylcarbofuran + TX, Dioxacarb + TX, Isochlorphos + TX, Dichlofenthion + TX, Dicresyl + TX, Cyclaniliprole + TX, Dieldrin + TX, Diethyl 5-methylpyrazol-3-yl phosphate + TX, Theophylline + TX, Transfluthrin + TX, Desmedipham + TX, Pyrethrins + TX, Methacrifos + TX, Dimethoate + TX, Propanil + TX, Phenthoate + TX, DSP + TX, Ecdysterone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, Etaphos + TX, Ethiofencarb + TX, Ethyl formate + TX, Ethylene dibromide + TX, Ethylene dichloride + TX, Ethylene oxide + TX, EXD + TX, Fenchlorphos + TX, Ethiofencarb + TX, Fenitrothion + TX, Oxamyl + TX, Pyraclofos + TX, Fensulfothion + TX, Ethyl fenthion + TX, Flucarbazone + TX, Butathiofos + TX, Phosphamidon + TX, Butocarboxim + TX, Pyrethrum + TX, Guazatine + TX, Guazatine acetate + TX, Sodium tetrathiocarbonate + TX, Bifenazate + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Sumithion + TX, HHDN + TX, Hydrogen cyanide + TX,Quinolinecarb + TX, IPSP + TX, chlorfenthion + TX, carbon chlorine + TX, isoaldrin + TX, isofenphos + TX, transplanting spirit + TX, rice blast + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiazophos + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, aphidite + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifene + TX, metamifene potassium salt + TX, metamifene sodium salt + TX, methylsulfonyl fluoride + TX, butenylphos + TX, methoprene + TX, methylthiophene + TX, methoxychlor T + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, oxadiazine + TX, anthelmintic + TX, naphthion + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, orthonicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-ylphosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, amidophos+TX, profluthrin+TX, fenthion+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, oxazolidinone+TX, iodophos+TX, resmethrin+TX, rotenone+TX, thiamethoxam+TX, ryanodine+TX, saba Veratrum (sabadilla) + TX, octamethrin + TX, clomiphene + TX, SI-0009 + TX, thiopropionitrile + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron sodium salt + TX, sulfuryl fluoride + TX, thiopromide + TX, tar + TX, thiocarb + TX, TDE + TX, butylpyrimidinphos + TX, dimethophos + TX, cyclopentyl thiocarb + TX, tetrachloroethane + TX, thiochlorvos + TX, cyclohexane + TX, cyclohexane oxalate + TX, cyfluthrin + TX,Insecticide monohydrate + TX, insecticide monosodium + TX, tetrabromothrin + TX, transpermethrin + TX, triazolam + TX, isothiocarb-3 + TX, chlorpyrifos + TX, methoxycarb + TX, triflumethocarb + TX, chlorpyrifos + TX, methoxystrobin + TX, veratridine + TX, veratridine + TX, XMC + TX, ζ-cypermethrin + TX, zinc phosphide + TX, tolfenphos + TX, chlorflumethrin + TX, tetraflumethrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, iron phosphate + TX, niclosamide-ethanolamine + TX , tributyltin oxide + TX, pyroximate + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thio-1,3,5-thiadiazine-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, fluorophenyladenine + TX, chlorothiophene + TX, cytokinin + TX, DCIP + TX, furfural + TX, isoamidophos + TX, kinetin + T X, Verrucospore Myrophyte composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethyl xanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Polygonum cuspidatum extract + TX, α-chlorohydrin + TX, antu + TX, barium carbonate + TX, bifenthrin + TX, brodifacoum + TX, brodifacoum + TX, brofenthrin + TX, chlorfenthrin + TX, cholecalciferol + TX, chlorfenthrin + TX, rat killing + TX, rat killing naphthalene + TX, rat killing pyrimidine + TX, rat decoction + TX, thiazolin + TX, diazinon + TX, diazinon Rat + TX, calciferol + TX, fludioxaline + TX, fluoroacetamide + TX, fludioxaline + TX, fludioxaline hydrochloride + TX, fosfos + TX, phosphorus + TX, warfarin + TX, warfarin + TX, scillarin + TX, scutellaria glycoside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, -2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, synergistic acetylene ether + TX, MGK 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomer+TX, S421+TX, synergistic powder+TX, sesamelin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, salen+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, chloroindole hydrazide+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, nitrobenzamide+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX,Furapyramat + TX, Hexaconazole + TX, Imazalil + TX, Imibenconazole + TX, Tebuconazole + TX, Metconazole + TX, Cyproconazole + TX, Paclobutrazol + TX, Blasticidin-S + TX, Triflumizole + TX, Prothioconazole + TX, Pyrifenox + TX, Prochloraz + TX, Propiconazole + TX, Picoxystrobin + TX, Flusilazole + TX, Tebuconazole + TX, Fluoxastrobin + TX, Triadimefon + TX, Triadimenol + TX, Triflumizole + TX, Tricyclazole + TX, Ancymidol + TX, Fenarimol + TX, Fluoromide + TX, Tridemorph + TX, Fenpropidin + TX, Spiroxamine + TX, Tridemorph + TX, Cyprodinil + TX, Fenoxanil + TX, Pyrimethanil + TX, Fuberidazole + TX, Fludioxonil + TX, Metalaxyl + TX, Ofurace + TX, Metalaxyl + TX, R-Metalaxyl + TX, Furalaxyl + TX, Oxadixyl + TX, Carbendazim + TX, Imibenconazole + TX, Ditylenol + TX, Thiabendazole + TX, Ethirimol + TX, Procymidone + TX, Sclerotinia + TX, Iprodione + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Methfuroxam + TX, Flutolanil + TX, Oxycarboxin + TX, Pyraclostrobin + TX, Dimoxystrobin + TX, Enestroburin + TX, Enestrobin + TX, Fluoxastrobin + TX, Fluoxastrobin + TX, Trifloxystrobin + TX, Metominostrobin + TX, Trifloxystrobin + TX, Zoxamide + TX, Zoxamide + TX, Zoxamide + TX, Ferbam + TX, Mancozeb + TX, Maneb + TX, Metiram + TX, Zineb + TX, Zineb + TX, Captafol + TX, Captan + TX, Dazomet + TX, Chlorothalonil + TX, Cyflufenamid + TX, Cymoxanil + TX, Tricyclazole + TX, Dichlofluanid + TX, Etridiazole + TX, Thiabendazole + TX, Pencycuron + TX, Iprovalicarb + TX, Fluopicolide + TX, Fluopyram + TX, Fluopyram + TX, Fluopyrazamine + TX, Flusulfamide + TX, Flusulfamide + TX, Phosphorous acid + TX, Hymexazol + TX, Propineb + TX, Cyazofamid + TX, Sulfuram + TX, Metrafenone + TX, Tebufenozide + TX, Phthalide + TX,Polyoxin + TX, Propamocarb + TX, Pyroquilon + TX, Iodosulfuron + TX, Pyroquilon + TX, Benzovindiflupyr + TX, Quinoxyfen + TX, quintozene + TX, Tiadinil + TX, Imazalil + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Valifenalate + TX, Zoxamide + TX, Mandipropamid + TX, Fluopyram + TX, Isopyrazam + TX, Fluxapyroxad + TX, Benzovindiflupyr + TX, Fluopyram + TX, 3-(Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3’,4’,5’-trifluoro-biphenyl-2-yl)-amide + TX, Isopropylpyrimiphos-methyl + TX, Isotianil + TX, Tioxymid + TX, 6-Ethyl-5,7-dioxopyrrolo[4,5][1,4]dithieno[1,2-c]isothiazole-3-carbonitrile + TX, 2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-Difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(Difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-Bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-Bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, Fluindapyr + TX, Jiaxiangjunzhi + TX, Chlorobenzamide + TX, Dichlofluanid + TX, Mandestrobin + TX, 3-(4,4-Difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-Fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, Tioxymid + TX, N-[6-[[[(1-Methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid tert-butyl ester + TX, Fluopyram + TX, Indoxacarb + TX, Trolprocarb + TX, Fluopyram + TX, Isotrifluron + TX, 2-(Difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-Dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-Dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-Bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate + TX,But-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylidene]amino]oxymethyl]-2-pyridyl]carbamate + TX, Methyl N-[[5-[4-(2,4-dimethylphenyl)-1,2,3-triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, Fluopyram + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-1H-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethyl-1H-pyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one + TX, Amisulbrom + TX, Ametoctradin + TX, Indaziflam + TX, Fluxapyroxad + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, Fluopyram + TX, Bixafen + TX, Picolinafen + TX, Isobutamox + TX, Iproquat + TX, Fluquat + TX, Isotianil + TX, Ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090), Ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoroprop-1-en-1-yloxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090), Methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), Methyl N-[[4-[1-(2,6-difluoro-4-isopropylphenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391),6-Chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichlorophenoxy]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, Benzothiazole + TX, Cyenopyrafen + TX, Zinc 5-amino-1,3,4-thiadiazole-2-thiolate (2:1) + TX, Fluopyram + TX, Flufenoxadiazam + TX, Fluopyramide + TX, Fluopyramide + TX, Pyrapropoyne + TX, Picarbutrazox + TX, 2-(Difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(Difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Metyltetraprole + TX, 2-(Difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-Dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol + TX, Fluoxapiprolin + TX, Enoxastrobin + TX, (Z)-Methyl 3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate, (Z)-Methyl 3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate, (Z)-Methyl 2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxyprop-2-enoate, (Z)-Methyl 3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate, (Z)-Methyl 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), (Z)-Methyl 2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxyprop-2-enoate,(Z)-Methyl 2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyprop-2-enoate + TX (These compounds can be prepared by the methods described in WO 2020 / 193387), 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-sulfanyl-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-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, anti-lodging acid + TX, caryomycin + TX, zhongshengmycin + TX, thiodiazole copper + TX, thiazole zinc + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-isopropyl-N-methylformamidine + TX (These compounds can be prepared by the methods described in WO2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine + TX (This compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylformamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxyethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methylformamidine + TX (These compounds can be prepared by the methods described in WO2018 / 228896); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methylformamidine + TX,N-Ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (These compounds can be prepared by the methods described in WO 2019 / 110427); 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-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + 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, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, 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 (These compounds can be prepared by the methods described in WO 2017 / 153380); 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, 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, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (These compounds can be prepared by the methods described in WO 2017 / 025510); 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, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenta[d]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared from WO 2017 / 055473, WO 2017 / 055469,Prepared by the methods described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamine + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine + TX (this compound can be prepared by the method described in WO2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylinden-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-Methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (These compounds can be prepared by the methods described in WO 2017 / 220485); 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (This compound can be prepared by the methods described in WO 2018 / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (This compound can be prepared by the methods described in WO2018 / 158365); 2,2-Difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + 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-[N-Methoxy-C-methyl-carbamimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (These compounds can be prepared by the methods described in WO 2018 / 202428);

[0537] Microbial agents, which include: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri, Acremonium obclavatum, Adoxophyes orana granulovirus (AdoxGV) + TX, Agrobacterium radiobacter strain K84 + TX, Alternaria alternata + TX, Alternaria cassiae + TX, Alternaria destruens + TX, Ampelomyces quisqualis + TX, Aspergillus flavus AF36 + TX, Aspergillus flavus NRRL 21882 + TX, Aspergillus species + TX, Aureobasidium pullulans + TX, Azospirillum TAZO ) + TX, Azotobacter + TX, Azotobacter chroococcum + TX, Azotobacter cystogenes (BionaturalBlooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (e.g., Biostart TM , previous )+TX, Bacillus licheniformis strain 3086( Green )+TX, Bacillus circulans+TX, Bacillus firmus +TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Milky Spore )+TX, Brevibacillus species+TX, Brevibacillus strain GB34 (Yield )+TX, Brevibacillus strain AQ717+TX, Brevibacillus strain QST 2808( Ballad )+TX, Bacillus sphaericus +TX, Bacillus species+TX, Bacillus species strain AQ175+TX, Bacillus species strain AQ177+TX, Bacillus species strain AQ178+TX, Bacillus subtilis strain QST 713 +TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 +TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis +TX, Bacillus thuringiensis kurstaki ( Scutella Turilav Dipel ) + TX, Bacillus thuringiensis kurstaki BMP 123 +TX, Bacillus thuringiensis HD-1 +TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai +TX, Bacterial genus species +TX, Bacteriophage of Clavipacter michiganensis +TX, +TX, Beauveria bassiana ( Brocaril ) + TX, Beauveria bassiana GHA (Mycotrol Mycotrol ) + TX, Beauveria brongniartii ( Schweizer ) + TX, Beauveria spp. + TX, Botrytis cinerea + TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis +TX, BtBooster + TX, Burkholderia cepacia ( Blue )+TX, Burkholderia gladii+TX, Burkholderia gladii+TX, Burkholderia species+TX, Canadian thistle fungus (CBH Canadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana +TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea davisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea +TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola+TX, Cryptococcus infirmo - miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus +TX, Cydia pomonella granulovirus( Plus, Max, Carpovirusine )+TX, Cylindrobasidium laeve +TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta +TX, Epicoccum nigrum+TX, Epicoccum purpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum ( Biofox ) +TX, Fusarium proliferatum +TX, Fusarium spp. +TX, Galactomyces geotrichum +TX, Gliocladium catenulatum +TX, Gliocladium roseum +TX, Gliocladium spp. +TX, Gliocladium virens +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas spp. +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hanseniaspora uvarum +TX, Helicoverpa armigera nucleopolyhedrovirus +TX, Helicoverpa zea nuclear polyhedrosis virus +TX, Isoflavone-formononetin +TX, Kloeckera apiculata +TX, Kloeckera spp. +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria Dispar nucleopolyhedrosis virus +TX, Marinococcus halophilus+TX, Meira geulakonigii+TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowiapulcherrima+TX, (Microdochium dimerum) +TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.( Root )+TX, Myrothecium verrucaria strain AARC-0255 +TX, BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomycesfarinosus+TX, Paecilomyces fumosoroseus +TX, Paecilomyces linacinus (Biostat )+TX, Paecilomyceslilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea spp.+TX, Pasteuria spp. +TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai +TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean +TX, phosphate solubilizing bacteria +TX, Phytophthora cryptogea+TX, Phytophthora palmivora +TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae +TX, Pseudomonas viridiflava+TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22UL (Sporodex )+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood )+TX, Pythium paroecandrum+TX, Pythium oligandrum +TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia +TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua multiple nucleopolyhedrovirus +TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus +TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces griseoplanus+TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.+TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22( PlantShield )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly Gliocladium virens GL-21) +TX, Trichoderma virens+TX, Trichoderma virens strain ICC 080 +TX, Trichosporon pullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichothecium roseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii +TX, Ustilago maydis+TX, various bacteria and nutritional supplements (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii +TX, Vip3Aa20 +TX, Virgibacillus marismortui+TX, Xanthomonas campestris pv. Poae +TX, Xenorhabdus bovienii+TX, and Xenorhabdus nematophila+TX;

[0538] Plant extracts, including: pine oil +TX, Azadirachtin (Plasma Neem )+TX, Plant IGR +TX, Canola Oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, Chrysanthemum Extract +TX, Neem Oil Extract +TX, Essential Oil of Labiatae +TX, Extract of Clove - Rosemary - Peppermint and Thyme Oil (Garden insect )+TX, Betaine +TX, Garlic +TX, Lemongrass Oil +TX, Neem Oil +TX, Nepeta cataria (Catnip Oil)+TX, Nepeta catarina+TX, Nicotine+TX, Oregano Oil +TX, Oil of Pedaliaceae +TX, Pyrethrum +TX, Quillaja saponaria +TX, +TX, Rotenone (Eco )+TX, Plant Extract of Rutaceae +TX, Soybean Oil (Ortho )+TX, Extract of Melaleuca alternifolia (Also called Tea Tree Oil)(Timorex )+TX, Thyme Oil +TX, MMF +TX, +TX, Mixture of Rosemary - Sesame - Peppermint - Thyme and Cinnamon Extracts (EF )+TX, Mixture of Clove - Rosemary and Peppermint Extracts (EF )+TX, Mixture of Clove - Peppermint - Garlic Oil and Mint (Soil )+TX, Kaolin +TX, Storage Glucan of Brown Algae +TX;

[0539] Pheromones, including: Pheromone of Blackheaded Fireworm (3M Sprayable Blackheaded Fireworm )+TX, Pheromone of Codling Moth (Paramount dispenser-(CM) / Isomate )+TX, Grapevine leafroll-associated virus pheromone (3MMEC-GBM Sprayable )+TX, Leafroller pheromone (3MMEC-LR Sprayable )+TX, Housefly pheromone (Muscamone)(Snip7Fly Starbar Premium Fly )+TX, Oriental fruit moth pheromone (3Morientalfruit mothsprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm pheromone (3M Sprayable )+TX, Entostat powder (extract from palm tree)(Exosex )+TX, (3E,8Z,11Z)-3,8,11-Tetradecatriene acetate +TX, (7Z,11Z,13E)-7,11,13-Hexadecatriene aldehyde +TX, (E,Z)-7,9-Dodecadien-1-yl acetate +TX, 2-Methyl-1-butanol +TX, Calcium acetate +TX, +TX、 +TX、 +TX、Lavandulyl senecioate +TX;

[0540] Macrobial agents, including: Aphytis melinus +TX, Aphidius ervi +TX, Acerophagus papaya +TX, Adalia bipunctata +TX, Adalia bipunctata +TX, Adalia bipunctata +TX, Ageniaspis citricola +TX, Copidosoma koehleri +TX, Amblyseius andersoni +TX, Amblyseius californicus +TX, Amblyseius cucumeris Bugline )+TX, Pseudaphyseius +TX, Amblyseius swirskii (Bugline )+TX, Amblyseius oudemansi +TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci +TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis +TX, Aphidius sp. with short ovipositor +TX, Aphelinus asychis+TX, Aphidius colemani +TX, Aphidius sp. of Aphis gossypii +TX, Aphidius gifuensis+TX, Aphidius sp. of Myzus persicae +TX, Aphidoletes aphidimyza +TX, Aphidoletes aphidimyza +TX, Aphytis lingnanensis+TX, Aphytis indica+TX, Aprostocetus hagenowii+TX, Atheta coriaria +TX, Bombus spp.+TX, Bombus terrestris )+TX, Bombus terrestris +TX, Cephalonomia stephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea +TX, Chrysoperla carnea +TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Apanteles flavipes+TX, Cotesia plutellae+TX, Cryptolaemus montrouzieri +TX, Cybocephalus niponicus+TX, Cardiochiles sibiricus+TX, Cardiochiles sibiricus +TX, Diglyphus isaea +TX, Delphastus catalinae +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diadromus collaris+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea +TX, Cardiochiles sibiricus +TX, species of Ceranisus+TX, Aphelinus mali+TX, Encarsia )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Sphaerophoria scripta +TX, Eretmocerus siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( Eretline )+TX, Eretmocerus eremicus +TX, Eretmocerus hayati+TX, Eretmocerus montrouzieri +TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga +TX, Feltiella acarisuga +TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, Formononetin (Wirless ) + TX, Thrips abdominalis ) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis ) + TX, Heterorhabditis spp. (Lawn ) + TX, Heterorhabditis bacteriophora (NemaShield NemAttack ) + TX, Heterorhabditis megidis (Nemasys BioNem Exhibitline ) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer ) + TX, Hypoaspis miles (Hypoline ) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii ) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar ) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus ( Macroline ) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus +TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris +TX, Neoseiulus fallacis+TX, Nesideocoris tenuis +TX, Ophyra aenescens +TX, Orius insidiosus +TX, Orius laevigatus( Oriline )+TX, Orius majusculus(Oriline )+TX, Orius strigicollis +TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis( Phytoline )+TX, Podisus maculiventris +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae +TX, Steinernema carpocapsae (Nematac BioNem )+TX, Steinernema feltiae Nemasys BioNem Exhibitline )+TX, Steinernema kraussei (Nemasys BioNem Exhibitline )+TX, Steinernema riobrave +TX, Steinernema scapterisci (Nematac )+TX, Steinernema spp.+TX, Guardian of Steinernematid )+TX, Stethorus punctillum +TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae (Tricholine )+TX, Trichogramma brassicae +TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator+TX;

[0541] Other biological agents, including: abscisic acid+TX, +TX, Chondrostereumpurpureum (Chontrol )+TX, Colletotrichum gloeosporioides +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin)( Ni-HIBIT Gold )+TX, fatty acids from natural by-products of extra virgin olive oil ferric phosphate +TX, Funnel trap +TX, +TX, Grower's +TX, homo-brassonolide+TX, ferric phosphate (Lilly Miller Worry Free Ferramol Slug&Snail )+TX, MCP hail trap (Trapline )+TX, the parasitic insect Microctonus hyperodae+TX, Mycoleptodiscus terrestris +TX、 +TX、 +TX、 +TX, the pheromone trap (Thripline )+TX, potassium bicarbonate +TX, potassium salts of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX、 +TX, spider venom+TX, Nosema locustae (Semaspore Organic Grasshopper )+TX, sticky trap (Trapline Rebell )+TX and trap (Takitrapline y+ )+TX;

[0542] (1) An antibacterial agent selected from the following group:

[0543] (1.1) Bacteria, examples of which are Bacillus mojavensis strain R3B (registration number NCAIM(P)B001389) (WO 2013 / 034938), from Certis USA LLC+TX; Bacillus pumilus, especially strain BU F-33, with NRRL registration number 50185 (from BASF Corporation EPA registration number 71840-19)+TX; Bacillus subtilis, especially strain QST713 / AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, with NRRL registration number B21661, US Patent No. 6,060,051)+TX; Bacillus subtilis strain BU1814, (from BASF SE PLUS、 FLEX and EXTRA)+TX; Bacillus amyloliquefaciens var. strain FZB24, with registration number DSM 10271 (available as or ECO (EPA registration number 70127 - 5), obtained from Novozymes) + TX; Bacillus subtilis CX - 9060 from Certis USA LLC + TX; Bacillus species, especially strain D747 (available as DOUBLE obtained from Kumiai Chemical Industry Co., Ltd.), with accession number FERM BP - 8234, US Patent No. 7,094,592 + TX; Paenibacillus species strain with accession number NRRL B - 50972 or accession number NRRL B - 67129, WO 2016 / 154297 + TX; Paenibacillus polymyxa, especially strain AC - 1 (e.g., from Green Biotech Company Ltd.) ) + TX; Pantoea agglomerans, especially strain E325 (accession number NRRL B - 21856) (available as BLOOMTIME BIOLOGICAL TM FD BIOPESTICIDE obtained from Northwest Agri Products) + TX; Pseudomonas proradix (e.g., from Sourcon Padena) ) + TX; and

[0544] (1.2) Fungi, examples of which are blastospores of Aureobasidium pullulans, especially strain DSM14940, blastospores of strain DSM14941, or a mixture of blastospores of strain DSM14940 and DSM14941 (e.g., from bio - ferm in Switzerland) and BLOSSOM )+TX; Pseudozyma aphidis (as disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem)+TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (as disclosed in WO 2010 / 086790, from Lesaffre et Compagnie of France)+TX;

[0545] (2) A biofungicide selected from the group consisting of:

[0546] (2.1) Bacteria, an example of which is the radiobacterium Agrobacterium strain K84 (e.g., AgBioChem, California, USA). )+TX; Radiation-forming Agrobacterium strain K1026 (e.g. NOGALL from BASF TM )+TX; Bacillus subtilis variant amyloliquefaciens strain FZB24, with accession number DSM10271 (can be used as or ECO (EPA registration number 70127-5) obtained from Novozymes) + TX; Bacillus amyloliquefaciens, specifically strain D747 (available as Double Nickel TM obtained from Kumihiko Chemical Industries, Ltd., with accession number FERM BP-8234, U.S. Patent No. 7,094,592) + TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (obtained from Marrone BioInnovations )+TX; Bacillus amyloliquefaciens strain FZB42, registration number DSM 23117, (can be used as from ABiTEP, Germany) + TX; Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN from the University of Pretoria) TM )+TX; Bacillus licheniformis, in particular strain SB3086, having accession number ATCC 55406, WO 2003 / 000051 (available as Biological fungicides and GREEN RELEAF TM Obtained from Novozymes A / S and)+TX; Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (from FMC Corporation (WG) and (WP))+TX; Bacillus methylotrophicus strain BAC-9912 (from the Institute of Applied Ecology, Chinese Academy of Sciences)+TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (WO 2013 / 034938), from Certis USA LLC)+TX; Bacillus mycoides isolate, having accession number B-30890 (available as BMJ or WG and LifeGard TM Obtained from Certis USA LLC)+TX; Bacillus pumilus, especially strain QST2808 (available as Obtained from Bayer CropScience LP, USA, having accession number NRRL B-30087 and described in US Patent No. 6,245,551)+TX; Bacillus pumilus, especially strain GB34 (available as Yield Obtained from Bayer AG, Germany)+TX; Bacillus pumilus, especially strain BU F-33, having NRRL accession number 50185 (available as part of the CARTISSA product from BASF, EPA registration number 71840-19)+TX; Bacillus subtilis, especially strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, having NRRL accession number B21661, and described in US Patent No. 6,060,051)+TX; Bacillus subtilis Y1336 (available as WP obtained from Bion-Tech, Taiwan, China, registered as a biological fungicide in Taiwan, China under registration numbers 4764, 5454, 5096 and 5277)+TX; Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF, having accession number NRRL B-50595, US Patent No. 5,061,495)+TX; Bacillus subtilis strain GB03 (available as Obtained from Bayer AG, Germany)+TX; Bacillus subtilis strain BU1814, (available as PLUS, FLEX and EXTRA obtained from BASF SE)+TX; Bacillus subtilis CX-9060+TX from Certis USA LLC; Bacillus subtilis KTSB strain (from Donaghys ))+TX; Bacillus subtilis IAB / BS03 (AVIV from STK Bio-Ag Technologies TM ), from Idai Nature )+TX; Bacillus subtilis strain Y1336 (available as WP obtained from Baitai Co., Ltd. in Taiwan, China, registered as a biocidal fungicide in Taiwan, China under registration numbers 4764, 5454, 5096 and 5277)+TX; Paenibacillus epiphyticus (WO 2016 / 020371), from BASF SE)+TX; Paenibacillus polymyxa plant species (WO 2016 / 020371), from BASF SE)+TX; Paenibacillus sp. strain, with registration number NRRL B-50972 or registration number NRRL B-67129, WO 2016 / 154297)+TX; Pseudomonas chlororaphis strain AFS009, with registration number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER from AgBiome Innovations in the United States TM and )+TX; Pseudomonas chlororaphis strain, especially strain MA342 (e.g., from Bioagri and Koppert and )+TX; Pseudomonas fluorescens strain A506 (e.g., A506 from NuFarm )+TX; Pseudomonas proradix (e.g., from Solk-Pardner )+TX; Streptomyces griseoviridis strain K61 (also known as Streptomyces flavidovirens strain K61) (registration number DSM7206) (from Verdera from BioWorks See Crop Protection 2006, 25, 468 - 475)+TX; Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (from Novozymes A / S and )+TX; and

[0547] (2.2) Fungi, examples of which are Ampelomyces quisqualis, in particular strain AQ 10 (e.g., AQ from IntrachemBio Italia )+TX; Ampelomyces quisqualis strain AQ10, having the accession number CNCM I - 807 (e.g., AQ from IntrachemBio Italia )+TX; Aspergillus flavus strain NRRL21882 (as a known product from Syngenta / ChemChina )+TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940+TX; Aureobasidium pullulans, in particular blastospores of strain DSM 14941+TX; A mixture of blastospores of Aureobasidium pullulans, in particular strains DSM14940 and DSM 14941 (e.g., from Biobest AG, Switzerland )+TX; Chaetomium cupreum (accession number CABI 353812) (e.g., BIOKUPRUM from AgriLife TM )+TX; Chaetomium globosum (available as obtained by Rivale ) + TX; Cryptococcus flavescens, strain 3C (NRRL Y-50378), (B2.2.99) + TX; Dactylaria candida + TX; Dilophosphora alopecuri (available as TWIST obtained) + TX; Fusarium oxysporum, strain Fo47 (available as obtained from Natural Plant Protection) + TX; Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g., Prestop from Lallemand )+TX; Gliocladium roseum (also known as Clonostachys rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can J. Plant Sci., 2003, 83(3):519-524), or 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' [with particular emphasis on the development of a biocontrol agent for plant disease control using the near-commercial fungal antagonist Glechoma rosea strain 'IK726'], Australasian Plant Pathol. 2007, 36(2):95-101) + TX; conidia of Lecanicillium lecanii (formerly Verticillium lecanii) strain KV01 (e.g., from Corbett / Arysta ) + TX; Metschnikowia fructicola, especially strain NRRL Y - 30752, (B2.2.3) + TX; Microsphaeropsis ochracea + TX; Muscodor roseus, especially strain A3 - 5 (accession number NRRL 30548) + TX; Penicillium steckii (DSM 27859, WO 2015 / 067800) from BASF + TX; Penicillium vermiculatum + TX; Phlebiopsis gigantean strain VRA 1992 (from Danstar Ferment) C) + TX; Pichia anomala, strain WRL - 076 (NRRL Y - 30842), U.S. Patent No. 7,579,183 + TX; Pseudozyma flocculosa, strain PF - A22 UL (available as L obtained from Plant Products Co. in California) + TX; Saccharomyces cerevisiae, especially strain LASO2 (from Agro - Levures et Dérivés), strain LAS117 cell wall (from Lesaffre from BASF ), strains CNCM No. 1 - 3936, CNCM No. 1 - 3937, CNCM No. 1 - 3938, CNCM No. 1 - 3939 from Lesaffre in France (WO 2010 / 086790) + TX; Simplicillium lanosoniveum + TX; Talaromyces flavus, strain V117b + TX; Trichoderma asperelloides JM41R (accession number NRRL B - 50759) (TRICHO from BASF ) + TX; Trichoderma asperellum, especially strain kd (e.g., T-Gro from Andermatt Biocontrol) + TX; Trichoderma asperellum, especially strain SKT-1, with accession number FERM P-16510 (e.g., from Kasei Chemical Industry Co., Ltd.) ), strain T34 (e.g., T34 from Biocontrol Technologies S.L. in Spain) or strain ICC012 from Isagro + TX; Trichoderma atroviride, especially strain SC1 (accession number CBS 122089, WO2009 / 116106 and US Patent No. 8,431,120 (from Bi-PA)), strain 77B (T77 from Andermatt Biocontrol) or strain LU132 (e.g., Sentinel from Agrimm Technologies Limited) + TX; Trichoderma atroviride, strain CNCM1-1237 (e.g., from Agrauxine in France) WP) + TX; Trichoderma atroviride, strain number V08 / 002387 + TX; Trichoderma atroviride, strain NMI number V08 / 002388 + TX; Trichoderma atroviride, strain NMI number V08 / 002389 + TX; Trichoderma atroviride, strain NMI number V08 / 002390 + TX; Trichoderma atroviride, strain LC52 (e.g., Tenet from Agrimo Technology Co., Ltd.) + TX; Trichoderma atroviride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma atroviride, strain T11 (IMI 352941 / CECT 20498) + TX; Trichoderma atroviride, strain SKT-1 (FERM P-16510), Japanese Patent Publication (Kokai) 11-253151A + TX; Trichoderma atroviride, strain SKT-2 (FERM P-16511), Japanese Patent Publication (Kokai) 11-253151A + TX; Trichoderma atroviride, strain SKT-3 (FERM P-17021), Japanese Patent Publication (Kokai) 11-253151A + TX; Trichoderma fertile (e.g., TrichoPlus from BASF SE) + TX; Trichoderma gamsii (formerly Trichoderma viride), strain ICC080 (IMI CC 392151 CABI, e.g., BioDerma from AGROBIOSOL DE MEXICO, S.A. DE C.V.) + TX; Trichoderma gamsii (formerly Trichoderma viride), strain ICC 080 (IMI CC 392151 CABI) (available as Obtained from Agrí Bayer S.A. de C.V.) + TX; Trichoderma harmatum + TX; Trichoderma harmatum, with accession number ATCC 28012 + TX; Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Koppert B.V.) or strain Cepa SimbT5 (from Simbiose Agro) + TX; Trichoderma harzianum + TX; Trichoderma harzianum rifai T39 (e.g., from Makhteshim of the United States of ) + TX; Trichoderma harzianum, strain ITEM 908 (e.g., Trianum-P from Koppert B.V.) + TX; Trichoderma harzianum, strain TH35 (e.g., Root-Pro from Mycontrol) + TX; Trichoderma harzianum, strain DB 103 (available as 7456 obtained from Dagutat Biolab) + TX; Trichoderma polysporum, strain IMI206039 (e.g., Binab TFWP from BINAB Bio-Innovation AB of Sweden) + TX; Trichoderma stromaticum, with accession number Ts3550 (e.g., Tricovab from CEPLAC of Brazil) + TX; Trichoderma virens (also known as Gliocladium virens), especially strain GL-21 (e.g., SoilGard from Certis of the United States of America) + TX; Trichoderma virens strain G-41, formerly known as Gliocladium virens (accession number ATCC 20906) (e.g., from Bioworks of the United States of America PLUSWP and PLUS WP)+TX; Trichoderma viride, strain TV1 (e.g., Trianum-P from Koppert B.V.)+TX; Trichoderma viride, especially strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie [Scientific Papers of the Agricultural University of Szczecin] 161:125 - 137)+TX; a mixture of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012) (with accession number CABI CC IMI 392716) and Trichoderma gamsii (former Trichoderma viride) strain ICC 080 (with accession number IMI 392151) (e.g., BIO-TAM from Isagro USA TM and from Agrí Bayer S.A. de C.V. of Mexico )+TX; Ulocladium oudemansii strain U3, with accession number NM 99 / 06216 (e.g., from Botry-Zen Ltd of New Zealand and from Bioworks Inc. )+TX; Verticillium albo-atrum (former V. dahliae), strain WCS850, with accession number WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH from Tree Care Innovations )+TX; Verticillium chlamydosporium+TX;

[0548] (3) Biocontrol agents having an effect of improving plant growth and / or plant health selected from the following group:

[0549] (3.1) Bacteria, examples of which are Azospirillum brasilense (e.g., from KALO, Inc.) )+TX; Azospirillum lipoferum (e.g., VERTEX-IF from TerraMax, Inc.) TM) + TX; Azorhizobium caulinodans, especially strain ZB - SK - 5 + TX; Azotobacter chroococcum, especially strain H23 + TX; Azotobacter vinelandii, especially strain ATCC 12837 + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as ) obtained from Agrinos + TX; Bacillus amyloliquefaciens pm414 (from Biofilm Crop Protection ) + TX; Bacillus amyloliquefaciens SB3281 (ATCC#PTA - 7542, WO 2017 / 205258) + TX; Bacillus amyloliquefaciens TJ1000 (available as ) obtained from Novozymes + TX; Bacillus amyloliquefaciens, especially strain IN937a + TX; Bacillus amyloliquefaciens, especially strain FZB42 (e.g., from ABiTEP GmbH, Germany ) + TX; Bacillus amyloliquefaciens BS27 (Accession No. NRRL B - 5015) + TX; a member of the Bacillus cereus family EE128 (NRRL No. B - 50917) + TX; a member of the Bacillus cereus family EE349 (NRRL No. B - 50928) + TX; Bacillus cereus, especially strain BP01 (ATCC 55675, e.g., from Arysta Lifescience, USA ) + TX; Bacillus firmus, especially strain CNMC 1 - 1582 (e.g., from BASF ) + TX; Bacillus mycoides BT155 (NRRL No. B - 50921) + TX; Bacillus mycoides EE118 (NRRL No. B - 50918) + TX; Bacillus mycoides EE141 (NRRL No. B - 50916) + TX; Bacillus mycoides BT46 - 3 (NRRL No. B - 50922) + TX; Bacillus pumilus, especially strain QST2808 (Accession No. NRRL No. B - 30087) + TX; Bacillus pumilus, especially strain GB34 (e.g., from Bayer CropScience, Germany YIELD ) + TX; Bacillus siamensis, particularly strain KCTC 13613T + TX; Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Patent No. 6,060,051, available as OPTI or ASO obtained from Bayer CropScience, USA) + TX; Bacillus subtilis, particularly strain AQ30002 (accession number NRRL No. B-50421 and described in U.S. Patent Application No. 13 / 330,576) + TX; Bacillus subtilis, particularly strain AQ30004 (and NRRL No. B-50455 and described in U.S. Patent Application No. 13 / 330,576) + TX; Bacillus subtilis strain BU1814 (available as obtained from BASF), Bacillus subtilis rm303 (from Biofilm Crop Protection ) + TX; Bacillus thuringiensis BT013A (NRRL No. B-50924), also known as Bacillus thuringiensis 4Q7 + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as (WG), (WP) obtained from FMC Corporation) + TX; Bacillus subtilis, particularly strain MBI 600 (e.g., from BASF ) + TX; Bacillus tequilensis, particularly strain NII-0943 + TX; Bradyrhizobium japonicum (e.g., from Novozymes ) + TX; Delftia acidovorans, particularly strain RAY209 (e.g., from Brett Young Seeds ) + TX; Mesorhizobium cicer (e.g., NODULATOR from BASF) + TX; Lactobacillus species (e.g., from LactoPAFI ) + TX; Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF) + TX; Pseudomonas proradix (e.g., from Solac Padena zo ) + TX; ) + TX; Pseudomonas aeruginosa, especially strain PN1 + TX; Rhizobium leguminosarum, especially strain Z25 (accession number CECT 4585) of Rhizobium leguminosarum bv. viceae + TX; Paenibacillus polymyxa, especially strain AC-1 (e.g., from Green Biotechnology Co., Ltd. ) + TX; Serratia marcescens, especially strain SRM (accession number MTCC 8708) + TX; Sinorhizobium meliloti strain NRG-185-1 (from Bayer CropScience AG's GOLD) + TX; Thiobacillus sp. (e.g., from Cropaid Ltd in the UK ) + TX; and

[0550] (3.2) Fungi, examples of which are Purpureocillium lilacinum (formerly known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g., BioAct from Bayer CropScience Biologicals) + TX; Penicillium bilaii, strain ATCC 22348 (e.g., from Acceleron BioAg )), Talaromyces flavus, strain V117b + TX; Trichoderma atroviride strain CNCM I-1237 (e.g., from Agronutrition in France WP), Trichoderma viride, e.g., strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie [Scientific Papers of the Agricultural University of Szczecin] 161:125 - 137) + TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g., from Agri-Mo Technologies Ltd ) + TX; Trichoderma atroviride strain SC1 (described in WO2009 / 116106) + TX; Trichoderma asperellum strain kd (e.g., T-Gro from Andermatt Biocontrol) + TX; Trichoderma asperellum strain (Eco-T from Plant Health Products of New Zealand) + TX, Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Koppert) + TX; Myrothecium verrucaria strain AARC-0255 (e.g., DiTera from Valent Biosciences) TM ) + TX; Penicillium bilaii strain ATCC ATCC20851 + TX; Pythium oligandrum strain M1 (ATCC 38472, e.g., Polyversum from Bioprepraty of the Czech Republic) + TX; Trichoderma virens strain GL-21 (e.g., from Certis USA) ) + TX; Verticillium albo - atrum (formerly V. dahliae) strain WCS850 (CBS276.92, e.g., DutchTrig from Arborcare Innovations) + TX; Trichoderma atroviride, especially strain number V08 / 002387, strain number NMI number V08 / 002388, strain number NMI number V08 / 002389, strain number NMI number V08 / 002390 + TX; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum strain TSTh20 + TX; Trichoderma harzianum strain 1295 - 22 + TX; Pythium oligandrum strain DV74 + TX; Rhizopogon amylopogon (e.g., Myco - Sol from Agri - Enterprise, LLC, formerly Helena Chemical Company) + TX; Rhizopogon fulvigleba (e.g., Myco - Sol from Agri - Enterprise, LLC, formerly Helena Chemical Company) + TX; Trichoderma virens strain GI - 3 + TX;

[0551] (4) Insecticidal active biocontrol agents selected from the following

[0552] (4.1) Bacteria, examples of which are Agrobacterium radiobacter strain K84 (Galltrol from Eiger Biochemicals) + TX; Bacillus amyloliquefaciens, especially strain PTS - 4838 (e.g., AVEO from Valent Biosciences Corporation, USA) + TX; Bacillus firmus, especially strain CNMC 1 - 1582 (e.g., from BASF ) + TX; Bacillus mycoides, isolate J. (e.g., BmJ from Certis USA, LLC) + TX; Bacillus sphaericus, especially serotype H5a5b strain 2362 (strain ABTS - 1743) (e.g., from Valent Biosciences Corporation, USA ) + TX; Bacillus thuringiensis subsp. aizawai, especially strain ABTS - 1857 (SD - 1372, e.g., from Valent Biosciences Corporation of ) + TX; Bacillus thuringiensis subsp. aizawai, especially serotype H - 7 (e.g., from Valent Biosciences Corporation of the United States of WG) + TX; Bacillus thuringiensis israelensis strain BMP 144 (e.g., from Becker Microbial Products of Illinois of ) + TX; Bacillus thuringiensis subsp. israelensis (serotype H - 14) strain AM65 - 52 (Accession No. ATCC 1276) (e.g., from Valent Biosciences Corporation of the United States of ) + TX; Bacillus thuringiensis subsp. ai zawa i) strain GC - 91 + TX; Bacillus thuringiensis var. Colmeri (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory) + TX; Bacillus thuringiensis var. japonensis strain Buibui + TX; Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products of Illinois, BARITONE from Bayer CropScience) + TX; Bacillus thuringiensis subsp. kurstaki strain HD - 1 (e.g., from Valent Biosciences Corporation of the United States of ES) + TX; Bacillus thuringiensis var. kurstaki strain EVB - 113 - 19 (e.g., from AEF Global of ) + TX; Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX; Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX; Bacillus thuringiensis subsp. kurstaki strain SA 11, (JAVELIN from Certis USA, Inc.) + TX; Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis USA, Inc.) + TX; Bacillus thuringiensis subsp. kurstaki strain EG 2348 (from Certis USA, Inc. of ) + TX; Bacillus thuringiensis subsp. kurstaki strain EG 7841 (from Certis USA, Inc. of ) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD - 5428, e.g., from BioFa of Germany of FC) + TX; Brevibacillus laterosporus (from Ecolibrium Biologicals of ) + TX; Burkholderia spp., especially Burkholderia rinojensis strain A396 (also known as Burkholderia strain MBI 305) (Accession No. NRRL B - 50319); WO 2011 / 106491 and WO 2013 / 032693; e.g., MBI206 TGAI from Marrone BioInnovations, Inc. and ) + TX; Chromobacterium subtsugae, especially strain PRAA4 - 1T (e.g., MBI - 203; e.g., from Marrone BioInnovations, Inc. of ) + TX; Lecanicillium muscarium Ve6 (MYCOTAL from Koppert B.V.) + TX; Paenibacillus popilliae (formerly Bacillus popilliae) + TX; for example, MILKY SPORE POWDER from St. Gabriel Laboratories TM or MILKYSPORE GRANULAR TM ) + TX; Pasteuria nishizawae strain Pn1 (CLARIVA from Syngenta / ChemChina) + TX; Serratia entomophila (e.g., from Wrightson Seeds) ) + TX; Serratia marcescens, especially strain SRM (Accession No. MTCC 8708) + TX; Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX; Wolbachia pipientis strain ZAP (e.g., ZAP from MosquitoMate) ) + TX; and

[0553] (4.2) Fungi, examples of which are Beauveria bassiana strain ATCC 74040 (e.g., from Intrac Chemicals Italy) ) + TX; Beauveria bassiana strain GHA (Accession No. ATCC 74250, e.g., from Laverlam International Corporation) ES and ) + TX; Beauveria bassiana strain ATP02 (Accession No. DSM 24665) + TX; Isaria fumosorosea (formerly Paecilomyces fumosoroseus strain Apopka 97) (from SePRO) ) + TX; Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 and disclosed in WO 2017 / 066094; Pioneer Hi-Bred International, Inc.) + TX; Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX; Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX; Paecilomyces lilacinus strain 251 (from Certis USA, LLC) + TX; Zoophthora radicans + TX; z ium robertsii) 15013-1 (deposited under NRRL accession number 67073) + TX; Metarhizium robertsii z ium robertsii) 23013-3 (deposited under NRRL accession number 67075) + TX; Paecilomyces lilacinus strain 251 (from Certis USA, LLC) + TX; ) + TX; Zoophthora radicans + TX;

[0554] (5) A virus selected from the group consisting of: Adoxophyes orana granulovirus (GV) + TX; Cydia pomonella granulovirus (GV) + TX; Helicoverpa armigera nucleopolyhedrovirus (NPV) + TX; Spodoptera exigua multiple nucleopolyhedrovirus (mNPV) + TX; Spodoptera frugiperda multiple nucleopolyhedrovirus (mNPV) + TX; Spodoptera littoralis nucleopolyhedrovirus (NPV) + TX;

[0555] (6) Bacteria and fungi selected from the following that can be added as "inoculants" to plants or plant parts or plant organs and that promote plant growth and plant health due to their specific properties: Agrobacterium spp. + TX; Azorhizobium caulinodans + TX; Azospirillum spp. + TX; Azotobacter spp. + TX; Bradyrhizobium spp. + TX; Burkholderia spp., especially Burkholderia cepacia (formerly Pseudomonas cepacia) + TX; Gigaspora spp. or Gigaspora monosporum + TX; Glomus spp. + TX; Laccaria spp. + TX; Lactobacillus buchneri + TX; Paraglomus spp. + TX; Pisolithus tinctorus + TX; Pseudomonas spp. + TX; Rhizobium spp., especially Rhizobium trifolii + TX; Rhizopogon spp. + TX; Scleroderma spp. + TX; Suillus spp. + TX; Streptomyces spp. + TX;

[0556] (7) Plant extracts and products formed by microorganisms (including proteins and secondary metabolites) that can be used as biological control agents, selected from garlic (Allium sativum) (NEMGUARD from Eco-Spray; BRALIC + TX from ADAMA; Armour-Zen + TX; wormwood (Artemisia absinthium) + TX; azadirachtin (e.g., AZATIN XL from Certis USA) + TX; Biokeeper WP + TX; Brassicaceae extracts, especially rapeseed meal or mustard powder + TX; Cassia nigricans + TX; Celastrus angulatus + TX; Chenopodium anthelminticum + TX; chitin + TX; Dryopteris filix-mas + TX; Equisetum arvense + TX; Fortune Aza + TX; Fungastop + TX; quinoa saponin extract from quinoa seeds (e.g., Heads (saponins of quinoa)) + TX; naturally occurring Blad polypeptide extracted from lupin seeds (from Certis EU ); naturally occurring Blad polypeptide extracted from lupin seeds (from FMC ); Pyrethrum / pyrethrins + TX; Quassia amara + TX; Quercus + TX; Quillaja extract (QL AGRI 35 from BASF) + TX; giant knotweed extract (MAXX from MarroneBio ); "Requiem TMInsecticides "+TX; Rotenone +TX; Ryania / ryanodine +TX; Symphytum officinale +TX; Tanacetum vulgare +TX; Thymol +TX; Thymol mixed with Geraniol (CEDROZ from Eden Research) +TX; Thymol mixed with Geraniol and Eugenol (from Eden Research ) +TX; Triact 70 +TX; TriCon +TX; Tropaeulum majus +TX; Melaleuca alternifolia extract (TIMOREX GOLD from STK) +TX; Urtica dioica +TX; Veratrin +TX; and Viscum album +TX; and

[0557] Safeners such as cloquintocet +TX, cloquinate (including mefenpyr-diethyl) +TX, cyprosulfamide +TX, dichlormid +TX, oxabetrinil (including oxabetrinil-ethyl) +TX, dichlomezine +TX, flurazole +TX, isoxadifen-ethyl +TX, isoxazolidinone (including isoxazolidinone-ethyl) +TX, mefenpyr (including mefenpyr-diethyl) +TX, metcamifen +TX and dichlobenil +TX.

[0558] In addition, the compositions of the invention can also be applied together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0559] The compounds of formula (I) as defined in the present invention are generally used in the form of compositions and can be applied to the crop area or the crop to be treated simultaneously or sequentially with additional compounds. For example, these additional compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with additional carriers, surfactants or adjuvants for facilitating application that are commonly used in the formulation art.

[0560] The compounds of formula (I) as defined in the present invention can be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, these compositions comprising at least one compound of formula (I) as defined in any one of Examples 1 to 43 or at least one of the various preferred compounds as defined above as active ingredient (in free form or in agrochemically acceptable salt form), and comprising at least one of the above adjuvants.

[0561] Accordingly, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in the present invention, an agriculturally acceptable carrier and optionally an adjuvant. 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 the compound of formula (I) as defined in the present invention, the composition may comprise at least one or more pesticidal active compounds, for example, additional fungicidal active ingredients.

[0562] Another aspect of the present invention relates to a method for controlling or preventing plants (such as useful plants (e.g., crop plants)), their propagation materials (e.g., seeds), harvested crops (e.g., harvested food crops), or inanimate materials from being infected by phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), the method comprising applying a compound of formula (I) as defined in the present invention or preferably the various compounds as defined above as active ingredient to these plants, parts thereof or their sites, their propagation materials, or any part of these inanimate materials.

[0563] Controlling or preventing means reducing the infection by insects or phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms) to a proven improved level.

[0564] A preferred method for controlling or preventing crop plants from being infected by phytopathogenic microorganisms (especially fungal organisms) is foliar application, which comprises applying a compound of formula (I) as defined in the present invention or an agrochemical composition containing at least one of said compounds. The application frequency and application rate will depend on the risk of infection by the corresponding pathogen or insect. However, the compound of formula (I) as defined in the present invention can also penetrate plants through the roots (systemic action) via the soil by soaking the sites of plants with a liquid formulation or by applying the compound in solid form, for example in granular form, to the soil (soil application). In rice crops, such granules can be applied to flooded paddy fields. The compound of formula (I) as defined in the present invention can also be applied to seeds (coating) by impregnating seeds or tubers with a liquid formulation of a fungicide or coating them with a solid formulation.

[0565] Formulations (for example, compositions containing a compound of formula (I) as defined in the present invention, and, if desired, solid or liquid adjuvants or monomers for encapsulating the compound of formula (I) as defined in the present invention) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders (such as solvents, solid carriers and optionally surface-active compounds (surfactants)).

[0566] The methods of applying these compositions, i.e., the methods of controlling pathogens of the above types, such as spraying, atomizing, dusting, brushing, coating, broadcasting or watering - which are selected to be suitable for the intended purpose of the general situation - and the use of these compositions for controlling pathogens of the above types are other subjects of the present invention. Typical concentration ratios are active ingredients between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. 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 reagent, the appropriate dose is from 10 mg to 1 g of active substance / kg of seed.

[0567] When the combination of the present invention is used for treating seeds, a ratio of 0.001 to 50 g of the compound of formula (I) / kg of seeds, preferably from 0.01 to 10 g / kg of seeds, is generally sufficient.

[0568] Suitably, the compositions according to the present invention containing a compound of formula (I) as defined in the present invention are applied prophylactically (meaning before the development of the disease) or therapeutically (meaning after the development of the disease).

[0569] The compositions of the present invention can be used in any conventional form, for example, in the form of a two-pack, a 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 suspo-emulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (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 formulation (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid formulation (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0570] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable formulation inert agents (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional slow-release formulations intended for long-term sustained efficacy can also be used. In particular, formulations to be applied in spray form (such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules) can contain surfactants (such as wetting agents and dispersants) and other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0571] Using the combination and diluent of the present invention, in the form of a suitable seed dressing formulation, for example in the form of an aqueous suspension or a dry powder having good adhesion to the seeds, the seed dressing formulation is applied to the seeds in a manner known per se. Such seed dressing formulations are known in the art. The seed dressing formulation can contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as slow-release capsules or microcapsules.

[0572] Generally, the formulation comprises from 0.01% to 90% by weight of the active ingredient, from 0 to 20% of an agriculturally acceptable surfactant and from 10% to 99.99% of a solid or liquid formulation inert agent and one or more auxiliaries, the active agent being composed of at least the compound of formula (I) defined by the present invention together with components (B) and (C), and optionally other active agents (especially microbicides or preservatives or the like). The concentrated form of the composition generally contains from about 2% to 80% by weight, preferably from about 5% to 70% by weight, of the active agent. The application form of the formulation can contain, for example, from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight, of the active agent. However, commercial products will preferably be formulated as concentrates and the end user will generally use diluted formulations.

[0573] However, it is preferred to formulate commercial products as concentrates and the end user will generally use diluted formulations.

[0574] Example

[0575] The following examples serve to illustrate the present invention. The difference between certain compounds of the present invention and known compounds can lie in greater efficacy at low application rates, which can be confirmed by a person of ordinary skill in the art using the experimental procedures outlined in the examples.

[0576] Compounds having formula (I) can have any number of benefits, including in particular a favorable level of biological activity for protecting plants against diseases caused by fungi or superior properties for use as an agrochemical active ingredient (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

[0577] Throughout this specification, temperatures are given in degrees Celsius (°C) and "MP" means melting point. LC / MS means liquid chromatography mass spectrometry, and the apparatus and methods are described as follows.

[0578] Formulation example

[0579]

[0580]

[0581] The active ingredient is thoroughly mixed with adjuvants 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.

[0582]

[0583] The active ingredient is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable grinder to provide a powder that can be used directly for seed treatment.

[0584] Emulsifiable concentrate

[0585]

[0586] Emulsions having any desired dilution that can be used in plant protection can be obtained by diluting with water from this concentrate.

[0587]

[0588]

[0589] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry dressing of seeds.

[0590] Extruder granule

[0591]

[0592] The active ingredient is mixed and ground with adjuvants, and the mixture is wetted with water. The mixture is extruded and then dried in an air stream.

[0593] Coated granule

[0594] Active ingredient [compound of formula (I)] 8%

[0595] Polyethylene glycol (molecular weight 200) 3%

[0596] Kaolin 89%

[0597] The finely ground active ingredient is uniformly applied in a mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0598] Suspension concentrate

[0599]

[0600] The finely ground active ingredient is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation material can be treated and protected against microbial infestation by spraying, watering or dipping.

[0601] Flowable concentrate for seed treatment

[0602]

[0603] The finely ground active ingredient is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation material can be treated and protected against microbial infestation by spraying, watering or dipping.

[0604] Sustained release capsule suspension

[0605] 28 parts of a combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of an antifoaming agent and 51.6 parts of water until the desired particle size is reached. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water are added to this emulsion. The mixture is stirred until the polymerization reaction is complete.

[0606] The obtained capsule suspension is stabilized by adding 0.25 part of a thickening agent and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the medium capsules is 8 - 15 µm.

[0607] The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0608] Analytical method

[0609] Method A:

[0610] Equipment: Shimadzu LCMS2020 mass spectrometer; column: HALO C 18 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% over 1.4 minutes, held for 0.6 minutes, total run time 2.5 minutes; flow rate: 1.8 mL / min; column temperature: 50 °C; wavelengths: 214 and 254 nm PDA.

[0611] Method B:

[0612] Spectra were recorded on a mass spectrometer from Waters Corporation (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switching, capillary: 0.8 kV, cone voltage range: 25 V, extractor: V (no extractor voltage for QDa detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow rate: 50 L / h, desolvation gas flow rate: 1000 L / h, mass range: 110 to 850 Da) and an Acquity UPLC from Waters Corporation: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 x 2.1 mm, temperature: 40 °C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH: gradient: 0 min 10% B; 0. - 0.2 min 10% - 50% B; 0.2 - 0.6 min 50 - 100% B; 0.6 - 1.3 min 100% B; 1.3 - 1.4 min 100 - 10% B; 1.4 - 1.6 min 10% B; flow rate (mL / min) 0.6.

[0613] Method C:

[0614] Spectra were recorded on a mass spectrometer (SQD, SQDII or QDA single quadrupole mass spectrometer) from Waters Corporation, equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 0.8 - 3.00 kV, cone voltage: 5 - 30 V, source temperature: 120 °C - 150 °C, desolvation temperature: 350 °C - 600 °C, cone gas flow rate: 50 - 150 l / h, desolvation gas flow rate: 650 - 1000 l / h, mass range: 110 to 950 Da and an Acquity UPLC from Waters Corporation: binary pump, heated column compartment, diode array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60 °C, DAD wavelength range (nm): 210 to 400, run time: 1.5 min; solvents: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; flow rate (mL / min) 0.85, gradient: 10% B isocratic for 0.2 min, then 10% - 100% B in 1.0 min, 100% B isocratic for 0.2 min, 100% - 10% B in 0.05 min, 10% B isocratic for 0.05 min

[0615] Method D:

[0616] Spectra were recorded on the following: a mass spectrometer (single quadrupole mass spectrometer) from Agilent, equipped with multimode electrospray and APCI (polarity: positive and negative ions), capillary: 4.00 kV, corona current 4.0 μA, charging voltage, 2.00 kV, nitrogen flow rate: 12.0 L / min, nebulizer pressure: 40 psig, mass range: 100 to 1000 m / z), drying gas temperature 250 °C, evaporator temperature 200 °C, and a UPLC from Waters: quaternary pump, heated column compartment, variable wavelength detector. Column: X - Bridge BEH C18, 2.5 μm (2.1 * 50 mm), column temperature: ambient, wavelength (nm): 215 nm, gradient: A = 0.05% TFA in water, B = 0.05% TFA in acetonitrile. Gradient: time / % B: 0 / 5, 1 / 5, 5 / 70, 7 / 95, 8.5 / 95, 8.6 / 5, 10 / 5; flow rate: 0.6 mL / min.

[0617] Table A below summarizes for the compounds of formula (I):

[0618] - LC / MS data such as retention time (RT), [M + H] + ,

[0619] - Type of method, and / or

[0620] - Melting point (MP).

[0621] Table A:

[0622]

[0623]

[0624]

[0625]

[0626]

[0627]

[0628]

[0629]

[0630]

[0631]

[0632]

[0633]

[0634]

[0635] Example 1: Preparation of N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1-yl]phenyl]carbamic methyl ester (Compound 69)

[0636]

[0637] Step 1: Preparation of N-[4-[(4-chlorophenyl)-methyl-carbamoyl]phenyl]-N-methyl-carbamic acid tert-butyl ester Step 2: Preparation of N-(4-chlorophenyl)-N-methyl-4-(methylamino)benzamide

[0638]

[0639] To a mixture of 4-[tert-butoxycarbonyl(methyl)amino]benzoic acid (CAS 263021-30-3, 600 mg, 1.91 mmol) and 4-chloro-N-methylaniline (307 mg, 0.262 mL, 2.10 mmol, 1.10 eq) in dichloromethane (36.0 mL) was added N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (411 mg, 2.10 mmol, 1.10 eq), 1-hydroxy-7-azabenzotriazole (298 mg, 2.10 mmol, 1.10 eq) and pyridine (0.468 mL, 5.73 mmol, 3.00 eq). The reaction mixture was stirred overnight at room temperature, then the yellow solution was diluted with dichloromethane and quenched with water. The organic phase was separated, washed successively with water and brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (cyclohexane / ethyl acetate) to give tert-butyl N-[4-[(4-chlorophenyl)-methyl-carbamoyl]phenyl]-N-methyl-carbamate as pale yellow crystals.

[0640] LC / MS (method C) retention time = 1.12 min; [M+H] + = 375

[0641] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.24 - 7.28 (m, 2H), 7.18 - 7.23 (m, 2H), 7.07 - 7.11 (m, 2H), 6.96 - 7.01 (m, 2H), 3.47 (s, 3H), 3.21 (s, 3H), 1.41 (s, 9H).

[0642] Step 3: Preparation of N-[3-bromo-4-[(E)-[4-[(4-chlorophenyl)-methyl-carbamoyl]-N-methyl-anilino]azo]phenyl]carbamic acid tert-butyl ester

[0643]

[0644] To a solution of tert-butyl N-[4-[(4-chlorophenyl)-methyl-carbamoyl]phenyl]-N-methyl-carbamate (515 mg, 1.24 mmol) in dichloromethane (21.0 mL) at 0 °C under argon was added dropwise trifluoroacetic acid (1.44 mL, 18.5 mmol, 15.0 eq). The reaction mixture was then warmed to room temperature and stirred for an additional 5 h. The mixture was then quenched with saturated NaHCO3 until pH 9 and extracted with dichloromethane. The organic layer was washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give N-(4-chlorophenyl)-N-methyl-4-(methylamino)benzamide. The crude product was used without further purification.

[0645] LC / MS (Method C) retention time = 0.95 min; [M+H] + = 275

[0646] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.17 - 7.25 (m, 4H), 6.96 - 7.06 (m, 2H), 6.35 - 6.39 (m, 2H), 3.46 (s, 3H), 2.82 (s, 3H), 3.97 (br s, 1H).

[0647] Step 4: N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1-yl]phenyl]carbamic ​

[0648]

[0649] At 0 °C, 32% aqueous HCl solution (0.422 mL, 4.30 mmol, 5.00 equiv) was added to a solution of N-(4-amino-3-bromo-phenyl)carbamic acid tert-butyl ester (CAS 1554844-65-3, prepared as described in WO2014140075A1) (260 mg, 0.860 mmol) in acetonitrile (2.60 mL). The mixture was cooled to -10 °C and stirred for 15 minutes, after which a solution of sodium nitrite (63.6 mg, 0.903 mmol, 1.05 equiv) in cold water (1.00 mL) was added dropwise. The resulting diazonium salt was stirred at -10 °C for 30 minutes and then added at -10 °C to a mixture of N-(4-chlorophenyl)-N-methyl-4-(methylamino)benzamide (283 mg, 0.946 mmol, 1.10 equiv) and potassium carbonate (300 mg, 2.15 mmol, 2.50 equiv) in acetonitrile / water (1:2, 7.80 mL). The reaction mixture was stirred at -10 °C for an additional 2 hours and then slowly warmed to room temperature, after which it was diluted with ethyl acetate and quenched with water. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (cyclohexane / ethyl acetate) to give tert-butyl N-[3-bromo-4-[(E)-[4-[(4-chlorophenyl)-methyl-carbamoyl]-N-methyl-anilinio]azo]phenyl]carbamate as yellow crystals.

[0650] LC / MS (Method C) retention time = 1.31 min; [M+H] + = 574

[0651] 11H NMR (400 MHz, CDCl3, ppm) δ = 7.86 (s, 1H), 7.49 (d, J = 8.8 Hz, 1H), 7.35 - 7.39 (m, 2H), 7.29 - 7.34 (m, 2H), 7.24 - 7.27 (m, 2H), 7.19 - 7.23 (m, 1H), 7.00 - 7.07 (m, 2H), 6.51 (s, 1H), 3.65 (s, 3H), 3.51 (s, 3H), 1.53 - 1.56 (m, 9H).

[0652] ​ Preparation of tert-Butyl Ester

[0653]

[0654] To a solution of tert-butyl N-[3-bromo-4-[(E)-[4-[(4-chlorophenyl)-methyl-carbamoyl]-N-methyl-anilinyl]azo]phenyl]carbamate (150 mg, 0.249 mmol) in dimethylformamide (3.00 mL) was added potassium acetate (29.6 mg, 0.298 mmol, 1.20 equiv) and the mixture was purged with argon for 5 minutes. Palladium(II) acetate (2.9 mg, 0.012 mmol, 0.050 equiv) and 1,3-bis(diphenylphosphino)propane (15.7 mg, 0.0373 mmol, 0.150 equiv) were added to the yellow solution, the vial was sealed and stirred at 100 °C overnight. The mixture was diluted with tert-butyl methyl ether, quenched with water and extracted with tert-butyl methyl ether. The organic layer was washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (tert-butyl methyl ether / ethyl acetate) to give tert-butyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1-yl]phenyl]carbamate as a brown resin.

[0655] LC / MS (method C) retention time = 1.13 min; [M+H] + = 478

[0656] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.96 (dd, J = 8.8, 0.7 Hz, 1H), 7.66 (s, 1H), 7.59 - 7.64 (m, 2H), 7.45 - 7.51 (m, 2H), 7.39 (dd, J = 8.6, 1.3 Hz, 1H), 7.18 - 7.27 (m, 2H), 6.97 - 7.07 (m, 2H), 6.73 (s, 1H), 3.24 (s, 3H), 1.21 (s, 9H).

[0657] Step 5: Preparation of 3-(4-Aminophenyl)-N-(4-chlorophenyl)-N-methyl-benzotriazole-5-carboxamide

[0658]

[0659] Under argon, at 0 °C, trifluoroacetic acid (0.189 mL, 2.43 mmol, 15.0 eq) was added to a solution of tert-butyl N-[4-[6-[(4-chlorophenyl)methylcarbamoyl]benzotriazol-1-yl]phenyl]carbamate (84.0 mg, 0.162 mmol) in dichloromethane (4.00 mL). The resulting mixture was then slowly warmed to room temperature and stirred overnight. The mixture was then evaporated, the resulting resin was diluted with dichloromethane, treated with saturated NaHCO3 and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (tert-butyl methyl ether / ethyl acetate) to give 3-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-benzotriazole-5-carboxamide as an orange resin.

[0660] LC / MS (Method C) retention time = 0.91 min; [M+H] + = 378

[0661] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.92 - 7.96 (m, 1H), 7.62 (s, 1H), 7.38 (dd, J = 8.4, 1.5 Hz, 1H), 7.28 - 7.30 (m, 2H), 7.23 - 7.27 (m, 2H), 6.99 - 7.05 (m, 2H), 6.82 - 6.87 (m, 2H), 3.98 (br s, 2H), 3.54 (s, 3H).

[0662] Step 6: N-[4-[6-[(4-Chlorophenyl)-methyl-carbamoyl]benzotriazol-1-yl]phenyl]carbamic Methyl Ester (Compound 69) Preparation

[0663] At 10 °C, methyl chloroformate (0.014 mL, 0.18 mmol, 2.5 equiv) was added dropwise to a solution of 3-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-benzotriazole-5-carboxamide (30.0 mg, 0.0731 mmol) and pyridine (0.018 mL, 0.22 mmol, 3.00 equiv) in dichloromethane (1.00 mL). The reaction mixture was then warmed to room temperature and stirred for an additional 2 hours. The reaction mixture was diluted with dichloromethane, quenched with saturated aqueous NaHCO3, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (tert-butyl methyl ether / ethyl acetate) to afford N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]benzotriazol-1-yl]phenyl]methyl carbamate as yellow crystals.

[0664] LC / MS (method A) retention time = 0.97 min; [M+H] + = 436

[0665] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.97 (d, J = 8.4 Hz, 1H), 7.66 (br s, 1H), 7.64 (d, J = 8.8 Hz, 2H), 7.46 - 7.55 (m, 2H), 7.39 (dd, J = 8.8, 1.5 Hz, 1H), 7.25 - 7.28 (m, 2H), 7.03 (d, J = 8.8 Hz, 2H), 6.86 (s, 1H), 3.87 (s, 3H), 3.54 (s, 3H).

[0666] Example 2 : N-[4-[2-[(4-Chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamic Methyl Ester (Compound 66) Preparation

[0667]

[0668] Step 1: Preparation of tert-Butyl N-[4-[(5-Amino-2-chloro-pyrimidin-4-yl)amino]phenyl]carbamate

[0669]

[0670] To a solution of 5-amino-2,4-dichloropyrimidine (2.00 g, 11.8 mmol) in toluene (80.0 mL) was added tert-butyl (4-aminophenyl)carbamate (5.03 g, 23.7 mmol, 2.00 equiv) and triethylamine (5.00 mL, 35.5 mmol, 3.00 equiv). The resulting mixture was heated to 110 °C and stirred for 114 h. After cooling the reaction mixture to room temperature, it was directly dissolved on isolute and purified by flash chromatography on silica gel (ethyl acetate / methanol) to give tert-butyl N-[4-[(5-amino-2-chloropyrimidin-4-yl)amino]phenyl]carbamate as a purple solid.

[0671] LC / MS (method C) retention time = 0.91 min; [M+H] + = 336

[0672] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 7.79 (s, 1H), 7.51 - 7.54 (m, 2H), 7.36 (br d, J = 8.8 Hz, 2H), 7.02 (s, 1H), 6.49 (br s, 1H), 3.11 (br s, 2H), 1.53 (m, 9H).

[0673] Step 2: Preparation of tert-Butyl N-[4-(2-Chloropurin-9-yl)phenyl]carbamate

[0674]

[0675] To a solution of tert-butyl N-[4-[(5-amino-2-chloropyrimidin-4-yl)amino]phenyl]carbamate (2.60 g, 6.97 mmol) in acetic acid (15.6 mL) was added triethyl orthoformate (17.6 mL, 105 mmol, 15.0 equiv) and the reaction mixture was stirred at 120 °C overnight. The reaction mixture was then cooled and acetic acid was removed under reduced pressure. The resulting residue was diluted with water, basified with aqueous Na2CO3 and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate / methanol) to give the desired compound, which was further purified by crystallization using a mixture of chloroform and ethyl acetate. The solid was filtered and dried under reduced pressure to give tert-butyl N-[4-(2-chloropurin-9-yl)phenyl]carbamate as an off-white solid.

[0676] LC / MS (method C) retention time = 0.97 min; [M+H] + = 346

[0677] 11H NMR (400 MHz, CDCl3, ppm) δ = 9.10 (s, 1H), 8.41 (s, 1H), 7.61 (app s, 4H), 6.74 (br s, 1H), 1.55 (s, 9H).

[0678] Step 3: Preparation of Methyl 9-[4-(tert-Butoxycarbonylamino)phenyl]purine-2-carboxylate

[0679] To a solution of 1,1'-bis(diphenylphosphino)ferrocene (35 mg, 0.061 mmol, 0.04 equiv) and bis(benzonitrile)palladium(II) chloride (12 mg, 0.031 mmol, 0.02 equiv) in methanol (22.0 mL) was added N-[4-(2-chloropurin-9-yl)phenyl]carbamic acid tert-butyl ester (567 mg, 1.52 mmol) and triethylamine (0.279 mL, 1.98 mmol, 1.30 equiv). The reaction mixture was purged with argon for 5 minutes and then stirred at 80 °C under 10 bar CO overnight. After cooling and purging of CO, the mixture was directly adsorbed onto isolute and purified by flash chromatography on silica gel (ethyl acetate / methanol) to give methyl 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylate as a pale red solid.

[0680] LC / MS (method C) retention time = 0.87 min; [M+H] - = 368

[0681] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 9.39 (s, 1H), 8.50 (s, 1H), 7.59 - 7.69 (m, 4H), 6.91 (s, 1H), 4.09 (s, 3H), 1.52 (s, 9H).

[0682] Step 4: Preparation of 9-[4-(tert-Butoxycarbonylamino)phenyl]purine-2-carboxylic Acid

[0683]

[0684] At 5 °C, lithium hydroxide (89.6 mg, 2.09 mmol, 1.50 equiv) was added to a solution of 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylate (560 mg, 1.39 mmol) in tetrahydrofuran / water (3:1, 14.0 mL). The reaction mixture was warmed to room temperature and then stirred for an additional 5 h, then diluted with water and the tetrahydrofuran was evaporated under reduced pressure. The resulting aqueous mixture was extracted with tert-butyl methyl ether, then the aqueous layer was acidified to pH 3 with 1 N HCl and extracted with ethyl acetate. The combined ethyl acetate layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give crude 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylic acid as beige crystals. The product was used in the next step without further purification.

[0685] LC / MS (method C) retention time = 0.78 min; [M+H] + = 356

[0686] 1 1H NMR (400 MHz, DMSO-d6) δ ppm 13.29 (br s, 1H), 9.69 (s, 1H), 9.37 (s, 1H), 9.11 (s, 1H), 7.78 (d, J = 9.2 Hz, 2H), 7.71 (d, J = 9.2 Hz, 2H), 1.51 (m, 9H).

[0687] Step 5: Preparation of tert-Butyl N-[4-[2-[(4-Chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamate Step 6: Preparation of 9-(4-Aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2-carboxamide

[0688]

[0689] A mixture of 9-[4-(tert-butoxycarbonylamino)phenyl]purine-2-carboxylic acid (490 mg, 1.27 mmol), 4-chloro-N-methylaniline (0.174 mL, 1.40 mmol, 1.10 equiv), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (273 mg, 1.40 mmol, 1.10 equiv), 1-hydroxy-7-azabenzotriazole (198 mg, 1.40 mmol, 1.10 equiv) and pyridine (0.311 mL, 3.81 mmol, 3.00 equiv) was dissolved in dichloromethane (24.0 mL) under argon and stirred overnight at room temperature. The reaction mixture was diluted with additional dichloromethane and quenched with water. The organic layer was separated and washed successively with water and brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (ethyl acetate / methanol) to give tert-butyl N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamate as a colorless gum.

[0690] LC / MS (Method C) retention time = 1.02 min; [M+H] + = 479

[0691] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 9.11 (br s, 1H), 8.31 (s, 1H), 7.56 (br d, J = 8.8 Hz, 2H), 7.31 (br d, J = 7.7 Hz, 2H), 7.16 (br d, J = 8.1 Hz, 2H), 7.05 (br d, J = 7.3 Hz, 2H), 6.80 (br s, 1H), 3.53 (br s, 3H), 1.55 (s, 9H).

[0692] Step 7: Preparation of Methyl N-[4-[2-[(4-Chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]carbamate (Compound 66)

[0693]

[0694] At 0 °C, HCl (4 M in dioxane, 2.00 mL, 7.88 mmol, 10.0 eq) was added dropwise to a solution of tert-butyl N-[4-[2-[(4-chlorophenyl)methylcarbamoyl]purin-9-yl]phenyl]carbamate (410 mg, 0.788 mmol) in methanol (10.0 mL). The reaction mixture was stirred at room temperature for 72 h, then concentrated under reduced pressure. The residue was stirred in a mixture of water and ethyl acetate, and the basic layer was alkalized to pH 9 - 10 with NaOH. The mixture was extracted with ethyl acetate, and the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (ethyl acetate / methanol) to give 9-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2-carboxamide as a beige solid.

[0695] LC / MS (Method A) retention time = 0.78 min; [M+H] + = 379

[0696] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 9.11 (s, 1H), 8.26 (s, 1H), 7.01 - 7.25 (m, 6H), 6.79 (d, J = 8.4 Hz, 2H), 3.96 (br s, 2H), 3.54 (br s, 3H).

[0697] Example 3: Preparation of Methyl N-[5-[6-[(4-Fluoro-3-methoxyphenyl)-methyl-carbamoyl]-4-methyl-benzimidazol- 1-yl]-2-pyridyl]carbamate (Compound 26)

[0698] To a solution of 9-(4-aminophenyl)-N-(4-chlorophenyl)-N-methyl-purine-2-carboxamide (66.0 mg, 0.166 mmol) and pyridine (0.041 mL, 0.50 mmol, 3.0 equiv) in dichloromethane (3.00 mL) at 10 °C was added dropwise methyl chloroformate (0. mL, 0.41 mmol, 2.5 equiv). The reaction mixture was then warmed to room temperature and stirred for an additional 2 h. The reaction mixture was diluted with dichloromethane, quenched with aqueous NaHCO3 and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (cyclohexane / ethyl acetate) to afford N-[4-[2-[(4-chlorophenyl)-methyl-carbamoyl]purin-9-yl]phenyl]methyl carbamate as a white solid.

[0699] LC / MS (method C) retention time = 0.86 min; [M+H] + = 437

[0700] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 9.10 (s, 1H), 8.32 (s, 1H), 7.59 (br d, J = 8.4 Hz, 2H), 7.32 (br d, J = 8.1 Hz, 2H), 7.15 (br s, 5H), 7.06 (br d, J = 7.7 Hz, 2H), 3.80 (s, 3H), 3.54 (s, 3H).

[0701] Step 1: Preparation of 3-tert-Butoxycarbonyl-7-methyl-benzimidazole-5-carboxylic Acid Step 2: Preparation of tert-Butyl 6-[(4-Fluoro-3-methoxyphenyl)-methyl-carbamoyl]-4-methyl-benzimidazole-1-carboxylate

[0702]

[0703] Step 3: Preparation of N-(4-Fluoro-3-methoxyphenyl)-N,7-dimethyl-3H-benzimidazole-5-carboxamide

[0704]

[0705] To a yellow suspension of 7-methyl-3H-benzoimidazole-5-carboxylic acid (CAS: 398452-96-5; 7.0 g, 40 mmol) in acetonitrile (160 mL) and water (1.50 mL) was added triethylamine (11.0 mL, 79.0 mmol, 2.00 eq), then 4-dimethylaminopyridine (490 mg, 4.00 mmol, 0.10 eq) was added and di-tert-butyl dicarbonate (11.0 mL, 48.0 mmol, 1.20 eq) was added in portions. The reaction mixture was stirred at room temperature for 2 h and then diluted with ethyl acetate and water. The aqueous layer was acidified to pH 1 with 2 M HCl and the mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give 3-tert-butoxycarbonyl-7-methyl-benzoimidazole-5-carboxylic acid as a pale yellow solid.

[0706] LC / MS (method C) retention time = 0.89 min; [M+H] - = 275

[0707] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ = 12.95 (br s, 1H), 8.76 (s, 1H), 8.41 (s, 1H), 7.80 (s, 1H), 2.60 (s, 3H), 1.67 (s, 9H).

[0708] Step 4: Preparation of Methyl N-[5-[6-[(4-Fluoro-3-methoxyphenyl)-methyl-carbamoyl]-4-methyl-benzimidazol- 1-yl]-2-pyridyl]carbamate (Compound 26)

[0709]

[0710] To a solution of 4-fluoro-3-methoxy-N-methylaniline (320 mg, 1.96 mmol, 1.05 eq), N,N-diisopropylethylamine (0.96 mL, 5.60 mmol, 3.0 eq) and 3-tert-butoxycarbonyl-7-methyl-benzoimidazole-5-carboxylic acid (516 mg, 1.87 mmol) in ethyl acetate (7.5 mL) was added propylphosphonic anhydride solution (50 wt% in ethyl acetate, 2.0 mL, 3.36 mmol, 1.8 eq) in portions. The reaction mixture was stirred at room temperature for 4 h and then poured into water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography (cyclohexane / ethyl acetate) to give tert-butyl 6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]-4-methyl-benzoimidazole-1-carboxylate as a brown gum.

[0711] LC / MS (method C) retention time = 1.04 min; [M+H]+ = 414

[0712] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 8.39 (s, 1H), 7.79 (s, 1H), 7.26 (d, J = 0.7 Hz, 1H), 6.92 (dd, J = 10.9, 8.7 Hz, 1H), 6.72 (dd, J = 7.4, 2.4 Hz, 1H), 6.61 - 6.66 (m, 1H), 3.75 (s, 3H), 3.51 (s, 3H), 2.57 (s, 3H), 1.68 (s, 9H).

[0713] Example 4: Preparation of N-[5-[6-[(4-Fluoro-3-methoxyphenyl)-methyl-carbamoyl]imidazo[4,5-c]pyr

[0714]

[0715] A mixture of tert-butyl 6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-4-methyl-1H-benzoimidazole-1-carboxylate (795 mg, 1.92 mmol), toluene (5.8 mL) and trifluoroacetic acid (1.03 mL, 13.5 mmol, 7.00 equiv) was stirred overnight at room temperature, then concentrated under reduced pressure and dissolved in water. The mixture was neutralized with saturated aqueous NaHCO3 and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give crude N-(4-fluoro-3-methoxyphenyl)-N,7-dimethyl-3H-benzoimidazole-5-carboxamide as a brown gum. The product was used in the next step without further purification.

[0716] LC / MS (method C) retention time = 0.67 min; [M + H] + = 314

[0717] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 8.37 (s, 1H), 7.77 (s, 1H), 7.25 (s, 1H), 6.90 (dd, J = 10.9, 8.7 Hz, 1H), 6.71 (dd, J = 7.6, 2.5 Hz, 1H), 6.58 - 6.66 (m, 1H), 3.74 (s, 3H), 3.50 (s, 3H), 2.56 (s, 3H).

[0718] idin-1-yl]-2-pyridyl]carbamate (Compound 24) Step 1: Preparation of Methyl N-[5-[(2-Chloro-5-nitro-4-pyridyl)amino]-2-pyridyl]carbamate

[0719] To a mixture of N-(4-fluoro-3-methoxyphenyl)-N,7-dimethyl-3H-benzoimidazole-5-carboxamide (100 mg, 0.319 mmol), boric acid (60 mg, 0.958 mmol, 3.0 eq), and copper(II) acetate (174 mg, 0.958 mmol, 3.0 eq) in acetonitrile (1.0 mL) was added N,N-diisopropylethylamine (0.170 mL, 0.958 mmol, 3.0 eq), and then a suspension of N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamic acid methyl ester (266 mg, 0.958 mmol, 3.0 eq) in acetonitrile (2.0 mL) was added dropwise. The reaction mixture was stirred at 60 °C overnight. Then the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The resulting residue was dissolved in ethanol, filtered through a pad of diatomaceous earth, and the filtrate was concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel (cyclohexane / ethyl acetate), and then rinsed with acetonitrile to give N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]-4-methyl-1H-benzoimidazol-1-yl]-2-pyridyl]carbamic acid methyl ester as an off-white solid.

[0720] LC / MS (Method C) retention time = 0.86 min; [M+H] + = 464

[0721] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 8.22 (d, J = 2.2 Hz, 1H), 8.19 (d, J = 8.7 Hz, 1H), 8.04 (s, 1H), 7.72 (br s, 1H), 7.55 (dd, J = 8.7, 2.5 Hz, 1H), 7.27 - 7.29 (m, 1H), 7.15 (br s, 1H), 6.94 (dd, J = 10.7, 8.5 Hz, 1H), 6.67 (dd, J = 7.4, 2.4 Hz, 1H), 6.60 (ddd, J = 8.6, 3.7, 2.5 Hz, 1H), 3.88 (s, 3H), 3.72 (s, 3H), 3.48 (s, 3H), 2.62 (s, 3H).

[0722] Step 2: Preparation of Methyl N-[5-[(5-Amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamate Step 3: Preparation of Methyl N-[5-(6-Chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridyl]carbamate

[0723]

[0724] Step 4: Methyl 1-[6-(Methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6-carboxylate

[0725]

[0726] To a solution of 2,4-dichloro-5-nitropyridine (10.5 g, 51.7 mmol) and N-(5-amino-2-pyridyl)carbamic acid methyl ester (9.10 g, 51.7 mmol, 1.0 equiv) in ethanol (150 mL) was added N,N-diethylethylamine (21.2 mL, 155 mmol, 3.0 equiv) and the reaction mixture was stirred at 100 °C for 16 h. After cooling to room temperature, it was concentrated under reduced pressure, then water was added to the residue. The mixture was stirred at room temperature for 1 h, then the precipitate was filtered, washed with water and hexane and dried in vacuo to give N-[5-[(2-chloro-5-nitro-4-pyridyl)amino]-2-pyridyl]carbamic acid methyl ester as a solid.

[0727] 1H NMR (400 MHz, DMSO-d6, ppm) δ = 10.37 (s, 1H), 9.92 (s, 1H), 8.97 (s, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.94 (d, J = 8.8 Hz, 1H), 7.80 (dd, J = 11.6 Hz, 2.8 Hz, 1H), 6.71 (s, 1H), 3.70 (s, 3H).

[0728] ​

[0729]

[0730] To a solution of N-[5-[(2-chloro-5-nitro-4-pyridyl)amino]-2-pyridyl]carbamic acid methyl ester (250 mg, 0.734 mmol) in ethanol (15.0 mL) and water (5.00 mL) was added iron (81.9 mg, 1.47 mmol, 2.00 equiv), followed by ammonium chloride (392 mg, 7.34 mmol, 10.0 equiv). The reaction mixture was stirred at 100 °C for 2 h, then it was filtered through a pad of diatomaceous earth and washed with excess ethyl acetate. The filtrate was concentrated under reduced pressure, diluted with water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to give N-[5-[(5-amino-2-chloro-4-pyridyl)amino]-2-pyridyl]carbamic acid methyl ester as a solid. The product was used in the next step without further purification.

[0731] 1H NMR (400 MHz, DMSO-d6, ppm) δ = 10.12 (s, 1H), 8.13 (d, J = 2.0 Hz, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.74 (s, 1H), 7.64 (dd, J = 11.6 Hz, 1H), 7.60 (s, 1H), 6.54 (s, 1H), 5.00 (s, 2H), 3.68 (s, 3H).

[0732] ​

[0733]

[0734] To a solution of N-[5-[(5-amino-2-chloro-4-pyridinyl)amino]-2-pyridinyl]carbamic acid methyl ester (5.00 g, 16.2 mmol) in diethoxymethoxyethane (25.0 mL) was added hydrogen chloride 36 mass%, 1.64 g, 16.2 mmol, 1.00 equivalent), and the reaction mixture was stirred at 100 °C for 1 hour. After cooling to room temperature, the mixture was concentrated under reduced pressure, and the residue was treated with water and stirred for 20 minutes. The precipitate was filtered, washed with water and n-hexane, and dried under reduced pressure to give N-[5-(6-chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridinyl]carbamic acid methyl ester as a solid. The product was used in the next step without further purification.

[0735] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ = 10.61 (s, 1H), 8.90 (s, 1H), 8.77 (s, 1H), 8.643 (d, J = 2.4 Hz, 1H), 8.17 (dd, J = 11.6, 2.4 Hz, 1H), 8.06 (d, J = 9.2 Hz, 1H), 7.77 (s, 1H), 3.72 (s, 3H).

[0736] ​ Preparation

[0737]

[0738] In a steel autoclave, N-[5-(6-chloroimidazo[4,5-c]pyridin-1-yl)-2-pyridinyl]carbamic acid methyl ester (3.00 g, 9.38 mmol) and sodium acetate (2.31 g, 28.2 mmol, 3.00 equivalents) were dissolved in methanol (100 mL), and the mixture was degassed with argon for 10 minutes. To this mixture were added diphenyl-[(rac-(4S,4'R)-1'-diphenylphosphinoferrocen-1-yl)]phosphane (260 mg, 0.469 mmol, 0.05 equivalent) and palladium(II) acetate (105 mg, 0.469 mmol, 0.05 equivalent), carbon monoxide gas (200 psi pressure) was introduced, and the reaction mixture was stirred at 100 °C for 16 hours. After cooling to room temperature, it was filtered and washed with methanol. The filtrate was concentrated under reduced pressure to give methyl 1-[6-(methoxycarbonylamino)-3-pyridinyl]imidazo[4,5-c]pyridine-6-carboxylate as a solid.

[0739] 1 H NMR (400 MHz, DMSO-d6, ppm) δ = 10.60 (s, 1H), 9.17 (s, 1H), 8.91 (s, 1H), 8.66 (s, 1H), 8.21 (br s, 2H), 8.10 (br s, 1H), 3.89 (s, 3H), 3.73 (S, 3H).

[0740] Step 5: Preparation of lithium 1-[6-(methoxycarbonylamino)-3-pyridinyl]imidazo[4,5-c]pyridine-6-carboxylate

[0741]

[0742] To a solution of methyl 1-[6-(methoxycarbonylamino)-3-pyridinyl]imidazo[4,5-c]pyridine-6-carboxylate (800 mg, 2.20 mmol) in tetrahydrofuran (15.0 mL), methanol (10.0 mL) and water (10.0 mL) was added lithium hydroxide (369 mg, 8.80 mmol, 4.00 equivalents), and the resulting reaction mixture was stirred at room temperature for 16 hours. The mixture was then concentrated under reduced pressure, the residue was stirred in water, and the precipitate was filtered and washed with methanol. The solid was dried under reduced pressure to give lithium 1-[6-(methoxycarbonylamino)-3-pyridinyl]imidazo[4,5-c]pyridine-6-carboxylate as a solid.

[0743] 1 H NMR (400 MHz, DMSO-d6, ppm) δ = 10.59 (s, 1H), 8.92 (app br s, 1H), 8.76 (s, 1H), 8.62 (s, 1H), 8.24 - 8.00 (m, 3H), 3.73 (s, 3H).

[0744] Step 6: Preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]imidazo[4,5-c]pyridin-1-yl]-2-pyridinyl]carbamate (Compound 24) Example 5: Preparation of methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]benzimidazol-1-yl]-2-pyridinyl]carbamate (Compound 22)

[0745] To a solution of lithium 1-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[4,5-c]pyridine-6-carboxylate (250 mg, 0.744 mmol) and 4-fluoro-3-methoxy-N-methylaniline (173 mg, 1.12 mmol, 1.50 equiv) in N,N-dimethylformamide (10.0 mL) was added diisopropylethylamine (0.401 mL, 2.23 mmol, 3.00 equiv) and 1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (565 mg, 1.49 mmol, 2.00 equiv). The resulting reaction mixture was stirred at room temperature for 16 h, then diluted with water, the formed precipitate was filtered off, and the aqueous layer was concentrated under reduced pressure. The resulting residue was purified by C-18 cartridge reverse-phase chromatography (acetonitrile / water) to give methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]imidazo[4,5-c]pyridin-1-yl]-2-pyridyl]carbamate as an off-white solid.

[0746] 1 H NMR (400 MHz, DMSO-d6, ppm) δ = 10.61 (s, 1H), 8.80 (br s, 1H), 8.77 (s, 1H), 8.68 (s, 1H), 8.08 (app s, 2H), 7.82 (s, 1H), 7.09 (d, J = 6.4 Hz, 1H), 7.00 (br s, 1H), 6.67 (br s, 1H), 3.73 (s, 3H), 3.65 (S, 3H), 3.39 (s, 3H).

[0747] Step 1: Preparation of a mixture of 1-tert-butoxycarbonylbenzimidazole-5-carboxylic acid and 3-tert-butoxycarbonylbenzimidazole-5-carboxylic acid Step 2: Preparation of tert-butyl 6-[(4-fluorophenyl)methylcarbamoyl]benzimidazole-1-carboxylate and tert-butyl 5-[(4-fluorophenyl)methylcarbamoyl]benzimidazole-1-carboxylate

[0748]

[0749] Preparation of N-(4-fluorophenyl)-N-methyl-3H-benzimidazole-5-carboxamide Step 4: Preparation of methyl N-[5-[6-[(4-fluorophenyl)methylcarbamoyl]benzimidazol-1-yl]-2-pyridinyl]carbamate (Compound 22)

[0750]

[0751] At room temperature, a solution of di-tert-butyl pyrocarbonate (2.66 g, 12.1 mmol) in dioxane (9.0 mL) was added dropwise to a mixture of 3H-benzoimidazole-5-carboxylic acid (1.00 g, 6.04 mmol) and sodium carbonate (1.54 g, 14.5 mmol) in water (15.1 mL). The reaction mixture was stirred overnight at room temperature and then poured into water. The mixture was extracted with diethyl ether, and the aqueous layer was acidified with 2 M HCl to pH 1 and extracted again with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure to give a mixture of 1-tert-butoxycarbonylbenzoimidazole-5-carboxylic acid and 3-tert-butoxycarbonylbenzoimidazole-5-carboxylic acid isomers, which was used in the next step without further purification.

[0752] LC / MS (method C) retention time = 0.81 & 0.84 min; [M+H] + = 261

[0753] Example 6: Preparation of methyl N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-4-methylbenzimidazol-1-yl]-2-pyridinyl]carbamate (Compound 64) Step 1: Preparation of (7-fluoro-2,3-dihydro-1,4-benzoxazin-4-yl)-(7-methyl-3H-benzimidazol-5-yl)methanone

[0754]

[0755] At room temperature, a solution of propylphosphonic anhydride (50 wt% in ethyl acetate, 2.40 mL, 4.00 mmol, 1.80 eq) was added dropwise to a mixture of 1-tert-butoxycarbonylbenzoimidazole-5-carboxylic acid and 3-tert-butoxycarbonylbenzoimidazole-5-carboxylic acid (580 mg, 2.20 mmol), 4-fluoro-N-methylaniline (300 mg, 2.30 mmol, 1.05 eq) and N,N-diisopropylethylamine (1.10 mL, 6.60 mmol, 3.00 eq) in ethyl acetate (8.80 mL) and the reaction mixture was stirred overnight. Then the mixture was poured into water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure to give a mixture of 6-[(4-fluorophenyl)-methyl-carbamoyl]benzoimidazole-1-carboxylic acid tert-butyl ester and 5-[(4-fluorophenyl)-methyl-carbamoyl]benzoimidazole-1-carboxylic acid tert-butyl ester isomers as a brown gum. The mixture was used in the next step without further purification.

[0756] LC / MS (method C) retention time = 0.97 & 1.00 min; [M+H] + = 370

[0757] Step 3: Step 2: Preparation of methyl N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-4-methylbenzimidazol-1-yl]-2-pyridinyl]carbamate (Compound 64)

[0758]

[0759] A mixture of tert-butyl 6-[(4-fluorophenyl)-methyl-carbamoyl]benzimidazole-1-carboxylate and tert-butyl 5-[(4-fluorophenyl)-methyl-carbamoyl]benzimidazole-1-carboxylate (830 mg, 2.20 mmol) in trifluoroacetic acid (1.20 mL, 16.0 mmol, 7.00 eq) and toluene (6.70 mL) was stirred overnight at room temperature. The reaction mixture was then concentrated under reduced pressure, and the resulting residue was dissolved in water and neutralized with saturated aqueous NaHCO3. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure to give N-(4-fluorophenyl)-N-methyl-3H-benzimidazole-5-carboxamide as a beige solid.

[0760] LC / MS (method C) retention time = 0.54 min; [M+H] + = 270

[0761] 1 1H NMR (400 MHz, CDCl3, ppm) δ = 8.99 - 9.50 (br s, 1H), 8.04 (s, 1H), 7.70 (br s, 1H), 7.45 (br s, 1H), 7.20 - 7.27 (m, 1H), 7.05 (dd, J = 8.9, 4.9 Hz, 2H), 6.86 - 6.95 (m, 2H), 3.53 (s, 3H).

[0762] Example 7: This example demonstrates the preparation of methyl N-[5-[6-[(4-fluoro-3-methoxyphenyl)methylcarbamoyl]-4-(methoxymethyl)benzimidazol-1-yl]-2-pyridinyl]carbamate (Compound 1) Step 1: Preparation of methyl 6-bromo-1-(2-trimethylsilylethoxymethyl)benzimidazole-4-carboxylate

[0763] To a solution of N-(4-fluorophenyl)-N-methyl-3H-benzimidazole-5-carboxamide (210 mg, 0.780 mmol), boric acid (97.4 mg, 1.56 mmol, 2.00 eq) and copper(II) acetate (212.5 mg, 1.17 mmol, 1.50 eq) in acetonitrile (20.3 mL) at room temperature was added N,N-diisopropylethylamine (0.277 mL, 1.56 mmol, 2.00 eq), and then N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamic acid methyl ester (434 mg, 1.56 mmol, 2.00 eq) was added. The reaction mixture was stirred at 60 °C under an air atmosphere for 2.5 h. The reaction mixture was cooled to room temperature and poured into water. The aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by preparative HPLC column (CO2 / methanol) to give N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl]benzimidazol-1-yl]-2-pyridyl]carbamic acid methyl ester as a pale pink solid.

[0764] LC / MS (Method C) retention time = 0.82 min; [M+H] + = 420

[0765] 1 H NMR (600 MHz, CDCl3, ppm) δ = 8.28 (d, J = 2.4 Hz, 1H), 8.21 (d, J = 8.9 Hz, 1H), 8.07 (s, 1H), 7.81 (s, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (dd, J = 8.8, 2.6 Hz, 1H), 7.40 - 7.47 (m, 1H), 7.31 (dd, J = 8.4, 1.4 Hz, 1H) 7.03 (dd, J = 8.88, 4.6 Hz, 2H), 6.90 - 6.98 (m, 2H), 3.88 (s, 3H), 3.50 (s, 3H).

[0766] Step 2: Preparation of [6-bromo-1-(2-trimethylsilylethoxymethyl)benzimidazol-4-yl]methanol Step 3: Preparation of 2-[[6-bromo-4-(methoxymethyl)benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane

[0767]

[0768] Step 4: Preparation of methyl 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylate Step 5: Preparation of 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylic acid (Intermediate I-1)

[0769]

[0770] To a solution of 7-methyl-3H-benzimidazole-5-carboxylic acid (CAS 398452-96-5, commercially available and can be prepared according to WO2009144554A1) (500 mg, 2.84 mmol) in N,N-dimethylformamide (7.00 mL) was added 1-methylimidazole (699 mg, 8.51 mmol, 3.00 equiv), N,N,N',N'-tetramethylchloroformamidinium hexafluorophosphate (956 mg, 3.41 mmol, 1.20 equiv) and 7-fluoro-3,4-dihydro-2H-1,4-benzoxazine (CAS 56346-41-9, 435 mg, 2.84 mmol, 1.00 equiv). The reaction mixture was stirred at room temperature for 4 h, then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (ethyl acetate / petroleum ether) to give (7-fluoro-2,3-dihydro-1,4-benzoxazin-4-yl)-(7-methyl-3H-benzimidazol)-5-yl)methanone as a yellow solid.

[0771] LC / MS (Method A) retention time = 0.91 min; [M+H] + = 312

[0772] Step 6: Preparation of N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxamide ​

[0773] To a solution of (7-fluoro-2,3-dihydro-1,4-benzoxazin-4-yl)-(7-methyl-3H-benzimidazol-5-yl)methanone (165 mg, 0.530 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridinyl]carbamic acid methyl ester (295 mg, 1.06 mmol, 2.00 equiv) in methanol (3.00 mL) was added copper(I) oxide (228 mg, 1.59 mmol, 3.00 equiv). The reaction mixture was stirred at room temperature under an oxygen atmosphere for 24 h, then filtered through a pad of Celite, and the filtrate was concentrated under reduced pressure. The crude residue was first purified by flash chromatography on silica gel (dichloromethane / methanol) and then further purified by preparative HPLC chromatography (CO2 / ethanol) to afford N-[5-[6-(7-fluoro-2,3-dihydro-1,4-benzoxazine-4-carbonyl)-4-methyl-benzimidazol-1-yl]-2-pyridinyl]carbamic acid methyl ester as an off-white solid.

[0774] LC / MS (method A) retention time = 1.18 min; [M+H] + = 462

[0775] 1H NMR (400 MHz, DMSO-d6, ppm) δ = 10.54 (s, 1H), 8.64 (s, 1H), 8.55 (s, 1H), 8.04 (d, J = 8.4 Hz, 2H), 7.56 (s, 1H), 7.40 (s, 1H), 7.31 (s, 1H), 6.80 (dd, J = 10.0, 2.9 Hz, 1H), 6.65 (td, J = 8.7, 2.7 Hz, 1H), 4.29 - 4.27 (m, 2H), 3.88 - 3.86 (m, 2H), 3.72 (s, 3H), 2.61 (s, 3H).

[0776] ​ ​

[0777]

[0778] ​

[0779]

[0780] Under 0 °C and nitrogen atmosphere, sodium hydride 60% (2.82 g, 70.6 mmol, 1.20 eq) was added to a solution of methyl 6-bromo-1H-benzoimidazole-4-carboxylate [CAS 1806519-50-9] (15.0 g, 58.8 mmol) in dry DMF (400 mL). After stirring at 0 °C for 20 minutes, 2-(chloromethoxy)ethyl-trimethyl-silane (11.8 g, 70.6 mmol, 1.20 eq) was added dropwise. The resulting reaction mixture was slowly warmed to room temperature, stirred at room temperature for 2 hours, then quenched with saturated NH4Cl solution 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 (eluting with dichloromethane / methanol) to give methyl 6-bromo-1-(2-trimethylsilylethoxymethyl)benzoimidazole-4-carboxylate and methyl 6-bromo-3-(2-trimethylsilylethoxymethyl)benzoimidazole-4-carboxylate as a brown solid.

[0781] LC / MS (method A) retention time = 1.46 min; [M+H] + = 385

[0782] ​

[0783]

[0784] Under nitrogen atmosphere, lithium chloride (7.26 g, 171 mmol, 10.0 eq) was added to a solution of methyl 6-bromo-1-(2-trimethylsilylethoxymethyl)benzoimidazole-4-carboxylate (6.60 g, 17.1 mmol) in dry methanol (200.00 mL). Then sodium borohydride (6.31 g, 171 mmol, 10.0 eq) was added in portions. The resulting reaction mixture was stirred at 40 °C for 12 hours. The reaction mixture was quenched with saturated NH4Cl solution and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, and concentrated under reduced pressure to give [6-bromo-1-(2-trimethylsilylethoxymethyl)benzoimidazol-4-yl]methanol as a brown oil.

[0785] LC / MS (method A) retention time = 1.35 min; [M+H] + = 357

[0786] ​ ​

[0787]

[0788] To a solution of [6-bromo-1-(2-trimethylsilylethoxymethyl)benzimidazol-4-yl]methanol (7.50 g, 21.0 mmol) in tetrahydrofuran (100 mL) at 0 °C was added sodium hydride 60% (1.01 g, 25.2 mmol, 1.20 equiv) portionwise. The reaction mixture was stirred for 20 minutes and then iodomethane (5.96 g, 42.0 mmol, 2.0 equiv) was added. The resulting reaction mixture was stirred at room temperature for 3 hours and 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 to give 2-[[6-bromo-4-(methoxymethyl)benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane as a pale yellow liquid.

[0789] LC / MS (method A) retention time = 1.42 min; [M+H] + = 371

[0790] ​ ​

[0791]

[0792] To a reaction autoclave was charged 2-[[6-bromo-4-(methoxymethyl)benzimidazol-1-yl]methoxy]ethyl-trimethyl-silane (14.0 g, 37.7 mmol), methanol (350.0 mL), 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II) dichloromethane complex (1.53 g, 1.89 mmol, 0.05 equiv), and N,N-diethylethylamine (11.4 g, 113 mmol, 3.0 equiv). The autoclave was then flushed with carbon monoxide, sealed, and pressurized with carbon monoxide to 2.5 MPa. The reaction mixture was stirred at 100 °C for 36 hours and then the vessel was cooled to room temperature and the pressure was released. The reaction mixture was concentrated to dryness and purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give methyl 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylate as a brown oil.

[0793] LC / MS (method A) retention time = 1.47 min; [M+H] + = 351

[0794] ​ ​

[0795]

[0796] To a stirred mixture of methyl 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylate (10.0 g, 28.5 mmol) in tetrahydrofuran / water (150.0 mL) was added lithium hydroxide (2.05 g, 85.6 mmol, 3.0 equiv) portionwise. The resulting reaction mixture was stirred at 40 °C for 4 h and then diluted with water (75.00 mL). The tetrahydrofuran was evaporated off and the mixture was then extracted with diethyl ether. The aqueous phase was acidified to pH = 2 with 2 M aqueous HCl. The precipitate was collected by filtration, washed with water and concentrated under reduced pressure to give 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylic acid as a brown solid.

[0797] LC / MS (Method A) retention time = 0.75 min; [M+H] + = 337

[0798] ​ ​

[0799]

[0800] Under a nitrogen atmosphere at 70 °C, propylphosphonic anhydride (50.0% in ethyl acetate, 5.80 mmol, 3.00 equiv) was added dropwise to a solution of 4-fluoro-3-methoxy-N-methylaniline [CAS 904321-01-3] (300 mg, 1.93 mmol) and 7-(methoxymethyl)-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxylic acid (Intermediate I-1, 683 mg, 2.03 mmol, 1.05 equiv) in pyridine (15 mL). The resulting reaction mixture was stirred for 3 h and then quenched with saturated aqueous NaHCO3 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 / methanol) to give N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxamide as a pale yellow solid.

[0801] LC / MS (Method A) retention time = 1.43 min; [M+H] + = 474

[0802] Step 7: Preparation of N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3H-benzimidazole-5-carboxamide Preparation

[0803]

[0804] To a solution of N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3-(2-trimethylsilylethoxymethyl)benzimidazole-5-carboxamide (750 mg, 1.58 mmol) in dichloromethane (7 mL) was added dropwise 2,2,2-trifluoroacetic acid (7 mL) at room temperature. The reaction mixture was stirred at room temperature for 8 hours. The reaction mixture was adjusted to pH 9 with saturated aqueous NaHCO3 and then partitioned between dichloromethane (150 mL) and aqueous NaHCO3 solution. The separated organic layer was evaporated to dryness and purified by silica gel column chromatography (dichloromethane / methanol) to give N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3H-benzimidazole-5-carboxamide as a pale yellow solid.

[0805] LC / MS (method A) retention time = 0.86 min; [M+H] + = 344

[0806] Step 8: Preparation of N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methylcarbamoyl]-4-(methoxymethyl)benzimidazol-1-yl]-2-pyridyl]methyl carbamate (Compound 1) Preparation

[0807] To a solution of N-(4-fluoro-3-methoxyphenyl)-7-(methoxymethyl)-N-methyl-3H-benzimidazole-5-carboxamide (200 mg, 0.582 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamic acid methyl ester [CAS 1073372-02-7] (324 mg, 1.16 mmol, 2.0 equiv) in methanol solution (15.0 mL) was added copper(I) oxide (250 mg, 1.75 mmol, 3.0 equiv). The reaction mixture was stirred at 35 °C under an oxygen atmosphere for 24 hours. Then the mixture was filtered through Celite. The filtrate was concentrated under reduced pressure to give a crude product, which was purified by silica gel column chromatography (methanol / dichloromethane). It was further purified by SFC and then triturated in ether to give N-[5-[6-[(4-fluoro-3-methoxyphenyl)-methyl-carbamoyl]-4-(methoxymethyl)benzimidazol-1-yl]-2-pyridyl]carbamic acid methyl ester as an off-white powder.

[0808] LC / MS (method A) retention time = 1.10 min; [M+H] + = 494

[0809] 11H NMR (400 MHz, DMSO-d6, ppm) δ = 10.56 (s, 1H), 8.56 (s, 1H), 8.47 - 8.42 (m, 1H), 8.05 (dd, J = 8.9, 0.7 Hz, 1H), 7.84 (dd, J = 8.9, 2.8 Hz, 1H), 7.40 (d, J = 1.5 Hz, 1H), 7.31 (d, J = 1.5 Hz, 1H), 7.22 (dd, J = 7.9, 2.5 Hz, 1H), 7.01 (dd, J = 11.3, 8.6 Hz, 1H), 6.65 (ddd, J = 8.6, 3.9, 2.5 Hz, 1H), 4.75 (s, 2H), 3.74 (s, 3H), 3.69 (s, 3H), 3.37 (s, 3H), 3.21 (s, 3H)

[0810] Example 8: Preparation of N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]methyl carbamate (Compound 2) Preparation

[0811]

[0812] Step 1: Preparation of 7-methyl-3-tetrahydropyran-2-yl-benzimidazole-5-carboxylic acid (Intermediate I-2)

[0813]

[0814] To a suspension of 7-methyl-3H-benzoimidazole-5-carboxylic acid [CAS 398452-96-5] (3.00 g, 17.0 mmol) in tetrahydrofuran (250.0 mL) was added 3,4-dihydro-2H-pyran [CAS 110-87-2] (28.6 g, 341 mmol, 20 eq) and (7,7-dimethyl-2-oxo-norbornan-1-yl)methanesulfonic acid (0.396 g, 1.70 mmol, 0.10 eq). The reaction mixture was refluxed under a nitrogen atmosphere for 24 h. The reaction was quenched with water, the tetrahydrofuran was evaporated, and the resulting aqueous residue was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give 7-methyl-3-tetrahydropyran-2-yl-benzoimidazole-5-carboxylic acid (Intermediate I-2) as a brown solid.

[0815] LC / MS (Method A) retention time = 0.86 min; [M + H] + = 261

[0816] Step 2: Preparation of 3-(4-fluoro-3-methoxyanilino)propanenitrile

[0817]

[0818] At 25 °C under a nitrogen atmosphere, 4-fluoro-3-methoxyaniline [CAS 64465-53-8] (3.00 g, 21.3 mmol) was successively added to a suspension of copper(I) iodide (0.283 g, 1.49 mmol, 0.07 equiv), potassium tert-butoxide (0.477 g, 4.25 mmol, 0.20 equiv), and 1,3-bis[2,6-bis(1-methylethyl)phenyl]-1H-imidazolium chloride (0.635 g, 1.49 mmol, 0.07 equiv) in toluene (70.00 mL). The reaction mixture was pre-mixed for 30 minutes, and then a solution of propan-2-carbonitrile [CAS 107-13-1] (2.26 g, 42.5 mmol, 2.0 equiv) in toluene (10 mL) was added to the reaction mixture. The resulting reaction mixture was stirred at room temperature for 3 hours, then quenched with saturated aqueous NH4Cl and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate) to give 3-(4-fluoro-3-methoxyanilino)propanenitrile as a brown solid.

[0819] LC / MS (Method A) retention time = 1.06 min; [M+H] + = 195

[0820] Step 3: Preparation of N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3-tetrahydropyran-2-yl-benzimidazole-5-carboxamide Preparation

[0821]

[0822] At 0 °C, phosphorus oxychloride(V) (707 mg, 4.61 mmol, 3.0 equiv) was added dropwise to a solution of 7-methyl-3-tetrahydropyran-2-yl-benzimidazole-5-carboxylic acid (Intermediate I-2, 400 mg, 1.54 mmol) and 3-(4-fluoro-3-methoxyanilino)propanenitrile (313 mg, 1.61 mmol, 1.05 equiv) in pyridine (15.0 mL). The resulting solution was slowly warmed to room temperature and stirred for 4 hours. Then it was quenched with saturated aqueous 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 / methanol) to give N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3-tetrahydropyran-2-yl-benzimidazole-5-carboxamide as a viscous oil.

[0823] LC / MS (Method A) retention time = 1.08 min; [M+H] + = 437

[0824] Step 4: Preparation of N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3H-benzimidazole-5-carboxamide Preparation

[0825]

[0826] Under a nitrogen atmosphere, pyridinium 4-methylbenzenesulfonate (117 mg, 0.467 mmol, 1.20 equiv) was added to a solution of N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3-tetrahydropyran-2-yl-benzimidazole-5-carboxamide (170 mg, 0.389 mmol) in ethanol (15.0 mL). The reaction mixture was stirred at 75 °C for 8 h, then the resulting reaction 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 (ethyl acetate / petroleum ether) to give N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3H-benzimidazole-5-carboxamide as a brown solid.

[0827] LC / MS (method A) retention time = 0.80 min; [M+H] + = 353

[0828] Step 5: Preparation of N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]methyl carbamate (Compound 2) Preparation

[0829] To a solution of N-(2-cyanoethyl)-N-(4-fluoro-3-methoxyphenyl)-7-methyl-3H-benzimidazole-5-carboxamide (110 mg, 0.312 mmol) and N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamic acid methyl ester [CAS 1073372-02-7] (174 mg, 0.624 mmol, 2.0 equiv) in methanol (10.00 mL) was added copper(I) oxide (134 mg, 0.937 mmol, 3.0 equiv). The reaction mixture was stirred at 35 °C under an oxygen atmosphere for 24 h. Then the mixture was filtered through diatomaceous earth and the filtrate was concentrated under reduced pressure to give the crude product, which was purified by silica gel column chromatography (dichloromethane / methanol). It was further purified by trituration in diethyl ether to give N-[5-[6-[2-cyanoethyl-(4-fluoro-3-methoxyphenyl)carbamoyl]-4-methyl-benzimidazol-1-yl]-2-pyridyl]carbamic acid meth...

Claims

1. A compound having the formula (I) wherein Z is O or S, and preferably Z is O; A is CH or N; A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; A 2 is independently CR 2 or N, provided that no more than three A 2 are N, preferably no more than two A 2 are N, preferably no more than one A 2 are N, and more preferably four A 2 are CR 2 ; R 2 independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, wherein said C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 each of the alkylcarbonyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN; A 3 is independently CR 3 or N; R 3 independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, di-C 1-6 -alkylamino and C 3-6 cycloalkylamino, wherein each of said C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, di-C 1-6 -alkylamino and C 3-6 each of the cycloalkylamino groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN; R 4 selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl, di-C 1-6 alkylaminocarbonyl-C 1-6 alkyl 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, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl and di-C 1-6 alkylaminocarbonyl-C 1-6 each of the alkyl groups is optionally substituted with one to three substituents independently selected from: halogen and CN; Wherein A 3 and R 4 optionally form a ring together, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring; and R 5 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 alkoxyC 1-6 alkyl, C 1-6 alkylamino, diC 1-6 alkylamino and C 1-6 alkylC 1-6 alkoxyamino, wherein each of said groups is optionally substituted with one to three substituents independently selected from: halogen and CN; or a salt or N-oxide thereof.

2. The compound according to claim 1, wherein the four A 1 is CR 1 .

3. The compound according to claim 1, wherein the two A 1 are CR 1 and the two A 1 are N.

4. The compound according to claim 1, wherein three A 1 are CR 1 and one A 1 is N.

5. A compound according to any one of the preceding claims, wherein R 1 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl, and is preferably independently selected from hydrogen and C 1-6 alkyl.

6. The compound according to any one of the preceding claims, wherein is is preferably and is more preferably 7. A compound according to any one of the preceding claims, wherein R 2 is independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl and C 1-6 alkoxy-C 1-6 alkoxy, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, wherein each of the C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di-C 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl groups is optionally substituted by one to three substituents independently selected from halogen, hydroxy and CN.

8. The compound according to any one of the preceding claims, wherein R 3 is independently selected from hydrogen, hydroxy, halogen, CN, 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, C 3-6 cycloalkyl-C 1-6 alkyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino and C 3-6 cycloalkylamino, wherein each of the C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, amino, C 1-6 alkylamino, diC 1-6 -alkylamino and C 3-6 cycloalkylamino groups is optionally substituted by one to three substituents independently selected from halogen, hydroxy and CN.

9. The compound according to any one of the preceding claims, wherein the four A 2 are CR 2 and A 3 is N.

10. The compound according to any one of claims 1 to 8, wherein Yes And preferably, three A 2 is CR 2 And A 3 is CR 3 .

11. The compound according to any one of claims 1 to 8, wherein is And preferably, three A 2 is CR 2 And A 3 is CR 3 .

12. The compound according to any one of claims 1 to 8, wherein the four A 2 is CR 2 and A 3 is CR 3 , and preferably is 13. A composition comprising a fungicidally effective amount of the compound according to any one of claims 1 to 12.

14. The composition according to claim 13, 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.

15. A method for combating, preventing or controlling phytopathogenic diseases, the method comprising applying a fungicidally effective amount of the compound according to any one of claims 1 to 12 or a composition comprising the compound according to any one of claims 1 to 12 or the composition according to claim 13 or 14 to a plant pathogen, the locus of a plant pathogen, a plant susceptible to attack by a plant pathogen, or plant propagation material thereof.

16. A compound having the formula (XVI) wherein A is CH or N; A 1 independently is N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; and R 5 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; or a salt or N-oxide thereof; or A compound having the formula (XVII) wherein A is CH or N; A 1 independently is N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; R 5 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of said groups is optionally substituted with one to three substituents independently selected from: halogen and CN; and R 9 is a C1-C6 alkyl group; or A compound having the formula (XVIII) wherein A is CH or N; A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; R 5 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; and X is Cl, Br or I.

17. A compound having the formula (XXIII) wherein A is CH or N; A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; R 5 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, di-C 1-6 alkylamino and C 1-6 alkyl C 1-6 alkoxyamino, wherein each of said groups is optionally substituted by one to three substituents independently selected from: halogen and CN; and R 9 is a C1-C6 alkyl group.

18. A compound having the formula (XXV) wherein A is CH or N; A 1 is independently N or CR 1 ; provided that no more than three A 1 are N, preferably no more than two A 1 are N, preferably no more than one A 1 are N, and more preferably four A 1 are CR 1 ; R 1 independently selected from hydrogen, hydroxy, 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 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy, amino and NHC(O)C 1-6 alkyl; A 2 Independently is CR 2 or N, provided that no more than three A 2 are N, preferably no more than two A 2 are N, preferably no more than one A 2 are N, and more preferably four A 2 are CR 2 ; R 2 independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 alkylcarbonyl, 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, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, diC 1-6 alkylaminocarbonyl and C 1-6 each of the alkylcarbonyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN; A 3 independently is CR 3 or N; R 3 independently selected from hydrogen, hydroxy, halogen, CN, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, di-C 1-6 -alkylamino and C 3-6 cycloalkylamino, 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, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylthio, C 1-6 alkylsulfinyl, C 1-6 alkylsulfonyl, amino, C 1-6 alkylamino, di-C 1-6 -alkylamino and C 3-6 each cycloalkylamino group is optionally substituted by one to three substituents independently selected from halogen, hydroxy and CN; R 4 selected from C 1-6 alkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl, diC 1-6 alkylaminocarbonyl-C 1-6 alkyl 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, C 1-6 alkoxy, C 1-6 alkylthio-C 1-6 alkyl, C 1-6 alkylsulfinyl-C 1-6 alkyl, C 1-6 alkylsulfonyl-C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-6 alkyl, C 1-6 alkylaminocarbonyl-C 1-6 alkyl and diC 1-6 alkylaminocarbonyl-C 1-6 each of the alkyl groups is optionally substituted with one to three substituents independently selected from: halogen and CN; wherein A 3 and R 4 together optionally form a ring, more preferably a 5- to 8-membered heterocyclic ring, more preferably a 6-membered heterocyclic ring.

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